H
T
IL U
I M MET
ALX
O
D
I ES (MET
AL=MAN
A
GN
ESE, CHR
M
OU
I M, CO
A
B ,T
L
O
RAL
UMIN
IUM) AS CAT
HO
DE N
IH
IL
T IUM N
O
IB
AT
EY
R
MD. MO
H
KE
LSURA
R HMAN
A thesis submitted in fulfilment of the
req
uirements for the aw
ard of the deg
ree of
Master of Science (Chemistry
)
aFcultyof Science
Univ
ersiti T
enkologi Malaysia
SEP
T
EMB
ER2006
iii
This thesis is dedicated to the memories of my beloved late sister
iv
ACKNOWLEDGEMENT
At the very outset, I express my satisfaction to praise the Almighty Allah.
Regarding the outcome of this thesis, I express my deepest sense of gratitude, sincere
appreciation, indebtedness and cordial respect to my supervisor Associate Professor
Dr. Madzlan Aziz and cosupervisor Associate Professor Hj. Jamil Yusof for giving
me the opportunity to work on their project as well as for their valuable guidance,
support and untiring efforts. I would also acknowledge the financial support (VOTE
74187) from the Ministry of Science, Technology and Innovation (MOSTI),
Malaysia
I am also grateful to all teachers, faculty members and staffs in the Chemistry
Department of UTM for their enormous help with my study. I would also extend my
sincere appreciation to other faculties and institutions related to my job with them.
I thank all of my friends, colleagues and laboratory personnel who extended
their time, expertise, generous advice, criticism, technical assistance and
encouragement during my research. I like to acknowledge everyone, but I am to be
constrained to a few in mentioning names as Mr. Ayob Jabal, Mr. Hanan Basri,
Mr. Azmi M. Rais, Mrs. Z. Ain Jalil, Mr. Hj. Yasin M. Sirin, Miss Nurul H. Sapiren,
Mr. M. Nazri Zainal, Mr. Dinda Hairul, Mr. Hamzah, Mr. Abdul Kadir,
Mrs. Mekzum, Mr. Amin Derani, Mr. Abdul Rahim, Mrs. Mariam Hassan,
Mr. Azani Ishak of Chemistry Department and who indebted me most for their
assistance in pursuing laboratory work.
I am sincerely thankful to Dr. Abu Affan, Lecturer, Chemistry Department,
University Malaysia Sarawak (UNIMAS), Dr. Mokhlesur Rahman, Lecturer,
Chemistry Department, KUSTEM and Mohammad Adil, Chemist, Ammonia Plant,
Chittagong, Bangladesh for their constant vigilance and valuable suggestions
throughout this study.
I express my whole hearted thanks to Chand Sultana Sharmin who is waiting
for a long time wishing my all over success to submit this thesis. Finally thanks are
due to all of the members of my family, friends and all wishers for their
encouragement and inspiration.
v
ABSTRACT
Spinel LiMn2O4 (CA-EG mixture assisted), LiMn2O4 (CA assisted), LiMn2O4
(PA assisted), Cr-doped LiCrxMn2-xO4 and layered LiCo0.7Al0.3O2 (CA and PA assisted)
cathode materials have been synthesized by a sol-gel method using organic acid as a
chelating agent. This technique offers better homogeneity, preferred surface
morphology, reduced heat treatment conditions, sub-micron sized particles and better
crystallinity. The dependence of the physiochemical properties of the powder materials
on the various calcination temperatures and organic acid quantity have been extensively
studied. Electrochemical behaviors of the prepared powder materials were analyzed
using galvanostatic charge-discharge cycling studies in the voltage range 3.0-4.3 V (vs.
Li metal) using 1 M LiPF6-EC/DMC as electrolyte. Materials LiMn2O4 (CA-EG mixture
assisted), LiMn2O4 (CA assisted), LiMn2O4 (PA assisted), Cr-doped LiCrxMn2-xO4,
LiCo0.7Al0.3O2 (CA assisted) and LiCo0.7Al0.3O2 (PA assisted) delivered initial discharge
capacity of 29.66, 20.94, 41.65, 49.50, 97.34 and 74.43 mA h/g with the capacity
retention of 71.4, 93.7, 90.6 , 91.6, 90.8 and 98.4 % of its initial capacity over only 3rd
cycle, respectively. Coulombic efficiency for the materials of LiMn2O4 (CA-EG mixture
assisted), LiMn2O4 (CA assisted), LiMn2O4 (PA assisted), Cr-doped LiCrxMn2-xO4,
LiCo0.7Al0.3O2 (CA assisted) and LiCo0.7Al0.3O2 (PA assisted) were found to be 96.2,
89.18, 74.8, 97.6, 92.8 and 94.7 % after only three cycles, respectively. Electrochemical
evaluation shows that LiCo0.7Al0.3O2 (CA assisted) materials exhibit higher initial
discharge capacity whereas LiCo0.7Al0.3O2 (PA assisted) materials exhibit a better
capacity retention and good coulombic efficiency.
vi
ABSTRAK
Bahan katod spinel LiMn2O4 (campuran bantuan CA-EG), LiMn2O4 (bantuan
CA), LiMn2O4 (bantuan PA), LiCrxMn2-xO4 terdopkan Cr dan lapisan LiCo0.7Al0.3O2
(bantuan CA dan PA) telah berjaya disintesis melalui teknik sol-gel menggunakan
asid organik sebagai agen pengkelat. Teknik ini mampu memberikan kehomogenan
yang lebih baik, kepilihan morfologi permukaan, pengurangan keadaan rawatan
haba, partikel bersaiz sub-mikron dan penghabluran yang lebih baik. Pergantungan
antara sifat fisiokimia bahan serbuk terhadap pelbagai suhu pengkalsinan dan
kuantiti asid organik telah dikaji secara meluas. Sifat elektrokimia bahan serbuk
yang telah disediakan diuji dengan kaedah kitaran cas-discas galvanostatik dengan
julat voltan antara 3.0 hingga 4.3 V (terhadap logam Li) menggunakan 1 M LiPF6EC/DMC sebagai elektrolit. Bahan LiMn2O4 (campuran bantuan CA-EG), LiMn2O4
(bantuan CA), LiMn2O4 (bantuan PA), LiCrxMn2-xO4 terdopkan Cr, LiCo0.7Al0.3O2
(bantuan CA) dan LiCo0.7Al0.3O2 (bantuan PA) menghasilkan kapasiti discas
permulaan sebanyak 29.66, 20.94, 41.65, 49.50, 97.34 dan 74.43 mA h/g dengan
kapasiti penahanan sebanyak 71.4, 93.7, 90.6, 91.6, 90.8 dan 98.4 % daripada
kapasiti permulaan selepas kitaran ketiga. Kecekapan coulomb bagi LiMn2O4
(campuran bantuan CA-EG), LiMn2O4 (bantuan CA), LiMn2O4 (bantuan PA),
LiCrxMn2-xO4 terdopkan Cr, LiCo0.7Al0.3O2 (bantuan CA) dan LiCo0.7Al0.3O2
(bantuan PA) didapati sebanyak 96.2, 89.18, 74.8, 97.6, 92.8 dan 94.7 % selepas
hanya tiga kitaran. Evolusi elektrokimia menunjukkan bahawa LiCo0.7Al0.3O2
(bantuan CA) menunjukkan kapasiti discas permulaan yang tinggi manakala
LiCo0.7Al0.3O2 (bantuan PA) menunjukkan kapasiti penahanan dan kecekapan
coulomb yang lebih baik.
vii
TABLE OF CONTENTS
CHAPTER
TITLE
PAGE
THESIS STATUS DECLARATION
SUPERVISOR’S DECLARATION
1
TITLE PAGE
i
DECLARATION
ii
DEDICATION
iii
ACKNOWLEDGEMENT
iv
ABSTRACT
v
ABSTRAK
vi
TABLE OF CONTENTS
vii
LIST OF TABLES
xi
LIST OF FIGURES
xiii
LIST OF SYMBOLS
xviii
LIST OF ABBREVIATIONS
xx
LIST OF APPENDICES
xxii
INTRODUCTION
1
1.1
istorical Backgr ound of eScondary Batteries
H
1
1.1.1 Definition of Battery
1
1.1.2 eScondary Lithium Battery
2
1.1.3 Rechargeable Lithium-ion Battery
4
Major Compone nts of Cell and Battery
7
1.2.1 Chemistry of Positive Electrode
8
Fundamentals of Electrochemistry
10
1.2
1.3
viii
1.3.1 Thermodynamic Background
12
1.3.1.1 Theoretical voltage
13
1.3.1.2
Theoretical capacity
13
1.3.1.3
Free energy
14
1.3.2 Operation of a cell
2
15
1.3.2.1 Discharge
15
1.3.2.2 Charge
16
1.4
Cell Geometry
17
1.5
Battery Terminology
18
1.6
cSope of Research
18
1.7
Research Objectives
19
1.8
Problems S
tatement and S
olution Approach
19
23
LITERATURE REVIEW
2.1
2.2
Conventional and Advanced Methods to Prepare
Cathode Raw Materials-A Brief Review
23
Cathode Raw Materials for Lithium-ion Batteries
29
2.2.1 LiMO2 Materials
30
2.2.1.1 LiCoO2
31
2.2.1.2 LiN
iO
33
2
i)
2.2.1.3 LiMO2 (M =Co, N
Derivatives
2.2.2 pSinel Manganese Oxide
3
34
35
MATERIALS AND METHODS
39
3.1
Chemicals and Reagents
39
3.2
Instruments
40
3.3
Research Design and Methodology
40
3.4
Preparation of Cathode Raw Materials
42
3.4.1 oSl-Gel Method
42
3.4.2 CA-EG (Citric Acid-Ethylene Glycol)
Mixture Assisted, oSl- Gel Route for the
Preparation of LiMn2O4 Cathode Raw
Materials
45
ix
3.4.3
CA (Citric Acid) Assisted, oSl-Gel Route for
the Preparation of LiMn2O4 Cathode Raw
Materials
45
3.4.4 PA (Propionic Acid) Assisted, S
ol-Gel
Route for the Preparation of LiMn2O4
Cathode Raw Materials
46
3.4.5 Preparation of Cr doped LiCrxMn2-xO4 (x =
0.00, 0.01, 0.02, 0.05, 0.10, 0.20) Cathode
Raw Materials
3.4.6
47
CA (Citric Acid) and PA (Propionic Acid)
Assisted, S
ol-Gel Route for the Preparation
of LiCo0.7Al0.3O2 Cathode Raw Materials
3.5
48
Characterizations of Prepared Cathode Raw
Materials
3.5.1
Determination of S
urface Area
49
49
3.5.2 Thermogravimetric-Differential Thermal
Analysis (TG-DTA)
50
3.5.3 uSrface Morphology (S
canning Electron
microscopy, E
S M)
4
50
3.5.4 Energy Dispersive X-ray Analysis (EDAX)
50
3.5.5
51
X-ray Diffraction (XRD) Analysis
3.6
Cathode Preparation
51
3.7
Cell Fabrication
52
3.8
Electrochemical characterization of Fabricated Cells
53
RESULTS AND DISCUSSION
55
4.1
Characterization of Prepared Cathode Raw Materials
55
4.2
Characterizations
55
4.2.1 Thermogravimetry-Diffrential Thermal
Analysis (TG-DTA)
55
4.2.2
BET surface area
62
4.2.3
X-ray Diffraction Analysis (XRD)
68
x
4.3
4.4
5
4.2.4 tSructure Analysis
77
4.2.5 uSrface morphology
81
4.2.6 Energy Dispersive X-ray Analysis (EDAX)
87
Electrochemical Characterizations
98
4.3.1 Charge-Discharge tSudies
98
4.3.2 Cycleability S
tudies
102
4.3.3
104
Coulombic Efficiency
Overall Performance of the Fabricated Cells
106
CONCLUSIONS AND FUTURE INVESTIGATIONS
107
5.1
Conclusions
107
5.2
S
cope and Limitations
109
5.3
Recommendations for Future S
tudy
109
REFERENCES
111
APPENDICES A –B
122
xi
LIST OF TABLES
TABLE NO.
