ELECTROCHEMICAL KINETICS STUDIES OF COPPER ANODE MATERIALS

IN LITHIUM ION BATTERY ELECTROLYTE

A dissertation presented to

the faculty of

the College of Arts and Sciences of Ohio University

In partial fulfillment

of the requirements for the degree

Doctor of Philosophy

Mingming Xu

June 2005
 This dissertation entitled

ELECTROCHEMICAL KINETICS STUDIES OF COPPER ANODE MATERIALS

IN LITHIUM ION BATTERY ELECTROLYTE

by

MINGMING XU

has been approved for

the Department of Chemistry and Biochemistry

and the College of Arts and Sciences by

Howard D. Dewald

Professor of Chemistry

Leslie A. Flemming

Dean, College of Arts and Sciences

XU, MINGMING. Ph.D. June 2005. Analytical Chemistry.

Electrochemical Kinetics Studies of Copper Anode Materials in Lithium Ion Battery

Electrolyte (108 pp.)

Director of Dissertation: Howard D. Dewald

The kinetic processes at the interface of uncoated copper foil or graphite-

coated copper (Cu-C) foil anodes and lithium ion battery electrolyte were studied in

this dissertation through different electrochemical approaches.

First, as part of an intrinsic stability study of copper foil in Li ion battery

electrolyte solutions, the effect of trace amounts of HF in the electrolyte was studied.

The open circuit voltage (OCV) results of HF doped electrolyte, along with other

OCV results from previous studies, indicate that the adsorption of HF on the graphite

coating protected the Cu foil beneath the coating from corrosion.

Controlled-potential electrolysis of copper foil and graphite-coated copper foil

electrodes in a typical lithium ion battery electrolyte was then performed in order to

construct Tafel plots to obtain values of the exchange current, i0, and charge transfer

coefficient, α. The charge transfer coefficients of both electrodes were found to be

small (α = ~0.25), which was consistent with an assumption of a dominant anodic

process in the cell. At 25 ˚C the graphite-coated copper foil was found to have a higher

exchange current than the copper foil. This can be explained by the intercalation of

lithium ions into the graphite coating which increases the electron transfer rate. In the

range of 0 ˚C to 50 ˚C, the exchange currents of both electrodes increased with

temperature, but at different rates, while the charge transfer coefficients were not

significantly affected by temperature.

Finally, the electrochemical impedance spectroscopy (EIS) of copper foil and

graphite-coated copper foil electrodes was studied. It was found that both electrodes

gave similar impedance spectra of two successive semicircular arcs. Detailed studies

of the effects of different cell parameters including overpotential (η), temperature and

graphite-coating saturation time were then performed. Based on the impedance spectra

results of the electrodes, it appeared that the high frequency response represented a

surface oxide layer. At low frequency further oxidation occurs at both electrodes, but

is kinetically controlled for bare copper, while the graphite-coated copper undergoes

diffusional blocking through the porous carbon layer. An equivalent circuit of the

impedance spectrum was also proposed.

Approved: Howard D. Dewald

Professor of Chemistry
 Acknowledgments

My deepest gratitude goes to my advisor Dr. Howard D. Dewald, not only for

his guidance through the course in preparation of this dissertation, but also for all his

help and care during all these years. His confidence in me always encourages me to do

better. His patience, accessibility and guidance are one of the best memories I have for

the time I spend in Ohio University. I feel so fortunate for choosing him as my advisor

years ago.

I also would like to express my sincere appreciation to my research committee,

Dr. Wenjia Chen, Dr. Tadeusz Malinski, Dr. Bruce McCord and Dr. Frederick Lemke

for their invaluable and professional aid to me.

I am gratitude to Ohio University and Department of Chemistry and

Biochemistry to have given me the opportunity and the financial support to pursue a

doctoral degree. The Condensed Matter and Surface Science Program of Ohio

University also provided me a quarter of scholarship.

I would like to thank all of the members of the Department. My special thanks

shall go to Dr. Frederick Lemke for the use of the dry box. Dr. Mingchuan Zhao,

Qingzhou Cui, Junfeng Huang and Xueguang Jiang are thanked for their friendship

and peer advice.

Ms. Li Wang is specially thanked for all her heart-warming help and support

through the years.

 Finally, I want to thank my parents. Although we are separated by distance, I

can still feel their support every minute of every day. Without that, I would not be able

to earn this degree.

 vii

Table of Contents

Abstract ........................................................................................................................ iii

Acknowledgments ........................................................................................................ v

Table of Contents ....................................................................................................... vii

List of Tables ................................................................................................................ x

List of Figures............................................................................................................... xi

Abbreviations ............................................................................................................. xv

Chapter 1 - Brief Review of Lithium-Ion Batteries and Motivation for

This Work ..................................................................................................................... 1

1.1 General Concepts ............................................................................................. 2

1.2 Review of Lithium Batteries ........................................................................... 6

1.2.1 Lithium Metal Batteries ..................................................................................... 6

1.2.2 Lithium Ion batteries ......................................................................................... 8

1.3 Research Motivation ........................................................................................... 12

Chapter 2 - HF Impurity Studies in Lithium Ion Battery Electrolyte........................... 17

2.1 Introduction ................................................................................................... 17

2.2 Materials and Reagents .................................................................................. 18

2.3 Electrochemical Cell Assembly .................................................................... 19

2.4 Instrumentation .............................................................................................. 21

2.5 Procedure ....................................................................................................... 23

 viii

2.6 Results and Discussion .................................................................................... 23

2.7 Conclusions ..................................................................................................... 29

Chapter 3 - Controlled-potential Electrolysis Studies of Copper Foil and

Graphite-Coated Copper Foil Electrodes in Lithium-ion Battery Electrolyte............. 30

3.1 Introduction . ................................................................................................. . 30

3.2 Experimental Section ..................................................................................... 32

3.3 Results and Discussion .................................................................................. 33

3.4 Conclusions ................................................................................................... 41

Chapter 4 - Impedance Studies of Copper Foil and Graphite-Coated Copper

Foil Electrodes in Lithium-ion Battery Electrolyte .................................................... 42

4.1 Introduction ......................................................................................................... 42

4.2 Experimental Section .......................................................................................... 44

4.3 Results and Discussion ....................................................................................... 45

4.3.1 Impedance at Room Temperature and Open Circuit Voltage ........................... 45

4.3.2 Impedance at Different Overpotentials ............................................................ 52

4.3.3 Impedance of Graphite-coated Copper Foil Electrode with

Different Saturation Time in the Electrolyte............................................................... 66

4.3.4 Impedance at Different Temperatures............................................................... 68

4.3.5 Impedance of Graphite-coated Copper Foil Electrode at

Different Temperatures After Saturation ........................................................ 78

 ix

4.4 Conclusion ..................................................................................................... 84

Chapter 5 - Summary and Future Work ...................................................................... 86

5.1 Summary and Conclusions ............................................................................ 86

5.2 Suggestions for Future Research ................................................................... 88

References .................................................................................................................. 89
 x

List of Tables

Table 1-1. Comparison of performance parameters of different batteries. ............... 5

Table 1-2. Comparison of the performance parameters of lithium, cadmium

and zinc anodes. ....................................................................................... 7

Table 1-3. Ionic conductivity of some organic liquid electrolytes (1M). ................ 13

Table 2-1. Dynamic range of experimental parameters of

CHI-604A Electrochemical analyzer. ................................................... 22

Table 3-1. Linear regression results of Tafel plot of Cu foil and

Cu-C foil electrode in 1M LiPF6 in PC:EC:DMC [1:1:3 vol]................ 38

Table 3-2. Linear regression analysis of Tafel plots, exchange current

and transfer coefficient of Cu foil and Cu-C foil electrode in 1M
LiPF6 in PC:EC:DMC [1:1:3 vol]. ......................................................... 40

Table 4-1. Comparison of peak impedance value of both copper foil

and graphite coated copper foil electrode in the kinetic controlled
process. .................................................................................................. 56

Table 4-2. Comparison of peak impedance value of both copper foil

and graphite coated copper foil electrode at different temperature. ....... 72

Table 4-3. Values of equivalent circuit parameters for both copper foil
and graphite coated copper foil electrodes at different temperatures..... 77

Table 4-4. Comparison of peak impedance value of graphite-coated

copper foil electrode after 48 h of electrolyte saturation
at different temperatures. ....................................................................... 81
 xi

List of Figures

Figure 1-1. Schematic description of the charge-discharge process of a

lithium-ion cell. ....................................................................................... 4

Figure 2-1. The schematic of the homemade cell. Electrolyte solutions

flooded just above the 1×1 cm2 portion of Cu foil when
the cell was assembled in a dry box. ..................................................... 20

Figure 2-2. OCV vs. time of Cu-C foil electrode in 1 M LiPF6/ PC:EC:DMC
(1:1:3 vol.). Reference electrode was made fresh. ................................. 25

Figure 2-3. Comparison of the initial part of the OCV of Al-C and Cu-C
in 1 M LiPF6/ PC:EC:DMC (1:1:3 vol.). ............................................... 26

Figure 2-4. OCV vs. time of Cu-C foil electrode in 1 M LiPF6/ PC:EC:DMC
(1:1:3 vol.) doped with (a) 500 ppm HF and (b) 1000 ppm HF. ........... 28

Figure 3-1. Electrolysis of copper foil electrode in 1M LiPF6/ PC:EC:DMC

[1:1:3 vol.] at 25 ˚C; Initial potential at OCV
= 3.40 V; Overpotential from 50mV to 350 mV. .................................. 35

Figure 3-2. Electrolysis of graphite-coated copper foil electrode in

1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at 25 ˚C;
Initial potential at OCV = 3.39 V; Overpotential from 50mV to
350 mV. ................................................................................................. 36

Figure 3-3. Tafel plots of (a) copper foil electrode; and (b) graphite-
coated copper foil electrode in 1M LiPF6/ PC:EC:DMC
[1:1:3 vol.]. ............................................................................................ 37
 xii

Figure 4-1. Nyquist plot of the impedance spectroscopy of copper foil

electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.]; Initial
potential at OCV = 3.30 V; Frequency range 100 kHz to
0.01 Hz. ................................................................................................. 47

Figure 4-2. Nyquist plot of the impedance spectroscopy of graphite-

coated copper foil electrode in 1M LiPF6/ PC:EC:DMC
[1:1:3 vol.]; Initial potential at OCV = 3.29 V; Frequency
range 100 kHz to 0.01 Hz. ..................................................................... 48

Figure 4-3. Microscopic image of copper foil electrode surface (200×)

a) before experiment and b) 24 h after experiment.
Scale as shown in a). ............................................................................. 50

Figure 4-4. Microscopic image of graphite-coated copper foil electrode

surface (200×) a) before experiment and b) 24 h
after experiment. Scale as shown in a). ................................................. 51

Figure 4-5. Nyquist plot of the impedance spectroscopy of copper foil

electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at different
overpotentials (OCV–100 mV to OCV+100 mV); Frequency
range 100 kHz to 0.01 Hz.. .................................................................... 53

Figure 4-6. Nyquist plot of the impedance spectroscopy of graphite-

coated copper foil electrode in 1M LiPF6/ PC:EC:DMC
[1:1:3 vol.] at different overpotentials (OCV–100 mV to
OCV+100 mV); Frequency range 100 kHz to 0.01 Hz. ........................ 54

Figure 4-7. Three dimensional plot of the impedance spectroscopy of

copper foil electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.]
at different overpotentials (OCV–100 mV to OCV+100 mV);
Frequency range 100 kHz to 0.01 Hz. ................................................... 57

Figure 4-8. Three dimensional plot of the impedance spectroscopy of

graphite-coated copper foil electrode in 1M LiPF6/ PC:EC:DMC
[1:1:3 vol.] at different overpotentials (OCV–100 mV to
OCV+100 mV); Frequency range 100 kHz to 0.01 Hz. ........................ 58
 xiii

Figure 4-9a. Bode representation of impedance spectroscopy of

copper foil electrode; in 1M LiPF6/ PC:EC:DMC
[1:1:3 vol.] log (Impedance) vs. log (Frequency). ................................. 60

Figure 4-9b. Bode representation of impedance spectroscopy of graphite-coated

copper foil electrode; in 1M LiPF6/ PC:EC:DMC
[1:1:3 vol.] log (Impedance) vs. log (Frequency). ................................. 61

