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Materials Science and Engineering R 98 (2015) 1–71

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Materials Science and Engineering R


journal homepage: www.elsevier.com/locate/mser

A comprehensive review of Li4Ti5O12-based electrodes for lithium-ion


batteries: The latest advancements and future perspectives
Bote Zhao a,b, Ran Ran a, Meilin Liu b,*, Zongping Shao a,*
a
State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, No. 5 Xin Mofan Road, Nanjing 210009, PR China
b
School of Materials Science and Engineering, Center for Innovative Fuel Cell and Battery Technologies, Georgia Institute of Technology, Atlanta, GA 30332-
0245, USA

A R T I C L E I N F O A B S T R A C T

Article history: Advanced electrical energy storage technology is a game changer for a clean, sustainable, and secure
Available online energy future because efficient utilization of newable energy hinges on cost-effect and efficient energy
storage. Further, the viability of many emerging technologies depends on breakthroughs in energy
Keywords: storage technologies, including electric vehicles (EVs) or hybrid electric vehicles (HEVs) and smart grids.
Lithium-ion battery Lithium-ion batteries (LIBs), a great success in the portable electronics sector, are believed also the most
Li4Ti5O12 promising power sources for emerging technologies such as EVs and smart grids. To date, however, the
Anode existing LIBs (with LiCoOx cathode and graphite anode) are still unable to meet the strict requirements
Electrode materials for safety, cycling stability, and rate capability. The development of advanced anode materials, which can
Spinel
overcome the shortcomings of graphite anode (such as formation of dendritic lithium during charge and
undesirable solid electrolyte interface), is of critical importance to enhancing the cycling stability and
operational safety of LIBs. Lithium titanate (Li4Ti5O12) has recently attracted considerable attentions as a
potential anode material of LIBs for high power applications due to several outstanding features,
including a flat charge/discharge plateaus (around 1.55 V vs. Li/Li+) because of the two-phase lithium
insertion/extraction mechanism and minimum chance for the formation of SEI and dendritic lithium,
dramatically enhance the potential for high rate capability and safety. In addition, there is almost no
volume change during the lithium insertion and extraction processes, ensuring a high cycling stability
and long operational life. However, the electronic conductivity of Li4Ti5O12 is relatively low, resulting in
large polarization lose, more so at higher cycling rates, and poor rate performance. Currently,
considerable research efforts have been devoted to improving the performance of Li4Ti5O12 at fast
charge/discharge rates, and some important progresses have been made. In this review, we first present a
general overview of the structural features, thermodynamic properties, transport properties, and the
electrochemical behavior of Li4Ti5O12 under typical battery operating conditions. We then provide a
comprehensive review of the recent advancements made in characterization, modification, and
applications of Li4Ti5O12 electrodes to LIBs, including nanostructuring, surface coating, morphological
optimization, doping, and rational design of composite electrodes. Finally, we highlight the critical
challenges facing us today and future perspectives for further development of Li4Ti5O12-based
electrodes. It is hoped that this review may provide some useful guidelines for rational design of better
electrodes for advanced LIBs.
ß 2015 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1. Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2. History. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Fundamental properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1. Crystal structure, phase stability, and defects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2. Thermodynamic properties (including theoretical capacity) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

* Corresponding authors.
E-mail address: meilin.liu@mse.gatech.edu (M. Liu).

http://dx.doi.org/10.1016/j.mser.2015.10.001
0927-796X/ß 2015 Elsevier B.V. All rights reserved.
2 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

2.3. Transport properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6


2.4. Electrochemical behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3. Tailoring the nanostructure, morphology, and defect chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1. Nanostructuring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.1.1. Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1.2. 1–3D nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2. Morphological control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2.1. Porous electrodes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2.2. Nano/microspheres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.2.3. Thin-film electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.3. Surface coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3.3.1. Carbon coating. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.3.2. Coating/modification with other materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.3.3. Surface treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.4. Doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.5. Formation of composite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.5.1. Li4Ti5O12/graphene. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.5.2. Li4Ti5O12/carbon nanotubes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.5.3. Li4Ti5O12/SnOx . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
3.5.4. Li4Ti5O12/TiO2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
3.5.5. Li4Ti5O12/transition-metal oxides (MO, where M is Co, Ni, Cu, Fe or Zn) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4. Electrochemical behavior in different battery systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.1. Combination with different cathodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.2. Combination with different electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
4.3. Electrochemical performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
5. Critical challenges and new directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5.1. Low theoretical capacity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5.2. Compromise between tap density and rate capability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5.3. Poor performance at low temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
5.4. Gassing problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
5.5. Other applications in addition to electrode for LIBs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
5.5.1. As a coating layer to enhance the performance of other electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
5.5.2. As an electrode material for rechargeable sodium-ion batteries. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5.5.3. As an electrode material for hybrid supercapacitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
6. Conclusions and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

1. Introduction reliance on fossil fuels. The properties and performance of the


batteries used in HEVs, PHEVs and EVs determine the success of the
1.1. Background integration of green vehicles into daily life. The batteries for both
stationary energy storage (e.g., smart grids) and mobile applica-
During the past century, our society has relied heavily on fossil tions (e.g., EVs) are required to have long cycling lifetimes, high
fuels (oil, coal, and natural gas) for the development of our rate capability, safety, reliability, durability, and low cost.
industry, economy, and modern conveniences. However, the Since the early 1990s, lithium ion batteries (LIBs) have been
excessive and low-efficiency use of fossil fuels, which is based widely used in portable electronic devices. Recently, their potential
largely on traditional combustion technology, has resulted in for electrical energy storage and as power sources for HEVs, PHEVs,
serious problems such as global warming and environmental and EVs have also been recognized due to their high voltage, light
pollution. In addition, our dependence on those ever-diminishing weight, high power density, lack of memory effect, and environ-
energy resources puts us at risk of a non-sustainable future. The mental benignness [3–6]. LIBs store electrical energy in both
search for clean and renewable energies is our only option for a electrodes, which are made of lithium intercalation (or insertion)
secure and sustainable future. compounds, as schematically shown in Fig. 1. In a typical LIB, a
Solar and wind energies are among the most abundant porous polymer membrane is usually used as the separator, and a
renewable energies and may play important roles in future clean lithium salt (e.g., LiPF6) dissolved in a mixture of organic solvents
energy systems. However, integration of such intermittent energy (e.g., ethylene carbonate and dimethyl carbonate) is used as the
sources challenges the existing electric power grid. Low-cost electrolyte. During discharge, lithium ions move from the anode
energy storage is thus required to provide consistent renewable through the electrolyte to the cathode, as electrons flow from the
energy production with the introduction of a new green, or smart, anode through an external circuit to the cathode, producing
power grids [1,2]. Among the potential methods of energy storage, electrical power. These spontaneous processes are driven by the
electrochemical energy storage is generally accepted as the most difference in electrochemical potentials of the two electrode
promising, while secondary batteries are particularly attractive for materials. During charge, these processes are reversed under the
their high energy density and low cost. Hybrid electric vehicles influence of an applied electric field (or voltage): lithium ions are
(HEVs), plug-in hybrid electric vehicles (PHEVs) and pure electric extracted from the cathode and inserted into the anode, as
vehicles (EVs) have also attracted considerable worldwide atten- electrons are pumped from the cathode through an external circuit
tion because of their potential for replacing conventional internal to the anode, consuming electric power. The electrochemical
combustion engines to reduce greenhouse gas emission and our performance of LIBs depends sensitively on the properties of
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 3

coefficient (108 to 1013 cm2 s1) [13–17], which greatly limit


its rate performance. Recently, considerable research has been
conducted on the morphological optimization, doping, and
nanostructuring of Li4Ti5O12, or a combination of these, to improve
its capacity and rate capability.

1.2. History

Spinel Li4Ti5O12 (also reported as Li1.33Ti1.67O4, Li4/3Ti5/3O4, or


[Li]8a[Li1/3Ti5/3]16d[O4]32e) is an important member of the solid
solution family, Li3+xTi6xO12 (0  x  1) [18], which was first
reported by Jonker in 1956 [19]. Materials with a spinel structure
have a general chemical formula of AB2O4, in which the oxygen
ions (32e) form a cubic-close-packed (ccp) array with tetrahedrally
(8a, 8b, 48c) and octahedrally (16c, 16d) coordinated interstices
partially occupied by the A and B cations. Li3+xTi6xO12 initially
excited interest for its superconductivity at low temperatures. For
example, LiTi2O4, one extreme of Li3+xTi6xO12 (for x = 0), exhibits
superconductivity at temperatures below 10 K [20,21]. In contrast,
Li4Ti5O12, the other extreme of Li3+xTi6xO12 (for x = 1), is a
semiconductor down to liquid helium temperatures [22]. Murphy
et al. first reported the capability of Li4Ti5O12 for lithium
intercalation [23]. In 1989, Colbow et al. first measured the
galvanostatic charge–discharge properties of a Li/Li4Ti5O12 half-
Fig. 1. The components of a typical LIB and the corresponding electrochemical cell and found that the material exhibited a plateau in its discharge
charge/discharge processes. The cathode and anode materials shown here are voltage profile and stable performance starting with the 25th cycle
LiCoO2 and Li4Ti5O12, respectively. during a cycling test of up to 100 iterations [24].
The relatively low lithium insertion/extraction potential
(1.55 V) prohibits the application of Li4Ti5O12 as a cathode in
electrode materials. The most advanced LIBs can exceed most other LIBs; however, it can serve as a negative electrode when coupled
competitive battery technologies in energy density by a factor of with high-voltage cathodic materials such as LiCoO2 and LiMn2O4
2.5 [7]. The high specific energy density of LIBs is closely related to yield safe 2.5–3.0 V lithium-ion cells with long lifetimes. Ferg
to the low molecular weight, small ionic radius, and low redox et al. may have been the first to propose Li4Ti5O12 as an anode
potential of lithium. material for LIBs [25], but their work has been followed by
Conventional LIBs are composed of a LiCoOx cathode and a considerable research into the application of Li4Ti5O12 as a
carbon/graphite anode. The graphite anode has a theoretical potential anode for LIBs. Fig. 2 shows the Li4Ti5O12-related
capacity of 372 mA h g1, and the lithium insertion primarily published items in the Web of Science Core Collection for each
occurs at a voltage below 0.1 V (vs. Li/Li+), close to the lithium year from 2000 to 2014. By 2007, the number of published items
electroplating potential [8]. At a high discharge rate, the carbon/ per year was over 50, which increased rapidly ever since, reaching
graphite electrode can be polarized to such an extent that highly more than 100 in 2011 and more than 200 in 2013, suggesting
reactive dendritic lithium may form on the electrode surfaces, great interest in Li4Ti5O12 anodes in the past few years.
which may easily penetrate through the porous separator and
cause an internal short circuit, thus posting significant safety
concern. However, as power sources for HEVs, PHEVs and EVs, the
batteries are frequently charged or discharged at a high rate over a
wide temperature range (from 30 to 60 8C). In addition, the
carbon/graphite electrodes suffer from a lack of clear end-of-
charge indicator in their voltage profiles, suggesting that the state-
of-the-art graphite anodes may not meet the strict safety and rate
performance requirements for many emerging applications.
Currently, considerable research is being conducted to develop
alternative anode materials with improved safety, cycling stability,
and rate performance.
Li4Ti5O12 is a lithium intercalation compound (or insertion
host) with a high lithium insertion/extraction voltage of approxi-
mately 1.55 V [9], well above the potential for formation of an SEI
from the reduction of the organic electrolyte and for the formation
of dendritic lithium, thus offering excellent safety. In addition to
being nontoxic and relatively inexpensive, the material experi-
ences little change in volume during the lithium insertion/ Fig. 2. Li4Ti5O12-related published items for each year in the Web of Science Core
extraction processes and possesses high thermal stability, ensuring Collection, date: January/31/2015, search strategy: TOPIC: (‘‘lithium batter*’’ OR
a long cycling lifetime. Recently, Li4Ti5O12 has attracted consider- ‘‘lithium ion batter*’’ OR ‘‘lithium cell*’’ OR ‘‘lithium ion cell*’’ OR ‘‘li-ion batter*’’ OR
‘‘Lithium-Ion Batter*’’ OR ‘‘Li rechargeable batter*’’ OR ‘‘rechargeable Li batter*’’ OR
able attention as a potential anodic material for LIBs for use in
‘‘lithium secondary batter*’’ OR ‘‘Lithium Storage’’) AND TOPIC: (Li4Ti5O12 or
electrochemical energy storage and electric vehicles. However, Li1.33Ti1.67O4 or Li4/3Ti5/3O4 or Li[Li1/3Ti5/3]O4 or Li[Li1/3Ti5/3]O 4 or ‘‘lithium
Li4Ti5O12 exhibits low electronic conductivity (in the range of titanate’’). Timespan: 2000–2014. Indexes: SCI-EXPANDED, SSCI, A&HCI, CPCI-S,
108 to 1013 S cm1) [10–12] and low lithium-ion diffusion CPCI-SSH, BKCI-S, BKCI-SSH, CCR-EXPANDED, IC.
4 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

2. Fundamental properties

2.1. Crystal structure, phase stability, and defects

A detailed structural analysis of Li4Ti5O12 based on a single


crystal was first reported by Deschanvres et al. in 1971
[18]. Kataoka et al. determined the structure of single crystals
prepared via a LiCl flux method using a four-circle diffractometer
[26]. The basic crystal structure of Li4Ti5O12, as shown in Fig. 3 [27],
is a cubic spinel with an Fd3m space group and a unit cell
¯
parameter reported to be between a = 8.352 and 8.370 Å
[9,23,24,28–31]. At room temperature, the tetrahedral 8a sites
of the Li4Ti5O12 are believed to be occupied by Li+ ions alone, while
the octahedral 16d sites are randomly occupied by 1/6 Li+ ions and
5/6 Ti4+ ions [32]. All of the 32e sites are occupied by O atoms,
which form a ccp structure. The other half of the octahedral cation
sites in the ccp structure (16c sites) and both the tetrahedral 8b and
48f cationic sites are empty and are suitable for lithium insertion
and extraction. However, using infrared spectroscopy, Pecharro-
man et al. demonstrated that the lithium ions in the 8a tetrahedral
sites can shift to the 16c octahedral sites with increasing
temperature [33]. Based on the Rietveld refinement of X-ray and
neutron powder diffraction data, Leonidov et al. supported the
finding that the tetrahedral 8a sites in Li4Ti5O12 were occupied
solely by lithium ions at room temperature [30]. However, high-
temperature Raman spectroscopy and the electrical conductivity
data indicated that the lithium ions in the 8a sites can migrate into
16c sites at temperature above 177 8C to induce two successive
order–disorder phase transitions [30]. By applying high-tempera-
ture 6Li magic-angle spinning nuclear magnetic resonance
(MASNMR), Vijayakumar et al. also demonstrated that the lithium
ions can migrate from the tetrahedral 8a sites to the 16c octahedral
sites in Li4Ti5O12 with increasing temperature accompanied by a
progressive phase transition from a spinel to a defective NaCl-type
structure [27].
‘‘Zero-strain’’ characteristic, which is one of the most important
features of Li4Ti5O12, was first reported by Ohzuku et al. in 1995
[9]; there is almost no change in lattice dimension during lithium
ion and electron insertion into/extraction from the solid matrix
when the composition is changed between the initial state of
Li4Ti5O12 and the final state of Li7Ti5O12. Ohzuku et al. synthesized
Li4Ti5O12 samples and demonstrated that it had a defect spinel-
framework structure Li(8a)[Li1/3Ti5/3](16d)O4(32e) with a lattice
parameter a = 8.365 Å (Fd3m; oxygen positional parameter
¯ Fig. 3. Top figure: crystal structure of Li4Ti5O12 showing the three lithium sites:
u = 0.265) via XRD analysis [9]. They further found that the lattice tetrahedral 8a (yellow), octahedral 16c (green) and octahedral 16d (blue). Titanium
constant for the initial state of Li[Li1/3Ti5/3]O4 is the same as those and oxygen atoms are shown as small gray and large red balls, respectively. All three
for the other 8 different states of Li1+x[Li1/3Ti5/3]O4 (0  x  0.91) sites are shown as occupied for presentation purposes. Bottom figure: inter-atomic
distances between 16d and 16c (2.95 Å), 16c–8a (1.81 Å), and 8a–16d (3.46 Å) site
(a = 8.370  0.005 Å), indicating the zero-strain characteristic of
pairs based on the structure. [27]. (For interpretation of the references to color in
Li4Ti5O12 (Fig. 4). From then on, the ‘‘zero-strain’’ characteristic of this figure legend, the reader is referred to the web version of this article.)
Li4Ti5O12 material was further confirmed by many researchers [34–
36]. Fig. 4b shows XRD patterns of Li1+x[Li1/3Ti5/3]O4 in different
charge/discharge status (0  x  0.91). An I(5,3,3)/I(6,2,2) ratio change Li4Ti5O12 [37–41]. For the partially lithiated Li4+xTi5O12 prepared
was observed; the ratio decreased to approximately 1 when x = 0.46, by chemically inserting lithium into Li4Ti5O12, Aldon et al. used 6,7Li
and further decreased when x was increased; the ratio recovered nuclear magnetic resonance (NMR), Raman spectroscopy, X-ray
during the subsequent lithium extraction process. This result was diffraction (XRD) and neutron diffraction to demonstrate that the
explained by the inserted lithium ions occupy the octahedral 16c sites lithium ions were trapped in the 48f sites of the spinel structure and
process (Fig. 4c). During the electrochemical lithium insertion were not able to be extracted through electrochemical means; in
process, the incoming lithium ions are believed to occupy the addition, this chemical insertion process did not cause a transition in
octahedral 16c sites. The lithium ions that initially locate at the the phase structure [37]. Using a similar chemical insertion method,
tetrahedral 8a sites are simultaneously displaced into the neighbor- Wagemaker et al. were unable to observe a 48f lithium occupation
ing 16c octahedral sites due to electrostatic repulsion effects that [42]. Based on the neutron and XRD patterns of chemically lithiated
generate a rock-salt phase, [Li2]16c[Ti5/3Li1/3]16dO4, which has the Li4+xTi5O12 samples, Wagemaker et al. demonstrated that the inserted
same lattice symmetry as Li4Ti5O12 (Fd3m) [34]. Recently, various lithium could co-exist in a single phase with a mixed 8a and 16c
¯
characterization techniques including neutron diffraction, Mossbauer occupation in the lattice [42], although the co-existence of 8a and 16c
spectrometry, Raman spectroscopy, and XRD have been used to lithium ions is believed to introduce a large electrostatic repulsion
characterize the phase evolution during lithium insertion into energy due to the short lithium ion–lithium ion distance. Using
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 5

Fig. 4. (a) Records on the preparation of Li1+x[Li1/3Ti5/3]O4 for XRD examinations. Arrows directed upward indicate the locations at which XRD examinations were done for the
reduction of Li[Li1/3Ti5/3]O4, and arrows directed downward for the oxidation of the samples following 160 mA h g1 of reduction. (b) XRD patterns of Li1+x[Li1/3Ti5/3]O4 in the
status as shown in (a): (b0) x = 0, (b1) x = 0.46, (b2) x = 0.91, (b3) x = 0.46, and (b4) x = 0. XRD samples were prepared by (b0) 0, (b1) 80, and (b2) 160 mA h g1 of reduction of
Li[Li1/3Ti5/3]O4, and by (b3) 80 and (b4) 160 mA h g1 of oxidation following 160 mA h g1 of reduction. Capacity in mA h g1 is based on Li[Li1/3Ti5/3]O4 sample weight. (c) The
topotactic reaction of lithium insertion into/extraction from Li[Li1/3Ti5/3]O4 structure. [9].

difference Fourier synthesis map method, Kataoka et al. also octahedral sites, and the lithium ions at the 8a sites simultaneously
investigated the lithium insertion sites based on single crystals of transfer to the 16c sites. The total number of lithium ions that can
Li4+xTi5O12, prepared by means of an electrochemical Li-ion be inserted into the 16c sites from external sources equals half the
intercalation technique using single parent Li4Ti5O12 crystals, and number of empty 16c sites because the other half of the lithium
determined that the lithium ions were inserted into both the 8a and ions are transferred from the previously occupied tetrahedral 8a
16c sites [43]. sites. Thus, the insertion process can be expressed by the equation
The insertion of lithium into Li4Ti5O12 causes the reduction of as shown in Fig. 4c, and can be briefly expressed by the following
Ti4+ to Ti3+. Because Ti3+ (0.670 Å, CN = 6) has a larger ionic radius equation:
than Ti4+ (0.605 Å, CN = 6), an elongation of the Ti-O bond is
expected following the lithium insertion. In this case, however, a Li4 Ti5 O12 þ 3e þ 3Liþ ¼ Li7 Ti5 O12 (1)
slight dimensional shrinking was normally observed when
Li4Ti5O12 was reduced to Li7Ti5O12 following the lithium insertion The capacity, as calculated using the mass of Li4Ti5O12
[34], although the reported values of the lattice parameters varied according to above equation, is 175 mA h g1, which is generally
somewhat among the different researchers [9,23,24,28–31]. Ronci accepted as the theoretical value.
et al. conducted high-resolution in situ structural measurements of From a structural point of view, the Li7Ti5O12 could accommo-
Li4Ti5O12 using a high-energy (87.5 keV) synchrotron beam and date more lithium ions because there are empty 8a sites that can
confirmed little variation in the lattice parameter of 0.07% accept lithium ions, although they are energetically less favorable
[35,40]. The small change in the cell volume after inserting lithium than the 16c sites. In addition, 40% of the titanium in the 16d
into Li4Ti5O12 is beneficial for stable cycling. Ariyoshi et al. octahedral sites is in the Ti4+ oxidation state, which can be reduced
provided a detailed investigation of the zero-strain mechanism of to Ti3+ during the accommodation of additional lithium. Because a
Li4Ti5O12 by ex situ XRD [36]. After the reduction of Li4Ti5O12 to low discharge voltage may lead to the formation of SEI over the
Li7Ti5O12, the oxygen positional parameter at the 32e sites Li4Ti5O12 electrode, while lithium intercalation occurs at a voltage
decreased from 0.266 to 0.257. Thus, the authors suggested that of approximately 1.55 V, an end of discharge voltage of 1.0 V is
the zero strain of Li4Ti5O12 was closely related to the oxygen swing often selected in the literature to investigate the charge–discharge
in the lattice during the lithium insertion process. properties of Li4Ti5O12. However, upon closer examination of the
galvanostatic charge–discharge profiles reported by Huang et al.
2.2. Thermodynamic properties (including theoretical capacity) (Fig. 5), who conducted discharge studies of Li4Ti5O12 down to
0.5 V [45–47], non-negligible reversible capacity is observed in the
The insertion of lithium into Li4Ti5O12 spinel is believed to potential range of 1.0–0.5 V, suggesting that lithium can further
primarily follow a two-phase mechanism [9,23,24,34,44]. During insert into Li7Ti5O12 at a lower intercalation potential. Ge et al., Yao
the discharge process, the incoming lithium ions insert into the 16c et al. and Ahn et al. reported the discharge of Li4Ti5O12 down to a
6 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 5. Typical galvanostatic charge–discharge profiles for Li4Ti5O12 down to 0.5 V.


[45].

near zero voltage [48–50] noting a considerable capacity


contribution to the total reversible capacity of Li4Ti5O12 at Fig. 6. Schematic illustration for the Li+ insertion into/extraction from spinel
Li4Ti5O12 structure at (a) 3 V, (b) 1–3 V and (c) 0.01–1 V. [54].
discharge voltages lower than 0.5 V. This total reversible capacity,
approaching 250 mA h g1, exceeds the generally accepted theo-
retical capacity of 175 mA h g1. 1013 S cm1) [10–12]. After the lithium atoms are inserted into
Based on the XRD and electrochemical galvanostatic charge/ the Li4Ti5O12 lattice, however, additional electrons are introduced
discharge experiments, Ge et al. demonstrated that the tetrahedral that occupy the Ti-3d states to cause a shift in the Fermi level
(8a) sites of Li7Ti5O12 can be accommodated with lithium ions at toward the conduction band, making the system more electroni-
potentials below 0.6 V vs. a Li/Li+ reference electrode [51]. The cally conductive. The value of the electronic conductivity for the
authors further proposed the following insertion/extraction Li7Ti5O12 phase was found to be in the range of 102 S cm1 [34],
mechanism for lithium ions into/from Li7Ti5O12: much higher compared to that of the initial phase
Li4Ti5O12. Improving the electronic conductivity during the initial
Li6ð16cÞ ½LiTi3 3þ Ti2 4þ ð16dÞ O12ð32eÞ þ 2e þ 2Liþ discharge stage is critical to enhancing the rate capability of the
$ Li2ð8aÞ Li6ð16cÞ ½LiTi5 3þ ð16dÞ O12ð32eÞ (2) Li4Ti5O12 electrode. Surface coating and doping are the two most
widely used approaches for enhancing transport properties.
Ge et al. also suggested that the theoretical capacity of Li4Ti5O12 Kamata et al. studied the lithium motion in Li4Ti5O12 and
is 293 mA h g1 (2.5–0.01 V), limited by the number of tetravalent determined lithium diffusion coefficient at elevated temperatures
titanium ions, not the number of octahedral or tetrahedral sites using neutron radiography [56,57]. The transport number of the
available to accommodate the lithium ions. The final composition lithium ions and the lithium diffusion coefficient in de-lithiated
following lithium intercalation was suggested to be Li9Ti5O12. The Li4Ti5O12 at 900 8C were determined to be 0.99 and
availability of tetrahedral 8a sites for lithium-ion storage was also 1.8  106 cm2 s1, respectively. The value for lithium diffusion
supported by Borghols et al. during their investigation of size coefficient is relatively high. However, for practical applications,
effects on the Li4+xTi5O12 spinel [52]. By applying first-principles LIBs are typically operated at room temperature. The lithium ion
calculations, Zhong et al. demonstrated that Li4Ti5O12 can be reportedly can migrate from the 8a tetrahedral sites to the
intercalated into a final state of Li8.5Ti5O12 [53] instead of octahedral 16c sites at elevated temperatures and can induce a
Li9Ti5O12. Thus, the theoretical capacity of Li4Ti5O12 is calculated progressive phase transition from a spinel to a defective rocksalt
to be approximately 263 mA h g1. The predicted intercalation structure, leading to an increase in lithium-ion conductivity [30]
potentials are 1.48 and 0.05 V (vs. Li/Li+) for the Li4Ti5O12/Li7Ti5O12 due to increased number of vacancies at the 8a sites that facilitate
and Li7Ti5O12/Li8.5Ti5O12 redox pairs, respectively. The further the lithium diffusion through 16c–8a–16c pathways [27]. Howev-
insertion of lithium into the Li7Ti5O12 phase induces only a small er, lithium diffusion coefficient drops sharply as temperature is
volumetric change. The lattice expansion of Li8.5Ti5O12 with decreased. For example, Fehr et al. demonstrated a substantial
respect to Li4Ti5O12 was found to be only 0.4% based on the decrease in electrical conductivity of Li4Ti5O12 from 104 to
theoretical calculations. A schematic illustration of the Li+ insertion 106 S cm1 at 500 K to only 3  1010 S cm1 at 300 K
into and extraction from a spinel Li4Ti5O12 structure is shown in [58]. Wilkening et al. measured the low-temperature lithium
Fig. 6 [54]. diffusion in a phase-pure Li4Ti5O12 sample via 7Li NMR spectros-
copy [59,60] and demonstrated that the lithium diffusion rate at
2.3. Transport properties low temperatures was extremely slow. For example, the Li self-
diffusion coefficients at 298 and 320 K are only 2.7(4)  1012 and
Since Li+ insertion into and extraction from a Li4Ti5O12 electrode 9.2(5)  1012 cm2 s1, respectively [60], which are much lower
inevitably involve transport of both lithium ions and electrons, the than those reported by Esaka at 1173 K [56,57]. Chen et al. studied
rate capability of the electrode depends sensitively on lithium-ion the lithium-ion dynamics in Li4+xTi5O12 spinel by first-principles
and electronic conductivity. Because a band gap opens between the calculations and demonstrated a sharp decrease in lithium
occupied O-2p states and the empty Ti-3d states in Li4Ti5O12 [55], diffusion coefficient for Li4+xTi5O12 as temperature is lowered at
the electronic conductivity is relatively low (108 to different states [61], suggesting that the rate capability of Li4Ti5O12
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 7

could be severely limited by slow lithium diffusion at low-


temperature operation. In addition, the lithium-ion diffusion
coefficient was also closely related to the degree of lithium
insertion into Li4Ti5O12. Takami evaluated the apparent lithium
diffusion coefficients in the Li7Ti5O12 and Li4Ti5O12 phases from the
results of potential step chronoamperometry with a spherical
diffusion model. The lithium diffusion coefficients were found to
be approximately 1  1012 and 1.6  1011 cm2 s1, respectively
[62], suggesting a lower lithium diffusion coefficient for Li7Ti5O12
than Li4Ti5O12.

2.4. Electrochemical behavior

Fig. 7 shows some typical galvanostatic charge–discharge


profiles for a Li4Ti5O12 anode within a potential range of 1.0–3.0
or 0.01–3.0 V. Usually, the electrochemical performance of an
anode is evaluated using lithium foil as a counter electrode (i.e., a
half-cell configuration). In this case, the Li4Ti5O12 electrode acts as Fig. 8. (a) A schematic illustration of two-phase mechanism for Li4Ti5O12 electrode
during the charge/discharge processes. The charge/discharge profiles were derived
a ‘‘cathode’’ and lithium foil is the anode. Thus, the insertion of
from literature. [292].
lithium into the cathode (i.e., Li4Ti5O12) is usually named as the
discharge process (Fig. 7). However, in a full cell with Li4Ti5O12 as
the anode, the extraction of lithium from the anode is named as the nearly constant during the subsequent discharge process until
discharge process (Fig. 1). Thus, the charge curve for the anode another smooth decrease in voltage occurs near the end of the
would be more important for real application since it determines discharge to an endpoint of 1.0 V. As mentioned previously, it is
the output voltage of the full cell. The potential range of 1.0–3.0 V generally accepted that the lithiation/de-lithiation related to a
was the most commonly studied due to the unique charateristics of Li4Ti5O12 electrode involves a two-phase mechanism (Fig. 8)
Li4Ti5O12 anode. Li4Ti5O12 features a rapid decrease in the potential [9,23,24,34,44], similar to a LiFePO4 cathode [63]. However, at the
at the initial discharge (intercalation) to reach a voltage of beginning and near the end of the charge/discharge processes, the
approximately 1.55 V [23,24]. Then, the discharge voltage remains electrode reaction could still have a single-phase mechanism. At the
beginning, the lithium insertion leads to the formation of a single
solid solution, Li4+aTi5O12 (Li4Ti5O12 + aLi+ + ae!Li4+aTi5O12),
which has identical phase structure to Li4Ti5O12. As a result, a
smooth drop in potential is observed with increasing lithium
insertion until the statured concentration of the single phase is
reached. Further increases in the degree of lithium insertion into the
Li4Ti5O12 cause the appearance of a new rock-salt-like phase,
Li7bTi5O12, via the following reaction: (spinel) Li4Ti5O12 + (3  -
b)Li+ + (3  b)e = Li7bTi5O12 (rock salt). Following that reaction,
the lithium insertion involves the Li4+aTi5O4–Li7bTi5O12 two-phase
mechanism to yield a fixed electrical potential based on the Gibbs
phase rule with a value of approximately 1.55 V. Near the end of the
discharge, a single-phase insertion reappears (Li7bTi5O12), and the
insertion is controlled by the lithium diffusion through the solid
solution. A smooth potential drop is again observed from 1.55 V until
the final insertion voltage of 1.0 V. The charge process proceeds in a
similar manner, but in the reverse direction. A core–shell mode,
which is frequently used to explain the lithium insertion/extraction
related to a LiFePO4 positive electrode [64], can also be applied to
describe the lithiation/de-lithiation process of the Li4Ti5O12 anode
[65].
The single-phase ranges at the beginning/end of charge/
discharge depend closely on the Li4Ti5O12 particle size (Fig. 9a
and b) [66,67] and the surface coating (Fig. 9c) [68]. For example,
Park et al. and Wang et al. demonstrated that the surface coating of
Ti(III)/carbon and TiN on Li4Ti5O12 (Fig. 9c) can increase the domain
of the single-phase lithium insertion/extraction [68,69]. Wage-
maker et al. assumed that the presence of a solid solution is
beneficial for Li-ion mobility [42,70]. A single phase implies
intimate mixing of the 8a and 16c occupation sites in contrast to
the two-phase region where the 8a and 16c occupation sites are
separated. The single phase is beneficial for increasing both the
apparent electronic and lithium-ion conductivity, and thus the rate
capability. Based on the neutron and X-ray diffraction of
Fig. 7. The typical first discharge/charge profiles of Li4Ti5O12 electrode using a
current density of 175 mA g1 in the potential ranges of (a) 1.0–3.0 V and (b) 0.01–
chemically lithiated Li4+xTi5O12 at different temperatures, Wage-
3.0 V. Li4Ti5O12 was synthesized using a facile cellulose-assisted combustion maker et al. proposed that faster Li insertion leads to a kinetically
method [292]. induced effective two-phase reaction, which is a non-equilibrium
8 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 9. The relationship between the single-phase range in the charge/discharge curves and properties of Li4Ti5O12 material: (a, b) particle size, and (c) surface coating. (a)
Discharge curves of the fifth discharge (1 C) of various as-prepared Li4Ti5O12 nanoparticle electrodes [66]. (b1) Calculated voltage profiles for the Li4Ti5O12-Li7Ti5O12 system.
The pink voltage curve corresponds to a composite for particles combining Li insertion into vacant 16c sites in a Li4Ti5O12 host without nearest 8a-16c neighbors at the
interface from (1 1 0) facets and Li insertion into a Li7Ti5O12 host with vacant 8a sites from (1 1 1) facets corresponding to the Wulff shape. The purple and black curves
correspond to particle sizes of 30 and 100 nm. The green-shaded area represents the region under 0 V, where no Li intercalation is feasible. The inset is Wulff shape
determined from the calculated surface energies of pure LiTi2O4 spinel, (b2) corresponding schematic illustration of lithium-ion insertion into Li 4Ti5O12[67]. (c) Charging (Li+
insertion) voltage curves of (A) pristine Li4Ti5O12 and the nitridated powders at 700 8C for (B) 10, (C) 20, (D) 30, and (E) 60 min and the corresponding two-phase equilibrium
region with different reaction time and the lattice parameters of 60 min-nitridated Li 4Ti5O12 [68]. (For interpretation of the references to color in this figure legend, the reader
is referred to the web version of this article.)

situation that will ultimately relax to a single phase at room 3.1. Nanostructuring
temperature [42,70]. The single-phase range of the curve for
Li4Ti5O12 typically appeared wider for smaller nanoparticles By reducing the particle size to the nanoscale, some unique
(Fig. 9a) than that for larger particles (Fig. 7). Similar trend was mechanical, electrical, and optical properties appear [74–
also observed for TiO2 anode, which was attributed to capacitive 77]. Nanostructuring reduces the diffusion distance for both the
lithium storage on the surface of nanosized TiO2 [71–73], lithium ions and the electrons within the bulk of the electrode
suggesting its highly related to the surface property. Using density materials. In addition, nanostructuring increases the surface area
functional theory to calculate voltage profiles, Ganapathy et al. [67] available for interfacial charge transfer and, consequently, can
revealed that the favorable lithium-ion insertion into the (1 0 0)
surfaces of the defective spinel Li4Ti5O12 contributed to the initial
capacity at high voltages due to surface storage; and the lowest
energy (1 1 0) surface was predicted to be energetically favorable
for lithium-ion insertion into the vacant 16c sites. Especially, they
found that the (1 1 1) surface allowed further lithium-ion insertion
into the Li7Ti5O12 by occupation of 8a sites in addition to the fully
occupied 16c sites via surface relaxation effects, which could
explain the slight higher capacity of nanosized Li4Ti5O12 compared
to the theoretical capacity even after initial activation. Accordingly,
the size effect on the voltage profiles was summeried as shown in
Fig. 9b. Furthermore, it is predicted that reducing the size and
tailoring the shape to increase the relative amount of (1 1 1) facets
may increase the storage capacity.