TITLE
PAGE
1.1
Positive electrode materials and some of their characteristics
3
1.2
Characteristics of rechargeable batteries
5
1.3
Commercial rechargeable Li-ion batteries available in the
market
3.1
Preparation conditions of various types of cathode raw
materials
4.1
44
The BET surface area of the materials prepared from
different calcination temperatures
4.2
6
64
The BET surface area for LiMn2O4 and Cr doped
LiCrxMn2-xO4 powders prepared from different molar ratios
of chelating agents to total metal ions and different dopant
concentrations respectively
4.3
67
XRD results obtained on LiMn2O4 (CA-EG mixture assisted)
materials calcined at 300, 400 and 450 oC with the molar
ratio of CA-EG mixture to total metal ions of 1.0
4.4
78
XRD results obtained on LiCo0.7Al0.3O2 (PA assisted)
materials calcined at 350, 550 and 750 oC, where chelating
agent concentration was 1 M
4.5
79
Composition analysis of LiMn2O4 (CA-EG mixture assisted)
materials calcined at 250, 400 and 450 oC.
94
xii
4.6
Composition analysis of LiMn2O4 (CA assisted) materials
calcined at 300 and 700 oC
4.7
Composition analysis of LiMn2O4 (PA assisted) materials
calcined at 350 and 750 oC.
4.8
96
Composition analysis of LiCo0.7Al0.3O2 (CA and PA
assisted) materials calcined at 350 and 750 oC
4.10
95
Composition analysis of Cr doped LiCrxMn2-xO4 materials
calcined at 800 oC
4.9
95
97
Cycleability data for the three cycles obtained from
charge/discharge characterization of the A cell, B cell, C cell,
D cell, E cell and F cell
103
xiii
LIST OF FIGURES
FIGURE NO.
TITLE
PAGE
1.1
Schematic of a basic Li-Sn cell
11
1.2
Electrochemical operation of cell (discharge)
15
1.3
Electrochemical operation of cell (charge)
16
1.4
Typical design of a cylindrical 18650 cell
17
2.1
Structure of the rhombohedral elementary cell of LiMO2
oxides
31
2.2
Structure of spinel unit cell (AB2O4)
37
3.1
The methodology scheme of overall research
41
3.2
A flow diagram of cathode raw materials preparation
43
3.3
A photograph of fabricated coin cell sample
Model: CR2032, Diameter 20 mm, Thickness: 3.2 mm
4.1
52
TG-DTA curves for the gel precursors of LiMn2O4
(CA-EG Mixture Assisted) pretreated in vacuum dryer at
100 oC for 24 hours prior to calcination. Heating rate:
10 oC/min and N2 flow 200 mL/min
4.2
56
TG-DTA curves for the gel precursors of LiMn2O4 (CA
Assisted) pretreated in a vacuum dryer at 100 oC for 24
hours prior to calcination. Heating rate: 10 oC/min and
N2 flow 200 mL/min
58
xiv
4.3
TG-DTA curves for the gel precursors of LiMn2O4 (PA
Assisted) pretreated in a vacuum dryer at 100 oC prior to
thermal analysis in the air. Heating rate: 10 oC/min and
N2 flow 200 mL/min
4.4
59
TG-DTA curves of the LiCrxMn2-xO4 (x = 0.05) grown
by propionic acid assisted sol-gel technique. This
measurement was carried out at a heating rate of
10 oC/min with N2 flow rate of 200 mL/min.
4.5
60
TG-DTA curves for the gel precursors of LiCo0.7Al0.3O2
(CA and PA assisted) pretreated in a vacuum dryer at
100 oC for 24 hours prior to calcination. Heating rate:
10 oC/min and N2 flow 200 mL/min
4.6
61
Dependence of the specific surface area for the (a)
LiMn2O4 powders (CA-EG mixture assisted), (b)
LiMn2O4 powders (CA assisted), (c) LiMn2O4 powders
(PA assisted), (d) LiCo0.7Al0.3O2 powders (CA assisted)
and (e) LiCo0.7Al0.3O2 powders (PA assisted) on the
calcination temperatures
4.7
63
Dependence of the specific surface area for the (a)
LiMn2O4 powders (CA-EG mixture assisted), (b)
LiMn2O4 powders (CA assisted) (c) LiMn2O4 powders
(PA assisted) and d) Cr doped LiCrxMn2-xO4 powders on
the molar ratios and dopant concentrations respectively
4.8 a
65
XRD pattern for gel derived LiMn2O4 (CA-EG mixture
assisted) materials calcined at 450 oC temperature for 5
hours in air, where the molar ratio of citric acid-ethylene
glycol (CA-EG) mixture to total metal ions was 1.0.
4.8 b
69
XRD pattern for gel derived LiCo0.7Al0.3O2 (PA assisted)
materials calcined at 550 oC temperature for 5 hours in
air, where chelating agent concentration was 1 molar.
69
xv
4.9 a
Stacking of X-ray diffraction patterns of LiMn2O4 (CAEG mixture assisted) materials calcined at various
temperatures on the molar ratio of citric acid-ethylene
glycol (CA-EG) mixture to total metal ions of 1.0.
4.9 b
70
Stacking of X-ray diffraction patterns of LiMn2O4 (CA
assisted) materials calcined at various temperatures on
the molar ratio of citric acid to total metal ions of 1.0.
4.9 c
71
Stacking of XRD patterns of LiMn2O4 (PA assisted)
materials calcined at various temperatures on the molar
ratio of propionic acid to total metal ions of 1.5.
4.9 d
Stacking of XRD patterns of LiCo0.7Al0.3O2 (CA
assisted) materials calcined at 350, 550 and 750 oC
4.9 e
72
Stacking of XRD patterns of LiCo0.7Al0.3O2 (PA assisted)
materials calcined at 350, 550 and 750 oC
4.10 a
71
72
Stacking of X-ray diffraction patterns of LiMn2O4 (CAEG mixture assisted) materials calcined at 450 oC for 5
hours at the molar ratio of citric acid-ethylene glycol
mixture to total metal ions of (a) 0.25, (b) 0.50 and (c)
74
1.0
4.10 b
Stacking of X-ray diffraction patterns of LiMn2O4 (CA
assisted) materials calcined at 600 oC for 10 hours at the
molar ratio of citric acid to total metal ions of (a) 0.5, (b)
1.0 and (c) 1.5
4.10 c
74
Stacking of X-ray diffraction patterns of LiMn2O4 (PA
assisted) materials calcined at 350 oC for 5 hours at the
molar ratio of propionic acid to total metal ions of ( a)
0.5, (b) 0.83, (c) 1.5, and (d) 2.0
4.10 d
75
Stacking of XRD patterns for Cr doped LiCrxMn2-xO4
materials calcined at 800 oC for 4 hours at the dopant
concentrations of x = 0.00, 0.01, 0.02, 0.05, 0.10, 0.20
75
xvi
4.11 a
Scanning electron micrographs of LiMn2O4 (CA-EG
mixture assisted) powders calcined at (a) 250 oC, (b)
400 oC and (c) 450 oC where citric acid-ethylene glycol
mixture to total metal ions was 1.0
4.11 b
82
Scanning electron micrographs for LiMn2O4 (CA-EG
mixture assisted) powders calcined the gel precursors of
the molar ratio of citric acid-ethylene glycol mixture to
total metal ions of (d) 0.25 and (e) 0.50 at 450 oC.
4.12
83
Scanning electron micrographs of LiMn2O4 (CA
assisted) powders calcined at (a) 300 oC and (b) 700 oC
where citric acid to total metal ions was 1.0
4 .13
83
Scanning electron micrographs of LiMn2O4 (PA assisted)
powders calcined at (a) 350 oC and (b) 750 oC where
propionic acid to total metal ions was 1.5
4.14
Scanning
electron
micrographs
for
84
LiCrxMn2-xO4
materials calcined at 800 oC for 4 hours: (a) x = 0.00, (b)
x = 0.01, (c) x = 0.02, (d) x = 0.05 and (e) x = 0.20
4.15
86
Scanning electron micrographs for the materials of
LiCo0.7Al0.3O2 (CA assisted) calcined at (a) 250 oC and
(b) 550 oC and for the materials of LiCo0.7Al0.3O2 (PA
assisted) calcined at (c) 250
o
C and (d) 550
o
C,
respectively.