Figure 4-10a. Phase angle vs. log (Frequency) of impedance spectroscopy

of copper foil electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.]
at different overpotentials. ..................................................................... 62

Figure 4-10b. Phase angle vs. log (Frequency) of impedance spectroscopy

of graphite-coated copper foil electrode in 1M LiPF6/
PC:EC:DMC [1:1:3 vol.] at different overpotentials. ........................... 63

Figure 4-11. Proposed equivalent circuit of both copper foil and graphite-
coated foil electrode; Rs: uncompensated resistance; C1:
capacitance of surface process; CPE: constant phase element
of kinetics controlled process; Rct1: charge transfer resistance of
surface process; Rct2: charge transfer resistance of kinetics
controlled process; Zwr: reflective Warburg impedance;
Zwt: transmissive Warburg impedance. ................................................. 65

Figure 4-12. Nyquist plot of the impedance spectroscopy of graphite-

coated copper foil electrode after 24 h, 48 h, 60 h of saturation
in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.]; Initial potential at
OCV = 3.36 V; Frequency range 100 kHz to 0.01 Hz. ......................... 67

Figure 4-13. Nyquist plot of the impedance spectroscopy of copper foil

electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at
different temperatures ( from 0 ˚C to 50 ˚C ); Frequency
range 100 kHz to 0.01 Hz...................................................................... 69

Figure 4-14. Nyquist plot of the impedance spectroscopy of graphite-

coated copper foil electrode in 1M LiPF6/ PC:EC:DMC
[1:1:3 vol.] at different temperatures ( from 0 ˚C to 50 ˚C );
Frequency range 100 kHz to 0.01 Hz. ................................................... 70

Figure 4-15a. Bode representation of impedance spectroscopy of copper

foil electrode at different temperature; in 1M LiPF6/ PC:EC:DMC
[1:1:3 vol.] log (Impedance) vs. log (Frequency). ................................. 73
 xiv

Figure 4-15b. Bode representation of impedance spectroscopy of

graphite-coated copper foil electrode at different
temperature; in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.]
log (Impedance) vs. log (Frequency). .................................................... 74

Figure 4-16a. Phase angle vs. log (Frequency) of impedance spectroscopy

of copper foil electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.]
at different temperature. ........................................................................ 75

Figure 4-16b. Phase angle vs. log (Frequency) of impedance spectroscopy

of graphite-coated copper foil electrode in 1M LiPF6/
PC:EC:DMC [1:1:3 vol.] at different temperatures. ............................. 76

Figure 4-17. Nyquist plot of the impedance spectroscopy of graphite-

coated copper foil electrode saturated for 48 h in 1M LiPF6/
PC:EC:DMC [1:1:3 vol.] at different temperatures ( from
0 °C to 50 ˚C ); Frequency range 100 kHz to 0.01 Hz. ......................... 79

Figure 4-18. Bode representation of impedance spectroscopy of graphite-

coated copper foil electrode saturated for 48 h in 1M LiPF6/
PC:EC:DMC [1:1:3 vol.] at different temperature;
log (Impedance) vs. log (Frequency). .................................................... 82

Figure 4-19. Phase angle vs. log (Frequency) of impedance spectroscopy

of graphite-coated copper foil electrode saturated for 48 h in
1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at different temperatures. ........... 83
 xv

Abbreviations

AE ......................................... auxiliary electrode

Al-C ...................................... aluminum foil coated with graphite and binder

Cu-C ..................................... copper foil coated with graphite and binder

CPE ....................................... constant phase element

CT ......................................... charge transfer

CV ......................................... cyclic voltammetry

DEC ...................................... diethyl carbonate

DMC ..................................... dimethyl carbonate

DME ..................................... 1, 2-dimethoxyethane

EC ......................................... ethylene carbonate

EIS ........................................ electrochemical impedance spectroscopy

FT ......................................... Fourier transform

GC ......................................... glassy carbon

MCMB .................................. mesocarbon microbeads

MEC ..................................... methyl ethyl carbonate

NiMH .................................... nickel metal hydride

OCV ...................................... open circuit voltage

PC ......................................... propylene carbonate

ppm ....................................... parts per million (mg L-1)

 xvi

PVDF .................................... polyvinylidene fluoride

RC ......................................... resistance-capacitance

RE ......................................... reference electrode

SEI ........................................ solid electrolyte interface

SPE ....................................... solid polymer electrolyte

WE ........................................ working electrode

 1

Chapter 1 – Brief Review of Lithium-ion Batteries and Motivation for This Work

In the past two decades, with the prevalence of portable consumer electronics,

the demand for rechargeable energy storage sources of high energy density and low

weight has been growing rapidly. Currently, larger applications such as zero emission

electric vehicles and satellites put up even more stringent requirements for energy

storage devices in both energy density and power density. In all of these applications,

high performance batteries are more and more desired. Lithium secondary batteries are

a very promising fulfillment for such demands because of some outstanding

characteristics such as their high energy density, intrinsic discharge voltage, relatively

light weight and less environmental concerns. Since its first introduction into the

market by Sony Energetic, Inc. in 1991, the lithium ion battery has become dominant

in small rechargeable battery applications including cellular phones, notebook

computers, personal digital assistants (PDA), etc.1

Its excellent characteristics certainly make the lithium ion battery a favorable

candidate for large applications such as satellites and electric vehicles. For this

purpose intensive research efforts have been directed at lithium ion cells by many

universities, government agencies, and, battery companies. However, some problems

still have to be solved before complete success of the lithium ion battery is achieved

for these applications. Among the concerns are long-term stability of cell components,

heat control of the cell, higher quality and better cost-performance requirements. The
 2

research work this area has resulted in hundreds of publications and symposia at

national and international conferences, including the semi-annual meetings of The

Electrochemical Society (ECS) and the annual meting of the International Meeting of

Lithium Batteries (IMLB).

In this chapter, some general concepts of lithium ion batteries are introduced,

followed by a brief review of the lithium ion battery. The motivation for the work in

this dissertation is then discussed at the end.

1.1 General Concepts

A battery consists of a group of interconnected electrochemical cells. How

many cells are packaged and how they are connected depends on the specific

application they are designed for. An electrochemical cell composed of a negative

electrode (anode), a positive electrode (cathode) and electrolyte are the elemental

building blocks of a battery.

Lithium ion cells use a solid reductant as the anode and a solid oxidant as the

cathode. A present-day lithium ion cell uses carbon-based material as the active anode

material and a lithiated transition metal oxide as the active cathode material. On

charge, the cathode material releases Li ions to the electrolyte (deintercalation) and

electrons are removed from cathode by an external field and transferred to the anode.

Charge-compensating Li ions are then attracted into the carbonaceous anode material

(intercalation). The chemical reaction at the anode and cathode of a Li ion cell is

reversible. On discharge, the anode supplies intercalated Li ions to the Li ion

 3

electrolyte and electrons to the external circuit, the cathode is an electronically

conducting host into which the Li ions intercalate from the electrolyte and compensate

the charge of the electrons from the external circuit. Since both anode and cathode are

hosts for the reversible intercalation/deintercalation of Li ions from/into the electrolyte,

the electrochemical cell is known as a “rocking-chair” cell. Pending different

requirements for different applications, the common carbon material for the anode is

either graphite or coke type, or a combination of both. Common cathode materials

include LiMn2O4, LiCoO2 and LiNiO2. Electrolyte can be either liquid or solid. Liquid

electrolyte is usually a nonaqueous solution of a lithium salt and various solvents

including different types of esters, ethers and carbonates. A schematic of a typical Li

ion cell is shown in Fig 1-1.2

The reactions at both electrodes and the cell as a whole for a typical Li ion cell

are shown as:3

C h a rg e
Cathode: LiMO2 D is c h a rg e Li1-xMO2 + xLi+ + xe (1-1)

C h a rg e
Anode: C + xLi+ + xe LixC (1-2)
D is c h a rg e

C h a rg e
Overall: LiMO2 + C D is c h a rg e
LixC + Li1-xMO2 (1-3)

LiMO2 represents the lithiated transition metal oxide.

Table 1-1 listed some parameters that have been used to evaluate battery

performance of both lithium and lithium ion batteries, as well as, some traditional

rechargeable batteries including lead/acid, nickel/cadmium and nickel metal hydride

battery systems. 3 The lithium ion battery shows a superior advantage in both energy
 4

Li(1-x)MO2 LixC6

Aluminum Copper
Current Current
Collector Collector

Figure 1-1. Schematic description of the charge-discharge process of a lithium-ion

cell. [Adapted from: D. A. J. Rand, R. Woods, R. M. Dell, in Batteries for Electric
Vehicles, N. E. Bagshaw, Editor, p. 427, Research Studies Press Ltd., Somerset,
England (1998).]
 5

Table 1-1. Comparison of performance parameters of different batteries.

[Adapted from: S. Hossain, in Handbook of Batteries, 2nd ed., D. Linden, Editor,
McGraw-Hill Inc., New York, NY (1995).]

Battery Type
Parameters
Lead Acid Ni/Cd NiMH Lithium Metal Lithium Ion

Wh/kg 30-35 30-40 60-80 150-200 100-125

Energy
Density* 70- 140-
Wh/L 80-90 300-400 260
100 180
Voltage V 2 1.2 1.2 3.6 3.6
Self
%/month 8 10-20 10-20 2-3 9-12
Discharge
Cycle 500- 500-
100-500 100-150 300-800
Life** 1000 1000
*
Energy density (both gravimetric and volumetric) delivered by typical cells.
**
Cycle life - to 80% capacity, 100% depth of discharge.
 6

density and cell voltage compare to its competitors. These excellent characteristics

brought the lithium ion battery its success in the small application market and the

interest in possible large applications.

1.2 Review of Lithium Batteries

1.2.1 Lithium Metal Batteries

Being the lightest and the most electropositive metal, lithium is the first choice

as the negative electrode material for a high power density energy storage system.

Theoretically, lithium has a specific capacity to store 3860 Ah/kg compared to 820

Ah/kg for zinc and 260 Ah/kg for lead.2 A comparison of the performance parameters

of different metal anodes is shown in Table 1-2. The concept of “lithium secondary

batteries” was first presented by Chilton and Cook at The Electrochemical Society fall

meeting in Boston in 1962.4 However, many difficulties, including finding a stable

electrolyte medium and a reversible positive electrode material, had to be overcome

before the concept could be turned into a reality.

The high reactivity of lithium made an aqueous electrolyte impossible.

Therefore, a nonaqueous electrolyte was required for the lithium metal anode. Chilton

and Cook proposed the LiCl-AlCl3 electrolyte dissolved in propylene carbonate.4 As

for the cathode, different halides, such as AgCl, CuCl, CuCl2, CuF2 and NiF2 were

investigated in early prototype cells.5 During the discharge process they form lithium

halide and the corresponding metallic phase. The formation of soluble complexes of
 7

Table 1-2. Comparison of the performance parameters of lithium, cadmium and

zinc anodes. [Reproduced from: D. A. J. Rand, R. Woods, R. M. Dell, in Batteries
for Electric Vehicles, N. E. Bagshaw, Editor, p. 420, Research Studies Press Ltd.,
Somerset, England (1998).]

Parameter Lithium Cadmium Zinc

Capacity density (Ah/ cm3) 2.05 4.13 5.85

Specific capacity (Ah/g) 3.86 0.48 0.82

Standard potential (V) -3.04 -0.40 -0.76

Specific Energy (Wh/g) 11.7 0.19 0.62

 8

the cathode such as CuCl2¯ is a major drawback of this system since it leads to a high

self-discharge rate.

The breakthrough in cathode material came in the early 1970s when the

reversible “topotactical” electrochemical reaction of the insertion compounds such as

chalcogenides was discovered.6 These materials could host lithium ions inside their

crystal structure while simultaneously reducing the transition metal from a higher

oxidation state. One of these compounds TiS2 was used as the cathode material in the

first commercial lithium rechargeable battery manufactured by Exxon in the mid

1980s.

Using lithium metal as the anode created a series of problems for this relatively

new technology. First, lithium corrosion and dendrite formation during cycling caused

a high volume change of the anode and resulted in a poor cycling efficiency (less than

200 cycle life).3, 5 More importantly, the high reactivity of lithium raised many safety

concerns about this type of cell. Lithium alloys with other metals such as aluminum

were studied to replace lithium metal,7 but the problem of large anode volume change

was not solved until the introduction of the concept of lithium ion cells.

