A Study of Electro Materials For Lithium-Ion Batteries

University of Wollongong Theses Collection
University of Wollongong Theses Collection

University of Wollongong Year 
A study of electro materials for

lithium-ion batteries
Yueping Yao
University of Wollongong
Yao, Yueping, A study of electro materials for lithium-ion batteries, PhD thesis, In-
stitute for Superconducting and Electronic Materials, University of Wollongong, 2008.
http://ro.uow.edu.au/theses/88
This paper is posted at Research Online.

http://ro.uow.edu.au/theses/88
A STUDY OF ELECTRO MATERIALS
FOR LITHIUM-ION BATTERIES
A thesis submitted in fulfillment of

the requirements for the award of
Doctor of Philosophy
YUEPING (Jane) YAO, B.Sc. M. Eng
University of Wollongong
Institute for Superconducting & Electronic Materials

Faculty of Engineering
2008
CANDIDATE’S CERTIFICATE
This is to certify that the work presented in this thesis is original and was carried out by
the candidate in the laboratories of the Institute for Superconducting & Electronic
Materials (ISEM) and the Faculty of Engineering at the University of Wollongong, New
South Wales, Australia. It has not been submitted for a degree to any other university or
institution.
Yueping (Jane) Yao
Wollongong, Australia
2008
i
ACKNOWLEDGEMNENTS
I would firstly like to express my sincere gratitude and thanks to my research supervisors,
Professor H. K. Liu and Dr. K. Konstantinov, for their consistent academic supervision,
guidance and encouragement throughout may research. I also express my gratitude to the
Director of ISEM, Professor Shixue Dou, for support and financial assistance for my PhD
project. I am deeply indebted to the Australian Research Council (ARC) for the financial
support through the ARC Linkage project LP0453766.
I thank all the hard-working technical and administrative staff in ISEM and the Faculty of
Engineering, in particular Mr. Ron Kinnel, Mr. N. Mackie, and Mr. G. Tillman. They have
provided me with tremendous help in all my experiments. Thanks are also to Dr. T. Silver
for providing great help in proofreading this thesis.
Finally, I would like to express my gratitude to all other staff and to my fellow students at
the Institute for Superconducting and Electronic Materials for their constant
encouragement.
ii
Abstract
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Abstract
Lithium-ion batteries (or rechargeable lithium batteries) are most advanced battery
technology for modern portable electronics such as mobile phones, notebook
computers and cameracorders. There are also big potentials for lithium-ion batteries
to be used for electric vehicles (EVs), hybrid electric vehicles (HEVs) and stationary
power storage. In particular, the later will bring a significant contribution to reduce
green-house gas emissions and address global warming and climate change. Materials
research plays a key role in the development of next generation of advanced
lithium-ion batteries with high energy density, high power density, and long cycle
life.
This PhD thesis describes my exploration on developing new anode materials and
cathode materials for lithium-ion batteries. I firstly investigated silicon based anode
materials since silicon has the highest theoretical lithium storage capacity of about
4200 mAh/g when forming Li21Si5 alloys. The reversible lithium storage mechanism
is totally different from that of graphite based anode. It relies on a process called
alloying and dealloying instead of intercalation and de-intercalation. However, the
formation of Li21Si5 alloys can induce more than 400% volume expansion. The
repeated expansion and shrinkage of the silicon electrode will cause cracking and
eventually failure of the battery system. A general strategy has been employed to
solve this problem. Firstly nanosize silicon powders were used to minimize the
volume expansion in local domains. Secondly, silicon particles were embedded in
carbon matrix to buffer the volume change during the reaction with lithium.
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Abstract
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Si-mesocarbon microbeads (MCMB) composite anode materials were produced by
ball-milling. Si-MCMB composite electrodes demonstrated superior performance
(high capacity and satisfactory cyclability), compared to bare MCMB and bare
nano-Si electrodes. Silicon-amorphous carbon composite anode materials were also
prepared by carbon aerogel method, through which nanosize silicon particles are
homogeneous distributed in carbon matrix. A reversible capacity of 1450 mAh/g for
Si-C composite anodes was achieved. The good cyclability should be attributed to the
usage of nanosize Si powders and their homogeneous distribution in an amorphous
carbon matrix.
Carbon nanotubes have many unique and intriguing properties, including as anode
materials for lithium-ion batteries. Vertically aligned multiwalled carbon nanotubes
(VAMWCNTs) were prepared by chemical vapor deposition method. Nanosize
SnO2-MWCNTs composites were also synthesized. The VAMWCNTs have a typical
diameter of several tens of nanometers and consist of compartment structures. Cyclic
voltammetry measurements show that the carbon nanotubes are electrochemically
active to lithium insertion and extraction. A reversible lithium storage capacity of 950
mAh/g has been achieved for CNTs anodes. The solution-based chemical process
enables Sn2+ ions to penetrate into the inner cavity of the carbon nanotubes. The
SnO2-CNTs composite electrodes exhibited stable cyclability with a lithium storage
capacity of 410 mAh/g after fifty cycles.
Transition metal phosphides such as MnP4 and Zn3P2 were discovered to exhibit
interesting phenomena with respect to reversible lithium storage. They were
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Abstract
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conventionally synthesized by solid state sintering at high temperature for long
periods. After sintering, the products were purified by acid etching, which is a very
tedious process. Crystalline iron phosphide (FeP4) powders were directly prepared by
a solvothermal synthesis technique. Cyclic voltammetry measurements demonstrated
the reversible reactivity of FeP4 anodes towards lithium insertion and extraction. The
FeP4 anode exhibited a stable lithium storage capacity about 700 mAh/g.
Lithium iron phosphate has been emerging as a new cathode material for lithium-ion
batteries with low cost. However, lithium iron phosphate has a very lost electronic
conductivity, inducing low rate capacity and preventing commercial application.
Various cation dopings have been studied with the goal to improve the overall
electrochemical performance of lithium iron phosphate. The synthesis, crystal
structure refinement, magnetic and electrochemical properties of a series of
LiMnxFe1-xPO4 cathode materials was investigated. A number of conductive
phosphides and manganese phosphates were found to be formed during the sintering
process with the effect of enhancing the electronic conductivity of the materials. The
effect of sintering temperature towards the crystal size of LiFePO4 and
Li0.95Mg0.05PO4 compounds were systematically investigated. LiFePO4 and
Li0.95Mg0.05PO4 samples exhibit a typical antiferromagnetic behaviour. This
antiferromagnetism could be induced by long range Fe-O-P-O-Fe triple exchange due
to the lack of direct Fe-O-Fe interactions. LiFePO4 and Li0.95Mg0.05PO4 electrodes
show specific capacity in the range 150 mAh/g – 160 mAh/g.
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Contents
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Contents
CANDIDATE’S CERTIFICATE i
ACKNOWLEDGEMENTS ii
ABSTRACT iii
CONTENTS vi
CHAPTER 1 INTRODUCTION 1
CHAPTER 2 LITERATURE REVIEW
2.1 Batteries 4
2.2 Rechargeable batteries 6
2.3 An introduction of lithium-ion batteries 7
2.4 Fundamentals of Lithium ion Batteries 10
2.5 Cathode Materials for Lithium-ion Batteries 14
2.5.1 LiCoO2 and doped LiMxCo1-xO2 cathode materials 15
2.5.2 LiNiO2 and doped LiMxNi1-xO2 cathode materials 19
2.5.3 Layered LiMnO2, orthorhombic LiMnO2 and their doped
compounds 23
2.5.4 Spinel LiMn2O4 and LiMxMn2-yO4 cathode materials 28
2.5.5 Lithium iron phosphate based cathode materials 36
2.5.5.1 Crystal structure of LiFePO4 38
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2.5.5.2 Enhancement of electronic conductivity and
improvement of electrochemical properties of
LiFePO4 cathode material 43
2.6 Anode Materials for Lithium-ion Batteries 46
2.6.1 Carbon based anode materials 47
2.6.2 Alloy based anode materials 52
2.6.3 Metal oxide anode materials 56
2.6.3.1 Tin oxide anode materials 56
2.6.3.2 Transition metal oxide anode materials 59
CHAPTER 3 EXPERIMENTAL
3.1 Materials and chemicals 62
3.2 Materials synthesis techniques 63
3.2.1 High energy ball milling 63
3.2.2 Carbon aerogel synthesis 63
3.2.3 Chemical vapor deposition (CVD) 64
3.2.4 Hydrothermal synthesis 64
3.2.5 Sol-gel synthesis 64
3.2.6 Solid-state reaction synthesis 65
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3.3 Materials characterization 65
3.3.1 Structure characterization 65
3.3.2 Material morphology observation 66
3.3.3 Magnetic property measurement 68
3.3.4 Electrochemical testing 68
3.3.4.1 Electrode fabrication 68
3.3.4.2 Cell assembly 69
3.3.4.3 Electrochemical testing 70
(i) Charge/discharge of cells 70
(ii) Cyclic voltammetry 70
CHAPTER 4 PREPARATION AND CHARACTERIZATION OF Si-
MCMB AND SI-CARBON COMPOSITE ANODE MATERIALS
4.1 Introduction 72
4.2 Experimental 73
4.2.1 Preparation of Si-MCMB composite 73
4.2.2 Preparation of Si-carbon composite 74
4.3 Results and discussion 75
4.3.1 Si-MCMB composite anode materials 75
4.3.2 Si-carbon composite anode materials 87
4.4 Conclusions 94
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Contents
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CHAPTER 5 MULTIWALLED CARBON NANOTUBES (CNTs) ANODE
MATERIALS
5.1 Introduction 96
5.2 Experimental 97
5.2.1 Synthesis of vertically aligned CNTs 97
5.2.2 Synthesis of SnO2-CNTs composites 99
5.2.3 Physical and structural characterization 99
5.2.4 Electrochemical measurement 100
5.4 Conclusions 116
CHAPTER 6 SYNTHESIS AND ELECTROCHEMICAL
CHARACTERISATION OF IRON PHOSPHIDE AS ANODE MATERIAL
FOR LITHIUM-ION BATTERIES
6.1 Introduction 118
6.2 Experimental 119
6.4 Conclusions 127
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Contents
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CHAPTER 7 CHARACTERISATION OF OLIVINE-TYPE LiMnxFe1-xPO4
CATHODE MATERIALS
7.2.1 Materials synthesis 129
7.2.2 Magnetic measurement 130
7.2.3 X-ray diffraction and SEM analysis 130
7.4 Conclusions 138
CHAPTER 8 ELECTROCHEMICAL AND MAGNETIC
CHARACTERISTICS OF LiFePO4 AND Li0.95Mg0.05FePO4 CATHODE
MATERIALS
8.2.1 Materials synthesis 143
8.2.2 Magnetic measurement 144
8.3.1 XRD and SEM analysis 145
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8.3.2 Magnetic properties of LiFePO4 and Li0.95Mg0.05PO4 150
8.3.3 Electrochemical performance of LiFePO4 and
Li0.95Mg0.05PO4 cathode materials 157
8.4 Conclusions 161
CHAPTER 9 GENERAL CONCLUSIONS AND SUGGESTIONS FOR
FUTURE STUDY
9.1 General conclusions
9.1.1 Silicon based composite anode materials 162
9.1.2 Carbon nanotubes and tin oxide – carbon nanotubes anode
materials 163
9.1.3 Novel iron phosphide anode materials 163
9.1.4 Lithium iron phosphate and manganese doped lithium iron
phosphate cathode materials 164
9.1.5 Electrochemical and magnetic properties of magnesium
doped lithium iron phosphate cathode materials 164
9.2 Recommendations for future studies 165
REFERENCES 167
FIGURE CAPTIONS AND TABLES 183
PUBLICATIONS 189
xi
Chapter 1 Introduction
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Our modern societies currently are heavily reliant on fossil fuels to supply energy for
all our daily lives. Global warming and climate change are among the most serious
challenges facing us today. The main cause is increasing greenhouse gas
concentrations, primarily due to the burning of fossil fuels. To protect the health and
economic well-being of our global society, we must reduce greenhouse gas emissions
by using clean energy and renewable energy. The combustion of fossil fuels in
vehicles is responsible for about 22% of global CO2 emissions. The rechargeable
battery is an important system for electrochemical energy storage and conversion.
Lithium-ion batteries have the highest energy density among all the secondary battery
systems and represent state-of-the-art power sources for consumer electronics.
Although lithium-ion batteries possess a high energy storage capability, they still
cannot meet the requirements for large-scale energy storage and electric vehicles
applications. On the other hand, the global market for small rechargeable batteries is
on an impressive scale and growing, mainly due to the spectacular increase in the use
of mobile communications and portable electronics. All of these factors drive the
development of the next generation of rechargeable lithium batteries with excellent
performance characteristics, such as high energy density, long cycle life, and
absolutely safe operation. The electrochemical performance of lithium-ion batteries is
mainly determined by the physical, chemical, and structural properties of the cathode
materials and anode materials used in the battery system. This PhD thesis aims at
exploring and investigating a number of new and innovative anode materials and
cathode materials for lithium-ion batteries. A systematic study has been performed,
1
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including materials preparation, structural characterisation, physical characterisation
and electrochemical testing.
Chapter 2 presents a literature review on lithium-ion batteries and electrode materials
for the lithium-ion battery system. The basic concepts of batteries, rechargeable
batteries and lithium-ion batteries are reviewed. Then, the properties and current
status of all cathode materials for lithium-ion batteries are summarised. These include
LiCoO2 and doped LiCoO2, LiNiO2 and doped LiNiO2, layered LiMnO2, spinel
LiMn2O4, LiFePO4, and their transition metal doped derivatives. Finally, a
comprehensive survey on anode materials for lithium-ion batteries is conducted. The
merits, disadvantages, and challenges of carbon based anode materials, alloy based
anode materials, and metal oxide materials are analysed.
Chapter 3 contains the experimental details of this study. The experimental
procedures are fully described, along with all materials, chemicals, and facilities used
in this work.
Chapter 4 presents the synthesis, structural characteristics, and electrochemical
performance of two types of anode materials: Si-mesocarbon microbead (MCMB)
composites and nanocrystalline Si-carbon composites. By combining the high
capacity element Si and carbon, the composite anode materials can deliver much
higher capacity than bare carbon and also maintain good cyclability.
Carbon nanotubes are a new emerging one dimensional materials with many unique
functions. In Chapter 5, the reversible lithium storage properties were investigated.
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Vertically aligned carbon nanotubes were synthesised by a controlled chemical
vapour deposition (CVD) technique. Tin oxide – carbon nanotubes composites were
prepared to increase the specific capacity by utilizing the high capacity of SnO2.
Chapter 6 presents the preparation and electrochemical testing of iron phosphide
anode materials. Iron phosphide compounds were prepared by hydrothermal
synthesis. The as-prepared iron phosphide anode materials were electrochemically
active in lithium-ion cells and demonstrated a stable lithium storage capacity of about
700 mAh/g.
Chapter 7 describes the structural characteristics, magnetic properties and
electrochemical performance of a series of manganese doped lithium iron phosphate
cathode materials. The detailed lattice parameters of LiMnxFe1-xPO4 compounds
were obtained through Rietveld refinement on the X-ray diffraction patterns. The
undoped lithium iron phosphate cathode shows better electrochemical performance
than the doped cathode materials.
Chapter 8 presents the electrochemical and magnetic properties of lithium iron
phosphate and magnesium doped lithium iron phosphate cathode materials, in which
magnesium ions are doped into Li sites. It was found that the electrochemical
performance of lithium iron phosphate is closely related to the sintering temperature.
Finally, an overview and summary of this study are presented in Chapter 9, and
suggestions for future work are also proposed.
3
Chapter 2 Literature Review
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2.1 Batteries
Energy consumption/production relying on fossil fuels has a detrimental impact on
the world economy and environment. Electrochemical energy is regarded as an
alternative green energy/power source. There is an increasing need for efficient, high
energy power sources for a variety of applications. Batteries, in particular,
rechargeable battery systems, are important systems for electrochemical energy
storage and conversion. In his 2006 State of the Union Address, the U.S. president
George W. Bush claimed, “We must change how we power our automobiles. We will
increase our research on better batteries for hybrid and electric cars.” The discovery of
new electrode materials for batteries could dramatically increase energy density,
reducing the cost of electrochemical power systems, and so open up the capacity to
advance into an electric vehicle/hybrid electric vehicle (EV/HEV) age.
Batteries are self-contained units that store chemical energy and convert it directly
into electrical energy to power various devices. Batteries are generally categorized
into three classes: (i) Primary batteries. They are discharged once and discarded, (ii)
Rechargeable batteries. They can be repeatedly discharged and charged many times.
The batteries can be restored to their original condition by charging with a reverse
current flow, (iii) Specialty batteries. They are designed to meet a special purpose.
Specialty batteries are mainly used for military and medical applications. Batteries
provide power sources serving all aspects of both our daily lives and industry. The
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estimated battery market is about US $50 billion worldwide. Basically, batteries
consist of a positive electrode (the cathode), an electrolyte, and a negative electrode
(the anode). The cathode is an electron acceptor, such as lead oxide, manganese
dioxide, or lithium cobalt oxide. The anode is an electron donor, such as lead, zinc, or
lithium. The electrolyte usually is a pure ionic conductor that physically separates the
anode from cathode, allowing only ionic transport but not electronic conduction. A
schematic of battery operation is illustrated in Fig. 2.1 [1]. Battery electrolytes are
usually used in the form of a porous electrically insulating material soaked with
electrolyte. Battery electrolytes can be divided into aqueous, nonaqueous, and
solid-state electrolytes. The aqueous electrolytes are normally salts of acids or bases,
and have high ionic conductivity, on the order of 1 S/cm. From the thermodynamic
and kinetic point of view, aqueous electrolytes have an electrochemical stability
limitation less than 2.0 V. The nonaqueous organic solvent-based electrolytes have
lower ionic conductivity, on the order of 10-2 – 10-3 S/cm. The operating voltage of an
organic electrolyte is limited to ~ 4.6 V. Solid-state electrolytes are referred to as
polymer-based electrolytes and usually have low ionic conductivity in the range of
10-4 – 10-6 S/cm.
Fig. 2.1 Schematic diagram of the battery and battery operation.
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2.2 Rechargeable batteries
A rechargeable battery system is defined as a system that can be discharged and
charged again for many times over a long period. The chemical energy can be restored
by charging the battery using a reverse current. Rechargeable batteries can be
generally divided into lead acid batteries, lithium-ion batteries, and nickel cadmium
batteries, nickel metal hydride batteries. The energy densities of those recharge able
battery systems are compared in Fig. 2.2 [2]. Among all the rechargeable battery
systems, lithium-ion batteries have the highest energy density.
Fig. 2.2 Gravimetric and volumetric energy densities of different rechargeable battery
systems [2].
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2.3 An introduction to lithium-ion batteries
In the past, the development of the lithium based battery system was motivated by the
fundamental properties of the element lithium. Lithium is the most electronegative
(-3.04 V) element versus the standard hydrogen electrode (SHE) and also the lightest
(MW = 6.94 g/mol, ρ = 0.53g/cm3). Therefore, a battery system with lithium as the
electrode could deliver high energy density. The earliest version of the lithium battery
was the Li/(CF)n battery with a cell potential of 2.8 – 3.0 V. It was proposed that
lithium initially intercalates into the carbon mono fluoride lattice and then forms
lithium fluoride as the final reaction product [3, 4].
Li + (CF)n → Lix(CF)n → C + LiF (2.1)
Later, in the early 1970s, various primary lithium batteries were developed and
demonstrated in the United States. The Li/SOCl2 cell was one of primary lithium
battery systems [5]. Sanyo also successfully developed and marketed lithium batteries
with the Li/MnO2 cell [6]. Most primary lithium batteries have been developed for
medical and military applications. For example, implantable cardiac defibrillators use
Li/Ag2V4O11 batteries [7, 8]. The development of rechargeable lithium batteries came
from the discovery of some inorganic compounds that can react with lithium ions in a
reversible way. This led to the development of battery systems that use lithium as
anode and layered transition metal dichalchogenides (TiS2), chalcogenides (NbSe3),
and molybdenum sulfide (MoS3) as cathode [9, 10]. The discovery of so-called
intercalation compounds was a crucial step in the development of rechargeable
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lithium batteries. The intercalation materials host lithium ions inside their crystalline
structure. The lithium ions can be reversibly inserted into and extracted from the hosts.
This topotactical electrochemical reaction could occur reversibly without a major
phase change and with no damage to the material structure. From that time, a new
electrochemistry for energy storage started to spring up, involving more and more
solid state chemistry. However, many difficulties were encountered during the early
development of rechargeable lithium batteries. A stable electrolyte medium
containing lithium had to be identified. The electrolyte must consist of some lithium
salts dissolved in an organic solvent. A reversible positive electrode material needed
to be found.
Lithium metal was initially used as the negative electrode in the rechargeable lithium
battery system. However, lithium dendrites usually grow during repeated
charge/discharge cycling, resulting in short cycle life and cell shorting. A short circuit
could cause serious safety problems such as fire and explosion, and the eventually led
to the abandonment of lithium metal as the anode material in rechargeable lithium
batteries. Substituting Al for lithium metal solved the dendrite problem, but the
electrode could only be charged and discharged for a limited number of cycles due to
significant volume change [11]. Since then, many lithium alloys have been developed
as alternative anode materials. The energy densities of lithium alloys normally are
reduced by a factor of two or three, compared to pure lithium metal. Unfortunately,
the volume changes related to the insertion/extraction of Li into/from alloy matrices
are quite substantial (200 – 600 %) [12-16]. These cause a fast disintegration of the
alloy anodes by cracking and crumbling. As a result, short cycle life and low cycling
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efficiency are induced. In the late 1980s, graphitic carbon was found to be
dimensionally stable for lithium insertion and extraction. Intercalation of lithium ions
corresponding to the composition LiC6 results in only about a 10% increase in the
layer distance [17, 18]. Therefore, graphite became the choice of anode materials for
the lithium-ion battery in place of lithium metal and lithium alloys.
The cathode material is also a critical electrode material for the development of
rechargeable lithium batteries. The search for cathode hosts has been continued for
more than two decades. Except for low-dimensional materials, the three dimensional
framework structure compound V6O13 was also found to function for lithium perfectly
intercalation and de-intercalation [19]. The family of lithium metal oxides LixMO2
(where M is Co, Ni, or Mn), was first reported as a source of cathode materials for
rechargeable lithium batteries by Mizushima and Goodenough et al. in 1980 [20].
This family of cathode compounds is the predominant choice in current commercial
lithium ion battery production.
The electrochemical performance of the lithium-ion battery is also strongly dependent
on the electrolyte. Many solutions were proposed, from well-known propylene
carbonate (PC) and ethylene carbonate (EC) to ether-based solutions, such as
1,3-dioxolane or 3-MeTHF [21]. In general, electrolytes for the lithium-ion battery
are based on organic systems, which consist of organic solvents and lithium salts. The
moisture is strictly controlled to avoid any side reaction. Polymer electrolytes have
also been developed to construct so-called all-solid-state lithium-ion batteries. Such a
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system provides a fundamental safeguard for battery operation since no liquid
electrolyte is present inside the battery [22, 23].
The combination of an intercalation anode host and cathode host, as well as an
appropriate organic electrolyte, has been emerging in lithium-ion battery technology
since 1990. This battery technology is also called rocking-chair technology. Sony
Corporation successfully commercialized rechargeable lithium batteries with
C/LiCoO2 in 1991 [24]. This new class of rechargeable batteries had a potential
exceeding 3.6 V (almost three times that of alkaline systems) and energy densities of
120 – 150 Wh/kg (two to three times that of Ni-Cd and Ni-MH batteries). Today,
lithium-ion batteries are becoming the dominant power sources for portable electronic
devices, military applications, aerospace, and, especially, for wireless
telecommunication.
2.4 Fundamentals of Lithium ion Batteries
Lithium metal free lithium batteries were originally termed “rocking chair” batteries
(RCB) by Armand [25]. The basic concept of operation for the RCB system was
partially derived from concentration cells, which consist of essentially identical
electrodes in different reactant concentrations [26]. After the RCB concept was
revealed, this concept was demonstrated using transition metal compound anodes and
cathodes [27-28]. Later, new names for this technology appeared: lithium ion,
Shuttlecock and Swing Electrode System, etc., but the fundamental concept remained
the same.
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Fig. 2.3 The operating principle of the lithium-ion battery.
In a lithium-ion cell, the Li+ ions shuttle between the cathode and anode hosts during
the discharge and charge processes. The principles of lithium-ion battery operation
are shown in Fig. 2.3 [29]. Lithium ions are extracted from the cathode, go through
the electrolyte and separator and are inserted into the anode structure. The reverse
process happens during discharging. In order to achieve high cycling efficiency and
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long cycle life, the movement of Li ions in anode and cathode hosts should not change
or damage the host crystal structure. The design of a lithium-ion battery system
requires careful selection of electrode pairs to obtain a high operating voltage (Vc).
The operation of lithium-ion batteries obeys the thermodynamic laws. Therefore, the
electrochemical reaction in lithium-ion batteries follows the Gibbs-Helmholtz
equation:
ΔG = ΔH - TΔS (2.2)
ΔG - free energy of the reaction
ΔH – reaction enthalpy
ΔS – reaction entropy
The free energy ΔG is also related to cell voltage for the electrochemical reactions
occurring at the two separate electrodes, based on Faraday’s law:
ΔG = -nFE (2.3)
Where n is the number of electrons transferred; F is the Faraday constant (96500); and
E is the cell voltage (the potential difference between positive electrode and negative
electrode).
A high Vc can be realized with an anode and cathode that have, respectively, smaller
and larger work functions φa and φc. The open-circuit voltage Voc of the cell can be
calculated from the following formula:
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Voc = (φc - φa) / e (2.4)
where e is the electronic charge. A schematic energy level diagram showing the work
functions is presented in Fig. 2.4.
E
Ec
ϕa
EF
φc Eg
Voc
EF
Ev
Cathode Electrolyte/separator Anode
Fig. 2.4 Schematic energy diagram of a cell at open circuit.
The Fermi energies (EF) of the anode and cathode must lie within the band gap (Eg) of
the electrolyte. Therefore, the anode and cathode materials are thermodynamically
stable in contact with the electrolyte, and there will be no side reduction or oxidation
of the electrolyte.
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2.5 Cathode Materials for Lithium-ion Batteries
Cathode materials play an important role in the operation of lithium-ion batteries.
They provide lithium ion sources (Li+) for the Li-ion “shuttle” between the cathode
and the anode. Since carbon materials are widely used as anodes in lithium-ion
batteries, which have a potential close to that of Li/Li+ reference electrode, the voltage
of lithium-ion batteries is mainly determined by the potential of cathode materials.
Therefore, cathode materials must meet some strict requirements: (i) The cathode host
must be structurally stable for repeated lithium ion intercalation and de-intercalation.
The variation of the lattice structure should be as small as possible during the battery
operation process to maintain long cycle life. (ii) The cathode materials must have a
high potential relative to Li/Li+ reference electrode to enable high operating voltage
(high energy density). (iii) The cathode materials should contain as great an amount of
lithium as possible, and those lithium atoms must be electrochemically extractable
from the host crystal structure (high capacity). (iv) The cathode materials should have
high electronic conductivity and high lithium chemical diffusion coefficient to keep
high rate capacity (high power density). (v) The cathode materials should be low cost,
non-toxic, and easy to prepare. A large number of materials were investigated as
cathode materials for lithium-ion batteries. However, the number of different
compounds which are suitable as cathode hosts for lithium-ion batteries is quite
limited, due to the critical requirements such as high energy density, good cyclability,
and safety.
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Although LiCoO2 cathode materials are popularly used in commercial lithium-ion
battery production, currently, new layered and spinel structure cathode materials are
under extensive investigation worldwide. Their selection is mainly driven by reasons
such as reducing the cost, increasing environmental friendliness, and developing a
new generation of lithium-ion batteries for power storage and electric vehicle (EV)
applications. The layered and spinel structure cathode materials for lithium-ion
batteries mainly include layered structure LiCoO2, LiNiO2, LiMnO2, and spinel
LiMn2O4, as well as their doped derivatives. Recently, lithium iron phosphate
compounds have also emerged as new cathode materials for lithium-ion batteries.
2.5.1 LiCoO2 and doped LiMxCo1-xO2 cathode materials
In 1980, J.B. Goodenough et al. proposed and tested LiCoO2 as cathode for lithium
batteries. It was surprisingly found that LiCoO2 cathode had a high charge and
discharge voltage in the range of 3.6 – 3.8 V in the cell configuration of LixCoO2 / Li
[30]. After almost 10 years, SONY made the first batch of lithium-ion batteries with
the combination of a LiCoO2 cathode and a carbon anode [31]. Since then, lithium-ion
batteries have been under massive commercial production and dominated the
rechargeable battery market.
LiCoO2 compound has a layered α-NaFeO2 type structure (SP: R3m), with the
oxygen in a cubic close-packed array. This structure is closely related to the rock-salt
structure. The Li+ and Co3+ ions are located at octahedral 3(a) and 3(b) sites and
ordered on alternating (111) planes, inducing a hexagonal symmetry. The LiCoO2
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crystal lattice has lattice parameters of a = 2.816 Å and c = 14.08 Å. Fig.2.5 shows a
schematic of the LiCoO2 crystal structure.
Fig. 2.5 The structure of layered LiCoO2.
T. Ohzuku et al [32] investigated the mechanism of the reaction at the LiCoO2
electrode in lithium cells using in situ X-ray diffraction (XRD) and concluded that the