3. Tailoring the nanostructure, morphology, and defect


chemistry

Although Li4Ti5O12 is highly promising as an anode material of


LIBs, its practical application in electrochemical energy storage as
well as electric vehicles is hindered by its low electronic
conductivity and relatively poor lithium diffusion rate. Thus, a
Li4Ti5O12 electrode composed of coarse powder usually shows poor
capacity retention during cycling, more so at higher discharge/
charge rates. To achieve high specific capacity, high rate capability
and good cycling stability, several strategies have been investigat-
ed in the past decade (Fig. 10), including nanostructuring, Fig. 10. The typical strategies for improving the electrochemical performance of
morphological optimization, surface coating, doping, and forma- Li4Ti5O12 electrode. All insets are derived from the literatures
tion of composite, and significant progress has been made. [27,133,137,162,186,191,239,245,453].
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 9

Fig. 11. The schematics of reported Li4Ti5O12 nano/microstructures (0–3D) and corresponding microscope images [133,136,137,154,159,160,245,285].

substantially improve the electrode performance. Thus, nano- wide range of functional materials with better morphological
structured electrodes typically exhibit higher specific power control, higher phase purity, smaller particle size and narrower
density than those composed of coarse powders [77,78]. To date, particle size distribution than solid-state reactions [84,85]. In a
various nano/microstructures of Li4Ti5O12 have been reported, as typical sol–gel process, the raw materials are first dispersed in a
schematically shown in Fig. 11. The details of these structures will solvent, and the hydrolysis is conducted in a controlled manner to
be discussed in the following sections. produce a sol and to generate a certain spatial structure of gel via
aging. The gel is then dried and heat-treated to yield a product with
3.1.1. Nanoparticles the desired composition. Because the sol–gel process allows the
Conventionally, spinel Li4T5O12 has been prepared by a solid- reactants to be homogeneously mixed at the molecular level, the
state reaction using TiO2 (rutile or anatase) and Li2CO3 or LiOH as temperature of formation for the phase-pure composite can be
raw materials at a calcination temperature above 800 8C over a significantly reduced; consequently, the product may have an
prolonged period of time (12–24 h to ensure high phase purity) ultrafine particle size and a high surface area.
[34,65,79–83]. The as-synthesized powders usually have large The sol–gel method has also been applied to the synthesis of
grains with inhomogeneous phase compositions and low specific Li4Ti5O12 [86–96]. Bach et al. first applied a sol–gel process to the
surface areas. Considerable efforts have been made to synthesize preparation of Li4Ti5O12; they conducted the synthesis in a non-
nanosized Li4Ti5O12 by exploiting advanced synthetic techniques. aqueous medium with lithium acetate (LiAc) and titanium (IV)
Soft chemical routes allow the mixing of raw materials on a isopropoxide (titanium tetraisopropoxide, TTIP) as the raw
molecular level and thus may lead to significant reduction in the materials [15,87]. Later, Shen et al. applied a similar process to
synthesis temperature for the formation of phase-pure the synthesis of Li4Ti5O12 [88]. The sol–gel process is typically
Li4Ti5O12. Because the material sintering is thermally activated, based on inorganic polymerization from a molecular precursor,
a reduction in synthesis temperature will effectively suppress the which leads to highly dispersed colloids, or two-phase systems
grain growth, and nano Li4Ti5O12 particles may be obtained. with small oxide particles dispersed in a liquid medium
The sol–gel process is a well-developed soft chemical synthetic [84,85]. The pyrolysis speed is key to determining the particle
technique that has been extensively applied to the synthesis of a size of the product because rapid hydrolysis results in large
10 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

850 8C (CA) was still required to obtain phase-pure Li4Ti5O12. As


observed by scanning electron microscopy (SEM), the products had
relatively large grain sizes of 105–223 nm and 500 nm,
respectively, with TEA and CA as the complexing agents.
Venkateswarlu et al. successfully prepared high-purity nanosized
Li4Ti5O12 with a crystal size of 39 nm, using a sol–gel process after
further calcination at 800 8C for 12 h with TTIP and LiAc dihydrate
as the raw materials [91]. The discharge and charge capacities of
the as-synthesized electrode materials reached 255 and
142 mA h g1, respectively, in the potential range of 0.01–1.75 V
at a 0.1 C rate, while a specific charge capacity of 126 mA h g1 in
the potential range of 1.0–2.0 V was achieved at 0.2 C with good
cycling stability. Khamane et al. applied a simple cetyltrimethy-
lammonium bromide (CTAB)-assisted sol–gel technique to syn-
thesize Li4Ti5O12 [92]. The nanosized Li4Ti5O12 calcinated at 800 8C
exhibited an initial discharge capacity of 174 mA h g1 at a 0.2 C
rate. A capacity of 164 mA h g1 was maintained even after cycling
30 times at the same rate. In contrast, the sample prepared without
CTAB had an initial discharge capacity of only 140 mA h g1, which
decayed to only 110 mA h g1 after cycling 30 times at a 0.2 C rate.
In each of the above-described sol–gel processes, further
calcination at 800 8C or higher was conducted or required to
produce Li4Ti5O12 with sufficient purity; however, such high
calcination temperatures may cause serious aggregation of the
particles. For example, Wang et al. prepared nano Li4Ti5O12
powders via a gel process using acrylic acid, TBOT and lithium
nitrate as the precursors [93]. Although the samples exhibited
attractive properties, severe sintering was observed as shown in
Fig. 12, and the samples calcinated at 700, 750 and 800 8C had low
specific surface areas of only 5.8, 1.3 and 1.0 m2 g1, respectively.
Jiang et al. demonstrated that high dispersivity is important to
increasing the rate performance of a Li4Ti5O12 electrode [94]. They
applied Pluronic P123 as a surfactant to suppress particle
aggregation during the sol–gel synthesis of Li4Ti5O12. The capacity
at a discharge rate of 1 A g1 for the sample prepared without the
surfactant was only 30% of that at a rate of 0.1 A g1, while the
capacity at a rate of 1 A g1 for the sample prepared by applying
the surfactant reached approximately 88.6% of that at the 0.1 A g1
rate. Recently, Zhang et al. used a modified sol–gel method with
both ethylene diamine tetraacetic acid (EDTA) and CA as chelating
agents to prepare Li4Ti5O12 [97]. Li4Ti5O12 nanoparticles with pure
phase were obtained at 750 8C; this product delivered a capacity of
164 mA h g1 at 1 C and an outstanding capacity retention of 97%
after 1000 cycles, even though a network morphology due to the
sintering was observed.
Aggregation can be reduced by reducing the calcination
temperature and/or shortening the calcination time. For example,
Kavan et al. successfully prepared Li4Ti5O12 nanoparticles with
high surface areas of 53–183 m2 g1 and small particle sizes of 9–
19 nm using a sol–gel process employing lithium ethoxide and
Ti(V) alkoxides as the raw materials with subsequent calcination at
a low temperature of 500 8C for only 30 min [95]. The as-prepared
Li4Ti5O12, in a thin-film electrode configuration with a thickness of
2–4 mm, exhibited excellent activity toward Li insertion even at
250 C (Fig. 13). However, a small quantity of anatase phase (0.3–
0.6%) remained in the synthesized samples. Kalbac et al. further
modified the sol–gel process by controlling the hydrolysis of the
metal alkoxides by adding polyethylene glycol (PEG) and
Fig. 12. Field-emission SEM (FE-SEM) images of Li4Ti5O12 powders calcined at
different temperatures: (a) 800 8C, (b) 750 8C, and (c) 700 8C [93]. successfully prepared phase-pure Li4Ti5O12 with a high surface
area of 183–196 m2 g1 and a crystalline size of only 9–12 nm [96].
The microemulsion method was also applied to synthesize
aggregates. To control the hydrolysis speed, Hao et al. applied Li4Ti5O12 nanoparticles. Liu et al. successfully prepared pure-phase
triethanolamine (TEA) and citric acid (CA) as complexing agents for Li4Ti5O12 nanocrystalline using a facile microemulsion method
the titanium ion during the sol–gel synthesis of Li4Ti5O12 using [98]. The as-prepared Ti(OC3H7)4/n-pentanol/CTAB/cyclohexane
tetrabutyl (ortho) titanate (TBOT) as the titanium source solution and LiOHH2O/n-pentanol/CTAB/cyclohexane solution
[89,90]. However, a calcination temperature of 800 8C (TEA) or were mixed and aged. After washing, drying and calcining
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 11

[99]. The powder synthesized via the supercritical hydrothermal


method after a short treatment period of 15 min and subsequent
calcination at 700 8C for 24 h is a quasi-sphere with a principal
grain size in the range of 150–200 nm. Grain sizes of 50–100 nm
can be obtained in samples synthesized via hydrothermal
treatment over 6 h without subsequent calcination. The combina-
tion of supercritical water hydrothermal treatment over a short
time with subsequent low-temperature calcination was found to
be better for achieving high performance with capacities of 193,
160 and 140 mA h g1 at 1, 10 and 20 C, respectively. Laumann
et al. developed a novel rapid, continuous flow hydrothermal
process for the synthesis of Li4Ti5O12 in sub- and supercritical
water [100]. They claimed that crystalline Li4Ti5O12 nanoparticles
of 4.5 nm with a specific surface area greater than 230 m2 g1
were successfully prepared in a single step and in less than 1 min
by the novel hydrothermal process using TTIP and lithium
dissolved in ethanol. After further calcination at approximately
600 8C, the sample delivered capacities greater than 180, 156, 143,
124, 112, and 96 mA h g1 at 0.1, 1, 2, 4, 10 and 20 C, respectively,
and a capacity of 157 mA h g1 was maintained following
50 cycles at a rate of 1 C. Zhang et al. reported a glycerol assisted
hydrothermal method to synthesize Li4Ti5O12 nanoparticles
[101]. Different initial Ti:Li molar ratios and calcining tempera-
tures were studied, and ultrafine pure Li4Ti5O12 nanoparticles with
sizes of 25 nm were successfully obtained with a Ti:Li ratio of
1:4.5125 and calcining temperature of 500 8C, which delivered a
high rate performance with a discharge capacity of 155 mA h g1
even at 20 C and stable cycling performance with a capacity
retention of 93.3% after 500 cycles at 5 C. Li et al. synthesized 70–
200 nm lump Li4Ti5O12/C using a facile hydrothermal method with
Ti(OC4H9)4 and LiAc as raw materials and CTAB as a surfactant
[102]. Super rate performance with specific capacities of 151 and
136 mA h g1 at 10 and 20 C was achieved for the lump Li4Ti5O12/C.
The authors found that the presence of CTAB is very important to
obtain a larger lithium ion diffusion coefficient and smaller charge-
transfer resistance for the Li4Ti5O12/C composite. To continuously
produce Li4Ti5O12 nanoparticles, a supercritical flow hydrothermal
reaction system was applied with appropriate Ti sources and Li/Ti
ratio [103]. Pure-phase Li4Ti5O12 with a particle size of approxi-
mately 100 nm was successfully synthesized using titanium
dioxide sols (M-6: TiO2 6%, crystallite size 5 nm, pH 3.4; A-6:
TiO2 6% pH 10) as raw materials with initial Li/Ti molar ratios >2.5
for M-6 and >2.0 for A-6. Based on the ability of continuous
synthesis, the supercritical flow hydrothermal reaction may be a
good choice for large-scale industry production of Li4Ti5O12
nanoparticles.
Solvothermal processes in polyol medium have received
attention for the synthesis of Li4Ti5O12 from a low-cost precursor
Fig. 13. Chronopotentiometric plot of (A) Li4Ti5O12 prepared from Ti(IV) butoxide–Li with simple processing. Kim et al. prepared Li4Ti5O12 nanoparticles
ethoxide compared to (B) commercial Li4Ti5O12 spinel (LT-2 from Titan Kogyo
Japan). Electrolyte solution: 1 M LiN(CF3SO2)2 + EC/DME (1:1 by mass). The
by precipitation from an ethylene glycol (EG) solution of TTIP and
charging/discharging current, i, was adjusted to charging rate of 2, 50, 100, 150, Li2O2 after refluxing at 197 8C for 12 h under ambient pressure
200, and 250 C for solid curves from top to bottom. Dashed curves display the [104]. The as-prepared sample and the products of further
corresponding galvanostatic discharging at the same rates. For the sake of clarity, calcination at 320, 500, and 800 8C for 3 h showed particle sizes
the time (t) is multiplied by the absolute value of i [95].
of 5, 8, 10 and 400 nm respectively, and their corresponding initial
capacities at a discharge rate of 0.05 mA cm2 reached 200, 310,
320 and 260 mA h g1, respectively, all exceeding the theoretical
(600 8C, 2 h), pure-phase Li4Ti5O12 with sizes of 30–50 nm could be value of 175 mA h g1. However, the samples showed relatively
obtained. The as-synthesized Li4Ti5O12 nanocrystalline exhibited poor cycling stability. The sample calcined at 500 8C exhibited the
high capacities of 166, 136 and 130 mA h g1 at 1, 5 and 10 C after best capacity retention; a value of approximately 200 mA h g1
50 cycles, respectively. was maintained after 60 charge–discharge cycles at rates varying
Hydrothermal/solvothermal methods are also important soft from 0.05 to 0.4 mA cm2. Lim et al. prepared nanosized Li4Ti5O12
chemical methods used for the facile preparation of nanoparticles via the solvothermal treatment of LiOH, TTIP and (HOCH2CH2)2O in
at controlled temperatures and pressures with versatile morphol- polyol medium at 235 8C for 16 h [105]. After further calcination at
ogies and properties. Nugroho et al. successfully synthesized 500 8C for 5 h in air, the resulting powder exhibited a particle size
nanosized Li4Ti5O12 through the hydrothermal treatment of of 10–20 nm with initial discharge/charge capacities of 230/
LiOHH2O and TTIP in supercritical water at 400 8C and 300 bar 179 mA h g1 at a current density of 0.1 mA cm2 in the voltage
12 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

and atomized to micrometer-sized droplets through a nozzle. The


particles are then calcined in a high-temperature furnace to
quickly form powders with the desired composition. There are
several advantages to synthesizing ceramic powders by spray
pyrolysis including a spherical particulate shape, uniform particle
size, a low degree of aggregation and high purity of the product,
continuous preparation and a short reaction time for the synthetic
process. Accordingly, spray pyrolysis was also applied to the
synthesis of Li4Ti5O12. Ernst et al. prepared a series of inorganic
composites including Li4Ti5O12 nanoparticles for LIBs via flame
spray pyrolysis; the as-prepared Li4Ti5O12 was 85% pure with a
particle size of approximately 18 nm and a specific surface area of
86 m2 g1 [117]. Doi et al. successfully prepared well-crystallized
Li4Ti5O12 nanoparticles with a fairly uniform particle size of only
approximately 12 nm via the electrospray pyrolysis of a Ti(OC3H7)4
and lithium acetonate starting solution in 2-propanol at 400 8C
[118]. Bresser et al. successfully synthesized 20–30 nm Li4Ti5O12
nanoparticles using a flame spray pyrolysis [119]. Although several
phase impurities of rutile TiO2, anatase TiO2 and Li3Ti3O7 were
observed in the as-synthesized nanoparticles, the electrode still
exhibited superior cycling performance with a stable capacity of
approximately 116 mA h g1 at 10 C through 1000 cycles. The
introduced impurities might be due to the evaporation of lithium
during the flame spray pyrolysis; increasing the amount of initial
lithium source may address this issue. Kim et al. successfully
prepared phase-pure Li4Ti5O12 nanoparticles via the flame spray
pyrolysis method with a 15% excess of lithium source and a post-
treatment at 800 8C [120]. The as-prepared nanoparticles with
sizes of 300 nm exhibited an initial capacity of 151 mA h g1 and
a high Coulombic efficiency of 99%.
The use of expensive Ti(IV) alkoxides as a raw material (TTIP or
titanium n-butoxide) makes all of the above-described processes
economically less attractive for practical applications. Therefore, the
synthesis of nano-sized Li4Ti5O12 via less complex and lower-cost
techniques has recently received attention. Although solid-phase
reactions may result in coarse particles with inhomogeneous phases,
Fig. 14. (a) FE-SEM micrograph of Li4Ti5O12 powder calcined at 800 8C (b) A
magnified FE-SEM view of the selected section of (a) [111]. their simplicity, low cost and mass production capability make them
highly attractive methods for powder synthesis. For many decades,
solid-state reactions were widely applied in industrial processes. In a
range of 1.0–2.5 V. In comparison, the sample prepared from a conventional solid-phase reaction, the product is first formed at the
solid-phase reaction had discharge/charge capacities of only 162/ reactant interface, which creates a diffusion block for further
154 mA h g1. Even at high rates of 30 and 60 C, the sample reactions. Thus, calcination at high temperatures for a long period is
prepared using solvothermal synthesis exhibited charge capacities required to overcome such a diffusion block, leading to substantial
of 159 and 137 mA h g1. grain growth of the product. The solid-state reaction mechanism of
In addition to soft chemical methods, combustion techniques Li4Ti5O12 from anatase TiO2 was studied via in situ high temperature
have been extensively investigated for the preparation of advanced powder X-ray diffraction and thermal gravimetry-differential
functional materials. These techniques allow the temperature to thermal analysis: in a typical reaction process, monoclinic Li2TiO3
instantly reach several thousand degrees Celsius during the was formed from the reaction between TiO2 and Li2CO3; it further
synthesis [106,107]. Such a high temperature promotes the reacted with the remaining TiO2 to form a Li4Ti5O12 phase at a higher
solid-state reaction, while the short combustion time effectively temperature [121]. The authors found that decreasing crystallite
suppresses the grain growth. As a result, high-purity products with sizes could result in a reduced initial reaction temperature. During
ultrafine particle sizes can be easily prepared. The combustion the past several years, attempts have been made to modify solid-
synthesis of Li4Ti5O12 has been examined over the past several phase reactions to reduce the calcination temperature and time, thus
years [108–113]. Depending on the synthetic conditions, the reducing the particle size. These attempts include microwave-
resulting Li4Ti5O12 can be dense, micrometer-sized particles, sub- assisted solid-state synthesis [122] and high-energy ball milling
micrometer-sized particles with a porous morphology, or nano- (HEBM)-assisted solid-state synthesis [123–131]. Both processes
meter-sized particles. Raja et al. applied an aqueous combustion can effectively promote the solid-state reaction at a lower
technique for the synthesis of Li4Ti5O12 using the amino acid temperature by providing an additional energy source. Lee et al.
alanine as a fuel, Ti(OCH3)4 and LiNO3 as cation sources, and HNO3 introduced a novel method based on a solid-phase reaction for the
as an oxidant [111]. Li4Ti5O12 nanoparticles with sizes in the range preparation of homogeneous Li4Ti5O12 nanoparticles with high
of 40–80 nm (Fig. 14) and a phase purity of 90% were successfully purity [132]. They first prepared 2–5-nm-thick LiOH-coated TiO2
obtained after further calcination of the primary product from nanoparticles via a sonochemical method. These nanoparticles were
direct solution combustion at 800 8C for 10 h in air. then thermally treated at 500 8C to produce Li4Ti5O12 particles with
Spray pyrolysis is a powerful technique for synthesizing a wide an average grain size of 30–40 nm.
range of ceramic powders with small particle sizes [114–116]. For Most of the Li4Ti5O12 nanoparticles prepared via the above-
a typical synthesis, the raw materials are first mixed into a solution described processes, however, had a large size distribution and
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 13

process with as-prepared TiO2 treated in a concentrated LiOH


solution to achieve lithiation is usually named chemical lithiation.
The chemical lithiation was initially used for synthesis of
nanocrystalline Li4Ti5O12 [134], and was later expanded to
synthesize Li4Ti5O12 with various nanostructures. Fig. 16 compares
the chemical lithiation route for preparing Li4Ti5O12 with the
common synthesis route. In a common synthesis route, the initial
Li:Ti ratio of feeded raw materials is usually 4:5; some excess
lithium was used to compensate the lithium loss by evaporation
during calcination. In a chemical lithiation synthesis, however, a
concentrated LiOH solution is used as the lithium source, implying
that the initial Li:Ti ratio is much higher than 4:5. The
thermodynamically stable phase rutile TiO2 usually could not be
chemically lithiated, anatase TiO2 or amorphous TiO2 is preferred.
After proper calcination, however, a pure spinel phase could be
easily obtained. It seems that the chemical lithiation process could
result in formation of Li–Ti–O intermediate phase, which could
easily become a spinel phase. The chemical lithiation in LiOH
solution is usually carried out at low temperatures (i.e., <200 8C)
for a long period of time, and the subsequent calcination
temperature could also be relatively low when a nanosized TiO2
was used. Thus, the nanostructure of TiO2 could be retained in the
final Li4Ti5O12 phase, resulting in outstanding electrochemical
performance. To date, however, the Li–Ti–O intermediate phase
structure, the chemical lithiation mechanism, and the final Li:Ti
ratio are still not yet fully understood and could be further studied
using advanced characterization techniques.

3.1.2. 1–3D nanostructures


As previously mentioned, reducing the particle size of Li4Ti5O12
to the nanometer range can significantly reduce the diffusion
distance for both electrons and lithium ions within the electrode
bulk. The reduced particle size can also increase the specific surface
area for an interfacial reaction; as a result, the electrode may exhibit
improved performance even without surface coating and/or lattice
doping. However, some detrimental effects are introduced when
ultrafine nanoparticles are used as electrodes including an increased
difficulty in electric wiring and loss of the electrode material.
Improper wiring can render some particles electrochemically
inactive; thus, reducing the electrode performance of the nanoelec-
trodes compared to that of the micrometer-sized electrodes. In
addition, the nanoparticles released from the electrode surface may
cross the porous separator, which has a pore size in the micrometer
range, and agglomerate on the other electrode, resulting in a loss of
capacity and an internal short circuit [135]. One effective method of
solving the above-mentioned problems requires the development of
one-dimensional (1D) nanostructures such as nanotubes, nano-
Fig. 15. (a) TEM and (b) SEM images for nano-sized Li4Ti5O12 crystals [133]. wires, nanorods, and nanofibers (Fig. 11). These nanostructures
possess the properties of nanoparticles such as high surface area and
short diffusion distance of charges within the bulk. However, these
varying degrees of aggregation. Lu et al. proposed a novel process nanostructures are of the micrometer size in one dimension, which
for the preparation of nearly uniform Li4Ti5O12 single crystals with facilitates current collection.
a size of 40 nm [133]. They first prepared a-Li2TiO3 via the Nanotubes are 1D nanostructures with hollow interior chan-
hydrothermal treatment of anatase TiO2 with a uniform particle nels. Because of their large surface areas, high surface-to-weight
size of 4.5 nm in a 2 M LiOH aqueous solution, which was then ratios and nanosize, nanotubes are highly attractive for energy
reacted with a proper amount of HCl to allow an ion exchange storage applications. Lee et al. applied a two-step process for the
between the a-Li2TiO3 and the solution leading to the formation of synthesis of Li4Ti5O12 nanotubes [136]. In this synthesis, plate-
(Li0.4H0.6)2TiO3 nanocrystals. Well-dispersed Li4Ti5O12 nanocrys- shaped Li4Ti5O12 was first prepared via heat treatment at 500 8C of
tals were obtained after the further calcination of the (Li0.4H0.6)2- the primary product from the reaction of a mixture of titanium n-
TiO3 at 400 8C for 2 h. Fig. 15 provides transmission electron butoxide, cetyltrimethylammonium chloride and lithium hydrox-
microscopy (TEM) and SEM images for the as-prepared Li4Ti5O12 ide at 120 8C for 2 h, which was then further hydrothermally
nano-sized single crystals. The materials demonstrated reversible treated at 120 8C in 10 M aqueous NaOH. The as-prepared sample
capacities of 172, 165, and 140 mA h g1 at discharge rates of 0.5, 1, exhibited a nanotube morphology with an open-ended structure
and 5 C, respectively. After 60 cycles at various rates, the capacity that had outer and inner diameters of 11 and 6 nm,
at a rate of 1 C recovered to nearly the initial value, suggesting a respectively, and a specific surface area of 53.7 m2 g1. The
high cycling stability of the as-prepared electrode. Such a synthesis product showed a reversible capacity of 156 and 145 mA h g1 at
14 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 16. Schematic illustration of the chemical lithiation synthesis route for preparing Li4Ti5O12 compared to the common synthesis route.

rates of 0.1 and 2 C, respectively. The electrode also demonstrated sonochemical–hydrothermal reaction in concentrated 10–15 M
good cycling stability and no obvious capacity fade after NaOH at 120–170 8C for 24–72 h. TEM and SEM images of the
25 charge–discharge cycles at a rate of 0.1 C. various samples at different stages are shown in Fig. 17. A higher
Li et al. prepared 1D nanostructured Li4Ti5O12 from hydrogen NaOH concentration with higher temperature and increased
titanate nanotube precursors via a hydrothermal lithium ion reaction time resulted in hydrogen titanate nanowires, not
exchange process. The as-prepared Li4Ti5O12 had an outer nanotubes. Further hydrothermal treatment of the H-TiO2
diameter of 10 nm and lengths of several hundred nanometers nanotube/nanowires in the aqueous LiOH solution allows an ion
to over several micrometers [137]. The hydrogen titanate exchange between H-TiO2 and the solution to form a Li4Ti5O12
nanotube was prepared from industrial TiO2 powders via a precursor, which was converted to crystallized Li4Ti5O12 by further

Fig. 17. (a) TEM micrograph of hydrothermal (120 8C for 24 h) lithium ion exchanged lithium titanate nanotubes before heat treatment. (b) Sample (a) after heat treatment at
350 8C for 2 h in air atmosphere. (c) SEM micrograph of hydrothermal (120 8C for 24 h) lithium ion exchanged lithium titanate nanowires before heat treatment. (d) A single
nanowire TEM micrograph of sample (c) after heat treatment at 500 8C for 2 h in air atmosphere [137].
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 15

Fig. 18. (a) Typical SEM and (b) TEM images of LT-E6 calcined at 500 8C, (c) cycling behavior at different C rates for the LT-E6-500, LT-E6-700, LT-E8-500, and LT-E8-700
powders, respectively. LT represents Li4Ti5O12, E6 represents the solvothermal reaction in various mixed solvents including ethanol 60 vol.%, 700 represents calcination at
700 8C [141].

calcination at 300–500 8C for 2–6 h. Neither the hydrothermal ion Electrospinning has proven to be a versatile technique for the
exchange nor the subsequent calcination induced a change in fabrication of nanofibers of varied dimensions with versatile
powder’s morphology. Kim et al. prepared Li4Ti5O12 nanowires morphologies, such as hollow fibers, solid fibers and porous
with a diameter of 180 nm, a length of several micrometers and a fibers [142–146]. Such nanofibers can be easily assembled into
specific surface area of 38 m2 g1 by firing a mixture of
TiO21.25H2O nanowires and LiAc at 800 8C for 3 h [138]. The
as-prepared Li4Ti5O12 nanowires exhibited capacities of 165,
157 and 155 mA h g1 at rates of 0.1, 5 and 10 C, respectively.
No noticeable capacity decay was observed after 30 cycles at a rate
of 0.1 C. By applying a process similar to that reported by Li et al.
[137], Li et al. successfully synthesized Li4Ti5O12 nanorods with
excellent electrochemical performance [139]. They first prepared
TiO2 nanorods via the hydrothermal treatment of rutile TiO2
powder in 10 M NaOH at 180 8C. Following an acid treatment, the
resulting titanate nanorods were dispersed in an aqueous LiOH
solution for further hydrothermal treatment. The nanorods were
finally calcined at 500–800 8C to obtain well-crystallized Li4Ti5O12
nanorods. At a discharge current density of 50 mA g1, the sample
calcined at 800 8C exhibited a reversible capacity of 147.5 mA h g1
after 100 cycles, and a capacity of 133.8 mA h g1 was achieved
even at a high discharge current density of 1600 mA g1. Such high
performance was attributed to the good crystallinity, the unique
nanorod particulate morphology, and the short diffusion distances
of both the lithium ion and the electron. To further eliminate the
tedious acid-washing procedure, hydrothermally synthesized
sodium titanate (Na2Ti2O4(OH)2) nanotubes were treated in
0.8 M LiOH solution under stirring at room temperature and were
finally converted into the Li4Ti5O12 phase by calcining at 400–
700 8C [140]. The sample calcined at 500 8C exhibited the best
electrochemical performance with a specific capacity of
146 mA h g1 at 10 C and a stable capacity retention of only
0.7% decay after 200 cycles, even though the initial tubular
morphology was destroyed after calcination.
Lee et al. synthesized nanoparticle-modified Li4Ti5O12 nano-
wires through a solvothermal reaction using Li(OH)H2O and
protonated trititanate (H2Ti3O7) nanowires as the templates in an
ethanol/water mixture with subsequent heat treatment [141]. As
shown in Fig. 18, the resulting nanowires had diameters of 130 nm,
lengths in the range of 1–3 mm and high rate capacities with values
of 151, 139, 128 and 114 mA h g1 at 1, 5, 10 and 20 C, respectively.
A capacity of 125 mA h g1 was retained after 500 charge– Fig. 19. SEM images of (a) Li4Ti5O12/PVP fibers after calcining in air at 750 8C for 1 h
fabricated by electrospinning, (b) Li4Ti5O12 fibers after electrochemical reaction [147].
discharge cycles at a rate of 1 C, suggesting a high cycling stability.
16 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 20. (a, b) SEM, (c) TEM and SAED images (inset in c) of the Li4Ti5O12 nanosheet, (d) a HRTEM image of Li4Ti5O12 recorded on the corner of a sheet [158].

nonwoven nets with three-dimensional (3D) architectures to serve even though the electrospinning method is powerful for preparing
as freestanding film electrodes without the need for an additional a flexible film electrode for LIBs [145]. This is mostly due to the
binder or conductive additive. Lu et al. fabricated Li4Ti5O12 presence of a reaction between lithium and titanium sources for
nanofibers via the electrospinning method with an average forming the spinel phase since the flexible TiO2/C film electrode
diameter of 150  50 nm that were composed of small crystalline could be easily prepared without application of lithium. The
grains with an average size of less than 100 nm [147], as shown in preparation of flexible carbon fiber film and growth of Li4Ti5O12
Fig. 19. Such nanofibers were packed in cross-shape to form 3D nanostructure on it could be a good way to obtain a flexible
nonwoven films. When these films were applied directly as Li4Ti5O12/C fiber film electrode.
electrodes, they exhibited high first discharge capacities of Beyond 1D structures, two-dimensional (2D) structures
192 and 170 mA h g1 at 0.5 and 1.5 C, respectively. However, a (Fig. 11) (e.g., nanosheets and nanoplates) usually have shorter
relatively large capacity decay rate was observed; the capacities after diffusion distances for both electrons and lithium ions due to the
cycling at rates of 0.5 and 1.5 C reduced to 140 and 87 mA h g1, ultrathin thickness compared with the diameter of 1D structures
respectively. Electrospun Li4Ti5O12 nanofibers with diameters of and better current collection due to the sheet morphology
230 nm were also fabricated by Wang et al. [148]. The electrodes compared with 1D structure and are expected to exhibit even
were prepared using a conventional coating method with 70 wt.% of better electrochemical performance. Lamellar Li4Ti5O12 (called a
Li4Ti5O12 nanofibers, 20 wt.% carbon black and 10 wt.% binder. The flower-like structure) was synthesized by a solvothermal method
sample calcined at 700 8C exhibited good rate performance with with as-synthesized amorphous TiO2 spheres and LiOH as the
specific capacities of 163.3, 138.7, 123.4 and 90.4 mA h g1 at 1, 10, sources and ethanol as the solvent [157]. A pure spinel phase could
20 and 60 C, respectively. Moreover, the capacity remained at be obtained after calcination at a relatively low temperature of
120.1 mA h g1 after 300 cycles at 20 C. 600 8C for 3 h. The thickness of the as-calcined lamellar Li4Ti5O12
Li4Ti5O12/C composite fibers have also been fabricated via the was only 10 nm, which is beneficial for lithium ion insertion/
electrospinning method [149–155]. The introduction of carbon extraction. As a result, superior capacities of 148, 138,
into the fibers not only effectively increased the apparent 118 mA h g1 at 0.5, 5, 30 C, respectively, was demonstrated. Li
electronic conductivity, which improves the charge transfer and et al. prepared single-crystalline Li4Ti5O12 nanosheets with
current collection, but also created mesopores in the nanofibers, thicknesses of 10–20 nm (Fig. 20) by the calcination of hydrother-
facilitating the penetration of liquid electrolytes and thus mally synthesized Li1.81H0.19Ti2O5xH2O nanosheets at 500 8C for
benefiting the interfacial reactions. Especially, Yang et al. observed 2 h [158]. A hydrolysis–Kirkendall effect–Ostwald ripening process
that the presence of carbon calcined under Ar atmosphere resulted was proposed for the formation of lithium titanate oxide hydrate
in the formation of a pure Li4Ti5O12 phase instead of Li4Ti5O12 and nanosheets during the hydrothermal synthesis. The as-calcined
TiO2 phases after calcination under air atmosphere [153]. There- Li4Ti5O12 nanosheets delivered a discharge capacity of
fore, these Li4Ti5O12/C fiber electrodes exhibited enhanced 120 mA h g1 even after 300 cycles at a 10 C rate. Recently, Sha
electrochemical performance. Li et al. demonstrated that by et al. synthesized well-crystallized Li4Ti5O12 nanoplates via
doping Li4Ti5O12 with Nb5+, the electrospun Li4Ti4.95Nb0.05O12/ hydrothermal synthesis in a benzyl alcohol–NH3H2O solvent
carbon nanofibers exhibited even better rate capability with using LiOHH2O and TBOT as raw materials and a subsequent
capacities of 167.5 and 110.6 mA h g1 at 1 and 25 C, respectively, calcination at 500 8C [159]. Although the calcination temperature
than the electrospun Li4Ti5O12/C nanofibers (163 and 50 mA h g1 is as low as 500 8C, but the as-synthesized Li4Ti5O12 nanoplates
at 1 and 25 C, respectively), although both exhibited excellent obtained from a 6-h hydrothermal reaction exhibited a well-
cycling stability [156]. However, most of these Li4Ti5O12/C crystallized nature (Fig. 21) as well as an excellent rate capability
composite fibers did not appear to be flexible free-standing film and cycling stability with a discharge capacity of 153 mA h g1
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 17

Fig. 21. (a) TEM, (b) HR-TEM and (c) the cycling performance (10 C) of the as-prepared Li4Ti5O12 nanoplates [159].

Fig. 22. TEM image of wavelike Li4Ti5O12 nanosheet annealed at 600 8C. The inset in (c) is a corresponding schematic illustration of the wavelike nanosheet [160].

after 1000 cycles at a 10 C rate. Liu et al. prepared similar Li4Ti5O12 After careful observation, these nanoplates were wave-like
nanoplates via hydrothermal synthesis, in which metallic lithium nanosheets as shown in Fig. 22c. By calcination of the sample in
was reacted with N,N-dimethylethanolamine at first and the as- the absence of oxygen, nitrogen-doped carbon derived from N,N-
obtained solution was mixed with tetrabutyl titanate with a Li/Ti dimethylethanolamine was introduced into the sample, even
ratio of 4:5 followed by hydrothermal treatment and further though the carbon content was as low as 0.6 wt.%, excellent
calcination [160]. Fig. 22 shows the typical TEM images of the electrochemical performance was achieved with capacities of
sample after calcination at 600 8C for 2 h, the microstructure of the around 171, 164, 151 and 122 mA h g1, at 20, 30, 50 and 100 C,
Li4Ti5O12 were mainly nanoplates as shown in Fig. 22a. A magnified respectively. Furthermore, the electrode exhibited outstanding
image (Fig. 22b) shows that the morphology of nanoplates performance even at 10 C, demonstrating capacities of 172, 154,
appeared to be similar to that reported by Sha et al. (Fig. 21a). and 135 mA h g1 at 0, 10 and 20 8C respectively.
18 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 23. Typical routes for synthesis of porous Li4Ti5O12, and the corresponding representative synthesis method.