1.2.2 Lithium Ion Batteries

Lazzari and Scrosati proposed the “rocking chair concept” in 1980 using two

insertion compounds based on metallic sulfides and oxides as both positive and

negative electrodes.8 By replacing the lithium metal anode with WO2, the safety
 9

problem was solved. However, with only a 1.8 V whole cell voltage, the energy

density of this system was far less than lithium metal cells.

The unexpected discovery of the lithium insertion property of carbon in the

mid 1980s led to the use of carbon as the anode material in the new “Li ion cell”

concept.1 During the charging and discharging process, lithium ion can intercalate into

and deintercalate from carbon without significant change in volume and electrical

properties. Compared to lithium metal, lithiated carbon has a very close potential

(potential difference of lithium metal vs. lithiated carbon is ≤ 0.5V) which gave Li ion

cells a comparable whole cell voltage to the lithium metal cells.3 Extensive research

on a variety of carbonaceous materials also indicated that the carbon morphology

played a critical role in the lithium intercalation process.5 Hard carbon, including

glassy carbon and some carbon fibers, is a highly disordered non-crystalline carbon,

usually prepared from a polymer. It is less sensitive to electrolyte decomposition and

has a higher lithium capacity with a deep first charge.9 Using such a non-crystalline

carbon anode, Sony manufactured the first commercial rechargeable lithium ion

battery in 1990.1 However, high irreversible specific capacity during cycling makes

hard carbon an undesirable anode material. Other carbonaceous materials studied

include crystalline carbon, such as graphite, and less crystalline but highly oriented

“soft carbon”, such as petroleum coke and mesocarbon microbeads (MCMB).1-3

Graphite has a desirable lithium intercalation ratio of 1:6 (LiC6), while for coke the

ratio is 0.5:6 (Li0.5C6). The first attempts to use graphite as the anode material failed

because of severe exfoliation of the graphite resulted from gas releasing in the graphite
 10

structure after lithium intercalation in some electrolyte.10 Soft carbon, despite the

lower specific capacity, has the advantage of being less sensitive to the nature of the

electrolyte used. Dahn et al. studied the dependence of the intercalation process on the

crystal structure of a variety of carbons.11 It seemed that the optimum choice of carbon

for a negative electrode should be a combination of graphite and soft carbon with a

carefully designed electrolyte composition.

Layered TiS2 stood for a long time as the standard positive electrode material

for lithium metal cells as it provided high drain capability and good reversibility.12

However, to build the lithium ion cell with pure carbon as the negative electrode, a

fully lithiated material at the discharge state is required for the positive electrode.

Sony’s first Li ion cell chose LiCoO2, which is now the most prevalent positive

electrode material. Two other materials, LiNiO2, LiMn2O4 and their derivatives, have

also been widely studied.5 LiNiO2 has the same layered structure with LiCoO2 and

excellent specific capacity. However, it is more difficult to synthesis and is

significantly less stable than the other two materials. It is generally not used in any

commercial cells. LiMn2O4 has a three-dimensional spinel structure. Compared to

LiCoO2 and LiNiO2, LiMn2O4 is less expensive because of the natural abundance of

manganese. It also has a slightly higher discharge voltage. The major difficulties in the

applications of LiMn2O4 are fading and losses of storage, expecially with increasing

temperature.13 Despite this, a limited amount of Li ion cells with LiMn2O4 as the

cathode material are now available from Moli Energy Ltd for portable equipments.

The average voltages of LiCoO2, LiNiO2 and LiMn2O4 versus Li/Li+ at low discharge
 11

rate are 3.7 V, 3.5 V and 3.8 V, respectively.3 Numerous research efforts, such as

partial or multiple substitutions with other transition metals, are still ongoing

worldwide in attempts to understand and improve the behavior of these three oxide

families.5

One of the major reasons for the success of the Li ion cell is the solid

electrolyte interface (SEI). It is a stable, protective passivating layer formed on the

surface of the carbon anode during the charging process.14 While the mechanism of

SEI formation is still not fully understood; it is believed to be an insulating lithium ion

permeable layer formed by the electrolyte solution reduction.1-3, 5 This makes the

choice of electrolyte even more important. A suitable electrolyte should have

characteristics such as high ion conductivity (>10-3 S/cm), wide voltage window (0 to

5 V), thermal stability (up to 90 °C), etc. Various lithium salts and organic solvents

have been studied as the components of Li ion cell electrolyte. Such lithium salts

include LiClO4, LiAlCl4, LiBF4, LiAsF6, LiPF6, LiCF3SO3, and LiN(CF3SO2)2.15 Each

salt has its own drawbacks. LiClO4 constitutes an explosive hazard with an organic

solvent; LiBF4 has low ionic conductivity; and LiAsF6 has environmental issues

because the presence of As, etc. LiPF6 is currently the most widely used salt for Li ion

cell electrolyte and is also used in the work performed in this dissertation.

The most commonly used solvent for the electrolyte are nonaquous aprotic

organic compounds including different carbonates, esters and ethers. Currently the

carbonates such as propylene carbonate (PC) and ethylene carbonate (EC) are the most

widely used solvents since they yield double lithium alkyl carbonates with a good
 12

passivating ability. Research also indicates that an electrolyte with a mixture of

carbonate solvents may be the best overall for different electrodes.15 Table 1-3 shows

the ionic conductivity of electrolytes with different lithium salts and solvents used in

Li ion battery systems.

Solid electrolytes for Li ion cells are also under extensive study. These

electrolytes include solid polymer electrolytes (SPE) and inorganic electrolytes. SPE

are produced by incorporating lithium salts into polymer matrices and casting into thin

films. Inorganic electrolytes include crystalline materials, such as lithium halides, and

glassy materials, such as lithium beta-alumina.3 Although bearing a much lower ionic

conductivity compared to liquid electrolytes, solid electrolytes offer the advantages of

a “nonliquid” battery and the flexibility of designing thin batteries with different

configurations.

Ever since its first introduction into the market, the Li ion battery has prevailed

its way to the top rapidly. In 1999 the sales volume of lithium batteries exceeded 50%

of the market total of all rechargeable batteries.5 According to Business

Communication Co.’s report GB-210N, “Lithium Batteries: Materials and Markets”,

the U.S. lithium battery market grew to over $1.7 billion in 2002 and is projected to

grow to over $2.6 billion by 2009.16

1-3 Research Motivation

Thanks to their outstanding characteristics, lithium ion rechargeable batteries

have achieved great commercial success and established dominance in small cell
 13

Table 1-3. Ionic conductivity of some organic liquid electrolytes (1M). (Adapted
from: S. Hossain, in Handbook of Batteries, 2nd ed., D. Linden, Editor, p. 36.1,
McGraw-Hill Inc., New York (1995).
Conductivity at different ˚C (mS/cm)
Solvent
Salt Solvents
vol.% -40 -20 0 20 40 60 80

EC/PC 50/50 0.23 1.36 3.45 6.56 10.34 14.63 19.35

EC/DMC 33/67 - 1.2 5.0 10.0 - 20.0 -

LiPF6
EC/DME 33/67 - 8.0 13.6 18.1 25.2 31.9 -

EC/DEC 33/67 - 2.5 4.4 7.0 9.7 12.9 -

EC/DME 50/50 * 5.27 9.50 14.52 20.64 26.65 32.57

LiAsF6
PC/DME 50/50 * 4.43 8.37 13.15 18.46 23.92 28.18

EC/PC 50/50 0.02 0.55 1.24 2.22 3.45 4.88 6.43

LiCF3SO3 PC/DME 50/50 - 2.61 4.17 5.88 7.46 9.07 10.61

PC/DMC 50/50 - * 5.32 7.41 9.43 11.44 13.20

EC/PC 50/50 0.28 1.21 2.80 5.12 7.69 10.70 13.86

LiN(CF3SO2)2 EC/DME 50/50 - * 7.87 12.08 16.58 21.25 25.97

PC/DME 50/50 - 3.92 7.19 11.23 15.51 19.88 24.30

 14

Table 1-3. Ionic conductivity of some organic liquid electrolytes (1M). (contd.)

EC/PC 50/50 0.19 1.11 2.41 4.25 6.27 8.51 10.79

EC/DMC 33/67 - 1.3 2.5 4.9 6.4 7.8 -

LiBF4
EC/DEC 33/67 - 1.2 2.0 3.2 4.4 5.5 -

EC/DME 33/67 - 6.7 9.9 12.7 15.6 18.5 -

EC/DMC 33/67 - 1.0 5.7 8.4 11.0 13.9 -

LiClO4 EC/DEC 33/67 - 1.8 3.5 5.2 7.3 9.4 -

EC/DME 33/67 - 8.4 12.3 16.5 20.3 23.9 -

*: Electrolyte freezes at such temperature;

EC = ethylene carbonate;
PC = propylene carbonate;
DMC = dimethyl carbonate;
DEC = diethyl carbonate;
DME = 1, 2-dimethoxyethane.
 15

applications, such as batteries for portable electronic devices, since their first

emergence in 1991. Their high energy density and intrinsic discharge voltage also

make them a desirable solution for larger applications, including electronic vehicles

and satellites. Such applications also brought a higher performance standard for

lithium ion batteries. Low cycling efficiency under critical environmental conditions,

electrode decomposition related to possible over-discharge, and long term stability of

electrode and electrolyte materials are some of the difficulties this technology is facing.

As stated earlier, a copper foil current collector as the negative electrode is

used in most commercially available Li ion cells. A coating of carbonaceous material

is fabricated from a slurry of carbon, binder and an appropriate solvent onto the copper

foil by a casting or pressing procedure. The cell is usually assembled in a total

discharged state from unlithiated carbon and fully lithiated positive electrode. During

the first charge lithium ion will intercalate into the carbon and form the SEI

passivation film to protect the air sensitive lithiated electrode. The electrode is

expected to be stable. However, the shelf life (i.e. the time before the first charging of

the cell) of the cell depends on the intrinsic stability of the electrode materials.

The electrochemical behavior of copper in nonaqueous environments and as

the negative electrode current collector in Li ion batteries has not been systematically

studied. Kawakita and Kobayashi observed oxidative dissolution of copper in

LiClO4/propylene carbonate caused by anodic polarization.17 Previous open circuit

voltage (OCV) studies of both copper foil and graphite-coated copper foil electrodes

in this laboratory attributed copper dissolution to impurities in the electrolyte.18, 19

 16

However, the nature of the kinetic processes of both copper and graphite-coated

copper foil has remained unclear.

The research results presented in this dissertation have been aimed at studying

the kinetic processes at the interface of the Cu anode and the Li ion battery electrolyte

through different electrochemical approaches. It will fill some of the void in the

understanding of copper stability in nonaqueous media by providing fundamental

kinetic information of the electrode process. The results from this research work

should also be helpful in practical applications such as the design of batteries and

electrodes.
 17

Chapter 2 – HF Impurity Studies in Lithium Ion Battery Electrolyte

2.1 Introduction

Lithium ion batteries have proven to be a great commercial success since their

first introduction into the market in the early 1990s.1 Excellent characteristics such as

high energy density and more environmentally friendly materials have resulted in Li-

ion battery dominance in portable cell applications. Recent studies have been focused

on larger application of lithium ion batteries, such as satellites and electric

automobiles.2, 5 Long term chemical stability of battery materials and components is

one of the major concerns in these large applications. Among these components, the

electrochemical stability of the anode material has been the focus of this study.

All current commercially-available lithium ion batteries use a carbonaceous

coating applied on a copper foil substrate as the anode. During the charging and

discharging processes lithium ions in liquid electrolyte can intercalate and

deintercalate from this coating with the copper foil as the current collector.

Throughout this work, anode materials have been studied in a simplified homemade

cell. This chapter is focused on the experimental conditions including material used,

cell assembly and instrumentation. Also, some experiments with HF impurity in

lithium ion battery electrolyte were performed to study its effects on OCV.