reaction at the LiCoO2 electrode in lithium cells can be divided into three regions. In
the region 0 < x < 1/4 in Li1-xCoO2, the coexistence of two hexagonal phases was
observed. The reaction in terms of lithium insertion and extraction in this region is a
topotactic two-phase reaction. In the region 1/4 < x < 3/4 in Li1-xCoO2, the reaction
taken as a whole is a single phase reaction. In the region 3/4 < x < 1, the reaction is a
two-phase reaction [32]. Removal of lithium corresponding to 1 mole Li per formula
LiCoO2 delivers a theoretical capacity of about 274mAh/g. However, only part of the
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lithium can be reversibly extracted and inserted due to structural restriction [33]. If the
charging voltage is limited to 4.2 - 4.25 V versus Li/Li+, LiCoO2 cathode can provide
a specific capacity of 150mAh/g over 1000 charge-discharge cycles without
significant specific capacity loss.
Electrochemically active LiCoO2 compounds can be prepared by many synthetic
techniques. Solid-state reaction is commonly used by sintering a mixture of cobalt
oxide (or cobalt carbonate) and lithium carbonate (or lithium hydroxide) at high
temperature. Some solution approaches such as sol-gel or organo-chemical synthesis
for the LiCoO2 compound have also been reported [5, 6]. In general, the different
synthesis methods using high temperature sintering have no significant impact on the
electrochemical performance of the LiCoO2 electrode. However, LiCoO2 material
synthesized at low temperature demonstrated a high specific capacity in the initial few
cycles, but with poor cycle life [36].
An interfacial layer, called the solid electrolyte interphase (SEI), usually is formed on
the surface of the LiCoO2 electrode during the charge/discharge process. The
formation of this interfacial film, caused by the reaction between the electrolyte and
the LiCoO2 compound, has an important influence on the electrochemical properties
of the LiCoO2 electrode. The characterization of this interfacial film has been
conducted by many researchers via a.c. impedance, electron microscopy and atomic
force microscopy(AFM) [37, 38].
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Since mineral resources of cobalt are very limited, it is better to partially replace Co
with other cheap transition metal elements in the LiCoO2 crystal structure to reduce
the cost of cathode materials. LiNiO2 can form a solid solution with LiCoO2 over the
entire composition range LiNixCo1-xO2 (0 ≤ x ≤ 1) [39]. R. Alcántara et al.
investigated both Co rich and Ni rich LiNixCo1-xO2 compounds. It was found that the
electrochemical behavior of LiNixCo1-xO2 solid solutions was significantly influenced
by the synthesis temperature. For a Ni rich composition (LiNi0.88Co0.12O2), the
electrochemical performance was poor, if prepared below 750 ºC. However, if the
sample was prepared at 750 ºC, it showed better reversibility, higher than that of a
Co-rich composition [40]. Tsutomu Ohzuku et al theoretically studied the solid- state
redox potentials of LiCoO2, LiCo1/2Ni1/2O2, and LiNiO2. They found that a one-to-one
mixture of Co and Ni in the layered structure induced a mixing effect on the redox
potentials. LiCo1/2Ni1/2O2 cathode has characteristic redox potential systems at 4.58 V,
4.05 V, and 3.58 V, respectively. The electron donating or accepting center in
LiCo1/2Ni1/2O2 is predominantly the Co at the potential of 4.58 V and Ni at the
potential of 3.58 V [41]. Al, which is not a transition metal, can also substitute for Co
in the LiCoO2 structure, because the ionic radii of Al3+ (0.54 Å) and Co3+ (0.55 Å) are
very close, and α-LiAlO2 is isostructural with LiCoO2. LiAlxCo1-xO2 compounds (0.1
≤ x ≤ 0.3) have been successfully synthesized by solid-state reaction. The redox
potential increases, due to the substitution of Al in LiCoO2. A high initial capacity of
160mAh/g was observed for LiAl0.15Co0.75O2 cathode with stable cyclability [42].
The capacity and cyclability of LiCoO2 cathode can be further improved by coating a
metal oxide or phosphate on the surface of the cathode material particles. The coated
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LiCoO2 cathode demonstrated an increased capacity of 170 mAh/g when cycled
between 2.75 V and 4.4 V. The mechanism could be attributed to minimizing the
reactivity of Co4+ with the acidic HF in the electrolyte in the fully charged state [43,
44]. It has also been identified that a coating of high-fracture-toughness metal oxide
such as ZrO2, Al2O3, TiO2 or B2O3 on LiCoO2 particles can effectively suppress the
change in the lattice constants during the lithium intercalation and de-intercalation
processes, and therefore suppresses the phase transition. The capacity retention of
LiCoO2 cathode can be dramatically enhanced through such a coating [45, 46].
The use of LiCoO2 as the cathode material in large scale lithium prototype batteries
has been demonstrated by several institutions. Cylindrical 1.5 - 2 Ah and 8 Ah cells,
having a flat plate construction inside, were assembled and tested [47]. Cylindrical
“C” size cells showed high capacity and a cycle life of more than 100 cycles.
Although LiCoO2 compound has excellent electrochemical properties as a cathode
material in lithium ion batteries, some drawbacks have to be addressed and cannot be
ignored. The major drawback is the high cost for LiCoO2 due to the high price and
limited natural abundance of Co. Another problem is the toxicity of Co, which causes
a serious environmental impact when batteries are disposed of. These two factors
forbid the application of LiCoO2 as the cathode material in any large batteries for
electric vehicle and power storage applications.
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2.5.2 LiNiO2 and doped LiMxNi1-xO2 cathode materials
LiNiO2 is an attractive candidate for lithium ion batteries because the natural
resources of nickel are relatively abundant. The theoretical capacity of LiNiO2
cathode is close to that of LiCoO2, i.e. 275 mAh/g. However, it can deliver a practical
specific capacity in the range of 185 – 210 mAh/g by charging up to 4.1 – 4.2 V vs.
LiNiO2 cathode suffers from a high capacity fading rate and poor thermal stability in
the highly oxidized state (Ni4+). LiNiO2 is isostructural with LiCoO2. The lattice
dimensions of the LiNiO2 unit cells (ah = 2.9 Å, ch = 14.2 Å, ch/ah = 4.9 Å in the
hexagonal setting) are very close to the parameters of a cubic unit cell (ac = ch / 2 3
= 4.1 Å), implying that nickel and lithium ions can easily displace each other in the
crystal structure. Once nickel ions occupy the Li ion position (3a) in the LiNiO2
structure, Ni3+/Ni4+ ions will block Li+ diffusion, resulting in a low lithium diffusion
coefficient and low capacity of the electrode [48].
Poor cycle ability of LiNiO2 electrode has been reported, but the cycle life of the
LiNiO2 electrode is greatly influenced by the way the compound is prepared. If
properly synthesized, the cycle life of LiNiO2 can be improved to an acceptable level.
No evolution of the structure of the LiNiO2 compound was observed even after 1200
cycles. Solid-state reactions are generally used to synthesize the LiNiO2 compound
under appropriate temperature and strongly oxidizing conditions. Unlike to LiCoO2,
which can be prepared by sintering a mixture of almost any Li, Co and O sources, the
precursors for the preparation of LiNiO2 have to be carefully chosen. The typical
approach is to heat a mixture of hydroxides (e.g. nickel hydroxide and lithium
- 20 -
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hydroxide), nickel hydroxide and lithium nitride, nickel oxide and lithium hydroxide
or by the use of Na2O2 and Ni sources, followed by ion exchange with LiNO3 at
elevated temperature. With careful control of all of the above factors, LiNiO2
compound with good electrochemical performance as cathode materials for lithium
batteries could be obtained. Li/LiNiO2 and C/LiNiO2 cells have been assembled using
liquid electrolyte. Results using personal area network (PAN) based hybrid polymer
electrolyte were also obtained [49]. Long cycle life, excellent high temperature
performance and low self-discharge rates have all been demonstrated using
LiNiO2/coke cells [50].
Layered LiNiO2 compounds have been synthesized using a variety of conditions
including varied nominal Li: Ni ratios, different sintering temperatures and different
atmospheres [51]. When sintered at low temperatures such as 650 ºC or 700 ºC, the
impurity phases Li2O and NiO were present in the final product. It was also revealed
that too much excess Li (Li:Ni = 1.14:1) also induces the presence of Li2O impurity.
An appropriate amount of excess lithium in the precursors can compensate for the loss
of the volatile Li at high temperature, and therefore is necessary. The decomposition
product Li1-xNi1+xO2 has a disordered cation distribution, with nickel ions partially
occupying the lithium ion sites in the layered structure, resulting in very poor
electrochemical performance. So, the synthesis temperature for LiNiO2 should be kept
below 860 ºC to avoid any decomposition and oxygen evolution. The properly
prepared LiNiO2 cathode showed a discharge capacity of 180 mAh/g with good
reversibility. A.c. impedance analysis was performed on LiNiO2 cathode tostudy the
kinetic processes of lithium insertion and extraction. LiNiO2 compound synthesized
- 21 -
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in air has a high charge-transfer resistance (RCT) and low exchange current density.
Oxygen atmosphere is favorable for preparing ordered LiNiO2 compound.
Many efforts have been made to improve the electrochemical performance of LiNiO2
cathode by partial substitution of Ni by other metal elements such as Mg, Al, Mn, Cr,
Fe and Ti respectively [52 - 54]. LiCoxNi1-xO2 solid solutions ( x = 0, 0.25, 0.5, 0.75
and 1) were prepared by sintering the precursor reagents LiOH.H2O, NiO, and CoO at
750 ºC for 24 h under oxygen flow [55]. Electrochemical testing showed that LiNiO2
cathode had a higher initial capacity, but less stability on cycling comparing to
LiCoO2 cathode. The cyclability of LiNi0.5Co0.5O2 and LiNi0.25Co0.75O2 cathodes are
satisfactorily good, with a capacity fading rate of 0.3 and 0.18mAh/g per cycle
respectively. The replacement of Ni by Co in LiCoxNi1-xO2 cathode can improve the
cyclability, but with a sacrifice of the initial capacity.
The structural integrity of the LiNiO2 cathode could be preserved via inert Al3+ cation
doping to prevent overcharge of the electrode, which is beneficial for extending the
cycle life of the cell. LiAlxNi1-xO2 ( x = 0, 0.1, 0.2 and 0.25) solid solutions were
synthesized by sintering LiOH.H2O, NiO, and Al powders at 750 ºC under an oxygen
stream for 24 – 40 h [56]. Single phase LiAlxNi1-xO2 solid solutions were obtained.
The Al doped LiAlxNi1-xO2 cathodes demonstrated almost the same charge and
discharge behavior as the LiNiO2 cathode. Both the initial charge and discharge
capacities of LiAlxNi1-xO2 cathodes decreased with increasing Al3+ of dopant cations.
However, the cyclability of the cathode was improved for doped LiAlxNi1-xO2
cathodes in the voltage window of 3.0 – 4.3 V. This could be because the effects of
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Al3+ dopant prevent Li+ extraction in the voltage range of 4.1 – 4.3 V, thus avoiding
the two-phase region for 0.75 < x < 1 in LiAlxNi1-xO2.
LiAlxNi1-xO2 ↔ □1-xLixAlxNi1-xO2 + (1-x) Li+ + (1-x) e- (2.5)
The fully charged state of LiAlxNi1-xO2 is □1-xLixAlxNi1-xO2, in which the valence
electrons of Al3+ and Ni4+ are 3S0, so that this material is an electronic insulator. Li+
ions cannot be further electrochemically extracted from the structure because no
electrons can be removed from either Al3+ or Ni4+. Residual Li+ and Al3+ are useful to
suppress the dimensional change of the interlayer distance due to the extraction of Li+
ions. This effect contributes to maintaining the structural integrity of the cathode and
enhancing the cyclability.
2.5.3 Layered LiMnO2, orthorhombic LiMnO2 and their doped compounds
The LiMnO2 system contains some of the most intensively investigated cathodic
materials for rechargeable lithium batteries, due to its low-cost, non-toxicity, and high
energy density. Theoretically, if all the lithium can be reversibly extracted from and
inserted into the LiMnO2 structure, it can deliver a specific capacity of about 270
mAh/g. LiMnO2 compound has two types of crystal structure e.g. a layered structure
(monoclinic C2/m, or m-LiMnO2) and an orthorhombic structure (Pmnm or
o-LiMnO2). These two structures have to be synthesized under different synthetic
conditions. The layered LiMnO2 (m-LiMnO2) is not thermodynamically stable at
elevated temperature. Therefore, it can not be prepared by the normal high
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temperature sintering process. Layered LiMnO2 was successfully prepared in 1996 by
an ion exchange technique from NaMnO2 [57, 58]. Firstly, layered NaMnO2 was
synthesized by solid-state reaction between stoichiometric Na2CO3 and Mn2O3 at 700
– 730 ºC under flowing argon. Then, LiMnO2 was obtained by refluxing NaMnO2
with excess LiCl in n-hexanol at 145 – 150 ºC, during which Li+ ions replace Na+ ions.
Neutron diffraction confirmed the monoclinic layered structure with unit cell
dimensions: a = 5.4387(7) Å, b = 2.80857(4) Å, c = 5.3878(6) Å, and β = 116.006(3)
º. The orthorhombic LiMnO2 has an ordered rock-salt structure in which LiO6 and
MnO6 octahedra are arranged in corrugated layers. It can be easily prepared via
solid-state reaction at high temperature with lattice parameters: a = 2.805 Å, b = 5.746
Å, and c = 4.574 Å [59].
Both m-LiMnO2 and o-LiMnO2 are electrochemically active as cathodes in
lithium-ion cells. It was found that up to 0.95 lithium per formula of LiMnO2 can be
extracted from m-LiMnO2 cathode on the initial charging [31]. When lithium ions are
removed from LiMnO2, the Jahn-Teller Mn3+ ions are oxidized to Mn4+, inducing the
loss of the monoclinic distortion. X-ray diffraction has identified that the layered
LiMnO2 is converted to a spinel structure during the charge and discharge cycling
[60]. The mechanism for this structural conversion on cycling could be related to the
fact that the random distribution of lithium and manganese in a cubic-close-packed
array of oxygen ions is much closer to the spinel structure, and also, the spinel
structure represents a uniform, isotropic distribution of manganese ions in a
close-packed oxygen lattice and thus is thermodynamically stable. On the other hand,
o-LiMnO2 has much better electrochemical performance than that of layered
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m-LiMnO2 cathode. The low-temperature (~100 ºC) synthesized o-LiMnO2 cathode
showed an initial reversible capacity of 170 mAh/g and exhibited little capacity loss
with cycle number when cycled either the 3 V or the 4 V plateau, but rapid capacity
loss when cycled over both voltage plateaus [61]. It was also found that the o-LiMnO2
was gradually converted to the single phase spinel structure on cycling [62]. The
layered LiMnO2 structure can be efficiently stabilized via replacement of Mn by other
metal elements such as Al, Co, Ni, Cr, etc.. The doped m-LiMxMn1-xO2 compounds
can be prepared via solid-state reaction by sintering at high temperature, which is an
important advantage over the ion-exchange approach. Ab initio calculations showed
that LiAlO2 has a theoretical intercalation voltage plateau of 5.4 V vs. Li/Li+ reference
electrode, therefore Al doping can potentially increase the intercalation voltage
plateau and cathode energy density. Y. Jang et al. first reported the stabilization and
electrochemical performance of Al doped LiMnO2 cathode material [63]. Compounds
with two compositions, LiAl0.05Mn0.95O2 and LiAl0.25Mn0.75O2, were synthesized. It
was found that m-LiMnO2 becomes the major phase when oxygen partial pressures
are below 10-5atm. Energy dispersive X-ray mapping using scanning and transmission
electron microscopy (SEM and TEM) confirmed the homogeneous distribution of Al
and Mn through the LiAlxMn1-xO2 particles. The LiAl0.25Mn0.75O2 cathode exhibited
148mAh/g reversible capacity at C/5 rate and 182 mAh/g at the C/15 rate with
excellent cyclability when cycled in the voltage range of 2.0 V – 4.5 V.
The stability of Co doped LiMnO2 was predicted by ab initio calculations using the
scalar-relativistic, spin-polarized Green’s function technique based on the full charge
exact muffin-tin orbital (EMTO) method [64]. The calculations were performed for
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three (pmmn, C2/m, and R3m) crystallographic allotropes of LiCoxMn1-xO2 in
ferromagnetic (FM), antiferromagnetic (AF), and disordered local moment (DLM)
states. The substitution of 10 at. % of Mn by Co makes the AF monoclinic structure
less stable than the orthorhombic structure in the DLM state. When there is 30 at. %
Co in LiCoxMn1-xO2, the FM orthorhombic structure has the lowest energy. Finally,
with ~ 60 at.% manganese replaced by Co, the desired layered R3m LiMnO2 structure
is stabilized. It is a thermodynamically stable equilibrium structure that can be easily
prepared by solid-state reaction. However, such a prediction does not represent the
successful preparation of Co doped LiMnO2 with the layered structure via soft
chemical approaches. P.G. Bruce et al. [65, 66] have successfully synthesized
LiCoxMn1-xO2 (0 ≤ x ≤ 0.5) using a solution based route coupled with ion exchange.
Five compositions of LiCoxMn1-xO2 ( x = 0.1, 0.2, 0.3, 0.4, and 0.5) were examined by
powder neutron diffraction. They were all identified as layered structure with the
space group R3m. The lattice parameter a decreases with increasing of Co content,
while c increases with increasing Co content. The Co doped LiMnO2 cathodes could
be charged and discharged over a wide voltage range of 2.6 – 4.8 V. The
LiCo0.1Mn0.9O2 cathode yielded an initial discharge capacity of 210mAh/g. As a
general trend, with increasing Co dopant level, LiCoxMn1-xO2 cathodes exhibit lower
initial capacity, but better cyclability. Through analyzing the incremental capacity
plots, they found that the transformation to spinel is relatively facile for LiCoxMn1-xO2
with low Co content (< 30 at. %), but much slower above this composition. This could
be responsible for the increased stability as the Co doping content increases. They
also concluded that Co doping can significantly modify the structure chemistry and
electrochemistry of layered LiMnO2, that 10 at. % Co doping can efficiently prevent
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the capacity loss on the first cycle, and that higher Co level doping can suppress the
transition to a spinel-like structure, resulting in long cycle life.
LiNixMn1-xO2 cathode materials have also been extensively investigated. The
synthesis and electrochemical performance of LiNixMn1-xO2 solid solutions were
reported by Dahn et al. in 1992 [67]. The electrochemical properties deteriorated with
increasing Mn content. The optimum electrochemical behavior was found for the
composition of LiNi0.5Mn0.5O2 by different research groups [68 – 70]. X-ray
photoelectron spectroscopy (XPS) and magnetic property measurements show the
existence of Ni2+ and Mn4+ rather than Ni3+ and Mn3+. Noguchi et al. [71]
systematically studied the phase diagram and electrochemical properties of
Li-Ni-Mn-O compounds. The LiNixMn1-xO2 solid solutions between LiNiO2 and
Li2MnO3 can be prepared by the usual methods. They are rhombohedral (R3m) when
x ≤ 0.3, and have monoclinic symmetry (C2/m) when x ≥ 0.5. Ex situ XRD and
chronopotentiograms showed that complex phase transitions can be completely
suppressed with x ≥ 0.5. The electrochemical properties of the two compositions,
Li1.04Mn0.1Ni0.86O2 and Li1.13Mn0.26Ni0.61O2, were tested at a current density of 0.55
mA/cm2 and exhibited average discharge capacities of 165 mAh/g and 150 mAh/g
respectively.
The layered LiMnO2 structure can also be effectively stabilized at room temperature
by Cr doping. The groups of both Davidson and Ammundsen have described the
successful synthesis and excellent electrochemical properties of Cr doped LiMnO2
cathode materials [72 - 76]. The Li1.2Cr0.4Mn0.4O2 cathode compound was prepared
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by reacting stoichiometric amounts of co-precipitated mixed hydroxides of chromium
and manganese with lithium carbonate at 800 ºC in argon atmosphere. X-ray
diffraction confirmed the layered hexagonal structure in the R3m space group, with
unit cell parameters of a = 2.886 Å and c = 14.372 Å. k edge X-ray absorption near
edge specter (XANES) showed that Cr is trivalent and in octahedral sites, and Mn is
tetravalent and in regular octahedral coordination. In Li1.2Cr0.4Mn0.4O2, the k edge
extended X-ray absorption fine structure (EXAFS) spectra supporteded a structural
model for Li1.2Cr0.4Mn0.4O2, in which the transition metal layers consist of clusters of
[Li1/3Mn2/3] and clusters of transition metal, predominantly Cr. The Li1.2Cr0.4Mn0.4O2
cathodes exhibited very stable cyclability, both at room temperature (20ºC) and at an
elevated temperature of 55ºC, with average capacities of 135 mAh/g and 170 mAh/g,
respectively. The LiCrxMn1-xO2 (0 ≤ x ≤ 0.5) compands and their delithiated /
relithiated derivatives were investigated via X-ray absorption spectroscopy (XAS)
and micro-Raman spectroscopy analysis [77]. It was identified that the trivalent Cr
ions are fixed to the octahedral site in the (Mn, Cr) O2 layer before and after
electrochemical cycling. The Cr doping can reduce the local structural variation of
manganese in LiCrxMn1-xO2 upon lithium extraction/insertion.
2.5.4 Spinel LiMn2O4 and LiMxMn2-yO4 cathode materials
The spinel-type oxide LiMn2O4 and its derivatives have been studied for more than a
decade as cathode materials for lithium ion batteries. The lithium insertion and
extraction in LiMn2O4 spinel provides an average voltage of 4 V versus Li/Li+, which
is similar to LiCoO2 and LiNiO2. Significant efforts have been made to extend the
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capacity of the 4 V plateau to the 3 V plateau without compromising the specific
capacity. Spinel LiMn2O4 has the advantages over the Co- and Ni- containing
systems of being inexpensive, environmentally benign, and having a larger thermal
stability domain especially when overcharged. However, the theoretical capacity of
LiMn2O4 is only 148 mAh/g. The high rate of capacity fading on cycling is another
serious drawback for LiMn2O4 spinel electrodes. Fortunately, the problems related to
the capacity fading can be circumvented by doping Mn with other transition metals M
to suppress the Jahn-Teller (Mn3+) effect. Therefore, LiMn2O4 spinel is still an
attractive cathode candidate for lithium ion batteries. Some doped LiMxMn2-xO4
spinels have already been used in commercial production.
Spinel LiMn2O4 belongs to the cubic system with a space group of Fd3m, in which Li+,
Mn3+/4+ and O2- ions occupy tetragonal 8a and octahedral 16d and 32e position in the
cubic-closed-packed (ccp) oxygen array. This structure provides a three dimensional
network of face-sharing tetrahedra and octahedra for lithium ion diffusion. In the [M2]
O4 spinel framework, 75% of the metal cations occupy alternate layers between the
ccp oxygen planes; the remaining 25% of the metal cations are located in the adjacent
layers. Therefore, sufficient metal M cations exist in every layer to provide a
sufficiently high binding energy to maintain an ideal ccp oxygen array when lithium
ions are extracted from the structure. The unit cell of the spinel structure expands and
contracts isotropically [78]. The electrodes with such a structure are likely to be more
stable under electrochemical cycling than those in which there is a large anisotropic
expansion or contraction of the lattice parameters. For example, the spinels
Li[M1.67Li0.33]O4 (M = Mn, Ti) are extremely tolerant to cycling, because the volume
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variation of the cubic unit cell is less than 1% within controlled compositional limits
[79, 80].
The LiMn2O4 spinel electrode offers a 4 V voltage versus lithium in the compositional
range 0 ≤ x ≤1 in LixMn2O4. Lithium ions can further insert into LiMn2O4 to form
Li1+xMn2O4 at 3 V against lithium. For Li1+xMn2O4, the electrode consists of two
phases: cubic phase LiMn2O4, and tetragonal phase Li2Mn2O4. The tetragonal phase
grows at the expense of the cubic phase. In the LiMn2O4 spinel structure, the strong
Mn-O bond maintains the structural integrity of the electrode during lithium ion
insertion and extraction. However, the Jahn-Teller distortion effect starts at Mnn+ =
3.5 (c/a = 1) and reaches a maximum at the valence of Mnn+ = 3 (c/a = 1.16), which
reduces the symmetry of the cubic spinel phase to tetragonal phase Li2Mn2O4 and
increases c/a to 1.16 concomitantly. Such distortion accompanying the volume
change of the unit cell would cause the crystal structure of the electrode to be
degraded and the electrochemical properties to deteriorate.
In practice, when the discharge voltage is close to 3.0 V, it is plausible that a few
spinel particles may result in an overall composition, Li1+xMn2O4, in which the
average Mn oxidation state falls below 3.5. A Jahn-Teller distortion might occur at the
particle surface, inducing the growth of tetragonal phase. The incompatibility
between the oxygen arrays of the cubic and tetragonal phases could then cause a
highly crystalline electrode particle to be degraded at the crystal surface, which would
damage the structural integrity and particle-to-particle contacts. Therefore, the
electronic conductivity and lithium diffusivity will deteriorate. Fortunately, this
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damaging effect can be reduced by suppressing the onset of the Jahn-Teller distortion
by modifying the composition of the spinel electrode to keep the average Mn
oxidation state slightly above 3.5 at the end of the 4.0 V discharge plateau.
To combat the Jahn-Teller distortion effect, doping the LiMn2O4 spinel structure with
low valence ions is an effective approach. Since the average valence of Mn in
LiMn2O4 is + 3.5, when partially replacing Mn with other low valence ions, the
average valence of Mn will be increased above + 3.5. Correspondingly, at the end of
the 4 V discharge (lithium insertion into the spinel structure), the average valence of
Mn will be kept slightly above +3.5. Because the Jahn-Teller distortion starts at Mnn+
= 3.5, low valence ion doping can suppress the Jahn-Teller effect in LiMn2O4 spinel.
However, the theoretical capacity of LiMn2O4 spinel decreases with increasing
amounts of dopant ions. It is believed that the redox reaction accompanying lithium
insertion and extraction relies on the valence change of Mn in LiMn2O4 spinel [80].
Doping Mn with other ions inevitably reduces the amount of lithium which can be
reversibly extracted from the spinel structure. So, a trade-off has to be made to achieve
the optimum balance between suppressing the Jahn-Teller effect and keeping an
appropriate capacity.
A series of alien cation doped spinel compounds with the general formula of
LiMδMn2-2δO4 (M = Co, Zn and Mg; δ = 0.02, 0.03, and 0.05) were synthesized [79].
In this type of doped LiMδMn2-2δO4 spinel, one fraction of M ion substitutes for 2
fractions of Mn ions. Therefore, the average valence of Mn can be maximally
increased to suppress the Jahn-Teller distortion effect. The resulting compound
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LiMδMn2-2δO4 is cation deficient. The triple or double valence of the M cations
partially substitute for Mnn+ ions at 16d sites. Thus, there are unoccupied 16d sites in
LiMδMn2-2δO4 spinels. It is expected that more Li ions can be accommodated by such
partial substitution. Table 1 summarizes the structural and electrochemical parameters
of LiMδMn2-2δO4 (M = Co, Zn, and Mg) cathode materials.
Table 2.1 The structural and electrochemical parameters of LiMδMn2-2δO4 cathodes
[79].
Compounds Lattice Theoretic Fully Oxidised Theoretic Initial The av. Rate
Constants Mn oxidation Composition al discharge of capacity
(A) state in ( n+Mn=4) Capacity capacity fade
LiMδMn2-2δO4 (mAh/g) (mAh/g) (mAh/g per
cycle)
LiMn2O4 8.2495 3.5 Mn2O4 154 125 0.5
LiCo0.02Mn1.96O4 8.2458 3.54 Li0.1Co0.02Mn1.96O4 139 120 0.15
LiCo0.03Mn1.94O4 8.2422 3.56 Li0.15Co0.03Mn1.94O4 131 116 0.06
LiCo0.05Mn1.9O4 8.2418 3.61 Li0.25Co0.05Mn1.9O4 116 109 0.08
LiZn0.02Mn1.96O4 8.2460 3.55 Li0.12Zn0.02Mn1.96O4 134 118 0.32
LiZn0.03Mn1.94O4 8.2432 3.58 Li0.18Zn0.03Mn1.94O4 126 111 0.24
LiZn0.05Mn1.9O4 8.2426 3.63 Li0.3Zn0.05Mn1.9O4 108 101 0.24
LiMg0.02Mn1.96O4 8.2410 3.55 Li0.12Mg0.02Mn1.96O4 136 114 0.28
LiMg0.03Mn1.94O4 8.2400 3.58 Li0.18Mg0.03Mn1.94O4 127 108 0.25
LiMg0.05Mn1.9O4 8.2362 3.63 Li0.3Mg0.05Mn1.9O4 109 98 0.22
As is shown, not all of the lithium can be electrochemically extracted from the doped
LiMxMn2-2xO4 spinel structure, because complete removal of lithium would result in an
- 32 -
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average oxidation state of Mnn+> 4, which is chemically impossible. Residual lithium
could also help to suppress the chemical decomposition of the electrode at a high level
of the charge. The reasons for the degradation of spinel electrodes on cycling have
been identified as: (i) the structural damage to the electrode due to the volume change
in the unit cell caused by Jahn-Teller distortion in the 3V discharge regime; (ii) the
disproportionation reaction of Mn3+ from the cathode with the electrolyte: Mn3+ →
Mn2+ + Mn4+; and (iii) instability of the organic electrolyte at high voltage. The dopant
effect can combat (i) to suppress Jahn-Teller distortion and preserve the structural
integrity of the spinel electrode during cycling. Since we use LiPF6 electrolyte in
EC+DMC, which can resist oxidation even at 5 V, cause (iii) could be excluded. Co
doped spinel electrodes have demonstrated excellent cyclability. It is possible that the
Co dopant effect prevents the disproportionation reaction of Mn3+ with the electrolyte
[81]. Wakihara et al. proposed that the improvement in cycling behavior of the Co
doped LiMn2O4 compound could be attributed to enhancement in the stability of the
spinel skeleton structure. This is because the binding energy of CoO is larger than that
of MnO [82].
The Co and Cr doped LiMn2O4 spinels synthesized by solid-state reaction have shown
the greatest improvement in cycle life without dramatically sacrificing the initial
capacity [83, 84]. However, the solid-state reaction produces heterogeneous spinels
with uneven distribution of the dopant cations. LiCrxMn2-xO4 spinels (x = 0, 0.02,
0.04, 0.06 and 0.1) have been synthesised by the Pechini method, in which the cations
can be mixed on an atomic scale [85 – 87]. With more homogeneous distribution of
the dopant Cr ions in the spinel structure, the electrochemical properties of LiMn2O4
- 33 -
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spinel possibly could be optimised. Neutron diffraction was performed on
LiCrxMn2-xO4 spinels to determine their structural characteristics. Using XRD
analysis alone, it is not possible to provide sufficient evidence to judge definitely
whether there is a mixture of Li+ and Mn3+/4+ at the 8a and 16d sites and whether
dopant Cr ions are present instead of Mn ions at 16d sites. Consequently, Lu et al,
performed neutron diffraction on three samples: pure LiMn2O4, LiCr0.02Mn1.98O4, and
LiCr0.04Mn1.98O4. Because of the distinctive properties of thermal neutrons, light
elements such as Li can be easily located [88].
Fig. 2.6 shows the neutron diffraction patterns obtained for pure LiMn2O4 and
LiCr0.04Mn1.96O4 spinels. The Rietveld method and LHPM program were employed to
refine the neutron diffraction patterns [89]. The determination of the crystal structure
of a compound depends very much on calculating the diffraction pattern, assuming a
model of the crystal structure, and comparing the calculated diffraction pattern with
the observed one [90]. For undoped LiMn2O4, there is a substantial difference
between the experimental data and the calculated pattern. When we assumed that
there was some mixing of Li+ and Mn3+/4+ at 8a and 16d sites, when it was assumed
that all of the Li ions were in 8a sites and the Mn ions were in 16d sites, the best fit
was obtained. During the refinement of the LiCrxMn2-xO4 structure (x = 0.02 and
0.04), when we assumed that there were some Cr ions in 8a Li sites, the differences
between the experimental data and the calculated pattern were obvious. Only when it
was assumed that all Cr ions were in 16d Mn sites, did the calculated intensities best
fit the observed ones, and the differences were almost negligible. It was clearly
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elucidated that there was no mixing of Li and Mn ions in the LiMn2O4 spinel structure
and that the dopant Cr ions occupy 16d Mn sites in doped LiCrxMn2-xO4 spinels.
Cr doped LiCrxMn2-xO4 spinels demonstrated substantially improved capacity
retention on cycling compared to the undoped LiMn2O4 spinel. The Cr doping effect
could also modify the surface states of the spinel electrode in the highly charged state,
reducing the self-discharge rate.
1.0 (a) LiMn2O4 Observed data

