THE HONG KONG POLYTECHNIC UNIVERSITY

Full-Time BEng Honours Degree in Mechanical Engineering

Oxidative chemical vapor deposition (oCVD) of ultra-conformal conductive

polymers coating

by

Cheung Ching Yu

Lai Shek Yu

Lantau Chan

Report submitted in partial fulfilment of the requirements for the Honours Degree of

Bachelor of Engineering in Mechanical Engineering

(Insert Date of Submission here)

 Acknowledgement
We three student of Mechanical Engineering of 4th year in THE HONG KONG
POLYTECHNIC UNIVERSITY, currently working on the final year project
“Oxidative chemical vapor deposition (oCVD) of ultra-conformal conductive
polymers coating”. We would like to express our deep gratitude to Dr. Liu
Qiang, our research supervisor, for his patient guidance, passionate
encouragement, and helpful suggestions of this research work. His
willingness to give his time so generously has been very much appreciated.
We would also like to thank the teaching assistant Mr. of the tutorial works
for enabling us to follow the laboratory process and the instructions. His
assistance and advice has been a great help.
Contents
Abstract ..................................................................................................................... 4
Nomenclature ............................................................................................................ 4
Chapter 1: Introduction of lithium battery ................................................................ 4
Lithium battery...................................................................................................... 4
Overview ........................................................................................................... 4
Working principle ............................................................................................. 5
Lithium batteries Cathode materials ..................................................................... 6
Overview of Cathode materials......................................................................... 6
NCM Cathode materials.................................................................................... 6
The challenges of NCM cathode materials ........................................................... 8
Residual lithium compounds ............................................................................. 8
Gas evolution .................................................................................................... 9
Rock-salt phase formation ................................................................................ 9
Dissolution of transition metal ions ................................................................ 10
Micro-cracking ................................................................................................ 11
Initial capacity loss ......................................................................................... 11
CEIs layer........................................................................................................ 12
Objectives of the project ..................................................................................... 12
Major work outline ............................................................................................. 12
Chapter 2: Coating .................................................................................................. 12
Surface coating.................................................................................................... 12
Functionality of surface coating .......................................................................... 13
HF scavenger .................................................................................................. 13
Physical protection layer ................................................................................. 14
Ultra-thin film coating .................................................................................... 17
oCVD Surface coating Technology .................................................................... 17
Advantages of oCVD Solvent-free synthesis.................................................. 19
Uniformly coating ........................................................................................... 19
Mechanical flexible films Another works of oCVD on LIBs ........................ 19
Chapter 3: Experiments........................................................................................... 22
Introduction ......................................................................................................... 22
Preparation .......................................................................................................... 22
Characterization .................................................................................................. 23
Result and discussion .......................................................................................... 23
Conclusion .............................................................................................................. 23
References ............................................................................................................... 23
appendices ............................................................................................................... 23

Abstract
Nomenclature

Chapter 1: Introduction of lithium battery

Lithium battery
Overview
Modern society has become dependent on fossil fuels, which have a limited supply
and unbalance geographic distribution. It will eventually cause two major
consequences: the supply chain of fossil fuels becomes weak and our
environmental pollution becomes worse. [1]
The Lithium-ion rechargeable battery brings us evolution in technology. Many
essential tools in our daily life, such as laptops, mobile phones or cameras, etc., are
relying on Li-ion batteries to provide rechargeable, stable, and high-performance
energy to be functional. In Shin & Choi’s essay, it indicated that the rechargeable
battery industry has often been closely intertwined with socio-technological trends
of the times. Showing how important the Li-ion battery to our daily life.[2]
All lithium-ion batteries mainly consist of four components, anode, cathode,
separator and an electrolyte between anode and cathode.

Components Function

Anode Discharged state: To release electrons and Lithium-ions

Charging state: To receive electrons and Lithium-ions

Cathode Discharged state: To receive electrons and Lithium-ions

Charging state: To release electrons and Lithium-ions

Separator To avoid the electrical short circuits occurring, which is led by the contact between
the anode and cathode

Electrolyte To allow for lithium-ions to migrate over from one side to the other side, which is
cathode and anode, while not allowing the electrons to move through it.