In order to understand the intrinsic stability of the anode materials in Li-ion

battery electrolytes, this lab has studied previously the electrochemical behavior of Cu
 18

foil electrodes and Cu-C foil electrodes in different nonaqueous organic carbonate Li-

ion battery electrolyte solutions in half-cell reactions.20, 21 Open-circuit voltage (OCV)

studies on Cu foil electrodes (without graphite coating) have also been performed.19

The OCV variation over time of Cu foil electrodes was observed and subsequently

studied in detail. Combined with previous findings of Cu dissolution, it was suggested

that impurities, such as HF, could oxidize copper foils in nonaqueous electrolyte

solutions, which resulted in the OCV variation of Cu foil electrodes over time. The

OCV studies provided some insight into the intrinsic stability of uncoated Cu foil in

the Li-ion electrolyte solutions. In the work reported here, as one of the pertinent cell

factors, the effect of trace amounts of HF in the electrolyte was studied. The OCV

results of HF doped electrolyte, along with other OCV results from previous studies,

are compared with the findings on uncoated Cu foil electrodes and summarized.

2.2 Materials and Reagents

The battery grade copper foil and the graphite coated copper foil were supplied

by Saft and used as received. The copper foil used was 12 μm thick, grade LP1/LP3

(Fukuda Metal Foil and Powder Co.). The electrodeposited copper foil had a purity of

99.9% with the major trace element Cr at ≤ 130 ppm. The graphite coating was a

blend of 50 wt % mesocarbon microbeads (MCMB 10-28) and 50 wt % Timcal SFG-

44 graphite using 4.5% polyvinylidene fluoride (PVDF) as a binder. The carbon

loading per electrode was ~ 26 mg/ cm2 (double side coated). The graphite-coated

copper foil was calendered (roll-pressed) between rollers after solvent evaporation
 19

from the drying process. The calendered graphite-coated copper foils used in these

studies sat as small coupons and likely were subject to a relaxation process whereby

the graphite coating springs back. The extent of relaxation is unknown.

The electrolyte used in this study was 1 M LiPF6 in a ternary mixture of

propylene carbonate (PC)-ethylene carbonate (EC)-dimethyl carbonate (DMC) [1:1:3

vol.]. The electrolyte was obtained from EM Industries/Merck K. G. a. A. and was

prepared from 99.98% purity solvents (<20 ppm H2O as determined by a Karl Fischer

titration) and Stella LiPF6. The electrolyte was guaranteed at <80 ppm HF and was

analyzed at Saft as <50 ppm using an acid base titration. Electrolyte was frozen before

degassing for 30 min and then thawed. This procedure was repeated three times before

the electrolyte was transferred to a dry box and stored.

Lithium metallic foil was also obtained from Saft Research and Development

Center (Cockeysville, MD). It was manufactured by Fukuda Metal Foil and Powder

Co.

Hydrofluoric acid (HF) used as the doping reagent is a 49% HF solution

(A147-1) from Fisher Scientific Inc.

2.3 Electrochemical Cell Assembly

All of the electrochemical studies performed used a homemade three-electrode

cell (Fig. 2-1). The cell body was an end-sealed 25 mm Ace-thred glass connector

(Ace Glass, catalog No. 7644-20). The cell cap was an O-ring sealed threaded Teflon

plug with three electrode ports and a rubber septum port. The working electrodes (WE)
 20

WE (Cu foil connected

to Ni wire)
RE (Ni wire connected
to Li metal)
AE (isolated Pt
Glass Electrode Tube wire coil)

(sealed at opening Rubber Septum

Internally Threaded
Glass Cell

Ni Wire Connected
Li Metal to Cu Foil

1×1 cm2 Cu Foil

Porous Vycor Tip

Stirring Bar

Figure 2-1. The schematic of the homemade cell. Electrolyte solutions flooded just
above the 1×1 cm2 portion of Cu foil when the cell was assembled in a dry box.
 21

were battery-grade copper foil and graphite-coated copper foil that were cut into a

“flag” with a 1 × 1 cm2 working area. The flags were then connected to a 22-gauge

nickel wire by pressing the tip of the nickel wire on to the flag pole. The reference

electrodes (RE) were made by rolling and pressing a 1 × 1 cm2 lithium foil onto the tip

of a nickel wire and assembled in a dry box in electrolyte solution in a glass tube with

a 6 mm diameter porous VycorTM tip (Bioanalytical Systems, BAS, MF-2042). The

auxiliary electrode (AE) was a 0.5 mm diameter, 23 cm long platinum wire coil (BAS,

MW-1033). All working electrodes were rinsed with acetone and air-dried before

assembly of the cell.

2.4 Instrumentation

All the cells were assembled and sealed in a glove box filled with argon. Both

water and oxygen content inside the glove box were less than 1 ppm.

All electrochemical experiments (except the open circuit voltage experiment in

the preliminary work) were performed with a CH Instruments CH-604A

electrochemical analyzer. It is a computerized electrochemical instrument with a fast

digital function generator, a high speed data acquisition circuitry and a potentiostat.

The dynamic range of experimental parameters of the CH-604A electrochemical

analyzer is listed in Table 2-1. 22

The OCV experiments in the preliminary work were performed with a Cypress

Systems CS-2000 computer-controlled electrochemical system potentiostat

/galvanostat. The input impedance of this instrument is ~ 1011 ohms.

 22

Table 2-1. Dynamic range of experimental parameters of CHI-604A

Electrochemical analyzer 20

Parameters Dynamic Range Techniques Involved

Potential (V) -10 to +10 all
Current (A) 0 to ± 0.25 all
Sensitivity (A/V) 1 × 10-12 to 0.1 all
Scan Rate (V/s) 1 × 10-6 to 5000 CV, LSV
Pulse Width (s) 1 × 10-4 to 1000 CA, CC
Frequency (Hz) 1 × 10-4 to 1 × 105 IMP
Measurable Current (A) < 1 × 10-11 CV, CA
Input Impedance (Ω) 1 × 1012 OCV
 23

2.5 Procedure

OCV studies of Cu-C foil electrodes were performed using the homemade

three-electrode cell and the materials as described earlier in this chapter. HF was then

introduced to the assembled cell with a GC syringe. The two concentrations of HF

studied were 500 ppm and 1000 ppm. The time of each OCV experiment was set as 40

h. During assembly of the cell, the WEs were kept above the electrolyte solution. Just

before the OCV measurement, the WEs were immersed into the electrolyte solution,

which ensured that the OCV measurements had the same starting time. Results from

several previously performed experiments were analyzed together: (1) OCV studies of

Cu-C foil electrodes in electrolyte without doping; (2) OCV measurement of a cell

consisting of Al-C foil as the working electrode for comparison to Cu-C.

2.6 Results and Discussion

In previous electrochemical studies of Cu foil electrodes in Li-ion battery

electrolytes, the OCV was shown to be an effective way to study the interfacial change

of the Cu over time. This provided some insight into the intrinsic stability of the

electrodes and the role of impurities in electrolyte solutions. Similar OCV studies were

performed on Cu-C foil electrodes by continuous measurement of the OCV for an

extensive period of time (up to 40 h) when the electrode was immersed into electrolyte

solution.

From the OCV results in Figure 2-2 one can see that the OCV appears to

follow a two step process. In the first step, the OCV decreased quickly until reaching a
 24

minimum. This was followed by increasing gradually until reaching a steady state.

The initial OCV drop was 0.29 V and took about 35 min. The OCV increase from the

minimum to the steady state was about 0.20 V and took about 1200 min.

As compared with the OCV results obtained from Cu foil electrodes6, it can be

seen that the characteristic OCV signals of Cu-C electrodes are quite different from

that of Cu foil electrodes even though the OCV variation of Cu foil electrodes also

showed a two-step process over time. In the first step, the initial OCV drop of Cu-C

foil electrode was about two times larger than that of Cu foil electrode. In the second

step, the OCV of the Cu foil electrodes never achieved a real steady state, but the

OCV of the Cu-C foil electrodes did.

Figure 2-3 shows a close comparison of the OCVs of graphite coated

aluminum (Al-C) and Cu-C. It can be seen that the initial drop in the OCV of the Al-C

foil electrode was more gradual and lagged as compared with that of a Cu-C foil

electrode while the rising portion of the OCV of Cu-C is more gradual than that of Al-

C. Despite the difference, the magnitude of the initial OCV drop and the subsequent

OCV increase of both electrodes are close to each other. In addition, both electrodes

achieved a steady state. These results suggest that the graphite coating is the main

factor causing the characteristic two-step OCV variation over time. The foil substrate

has limited influence.

It is a well accepted concept that the OCV of an electrode is determined by the

double-layer charge formed on the interface between electrode and solution.

Investigations of interfacial structure of both Hg/PC and Hg/EC proved that the
 25

Figure 2-2. OCV vs. time of Cu-C foil electrode in 1 M LiPF6/ PC:EC:DMC (1:1:3
vol.). Reference electrode was made fresh. (Reproduced from Reference 18)
 26

Figure 2-3. Comparison of the initial part of the OCV of Al-C and Cu-C in 1 M
LiPF6/ PC:EC:DMC (1:1:3 vol.). (Reproduced from Reference 18)
 27

capacity of the interface changed as the result of the reorientation of the solvent

molecules (PC or EC).23, 24 It appears that the adsorption of the electrolyte solvents on

the graphite surface resulted in the initial OCV drop of Cu-C and Al-C electrodes due

to the transfer of negative charge from the solvent molecules to the electrodes. The

OCV reached its minimum after a complete, highly oriented layer was formed on the

graphite surface. After the OCV minimum, the increase in the OCV denotes a gradual

discharge of the accumulated charge. It appears that the specific adsorption of an

impurity of HF into the graphite coating from the electrolyte solution resulted in the

positive shift in the OCV.

It is known that clean carbon surfaces are reactive to form surface oxides in the

form of chemisorption from the uncompensated valences.25 On acid-adsorbing carbons,

the accumulated positive charge resulted from the specific adsorption of H+ to the

graphite coating caused the positive shift of OCV. Panzer and Elving describe this

process with equation: 26

(CxO) + H+ + A− → (CxOH)+ + A− (2-1)

Since the rate of the adsorption process is mainly controlled by the diffusion rate of H+

to the graphite coating, the OCV shift is gradually increased until the adsorption

saturation is achieved, which corresponds to the OCV steady state.

To study the influence of impurity on the OCV variation of a Cu-C foil electrode,

measurements were then performed in electrolyte doped with 500 ppm and 1000 ppm

concentrated aqueous HF (49 wt %, Fisher). The results are shown in Fig. 2-4. The

magnitude of the initial OCV drop is smaller (0.19V in the 1000 ppm electrolyte
 28

(a)

(b)

Figure 2-4. OCV vs. time of Cu-C foil electrode in 1 M LiPF6/ PC:EC:DMC (1:1:3
vol.) doped with (a) 500 ppm HF and (b) 1000 ppm HF.
 29

solution) and took longer (over 2 h) to reach the minimum than observed in Fig. 2-2.

The subsequent OCV increase from its minimum to the steady state was also smaller

than observed in the absence of HF. These observations further indicate that the

adsorption of HF on the graphite coating protected the Cu foil beneath the coating

from corrosion.

2.7 Conclusions

The OCV of Cu-C foil was known to undergo a two-step process over time,

which resulted from the interaction between the graphite coating and the electrolyte

solution. In the first step, the OCV dropped quickly until reaching a minimum as a

result of adsorption of electrolyte solvents on the graphite coating. In the second step,

the OCV gradually increased as a result of specific adsorption of HF in the graphite

coating, which protected the Cu substrate from oxidation. HF impurities in the

solution resulted in a smaller and longer OCV drop, as well as a smaller subsequent

OCV incensement. The foil substrate had limited influence on the OCV variation.
 30

Chapter 3 – Controlled-potential Electrolysis Studies of Copper Foil and

Graphite-Coated Copper Foil Electrodes in Lithium-ion Battery Electrolyte

3.1 Introduction

Kinetic and mechanistic studies of copper electrodissolution in neutral and

acidic solutions have been performed for more than half a century 27 and continue to

attract the interest of researchers working in fields related to corrosion,

superconductivity, alloys, biochemistry, batteries, etc.. 28-32 Less systematic effort has

been directed to similar studies of copper in nonaqueous environments 27 and in

particular as negative electrode current collectors in Li ion batteries. 33, 34, 35

Owing to outstanding characteristics such as high energy density, high cell

voltage and few safety concerns over conventional rechargeable cells, Li-ion batteries

have achieved high use since first being introduced to the market in 1991 by Sony. 1

Extensive studies have been dedicated to rechargeable Li-ion batteries operating at

ambient temperature. 2 Today Li-ion batteries are the most promising energy sources

for various portable electronic devices including cell phones and notebook computers.