4.16 a
87
EDAX spectrum of LiMn2O4 (CA-EG mixture assisted)
materials calcined at 250, 400 and 450 oC with citric
acid-ethylene glycol mixture to total metal ions of 1.0
4.16 b
89
EDAX spectrum of LiMn2O4 (CA-EG mixture assisted)
materials calcined at 450 oC with citric acid-ethylene
glycol mixture to total metal ions of 0.25, 0.50 and 1.0
4.17
90
EDAX spectrum of LiMn2O4 (CA assisted) materials
calcined at 300 and 700 oC with citric acid to total metal
ions of 1.0
91
xvii
4.18
EDAX spectrum of LiMn2O4 (PA assisted) materials
calcined at (a) 350 oC and (b) 750 oC with propionic acid
to total metal ions of 1.5
4.19
91
EDAX spectrum of Cr doped LiCrxMn2-xO4 materials
calcined at 800
o
C where dopant concentrations of
x = 0.00, 0.01, 0.02, 0.05, 0.20
4.20
EDAX
spectrum of
LiCo0.7Al0.3O2 (CA
92
assisted)
materials calcined at (a) 350 oC and (b) 750 oC
4.21
EDAX
spectrum
of
LiCo0.7Al0.3O2 (PA
93
assisted)
materials calcined at (a) 350 oC and (b) 750 oC
4.22
93
Charge-discharge characteristics with the number of
cycles for the (a) A cell, (b) B cell, (c) C cell and (d) D
cell where the raw materials calcined at 400, 700, 750
and 800
o
C respectively. Cycling was carried out
galvanostatically at constant charge-discharge current
density of 0.2 mA/cm2 (200 µA) between voltage region
3.0 to 4.3 V
4.23
100
Charge-discharge characteristics with the number of
cycles for the (e) E cell and (f) F cell where the raw
materials calcined at 550 oC respectively. Cycling was
carried out galvanostatically at constant charge-discharge
current density of 0.2 mA/cm2 (200 µA) between voltage
region 3.0 to 4.3 V
4.24
101
Cycleability for the A cell, B cell, C cell, D cell, E cell
and F cell with a 0.2 mA/cm2 current density at the
voltage range of 3.0-4.3 V
4.25
102
Coulombic efficiency for the A cell, B cell, C cell, D
cell, E cell and F cell with the number of cycles.
105
xviii
LIST OF SYMBOLS
°C
-
Degree Celsius
ș
-
Scattering Angle
µ
-
Chemical Potential
e
-
Charge of an Electron
e-
-
Electron
g
-
Gram
L
-
Liter
m
-
Meter
M
-
Molar
mA
-
Milliampere
Ah
-
Ampere hour
V
-
Voltage
mg
-
Milligram
min
-
Minute
Ai
-
Activity of Relevant Species
R
-
Gas Constant
T
-
Absolute Temperature
W h/g
-
Watt hour per gram
mA h/g
-
Milliampere-hour per gram
nm
-
Nanometer
o
-
Standard Potential
-
Faraday Constant
-
Standard Free Energy
E
F
'G
o
xix
n
-
Number of Electron
Å
-
Angstrom
µg
-
Microgram
µm
-
Micrometer/Micron
µmol
-
Micromole
xx
LIST OF ABBREVIATIONS
SLI
-
Starting-Lighting-Ignition
CA-EG
-
Citric Acid-Ethylene Glycol
CA
-
Citric Acid
EG
-
Ethylene Glycol
PA
-
Propionic Acid
PE
-
Positive Electrode
NE
-
Negative Electrode
NHE
-
Normal Hydrogen Electrode
PC
-
Propylene Carbonate
PEO
-
Polyethylene Oxide
EV/HEV
-
Electric Vehicles / Hybrid Electric Vehicles
EIS
-
Electrochemical Impedance Spectroscopy
EAS
-
Electro-analytical Study
SEI
-
Solid Electrolyte Interphase
CV
-
Cyclic Voltamettry
EC
-
Ethylene Carbonate
DEC
-
Diethyl Carbonate
TG-DTA
-
Thermogravimetry-Differential Thermal Analysis
BET
-
Brunauer-Emmett and Teller
EDAX
-
Energy Dispersive X-ray Analysis
XRD
-
X-ray Diffraction
SEM
-
Scanning Electron Microscopy
TEM
-
Transmission Electron Microscopy
xxi
XPS
-
X-ray Photoelectron Spectra
SPE
-
Solid Polymer Electrolyte
Ni-Cd
-
Nickel Cadmium
NiM-H
-
Nickel Metal-Hydride
ICP
-
Inductive Coupled Plasma
Li-ion
-
Lithium Ion
A cell
-
Li/1 M LiPF6-EC/DMC/LiMn2O4 (CA-EG)
B cell
-
Li/1 M LiPF6-EC/DMC/LiMn2O4 (CA)
C cell
-
Li/1 M LiPF6-EC/DMC/LiMn2O4 (PA)
D cell
-
Li/1 M LiPF6-EC/DMC/LiCrxMn2-xO4
E cell
-
Li/1 M LiPF6-EC/DMC/LiCo0.7Al0.3O2 (CA)
F cell
-
Li/1 M LiPF6-EC/DMC/LiCo0.7Al0.3O2 (PA)
xxii
LIST OF APPENDICES
APPENDIX
TITLE
PAGE
A1
In details Report of Li/1 M LiPF6EC/DMC/LiCo0.7Al0.3O2 (CA assisted)
[E cell] Cell Test Data for the First
Cycle Charge
122
A2
In details Report of Li/1 M LiPF6EC/DMC/LiCo0.7Al0.3O2 (CA assisted)
[E cell] Cell Test Data for the First
Cycle Discharge
139
A3
In details Report of Li/1 M LiPF6EC/DMC/LiCo0.7Al0.3O2 (CA assisted)
[E cell] Cell Test Data for the 2nd Cycle
Charge
147
A4
In details Report of Li/1 M LiPF6EC/DMC/LiCo0.7Al0.3O2 (CA assisted)
[E cell] Cell Test Data for the 2nd Cycle
Discharge
156
A5
In details Report of Li/1 M LiPF6EC/DMC/LiCo0.7Al0.3O2 (CA assisted)
[E cell] Cell Test Data for the 3rd Cycle
Charge
164
A6
In details Report of Li/1 M LiPF6EC/DMC/LiCo0.7Al0.3O2 (CA assisted)
[E cell] Cell Test Data for the 3rd Cycle
Discharge
172
xxiii
B
Performance
Data
of
Synthesized
Cathode Materials and Commercial
Positive Electrode Materials (LiCoO2)
Used by Different Manufacturers
179
CHAPTER 1
INTRODUCTION
1.1
Historical Background of Secondary Batteries
Secondary batteries have been in existence for over 100 years. The lead-acid
battery was developed in 1859 by Plante´. It is still the most widely used battery,
albeit with many design changes and improvements, with the automotive SLI battery
by far the dominant one. The nickel-iron alkaline battery was introduced by Edison
in 1908 as a power source for the early, but short-lived, electric automobile. The
pocket-plate nickel-cadmium battery has been manufactured since 1909 and was
used primarily for heavy-duty industrial applications. As with the primary battery
systems, significant performance improvements have been made with the older
secondary battery systems, and a number of newer types, such as the silver-zinc, the
nickel-zinc, the hydrogen, lithium, and halogen batteries, and the high temperature
systems, have been introduced into commercial use or serious development
(Linden, 1994).
1.1.1 Definition of Battery
A battery is a device that converts chemical energy contained in its active
materials to electric energy by means of spatially separated electrochemical
oxidation and reduction reactions. The overall (redox) reaction occurs by electron
2
transfer from negative electrode material to positive electrode material through an
external electrical circuit. In a non-electrochemical redox reaction, such as rusting or
burning, the transfer of electrons occurs locally and chemical energy is converted to
heat only. Although the terms “cell and battery” are often used interchangeably, the
basic electrochemical reactor is the “cell” consisting of a single set of positive and
negative electrodes.
Batteries can be divided into primary (non-rechargeable) and secondary
(rechargeable) batteries according to the capability of electrical regeneration after
chemical energy has been converted fully to electrical energy during discharge.
Primary batteries cannot be recharged, i.e. the electrochemical reaction cannot be
reversed. Hence, they are discharged once and discarded or recycled chemically.
Nevertheless primary batteries have found many applications due to shelf life, high
energy density at low to moderate discharge rate, compactness, and ease of use.
Secondary batteries, also referred to as rechargeable batteries, are systems in which
the electrochemical reaction can be reversed by passing current through the battery
in the direction opposite of that of discharge. Although this is, in principle, possible
for all batteries at very low rates i.e. practically useful secondary batteries are
characterized by relatively high power density in charge as well as discharge, flat
discharge curves, and acceptable low temperature performance. Moreover,
rechargeable batteries have an advantage over primary batteries from an
environmental point of view, because they are inherently being “recycled”.
1.1.2 Secondary Lithium Battery
Secondary lithium batteries have the same geometry and components as
primary ones but both electrodes function as secondary lithium electrodes, for
example by lithium intercalation in the electrode material on either side. Almost at
the same time that primary lithium batteries were introduced, it was discovered that
lithium could be inserted or intercalated reversibly in several compounds, which
makes it possible to use these compounds as insertion cathodes in rechargeable
lithium batteries. The choice of materials that can be used for the insertion cathode is
3
relatively wide. The best cathodes for secondary lithium batteries are those where
bonding with lithium occurs at low energy levels and the structural modification of
the active materials during lithium insertion/extraction is minimal (such insertion
reactions are typical for certain 2-D lattices, in which case they are called
intercalation reaction).
Table 1.1 shows characteristics of some of the compounds that have been
used in lithium secondary batteries.
Table 1.1:
Positive electrode materials and some of their characteristics
(Hossain, 1995).