Working principle
A lithium-ion battery is combined with one or more interconnected electrochemical
cells. An Electrochemical cell is made of four major components: electrodes (both
anode and cathode), electrolyte, and separator. [1] In the anode, as well as the
negative terminal, lithium is stored between layers of carbon graphite. Graphite has
a nice crystal structure of layered planes, which is an ideal material for lithium
intercalation. Graphite acts as a stable storage space for lithium atoms. [3] As
lithium has the greatest electron chemical potential, it is very likely to donate an
electron through the external circuit to the cathode. At the same time, the lithium
leaves the graphite and becomes positive and is called lithium-ion. When a lot of
lithium atoms leave from the graphite at the same time, a flow of electrons is built
up.

In the cathode, as well as the positive terminal. A common type of cathode is made
by cobalt. Cobalt will lose some electrons to the oxygen and become positive. As a
result, the cathode intends to gain back electrons. Therefore, when we connect the
negative and positive terminal through the external circuit, electrons hence flow from
the lithium to the cobalt. With the flow of electrons transfer from anode to cathode.
The cathode side grows more negatively charged, and the other side is positively
charged. Due to opposite charges attract and similar charges repel, electrons less
likely to flow to an area that is growing more negatively charged. Hence, an
electrolyte is needed between the anode and cathode, to let positively charged lithium
ions leave the graphite and move to the other side.

When the lithium gets to the cathode side, it intercalates with the cathode and oxygen
to become Lithium Cobalt (a cathode example) Oxide and balances the charge build-
up.
When the battery is recharging, the charger applies a higher force on a flow of
electrons in the opposite direction. Electrons are pulled out of the cathode and
forced into the anode, causing the cathode to return to a positive state and lithium
back to the anode through the electrolyte. [4]

Figure 1 Schematic representation of the flows of electrons and lithium-ions. AS illustrated in [4]

Lithium batteries Cathode materials

Overview of Cathode materials
The cathode, as an important role for the cell, dominates most of the battery cost
since it limits the energy density inside. Therefore, the studying and researching of
the cathode materials are meaningful and important for the progress of the battery
industry. As the voltage of the cell is determined by the potential difference between
the anode and the cathode, also means the lower energy of the cathode the better,
which implies that the cathode would require the stabilization of higher oxidation
states with a lower-lying energy band. [5] The most generally used materials for the
cathode including Lithium Cobalt Oxide (LCO), Lithium Nickel Manganese Cobalt
Oxide (NMC), Lithium Manganese Oxide (LMO). Also, the materials being used for
the cathode is classified into layered oxides, spinel oxides, polyanion oxides.

NCM Cathode materials

The short term ‘NCM’ is representing three metal elements: Nickel, Manganese,
and Cobalt. With the layered structure, NCM has a robust rhombohedral structure
and generally shows good reversibility for lithium insertion/ extraction. In order to
satisfy the continuously increasing demand for high-energy-density LIBs,
researchers nowadays pay more attention to the NCM family with Ni content ≥60%
(also known as Ni-rich layered oxides). Ni-rich layered oxides have a high
practical capacity (≥ 180 mAh g–1), high working potential (~3.7 V vs. Li+ /Li),
and acceptable manufacturing cost. [6]
Figure 2(a)Phase diagram of the ternary layered oxides generated from LiNiO2, LiCoO2and LiMnO2.
(b) The discharge capacity, thermal stability, and capacity retention of NCM materials with different
Ni contents [6]

Every transition metal element has its unique function in Ni-rich layered oxides.
For example, Ni associated with capacity, Co, and Mn is crucial for kinetics and
safety of Ni-rich layered oxides, shown in figure 1b. In figure 1c, it is observed that
with increased Ni content and decreased Co/Mn content, Ni-rich layered oxides
deliver higher capacity (e.g. NCM 622: ~180 maAhg^-1, NCM811: ~200mAhg^-
1) but at the expense of capacity retention and thermal stability, as well as other
concomitant problems. [6]

