A

Progress Report
On

Use of Graphene Nano composites for Ultrafast Charging

of Lithium-Ion Batteries

Submitted By

Rajwardhan Pawar
(15MNT0016)
Guided By

Prof. Sathyanarayanan P.

School of Electronics and Electrical engineering (SENSE)

VIT, University Vellore
2016-2017
 ABSTRACT

Due to low kinetics of Coulombic reactions involving electron transfer and ion diffusion in
both anode and cathode materials, Lithium ion batteries still suffering from Slow charging
problem. Here we investigate suitability of two battery performances i.e. With LiFePO4
cathode & Graphene Oxide as anode and All Graphene battery . LiFePO4 battery is found to
be having energy density about 190Wh/kg (at 1C rate for 80cycles ) & All Graphene Battery is
giving 225Wh/kg .We are comparing the suitability of these two batteries for the ultrafast
charging aspect (2C,5C,10C) & Comparing use of various Metal oxides (Tio2 ,SnO2
etc )Composites with Graphene as anode & observe the performance on above mentioned
batteries.
1.Introduction:

LIBs were first introduced in the 1970’s but then only as non-rechargeable batteries. With a
high capacity and wide range of possible discharge rates, it quickly conquered the market for
small portable electric devices.
During the same time, much effort was invested in producing a rechargeable battery using the
benefits from Li. However, these early attempts revealed big risks when using Li-metal as the
negative electrode. In 1991, a major breakthrough in LIBs was presented by Sony Corporation.
The positive electrode was made of LiCoO2 but instead of using metallic Li as negative
electrode they used coke, where Li-ions could be intercalated into the atomic structure. This
enabled Li to be stored in an ionic state instead of a metallic state, which improved the safety.
Although LIBs have developed further (e.g. replacing coke with graphite in negative
electrodes), basically the same materials are still used in LIBs today.
The total capacity for the two electrodes in a battery are calculated using equation (1) where CP
is the capacity for the positive electrode and CN is the capacity for the negative electrode.
1.1 How Lithium Ion Battery Works?

Fig1 Lithium-ion and Electron Charge and Discharge

 Lithium Ion and Electron dissociate from the anode material simultaneously and move
toward opposite directions via solid-state diffusion

 The Li-ion approaches the electrode/electrolyte interface, and diffuses through the
electrolyte.
 The Electron driven by the higher potential of the cathode side, passes through anode
particles and their interfaces toward the current collector instead of riding into the
electrolyte, and migrates via the external circuit to power a device.
 When the Li-ion reaches the positive electrode, it reacts together with an electron and
the positive electrode material forming a new material (LiY)

 Both half-cell reactions in a LIB are possible to study by using Li-metal as the counter
electrode material. A positive or negative electrode together with a Li-metal counter
electrode is often used as experimental scale battery; this kind of battery is referred to as
a “half-cell”. A discharge process followed by a charge process, or a de-lithiation
followed by a lithiation process, is called cycling.
1.2 Battery Parameters

1.2.1 Open circuit voltage (OCV) or cell potential, is an important parameter when
describing batteries. The OCV tells us of how big the driving forces are to attain equilibrium
when two materials are in contact. The OCV is calculated theoretically with knowledge of the
two electrode reactions. However, theoretical values of the OCV are never obtained due to
side reactions and the difficulty for electrodes to be in equilibrium.

1.2.2 Specific capacity (C) is another important factor, and it tells us how much charge there
theoretically is per gram of the material: the unit of C is Ah kg-1. It is calculated from the
number of electrons participating in the reactions (n), Faraday constant (F) and the molecular
mass (M) of the electroactive components according to equation (2)

1.2.3 The energy density of a battery is the product of the experimental OCV and the
specific capacity. The unit of energy density hereby becomes Wh kg-1. Hence the expression
for the energy density would be as in equation (3).

1.2.4 Columbic efficiency is the ratio of the capacity output (Co) during discharge and the
capacity input (Ci) during charge, see equation (4).