Calculated pattern
0.8
Intensity (Normalised)
0.6
0.4
0.2
0.0
-0.2
20 30 40 50 60 70 80 90 100 110 120 130
2 Theta (degree)
1.0 (b ) LiC r 0.04 M n 1.96 O 4 O bserved data

C alculated pattern
0.8
Intersity (Normalised)
0.6
0.4
0.2
0.0
-0.2
20 30 40 50 60 70 80 90 100 110 120 130
2 T heta (degree)
Fig. 2.6 Neutron diffraction patterns of (a) LiMn2O4 (b) LiCr0.04Mn1.96O4.
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2.5.5 Lithium iron phosphate based cathode materials
Iron based oxides have long been pursued as cathode materials for lithium-ion
batteries, because iron (Fe) is abundant, inexpensive, and less toxic than Co, Ni, or
Mn. LiFePO2 was initially prepared by ion-exchange from α-NaFePO2, but showed
little capability for reversible lithium intercalation and de-intercalation [91]. Later,
attention has been shifted to compounds with a NASICON (sodium super ionic
conductor) framework, allowing high mobility for lithium ion diffusion. This class of
compounds are built on corner-sharing MO6 octahedra (where M is Fe, Ti, V, or Nb)
and XO4n- tetrahedral anions (where X is S, P, As, Mo or W). The choice of the
transition metal M has a significant effect on the cell voltage, as it is primarily
dependent on the redox couple of the metal atom present in the structure. The
transition-metal redox couples are actually stabilized, and the potentials are made
more positive by the presence of the XO4 tetrahedra in the structure, due to strong
polarization of the oxygen atoms towards the X-cation and lowering of the covalent
component in the M-O bond by the inductive effect.
In 1997, J.B. Goodenough et al. discovered the electrochemically active lithium iron
phosphate olivine compounds [92 -93]. This is a new cathode material with
potentially low cost natural abundance of raw materials and environmentally
friendliness. It is expected that lithium iron phosphate will have a significant impact
in electrochemical energy storage. It has the following characteristics:
• A high theoretical capacity (170 mAh/g);
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• A high and relatively stable open-circuit voltage of 3.4V relative to lithium
metal
• Easy to synthesize and inexpensive to fabricate;
• Little hygroscopicity, which makes it easy to handle;
• Excellent stability during cycling when used with common organic electrolyte
systems (Since LiFePO4 does not react with the electrolyte) and long cycle life
(up to 2000, cycles compared to 400 cycles with LiCoO2);
• Good overcharge tolerance compared to other cathode materials, so that on
overcharge, there is less heat released and thus less risk of fire or explosion;
• Good capacity retention during cycling;
• Non-toxic and safe in operation;
• Environmentally benign;
• Low cost.
However, lithium iron phosphate cathode material also has several disadvantages,
which impede its industrial applications. These include: (i) very low electronic
conductivity in its pure form, on the order of 10-9 S cm-1; (ii) slow lithium diffusion in
the solid phase; and (iii) Low rate capacity. Those drawbacks can be overcome by
various strategies, including carbon coating, conductive additives, alien cation doping,
and synthesis of nanosize crystallites.
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2.5.5.1 Crystal structure of LiFePO4
LiFePO4 has an ordered orthorhombic olivine crystal structure. Olivines belong to a
general class of ‘polyanion’ compounds having compact tetrahedral anion structural
units (XO4) n- (X = P, S, As, Mo or W) with strong covalent bonding, combined with
MO6 octahedra (M = Mn, Fe, Co, Ni, etc.) to produce a 3D network [94, 95]. Amongst
the various polyanion compounds that are known, this olivine structure has the most
extensive interconnection of octahedra. For a general M2XO4 olivine, the M atoms
occupy half of the octahedral sites and X atoms one-eighth of the tetrahedral sites of a
hexagonal close-packed (hcp) oxygen array [96]. A diagram of an olivine structure is
given in Fig. 2.7 [2].
According to Fig. 2.7, the two octahedral sites (M1 and M2) are crystallographically
distinct and have different sizes, which favors ordering in MM’XO4 olivines
containing M and M’ ions of different sizes and charges. In the actual structure
(Figure 1b), the M2 octahedron has mirror symmetry with M1, the M-O bond
distances are greater than in M1, and it is slightly distorted compared to the ideal
model. The M1 sites form linear chains of edge-sharing octahedra running parallel to
the c-axis in alternate a-c planes, and the M2 sites form zigzag planes of corner-shared
octahedra running parallel to the c-axis in the other a-c planes [16]. Each M1 site
shares its edges with two M2 sites and two X sites, while there is one edge shared by a
M2 site with an X site. The distortion of the array is related to the repulsion of positive
units across the shared edges.
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Fig. 2. 7 The crystal structure of olivine LiFePO4 along [001]. Left: Expanded view of
the framework built on FeO6 octahedra and PO4 tetradedra. Right: Restricted view of
Li, Fe, and P distribution between two distorted h.c.p. (hexagonal close packed)
oxygen-dense layers (PTd[LiFe]octO4). LiO6 octahedra share edges and Li ions may
diffuse along [010] and [001].
On the removal of lithium, FePO4 phase is formed. LiFePO4 and FePO4 have
essentially the same crystal structure. FePO4 is isostructural with heterosite.
Therefore, it is a two-phase system with LiFePO4 in equilibrium with FePO4. The
conversion of the crystal structure between LiFePO4 and FePO4 is illustrated in Fig.
2.8 [97].
- 39 -
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Fig. 2.8 Crystal structures of orthorhombic LiFePO4 (left) and trigonal quartz-like
FePO4 (right).
The striking similarity in crystal structure similarity between LiFePO4 and FePO4 is
responsible for the superior reversibility of the cells on continuous cycling. The
connections among the different types of atoms are also shown. According to Fig. 2.8,
both phases have the same space group. On extraction of lithium from LiFePO4 [in
terms of lithium extraction/reinsertion, the material should be written as Li1-xFePO4 (0
< x < 1), where x is the number of lithium ions that are extracted from a unit cell], the
host matrix structure changes slightly, with a contraction in the a and b lengths but a
small increase in the c length. The volume is reduced by 6.81% and the density by
2.59%. Even though the overall changes to the FePO4 framework are only slightly
displacive, there is still a limit to the reversible first-order transition reaction between
the two phases [98]. This is because the transition would require a cooperative elastic
deformation of the framework. In other words, the principal change in the framework
- 40 -
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on delithiation is an adjustment due to the coulombic repulsion between the O2- ion
sheets occupying the interface between delithiated planes.
Fig. 2.9 displays a 3D structural model of LiFePO4. The unit cell contains a total of 28
atoms [99, 100]. In the structure, the cations that occupy the M2 sites (Fe sites in
LiFePO4) form a corner-sharing network of octahedra in the (010) plane, and the
cations on M1 (Li) sites form octahedra edge-sharing chains in the [100] direction.
For LiFePO4, there are three different O sites, and the crystal can be viewed as
interconnected but distorted LiO6 and FeO6 octahedra, sharing oxygen vertices with
PO4 tetrahedra [3]. In particular, the O-O distance in the PO4 tetrahedron is small and
three of its edges are shared by the octahedra. Figure 4d shows that the FeO6
octahedra are linked through common corners in the bc plane and the LiO6 octahedra
form edge-sharing chains in the b direction. One FeO6 octahedron has common edges
with two LiO6 octahedra, while the PO4 groups share one edge with an FeO6
octahedron and two edges with LiO6 octahedra.
The separation between the octahedra and the tetrahedra hinders the ionic
conductivity, because the PO4 tetrahedra will bridge the two adjacent FeO6 octahedra
planes, which constrains the free volume in which the Li+ ions can move. Thus the
electrode supports only small current densities at room temperature compared to other
electrode materials. If the current density is increased, it will not reduce the open
circuit voltage Voc; rather it decreases, reversibly, the cell capacity (i.e. reducing the
current restores the capacity). Also, the low value of the electronic conductivity is
believed to be due to the large electron effective mass in the structure. Nevertheless,
- 41 -
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because of having lithium in a continuous chain of edge-shared octahedra and
interstitial voids, reversible extraction/insertion of lithium is still possible. In fact,
ideally up to 0.9 Li+ ions/formula unit can be reversibly intercalated when electronic
conductors (i.e. carbon and dopant atoms) are introduced. The ions will diffuse
through the two-dimensional pathway provided by the interconnected octahedra and
tetrahedra [101-102].
- 42 -
-------------------------------------------------------------------------------------------------------------------------
Fig. 2.9 Model displaying the connection among FeO6, LiO6, and PO4 structural
units (a); Structure viewed along the c-axis (b).
2.5.5.2 Enhancement of electronic conductivity and improvement of
electrochemical properties of LiFePO4 cathode material
Good electronic conductivity of LiFePO4 cathode materials can be effectively
achieved by carbon coating. Carbon can be added into the bulk of the LiFePO4
material via either in situ (formed during the preparation process of the active
material) or ex situ (mixed with carbon powders) methods. Graphite was found to be
the best carbon source, and it offers the highest electronic conductivity for LiFePO4.
When uniformly dispersed throughout the LiFePO4 material, it optimizes its
- 43 -
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morphology and enhances the kinetics of the electrochemical process by improving
electron transfer.
Carbon is often deposited on the surface of each LiFePO4 particle and forms a thin
layer, and so it is commonly referred to as carbon coating. This coating is porous, so
that the lithium ions from the electrolyte solution can penetrate it to reach the surface
of the LiFePO4 particle with little resistance. Without carbon, the utilization of the
pure material, even at relatively low discharge rates, is poor, due to the voltage
reaching the cutoff potential much before any transport limiting factors such as
particle size become important; thus the electrode becomes ohmically limited. It has
been estimated that for solid-state synthesis techniques, approximately 20 wt% of the
cathode needs to be carbon in order for LiFePO4 to reach its theoretical capacity [12].
However, if using advanced methods to produce LiFePO4 such as chemical sol-gel
synthesis and hydrothermal synthesis, only 5 wt % carbon is sufficient to improve the
performance of the electrode [103-105].
Transition metal cation doping is another strategy to increase the electronic
conductivity of LiFePO4 cathode material. In comparison with LiFePO4, the doped
LiFePO4 materials were reported to reach conductivity values of > 10-2 S cm-1 at
room temperature, show near-theoretical energy density at low charge/discharge
rates, and retain significant capacity with little polarization at rates as high as 6000
mA g-1 (40C rate). Experiments have been carried out to study LiFePO4 samples
doped with various cations, including Mg2+, Al3+, Ti4+, and Zr4+.
- 44 -
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Electrical conductivity measurements have been performed on all the different
samples sintered at various temperatures and sectioned from pellets. They clearly
show that all doped compositions Li1-xMxFePO4 (M = Mg, Al, Ti, Nb or W) have
room temperature conductivities in excess of 10-3 S cm-1 [106]. Another experiment
found that a pressed Li0.99Zr0.01FePO4 pellet sintered at high temperature had an
electronic conductivity of 2 x 10-2 Scm-1 [106, 107].
The study also examined the relationship between the conductivity and the dopant
concentration. For example, in the Nb sample, it was observed that doping levels of
0.1, 0.5 and 1.0 atom% Nb resulted in room temperature conductivities of 1.1 x 10-3,
4.1 x 10-2, and 2.2 x 10-2 S cm-1 respectively, for samples fired at 700°C. At higher
doping levels of 2 and 4 atom%, Nb-enriched impurity phases appeared, and the
conductivity was reduced to 2.8 x 10-3 and ~10-6 S cm-1 respectively. Thus, it seemed
that there was a lack of proportionality between the dopant level and the conductivity
within the solid solution [108].
The electrochemical performance of LiFePO4 can also be improved by reduced
crystal size, such as in the nanometer domain. Smaller crystals mean a higher surface
area for lithium insertion/extraction reactions and higher specific capacity due to
more utilization of the active material. Nanosize LiFePO4 powders have been
synthesized by heating amorphous LiFePO4. The amorphous precursor was obtained
by lithiation of FePO4 synthesized by spontaneous precipitation from equimolar
aqueous solutions of Fe (NH4)2(SO4)2.6H2O and NH4H2PO4, using hydrogen peroxide
as the oxidizing agent. The as-prepared LiFePO4 powders have a relatively high BET
- 45 -
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specific surface area of 16.5m2g-1. Nanocrystalline LiFePO4 showed very good
electrochemical performance, with a capacity near the full theoretical capacity (170
mAh/g) when cycled at the C/10 rate [109]. Nanocomposites of LiFePO4 and
conductive carbon were prepared, leading to enhanced electrochemical accessibility
of the Fe redox centers in this insulating material. The resultant LiFePO4/C composite
achieves 90% theoretical capacity at C/2 rate, with very good rate capability and
excellent stability [110]. It was also found that the nanophase phosphide network that
is created in situ within the grain boundaries of the insulating LiMPO4
nanocrystallites forms an efficient electrical conduit. Metal phosphide formation can
significantly enhance the electronic conductivity of LiFePO4 cathode materials [111].
2.6 Anode Materials for Lithium-ion Batteries
Lithium metal (lithium foil) was traditionally used for anodes in lithium primary
batteries (non-rechargeable). When lithium is used as anode in rechargeable lithium
batteries, lithium is often deposited in a dendrite form during repeated
charge/discharge cycles. These lithium dendrites are porous, have high surface area,
and are very reactive in organic electrolytes. Once lithium dendrites grow and
penetrate the separator after a certain number of cycles, it will cause short circuiting
and lead to fire or explosion. Therefore, this problem has driven research to find
alternative anode materials for rechargeable lithium batteries.
The basic requirements for anode materials used in rechargeable lithium batteries
include:
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(i) The potential of lithium insertion and extraction in the anode versus
lithium the need to keep as low as possible.
(ii) The amount of lithium which can be accommodated by the anode material
should be as high as possible to achieve a high specific capacity.
(iii) The anode hosts should endure repeated lithium insertion and extraction
without any structural damage to obtain long cycle life.
2.6.1 Carbon based anode materials
Carbon materials are currently used in commercial lithium battery production. The
most widely used carbon anode materials are various types of graphitized carbon.
Graphite exists in various crystalline and amorphous forms. Carbon anode materials
can be produced from a variety of sources, such as natural graphite, oil, pitch, coal tar,
benzene, polymer resins, hydrocarbon gas, etc. In general, carbon anodes can be
categorized into:
(1) Graphite.
(2) Hard carbon - non-graphitized glass-like carbon which does not graphitized
even when heat treated at high temperature.
(3) Soft carbon – changing with heat treatment.
Schematics of the structures of these three types of carbons are shown in Fig. 2.10.
- 47 -
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Please see print copy for Figure 2.10
Fig. 2.10 Schematics of the structural of three types carbons [29].
Graphite consists of ABAB layers (graphene layers), which are held together by van
der Waals forces. Each graphene layer contains sp2 bond. Lithium ions can intercalate
into the interlayer between graphene layers to form LiC6 intercalation compounds.
The theoretical capacity of graphite is 372 mAh/g (850 mAh.cm-3), based on the
reaction to form the LiC6 compound.
Li+ + 6C + e- LiC6 (2.6)
The insertion compound LiC6 has a golden color and belongs to the graphite
intercalation compounds (GICs) of stage1, where the stage number corresponds to the
number of graphite layers which separate two successive intercalated planes.
The intercalation of lithium into graphite and the related electrochemical properties
have been well investigated [112-113]. Graphite synthesized at 3000 °C has a
capacity of 400 mAh/g in charging and delivers a capacity of 290 mAh/g on
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discharging. This is because a thin lithium ion conductive film (solid electrolyte
interface, SEI) is formed on the surface of the graphite anode in the initial
charge/discharge cycle. Dahn et al. described three classes of lithium-ion battery
relevant carbons [114-115]. One is graphitic carbons, which are normally prepared
by heating so-called soft carbon precursors to temperatures above ~ 2400°C, where
well graphitized materials result. The second one is hydrogen containing carbons,
which are prepared from pyrolyzed organic precursors at temperatures near 700°C.
The third class of carbons are hard carbons or non-graphitized carbons. The structure
and chemistry of carbons strongly depends on the procedures of heating the organic
precursors. During the early stages of pyrolysis in inert gas (below 600 °C), organic
compounds decompose and emit gases that contain carbon, such as CO and CH4. The
remaining C atoms condense into planar aromatic structures (graphene sheets). If the
decomposing precursor forms a semifluid state, then these planar sheets can align in a
more parallel fashion that leads to easy graphitization upon heating to very high
temperatures. Such precursors yield “soft” or graphitizable carbons. However, if the
organic precursor is sufficiently cross-linked, then a fluid state is not realized during
decomposition and the planar aromatic structure cannot align. These carbon materials
are difficult to graphitize at high temperature and thus are called “hard” or
nongraphitizable carbons. All carbon materials formed by heating up to about 1300 –
1500 °C (so called soft carbon) have been shown to consist of small domains of
graphite-like hexagonal layers of carbon atoms with a diameter of 1-1.5 nm and
parallel stacking of two or three layers. These have been called basic structure units
(BSUs) [116，117].
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Highly orientated pyrolytic graphite (HOPG) is a typical example of synthetic
graphite having a high degree of plane orientation. The second classification scheme
relates to the axial orientation of layers, which consists of coaxial and radial cases. All
of the fibrous carbon materials have this scheme of orientation. The third scheme is
the orientation of the BSUs around a reference point (point orientation), in which two
cases have to be differentiated, radial and concentric. Most of the spherical carbon
particles have this texture.
The spherical graphite particles are obtained from pitches, so-called mesophase
spheres (or mesocarbon microbeads, MCMB), and also by pressure carbonization of a
mixture of polyethylene with a small amount of polyvinyl chloride, called carbon
spherules. These particles were found to have a radial arrangement of BSUs.
The structure of carbon materials strongly depends on the precursors and the heat
treatment conditions (temperature and pressure). The average interlayer spacing
between neighbouring hexagonal carbon layers, d002, the crystallite sizes along the c
and a axes, Lc and La, and the probability of graphitic AB stacking between adjacent
layers, P1, are commonly used as fundamental structural parameters. In general, the
degree of graphitization, P1, and the crystallite thickness, Lc(002), increase with the
heat treatment temperature.
The lithium insertion behavior in hard carbon electrodes such as coke is somewhat
different from that observed in graphite electrodes. In contrast with graphite, the
cycling profile of hard carbon electrode shows no evidence of staging plateaus but
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rather continuous charge/discharge curves associated with lithium intercalation that
slope between 1.2 V and 0.2 V [118]. It is believed that the insertion of lithium in
hard carbon electrodes corresponds to the filling of micro-pores in the carbon by
clusters of lithium. This mechanism would be expected to produce weakly bound
lithium (relative to that in Li metal) and to show a very low plateau, consistent with
experimental results. Hard carbon materials consisted primarily of small single layers
of carbon arranged more or less like a house of cards. Lithium could be absorbed on
both surfaces of these single sheets, leading to more lithium per carbon than in
intercalated graphite, which would have the theoretical maximum capacity of Li2C6 or
740 mAh/g. In the structurally disordered coke electrodes, the intercalation process
does not promote formation of the staging phases, and due to its lack of crystallinity,
these electrodes are not as sensitive to the nature of the electrolyte as is the case for the
graphite electrodes. In fact, coke electrodes are successfully used in commercial
lithium-ion batteries, such as the Sony Camcorder battery.
Hydrogen-containing carbons can deliver high lithium intercalation capacities up to
800 – 900 mAh/g. The hydrogen could be playing a crucial role in the mechanism of
lithium insertion. The reversible capacity increases with an increasing H/C atomic
ratio in this material. It has been suggested that lithium atoms can bind in the vicinity
of H atoms in the hydrogen-containing carbons. The inserted lithium could transfer
part of its 2s electrons to a nearby hydrogen, resulting in a corresponding change to
the H-C bond, which would cause changes in the relative atomic positions of the C
and H atoms. Hydrogen-carbon electrodes do not maintain their large capacities over
long term cycling [119, 120].
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Carbon anode materials are still under intensive investigation to improve their
specific capacity and cycle life. Some super carbons prepared by pyrolsyzing special
precursors have demonstrated a capacity of more than 1000 mAhg-1 [121], but with
short cycle life. Nanocrystalline carbons prepared via high energy ballmilling had a
lithium-insertion capacity of up to 2500 mAh/g in the first charge. Unfortunately,
only half of this capacity was reversible during the first discharge. Such large
irreversible capacity in the first cycle is unacceptable for any practical application
[122, 123]. Nevertheless, it is expected that carbon materials will reach a capacity of
600 – 700 mAh/g with satisfactory cycle life and reversible capacity.
2.6.2 Alloy based anode materials
Many metallic elements (M) can react with lithium to form LixMy alloys. The
gravimetric capacities of some lithium-alloy forming metal elements are presented in
Fig. 2.11. Pure lithium has the largest specific capacity of all the metallic elements.
Silicon also has very high specific capacity when forming Li4.2Si alloys. However,
these metal anodes experienced a dramatic volume increase upon reacting with
lithium, causing cracking which eventually leads to the failure of the electrode.
In order to circumvent the problem of volume change upon lithium insertion, alloy
powders with small particle size have been synthesized by a chemical reaction
method. Powders of Sn, SnSb, and SnAg (typical grain size: 200-400 nm) were
prepared by J.Besenhard et al.,
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5000
4500
4000
Specific capacity (mAh/g)