The challenges of NCM cathode materials

Residual lithium compounds
In order to fulfil the requirement of high capacity, good capacity retention, and
reliable safety. Ni-rich layered compounds are very attractive in terms of capacity
and its retention upon cycling. However, controlling the Li/Ni ratio is difficult,
particularly in the Li layer. [7] To overcome this defect, Arai et al. suggested that the
addition of excessive lithium is effective in the reduction of cation mixing in the Li
layer. [8] Hence, the structure keeps the well-done layer with low cation mixing.
Therefore, the materials can have better capacity upon cycling. As an excessive
amount of lithium is added, unreacted lithium ingredients can remain on the surface
of active materials, presumably as an oxide form, Li2O. Also, the outer part of the
Li2O is contaminated moisture and Co2 in air, forming LiOH and Li2Co3
RLCs unavoidable occur in the Ni-rich layered oxides, and their amount
increase with the Ni content. RLCs are present initially in the form of Li2O
and gradually convert to LiOH and Li2Co3 in storage by reacting with H2o
and Co2 in air. As a result, RLCs are commonly detected in the form of a
mixture of Li2O, LiOH, and Li2Co3 depending on the ratio varying with
storage condition such as humidity and time.
Two aspects of problems are caused by RLCs, one is slurry gelation in the cathode
coating process and the other is battery swelling due to the strong alkalinity of
RLCs. [9]
This reaction is not favoured because it is irreversible, causing irreversible
capacity. [7]

Gas evolution
Oxygen evolution was observed near the end of charge from all layered oxide
cathodes due to the thermodynamic instability of the H3 phase, and the degree of the
oxygen evolution declines with an increase in the Ni content. [9] Gas evolution
relating to interactions with the cathode can occur by electrolyte oxidation and
surface contaminants. The gas evolution initially occurring at an onset potential of
approximately 3.8V is commonly attributed to the electrochemical decomposition of
lithium carbonate (Li2Co3) which is formed on the NCM electrodes surface during
manufacture and storage. A method for studying the gas evolution derived from
lithium carbonate mentioned in Ben Rowden’s review is isotopically enriching
transition metal oxide electrodes with 18O and cycling of lithium carbonate
electrodes. Table 1 is indicating the decomposition of lithium carbonate is expected
to produce Co2 and singlet oxygen through reaction 7. [10]

Figure 3 Oxidation reactions occurring at the cathode in lithium-ion batteries [10]

Rock-salt phase formation

The formation of the rock-salt phase is an inevitable result of the Ni/Li mixing and
oxygen evolution rate (OER), whose net result is the loss of oxygen from the
cathode materials. Such a formation was aggravated with increasing Ni content,
state of charge (SOC), and temperature. Equation (8) and (9) showing the
transition takes place through Ni disproportion and OER at low SOC. Equation
(13) and (14) showing the transition undergoes predominantly through OER.
Ni/Li mixing is a process about the migration of metal ions with low valence into
the Li+ ion layer and occupies the position of Li+ ions, which happens in all types
of layered oxides and the whole life of the battery. In the NCM cathode, Ni ions have
the strongest tendency to mix with Li-ions due to the similarity in ionic radius
between the Ni and Li-ions, The Ni/Li mixing causes the capacity of both Ni/Li and
Li mobility to be reduced. Accordingly, the crystal structure is transformed from
layered over spinel to Nio-like rock salt phase. [9]

Oxygen evolution in the bulk is kinetically blocked, and the active oxygen
intermediates on the surface are rapidly reacted by the electrolyte solvents,
pushing the OER forward. Hence, Since the NiO rock salt phase and solvent
decomposition products are neither electrochemically active nor ionic
conductive, they will accumulate and become the formation of a thick and
highly resistive surface layer, which consequently increases the battery's
impedance.
Figure 4 Schematic illustration of OER and resultant gas generation and layered-spinel-rock
salt phase transition. [9]

Dissolution of transition metal ions

Dissolution of transition-metal ions is also a critical problem for Ni-rich layered
oxides, which can be attributed to Li/Ni cationic mixing, O2 evolution, and trace
amounts of H2O in battery systems.[6]On one hand, the Li/Ni cationic mixing and
O2 evolution lead to the formation of low-valence transition-metal ions whose salts
show higher solubility in electrolyte than those with high-valence transition-metal
ions. On the other hand, trace amounts of H2O would promote the hydrolysis of
LiPF6, generating HF to attack the cathode, and thus resulting in the dissolution of
transition-metal ions.[9]The dissolution problem causes the loss of active transition-
metal ions, which means decreasing the capacity and working voltage, and the
migration of transition metal ions to the anode, affecting the ratio of negative to
positive electrodes and increasing impedance of solid electrolyte interphase. [6]