The total sale value of Li-ion batteries exceeded that of conventional NiCd and NiMH

rechargeable cells in 1999 and continues to expand. 3 In all commercially available Li-

ion cells, copper foil or graphite-coated copper foil is used as the negative electrode

current collector while aluminum foil is used as positive electrode current collector.

The electrolyte is either a nonaqueous liquid electrolyte comprised of a lithium salt

 31

and various carbonate, ether, or ester solvents or a solid polymer electrolyte. Recently,

higher energy density required by both commercial and military applications including

zero emission electric vehicles and satellites has drawn increasing interest in large Li-

ion cells. 1, 3 Long term stability of all cell components is crucial in these applications.

One of the concerns is the electrochemical stability of anode materials.

Kawakita and Kobayashi found that anodic polarization in LiClO4/propylene

carbonate (PC) brought about oxidative dissolution of the copper substrate. 17 Open

circuit voltage (OCV) studies of both copper foil and graphite-coated copper foil

electrodes suggested that impurities such as HF could oxidize copper foil in

nonaqueous electrolyte solutions. 18, 19 The OCV change was attributed to copper

dissolution. However, the nature of the kinetic processes of both copper and graphite-

coated copper foil remains unclear in nonaqueous liquid electrolyte.

Controlled-potential electrolysis is useful as an electrochemical technique for

metal dissolution and deposition. It is also a suitable technique for electrochemical

kinetic studies. A square-wave voltage signal is used as the excitation signal to step

the electrode potential from a value at which no Faradaic current occurs, Ei, to a

potential Es, at which oxidation of the metal proceeds. Current as a function of time is

monitored as the system response. The difference between Es and the equilibrium

potential of the electrode, Eeq is called overpotential. When the overpotential exceeds a

certain limit, where it may be assumed that the rate of one of the electrode reactions

becomes negligible, the relation between overpotential (η) and the net current (inet) is

shown in the Tafel equation:

 32

inet = i0 e-αnfη or ln inet = ln i0 - αnfη (1)

From the ln inet versus η Tafel plot one can calculate the exchange current, i0,

which is the current on both anode and cathode at equilibrium and the charge transfer

coefficient, α, which is the symmetry factor between the potential curves of the two

electrodes.

Electrolysis experiments were performed on both copper foil and graphite-

coated copper foil electrodes at different overpotentials. Tafel plots were then made to

calculate the exchange current and charge transfer coefficient. A similar set of

experiments was undertaken at different temperatures to determine the change in the

exchange current or the charge transfer coefficient.

3.2 Experimental Section

All experiments were performed using a homemade three-electrode cell. The

schematic and the details of the cell were described in Chapter 2. All electrolysis

experiments were performed with a CH Instruments CH-604A electrochemical

analyzer. A J-KEM Scientific Model-150 temperature control unit and an oil bath

were used for 50 ˚C experiment. The same temperature control unit and an ice/water

bath were used for 0 ˚C experiment.

The electrolysis studies were performed in two steps. First, experiments were

performed on both copper foil and graphite-coated copper foil WEs in the electrolyte

solution at 25 ˚C at different overpotentials (η) from 50 mV to 350mV with a 50 mV

interval. All the REs were made fresh in these cells. All the WEs were rinsed with
 33

acetone and then air-dried before the cell assembly. Next the same electrolysis

experiments on the same electrodes were performed at 0 ˚C and at 50 ˚C. In these

experiments the cell body was submerged in the temperature bath for 1.5 h to ensure

that the entire cell reached the desired temperature. All electrolysis experiments were

performed with a single 30 s step width and the current was recorded with a 0.1 s

interval.

3.3 Results and Discussion

Previous studies from this laboratory showed that the open circuit voltage of

both copper foil and graphite-coated copper foil electrodes in a typical Li ion battery

electrolyte was not as stable as expected. 21 To better understand the copper

dissolution and the electrochemical processes at the electrode surface, controlled-

potential electrolysis experiments were preformed on both electrodes.

Before beginning the electrolysis experiments, the open circuit voltage (OCV)

measurement was obtained on the assembled cells. The OCV was set as the initial

potential of the electrolysis experiments. The cell potential was stepped from the

initial value to the desired overpotential (η) for 30 s. The current through the cell was

recorded and plotted versus elapsed time. The 30 s experiment duration was chosen

based on two considerations. First, the length of time should be sufficient enough for

the oxidation processes to take place. Second, at high overpotentials, copper

dissolution is severe, especially for the uncoated copper foil electrode; a longer time at

the highest overpotential sometimes can cause extensive oxidation to the electrode.
 34

Both the copper foil and graphite-coated copper foil electrode were in the same

cell assembly and tested under the same conditions. The results from different

overpotentials for copper foil and graphite-coated copper foil are shown in Fig. 3-1

and Fig. 3-2, respectively. Fig. 3-1 shows the electrolysis of the copper foil electrode

in 1 M LiPF6 in PC:EC:DMC [1:1:3 vol.] electrolyte at an initial potential of 3.40 V

and after each successively increasing 50 mV potential step. Fig. 3-2 shows the

electrolysis of a graphite-coated copper foil electrode in the same electrolyte at an

initial potential of 3.39 V and again after each potential step. Both sets of data show a

logarithmic increase in current in the low overpotential region (η<250 mV), the Tafel

region.

Figure 3-3 shows the Tafel plots of copper foil and the graphite-coated copper

foil electrodes, respectively. In both plots a linear relationship in the low overpotential

range (η<250 mV) was readily observed. Linear regression was performed on the

Tafel plot data to extract the slope and the intercept in order to obtain the exchange

current and the charge transfer coefficient, as shown in Table 3-1. The value of the

exchange current was 0.091 mA for copper foil and 0.11 mA for graphite-coated

copper foil electrodes. For the graphite-coated copper foil electrode, the higher

exchange current can be attributed to the intercalation of lithium ions from the

electrolyte into the graphite layer which facilitated the electron transfer. The values of

the charge transfer coefficient for the copper foil and graphite-coated copper foil were

0.24 and 0.20, respectively (using n equal to 2). The small value (α< 0.25) of the

charge transfer coefficient for both electrodes indicates that anodic current is dominant.
Figure. 3-1. Electrolysis of copper foil electrode in 1M LiPF6/ PC:EC:DMC [1:1:3
vol.] at 25 ˚C; Initial potential at OCV = 3.40 V; Overpotential from 50mV to 350
mV.
Figure. 3-2. Electrolysis of graphite-coated copper foil electrode in 1M LiPF6/
PC:EC:DMC [1:1:3 vol.] at 25 ˚C; Initial potential at OCV = 3.39 V; Overpotential from
50mV to 350 mV.
 37

a)

b)

Figure. 3-3. Tafel plots of (a) copper foil electrode; and (b) graphite-coated copper
foil electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.].
 38

Table 3-1. Linear regression results of Tafel plot of Cu foil and Cu-C foil
electrode in 1M LiPF6 in PC:EC:DMC [1:1:3 vol]
Exchange Charge
Intercept Slope
Electrode Current Density Transfer R2
(log µA) (log µA / V)
(mA/cm2) Coefficient

Cu 4.51 ± 0.16 9.12 × 10-2 18.88 ± 1.19 0.24 0.992

Cu-C 4.72 ± 0.16 1.12 × 10-1 15.72 ± 0.95 0.21 0.989

 39

The difference between the charge transfer coefficients of the two electrodes may be

explained by different copper dissolution rates of each electrode.

Temperature is an important factor both in the theory of and measurement of

electrode oxidation processes. A range of 0 ˚C to 50 ˚C is a common working

temperature for most commercially available lithium ion batteries. Thus the behavior

of both copper foil and graphite-coated copper foil electrodes at 0 ˚C and 50 ˚C was

studied and compared with that of 25 ˚C, as shown in Table 3-2. For the copper foil

electrode the exchange current increased with the increasing temperature. At 0 ˚C, the

exchange current was 0.016 mA. It increased to 0.091 mA at 25 ˚C, while at 50 ˚C, it

increased significantly to 0.18 mA. The exchange current of graphite-coated copper

foil also showed the same increasing values with temperature. However, the

differences in exchange current between temperatures were not as significant as the

bare copper electrode. The exchange current increased from 0.077 mA at 0 ˚C to 0.11

mA at 25 ˚C. When the temperature increased to 50 ˚C the exchange current increased

to 0.14 mA. The α value, on the other hand, does not show a significant effect of

temperature in the operating temperature range of 0 ˚C to 50 ˚C on either of the two

electrodes. Instead, the charge transfer coefficient of both electrodes was ~0.25.

The i0 and α values obtained for copper electrolysis in the nonaqueous

electrolyte compare reasonably well with values reported for dissolution of copper in

aqueous electrolyte. 29 The assessment of the effect of surface layers on anodic mass

transfer cannot be fully elucidated by steady-state electrolytic experiments. Thus

 41

electrochemical impedance spectroscopy (EIS) was used to further elucidate the

effects of oxide layer coverage and the graphite coating on the copper foils. 33 These

results have been described in the next chapter.

3.4 Conclusions

Controlled-potential electrolysis of both copper foil and graphite-coated copper

foil electrodes was used to construct Tafel plots and calculate values of exchange

currents and charge transfer coefficients in a typical lithium ion battery electrolyte. At

25 ˚C the graphite-coated copper foil was found to have a higher exchange current

than copper. This may possibly be explained by the intercalation of lithium ion into

the graphite coating which increases the electron transfer rate. The small value of the

charge transfer coefficient is consistent with the assumption of a dominant anodic

current. Also, experiments at 0 ˚C and 50 ˚C showed that exchange current increases

with temperature for both electrodes, but at different rates. However, the operating

temperatures showed no significant effect on the electron transfer coefficient. The

charge transfer coefficient for both electrodes tended to be stable at ~0.25.

 42

Chapter 4- Impedance Studies of Copper Foil and Graphite-Coated Copper Foil

Electrodes in Lithium-ion Battery Electrolyte

4.1 Introduction

Ambient temperature rechargeable Li-ion batteries have been under extensive

study since first introduced into the market by Sony in 1991. 1 Some outstanding

characteristics including high energy density, higher cell voltage and fewer safety

concerns over conventional rechargeable cells have made Li-ion batteries a great

success. 3 Portable Li-ion batteries are widely used in electronic devices, such as

cellular phones and notebook computers. Total sale value of Li-ion cells exceeded that

of NiMH and NiCd rechargeable cells in the portable cell market in 1999. 5 Copper

foil is used as the negative electrode current collector and aluminum foil is used as the

positive electrode current collector in all commercially available Li-ion cells. The

electrolyte can be either a solid polymer electrolyte or a nonaqueous liquid electrolyte

comprised of a lithium salt and various carbonate, ether, or ester solvents. Recently,

commercial and military applications requiring larger power density and energy

density, such as electrical vehicles and satellites has increased interest in large Li-ion

cells. 3, 5 Long-term stability of cell components is required. The electrochemical

stability of anode materials, copper foil or graphite coated copper foil, is one of the

concerns.
 43

Only a few studies have been reported on the electrochemical behavior of

copper as the negative electrode current collector in Li ion batteries. 34, 35, 36 Recently,

Kawakita and Kobayashi found that anodic polarization in LiClO4/propylene

carbonate brought about oxidative dissolution of the copper substrate. 17

Previously, the electrochemical behavior of copper foil and graphite coated

copper foil electrodes in different nonaqueous Li-ion battery electrolyte solutions in

half-cell reactions has been reported from this laboratory. 21, 22 Further, open circuit

voltage studies of both copper foil and graphite-coated copper foil electrodes

suggested that impurities such as HF could oxidize copper foil in nonaqueous

electrolyte solutions. 18, 19 Thus the OCV changes in this study were concerned with

copper electrodissolution. However, owing to a lack of systematic work on the

electrochemistry of copper in nonaqueous environments, 27 the nature of the surface

and kinetic processes for both the copper and graphite-coated copper electrodes is

uncertain.

Impedance spectroscopy (EIS) is increasingly being applied to electrochemical

studies because of its ability to characterize many of the electrical properties of

materials, as well as, the electrode-electrolyte interfaces. 37, 38 EIS studies of copper in

aqueous media have been reported for over a quarter century. 30, 31, 32, 39, 40 Braithwaite,

et al. used EIS to study Al current collectors in Li ion battery electrolyte, 34 but

previous EIS studies of copper in nonaqueous media have not been reported. In the

work reported here, EIS was performed on both copper foil and graphite-coated

copper foil electrodes in 1 M LiPF6 in a ternary mixture of organic carbonates. The

 44

initial potential of the impedance experiments was chosen near the open circuit

voltage since it is the voltage that the electrode operates under most of the time. An

equivalent circuit is proposed for the electrode process.