Additionally, 2D structures can stack to form 3D structures such as-synthesized products contained impurity phases of Li2TiO3,
as flower-like microspheres composed of nanosheets or nano- rutile TiO2 and anatase TiO2 of approximately 10% of the total mass.
flakes; Li4Ti5O12 with a wide range of different 3D structures will Woo et al. prepared an 80-mm-thick 3DOM Li4Ti5O12 film via a
be discussed in the following sections. colloidal crystal (monodispersed polystyrene (PS) spheres) templat-
ing process [162] similar to that applied by Sorensen et al. [161]. A
3.2. Morphological control precursor of sol consisting of TTIP and LiAc was first impregnated
into the void space of the template. The precursor was then calcined
3.2.1. Porous electrodes at 800 8C to obtain a macroporous Li4Ti5O12 membrane with an
Incorporating pores into micrometer-sized particles is another inverse opal structure. As shown in Fig. 24, the interconnected pores
effective method for increasing the rate performance of electrode of uniform size (0.8 mm) were clearly observed with a pure Li4Ti5O12
materials. Such micrometer-sized porous electrodes have the phase composition. The 3DOM Li4Ti5O12 membrane exhibited a
advantages of easy current collection and short diffusion pathways discharge capacity of 160 mA h g1 at a rate of 0.1 C and retained a
for lithium ion. The porous structure increases the surface area, thus capacity of approximately 60 mA h g1 at a high rate of 10 C. The
producing more surface sites for lithium to insert into the electrode 3DOM Li4Ti5O12 film electrode also exhibited good cycling stability
material, while the nanometer-thick walls shorten the lithium with a discharge capacity decay rate of approximately 0.1 mA h g1
diffusion distances. Both properties are helpful for reducing the per cycle during 100 charge/discharge cycles at a rate of 1 C. Shao
electrode polarization. The micrometer-sized particles with 3D
structures also ensure inter-particle contact and increase the
electrode stability, thus suppressing capacity loss. Summarized in
Fig. 23 are three typical routes for synthesis of porous Li4Ti5O12. The
first route is using template or pore former to create pores in the
samples. The pore size and porosity could be easily controlled by
using different template or pore former. The second route is
combustion synthesis. The pores are mainly created by the diffusion
gases in the process. It is relatively simple but less controllable. The
third route is the self-assembling synthesis. The pores were from the
void space created from the special structures as well as the sites left
by removing some organic groups.
Sorensen et al. prepared three-dimensionally ordered macro-
porous (3DOM) Li4Ti5O12 using poly (methyl methacrylate) colloidal
crystal templates and metal organic aqueous precursors [161]. The
electrode performance was found to be closely related to the status
of the voids in the templates filled by the metal organic aqueous
precursors. If the voids were underfilled or perfectly filled, the rate
capability of Li4Ti5O12 was markedly improved, while the perfor-
mance was reduced with overfilled voids due to the decreased
porosity and the increased wall thickness. Unfortunately, the Fig. 24. SEM image of 3DOM Li4Ti5O12 annealed at 800 8C [162].
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 19

et al. also used monodisperse PS spheres as templates to obtain at 800 8C for 8 h exhibited a phase-pure spinel structure, and the
porous Li4Ti5O12 using a sol–gel method [163]. After calcination, the sample contained mesopores primarily concentrated in the range
pores with an average diameter of approximately 100 nm were of 2–20 nm with discharge capacities of 167, 164, 138, 112, 71 and
created by burning of 350 nm PS sphere templates. The nanoporous 62 mA h g1 at 0.2, 0.4, 1, 2, 10, and 20 C, respectively. Recently, Lai
Li4Ti5O12 exhibited good cycling performance with a capacity of et al. reported a mesoporous Li4Ti5O12 with a specific surface area
170 mA h g1 after 100 cycles at 0.1 C (0.5–3.0 V). of 153.7 m2 g1 prepared via a ball-milling-assisted solid-state
Solid-state reactions are still the most widely used methods for reaction using TiOSO4xH2O and LiOHH2O as raw materials
industrial powder synthesis due to their simplicity and mass [166]. A high specific capacity of 143.4 mA h g1 was achieved
production capability. However, the products typically exhibit at a 10 C rate even after 50 cycles for this mesoporous
large, dense grains and phase inhomogeneity. By tailoring the Li4Ti5O12. The key to obtaining such a mesoporous structure could
synthetic parameters, solid-state reactions may also be used to be the calcination at a low temperature of 500 8C and the
synthesize porous electrodes for LIBs. Lin et al. introduced a utilization of washing of Li2SO4 impurities to generate mesopores.
modified solid-phase reaction for the synthesis of porous Li4Ti5O12 Combustion synthesis is an effective fabrication technique that
with improved electrochemical performance [164] by using LiCl has also been applied to the synthesis of porous Li4Ti5O12. In a
and TiCl4 as raw materials and oxalic acid as a pore former. The solution combustion process, the enormous quantity of gases
initial capacities of the resulting electrode material reached produced during the synthesis may facilitate the formation of rich
167 and 133 mA h g1 at 0.5 and 1 C charge/discharge rates, pores in the final product. Prakash et al. applied a single-step
respectively, and the capacity was maintained at 98% after solution combustion method for the synthesis of highly porous
200 charge/discharge cycles at room temperature. At rates of spheres composed of well-crystallized Li4Ti5O12 nanoparticles with
10 and 50 C, the electrode still delivered stable capacities of 70 a primary particle size between 20 and 50 nm and nano- and
and 30 mA h g1, respectively. Lv et al. synthesized porous micropores with sizes ranging from 0.15 to 1.5 mm (Fig. 25)
Li4Ti5O12 via a solid-phase reaction using phenol-formaldehyde [110]. Such hierarchically nanostructured microscale materials
resin as a template [165]. The Li4Ti5O12 produced from calcination exhibited good rate performance (Fig. 25), achieving a

Fig. 25. (a) Digital photograph of voluminous Li4Ti5O12 formed after the combustion of corresponding metal nitrates with glycine at 800 8C, (b) corresponding SEM image, and
(c) capacity-voltage profiles for nanocrystalline Li4Ti5O12 synthesized by the combustion method at different rates. The inset shows the capacity voltage profile for bulk
Li4Ti5O12 prepared by the solid-state method [110].
20 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

near-theoretical capacity of 170 mA h g1 at a rate of 0.5 C. The and lithium hydroxide precursors [168]. The electrode exhibited a
electrode continued to deliver high capacities of 105 and discharge capacity of up to 160 mA h g1 even at a discharge rate of
70 mA h g1 even at ultrahigh discharge rates of 50 and 100 C, 20 C. In addition, a full battery with a Li4Ti5O12 anode and a lithium
respectively. In addition, the samples exhibited good cycling manganese oxide cathode had almost no capacity fade after
stability, with a capacity retention greater than 95% after 100 cycles 1000 charge/discharge cycles at a rate of 5 C at temperatures up to
at different rates. Such excellent performance was attributed to the 55 8C. Chen et al. synthesized a defective mesoporous Li4Ti5O12y
mesoporous powders made of fused nanoparticles. However, too (100–500 nm) by a solvothermal method with a subsequent
much porosity may lead to a low tap density and thus a low calcining process in N2 atmosphere [169]. The defective Li4Ti5O12y
volumetric energy density. exhibited a capacity of 139 mA h g1 at 20 C, and 91.4% of the
As versatile synthetic techniques, hydrothermal methods were capacity was retained over 300 cycles. Hasegawa et al. prepared a
widely applied for the synthesis of hierarchically structured porous porous Li4Ti5O12 structure with a hierarchical architecture via
Li4Ti5O12. For example, Lai et al. prepared microsized Li4Ti5O12 hydrothermal treatment of TiO2 wet gel in an aqueous LiOH
nanosheets via a facile hydrothermal route [167]. The microsized solution followed by calcination [170]. The typical SEM and TEM
grains had irregular shapes consisting of random sheet-like images of the as-obtained porous Li4Ti5O12 structure calcined at
Li4Ti5O12 with thicknesses of 10–16 nm. The nanosheets intro- 700 8C are shown in Fig. 26. It appears that the porous structure is
duced a pseudocapacitive effect, leading to improved capability at flower-like, composed of platy crystallites. TEM observation
high discharge rates. The as-prepared electrode exhibited a further revealed that the petal of the flower-like structure was a
capacity of 147.3 mA h g1 at 1.1 C rate and retained 128 mA h g1 100–200 nm single-crystalline nanosheet (Fig. 26b). Three lattice
1 at 11.4 C rate. Amine et al. have also developed hierarchically fringes with spacings of 0.41 nm, 0.48 nm and 0.49 nm were
structured Li4Ti5O12, micrometer-sized secondary particles (0.5– observed from the HR-TEM image (Fig. 26c), which could be
2 mm) composed of nanometer-sized particles (<10 nm) and assigned to the d spacings of (0 0 2), (1 1 1) and (1 1 1) planes of
nanopores, via a hydrothermal process using titanium oxy-sulfate Li4Ti5O12 phase, respectively. The porous Li4Ti5O12 structure with a

Fig. 26. (a) SEM image of the porous Li4Ti5O12 sample calcined at 700 8C; inset is a typical magnified image. (b) TEM image of a typical nanosheet in the sample calcined at
700 8C. (c) HR-TEM image of the nanosheet shown in (b). The inset shows a crystal structure of spinel lithium titanate viewed along [110] zone axis [170].
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 21

64 C, a capacity of 148 mA h g1 was retained with a capacity fade


rate of only 1.5  103% per cycle. These results are exciting. Such
porous Li4Ti5O12 thin films are highly promising as high-rate
anodic materials for thin-film micro-batteries. Jiang et al. prepared
porous Li4Ti5O12 with a spherical pore structure using a sol–gel
method with carbon spheres as the hard template [172]. The
porous Li4Ti5O12 had a particle size of approximately 1 mm and a
wall thickness of approximately 100 nm, which delivered a first
discharge capacity of 175 mA h g1. As a comparison, the micro-
sized and densely aggregated Li4Ti5O12 prepared without using a
carbon sphere template showed a slightly lower capacity of
160 mA h g1 at 0.57 C. However, at 5.7 C, the porous Li4Ti5O12 still
delivered a capacity of 121 mA h g1, while the densely aggregated
Li4Ti5O12 decreased sharply to only 46 mA h g1.
Fig. 27. Specific capacity and Coulombic efficiency for the first 3000 cycles at a rate The emulsion method was also studied for the preparation of
of 64 C (184 mA/cm2) of KLE-templated Li4Ti5O12 thin film electrodes calcined at porous Li4Ti5O12. Huang et al. synthesized mesoporous Li4Ti5O12
650 8C. Cutoff voltages were set at 3.5 and 1.40 V vs. Li/Li+ [171]. with a spherical pore structure using a macroemulsion method
[173]. As shown in Fig. 28, the authors synthesized porous
Li4Ti5O12 via macroemulsion in a two-phase solution consisting of
n-heptane and ethanol with a P123 triblock copolymer as the
emulsifier. First, a macroemulsion was formed after mixing the
ethanol solution (containing LiAc and P123) and n-heptane in
which the surface layer of the emulsion droplet consisted of P123,
while the inner phase of the droplets contained the LiAc ethanol
solution and the outer phase consisted of the Ti(OC4H9)4 n-heptane
solution. Then, water was dropped into the Ti(OC4H9)4 in the n-
heptane phase outside the emulsion droplets. With the slow
evaporation of n-heptane and ethanol, the TiO2 formed on the
emulsifier layer and the lithium salt deposited homogeneously on
the TiO2. Finally, following the complete removal of solvents, the
precursor was formed with a hollow spherical structure. After
further heat treatment, the hollow spherical Li4Ti5O12 powder was
obtained. The pores with diameters of approximately 1 mm were
formed by 100 nm nanoparticles. The samples delivered capaci-
ties of 162, 150, 128, 115 and 95 mA h g1 at 0.5, 1, 5, 10 and 20 C,
Fig. 28. Schematic illustration of hollow spherical Li4Ti5O12 fabrication [173]. respectively. After 500 charge/discharge cycles at 2 C, a capacity of
135 mA h g1 was maintained with an average capacity loss of only
0.01% per cycle. The high capacity and good cycling stability was
hierarchical architecture delivered an outstanding rate perfor- attributed to the hollow morphology and the nanosized Li4Ti5O12
mance with specific capacities of 165, 155, and 121 mA h g1 at 0.1, particles.
10, and 30 C rate, respectively, and further stable cycling Kang et al. synthesized a meso-structured Li4Ti5O12-carbon
performance with a capacity retention of 98% after 500 cycles at nanocomposite with uniform pores larger than 15 nm via block
5 C. copolymer self-assembly by applying polyisoprene-block-poly(-
Haetge reported a facile polymer-directed sol–gel route via the ethylene oxide) with an sp2-hybridized carbon-containing hydro-
co-assembly of titanium(IV) n-butoxide and anhydrous LiAc phobic block as a structure-directing agent [174]. After further
molecular inorganic precursors with the large diblock copolymer calcination at 700 8C, the Li4Ti5O12 phase was formed, and the
KLE to a nanocrystalline Li4Ti5O12 thin film with a well-defined partial polyisoprene was converted to carbon, which coated the
mesoporous morphology [171]. The thin-film electrode exhibited a pore walls of the mesoporous Li4Ti5O12. A schematic representa-
capacity of 175 mA h g1 even at a rate of 2 C, which was close to tion of the synthesis is shown in Fig. 29. The mesopores with sizes
the theoretical capacity. As shown in Fig. 27, after 3000 cycles at of 20 nm are organized in a short-range ordered channel with

Fig. 29. Schematic representation of the synthesis of meso-Li4Ti5O12-C [174].


22 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 30. (a) Schematic illustration of the fabrication process of hierarchical mesoporous nest-like Li4Ti5O12. (b) SEM and (c–e) TEM images of hierarchical mesoporous nest-like
Li4Ti5O12 with different magnifications (the inset in (d) shows the SAED pattern) [175].

wormhole-like structures. The resulting mesoporous micrometer- The above reported porous electrodes were actually porous
sized Li4Ti5O12/C particles exhibited excellent rate performance and active materials themselves. Recently, Singh et al. developed a
a capacity of 115 mA h g1 even after 500 cycles at a rate of 10 C in a porous Li4Ti5O12 electrode by adding NH4HCO3 as a template to the
potential range of 1.0–2.5 V with a capacity retention of 89.7%. Chen slurry before the conventional electrode coating process [177]. Brief-
et al. prepared hierarchical mesoporous nest-like Li4Ti5O12 via a ly, NH4HCO3, Li4Ti5O12/C, polyvinylidene fluoride (PVDF), and Super
hydrothermal method with a typical process as shown in Fig. 30 P were mixed in an NMP solvent to form a slurry, which was then
using CTAB as a surfactant and a water-soluble titanium complex, coated onto a current collector. After drying at 50 8C, the electrode
[NH4+]4[H+]2 [Ti4(C2H2O3)4(C2H3O3)2(O2)4O2]6, as the titanium was further heated at 90 8C to decompose the NH4HCO3 to form a
source [175]. As shown in Fig. 30, the as-prepared Li4Ti5O12 had a porous network that could act as an ionic pathway for fast lithium
mesoporous nest-like structure composed of nanosized Li4Ti5O12 storage. As a result, the porous electrode exhibited greatly enhanced
with a crystalline size of 8.2 nm, falling primarily into the ranges of electrochemical performance, especially at high rates.
4 and 6 nm. The mesopores had wall thicknesses of 50–80 nm. Such
a unique morphological structure resulted in a large specific surface 3.2.2. Nano/microspheres
area of 219.2 m3 g1. High and stable capacities of 135.1 and Although the above-mentioned porous electrodes showed
113.6 mA h g1 at discharge current densities of 2.5 mA g1 and attractive capacities, rate capabilities, and/or cycling stabilities,
10 A g1, respectively, following 200 charge/discharge cycles were they usually can not achieve high tap densities, and thus fail to meet
also demonstrated. both the energy and power demands for practical applications.
Sun et al. prepared mesoporous Li4Ti5O12 nanoclusters with Among the various particulate morphologies, spheres have received
rich mesopores of 2–6 nm and a high surface area of 142 m2 g1 particular attention as they can minimize the length of the diffusion
using a facile solution method and low-temperature calcination pathway and increase the tap efficiency of the particles. Up to now,
[176]. Briefly, the C16H36O4Ti solution was added to a LiOH solution various Li4Ti5O12 nano/microspheres have been synthesized and
under stirring at 80 8C, and the as-obtained precursor was calcined investigated as shown in Fig. 31. The Li4Ti5O12 nano/microspheres,
at 400 8C to form a mesoporous structure. Although Li2CO3 especially with hierarchical porous structures, have received
impurities remained in the sample, the nanoclusters delivered a considerable attention for their high rate performance and high
high capacity of 162 mA h g1 after 60 cycles at 0.5 C. volumetric energy density.
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 23

Fig. 31. Schematic illustration of various reported Li4Ti5O12 nano/microspheres and corresponding microscope images: dense sphere [191], porous sphere [191], hollow
sphere [204], yolk–shell sphere [183], hollow–yolk–shell sphere [379], flower-like sphere [203], hollow flower-like sphere [207].

Spray drying is a facile and universal method for mass introduction of pores into the microspheres prepared via the
producing micrometer-sized spherical particles for use in a wide spray drying method improved the electrode performance [80];
range of products from medicines to ceramics. Nakahara et al. may they prepared two types of Li4Ti5O12 spherical particles via spray
have been the first to apply spray drying to the preparation of drying—one porous and the other dense. At a discharge rate of 20 C,
microsized spherical Li4Ti5O12 particles [178]. They obtained the electrode with porous spherical particles reached a capacity of
spherical Li4Ti5O12 with an average particle size of 8.5 mm, by 73 mA h g1, four times that of the electrode with dense spherical
spray drying a mixture of anatase TiO2 dispersed in a LiOHH2O particles (17 mA h g1).
solution at 110 8C followed by calcination at 875 8C for 6 h in air. Wen et al. applied a similar spray drying method for the
The as-obtained spherical particles exhibited a tap density of preparation of spherical Li4Ti5O12 using Li2CO3 and rutile TiO2 as
approximately 0.7 g mL1 and a specific surface area of precursors and polyvinyl butyral (PVB) as a pore former [45]. The
3.0 m2 g1. Although the capacity stability appears adequate, the experimental results showed that porous and spherical morphol-
rate performance is not. The authors demonstrated that breaking ogies of the spray-dried powders were created and maintained
down the spherical particles to fine powders with sizes of during the subsequent heat treatment. The Li4Ti5O12 spheres
approximately 0.7 mm by milling improved the capacity at higher ranged in size from several microns to 20 mm and exhibited
discharge rates, suggesting that the microspheres likely had increased porosity compared with those prepared by Nakahara
insufficient current collection due to the large sizes and low et al. [178], likely due to the use of the PVB pore former. The first
surface areas of the spherical particles, which resulted in a large discharge capacity reached 153 mA h g1 between 2.5 and 1.0 V at
polarization resistance at high discharge rates. Han et al. prepared an unknown discharge rate. However, the authors provided no rate
Li4Ti5O12 microspheres by initial high-energy ball-milling of performance information. The relatively poor performance of the
Li2CO3 and anatase TiO2 and subsequent spray drying [179]. After Li4Ti5O12 microspheres may be due to their large size (several to
calcination, the microspheres exhibited porous structures and 20 mm) and lack of surface coating. Moreover, the influence of
enhanced lithium storage properties with a specific capacity of calcining temperature (650–800 8C) and Li/Ti atomic ratios (0.784,
139 mA h g1 at 10 C. Hsiao et al. demonstrated that the 0.800, 0.816 and 0.832) on the characteristic and performance of
24 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 32. SEM images of the Li4Ti5O12 powders prepared from spray solutions with different concentrations of citric acid (CA) and ethylene glycol (EG) [182].

Li4Ti5O12 by spray drying were studied by Wu et al. [180] and He to be dense. Because of their unique structure and higher contact
et al. [181], respectively. The results from Wu et al. [180] area with the electrolyte, the yolk-shell-structured Li4Ti5O12
demonstrated that there was no impurity phase for any of the microspheres after post-treatment at 800 8C exhibited enhanced
samples calcined at 650–800 8C, and the samples calcined at lower electrochemical performance with a discharge capacity of
temperatures of 650 and 700 8C maintained their spherical shapes 172 mA h g1 even after 100 cycles compared with that of dense
and exhibited better rate capabilities because of the higher surface microspheres.
areas and lower crystallite sizes. Another Li/Ti atomic ratio study Li4Ti5O12 is known to have poor electronic conductivity; thus, it
indicated that after calcining at 700 8C for 16 h, the as-prepared induces a large polarization resistance, especially at rapid discharge
pure-phase Li4Ti5O12 with a Li/Ti ratio of 0.816 exhibited the best rates. The microspheres prepared by spray drying or pyrolysis did
performance, indicating that the Li/Ti ratio is important and that not have sufficient surface conductivity. Therefore, modification of
the volatilization of lithium at high temperature should be their surfaces with conductive agents such as porous carbon to
considered during the synthesis process. increase the current collection efficiency of the microspherical
Spray pyrolysis allows the simultaneous formation of spherical Li4Ti5O12 is necessary. Improved electrochemical performance
particles and the phase structure by spraying a mixed solution especially for rate performance was observed by introducing carbon
containing the reactants into a high-temperature furnace to allow into the Li4Ti5O12 prepared via spray drying [184–187]. Zhao et al.
the rapid formation of the desired product via fast pyrolysis. The [184] and Zhu et al. [185] prepared N-doped carbon coated porous
large amount of gas produced may also allow the formation of Li4Ti5O12 spheres and carbon-coated nanosized Li4Ti5O12 nanopor-
hierarchical pores within the spherical products. Ju et al. ous microspheres, respectively, by applying the spray drying
synthesized Li4Ti5O12 microspheres via spray pyrolysis using method. Zhao et al. first prepared Li4Ti5O12 microspheres using
lithium nitrate and TTIP as reactants with dimethyl acetamide the same method as Wen et al. [45] and mixed the sample with an
(DMA) as a drying control chemical additive, and CA and EG ionic liquid of 1-ethyl-3-methylimidazolium dicyanamide (EMIm-
for morphology control [182]. As shown in Fig. 32, the as-prepared dca) followed by further heat treatment at 600 8C in Ar. The obtained
Li4Ti5O12 exhibited good spherical shape with particle Li4Ti5O12 spheres had sizes of 3–5 mm and surfaces covered with a
diameter of 0.3–2.5 mm. At a current density of 0.17 mA g1, homogenous layer of N-doped carbon with a content of approxi-
the Li4Ti5O12 spheres had an initial capacity of approximately mately 7.0 wt.%. At a low discharge rate of 0.5 C, the discharge
167 mA h g1. Recently, Li4Ti5O12 microspheres with yolk–shell capacities of the carbon-coated and pristine Li4Ti5O12 reached
structures were directly prepared by large-scale ultrasonic spray 161 and 169 mA h g1, respectively. However, the carbon coating
pyrolysis using LiNO3 and TTIP as raw materials with the addition significantly increased the rate performance; the coated sample
of sucrose (Fig. 33) [183]. As observed in Fig. 33, the as-prepared exhibited capacities of 145 and 129 mA h g1 at 5 and 10 C,
Li4Ti5O12 microspheres appeared to exhibit a unique yolk-shell respectively, while the corresponding capacities for the pristine
structure with outside diameters ranging from several hundreds samples were only 60 and 15 mA h g1. Zhu et al. applied
to approximately 2 mm. However, the microspheres prepared commercial anatase TiO2—pre-coated with a thin layer of carbon
under a similar process without the addition of sucrose appeared using sugar as precursor and fired at 600 8C—and Li2CO3 as raw
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 25

Fig. 33. (a) Schematic diagram of the large-scale ultrasonic spray pyrolysis process for preparation of Li4Ti5O12 yolk-shell powders, (b) SEM image, (c) TEM image, (d) high-
resolution TEM image, and (e) corresponding EDX elemental distribution of the Li4Ti5O12 yolk-shell powders post-treated at 800 8C [183].

materials. The spherical precursors were prepared by spray drying, 160 mA h g1 at 0.2 C, and 126.4 mA h g1 at 20 C and excellent
and the spherical Li4Ti5O12/C composite was finally prepared cycling stability with a capacity retention of 95% after 1000 cycles at
following calcination at 800 8C under a nitrogen flow [185]. The a rate of 1 C. Thus, the spray drying method is promising. The results
spherical particles had diameters of 10–20 mm, which were emphasize the importance of carbon coating for the preparation of
constructed from nanoparticles of approximately 200 nm. The high-performing Li4Ti5O12 microspheres for use as anodes in LIBs.
nanoparticles packed to form nanopores with sizes between 10 and Jung et al. prepared carbon-coated Li4Ti5O12 powders by first
20 nm and were distributed homogeneously from the surface to the synthesizing carbon-free, spherical Li4Ti5O12 via a spray-drying
bulk of particles. Due to the carbon coating, the apparent electrical process followed by calcination at 900 8C in air for 20 h and
conductivity of the sample increased substantially to 10 S cm1. The subsequent coating with pitch in combination with calcination at
as-synthesized electrodes exhibited a reversible capacity of 750 8C for 5 h in argon [186], similar to the method applied by Zhu
et al. [185]. The carbon coating significantly increased the electronic
conductivity of the Li4Ti5O12. The as-prepared spherical Li4Ti5O12–
3.25-wt.% carbon composite had a carbon layer with thickness of
approximately 3 nm uniformly coating the primary particles. The
composite exhibited an electronic conductivity of
5.24  103 S cm1, while the pristine Li4Ti5O12 had a conductivity
of only 1.58  109 S cm1. As shown in Fig. 34, the as-prepared
Li4Ti5O12/C composite exhibited a capacity of 170.2 mA h g1 at 1 C
and 81.7 mA h g1 at 100 C. For comparison, the pristine, spherical
Li4Ti5O12 exhibited a poor rate capability, the capacity decreased
quickly to 30 mA h g1 at 100 C. The Li4Ti5O12/C composite also
showed good cycling stability; a capacity of 166 mA h g1 was
maintained after 100 cycles at 1 C.
The organic carbon source was found to have significant effect
on the microstructure and consequently the electrochemical
Fig. 34. Rate capability of carbon-free and carbon-coated (1.14 and 3.25 wt%) properties of the prepared Li4Ti5O12/C spherical particles. Lactic
Li4Ti5O12 electrodes at rates ranging from 1 C (175 mA g1) to 100 C (17.5 A g1). acid was found to be superior to CA and malic acid as a carbon
The charging rate was 1 C [186]. source for improving the electrode performance of Li4Ti5O12/C
26 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

prepared by spray pyrolysis [188]. The proper selection of a carbon Li4Ti5O12, which had a diameter of 2–3 mm, demonstrated stable
source is critical to achieving high performance in the electrodes capacities of 140 mA h g1 at 0.5 C, and 80 mA h g1 at a rate as
prepared by the spray-drying/pyrolysis method. high as 30 C, which was much better compared to that of dense
Hydrothermal/solvothermal methods have been extensively Li4Ti5O12 microspheres. Lin et al. further synthesized monodis-
applied to the synthesis of micrometer-sized spherical/spheroidic persed mesoporous Li4Ti5O12 microspheres by a solvothermal
particles with different microstructures and have recently been process with as-prepared amorphous monodispersed TiO2 spheres
adopted for the preparation of spherical Li4Ti5O12 or Li4Ti5O12/C as the precursor, which reacted with LiAc in an ethanol solvent
composites [189–196]. Tang et al. successfully synthesized [197]. The Li4Ti5O12 microspheres delivered capacities of 147,
nanoporous Li4Ti5O12 spheres with diameters of 200–400 nm 107 and 93 mA h g1 at 1, 3 and 5 C, respectively. Shen et al.
[189], which were constructed from nanoparticles with sizes of applied a template-free hydrothermal method using commercial
approximately 20 nm to form 5–10 nm pores using a template-free crystalline anatase titania powder and LiOH as reactants,
hydrothermal process in an ethanol–water mixture followed by hydrothermally treated at 180 8C for the appropriate time to
heat treatment. In their synthesis, the mono-dispersed, amorphous obtain well-formed hierarchically porous microspheres with
spherical TiO2 colloids were first prepared by controlled hydrolysis diameters of approximately 4 mm [198]. A specific discharge
of TTIP in ethanol. Then, the hydrous titanium oxide was mixed capacity of 165.8 mA h g1 was achieved at a rate of 0.5 C and was
with LiOH ethanol–water mixtures and hydrothermally treated at maintained at 92.3 mA h g1 at a rate of 20 C.
180 8C for 12 h followed by calcination at 500 8C for 1 h. The as- Because Li4Ti5O12 has poor electronic conductivity, to further
fabricated mesoporous spheres had a tap density of 0.81 g cm3, increase the rate performance, Shen et al. prepared meso-structured
and the electrode exhibited a specific discharge capacity of micro-sized Li4Ti5O12-C spheres with a high surface area through the
approximately 150 mA h g1 after performing 10 charge/discharge solvothermal treatment of TBOT and LiAc in the presence of furfural
cycles at a rate of 1 C. Even at a rate of 30 C, the specific capacity in allowing the formation and co-assembly of carbon and Li4Ti5O12
the 10th cycle reached 114 mA h g1, nearly 76% of the capacity at crystallites into an interpenetrating Li4Ti5O12-C nano-architecture
1 C. The electrode retained a discharge capacity of 137 mA h g1 [199]. The evenly distributed carbon (5 wt.%) in the microspheres
after 200 cycles, and the total capacity fade was only 5.5% during enhanced the electronic conductivity and prevented particle
the 10–200 cycles. After 200 cycles at a rate of 20 C, the electrode coalescence. The as-fabricated 0.2–1 mm spheres were composed
exhibited a discharge capacity of 125.3 mA h g1 with almost no of large quantities of small crystallites with particle sizes of
capacity fade from the second cycle. Recently, Lin et al. also approximately 11 nm. The Brunauer–Emmett–Teller (BET) specific
synthesized Li4Ti5O12 submicrospheres with a high tap density via surface area reached 159.4 m2 g1. The pores showed a narrow pore-
a solvothermal method under water-ethanol solvents using sol– size distribution with an average pore diameter of 4.3 nm. The
gel-prepared TiO2 submicrospheres and LiOH as raw materials resulting spherical Li4Ti5O12/C composite had a capacity of
[190]. Various ratios of water to ethanol in the solvents (0– 165.3 mA h g1 at a rate of 0.2 C, based on the mass of the
90 vol.%) and calcination temperatures (500–700 8C) were studied. Li4Ti5O12/C composite. Even at a rate of 50 C, a capacity of
The sample prepared using a water-ethanol ratio of 60 vol.% and a 97.1 mA h g1 was still achieved, higher than that of the electrode
calcination temperature of 600 8C exhibited a specific surface area without a carbon coating. The electrode also exhibited good cycling
of 15.5 m2 g1 and a high tap density of 1.62 g cm3. Additionally, stability with a capacity loss of only 2.6% at 1 C and 2.5% at 50 C after
outstanding electrochemical performances with a high charge 100 cycles. Jung et al. developed a facile method for the fabrication of
capacity of 109 mA h g1 at 10 C and a capacity retention of 97.8% spherical carbon-coated Li4Ti5O12 based on a hydrothermal process
over 100 cycles were achieved by this sample. Lin et al. synthesized [200]. As shown in Fig. 36, first, a highly mesoporous anatase phase
porous Li4Ti5O12 microspheres via hydrothermal synthesis in TiO2 was prepared via a hydrothermal method using a high-purity
combination with a high temperature calcination by combining mixture of TiCl4, urea, and ammonia sulfate in a distilled water–
TTIP and a LiAc solution with acidized carbon black as pore former ethanol mixture that was heated at 120 8C for 24 h in a teflon-lined
[191]. As shown in Fig. 35, the as-prepared porous spherical autoclave. Then, the precipitate was further calcined at 400 8C for 5 h

Fig. 35. (a, b) SEM images of (a) mesoporous and (b) non-porous Li4Ti5O12 spheres, (c) the ratio of capacity between several current rates and 0.5 C of mesoporous and non-
porous Li4Ti5O12 spheres [191].
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 27

property. Li et al. prepared a N-doped carbon-coated Li4Ti5O12


microspheres using polydopamine as the carbon source via chemical
lithiation of N-doped carbon-coated TiO2 microspheres under a
hydrothermal process [201]. The as-synthesized N-doped carbon-
coated Li4Ti5O12 microspheres delivered a specific capacity of
123 mA h g1 at 30 C and a good capacity retention with a capacity
of 136.5 mA h g1 after 200 cycles at 10 C.
As a versatile method, the hydrothermal/solvothermal method
can be further used to synthesize other unique Li4Ti5O12 micro-
spheres with special microstructures beyond the above micro-
spheres composed of Li4Ti5O12 nanoparticles. Tang et al.
synthesized a flower-like spherical Li4Ti5O12 composed of
nanosheets using a hydrothermal method with LiOH and TTIP
and ammonia as reactants in the presence of EG at 170 8C for 36 h
with subsequent calcination at 500 8C for 2 h [202]. The electrode
showed capacities of 167, 163 and 152 mA h g1 at rates of 0.2,
1 and 8 C, respectively, even after 100 charge/discharge cycles. By
adding H2O2 during the hydrothermal treatment, Chen et al.
demonstrated that the morphology of the Li4Ti5O12 changed
slightly [203]. Li4Ti5O12 spheres with a diameter of 0.4–0.6 mm
assembled from smooth-surfaced, sawtooth-like nanosheets were
obtained after hydrothermal treatment at 130 8C for 12 h by
applying TTIP and LiOH as reactants in the presence of H2O2 with a
subsequent thermal treatment at 550 8C for 6 h in air. The spheres
contained pores primarily with sizes of 2.5 and 8 nm and a specific
surface area of 139.4 m2 g1. Specific capacities of 177, 169, 161,
150 and 143 mA h g1 at discharge current densities of 200 mA g1
(1.1 C), 1000 mA g1 (5.5 C), 2500 mA g1 (14 C), 5000 mA g1
(28.5 C) and 1000 mA g1 (57 C), respectively, were demonstrated.
Yu et al. successfully prepared mesoporous Li4Ti5O12 hollow
spheres using silica nanospheres as templates [204]. As shown in
Fig. 37, TiO2 was first coated on the surface of silica nanospheres,
and the composite was treated with a LiOH solution to complete
the chemical lithiation. After further calcination, mesoporous
Li4Ti5O12 hollow spheres were obtained, which exhibited a BET
specific surface area of approximately 220 m2 g1 and excellent
electrochemical performance with a capacity of 104 mA h g1 even
at 20 C. Moreover, the addition of various amounts of TBOT could
easily be used to control the shell thickness, as shown in Fig. 37 b-d.
Cheng et al. prepared hierarchical hollow Li4Ti5O12 urchin-like
Fig. 36. (a) Schematic illustration of synthetic process of microscale, spherical,
microspheres using silica nanospheres as templates using a
carbon-coated Li4Ti5O12 and photographs of material formed during synthesis, (b)
rate capability of 5.2 wt% C-coated Li4Ti5O12 and (b) cyclability of 5.2 wt% C-coated synthesis route (Fig. 38) [205] similar to that reported by Yu
Li4Ti5O12 from 1 C-rate (0.17 A g1) to 10 C-rate (1.7 A g1) in comparison with C- et al. [204]. The differences in microstructures seem to be due
free Li4Ti5O12 cycled at 1 C-rate (0.15 A g1). Charged at 1 C-rate [200]. mainly to the difference in concentration of the aqueous LiOH
solution (0.4 M vs. 0.5 mM). By controlling the reaction time, Zhao
et al. developed advanced yolk-shell Li4Ti5O12 microspheres with
in air. The as-obtained mesoporous TiO2 was mixed with a hierarchical macro-mesopores by the hydrothermal treatment of
stoichiometric amount of Li2CO3 and varying quantities of pitch TTIP, LiOH and CTAB in EG and distilled water environment at
as a carbon source, then calcined at 900 8C for 20 h under a flowing Ar 170 8C for 48 h followed by calcination at 500 8C for 2 h, and these
atmosphere. The pitch is critical to preserving the spherical researchers observed that the structure formed during the Ostwald
morphology of TiO2 into the Li4Ti5O12. The spherical Li4Ti5O12 ripening process during the hydrothermal treatment [206]. Based
particles had diameters of 1–2 mm, which were composed of the on the unique structure, an outstanding high-rate performance
primary particles with sizes of 10–20 nm. The external surfaces of with a discharge capacity of 117.9 mA h g1 at 10 C (1700 mA g1)
the particles were uniformly encapsulated in an approximately 50- was achieved.
nm-thick layer of carbon to yield a carbon content of 5.25 wt.%. The The introduction of conductive carbon into such advanced
carbon layer provided an electrically conducting network improving Li4Ti5O12 microspheres with unique microstructures was also
the electrical conductivity to 1.21  102 S cm1, more than five studied to further improve their electrochemical performance.
orders of magnitude higher than the carbon-free Li4Ti5O12 prepared Zhang et al. successfully synthesized hierarchical hollow Li4Ti5O12
via a similar process. Furthermore, the calcination of the pitch in the microspheres composed of N-doped carbon-coated nanosheets
Ar atmosphere led to the creation of Ti3+ in the oxide bulk. Both using a hydrothermal method with amorphous TiO2 microspheres
results significantly improved the electrode performance. The and LiOHH2O as raw materials (Fig. 39) [207]. The use of
5.2 wt.% carbon-containing spherical Li4Ti5O12 delivered discharge hexadecylamine in the preparation of TiO2 microspheres intro-
capacities of 165, 160 and 123 mA h g1 at 1, 10 and 100 C discharge duced N-doped carbon into the final Li4Ti5O12 microspheres,
rates (charge rate: 1 C), respectively, without obvious capacity resulting in excellent rate capability with a specific capacity of
fading over testing for 100 cycles (Fig. 36). The material also 140.8 mA h g1 at 20 C. A one-pot template-free solvothermal
exhibited high tap density of 1.31 g cm3, another highly attractive method based on the benzyl alcohol route was studied by Yu et al.
28 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 37. (a) Schematic illustration of the formation of mesoporous Li4Ti5O12 hollow spheres through a templating approach: (I) uniform coating of an a-TiO2 shell on the silica
sphere through a sol-gel process; (II) chemical lithiation in a LiOH solution under hydrothermal environment and subsequent annealing treatment to convert the core-shell
sphere into the mesoporous Li4Ti5O12 hollow sphere, (b–d) TEM images of as-synthesized Li4Ti5O12 hollow spheres with different shell thicknesses by adding different
amounts of TBOT: (b) 1, (c) 3, and (d) 5 mL [204].

Fig. 38. (a) Schematic illustration of the synthesis procedure for the hierarchical hollow Li4Ti5O12 urchin-like microspheres. (b–d) TEM images of the hollow
(Li1.81,H0.19)Ti2O52H2O urchin-like microspheres with different hydrothermal reaction times: (b) 30 min, (c) 2 h, and (d) 24 h [205].

[208] for the synthesis of micrometer-sized Li4Ti5O12. This method excellent rate capability with discharge capacities of 169, 152, 130,
primarily involves the solvothermal treatment of lithium and 116, 93, and 76 mA h g1 at 0.2, 1, 2, 5, 30 and 60 C, respectively.
titanium alkoxide in benzyl alcohol. The as-synthesized material Even though the above advanced Li4Ti5O12 microspheres
consists of 1–2-mm-sized spherical particles made of 10-nm exhibit unique morphology and further improved electrochemical
crystalline nanoplatelets containing 2.5 wt.% carbon. The nano- performance compared with that composed of nanoparticles, the
crystals are crystallographically oriented randomly with respect to large space inside the microspheres results in a low tap density and
each other. The coulombic efficiency of the calcined sample low volumetric energy density. For the synthesis of Li4Ti5O12
reached 94.8% for the first cycle, and the reversible capacity at a microspheres as an anode for LIBs, the authors suggest that we
rate of 20 C still achieved approximately 100 mA h g1, corre- should simultaneously focus on the electrochemical performance
sponding to 85% of the total capacity at 1 C. After calcination, the and tap density by optimizing the microstructure and coating
sample still exhibited good rate performance, although its specific carbon instead of developing a unique morphology with low tap
surface area was reduced to only 8 m2 g1. Recently, Li4Ti5O12/C density.
hollow microspheres were successfully by prepared using In addition to the methods described above, other techniques
solvothermally synthesized TiO2/polyfurfural hollow micro- have also been exploited for the synthesis of spherical Li4Ti5O12 or
spheres as raw materials [209]. LiOHH2O was applied as the Li Li4Ti5O12/C composite, including the emulsion gel process [210]
source and mixed with the Ti source in a Li/Ti molar ratio of 4.5:5 in and supercritical alcohol route [211,212]. Gao et al. reported an
methanol. After calcination at 800 8C for 10 h under Ar atmosphere, ‘‘inner gel’’ method for the preparation of spherical Li4Ti5O12 or
Li4Ti5O12/C hollow microspheres were obtained, which exhibited Li4Ti5O12/C composite for use as an anode in LIBs [213,214]. In their
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 29

Fig. 39. (a, b) SEM, (c) TEM, and (d, e) HRTEM images of hierarchical hollow Li4Ti5O12 microspheres composed of N-doped carbon coated nanosheets, (d) and (e) are from the
top view and side view of one single nanosheet, respectively [207].

processes, TiCl4 was dissolved in de-ionized water to first form a respectively. Although no-structure-directing chemicals or tem-
solution, which was mixed with (CH2)6N4 and carbamide CO(NH2)2 plates were applied in the synthesis process, a high-pressure
by stirring at less than 10 8C. The mixture was dripped into coal oil reactor at 400 8C was needed to achieve a supercritical condition,
under stirring; then the mixed slurry was heated at 70 8C for limiting its large-scale application.
10 min to obtain the spherical gel precursor, which was mixed Besides the classical sphere structure, other deuterogenic
uniformly with Li2CO3 and sintered at 800 8C for 16 h to form microstructures were also studied. Recently, donut-shaped
spherical Li4Ti5O12 particles with diameters of 5–10 mm. Spherical Li4Ti5O12 structures prepared by combining sol–gel and electro-
particles of a Li4Ti5O12/C composite were also prepared when spinning techniques were reported (Fig. 40a and b) [215]. The
carbon black was introduced into the TiCl4 solution during the unique structures were composed of well-sintered and highly
preparation of the spherical gel precursor. The resulting spheres interconnected nanograins that offer shorter Li+ diffusion lengths,
have tap densities as high as 1.64 and 1.73 g cm3 for the Li4Ti5O12 and its mesoporous structure was beneficial to electrolyte
and Li4Ti5O12/C composite, respectively, which are among the transport (Fig. 40c). The donut-shaped Li4Ti5O12 electrode deliv-
highest reported in the literature for such electrodes. The Li4Ti5O12 ered specific capacities of 159, 144, 131, 120, and 100 mA h g1 at
spheres are relatively dense with few pores, while the spheres 0.1, 1, 3, 5 and 10 C rates, respectively.
created with the carbon black have more pores and smaller particle
sizes. The electrode without the carbon had a discharge capacity of 3.2.3. Thin-film electrodes
161 mA h g1 at a current density of 0.08 mA cm2 that quickly Thin-film batteries have been found many potential applica-
decreased to 121.5 mA h g1 at a current density of tions in microelectronic mechanical systems, smart cards, on-chip
0.32 mA cm2. The Li4Ti5O12/C electrode exhibited discharge power sources and portable electronic devices. Recently, thin-film
capacities of 158.2, 150.6 and 132.4 mA h g1 at current densities electrode has been a popular subject in the literatures. A thin-film
of 0.08, 0.32, and 3.2 mA cm2, respectively, and the carbon electrode can effectively reduce the electrode polarization by
coating improved the rate performance of the electrode. Recently, reducing the lithium diffusion distance in the electrode. Brousse
Nugroho et al. successfully prepared mesoporous Li4Ti5O12 et al. successfully prepared a 2-V thin-film cell with a thin-film
microspheres using a facile supercritical methanol route [211]. Pre- Li4Ti5O12 anode, a thin-film LiCoO2 cathode and a thick solid
cursor microspheres were formed during the supercritical alcohol Li0.33La0.56TiO3 electrolyte [216] in which both the Li4Ti5O12 anode
reaction in a high-pressure reactor in a molten salt bath at 400 8C and LiCoO2 cathode were prepared via spray pyrolysis. By applying
and were transformed into the Li4Ti5O12 phase after calcination at an electrostatic spray deposition technique and using LiAc and
500–700 8C under air. The sample obtained at 600 8C displayed the titanium butoxide as the starting materials, Yu et al. successfully
best rate performance with capacities of 155.6, 108.5 and prepared a thin-film Li4Ti5O12 electrode without the application of
79.7 mA h g1 at 4, 10 and 20 C, respectively. Nugroho et al. an electrically conducting additive. An initial capacity of approxi-
further prepared mesoporous Li4Ti5O12/C microspheres using the mately 175 mA h g1 was achieved at a C/18 rate, and the capacity
same supercritical alcohol (methanol, ethanol and isopropanol) still reached approximately 155 mA h g1 after 70 cycles [208]. By
route followed by calcination under 5%H2/Ar [212]. The sample using a pulsed laser deposition technique, Deng et al. prepared a
obtained using methanol exhibited a smaller crystallite size, larger thin-film Li4Ti5O12 electrode on Pt/Ti/SiO2/Si substrates. A high
surface area, and higher carbon and Ti3+ contents and the optimal capacity of 146 mA h g1 was achieved at a discharge rate of
electrochemical performance with stable discharge capacities of approximately 3.45 C [217]. Nano-sized epitaxial Li4Ti5O12 (1 1 0)
173.2, 159.1, 116.9 and 93.5 mA h g1 at 0.1, 1, 10 and 20 C, films were also prepared using a pulsed laser deposition technique
30 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 40. (a, b) FE-SEM images of Li4Ti5O12 sub-micrometer donuts after calcination. (c) Schematic to compare the lithium ion diffusion kinetics in Li4Ti5O12 submicrometer
particles and donut shapes with nanograins [215].