Micro-cracking
Initial capacity loss

Initial capacity loss can be attributed to the loss of available Li-ions and the
development of impedance in both anodes and cathodes. The parasitic
reaction consuming Li+ [13]and sluggishness of Li+ diffusion into the few
vacancies of the Li-layer [14] are resulting in the disability of NMC to return
to the fully lithiated state after the initial cycling.[12]Additionally, it is
suggested that the initial capacity loss is related to C-rate since it is kinetically
influenced. Moreover, Partial losses of the cathodic Li available
Compensation of damages of anodic Li+ to SEIs [12]and Other losses of Li
during the cycle process can be due to Parasitic reactions, including the
immobilization of Li. SEI and expanded polarization, which are becoming
important Lower potential reduction. [12]

CEIs layer
During the highly charged states, cathode materials prefer to produce large amounts
of Ni4+, it will react with electrolytes. The cathode–electrolyte interfaces (CEIs) will
hereby be thickened. The thicken CEIs layer will absorb the available Li+, the
impedance to electrochemical performance will be increased. [15]

Objectives of the project

-Briefly sum-up all the problems that LIBs facing, introducing the
coating method, especially oCVD method, which can improve the
performance of LIBs
Major work outline
-Idea (literal content)
-Preparation (oCVD process)
-Characterization (LIB assembling)
-Data analysis
-Discussion
-Conclusions

Chapter 2: Coating
Surface coating
Overview of Surface coating

The cathode and anode materials will have some side reactions with non-
aqueous electrolytes at the higher temperatures or slowly happen at the
ambient temperature. These reactions can cause the degradation of electrode
materials (stated above). The battery performance can hereby be affected.
Surface coatings are found to improve these situations and suppress the
reactions to extend battery performance. [16]

The surface coating has proven to be effective for improving the capacity
retention, rate capability, and even thermal stability of cathode materials for
lithium-ion batteries. First, it can be the electron-conducting media to
improve the charge transport. Second, it can be the HF scavenger to react with
HF to reduce the acidity of the non-aqueous electrolyte, and hereby the metal
dissolution can be suppressed. Third, it is a physical protection barrier that
suppresses the side reactions caused by the contact between cathode materials
and non-aqueous electrolytes. [16]

Functionality of surface coating

Improving the conductivity
The surface coating can enhance the conductivity of cathode materials. One of the
surface coatings, carbon coating, being coated on cathode materials has been
proven that it can effectively increase the conductivity of the cathode materials.
Firstly, carbon coating can improve the electrons transfer and therefore accelerate
the Li+ transfer process on the cathode surface. [16]Secondly, it provides extra
paths for electrons conducting between the cathode particle and the current
collector.[17]

Figure 5 Schematic illustration of the synthesis process of carbon-coated NCM811. [17]

HF scavenger
HF, which is one of the products produced by the reaction between PF5and H2O. [15]
The corrosion of cathode materials can be caused by it, the electrochemical
performance will be hereby affected. The nano-sized oxide particles play the role of
HF scavenger. The HF scavenger generally is in Lewis based on the coated surface,
it can neutralize the acidity of electrolyte and the HF in electrolyte tends to react with
HF scavenger. The situation caused by the corrosion of cathode materials can
therefore be improved by coating the nano-size oxide particles on the surface of
cathode materials. Hereby, the improvement of the capacity retention for the lithium-
ion cells can be obtained by surface coating.[16]
Taking ZnO and Al2O3, which are the coating materials, as examples:
𝑍𝑛𝑂 + 2𝐻𝐹 → 𝑍𝑛𝐹2 + 𝐻2 𝑂
𝐴𝑙2 𝑂3 + 6𝐻𝐹 → 2𝐴𝑙𝐹2 + 3𝐻2 𝑂
The evidence above shows that the concentration of HF can be reduced by the HF
scavenger.
Physical protection layer
The surface coating can also play a physical barrier role for cathode materials. The
coating materials which are suitable for this purpose include Al2O3, ZrO2, Zr (OH)4,
TiO2, Co3O. These coating materials have the important advantage that is the stable
valence state at the ambient conditions. [16] These coating materials can hereby
provide cathode materials with protection to suppress the undesired reactions caused
by the contact between cathode surfaces containing highly reactive Ni 4+and
electrolyte, such as the migration of transition metal during the Li insertion or
extraction [18], CEI formation[15]and rock-salt phase transition (NiO) [18]. Fig
6 shows the protection from the Al2O3.