4.2 Experimental Section

All experiments were performed using a homemade three-electrode cell. The

schematic and the details of the cell were described in Chapter 2. All impedance

experiments were performed with a CH Instruments CH-604A electrochemical

analyzer. A J-KEM Scientific Model-150 temperature control unit and an oil bath

were used for 50 ˚C experiment. The same temperature control unit and an ice/water

bath were used for 0 ˚C experiment. Microscopic images were taken with an Intelplay

QX3+ computer microscope.

The impedance studies in this work can be classified into a few sets of

experiments. First, impedance studies of (1) copper foil electrode; and (2) graphite-

coated copper foil electrode were performed in the electrolyte solution at open circuit

voltage (OCV). All the REs were made fresh in these cells. All the WEs were rinsed

with acetone and then air-dried before the cell assembly. Microscopic images of the

electrode surface were taken both before and after the experiment. The second set of

impedance experiments were performed on the same electrodes at different

overpotentials (η) (1) 100 mV lower than OCV; (2) 50 mV lower than OCV; (3) OCV;

(4) 50 mV higher than OCV; (5) 100 mV higher than OCV. The impedance

experiments were then performed under different temperatures. 50 ˚C and 0 ˚C were

 45

chosen as the high and low temperature in this study as 0 ˚C to 50 ˚C is usually the

working temperature range for most commercially available lithium ion cells in the

market. The aging effect of the electrolyte to the graphite-coated copper foil electrode

is also studied as a part of this work through another set of experiments. The

experiments were performed after different electrode saturation time of the electrode

in the electrolyte. The frequency range investigated in all the experiments in this study

was from 100 kHz to 0.01 Hz, and the a.c. perturbation amplitude was 5 mV. The

measurement model for frequencies above 100 Hz in the impedance experiments was

the Fourier transform (FT).

4.3 Results and Discussion

4.3.1 Impedance at Room Temperature and Open Circuit Voltage

Impedance spectroscopy is widely used to investigate interfaces in

electrochemical systems. The data presented previously in Chapter 3 showed that the

exchange current of the copper foil electrode (0.091 mA) was smaller than that of the

graphite-coated copper foil electrode (0.11 mA) through controlled-potential

electrolytic experiments. Thus, to further study the copper oxidation processes at the

electrode-electrolyte interface, impedance spectroscopy experiments were performed

on both electrodes.

Open circuit voltage (OCV) experiments of freshly assembled cells were

performed before any other experiments to obtain initial voltages for the impedance

experiments. The impedance experiment was then performed on a cell with the initial
 46

potential set at OCV. Both copper foil electrode and graphite-coated copper foil

electrode were in the same cell assembly and tested under same conditions. Fig. 4-1

shows the Nyquist impedance spectrum of a copper foil electrode in 1 M LiPF6 in

PC:EC:DMC [1:1:3 vol] electrolyte at an initial potential of 3.30 V. Figure 4-2 shows

the Nyquist impedance spectrum of a graphite-coated copper foil electrode in the same

electrolyte at an initial potential of 3.29 V. The offset on both spectra shows the high

frequency range impedance for both electrodes. A similar trend of a small semicircle

in the high frequency range followed by a much bigger semicircle in the low

frequency range can be seen in both spectra. It appeared that at the high frequency

range both electrodes showed a similar behavior while at the low frequency range the

graphite-coated copper foil electrode had larger impedance. The two-semicircle

structure of the impedance spectra indicates a two step electrode process, a surface

process(oxide film coverage) step in the high frequency range at the beginning of the

experiment and a kinetic controlled electrode process step in the low frequency range

later in the experiment. The graphite-coated copper foil electrode showed much higher

impedance. It is believed that the high impedance at the graphite-coated copper foil

electrodes resulted from the surface being blocked to reaction.

It was also observed that after the impedance experiments, the copper foil

electrode showed a certain degree of oxidation on the edges of the electrode. The

graphite-coated copper foil, on the other hand, showed no signs of oxidation that could

be observed by unaided eyes, but on the electrode surface there were visible spots of

the graphite layer peeled off from the copper foil inside. Fig. 4-3 shows the
 47

Figure 4-1. Nyquist plot of the impedance spectroscopy of copper foil electrode in 1M
LiPF6/ PC:EC:DMC [1:1:3 vol.]; Initial potential at OCV = 3.30 V; Frequency range
100 kHz to 0.01 Hz.
 48

Figure 4-2. Nyquist plot of the impedance spectroscopy of graphite-coated copper foil
electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.]; Initial potential at OCV = 3.29 V;
Frequency range 100 kHz to 0.01 Hz.
 49

microscopic images of the copper electrode surfaces before cell assembly (a) and 24 h

after (b) the impedance experiments.The same images of the graphite-coated copper

foil electrode are shown in Fig. 4-4 (a) and (b), respectively. The electrodes were

pulled out of the electrolyte solution but still kept inside the sealed cell body for 24 h

after the experiment to allow the carbonate solvent to dry before the microscopic

images were taken. Fig. 4-3a and Fig. 4-4a show the rough surfaces of copper and

graphite in the two electrodes, respectively. A bottom light source was used with the

image in Fig. 4-3b. It can clearly be seen that there is significant copper dissolution at

the edge of the copper foil electrode. Fig. 4-4b shows a spot where the graphite peeled

from the graphite-coated copper foil electrode. A salt crystal can be seen protruding

from inside the graphite layer. The crystal is thought to be a lithium salt. The different

extent of oxidation for the two electrodes further illustrated the blocking effect of the

graphite layer.

The copper dissolution observed here is consistent with previous study in this

lab which suggested that the trace amount of HF presented in the electrolyte solution

can cause oxidation of the unprotected copper foil. 18 It is well known that clean

carbon surface are reactive to form surface oxides in the form of chemisorption from

unsatisfied valences. 25 Panzer and Elving described the acid adsorption of carbon

material to the interaction between the acid in the solution and the surface oxide by the

following equation: 26

H+ + A- + CxO → (CxOH)+ + A- (4-1)

 50

a)

0.1 mm

b)

Figure 4-3. Microscopic image of copper foil electrode surface (200×) a) before
experiment and b) 24 h after experiment. Scale as shown in a).
 51

a)

b)

0.1 mm

Figure 4-4. Microscopic image of graphite-coated copper foil electrode surface (200×)
a) before experiment and b) 24 h after experiment. Scale as shown in a).
 52

Thus, the observed difference of copper oxidation between copper foil and graphite-

coated copper foil electrode can be attributed to the specific adsorption of HF on the

graphite coating in the latter that gives protection to the copper foil substrate from

oxidation. The peeled graphite spots are considered exfoliation caused by gas

releasing following the intercalation of lithium ion into the graphite coating.

4.3.2 Impedance at Different Overpotentials

During the charging and discharging processes, a rechargeable cell is

constantly under potentials either lower or higher than its open circuit voltage. To

better understand the electrode behavior under these circumstances, a series of

experiments were performed under different overpotentials (η) for both copper foil

and graphite-coated copper foil electrodes in the same electrolyte solution. To avoid

possible overcharge and over-discharge, overpotential values in this set of experiment

were set from 100 mV higher than OCV to 100 mV lower than OCV with a 50 mV

interval between each tested value.

Fig. 4-5 and Fig. 4-6 show the Nyquist impedance spectra of copper foil and

graphite-coated copper foil electrode at different overpotentials, respectively. The

offset on both spectra also reflected the impedance at the high frequency part (> 1 kHz)

of the experiments. It can be seen that the impedance of both electrodes shows the

same two step electrode process at all the tested η values. The surface process (oxide

film coverage) step remains the same for both electrodes at different overpotentials. In

the kinetic controlled process step, the impedance decreases with increasing
 53

Figure 4-5. Nyquist plot of the impedance spectroscopy of copper foil electrode in 1M
LiPF6/ PC:EC:DMC [1:1:3 vol.] at different overpotentials (OCV–100 mV to
OCV+100 mV); Frequency range 100 kHz to 0.01 Hz.
 54

Figure 4-6. Nyquist plot of the impedance spectroscopy of graphite-coated copper foil
electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at different overpotentials (OCV–
100 mV to OCV+100 mV); Frequency range 100 kHz to 0.01 Hz.
 55

overpotential which is seen as smaller semicircles on the spectra. For copper electrode,

the maximum imaginary impedance for this process decreased from around 6000 Ω at

OCV – 100 mV to about 1200 Ω at OCV, and then to only about 100 Ω at OCV + 100

mV. As for the graphite-coated copper foil electrode, the decrease of the same value is

from about 8000 Ω at OCV – 100 mV to about 4000 Ω at OCV, and then to about 600

Ω at OCV + 100 mV. The relative real impedance values for this process are also

decreasing respectively with different overpotentials. The detailed maximum

impedance values for both processes are listed in Table 4-1. An obvious reason for the

decrease of the impedance with increasing overpotential in the kinetic controlled

process is that a higher voltage makes the electrons transfer faster in the cell system,

thus lowering the impedance of the system. The low frequency looks like depressed

semicircle which is related to a finite diffusion length.

In Figure 4-7 and Figure 4-8 the three dimensional impedance spectra were

constructed for copper foil and graphite-coated copper foil electrodes. Only the kinetic

controlled process can be observed due to the large scale of the figure. It can clearly be

seen that compared to the spectra of graphite-coated copper foil electrode, the

impedance of copper foil electrode showed a more drastic change in impedance with

the decrease of the overpotential. This observation is consistent with the discussion

earlier in this chapter that the graphite coating protected the copper foil from oxidation

during the electrode process. Higher overpotentials produced a higher oxidation

current and a more severe dissolution of the copper foil. Both of the two factors

lowered the
 56

Table 4-1. Comparison of peak impedance value of both copper foil and
graphite coated copper foil electrode in the kinetic controlled process.

Electrode Overpotential (mV) R’ (Ω) -R” (Ω)

OCV -100 7894 6128

OCV-50 6148 3685

Cu OCV 1828 1192

OCV + 50 825 454

OCV + 100 145 97

OCV -100 4623 7509

OCV-50 4301 6875

Cu-C OCV 3802 3975

OCV + 50 1441 1085

OCV + 100 908 572

R’: Real impedance

R”: Imaginary impedance
Figure 4-7. Three dimensional plot of the impedance spectroscopy of copper foil electrode in
1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at different overpotentials (OCV–100 mV to OCV+100
mV); Frequency range 100 kHz to 0.01 Hz.
Figure 4-8. Three dimensional plot of the impedance spectroscopy of graphite-coated copper
foil electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at different overpotentials (OCV–100 mV
to OCV+100 mV); Frequency range 100 kHz to 0.01 Hz.
 59

impedance of the system even further that the protected graphite-coated copper foil

electrode.

To better understand the impedance, Bode representations of the impedance

spectra shown in Figure 4-5 and 4-6 are plotted in Figure 4-9 and 4-10. Figure 4-9 (a)

and (b) show the relationship between the logarithmic values of the impedance and the

logarithmic value of the frequency for the copper foil and graphite-coated copper foil

electrodes, respectively. For both electrodes the impedance increased with decreasing

frequency. The small increasing slope in the high frequency range represents the

surface process and the large increasing slope in the low frequency range represents

the kinetic controlled process. All the increasing curves tend to level off at the end of

second step which clearly indicated the kinetic controlled process transformed into a

diffusion controlled process when the frequency was low enough. The kinetic

controlled process started at ca. 10 kHz for copper foil and ca. 100 Hz for graphite-

coated copper foil. Figure 4-10 shows the relationship between phase angle (φ) and log

[frequency] of (a) copper foil and (b) graphite-coated copper foil. The maximum phase

angle of copper foil ~ 72° appeared around 100 Hz and decreased with increasing η

values in the investigated range. For graphite-coated copper foil, the maximum phase

angle ~ 82° appeared around 1 Hz with the same decreasing tendency with increasing

overpotential.