[218]. The initial discharge capacity was as high as 217 mA h g1; painted on any arbitrary surface. However, a liquid electrolyte was
however, the capacity decreased in subsequent cycles. Recently, still required, which limited its wide application. Additionally, this
epitaxial growth of a Li4Ti5O12 thin film was realized using a pulsed Li4Ti5O12 film electrode suffers from the disadvantages of the use of
laser deposition technique with SrTiO3 single-crystal substrates, additives, as in the conventional electrode.
i.e., Li4Ti5O12 (1 1 1) on SrTiO3 (1 1 1), Li4Ti5O12 (1 1 0) on SrTiO3 In the conventional slurry-coating Li4Ti5O12 electrode, additives
(1 1 0) and Li4Ti5O12 (1 0 0) on SrTiO3 (1 0 0) [219]. Wunde et al. (a conductive agent and binder) are necessary; the conductive
fabricated Li4Ti5O12 thin films using the ion beam sputtering agent is used to enhance the electron transformation and a binder
method and measured the lithium diffusion coefficient is used for cohering the active materials and conductive agent to
(3.27  1016 m2 s1) [220]. A Li4Ti5O12 thin film was also the current collector. However, these additives are usually
successfully prepared using a PVP sol–gel coating method electrochemically inactive, which reduces the volumetric/gravi-
[221]. At a rate of 1 C, a capacity of approximately 140 mA h g1 metric energy density of the electrode; furthermore, the binder
was achieved after 300 cycles at the 1 C rate. A thin-film Li4Ti5O12 usually cannot store/transport lithium ions or electrons, resulting
electrode was also successfully deposited on an Au/Ti/SiO2/Si in a negative effect on the electrochemical performance. Although
substrate by applying a magnetron sputtering technique [222]. Zhao several works on the modification of the binder for Li4Ti5O12
et al. applied a versatile ink-jet printing technique for the anodes have been performed, such as introducing conductive
preparation of thin-film Li4Ti5O12 electrodes on Au substrates; the graphene into the conventional PVDF binder [228] and using an
film had a porous microstructure with a thickness of 1.7–1.8 mm alternative binder (sodium-carboxymethyl cellulose (CMC) [229],
[223]. Under optimized fabrication conditions, the as-obtained thin- polyacrylonitrile (PAN) [230], water soluble Acryl S020 [231],
film electrode exhibited a capacity of 153 mA h g1 even after lithium-ion-conductive PEG-based copolymer [232], polymeric
300 cycles at a current density of 10.4 uA cm2. Homogeneous, ionic liquid nanoparticles [233], etc.). However, these binders will
crack-free Li4Ti5O12 thin films were also prepared by spin coating still reduce the volumetric/gravimetric energy density of the
using a rapid thermal annealing process [224]. Compared with Li4Ti5O12 electrode. Recently, binder-free thin films have received
conventional furnace annealing, the rapid thermal annealing increasing attention as electrodes for LIBs [73,145,234,235]. Sever-
resulted in a smaller Li4Ti5O12 grain size, higher capacity al strategies have also been applied to develop binder-free
(59.5 mAh cm2 mm1 compared with 55.9 mAh cm2 mm1) and Li4Ti5O12 film electrodes.
more stable cycling performance. A binder-free multi-layer electrode with porous Li4Ti5O12
The Li4Ti5O12 thin-film electrodes prepared via the above sphere layer sandwiched between carbon nanotube and graphene
techniques are more suitable for basic scientific research than network layers was designed and prepared by Choi et al. [236] via a
practical applications because these techniques usually require multi-step spraying process as shown Fig. 42a, including air-spray
expensive equipment or complicated processes as well as special coating of graphene layer on current collector and the following
inactive substrates and the mass loading of Li4Ti5O12 is relatively electrostatic spray (E-spray) coating of ball-milled Li4Ti5O12
low. Beyond these conventional techniques for the preparation of nanoparticles, and subsequent air-spray coating of CNTs layer.
Li4Ti5O12 thin-film electrodes, novel techniques have recently been During the E-spray coating, the ball-milled Li4Ti5O12 aggregate
developed. together to be porous spheres. The typical morphology of resultant
Printing and painting have been successfully used to fabricate hybrid was shown in Fig. 42b. The binder-free multi-layer
Li4Ti5O12 thin-film electrodes, such as 3D patterned Li4Ti5O12 electrode exhibited an outstanding rate capability with a specific
electrodes [225] and Li4Ti5O12-entrapped cross-linked carbon capacity of 109.3 mA h g1 at 100 C rate, much better than that of
nanotube (CNT) film network film electrodes [226]. For example, the pristine and bead-milled Li4Ti5O12 powder electrode prepared
a paintable battery was developed as shown in Fig. 41, in which a via a conventional slurry-coating technique (Fig. 42c). The
porous Li4Ti5O12 film electrode could be easily obtained using a electrochemical performance was attractive, but the electrode
slurry including commercial Li4Ti5O12 powders, conductive agent fabraction process was really complicated. Future work could focus
and binder [227]. This work highlighted that the battery could be on the development of a simplified one-step spraying process of
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 31

exhibited an outstanding cycling stability with specific capacities


of 153 and 115 mA h g1 at 2 C and 20 C rate, respectively, even
after 5000 cycles. Other than the nanowire array structure, a
nanotube array is believed to be more beneficial to Li+/electron
diffusion. Cha et al. prepared an anodized TiO2 nanotube array;
however, the nanotube structure was not maintained after
calcination with Li2CO3 because of the solid-state reaction at such
a high temperature of 800 8C [238]. A relatively dense Li4Ti5O12
film was obtained instead of Li4Ti5O12 nanotube arrays after such
lithiation, resulting in unattractive electrochemical performance.
Recently, Liu et al. successfully prepared Li4Ti5O12 nanotube arrays
by chemical lithiation of template-synthesized TiO2 nanotube
arrays in a 3 M LiOH solution with subsequent calcination at the
low temperature of 550 8C (Fig. 44b) [239]. After carbon coating,
the as-prepared Li4Ti5O12-C nanotube arrays delivered outstand-
ing rate capability with specific capacities of 165, 154, 135, 106 and
81 mA h g1 at 1, 10, 30, 60 and 100 C, respectively, and stable
cycling performance at 10 C for 500 cycles.
In addition, Li4Ti5O12 nanosheet array was also successfully
synthesized by Chen et al. through a hydrothermal treatment of Ti
foil in LiOH solution and a subsequent calcination [240]. The
typical SEM and TEM images of the nanosheet array were shown in
Fig. 44c1 and c2, respectively, with vertically aligned rectangular
nanosheets of 14 nm in thickness. Even though an outstanding
rate capability with a specific capacity of 78 mA h g1 at 200 C rate
was reported for the Li4Ti5O12 nanosheet array (Fig. 44c3), the
mass loading of Li4Ti5O12 was too low. Gao et al. reported a porous
Li4Ti5O12–TiO2 nanosheet array by a hydrothermal synthesis [242],
even though the electrochemical performance was not as
attractive as the results reported by Chen et al. [240], the mass
loading of the active materials was increased to
0.3 mg cm2. However, this value was still too low for commer-
cial application. While such a large open space among nanowires/
nanotubes/nanosheets is definitely beneficial to the electrochemi-
cal performance, it inevitably results in low volumetric energy
density of the electrode (Fig. 43).
Direct growth of Li4Ti5O12 on a 3D conductive substrate (3D
Fig. 41. (a) Schematic illustration of direct fabrication of Li-ion battery on the
surface of interest by sequentially spraying component paints stencil masks
current collector) is also an effective approach for the preparation
tailored to desired geometry and surface, (b) cross-sectional SEM micrograph of a of a high-performance binder-free thin film Li4Ti5O12 electrode,
spray painted full cell showing its multilayered structure, with interfaces between which could result in maximum utilization of the active material.
successive layers indicated by dashed lines for clarity [227]. Shen et al. used a commercial carbon fiber cloth as a substrate and
grew TiO2 nanosheets on it via a solvothermal method with
subsequent chemical lithiation and calcination to form Li4Ti5O12
Li4Ti5O12, graphene sheet, and CNTs mixture ink, as well as further nanocrystals [243]. The as-prepared thin-film electrode with such
improvement of Li4Ti5O12 mass loading. a 3D structure delivered excellent rate performance with specific
Binder-free Li4Ti5O12 nanowire/nanotube/nanosheet arrays on capacities of 177, 152, 134, 119 and 103 mA h g1 at 1, 10, 30,
metal substrates have been successfully developed, as schemati- 60 and 90 C, respectively. Such an excellent rate capability as well
cally summarized in Fig. 43 [237–240], where the nanostructure is as its stable cycling performance at 10 C for 200 cycles are very
beneficial to Li+/electron diffusion, and the large open space among attractive; however, the large diameter of the carbon fiber
the nanowires/nanotubes ensures a good contact between the (10 mm) resulted in low mass loading of Li4Ti5O12 nanocrystals
electrolyte and electrode for fast lithium storage. Because it would and a low gravimetric energy density. Furthermore, the large space
be difficult to directly obtain Li4Ti5O12 nanowire/nanotube arrays, between the fibers leads to a low volumetric energy density. Li
the Ti-based (e.g., H2Ti2O5H2O or TiO2) nanowire/nanotube arrays et al. reported a thin, flexible, lightweight and high-performance
were usually first synthesized via hydrothermal treatment [237] or LIB with graphene foam as the current collector [244]. Typically,
the template method [239], and then, a chemical lithiation was graphene foam was first synthesized by vapor deposition and was
performed to transform the TiO2 phase into the spinel Li4Ti5O12 then hydrothermally treated in LiOH and Ti(OC3H7)4 solution. After
phase. To further increase the electrochemical performance of calcination, the Li4Ti5O12 nanosheets formed homogeneously on
these arrays, strategies for enhancing the electronic conductivity the surface of graphene foam as shown in Fig. 45. The as-prepared
were applied, for example, calcination under 5% H2/Ar to obtain Li4Ti5O12/graphene exhibited an outstanding capacity of
hydrogenated Li4Ti5O12 nanowire arrays (Fig. 44a) [237], which 135 mA h g1 at high rate as high as 200 C (discharge in 18 s)
demonstrated excellent rate performance with capacities of 173, and stable cycling stability at 30 and 100 C for 500 cycles.
166, 157, 145 and 119 mA h g1 at 0.2, 1, 5, 10, 30 C rate, Importantly, the Li4Ti5O12 content in the film electrode could reach
respectively. Wang et al. used a similar hydrothermal route with 88 wt.%, suggesting that high gravimetric energy density could
modification to prepare a web-like Li4Ti5O12 anode without be achieved. However, achieving a high volumetric energy density
hydrogenation; the as-obtained nanowires had a length of about remains a major challenge because of the presence of pores on the
20 mm [241]. Such a binder-free web-like Li4Ti5O12 electrode scale of hundreds of micrometers in the graphene foam. Li et al.
32 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 42. (a) Schematic illustration of sequential fabrication steps for the multi-stacked graphene sheets/Li4Ti5O12/CNTs electrode consisting of the self-aggregated nanoporous
Li4Ti5O12 interconnected by graphene sheets and CNTs. (b) SEM image of the self-aggregated nanoporous Li4Ti5O12 hybrid electrode interconnected by graphene sheets and
CNTs. (c) discharge (Li-insertion) capacities of graphene sheets/Li4Ti5O12/CNTs (G-LTO-C), the pristine Li4Ti5O12 electrode (P-LTO; 1.3 mg cm2), and the bead-milled
Li4Ti5O12 electrode (BM-LTO; 1.3 mg cm2) during cycling with different current densities [236].

Fig. 43. Schematic illustration of reported binder-free Li4Ti5O12 nanostructure arrays on metal substrates: (a) nanowire arrays, (b) nanotube arrays, and (c) nanosheet arrays.
The advantages and disadvantages of the Li4Ti5O12 nanostructure arrays are also given below the schematics.
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 33

Fig. 44. (a1, a2) Cross-sectional SEM images of hydrogenated Li4Ti5O12 nanowire arrays annealing at 600 8C under 5% H2/Ar; and (a3) schematic illustration of the
electrochemical reaction of hydrogenated Li4Ti5O12 nanowire arrays [237]. (b1) SEM images of Li4Ti5O12-C nanotube arrays on stainless steel foil, showing that the whole
surface of the steel foil is uniformly coated by well-aligned Li4Ti5O12-C nanotubes; (b2) TEM images of some typical Li4Ti5O12-C nanotubes exhibiting their wall thickness of
approximate 20–30 nm; (b3) HRTEM image of a well-crystallized carbon-coated Li4Ti5O12 nanotube showing its lattice planes and the amorphous carbon thin layer; and (b4)
schematic representation of diffusion of Li+ and electrons during discharge/charge processes of the self-supported electrode, which possess a large specific space that
facilitates the fast transfer of Li+, while the electronic conductivity of Li4Ti5O12 nanotubes can be significantly improved by the inner and outer surface-coated carbon layers
[239]. (c1) Cross-sectional SEM images of Li4Ti5O12 nanosheet arrays standing on Ti foil; (c2) TEM image of large Li4Ti5O12 nanosheets scratched from Ti foil; and (c3) Rate
performances of the binder-free anodes made of the self-supported arrays of Li4Ti5O12 nanosheets 14 nm in thickness (LTO-NSA-1) and thicker Li4Ti5O12 nanosheets
80 nm in thickness (LTO-NSA-2), as well as the traditional anode made of the randomly dispersed Li4Ti5O12 nanosheets (LTO-NS) [240].

further developed a flexible binder-free electrode via vacuum- N-doped-carbon-coated Li4Ti5O12 nanosheets used for vacuum
filtration of N-doped-carbon-coated Li4Ti5O12 nanosheets (Fig. 46) filtration appeared to be thin and transparent, as observed in
[245]. This strategy is similar to the recently reported formation of Fig. 46 a, which is similar to graphene sheet. Atomic force
a self-standing graphene film, and the key process should be the microscopy (AFM) analysis revealed that the thickness of
synthesis of appropriately sized nanosheets. The as-synthesized nanosheet was approximately 2.5 nm. With the above unique

Fig. 45. (a) SEM and (b) TEM images of the Li4Ti5O12/graphene foam, (c) discharging voltage curves of the Li4Ti5O12/graphene foam with different charge/discharge rates, and
(d) capacities of the Li4Ti5O12/graphene foam charged/discharged at constant 30 and 100 C rates for 500 cycles [244].
34 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 46. (a) TEM image and (b) representative AFM image of N-doped carbon-coated Li4Ti5O12 nanosheets; (c) corresponding thickness analysis taken along the white line in
(b), which reveals a thickness of about 2.5 nm for the nanosheets; (d) digital photograph of a self-standing N-doped carbon-coated Li4Ti5O12 nanosheet film electrode being
bent, showing its good flexibility; (e) cross-section SEM image and (f) high-magnification image of the film electrode [245].

characteristics, a free-standing film (Fig. 46d–f) could be easily 3.3. Surface coating
obtained by vacuum filtration. Importantly, the flexible film
electrode delivered an outstanding rate performance with a Due to low electronic conductivity of Li4Ti5O12, the transfer of
specific capacity as high as 72% of the theoretical capacity at an electrons from Li4Ti5O12 particles in the electrode to the external
ultrahigh rate of 100 C (corresponding to 36 s charge/discharge), circuit is difficult, leading to high electrode polarization resistance
and the carbon content in this film electrode was only 4 wt.%; during the charge/discharge processes, especially at a high
therefore, the high gravimetric energy density could be further discharge rate. One way to overcome this problem is to modify
improved compared with that of their graphene foam-based the surface of Li4Ti5O12 particles with a thin layer of a conductive
electrode, and the volumetric energy density was also estimated to material that is permeable to lithium. In addition to enhancing the
be much higher because of the reduced void space in this structure conductivity of the electrode material, the surface coatings on the
(Fig. 46e and f) relative to their graphene foam-based electrode Li4Ti5O12 material may affect other properties as well, as
(Fig. 45 a). Besides, assembly of free-standing Li4Ti5O12/CNT film summarized in Fig. 47, such as suppressing the decomposition
via filtration was also explored [246,247], which result in of the electrolyte on the surface of Li4Ti5O12 and influencing the
enhanced electrochemical performance. phase structure in some cases.

Fig. 47. Schematic illustration of the effects of the surface coating on the Li4Ti5O12 materials.
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 35

Cheng et al. prepared carbon-coated Li4Ti5O12 via thermal vapor [258], acetylene gas [249], sucrose [11], glycine [259], glucose
decomposition using toluene vapor as a carbon source [248]. The [260], PVB [261], acetyl glucosamine [262], amphiphilic carbona-
treatment of the Li4Ti5O12 in the toluene vapor at 800 8C resulted in ceous material (from green needle coke) [263], oleic acid [264],
a uniformly graphited carbon layer on the particle surfaces with a chitosan [265] and so forth. All investigations have demonstrated
thickness of approximately 5 nm. The resulting Li4Ti5O12/C that a carbon coating improves the electrode performance
composite exhibited an electrical conductivity as high as (capacity, rate capability, or cycling stability).
2.5 S cm1, while the electrical conductivity was less than The carbon source and carbon content were found to affect the
1013 S cm1 for the pristine Li4Ti5O12. At 24 C, the carbon-coated performance of Li4Ti5O12. Hu et al. systematically investigated the
Li4Ti5O12 retained 50% of its initial capacity at an 8 C rate. This effect of the carbon source and carbon content on the electrode
value was only 29% for the pristine Li4Ti5O12. performance of Li4Ti5O12/C prepared by in situ carbon formation
Kellerman et al. demonstrated that the surface coating also had during high temperature calcination for the Li4Ti5O12 phase
an effect on the structure of the Li4Ti5O12 phase [249]. First, formation using PAALi + TiO2, CALi + TiO2, MALi + TiO2 and PVA + -
Li4Ti4.92(CrV)0.04O12 was prepared by calcining a mixture of TiO2 LiOH + TiO2 as reactants in which PAA, CA, MA and PVA represent
anatase, lithium carbonate (Li2CO3), Cr2O3 and vanadium oxide polyacrylate acid, CA, maleic acid and polyvinyl alcohol, respectively
(V2O5) at 800 8C in air. Then, they treated the samples under an [266]. PAA was found to be the best carbon source in terms of
argon/acetylene gas mixture with a volumetric ratio of 40:1 at electrochemical performance. The optimum carbon content was
800 8C. The treatment in acetylene gas not only resulted in the found to be approximately 3.5 wt.% in the Li4Ti5O12/C composite and
formation of a carbon coating but also caused a structural exhibited capacities of 168.6, 143.5 and 132.7 mA h g1 at 0.2, 8 and
transformation in the Li4Ti5O12 by inducing a lithium transfer 10 C, with a capacity loss of 2.8, 8.7 and 9.9% after 50 charge/
from the tetrahedral 8a sites to the vacant octahedral 16c sites. discharge cycles, respectively. Hu et al. further investigated the
Such a phase transformation reportedly increases the electronic synthesis of carbon-coated Li4Ti5O12 via a solid-state reaction using
conductivity [42,70], thus increasing the electrode performance. LiOHH2O and TiO2 as reactants and PAA as a carbon source
In addition to increasing the surface conductivity and possibly [267]. They demonstrated that the properties and electrochemical
affecting the lattice structure, He et al. demonstrated that a surface performance of the as-synthesized Li4Ti5O12/C composite was
coating may also suppress the decomposition of the electrolyte on strongly affected by the molecular weight of the polyacrylic acid,
the Li4Ti5O12 electrode [250]. Lithium batteries using Li4Ti5O12 as an the heating rate and the sintering time. PAA, with the molecular
anodic material are easily inflated during the charge/discharge weight of 10,000, heated at 20 8C min1 and sintered over 8 h was
processes, especially at high temperatures when reduction gases optimal, and the resulting Li4Ti5O12/C composite exhibited a
such as hydrocarbon gases and CO are generated in the batteries. The capacity of 116.4 mA h g1 at 20 C and a capacity retention of
reduction reactivity of the electrolyte on the uncoated Li4Ti5O12 87.6% after 50 cycles.
electrode differed greatly from that on the carbon-coated Li4Ti5O12 There are two primary ways to introduce carbon (Fig. 48), i.e.,
composite electrodes. The reduction decomposition reaction introducing carbon after the synthesis of Li4Ti5O12 (Fig. 48a) and in
appeared at 0.7 V on the uncoated Li4Ti5O12 electrode during situ forming carbon during the phase formation of Li4Ti5O12
cycling from 2.5 to 0.0 V, whereas the same reaction occurred at the (Fig. 48b). Another minor way is to first coat carbon on the TiO2,
first cycle on the carbon-coated electrode. This observation is in and then to carry out lithiation and calcination processes to obtain
agreement with the findings of Ding et al. indicating that the carbon a spinel Li4Ti5O12 phase (Fig. 48c). For the post-synthesis method,
coating can reduce the activity of the Li4Ti5O12 surface [251]. Li4Ti5O12 crystalline phase is first prepared, and then the sample is
Song et al. questioned the necessity of conductive carbon in the calcinated under an inert or reducing atmosphere at an elevated
Li4Ti5O12 electrode for achieving high capacities at a high rate temperature in the presence of a liquid or gaseous organic carbon
[252] by demonstrating that excellent electrochemical perfor- source [186,248,268]. The organic carbon source is decomposed and
mance can still be achieved without any carbon additive. They
prepared a carbon-free Li4Ti5O12 composite film on Al foil with
only a PVDF binder, free of any conductive agent. This electrode
had capacities at different rates between 0.1 and 10 C, nearly
identical to those of the electrode containing a 5 wt.% carbon
additive. This result suggests that the electronic conductivity of
Li4+dTi5O12 and its interphase boundary with Li7Ti5O12 is likely the
origin of its interesting electrochemical properties. However, the
low-carbon content of 5 wt.% for the carbon-containing electrode
may still be insufficient to improve the current collection
efficiency, and the higher content of PVDF in carbon-containing
electrode (5 wt.%) compared to that of carbon-free electrode
(2 wt.%) may also have a detrimental effect on the rate capability.
Moreover, for practical application, higher mass loading will be
required, thus, carbon still be required for a high current collection
efficiency since carbon has a much higher electronic conductivity
compared to that of Li4+dTi5O12/Li7Ti5O12.

3.3.1. Carbon coating


Carbon is one of the most attractive surface coating materials
due to its low cost, easy preparation and versatile origins. Carbon
coating has turned out to be highly effective in improving the rate
performance of the well-known LiFePO4 cathode [253,254], which
also has the disadvantage of low electronic conductivity. Several
materials have been exploited as carbon sources, including pitch Fig. 48. Schematic illustration of the ways to introduce carbon on Li4Ti5O12
[186], sugar [255], CA [256], Super P [257], toluene [248], starch materials.
36 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 49. (a, b) SEM images of (a) carbon-free and (b) 5 wt% pitch-coated Li4Ti5O12 powders, (c) HRTEM image of the 5 wt% pitch-coated Li4Ti5O12 after calcination at 750 8C [186].

deposited on the surface of the Li4Ti5O12 to form a thin carbon layer with capacity retention of 86%. In comparison, the pristine Li4Ti5O12
during the calcination. H.G. Jung first prepared carbon-free spherical had capacities of only 61 and 30 mA h g1 at 5 and 10 C, respectively.
Li4Ti5O12 by spray drying and subsequent solid-state calcination at The in situ creation of carbon during the formation of the
900 8C for 20 h in air. The material was then mixed with a proper Li4Ti5O12 phase has been applied more widely. The raw materials
amount of pitch and calcined for 5 h at 750 8C in a furnace purged for Li4Ti5O12 and the carbon source are mixed in the precursor
with Ar [186]. Fig. 49a&b shows typical SEM images of carbon-free stage, which are further calcinated at elevated temperatures under
Li4Ti5O12 spheres and a Li4Ti5O12/C composite. The sample color an inert or reducing atmosphere. During the calcination, the
darkens after the carbon coating. The carbon coating was homoge- formation of a crystalline Li4Ti5O12 phase and solid carbon happen
neous over the Li4Ti5O12 grains with a thickness of 3 nm as shown in simultaneously. Because only one calcination step is involved, the
Fig. 49c. The electronic conductivity increased substantially from process is cost effective. In addition, the in situ-formed carbon acts
1.58  109 S cm1 for the pristine Li4Ti5O12 to 5.24  103 S cm1 as a diffusion block to suppress the grain growth of the Li4Ti5O12
for the carbon-coated Li4Ti5O12 with a carbon content of 3.25 wt.%. phase, and the particles of the as-synthesized Li4Ti5O12/C are
An improved rate performance was demonstrated after the carbon typically of smaller size than that of the pristine Li4Ti5O12 prepared
coating; within the potential range of 1.0–3.0 V, the pristine under the same conditions. Both carbon coating and the reduced
Li4Ti5O12 delivered capacities of 164, 142, 120, 90, 33, and particle size help to improve the electrode performance, especially
29 mA h g1, at 1, 5, 10, 20, 50, and 100 C rates, respectively, while at high discharge/charge rates. Yin et al. synthesized a Li4Ti5O12/
the corresponding capacities after the carbon coating were 175, carbon composite using TiO2, LiOHH2O and PAN as starting
172, 171, 170, 116, and 82 mA h g1, respectively. The conversion of materials calcined at 800 8C for 12 h under a nitrogen atmosphere
conventional organic substances to solid carbon typically requires a [270]. The high temperature allowed the formation of a Li4Ti5O12
temperature higher than 700 8C. Such a high calcination tempera- phase and enabled the simultaneous pyrolysis of PAN to solid
ture not only increases the energy consumption but also promotes carbon. The carbon primarily coated over the Li4Ti5O12 surface as
the sintering of the Li4Ti5O12 particles. Jian et al. proposed the use of shown by TEM and had a thickness of 1–10 nm. Using 10 wt.% PAN
C28H16Br2 as a carbon source and successfully prepared few-layer during the synthesis, the surface area reached 4.42 m2 g1,
graphene on porous Li4Ti5O12 at a calcination temperature as low as compared with 0.35 m2 g1 for the pristine Li4Ti5O12, suggesting
400 8C [269]. The as-synthesized Li4Ti5O12/C composite with that the carbon suppresses the grain growth of the Li4Ti5O12 phase.
3.51 wt.% carbon exhibited capacities of 153, 134 and 104 mA h g1 The carbon coating also resulted in an increased tap density to
1 at rates of 0.5, 5 and 10 C, respectively, and a capacity of 1.51 g cm3 for Li4Ti5O12/C (with 10 wt.% during the synthesis)
124.4 mA h g1 was maintained at a rate of 2 C after 2400 cycles compared with 1.13 g cm3 for pristine Li4Ti5O12. The capacities of
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 37

the Li4Ti5O12/C reached 158, 138, 121 and 100 mA h g1, at 1/5, 1/3, cycling performance compared with that of Li4Ti5O12 coated via
3 and 6 C, respectively, while the corresponding values are 114, chemical vapor deposition with normal carbon derived from
111, 104 and 65 mA h g1 for pristine Li4Ti5O12. The improved toluene. The reversible capacities of the Li4Ti5O12/C–N with
capacities can be explained by the increased surface electronic 4.9 wt.% carbon are 149 and 133 mA h g1 at 5 and 10 C,
conductivity and the reduced particle size. By applying thermo- respectively, while the corresponding capacities for Li4Ti5O12/C
gravimetric (TG) analysis, Hu et al. further analyzed the kinetics of with similar carbon content (4.5%) are 130 and 97 mA h g1,
the solid-state reaction for the formation of Li4Ti5O12/C using respectively. Based on first-principles calculations, the authors
LiOHH2O and PAALi as reactants [82]. The TG analysis revealed demonstrated strong binding between the graphene coating layer
two endothermic reactions, which were assigned to the thermal and the Ti-terminated Li4Ti5O12 surface, which greatly reduced the
decomposition of PAALi and solid-state reaction (350–550 8C) and surface activity of the Li4Ti5O12 due to a charge transfer between
the Li4Ti5O12 crystal particle growth and crystalline perfection the graphene layer and the Li4Ti5O12 substrate, thus stabilizing the
(550–650 8C). Using the Flynn–Wall–Ozawa (FWO) and Friedman– electrode/liquid electrolyte interface and improving the electrical
Reich–Levi (FRL) methods, the reaction mechanism was well conductivity of the interface. The nitrogen doping further
described by the Jander equation: a 3D diffusion with spherical increased the interfacial stability, the electrical conductivity, the
symmetry. The formation of the Li4Ti5O12/C composites was found defect for the penetration of the liquid electrode and resulted in a
to have an entropy-driven one-step solid-state reaction mecha- further improvement in the electrode performance.
nism. Shen et al. designed and synthesized carbon-coated Li4Ti5O12
using a facile and general solid-state reaction [271]. The metal 3.3.2. Coating/modification with other materials
acetylacetonate was used as titania and the single-source carbon Metals have a very high electronic conductivity; silver and
source. After mixing with Li2CO3 and heat treatment, nanostruc- copper are among the best electronic conductors. The modification
tured Li4Ti5O12 with a nanoscale carbon coating layer was of Li4Ti5O12 with metals has recently received attention. Silver was
obtained. The as-prepared Li4Ti5O12 exhibited a superior rate widely investigated for modification of Li4Ti5O12 [47,277–279], not
performance with discharge capacities of 153, 146, 138, and only because of its high electronic conductivity but also because of
119 mA h g1 at 1, 5, 10, and 30 C, respectively. its easy preparation by thermal decomposition from silver salt
Wang et al. developed a facile method to prepare carbon-coated (e.g., AgNO3) without the application of a reducing agent or
Li4Ti5O12 nanoparticles that simultaneously achieved nanosize reducing atmosphere. Huang et al. prepared a Li4Ti5O12 surface
structure and double surface conductive modification based on modified with silver particles via the thermal decomposition of
Ti(III) and carbon [69]. In this method, the nanosized TiO2 was first AgNO3 added to Li4Ti5O12 powders [47]. The Ag content and mixing
prepared with polyaniline (PANI) coatings through a concurrence of media played an important role in the electrochemical perfor-
the hydrolysis of Ti(OC3H7)4 and the polymerization of aniline. The mance of the as-prepared composite. A composite with 5 wt.% Ag
PANI-coated TiO2 and Li2CH3COO were then milled for 1 h and yielded the best performance. As a mixing medium, water resulted
calcined at 400 8C in 5% H2–Ar for 4 h, re-milled for 1 h, and finally in smaller silver particles and a more homogenous dispersion than
calcined again at 800 8C for 24 h under a 5% H2–Ar atmosphere. The alcohol. The Ag/Li4Ti5O12 with 5 wt.% Ag prepared using a water
PANI was carbonized during the high temperature calcination with medium exhibited a reversible capacity of 184.2 mA h g1 in the
the formation of solid carbon, which covered the particle surfaces. potential range of 0.5–2.5 V. After 50 charge/discharge cycles, a
The carbonization of PANI was found to effectively restrict the grain capacity degradation rate of 0.067% per cycle was demonstrated.
growth of the Li4Ti5O12. Even after sintering at 800 8C for the S.H. Huang also investigated copper, which was introduced by
prolonged time of 24 h, the resulting powders had small particle the thermal decomposition of a mixture of Cu(NO3)2 and the
sizes of only 50–70 nm, and the surface was modified with both precursor Li4Ti5O12 under an H2-N2 or air atmosphere, as an
carbon and Ti(III) (LiTiO2). These results suggested a unique additive to improve the conductivity of Li4Ti5O12 [280]. The
morphological structure that not only increased the surface conductivities of pristine Li4Ti5O12, Li4Ti5O12/Cu prepared under a
conductivity but also extended the single phase insertion/extraction hydrogen atmosphere and Li4Ti5O12/Cu prepared under an air
region. As a result, the material demonstrated a high rate atmosphere are 2.5  107, 1.45  106 and 1.3  107 S cm1,
performance, achieving 160 mA h g1 at a current density of respectively. The improved conductivity for the sample prepared
0.1 A g1 and 70 mA h g1 at 3.0 A g1. However, the potential under a hydrogen atmosphere could be attributed to the partial
partial reduction of Ti4+ in the bulk phase to Ti3+ cannot be excluded reduction of Ti4+ in the Li4Ti5O12 or to the reduction of CuxO to
due to the application of the reducing atmosphere of 5% H2–Ar metallic copper in hydrogen. The composite prepared under a
during the high temperature calcination. Cheng et al. further hydrogen atmosphere showed a capacity of 137.6 mA h g1 after
modified the preparation process of Wang et al. by preparing a 100 cycles with a capacity loss of 5.6%, while the capacity of the
carbon-coated TiO2 via chemical vapor decomposition and further composite prepared in air decreased to only 68.8 mA h g1 with a
reacting the resulting TiO2/C with lithium salt at elevated capacity loss of up to 13.7%. Clearly, the improved performance of
temperatures to form a Li4Ti5O12/C composite (Fig. 48c) [272]. By the Li4Ti5O12/Cu prepared under a hydrogen atmosphere over that
selecting TiO2 with different morphologies, including nanorods, of the Li4Ti5O12/Cu prepared under an air atmosphere is closely
hollow spheres and nanoparticles, the morphologies can success- related with the improved electronic conductivity. Huang et al.
fully transfer to the as-synthesized Li4Ti5O12/C composites, thus further prepared a Li4Ti5O12/Cu composite using an electroless
providing a facile way to prepare carbon-coated Li4Ti5O12 with deposition of copper particles [46]. A small quantity of copper
varying morphologies. (with a copper concentration as low as 1%) resulted in an increase
Beyond the traditional carbon coating, a heteroatom-doped in the electronic conductivity by two orders of magnitude. The
carbon coating on Li4Ti5O12 has also been studied for further Li4Ti5O12/Cu electrodes exhibited stable capacities of 171, 166.6,
improving the electrode performance, such as nitrogen-doped 153.6, 144.6 and 141.6 mA h g1 at 1, 2, 4, 8 and 10 C, respectively,
carbon coating [184,262,273–275], and boron-doped carbon in a voltage range of 2.0–0.5 V. The corresponding capacities for the
coating [276]. Ding et al. investigated the effects of carbon coating, pristine Li4Ti5O12 are 164.2, 155, 117.3, 72.5 and
with and without nitrogen doping, on the electrochemical 61.2 mA h g1. Cheng et al. prepared a Li4Ti5O12/Cu composite
performance of Li4Ti5O12 in detail [251] and found that Li4Ti5O12 by calcining a mixture of Cu(NO3)23H2O and a precursor of
coated with C-N derived from pyridine using chemical vapor hydrothermal-synthesized Li4Ti5O12 under N2[281]. The as-
deposition exhibited a significant improvement in the rate and formed copper nanoparticles were highly dispersed on the surface
38 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

of Li4Ti5O12, and improved electrochemical performance at range of 1.0–3.0 V [291]. Since SiO2 has poor electronic conductiv-
different rates was observed after modification with copper ity, the SiO2 coating may increase the resistance of the electrode;
nanoparticles. Li et al. synthesized a Li4Ti5O12/Cu composite using however, a decrease in electrochemical polarization was reported.
a one-pot solvothermal method using LiOHH2O, TTIP, and Thus, the real reason for the improved electrochemical perfor-
Cu(NO3)23H2O as starting materials [282]. The effect of different mance was still not clear in this case. Jiang et al. systematically
amounts of copper (0, 3.75, 7.5, 15 and 22.5 wt.%) on the studied Li4Ti5O12 and SiO2-incorporated Li4Ti5O12 as anodes under
morphology and electrochemical performance was investigated. different conditions, including discharge to an end potential of 1.0/
Although the elemental mappings demonstrated that the copper 0.01 V at room/elevated temperature (55 8C) [292]. XRD Rietveld
was not homogeneously distributed in the composite, enhanced refinement analysis indicated that the SiO2 was incorporated into
electrochemical performance for the Li4Ti5O12/Cu composite, Li4Ti5O12 in two forms, Si-doping (53.5%) into the Li4Ti5O12 spinel
especially with 15 wt.% copper, was achieved with a specific lattice and a SiO2 (46.5%) separate phase as a coating layer. The
discharge capacity of 107 mA h g1 even after 1000 cycles (87% effect of SiO2-coating on the electrochemical performance was
retention). Further improvement in the rate performance may be negligible within a potential range of 1.0–3.0 V; however, it
achieved by introducing a continuous conductive copper phase somewhat improved cycling stability at 55 8C compared to the
instead of dispersed copper nanoparticles. unmodified Li4Ti5O12. Within the potential range of 0.01–3.0 V,
Other methods, such as the electroplating method [283], have both Li4Ti5O12 and SiO2-incorporated Li4Ti5O12 electrodes exhib-
also been applied to coat copper on the Li4Ti5O12 to achieve surface ited a stable cycling performance at room temperature for
modification, resulting in improved electrochemical performance, 400 cycles at a current density of 175 mA g1 as shown in
especially for the rate capability. Hsieh et al. deposited a thin layer of Fig. 50a. At an elevated temperature of 55 8C, both electrodes
zinc via microwave irradiation onto the surface of the Li4Ti5O12 with exhibited an interesting ‘‘decrease-increase-decrease’’ cycling
a thickness of 1–10 nm by using zinc nitrate as a raw material behavior (Fig. 50b), and a mechanism of ‘‘SEI film formation-SEI
[284]. The Zn coating significantly improved the capacity retention dissolution/delamination-SEI reformation/consumption of elec-
at high rates—78.1% at a 10 C rate (142.9 mA h g1) over that at a rate trolyte’’ was proposed (Fig. 50c) and supported by EIS (Fig. 50d and
of 0.2 C (183 mA h g1) with a coulombic efficiency greater than e) and TEM analysis. Importantly, the SiO2 coating layer did help to
99.9% attributed to the increased electronic conduction and reduced effectively increase the cycling stability of Li4Ti5O12 at an elevated
cell polarization due to the zinc coating. In comparison, the temperature between 0.01 and 3.0 V (Fig. 50b). Coatings of other
capacities of the pristine Li4Ti5O12 are 175 and 96.6 mA h g1 at oxides, e.g., ZnO, were also reported to improve the cycling
0.2 and 10 C, respectively, with capacity retention of only 55.2% at performance of Li4Ti5O12 electrodes [293].
10 C with respect to that at 0.2 C. Gold has also been studied as a Conductive polymers are also attractive coating materials. Yu
coating metal on Li4Ti5O12 nanorod aggregates using a liquid et al. prepared a Li4Ti5O12/polyacene composite via the in situ
method with Au (III) solution as the Au source [285]. After Au carbonization of a phenol–formaldehyde resin to from a carbon-
coating, the Li4Ti5O12/Au composite material exhibited much higher based composite [294]. The electronic conductivity of the Li4Ti5O12/
electronic conductivity (approximately 8.53  103 S cm1) com- polyacene is 108 times higher than that of the pristine
pared with that of pure Li4Ti5O12 (approximately 1013 S cm1) and Li4Ti5O12. After 200 cycles, the pristine Li4Ti5O12 has capacity
enhanced electrochemical performance, especially at high rates. retention of 57.4% at a 5 C discharge rate, while the capacity
However, the high cost and scarcity of gold limits its commercial retention is 87.6, 80 and 78.2% at discharge rates of 3, 5 and 10 C for
application. Li4Ti5O12/polyacene, respectively. Wang et al. successfully coated a
TiN is a hard refractory material and an excellent metallic-type poly (3,4-ethylenedioxythiophene) (PEDOT) layer on spinel
conductor [286]. Snyder et al. firstly applied an approximately 5.8- Li4Ti5O12 nanorods [295]. A sample of Li4Ti5O12/C with calcination
nm thin layer of TiN as a coating on Li4Ti5O12 using an atomic layer of Li4Ti5O12/PEDOT to obtain a carbon-coating layer was also
deposition technique [287]. Compared to pristine Li4Ti5O12, the TiN- prepared and studied. The Li4Ti5O12/PEDOT sample exhibited the
coated Li4Ti5O12 showed improved capacities in the range of 0.05– highest electronic conductivity of 0.083 S cm1 compared with that
0.2 C. Zhang et al. fabricated Li4Ti5O12/TiN composites using a facile of pure Li4Ti5O12 nanorods (109 S cm1) and Li4Ti5O12/C
high-energy ball-milling method by mixing spinel Li4Ti5O12 and TiN (0.051 S cm1) and the best electrochemical performance. High
powder with different mass ratios [288]. The HRTEM results rate performance with a discharge capacity of 135.2 mA h g1 at
indicated that TiN formed a 1.5-nm thin layer on the surface of 10 C and stable cycling performance with a capacity of
Li4Ti5O12 with a mass ratio of 100:2 (Li4Ti5O12:TiN). This composite 168.7 mA h g1 after 100 cycles at 1 C were achieved for the
sample exhibited a high capacity of 130 mA h g1 at 20 C, which is PEDOT-coated sample.
10 times that of pristine Li4Ti5O12. Ming et al. introduced urea into
the synthesis process of Li4Ti5O12 including hydrolysis of tetrabutyl 3.3.3. Surface treatment
titanate and ball-milling with Li2CO3 and observed that N–C and TiN (1) N-containing environment (e.g., ammonia atmosphere, solid
were formed [289]. TiN was detected by X-ray photoelectron nitrogen sources)
microscopy (XPS) and Raman analysis. With proper amounts of urea, Because both TiN and TiO2 contain titanium, they can easily be
the as-synthesized Li4Ti5O12 composite exhibited a smaller particle fabricated through calcination of Li4Ti5O12 in an ammonia-
size and enhanced electrochemical performance. containing atmosphere [68,296]. Park et al. reported the modifi-
Oxides have also been used as coatings to improve the cation of the surface structure of Li4Ti5O12 by thermal nitridation
electrochemical performance of Li4Ti5O12 anodes, e.g., CeO2 was via annealing in an ammonia atmosphere [68]. High resolution
coated on Li4Ti5O12 to form core-shell nanospheres using a one-pot transmission electron microscopy (HR-TEM) and XPS results
co-precipitation method; the as-form composite nanosphere (Fig. 51a) showed that a thin TiN layer of several nanometers
exhibited enhanced performance with a capacity of 152 mA h g1 formed over the Li4Ti5O12 surface to create a core-shell composite
1 at 10 C even after 180 cycles [290]. The enhanced performance with a Li4Ti5O12 core and a TiN + Li2CO3 shell. The white color of the
could be mainly attributable to the unique core-shell nanosphere initial Li4Ti5O12 suggests its inherent low electronic conductivity.
microstructure compared with the irregular and aggregated The color of white Li4Ti5O12 became dark after thermal nitridation
particles of pure Li4Ti5O12. SiO2 was coated on the surface of under NH3 atmosphere, and it was apparently black after 1 h
commercial Li4Ti5O12 via a facile sol–gel method followed by (Fig. 51b). Because TiN is a metallic conductor, the apparent
calcination, resulting in improved rate capability within a potential conductivity of the modified Li4Ti5O12 is expected to increase
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 39