However, there are some shortcomings with these materials. It is because these
materials generally are inactive to Li and contain low lithium-ion conductivity, the
excessive coating can result in the block of the Li transportation and low Li-ion
diffusivity, which leads to the loss of rate or power capability. Therefore, the ratios
of coating these materials on the cathode surface must be carefully concerned. [15]

The excessive surface Li can form a conductive protection layer. Some coating
materials, such as AlO2and V2O5, can react with the Residual Lithium Compounds
(RLCs)on the Ni layered oxide, such as LiOH and Li2Co3, to generate Li intercalation
compounds, such as LixAlO2, LixTi2O4, LixAlPO4, LixCoPO4and LixV2O5. (Figure 7)
This is a cost-saving way to improve the situations caused by excessive Li. [15]

Figure 6 Schematic representations of the protection mechanisms of the ALD Al2O3-coated LiNi0.4Co0.2Mn0.4O2 electrode
[18]
Figure 7 Schematic of the composition of V2O5-coated LiNi0.75Co0.11Mn0.14O2 particle [18]

Type of surface coating

To obtain different functionalities, the morphology of the coated materials is a key
role. The surface coating can be generally divided into three main types, such as
rough coating, core-shell coating, and ultra-thin-film coating.
Rough coating
To obtain this morphology after surface coating, it consists of mixing the coating
precursors and cathode materials. (Figure 5) This method usually produces the
coated materials with a rough surface, some areas of the cathode materials are coated
and some areas are not coated. (Figure 8)

Figure 8 Transmission electron microscopic images of (a) bare LiCoO2 and (b) coated LiCoO2 with ZrO2 [16]

Core-shell coating
This type of surface coating provides the cathode materials with full-coverage
protective shell, it is suitable for the cathode particles with the properties of high
electron and Li transport performance, for example, the LiNi0.8Co0.1Ni0.1O2.[16](Figure

Figure 9 Discharge capacity of lithium-ion cells using graphite anode and different cathode. One of the
electrodes is core-shell structured Li[(Ni0.8Co0.1Mn0.1)0.8(Ni0.5Mn0.5)0.2]O2, and the other is
LiNi0.8Co0.1Mn0.1O2 [16]

9)
From the above result, the core-shell structure with the core LiNi0.8Co0.1Mn0.1O2, and
coated materials, Ni0.5Mn0.5, reached higher capacity retention than the bare core
cathode material. This is strong evidence that the shell formed by the surface coating
can increase the electrochemical performance.

There are still some disadvantages of this morphology of surface coating, including
the thickness of the shell and crystal mismatch. The shell formed by it is thick, it
can block the Li and electron transport. Therefore, it is not suitable for stable
oxides and fluorides. The crystal mismatch can cause mechanical stress, the cracks
in the cathode hereby occur. [16]

Ultra-thin film coating

This coating provides coverage with a thin film. This coating morphology can be
obtained by atomic layer deposition (ALD) or chemical vapor deposition (CVD).
[16] The controllable thickness of the coating layer can be produced by the precise
calculation with ALD. The coating layer can be obtained down to 0.1 nm. [16] It can
decrease the mechanical stress caused by crystal mismatch. The thickness of the
coating layer should be controlled carefully, I can increase the impedance for the
electron transport and affect the electrochemical performance.