Materials
Average
Practical specific
voltage
energy (W h/kg)
(V)
Lithium /mole
Comments
a
MoS2
1.7
230
0.8
Naturally occurring
MnO2
3.0
650
0.7
Inexpensive
LiCoO2
3.7
500
0.5
Good for lithium
ion system
LiNiO2
3.5
480
0.5
Good for lithium
ion system
LiMn2O4
3.8
450
0.8
Good for lithium
V6O13
2.3
300
2.5
Good for SPE
ion system
system
V2O5
2.8
490
1.2
Good for SPE
system
SO2
3.1
220
0.33
Toxic electrolyte,
good for pulse
power application
CuCl2
3.3
660
1
Toxic electrolyte,
good for pulse
power application
Polyacetylene
3.2
340
1
For polymer
electrodes
Polypyrrole
3.2
280
1
For polymer
electrodes
a
Voltage vs. Lithium metal
4
During the 1970s and 80s many researchers were involved in programs to
develop rechargeable batteries. However, until 1990, only small-scale rechargeable
coin cells survived in the market despite their advantage over conventional systems
in terms of energy density and environmental control. On the other hand, primary
lithium batteries captured a significant market in various size and capacities. The
major reasons for the small market share of rechargeable lithium batteries with
lithium metal NE were their limited cycleability and, especially, potential safety
hazards. The limited cycleability means that, although lithium metal may be plated
with almost 100 % efficiency during charging in propylene carbonate (Chilton et
al.,1965; Selim and Bro,1974), it can not be stripped (oxidized during discharge) as
efficiently, particularly if stripping does not immediately follow deposition and the
deposit is allowed to stand in contact with solution.
Although a lithium plate becomes less electro-strippable upon standing, it is
mostly still in the form of metal (Selim and Bro, 1974). This metal layer has become
electrically isolated from the substrate by ionically conducting layer, which forms
due to corrosion (Li oxidation under reduction of electrolyte). Therefore, the lithium
layer is effectively passivated. Passivation prevents further corrosion but the
passivating film cause an increase in the internal cell resistance and release of
corrosion products. Thus cycle by cycle, the morphology deteriorates and the plating
(charging)-stripping (discharging) efficiency decreases. Moreover, the most
deleterious effect of the (non-uniform) passivation layer is that it causes nonuniform
lithium plating during the charging process, to an extent which may ultimately lead
to total cell failure (due to dentritic short circuiting) or even to serious safety hazard
(due to local over heating).
1.1.3 Rechargeable Lithium-ion Battery
There are four major rechargeable batteries currently in use (Abraham,
2001): the lead-acid battery (Pb-Acid), the nickel-cadmium battery (Ni-Cd), the
nickel metal-hydride batteries (NiM-H) and the lithium-ion batteries (Li-ion). The
lead-acid and nickel-cadmium batteries have a very long history of consumer use.
5
The nickel metal-hydride and lithium-ion are relatively new battery systems having
come into existence in the early nineteen nineties. The first three batteries contain
water-based (aqueous) electrolytes, whereas the lithium-ion battery utilizes
electrolytes composed of lithium salt solutions in organic (non-aqueous) solvents.
The Li-ion battery has many advantages over the three aqueous electrolyte-based
systems (See Table 1.2) and these include:
a) Two to three times higher voltage per single cell
b) Two to five times higher specific energy, i.e., watt-hours per kilogram
(W h/kg) of battery weight, and two to four times higher energy density, i.e.,
watt-hours per liter (W h/l) of battery volume.
c) Low self-discharge and long shelf life, i.e, the battery does not loose a
significant amount of its capacity while sitting idle on the shelf.
d) No memory effect, i.e., the available capacity in a fully charged Li-ion
battery is independent of its operational history, unlike the Ni-Cd system.
e) Long charge-discharge cycle life. Li-ion batteries are capable of 500-1000
cycles at full depth of discharge.
Due to these advantages Li-ion batteries are increasingly becoming the battery of
choice for portable consumer products such as cellular telephones and notebook
computers.
Table 1.2:
Characteristics of rechargeable batteries
Attribute
Li-ion
NiM-H
Ni-Cd
Small Pb-Acid
Voltage (V)
3.6
1.2
1.2
2.0
Specific Energy
150
90
70
30
350
300
180
80
>1000
>1000
1500
500
(W h/kg)
Energy Density
(W h/l)
Life Cycles
6
As result of the proliferation of these and other portable consumer products, the
Li-ion battery business is expected to generate tens of billions of US dollars in sales
in the not too distant future.
In lithium-ion batteries, the metallic lithium anode is replaced with a lithium
insertion electrode consisting of carbon material. The introduction of carbon as an
anode material and the development of insertion-type cathode materials have
produced substantial improvements in energy density, cycleability, cost, and safety
of secondary lithium batteries. In 1990 Sony Inc. introduced the first generation of
lithium-ion batteries without metallic lithium (Ngaura et al., 1990). The new concept
and the excellent characteristics of the “lithium-ion” battery were enough to obtain
worldwide attention. A very large research effort continues in this field, after the first
generation of lithium-ion batteries. Table 1.3 shows some of the current lithium-ion
battery makers and their product line.
Table 1.3:
Commercial rechargeable Li-ion batteries available in the market
(Kim, 2001)
Manufac.
Toshiba (A&T)
Sony
Sanyo
Panasonic
E-One (Moli)
Type of
Type of
cathode
anode
LiCoO2
Graphite
Ɏ17×50~Ɏ18.3×65
740~1350
Coke
6.3×30×4.8~14.5×34×48
500~1600
LiCoO2
Hard carbon
8.0×33.7×48.1~10.0×34.1×47.2
500~2800
LiNi0.8Co0.2O2
Graphite
Ɏ14×42.8~Ɏ26.3×65.4
LiCoO2
Graphite
Ɏ14×50~Ɏ18×65
580~1600
19.5×48×6.1~35.1×67.3×6.5
320~1400
Soft Carbon
Ɏ17×49.5~Ɏ18.3×64.7
830~1800
Graphite
29.8×47.5×6.4~34×49.8×10.4
630~1550
LiMn2O4
Graphite
Ɏ18.2×65,Ɏ26.0×65
1400~320
LiCoO2
-
8.6×34×48
1000
LiCoO2
Manufac. = Manufacturer
Dimension (mm)
Capacity
(mA h)
7
As the result of that, many parts have been improved. So far, more than 10 major
companies are sharing the market and more companies are expected to enter shortly,
as they are still in the phase of developing and engineering.
The lithium-ion battery industry is growing fast as consumer electronic
companies demand smaller and lighter energy storage device with high energy
density. Many battery manufacturers are pursuing the development of lithium ion
battery packs for application to electric vehicles. In 1998 Nissan and Sony
Corporation released the first electric vehicle fleet model, which is powered by a
lithium-ion battery (Kim, 2001). The battery pack consists of 12 modules and each
module contains 8 cylindrical cells encased in a resin module. Each battery has a
built-in cell controller to ensure that each cell is operating within a specific voltage
range of 2.5 V and 4.2 V during cycling. Total battery pack capacity is 94 A h and
voltage is 345 V.
1.2
Major Components of Cell and Battery
A battery consists of one or more of cells, connected in series or parallel, or
both, depending on the desired output voltage and capacity. The cell consists of three
major components as below:
a) The cathode or positive electrode:
It is oxidizing electrode which
accepts electrons from the external circuit and is reduced during the electrochemical
reaction.
b) The anode or negative electrode: It is reducing or fuel electrode which
gives up electrons to the external circuit and is oxidized during the electrochemical
reaction.
c) The electrolyte: It is ionic conductor which provides the medium for
transfer of electrons, as ions, inside the cell between the anode and cathode. The
electrolyte is typically a liquid, such as water or other solvents, with dissolved salts,
acids or alkalis to impart ionic conductivity.
8
The cathode must be an efficient oxidizing agent, be stable when in contact
with the electrolyte, and have a useful working voltage. However, many of the
cathode materials are metallic oxides, while other cathode materials are used for
advanced battery systems giving high voltage and capacity.
In a practical system, the anode is selected with the following properties in
mind: efficiency as a reducing agent, high columbic output (A h/g), good
conductivity, stability, ease of fabrication, and low cost.
The electrolyte must have good ionic conductivity but not be electrically
conductive, as this would cause internal short circuiting. Other important
characteristics are nonreactivity with the electrode materials, little change in
properties with change in temperature, safeness in handling, and low cost.
Physically the anode and cathode electrodes are electronically isolated in the
cell to prevent internal short circuiting, but are surrounded by the electrolyte. In
practical cell designs a separator material is used to separate the anode and cathode
electrodes mechanically. The separator, however, is permeable to the electrolyte in
order to maintain the desired ionic conductivity. In some cases the electrolyte is
immobilized for non spill design.
1.2.1 Chemistry of Positive Electrode
The process, however, is even more complex for rechargeable batteries as the
cell chemistry must be reversible and the reactions that occur during recharge affect
all of the characteristics and the performance on subsequent cycling.
There is a relatively wide choice of materials that can be selected for the
positive electrodes of lithium batteries. However, many of these, which involve
reactions which break and rearrange bonds during discharge, cannot be readily
reversed and are limited to primary nonrechargeable batteries. The best cathodes for
9
rechargeable batteries are those where there is little bonding and structural
modification of the active materials during the discharge-charge reaction (Scrosati et
al., 1993).
Intercalation Compounds: The insertion or intercalation compounds are
among the most suitable cathode materials. In these compounds, a guest species such
as lithium can be inserted interstitially into the host lattice (during discharge) and
subsequently extracted during recharge with little or no structural modification of the
host. The intercalation process involves three principal steps:
a) Diffusion or migration of solvated Li+ ions
b) Desolvation and injection of Li+ ions into the vacancy structure
c) Diffusion of Li+ ions into the host structure
The electrode reactions which occur in a Li /Lix (HOST) cell, where (HOST) is an
intercalation cathode, are
y Li
y Li+ + y e- at the Li metal anode
y Li+ + y e- + Lix (HOST)
Lix+y (HOST) at the cathode
Leading to overall cell reaction of
y Li + Lix (HOST)
Lix+y (HOST)
A number of factors have to be considered in the choice of the intercalation
compound, such as reversibility of the intercalation reaction, cell voltage, variation
of the voltage with the state of the charge, availability and cost of the compound.