1.3 Aim of Thesis

This thesis aimed to evaluate use of Different Graphene based Nanocomposites withTiO2,
SnO2 as negative electrode material for LIBs. Firstly Electrodes had to be produced and
assembled into half-cells, and thereafter electrochemically de-lithiated and lithiated (cycled).
In what way the electrode performance is affected by cycling rates, production parameters
and electrolytes was of special interest. These investigations also intended to gain more
understanding of the suitability of these materials for the ultrafast charging aspect of Lithium
Ion Batteries (LIB’s).
2. Materials in Li-ion batteries
2.1. Negative electrode materials
The negative electrode materials in LIBs should have a low potential vs. the positive
Electrode, and also be able to reversibly give away and take up Li-ions. Li-metal is a
Possible material that fulfills these criteria, but it reacts strongly with water and air, and is
therefore a safety issue. Another safety problem when using Li-metal as negative electrode is
that during cycling it tends to grow dendrites towards the counter electrode. If the dendrite
reaches the counter electrode, the battery will short circuit and it may cause a fire. The
theoretic capacity of Li-metal as negative electrode material is very high, 3862 mAh g-1 .

One alternative to metallic Li is to use carbonaceous materials; and especially graphitic

carbon works well as negative electrode. In commercial LIBs, graphite is the dominant
negative electrode material. The carbon atoms in graphite are arranged in layers kept together
by van der Waals forces. Li-ions are intercalated into the layer structure during charge and
are de-intercalated during discharge. Insertion of one Li-ion for every six carbon atoms is
possible, and gives graphite a theoretical capacity of 372 mAh g-1 . For applications, it is
desirable to improve the capacity of the negative electrode and therefore several compounds,
which reversibly react with Li, have been investigated. Among these, Sn-based oxides have
shown capacities around 500-600 mAh g-1. Alloys with Sn and Sb have also shown high
capacities and good cycling performances. Oxides with the transition metals Co, Fe, Ni and
Cu have attained much attention and have showed good performances.

Fig 2: Voltage versus capacity chart for anode and cathode materials for high-rate LIB application.
2.1.1 Why Oxides? Why not Sulfides?

Answer to this question is that they (sulfides) doesn’t work on the principle of intercalation
chemistry. At Solid Electrolyte Interface (SEI) they form the insulating layer so that they
electrical conductivity is reduced.

Reversible rate cycling is very less, so this results into the capacity fading over the time.

2.1.2 Advantages of using TiO2:

The advantages of using TiO2 as an anode in rechargeable lithium ion batteries lie in its
characteristic safety and stability Choosing an anode with a higher lithiation potential such as
TiO2 (!1.6 V vs Li/Li+) greatly reduces the chance of this type of battery failure. Among the
common polymorphs, TiO2(B) has attracted recent attention due mainly to high energy
density, but also because of the ability to nanostructure this polymorph into several distinct
architectures which provides opportunities to systematically study the charge storage
mechanism. TiO2(B) was first synthesized in 1980 by Marchand and co-workers from the
layered titanate K2Ti4O9 which was converted to H2Ti4O9 via acid washing and finally
dehydrated to the layered TiO2(B) structure. TiO2(B) has a monoclinic C2/m structure
comprised of edge- and corner sharing TiO6 octahedra with an open channel parallel to the
b-axis that sits between axial oxygen’s. Initially TiO2(B) lithiates as shown in eq.

xLi +TiO2(B) +xe- LixTiO2(B)

In subsequent cycles, LixTiO2(B) is reversibly lithiated/delithiated as shown in following

eq .
LixTiO2(B) Li(x –y)TiO2(B) + yLi+ + ye-

The unit cell contains 8 Ti sites and 10 Li+ sites, giving a theoretical capacity of 1.25 Li+/Ti
(~420 mAh/g), though calculations suggest that because of Li+-Li+ repulsions
only 8 Li+ sites can be filled giving a capacity of 1.00 Li/Ti (335mAh/g).
 Fig 3. Unit cell of TiO2(B) with idealized Liþ insertion sites.

2.1.3 SnO2 composites as anode material for lithium ion Battery

Sn-based nanomaterials have created much attention in materials chemistry owing to their
potential application in Li-ion batteries. The present anode material, graphite, has an inherent
limitation with a theoretical gravimetric capacity of 372 mAh/g . Sn-based nanomaterial’s
show a large theoretical capacity value due to the formation of Li–Sn alloy, which initiates
much effort to explore these materials as anode for Li-ion battery. In recent days, Sn-based
materials such as SnO2, SnS2, and SnS have been prepared by various techniques with
different size and morphology and explored for Li-ion battery application. Among these
materials, SnO2 have been extensively studied. Indeed, the low electrical conductivity and
large volume expansion/contraction (during charging and discharging) results poor
cyclability. Thus, the practical application of these materials has not been attained so far. To
overcome the above issues, attempts have been made to prepare nanostructured materials
with diverse morphologies such as Nano sheets, Nano rods, nanoparticle, and Nano plates
etc. Reducing the particle size will increase the surface to volume ratio and that would
decrease the volume changes during the Li insertion and extraction. Also, it is proposed that
preparation of layered crystalline nanostructured materials similar to the structure of graphite
can minimize the volume change during cycling and offer more active cites for the
accommodation of Li-ions.