Fig. 50. (a, b) Cycling performance of the cellulose-assisted combustion-synthesized unmodified Li4Ti5O12 (CS-LTO) and SiO2-incorporated Li4Ti5O12 (CS-SiO2/LTO) electrodes
tested at (a) room temperature and (b) 55 8C between 0.01 and 3.0 V (discharge/charge current density: 175 mA g1). (c) The schematic illustration of mechanism for the
‘‘decrease-increase-decrease’’ cycling behavior of Li4Ti5O12 between 0.01 and 3.0 V at 55 8C. (d) Impedance spectra of CS-LTO at different cycle times (tested at 1.6 V after
cycling between 0.01 and 3.0 V at 55 8C); (e) equivalent circuit [292].

substantially. The capacities after nitridation were not substan- was further confirmed by XPS. The nitridated Li4Ti5O12 nanofiber
tially different from those of pristine Li4Ti5O12 at rates below 1 C electrode achieved a discharge capacity of approximately
(Fig. 51c). However, the discharge capacities of the Li4Ti5O12 1.35 times that of a pristine nanofiber electrode at 10 C rate.
treated even after 10 min of nitridation are 6 times higher than However, in addition to the formation of the conductive TiN, the
those of pristine Li4Ti5O12 at a high discharge/charge rate of 10 C. partial reduction of Li4Ti5O12 by the reducing ammonia atmo-
The treatment also resulted in an increase in the single solution sphere may play an important role in the improved rate
region during the lithium insertion/extraction processes, as shown performance. Lin et al. demonstrated that ammonia was primarily
in Fig. 9c, which is believed to benefit the lithium intercalation/de- reduced to H2 and N2 at elevated temperatures [298], while the
intercalation because of an apparent increase in the electron and Li4Ti5O12 can be partially reduced by H2 via a substantial increase
lithium-ion conductivity [42,70]. Park et al. treated the 1D in the electronic conductivity, leading to an increase in the rate
electrospun nanofibers under ammonia at 700 8C to obtain TiN/ performance of the Li4Ti5O12 [299]. Because TiN is inert to lithium
TiOxNy-coated Li4Ti5O12 nanofibers [297]. HR-TEM analysis insertion, the coating layer thickness should be sufficiently thin;
revealed the formation of an amorphous TiN/TiOxNy layer, which otherwise, it may block the lithium transport into the Li4Ti5O12

Fig. 51. (a) XPS analysis of the Ti 2p3/21/2, and N 1s core peaks performed onto Li4Ti5O12 before and after nitridation: pristine Li4Ti5O12 and the nitridated powders at 700 8C
for 10, 30, 60 min. (b) Li4Ti5O12 powder color change after thermal nitridation at 700 8C with NH3 gas flow. The annealing time is indicated on each powder samples. (c)
Reversible capacities of pristine and 10 min-nitridated Li4Ti5O12 with different charge/discharge current densities during cycling [68].
40 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

phase. The coating layer thickness can be controlled by adjusting via a solid-state reaction and then was mixed with melamine
the ammonia concentration, the calcination temperature, and the followed by a calcination at 700 8C under Ar atmosphere. XPS, TEM
calcination time during the thermal nitridation process. Wan et al. and corresponding linear scanning energy-dispersive X-ray
reported a facile solid-state reaction method for preparing spectroscopy (EDX) results demonstrated the formation of a
nitrogen- and TiN-modified Li4Ti5O12 with a calcining precursor homogenous TiN layer on the surface of Li4Ti5O12. Such an as-
under NH3/N2 (3, 7, 13, 20 and 100%) atmosphere [300]. Calcination formed TiN layer resulted in enhancement in the electronic
in the NH3-containing atmosphere resulted in partial reduction of conductivity, and further rate capability and cycling performance.
Ti4+ to Ti3+ and a TiN phase formed in a NH3/N2 7% atmosphere, (2) Reducing environment (e.g., H2, solid carbon for carbothermal
which could both improve the electronic conductivity. However, reduction)
the sample calcined at 3% NH3/N2 exhibited the best rate In addition to formation of a TiN coating layer by surface
performance with a specific capacity of 103 mA h g1 at 20 C rate, treatment, partial reduction of Ti4+ to Ti3+ on the surface of Li4Ti5O12
which was more than three times that calcined in air. It was by a thermal treatment in a reducting atmosphere (e.g., H2, H2/Ar)
suggested that sufficient electronic conductivity was already was also reported to result in an enhancement in electronic
reached from the partial reduction of Ti4+ to Ti3+ by the reducing conductivity and further electrochemical performance. Industrial
atmosphere, and the formed TiN layer in this situation mainly grade white Li4Ti5O12 powders were treated under a 40 bar H2
acted as a diffusion block for lithium ions. atmosphere at 500 8C by Qiu et al. [303], and it was found that the
Although an ammonia atmosphere was effective for forming white color became blue (Fig. 52a), suggesting an enhancement in
TiN- or/and nitrogen-modified Li4Ti5O12, the toxic nature limits the the electronic conductivity. Such treatment did not significantly
application of an ammonia atmosphere. Recently, solid nitrogen affect the microstructure and phase structure of the Li4Ti5O12
sources were also used to achieve a nitridation process of (Fig. 52b), but dramatically altered the defect structure. Importantly,
Li4Ti5O12. Zhao et al. used urea as a nitrogen source and mixed the electrochemical performance was much improved after the
it with Li4Ti5O12 for a solid-state reaction by planetary ball milling treatment under H2 atmosphere; the reversible capacities was
[301]. Li4Ti5O12/TiN composites with different amounts of urea increased from 135 mA h g1 (before reduction) to 173.6 mA h g1
were successfully synthesized, and the formation of TiN was (after reduction) at a rate of 0.5 C (Fig. 52c). The rate capability was
directly evidenced by Raman measurements. An improved rate also enhanced after reduction. Wolfenstine et al. prepared Li4Ti5O12
performance and much enhanced cycling stability were achieved samples from rutile TiO2 and Li2CO3 using a solid-state method, in
after the modification of TiN. The composite treated with 6% urea which the sample was calcined at 800 8C under air or 3 vol.% H2/Ar to
exhibited the best rate performance with a specific capacity of understand the effect of reducing atmosphere on the electronic
116.1 mA h g1 at a cycling rate of 10 C rate and enhanced cycling conductivity and further rate performance [299]. The Li4Ti5O12
performance with a capacity of 148.3 mA h g1 after 600 cycles at a sample reduced in H2/Ar turned to gray with an electronic
3 C rate, which was approximately 90% of the initial capacity. conductivity of 1  105 S cm1, which is much higher than that
Melamine was also reported as a solid nitrogen source for the for the white Li4Ti5O12 sample. As expected, the Li4Ti5O12 sample
nitridation of Li4Ti5O12 [302], in which Li4Ti5O12 was synthesized reduced in H2/Ar exhibited improved rate capability.

Fig. 52. (a) Digital photos, (b) XRD patterns, and (c) specific charge and discharge capacities at various C rates of the initial white Li4Ti5O12 and blue Li4Ti5O12 obtained at
500 8C under a 40 bar H2 atmosphere [303]. (d) Digital photos of as-prepared materials and that after storage for 5 weeks: LTO-O (undoped LTO in an oxidizing atmosphere),
LTO-R (undoped LTO in a reducing atmosphere), Mo-LTO-O (Mo-doped LTO in an oxidizing atmosphere), and Mo-LTO-R (Mo-doped LTO in a reducing atmosphere) [304]. (e)
Electron paramagnetic resonance signals, and (f) rate capability of LTO-O, LTO-R and Mo-LTO-R [304]. (For interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.)
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 41

Even though the treatment under a reducing atmosphere is Li2CO3 and TiO2) and then heat-treatmented at 850 8C under Ar
facile and an effective way to improve the electrochemical atmosphere. The as-obtained Li4Ti5O12 appeared to be blue as
performance, it suffers from two shortcomings [304]. First, the shown in Fig. 53, consistent with the color of the sample obtained
reduced state Ti3+ in the lattice is not very stable and will be re- under a reducing atmosphere (Fig. 52a and d). In contrast, the color
oxidized, resulting in gradually retrogressing of electronic of the sample prepared under similar conditions but calcined in
conductivity. Second, the formed oxygen vacancies may induce ambient air was white (Fig. 53). Importantly, the carbothermally
lattice distortion, leading to a decrease in lithium-ion mobility in synthesized blue Li4Ti5O12 demonstrated an enhanced electronic
the lattice. Accordingly, a higher valence metal cation doping may conductivity of 1.34  104 S cm1 and further improved electro-
result in stabilization of the lattice treated under a reducing chemical performance, compared to that of sample obtained in
atmosphere. Song et al. selected Mo6+ as a dopant and found a ambient air (4.03  108 S cm1).
prominent stabilization of the structure of the Li4Ti5O12 after (3) Other environment
calcination under a reducing atmosphere (10% H2 in Ar) [304]. As Nakajima et al. investigated the effects of surface fluorination
shown in Fig. 52d, the undoped Li4Ti5O12 obtained under a and conductive additives on the charge/discharge properties of
reducing atmosphere appeared to be blue with an electronic Li4Ti5O12 [305,306]. The surface fluorination of Li4Ti5O12 powder
conductivity of 8.1  106 S cm1, and its color changed signifi- was conducted using low-pressure F2, NF3 or ClF3 as a treating
cantly from dark blue to light blue after 5 weeks. However, the atmosphere. After fluorination by F2, a LiF film was formed on the
color of the Mo-doped Li4Ti5O12 obtained under a reducing Li4Ti5O12 surface, while the number of small mesopores with
atmosphere was maintained after 5 weeks, and the change in diameters of 2 nm increased following the fluorination with
electronic conductivity was negligible, from 1.1  102 to ClF3. An improved capacity at high rate was also observed after the
1.4  102 S cm1. XPS analysis indicated that the presence of fluorination of the electrode at a proper temperature. By adding
rich Ti3+ and Mo6+ in the Mo-doped Li4Ti5O12 obtained under a vapor-grown carbon fiber, the electrical contact between the
reducing atmosphere, and electron paramagnetic resonance Li4Ti5O12 particles and the current collectors was further increased,
demonstrated its signal was significantly lower than that observed resulting in an improved rate performance.
for the undoped Li4Ti5O12 obtained under a reducing atmosphere Jo et al. successfully prepared phosphidated Li4Ti5O12 nano-
(Fig. 52e), suggesting that fewer oxygen vacancies were present in particles via the thermal decomposition of trioctylphosphine (TOP)
the lattice. These results demonstrated the successful enhance- [307]. The surface layer corresponds to Li–O–P bonding with
ment in electronic conductivity and in structure stability by Mo coordinated Ti3+. The insulating character of the Li4Ti5O12 can be
doping into Li4Ti5O12 under a reducing atmosphere. Accordingly, attributed to the Ti–O dangling bond. The empty Ti 3d states were
the Mo-doped Li4Ti5O12 obtained under a reducing atmosphere reduced by the TiO–P and LiO–P bonds, thus enhancing the
exhibited excellent rate capability with a specific capacity of electronic conductivity of the Li4Ti5O12 during the electrochemical
167 mA h g1 even at a rate of 10 C (Fig. 52f), and the performance reaction. The phosphidation appeared to facilitate electronic or
could be maintained after 5 weeks. ionic conduction through the surface of the Li4Ti5O12, as glassy
As an alternative thermal reduction method, carbothermal lithium phosphates are known to be stable Li+ conductors and can
reduction was also used to enhance the electronic conductivity of be doped with transition metals to achieve good electronic
the Li4Ti5O12 very recently (Fig. 53) [12]. In a typical process, small conduction. The capacity of the phosphidated Li4Ti5O12 was found
amount of acetylene black was mixed with the raw materials (i.e., to be approximately 140 mA h g1 at a rate of 0.1 C with attractive

Fig. 53. The schematic illustration of formation process of carbothermal reduction for Li4Ti5O12. The insets are the corresponding digital photos of as-prepared Li4Ti5O12
calcined under Ar and air [12].
42 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

cycling stability within 50 cycles in comparison with a capacity tivity, extensive research has been conducted to increase the
of 120 mA h g1 for pristine Li4Ti5O12 in the voltage range of transport properties, thus the performance of the Li4Ti5O12 oxide
3.0–1.0 V. At a high current density of 10 C, the phosphidated through doping at the 8a tetrahedral Li+ site, the octahedral 16 d
Li4Ti5O12 maintained a capacity of 100 mA h g1, which is Ti4+ site, the oxygen anion site, or a combination of these sites.
20 mA h g1 larger than that of the pristine Li4Ti5O12. Currently, only doping at the tetrahedral 8a sites, octahedral 16d
sites and oxygen anion sites has been attempted, with a focus on
3.4. Doping the octahedral sites. Dopants including Mg2+ [10,308–310], Sn2+/4+
[311,312], Mo4+ [313,314], V5+ [315–318], Ta5+ [319], Nb5+
Doping is sometimes effective at altering the structural [156,320–323], Zr4+ [324–328], Si4+ [328], Mnx+ [329–332], Fe3+
properties and thus the performance of many oxides. A small [333–336], Cr3+ [17,337–340], Ni3+/2+ [338,341], Al3+ [342–348],
amount of aliovalent-cation doping will not cause a change in the La3+ [349–352], Co3+ [353], Sc3+ [354], Cu2+ [355–357], Zn2+ [358–
phase structure of the parent oxide; however, it may significantly 363], Na+ [364–366], K+ [367], Ag+ [368], Ca2+ [369,370], Sr2+ [371],
affect the bond strength, the local environment of the lattice, the Y3+ [372], Nd3+ [373], Ru4+ [374], W6+ [375–377], F [342,378,379],
valence state of the compositional cations, and it may introduce a and Br [377] have been exploited. Different dopants may have
lattice defect. As a result, the charge transport properties of the different solubilities, preferred doping sites, and varying effects on
oxides are modified. To mitigate the drawbacks of Li4Ti5O12, such the phase structure, and thus the conductivity and electrochemical
as its poor electronic conductivity and poor lithium-ion conduc- performance of the oxides. Table 1 lists dopants, structural formula,

Table 1
Doped Li4Ti5O12 with different dopants.

Dopant Structural formula, doping amount Phase structure Doping site Change after doping Ref.

Mg2+ Li4xMgxTi5O12 (0  x  1) Spinel 8a, 16d High conductivity (s = 102 S cm1, x = 1.0), increased rate [10]
(+Li2MgTi3O8 + capability (x = 0.25)
MgTi2O5, x > 0.75)
Li4xMgxTi5O12 (0.05  x  0.2) Spinel 8a, 16d Improved reversible capacity and cycling stability, especially [308]
for x = 0.1
Li(42x)MgxTi(5x)/3O4 (0x < 0.6) Spinel 8a, 16d Increased ionic conductivity of Li+ by the calculations, but [309]
opposite results by experimental measurements
Li20MgTi27O64 Spinel + minor 8a Smaller particle size, higher electronic conductivity, improved [310]
anatase rate performance and cycling stability
TiO2

Sn2+ Li3.9Sn0.1Ti5O12 Spinel / Coating of carbon, creation of nanopores, increased rate [311]
capability, 100% capacity retention after 100 cycles (5 C)
4+
Sn Li4Ti5xSnxO12 (x = 0, 0.05, 0.1) Spinel + SnO2 / Smaller particle size, higher DC electrical conductivity; [312]
improved electrochemical performance (0–3.0 V, x = 0.1)

Mo4+ Li4Ti5xMoxO12 (0.5  x  1.5) Spinel 16d Increased electronic conductivity (1.6, 2.8, and [313]
(+Li4Mo5O12, x = 1.5) 5.8  103 S cm1, x = 0.5, 1.0, 1.5)
Li4Ti4.95Mo0.05O12 Spinel / Enhanced electronic conductivity, increased rate capability [314]
(117.03 mA h g1 at 10 C, 94.24 mA h g1 at 30 C), only 5.8% of
capacity loss (100 cycles, 1 C)

V5+ Li4Ti5xVxO12 (0  x  0.3) Spinel (0  x  0.1), 16d Excellent cycling capability of Li4Ti4.95V0.05O12 (between [315]
appeared TiO2 1.0 and 2.0 V), Li4Ti4.9V0.1O12 (183 mA h g1 after 100 cycles
and VO2 phase between 0.5 and 2.0 V, 229 mA h g1 after 130 cycles between
(x 0.15) 0.0 and 2.0 V)
Li4Ti4.95V0.05O12 Spinel / Good cycling performance and high discharge capacity [316]
(218.4 mA h g1 after 50 cycles)
Li4Ti4.9V0.1O12 Spinel / Enhanced conductivity (e, Li+) and narrower particle size [317]
distribution, 177.5 (0.1 C), 166 (0.5 C), 142.8 (2 C), and
117.3 mA h g1 (5 C). Capacity retention is 97.9% after
1713 cycles (2 C) and 93.2% after 4374 cycles (5 C)
Li4Ti5xVxO12/C Spinel / Enhanced electron conductivity and Li diffusion coefficient, [318]
(x = 0.05, 0.1, 0.15) e.g., 5.44  106 S cm1 and 2.84  1011 cm2 s1 for
Li4Ti4.9V0.1O12/C, respectively. The composite (x = 0.1) achieves
discharge capacities of 165.59 and 76.76 mA h g1 at a 0.2/1 C
and 0.2/20 C rate (0.5–2.5 V), respectively
Ta5+ Li4Ti4.95Ta0.05O12 Spinel 16d Enhanced electronic conductivity (1  103 S cm1) [319]
synthesized under 3 vol.%H2/Ar

Nb5+ Li4Ti4.95Nb0.05O12/C Spinel / Enhanced conductivity (0.072 S cm1 of Li4Ti4.95Nb0.05O12/C [156]


compared to 0.011 S cm1 of Li4Ti5O12/C), increased rate
capability (140.0 mA h g1 at 10, 110.6 mA h g1 at 25 C)
Li4Ti4.95Nb0.05O12 Spinel / Increased capacity of 231.2 mA h g1 after 100 cycles [320]
(35 mA g1, 0–2.5 V)
Li4+xTi4.95xNb0.05O12d Spinel (700–900 8C) 16d Enhanced rate capability (140 mA h g1 at 3 C rate) [321]
(x = 0.110.13)
Li4Ti4.95Nb0.05O12 Spinel / Increased conductivity (1.127  109 S cm1 of [322]
Li4Ti4.95Nb0.05O12 compared to 6.615  1010 S cm1 of
Li4Ti5O12 is), excellent rate capability (135 mA h g1 at 10 C and
80 mA h g1 at 40 C)
Li4Ti4.995Nb0.005O12 Spinel / Slightly decreased electrical conductivities [323]
(Li4Ti4.995Nb0.005O12), but it is much enhanced after Ar
annealing
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 43

Table 1 (Continued )

Dopant Structural formula, doping amount Phase structure Doping site Change after doping Ref.

Zr4+ Li4Ti5xZrxO12 (x = 0, 0.05, 0.1, 0.2) Spinel, appeared ZrO2 / Good rate capability and cycling stability (x = 0.1, 143 mA h g1 [324]
phase (x = 0.1, 0.2) at 5 C and 118 mA h g1 at 20 C; 141 mA h g1 after 100 cycles at
5 C)
Li4Ti5xZrxO12/C (x = 0, 0.05) Spinel 16d Good cycling stability (289.03 mA h g1 after 50 cycles at 0.2 C, [325]
0–2.5 V)
Li4Ti5xZrxO12 (0  x  0.25) Spinel + ZrO2 / Improved specific capacity and rate performance (0–2.5 V, 1.0– [326]
2.5 V)
Li4Ti5xZrxO12 (x = 0, 0.05, 0.1, 0.15) Spinel, appeared / Increased Li+ diffusivity and improved specific capacity, rate [327]
ZrO2 phase capability, and cycling properties (x = 0.05)
(x = 0.1, 0.15)
Zr4+ Li4Ti5xZrxO12 (x = 0, 0.05, 0.1) Spinel + Li2TiO3 / Enhanced DC conductivity for x = 0.05, decreased conductivity [328]
(x = 0, 0.05) for y = 0.05;
(+TiO2, x = 0.1)
Si4+ Li4Ti5ySiyO12 (y = 0, 0.05, 0.1) Spinel + Li2TiO3 + Sample with x = 0.05 exhibited best electrochemical
TiO2 + Li2TiSiO5 performance
(y = 0.05, 0.1)

Mn4+ Li4Ti4.5Mn0.5O12, Li4Ti4.75V0.25O12, Spinel + Li2TiO3 8a, 16d 16d Decreased the mass capacities [329]
V4+ Li4.25Ti4.75Fe0.25O12 Spinel 8a, 16d
Fe3+ Spinel

Mn3+ Mn-doped Li4Ti5O12 Spinel (+TiO2, 8a, 16d 8a Decreased conductivity [330]
Mn2+ (Mnx+30% of Tix+) Li2TiO3, LiMn2O4)

Mn4+ Li4Ti5xMnxO12 (x = 0.0, 0.05, 0.1) Spinel (+MnO2, x = 0.1) / Reduced particle size, improved cell performance (0.01–3.0 V) [330]
Mn2+ Li4Ti5xMnxO12 Spinel + Li2TiO3 / Enhanced ionic conductivity [332]
(x = 0, 0.005, 0.025, 0.01, 0.05, (+TiO2, x = 0.005)
0.075, 0.1, 0.2)

Fe3+ Li0.5+0.5xFe2.51.5xTixO4 (0  x  1.66) Spinel with space Fd3m: 8a; P4332: / [333]
¯
group Fd3m 8c, 12d
¯
(0.4  x  1.2 and
1.57  x  1.66);
space group P4332
(0  x  0.4 and
1.2  x  1.57)
Li4/35y/3(3y)Fe5y/(3y)Ti5(1y)/(3y)O4 Spinel (y < 0.5), 8a (y = 0–0.143) Poor insertion/extraction electrochemistry (y 0.5) [334]
(0  y  1.66) inverse spinel (y 0.5) 8a, 16d (0.143–1)
1
Li1+xFe13xTi1+2xO4 (0.0  x  0.33) Spinel (non-normal) 8a Reversible capacities in excess of 150 mA h g over 20 cycles [335]
(x = 0.30, Vlimits = 0.01–2.00 V, i = 100 mA)
Li1.3Fe0.1Ti1.6O4 Spinel (Fd3m) P4332 8a, 16d Stable capacity over 100 cycles [336]
¯
Li1.25Fe0.25Ti1.5O4 8c

Cr3+ Li[Li(1x)/3CrxTi(52x)/3]O4 (0  x  1.0) Spinel (+TiO2) 16d Low area specific impedance and increased rate capability [17]
(88 mA h g1 at 2 C)
Li(4x)/3Ti(52x)/3CrxO4 (0  x  0.9) Spinel 16d Sample of x = 0.7 exhibited best electrochemical performance [337]
Li4Ti2.5Cr2.5O12 Spinel + TiO2 16c High-rate cycling stability (132 mA h g1 after 20 cycles at 5 C) [339]
Li4x/3Ti52x/3CrxO12 Spinel / Increased electronic conductivity; increased Li+ ion diffusivity [340]
(x = 0, 0.25, 1.00, 2.00, 3.00) due to decreased structural disorder
Cr3+ Li1.317Cr0.050Ti1.633O4 Spinel 16d Increased conductivity [338]
Ni3+ Li1.317Ni0.050Ti1.633O4 Spinel + TiO2 + Li2TiO3 16d Decreasd conductivity
Al3+/F Li4AlxTi5xFyO12y Spinel / Increased (Al3+)/decreased (F) reversible capacity and cycling [342]
stability

Al3+ Li4xAlxTi5O12 (x = 0, 0.05, 0.1, 0.2) Spinel / Decreased specific capacity but increased rate-capability [343]
Li4Ti4.85Al0.15O12 Spinel 8a, 16d Decreased crystallite size, increased surface area, enhanced [344]
first discharge capacity and rate performance
Li4Ti4.95Al0.05O12/C Spinel 16d Improved initial capacity and cycling performance [345]
Li4AlyTi5yO12 (y = 0.10, 0.15, 0.25) Spinel / High reversible capacity and high coulombic efficiency [346]
(+LiAlO2, y = 0.25) (y = 0.15)
Li4Ti4.95Al0.05O12 Spinel 16d Enhanced electronic conductivity, and high rate capability [347]
(1.0–2.5 or 0–2.5 V)
Li4x/3AlxTi52x/3O12 Spinel (+TiO2, x = 0.01, 8a, 16d Increased reversible capacity and cycling stability (x = 0.01, [348]
(x = 0, 0.01, 0.05, 0.1, 0.15, 0.2) 0.1, 0.15, 0.2) 0.05, 0.1)

La3+ La3+-doped Li4Ti5O12 Spinel / Improved initial discharge capacity of 161.5 mA h g1 at 0.1 C, [349]
(La/Ti = 1:100, mol/mol) 135.4 mA h g1 after 50 cycles
Li4Ti5xLaxO12 (0  x  0.2) Spinel + Li3xLa2/3xTiO3 Little Formation of Li3xLa2/3xTiO3-Li4Ti5O12 solid solution, improved [350]
La3+ enter the electronic conductivity and lithium diffusion coefficient
crystal lattice (x = 0.05)
La3+-doped Li4Ti5O12 Spinel + Li0.35La0.55TiO3 8a (part of La3+) Smaller particle size, higher surface area, and improved rate [351]
(La/Ti = 0.75:100, mol/mol) capability with reversible capacities of 156.2 and
150.8 mA h g1 at 1 and 5 C, respectively
Li3.95La0.05Ti5O12 Spinel / Improved specific capacity, cycling performance and rate [352]
capability
3+
Co Li1.33xCo22xTi1+0.67xO4 (0  x  1) Spinel (Fd3m) / Improved electrical properties of the electrode materials [353]
¯
(0  x  0.40, x = 1)
P4332 (0.50  x  0.875)
44 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Table 1 (Continued )

Dopant Structural formula, doping amount Phase structure Doping site Change after doping Ref.
3+
Sc Li4Ti4.95Sc0.05O12d Spinel 16d Smaller particle size and higher specific surface area, improved [354]
rate performance and cycling stability

Cu2+ Li4Ti5CuxO12+x Spinel (x  0.6) / Improved rate performance [355]


(x = 0, 0.075, 0.15, 0.3, 0.6, 1.20, 1.67) Spinel + TiO2 + CuO
(x = 1.20, 1.67)
Li4xCuxTi5O12 (x = 0, 0.1, 0.2) Spinel / Decreased charge transfer resistance, improved cycling [356]
stability and rate capability
Li42xCu3xTi5xO12 (0  x  0.15) Spinel 16d Enhanced electronic conductivity and Li+ diffusion coefficient [357]
by at least two orders of magnitude and four times,
respectively. After further introducing CNTs, Li3.8Cu0.3Ti4.9O12/
CNTs delivered 114 mA h g1 at 10 C, whereas that of Li4Ti5O12
is only 11 mA h g1

Zn2+ LiZn0.5Ti1.5O4 Spinel (disordered) Fd3m: 8a, 16d; / [358]


¯
P4332: 8c, 4b
Li2xZn2–3xTi1+xO4 (0.33  x  0.67) Spinel (Fd3m, P4132 8a, 16d Maximal lithium conductivity while lithium initially [359]
¯
or P4332) completely occupies 8a sites
Li4Ti5xZnxO12 (0  x  0.2) Spinel 16d Improved lithium ion diffusion coefficient, higher and more [360]
stable cycling performance at high rate of 5 C (180 mA h g1,
x = 0.2, 0–2.5 V)
Li3.95Zn0.05Ti5O12 Spinel / Thinner thickness of nanosheets, larger specific surface area [361]
(about twice compared to that of Li4Ti5O12), and enhanced rate
performance
Li4Ti4.95Zn0.05O12 Spinel / Higher capacity and improved rate performance (0–2.5 V) [362]
Li4Ti4.95Zn0.05O12 Spinel 16d Higher capacity and improved rate performance (0–2.5 V) [363]

Na+ Li4xNaxTi5O12 (0  x  0.2) Spinel / Smaller particle size, enhaced ionic and electronic conductivity, [364]
and rate capability (x = 0.1, 0.15)
NaxLi4xTi5O12 Spinel + 4.3% TiO2 8a Expanded oxygen framework and facilitated Li ion diffusion, [365]
(Na0.24Li3.93Ti5.00O12, by ICP-AES) enhanced rate capability and cycling performance
Li4xNaxTi5O12 (x = 0, 1, 2, 3, 4) Spinel + Li2TiO3 (x = 0) Substituting Low operation potential, decreased rate performance [366]
Spinel + Li2TiO3 + instead doping
NaLiTi3O7 (x = 1)
NaLiTi3O7 (x = 2)
NaLiTi3O7 + Na4Ti5O12
(x = 3)
Na4Ti5O12 (x = 4)
K+ Li4xKxTi5O12 Spinel / Good rate capability and cycling stability (x = 0.04), [367]
(x = 0.02, 0.04, 0.06) 138 mA h g1 at 3 C (138 mA h g1 after 200 cycles),
121 mA h g1 at 5 C
Ag+ Ag-Li4Ti5O12 Spinel + Ag Ag did not enter Improved electronic conductivity, high rate discharge capacity [368]
and cycling stability
Fe3+ Li1+xM13xTi1+2xO4 Spinel 8a Great capacity fade for M = Ni [380]
Ni3+ M = Fe, Ni, Cr (x = 0.30) 16d
Cr3+ 16d

Ni2+ Li(Ni1/6Li2/9Ti1/9)Ti3/2O4 Spinel 16d Enhanced rate capability and good cycling stability [381]
Li42xNi3xTi5xO12 (0  x  0.25) Spinel 16d Improved electronic conductivity (3.1  108 S cm1, x = 0.075) [341]
and rate performance

Ca2+ Li4xCaxTi5O12 Spinel 8a Improved rate capability and cycling stability, especially for [369]
(x = 0, 0.05, 0.1, 0.15, 0.2) x = 0.1
Li3.9Ca0.1Ti5O12 Spinel 8a Higher specific capacity, better cycling stability and improved [370]
rate capability (0–2.5 V)
Sr2+ Sr-doped Li4Ti5O12 (Sr/Ti = 0.01/1, Spinel + SrLi2Ti6O14 May be 8a Smaller particle size, decreased charge transfer resistance, and [371]
0.02/1, 0.03/1, mol/mol) enhanced the rate capability with a capacity of about
1.62 times that of Li4Ti5O12 at 5 C; SrLi2Ti6O14 impurity also
makes a contribution to the specific capacity
Y3+ Y-doped Li4Ti5O12 (Y/Ti = 0.004/1, Spinel / Enhanced electronic and ionic conductivities, excellent long- [372]
0.008/1, 0.012/1, 0.016/1, term cyclability (over 1000 cycles) at 10 C and outstanding rate
0.02/1, mol/mol) capabilities (especially for the sample of Y/Ti = 0.012/1)
Nd3+ Li4Ti5xNdxO12 Spinel / Improved rate capability, Li4Ti4.98Nd0.02O12 exhibited excellent [373]
(x = 0, 0.01, 0.02, 0.03) rate capability and cycling stability at 5 C even without
conductive additive
Ru4+ Li4Ti5xRuxO12 Spinel (+RuO2, / Li4Ti4.95Ru0.05O12 shows the best rate performance and cycling [374]
(x = 0, 0.05, 0.10, 0.15) x = 0.10, 0.15) stability with a capacity of 131 mA h g1 over 100 cycles even at
17,500 mA g1 (0.01–2.5 V)

W6+ Li4Ti4.95W0.05O12 Spinel / Improved cycling stability and rate performance with a [375]
capacity of 118.6 mA h g1 at 20 C compared to that
(69.2 mA h g1) of undoped Li4Ti5O12
Li4Ti5xWxO12 Spinel 16d Improved electronic conductivity (1.5  101 S cm1, x = 0.1), [376]
(x = 0.05, 0.1, 0.15, 0.2) rate capability and cycling stability
Li4Ti5xWxO12xBrx Spinel 16d Increased electrical conductivity and Li+ diffusion coefficient, [377]
(x = 0.025, 0.050, 0.100) and further electrochemical performance by W6+ and Br
co-doping
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 45

Table 1 (Continued )

Dopant Structural formula, doping amount Phase structure Doping site Change after doping Ref.