oCVD Surface coating Technology

Overview of oCVD technology

oCVD (oxidate chemical vapor deposition), which is a coating method that is widely
used in producing high electrically, optical transparency, and mechanical flexibility
conducting polymers on the surfaces of particles. Solvent-free, all-dry environment
and low process temperature are the few features of oCVD. Applications have been
widely used in different areas such as the Lithium-ion battery industry,
electrocatalysis, and heat exchanger, etc. [19]

oCVD mechanism
The OCVD process is designed to mimic oxidative polymerization, which is a
technique that aims to introduce the monomer and oxidant to the reactor and combine
them together to participate in the step-growth polymerization. [19] Then the
procedures of polymerization follow these steps: (1) Oxidant and a monomer will
cause the reactions that form radical cation of the monomeric unit. (2) Pairs of radical
cations will dimerize. (3) By the reaction with the oxidant, the dimers will be
deprotonated and the conjugated species can hereby be produced. (4) Those
deprotonated dimers then oxidize and react with other radical cations to form higher-
order oligomers. By the step-growth of polymerization, the conducting growth can
create longer chains.
Figure 10 Schematic illustration of step-growth polymerization in the oCVD method [20]

The monomers
The volatility of the monomer plays an important role in forming the thin film on the
surface. The monomers obtain high volatility before they dimerize. It can easily be
introduced into a vacuum deposition chamber. After the monomers turn to dimer,
they are expected to have lower volatility and low vapor pressure for the long
polymeric chains. The polymerization reaction hereby occurs on the surface of the
particle rather than in the gas phase. The liquid-like film will therefore be produced
to cover the substrate surface. [19, 20]

The oxidants
The oxidant is one of the key elements to reach step-growth polymerization. The
oxidant vapor was added to the reactor, it can transfer the monomer film into solid
polymer covering film. However, due to the low volatility, introducing the oxidants,
especially solid oxidants, to the oCVD reactor is more challenging than the vapor
delivery of the monomers. Usually, a rinsing step is required to remove the residual
solid oxidants and their oxidation byproducts. Some volatile oxidants can be
introduced as a vapor phase into the reactor, such as VOCl 3, SbCl5, these volatile
oxidants can eliminate the need for rinsing. [20]
Monomers Oxidants

3.4-Ethylenedioxythiophene (EDDOT)
Iron (III) chloride (FeCI3)

Iron (III) tosylate

Pyrrole Iron (III) chloride (FeCI3)

 Aniline Antimony (V) chloride (SbCI5)

Table 1 Commonly used Monomer and oxidants in oCVD application. As illustrated in [21]

Advantages of oCVD
Solvent-free synthesis
The solvent is not required for the OCVD technique. [22] Due to the low solubility
of the conjugated polymers, such as PEDOT, PPy, and PANi, these polymers are
insoluble to the solvents. Other methods are hereby required to add a soluble
macromolecular dopant, such as PPS, to the polymers to obtain the solvable
properties. In contrast, OCVD is all-dry processing, it is not required to use the
solvents. Therefore, the OCVD method not only reduces the cost but also avoids the
dewetting phenomena which can cause pinhole defects. In addition, oCVD will not
have any potential for letting the solvents dissolve, swell, or degrade substrate. [20]

Uniformly coating
Figure 11 Demonstrations of the advantages of oCVD. Conformality of micron-sized
trenches in silicon coated with conductive PEDOT by (a) spin-casting Fe(III)Cl3 and
EDOT monomer, followed by in situ polymerization, (b) oCVD using Fe(III)Cl3 as
the oxidant, and (c) oCVD using the CuCl2 as the oxidant. [23]

Figure 11 Demonstrations of the advantages of oCVD. Conformality of micron-sized trenches in silicon coated with
conductive PEDOT by (a) spin-casting Fe(III)Cl3 and EDOT monomer, followed by in situ polymerization, (b) oCVD using
Fe(III)Cl3 as the oxidant, and (c) oCVD using the CuCl2 as the oxidant. [23]

Mechanical flexible films

The thickness of the conformal coating film can be readily controlled by the reaction
time. [22]According to the working process of OCVD, the monomers will react with
the oxidants in the reactor to obtain the step-growth polymerization to finally
produce the long chain of the conjugated system. When the reaction time is longer,
the long-chain will also become longer. Hereby, people can readily control the
thickness of coating film by the reaction time. [19]
Another works of oCVD on LIBs
Su et al. [20] conducted an experiment and demonstrated the performance of oCVD
on LIBs. Two types of CVD polymerization techniques were utilized for
synthesizing polymers, oCVD, and iCVD (initiated CVD). The oCVD was applied
for growing a conducting PEDOT film and focused.