The key requirements for positive-electrode intercalation materials (LixMOz) used in
lithium cells are given below:
1) High free energy of reaction with lithium
2) Wide range of x (amount of intercalation)
3) Little structural change upon reaction
4) Highly reversible reaction
5) Rapid diffusion of lithium in solid
6) Good electronic conductivity
7) No solubility in electrolyte
8) Readily available or easily synthesized from low cost reactants
Transition metal oxides, sulfides (MoS2, TiS2), and selenides (NbSe3) are used
in lithium rechargeable batteries. The LiMn2O4 spinel framework possesses a three
10
dimensional space via face sharing octahedral and tetrahedral structures, which
provide conducting pathways for the insertion and extraction of lithium ions. The
removal and insertion of the lithium ion for the three lithiated transition metal oxides
are
LiCoO2
Li1-xCoO2 + x Li+ + x e-
LiNiO2
Li1-xNiO2 + x Li+ + x e-
LiMn2O4
Li1-xMn2O4 + x Li+ + x e-
The reversible value of x for LiCoO2 and LiNiO2 is less than or equal to 0.5,
and the value is greater than or to 0.85 for lithiated manganese oxide. Thus although
the theoretical capacity of LiCoO2 and LiNiO2 (274 mA h /g) is almost twice as high
as that of LiMn2O4, the reversible capacity of the three cathode materials is about the
same (135 mA h/g). In the long run it is expected that the manganese-based
compounds will become the material of choice as they are more abundant, less
expensive, and non-toxic.
1.3
Fundamentals of Electrochemistry
Electrochemistry includes the study of chemical properties and reactions
involving ions either in solution or in solids. In order to study these properties,
generally electrochemical cells are constructed. Typical cell consists of two solid
electrodes, the cathode and anode, in contact with an ionic conducting electrolyte. To
prevent cell self-discharge, an electronically insulating material that is permeable to
the working ions physically separates the electrodes. The two electrodes are put in
electrical contact by an external electronically conductive wire. Two different types
of electrochemical cells can be defined: electrolytic cells, and galvanic cells. In
electrolytic cells an applied electrical current causes the active material to undergo
decomposition; a process corresponding to the conversion of electrical energy to
chemical energy. Galvanic cells, however, are capable of converting chemical
energy into electrical energy. Galvanic cells generate electrical energy by the
spontaneous electrode reactions that give rise to electrical current.
11
To understand the lithium-ion battery it is useful to consider a simple Li cell, Figure
1.1
Figure 1.1:
Schematic of a basic Li-Sn cell
The reaction for a cell with a negative Li-metal electrode and a positive tin
(Sn) electrode is presented below. This cell is very important to the rest of the thesis,
so it a good place to start. The discharge of a Li-Sn cell involves two half cell
reactions. During discharge of a lithium cell, Li+ ions are generated at the
anode/electrolyte interface, and Li+ is inserted into the cathode structure at the
cathode/electrolyte interface. The electrode reactions are given below.
n Li+ + n e- (Negative) [Oxidation Reaction]
n Li
n Li+ + Sn + n e-
LinSn (Positive) [Reduction Reaction]
The full cell reaction is:
n Li + Sn
LinSn (Full Cell)
The difference in chemical potential (µ) of Li in the negative electrode compared to
the positive electrode drives the reaction. The voltage difference between the
electrodes is given by:
V
(µ positive - µ negative)
e
12
where e is the magnitude of the charge on an electron. To charge the cell the reaction
must be reversed. Energy is required to remove Li from Sn and re-deposit it onto the
negative electrode, recharging the cell. The roles of the cathode and anode are
reversed when the battery is being charged.
1.3.1 Thermodynamic Background
In a cell, reactions essentially take place at two areas or sites in the device.
These reaction sites are the electrodes. In generalized terms, the reaction at one
electrode (reduction in the forward direction) can be represented by:
aA + ne
cC
(a)
where a molecules of A take up n electrons e to form c molecules of C. At the other
electrode, the reaction (oxidation in forward direction) can be represented by:
bB - ne
dD
(b)
The overall reaction in the cell is given by addition of these two half cell reactions
aA + bB
cC + dD
(c)
The change in the standard free energy ' G o of this reaction is expressed as
' G o = - nFEo
(d)
where F = constant known as Faraday (96,487 C)
Eo = standard electromotive force
n = number of electrons involved in stoichiometric reaction
When conditions are other than in the standard state, the voltage E of a cell is given
by the Nernst equation,
o
RT
E=E -
ln
nF
where ai = activity of relevant species
R=
gas constant
T = absolute temperature
acC adD
aaA abB
(e)
13
The change in the standard free energy ' G o of a cell reaction is the driving force
which enables a battery to deliver electric energy to an external circuit. The
measurement of the electromotive force, incidentally, also make available data on
changes in free energy, namely, entropies and enthalpies together with activity
coefficients, equilibrium constants, and solubility products. Direct measurement of
single (absolute) electrode potentials is considered practically impossible. To
establish a scale of cell or standard potentials, a reference potential “Zero” must be
established against which single electrode potentials can be measured. By
convention, the standard potential of the H2/H+(aq) reaction is taken as zero and all
standard potentials are referred to this potential.
1.3.1.1
Theoretical voltage
The standard potential of the cell is determined by its actives materials and
can be calculated from free energy data or obtained experimentally. The standard
potential of a cell can also be calculated from the standard electrode potentials as
follows (the oxidation potential is the negative value of the reduction potential):
Anode (oxidation potential) + cathode (reduction (potential) = standard cell potential
For example, in the reaction Zn + Cl2
ZnCl2
Zn
Zn+2 + 2e-
Cl2
-
-
2Cl - 2e
- (- 0.76 V)
1.36 V
2.12 V
The cell voltage is also dependent on other factors, including concentration,
temperature etc.
1.3.1.2
Theoretical capacity
The capacity of a cell is expressed as the total quantity of electricity involved
in the electrochemical reaction and is defined in terms of coulombs or ampere-hours.
The “ampere-hour capacity” of a battery is directly associated with the quantity of
14
electricity obtained from the active materials. Theoretically 1 gm-equivalent weight
of material will deliver 96,487 C or 26.8 A h. (A gram-equivalent weight is the
atomic or molecular weight of the active material in grams divide by the number of
electrons involved in the reaction). The theoretical capacity of a battery system,
based only on the active materials participating in the electrochemical reaction, is
calculated from the equivalent weight of the reactants. Hence the theoretical capacity
of the Zn/Cl2 system is 0.394 A h / g, that is,
Zn +
Cl2
0.82 A h / g
0.76 A h / g
1.22 g /A h
1.32 g / A h
ZnCl2
=
2.54 g/ A h or 0.394 A h / g
The capacity of battery is also considered on an energy (Watt hour) basis by taking
the voltage as well as the quantity of electricity into consideration,
Watt hour (W h) = voltage (V) × ampere-hour (A h)
In the Zn / Cl2 cell example, if the standard potential is taken as 2.12 V, the
theoretical watt hour capacity per gram of active material (theoretical gravimetric
energy density) is Watt hour / gram capacity = 2.12 V × 0.395 A h/g = 0.838 W h /g
Similarly, the ampere-hour or watt hour capacity on a volume basis, can be
calculated by using the appropriate data for ampere-hours per cubic centimeter.
1.3.1.3 Free energy
Whenever a reaction occurs, there is a decrease in the free energy of the
system, which is expressed as
Go = - nFE o
where F = constant known as Faraday ( | 96,500 C or 26.8 A h)
n = number of electrons involved in stoichiometric reaction
Eo = standard potential, V
15
1.3.2 Operation of a cell
A battery consists of one or more cells, connected in series or parallel, or
both, depending on the desired output voltage and capacity.
1.3.2.1
Discharge
The operation of a cell during discharge is shown schematically in the Figure
1.2
Electron flow
Load
-
+
Anode
Cathode
Flow of anions
Flow of cations
Figure 1.2:
Electrochemical operation of cell (discharge)
When the cell is connected to an external load, electrons flow from the anode, which
is oxidized, through the external load to the cathode, where the electrons are
accepted and the cathode material is reduced. The electric circuit is completed in the
electrolyte by the flow of anions (negative ions) and cations (positive ions) to the
anode and cathode, respectively. The discharge reaction can be written, assuming a
metal as the anode material and a cathode material such as chlorine (Cl2), as follows
Negative electrode: anodic reaction (oxidation, loss of electrons)
Zn
Zn+2
+
2e-
16
Positive electrode: cathodic reaction (reduction, gain of electrons)
+ 2e-
Cl2
Overall reaction (discharge): Zn
1.3.2.2
2ClZn+2 + 2Cl- (ZnCl2)
+ Cl2
Charge
During the recharge of a rechargeable or storage battery, the current flow is
reversed and oxidation takes place at the positive electrode and reduction at the
negative electrode, as shown in Figure 1.3. As the anode is, by definition, the
electrode at which oxidation occurs and cathode the one where reduction takes place,
the positive electrode is now the anode and the negative the cathode.
-
DC
Power supply
+
+
Flow of anions
Anode
Cathode
Electron flow
Flow of cations
Electrolyte
Figure 1.3: Electrochemical operation of cell (charge)
In the example of the Zn/Cl2 cell, the reaction on charge can be written as follows:
Negative electrode: cathodic reaction (reduction, gain of electrons)
Zn2+
2e-
+
Zn
Positive electrode: anodic reaction (oxidation, loss of electrons)
2Cl-
Cl2 + 2e-
Overall reaction (charge): Zn2+ +
2Cl-
Zn + Cl2
17
1.4
Cell Geometry
The basic cell chemistry and design are the same for all types of Li-ion
batteries. Figure 1.4 shows a typical cell design. Thin layers of cathode (positive),
separator, and anode (negative) are rolled up on a central mandrel and inserted into a
cylindrical can. The gaps are filled with liquid electrolyte. The basic design remains
unchanged on substitution of one electrode material for another, although the layer
thickness might change. This is the same design used for most small commercial
cells, like the 18650 (18 mm in diameter, 65 mm long) used in devices such as
camcorders and laptops.
Figure 1.4:
Typical design of a cylindrical 18650 cell (Beaulieu, 2002)
The lithium-ion cell can be designed in any of the typical cell constructions:
flat or coin, spirally wound cylindrical, or prismatic configurations. While most of
the developments to date have concentrated on the smaller cells for portable
applications.