2.1.4 ZnO as a Anode for LIB’s

Zinc oxide (ZnO) has previously been studied as a negative electrode in LIBs because of its
low cost, good chemical stability and high theoretical capacity (988 mAhg−1). Other groups
have reported ZnO incorporated graphene oxide (GO) composites as anode materials in LIB,
using the blend of GO and ZnO.
2.3 Electrolytes
LIBs work in a wide voltage window and this requires that the electrolyte is stable in the
whole range, which can be from 0 V up to and above 4V vs. Li/Li+. The electrolyte is usually
comprised of a Li-salt dissolved in either an organic liquid phase, such as cyclic carbonates,
or in a solid polymer network. Polymer electrolytes can be produced in thin foils and then
used as a separator between the two electrodes. solid electrolyte increases the safety but has a
limited conducting ability. We use 1M LiPF6 in Ethylene Carbonate/ Dimethyl Carbonate
(EC/DMC) .

2.2 Positive electrode materials

The positive electrode material must, just like the negative electrode materials, be able to take
up, store and give away Li-ions reversibly. It should also have a high potential difference vs.
the negative electrode material.
The first positive electrode material for commercial LIBs was
LiCoO2 with a capacity for practical use of around 140 mAh g-1. LiNiO2 was considered a
promising positive electrode material, but suffered from safety and stability issues.
Substituting one of the two Ni atoms with equal amounts of Ti or Mg resulted in a safer
material with a capacity of 180 mAh g-1. An electrode material based on LiMnO2 has shown
even higher capacities of around 190 mAh g-1with good capacity retention . Another class of
positive electrode materials is metal phosphates where LiFePO4 quite recently has become
commercialized. Even though the capacity per gram does not exceed previously mentioned
positive electrode materials, the safety is higher.

Key Parameters for Ultrafast Charging of LIB’s

The High rate performance of LIB’s require both the anode and cathode materials possessing
high rate capability simultaneously with High reverse capacity. Therefore electrode material
requires to meet following requirements

1. Fast Electrochemical reaction kinetics

2. Achieving High Li-ion Diffusivity in electrode materials
3. Enhancing Li-ion conductivity in the electrolytes
4. Improving electronic conduction in electrode materials
5. Robust structure of Electrodes
6. External Methods like Conductive Agent Addition and Doping Addition
The major challenge in achieving these materials is that during ultrafast charge/discharge
processes volume expansion occurs, which can result in the partial pulverization of active
material. As a result, there is loss of electronic contact between active material and the current
collector, leading to capacity fading of the electrode. Also Cell faces deposition of lithium
metal in the form of dendrites or as a high surface area film over the anode due to which
internal short circuit and explosion can occur when dendrites reach the cathode during
charge/discharge process.

Table2 Discharge Current Parameters for Different Types of Batteries

Slow Charge <C/3

Quick Charge C/3<,<2C

Fast Charge >2C

Ultra-Fast Charge >10C

Lithium ions starts migrating from cathode to anode while discharging and during the charging
reverse of that happens. Here the functionalized graphene is the anode and we have made the
half cell with that anode and tested the capacity of the half-cell from that we come to know
about the charge storage capacity of the functionalized graphene anode .this we did with the
three samples and the cathode being the reduced graphene oxide . we have simulated the total
cell. And tested the capacity . once we have tested the capacity . we are trying for the oxides for
the ultrafast charging aspect such as Tio2 and SnO2 graphene composite.

SEM images clearly shows that graphene sheets are formed. FTIR & XRD and raman spectra
of the samples clearly shows that the we have prepared the functionalized Graphene with the
interlayer spacing between the layers around 0.88nm.

This interlayer spacing can be attributed to the carbonyl and hydroxyl groups present EDAX
spectrum shows the metal impurities are present in the material which is removed by washing
the sample with HCl and again with DI water & centrifugation afterword’s.