Based on the experimental results, an equivalent circuit for both electrodes is

proposed in Figure 4-11. Rs is the uncompensated resistance including the resistance

of electrolyte and the Ni wires. The value of the Rs is about 2 Ω for both electrodes.
Figure 4-9 (a) Bode representation of impedance spectroscopy of copper foil electrode; in 1M
LiPF6/ PC:EC:DMC [1:1:3 vol.] log (Impedance) vs. log (Frequency).
Figure 4-9 (b) Bode representation of impedance spectroscopy of graphite-coated copper foil
electrode; in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] log (Impedance) vs. log (Frequency).
Figure 4-10 (a) Phase angle vs. log (Frequency) of impedance spectroscopy of copper foil
electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at different overpotentials.
Figure 4-10 (b) Phase angle vs. log (Frequency) of impedance spectroscopy of graphite-coated
copper foil electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at different overpotentials.
 64

The first resistance-capacitance (RC) circuit represents the small semicircle in the

Nyquist plot of the impedance spectra at the high frequency range. For both electrodes,

it represents an oxide film formation on the copper foil surface. The resistance for both

electrodes during this process is about 10 Ω. The second RC circuit represents the

large half circle in the Nyquist plot of the impedance spectra in the low frequency

range. The capacitance has been replaced with a CPE (constant phase element) to

represent the depressed semicircle. For the copper foil electrode, it represents a kinetic

controlled process during which charge transfer and further oxidation of the copper

occurs. The charge transfer resistance (RCT) values in this process for copper electrode

extracted from impedance spectra are about 4 kΩ at OCV, 1.6 kΩ at 50 mV above

OCV and 250 Ω at 100 mV above OCV. For potentials lower than OCV one can only

tell from the spectra that the RCT values are well over 10 kΩ. For the graphite-coated

copper foil electrode, this oxidation process is more complex related to a finite

diffusion length with a transmissive boundary condition through the porous carbon

layer which resulted in a higher impedance as compared to the copper foil electrode.

Oxidation of impurities is another contributing factor. 18, 19 RCT values extracted from

impedance spectra in this process are about 8 kΩ at OCV, 2000 Ω at 50 mV above

OCV and 1 kΩ at 100 mV. Similarly, for potentials lower than OCV the RCT values

are hard to extract and can only be reported as over 10 kΩ as well. ZWr and ZWt

represent reflective and transmissive Warburg impedances, respectively, which

dominate the extreme low frequency range.

 65

C1 CPE
Zwr
Rs

Rct1 Rct2 Zwt

Figure 4-11. Proposed equivalent circuit of both copper foil and graphite-coated foil
electrode; Rs: uncompensated resistance; C1: capacitance of the surface oxidation
process; CPE: constant phase element of kinetics controlled process; R ct1: charge
transfer resistance of surface oxidation process; Rct2: charge transfer resistance of
kinetic controlled process; Zwr: reflective Warburg impedance; Zwt: transmissive
Warburg impedance.
 66

4.3.3 Impedance of Graphite-coated Copper Foil with Different Saturation Time in

the Electrolyte

From discussion in 4.3.2 it is known that the graphite coating protected the

copper foil from oxidation. Since the graphite coating on the electrode is porous,

another set of impedance experiments was performed on the graphite coated electrode.

After the cell was assembled, the electrode was immersed in the electrolyte for a

certain period of time to allow for saturation before the measurement at open circuit

voltage. The Nyquist impedance spectra after 24, 48 and 60 h of saturation time are

shown in Figure 4-12. The impedance spectra at longer saturation times remain almost

identical after 60 h. It was found that the high frequency response remained the same

after saturation. On the other hand, the low frequency impedance decreased

significantly as compared to that without saturation. A reasonable explanation would

be that the electrolyte replaced the inert Ar gas in the porous graphite coating, thus

facilitating the electron transfer during the kinetic controlled process. A bare copper

electrode does not show a change in impedance spectra with different immersion times.
Figure 4-12 Nyquist plot of the impedance spectroscopy of graphite coated copper foil
electrode after 24 h, 48 h, 60 h of saturation in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.]; Initial
potential at OCV = 3.36 V; Frequency range 100 kHz to 0.01 Hz.
 68

4.3.4 Impedance at Different Temperatures

Temperature is a critical factor in lithium ion battery applications. With the

controlled-potential electrolysis study earlier in Chapter 3 it was found that

temperature plays an important role in the electrode oxidation process. As the range of

0 ˚C to 50 ˚C is a common working temperature for most commercially available

lithium ion batteries, the impedance spectra of both copper foil and graphite copper

foil electrodes were also studied at 0 ˚C and 50 ˚C and compared with that of the 25 ˚C.

Before each experiment the cell body was submerged in the temperature bath for 1.5 h

to ensure that the entire cell reached the desired temperature.

Nyquist impedance spectra of copper foil and graphite-coated copper foil

electrode at different temperatures were shown in Figure 4-13 and Figure 4-14,

respectively. The impedance of the high frequency part was also shown in the offset in

each figure. The two depressed semicircle structure of the impedance spectra can still

be clearly observed for both electrodes. The overall impedance for both electrodes

seems to be decreasing with the increasing temperature. This is consistent with our

observations in Chapter 3 that the exchange current increases with the increasing

temperature. In the kinetic controlled step, the maximum imaginary impedance

decreased from around 13 kΩ at 0 ˚C to about 1200 Ω at 25 ˚C then to only about 200

Ω at 50 ˚C for copper foil electrode. The same value for graphite-coated copper foil

electrode also decreased from nearly 12k Ω at 0 ˚C to about 4 kΩ at 25 ˚C and then to

a mere 6 Ω at 50 ˚C. It is also noticed that the high frequency semicircle also

decreased with the increasing temperature. Since the high frequency semicircle
Figure 4-13. Nyquist plot of the impedance spectroscopy of copper foil electrode in 1M LiPF6/
PC:EC:DMC [1:1:3 vol.] at different temperatures ( from 0 ˚C to 50 ˚C ); Frequency range
100 kHz to 0.01 Hz.
Figure 4-14. Nyquist plot of the impedance spectroscopy of graphite-coated copper foil
electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at different temperatures ( from 0 ˚C to 50
˚C ); Frequency range 100 kHz to 0.01 Hz.
 71

represents the surface process, an explanation for the decrease is that with the

increasing temperature, the surface oxidation of the copper is accelerated and

increases the electron flow in the circuit, thus lower the impedance of the process. The

detailed value of the impedance spectra is listed in Table 4-2.

Bode representations of the impedance spectra shown in Figure 4-13 and 4-14

are also plotted in Figure 4-15 and 4-16. Figure 4-15 shows the relationship between

the logarithmic values of the impedance and the logarithmic value of the frequency. It

can be clearly seen that for both electrodes the surface process occurs between ca. 100

kHz and ca. 10 kHz. The kinetic controlled process occurs between ca. 1 kHz and ca.

0.1 Hz for copper foil electrode. While for graphite coated copper foil electrode the

same process occurs between ca. 10 Hz and ca. 0.01 Hz. The increasing curves tend to

level off at extreme low frequency for both electrodes at all temperatures which

demonstrates the diffusive feature of the electrode process when frequency is low

enough. Figure 4-16 (a) and (b) show the relationship between phase angle (φ) and log

[frequency] of the impedance spectra for copper and graphite coated copper foil

electrodes, respectively. For both electrodes the maximum phase angle appeared at 0

˚C and decreased with increasing temperature. The maximum phase angle was 70° at

10 Hz for copper and 80° at 0.1 Hz for graphite-coated copper foil electrode.

Based on the experimental results and the equivalent circuit proposed earlier in

this chapter, some parameters of the equivalent circuit are calculated and listed in

Table 4-3. From the results it can be seen, the surface oxidation processes are almost

identical for copper foil and graphite-coated copper foil at 25 ˚C. Charge transfer
 72

Table 4-2. Comparison of peak impedance value of both copper foil and
graphite coated copper foil electrode at different temperature.

High Frequency Low Frequency

Electrode Temperature (˚C)
Z’ (Ω) -Z” (Ω) Z’ (Ω) -Z” (Ω)

0 18.8 16.1 16210 13260

Cu 25 10.9 4.8 1828 1192

50 8.4 5.5 468 237

0 17.2 12.4 6003 12410

Cu-C 25 6.0 4.1 3802 3975

50 4.9 3.7 51.8 18.5

Figure 4-15 (a) Bode representation of impedance spectroscopy of copper foil electrode at
different temperatures; in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] log (Impedance) vs. log
(Frequency)
Figure 4-15 (b) Bode representation of impedance spectroscopy of graphite-coated copper foil
electrode at different temperatures; in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] log (Impedance) vs. log
(Frequency).
Figure 4-16 (a) Phase angle vs. log (Frequency) of impedance spectroscopy of copper foil
electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at different temperatures.
Figure 4-16 (b) Phase angle vs. log (Frequency) of impedance spectroscopy of graphite-coated
copper foil electrode in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at different temperatures.
 77

Table 4-3. Values of equivalent circuit parameters for copper foil and graphite
coated copper foil electrodes at different temperatures.

Parameters
Electrode Temperature (°C)
Rs (Ω) C1 (μF) R ct1 (Ω)

0 2.7 0.13 32.2

Cu 25 1.9 0.26 9.4

50 2.5 0.82 10.8

0 4.8 0.17 24.8

Cu-C 25 2.2 0.23 8.2

50 0.2 0.46 7.4

 78

resistance decreased with increasing temperature while the respective capacitance

increased, for both copper foil and graphite-coated copper foil electrode. This

corresponds with the explanation of the temperature effect in the surface oxidation

process.

4.3.5 Impedance of Graphite-coated Copper Foil Electrode at Different

Temperatures After Saturation

In 4.3.3 it was found that the impedance of the graphite-coated copper foil

electrode decreased significantly after saturation in the electrolyte for a certain time. It

was also found in 4.3.4 that temperature played an important role in the impedance

study of the electrode. In this part of the work, the impedance behavior of pre-

saturated graphite-coated copper foil electrodes was studied under different

temperatures. After the cell assembly, the electrode was pretreated through immersion

into the electrolyte for 48 h at the desired temperatures (0 ˚C and 50 ˚C) in the

temperature bath. OCV experiments were carried out before all impedance

measurements to obtain the initial potential for each experiment. The results were then

compared with the 25 ˚C result.

Figure 4-17 shows the Nyquist impedance spectra of graphite-coated copper

foil electrode after electrolyte saturation at different temperatures. The high frequency

portion of the spectra was shown in the offset for better observation. The two

depressed semicircle structure remained the same in this set of experiments as was

expected. However, the overall impedance decreased significantly with the increasing
 600
0C
25 C
500 50 C

400
-Z" [ohm]

35
30
300
25

-Z" [ohm]
20
15
200
10
5

100 0
0 10 20 30 40 50 60
Z' [ohm]
0
0 200 400 600 800 1000 1200
Z' [ohm]

Figure 4-17. Nyquist plot of the impedance spectroscopy of graphite-coated copper foil electrode
saturated for 48 h in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at different temperatures ( from 0 °C to 50
˚C ); Frequency range 100 kHz to 0.01 Hz.
 80

temperature in both the high frequency and low frequency portion of the experiment.

In the surface process (oxide film coverage), the maximum imaginary decreased from

about 11.6 Ω at 0 ˚C to nearly 6.3 Ω at 25 ˚C and then 3.7 Ω at 50 ˚C. The increased

temperature and the replacement of the inert Ar gas to conductive electrolyte greatly

increased the speed of the oxide film formation at the copper surface under the

graphite coating. In the kinetic controlled step, the maximum imaginary impedance

was about 400 Ω at 0 ˚C. It dropped to only about 31 Ω at 25 ˚C and then 5.5 Ω at 50

˚C. Detailed impedance values are listed in Table 4-4.