18
1.5
Battery Terminology
What we commonly call a battery is actually a cell. Strictly speaking a
battery is a collection of individual cells, typically connected in series (i.e., car
battery). In this thesis, the terms battery and cell will be used interchangeably.
Discharge capacity, quoted in ampere-hours (A h), is equal to the amount of charge
delivered during discharge. The average voltage at which the charge is delivered
defines the amount of energy in the battery, where energy is the product of total
capacity and average voltage (W h). Specific energy is the energy per unit mass
(W h/kg). Energy density is the energy per unit volume (W h/L). Specific capacity
describes the capacity per unit mass (mA h/g). Volumetric capacity describes the
capacity per unit volume (mA h/cc). The terms anode and cathode refer to the
direction of charge transfer at the interface between the electrode and the solution,
strictly speaking, the terms should be interchanged during recharging. Potential
confusion is avoided by simply referring to the electrodes as negative or positive.
Cycling refers to repeated charge-discharge cycles. The host materials may be fully,
or only partially, charged/discharged during cycling. Cycleability refers to the
battery’s ability to perform numerous cycles without appreciable loss of original
capacity.
1.6
Scope of Research
The project includes the synthesis and characterization of new intercalation
materials, and their processing into battery electrodes in the form of pellets, in order
to develop accumulators exploiting lithium ion technology. The scope of this
research is to synthesize various types of cathode materials from metal salts (as a
metal source) and organic solvents (as a chelating agent). The synthesized cathode
materials will be characterized by different analyses and instrumental techniques
such as TGA-DTA (thermogravimetric-differential thermal analysis), X-ray
diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray
analysis (EDAX), and Brunauer-Emmett and Teller (BET) surface area. The
synthesized cathode materials used as the composite electrodes after cathode
19
fabrication. The synthesized cathodes were also characterized using various types of
electro-analytical techniques and the results were compared with those of the parent
cathode materials. The final step of the research is that the synthesized cathode
electrodes were examined systematically in order to evaluate electrochemical
performances of the lithium ion rechargeable battery. The focus of this work is on
the development of a desirable cathode or positive electrode materials for lithium-ion
batteries.
1.7
Research Objectives
Particularly the development of the active cathode materials preparation
method is based on the trial and error approach guided by the background reading of
the previous processes and reviewed articles. The following objectives have been
addressed to testify the hypothesis:
1. To synthesize new mixture of metal oxides for the cathode portion of Li-ion
battery
2. To make right combination of lithium with transition or nontransition metals
by sol-gel method
3. To characterize the synthesized materials with numerous techniques in order
to investigate the changes of physical and chemical properties
4. To increase the practical voltage around the theoretical voltage (6 volts)
5. To increase coulombic efficiency of Li-ion battery
1.8
Problems Statement and Solution Approach
The increased demand for power distribution systems, portable electronics
and zero emission vehicles has led to the examination of the electrochemical battery
as a solution to our energy storage needs. In particular, the rapid development in the
20
field of portable electronics including laptop computers, camcorders, cell phones and
wireless communication devices require high energy density batteries to power them.
Consumers have simple demands; they want a long lasting, lightweight, cheap, and
safe battery. To meet these demands, the development of rechargeable (secondary)
batteries has been the focus of considerable research. Portable, rechargeable lithium
ion batteries offer several advantages when compared to current primary and
secondary power sources. Lithium ion batteries have higher cell voltages 3.5-4.2 V
(Plicht et al., 1987; Megahed et al., 1995; Berndt, 1997), higher energy density and
longer cycle life. Improving the performance of current lithium-ion batteries in these
three areas (voltage, energy density, and cycle life) is very important.
However, it is crucial to improve both the safety aspects of this high voltage
system and the performance while using more abundant and low cost materials (Dai
et al., 2000). Many research groups have focused on improving the characteristics of
the positive electrode, particularly developing high voltage cathode materials.
Lithium manganese oxides spinel is an interesting and promising cathode material
for rechargeable lithium batteries (Thackeray et al., 1983; Tarascon et al., 1991;
Julien et al., 1999). In comparison with layered LiCoO2 and LiNiO2, its
three-dimensional structure permits a reversible electrochemical extraction of Li+
ions, at about 4 V versus Li/Li+, to Ȝ-MnO2 without lattice collapse (Thakeray et al.,
1984). Additional advantages are the relatively high theoretical capacity
(148 mA h/g), low cost with ease preparation and environmental harmlessness
(Tarascon et al., 1994).
A problem to overcome for commercial application of this material is its fast
capacity fading with charge/discharge cycling. This fact has been related to
instability of the active phase caused by several possible factors like a slow
dissolution of the cathode material into the electrolyte, high value of the relative
volume changes accompanying charge/discharge cycling, Jahn-Teller distortion
effect in deeply discharged electrodes (Rodriguez et al.,1998; Gummow et al.,1994).
Presently, the capacity of lithium-ion batteries is limited by the capacity of cathode
material. Though the commercially employed cathode, LiCoO2 for Li-ion batteries
21
has a theoretical capacity of 274 mA h/g, the practical attainable capacity is found to
be only 120-130 mA h/g in the voltage range 2.7-4.2 V (Fan et al.,1998). The other
viable and commercially available cathode material, lithium manganese oxide with
the spinel structure LiMn2O4, has a theoretical capacity of 148 mA h/g and its
practically attainable value is 100-120 mA h/g (Aurbach et al., 1999). In addition,
LiMn2O4 is found to be unstable on cycling and shows severe capacity fading
problems during cycling in the long run use. This can be overcome by doping
various types of metals such as Cr, Zn, Fe, Al, Ni, Ga, Mg, V, Cu in LiMn2O4. The
addition of dopants, may also decrease the initial capacity of the cell.
Amine et al., 1997 found a way to engineer a 5 volt battery to have
consistently high capacity for multiple cycles. They prepared LiNi0.5Mn0.5O4 using
sol-gel method and was the first made and tested in mid 1990s. The material has
been shown to have a high voltage reaction at 4.7 V. Doping of the transition metals
such as Ni, Fe, Co, Cr etc in lithium rich spinels considerably improved the
rechargeability on cycling but they delivered significant loss of the initial capacity.
An improved operational capacity may be achieved by using LiNiO2 and its
derivatives (Fan et al., 1998; Chowdari et al., 2001). The latter materials, however,
are not stable on cycling and their cathodic capacity fades drastically, especially
when charged and discharged at high current rates. The unsafe operation of these
materials is also of concern. Therefore, to realize cost effective Li-ion batteries, the
challenge is to identify an alternate cathode material with higher capacity which is
cheaper, safe and non-toxic to replace LiCoO2 (Shaju et al., 2002).
The stoichiometry, crystal structure and morphology of the active materials
are of essential importance for its electrochemical properties (Gadjov et al., 2004).
All these factors are closely related to the method of synthesis. Many procedures for
the preparation of cathode materials have been proposed in the literature during last
years. The classical ceramic synthesis by a solid-state-reaction between oxides
(Guan et al., 1998; Yamada et al., 2000) has been used extensively, but it requires
prolonged heat treatment at relatively high temperatures (>700 oC) with repeatedly
intermediate grinding. Moreover, this method does not provide good control on the
22
crystalline growth, compositional homogeneity, morphology and microstructure. As
a consequence, the final product consist in relatively large particles (>1 µm) with
broad particle size distribution.
In order to overcome these disadvantages, various preparative techniques,
known as “soft-chemistry” methods, have been developed. Such techniques are
based on the processes of co-precipitation, ion-exchange or thermal decomposition at
low temperature of appropriate organic precursors obtained by sol-gel synthesis
(Hernan et al., 1997; Kang et al., 2000), Xero-gel (Prabaharan et al., 1995), Pechini
(Liu et al., 1996; Liu and Kowal et al., 1996), freeze-drying (Zhecheva et al., 1999),
and emulsion-drying (Hwang et al., 1998) methods. This soft chemistry techniques
offer many advantages (Thirunakaran et al., 2004) such as better homogeneity, low
calcination temperature, shorter heating time, regular morphology, sub-micron sized
particles, less impurities, large surface area, and good control of stoichiometry.
In the last 20 years, the lithium-ion battery has become a highly researched
topic. The high voltage and energy capacity of the system classify the lithium-ion
battery as the most promising energy storage source. However, several
improvements must be made before the battery is recognized as a dependable power
source for all high voltage applications.
CHAPTER 2
LITERATURE REVIEW
2.1
Conventional and Advanced Methods to Prepare Cathode Raw Materials
A Brief Review
In recent years, electronic mobile devices have become omnipresent and rapid
progress in various types of mobile devices has yet lead to the fast development and
commercialization of secondary batteries. Among them, lithium-ion batteries have been
produced on large scale and used extensively in the commercial mobile devices since
they have high working voltage, large capacity, and no memory effect compared with
other candidates such as metal-hydride batteries and nickel-cadmium batteries.
Among the components of lithium-ion batteries, the positive-electrode (cathode)
material attracts much attention. This is because the composition and structure of the
cathode plays a crucial role in effective lithiation and delithiation during the respective
charge and discharge processes. Numerous forms of lithium compounds such as
LiCoO2, LiNiO2, and LiMn2O4 (Naganuraaftd et al., 1991; Ebner et al., 1994; Tarascon
et al., 1991) have been developed for high specific energy and better structural stability.
Scientific and commercial interest has continued to increase this year for Li batteries.
Work in this area is very diverse, including the manufacture of prototype commercial
24
products, further studies of existing materials and the search for new improved Li
intercalation hosts.