3500
3000
2500
2000
1500
1000
500
0
Li C(LiC6) Si As Al Sn Sb Pb
(Li21Si5) (Li As)
3
(LiAl) (Li21Sn5) (Li3Sb) (Li22Pb5)
Fig. 2.11 Gravimetric capacity of lithium-alloy forming elements
These fine-grained alloy elements have demonstrated excellent cycling performance
[124]. A model for lithium insertion in alloys with small particle size has been
proposed. Many pores and cavities exist in a loosely packed small particle size
metallic matrix. During lithium insertion, even 100% volume expansion of individual
particles will not crack the electrode as the absolute changes in dimensions are still
small. In other words, the pores and cavities have the effect of buffering the expansion
of individual particles. During the extraction of lithium from LixM particles, the
expanded particles do not contract very much, thus the overall dimensions of the
electrode remain almost constant in the subsequent cycles. Wolfenstine [125] made a
prediction of the critical grain size below which microcracking does not occur, based
on volume change as a result of Li insertion into brittle Li-alloys. The predicted
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critical grain size was less than the unit cell size for single-phase materials, which
suggests that decreasing the particle/grain size cannot fundamentally solve the
mechanical instability problem associated with Li-alloys. Some potential solutions to
solve the mechanical instability problems were proposed: (i) incorporating within the
Li-alloys a ductile Li-ion conducting metal or polymer matrix, and (ii) embedding the
alloys within a matrix which places them under compressive stress [126]. The use of
intermetallic alloys is one choice to provide a ductile matrix for lithium alloying.
The intermetallic alloys MM’ have emerged as a new class of anode materials for
lithium-ion batteries. The operating voltage of these alloy anode materials is a few
hundred millivolts above lithiated graphite, which is generally considered to be safer
than carbon anodes. In the intermetallic compound MM’, M is an “inactive” element,
and M’ is an “active” element which can react with lithium to form LixM’ alloy. The
reaction is supposed to proceed as follow:
xLi+ + MM’ + e- LixM’ + M (2.7)
The inactive M matrix is generated simultaneously. So, the reactions between lithium
and MM’ intermetallic alloys are generally described as displacement reactions, in
which domains of lithium alloy LixM’ are created within the inactive M’ matrix.
It is well known that LixM’ alloy systems undergo several phase changes when the
active element M’ alloys with lithium to form a series of LixM’ alloys. For example,
Sn can alloy with lithium to form various LixSn alloys: Li5Sn2, Li7Sn2, Li13Sn5, and
eventually, if heavily lithiated, Li22Sn5. Severe volume expansion and contraction are
- 54 -
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expected during charge/discharge cycling. These dramatic volume changes cause
cracking of alloy particles, damage the integrity of the electrode, and limit the cycle
life of the alloy electrode. This problem can be significantly improved by finely
dispersing the active lithium-alloying element in an inactive composite matrix. The
inactive matrix must be electrochemically conducting and mechanically ductile. It is
believed that the inactive matrix provides structural stability to the composite
electrode and combats the volume change of the active element. Various intermetallic
MM’ alloys show improved cycling performance compared to the pure
lithium-alloying metal. For example, some intermetallic alloys such as Cu6Sn5 [127],
FeSn2, and FeSn [128] have demonstrated much improved cycling behavior
compared to pure Sn. These alloys were prepared by either powder sintering or
ball-milling. When lithium ions insert themselves into these anode materials, a
displacement reaction occurs in which the intermetallic structure is broken down to
form a series of LixSn alloys within the inert Cu or Fe matrix. In situ x-ray diffraction
studies combined with Mossbauer spectroscopy have confirmed the formation of
metallic Cu and Fe in Cu6Sn5 and FeSn2 electrodes after cycling. This displacement
reaction is partially reversible. The capacity fade on cycling has been attributed to the
agglomeration of the inactive phase into larger grains.
Nanocrystalline alloys provide an approach to further improve the electrochemical
performance of intermetallic MM’ alloy anode materials. Since there exist countless
pores and cavities within nanocrystalline materials, these cavities provide some free
room for the volume expansion of the active element when reacting with lithium to
form LixM’ alloys. The generated inactive matrix is also nanocrystalline in nature,
- 55 -
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which will be compatible with the original MM’ alloys if the starting materials are
nanocrystalline.
Theoretically, the intermetallic MM’ alloys can be any combination of active
element, M’ and inactive element M, depending on their ability to react with lithium
to form lithium-alloy. Therefore, there will be many intermetallic alloys which have
the potential to be used as anode materials for lithium-ion batteries. Furthermore, the
intermetallic alloys can be ternary, or multi-element. This means that there can be
two, three, or more different active elements and vice versa for inactive elements.
Thus the possibilities for intermetallic alloys are many. Intensive research work is
required to explore and classify appropriate intermetallic alloys for lithium-ion
batteries.
2.6.3 Metal oxide anode materials
2.6.3.1 Tin oxide anode materials
The tin-based amorphous composite oxide (TCO) anode materials were first
developed by Fujifilm Celltec [129, 130]. The TCO anode yields a specific capacity
for reversible lithium adsorption more than 50 percent higher than those of the carbon
families. It provides a gravimetric capacity of > 600 mAh/g for reversible Li
adsorption and release, which corresponds in terms of reversible capacity per unit
volume to more than 2200 mAh cm-3. The tin-based composite oxide active material
has a basic formula represented by SnMxOy, where M is a group of glass-forming
- 56 -
-------------------------------------------------------------------------------------------------------------------------
metallic elements whose total stoichiometric number is equal to or greater than that of
tin (x ≥ 1), and is typically comprised of a mixture of B (III), P (V), and Al (III). In the
oxide structure, Sn (III) forms the electrochemically active center for Li insertion and
potential development, and the other metal group provides an electrochemically
inactive network of – (M-O)- bonding that delocalizes the Sn (II) active center. To
confer high reversibility in Li storage and release, the Sn-O framework is thus
anisotropically expanded by incorporating glass-forming network elements – B, P,
and Al, in view of the enhancement of Li-ion mobility in the anisotropic glass
structure, which is favorable for ionic diffusion and release. The TCO
SnB0.5P0.4Al0.42O3.6 was prepared by mixing SnO, B2O3, Sn2P2O7, and Al2O3, sintering
at the high temperature of 1100 °C for more than 10 hours, and then quenching to
room temperature [130]. TCO anode can be coupled successfully with several
cathode materials, such as LiCoO2, LiNiO2, LiMn2O4, and LiMnO2. Such lithium-ion
batteries have been tested to have an energy density of more than 420 wh/l and good
cyclability. The major drawback for the TCO anode is the large irreversible capacity
in the first cycle (~ 40 percent of the first charge), which requires excess cathode
material to compensate.
Various tin oxides have been investigated as anode materials for lithium-ion batteries,
including SnO, SnO2, Li2SnO3, and SnSiO3 glass. All of these oxides can react
reversibly with lithium with a capacity from 1200 mAh/g to 1500 mAh/g in the first
charge, but with large irreversible capacity. In situ x-ray diffraction measurement
revealed that these tin oxides and tin oxide composites follow a similar mechanism for
lithium insertion. When lithium ions are inserted into these oxides, Li2O and Sn are
- 57 -
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generated simultaneously. Then the lithium alloys with Sn to form a series of LixSn
alloys. The subsequent cycle is a process of alloying/de-alloying of lithium with tin.
This process is shown as follows.
6.4Li + SnO Li2O + Li4.4Sn Li2O + 4.4Li +Sn (2.8)
8.4Li + SnO2 2Li2O + Li4.4Sn 2Li2O + 4.4Li + Sn (2.9)
6.4Li + SiSnO3 Li2O + SiO2 + Li4.4Sn
Li2O + SnO2 + 4.4Li +Sn (2.10)
8.4Li + Li2SnO3 3Li2O + 4.4Li + Sn (2.11)
The formation of a Li2O and SiO2 matrix may act to retard the aggregation of tin
atoms into large coherent regions. When large tin regions form, the large volume
differences between coexisting bulk Li-Sn phases may introduce cracking and
crumbling of the electrode structure. Therefore, capacity will be lost.
The electrochemical performance of the SnO2 electrode can be improved by Mo
doping. It was found that the Mo doping influences the habit of growth of the SnO2
crystallites and facilitates growth along the [hk0] direction. The presence of Mo in the
Li-Sn alloy as it is formed may favor Sn atom dispersion, which contributes to the
improvement of the reversibility of the Li reaction [131,132].
- 58 -
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Much work has been done on TCO and tin oxides. Although TCO glass and some
nanocrystalline tin oxides have demonstrated excellent rechargeability, the problem
of large irreversible capacity related to oxygen in the first cycle is still not solved,
which prevents their commercial application.
2.6.3.2 Transition metal oxide anode materials
It was a surprise finding that MO-type compounds (where M is Co, Ni, Fe, Cu or Mn)
with a rock-salt structure and containing metal elements (M) that do not alloy with Li,
exhibited capacities two to three times those of carbon with 100% capacity retention
for up to 100 cycles. Anodes made of nanoparticles of transition-metal oxides (MO,
where M is Co, Ni, Cu, or Fe) have demonstrated electrochemical capacities of 700
mAh/g, with 100% capacity retention for up to 100 cycles and high recharging rates.
Fig. 2.12 shows the charge/discharge profiles and cyclability of MO anodes in
lithium-ion cells.
(a)
- 59 -
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(b)
Fig. 2.12 Electrochemical properties of MO anodes in lithium-ion cells. (a) The
voltage – composition profiles for MO/Li cells cycled between 0.01 V and 3 V of
CoO,NiO and FeO anodes at the C/5 rate. (b) Cyclability of Co3O4, CoO, FeO and
NiO anodes, with the data, also included demonstrating that the behaviour is not
specific to divalent oxides. The inset shows the rate capacity of a CoO electrode.
The reaction mechanism between Li and MO oxides differs from the classical Li
intercalation/de-intercalation or Li-alloying/de-alloying process. The whole process
involves the formation and decomposition of Li2O accompanying the reduction and
oxidation of metal particles (in the range of 1 – 5 nanometers). For example, the
reaction of CoO anode in a lithium-ion cell can be described as:
CoO + 2Li+ + 2e- ↔ Li2O + Co (2.12)
- 60 -
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2Li ↔ 2Li+ + 2e- (2.13)
CoO + 2Li ↔ Li2O + Co (2.14)
Bright-field imaging and selected area electron diffraction (SAED) analysis
confirmed the above reversible process. Furthermore, magnetic measurements and in
situ extended X-ray absorption fine structure (EXAFS) measurements also revealed
the reversible nature of the process between CoO and Li ions. Since then, many metal
oxides have been investigated as anode materials for lithium-ion batteries [134-135].
It is expected that the use of transition-metal nanoparticles to enhance surface
electrochemical reactivity will lead to further improvements in the electrochemical
properties of lithium-ion batteries.
- 61 -
Chapter 3 Experimental
--------------------------------------------------------------------------------------------------------------------------
3.1 Materials and chemicals
The materials, chemicals and reagents used in this study are listed in table 3-1.
Table 3.1 Materials and chemicals
Raw materials / Formula Purity Supplier

Chemicals
Lithium foil Li 99.999% Hosen Corporation,

Japan
LP30 electrolyte EC(Ethylene Merck
carbonate):DMC
(dimethyl carbonate)
=1:1 w/w
LP31 electrolyte EC:DMC=2:1 w/w Merck
CR2032 coin-cell Stainless steel Hosen Corporation,
hardwares Japan
Polyvinylidene fluoride (-CH2CF2-)n Aldrich
(PVDF)
Dimethyl phthalate C6H4-1,2-(CO2CH3)2 Aldrich
(DMP)
N-methyl-2-pyrrolidinone Aldrich
(NMP)
Carbon black powders Aldrich
Nanocrystalline Silicon Si (99.999%) Nanostructured &
Amorphous Materials
Inc., USA
Mesocarbon microbeads C 100% Hosen Corporation,
(MCMB-10 graphitizing) Japan
Resorcinol 98% Aldrich
Formaldehyde 37.6% in methanol Aldrich

Argon gas Ar 99.99% BoC Gas , Australia
Camphor Aldrich
Iron carbonyl Aldrich
Red phosphorus P 99% Aldrich
Iron chloride FeCl2.4H2O 99% Aldrich
Lithium hydroxide LiOH.H2O 99.9% Aldrich
Iron oxylate FeC2O4.2H2O 99 Aldrich
Manganese nitrate Mn(NO3)2.6H2O 99.9% Aldrich
Polyacrylic acid Aldrich
Citric acid Aldrich
Mixture gas (10% 10% H2 in Ar BOC Gas Limited,
hydrogen in argon) Australia
Ammonia phosphate NH4.H2PO4 97% Aldrich
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Magnesium acetate Mg(C2H3O2)2 99% Aldrich
Lithium carbonate Li2CO3 99.99% Aldrich

PTFE Membrane Hosen Corporation,
(separator) Japan
Silicon powder (325 Si 99%
mesh)
Acetone Aldrich
Ethanol (absolute) 100% Aldrich
Multiwalled carbon C Carbon
nanotubes (MWCNTs) Nanotechnology Inc.,
USA
Tin chloride SnCl2 99.9% Aldrich
3.2 Materials synthesis techniques
3.2.1 High energy ball milling
Si-MCMB composites were prepared by high energy ball milling. The ball-milling
facility used was a planetary ball-milling machine (Labtechnics, Australia). Stainless
steel balls with a diameter of 10 mm were used. The weight ratio between the material
powders and the balls was 1: 8-10. Home-made stainless steel milling jars were
employed, equipped with ventilation valve to allow evacuation of the milling-jar and
purging with argon gas. During the ball-milling process, a speed of 120 - 140 rpm was
maintained.
3.2.2 Carbon aerogel synthesis
Carbon aerogel was synthesized to prepare Si-Carbon composites. Carbon gel was
formed by reacting resorcinol and formaldehyde in a pH range of 6.5 – 7.4, in which
the pH value was adjusted with an ammonia solution. Simultaneously, nanosize
silicon powders were added and dispersed by ultrasonic probe and magnetic stirring.
- 63 -
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The gel formation was accomplished by conducting the reaction at 85 °C. Finally,
carbon gel was sintered at high temperature (650 °C) to be converted into amorphous
carbon.
3.2.3 Chemical vapor deposition (CVD)
Multiwalled carbon nanotubes were synthesized by the catalytic chemical vapor
deposition (CVD) approach. The CVD reaction chamber consists of three different
temperature zones controlled by 3 independent programmable temperature
controllers. Camphor was evaporated and carried by the flowing argon gas, and then
deposited on a silicon substrate downstream. The surface of the silicon wafer was
pre-deposited with iron carbonyl as catalyst. After deposition, carbon nanotubes were
harvested from the silicon substrates.
3.2.4 Hydrothermal synthesis
Nanocrystalline iron phosphide (FeP4) was synthesized by a hydrothermal process. A
Teflon lined autoclave (Parr Instrument Company, USA) was used with a maximum
temperature limitation of 300 °C. The ingredient reagents phosphorus, iron chloride
and de-ionized water were loaded in to an Autoclave. The autoclave was heated at 180
°C for 24 hours. After cooling down to room temperature, the reaction product was
taken out, washed thoroughly with distilled water, and dried in a vacuum oven.
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3.2.5 Sol-gel synthesis
Lithium iron phosphate and Mn and Mg doped lithium iron phosphate cathode
materials were prepared by the sol-gel synthesis method. Polyacrylic acid and citric
acid were used as complexing agents for the formation of a complex gel. The sol
solution was heated at 85 °C under vigorous stirring until forming a viscous gel was
formed. The gel was sintered at 500 °C to decompose the organic reagents into
carbon. The final products were obtained by sintering the intermediate product at 750
°C under argon atmosphere.
3.2.6 Solid-state reaction synthesis
Lithium iron phosphate and alien cation doped lithium iron phosphate compounds
were also synthesized via solid-state reaction. Stoichiometric quantities of reaction
reagents were hand-mixed with ethanol using an agate mortar and pestle. Then the
mixture was dried in a vacuum oven. The dried mixtures were pre-sintered in alumina
boats at 500 °C. Then, the pre-sintered mixtures were mixed again via mortar and
pestle. The re-mixed reagents were sintered again at 750 °C for 12 hours. The final
products were ground and then used for characterization and electrochemical testing.
3.3 Materials characterization
3.3.1 Structure characterization
The phases and crystal structure of all material samples were identified and
characterized by X-ray diffraction using a Philips PW-1730 diffractometer (40 kV,
25mA) with a monochromatized Cu Kα radiation (λ = 1.5418 Å) at a scan rate of
- 65 -
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1°/min and step size of 0.02 °. The crystallite sizes were calculated using the Scherrer
equation:
D = 0.9λ / β cosθ
Where λ is the x-ray wavelength, β is the observed full width at half maximum
(FWHM), and θ is the Bragg angle.
All X-ray diffraction patterns were analyzed using the Difftech Traces V6 software
program and checked with the International Centre for Diffraction Data (ICDD)
database. X-ray diffraction patterns were also refined by the Rietveld method using
the Rietical software program.
3.3.2 Material morphology observation
The morphologies of all the as-prepared powders were observed and analyzed using a
scanning electron microscope (SEM, JEOL JSM-6460A with a LAB-6 filament).
Surface element analysis and element mapping were performed using Energy
Dispersive X-ray Spectroscopy (EDXS) apparatus attached to the SEM. The SEM
facility is shown in Fig. 3.1. The morphologies and nanosize particles were analyzed
using transmission electron microscopy (TEM, JEOL 2011 TEM) and high resolution
TEM (HRTEM). The TEM apparatus is shown in Fig. 3.2. TEM samples were
prepared by dispersing powders in ethanol via ultrasonic vibration to form a
homogeneous suspension. Then, droplets of the suspension were dropped onto a
copper mesh coated with holey amorphous carbon films.
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Fig. 3.1 JEOL JSM-6460A SEM facility.
Fig. 3.2 JEOL 2011 TEM facility.
- 67 -
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3.3.3 Magnetic properties measurement
The magnetic properties of lithium iron phosphate and transition metal doped lithium
iron phosphate compounds were measured using a Quantum XL Magnetic Properties
Measurement System (MPMS). The measurements of the temperature dependence of
the magnetization of the samples under zero magnetic field cooling (ZFC) and applied
magnetic field cooling (FC) were carried out in a magnetic field of 5000 Oe and over
a temperature range of 5 K – 300 K. The Curie and Néel temperatures, as well as the
spin state of the magnetic cations, were calculated from the inverse magnetic
susceptibility (1/χ), based on the equation:
χ = C/ (T-Өp) + χo (3.1)
Where χo is the temperature independent susceptibility and Өp is the Pauli-Weiss
temperature.
3.3.4 Electrochemical testing
3.3.4.1 Electrode fabrication
The electrode materials were hand mixed with 10 wt% carbon black and 5-10 wt%
PVDF binder in NMP solvent by mortar and pestle to form viscous slurry. Electrodes
were prepared by coating slurries either of copper foil substrate (anode) or on
aluminum foil. After coating, the electrodes were dried in a vacuum oven for 12 h at
120 o C and pressed between two steel plates at 3.0 × 106 Pa/cm2. The area of each
electrode was 0.785 cm2.
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3.3.4.2 Cell assembly
CR2032 coin cells were assembled for all electrochemical testing. A microporous
plastic film (Cellgard 2500, Cellgard Co., USA) was used as separator. The
electrolyte was 1M LiPF6 dissolved in a 50:50 volume percent (v/o) mixture of
ethylene carbonate (EC) and diethyl carbonate (DEC), and a 300 μm thick, 0.78 cm2
lithium foil for the negative electrode was also used. Coin cells were assembled in an
argon-filled glove box (Unilab, Mbraun, Germany) with both water and oxygen
concentrations less than 0.1 ppm, as shown in Fig. 3.3.
Fig. 3.3 Atmosphere controllable glove box for assembling CR2032 coin cells.
- 69 -
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3.3.4.3 Electrochemical testing
(i) Charge/discharge of cells
Charge/discharge tests were carried out by using a battery test device
(charge/discharge unit, BT-5 Cell-Tester, Neware Technology Inc., China) with a
computer (PC) and software. Cell-Testers operate in the voltage range of -5 V - +5 V,
with a maximum current of 1 mA and accuracy of 1/10000. The system is capable of
switching between charge and discharge automatically, according to the cut off
potentials set.
(ii) Cyclic voltammetry
Fig. 3.4 CHI 660 B and 660C Electrochemical Work Stations.
- 70 -
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Cyclic voltammetry (CV) is one of the most reliable electrochemical approaches to
elucidate the nature of the electrochemical process, and to provide insights into the
nature of processes beyond the electron-transfer reaction. It was used in the present
work to study the electrochemical properties of electrode materials. CV is performed
by scanning the voltage between two chosen cut-off voltages at a given sweep rate,
while simultaneously, the response current arising from the electron transference is
measured and recorded. In a cyclic voltammogram, the positive current represents the
lithium de-intercalation process, and the negative current the lithium intercalation
process. Cyclic voltammograms were obtained by measuring the I-V response at a
scan rate of 0.01-0.1 mV/s and a cut-off voltage of 0.0 V – 2.0 V for anode materials
and 2.5 V – 4.4 V for cathode materials. CHI 660B and CHI660C Electrochemical
Work Stations (CHI Instruments, USA) were employed for all CV measurement
(shown in Fig. 3.4).
- 71 -
Chapter 4 Preparation and characterization Si-MCMB and Si-carbon composite anode materials
--------------------------------------------------------------------------------------------------------------------------
Chapter 4
Preparation and characterization of
Si-MCMB and Si-carbon composite anode
materials
4.1 Introduction
Silicon has a high theoretical lithium storage capacity of 4000mAh/g when forming
Li21Si5 alloys. Dahn et al. [136] synthesized nanodispersed silicon in carbon using
chemical vapour deposition (CVD). Although the Si-C anodes demonstrated a
reversible capacity of 500mAh/g, it is difficult to control the morphology of Si and C
using the CVD approach. Lee et al. [137] dispersed crystalline silicon (325 mesh) in a
sol-gel graphite matrix by ball-milling and achieved a reversible capacity of 832.2
mAh/g in the first cycle. Nano-Si-carbon composites which demonstrated a high
reversible capacity of 1700 mAh/g [138] have been prepared by hand mixing nano-Si
and carbon black. The lithium storage properties of nanostructured Si and Si film have
also been investigated [139, 140]. Since mesocarbon microbeads (MCMB) anode
materials have the best cyclability among all the various types of carbon anode
materials, the combination of MCMB and Si could result in Si-MCMB composite
anode materials with high capacity and satisfactory rechargeability. Based on this
hypothesis, we prepared nanocrystalline Si-MCMB composite materials by
72
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high-energy ballmilling. Their electrochemical properties as anodes in lithium-ion
cells were systematically evaluated.
On the other hand, the performance of Si anodes can be significantly improved by
preparing nanostructured electrode. This is because the mechanisms of fracture will
be changed when the crystals in the material have sizes on the tens of nanometers
scale. We synthesized nanostructured Si-C composites by dispersing nanocrystalline
Si in carbon aerogel. The electrochemical properties of nanostructured Si-C were
systematically evaluated. The improved electrochemical performance of Si-C could
originate from the unique mechanisms behind the lithiation and de-lithiation
processes in nanostructured Si-C composites.
4.2 Experimental
4.2.1 Preparation of Si-MCMB composite.
Nanocrystalline Si with an average particle size of 80 nm, was obtained from
Nanostructured & Amorphous Materials Inc.,USA (which was prepared by laser
driven silane gas reaction). MCMB (MCMB-10 graphitizing) was supplied by Osaka
Gas Co. (Japan). MCMB powders have an average particle size of 10 μm.
Nanocrystalline Si-MCMB composites were prepared by high-energy ball milling
using a planetary ball-milling machine (Labtechnics, Australia). The nanocrystalline
Si content in the composite is 20 % by weight. We chose this percentage based on the
results of a previous investigation on ball-milled Sn-graphite [141] and ball-milled
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Si-graphite [142]. The mixtures were ball-milled for 5, 10 and 20 hours respectively
to obtain 3 batches of Si-MCMB composites. The as-prepared Si-MCMB composites
were characterised by SEM (Leica / Cambridge Stereoscan 440 scanning electron
microscope) and x-ray diffraction with Cu Kα radiation ( MO3xHF22, MacScience,
Japan).
4.2.2 Preparation of Si-carbon composite
Nanocrystalline Si with an average particle size of 80 nm (which were prepared by
laser driven silane gas reaction). was purchased from Nanostructured & Amorphous
Materials Inc., USA. Resorcinol (98%, Sigma-Aldrich) and formaldehyde (37.6% in
methanol, Sigma-Aldrich) were used for preparing carbon aerogel. A typical carbon
gel was formed by mixing 0.29 M resorcinol and 0.57 M formaldehyde. The pH value
was adjusted to be in the range of 6.5 – 7.4 by adding NH3.H2O solution. The mixture
solution was put in an ampoule, sealed, and heated on a hot plate. The temperature
was maintained at 85 °C. The solution changed progressively from clear to milk white
to yellow to orange as the reaction progressed. When the solution became viscous,
nanocrystalline Si powders were added, and dispersed through magnetic stirring. The
ampoule was kept at 85 °C for 10 hours, and then carbon aerogel was formed, with Si
dispersed inside the gel. The obtained gel was then sintered at 650 °C under flowing
argon to yield an Si-C composite, containing 40% carbon by weight. The carbon
content was measured by thermogravimetric analysis (TG).
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4.2.3 Electrochemical testing.
The electrochemical properties of Si-MCMB composites and Si-carbon composites
were measured via coin cell testing. The Si-MCMB electrodes were made by
dispersing 84 wt % active materials, 8 wt % carbon black and 8 wt % polyvinylidene
fluoride (PVDF) binder in dimethyl phthalate solvent to form homogeneous slurry.
The slurry was spread onto a copper foil. The coated electrodes were dried in a
vacuum oven at 120 °C for 12 hours and then pressed to enhance the contact between
the active materials and the conductive carbons. The CR2032 coin cells were
assembled in an argon filled glove-box (Mbraun, Unilab, Germany) using lithium
metal foil as the counter electrode. The electrolyte was 1 M LiPF6 in a mixture of
ethylene carbonate (EC) and dimethyl carbonate (DMC) (1:1 by volume, provided by
MERCK KgaA, Germany). The cells were galvanostatically discharged and charged
in the voltage range of 0.01 – 3 V at a current density of 0.05 mA/cm2. Cyclic
voltammetry (CV) was performed on a potentiostat (Model M362, EG & G Princeton
Applied Research, USA), at a scanning rate of 0.1 mV/s.
4.3 Results and discussion
4.3.1 Si-MCMB composite anode materials
MCMB particles have a spherical shape. Fig. 4.1 (a) shows an SEM image of MCMB
particles, which each consist of many small graphite particles. The images of the
Si-MCMB composites ball milled for different times are shown in Fig. 4.1 (b), (c) and
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(d). After ball milling for 5 and 10 hours, the spherical agglomerates were partially
broken. But most of the particles still retained a spherical shape. However, after 20
hours of extensive ball milling, most of the spherical MCMB agglomerates were
destroyed and formed finely ground graphite debris. Energy dispersive spectroscopy
(EDS) was performed on the bulk of the Si-MCMB composites and confirmed the
presence of Si. Fig. 4.2 shows the X-ray diffraction (XRD) pattern of Si-MCMB. As
a comparison, the XRD patterns of bare MCMB and nanocrystalline Si are also
presented in the insets. The intensities of the diffraction lines of nanocrystalline Si are
much weaker than for MCMB graphite, indicating the nanocrystalline nature of the Si.
The ball-milling process caused slight broadening of the (002) peak of MCMB
graphite. The full width at half maximum (FWHM) of the (002) diffraction peak of
the MCMB were calculated to be 0.248 °, 0.250 °, 0.278 °, and 0.296 ° for pristine
MCMB, 5 h ball-milled Si-MCMB, 10 h ball-milled Si-MCMB, and 20 h ball-milled
Si-MCMB, respectively. No SiC phase was detected by x-ray diffraction. Therefore,
the mechanically added nanocrystalline Si formed Si-MCMB composites.
76
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(a)
(b)
77
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(c)
(d)
Fig. 4.1 SEM images of (a) bare MCMB graphite; (b) 20 wt% nano Si-MCMB ball
milled for 5 hours; (c) 20 wt% nano Si-MCMB ball-milled for 10 hours; and (d) 20
wt% nano-Si-MCMB ball-milled for 20 hours.
78
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Fig. 4.2 X-ray diffraction pattern of 20 wt% nano-Si-MCMB ball milled for 10 hours.
The insets show the XRD patterns of pristine MCMB and nanocrystalline Si for
comparison.
Cyclic voltammogramms of MCMB and Si-MCMB electrodes in lithium-ion cells, in
which a lithium foil was used as the counter electrode, and reference electrodes are
shown in Fig. 4.3 (a) and (b) respectively. In Fig. 4.3(a), the potential of the lithium
ion insertion peak in the cyclic voltammetric curve of the MCMB electrode is very
close to 0.0 V versus the Li/Li+ reference electrode, whereas the potential of lithium
extraction is in the range of 0.3 – 0.4 V versus the Li/Li+ reference electrode. In Fig.
4.3 (b), one pair of additional reduction and oxidation peaks appeared in the CV curve
of the Si-MCMB electrode, which are located at around 0.2 V and 0.51 V,
respectively versus the Li/Li+ reference electrode. This pair of redox peaks should
correspond to the lithiation and de-lithiation of Si in the MCMB matrix. The results of
79
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CV measurements clearly demonstrated that Si participated in the reaction with
lithium ions.
400
1st scanning cycle
300 25th scanning cycle
200
Current i (μA)
100
-100
-200
-300
-400
-500
0.0 0.5 1.0 1.5 2.0 2.5