Figure 4-18 and 4-19 are the Bode representations of the impedance spectra

shown in Figure 4-17. Figure 4-18 shows the relationship between the logarithmic

values of the impedance and the logarithmic value of the frequency. Despite the

obvious decreasing of the impedance value from low temperature to high temperature,

the surface process remains to occur between ca. 100 kHz and ca. 10 kHz. The kinetic

controlled process occurs between ca. 10 Hz and ca. 0.1 Hz. It seems that the higher

the temperature is, the slower the impedance increases with frequency. It is safe to say

that with the increasing temperature this whole electrode process becomes more and

more diffusion-controlled. Figure 4-19 shows the relationship between phase angle (φ)

and log [frequency]. In the kinetic controlled process, the maximum phase angle of

60° appeared at 1 Hz for 0 ˚C. At 25 ˚C the maximum phase angle dropped to 33°

which appear between 1 Hz and 10 Hz. When the temperature increased to 50 ˚C, the

maximum phase angle decreased to only 15° at higher than 10 Hz. The low frequency

semicircle was more depressed because the increased finite length diffusion with
 81

Table 4-4. Comparison of peak impedance value of graphite coated copper foil
electrode after 48 h of electrolyte saturation at different temperature

High Frequency Low Frequency

Electrode Temperature (˚C)
Z’ (Ω) -Z” (Ω) Z’ (Ω) -Z” (Ω)

0 13.2 11.6 700 400

Cu-C 25 9.6 6.3 60.1 31.0

50 5.6 3.7 21.1 5.5

 4

0C
3
25 C
log(Z/[ohm])

50 C

0
-3 -2 -1 0 1 2 3 4 5 6
log(frequency/[Hz])

Figure 4-18 Bode representation of impedance spectroscopy of graphite-coated copper

foil electrode saturated for 48 h in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at different
temperatures; log (Impedance) vs. log (Frequency).
 90

80
0 C
70 25 C
50 C
60
-Phase [deg]

50

40

30

20

10

0
-3 -2 -1 0 1 2 3 4 5 6
log(frequency/[Hz])

Figure 4-19 Phase angle vs. log (Frequency) of impedance spectroscopy of graphite-
coated copper foil electrode saturated for 48 h in 1M LiPF6/ PC:EC:DMC [1:1:3 vol.] at
different temperatures.
 84

transmissive boundary condition through the porous carbon layer with the increasing

temperature. In the surface process, although the impedance also decreased with

increasing temperature, the phase angle change remained almost the same.

4.4 Conclusion

The impedance spectra of both copper foil and graphite-coated copper foil

electrodes in a nonaqueous Li-ion battery electrolyte were shown to undergo a two-

step process. The first step for both electrodes is a surface oxidation process at the

interface of the electrode and the electrolyte at the beginning of the experiment in the

high frequency range. For the copper foil electrode the second step is a kinetic

controlled charge transfer and double layer process during which further copper

oxidation occurs. At the graphite-coated copper foil electrode the graphite coating

blocks the electrode surface area creating diffusional obstruction, which resulted in the

higher impedance value for the graphite-coated copper foil electrode in the kinetic

controlled process. The different impedances observed reflected the different

processes that occurred on the two electrodes in the low frequency range. Higher

electron transfer rate caused by increasing overpotential will decrease the impedance

of both electrode processes. The impedance of both electrodes decreased with

increasing temperature. This can be explained by the accelerated surface oxidation of

copper and increasing electron flow in the circuit. An equivalent circuit of the

electrode process for the two electrodes is proposed and some parameters are

calculated. Because of the porous nature of the graphite coating, the impedance of the
 85

graphite-coated copper foil electrode will be significantly reduced by electrolyte

saturation of the coating as the inert Ar gas is replaced by the conductive lithium ion

battery electrolyte.
 86

Chapter 5 –Summary and Future Work

5.1 Summary and Conclusions

Studies of the fundamental electrochemical behavior and stability of the anode

materials (battery-grade graphite-coated copper foil) of Lithium-ion batteries in Li-ion

battery electrolytes (nonaqueous organic carbonates) were performed in this

dissertation.

In Chapter 1, a brief review of the technical aspects of Li-ion cells was given

followed by a statement of the motivation of this research.

In Chapter 2, the experimental conditions of this study were introduced. Some

preliminary work for this study as part of the previous research in this laboratory was

also included in this chapter. The effect of trace amounts of HF in the electrolyte was

studied as one of the pertinent cell factors. It was found the OCV of Cu-C foil

electrode was shown to undergo a two-step process over time, which resulted from the

interaction between the graphite coating and the electrolyte solution. In the first step,

the OCV dropped quickly until reaching a minimum as a result of adsorption of

electrolyte solvents on the graphite coating. In the second step, the OCV gradually

increased as a result of specific adsorption of HF in the graphite coating, which

protected the Cu substrate from oxidation. The foil substrate was shown to have

limited influence on the OCV variation.

 87

To better understand the nature of the kinetic processes of battery grade

copper and graphite-coated copper foil electrodes, controlled-potential electrolysis of

both electrodes was performed in order to construct Tafel plots to obtain values of the

exchange current and transfer coefficient in Chapter 3. The transfer coefficients of

both electrodes were found to be a small value, which was consistent with an

assumption of a dominant anodic process in the cell. At 25 ˚C the graphite-coated

copper foil was found to have a higher exchange current value than the copper foil.

This can be explained by the intercalation of lithium ion into the graphite coating

which increases the electron transfer rate. In the temperature range of 0 ˚C to 50 ˚C,

the exchange currents of both electrodes increased with the temperature, but at

different rates, while the transfer coefficients were not significantly affected by the

temperature.

Impedance spectroscopy is increasingly being applied to electrochemical

studies because of its ability to characterize many of the electrical properties of

materials and the electrode-electrolyte interfaces. In Chapter 4 the electrochemical

impedance spectroscopy of both copper foil and graphite-coated copper foil electrodes

was obtained under different conditions. Detailed studies showed that both electrodes

gave similar impedance spectra of two successive semicircular arcs. When

overpotential was increased for both electrodes, the high frequency semicircles

remained the same on each electrode, but the second semicircle increased for both

electrodes. It was also found that the impedance of both electrodes decreased with

increasing temperature which can be explained by the accelerated surface oxidation of

 88

copper and increasing electron flow in the circuit. Because of the porous nature of the

graphite coating, the impedance of the graphite-coated copper foil electrode will be

significantly reduced by electrolyte saturation of the coating as the inert Ar gas is

replaced by the conductive lithium ion battery electrolyte. Based on the impedance

spectra results of the electrodes, it appeared that both electrodes went through a

surface charging process at high frequency. At low frequency oxidation occurs at both

electrodes, but is kinetically controlled for bare copper, while the graphite-coated

copper undergoes diffusional blocking through the porous carbon layer. An

equivalent circuit of the impedance spectrum was then proposed.

5.2 Suggestions for Future Research

The combination of reflective and transmissive Warburg impedance makes this

electrode process difficult to analyze quantitatively. In order to further investigate the

electrochemical stability of the anode materials in lithium ion batteries and the

reaction mechanism at the electrode/electrolyte interface, further impedance

spectroscopy studies can be performed if different lithium ion battery electrolytes and

copper foil with graphite coating at different thickness could be obtained. With the

known thickness of the graphite layer and the established equivalent circuit model,

calculation may be made to determine the diffusion coefficient of reactant through

carbon layer and also further analyze the contribution of different factors such as

electrode reactions, mass transfer or surface layers, etc. in the whole process.
 89

References

1. Y. Nishi, in Lithium Ion Batteries, M. Wakihara and O. Yamamoto, Editors, p.

181, Kodansha Ltd., Tokyo, Japan (1998).

2. D. A. J. Rand, R. Woods, R. M. Dell, in Batteries for Electric Vehicles, N. E.

Bagshaw, Editor, p. 427, Research Studies Press Ltd., Somerset, England

(1998).

3. S. Hossain, in Handbook of Batteries, 2nd ed., D. Linden, Editor, p. 36.1,

McGraw-Hill Inc., New York (1995).

4. J. E. Chilton Jr., G. M. Cook, in Abstract, ECS Fall Meeting, Boston, p. 90-91

(1962).

5. M. Broussely, P. Biensan, B. Simon, Electrochim. Acta, 45, 3 (1999).

6. M. S. Whittingham, Science, 192, 1126 (1976).

7. A. N. Dey, J. Electrochem. Soc., 118, 1547 (1971).

8. M. Lazzari, B. Scrosati, J. Electrochem. Soc., 127, 773 (1980).

9. N. Imanishi, Y. Takeda, O. Yamamoto, in Lithium Ion Batteries, M. Wakihara

and O. Yamamoto, Editors, p. 98, Kodansha Ltd., Tokyo, Japan (1998).

10. D. Aurbach, Y. Ein-Eli, J. Electrochem. Soc., 142, 1746 (1995).

11. J. R. Dahn, A. K. Sleigh, H. Shi, J. N. Reimers, Q. Zhong, B. M. Way,

Electrochim. Acta, 38, 1179 (1993).

12. M. S. Whittingham, J. Electrochem. Soc., 123, 315 (1976).

 90

13. M. M. Thackeray, M. F. Mansuetto, J. B. Bates, J. Power Sources, 68, 153

(1997).

14. E. Peled, J. Electrochem. Soc., 126, 2047 (1979).

15. M. Morita, M. Ishikawa, Y. Matsuda, in Lithium Ion Batteries, M. Wakihara

and O. Yamamoto, Editors, p. 156, Kodansha Ltd., Tokyo, Japan (1998).

16. http://www.bccresearch.com/energy/GB210N.html, Last accessed December

19, 2004.

17. J. Kawakita, K. Kobayashi, J. Power Sources, 101, 47 (2001).

18. M. Zhao, M. Xu, H. D. Dewald, R. J. Staniewicz, J. Electrochem. Soc., 150,

A117 (2003).

19. M. Zhao, Ph. D. Dissertation, Ohio University (2001).

20. M. Zhao, S. Kariuki, H. D. Dewald, F. R. Lemke, R. J. Staniewicz, E. J.

Plichta, R. A. Marsh, J. Electrochem. Soc., 147, 2874 (2000).

21. M. Zhao, H. D. Dewald, F. R. Lemke, R. J. Staniewicz, J. Electrochem. Soc.,

147, 3983 (2000).

22. Model 604A Electrochemical analyzer User’s Manual, CH Instruments Inc.

2001.

23. W. R. Fawcett, M. D. Mackey, J. Chem. Soc. Faraday Trans. 1, 69, 634 (1973).

24. T. Biegler, R. Parsons, J. Electroanal. Chem., 21, app. 4 (1969). [Chem. Abstr.

75:44267v]

25. R. L. McCreery, in Electroanalytical Chemistry, Vol. 17, A. J. Bard, Editor,

Marcel Dekker Inc., New York (1991).

 91

26. R. E. Panzer, P. J. Elving, Electrochim. Acta, 20, 635 (1975).

27. U. Bertocci, D. R. Turner, in Encyclopedia of Electrochemistry of the Elements,

A. J. Bard, Editor, Chapter II-6, p. 383, Marcel Dekker, Inc., New York (1974).

28. T. Hurlen, G. Ottesen, A. Staurset, Electrochim. Acta, 23, 39 (1978).

29. S. A. Awad, Kh. M. Kamel, Z. Abd-El-Hadi, H. A. Bayumi, J. Electroanal.

Chem., 199, 341 (1986).

30. J. -P. Diard, J.-M. Le Canut, B. Le Gorrec, C. Montella, Electrochim. Acta, 43,

2469 (1998).

31. G. Hinds, F. E. Spada, J. M. D. Coey, T. R. Ni Mhíocháin, M. E. G. Lyons, J.

Phys. Chem., 105, 9487 (2001).

32. M. R. F. Hurtado, P. T. A. Sumodjo, A. V. Benedetti, Electrochim. Acta, 48,

2791 (2003).

33. M. Xu, H. D. Dewald, Electrochim. Acta, Accepted March 2005.

34. J. W. Braithwaite, A. Gonzales, G. Nagasubramanian, S. J. Lucero, D. E.

Peebles, J. A. Ohlhausen, W. R. Cieslak, J. Electrochem. Soc., 146, 448 (1999).

35. E. Skou, R. Koksbang, S. Yde-Andersen, J. Thomas, in Batteries for Portable

Applications and Electric Vehicles, C. F. Holmes and A. R. Landgrebe, Editors,

p.19, PV 97-18, The Electrochemical Society, Pennington, NJ (1997).

36. P. Arora, R. E. White, M. Doyle, J. Electrochem. Soc., 145, 3647 (1998).

37. J. R. Macdonald, W. B. Johnson, in Impedance Spectroscopy: Emphasizing

Solid Materials and Systems, J. R. Macdonald, Editor, John Wiley & Sons, Inc.

New York (1987).

 92

38. A. W. Bott, Curr. Sep., 11, 61 (1992).

39. C. Deslouis, B. Tribollet, G. Mengoli, M. M. Musiani, J. Appl. Electrochem.,

18, 384 (1988).

40. A. V. Benedetti, P. T. A. Sumodjo, K. Nobe, P. L. Cabot, W. G. Proud,

Electrochim. Acta, 40, 2657 (1995).