This review will concentrate on specific areas of work reported. In recent years,
several low temperature preparation methods, such as sol-gel synthesis (Pereira-Romas,
1995), precipitation (Barboux et al., 1991), the pechini process (Liu et al., 1993), and a
hydrothermal method (Whittingam, 1996) have been used to prepare Lithium-MetalOxides spinels. Among them sol-gel method is a very widely spread technique for both
powders and film preparation due to some well known advantages: offers an easy way
to obtain homogenous distribution of precursors, the possibility to introduce controlled
amounts of dopants, chemical methods of reaction control, viscosity advanced control
as well as low processing temperature (Brinker and Scherer,1990). Lithium battery can
theoretically hold up to 6 volts energy (e.g., an Li/F2 battery); however, no massproduced rechargeable battery has yet been able to surpass more than 4 V. Amine et al.,
1997 of the Fundamental Technology Laboratory in Japan, found a way to engineer a 5
volt battery to have consistently high capacity for multiple cycles. The spinel oxide
materials they used, LiNi0.5Mn1.5O4 was prepared using a sol-gel method and was first
made and tested in the mid 1990s. The material has been shown to have high voltage
reaction at 4.7 V, which approaches 5 V (Amine et al.,1997).
Sun et al., 2004 have prepared a series of spinel-structured LiMn2-x-yNixCryO4
and their electrochemical performances as 5 V cathode materials for lithium ion
batteries are evaluated. The synthesis reactions for these materials are characterized by
TG/DSC, XRD and SEM. TG/DSC measurements show that the chemical reactions for
the final product are completed below 400 oC. XRD analysis indicates that spinel
structure is formed at around 650
o
C. However, SEM images show well-defined
polyhedron crystalline particles do not appear until 800 oC. Electrochemical evaluation
shows that LiMn1.4Ni0.4Cr0.2O4 prepared at 850 oC boasts the best electrochemical
performance with an initial discharge capacity of 128 mA h/g and a capacity retention of
more than 90 % after 230 cycles between 3.5 and 4.98 V.
25
By using conventional melt-impregnation method Denga et al., 2005 have
prepared LiMn2O4 spinel having the high rate capacity. Especially the high rate
discharge performance is another important aspect for the application of Mn-based
spinel cathodes for EV/HEV power sources besides the cycling performance that is now
intensively investigated. In this paper, spinel materials differing in chemical
composition and thermal processing history were investigated by discharging at constant
current rates from C/10 to 4 C at ambient temperature. It was found that the high-rate
discharge capability of Mn-based spinels is very excellent if prepared at temperatures
below 850 oC, no matter cation doping or not. In contrast, spinels synthesized over
950 oC showed much poorer high rate performance, and some kinds of impurities were
proposed to be responsible for the deteriorated behavior. Annealing at lower
temperatures was found to be useful for the significant improvement of the high rate
discharge capability of Mn spinels.
LiNi0.8Co0.2-xAlxO2 cathodes (x = 0.00, 0.01, 0.03, 0.05), which consist of sub
micron particles, are fabricated by a sol-gel method (Han et al., 2004). The structural
and electrochemical properties are investigated to examine the effect of Al doping on
initial discharge capacity and its retention. The cathodes are single-phase compounds
regardless of Al content in the range x = 0.05 and crystallize in a layered structure
(space group, R-3m). The initial discharge capacity decrease as the aluminum content is
increased. On the other hand, charge–discharge cycling performance is improved. There
is a small capacity loss in the cycle tests between 3.0 and 4.3 V. The relative
improvement due to Al doping is more pronounced in the higher voltage range
(3.0-4.5 V). The slow degradation of the electrochemical property of Al-doped
LiNi0.8Co0.2-xAlxO2 during cycling is attributed to the suppression of phase transitions by
maintaining the layered structure.
LiNi0.8Co0.2O2 as the cathode material for a lithium ion battery was prepared by
two different methods (Gong et al., 2004), sol-gel method and the solid-state reaction
process. The samples were characterized and tested by means of XRD, SEM, particle
size analysis, BET, and electrochemical methods. The results of XRD show that both
26
the LiNi0.8Co0.2O2 samples prepared by two different methods are iso-structural with
Į-NaFeO2 with a space group R-3m. The results of electrochemical studies show that
the sample prepared by the solid-state reaction process is superior to that by the sol-gel
method in electrochemical performance.
LiNi0.5Mn0.5-xTixO2 series was prepared by a simple solid state method using
MnO2, TiO2 and nickel carbonate basic as the starting materials (Decheng et al., 2004).
Its structural and electrochemical characteristics were also studied and compared with
those prepared by the spray dry method. As Ti content increases, the degree of cation
mixing increases and the structure of compound transforms gradually from a layered
structure to a disordered rock salt structure. There are two plateaus in the initial charge
curve for compounds with x < 0.3. One is around 4.0 V and the other is around 4.6 V.
Both the initial charge and discharge capacities decrease as Ti content increases.
Compounds with x < 0.3 exhibit good cyclic performance at room temperature.
Ning et al., 2004 have proposed mechanochemical methods to prepare materials
for lithium ion batteries. Compared with conventional solid-state reaction, the
mechanochemical methods appear to accelerate and simplify the synthesis process and
decrease the energy expenses as well as the cost of the materials. Furthermore, the
prepared materials also present good electrochemical performance. For example,
cathode materials such as LiMn2O4 spinels present better cycling behavior due to the
highly disordered nanocrystallines which can accommodate the Jahn-Teller distortions.
Li[NixLi(1/3-2x/3)Mn(2/3-x/3)]O2 (x = 0.17, 0.25, 0.33, 0.50) compounds have been
prepared (Park et al., 2004) by a simple combustion method. Compared with the mixed
hydroxide or sol-gel method, the combustion method is very simple, and will therefore
reduce the manufacturing cost of the cathode material. The structural and
electrochemical properties of the samples were investigated using X-ray diffraction
spectroscopy (XRD) and the galvanostatic charge-discharge method. Rietvelt analysis of
the XRD patterns shows that these compounds can be classified as Į-NaFeO2 structure
type. Compounds with high Ni content (x = 0.25-0.50) in Li[NixLi(1/3-2x/3)Mn(2/3-x/3)]O2
27
appear to be composed of two phases, namely Ni-rich and Ni-deficient phases with the
same Į-NaFeO2 structure. By contrast, the Li[Ni0.17Li0.22Mn0.61]O2 compound with a low
Ni content has good phase integrity with only a single phase. The initial chargedischarge and irreversible capacity become larger as x in Li[NixLi(1/3-2x/3)Mn(2/3-x/3)]O2
decreases. The Li[Ni0.50Mn0.50]O2 compound has a relatively low initial discharge
capacity of 200 mA h/g and exhibits a large loss in capacity during cycling. On the other
hand, Li[Ni0.17 Li0.22Mn0.61]O2 and Li[Ni0.25Li0.17Mn0.58]O2 compounds give high initial
discharge capacities of over 245 mA h/g and a stable cycle performance in the voltage
range 4.8-2.0 V. The XRD and electrochemical results suggest that the simple
combustion method is more appropriate for synthesizing Li[NixLi(1/3-2x/3)Mn(2/3-x/3)]O2
compounds with low Ni content.
The structural changes of spinel Li1.02Mn2O4 and Li1.02Co0.11Ni0.0.4Mn1.85O4
cathode materials have been studied by synchrotron powder X-ray diffraction and
differential scanning calorimetry (DSC) measurements (Tsai et al., 2003). The results
show that spinel Li1.02Mn2O4 undergoes a phase transition from cubic (Fd3m) to
orthorhombic symmetry (Fddd) at T = 285 K. However, substitution of a small amount
of Co3+ and Ni3+ ions suppresses phase transition and the cubic phase is maintained at
low temperature due to a decrease in the concentration of Jahn -Teller active Mn3+ ions.
Gering et al., 1975 reported that John-Teller effect is a phase transition which is
driven by the interaction between the electronic states of one of the constituent species
of ions in a solid and the collective lattice vibrations or phonons. The phase transition
may be of first or second order and in both these cases involves a symmetry-lowering
distortion of the crystal lattice and a splitting of the electronic energy levels. The names
of Jahn and Teller are associated with the effect because in 1937 they showed that in the
presence of a low-lying electronic degeneracy molecules are unstable with respect to
some distortion.
Ting-Kuo Fey et al., 2003 have synthesized LiNi0.8Co0.2O2 by a sol-gel method
with maleic acid as chelating agent, was investigated using galvanostatic charge
28
discharge cycling and electrochemical impedance spectroscopy. The impedance
response was found to be dependent on the extent of intercalation and deintercalation,
although it was independent of the electrolyte composition. However, the chargedischarge behavior of the cathode material was found to be dependent on the electrolyte
composition. Cells with 1 M LiPF6 in EC: DEC gave the height capacity. With this
electrolyte, the first cycle discharge capacity was 187 mA h/g. The first cycle capacities
obtained with the others electrolytes were lower, between 174 and 182 mA h/g. The
impedance parameters of the system at the different levels of intercalation and
deintercalation were derived using equivalent circuits models.
Zheng et al., 2002 proposed Li1.03Mn1.97O4 spinel material coated with a thin
layer of SiO2 by a sol-gel method. The surface modification was found to reduce the
Mn2+ dissolution into the electrolyte according to the inductively coupled plasma (ICP)
analysis results and improve the capacity retention of the Li1.03Mn1.97O4 spinel. The
structure and properties of the coating materials were also investigated by X-ray
photoelectron spectra (XPS) analysis, X-ray diffraction (XRD) patterns and
transmission electron microscope (TEM).
Single-phase lithium nickel oxides with the formula LiNi0.8Co0.2-2yTiyMgyO2,
y = 0.00-0.075 have been prepared and characterized (Chowdari et al., 2001). Their
electrochemical properties as cathode during charging and discharging are discussed.
Thermal behavior of the charged cathodes was studied by differential scanning
colorimetry DSC. Results show that the cathodic behavior of compounds with y = 0.00
and 0.03 and those with y = 0.05 and 0.075 are similar with respect to the initial
irreversible capacity, suppression of phase transitions, cycling behavior and capacity
fading. The composition with y = 0.05 shows a cathodic capacity of 120 mA h/g at the
0.5 C rate and 2.5-4.4 V window with only 7 % fading over 40 cycles. The thermal
behavior of the charged cathode with y = 0.05 is improved compared to y = 0.00 and
0.03. A qualitative explanation for the observed cathodic behavior with various y values
is offered in terms of the occupancy of the magnesium-ions in the Li and Ni layers in the
lattice.