F Li4Ti5O12xFx (0  x  0.5) Spinel 32e Improved rate capability (0.01–2.5 V), the best performance [378]
was achieved when x = 0.3
Li4Ti5O12xFx (x = 0.174, by XPS) Spinel 32e Increased electronic conductivity through Ti3+ generation, [379]
increased the robustness of structure, improved rate capability
(144, 123, 108, 91, and 60 mA h g1 at 5, 10, 30, 60, and 140 C,
respectively) and cycling stability
Br Li4Ti5xWxO12xBrx Spinel 32e Increased electrical conductivity and Li+ diffusion coefficient, [377]
(x = 0.025, 0.050, 0.100) and further electrochemical performance by W6+ and Br co-
doping

doping amount, phase structure, doping site and change after through the formation of Ti3+. Such dopants are typically +5
doping. cations, such as V5+, Ta5+, Nb5+ and Sb5+, or even +6 cation like W6+
Based on the defect equilibrium, the doping of an aliovalent [376]. In real synthetic conditions, the doping of Ti4+ with a high-
cation at a higher oxidation state into the tetrahedral 8a lithium valence-state cation may not necessarily lead to the formation of
sites or the octahedral 16d sites or an anion with a lower oxidation Ti3+ because the charge compensation may also conduct through
state into the O2 site, such as F and Br, can promote the the formation of a Li+ cation vacancy or a Ti4+ cation vacancy. When
formation of Ti3+ in the lattice, thus increasing the electron the charge compensation occurs through a Li vacancy, an increase
concentration in the bulk. The increase in electronic conductivity in Li-ion conductivity, not the electronic conductivity, is expected
improves the electrochemical performance of the Li4Ti5O12, compared with pristine Li4Ti5O12, while no significant increase in
especially the rate performance, if the polarization resistance of either the electronic conductivity or the Li-ion ionic conductivity is
the electrode process primarily derives from the electron charge likely if the defect model is in the form of a Ti vacancy. A typical
transfer. An Mg-substituted lithium titanate spinel provides a example is Ta-doped Li4Ti5O12. Wolfenstine et al. synthesized and
typical example of the successful doping of the tetrahedral 8a site investigated 1% Ta-doped Li4Ti5O12 [319] and found that the
in Li4Ti5O12 (at least partially) with a cation at a higher valence sample prepared via heat-treatment under an oxidizing atmo-
state to increase the electronic conductivity. Chen et al. synthe- sphere had a conductivity similar to that of pristine Li4Ti5O12, with
sized Li4xMgxTiO12 (0  x  1) via a solid-state reaction at an a value of approximately 1  109 S cm1. This result implies that
elevated temperature under a 3% H2–He reducing atmosphere the charge compensation due to the Ta5+ doping likely occurred
[10]. Powder XRD demonstrated that the substitution of Mg2+ for through the formation of a Ti vacancy. However, when calcined
Li+ in the structure did not affect the crystalline structure of the under a dilute hydrogen atmosphere, the Li4Ti4.95Ta0.05O12 sample
oxide at 0  x  0.75; however, additional peaks were observed for reached a much higher conductivity of 1  103 S cm1 in
samples at x > 0.75, which were attributable to small concentra- comparison with 3  105 S cm1 for the pristine Li4Ti5O12
tions of Li2MgTi3O8 and MgTi2O5 in the samples. The Mg cations synthesized under similar conditions, suggesting that the charge
were found to be distributed over both the tetrahedral (8a) sites compensation occurred primarily through the formation of Ti3+ in
and the octahedral (16d) sites of the cubic spinel structure (Fd- the oxide lattice.
3 m). Rietveld refinement for the compound with a nominal Among the various dopants, Mn2+, Al3+, Fe3+, Cr3+, Ni3+ and V5+
composition of Li3.5Mg0.5Ti0.5O12 showed that approximately 18% have been investigated most thoroughly. Based on the primary
of the tetrahedral sites were occupied by magnesium. The results of XAS measurements, Kubiak et al. claimed that Mn was
conductivity increased by many orders of magnitude from located as Mn4+ in the Mn-doped Li4Ti5O12, most likely on both the
s  1013 S cm1 for the pristine Li4Ti5O12 (x = 0) to tetrahedral and octahedral sites [329]. Capsoni et al. studied the
s  102 S cm1 for Li3MgTi5O12 (x = 1.0), although the reduction cation distribution and valence states in the Mn-substituted
of Ti4+ in Li4xMgxTi5O12 by the reducing atmosphere during the Li4Ti5O12 structure with a Mn-doping content of up to 30% of the Ti
calcination may also contribute to the high electronic conductivity. ions using a combination of X-ray powder diffraction, electron
The improved conductivity decreased the area-specific impedance paramagnetic resonance (EPR), 7Li MASNMR, and impedance
of the Li/Li4xMgxTi5O12 cells and increased the rate capability of spectroscopy techniques [330]. Mn was found to occupy both the
the electrodes for a small value of x. For example, Li3.75Mg0.25Ti5O12 tetrahedral 8a sites and the octahedral 16d sites, and the quantity
delivered a capacity of 63 mA h g1 at 17 C, which is nearly 50% of of Mn in the tetrahedral sites increased with an increase in the Mn
the capacity obtained at a C/2 rate (135 mA h g1). dopant from 3 to 10%, then remained constant with further
Dopants including Al3+, Mn4+, Fe3+, V4+ and Sn4+ were also able increases in the Mn dopant. All Mn was in the 2+ or 3+ valence
to incorporate into the tetrahedral 8a sites to some extent state; no Mn4+ was detected. Based on the EPR data, Mn2+ was
[311]. However, doping at the tetrahedral 8a sites is detrimental found to occupy only the tetrahedral sites, until a nearly constant
to the lithium-ion conductivity because it can reduce the Li+ value of 10% was reached for the Mn-substituted samples. The
concentration in the 8a sites. If the lithium bulk diffusion is the Mn3+ ions occupied both octahedral and tetrahedral sites, with a
principal controlling step for lithium insertion into Li4Ti5O12, a constant value in the tetrahedral sites (0.013), independent of the
decreased rate capability is expected. The reversible capacity of total quantity of Mn. The differences between Kubiak’s and
Mg-substituted Li4xMgxTi5O12 at a high Mg content was found to Capsoni’s observations of the Mn oxidation states strongly
be inferior to that of pristine Li4Ti5O12 [10]. suggests the significant impact of the synthetic method on the
To maintain a high capacity, doping of the octahedral 16d sites oxidation state of the multivalent dopant (Mn).
is preferred. Some elements are found to preferentially dope into A Cr- and Ni-doped Li4Ti5O12 compound has been characterized
the octahedral 16d sites, including Ni3+, Cr3+ and Mo4+ [313], while through the combined use of XRD, EPR, 7Li MASNMR, micro-
many other elements are able to dope into both the tetrahedral 8a Raman and magnetization measurements [338]. According to the
sites and the octahedral 16d sites, such as Mg2+, Al3+, Mn4+, Fe3+, structural refinement, supported by the neutron diffraction studies
V4+ and Sn4+. To increase the electronic conductivity by doping at of Cr-doped Li4Ti5O12, the Cr insertion into the spinel lattice
the octahedral 16d Ti4+ sites, the dopants should have a higher occurred in both the octahedral 16d Ti and Li sites. The electronic
valence state than Ti4+ to increase the electron concentration conductivity of the Cr-doped Li4Ti5O12 was slightly higher than
46 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

that of the pristine Li4Ti5O12 because the Cr 3d bands are close to compared with that of pristine Li4Ti5O12 was attributed to the
the Ti 3d bands. The Rietveld refinement suggests that Ni also fact that Li(Ni1/6Li2/9Ti1/9)Ti3/2O4 has an electronic conductivity of
inserted exclusively into the octahedral spinel site. The Ni-doped (108 S cm1) that is three orders of magnitude higher than that
Li4Ti5O12 oxides were found to have a lower electronic conductivi- of Li(Li1/3Ti5/3)O4 (1011 S cm1). The improved cycling stability
ty than the pristine Li4Ti5O12 because the Ni 3d bands are localized over that reported by Robertson et al. is likely due to the increased
and the electrons were not easily excited. Ganesan specifically ending potential applied in this study (1.0 V), which may avoid the
investigated the electrochemical performance of Cr-doped deep reduction of Ni2+ in the lattice.
Li4Ti5O12 with the nominal composition of Li4Ti2.5Cr2.5O12 Among the various dopants, Fe3+ is of particular interest due to
[339]. CV studies showed a shift in the discharge potential by its abundance and nontoxicity. Several composites with nominal
approximately 40 mW from 1.54 V for Li4Ti5O12 to 1.50 V for compositions of Li0.5+0.5xFe2.51.5xTixO4 (0  x  1.66) were syn-
Li4Ti2.5Cr2.5O12. This shift is interesting because a reduction in the thesized and characterized by Scharner et al. [333]. XRD and 57Fe
de-lithiation voltage can increase the operation potential and thus Mossbauer spectroscopy characterization demonstrated the ideal
the energy density of a cell. Based on the impedance study, lithium spinel structure with space group Fd3m was successfully obtained
¯
mobilities of 2.94  106 and 5.13  106 cm2 V1 s1 were found for the composites in the ranges of 0.4  x  1.2 and
for Li4Ti5O12 and Li4Ti2.5Cr2.5O12, respectively, implying that the 1.57  x  1.66, while ordered structures with the P4332 space
charge neutrality compensation from the Cr3+ doping likely group were observed for the composites in the ranges of
occurred, at least in part, through the formation of a lithium 0  x  0.4 and 1.2  x  1.57. Robertson et al. used neutron
vacancy. As a result, an improved capacity and cycling stability was refinement of Li1.3Fe0.1Ti1.6O4 (M = Fe, Ni, Cr) to demonstrate that
observed at higher rates after the Cr doping. Recently, Song et al. the iron occupied the tetrahedral 8a sites of the spinel structure,
discovered an interesting phenomenon that Cr3+-ion doping in while Ni and Cr occupied only the 16d octahedral sites [380], which
Li4Ti5O12 resulted in a decrease of structural disorder (Fig. 54), was in good agreement with the observations of Capsoni et al.
which was different from the common understanding that doping [338]. The structure of the iron-substituted lithium-titanium
may introduce a lattice defect [340]. These researchers first spinels with nominal compositions of Li1.3Fe0.1Ti1.6O4 (Fd3m) and
¯
observed the decreased structural disorder upon Cr doping using Li1.25Fe0.25Ti1.5O3 (P4332) were further investigated in detail by
Rietveld refinement of high-resolution powder diffraction, which Reale et al. [336]. Based on the Rietveld refinement, most of the
demonstrated that the oxygen parameter was more reliable for Cr- iron in Li1.3Fe0.1Ti1.6O4 was found to preferably occupy the
doped Li4Ti5O12. The phenomenon was then confirmed by analysis tetrahedral 8a sites, leading to a stoichiometry that can be written
of the Debye-Waller factor in EXAFS and absorption edge in XANES. as (Li0.91Fe0.09)(8a)[Li0.39Fe0.01Ti1.6](16d)O4(32e). In contrast, the
Moreover, the EELS results and DFT calculations revealed that the Li1.25Fe0.25Ti1.5O4 appeared isotropic to the Li0.5Fe2.5O4, indexed
reason for structural phenomenon was due to the charge in the P4332 space group with a formula written as Li0.5(4b)(Li0.75-
redistribution. Because of the increased lithium ion diffusivity Fe0.25)(8c) Ti1.5(12d)O4(8c,24e). These electrodes had reversible
due to the decreased structural disorder upon doping and capacities of 160–180 mA h g1 at 0.2 C in the 2.9–0.2 V potential
increased electronic conductivity due to impurity band formation range. Their electrochemical lithium insertion–extraction process-
upon doping, the Li4x/3Ti52x/3CrxO12 (x = 0.25) exhibited a high es respond quite differently to that of a pure Li4Ti5O12 electrode—
discharge capacity of 125 mA h g1 at 10 C, which was approxi- several one-phase and two-phase steps involved the electrochem-
mately twice that of undoped Li4Ti5O12. Although Li1.3Ni0.1Ti1.6O4 ical reduction/oxidation of both Ti4+ and Fe3+.
has a higher first discharge capacity than pristine Li4Ti5O12 in the The maximum quantity of lithium that can be incorporated into
potential range of 2.00–0.01 V, it had a higher capacity fading rate the spinel lattice is fixed, and the dopants by themselves typically do
during cycling, suggesting that Ni may be not an ideal dopant for not contribute additional lithium storage. Therefore, to increase the
Li4Ti5O12 [380]. Kim et al. produced a comparative study of pristine gravimetric energy density, a dopant with a small weight number is
Li4Ti5O12 and Ni-incorporated Li(Ni1/2xLi2x/3Tix/3)Ti3/2O4 (x = 1/3) preferred. Due to its light weight and its stability in an octahedral
anodes for use in rechargeable Li batteries [381]. Based on the environmental, Al3+ has attracted attention as a dopant for
Rietveld refinement of the XRPD, the Ni was completely doped into Li4Ti5O12. Huang et al. were the first to synthesize Li4Ti5O12-based
the 16d Li+ and Ti4+ sites, as expected. The Ni K-edge XANES spectra composites with the nominal composition of Li4AlyTi5yO12 (y = 0,
indicated that the nickel was primarily in a 2+ oxidation state. The 0.10, 0.15, 0.25) by a solid-state reaction [346]. The spinel phase with
Li(Ni1/6Li2/9Ti1/9)Ti3/2O4 exhibited a progressive decay in its an Fd-3 m space group was observed for all samples, although a
capacity over the first five cycles at 0.2 C; however, the capacity small quantity of LiAlO2 was detected at x = 0.25. The particle
was stabilized during subsequent cycling at various rates within a aggregation was clearly alleviated after the Al3+ doping. The
potential range of 1.0–2.5 V. The improved rate capability Li4AlyTi5yO12 (y = 0.10, 0.15) exhibited improved electrochemical

Fig. 54. Simulated structure of Li4x/3Ti52x/3CrxO12 in the [110] direction for (a) x = 0 and (b) x = 0.25. To more clearly demonstrate the difference, the bond angle is somewhat
exaggerated. Li is purple, Ti is gray, and O is red [340]. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 47

performance over that of pristine Li4Ti5O12. Among the various Li4Ti5O12. Electrochemical impedance spectroscopy (EIS) demon-
samples, Li4Al0.15Ti4.85O12 exhibited the largest reversible capacity strated that Li4Ti4.9V0.1O12 had a faster lithium-ion diffusivity than
and the highest columbic efficiency, with a discharge capacity in the that of Li4Ti5O12 with lithium diffusion coefficients of 6.5  1013
first and second capacity of 195.6 and 173.6 mA h g1, respectively, and 2.7  1015 cm2 s1, respectively. Between 1.0 and 2.5 V, the
within a discharge potential range of 2.5–0.5 V. Zhao et al. discharge capacities reached 166 and 117.3 mA h g1 at 0.5 and
synthesized and investigated an Al-doped Li4Ti5O12 with the 5 C, respectively. Li4Ti4.9V0.1O12 also exhibited a long-term
nominal composition Li4xAlxTi5O12 as an anodic material for LIBs cyclability, retaining over 97.9% of its initial discharge capacity
[343]. The incorporation of Al into Li4Ti5O12 lattice did not affect the beyond 1713 cycles at a rate of 2 C.
phase composition and the particulate morphology at x = 0.05 but Wang et al. [355] investigated copper as a dopant for
easily resulted in a lattice distortion and thus poor crystallinity of the Li4Ti5O12. Although copper was successfully doped into the lattice
oxide. The Li3.9Al0.1Ti5O12 exhibited an excellent cycling stability structure by synthesis under an oxidizing atmosphere, Cu2+ was
compared with that of pristine Li4Ti5O12. Wang et al. synthesized a reduced to the metallic element after the first discharge process.
carbon-coated Li4Ti4.95Al0.05O12/C via a solid-state reaction for use in Thus, it acted as a conductive modifier of the Li4Ti5O12 surface
a lithium-ion battery with discharge voltage down to 0 V during the subsequent cycling. Silver was also studied as a dopant
[345]. Based on the slight shift in the diffraction peak to a lower for Li4Ti5O12 [368]. However, the as-obtained sample was actually
2u angle, the authors concluded that the Al3+ was successfully doped a composite of metallic silver and the Li4Ti5O12 spinel phase, even
into the 16d octahedral site as targeted. The pristine Li4Ti5O12, though the synthesis was performed under an oxidized atmo-
Li4Ti5O12/C and Li4Ti4.95Al0.05O12/C have electrical conductivities of sphere (air). Although silver is a metal with ultrahigh electronic
8.2  108, 7.9  106 and 1.1  105 S cm1, respectively. The conductivity, its application as a surface modifier is not practical
Li4Ti4.95Al0.05O12/C has a slightly higher electrical conductivity than given its high price and heavy weight.
the Li4Ti5O12/C. However, such a small difference likely originated Although many dopants have been studied, improvements in
from experimental errors. The Li4Ti4.95Al0.05O12/C exhibited im- the electrochemical performance of Li4Ti5O12 via doping, in
proved initial capacity, cycling performance, and a discharge particular the rate capability and cycling stability, are minor
capacity reaching 248 mA h g1 after 50 cycles. The discharge compared with nanostructuring or surface coating. In some cases,
capacity for the Li4Ti5O12/C decreased to 226 mA h g1 between the doping was actually detrimental. Better dopant or doping
2.5 and 0.0 V. The capacity difference for the two samples was less mechanisms must be developed. Currently, most research has
significant when the discharge was conducted between 2.5 and focused on single cation doping. A synergistic effect may be created
1.0 V. Thus, the Al3+ doping seemed to improve the reversible by applying two or more dopants, thus significantly improving the
capacity between 1.0 and 0.0 V for the spinel lithium titanate. Cai electrochemical performance of the Li4Ti5O12 electrodes. Co-
et al. synthesized an Al-doped Li4Ti5O12 compound with a nominal doping was well exploited in ABO3 perovskite oxides to tailor
composition of Li4Ti4.85Al0.15O12 via a cellulose-assisted glycine– their properties over a wide range. However, co-doping with two
nitrate combustion method [344]. The Al3+ doping did not affect the or more elements was seldom applied to Li4Ti5O12. This subject
phase structure but increased the surface area and decreased the may be actively researched in the future. Both nanostructuring and
crystalline size possibly due to the increased crystal face energy of surface coating change only the surface properties. Once the
the oxide. The electrical conductivities of pristine Li4Ti5O12 and surface properties were well optimized, a further increase in the
Li4Al0.15Ti4.85O12 as measured by 4-probe DC method were electrode performance requires the modification of the bulk
7.0  108 and 4.0  107 S cm1, suggesting that most of the properties of the oxides. Doping is the only strategy that can
Al3+ was doped into the octahedral 16d Ti4+ site. A lithium diffusion modify the bulk properties. The development of advanced
coefficient of 4.03  1010 cm2 s1 was observed for the Li4Al0.15- Li4Ti5O12 anode materials by combining two or three strategies
Ti4.85O12, which is lower than the pristine Li4Ti5O12 value of can further improve their electrochemical performance, such as
5.43  109 cm2 s1. A small quantity of Al3+ may have been the recently reported porous Zr-doped Li4Ti5O12 microspheres
partially doped into the 8a tetrahedral Li+ site, which caused a block [382], 1D Na-doped Li4Ti5O12 nanorods [365], Fe2+ or Cr3+ doped
against lithium diffusion within the oxide lattice. The improved Li4Ti5O12/multi-wall carbon nanotube (MWCNT) composites
capacity and rate capability of the Li4Al0.15Ti4.85O12 over the [383], and Cu-doped Li4Ti5O12–TiO2 Nanosheets [384]. Ma et al.
Li4Ti5O12 were attributed to the increased surface area of the oxide developed a carbon-encapsulated F-doped Li4Ti5O12 composite
caused by the inhibited sintering effect of the aluminum. with a ball-in-ball structure via a hydrothermal synthesis and
Vanadium has also been investigated as a dopant for Li4Ti5O12 subsequent solid-state lithiation at high temperatures (Fig. 55)
due to its high valence state, wide availability and low weight. Yi [379], which delivered remarkable cycle stability with a capacity of
et al. synthesized and characterized Li4Ti5xVxO12 (0  x 0.3) 159 mA h g1 after 200 cycles at 1 C and outstanding rate
with a wide range of V content [315,316]. The XRD and Raman capability with specific capacities of 162, 144, 123, 108, 91, and
spectra demonstrated that the V5+ partially substituted the Ti4+ 60 mA h g1 at 1, 5, 10, 30, 60, and 140 C, respectively, due to the
and Li+ in the spinel. Li4Ti4.95V0.05O12 had the highest initial combined effect of fluoride doping, unique ball-in-ball microstruc-
discharge capacity and cycling performance among the samples ture, and presence of carbon. Thus, nanostructuring, surface
cycled between 1.0 and 2.0 V, while Li4Ti4.9V0.1O12 had the highest coating and doping could be conducted simultaneously to
initial discharge capacity and best cycling performance among the significantly improve the properties and performance of Li4Ti5O12
samples cycled between 0.0 and 2.0 V or between 0.5 and 2.0 V. spinel oxides, including their capacity, rate capability and cycling
Li4Ti4.95V0.05O12 exhibited excellent cycling performance between stability, and to promote their practical application as power
1.0 and 2.0 V. The capacities of Li4Ti4.9V0.1O12 reached sources for energy storage or EVs and HEVs.
183 mA h g1 after 100 cycles between 0.5 and 2.0 V and
229 mA h g1 after 130 cycles between 0.0 and 2.0 V. Yu et al. 3.5. Formation of composite
synthesized Li4Ti4.9V0.1O12 nanometric powders via a facile solid-
state reaction method under an inert atmosphere [317]. The In addition to nanostructuring, doping, morphological optimi-
electronic conductivity of the Li4Ti4.9V0.1O12 powders reached zation and surface coating, the electrode performance of Li4Ti5O12
2.9  101 S cm1, which could be attributed to the transformation can be improved by forming a composite with a different material
of some Ti4+ to Ti3+. The Li4Ti4.9V0.1O12 powders also had smaller [47,257,280,385]. The second phase can be an electron conductor
particles and a narrower particle size distribution than the pristine such as carbon, a lithium-ion conductor, or a mixed electron and
48 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 55. (a) Schematic of the preparation of carbon-encapsulated F-doped Li4Ti5O12 composites, (b) FE-SEM image of carbon-encapsulated F-doped Li4Ti5O12 composites at
low magnification; the inset in (b) is a TEM image of a single particle, (c) cycle stability of carbon-encapsulated F-doped Li4Ti5O12 composites at different C rates [379].

lithium-ion conductor. The electrodes in conventional LIBs can also have negligible lithium insertion capacity at potentials approach-
be treated as composites because large quantities of binders and ing 1.0 V, which is often selected as the end of discharge voltage for
conductive additives were added to the active material to improve a Li4Ti5O12 electrode, their content in the composite electrodes
the adhesion of the electrode to the current collector and to should remain at a low level to minimize the detrimental effect on
increase the current collection efficiency. The carbon-coated the gravimetric energy density. Researchers are currently inter-
Li4Ti5O12 may also be treated as a composite electrode, which ested in composite electrodes formed with electronically conduc-
has a specific core-shell morphological structure with low second- tive lithium-insertion materials as the second phase such as
phase content (typically less than 5 wt.%). By forming a composite metallic tin, which is a well-known lithium insertion host with a
electrode, the apparent electronic conductivity and lithium-ion high reversible capacity [403–405]. Sn is an attractive second
conductivity may both be improved. Another advantage to a phase because it can be easily electrochemically reduced from
composite electrode is that the second phase may also act as a SnO2; thus, the synthesis can be conveniently conducted under an
support to improve the mechanical properties of the electrode so oxidant atmosphere (air).
that the quantity of binder may be reduced or even omitted Interfacial design is a unique way to tune the electron/ion
completely, which can improve the gravimetric energy density, conducting properties of materials. This method has also received
operational safety and cycling life of the electrode as side reactions considerable attention for its ability to improve the performance of
between the binder and other additives within the liquid electrodes in LIBs including Li4Ti5O12. For polycrystalline materials,
electrolyte can be minimized or avoided. The electrodes can also the conduction of electrons and ions involves not only the surface
be prepared as self-standing thin films without the application of and bulk diffusion but also the grain boundary diffusion. For some
any additional binder or conductive additive. materials, the diffusion rate of the charges around the grain
Compounds with high electronic conductivity, such as amor- boundary may be higher than that of the bulk [311,406]. By
phous carbon [386–390], graphene [391–393], carbon nanotubes increasing the grain boundary density, the apparent conductivity of
[394,395], ordered porous carbon (CMK-3 [396,397], and ordered the materials may be significantly improved. Grain boundaries have
bimodal mesoporous carbon [398]) and other carbon materials been reported to act as either channels to allow Li+ to enter the
(Ketjen Black [399], Super P [400], carbon black Vulcan XC72R particles or as lithium reservoirs [407,408]. By tailoring the
[401]) are applied to form composite electrodes with Li4Ti5O12. In properties of the grain boundaries, both the electron and lithium-
addition, metals such as copper and silver have recently been ion transport properties of the polycrystalline Li4Ti5O12 may be
tested. Such second phases perform primarily as conductive improved, leading to a possible improvement in the rate perfor-
networks in the electrode to increase the current collection mance. By forming a composite, not only can the grain boundary
efficiency. For example, Wang et al. reported a composite electrode density be improved but also the grain boundary properties. In
with Li4Ti5O12 nanoparticles loaded on a bicontinuous Cu scaffold addition, the morphological stability may be further improved if
as shown in Fig. 56a and b [402]. The composite Li4Ti5O12/Cu several materials are combined in an appropriately structured
electrode exhibited ultrafast lithium storage properties with a composite. For example, a binary Li4Ti5O12–TiO2 composite was
specific capacity of 127 mA h g1 at a rate of 80 C (Fig. 56c) and synthesized and investigated as a novel electrode for LIBs and
excellent cycling stability at rate of 1 C for 2000 cycles (Fig. 56d). exhibited improved performance over pristine Li4Ti5O12 [409,410].
The structure of the as-obtained Li4Ti5O12 was further analyzed
(Fig. 56e) to understand the capacity of the composite at a low rate, 3.5.1. Li4Ti5O12/graphene
which was slightly higher than the theoretical value due to the Graphene is a 2D one-atom-thick sheet of carbon arranged in a
surface effect as shown in Fig. 9b. Because these conductive phases honeycomb network. Since its first successful isolation in 2004
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 49

Fig. 56. (a) Schematic illustration of a new ‘one stone, two birds’ strategy to fabricate a bicontinuous Li4Ti5O12/Cu electrode via a three-dimensional nanoporous Cu scaffold
template route, where Li4Ti5O12 nanoparticles can be encapsulated into the Cu nanopores. (b) TEM image of the Li4Ti5O12/Cu sample. The inset shows the schematic drawing
of the Li4Ti5O12/Cu. (c) Rate capabilities of Li4Ti5O12/Cu electrode. (d) The cycling performance and corresponding Coulombic efficiency of Li4Ti5O12/Cu electrode at 1 C. (e) The
enlarged (FFT inverse) image of Li4Ti5O12 nanoparticles taken from Li4Ti5O12/Cu composite, where the black holes denote the 16c (vacancy) sites and Li2 represents Li1/3Ti5/3.
[402].

[411], graphene has attracted intense interest from both the from 53.9 V for the pristine electrode to only 36.3 V after the
experimental and theoretical scientific communities because of its formation of the composite with graphene. A capacity of
unique properties. Due to its excellent thermal and electrical 132.2 mA h g1 was retained at 20 C for the first discharge and a
conductivities in two dimensions, its superior mechanical capacity of 124 mA h g1 was maintained after 300 cycles.
strength, its high flexibility and high specific surface area However, a trade-off exists between the improvement in electrical
(>2600 m2 g1), graphene’s application in energy production conductivity and the decrease in the initial columbic efficiency.
and storage has received considerable attention [412]. Although Guo et al. synthesized a carbon-coated Li4Ti5O12/graphene
it has poor reversible capacity to perform alone as an anode in LIBs composite by the ball milling of carbon-coated TiO2, Li2CO3, and
[413], many graphene-based composites have been investigated graphene in hexamethylene [419]. The carbon pre-coated on TiO2
for use in LIBs to improve the electronic conductivities and successfully avoided the aggregation and agglomeration of the
mechanical properties of the electrodes [414–416]. Li4Ti5O12 particles and optimized the combination between
The formation of a Li4Ti5O12/graphene composite to avoid Li4Ti5O12 particles and graphene sheets. The resultant composite
aggregation of the Li4Ti5O12 nanoparticles and to increase the exhibited a greatly improved electrochemical performance with a
apparent conductivity of the electrode has been recently reported capacity of approximately 102 mA h g1 at 10 C compared with
[391–393,417–420]. Apart from its excellent conductivity, the high that of a Li4Ti5O12/graphene composite (40 mA h g1) or pure
surface area of graphene can also improve the interfacial contact Li4Ti5O12 (30 mA h g1). Oh et al. successfully prepared gra-
with poorly conducting particles. The Li4Ti5O12 nanoparticles phene-wrapped Li4Ti5O12 via a solid-state reaction between
attached to graphene also effectively prevented the aggregation graphene-oxide-wrapped TiO2 and Li2CO3 [420]. The graphene-
and restacking of the graphene to maintain their large active oxide-wrapped TiO2 was prepared from TiO2 and graphene oxide
contact area between the electrode and liquid electrolyte. As a solution at pH 2 via electrostatic interactions. The as-prepared
result, the electrode performance, especially its rate capability, Li4Ti5O12 was wrapped with wrinkled-flexible graphene. The effect
may be improved even with very a low content of graphene of different amounts (1.0, 2.1, 4.5 wt.%) of graphene on the
[391,421]. Zhu et al. used 1 wt.% graphene as a conductive agent to electrochemical performance was investigated. The graphene-
fabricate graphene-embedded Li4Ti5O12 nanofibers that exhibited wrapped Li4Ti5O12 with 2.1 wt.% graphene exhibited outstanding
greatly improved surface conductivity and rate capability performance with a specific capacity of 147 mA h g1 at 10 C after
[391]. Zhang et al. introduced 1.86 wt.% graphene into Li4Ti5O12 100 cycles, which was also expected to be beneficial for the tap
powders by mixing Li4Ti5O12 with graphene oxide dispersion and density based on its stacking and relatively large particle size
further reducing, resulting in a significantly improved rate (150 nm). Xiang et al. prepared a Li4Ti5O12/graphene composite
capability with approximately twice the capacity at 20 C compared by applying graphene, obtained from the thermal expansion of
with that without graphene, even though the effect of the possible graphene oxide at elevated temperatures, as an additive to a
reduction of Ti4+ on the electrochemical performance has not been solution precursor for the sol–gel synthesis of Li4Ti5O12 [393]. The
considered [417]. Shi et al. prepared a Li4Ti5O12/graphene presence of graphene in the sol–gel synthesis effectively sup-
composite via the ball milling of Li4Ti5O12 powders with 5 wt.% pressed the grain growth of the Li4Ti5O12 phase during the
graphene [392]. The Li4Ti5O12 particles were found to be well calcination. At a rate of 0.2 C and a discharge–charge potential
dispersed among the graphene sheets, and the graphene extended range of 1.0–2.5 V, both the pristine Li4Ti5O12 and its composite
in all directions as in a stretched network, providing a conductive with 7.5 wt.% graphene had a similar capacity of approximately
connection between the Li4Ti5O12 particles. The charge transfer 175 mA h g1; however, at a rate of 10 C, the reversible capacity of
resistance at the Li4Ti5O12/liquid electrolyte interface decreased the Li4Ti5O12/graphene (146 mA h g1) is higher than that of the
50 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

pristine Li4Ti5O12 (131 mA h g1). In addition, the cycling stability posite with even a low graphene content of 3.5 wt.%. In the
was also improved at a rate of 10 C between 1.0 and 2.5 V. Such presence of graphene, the particle sizes of the as-obtained
improvement was attributed to the increased electronic conduc- Li4Ti5O12 in the composite were 20–50 nm (Fig. 57b), which were
tivity from the introduction of graphene. When the end of definitely smaller than that of pure Li4Ti5O12 (50–100 nm, Fig. 57c)
discharge potential extended to 0.0 V, the Li4Ti5O12/graphene prepared in the same fashion. Accordingly, the Li4Ti5O12/graphene
exhibited a reversible capacity of 228 mA h g1 compared with composite exhibited much better rate performance compared to
185 mA h g1 for the pristine Li4Ti5O12, suggesting a contribution that of pure Li4Ti5O12 (Fig. 57d) [424]. Chen et al. successfully
to the lithium reversible storage by graphene. Ding et al. synthesized mesoporous single crystal Li4Ti5O12 on reduced
successfully introduced 3 wt.% graphene into the hydrothermal graphene oxide through a route including preparation of TiO2/
synthesis of Li4Ti5O12 nanosheets [422]. The as-obtained Li4Ti5O12/ graphene using reflux reaction and hydrothermal reaction,
graphene demonstrated enhanced electrochemical performance chemical lithiation using hydrothermal reaction with LiOH, and
with a specific capacity of more than 120 mA h g1 at 1600 mA g1 final heat-treatment at 600 8C [425]. The as-synthesized composite
after 200 cycles compared with that of bare Li4Ti5O12 nanosheets exhibited high specific capacities of 171 and 132 mA h g1 at a rate
and Li4Ti5O12/conductive carbon black; the enhanced lithium of 0.5 and 40 C, respectively, and stable cycling performance at a
storage was attributed to the smaller Li4Ti5O12 nanocrystals on rate of 10 C with a 85% capacity retention after 2000 cycles. Ri et al.
graphene sheets, improved electronic conductivity, lower charge reported a Li4Ti5O12/graphene composite with Li4Ti5O12 nanopar-
transfer resistance, smaller diffusion impedance and especially the ticle sizes of 18 nm using a microwave-assisted hydrothermal
stronger faradaic pseudocapacitive effect. method using ionic liquid (C12H23ClN2) as an exfoliated agent
Instead of forming a Li4Ti5O12/graphene composite with [426]. In the presence of ionic liquid, the resultant composite
randomly distributed Li4Ti5O12 and graphene dual phases as exhibited optimized phase and pore structures, showing excellent
demonstrated by Shi et al. and Xiang et al. [392,393], Jian et al. cycling stability (159 mA h g1 at 0.5 C after 100 cycles) and high-
prepared a Li4Ti5O12/graphene composite with a specific morphol- rate performance (148.5 mA h g1 at 20 C). In the absence of an
ogy of porous Li4Ti5O12 spheres and a surface modified by few- ionic liquid, H.K. Kim successfully synthesized a Li4Ti5O12/
layer graphene using C28H16Br2 as a precursor for the graphene graphene composite with 7–10 nm Li4Ti5O12 nanoparticles uni-
with a low processing temperature of approximately 400 8C formly supported on the graphene surface via a microwave-
[269]. The composite containing 5.91 wt.% graphene exhibited assisted process [427]. The nanocomposite delivered an excellent
capacities of 134 and 104 mA h g1 at rates of 5 and 10 C, electrochemical performance with capacities of 168 mA h g1
respectively, which were improved over those of the pristine (based on the weight of Li4Ti5O12, content in the composite:
Li4Ti5O12 spherical electrode (61 and 30 mA h g1). 83 wt.%) at 1 C and 98 mA h g1 even at 50 C. Recently, Ni et al.
Based on the high conductivity of graphene, Shen et al. directly developed a simple ultrasonic-assisted liquid deposition method
anchored nanocrystalline Li4Ti5O12 onto conducting graphene for the scalable synthesis of high-performance Li4Ti5O12/graphene
nanosheets to maximize their current collection efficiency [428]. Briefly, a CH3COOLi solution in distilled water and ethanol
[423]. The TiO2 nanoparticles were first anchored to the graphene was dropped into a suspension with graphene oxide and
oxide and were then transformed in situ into the Li4Ti5O12 and C16H36O4Ti ultrasonically dispersed in ethanol. After further
highly conductive graphene via a hydrothermal process with a sonication and calcination, 100 nm Li4Ti5O12 nanoparticles on
subsequent post-annealing treatment. The electronic conductivity graphene were successfully prepared. The composite delivered
of the composite with 15.5 wt.% graphene reached outstanding rate performance with capacities of 162, 154 and
4.1  103 S cm1, which is more than 108 times higher than 149 mA h g1 at 1, 10 and 20 C, respectively. A stable cycling
that of the pristine Li4Ti5O12. The resulting composite exhibited performance with high retention of 98.9% for 200 cycles at 5 C was
higher electrochemical performance, especially for the rate also achieved.
capability (83 mA h g1 at 60 C), compared with that of pristine Li4Ti5O12 sphere/graphene composites were also reported to
Li4Ti5O12. Yang et al. prepared a Li4Ti5O12/graphene composite improve the electrochemical performance of Li4Ti5O12 spheres
using non-oxidative cathodically induced graphene using a similar [429,430]. Pang et al. prepared a mesoporous Li4Ti5O12 nano-
synthesis route as shown in Fig. 57a. An electronic conductivity of sphere/graphene composite by electrostatic assembly of graphene
1.2  104 S cm1 was achieved for the Li4Ti5O12/graphene com- oxide and positively charged Li4Ti5O12/carbon nanospheres

Fig. 57. (a) Schematic illustration for the fabrication of Li4Ti5O12/nonoxidative cathodically induced graphene (CIG) composite. (b, c) TEM images of (b) Li4Ti5O12/CIG
composite and (c) pure Li4Ti5O12 prepared in the same fashion. (d) Rate performance of Li4Ti5O12/CIG composite and pure Li4Ti5O12 [424].
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 51

[429]. Most of the Li4Ti5O12/carbon nanospheres were covered by improved capacities of 149 and 134 mA h g1 at 0.5 and 10 C,
graphene sheets to form an interconnected composite, and the respectively. EIS indicated that the charge transfer polarization
composite exhibited a greatly enhanced rate capability with a resistance was reduced after the introduction of the CNTs. The
capacity of 124 mA h g1 compared with that of the initial formation of conductive nanotube networks likely increased the
Li4Ti5O12/carbon nanospheres (40 mA h g1) at 20 C because of apparent conductivity of the electrode, thus improving its current
the presence of an efficient electronic conducting network. collection efficiency. By introducing a third carbon phase with the
formation of Li4Ti5O12/C/CNTs, the rate performance was further
3.5.2. Li4Ti5O12/carbon nanotubes improved [440].
Carbon nanotubes were first discovered in 1991 [431] and can Unlike Li et al. [440], who mixed pre-synthesized Li4Ti5O12 with
be seen as a single graphene sheet rolled on itself to form a tube. CNTs by ball milling, Jhan et al. introduced the CNTs during the
Due to their unique structures and physical properties, both single- solid-state synthesis of Li4Ti5O12 [441]. In addition to performing
wall and multi-wall carbon nanotubes have received tremendous as a support matrix to provide a 3D conductive network, the CNTs
attention for a wide range of potential applications, such as next- acted as an inhibitor to suppress the aggregation of the in situ-
generation electronics and optoelectronics [432–434]. CNTs are formed Li4Ti5O12 nanoparticles during the calcination process. As a
extremely strong and mechanically robust; in addition, they have result, a reduction in the particle size and aggregation of the
high electronic conductivity, a wide electrochemical window, a Li4Ti5O12 was observed, ensuring a short lithium diffusion path
high aspect ratio, high chemical stability and a large surface area. length. The formed composite exhibited 161 and 147 mA h g1
Recently, their potential applications for electrochemical energy after 100 cycles at rates of 1 and 10 C, respectively, while the
storage have been recognized [435]. CNTs have been used as pristine Li4Ti5O12 prepared by a similar ball milling-assisted solid-
additives to form composites with other active materials, serving state reaction had capacities of 112 and 68 mA h g1 after
as electron conducting channels and/or a volume expansion buffer 100 cycles. A third carbon phase (acetylene black) was also
in LIBs [436,437]. The electron conduction of the entire network is introduced during the solid-state synthesis by Fang et al. to form a
more important than the intrinsic electron mobility of the CNTs for Li4Ti5O12/C/CNT composite [442], excellent rate capability and
this application. cycling performance were achieved. Ni et al. successfully anchored
Huang and Jiang are the first to report the use of Li4Ti5O12/ nano-Li4Ti5O12 on CNTs by a facile liquid phase deposition
carbon nanotube composites as electrodes for LIBs. The composite [443]. The functionalized CNTs and TBOT were dispersed in
was prepared by applying MWCNTs as an additive during the sol–gel ethanol, and then, the LiAc ethanol–water solution was dropped
synthesis of Li4Ti5O12 [438]. The CNTs suppressed the grain growth and aged. After calcination, the as-prepared nano-Li4Ti5O12/CNTs
of the Li4Ti5O12 phase. The as-prepared sample delivered excellent exhibited high capacities of 171 and 112 mA h g1 at 1 and 20 C
rate capability and cycling performance within the potential range of rates, respectively.
1.0–2.5 V. The reduced grain size and the improved electronic Shen et al. grew a porous Li4Ti5O12 sheath on the outer surface
conductivity from the addition of the CNTs accounted for the of multi-walled CNTs to form a novel special coaxial nanocompo-
improved electrode performance. Li et al. synthesized a Li4Ti5O12/ site [444]. The resulting composite contains approximately
carbon nanotube composite using a simple physical mixing method 82.5 wt.% Li4Ti5O12 and 17.5 wt.% CNTs with a porous 25-nm-
and ball milling [439]. The pristine Li4Ti5O12 had capacities of only thick Li4Ti5O12 sheath. The material exhibited much improved
142 and 60 mA h g1 at 0.5 and 10 C, respectively. However, by cycling stability and rate capability compared to that of pristine
introducing only 3.04 wt.% graphitized CNTs with a diameter of Li4Ti5O12. A simple model (Fig. 58) was proposed to explain this
50 nm and lengths of 1–2 mm, the resulting composite showed improvement. By using the Li4Ti5O12/carbon nanotube composites