+
Potential (V vs. Li /Li)
(a)
2000
1500
1000 1st scanning cycle

15th scanning cycle
500
Current i / μA
-500
-1000
-1500
-2000
0.0 0.5 1.0 1.5 2.0 2.5

+
Potential ( V vs. Li /Li )
(b)
Fig. 4.3 Cyclic voltammograms of (a) MCMB electrode,
(b) nano-Si-MCMB electrode (sample E).
80
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The specific capacity and cyclability of nanocrystalline Si-MCMB composite
electrodes were measured by constant current charge/discharge testing. Table I shows
the discharge and charge capacities in the first cycle for different sample electrodes.
The bare MCMB electrode (sample A) delivered a reversible capacity of 325 mAh/g
in the first cycle with high efficiency. The bare nanocrystalline Si electrode (sample
B) delivered a very high lithium storage capacity of 3752 mAh/g, which is very close
to its theoretical capacity of 4000 mAh/g. However, this nanocrystalline Si anode had
a very high irreversible capacity of about 1821 mAh/g in the first cycle. The formation
of Li4.2Si alloy induces a 323% volume increase [143]. Such a high volume increase
could create microcracks and therefore destroy the integrity of the electrode, causing
high irreversible capacity and poor cyclability. Sample C is crystalline Si (2
μm)-MCMB composite prepared by ball milling for 10 hours. The sample C anode
shows a lower specific capacity and poorer rechargeability than for nanocrystalline Si
– MCMB electrodes (samples D, E and F). The chemical reactivity of coarse
crystalline Si is much lower than that of nanocrystalline Si. Correspondingly, the
contribution to lithium storage capacity from Si would be smaller. Because of the
effect of the coarse particle size, the volume change in local domains in the sample C
anode could be much larger than for nanocrystalline Si when embedded in MCMB.
Therefore, it is not surprising that sample C demonstrated lower specific capacity and
higher irreversible capacity on cycling.
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Table 4.1 Specific capacity in the first cycle for bare MCMB, bare nanocrystalline Si,
and Si-MCMB electrodes
Samples Qdischarge Qcharge Qirreversible Efficiency

(mAh/g) (mAh/g) (mAh/g) (%)
Sample A (bare MCMB) 355 325 25 91.5
Sample B (bare 3752 1931 1821 51.5

nanocrystalline Si)
Sample C (20 wt % Si (2 687 382 305 55.6
μm) +MCMB, ballmilled
for 10 h)
Sample D (20 wt % Si 1105 936 239 84.7

(nanocrystalline) +
MCMB, ballmilled for 5 h)
Sample E (20 wt % Si 1175 1066 115 90.7

(nanocrystalline) +
MCMB, ballmilled for 10
h)
Sample F (20 wt % Si 1273 1012 261 79.5

(nanocrystalline) +
MCMB, ballmilled for 20
h)
It was found that the ball milling time has a significant impact on the specific capacity
and rechargeability of Si-MCMB composite anodes. Sample E (ball milled for 10
hours) shows an optimal lithium storage capacity and capacity retention on cycling.
We intended to use the ball-milling process to disperse nanocrystalline Si in the
MCMB matrix. The longer the ball-milling time, the better the dispersing effect that
will be obtained. However, ball-milling inevitably breaks up the MCMB spherical
particles and destroys the graphite structure, therefore degrading the electrochemical
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properties of MCMB electrodes. Long-time ball-milling induces a high surface area in
the MCMB powders. The irreversible capacity in the first cycle is considered to come
from the formation of a passivating film, which consumes lithium at the electrode
material/electrolyte interface [144-146]. From SEM observations, we found that the
spherical MCMB particles were severely damaged after 20 hours of ball milling.
Therefore, the sample F (ball milling for 20 hours) anode exhibits a very high
irreversible capacity. To achieve better electrochemical performance for
nanocrystalline Si-MCMB anodes, Si has to be homogeneously dispersed in the
MCMB matrix without damaging the spherical MCMB structure. Sample E seems to
meet this requirement.
In order to combat the problems caused by volume increase in the alloying process,
reducing the particle size of Si is an efficient way to minimize the volume change in
local domains due to the formation of LixSi alloys. Another approach to overcome this
problem is to embed the active element in an inactive matrix, to let the inactive matrix
absorb or buffer the volume expansion. The intermetallic MM’ alloys and tin
composite oxides (TCO) are exactly designed to utilise this principle. We embedded
nanocrystalline Si particles in a MCMB matrix through moderate ball milling. When
lithium ions are inserted into Si-MCMB composites, nano-Si reacts with Li to form
LixSi alloys, and MCMB graphite reacts with Li to form LixC6. The intercalation of Li
in MCMB graphite causes only minor changes in the interlayer spacing and stacking
order. MCMB graphite is almost dimensionally invariable during lithium insertion
and extraction. Because Si particles are nanosize in nature, the volume increase in the
local environment is small, and can be easily absorbed by the ductile MCMB graphite
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matrix surrounding the nano-Si clusters. As a result, the volume change in the
macro-domain is small and negligible for Si-MCMB electrodes. During the lithium
extraction process, a similar phenomenon occurs. This allows the integrity of the
electrode to be preserved for repeated lithium insertion and extraction. A schematic
model of the lithiation and de-lithiation processes in Si-MCMB composite has been
proposed and is presented in Fig. 4.4.
Fig. 4.4 Schematic model of the lithiation and de-lithiation process as in Si-MCMB
composites. The volume increases due to the formation of LixSi alloys are small in
local domain and effectively buffered by the MCMB matrix.
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Fig. 4.5 shows the discharge/charge profiles in the first cycle for bare nanocrystalline
Si (sample B) and nano-Si-MCMB (sample E) anodes. The nanocrystalline Si
electrode shows a flat discharge plateau in the 0.2 – 0.05 V range, corresponding to
the reduction peak in the CV curve (Fig.4.3 (b)), indicating the highly reactive nature
of nanocrystalline Si powders. In contrast, the Si-MCMB (sample E) anode shows a
parabolic curve between 0.5 V and 0.2 V, and a flat plateau between 0.1 and 0.0 V,
which is typical for composite electrode materials. The cyclabilities of all the sample
anodes are shown in Fig. 4.6 The bare MCMB anode is very stable on cycling, but
with limited capacity. Although the bare nanocrystalline Si anode (sample B) had a
high initial capacity, its capacity decreased very quickly on cycling. Therefore, it is
not suitable to use nanocrystalline Si alone as an electrode in Li-ion cells. In general,
nanocrystalline Si-MCMB composite electrodes demonstrated superior performance
(high capacity and satisfactory cyclability), compared to bare MCMB and bare
nano-Si electrodes. In particular, sample E shows stable cyclability, similar to the bare
MCMB electrode, but with much higher capacity. We believe that the electrochemical
performance of nano-Si-MCMB composites can be further optimised through tuning
the material processing.
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2.0
1.5
Voltage (V)
1.0
0.5
0.0
0 500 1000 1500 2000 2500 3000 3500 4000

Capacity (mAh/g)
(a)
2.0
1.5
Voltage (V)
1.0
0.5
0.0
0 200 400 600 800 1000 1200 1400

Capacity (mAh/g)
(b)
Fig. 4.5 The discharge/charge profiles of (a) bare nano-Si electrode
(b) nano-Si-MCMB electrode (sample E).
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4000
3500 Sample A (MCMB)

Sample B (Nano-Si)
Specific capacity (mAh/g)

3000
Sample C ( Si (2μm)-MCMB)
Sample D (Nano-Si-MCMB, ball milled for 5 h)
2500
Sample E (Nano-Si-MCMB, ball milled for 10h)
2000 Sample F (Nano-Si-MCMB, ball milled for 20 h)
1500
1000
500
-500
0 5 10 15 20 25
Cycle number
Fig. 4.6 The discharge capacity of the samples versus cycle number
(Current density: 0.05 mAcm-2).
4.3.2 Si-carbon composite anode materials
Resorcinol reacts with formaldehyde to initially form chains of hydroxymethyl
derivatives of resorcinol, and these then further react with each other to form a
cross-linked 3-dimensional network (called RF gel). Fig. 4.7 shows a schematic
diagram of the reaction of resorcinol with formaldehyde. In the resorcinol structure,
an enhanced electron density exists in the 2, 4, and 6 ring positions. However, the
number 2 position is sterically hindered by the adjacent hydroxyl groups. So, the
reaction occurs primarily in the 4 and 6 positions [147,148]. Through cross-linking,
RF gel forms an interconnected bead structure (3-dimensional network). The
nanocrystalline Si was homogeneously embedded in this RF gel network. After heat
87
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treatment at 650 °C, the gel was carbonized to become amorphous carbon. The final
products were Si-C composites.
Fig. 4.7 A schematic diagram of the R-F gel reaction.
Fig. 4.8 shows an X-ray diffraction pattern of typical Si-C composites. All diffraction
lines are indexed to Si. No diffraction lines from crystalline carbon (graphite) were
observed, indicating the amorphous nature of carbon in the composites. A TEM image
of nanocrystalline Si is shown in Fig. 4.9 (a). The pristine Si powders contain
nanosize Si particles with a spherical shape. The size of individual particles ranges
from 20 nm to 80 nm. Some amorphous Si powders are also present. Fig. 4.9 (b)
shows a TEM image of nano Si-C composite powders. It clearly demonstrates that Si
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powders are surrounded by amorphous carbon. Spot EDX (energy dispersive x-ray)
analysis confirmed that the spherical black crystals in Fig. 4.9 (b) are Si. Therefore,
nanocrystalline Si particles are uniformly embedded in the amorphous carbon matrix
through the carbon aerogel synthesis process.
(111)
Intensity (a.u.)
(220)
(311)
(400)
20 30 40 50 60 70
2θ (degree)
Fig. 4.8 X-ray diffraction pattern of Si-C composites.
The electrochemical performance of the nanostructured Si-C composites was
systematically measured. Cyclic voltammograms of Si-C electrodes in a lithium-ion
cell, in which lithium foil was used as the counter electrode and reference electrode,
are shown in Fig. 4.10. The initial potential of the Si-C electrode is about 3.0 V in the
open-circuit state. In the first scanning cycle, there are two broad cathodic peaks
located at 0.60 V and 0.38 V, respectively, which disappear from the second cycle.
These reduction peaks could be attributed to the formation of a solid-electrolyte
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interphase (SEI) passivation layer on the surface of the composite electrode, due to the
reaction of lithium with electrolyte. Once the SEI layer is formed, it will be stable
under subsequent lithium insertion and extraction, which is evidenced by the
disappearance of these two reduction peaks from the second cycle. Two anodic peaks,
located at 0.38 V and 0.50 V, gradually evolve from the first scanning cycle and
become more distinct after the fourth cycle, which corresponds to the extraction of
lithium ions from the Si-C electrode. One additional cathodic peak at 0.20 V appears
from the fourth cycle. The two pairs of redox peaks remain stable from the fourth
scanning cycle until the twentieth cycle. We suggest that several cycles are required to
activate the Si-C composite electrode under a scanning rate of 0.1 mV/S. The
observed two redox peaks should be attributed to the reaction of lithium with Si to
form LixSi alloys as indicated in equation (4.1).
xLi + Si ↔ LixSi (4.1)
This observation in cyclic voltammetry is similar to that for thin-film Si electrodes
[139].
90
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(a)
(b)
Fig. 4.9 (a) TEM image of nanocrystalline Si powders,
(b) TEM image of nanostructured Si-C composites.
91
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600
1st scanning cycle
400 2nd scanning cycle
4th scanning cycle
200 20th scanning cycle
Current (μA) 0
-200
-400
-600
-800
-1000
-1200
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
+
Potential vs. Li/Li (V)
Fig. 4.10 Cyclic voltammograms of Si-C composite electrode.
The specific capacity and cyclability of nanostructured Si-C composite electrodes
were measured by constant discharge/charge testing. Fig. 4.11 shows the
discharge/charge profiles of a Si-C electrode at the rate C/10. The Si-C electrode
delivered a discharge capacity of about 2000 mAh/g in the first cycle, but with a
irreversible capacity of about 550 mAh/g. Part of this irreversible capacity was used to
form a SEI passivation layer on the surface of the electrode. The reversible capacity
was improved from the second cycle. In the first cycle, there is a discharge plateau in
the voltage range of 0.8 – 0.5 V, which corresponds to the formation of the SEI layer.
However, this discharge plateau disappears from the second cycle. This observation is
in good agreement with CV measurement. A stable discharge plateau between 0.30 V
and 0.02 V is evolved from the second cycle and remains stable.
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3.0
1st cycle
2.5 2nd cycle
Voltage (V) 2.0
1.5
1.0
0.5
0.0
0 250 500 750 1000 1250 1500 1750 2000

Capacity (mAh/g)
Fig. 4.11 The discharge/charge profiles of Si-C composite electrode.
2000
Discharge capacity (mAh/g)
1500
1000
500
0
0 5 10 15 20 25 30 35 40 45 50
Cycle number
Fig. 4.12 The discharge capacity versus cycle number for Si-C electrode.
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The results of the cycling tests are shown in Fig. 4.12, with indicates good cyclability
of the nanostructured S-C composite electrodes. It is well known that a 300% volume
increase accompanies to the lithium alloying process with Si to form Li4.4Si. This
dramatic volume variation could pulverize the electrode, inducing poor cyclability.
We resolve this problem by utilizing nanosize silicon powders and embedding Si in an
amorphous carbon matrix. Through the synthesis of carbon aerogel, Si powders are
homogeneously embedded in a three-dimensional carbon network matrix. Since Si
particles are nanosize in nature, the volume increase in the local sites is small and can
be easily cushioned by the carbon matrix surrounding the Si nanoclusters. Therefore,
the volume change in the macro-domain will be negligibly small for the Si-C
composite electrode, which allows the integrity of the electrode to be preserved for
repeated lithiation and de-lithiation processes. As a result, the Si-C composite
electrode demonstrates a high lithium storage capacity and good cycle life.
4.4 Conclusions
Nanocrystalline Si-MCMB composite anode materials were prepared by ball milling.
They are intended to utilise the high capacity of Si and the stable cyclability of
MCMB. The cyclic voltammetry measurements showed that Si participates in the
reaction with lithium in Li-ion cells. In this investigation, we achieved a reversible
capacity of 1066 mAh/g for nanocrystalline Si-MCMB composites and fairly good
cyclability. A reaction model was proposed for the lithiation and de-lithiation
processes in the Si-MCMB electrodes in lithium-ion cells.
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We also prepared nanostructured Si-C composite anode materials by dispersing
nanocrystalline Si powders in carbon aerogel, followed by heat treatment for
carbonization. Cyclic voltammetry measurements showed two pairs of redox peaks
associated with the lithiation and de-lithiation processes of LixSi alloys. A reversible
capacity of 1450 mAh/g for Si-C composite electrodes was achieved. The good
cyclability should be attributed to the usage of nanosize Si powders and their
homogeneous distribution in an amorphous carbon matrix.
95
Chapter 5 Multiwalled carbon nanotubes (CNTs) anode materials
--------------------------------------------------------------------------------------------------------------------------
Chapter 5
Multiwalled carbon nanotubes (CNTs)
anode materials
5.1 Introduction
Since the discovery of carbon nanotubes (CNTs) by Iijima [149], tremendous effort
has been devoted to the preparation, characterisation and applications of carbon
nanotubes, for both multiwalled CNTs (MWCNTs) and single walled CNTs
(SWCNTs) [150, 151]. Carbon nanotubes can be produced using various techniques
such as electric arc discharge [152], laser vaporization [153], and chemical vapour
deposition [154]. Carbon nanotubes have unique structural, mechanical, electronic,
and electrical properties. They are an attractive system with potential uses in a wide
range of applications, such as nanoscale electronics [155], chemical filters, energy
storage, and electron field emission technology [156, 157].
Carbon nanotubes have been proposed for application as lithium storage materials in
lithium-ion batteries. Carbon nanotubes have been reported with a reversible lithium
storage capacity in the range of 80 – 600 mAh/g [158 – 160]. The electrochemical
performance of carbon nanotubes strongly depends on their structure, morphology,
and disorder, and on the quality of the carbon nanotube bundles. Intermetallic alloy
(MM’) anodes rely on the reaction between lithium ions and the active element M to
96
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form LixM alloys. Transition metal oxides have been reported to exhibit high Li-ion
storage capacity in lithium-ion cells, which is based on the reversible reaction for the
formation of Li2O and metal oxide. Tin oxide (SnO2) has been extensively
investigated as an alternative anode materials for Li-ion batteries. The
electrochemical reaction of SnO2 anode in a Li-ion cell involves two steps: (i) the
formation of lithium oxide, and (ii) lithium alloying with Sn. The second step is an
alloying/de-alloying process, giving a maximum lithium storage capacity of 781
mAh/g. However, the significant volume variation during lithiation induces poor
cyclability [161, 162].
Vertically aligned carbon nanotubes were grown in this work on a planar quartz
substrate by a thermal CVD approach using camphor as the carbon source. The
electrochemical properties of these carbon nanotubes for lithium storage in
lithium-ion cells were systematically evaluated. The preparation, characterization,
and electrochemical performance of composite anode materials formed from CNTs
and SnO2 in lithium-ion cells are described in this chapter.
5.2 Experimental
5.2.1 Synthesis of vertically aligned CNTs
The vertically aligned carbon nanotubes were grown on planar quartz substrates with
a size of 20 × 20 mm by catalytic chemical vapour deposition (CVD), using
nanocrystalline iron as the catalyst. Fig. 5.1 shows a schematic diagram of the CVD
97
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quartz reactor, which consists of three different temperature zones heated by resistive
heating coils. The quartz substrate was placed in the hot zone and heated to 900 °C.
The low temperature zone was maintained at 350 °C. A quartz boat containing iron
carbonyl and another quartz boat containing camphor were also prepared. A small
piece of nickel wire was attached to the quartz boats for magnetic attraction. When the
temperatures in the heating zones reached the designated temperatures, the quartz
boat containing iron carbonyl was first moved into the low temperature zone with a
permanent magnet. The iron carbonyl was then evaporated and deposited on the
quartz substrate in the hot zone, to serve as a catalyst. The second quartz boat
containing camphor was then brought into the low temperature zone. The camphor
was then evaporated and decomposed in the high temperature zone, inducing carbon
nanotubes to grow on the quartz substrate. An argon gas flow was applied in the
opposite direction to the reaction gas at a speed of 20 ml/min.
Fig. 5.1 A schematic diagram of the CVD quartz reactor.
98
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5.2.2 Synthesis of SnO2-CNTs composites
Multiwalled carbon nanotubes (MWNTs, Carbon Nanotechnology Inc., USA), SnCl2
(99.9%, Sigma-Aldrich), and ethanol were mixed homogeneously with a high speed
mixer. The molar ratio of Sn:C was 0.1:1 in the mixture, with a nominal weight
percentage of 55.6 wt% SnO2 in the final product. The mixed suspension was put into
a vacuum oven heated to 90 ºC to evaporate the ethanol. The dried mixture was then
heated to 600 ºC to form SnO2. The calcined product was washed with de-ionized
water to remove Cl- by filtering, and then dried at 100 ºC under vacuum to obtain a
SnO2-CNT composite.
5.2.3 Physical and structural characterization
X-ray diffraction (XRD) measurements were carried out on a Philips PW 1730
diffractometer with Cu Kα radiation. The overall configuration and morphology of
the CNTs were observed by SEM (Leica/Cambridge Stereoscan 440 scanning
electron microscope). The detailed structure of the CNTs was examined by HRTEM
using a 300 KV JEOL JEM-3000F transmission electron microscope with field
emission. Thermogravimetric analysis (TGA) was employed to determine the
percentage of SnO2 in the composites.
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5.2.4 Electrochemical measurements
The electrochemical performance of the vertically aligned carbon nanotubes and
SnO2-CNT composites was tested by fabricating CR2032 coin cells. The working
electrode was prepared by mixing the active materials with 10 wt% carbon black and
10 wt% polyvinylidene fluoride (PVDF) binder in N-methyl-2-pyrrolidinone (NMP)
to form a slurry with appropriate viscosity. The slurry was then spread onto copper
foil, which was then cut out into φ12 mm electrodes. The thickness of each electrode
was approximately 60 – 80 μm, with a loading of 1.5 mg. The coin cells were
assembled in an argon filled glove box (Mbraun, Unilab, Germany), using a
hand-operated closing tool (Hosen Co., Japan). The electrolyte was 1 M LiPF6 in a
mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) (1:1 by volume,
provided by MERCK KGaA, Germany). The cells were galvanostatically charged
and discharged in the voltage range of 0 – 2.0 V versus Li/Li+. Cyclic voltammetry
(CV) measurements were carried out using a CHI660B Electrochemical Work Station
at a scanning rate of 0.1 mVs-1.
The configuration of the CNTs is shown in Fig. 5.2 (a) (b) (c) and (d). The as-prepared
CNTs are well-aligned over the quartz substrate. The CNTs have grown in a vertical
direction to the substrate and have a uniform distribution. The length of the CNTs is
about 70 - 80 μm. Fig. 5.2 (b) shows a vivid view of the vertically aligned CNTs
obtained by cutting the CNT layer with a razor. CNTs were then peeled off from the
100
--------------------------------------------------------------------------------------------------------------------------
substrate for further SEM study. Fig. 5.2 (c) shows the CNT bundles, which
demonstrate the feature of very long CNTs entangled with each other. Only very tiny
quantities of carbon clusters are present in Fig. 5.2 (c), indicating the high yield rate of
CNTs. Fig. 5.2 (d) shows a magnified view of the dispersed CNTs, which further
demonstrates the high quality of the CNTs obtained.
TEM and HRTEM analysis was performed on the CNTs grown on the quartz
substrate. The CNTs were peeled off and dispersed on a carbon coated microgrid. Fig.
5.3 (a) shows a TEM image of the CNTs. Except for some stand-alone multiwalled
carbon nanotubes, the CNTs are entangled together, forming bundles. Some catalyst
particles are encapsulated inside the CNTs. Spot EDS analysis confirmed that the
black dots are Fe catalyst. The outer diameter of the CNTs is about 40 – 60 nm. Fig.
5.3 (b) shows the HRTEM image of a single multiwalled carbon nanotube.
Compartment structures were observed in this carbon nanotube, which consists of a
few curved chambers. The walls of the CNT consist of approximately 10 graphite
sheets with clean fringes.
101
--------------------------------------------------------------------------------------------------------------------------
(a)
(b)
102
--------------------------------------------------------------------------------------------------------------------------
(c)
(d)
Fig. 5.2 SEM images of vertically aligned carbon nanotubes.
103
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(a)
(b)
Fig. 5.3 (a) TEM image of carbon nanotubes,
(b) HRTEM image of a carbon nanotube.
104
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Cyclic voltammetry was conducted on the carbon nanotube electrodes to determine
the electrochemical reactivity of the CNTs in lithium-ion cells, in which lithium metal
was used as both the working electrode and the reference electrode. Fig.5.4 shows
cyclic voltammograms of the carbon nanotube electrodes. The characteristics of the
CV curves demonstrated that lithium ions can reversibly intercalate and de-intercalate
in carbon nanotubes. The lithium insertion potential is very low, close to 0.0 V versus
the Li+/Li reference electrode. However, the potential for lithium extraction is in the
range of 0.15 - 0.30 V. A slight voltage hysteresis between lithium insertion and
extraction in the CNT electrodes is similar to the situation with other carbonaceous
materials [164]. The intensity of the redox peaks remained stable for many scanning
cycles, indicating good reversibility of the carbon nanotubes for lithium insertion and
extraction.
60
2nd scanning cycle
40
20th scanning cycle
20
Current i (μA)
-20
-40
-60
-80
-100
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
+
Potential (V) versus Li/Li
Fig.5.4 Cyclic voltammograms of the carbon nanotube electrode,
Scanning rate: 0.1mV/s.
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Fig. 5.5 shows the first discharge and subsequent discharge curves of a carbon
nanotube electrode. The first discharge curve shows a plateau at about 0.8 V, which is
associated with the formation of a SEI layer on the surface of the carbon nanotube
electrode. Carbon nanotubes usually have a large specific surface area. The
decomposition of the electrolyte and the formation of lithium organic compounds
occur on the surface of carbon nanotubes during the first discharge process. The
capacity used for SEI formation is not reversible [165]. In the subsequent cycles, the
discharge plateau at 0.8 V disappeared. A reversible lithium storage capacity of 950
mAh/g was obtained from the second cycle and remained stable, indicating good
cyclability. Multiwalled carbon nanotubes consist of graphite sheets rolled into closed
concentric cylinders. The concentric tubes are separated by van der Waals gaps of ~
3.4 Å, a typical interlayer spacing in turbostratically disordered graphite. Assuming
that lithium ions can only combine with every second hexagon on the external surface
of a rolled graphene sheet, the limiting stoichiometry would be LiC6, with a
theoretical capacity of 372 mAh/g. However, we obtained a reversible capacity of
950 mAh/g. We suggest that there are four possibilities for lithium intercalation in the
carbon nanotube electrode: (i) lithium ions intercalate into intratubal sites (the hollow
core); (ii) lithium ions intercalate into intertubal sites (the sites between individual
nanotubes ) through diffusion in the bundles; (iii) lithium ions intercalate into carbon
nanoclusters (since small quantities of carbon clusters have been identified in carbon
nanotubes); (iv) lithium ions intercalate into layered graphite structures, including
both nanotube structures and nanocluster structures. All these four possibilities could
contribute to the high lithium insertion capacity of carbon nanotube electrodes [166].
The lithium storage capacity versus cycle number is shown in the inset in Fig. 5.5.
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After the first cycle, the carbon nanotube electrode exhibited stable cyclability for
repeated lithium insertion and extraction.
2.0
1500
1000
1.5
500
Voltage (V)
0
5 10 15 20 25 30
1.0
0.5
3D
0.0 2D 1D
0 200 400 600 800 1000 1200 1400 1600

