Professional Documents
Culture Documents
A report on
APPLICATION OF CARBON
ALLOTROPES IN LITHIUM-ION
BATTERIES
Prepared By
Apoorv Vaish
2013A4PS252P
Under the Guidance of
ACKNOWLEDGEMENT
I would like to sincerely thank the institute and Dr Sachin U Belgamwar for giving
me the opportunity to do a Study Oriented Project on the topic of Application of
carbon allotropes in Lithium-Ion batteries under his vigilance, guidance and
support throughout the study and fabrication process. I would also like to thank him
for encouraging and motivating me to carry out this project under his constant
support and help and made me identify the flaws associated with my project and
eliminate them efficiently.
I would specially like to thank the various published sources which enlightened me
with the current research going on in the field of Lithium ion batteries and helped
me formulate and experimental procedure for the fabrication and testing.
I would like to thank Ms Sumita Choudhary who guided me through the DST-FIST
supported XRD apparatus and characterization in the Physics Department, BITS
Pilani, for the characterization of my samples.
Finally, I would also like to appreciate the help and support provided by my
instructors in the MEMS lab for helping me with the fabrication procedure and in
the various intricate processes involved in it.
PREFACE
I wanted to learn more about the carbon allotropes namely graphene and carbon
nanotubes(CNTs). Recently, these materials have been put forward as possible
candidates to wide range of applications like water desalination, hydrogen storage
and Lithium-ion batteries. I chose to focus on their application in LIBs since the
experimental analysis and fabrication will be easier to proceed with. I referred to a
number of papers to device an experimental procedure that can be carried out and
to tackle various problems.
ABSTRACT
Lithium-Ion Batteries (or LIBs) are the primary energy storing devices in portable
electronics and electric vehicles. Current research is going on using wonder
materials like Graphene and Carbon Nanotubes (CNTs) in batteries and supercapacitors. The aim of these is generally to increase the capacity of the battery for
the expansion of their application in renewable energy applications like wind, solar
or to produce flexible batteries for their application in flexible electronic devices in
future. These carbon allotropes have been used either directly or in form of
composites with metals, metal oxides or polymers, at cathode, anode and in
electrolytes in LIBs. The idea was to figure out what difference in electrical
properties does a PDMS-MWCNT composite make to PDMS and hence conclude
their potential application in LIBs. They can be used to create flexible and light
anodes that were chemically inert to electrolyte.
INTRODUCTION
Batteries and super-capacitors are the energy storing devices of tomorrow. Batteries are different
from super capacitors in the way they store their energy as chemical energy. Batteries can be
classified as wet/dry depending on the electrolyte phase being used in the battery. However, a
more useful classification of batteries is:
A battery is characterised as primary or secondary with the electrode materials used in it solely.
Discharging basically means that the electrochemical reaction occurring on application of an
external circuit is an exothermic one, giving enough energy for our device to run for a certain time
until equilibrium state of the cell reaction is attained. If the reaction rate k of the reverse reaction
is high enough for the reverse reaction to proceed in acceptable period of times, then the battery
can be used as a secondary battery. Many people have tried recharging primary batteries with fatal
or unsatisfactory results. This entire phenomenon is directly dependent on the activation energy
(EA) for the reverse reaction which determines reaction rate k via the equation
k =A eE / RT .
Lithium-ion battery and related technologies have become a pivotal area in technological
developments for future. Electric vehicles havent yet entered the mainstream market due to the
higher battery costs. Moreover their miles per charge value still remains low compared to petrol
or diesel powered vehicles. Another dimension to the LIB problem today is due to their
application in portable electronics. The electronics of tomorrow require lucrative characteristics
like flexibility, transparency, high capacities. All of these problems are being solved using LIBs
mostly due to their excellent operating characteristics compared to other secondary batteries like
lead-acid or nickel-cadmium batteries. However, LIBs tend to be about 40 percent costlier than
nickel-cadmium batteries per kWh.
Negative Electrode: This electrode is generally made up of Graphite with some additives.
The purpose of this electrode is to store Lithium ions by forming intercalated compounds
with the ion. The electrode reaction is as follows :
xLi+ + xe- + 6C LiC6
We see here that each Lithium ion gets intercalated with 6 Carbon atoms. This fact is
crucial to the capacity of the battery per unit mass of electrode. Extensive research has
been going on to find a substitute for Graphite which can store more Lithium ions per
atom. An interesting phenomenon hindering the research is that of pulverization.
Pulverization: The phenomenon can be explained using an alternative electrode material
like Aluminium. A single Aluminium atom can store about 2.8-3 atoms of Lithium. Thus
during charging cycle x amount of Li+ ions form an alloy with Aluminium atoms. During
discharging cycle, however, y(<x) Li+ ions leave the electrode breaking its lattice structure.
This results in crumbling of the electrode. This results in declining capacity over
successive charge and discharge cycle as some Lithium in each cycle stays at the anode
and is unable to come to the counter electrode on application of voltage.