Fig. 58. Schematic presentation of the electrochemical reaction path on MWNT@Li4Ti5O12 coaxial nanocables (left) and three Li4Ti5O12 particles (right) [444].
52 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

with specific co-axial morphological shapes, the effective reaction for lithium insertion into a SnO2 electrode, i.e., SnO2 is first reduced
area is greatly extended. The diffusion distance in the Li4Ti5O12 of to metallic tin by the insertion of lithium (SnO2 + 4-
the composite is only 25 nm, while it is 100 nm for the pristine Li+ + 4e ! Sn + 2Li2O); then, the further incoming lithium is
Li4Ti5O12, which ensures an easier lithium intercalation in the inserted into metallic Sn with the formation a Sn–Li alloy
composite. Moreover, the higher surface area of the composite (Sn + 4.4Li+ + 4.4e ! Li4.4Sn). Because only the second step is
provided a higher electrode/electrolyte contact surface area, reversible, SnO2 has a reversible capacity of 782 mA h g1 (based
resulting in a lower electrochemical reaction polarization resis- on the mass of SnO2), which is two times that of graphite. However,
tance. Recently, Kim et al. successfully prepared a Li4Ti5O12/CNT a large volume variation is experienced during the tin alloying and
composite with Li4Ti5O12 nanoparticle sizes of 15–20 nm uniform- de-alloying processes, and the volume expansion can reach up to
ly decorated on the CNTs using a simple microwave-solvothermal 300% when tin alloys with lithium to form Li4.4Sn [446]. By
reaction [445]. The CNT content in the composite (20 wt.%) is forming a Li4Ti5O12–SnO2 composite electrode, multiple benefits
similar to that reported by Shen et al. [444]; however, the rate may be derived: (i) because both Li4Ti5O12 and SnO2 are lithium-
capability was further improved with specific capacities of 172, insertion hosts, the composite may have a higher theoretical
151, 140 and 104 mA h g1 at 1, 10, 20 and 60 C, respectively. capacity than the composites with carbon, Cu or Ag inserted as the
Additionally, an excellent capacity retention of 98% at 10 C over second phase; (ii) Li4Ti5O12 is a material with almost no volume
1000 cycles was achieved. Jia et al. prepared a nanostructured change during the lithium insertion/extraction processes and can
Li4Ti5O12/CNT composite via aerosol spray drying process followed act as a buffer for the Sn phase, resulting in improved cycling
by calcination [246]. The composite was further built to be a stability of the Sn phase; (iii) as a metal, tin has a high electronic
flexible film electrode through a vacuum filtration of the mixture conductivity, which in turn acts as a surface modifier for Li4Ti5O12
dispersion of 80 wt.% of Li4Ti5O12/CNT composite particles and to increase its surface electronic conductivity and improve its rate
20 wt.% extra CNTs (Fig. 59a and b). The flexible Li4Ti5O12/CNT capacity.
composite film electrode delivered excellent electrochemical Lai et al. first reported Li4Ti5O12–SnO2 composites as potential
performance with specific capacities of 163, 143, and 108 mA h g1 anodic materials for LIBs [447,448]. They successfully prepared
1 at 1, 10, and 100 C rates, respectively (Fig. 59c). The rate Li4Ti5O12–SnO2 composites with a core-shell structure by solution
capability of Li4Ti5O12/CNT composite in traditional electrode is precipitation of SnO2 onto a pre-synthesized Li4Ti5O12 core. The
much lower, that is, 74 mA h g1 at 100 C rate. The flexible film composite contained 20 wt.% SnO2 and delivered capacities of
electrode exhibited an ultralong cycling stability at 1 A g1 with a 1089 and 182 mA h g1 for the first cycle and the 16th cycle,
capacity retention of 89% even after 8000 cycles (Fig. 59d), which respectively, between a potential range of 0.05–3.0 V. These
was much better compared to capacity retention of Li4Ti5O12/CNT capacities are higher than those of both pure SnO2 and Li4Ti5O12
composite electrode prepared by conventional slurry-coating electrodes, suggesting a synergistic interaction between the
technique (75% after 6000 cycles). Li4Ti5O12 and SnO2. The authors proposed that SnO2 acted as a
bridge between the spinel particles to reduce the contact
3.5.3. Li4Ti5O12/SnOx resistance between the Li4Ti5O12 particles, while the aggregation
SnO2 is an anode material with a first discharge capacity as high of small Sn particles was hindered by the Li4Ti5O12 phase. As a
as 1494 mA h g1. A two-step intercalation mechanism is proposed result, the composite electrode exhibited an improved reversible

Fig. 59. (a) Structure and fabrication of the flexible Li4Ti5O12/CNT electrode. (b) A digital photograph of the flexible electrode. (c) Rate performance of the flexible electrode
compared with traditional electrode. (d) Cycling stability and Coulombic efficiency of flexible Li4Ti5O12/CNT electrode at a current density of 1 A g1 [246].
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 53

capacity for the Li4Ti5O12 and improved cycling stability of the homogenously dispersed by TEM observation and mapping
SnO2 phase. Among the various Li4Ti5O12-SnO2 composites of (Fig. 60). However, the possibility of Sn-doping in the Li4Ti5O12
varying SnO2 content, Li4Ti5O12–SnO2 (5 wt.%) demonstrated the was not considered and studied. Nevertheless, the sample with a
best cycling stability. Following 42 charge/discharge cycles at a Li4Ti5O12/SnO2 ratio of 0.4/0.6 exhibited the best cycling stability
current rate of 0.5 mA cm2, the material maintained a capacity of with capacity retention of 70% after 60 cycles at a current density of
189 mA h g1. 700 mA g1 between 0.1 and 2.5 V.
Composites of Li4Ti5O12 nanosheets and SnO2 nanocrystals
were also fabricated by Han et al. via the crystal growth of SnO2 on 3.5.4. Li4Ti5O12/TiO2
the surface of 2D Li4Ti5O12 nanosheets and were tested between Fig. 61 shows the pseudobinary Li2O–TiO2 phase diagram
0.001 and 2.0 V [449]. However, the best sample exhibited a [454]. For the synthesis of Li4Ti5O12, the impurities of Li2TiO3 or
discharge capacity of 150 mA h g1 after 30 cycles, which is even TiO2 will be present with excess lithium or less lithium,
lower than the theoretical capacity of Li4Ti5O12 (175 mA h g1) respectively. Historically, pure-phase Li4Ti5O12 is expected to
between 1.0 and 3.0 V. A Li4Ti5O12/Sn composite formed by a exhibit better electrochemical performance. Thus, researchers
simple physical mixing method with the help of HEBM demon- always attempted to synthesize phase-pure Li4Ti5O12 to avoid the
strated improved cycling performance compared with pristine formation of impurities. Lithium excess was frequently adopted in
Li4Ti5O12 and Sn electrodes [450]. By using a cellulose-assisted the starting raw materials to compensate the potential lithium loss
combustion technique, Cai et al. prepared ultrafine Li4Ti5O12/Sn by evaporation during high-temperature calcination. However,
composites [451]. A certain chemical interaction was created Li4Ti5O12–TiO2 composites have been reported to demonstrate
between the Li4Ti5O12 and SnO2 phases during the synthesis; as a high electrochemical performance. Rahman et al. successfully
result, the grain growth of the SnO2 during the calcination was synthesized a Li4Ti5O12-anatase TiO2 composite by applying a basic
successfully suppressed. However, the tin oxide acted as a molten salt process using LiNO3, LiOHH2O, Li2O2 and
sintering aid for the Li4Ti5O12 phase, and the sintering of Li4Ti5O12 Ti[O(CH2)3CH3]4 as raw materials. The sample, synthesized at
became obvious at 700 8C. The proper selection of calcination is 400 8C, showed outstanding electrochemical performance, deliv-
therefore important to achieving high performance. A calcination ering initial discharge capacities of 193, 168, 146, 135 and
temperature of 500 8C was proposed, and the as-prepared 117 mA h g1 at rates of 0.2, 0.5, 1, 2 and 5 C, respectively, within
composite electrode with a Li4Ti5O12-to-Sn weight ratio of 9:1 the potential range of 1.0–3.0 V. A discharge capacity of
exhibited a capacity of 224 mA h g1 after 50 charge–discharge 135 mA h g1 was maintained at 1 C with capacity retention of
cycles at a current density of 100 mA g1. 95% after 100 cycles [409]. By introducing a third phase of
Yang et al. successfully prepared Li4Ti5O12/SnO2 hollow spheres amorphous carbon with the formation of a Li4Ti5O12–TiO2–C
by a spray drying process using LiNiO3, TTIP and tin oxalate composite prepared via the molten salt process, the electrode
(SnC2O4) as raw materials with 0.5 M CA as the chelating agent performance showed obvious improvement [410]. As shown in
[452]. These researchers further prepared and studied Li4Ti5O12/ Fig. 62, the composite reached initial capacities of 166 and
SnO2 hollow spheres using an ultrasonic spray pyrolysis process 135 mA h g1 at 0.5 and 10 C rates, respectively, while the
using the same raw materials with different Li4Ti5O12/SnO2 ratios corresponding values were 167 and 107 mA h g1 for a carbon-
[453]. Li4Ti5O12 and SnO2 phases with no impurities were observed free Li4Ti5O12–TiO2 composite and 147 and 57 for pristine
by XRD, and the corresponding nanocrystals were observed to be Li4Ti5O12. A capacity of 110 mA h g1 was maintained after

Fig. 60. TEM and dot-mapping images of the post-treated Li4Ti5O12-SnO2 (0.4/0.6) composite powders [453].
54 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 61. The pseudobinary Li2O–TiO2 phase diagram. [454].

100 cycles at a rate of 10 C, which is 82% of the initial capacity. In heat treatment [459]. A further hydrothermal treatment in glucose
comparison, the discharge capacities dropped to only 83 and solution was applied to coat the carbon to enhance electronic
40 mA h g1 for the Li4Ti5O12–TiO2 and Li4Ti5O12 electrodes, conductivity. Notably, a TiO2 phase formed simultaneously, which
respectively. may be transformed from an LiTiO2 impurity or Li4Ti5O12 after
By using a hydrothermal route in the presence of thiourea, Li carbon coating, which was beneficial to the electrochemical
et al. successfully synthesized a Li4Ti5O12-anatase TiO2 nanocom- performance. The carbon-coated Li4Ti5O12–TiO2 composite micro-
posite [455]. The results of galvanostatic charge–discharge, cyclic sphere exhibited a high capacity of >230 mA h g1 at 0.2 C. Chen
voltammetry and electrochemical impedance spectra indicated et al. synthesized a Li4Ti5O12-anatase TiO2 nanocomposite via a
that the composite presented improved electrochemical perfor- microemulsion-assisted hydrothermal method followed by calci-
mance over single-phase Li4Ti5O12 and anatase TiO2. After nation at 550 8C using a Li/Ti molar ratio of 4:5, whereas a pure
300 cycles at a rate of 1 C, the composite electrode retained a Li4Ti5O12 phase is formed using the Li/Ti molar ratio of
discharge capacity of 116 mA h g1. In addition, a pseudocapaci- 4.5:5[460]. The composite exhibited much enhanced electrochem-
tive effect was created with the formation of the composite due to ical performance with a capacity of 108.9 mA h g1 even at
the presence of abundant phase interfaces, which were believed to 7 A g1. This enhancement was attributed to the high theoretical
cause the enhanced rate capability and improved cycling stability. capacity of TiO2 and improved electronic conductivity in the
Liu et al. also successfully synthesized Li4Ti5O12-TiO2 nanocrys- presence of TiO2 by the authors. However, the abundant phase
tallines via a hydrothermal process under an appropriate interfaces, which were very important, were not considered and
temperature [456], and greatly enhanced electrochemical perfor- studied. More recently, Jiang et al. successfully synthesized
mance, especially the rate capability, was demonstrated. However, hierarchical Li4Ti5O12/TiO2 tubes composed of ultrathin nanoflakes
the actual weight ratio of the Li4Ti5O12 to TiO2 was not determined by a hydrothermal treatment of porous amorphous TiO2 and
and was difficult to control for the composite synthesized via the LiOHH2O followed by calcination at 400 8C [461]. The ordered
hydrothermal method. Lai et al. synthesized Li4Ti5O12-TiO2 fringe-like crystallographic defects and rich grain boundaries
microspheres using PANI/TiO2 microspheres and LiOHH2O as among the spinel Li4Ti5O12 and anatase TiO2 were clearly observed
raw materials with a Ti/Li mole ratio of 5:3.13[457]. The composite via TEM and HR-TEM analysis. Combined with the hierarchical
microspheres exhibited enhanced electrochemical performance structure, crystallographic defect and grain boundary, the as-
with a capacity of 156.9 mA h g1 at 1500 mA g1 compared with synthesized Li4Ti5O12/TiO2 composite delivered high initial dis-
that of pure Li4Ti5O12 microspheres (105.8 mA h g1). Wang et al. charge capacities of 420, 225, and 160 mA h g1 at 0.01, 0.1, and
introduced ammonia into a solvothermal synthesis process of 1.0 A g1, respectively, and a good capacity retention of 87% after
Li4Ti5O12 spheres, resulting in much smaller Li4Ti5O12–TiO2 100 cycles at 1.0 A g1. Besides, Li4Ti5O12–TiO2 nanosheet-nano-
nanoparticles and enhanced rate performance [458]. After further tube composites [462], and Li4Ti5O12–TiO2 hollow spheres
carbon coating, the composite delivered a reversible capacity of composed of nanoflakes [463] have also successfully synthesized
140 mA h g1 at 5 C even after 100 cycles. by solvothermal/hydrothermal process followed by a calcination
Liao et al. synthesized highly mesoporous lithium titanate process, which also demonstrated improved electrochemical
hierarchical microspheres using a hydrothermal method using properties. Wu et al. synthesized petal-like Li4Ti5O12–TiO2
hierarchical TiO2 spheres and LiOH as raw materials followed by nanosheets via a boiling treatment with further calcination using
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 55

Fig. 62. The initial galvanostatic charge-discharge profiles of (a) Li4Ti5O12, (b) Li4Ti5O12-TiO2, and (c) Li4Ti5O12-TiO2-C electrodes at different current densities from 0.5 to 10 C
between 2.5 and 1.0 V; (d) cyclic performance beyond 100 cycles at 10 C [410].

H2TiO3 and LiOHH2O as raw materials in the presence of H2O2 and Li4Ti5O12 nanowire array electrode and lower compared to that
ammonia; the composite exhibited good electrochemical perfor- of TiO2 nanowire array electrode, importantly, the superior rate
mance, especially with an initial discharge capacity of capability was achieved for Li4Ti5O12–TiO2 nanowire array
112.5 mA h g1 at 20 C [464]. Although the TiO2 phase was not electrode (Fig. 63c). The enhanced rate performance was attributed
designed to be introduced, excellent electrochemical performance to the rich grain boundary interfaces in the Li4Ti5O12–TiO2
was still achieved. nanowires, which mainly improve lithium storage kinetics. Shao
Liao et al. prepared a Li4Ti5O12–TiO2 nanowire array by et al. proposed a novel method based on an in situ nitriding-
controlling the chemical lithiation reaction time [465]. Li4Ti5O12 oxidizing process [466]. During the synthesis, TiO2 anatase and
and TiO2 nanowire arrays were also synthesized as a comparison. Li2CO3 were applied as the raw materials and were well mixed by
As shown in Fig. 63a and b, the characteristic redox peaks and HEBM followed by calcination at 800 8C under an ammonia
discharge/charge plateaus of Li4Ti5O12 and anatase TiO2 phases atmosphere for 3 h to yield a primary product composed of an N-
were distinctly observed in the curves of Li4Ti5O12–TiO2 nanowire doped Li4Ti5O12 and a TiN shell. The composite was then further
array electrode. Because of the higher theoretical capacity of TiO2, calcined under an air atmosphere at 600 8C for 3 h to allow the re-
the specific capacities at low rate (0.1–1 C) of Li4Ti5O12–TiO2 oxidation of TiN to TiO2. Finally, a micrometer-sized Li4Ti5O12–TiO2
nanowire array electrode were higher compared to that of composite with rich two-phase boundaries, but a small specific

Fig. 63. (a) CV curves of TiO2 nanowire, Li4Ti5O12-TiO2 composite nanowire, and Li4Ti5O12 nanowire electrodes. (b) The first three charge–discharge curves at 0.1 C of
Li4Ti5O12–TiO2 composite nanowire electrode. (c) The rate performance at various current rates from 0.1 to 30 C and then back to 0.1 C (1 C = 175 mA g1) of TiO2 nanowire,
Li4Ti5O12–TiO2 composite nanowire, and Li4Ti5O12 nanowire electrodes [465].
56 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

surface area, was obtained. The sample exhibited outstanding ZnO was also introduced into Li4Ti5O12 to form a composite via
capacity, rate capability and cycling stability, reaching a capacity of facile ball-milling [472], and the composite demonstrated
155 mA h g1 at 10 C with almost no capacity fade after enhanced electrochemical performance, especially the rate capa-
100 cycles. The high performance was attributed to the rich bility, within potential ranges of 0.01–3.0 and 1.0–3.0 V.
two-phase boundaries, while the micrometer particle size with a By changing the end potential to 1.0 V, the capacity of MO will
small surface area benefited the high cycling stability. By this facile be obviously reduced; however, it remains higher compared with
method, the Li4Ti5O12 to TiO2 ratio can be easily controlled. Thus, conductive graphite/carbon anodes. Additionally, MO has a higher
this method provides a novel way to develop high-performance density. Li4Ti5O12/Fe2O3 was designed and prepared by dispersing
Li4Ti5O12-TiO2 composites for LIBs. solid-state-synthesized Li4Ti5O12 powders in a Fe(OH)3 colloid
Rutile TiO2 is thermodynamically the most stable phase among combined with further calcination, which resulted in an obviously
the various TiO2 polymorphs. However, in bulk crystal form, it enhanced rate performance with a discharge capacity of
usually exhibits a poor lithium intercalation capability [467]. Im- 109.4 mA h g1 at 10 C compared with that of pure Li4Ti5O12 with
proved electrode performance was observed for Li4Ti5O12 by a capacity of only 40.5 mA h g1 [473].
forming a composite with rutile TiO2 [54]. C.T. Hsieh prepared a
Li4Ti5O12-rutile TiO2 composite by spray drying followed by a high- 4. Electrochemical behavior in different battery systems
temperature solid-state reaction. The composite had superior
performance in terms of capacity, rate capability and cycling To date, the Li4Ti5O12 anode has been combined with various
stability compared to pristine Li4Ti5O12, suggesting the beneficial cathode materials and electrolytes to build batteries for diverse
effects of a rutile TiO2 phase on the lithium insertion behavior of applications, such as power sources for thin-film electronics [216],
Li4Ti5O12. Such improvement likely has two causes. First, the auxiliary or main power sources for hybrid vehicles [474] including
presence of a rutile TiO2 phase provided additional capacity; start-stop applications [475], power systems for load leveling
second, the presence of a TiO2 phase effectively prevented the application [476], and electrochemical energy storage devices
occurrence of Li2O, LiOH and/or Li2CO3 impurity phases, which can [477].
be introduced during the synthesis of Li4Ti5O12 by applying
excessive Li raw materials and are believed to deteriorate the 4.1. Combination with different cathodes
intercalation properties of the Li4Ti5O12 phase by blocking the
interfacial charge transfer because of their low electronic and The replacement of a commercial graphite anode with a
lithium-ion conductivities [52]. Recently, Li4Ti5O12/rutile TiO2 Li4Ti5O12 anode in LIBs is believed to result in significantly
mesoporous microspheres were also designed and prepared using enhanced safety, rate capability, and cycling stability. However,
TiO2 microspheres as a precursor [468]. An enhanced lithium ion the voltage of batteries with a Li4Ti5O12 anode decreased compared
diffusion coefficient was obtained in the presence of the rutile TiO2 with that of conventional carbon anodes because of the higher Li+
phase, which was explained by the open channels along the [0 0 1] insertion/extraction potential (approximately 1.55 V) in
direction for elevated lithium ion diffusion with an appropriate Li4Ti5O12. Thus, combining a Li4Ti5O12 anode with befitting
amount of the rutile TiO2 phase, resulting in improved electro- high-voltage cathode materials raises concerns in terms of
chemical performance. Carbon was introduced to further improve obtaining the desired voltage output. Various cathodes have been
its performance, and discharge capacities of 170.9, 162.5, explored to combine with the Li4Ti5O12 anode; the corresponding
147.5 and 120.6 mA h g1 at 0.5, 1, 2 and 5 C were achieved, discharge/charge curves as well as operation voltage of the cells are
respectively. shown in Fig. 64.
(1) Layered oxide cathode
3.5.5. Li4Ti5O12/transition-metal oxides (MO, where M is Co, Ni, Cu, Fe Layered LiCoO2, which has been the most successful cathode
or Zn) over the past two decades, is usually combined with a conventional
Since the nano-sized transition-metal oxides (MO) were found graphite anode for commercial LIB applications. By replacing
to demonstrate high electrochemical activity and undergo a graphite with a Li4Ti5O12 anode, the Li4Ti5O12/LiCoO2 battery
conversion reaction by discharging to an end potential of 0.01 V in system has also been studied [216,478–480]. Brousse et al.
2000 [469], MO have attracted significant attention as promising fabricated all-oxide solid-state LIBs using a thin-film Li4Ti5O12
candidates for anodes for high-capacity LIBs. anode, a Li0.33La0.56TiO3 electrolyte and a thin-film LiCoO2 cathode,
However, MO usually suffers from large volume variation, which were successfully cycled for 100 times. However, the
which results in poor current collection, finally leading to poor current density was only 50 uA cm2, which could be attributed to
cycling performance. The benefits from using a Li4Ti5O12–MO the rather thick electrolyte of approximately 1 mm [216]. Gaikwad
composite as an anode are similar to those obtained for Li4Ti5O12– et al. reported a high areal capacity flexible Li4Ti5O12/LiCoO2
SnOx: MO will contribute a higher capacity compared with battery with nonwoven fibrous membrane-reinforced electrodes
Li4Ti5O12; Li4Ti5O12 acts as a stable matrix, which could in which freestanding CNT film as current collectors (Fig. 65)
accommodate the volume variation of MO; and MO will transform [481]. The reinforced electrode exhibited excellent mechanical
to a metal in a specific voltage range, which could increase the performance with a tensile strength of 5.5–7.0 MPa. Fig. 65d–f
conductivity of Li4Ti5O12. The use of several MO (M is Co, Ni, Cu, Fe shows the typical charge/discharge curves of the Li4Ti5O12/CNT
or Zn) has recently been attempted to form composites with electrode, LiCoO2/CNT electrode, and full battery, respectively. The
Li4Ti5O12 to achieve improved electrochemical performance [470– operation voltage of the full Li4Ti5O12/LiCoO2 battery was around
473]. Hu et al. synthesized Li4Ti5O12–MO (Fe2O3 and CuO) 2.4 V. The full battery delivered a high areal capacity of
composites as modified anodes with 5 wt.% MO [471]. The LTO– 1 mA h cm2 and a stable cycling performance with a capacity
CuO composite exhibited the best rate performance with a specific retention of 94% after 450 cycles at a C/2 rate. Although other
capacity of 106 mA h g1 at 20 C. However, the comparison of the researchers have attempted to understand the details for this
electrochemical performance of the composite within a voltage Li4Ti5O12/LiCoO2 battery system via EIS analysis [479], and to
range of 0.005–3.0 V and that of Li4Ti5O12 between 1.0 and 3.0 V is improve its electrochemical performance using a novel electrolyte
not reasonable because Li4Ti5O12 also exhibits electrochemical [480] and adding an additive [478], the key issues are the high-cost
activity below 1.0 V. Additionally, the preparation of the composite of the cobalt source and the oxygen release problem in LiCoO2
with MO, butyl titanate and LiNO3 may also make the M a dopant. during the charge/discharge process [482].
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 57

terms of safety, power and cycling life [490]. Based on the


superiority of LiFePO4 and Li4Ti5O12, a full cell composed of this
anode/cathode couple could achieve high rate capability and cycling
stability [244,318,491]. Li et al. developed a flexible graphene-foam-
based Li4Ti5O12/LiFePO4 full battery, which delivered a specific
capacity of 117 mA h g1 (calculated based on the weight of the
cathode active material) even at a 10 C rate, 88% of the capacity at a
1 C rate [244]. Note that this flexible full battery device avoids the
use of conventional additional conductive carbon black, binder, and
heavy metal foil current collectors; thus, a high gravimetric energy
density of the full battery could be achieved. Moreover, a stable
cycling performance at 10 C over 100 cycles with only 4% capacity
loss was achieved for this flexible full battery device. Long-term
cycling performance could also be easily achieved for the Li4Ti5O12/
LiFePO4 battery system due to the unique characteristics of the
electrode materials; for example, a specific capacity of
130 mA h g1 (calculated based on the weight of the lower weight
electrode) was delivered even after 1200 cycles at 0.5 C for a full cell
with Ketjen-black-modified LiFePO4 as the cathode and an
unmodified Li4Ti5O12 as the anode [491]. Although a high rate
capability and stable cycling performance have been successfully
achieved using the Li4Ti5O12/LiFePO4 couple, the relatively low
Fig. 64. The discharge/charge curves for various cathode materials including discharge potential plateau of 3.4 V (vs. Li/Li+) for LiFePO4 results in
LiNi0.5Mn1.5O4, LiMn2O4, LiCoO2, LiFePO4 (20 8C, 0.2 C rate) [500], LiCoPO4 (0.1 C
rate) [493], LiMn0.8Fe0.2PO4 (30 8C, 0.1 C rate) [496], LiMnPO4/C (0.05 C rate) [492],
a low voltage output of approximately 1.85 V (Fig. 64).
and LiNi1/3Co1/3Mn1/3O2 (25 8C, 20 mA g1) [484] combined with Li4Ti5O12 anode In comparison with LiFePO4, LiMnPO4 has a much higher
material [493]. All the curves are derived from the literatures with horizontally operation voltage of 4.1 V (vs. Li/Li+) and offers a competitive
flipping, smoothing and dyeing. energy density of 701 Wh kg1 (171 mA h g1  4.1 V). To deploy
LiMnPO4 as a cathode material and address its corresponding
Optimized layer oxide cathodes, LiNi0.8Co0.15Al0.05O2 and LiNi1/ issues (e.g., Jahn–Teller distortion, poor electronic and ionic
3Co1/3Mn1/3O2, which have received increasing attention [483– conductivity, and interfacial strain between the LiMnPO4 and
485], have also been combined with a Li4Ti5O12 anode to deliver MnPO4 phase, etc.), Ramar et al. prepared a mesoporous LiMnPO4/C
improved electrochemical performance [419,486–489]. Guo et al. cathode using a high-energy ball-mill-assisted soft template
combined a carbon-coated Li4Ti5O12/graphene composite anode method and combined this cathode with a Li4Ti5O12/C anode
with a LiNi1/3Co1/3Mn1/3O2 cathode; the full cell demonstrated [492]. This full cell delivered an average voltage and capacity of
excellent rate performance with a specific capacity of 2.3 V and 54 mA h g1 (calculated based on the weight of the
116 mA h g1 and 95 mA h g1 at 1 and 8 C, respectively [419]. cathode active material, the capacity was close to that at 1 C in the
(2) Lithium-phosphate cathode half-cell configuration vs. Li foil), respectively, at a rate of 1 C.
As a critical cathode material among the lithium-phosphate Relatively stable cycling performance within 20 cycles was also
group, olivine-structured LiFePO4, which undergoes a two-phase demonstrated. However, the capacity was relatively low, and the
mechanism with the reversible reaction during the electrochemi- end-of-charge indication in the voltage profile was not clear
cal lithium insertion/extraction processes [64], is outstanding in compared with that of the Li4Ti5O12/LiFePO4 couple.

Fig. 65. (a) Schematic of the flexible battery laminated within aluminum-lined pouch. (b) Demonstration of the flexible lithium-ion battery connected in series with a 200 V
resistor and a green light-emitting diode (LED). (c) Areal capacity (mA h cm2) and columbic efficiency (%) of the full cell cycled between C/4 and 1 C rate. The full cell had a total
active area of 2.5  2.5 cm2 and Li4Ti5O12 and LiCoO2 loading of 13.4 and 12.5 mg cm2, respectively. (d, e) Galvanostatic charge/discharge curves for (d) Li4Ti5O12/CNT anode and
(e) LiCoO2/CNT cathode cycled between 1.0 and 2.0 V vs. Li/Li+ and 3.0–4.2 V vs. Li/Li+, respectively, at C/4 rate. (f) Galvanostatic charge/discharge curves for the full cell cycled
between C/4 and 1 C rate. The capacity at C/4, C/2 and 1 C rate was 117, 104 and 90 mA h g1, respectively. Columbic efficiency of all the batteries was above 99.5% [481].
58 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Recently, another olivine-structured candidate from the lithi- was much improved with a stable 100 cycles at 0.2 C compared
um-phosphate group, LiCoPO4, which has a usable operation with that in the LiNi0.5Mn1.5O4-limited full cell due to the reduced
voltage (4.8 V vs. Li/Li+), was also combined with a Li4Ti5O12 anode utilization of the second two-phase transition reaction [502]. A
to achieve a high voltage output of 3.25 V [493,494]. However, the metal-doped LiNi0.5Mn1.5O4 cathode was also studied for combi-
reported cycling performances of the Li4Ti5O12/LiCoPO4 couple nation with the Li4Ti5O12 anode [503,504]. Ding et al. synthesized a
were definitely poorer compared with that of the Li4Ti5O12/LiFePO4 LiNi0.473Mn1.473Al0.054O4 nanotube cathode and combined it with a
couple, limiting its widespread commercial application. Other commercial Li4Ti5O12 anode, demonstrating a high rate capability
lithium-phosphate-like Li3V2(PO4)3/C composite was also com- with 158 mA h g1 (calculated based on the limited Li4Ti5O12
bined with a Li4Ti5O12 anode; the cell demonstrated three charge/ mass) at 0.5 C and 120 mA h g1 at 10 C and a further good cycling
discharge plateaus at 2.56/2.46 V (50%), 2.15/2.05 V and 2.07/ stability with a 87% capacity retention after 200 cycles at 1 C
1.97 V and an initial capacity of 117 mA h g1 at 0.5 C [495]. charge/5 C discharge rate [504]. Because of the benefit of an
To combine the advantages of LiMnPO4 and LiFePO4 and avoid appropriate Mn3+ content in the LiNi0.5Mn1.5O4 cathode material,
the decomposition of electrolyte solutions based on alkyl where Li+ ion transport can be accelerated in the crystalline
carbonate solvents at too high of a voltage, a promising cathode, structure [505], an optimized LiNi0.4Mn1.6O4 composition has been
LiMnyFe1yPO4, has been combined with a Li4Ti5O12 anode to developed [506]; in addition, studies in the battery system with a
obtain an improved battery system. Borgel et al. combined a Li4Ti5O12 anode have also been conducted. The output voltage of
commercial carbon-coated LiMn0.8Fe0.2PO4 cathode with a the Li4Ti5O12/LiNi0.4Mn1.6O4 battery system is especially attractive
Li4Ti5O12 anode; the cell works at a main potential of 2.5 V for commercial application; however, the selection of the
(80%), exhibiting good rate capability at 30 8C with discharge electrolyte with proper additive [505,507] is of significant
capacities of 153 and 118 mA h g1 (calculated based on the importance to prevent its degradation at high voltage and to
weight of the cathode active material) at 0.1 C and 5 C rates, further achieve a real stable electrochemical performance. To
respectively, and a stable cycling life with 100 cycles at 0.5 C further increase the working voltage, a cathode with a higher
[496]. Yang et al. used their V-doped Li4Ti5O12 (Li4Ti4.90V0.10O12/C) lithium-intercalation voltage is necessary. Panero et al. first
prepared by a solid-state method [318] as an anode and LiFe0.5- reported the combination of Li4Ti5O12/Li2Co0.4Fe0.4Mn3.2O8, two
Mn0.5PO4/C as a cathode; the cell demonstrated specific capacities high-voltage spinels, as the anode and cathode of LIBs to yield a
of 161, 141, 111, and 84 mA h g1 (calculation was undefined) at 3.5-V cell [508].
0.2, 1, 5, and 10 C, respectively, and exhibited stable cycling (4) Other cathodes
performance for 100 cycles at 1 C [497]. Thus, LiMnyFe1yPO4 is As one of the high-capacity cathode materials, vanadium
demonstrated to be a promising cathode to combine with a pentoxide (V2O5) is widely investigated [509,510]. Researchers
Li4Ti5O12 anode for commercial application. have also attempted to combine it with a Li4Ti5O12 anode, however,
(3) Spinel oxide cathode there is no lithium in V2O5; thus, a chemical lithiation process was
A spinel LiMn2O4 cathode has also been combined with a adopted. Typically, two discharge plateaus at 1.84 and 1.61 V
Li4Ti5O12 anode, and the battery system offers a relatively high were observed for chemically lithiated V2O5 particles [511]. How-
voltage output of 2.55 V. Combining Li4Ti5O12 nanorods with a ever, the cycling performance is poor even at a low current density
LiMn2O4 porous sphere cathode results in a good rate capability of 20 mA g1. Use of chemically lithiated electrospun V2O5
with discharge capacities of 44.1, 42.9, 37.4, and 34.1 mA h g1 nanofibers resulted in enhanced cycling performance of the full
(calculated based on the total weight of both the cathode and cell [512]; however, they remains unattractive for commercial
anode active electrode materials) at 0.5, 1, 10 and 20 C, application.
respectively [498]. A 60% capacity retention after 1000 cycles
at 10 C was also achieved. Reale et al. fabricated a cell with a 4.2. Combination with different electrolytes
Li4Ti5O12 anode and a LiMn2O4 cathode in a PVDF-based gel
electrolyte to yield operational voltages of 2.5 and 3.0 V, To date, various electrolytes have been developed and used for
respectively [499]. The Li4Ti5O12/LiMn2O4 cell delivered a capacity LIBs [513]. The most commonly used electrolyte is a carbonate
of 130 mA h g1. Even under an unoptimized configuration, the cell organic liquid electrolyte containing a dissolved lithium salt such
can be operated at rates exceeding 1.0 C with minor polarization. as LiPF6, which has an ionic conductivity higher than 103 S cm1
For the LiMn2O4 cathode, the high content of Mn3+ usually at room temperature. The typical carbonate solvent consists of
results in a Jahn–Teller distortion, that is, dismuting into Mn4+ and ethylene carbonate (EC) and dimethyl carbonate (DMC, or
highly soluble Mn2+. Partial substitution of Mn with Ni in the ethylmethyl carbonate (EMC)), in which EC allows good ionic
LiMn2O4 cathode has been recognized as an effective approach to dissociation of lithium salt to ensure acceptable ionic conductivity,
avoid the Jahn–Teller distortion because Mn4+ will form instead of and DMC (or EMC) acts as a thinning solvent to reduce the viscosity
Mn3+[500]. For instance, in ordered LiNi0.5Mn1.5O4, all the Mn [514]. Additionally, for the conventional graphite/carbon anode, a
elements should be in the +4 valence state. In particular, the passivating SEI layer could form from EC on the surface of graphite/
LiNi0.5Mn1.5O4 cathode material is highlighted because of its high carbon as a barrier to avoid further decomposition of the
operation voltage (4.7 V) and high energy density; thus, it has electrolyte [515,516]. For a Li4Ti5O12 anode that is usually operated
been recognized as a promising cathode to combine with Li4Ti5O12 above 1.0 V, most of the papers reviewed in Section 3 for Li4Ti5O12
anodes, and many related works have been performed modification are based on the conventional carbonate organic
[501,502]. Reale et al. further reported Li4Ti5O12/gel polymer liquid electrolyte (e.g., LiPF6 in EC/DMC (or EMC)); stable cycling
electrolyte (GPE)/LiNi0.5Mn1.5O4 batteries with a cell voltage of stability and excellent rate capability can be successfully achieved
3.1 V at room temperature [499]; the batteries were successfully at room temperature. Stable cycling performance can also been
operated at rates as high as 2.5 C with a capacity decay of only demonstrated even with an end potential of 0.01 V using these
10% after 100 cycling at 0.2 C. Zheng et al. investigated the effect conventional carbonate electrolytes [517].
of residual lattice Mn3+ on the electrochemical performance of a The replacement of conventional LiPF6 with other unique
Li4Ti5O12/LiNi0.5Mn1.5O4 full cell; they found that the benefit of lithium salts (e.g., lithium difluoro(oxalato)borate (LiDFOB)) can
lattice Mn3+ is more manifest in the Li+ deficient environment of result in improved electrochemical performance of the Li4Ti5O12/
the LiNi0.5Mn1.5O4-limited full cell, and importantly, they demon- LiFePO4 battery system, that is, cycling stability with a capacity
strated that the cycling stability in the Li4Ti5O12-limited full cell retention of 90% after 100 cycles compared with that based on
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 59