Fig. 5.5 Discharge curves of the carbon nanotube electrode. The inset shows the
discharge capacity versus cycle number for the carbon nanotube electrode.
The amount of SnO2 in the composite was determined by TGA analysis using air as
the carrying gas. The composite contains 55 wt % SnO2, which is consistent with the
nominal percentage. Fig. 5.6 shows the X-ray diffraction pattern of SnO2-CNT
composite. The SnO2 diffraction lines are clearly indexed, with broad diffraction
peaks indicating a nanocrystalline nature. The diffraction lines of CNTs are weak and
not distinguishable. The particle size of SnO2 was calculated to be in the range of 10 –
20 nm using the Scherrer equation. The distribution and morphology of the SnO2
particles were analyzed from TEM and HRTEM observations.
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(110)
Intensity (a.u.)
(101)
(211)
20 30 40 50 60 70
Angles (2θ)
Fig. 5.6 X-ray diffraction pattern of SnO2-CNT composites.
Fig. 5.7 (a) presents a TEM image showing a general view of the SnO2-CNT
composite, which clearly demonstrates that nanosize SnO2 particles are distributed
homogeneously on the carbon nanotube matrix. Fig. 5.7 (b) further shows a high
magnification TEM image of the composite, from which it was found that some SnO2
particles formed, inside carbon nanotubes. Therefore, we can conclude that SnO2
particles were formed not only on the outside walls of CNTs (inter-), but also inside
CNTs (intra-), when synthesized by the chemical treatment process.
108
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(a)
(b)
Fig. 5.7 TEM images of SnO2-CNT composites:
(a) a general view, (b) HRTEM image.
109
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(a)
(b)
110
--------------------------------------------------------------------------------------------------------------------------
(c)
(d)
Fig. 5.8 HRTEM images of SnO2-CNT composites.
111
--------------------------------------------------------------------------------------------------------------------------
Fig. 5.8 shows high resolution TEM images of SnO2-CNT composites. As shown in
Fig. 5.8 (a), a large number of SnO2 nanocrystals were formed, and they became
attached to the walls of the carbon nanotubes. Fig. 5.8 (b) shows the distribution of
SnO2 nanoparticles on a single carbon nanotube. The HRTEM images are shown in
Fig. 5.8 (c) and (d). We can see that the carbon nanotubes are multiwalled, with an
inner diameter of about 10 - 20 nm. The nature of the SnO2 nanocrystals is
demonstrated in further detail in Fig. 5.8 (d), from which the sizes of the SnO2
nanocrystals were measured to be in the range of 2 – 5 nm. Lattice images of SnO2
nanocrystals are clearly visible, with a 3.4 Å interplanar distance. Although those
SnO2 nanocrystals are of very small size, of the same order as quantum dots, they
have attained a well ordered crystalline state.
The electrochemical reactivity of SnO2-CNT composite electrode was examined by
cyclic voltammetry (CV). Fig. 5.9 shows the CV curves of SnO2-CNT composite
electrodes. In the first cycle, there is a strong reduction peak at 0.85 V, which is
associated with the reaction between Li+ and SnO2:
4Li+ + SnO2 → Sn + 2Li2O (5.1)
The strength of this reduction peak decreased substantially in the second scanning
cycle and gradually disappeared in the subsequent scanning cycles. Following the
formation of Sn and Li2O, there is a reduction peak at 0.15 V, which is associated with
lithium alloying with Sn:
112
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xLi+ + Sn + xe- → LixSn 0 ≤ x ≤ 4.4 (5.2)
The final reduction peak at 0.0 V is related to lithium insertion in carbon nanotubes:
xLi+ + C + xe- → LixC (5.3)
During the charging process, three oxidation peaks appeared on the CV curves. The
first oxidation peak (a small hump), which is related to the extraction of Li from
carbon nanotubes, is located at 0.1 V, indicating that a limited amount of Li was
inserted and extracted from the carbon nanotubes. The strongest oxidation peak is at
0.55 V. This is related to the de-alloying of lithium from LixSn alloy:
LixSn → xLi+ + Sn + xe- (5.4)
The last oxidation peak at 1.25 V is weak and decreases gradually. We suggest that
this oxidation line originates from the extraction of lithium from Li2O, which is
similar to the mechanism for transition metal oxides.
The specific capacity and cyclability of SnO2-CNT composite electrodes were tested
via galvanostatic charge and discharge cycling at the C/2 current rate using CR2032
coin cells. The voltage window was set between 0.0 V and 2.0 V vs. the Li/Li+ counter
electrode. Fig. 10 shows the charge and discharge curves of SnO2-CNT electrode in
the first and second cycles. In the first cycle, there is an irreversible capacity of about
390 mAh/g, which was caused by the formation of both Li2O and an SEI film on the
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surface of the electrode. However, the irreversible capacity decreased dramatically in
the second cycle. The cyclability of SnO2-CNTs is shown in Fig. 5.11. In the first ten
cycles, the lithium storage capacity decreased continuously, but the SnO2-CNT
electrode demonstrated stable cyclability thereafter. The electrode retained a lithium
storage capacity of 410 mAh/g after fifty cycles. The charging efficiency (the ratio of
charge capacity to discharge capacity) is shown in the inset in Fig. 5.11. The
SnO2-CNTs electrode demonstrated a very high charging efficiency (> 98%) after ten
cycles.
4.0x10-4
E
2.0x10-4
F
D
Current / A/cm2
0.0
-2.0x10-4
20th
2nd
-4.0x10-4
1st
-6.0x10-4 A
C
B
-8.0x10-4
0.0 0.5 1.0 1.5 2.0
Potential vs. Li/Li+ / V
Fig. 5.9 Cyclic voltammograms of SnO2-CNT composite electrode.
Scanning rate: 0.1 mV/s.
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2.5
2.0
Voltage (V)
1.5
1.0
0.5
1st
0.0 2nd
0 200 400 600 800 1000

Discharge capacity (mAhg -1 )
Fig. 5.10 The first and second discharge and charge curves of
SnO2-CNT composite electrode.
1100
1000 100
Discharge capacity / mAhg-1
90
80
Efficiency / ( /100)
900 70
60
800 50
40
30
700 20
10
600 0 10 20 30
Cycle number
40 50
500
400
300
200
100
0
0 10 20 30 40 50
Cycle number
Fig. 5.11 Discharge capacity vs. cycle number for SnO2-CNT composite electrode,
the inset presents the charging efficiency vs. cycle number.
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From TEM observation, we know that SnO2 crystals are very tiny (only a few
nanometers). They are well distributed and stick on both the inner and the outer
carbon nanotube walls. Due to the one dimensional characteristics of carbon
nanotubes, a network structures is formed when pasting SnO2-CNTs into a thick-film
electrode. Therefore, excellent electronic conductivity of the electrode is expected.
On the other hand, the volume expansion during the lithium reaction with SnO2 is
relatively small and limited due to the size of the SnO2 nanocrystals. Such a small
volume change can be effectively cushioned by the carbon nanotube matrix. We
believe that these two factors contributed to the good cyclability of the SnO2-CNT
electrodes.
5.4 Conclusion
Vertically aligned multiwalled carbon nanotubes were successfully prepared by
chemical vapour deposition. The carbon nanotubes have a typical diameter of several
tens of nanometers and consist of compartment structures. Cyclic voltammetry
measurements showed that the carbon nanotubes are electrochemically active to
lithium insertion and extraction. A reversible lithium storage capacity of 950 mAh/g
has been achieved for the as-prepared carbon nanotubes.
SnO2-CNT composite anode materials have been synthesized via chemical treatment
followed by heating at high temperature. The solution-based chemical process
enables Sn2+ ions to penetrate into the inner cavity of the carbon nanotubes. SnO2
nanocrystals were observed to be homogeneously distributed on the carbon nanotube
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matrix by TEM and HRTEM analysis. The SnO2-CNT composite electrodes
exhibited stable cyclability, with a lithium storage capacity of 410 mAh/g after fifty
cycles.
117
Chapter 6 Synthesis and electrochemical characterisation of iron phosphide as anode material for
--------------------------------------------------------------------------------------------------------------------------
Chapter 6
Synthesis and electrochemical
characterisation of iron phosphide as anode
material for lithium-ion batteries
6.1 Introduction
Lithium-ion batteries using a carbon anode and a lithium cobalt oxide cathode are the
state-of-the-art power sources for modern electronic devices [167–170]. Exploration
of new anode materials with high energy density is critical for the development of the
next generation of lithium-ion batteries. Nanosize electrode materials are expected to
result in significant advances in the search for high capacity anode materials. Systems
recently developed as non-carbonaceous anode materials include tin-based oxides,
intermetallic alloys, transition metal oxides, etc.. These anode materials have
demonstrated higher capacities than carbon anodes, but suffer from large irreversible
capacity and poor cycle life. For example, there have been intensive investigations on
tin, tin based alloys, and tin oxide composites [171,141,172]. The formation of Li4.4Sn
results in a theoretical capacity of 991mAh/g for elemental Sn. However, this alloying
process is accompanied by a 259% volume increase, causing the disintegration of the
electrode. This phenomenon can be partially alleviated by embedding Sn in an
inactive matrix to create a buffering effect. Silicon has the highest known theoretical
capacity of 4000 mAh/g when forming Li4.2Si alloys, far greater than that of carbon
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and Sn. However, this alloying process is also associated with a 300% volume
dilation, pulverizing the brittle electrode and inducing poor cyclability [173 - 175].
Transition metal phosphides such as MnP4 and Zn3P2 were discovered to exhibit
interesting phenomena with respect to reversible lithium storage [176, 177].
Transition metal phosphides have conventionally been synthesized by solid state
sintering at high temperature over long periods. After sintering, the products were
purified by acid etching [178-180]. Here we report the direct synthesis of transition
metal phosphides using a hydrothermal method. Crystalline iron phosphide (FeP4)
powders were prepared by a solvothermal synthesis technique.
6.2 Experimental
Red phosphorus powders (99%, Aldrich) and FeCl2.4H2O (99%, Aldrich) were
weighed out in appropriate amounts according to the stoichiometry to synthesize FeP4
compounds and loaded into a Teflon lined autoclave. De-ionised water was added as
solvent. The autoclave was inserted into an oven and kept at the reaction temperature
of 180 ˚C for 24 hours. The resulting product was filtered by vacuum suction and
washed with water, then dried at 110 ˚C. X-ray diffraction was performed on the
prepared FeP4 powders using Cu-Kα radiation (Philips PW1730 X-ray
diffractometer). The micro-morphology of the FeP4 powders was studied using a
scanning electron microscope (JEOL JSM-6460A).
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The electrochemical evaluation of the FeP4 anode materials was accomplished by
assembling CR2032 coin cells. The electrodes were made by dispersing 92wt %
active materials and 8wt % polyvinylidene fluoride (PVDF) binder in n-methyl
pyrolidone (NMP) solvent to form homogeneous slurry. The slurry was then spread
onto an Al foil to form the electrodes. The coated electrodes were dried in a vacuum
oven at 120 °C for 12 hours and then pressed to enhance the contact between the
active materials and the conductive carbon. The cells were assembled in an argon
filled glove-box (Mbraun, Unilab, Germany) using lithium metal foil as the counter
electrode. The electrolyte was 1 M LiPF6 in a mixture of ethylene carbonate (EC) and
dimethyl carbonate (DMC) (1:1 by volume, provided by MERCK KgaA, Germany).
The cells were galvanostatically charged and discharged over a voltage range of 0.02
– 1.5 V at a C/5 rate. Cyclic voltammetry (CV) measurements were performed using a
CH Instruments electrochemical workstation (CHI 660A) at a scanning rate of 0.1
mV/s.
We intended to synthesize FeP4 compounds by using a hydrothermal synthesis
method. Crystalline FeP4 has a monoclinic structure (space group: p21/c). Fig. 6.1
shows the X-ray diffraction pattern of the as-prepared iron phosphide compound.
Most of the diffraction lines could be indexed as the monoclinic phase, but some
small amounts of unknown impurities were also present. In general, the diffraction
peaks are weak and broad, indicating the nanosize nature of the synthesized FeP4
powders.
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350
(-112)
(012)
300
(121)
Intensity (a.u.)
(-121)
(100)
(031)
250
200
(140)
(042)
150
100
50
20 25 30 35 40 45 50 55 60 65 70 75
Angles 2θ (degree)
Fig. 6.1 X-ray diffraction pattern of the as-prepared FeP4 powders
SEM image of the FeP4 powders is shown in Fig. 6.2. The FeP4 powders
demonstrated the characteristics of a mixture of small crystalline particles and
amorphous cotton-like phases. The sizes of the individual crystals were less than 100
nm. Those individual crystals were agglomerated together to form large composite
particles. The observed amorphous phases could be impurity phases. SEM
observations revealed that the as-prepared FeP4 compounds produced via
hydrothermal reaction are nanosize. We performed energy dispersive spectroscopy
(EDS) analysis on the powder sample, which was spread onto a carbon tape without
any coating. The atomic ratio of Fe: P is 1:3.98, which confirmed the correct
stoichiometry of the prepared sample. Therefore, the as-prepared powders are
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primarily FeP4 compound with small amount of impurities. Conventionally, transition
metal phosphides have been synthesized via a tin-flux method at high temperature.
Under solvothermal conditions, red phosphorous becomes active, acting both as a
reducing agent and a reactant. The possible reaction is proposed as equation (6.1).
FeCl2 + P + H2O → FeP + HCl + O2 (6.1)
The reaction product FeP4 is a precipitate, which can be easily separated via filtration.
Fig. 6.2 SEM image of the FeP4 powders.
Cyclic voltammetry measurements (CV) were performed on the FeP4 electrode using
lithium metal foil as both a pseudo-reference and a counter electrode in a CR2032
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coin cell at a scanning rate of 0.1 mV/s in the voltage range of 0.0 V – 3.0 V. Fig. 6.3
shows the CV curves of FeP4. During the cathodic scanning process, there are three
well-distinguished reduction peaks at 1.50 V, 0.55 V, and 0.05 V respectively, while
in the anodic scanning process, there are two well-defined anodic peaks centred at 1.1
V and 1.3 V. Previously, it was proposed that the lithium insertion and extraction in
MnP4 proceed as MnP4 ↔ Li7MnP4, accompanied by a topotactic first–order
transition between different related crystal structures [176]. Our observed reaction
phenomena could be much more complicated.
0.30
0.25
0.20 1st scanning cycle

0.15
20th scanning cycle
0.10
Current (mA)
0.05
0.00
-0.05
-0.10
-0.15
-0.20
-0.25
-0.30
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
+
Potential vs. Li/Li
Fig. 6.3 Cyclic voltammograms of FeP4 anode in lithium-ion cell.
123
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Based on the CV curves, we propose the following reaction mechanisms.
Lithium insertion process:
Li + FeP4 → LixFeP4 (6.2)
Li + LixFeP4 → LiFeP4 + 3P (6.3)
Li + P → Li3P (6.4)
Lithium extraction process:
Li3P → Li+ + P (6.5)
LiFeP4 + P → FeP4 + Li+ (6.6)
However, the confirmation and further analysis of the reactions between lithium ions
and iron phosphides require in situ X-ray diffraction measurements.
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2.5
2.0
1.5
Voltage (V)
1.0
0.5
0.0 2nd 1st

20th
0 200 400 600 800 1000 1200

-1
Capacity (mAhg )
Fig. 6.4 Charge/discharge profiles of FeP4 anode.
The lithium storage capacity and reversibility of the FeP4 anodes were tested via
galvanostatic charge and discharge testing Fig. 6.4. The first discharge capacity of
FeP4 electrode reaches as high as 1130 mAh/g, which is equivalent to the intake of
4.33 mole lithium per formula FeP4. However, about 410 mAh/g of the capacity is
irreversible in the first charging process. After the first cycle, FeP4 electrode is fairly
stable for repeated charge and discharge, with a capacity of about 700 mAh/g. As
shown in Fig. 6.4, the FeP4 electrode showed the same charging and discharging
profile after the first cycle. During the charging process (lithium extraction), there are
two voltage plateaus, centred at 1.1 V and 1.3 V, respectively, which match the
observed oxidation peaks on the CV curves Fig. 6.3. During the discharging process
125
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(lithium insertion), the voltage of the electrode drops sharply from 2.0 V to 0.8 V, and
then gradually descends to a plateau centered at 0.5 – 0.6 V, followed by another steep
descent to 0.0 V. The 0.5 V plateau matches the reduction peak at 0.5 V that was
observed in CV measurements. There is no voltage plateau in the discharge profile
matching the reduction peaks at 1.5 V and 0.02 V. The cyclability of FeP4 with respect
to lithium insertion and extraction is shown in Fig. 6.5. In general, FeP4 electrode
exhibited stable cyclability after the first cycle, with a capacity of about 700 mAhg-1.
1200
1000
Discharge capacity (mAhg )
-1
800
600
400
200
0
0 10 20 30 40 50
Cycle number
Fig. 6.5 The discharge capacity of FeP4 anode vs. cycle number.
126
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6.4 Conclusion
We prepared nanosize FeP4 compound via the hydrothermal method. The as-prepared
products contain a majority of monoclinic FeP4 phase with some small amount of
impurities. SEM observation shows nanosize particles of FeP4 powders. Cyclic
voltammetry measurements demonstrated the reversible reactivity of FeP4 anodes
towards lithium insertion and extraction. The FeP4 anode exhibited a stable lithium
storage capacity of about 700 mAhg-1.
127
Chapter 7 Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials
--------------------------------------------------------------------------------------------------------------------------
Chapter 7
Characterisation of olivine-type
LiMnxFe1-xPO4 cathode materials
7.1 Introduction
Lithium polyanion compounds with the general formula LixMy(XO4)z (M: transition
metal; X: P, S, As, Mo，or W) have attracted worldwide interest as new cathode
materials for lithium-ion batteries [92，93，181 - 183]. Among them, LiFePO4 and
LiMnPO4 compounds are particularly interesting. Both LiFePO4 and LiMnPO4 have
an orthorhombic olivine structure (space group: Pnma), in which Li, Fe (Mn) and P
atoms occupy octahedral 4a, octahedral 4c，and tetrahedral 4c sites. The strong P-O
covalency stabilizes the anti-bonding Fe3+/Fe2+ (Mn3+/Mn2+) state through the Fe-O-P
(or Mn-O-P) inductive effects to generate a high operating potential. In the olivine
crystal structure, the oxygen atoms are in a slightly distorted, hexagonal close-packed
arrangement. The FeO6 (MnO6) octahedra share corners in the bc plane, and LiO6
octahedra form an edge sharing chain in the b-direction. The polyanion with strong
P-O covalency provides a stable crystal structure for lithium insertion and extraction,
inducing good cycle life and excellent safety when the compound is used as electrode
in lithium-ion cells. However, the separation of the FeO6 octahedra by PO4 polyanions
dramatically reduces the electronic conductivity of the material, causing poor rate
capacity of the electrode. The electronic conductivity of LiFe(Mn)PO4 olivines can be
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effectively improved by various techniques, such as carbon coating, supervalence
cation doping and synthesis of nanocrystalline grains [184 - 189].
Paddi et al. [1] have reported on the electrochemical characteristics of LiMnxFe1-xPO4
(x = 0.25, 0.50, 0.75, and 1.0), and found that the capacity rapidly decreases at x >
0.75. Yamada et al. [190–192] also performed intensive research on LiMnxFe1-xPO4
systems. They discovered that Mn-rich LiMnxFe1-xPO4 (x > 0.8) is not suitable as a
cathode material, due to the large anisotropic distortion of Mn3+. We report here the
synthesis, crystal structure refinement, and magnetic and electrochemical properties
of a series of LiMnxFe1-xPO4 cathode materials. We have identified a number of
conductive phosphides and manganese phosphates that were formed during the
sintering process, which could enhance the electronic conductivity of the materials.
7.2 Experimental
7.2.1 Materials synthesis
LiMnxFe1-xPO4 (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1) compounds were synthesised by a
sol-gel method. LiOH.H2O (99.9%, Aldrich), FeC2O4.2H2O (99%, Aldrich), and
Mn(NO3)2.6H2O (99.9%, Aldrich) were used as reactants. The stoichiometric
amounts of reactants were dissolved in de-ionised water, in which polyacrylic acid
and citric acid were added as complexing agents for the formation of the gel. The
solution was heated at 85 °C under vigorous stirring until a viscous gel was formed.
The as-formed gel was calcined at 500 °C for 4 hours to decompose the organic
129
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components under flowing argon gas. The decomposed precursors were then sintered
at 750 °C for 15 hours under a flowing gas mixture (10% H2 in Ar). The reducing
atmosphere was employed during the sintering process in order to prevent the
oxidation of Fe2+ and Mn2+ cations.
7.2.2 Magnetic measurement
The temperature-dependent dc magnetic susceptibility was measured using a
Quantum Design MPMS XL SQUID magnetometer in a magnetic field of 2000 Oe
from 5 K to 300 K with a 2 K step under field cooling (FC) conditions.
7.2.3 X-ray diffraction and SEM analysis
Powder X-ray diffraction patterns were obtained on a Sintag (X1) diffractometer
with Cu Kα radiation. The diffraction intensity was measured from 20 ° to 120 ° using
a step size of 0.02 ° with a counting time of 10 s per step. Rietveld refinement was
performed using the GSAS (General Structure Analysis System) program to obtain
the crystal structure parameters. Scanning electron micrographs were obtained with a
JEOL JSM-6460A scanning electron microscope (SEM).
7.2.4 Electrochemical testing
Electrochemical characterisation was performed by assembling CR2032 coin cells for
130
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cyclic voltammetry and galvanostatic charge/discharge measurements. The electrodes
were made by dispersing 80 wt% active material, 10 wt% carbon black and 10 wt%
polyvinylidene fluoride (PVDF) in n-methyl pyrrolidone (NMP) to form a slurry. The
slurry was then coated onto an Al foil. The coated electrodes were dried in a vacuum
oven and then pressed at 1200 kg/cm2. The thicknesses of the electrodes were about
100 µm, and the mass of the active materials was about 2 mg. The coin cells were
assembled in an argon filled glove box (Mbraun, Unilab, Germany) with lithium foil
as the counter electrode. The electrolyte was 1 M LiPF6 in a 1: 1 mixture of ethylene
carbonate (EC) and dimethyl carbonate (DMC).
X-ray diffraction patterns of the LiMnxFe1-xPO4 (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0)
samples are shown in Fig. 7.1 (a). The main diffraction lines are indexed as an
orthorhombic olivine crystal structure (triphylite, space group: Pnma). We performed
Rietveld refinement on the X-ray diffraction patterns using the GSAS program [193].
Fig. 7.1 (b) shows a typical Rietveld refinement on the XRD pattern of the
LiMn0.5Fe0.5PO4 sample. Several small fractions of impurities have been identified
from the Rietveld refinement, which are listed in Table 7.1.
It is worth noting that the impurity phases in LiFePO4 are Fe2P, FeP, and Li4P2O7.
With increasing Mn content, the impurity phases changed to Mn2P2O7. Iron
phosphides are usually formed during the sintering process under a reducing
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atmosphere [194]. The selected bond distances and angles for all the LiMnxFe1-xPO4
samples are described in Table 7.2.
(a) LiFePO4
(b) LiMn0.1Fe0.9PO4
(c) LiMn0.3Fe0.7PO4
(d) LiMn0.5Fe0.5PO4
(e) LiMn0.7Fe0.3PO4
(f) LiMn0.9Fe0.1PO4
(g) LiMnPO4
Intensity (a.u.)
(g)
(f)
(e)
(d)
(c)
(b)
(a)
20 25 30 35 40 45 50 55 60 65 70 75
2θ / degree
(a)
Intensity (a.u.)
LiFePO4
Mn2P2O7
Fe2P
FeP
10 20 30 40 50 60 70 80 90 100 110 120