Positive Electrode: It is usually made of Lithium metal salts like LiCoO 2 , LiFePO4 ,
LiMnO2. The most commonly electrode in electronics is that of LiCoO2 . Each of these has
some advantage over the others. LiCoO2 provides a better energy density than LiFePO 4 but
the latter offers better power density (rate at which energy can be supplied or gained) and
longer life. The purity of the electrode plays a major role in the rate of charging and
discharging as well. The cell reaction here is as follows :
LiMO2 Li1-xMO2 + xLi+ + xe
Note : The electrochemical roles of the electrodes reverse between anode and cathode during the
charging and discharging. For example during charging, the graphite electrode will undergo
reduction whereas the Lithium metal oxide electrode will undergo reduction. Vice-versa happens
during discharging cycle. However, general convention is that the electrode with graphite which
stores the Li+ ions as anode during charging cycle and the Li metal oxide electrode as cathode.
Method)
2. Graphene Oxide is by-product of above reaction as the spacing between sheets increases
due to water intercalation.
3. Ultrasonication or stirring is used to enhance exfoliation.
4. Treat GO with Hydrazine Hydrate or expose it to plasma or xenon flash tubes or heat GO
in a furnace or reaction with urea followed by heating and subsequent cooling to produce
rGO.
Percolation Threshold: The electrical properties of a composite wherein the matrix is electrically
resistive are adversely affected by the concentration of the filler material. An important factor is to
hit the percolation threshold. It is the critical concentration below which no continuous path is
formed from one side to the other side of the sample. Thus unless the matrix is electrically
conductive, the sample wouldnt show appreciable electrical conductivity. Above the critical filler
particle fraction as well, conductivity does not depend much on the filler concentration. PVDF, the
most common binder material has this limit around 2-3 percent of filler material, thus a small
amount of the relatively cheaper graphite makes it electrically conducting. We formulated this
experiment to formulate the find if we could create conducting PDMS with low levels of
MWCNT(0.35%(w/w)) and further characterize its electrical properties against a Li metal foil
cathode for their application in Lithium-ion batteries.
Experimental Procedure
PDMS is the common binder material used in batteries. However, we investigated if
PDMS(polydimethylsiloxane) could be used instead. The polymer is generally used in soft
lithography for components like micro-valves. Also due to difficulty in obtaining graphene, we
used MWCNTs. Two coin shaped electrodes of PDMS and PDMS+0.35%CNT(w/w) were
formed using the following procedure :
PDMS :
1. 2g of PDMS resin was added in a beaker carefully.
2. 0.2g of curing agent was added to this. The mixture was poured in a mould.
3. The resulting solution was stirred continuously to homogenize it.
4. The mould was vacuum pumped immediately to remove the air bubbles. This solution was set
to cure for about 20 hours.
PDMS+0.35% CNT(w/w) :
1. 20 mg MWCNT was added to 10 mL acetone in a test tube.
2. This solution was ultrasonicated in a bath sonication apparatus for about 20 minutes.
3. This was added to 5 grams of PDMS resin in a beaker.
4. The mixture was mixed manually and heated on a hot plate at 60 degree celcius for about
20 minutess to evaporate the remaining acetone.
5. 0.5g of curing agent was added to the resulting solution and poured in a mould. The
solution was stirred continuously to homogenize it.
6. The mould was vacuum pumped immediately to remove the air bubbles. This solution was
set to cure for about 20 hours.
CHARACTERIZATION OF ANODE
Characterization of anode was done using an optical microscope first at 20x magnification for
both the samples. The images are displayed below in figure 1.
1a) PDMS
More number of black spots are visible in the PDMS/CNT sample. Also the spots on PDMS are
circular, however they seem to be elongated in that of PDMS/CNT sample. However, no
conclusion can be made surely using the optical microscope if the spots are due to the presence of
CNT. An XRD analysis was thus carried out to further differentiate the two samples. XRD was
done at the DST-FIST supported XRD apparatus in the Physics Department, BITS Pilani.
(FWHM)CNT|16.7793 = 0.7228
(FWHM)CNT/PDMS|16.6878 = 0.638
(FWHM)CNT/PDMS|13.7779 = 0.638
(FWHM)CNT/PDMS|18.2466 = 0.638
ycal
1.80E+02
1.60E+02
1.40E+02
1.20E+02
1.00E+02
Intensity
8.00E+01
6.00E+01
4.00E+01
2.00E+01
0.00E+00
0.00E+00 1.00E+01 2.00E+01 3.00E+01 4.00E+01 5.00E+01 6.00E+01
2Theta
ycal(PDMS)
ycal(CNT+PDMS)
The following conclusions can be made by using the above plot obtained through XRD analysis :
Addition of Graphite along with CNT to increase conductivity and to cross percolation
threshold limit.