LiPF6 (75%) at high temperature (60 8C) [518]. However, the that exhibited a wide operation window of 5.2 V and a high ionic
conventional carbonate organic liquid electrolyte still suffers from conductivity of 1.14 mS cm1[534]. Combining 1 M LiPF6 in this
several issues, that is, the high flammability leads to a potential compound with 1 vol% vinyl carbonate as an electrolyte with a
safety issue, and the high reactivity above 50 8C results in Li4Ti5O12 anode and Li1.2Ni0.2Mn0.6O2 cathode resulted in a
decreased cycling performance [514]. These issues strongly limit battery system that demonstrated an initial capacity of
its practical application in the Li4Ti5O12–anode battery system. 161.3 mA h g1 and 86% capacity retention after 30 cycles (0.5–
Thus, alternative electrolytes have been developed and studied to 3.1 V, 18 mA g1).
meet the demands of safety, thermal stability, and even high In addition, solid-state electrolytes have also been combined
operation voltage window to match the high operation voltage with a Li4Ti5O12 anode, such as the recently reported electrolytes
cathode that is combined with the Li4Ti5O12 anode. Recently, most based on Li6PS5Cl [535], Li2SiO3 [536]; however, the electrochemi-
studies on alternative electrolytes for the Li4Ti5O12–anode battery cal performance compared with that of conventional liquid
system have focused on non-flammable electrolytes based on ionic electrolyte is not attractive.
liquids [519–524] and sulfone solvents [514,525–527].
Ionic liquids are generally defined as salts with a melting point 4.3. Electrochemical performance
below 100 8C [528]. Due to their high thermal stability, wide
potential windows and high flash points, ionic-liquid-based Even though there have been an increasing number of research
electrolytes have attracted increasing attention [523]. The typical papers published on Li4Ti5O12 as an anode in LIBs, as observed in
cations for ionic liquids are imidazolium, ammonium, pyrrolidi- Fig. 2, Li4Ti5O12 is no longer a material that remains confined to the
nium, and pyridinium. [529]. Although the advantages of ionic lab; this material is now being proposed for practical applications.
liquids are very attractive, they suffer from high intrinsic viscosity. Jansen et al. tested a lithium-ion battery composed of a Li4Ti5O12
Alternatively, mixtures of ionic liquids and alkylcarbonates have anode and a LiCoO2 cathode designed for potential application as a
recently been demonstrated to have potential application for the power assist in hybrid vehicles [474]. As demonstrated in Fig. 66, the
Li4Ti5O12–anode battery system [521–523]. Lombardo et al. used a authors reported the successful cycling of the batteries over 117,000
mixture of N-butyl-N-methylpyrrolidinium bis(trifluoromethane- times with each cycle taking 60 s, including a 9-s discharge pulse, an
sulfonyl)imide (Py14TFSI) and 1 M LiPF6 in EC:DMC in a weight 18-s rest, a 10-s charge pulse, and a 23-s low current charge. Such
ratio of 3:7 as a electrolyte, which demonstrated enhanced safety batteries are highly promising for use in high-power applications in
compared with that of flammable alkylcarbonate electrolyte which safety is a primary concern, such as EVs and HEVs. However,
[522]. A Li4Ti5O12/LiFePO4 battery system using this mixed two main problems arise in these batteries—the relatively low cell
electrolyte delivered a specific capacity of approximately voltage and large area-specific impedance. Du Pasquier et al.
150 mA h g1 (calculated based on Li4Ti5O12 mass) at a 0.2 C rate. proposed a hybrid battery–super capacitor using a nanostructured
Sulfone-based electrolytes were demonstrated to have an Li4Ti5O12 anode to bridge the power capacity gap between
ultrahigh anodic potential above 5.0 V vs. Li/Li+ [514] but suffer conventional LIBs and normal supercapacitors [537]. A 40 Wh kg1
from poor cathodic stability for the conventional graphite/carbon 1 Li-ion battery, which can be fully charged in 3 min, was fabricated
anode because they cannot form a stable SEI layer to prevent the in soft laminate packaging using a nanostructured Li4Ti5O12 anode,
electrolyte from further consumption [530]. Thus, sulfone-based activated carbon/LiCoO2 composite cathode and PVDF-hexafluor-
electrolytes are ideal partners for the Li4Ti5O12–anode battery opropylene (HFP) binder. The specific power of the battery reached
system because Li4Ti5O12 is usually operated above 1.0 V and a 4 kW kg1, which is comparable to that of an electrochemical
high operation potential cathode is required for combination with double-layer supercapacitor. As observed in Fig. 67, after 9000 cycles
Li4Ti5O12 to obtain a high voltage output. Abouimrane et al. used at a full depth of discharge, the capacity loss is only 20%. Similarly, Hu
the sulfone-based electrolytes for Li4Ti5O12/LiMn2O4 and et al. fabricated a hybrid battery capacitor using LiFePO4-activated
Li4Ti5O12/LiNi0.5Mn1.5O4 battery systems, which demonstrated carbon as a cathode and Li4Ti5O12 as an anode, which combined the
stable cycling performance [514]. In particular, a relatively stable advantages of the high rate capability of an activated carbon/
cycling performance with a capacity of 80 mA h g1 for Li4Ti5O12 hybrid capacitor and the high capacity of a Li4Ti5O12/
1000 cycles at 240 mA g1 was achieved for the Li4Ti5O12/1 M LiFePO4 battery [538].
LiPF6 in (tetramethyl sulfone (TMS)-EMC)/LiNi0.5Mn1.5O4 battery Zaghib et al. prepared the ‘‘18650’’ battery using carbon-coated
system. LiFePO4 as a cathode and carbon-free Li4Ti5O12 derived from a
Moreover, deep eutectic solvents (generally, a eutectic mixture solid-state reaction as an anode; this battery could deliver a
composed of 2 components; through hydrogen bond interac- capacity of 800 mA h [539]. More importantly, an outstanding
tions, its corresponding melting point is lower than that of each cycling stability was demonstrated, with a definitely stable
individual component and usually lower than 100 8C [531], e.g.,
lithium salt/N-methylacetamide) have also been used as electro-
lytes for the Li4Ti5O12/LiFePO4 battery system, which demonstrat-
ed good electrochemical performance [532]. The problem for deep
eutectic solvents is their high viscosity, which is even higher than
that of ionic liquids; thus, mixtures with low viscosity solvent may
currently be an effective selection.
Other liquid electrolytes with stability and a large window
have also been developed. Xiang et al. proposed a dimethylpho-
sphonate (DMMP)-based electrolyte of 1M LiPF6/
EC + DMC + DMMP (1:1:2 wt.) for a cell with a Li4Ti5O12 anode
and a LiNi0.5Mn1.5O4 cathode in a 3-V lithium-ion battery,
demonstrating that the nonflammable electrolyte exhibited good
compatibility with both the Li4Ti5O12 anode and the
LiNi0.5Mn1.5O4 cathode [533]. An oligo(ethylene oxide)-function- Fig. 66. Voltage profile for a Li4Ti5O12/LiCoO2 cell operated under the Partnership for
alized organosilicon compound (i.e., [3-(2-(2-methoxyethox- a New Generation of Vehicles (PNGV) 100-W h test profile. Data shown for every
y)ethoxy)-propyl]triethoxysilane) was developed by Qin et al. 200th cycle. [474].
60 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Batteries with Li4Ti5O12 anodes were believed to be much safer


than batteries with conventional graphite anodes because of their
higher lithium intercalation voltage and much higher thermal
stability. Several authors have conducted safety and stability
investigations of full cells with Li4Ti5O12 anodes. Belharouak et al.
examined the operational safety of a Li4Ti5O12/LiMn2O4 lithium-
ion battery system [540] by conducting accelerated rate calori-
metric tests on 18650 cells containing Li4Ti5O12 anodes and
LiMn2O4 cathodes and observed that no thermal runaway,
explosion or fire occurred. Amine et al. also demonstrated
outstanding abuse tolerance for a battery with a Li4Ti5O12 anode
and a LiMn2O4 cathode [168]. When the 2.5-V Li4Ti5O12/LiMn2O4
cell was overcharged to 15 V, the cell temperature reached only
80 8C with no explosion or thermal runaway; in addition, the cell
exhibited no capacity fade after 1000 cycles under aggressive
charge–discharge test conditions at 5 C and a temperature of 55 8C.
Takami tested a 2-V class lithium-ion battery system using a
Li4Ti5O12 anode [541] and observed that the short-circuit reaction
on the Li4Ti5O12 was 3 orders of magnitude slower than that on the
graphite anode. Thus, the Li4Ti5O12 anode was self-protecting
Fig. 67. Discharge capacity vs. cycle number for Li4Ti5O12/LiCoO2 cells made with
against the rapid discharge reaction of an internal short circuit,
55% LiCoO2 and 20% activated SuperP carbon, at matching ratio of 1.67.
(Galvanostatic cycling at 20 C charge–discharge rate between 1.6 and 3.0 V.) [537]. ensuring outstanding safety performance. Xiang et al. investigated
the effect of capacity matchup between a LiNi0.5Mn1.5O4 cathode
and a Li4Ti5O12 anode in the cell system [542] and observed that
capacity after 20,000 cycles at a charge rate of 10 C (6 min) and the cell with its capacity limited by Li4Ti5O12 exhibited better
discharge rate of 5 C (12 min), even a 95% capacity retention was tolerance to high voltage and overcharging than the cell with its
observed after 30,000 cycles at a charge rate of 15 C (4 min) and capacity limited by LiNi0.5Mn1.5O4. Thus, the former is recom-
discharge rate of 5 C, as shown in Fig. 68. High safety with no flame mended. All the above-mentioned tests demonstrate the out-
and no smoke detected during the testing was also reported, and standing safety of LIBs with Li4Ti5O12 anodes.
the maximum temperature reached was 72 8C. This battery was The Toshiba corporation developed a super charge/discharge
used in a real car with the charge time reduced to 5 min using three ion battery (SCiB) using Li4Ti5O12 as an anode that exhibited a high
levels charger in parallel (500 V, 125 A). Such outstanding stability level of safety, a long life of more than 6000 charge/discharge
gives the battery system great potential for EV applications. cycles—approximately 2.5 times more than regular LIBs, rapid
However, the low voltage of 1.9 V and correspondingly insufficient charging with 80% recharge in just 15 min, high power output
energy density (67.5 mWh g1) are the major limitations of this performance, and good cryogenic operation (down to 30 8C). This
battery system. type of SCiB has been applied in the i-MiEV (Mitsubishi innovative

Fig. 68. (a, b) Cycle life of a Li4Ti5O12/EC-DEC-1M LiPF6/LiFePO4 18650-cell: (a) the cycle charge rate is 10 C (6 min) at 100% SOC, the discharge rate is 5 C (12 min) at 100% DOD,
(b) the cycle charge rate is 15 C (4 min) at 100% SOC, the discharge rate is 5 C (12 min) at 100% DOD, (c) photographs of cars presented at the World Energy Council (Montréal,
September 2010), equipped with the Li4Ti5O12/LiFePO4 battery built with the same cells as described in the present work. The charging time is reduced to 5 min with three
levels charger in parallel (500 V, 125 A) [539].
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 61

The above conventional approach focused on the Li4Ti5O12


material itself to improve its specific capacity. Changing the
thinking patterns to pay attention to the electrode design instead
of the material itself will be a novel research direction, that is,
improvement of the total electrode capacity instead of the specific
capacity of Li4Ti5O12 itself. For example, in a typical commercial
anode electrode, there is usually 20 mg cm2 of active material,
(15 wt.%/85 wt.%)  20 mg cm2 of conductive agent and binder,
and 10 mg cm2 of current collector (i.e., copper foil) [437]. The
capacity based on the total electrode weight will only be
104 mA h g1 calculated from the theoretical capacity of Li4Ti5O12
(175 mA h g1). By designing a novel additive-free electrode with a
lightweight current collector (e.g., 2 mg cm2), the total electrode
capacity could increase to 152% compared with that of the
conventional electrode. Additionally, using a 3D current collector
Fig. 69. The critical challenges for the wide application of Li4Ti5O12 as an anode for to replace the conventional 2D current collector could effectively
LIBs. improve the current collection (Fig. 70) as well as the rate
capability and cycling performance. Several works are, or are
partially, consistent with this concept, such as Li4Ti5O12/graphene
electric vehicles) model by Mitsubishi Motors and used by Honda foam electrode [244], flexible thin film electrode from Li4Ti5O12
in its EV-neo and Fit EV electric scooters [543]. nanosheets [245] as presented in Section 3.2.3 (thin-film electro-
des), and Li4Ti5O12/CNT film electrode with an areal mass density
5. Critical challenges and new directions of 0.3 mg cm2 for its CNT current collector [544]. These
electrodes demonstrated excellent electrochemical performance;
With the concerted efforts of worldwide researchers and more importantly, these designs would significantly improve the
industry, the use of Li4Ti5O12 as an anode for LIBs has achieved capacity of the total electrode as well as the gravimetric energy
success even in practical application; however, it still faces several density of the battery system. However, there are still several
critical challenges for truly wide application as shown in Fig. 69. challenges for their commercial application, such as large open
spaces inside the Li4Ti5O12/graphene foam electrode [244] that will
5.1. Low theoretical capacity result in a low volumetric energy density, time-consuming
preparation process of flexible Li4Ti5O12 nanosheet film electrode
As mentioned in Section 2.2, the theoretical capacity of [245], and high cost for the methanol mediated floating catalyst
Li4Ti5O12 is 175 mA h g1 with a typical end potential of 1.0 V. chemical vapor deposition of CNTs [544]. Thus, future work to
As summarized in Section 3, the specific capacity of a Li4Ti5O12 overcome the low theoretical capacity of Li4Ti5O12 could be
anode could reach 160–170 mA h g1 and even the theoretical performed to focus on the novel electrode design instead of
capacity of 175 mA h g1 at a common rate (e.g., 1 C) by tailoring discharge to lower potential. Furthermore, the film-related
the nanostructure, morphology, composite and defect chemistry. properties (e.g., strength, repeated bendability, etc.), and prepara-
However, the challenge is that the theoretical capacity of Li4Ti5O12 tion cost should also be evaluated.
itself is low even compared with that of conventional graphite
anode (372 mA h g1) [8]. As mentioned in Section 2.2, a Li4Ti5O12 5.2. Compromise between tap density and rate capability
anode could deliver a significantly enhanced specific capacity with
an end potential lower than 0.5 V (e.g., 0.01 V). Importantly, The tap density is significant when an electrode material moves
Li4Ti5O12 still demonstrates a near zero-strain character with a from the lab to industry because it is directly related to the
lower end potential (i.e., 0 V) with only 0.4% lattice expansion volumetric energy density. The theoretical density of Li4Ti5O12 is
with 4.5 mol Li+ insertion according to theoretical calculations, 3.5 g cm3 [31,80,96,100]; a tap density of approximately half of
ensuring its structure stability within a potential range of 3.0–0 V. the theoretical density (i.e., 1.8 g cm3) remains very attractive for
Additionally, as summarized in Section 3.5, introducing a high commercial applications. As discussed in Section 3, Li4Ti5O12
theoretical capacity anode (e.g., SnOx and MO) into Li4Ti5O12 to materials with various nanostructures from 0D to 3D have been
form a composite anode operated within a potential range of 3.0– designed and successfully synthesized. These advanced nanos-
0.01 V should also be an effective approach to further improve the tructures resulted in greatly enhanced electrochemical perfor-
specific capacity; however, this approach will also cause the mance compared with that of the conventional coarse particles.
problem that the added high theoretical capacity anode usually Additionally, in the formation of a composite with a conductive
faces, that is, large volume variation during lithium insertion/ carbon substrate such as graphene, CNTs could also result in
extraction. In general, discharge to a lower end potential (e.g., improvement of the electrochemical performance of the Li4Ti5O12
0.01 V) results in an enhanced specific capacity for the Li4Ti5O12 anode. However, the above strategy usually introduces space (e.g.,
anode that still demonstrates near zero-strain character; however, larger mesopores, micropores, and space between particles) into
this approach also causes other problems: (1) an SEI layer will form the Li4Ti5O12 electrode material, leading to low tap density and
on the surface of the Li4Ti5O12 anode due to electrolyte energy density. Thus, there is a compromise between the tap
decomposition; because SEI is an electronic insulator, this will density and rate capability (or power density). Alternatively, the
lead to a negative effect on the electrochemical performance; (2) synthesis of microspheres or doping could achieve a high tap
the electrolyte selection will become a problem again for density as well as high power density. For microspheres, good
combination with a high operation potential cathode because control of the inner porosity is required to obtain a high tap
such an electrolyte usually appears to be unstable under 1.0 V; (3) density. As mentioned in Section 3.2.2, a high tap density of
the advantage of flat charge/discharge plateaus will disappear 1.62 g cm3 with a surface area of 15.5 m2 g1 as well as
because the charge/discharge curves between 0.5 and 0.01 V outstanding rate capability could be achieved for mesoporous
appear to be slope-shaped. Li4Ti5O12 submicrospheres [190]. Compared with the formation of
62 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Fig. 70. Schematic description of paths for electron transport in the conventional Li4Ti5O12 + additive electrode and the novel Li4Ti5O12/3D carbon current collector electrode
[601].

microspheres, doping could be achieved using a facile solid-state transfer could effectively result in enhanced low-temperature
method, which remains most preferred for commercial applica- performance. For instance, a smaller particle size could shorten the
tion. Importantly, the use of a solid-state method could easily diffusion length and offer more lithium insertion sites, which has
achieve a high tap density, and appropriate doping could improve demonstrated improved low-temperature performance compared
the electrochemical performance. For doping, a better understand- with that of a Li4Ti5O12 anode with larger particle size
ing of the mechanisms should be obtained; thus, researchers could [31,546,552]. Approaches for enhancing electron transfer in the
design and dope the proper element for required properties electrode have also been reported to result in improved low-
instead of trying every element from the periodic table. temperature performance, such as the formation of Li4Ti5O12/
Additionally, co-doping is suggested based on its success in carbon [11,547], and carbon-coated Li4Ti5O12/graphene compo-
ABO3 perovskite oxides. Treatment under a reducing atmosphere sites [419] and the use of a Cu/carbon composite as an conductive
during/after phase formation is also an affective approach to additive instead of common carbon (i.e., Super P) [548]. Doped
achieve a high tap density and rate capability because it can also be Li4Ti5O12 (La0.06Li3.94Ti5O12) has also been reported to result in
processed using a solid-state method. good low-temperature performance with a reversible capacity of
Briefly, to achieve a high tap density for a wide range of 118.3 mA h g1 at 0.1 C at a low temperature of 40 8C
commercial applications of Li4Ti5O12 anodes, it is suggested that [549]. Moreover, an impedance study suggested that the modifi-
future research should focus on the facile preparation of micro- cation of electrolyte-active material interfaces (e.g., optimization
spheres and the mechanisms of doping, co-doping, and treatment of the electrolyte composition) may also result in enhancement of
under reducing atmosphere as well as their effects on structural the low-temperature performance because there is obvious
stability instead of the development of hollow structures, high lithium ion transfer in the interface limiting process at lower
porosity and nanostructures with high specific surface area to temperature [550].
improve the rate capability. There are few reports on the low-temperature performance of
battery systems based on Li4Ti5O12 anodes [475,552–554]. Recent-
5.3. Poor performance at low temperatures ly, the low-temperature performance of a 18650 cell based on a
LiFePO4/carbon cathode and Li4Ti5O12/carbon anode was studied
The ability to adapt to a wide range of operating temperatures is [554]; even the electrochemical performance at 10 8C was
significantly important for the practical application of Li4Ti5O12 improved by using a low temperature electrolyte but it is still
anodes. As summarized in Section 2.3, lithium diffusion increases not very attractive. Thus, further research on the low-temperature
with increasing temperature. The enhanced kinetic performance of performance of Li4Ti5O12 should be performed, such as a detailed
Li4Ti5O12 anodes at higher temperature [545] could result in study of the mechanism and development of an effective approach
improved electrochemical performance compared with that at for improvement of the low-temperature performance. Impor-
room temperature. For the electrochemical performance of tantly, when researchers attempt to improve the specific capacity
Li4Ti5O12 anodes at elevated temperature, the problem should and tap density of the Li4Ti5O12 anode, the low-temperature
be the stability of the electrolyte instead of the Li4Ti5O12 anode performance should also be considered simultaneously because
itself. Thus, the low kinetic performance of the Li4Ti5O12 anode at Li4Ti5O12 is no longer only a material studied only in the lab but a
low temperature becomes a challenge for its commercial applica- material that is moving toward commercial application.
tion. Although numerous studies on the modification of Li4Ti5O12
anode have been performed, as described in Section 3, there are 5.4. Gassing problem
relatively few reports on its low-temperature performance
[11,31,160,419,546–552]. Such kinetic performance at low tem- For Li4Ti5O12 anode-based LIBs, gases (e.g., CO2, H2, CO) will
perature is highly related to the lithium ion and electron transfer in form during charge/discharge cycles and even during the storage
the electrode; enhancement of the lithium ion and/or electron process, which lead to serious swelling and further safety issues
B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71 63

[555,556]. Thus, the gassing problem (especially at elevated layer will form on the surface of a Li4Ti5O12 anode operated above
temperatures) is also a main obstacle for wide commercial 1.0 V because the operation potential is above the reduction-
application of Li4Ti5O12 anodes. He et al. observed that the reaction/decomposition of the electrolyte solution. However, He
formation of gases was mainly due to the reaction between et al. observed an SEI layer on the surface of Li4Ti5O12 via ex situ
Li4Ti5O12 and the electrolyte; CO2 will be generated even by simply TEM and indicated that the formation mechanism for Li4Ti5O12 was
soaking the electrode in electrolyte-free solvents, and H2 and CO different from that for graphite [556]. The formation of the SEI
(with minor gaseous hydrocarbon, e.g., CH4, C2H4 and C2H6, etc.) layer on the surface of Li4Ti5O12 was mainly due to the interfacial
will further form during the charge/discharge cycles [556]. Wu reactions between the electrolyte solution and Li4Ti5O12 instead of
et al. tested the cycling performance of a () Li4Ti5O12-C j a reduction reaction of the electrolyte solution. Song et al. also
electrolyte j LiNi1/3Co1/3Mn1/3O2 (+) soft-packed battery with 1 M observed an SEI layer on the surface of Li4Ti5O12 with an operation
LiPF6 in EC, DMC and EMC (1:1:1 in wt.% ratio) as the electrolyte potential above 1.0 V via TEM as well as XPS analysis [564]. These
and observed stable performance at 10 C with only 11% capacity researchers further indicated that the conductive carbon in the
loss after 5000 cycles at 25 8C [557]. The graphite anode cells electrode aids in the formation of the SEI layer on Li4Ti5O12 and acts
exhibited inferior performance with 20% capacity loss after as active sites for the SEI formation. These results suggest that an
1000 cycles at 25 8C. However, the Li4Ti5O12 anode cells exhibited SEI layer may form on the surface of Li4Ti5O12 with an operation
poor cycling performance at a high temperature of 55 8C because of potential above 1.0 V beyond the general understanding. However,
the gas generation (dominant gas: H2). These researchers further these studies were based on ex situ methods; future works using in
studied the mechanism of swelling of the Li4Ti5O12 anode-based situ characterization as well as powerful EIS analysis should be
battery system at elevated temperature and observed that the performed to further understand whether an SEI layer exists as
gassing problem was mainly attributable to the high electrochem- well as the formation mechanism.
ical redox potential compared with graphite [489]. They indicated In summary, the mechanism involved in the gassing problem
that the H2 and soluble species should originate mainly from linear remains unclear, and more detailed works should be performed to
carbonates; however, the gaseous alkylene and insoluble salts understand the reason for the gassing problem and enable the
were derived from cyclic carbonates. Guo et al. found that the discovery of an effective strategy to address this issue.
generated H2 and CO on the Li4Ti5O12 electrode might be highly
related to the (1 1 1) facet of Li4Ti5O12 phase based on comparative 5.5. Other applications in addition to electrode for LIBs
experiments of XRD analysis, electrochemical testing and gas
chromatography [558]. Belharouak et al. proposed another Because of the unique characteristics (e.g., zero-strain during
mechanism for H2 evolution in the Li4Ti5O12 anode-based battery charge/discharge cycling), Li4Ti5O12 has also been used for other
system, that is, H2 originated from moisture, whereas CO2 and CO purposes: as a coating layer to enhance the stability and
were suggested to be derived from the decomposition of the performance of other electrodes, as an electrode material for
electrolyte solution initiated by a strong Lewis acid (i.e., PF5) rechargeable sodium-ion batteries, and as an electrode material for
[555]. Recently, on-line electrochemical mass spectrometry was hybrid supercapacitors.
performed to investigate the gassing behavior to understand the
mechanism by Bernhard et al. [559], which supported Belharouak’s 5.5.1. As a coating layer to enhance the performance of other
hypothesis for H2 evolution. It was suggested that CO2 evolution electrodes
was due to a ring-opening reaction of alkyl carbonate caused by The use of Li4Ti5O12 in other anode materials to improve the
OH from H2O. However, the effect of the addition of water (200, electrochemical performance has been discussed in Sections
1000 and 2000 ppm) to the electrolyte (1 M LiPF6 in EC: EMC) on 3.5.3 and 3.5.5. In this section, we will briefly review the use of
the Li4Ti5O12/LiCoO2 battery system was recently investigated by Li4Ti5O12 as a coating layer to enhance the stability and
Burns et al. [560]. These researchers concluded that no major performance of other cathode materials.
detrimental effects on the electrochemical performance were Many cathode materials, especially Mn-containing cathode
observed in the presence of such amounts of water, suggesting materials, suffer from poor cycling performance, more so at elevated
relaxed requirements on the stringent control of water in the temperatures. Take LiMn2O4 as an example, the poor cycling
Li4Ti5O12/LiCoO2 battery system, which could further decrease the performance is originated from the dissolution of Mn ions by as-
cost of this system. Thus, the real mechanism for the gassing fromed HF acid, Jahn–Teller distortion, and decomposition of
problem remains unclear. Based on the above discussion, the main electrolyte on the surface of the electrode [565]. Surface coating of
reason for the gassing problem could be the reaction of the a proper material has been recognized as an effective approach to
electrolyte on the surface of Li4Ti5O12 or the presence of moisture. improve the cycling performance of the cathode materials. Various
Accordingly, the key to solving the gassing problem should be oxides, such as SiO2, Al2O3, and ZnO, have been studied as a coating
avoiding the reaction between Li4Ti5O12 and the electrolyte (e.g., layer due to their easy preparation. In addition, lithium-containing
surface coating [556,561,562]), or maintaining low moisture Li4Ti5O12 has been reported as a promising coating material for
content in the battery system. He et al. observed that a suitable cathodes, due to its zero-strain characteristic, and higher ion
nanoscale carbon coating along with a stable SEI film around conductivity compared to that of the conventional coating oxides.
Li4Ti5O12 could effectively prevent the interfacial gassing reaction Especially for a spinel cathode, a Li4Ti5O12 coating layer and cathode
[556]. Selecting a stable electrolyte is also important to obtain good could share the same spinel structure. Li4Ti5O12 has been reported as a
and stable performance for the Li4Ti5O12 anode, especially at coating layer for LiCoO2 [566–568], LiMn2O4 [565,569,570], LiMn1.4-
elevated temperatures. Zaghib et al. assembled and tested Ni0.4Cr0.2O4 [571], LiNi0.5Mn1.5O4 [572,573], Li1.5Ni0.25Mn0.75O2.5
Li4Ti5O12-C/LiFePO4-C batteries with different electrolytes [574], LiNi1/3Co1/3Mn1/3O2 [575], and Li[Li0.2Mn0.54Ni0.13Co0.13]O2
[563]. It was concluded that the cell with 0.5 M lithium [576] cathode materials to improve their electrochemical
bis(trifluoromethanesulfonyl)imide (LiTFSI) + 1 M LiBF4 in an EC- performance. For example, with a 3 wt.% Li4Ti5O12 coating layer,
g-butyrolactone electrolyte could operate at least up to 60 8C, even Li[Li0.2Mn0.54Ni0.13Co0.13]O2 electrode exhibited a stable cycling
at a high rate (>10 C). performance with a specific capacity of 245 mA h g1 after 50
Along with the gassing problem, another topic of interest is cycles at 25 mA g1 (capacity retention: 95%) compared to that of
whether significant SEI formation occurs on a Li4Ti5O12 anode uncoated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 electrode (specific capacity:
when operated above 1.0 V. It is generally accepted that no SEI 191 mA h g1 after 50 cycles; capacity retention: 74%) [576].
64 B. Zhao et al. / Materials Science and Engineering R 98 (2015) 1–71

Usually, Li4Ti5O12 coating is applied using a traditional sol–gel respect to standard hydrogen electrode (1 V vs. SHE), nanostruc-
process; however, it is difficult to produce a thin, uniform, robust, tured Li4Ti5O12 is considered an ideal material as the negative
and conformal coating layer. To further optimize the coating layer electrode for hybrid supercapacitors [477,586]. For example, a
to achieve a satisfactory electrochemical performance, other Li4Ti5O12/activated carbon couple with a typical nonaqueous
techniques for synthesis of Li4Ti5O12 shown in Section 3 could electrolyte (e.g., LiPF6 in EC/DMC) could exhibit a sloping voltage
be adopted, such as solvothermal-assisted processing [570] etc. profile from 3.0 to 1.5 V, 90% capacity utilization at 10 C rates, and
Even though a Li4Ti5O12 coating is superior to a conventional oxide 85–90% capacity retention after 5000 cycles [477]. The widened
coating, Li4Ti5O12 still suffer from its low electronic conductivity. operation voltage window has been reported to be 3.0–1.0 V [587],
Thus, it may be necessary to enhance the electronic conductivity and even 3.0–0.0 V [588]. The energy density of such a hybrid
and lithium-ion diffusivity of Li4Ti5O12, such as doping (Section supercapacitor depends sensitively on the property of the carbon
3.4), or surface treatment under a reducing environment (Section positive electrode material and cell operation voltage, whereas the
3.3.3, part (2)) by a controllable process. A more ‘‘conductive’’ power density is determined primarily by the properties of
Li4Ti5O12 coating would be more effective in improving the cycling Li4Ti5O12. As reported by Amatucci et al. in 2001, such a hybrid
stability and rate capability of the cathode materials. supercapacitor based on the Li4Ti5O12/carbon couple is no longer a
novel research topic, but it could bridge the gap in energy and
5.5.2. As an electrode material for rechargeable sodium-ion batteries power densities between electrical double-layer capacitors and
Since the physical and chemical properties of sodium are LIBs, which has attracted more interest during the past five years.
similar to those of lithium while sodium salts are less expensive than Besides the development of novel positive electrodes and
lithium salts, rechargeable sodium-ion batteries have received electrolytes, various Li4Ti5O12-based materials have been reported
extensive attention for various applications. Many electrode for superior hybrid supercapacitor with improved properties, such
materials for LIBs have been modified for use in sodium-ion as Li4Ti5O12 nanoparticles [589], doped Li4Ti5O12 [590], Li4Ti5O12
batteries, including Li4Ti5O12. By using Li4Ti5O12 as an anode for spheres [591], Li4Ti5O12 nanowire array [592], Li4Ti5O12/carbon
sodium-ion batteries, charge/discharge potential plateaus between nanofibers [150,155,593], Li4Ti5O12/carbon composite [594–596],
0.7 and 1.0 V vs. Na/Na+ was demonstrated and a reversible specific Li4Ti5O12/carbon hybrid nanotubes [597] and Li4Ti5O12/graphene
capacity of 145–155 mA h g1 could be achieved [577–580]. The [588,598,599]. However, the combination of more than one
potential plateaus are lower and the reversible specific capacity is strategies to enhance the performance of Li4Ti5O12 is yet rarely
comparable to that of Li4Ti5O12 anode in a LIB. Even though it was reported, such as doped Li4Ti5O12 on a carbon substrate. In fact, all
reported that 3 mol Na+ could be inserted into a Li4Ti5O12 unit, the the strategies as summarized in Section 3 could applied to further
mechanism was very different from that in LIBs; a three-phase improve the property of Li4Ti5O12 in a hybrid supercapacitor.
separation mechanism has been proposed with formation of
Li7Ti5O12 and Na6LiTi5O12 after Na-ion insertion, which has been 6. Conclusions and perspectives
confirmed by density functional theory calculations, in situ
synchrotron X-ray diffraction, and scanning transmission electron Carbon/graphite is the state-of-the-art anodic material for LIBs
microscope imaging techniques [578,579]. It was further proposed and has had great success in the portable electronics sector. For
that during the Na+ insertion process, the inserted Na+ will occupy two newly emerging fields, electrochemical energy storage and
the vacancy of 16c site and Li+ at 8a site will be driven into 16c site; a electric vehicles (including pure EVs, HEVs, and PHEVs), the
lattice volume expansion of 12.5% was found for the formation of carbon/graphite anode does not meet the safety and rate
Na6LiTi5O12 phase and the lattice volume expansion should be 6.3% performance requirements. Spinel Li4Ti5O12 is a promising
based on the Li7Ti5O12 and Na6LiTi5O12 two phases since the process alternative to the carbon/graphite anode given its outstanding
from Li4Ti5O12 to Li7Ti5O12 is zero-strain [578]. Thus, in the case for safety originating from its high lithium intercalation voltage and
sodium-ion batteries, Li4Ti5O12 is no longer a zero-strain material potentially long cycling stability, its zero-strain character and its
but is still attractive due to its low volume expansion during Na+ high thermal stability. However, the poor electronic conductivity
insertion/extraction. of Li4Ti5O12 limits its rate capability. To overcome this problem,
To date, several strategies have been adopt to improve the many strategies have been developed and some progress has been
electrochemical performance, such as synthesis of Li4Ti5O12 made. To realize large-scale commercial application of Li4Ti5O12 in
nanorods [581], hierarchically porous Li4Ti5O12 [170], Li4Ti5O12 LIBs, however, significant scientific and technological advances
nanoparticles embedded in carbon nanofibers [152], carbon- must still be made.
coated Li4Ti5O12 nanowires [582], carbon-nanotube decorated During the past several years, considerable attention has been
Li4Ti5O12 nanoparticles embedded in carbon nanofibers [583], and devoted to improving the rate capability and cycling stability of
copper-doped Li4Ti5O12/carbon nanofiber [584]. Even though an Li4Ti5O12. However, many of the technologies developed are too
improved electrochemical performance was demonstrated, the complicated to be cost-effective. Nanostructuring is widely applied
rate capability is still unsatisfactory compared to that in LIBs. and highly effective at improving the rate performance; however,
Typically, the specific capacity will decrease to <120 mA h g1 at it may increase the reactivity with liquid electrolytes and adversely
1 C rate as an anode for sodium-ion batteries, and even affect the cycling stability. In commercial LIBs, the electrodes are
<50 mA h g1 at 10 C rate [170]. Thus, future work could focus on the micrometer scale. Recently, we proposed a new concept for
on using a combination of several effective strategies (as discussed the development of a Li4Ti5O12-based electrode by forming a
in Section 3) to improve the electrochemical performance of composite with a solid lithium-ion conductor, lithium lanthanum
Li4Ti5O12 as an anode for sodium-ion batteries based on further titanate perovskite [600]. By introducing a lithium-ion conducting
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Bote Zhao is currently a postdoctoral fellow at the
School of Materials Science and Engineering at Georgia
Institute of Technology, USA. He received his B.S. and
Ph.D. from Nanjing Tech University, China. His research
Glossary
experiences include work with binder-free films,
Acronyms nanostructured materials and graphene-based materi-
als for lithium-ion batteries and supercapacitors as well
as the electrospinning synthesis of fibers, fabrication
1D: one-dimensional and water management of proton exchange membrane
2D: two-dimensional fuel cells, and hydrogen production from hydrous
3D: three-dimensional hydrazine. He is currently focusing on the synthesis
3DOM: three-dimensionally ordered macroporous and characterization of novel materials for batteries,
AFM: atomic force microscopy fuel cells, and supercapacitors.
BET: Brunauer–Emmett–Teller
CA: citric acid
CNTs: carbon nanotubes
CTAB: cetyltrimethylammonium bromide Ran Ran is an associate professor of Nanjing Tech
DMC: dimethyl carbonate University. She received her Ph.D. from Dalian Institute
DMA: dimethyl acetamide of Chemical Physics, Chinese Academy of Sciences, in
DMMP: dimethylphosphonate 2003. She was a visiting scholar of Petroleum Institute
EC: ethylene carbonate of Catalysis Madrid, Spain. She joined the college of
EDX: energy-dispersive X-ray spectroscopy chemistry and chemical engineering in Nanjing Tech
EG: ethylene glycol University in 2005. The main research fields: electrode
EIS: electrochemical impedance spectroscopy materials of lithium-ion batteries, hydrogen production
EMC: ethylmethyl carbonate process from hydrocarbon, anode coating catalyst of
EMIm-dca: 1-ethyl-3-methylimidazolium dicyanamide solid oxide fuel cells.
EPR: electron paramagnetic resonance
EVs: electric vehicles
FE-SEM: field-emission SEM
FRL: Friedman–Reich–Levi
FWO: Flynn–Wall–Ozawa Meilin Liu is a Regents’ Professor of Materials Science
GPE: gel polymer electrolyte and Engineering and Co-Director of the Center for
HEBM: high energy ball milling Innovative Fuel Cell and Battery Technologies at Georgia
HEVs: hybrid electric vehicles Institute of Technology, Atlanta, Georgia, USA. He
HFP: hexafluoropropylene received his BS from South China University of Technol-
HR-TEM: high resolution transmission electron microscopy ogy and both MS and Ph.D. from University of California
ICP-AES: Inductively coupled plasma atomic emission spectrometry at Berkeley. His research interests include in situ/
LiAc: lithium acetate operando characterization and multi-scale modeling of
LIBs: lithium-ion batteries charge and mass transfer along surfaces, across inter-
LiDFOB: lithium difluoro(oxalato)borate faces, and in membranes, thin films, and nanostructured
LiTFSI: lithium bis(trifluoromethanesulfonyl)imide electrodes, aiming at achieving rational design of
MA: maleic acid materials and structures with unique functionalities
MASNMR: magic-angle spinning nuclear magnetic resonance for efficient energy storage and conversion.
MiEV: Mitsubishi innovative electric vehicles
MWCNTs: multi-wall carbon nanotubes
NMR: nuclear magnetic resonance
P123: HO(CH2CH2O)20(CH2CH(CH3)O)70(CH2CH2O)20H Zongping Shao earned his Ph.D. from Dalian Institute
PAA: polyacrylate acid of Chemical Physics, Chinese Academy of Sciences, in
PAN: polyacrylonitrile 2000. He worked as a postdoc from 2002 to 2005 in
PANI: polyaniline California Institute of Technology, USA. He joined the
PEDOT: poly (3,4-ethylenedioxythiophene) college of chemistry and chemical engineering in
PEG: polyethylene glycol Nanjing Tech University in 2005, where he was
PHEVs: plug-in hybrid electric vehicles promoted to professor. Since then he is the director
PS: polystyrene of institute of new energy materials and technology. His
PVA: polyvinyl alcohol research interests include lithium-ion batteries, super-
PVB: polyvinyl butyral capacitors, solid oxide fuel cells, oxygen permeable
PVDF: polyvinylidene fluoride membranes and polymer electrolyte membrane fuel
SCiB: super charge/discharge ion battery cells. He has published over 300 international journal
SEI: solid electrolyte interface papers with a total citation of >9000.