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 .................................................................................................................................. 8
Rock-salt phase formation .............................................................................................................. 9
Dissolution of transition metal ions ................................................................................................ 9
Micro-cracking .............................................................................................................................. 10
Initial capacity loss ....................................................................................................................... 10
CEIs layer...................................................................................................................................... 11
Objectives of the project ................................................................................................................... 11
Major work outline ........................................................................................................................... 11
Chapter 2: Coating ................................................................................................................................ 11
Surface coating.................................................................................................................................. 11
Functionality of surface coating........................................................................................................ 12
HF scavenger ................................................................................................................................ 12
Physical protection layer ............................................................................................................... 12
Ultra-thin film coating .................................................................................................................. 15
oCVD Surface coating Technology .................................................................................................. 15
Advantages of oCVD Solvent-free synthesis ................................................................................ 17
Uniformly coating ......................................................................................................................... 17
Mechanical flexible films Another works of oCVD on LIBs ...................................................... 18
Chapter 3: Experiments......................................................................................................................... 20
Introduction ....................................................................................................................................... 20
Preparation ........................................................................................................................................ 20
Characterization ................................................................................................................................ 21
Result and discussion ........................................................................................................................ 21
Conclusion ............................................................................................................................................ 21
References ............................................................................................................................................. 21
appendices ............................................................................................................................................. 21

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 Ni4+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 9)

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]

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 VOCl3, 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

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]
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