2Θ / degree
(b)
Fig. 7.1 (a) X-ray diffraction patterns of LiMnxFe1-xPO4, (b) Rietveld refinement
on X-ray diffraction pattern of LiMn0.5Fe0.5PO4 sample.
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Table 7.1 Phase composition and lattice parameters of olivine phase for
LiMnxFe1-xPO4 compounds
Sample Phase composition Lattice parameters of olivine phase
Fraction
Phase * a, Å b, Å c, Å V, Å3
Olivine 7.3366
Li3PO4 0.34292
LiFePO4 10.32559(7) 6.00463(4) 4.68908(3) 290.729(3)
Fe2P 0.70963
FeP 0.079816
Olivine 11.714
LiFe0.9
Fe2P 0.092737 10.3366(2) 6.0130(1) 4.69465(8) 291.791(9)
Mn0.1PO4
FeP 0.23027
Olivine 46.819
LiFe0.7
Fe2P 0.44832 10.3548(3) 6.0279(2) 4.7031(1) 293.56(1)
Mn0.3PO4
FeP 0.63682
Olivine 78.076
LiFe0.5 Fe2P 0.17978
10.3873(1) 6.05132(7) 4.71797(6) 296.557(6)
Mn0.5PO4 FeP 3.0864
Mn2P2O7 1.9555
Olivine 20.368
LiFe0.3
FeP 0.064183 10.4160(2) 6.07332(9) 4.73074(8) 299.262(8)
Mn0.7PO4
Mn2P2O7 1.1980
LiFe0.1 Olivine 17.375

10.4323(3) 6.0913(2) 4.7375(1) 301.05(2)
Mn0.9PO4 Mn2P2O7 0.30770
Olivine 6.9780
LiMnPO4 10.44723(9) 6.10279(5) 4.74778(5) 302.705(5)
Mn2P2O7 1.1349
*Phase fraction in the sample is the phase fraction coefficient in the GSAS program.
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Table 7.2 Selected interatomic distances (Å) and angles (deg) for LiMnxFe1-xPO4
samples
LiMn0.1 LiMn0.3 LiMn0.5 LiMn0.7 LiMn0.9

LiFePO4 LiMnPO4
Fe0.8PO4 Fe0.7PO4 Fe0.5PO4 Fe0.3PO4 Fe0.1PO4
Fe(Mn)-O(1) 2.198(4) 2.202(3) 2.221(4) 2.234(4) 2.252(4) 2.262(4) 2.239(2)
Fe(Mn)-O(2) 2.097(4) 2.113(3) 2.114(4) 2.117(4) 2.122(4) 2.159(4) 2.11(1)
Fe(Mn)-O(3)×2 2.237(2) 2.252(2) 2.261(2) 2.272(2) 2.275(2) 2.271(2) 2.28(1)
Fe(Mn)-O(3) ×2 2.051(3) 2.075(2) 2.080(2) 2.099(2) 2.118(2) 2.116(2) 2.129(1)
Fe(Mn)-P 2.838(2) 2.846(1) 2.846(2) 2.853(2) 2.859(2) 2.853(2) 2.865(2)
P-O(1) 1.534(3) 1.530(3) 1.533(3) 1.543(3) 1.556(3) 1.534(3) 1.553(2)
P-O(2) 1.545(4) 1.551(3) 1.558(4) 1.561(4) 1.583(4) 1.556(4) 1.570(1)
P-O(3) ×2 1.563(3) 1.550(2) 1.551(2) 1.541(2) 1.539(3) 1.553(3) 1.548(1)
P-Li×2 2.658(1) 2.658(1) 2.658(1) 2.662(1) 2.664(1) 2.655(1) 2.656(2)
Li-O(1)×2 2.163(2) 2.170(2) 2.171(2) 2.178(3) 2.174(3) 2.206(3) 2.213(1)
Li-O(2)×2 2.093(2) 2.078(2) 2.080(2) 2.090(2) 2.088(2) 2.078(2) 2.115(1)
Li-O(3)×2 2.221(3) 2.178(2) 2.174(2) 2.170(3) 2.163(3) 2.174(3) 2.160(1)
O(2)-Fe(Mn)-O(3) 90.58(8) 90.03 89.95(7) 89.71(8) 89.89(8) 90.09(8) 89.57(0)
O(3)-Fe(Mn)-O(3) 120.8(1) 119.1(1) 118.71(13) 118.7(1) 118.4(2) 118.42(8) 118.00(1)
O(1)-P-O(2) 112.2(2) 113.6(2) 113.0(2) 112.5(2) 112.1(2) 112.9(2) 112.34(0)
O(2)-P-O(3) 107.8(1) 105.8(1) 105.7(1) 105.6(1) 105.3(1) 105.9(2) 106.4(0)
O(3)-P-O(3) 102.5(2) 103.5(2) 104.3(2) 104.6(2) 104.6(2) 104.5(2) 104.8(1)
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In general, Fe (Mn) – O bond distances increase with increasing Mn content.
However, the O-Fe-O and O-P-O bond angles vary with changing Mn content, but
without any specific trend. Refinement of atomic position occupancies gives a
relatively large value for the Li in LiMnPO4 compared to the stoichiometric
compound. Therefore, taking into account the phase composition of the LiMnPO4
sample, we suggest the following decomposition reaction of LiMnPO4:
(1+x) LiMnPO4 → x/2 Mn2P2O7 + Li1+xMnPO4+x/2 (7.1)
The variations in the lattice parameters of the olivine phases are shown in Table 7.1.
As the Mn content increases, the lattice parameters of the unit cell expand along all
the axes; a, b, and c, inducing an increase in the volume of the unit cell. This is in good
agreement with the fact that the Mn2+ ion (r = 0.84 Å) has a larger radius than that of
the Fe2+ ion (r = 0.74 Å) in octahedral coordination.
Fig. 7.2 shows SEM images of the LiFePO4, LiMn0.5Fe0.5PO4, and LiMnPO4 samples.
In general, all three samples have similar micromorphology and similar grain sizes,
regardless of the composition of the compounds. The average grain size is in the range
of 2 – 5 μm. As the Mn content increases, the micromorphologies of the materials
become cotton wool-like. For the LiMnPO4 sample, this characteristic becomes
especially salient. Thermogravimetric analysis (TGA) was performed on all the
samples. Our as-prepared samples contain about 2 % carbon, which was induced by
the composition of the organic precursors.
135
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(a)
(b)
136
--------------------------------------------------------------------------------------------------------------------------
(c)
Fig. 7.2 SEM images of LiMnxFe1-xPO4 sample powders:
A: LiFePO4 sample; B: LiMn0.5Fe0.5PO4 sample; C: LiMnPO4 sample.
The temperature dependencies of the molar magnetic susceptibilities of the LiFePO4
and LiMn0.5Fe0.5PO4 samples are shown in Fig. 7.3. The magnetic susceptibilities of
these two samples show a maximum at 50 ± 2 °K, demonstrating a paramagnetic –
antiferromagnetic transition with Curie-Weiss behaviour above the Néel temperature.
These two samples show similar dependencies of the magnetic susceptibilities on
temperature. A ferromagnetic transition exists at 225 °K for Mn doped samples,
which is caused by the ferromagnetic impurities Fe2P and FeP. In the triphylite
structure of LiFe(Mn)PO4 olivines, Fe2+ (Mn2+) ions occupy octahedral 4c sites.
Following the super and super-super exchange rule, the interactions between Fe(Mn)
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– O – Fe(Mn) induce antiferromagnetism, as shown by the magnetic measurements.
However, there is no direct Fe(Mn) – O – Fe(Mn) bonding, only Fe(Mn) – O – P – O
– Fe(Mn) bonding. Therefore, magnetic interactions in LiFe(Mn)PO4 could be long
range through Fe(Mn) – O – P – O – Fe(Mn) triple exchange [195-196].
0.026
0.024
0.022
χ emu/mol LiFePO4
0.020
0.018
0.016
0.014
0.012
0.010
0.008
0 50 100 150 200 250 300
Temperature (K)
(a)
0.040
0.035
0.030
χ emu/mol LiFe0.5Mn0.5PO4
0.025
0.020
0.015
0.010
0.005
0 50 100 150 200 250 300 350
Tem perature (K)
(b)
Fig. 7.3 Temperature dependencies of the molar magnetic susceptibilities of
(a) LiFePO4 sample, (b) LiMn0.5Fe0.5PO4 sample.
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200
180
160
Discharge capacity (mAh/g) 140
120 LiFePO4
LiMn0.1Fe0.9PO4
LiMn0.3Fe0.7PO4
100
LiMn0.5Fe0.5PO4
LiMn0.7Fe0.3PO4
80 LiMn0.9Fe0.1PO4
60
40
20
0
0 10 20 30 40 50
Cycle number
Fig. 7.4 Discharge capacity vs. cycle number for LiMnxFe1-xPO4 sample electrodes.
Current rate: C/8; Voltage range: 2.75 V – 4.30 V.
The electrochemical performance of all LiMnxFe1-xPO4 samples was tested via
constant current charge/discharge testing. Fig. 7.4 shows the specific capacities and
cyclabilities of all samples except for LiMnPO4 electrode. LiMnPO4 was found to
almost completely lack electrochemical activity. The cyclability measurements
exhibit a general trend that the specific capacity and cycle life decrease with
increasing Mn content. For the pure LiMnPO4 sample, the electrochemical reactivity
is very limited. Therefore, we concluded that the substitution of Mn for Fe in
LiMnxFe1-xPO4 cathode materials degrades the electrochemical performance.
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7.4 Conclusions
LiMnxFe1-xPO4 (x = 0. 0.1, 0.3, 0.5, 0.7, 0.9 and1.0) compounds were prepared via a
sol-gel synthetic method. Rietveld refinement on X-ray diffraction patterns has
identified a variety of impurities. LiMnxFe1-xPO4 materials show antiferromagnetic
characteristics. The electrochemical reactivity and cycle life degrade with increasing
Mn content for LiMnxFe1-xPO4 samples. Therefore, undoped LiFePO4 is the best
choice as a cathode material for Li-ion batteries.
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Chapter 8 Electrochemical and magnetic characteristics of LiFePO4 and Li0.95Mg0.05FePO4 cathode
materials
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Chapter 8
Electrochemical and magnetic
characteristics of LiFePO4 and
Li0.95Mg0.05FePO4 cathode materials
8.1 Introduction
Because of their high energy density lithium-ion batteries have become the dominant
power sources for portable electronic devices [2，197-199]. The current commercial
lithium-ion batteries use LiCoO2 as the cathode material, which limits their
applications to small batteries due to the high cost and toxicity of Co. In the past
decade, a number of new cathode materials, such as layer structured LiMnO2 [200,
201], LiMn2O4 spinels [202, 203], and LiMxNi1-xO2 compounds [204, 205], have been
developed as alternative cathode materials for lithium-ion batteries. However, none of
them are in popular industrial scale applications so far.
A group of lithium transition metal “polyanion” compounds, incorporating
polyanions XO43- (X = S, P, As and Mo) have been extensively investigated as new
cathode materials for lithium-ion batteries [206–210]. Among them, LiFePO4 olivines
have attracted particular interest because of the low cost and environmental
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friendliness of iron. LiFePO4 has a lithium intercalation/de-intercalation potential of
3.4 V – 3.5 V vs. Li/Li+ due to the tuning effect of the large polyanion [PO4]3+.
LiFePO4 is an ideal cathode materials for large-scale lithium-ion batteries for electric
vehicles (EVs) and stationary power storage. LiFePO4 has an ordered olivine
structure (space group: Pnma), in which Li, Fe, and P atoms occupy octahedral 4a,
octahedral 4c, and tetrahedral 4c sites. The oxygen atoms are arranged in a slightly
distorted, hexagonal close-packed arrangement. The FeO6 octahedra share common
corners in the bc plane, and the LiO6 octahedra form an edge-shares chain in the
b-direction. The separation of the FeO6 octahedra by PO4 polyanions significantly
reduces the electrical conductivity of the material. This causes poor rate capacity and
low utilisation of Li in the LiFePO4 host structure. Extensive investigations have been
made to improve the performance of LiFePO4, including carbon coating, addition of
conductive copper/silver powders, dispersion of high surface area carbon black,
supervalence cation doping, and synthesis of nanosize grains [211-218].
The formation of a nano-network for electronic conduction in LiFePO4 and LiNiPO4
olivines by creating conductive iron phosphides has been reported as one efficient
approach to improve the electronic conductivity [219]. However, the electrochemical
performance of these olivines has not been described. Here we show the
electrochemical and magnetic properties of LiFePO4 and doped Li0.95Mg0.05FePO4
compounds.
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8.2 Experimental
8.2.1 Materials synthesis
LiFePO4 and Li0.95Mg0.05FePO4 were prepared by a sol-gel preparation route.
Li(OH).H2O (99.9%, Aldrich), FeC2O4.2H2O (99%, Aldrich), NH4.H2PO4 (97%,
Aldrich), and Mg(C2H3O2)2 (99%, Aldrich) were used as reactants. The
stoichiometric reactants were dissolved in de-ionised water, in which polyacrylic acid
and active acid were added as complexing agents for the formation of the gel. The
solutions were heated and maintained at 85 °C under vigorous stirring until a viscous
gel was formed. The as-formed gel was heated to 500 °C to decompose the organics
under flowing argon gas. The decomposed precursors were further sintered at 700 °C,
800 °C, and 850 °C, respectively, under a flowing gas mixture (10% H2 in Ar). A
slightly reducing atmosphere was employed during the sintering process in order to
prevent the oxidation of Fe2+ cations. Six samples were prepared, which are shown in
Table 8.1.
X-ray analysis and SEM observation. X-ray diffraction was performed on the
prepared lithium iron phosphates to determine the phase purity using Cu Kα radiation
(MO3xHF22, MacScience, Japan). The morphology of lithium iron phosphate
powders was studied using a scanning electron microscope (JEOL JEM-3000).
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Table 8.1 Sintering temperature, label, and average crystal size of lithium iron
phosphates
Sintering Average crystal

Sample Label
Temperature( °C) Size (μm)
LiFePO4 700 °C LFP-700 0.6
LiFePO4 800 °C LFP-800 4.0
LiFePO4 850 °C LFP-850 8.0
Li0.95Mg0.05FePO4 700 °C LFPMg-700 0.8
Li0.95Mg0.05FePO4 800 °C LFPMg-800 4.5
Li0.95Mg0.05FePO4 850 °C LFPMg-850 10
8.2.2 Magnetic measurements
The magnetic properties of LiFePO4 and Li0.95Mg0.05PO4 samples sintered at 700 °C
and 850 °C were studied using a Quantum Design MPMS XL SQUID magnetometer.
The dc susceptibility was measured in a magnetic field of 5000 Oe from 5 K to 300 K.
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8.2.3 Electrochemical testing.
Electrochemical characterisation was performed by assembling CR2032 coin cells for
galvanostatic charge/discharge. The electrodes were made by dispersing 80 wt%
active material, 10 wt% carbon black, and 10 wt% polyvinylidene fluoride (PVDF) in
n-methyl pyrrolidone (NMP) to form a slurry. The slurry was then coated onto Al
foilto form the electrodes. The coated electrodes were dried in a vacuum oven and
then pressed at 1200 Kg/cm2. The coin cells were assembled in an argon filled glove
box (Mbraun, Unilab, Germany) with lithium foil as the counter electrode. The
electrolyte was 1 M LiPF6 in a 1: 1 mixture of ethylene carbonate (EC) and dimethyl
carbonate (DMC).
8.3.1 XRD and SEM analysis
X-ray diffraction was performed on the LiFePO4 and Li0.95Mg0.05PO4 powders. Fig.
8.1 shows the XRD patterns of LiFePO4 and Li0.95Mg0.05PO4 samples sintered at
different temperatures. Phase pure LiFePO4 and Li0.95Mg0.05PO4 were obtained after
sintering at both 700 °C, and 800 °C.
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o
(a) Sintered at 700 C
o
(b) Sintered at 800 C
o
(c) Sintered at 850 C
Intensity / a.u. Fe2P

FeP4
(c)
(b)
(a)
20 25 30 35 40 45
2θ / degree
(a)
o
(a) Sintered at 700 C
o
(b) Sintered at 800 C
o
(c) Sintered at 850 C
Fe2P
Intensity (a.u.)
(c)
(b)
(a)
20 25 30 35 40 45
2θ / degree
(b)
Fig. 8.1 X-ray diffraction patterns of (a) LiFePO4 and (b) Li0.95Mg0.05FePO4.
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All diffraction lines were indexed to an orthorhombic crystal structure (triphylite,
space group: Pnma). For LiFePO4 sintered at 850 °C, the main phase is still triphylite
LiFePO4, but there are substantial impurity phases such as FeP4 and Fe2P, as indicated
in Fig 1(a). However, for Li0.95Mg0.05PO4 sintered at 850 °C, the main phase is not
triphylite. There are numerous impurity phases that cannot be totally identified. The
strongest diffraction peak was identified as Fe2P. The x-ray diffraction analysis
confirmed a previous report [219] that iron phospides are formed in LiFePO4 and
Li0.95Mg0.05PO4 compounds when sintered at high temperature. The formation of iron
phosphides occurs more in Li0.95Mg0.05PO4 than in LiFePO4. Thermogravimetry
analysis was performed on the LiFePO4 and Li0.95Mg0.05PO4 samples. All the samples
contained 2 – 3 wt% carbon, which was induced by the sol-gel synthesis process.
Fig. 8.2 (a)–(c) shows SEM images of Li0.95Mg0.05PO4 powders sintered at 700 °C,
800 °C, and 850 °C, respectively. The sample sintered at 700 °C has a small grain size
of about 0.5 – 1 μm. When sintered at 800 °C, the grain size increased to 3 – 5 μm,
while the 850 °C sintered sample exhibits the biggest grain size of 5 – 10 μm. The
crystal size of the lithium iron phosphates was significantly influenced by the
sintering temperature. Fig. 8.3 shows the EDS elemental mapping of Li0.95Mg0.05PO4
powders. Fig. 8.3 A is the secondary electron image. A very uniform element
distribution was observed for the main elements Fe, P, and O. For reasons of the
distributions of the trace dopant Mg and carbon are not shown. Trace dopant Mg2+
ions are also observed to be homogeneously distributed in the crystal structures. This
should be attributed to the chemical synthesis process. The ingredient Li+, Fe2+, Mg2+,
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and PO43- ions were dissolved in water and mixed on the atomic scale in solution.
Following the subsequent gel formation and sintering, a uniform element distribution
in the as-prepared materials is expected.
(a)
(b)
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(c)
Fig. 8.2 SEM images of Li0.95Mg0.05FePO4 samples sintered at
(A) 700 °C (B) 800 °C and (C) 850 °C.
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Fig. 8.3 EDS elemental mapping by SEM. (A) Secondary electron image,
(B) Element Fe mapping, (C) Element P mapping, (D) Element O mapping.
8.3.2 Magnetic properties of LiFePO4 and Li0.95Mg0.05PO4
The temperature dependences of the molar magnetic susceptibilities of LiFePO4
samples sintered at 700 °C and 850 °C are shown in Fig. 8.4 (a) and (b) respectively.
The reciprocal susceptibilities are shown in the inset. The magnetic susceptibility of
LiFePO4 shows a maximum at 50 ± 2 °K, demonstrating a
paramagnetic-antiferromagnetic phase transition. This critical temperature is also
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called the Néel temperature (θN). A typical Curie-Weiss law behaviour was followed
above the Néel temperature. The two samples show similar dependences of the
magnetic susceptibilities on temperature, but the sample sintered at 850 °C shows
lower molar susceptibility. The magnetic moments in LiFePO4 are attributed to Fe2+
in the LiFePO4 crystal structure. As detected by x-ray diffraction analysis, a small
amount of iron phosphides were formed in LiFePO4 when sintering was at 850 °C, but
these have no contribution to the antiferromagnetic behaviour. Fig. 8.5 (a) and (b)
shows the molar magnetic susceptibilities of Li0.95Mg0.05FePO4 powders sintered at
700 °C and 850 °C, respectively. The Li0.95Mg0.05FePO4 sample sintered at 700 °C
shows the same magnetic behaviour as LiFePO4, with a typical anti-ferromagnetie
behavior below the Néel temperature. However, the Li0.95Mg0.05FePO4 sample
sintered at 850 °C shows ferromagnetic behaviour, which is totally different from its
counterpart sintered at 700 °C. The main phases for Li0.95Mg0.05FePO4 sintered at 850
°C are iron phosphides. Most of these phosphides (Fe2P, Fe3P, FeP4, and Fe75P15C4)
are ferromagnetic [220]. Therefore, the measured ferromagnetic behaviour also
confirmed the formation of substantial iron phosphides when sintering at high
temperature (850 °C).
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0.026
110
0.024 100
1/χ emu mol Fe

90
80
0.022
-1
70
60
50
0.020 40
χ emu/mol Fe
30
20
0.018 10
0
0 50 100 150 200 250 300
Temperature (K)
0.016
0.014
0.012
0.010
0.008
0 50 100 150 200 250 300
Temperature (K)
(a)
0.026
0.024 120
1/χ emu mol Fe
100
0.022
-1
80
χ emu/ mol Fe
0.020 60
0.018 40
0 50 100 150 200 250 300
Temperature (K)
0.016
0.014
0.012
0.010
0.008
0 50 100 150 200 250 300
Temperature (K)
(b)
Fig. 8.4 Temperature dependencies of molar magnetic susceptibilities of LiFePO4
samples (a) LFP-700 and (b) LFP-850. The insets are the reciprocal magnetic
susceptibilities.
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0.026
120
0.024
1/χ emu mol Fe