Figure 12 Schematics and polymerization mechanisms of oCVD.[20]

In the experiment, an oxidant (FeCI3) is sublimated by heating and spontaneously

reacts with the heated monomer vapors that flow into the oCVD reactor.
Polymerization and thin-film growth happen simultaneously on the surface of a
temperature-controlled substrate placed inside the custom-designed oCVD reactor.
Figure 13 Effect of polymer coatings on the rate capability of the LiMn2O4 electrode. (a) Discharge
curves of the coin cells using a pristine LiMn2O4 electrode, (b) PDVB-coated LiMn2O4 electrode,
and (c) PEDOT-coated LiMn2O4 electrode. (d) Statistical data summary of cell capacities with
respect to C-rates at room temperature, (e) at low temperature (0 °C), and (f) at high temperature
(50 °C). The statistical results are calculated from three-coin cells in each case. These results
indicate that the PEDOT coating improves the rate capability in a wide temperature range from 0 to
50 °C, whereas the PDVB coating has little effect. [20]

Figure 13a-c displays the discharge curves of the cells using pristine LiMn2O4(13a),
PDVB-coated(13b), and PEDOT-coated(13c) of the cathode. The overall shape of
the discharge curve is similar; however, it is observed the voltage drop is affected by
a polymer coating. Compared to the pristine cathode, the PEDOT-coated cathode
reduces the voltage drop, especially in high C rates. It is suggested that the PEDOT
coating can decrease the overall resistance of the coin cells and increases the
discharge capacities. Figure 13d-f indicates the cell capacities at different C rates.
All cells were charged at room temperature at C/3, which ensures the same starting
point for discharging. Making polymer coating is the only factor that influences the
discharge capacities. Under different temperature and C rates conditions, the
PEDOT-coated cathode all have better cell capacity performance than the pristine
cathode.

Figure 14 The cell cycling life is extended by the PEDOT coating, whereas it is reduced by the PDVB coating. (a) Specific capacity with
respect to the number of cycles and (b) capacity remaining with respect to the number of cycles. The tests were conducted at 50 °C
using 1 C as the charging and discharge rates. [20]

In figure 14, the cycling life of three types of cathode is shown. It is obviously
observed that the PEDOT coating is able to enhance the battery’s life. The PEDOT
not only increases the initial specific capacity from 105 to 115 mAhg, but it also
slows down the capacity degradation from 0.21 to 0.17 mAhg per cycle on average.
In figure 14b, by definition, the cycling life of a cell is defined as the number of
cycles that it can undergo before its capacity degrades to 80% of its initial capacity.
Therefore, the PEDOT coating can extend cell life from 87 cycles to 122 cycles.

Chapter 3: Experiments
Introduction
-Briefly discussion the objectives of the experiment,
producer, place, and tools of the experiment. Also,
the parameters of the experiment should also be
mentioned in this session, such as the model of the
coin cell, which type of cathode (NI-rich?) and
testing methods.

Preparation
-This session mainly discusses the oCVD process, a
diagram of oCVD should be included to introduce
the whole process of oCVD. The calculation of the
pressure about inserting the monomers are also
included. A compare picture indicating the outlook
of before – after of the flask is included, a picture
 showing the indicator (a paper fragment) is also
mentioned for showing the oCVD is making the
materials conductive. Also, the type of monomer,
initiator should be included.
Characterization
-This session is focus on the assembling the lithium
battery. The raw materials of cathode: cathode
powder, carbon black, blender is introduced. The
ration of solvents and cathode, the mixing process
, how to paint it into current collector, and how to
assembly the coin battery in the vacuum chamber.
At the end, a table should be created to indicate
the parameter, model, material of the coin battery.
The testing method and equipment should also be
introduced in this session.
An example:
Components Detail Weight
Cathode NCM cathode 0.18g
(BASA Ni-rich
Catode)
Carbon Black NA 0.01g
oCVD monomer EDOT N/A
Coin Cell CR25

Result and discussion

Conclusion
References
appendices