Half cells are assembled in the Glove-box compartment in Al foil pouch as follows.
3.Experimental

Samples Prepared:

1. Fabrication of functionalized graphene and reduced graphene oxide.

Graphite oxide (GO) was fabricated from natural graphite using the modified Hummers
method as follows43. NaNO3 (5 g) and H2SO4 (225 mL) were added to graphite (5 g)
and stirred for 30 min in an ice bath. KMnO4 (25 g) was added to the resulting solution, and
then the solution was stirred at 50uC for 2 h. Deionized (DI) water (500 mL) and H2O2 (30 mL,
35%) were then slowly added to the solution, and the solution was washed with HCl (750 mL,
10%). Additional washing with concentrated HCl (500 mL, 37%) afforded the GO product as a
powder. Next, the GO powder samples were annealed at 120oC for 6 h to synthesize
functionalized graphene. The reduced graphene oxide was prepared by high temperature
treatment of the functionalized graphene sample at 8000C.

2. SnO2/GNS synthesis
In a typical preparation, 0.95 g of SnCl4·5H2O (Wako, Japan) in 15 ml water was added to
graphene oxide solution (15 mL, ~15 mg/mL) and the solution was stirred for 30 min
vigorously and Ultrasonicated for 30 min. Then, 0.25 g of NH4OH (Wako, Japan) solution was
added drop wise and the resulting mixture was put in to Teflon lined stainless steel autoclave
and heat treated at 180 °C for 15 h. The resulting Nano composite powder was washed with
ethanol and water, and dried at 60 °C overnight. SnO2 loading on GNS have been varied by
altering the concentration of SnCl4·5H2O and keeping the GO solution as constant.

3. Self-assembled ZnO (SAZO) on GO

Graphene oxide (GO) was prepared from graphite powder (Bay Carbon Inc.) by a modified
Hummers method. In a typical synthesis, zinc acetate ((CH3CO2)2Zn, 0.92 g) was added to
N,N-dimethylformamide (DMF, 200 mL). The mixture was stirred for 20 min at the room
temperature. Graphene oxide (GO, 40 mg) was also dissolved in 50 mL of DMF and sonicated
for 30 min. Then, the graphene oxide solution was added to the zinc acetate solution under
vigorous stirring. The colorless solution changed to a dark blue color.The mixture was heated
to 95−125 °C under continuous stirring. After keeping for 5 h at 70−125 °C, the result products
were isolated by the addition of ethanol and deionized (DI) water, followed by centrifugation.
The resulting powder was transferred to a quartz tube furnace and annealed at 500 °C with
argon gas for 3 h.

4. TiO2-Graphene nanosheets
In a typical synthesis, 0.1 g PVP was dissolved in 10 mL Ethylene Glycol with stirring. Then a
solution of TBOT tetrabutoxytitanium (0.2 g) in 0.8 g of EG was injected in, and the mixture
was kept stirring at room temperature for 1 h. After 3 mL of GO, aqueous dispersion (about 0.5
mg/mL) was slowly added into the above suspension and then stirred for 10 min. The mixture
was transferred to a Teflon-lined stainless steel autoclave for solvothermal reaction at 150 _C
for 2 h. After the solvothermal treatment was completed, the autoclave was cooled and the final
product was collected by centrifugation and washed with ethanol.
Results

1. Self-assembled ZnO (SAZO) on GO

EDAX result SEM Image

2.Fabrication of functionalized graphene

For sample S1

EDAX SEM
SAMPLE S2

XRD of Sample S2

100

%T
646.15

80
1587.42
1693.50
3294.42

869.90

60
563.21
1130.29
1029.99

40

20

0
4000 3500 3000 2500 2000 1500 1000 500
RS2 1/cm

FTIR of Sample 2
SAMPLE S3

105

%T

1365.60

530.42
90

1045.42
1213.23
1728.22

1132.21
75

60

45

30

4000 3500 3000 2500 2000 1500 1000 500

RS3 1/cm

XRD of Sample S3 FTIR

 3.TiO2 –Graphene Composites

100
1213.23
1367.53
1629.85
3294.42

%T
1737.86

75

50

25
408.91

-25
4000 3500 3000 2500 2000 1500 1000 500
RS-1 1/cm

FTIR
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