100
0.022
-1
80
χ emu/mol Fe
0.020 60
0.018 40
0 50 100 150 200 250 300
0.016 Temperature (K)
0.014
0.012
0.010
0.008
0 50 100 150 200 250 300
Temperature (K)
(a)
0.16
0.14
0.12
χ emu/mol Fe
16
0.10
1/χ emu mol Fe
14
12
0.08
-1
10
0.06 8
6
0 50 100 150 200 250 300
0.04 Temperature (K)
0.02
0 50 100 150 200 250 300
Temperature (K)
(b)
Fig. 8.5 Temperature dependencies of molar magnetic susceptibilities
of Li0.95Mg0.05FePO4samples: (a) LFPMg-700 and (b) LFPMg-850.
The insets are the reciprocal magnetic susceptibilities.
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The effective magnetic moment was calculated using the paramagnetic formula μ =
(8χT)-1/2 [221], which is shown in Fig. 8.6. The measured μ values for the three
anti-ferromagnetic samples are in the range of 4.6 – 4.9 μB at room temperature. The
calculated μ for the ferromagnetic Mg doped Li0.95Mg0.05FePO4 sample is 12.61 μB,
which is much higher than that of the other three samples. The Curie temperature θC
was obtained by linear fitting of the reciprocal magnetic susceptibility above the Néel
temperature. Table 8.2 shows the magnetic parameters of the four samples. All three
anti-ferromagnetic samples have the same Néel temperature. The Mg doped sample
sintered at 700 °C shows a different Curie temperature of θC = - 76 K. The
ferromagnetic sample has a positive θC value of 110.5 K.
In the triphylite structure of LiFePO4, Fe2+ ions occupy octahedral 4c sites with
coordinates x = 0.28, y = 0.25, and z = 0.96. Due to the influence of the octahedral
crystal field, the five 3d orbitals of the Fe2+ ion split into three t2g and two eg
configurations. There are six electrons in 3d orbitals for the Fe2+ ion. Among them,
four electrons are on the three t2g orbitals (dxy, dxz, and dyz), in which three electrons
are spin up and the fourth electron spin down. The magnetic moments for the paired
two electrons in one of the t2g orbitals cancel each other. Therefore, there are a net two
spin-up electrons in t2g orbitals. Two electrons occupy two eg orbitals (dx2-y2 and dz2),
in which one electron is in each orbital with spin-up configuration. The Fe2+ ion
presents net four spin-up electrons (high spin), with an expected magnetic moment of
4μB on the basis of the spin-only value. However, the measured magnetic moment is
in the range of 4.7 – 4.9 μB, which is higher than the theoretical value. Since the
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angular momentum for the Fe2+ ion is not equal to 0, the Fe2+ ion could have a strong
spin-orbit coupling, inducing anisotropy and a non-quenched angular momentum.
The orbital momentum could contribute to the measured magnetic moment. The
magnetic structure of LiFePO4 has been identified to be along the b-axis,
corresponding to a spin sequence (+--+) with moments along [010]. Following the
super and super-super exchange rules, the interactions between Fe-O-Fe induce
antiferromagnetism, as exhibited by the magnetic measurements. However, in the
orthorhombic phase, there is no Fe-O-Fe bonding, only Fe-O-P-O-Fe bonding. So, the
magnetic interaction in LiFePO4 could be long-range through Fe-O-P-O-Fe triple
exchange [222–225].
4
o
LiFePO4 700 C sintered
μ / μB
o
LiFePO4 850 C sintered
3 o
Li0.95Mg0.05FePO4 700 C sintered
0
0 50 100 150 200 250 300
Temperature (K)
Fig. 8.6 The effective magnetic moment per mole of iron of LiFePO4 and
Li0.95Mg0.05FePO4 samples.
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Table 8.2 Magnetic parameters of LiFePO4 and doped Li0.95Mg0.05FePO4 samples.
Effective
Magnetic Néel Curie
Properties Magnetic
Temperature Temperature
Moment μeff (μB)
TN (K) θC (K)
at 25°C
Sample
LiFePO4
50 ± 2 -96.2 4.77
700 °C sintered
LiFePO4
50 ± 2 -96.2 4.55
850 °C sintered
Li0.95Mg0.05FePO4
50 ± 2 -76.0 4.57
700 °C sintered
Li0.95Mg0.05FePO4
~ +110.5 12.61
850 °C sintered
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8.3.3 Electrochemical performance of LiFePO4 and Li0.95Mg0.05PO4 cathode
materials
Electrochemical properties of LiFePO4 and Li0.95Mg0.05PO4 cathodes were
characterised via cyclic voltammetry (CV) and constant current charge/discharge
testing. Fig. 8.7 shows typical voltammograms of LiFePO4 and Li0.95Mg0.05PO4
electrodes. In Fig. 8.7(a), the reduction and oxidation peak positions for the LFP-700
and LFP-800 samples are the same, at 3.30 V and 3.51 V vs Li/Li+ respectively. There
is a shift of the redox potentials for the LFP-850 sample to 3.12 V and 3.60 V vs
Li/Li+. The shift of the redox potential could be related to the formation of iron
phosphite impurities in the LFP-850 sample. Fig. 8.7 (b) shows the CV curves of
Li0.95Mg0.05PO4 electrodes. The redox potentials for doped samples are different from
those of the undoped one, indicating that the Mg doping has an influence on the redox
potential of LiFePO4 cathode materials. Cyclic voltammetry measurements on the
LFPMg-850 sample failed, indicating that the sample electrode has no
electrochemical reactivity due to the change of the main phase into iron phosphides as
a result of sintering at high temperature.
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300
250
200
150
100
Current i (μA)
50
-50 LFP-700 sample

LFP-800 sample
-100 LFP-850 sample
-150
-200
-250
-300
2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8
Potential E vs. Li/Li+ (V)
(a)
300
250
200
150
100
Current i (μA)
50
-50 LFPMg-700 sample

LFPMg-800 sample
-100
-150
-200
-250
-300
2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8
+
Potential E vs. Li/Li (V)
(b)
Fig. 8.7 shows typical voltammograms of LiFePO4 and Li0.95Mg0.05PO4 electrodes.
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The capacities and cyclabilities of the LiFePO4 and Li0.95Mg0.05FePO4 electrodes
were tested by galvanostatic charge/discharge testing at a C/8 rate. Fig. 8.8 (a) and (b)
shows the voltage profiles in the first cycle for the LFP-700 and LFPMg-700 sample
electrodes, respectively, the cells were charged and discharged in the voltage range of
2.75 V – 4.2 V vs. Li/Li+. The profiles exhibit a flat charge and discharge plateau at
3.45 – 3.55 V, which matches the oxidation and reduction peaks in the CV curves.
The LiFePO4 electrode delivered a specific discharge capacity of 160 mAh/g in the
first cycle, whereas the Li0.95Mg 0.05FePO4 cathode shows a lower discharge capacity
of 150 mAh/g in the first cycle, which is due to the partial substitution of Li+ by
non-active Mg2+. The cyclabilities of all the sample electrodes are shown in Fig. 8.9.
5.0
4.5
4.0
Voltage (V)
3.5
3.0
2.5
2.0
0 50 100 150 200
Capacity (mAh/g)
(a)
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5.0
4.5
4.0
Voltage (V)
3.5
3.0
2.5
2.0
0 20 40 60 80 100 120 140 160 180
Capacity (mAh/g)
(b)
Fig. 8.8 Charge/discharge curves in the first cycle for (a) LiFePO4 and (b)
Li0.95Mg0.05FePO4 sample electrodes. Current rate: C/8.
200
150
100 LFP-700
LFP-800
LFP-850
LFPMg-700
LFPMg-800
50
0
0 10 20 30 40 50
Cycle number
Fig. 8.9 Discharge capacity vs. cycle number for LiFePO4 and
Li0.95Mg0.05 FePO4 sample electrodes. Current rate: C/8.
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In general, the as-prepared LiFePO4 and Li0.95Mg0.05FePO4 cathode materials sintered
at different temperatures demonstrated a stable capacity in the range of 150
mAh/g–160 mAh/g at the C/8 rate. The rate of degradation with cycling for the
LiFePO4 and Li0.95Mg0.05FePO4 sample electrodes increases with increasing sintering
temperature, which is due to the influence of the increased crystal size. The previously
proposed “Radial Model” and “Mosaic Model” for LiFePO4 can exactly explain the
observed phenomena [226, 227]. The process of lithium insertion and extraction in
LiFePO4 is a two-phase co-existing process. Therefore, the crystal size has a critical
influence on the transport of lithium ions and electrons into and out of the individual
crystals. The larger the crystal size, the greater the inefficiency of the full conversion
of LiFePO4 to FePO4 and back again, inducing a loss of capacity with cycling.
8.4 Conclusions
The sintering temperature has a significant influence on the crystal size of LiFePO4
and Li0.95Mg0.05PO4 compounds. Typical antiferromagnetic behaviour was
demonstrated for LiFePO4 and Li0.95Mg0.05PO4 samples with a Néel temperature TN =
50 ± 2 K. This antiferromagnetism could be induced by long range Fe-O-P-O-Fe
triple exchange, due to the lack of direct Fe-O-Fe interactions. LiFePO4 and
Li0.95Mg0.05PO4 compounds are electrochemically active with a specific capacity
between 150 mAh/g and 160 mAh/g.
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Chapter 9 Conclusions and suggestions for future study
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Chapter 9
Conclusions and suggestions
for future study
9.1 General conclusions
Studies on the performance of various anode materials and cathode materials have
been presented in the previous chapters. The outcomes are summarized as follows.
9.1.1 Silicon based composite anode materials
This part of the work was intended to utilise the high capacity of Si and the stable
cyclability of mesocarbon microbeads (MCMB). Si-MCMB composites were
prepared via high energy ball-milling. A reversible capacity of 1066 mAh/g and fairly
good cyclability was been achieved for nanocrystalline Si-MCMB composite anode
materials. A reaction model was proposed for the lithiation and de-lithiation process
in the Si-MCMB electrodes in lithium-ion cells. Nanostructured Si-C composite
anode materials were produced by dispersing nanocrystalline Si powders in carbon
aerogel, followed by heat treatment to induce carbonization in argon atmosphere.
Cyclic voltammetry measurements showed two pairs of redox peaks associated with
the lithiation and de-lithiation processes of LixSi alloys. A reversible capacity of 1450
mAh/g for Si-C composite electrodes was achieved. The good cyclability should be
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attributed to the usage of nanosize Si powders and the buffering effect provided by the
amorphous carbon matrix.
9.1.2 Carbon nanotubes and tin oxide – carbon nanotubes anode materials
Vertically aligned multiwalled carbon nanotubes were synthesised by chemical
vapour deposition using iron carbonyl as the catalyst. A reversible lithium storage
capacity of 950 mAh/g has been achieved for the as-prepared vertically aligned
carbon nanotubes. SnO2-CNT composite anode materials were prepared via chemical
treatment followed by sintering at high temperature. The solution-based chemical
process enabled Sn2+ ions to penetrate into the inner cavity of the carbon nanotubes.
SnO2 nanocrystals were observed to be homogeneously distributed on the carbon
nanotube matrix by TEM analysis. The SnO2-CNT composite electrodes exhibited
stable cyclability, with a lithium storage capacity of 410 mAh/g after fifty cycles.
9.1.3 Novel iron phosphide anode materials
Nanosize FeP4 compound was synthesised via the hydrothermal method. The
as-prepared products contain a majority of monoclinic FeP4 phase with some small
amount of impurities. Cyclic voltammetry measurements demonstrated the reversible
reactivity of FeP4 anodes towards lithium insertion and extraction. The FeP4 anode
exhibited a stable lithium storage capacity of about 700 mAh/g.
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9.1.4 Lithium iron phosphate and manganese doped lithium iron phosphate
cathode materials
A series of LiMnxFe1-xPO4 (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1) compounds were
synthesised by a sol-gel preparation route. X-ray diffraction and Rietveld structure
refinement revealed that the lattice parameters (a, b, and c) of orthorhombic
LiMnxFe1-xPO4 increase with increasing Mn content. Magnetic susceptibility
measurements showed antiferromagnetic behaviour for the LiMnxFe1-xPO4 samples.
The electrochemical properties of LiMnxFe1-xPO4 as cathodes in lithium-ion cells
were tested via cyclic voltammetry and galvanostatic charge/discharge
measurements. The electrochemical performance of LiMnxFe1-xPO4 degrades with
increasing Mn content.
9.1.5 Electrochemical and magnetic properties of magnesium doped lithium iron
phosphate cathode materials
LiFePO4 and Li0.95Mg0.05PO4 compounds were synthesised via the sol-gel route
followed by sintering at high temperature. Iron phosphides, which are electronic
conductors, were formed when sintering took place at 850 °C. Magnetic susceptibility
measurements on the powder samples show antiferromagnetic behaviour with TN =
50 ± 2 K for LiFePO4 and Li0.95Mg0.05PO4 sintered at temperatures below 850 °C. The
measured effective magnetic moments are in the range of 4.6 – 4.9 μB at room
temperature. The LiFePO4 and Li0.95Mg0.05PO4 cathodes show a stable
electrochemical capacity in the range of 150 – 160 mAh/g on cycling. The cyclability
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deteriorates with increasing sample sintering temperature due to the increased crystal
size.
9.2. Recommendations for future studies
As an important energy storage system, lithium ion batteries will continue to attract
worldwide investigation to improve their performance. Anode materials and cathode
materials play a critical role in determining the overall properties of lithium-ion
batteries. Therefore, exploration of new anode materials and cathode materials will
certainly provide synergy for the development of new generation lithium-ion batteries
to meet the challenging requirements of large-scale energy storage, electric vehicles,
and portable electronic devices.
Alloy based anode materials are a new direction with the potential to double or triple
the current carbon based anode materials used in lithium-ion batteries. In particularly,
tin and silicon or their alloy have high theoretical lithium storage capacities.
However, the problems related to volume expansion and contraction during the
lithiation and de-lithiation processes need to be overcome before any practical usage
is possible. Nanosize metal oxides are also candidate anode materials which can
provide high capacity.
Without a doubt, lithium iron phosphate is a very promising cathode material for
lithium ion batteries, particularly for large-scale lithium ion batteries, which are safe
in operation and cheap in terms of cost. However, low electronic conductivity induces
165
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low rate capacity and short cycle life. Carbon coating, metal ion doping, and the
synthesis of nanocrystalline materials could effectively combat this problem.
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Figure and table Captions
--------------------------------------------------------------------------------------------------------------------------
Figure 2.1 Schematic diagram of the battery and battery operation.
Figure 2.2 Gravimetric and volumetric energy densities of different
rechargeable battery systems.
Figure 2.3 The operating principle of the lithium-ion battery.
Figure 2.4 Schematic energy diagram of a cell at open circuit
Figure 2.5 The structure of layered LiCoO2.
Figure 2.6 Neutron diffraction patterns of (a) LiMn2O4 (b) LiCr0.04Mn1.96O4
Figure 2.7 The crystal structure of olivine LiFePO4 along [001]. Left:
Expanded view of the framework built on FeO6 octahedra and PO4
Tetradedra. Right: Restricted view of Li, Fe and P distribution
between two distorted h.c.p. (hexagonal close packed)
oxygen-dense layers (PTd [LiFe] octO4). LiO6 octahedra share edges
and Li ions may diffuse along [010] and [001].
Figure 2.8 Crystal structures of left: orthorhombic LiFePO4 and right: trigonal
quartz-like FePO4
Figure 2.9 a. Model displaying the connection among FeO6, LiO6 and PO4
structural units; b Structure viewed along the c-axis.
Figure 2.10 Structural schematics of three types of carbons.
Figure 2.11 Gravimetric capacity of lithium-alloy forming elements.
Figure 2.12 Electrochemical properties of MO anodes in lithium-ion cells. (a)
The voltage – composition profiles for MO/Li cells cycled between
183
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0.01 V and 3 V at a rate of C/5. (b) Cyclability of MO anodes, the
data also shows for a Co3O4/Li cell, demonstrating the behaviour is
not specific to divalent oxides. The inset is the rate capacity of a
CoO electrode.
Table 2.1 The structural and electrochemical parameters of LiMδMn2-2δO4
cathodes
Figure 3.1 JEOL JSM-6460A SEM facility
Figure 3.2 JEOL 2011 TEM facility
Figure 3.3 Atmosphere controllable Glove-box for assembling CR2032 coin
cells
Figure 3.4 CHI 660 B and 660C Electrochemical Work Stations
Table 3.1 Materials and chemicals
Figure 4.1 SEM image of (a) bare MCMB graphite (b) 20 wt% nano
Si-MCMB ball milled for 5 hours. (c) 20 wt% nano Si-MCMB ball
milled for 10 hours (d) 20 wt% nano-Si-MCMB ball milled for 20
hours
Figure 4.2 X-ray diffraction pattern of 20 wt% nano-Si-MCMB ball milled for
10 hours.
Figure 4.3 Cyclic voltammograms (a) MCMB electrode (b) nano-Si-MCMB
electrode (sample E)
Figure 4.4 Schematic model of the lithiation and de-lithiation process in
Si-MCMB composites. The volume increases due to the formation
184
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of LixSi alloys are small in local domain and effectively buffered by
MCMB matrix.
Figure 4.5 The discharge/charge profiles of (a) bare nano-Si electrode (b)
nano-Si-MCMB electrode (sample E).
Figure 4.6 The discharge capacity versus cycle number (Current density: 0.05
mAcm-2).
Figure 4.7 A schematic diagram of the R-F gel reaction.
Figure 4.8 X-ray diffraction pattern of Si-C composites.
Figure 4.9 (a) TEM image of nanocrystalline Si powders. (b) TEM image of
nanostructured Si-C composites.
Figure 4.10 Cyclic voltammetry of Si-C composite electrode.
Figure 4.11 The discharge/charge profiles of Si-C composite electrode.
Figure 4.12 The discharge capacity versus cycle number for Si-C electrode.
Table 4.1 Specific capacity in the first cycle for bare MCMB, bare
nanocrystalline Si, and Si-MCMB electrodes
Figure 5.1 A schematic diagram of the CVD quartz reactor.
Figure 5.2 (a) (b) (c) and (d) SEM images of vertically aligned carbon
nanotubes.
Figure 5.3 (a) TEM image of carbon nanotubes. (b) HRTEM image of a
carbon nanotube.
Figure 5.4 Cyclic voltammograms of the carbon nanotube electrode. Scanning
rate: 0.1 mV/s.
185
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Figure 5.5 Discharge curves of the carbon nanotube electrode (The inset is the
discharge capacity versus cycle number for the carbon nanotube
electrode).
Figure 5.6 X-ray diffraction pattern of SnO2-CNT composites
Figure 5.7 TEM images of SnO2-CNT composites.
Figure 5.8 HRTEM images of SnO2-CNT composites.
Figure 5.9 Cyclic voltammograms of SnO2-CNT composite electrode.
Scanning rate: 0.1mV/s.
Figure 5.10 The first and second discharge and charge curves of SnO2-CNT
composite electrode.
Figure 5.11 Discharge capacity vs. cycle number for SnO2-CNT composite
electrode. The inset presents the charging efficiency vs. cycle
number.
Figure 6.1 X-ray diffraction pattern of the as-prepared FeP4 powders
Figure 6.2 SEM image of FeP4 powders.
Figure 6.3 Cyclic voltammograms of FeP4 anode in lithium-ion cell.
Figure 6.4 Charge/discharge profiles of FeP4 anode.
Figure 6.5 The discharge capacity of FeP4 anode vs. cycle number.
Figure 7.1 (a) X-ray diffraction patterns of LiMnxFe1-xPO4 (b) Rietveld
refinement on X-ray diffraction pattern of LiMn0.5Fe0.5PO4 sample.
Figure 7.2 SEM images of LiMnxFe1-xPO4 sample powders, A: LiFePO4
sample; B: LiMn0.5Fe0.5PO4 sample; C: LiMnPO4 sample.
Figure 7.3 Temperature dependencies of molar magnetic susceptibilities of
186
--------------------------------------------------------------------------------------------------------------------------
(a) LiFePO4 sample (b) LiMn0.5Fe0.5PO4 sample
Figure 7.4 Discharge capacity vs cycle number for LiMnxFe1-xPO4 sample
electrodes. Current rate: C/8; Voltage range: 2.75 V – 4.30 V.
Table 7.1 Phase composition and lattice parameters of olivine phase for
LiMnxFe1-xPO4 compounds.
Table 7.2 Selected interatomic distances (Å) and angles (deg) for
LiMnxFe1-xPO4 samples.
Figure 8.1 X-ray diffraction patterns of (a) LiFePO4 and (b) Li0.95Mg0.05FePO4.
Figure 8.2 SEM images of Li0.95Mg0.05FePO4 samples sintered at (A) 700 °C,
(B) 800 °C, and (C) 850 °C.
Figure 8.3 EDS elemental mapping by SEM.
LiFePO4， samples (a) LFP-700 and (b) LFP-850. The insets are
reciprocal magnetic susceptibilities.
Li0.95Mg0.05FePO4 samples (a) LFPMg-700 and (b) LFPMg-850.
The insets are reciprocal magnetic susceptibilities.
Figure 8.6 The effective magnetic moment per mole of iron of LiFePO4 and
Li0.95 Mg0.05 FePO4 samples.
Figure 8.7 shows typical voltammograms of LiFePO4 and Li0.95Mg0.05PO4
electrodes.
Figure 8.8 Charge/discharge curves in the first cycle for (a) LiFePO4 and (b)
Li0.95 Mg0.05 FePO4 sample electrodes. Current rate: C/8.
187
--------------------------------------------------------------------------------------------------------------------------
Figure 8.9 Discharge capacity vs. cycle number for LiFePO4 and
Li0.95Mg0.05FePO4 sample electrodes. Current rate: C/8.
Table 8.1 Sintering temperature, label and average crystal size of lithium iron
phosphates.
Table 8.2 Magnetic parameters of LiFePO4 and doped Li0.95Mg0.05FePO4
samples.
188
Publications
------------------------------------------------------------------------------------------------------------------------
Publications
1. J. Yao, J.S Park, K. Konstantinov, G.X.Wang, J.H. Ahn, J. Wang and H.K. Liu
“Electrochemical performance of nanocrystalline SnO2-carbon nanotube
composites as anode in lithium-ion cells” Journal of Nanoscience and
Nanotechnology (in press).
2. J. Yao, K. Konstantinov, G.X. Wang, and H.K. Liu, “Electrochemical and magnetic
characterization of LiFePO4 and Li0.95 Mg0.05 FePO5 cathode materials” Journal of
Solid State Electrochemistry 11(5) (2007) 177 -185.
3. J. Yao, S. Bewlay, V.A. Drozd, R.S. Liu, X.L. Wang, H.K. Liu and G.X. Wang,
“Characterisation of olivine-type LiMnxFe1-xPO4 cathode materials” Journal of
Alloys and compounds 425 (2006) 362 – 366.
4. G.X. Wang, J. Yao, H.K. Liu, S.X. Dou and J.H. Ahn, “Growth and lithium storage
properties of vertically aligned carbon nanotubes” Metals and Materials
International 12(5) (2006) 413 – 416.
5. G.X. Wang, S. Needham, J. Yao, J.Z. Wang, R.S. Liu and H.K. Liu, “A study on
LiFePO4 and its doped derivatives as cathode materials for lithium-ion batteries”
Journal of Power Sources 159 (2006) 282 - 286.
6. G.X. Wang, Y. Chen, L. Yang, J. Yao, S. Needham, H.K. Liu and J.H. Ahn,
“Synthesis of nanocrystalline transition metal and oxides for lithium storage”
Journal of Power Sources 146 (2005) 487 - 491.
189
Publications
------------------------------------------------------------------------------------------------------------------------
7. G.X. Wang, S. Bewlay, J. Yao, J.H. Ahn, H.K. Liu and S.X. Dou,
“Characterisation of LiMxFe1-xPO4 (M=Mg, Zr, Ti) cathode materials prepared by
the sol-gel method” Electrochemical and Solid-state Letters 7(12) (2004) A503 –
A506.
8. G.X. Wang, J.H. Ahn, J. Yao, S. Bewlay and H.K. Liu, “Nanostructured Si-C
composite anodes for lithium-ion batteries” Electrochemistry Communication 6(7)
(2004) 689 – 692.
9. G.X. Wang, J. Yao and H.K. Liu “Characterization of Nanocrystalline Si-MCMB

Composite Anode Materials” Electrochemical and Solid-State Letters 7(8) (2004)
A250 –A253.
10. G.X. Wang, J. Yao, J.H. Ahn, H.K. Liu and S.X. Dou, “Electrochemical
properties of nanosize Sn-coated graphite anodes in lithium-ion cells” Journal of
Applied Electrochemistry 34 (2004) 187 – 190.
11. G.X. Wang, S. Bewlay, J. Yao, H. K. Liu, and S. X. Dou， “Tungsten Disulfide
Nanotubes for Lithium Storage”Electrochemical and Solid-State Letters 7 10
(2004) A321-A323.
190

A Study of Electro Materials For Lithium-Ion Batteries

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University of Wollongong Theses Collection

University of Wollongong Theses Collection

A study of electro materials for

This paper is posted at Research Online.

FOR LITHIUM-ION BATTERIES

A thesis submitted in fulfillment of

YUEPING (Jane) YAO, B.Sc. M. Eng

Institute for Superconducting & Electronic Materials

Yueping (Jane) Yao

support through the ARC Linkage project LP0453766.

for providing great help in proofreading this thesis.

technology for modern portable electronics such as mobile phones, notebook

research plays a key role in the development of next generation of advanced

alloying and dealloying instead of intercalation and de-intercalation. However, the

volume expansion in local domains. Secondly, silicon particles were embedded in

Si-mesocarbon microbeads (MCMB) composite anode materials were produced by

ball-milling. Si-MCMB composite electrodes demonstrated superior performance

nano-Si electrodes. Silicon-amorphous carbon composite anode materials were also

homogeneous distributed in carbon matrix. A reversible capacity of 1450 mAh/g for

usage of nanosize Si powders and their homogeneous distribution in an amorphous

materials for lithium-ion batteries. Vertically aligned multiwalled carbon nanotubes

(VAMWCNTs) were prepared by chemical vapor deposition method. Nanosize

SnO2-MWCNTs composites were also synthesized. The VAMWCNTs have a typical

diameter of several tens of nanometers and consist of compartment structures. Cyclic

voltammetry measurements show that the carbon nanotubes are electrochemically

SnO2-CNTs composite electrodes exhibited stable cyclability with a lithium storage

capacity of 410 mAh/g after fifty cycles.

interesting phenomena with respect to reversible lithium storage. They were

conventionally synthesized by solid state sintering at high temperature for long

a solvothermal synthesis technique. Cyclic voltammetry measurements demonstrated

conductivity, inducing low rate capacity and preventing commercial application.

electrochemical performance of lithium iron phosphate. The synthesis, crystal

structure refinement, magnetic and electrochemical properties of a series of

LiMnxFe1-xPO4 cathode materials was investigated. A number of conductive

effect of sintering temperature towards the crystal size of LiFePO4 and

Li0.95Mg0.05PO4 compounds were systematically investigated. LiFePO4 and

Li0.95Mg0.05PO4 samples exhibit a typical antiferromagnetic behaviour. This

antiferromagnetism could be induced by long range Fe-O-P-O-Fe triple exchange due

to the lack of direct Fe-O-Fe interactions. LiFePO4 and Li0.95Mg0.05PO4 electrodes

show specific capacity in the range 150 mAh/g – 160 mAh/g.

CHAPTER 2 LITERATURE REVIEW

2.2 Rechargeable batteries 6

2.3 An introduction of lithium-ion batteries 7

2.4 Fundamentals of Lithium ion Batteries 10

2.5 Cathode Materials for Lithium-ion Batteries 14

2.5.1 LiCoO2 and doped LiMxCo1-xO2 cathode materials 15

2.5.2 LiNiO2 and doped LiMxNi1-xO2 cathode materials 19

2.5.3 Layered LiMnO2, orthorhombic LiMnO2 and their doped

2.5.4 Spinel LiMn2O4 and LiMxMn2-yO4 cathode materials 28

2.5.5 Lithium iron phosphate based cathode materials 36

2.5.5.1 Crystal structure of LiFePO4 38

2.5.5.2 Enhancement of electronic conductivity and

improvement of electrochemical properties of

LiFePO4 cathode material 43

2.6 Anode Materials for Lithium-ion Batteries 46

2.6.1 Carbon based anode materials 47

2.6.2 Alloy based anode materials 52

2.6.3 Metal oxide anode materials 56

2.6.3.1 Tin oxide anode materials 56

2.6.3.2 Transition metal oxide anode materials 59

3.1 Materials and chemicals 62

3.2 Materials synthesis techniques 63

3.2.1 High energy ball milling 63