29
Cho et al., 2001 prepared coated LiNiO2 by a thin film of ZrO2 using a sol-gel
method. The ZrO2 coated LiNiO2 can effectively suppress lattice distortion and the
consequent phase transition. As a result, the cycling performance is greatly improved,
with only 2 % capacity loss after 70 cycles when cycling between 4.3 and 2.75 V. Other
kinds of oxides can be coated by sol-gel methods, but one thing should be taken into
consideration, namely that the coating should be situated at the surface of the LiNiO2
particles.
By using solution technique Yu et al., 2000 doped simultaneously magnesium
(Mg) and gallium (Ga) at the Ni-site in LiNiO2 and tried to improve the cathode
performance, in view of the recent reports that Ga or Mg dopants can suppress the
crystallographic phase transitions and decrease the irreversible capacity. The results
show that co-doping (2 atom % Ga and 3 atom % Mg) definitely has a large beneficial
effect in increasing the capacity (150 mA h/g) and cycling behavior. Comparison of the
differential capacity vs. voltage curves for pristine and co-doped LiNiO2 show
suppression of the phase transitions and stabilization of the hexagonal 2 (H1) phase.
Differential scanning colorimetry (DSC) data indeed confirm the above by way of
increased thermal stability of the charged cathode.
Harish Baht et al., 2000 used a novel microwave method for the preparation of
electrode materials required for lithium batteries. The method is simple, fast and carried
out in most cases with the same starting material as in conventional methods. Good
crystallinity has been noted and lower temperatures of reaction has been inferred in
cases where low temperature products have been identified.
2.2
Cathode Raw Materials for Lithium-ion Batteries
Cathode materials for lithium-ion batteries are strongly oxidizing in nature and
have a high reversible lithium intercalation voltage (above 3.0 V vs. Li). They may be
30
divided in three big groups: LiMO2 types of oxide (i.e., LiCoO2 and LiNiO2)
compounds, lithiated manganese oxides (i.e., LiMn2O4) and other materials. Among
these materials, LiCoO2 was used in the first commercial lithium-ion battery (Sony), and
currently is used by most lithium-ion battery manufacturers as a cathode material. It is
preferred for its electrochemical properties, although it is relatively expensive and
environmentally not quite kind. Nickel compounds are relatively inexpensive but much
more difficult to synthesize. For future lithium-ion batteries, the LiMn2O4 compounds
are favored over the other two compounds, based on abundance, ease of preparation,
material cost, and environmental friendliness (Shokoohi et al., 1995). However, much
work still has to be done to ensure stable performance of manganese oxides over a wide
range of operating conditions. The properties of these materials will be discussed in the
following sections.
2.2.1 LiMO2 Materials
Only high voltage LiMO2 materials are to be discussed in this section. Certain
transition metals which have high molecular weight e.g., LiWO2, LiMoO2, and LiRuO2
intercalate lithium at low voltage (lower than 2 V vs. Li) are not suitable for cathode
materials). LiVO2 and LiCrO2 are almost inactive in non-aqueous lithium cells. Layered
metal oxides of this type LiMO2 ( M = Co or Ni) have a rhombohedral structure
(Reimers et al.,1992; Ohzuku et al., 1993) in which lithium and transition metal atoms
are ordered alternate (111) planes in a slightly distorted cubic-close packed oxygen ion
array. In other words, transition metal ions and lithium ions locate at octahedral 3 (a)
and 3 (b) sites, respectively, and oxygen ions at 6 (c) sites (Figure 2.1). The layered host
framework provides a two-dimensional interstitial site that allows for the
intercalation/de intercalation of guest metal ions.
31
Figure: 2.1: Structure of the rhombohedral elementary cell of LiMO2 oxides
In the following subsections, LiCoO2, LiNiO2, and their derivatives will be
discussed in details.
2.2.1.1 LiCoO2
The lithium cobalt oxide was first described in 1980 (Mizushima et al., 1980)
and is used currently by most lithium-ion battery manufacturers as a cathode material. It
has a theoretical capacity of 274 mA h/g, which corresponds to complete lithium
removal (to x =1) in LixCoO2. However, due to structural restrictions, the amount of
lithium that may be removed and inserted reversibly is much smaller (normally~55 %).
In general a maximum of around 150 mA h/g may be reversibly cycled over many
charge/discharge cycles without major capacity degradation. In the same rate
32
insertion/extraction, the nominal reversible specific capacity lies in the range of
120~140 mA h/g.
Various synthesis routes have been explored to improve the electrochemical
performance of LiCoO2, including conventional ceramic technique with different
precursor materials such as carbonate mixtures (Ohzuku et al., 1990), nitrate mixtures,
LiOH and either carbonate (Antaya et al., 1993), an oxide or the nitrate of cobalt
(Xia et al., 1995). Generally the different procedure of high temperature synthesis has
little or no effect on the electrochemical performance of the LiCoO2 material since
essentially identical results are obtained. Reports on materials prepared at low
temperature show mostly higher initial capacity than materials prepared
at high
temperature. However, their capacity becomes limited in the following a number of
cycles.
The structural information about LiCoO2 and the structure changes during
lithium intercalation and extraction have been studied in details (Reimers et al., 1993).
This material has lattice parameters of a | 2.826 Å and c | 14.08 Å (Mizushima et al.,
1980). The effect of synthesis temperature (high and low) on the structural parameters
has also been discussed in the literature (Gummow and Thackeray, 1993). Lithium ion
transport (Thomas et al.,1985) has been described.
The formation of interfacial layers on LiCoO2 influences the insertion properties
(Thomas et al., 1985). The formation of the cathode electrolyte interfacial layer formed
by reaction between electrolyte (1 M LiBF4 / PC) and cathode components was studied
by EIS measurements. The layer has characteristics resembling those of the solid
electrolyte interface (SEI), in a model originally proposed by Peled and co-workers
(Peled, 1983) to characterize the interfacial properties between metallic lithium and nonaqueous electrolytes. The cathode interfacial layer model was expected to moderate the
electrochemical properties of the LiCoO2 composite electrode. The surface of the
composite cathode in contact with electrolyte has also been characterized by electron
micrography (Thomas et al.,1985). The thermal characteristics of LiCoO2 during
33
cycling have been investigated by various researchers using colorimetric techniques
applied to a LiCoO2 / Li half cell.
2.2.1.2
LiNiO2
Dyer et al., 1954 prepared this material first. LiNiO2 exists in two structural
modifications (rock-salt type and layered type), of which only the layered one is
electrochemically active (Ohzuku et al., 1991). The theoretical capacity of material is
close to that of the LiCoO2 compound, i.e., | 275 mA h/g. For similar reasons as in the
case of the cobalt compound, only a limited amount of capacity (~150 mA h/g) is
available in the actual cell test within the voltage range 2.5 V and 4.2 V (Xie et al.,
1995; Dahn et al., 1991; Sekai et al., 1993; Li et al., 1993). However, the reported
overall reversible specific capacity is 10~30 mA h/g higher than that of LiCoO2.
Generally good charge retention is observed after 100 cycles (Xie et al., 1995).The
cycle life is strongly dependent on the depth of decrease (Yamada et al.,1995). When
the capacity was restricted to about 100~120 mA h/g, high cycles number was achieved,
however, only a few cycles are possible at higher capacities. In addition to the
electrochemical activity for x < 1 in LixNiO2, LiNiO2 can react with lithium, forming a
voltage plateau near 1.9 V. This reaction is reversible but induces a large hysteresis in
the voltage for x < 1 (Dahn et al.,1990).
LiNiO2 compounds appear to be more difficult to synthesize than lithium cobalt
oxide, in electrochemically active form capable of reversible lithium insertion to a
significant extent. Unlike LiCoO2, the LiNiO2 compound needs to be prepared under
specially controlled strongly oxidizing conditions. Synthesis may start from hydroxide
mixtures annealed in O2 atmosphere (Xie et al.,1995; Nohma et al.,1995), or from
hydroxide and nitrate (Ohzuku et al.,1991; Moshtev et al.,1995) or use Na2O2 and a Ni
source (Nagura,1991; Sekai et al.,1993 ), followed by ion exchange with LiNiO3 at
elevated temperature.
34
Structural information on LixNiO2 with various x in the range of 0 d x d 2 was
prepared by several research groups. LixNiO2 has a structure closely related to rock-salt
structure, with a | 2.88 Å and c | 14.19 Å as lattice constant. The unit cell dimension of
LiNiO2 (ah = ~2.9 Å and ch = ~14.2 Å; ch / ah = 4.9 in hexagonal setting) are very close
to the corresponding value of cubic unit cell (ac = ch / 2
3 = ~ 4.1 Å), suggesting that
the displacement of nickel and lithium ions occur easily without a dimensional
mismatch compared to that for LiCoO2. This makes the preparation of electrochemically
active LiNiO2 difficult. The diffusivity of lithium ion in LixNiO2, D Li+, was measured
by EIS technique (Bruce et al., 1992) and has the value of ~10-7 cm2/s. Some other
physical/chemical properties were reported in a number of references (Reimers and
Dahn et al., 1993). The temperature of exothermic reaction is lower (~220 oC) and the
DSC peak is sharper than that of LiCoO2 (~250 oC) (Dahn et al., 1994; Zhang et al.,
1998). So, the use of LixNiO2 as a direct substitute for LixCoO2 raises safety concerns.
2.2.1.3 LiMO2 (M = Co, Ni) Derivatives
To improve the reversible capacity of either LiCoO2 or LiNiO2, many attempts
have been made to partial by substitute Co and Ni with each other, and with transition
metals such as Cr (Jones et al., 1994), Mn (Nitta et al., 1995; Rossen et al., 1992; Spahr
et al.1998), and Fe (Remiers, Dahn and Greedan et al., 1993). The most promising
result is the LixNiyCo1-yO2 series of compounds. Extensive studies have shown that
electrodes with 0 < y < 1 perform better on electrochemical cycling than the end
members of the system i.e., LiCoO2 (y = 0) and LiNiO2 (y = 1). The effect of synthesis
temperature on this material was investigated at small values of x (Gummow et al.,
1993) because of their (low temperature synthesis) lower insertion potential (better
electrolyte stability) compared to that for the pure cobalt oxide phase. Mixed oxides
with large values of y, in other words nickel rich materials are easier to prepare than the
pure nickel oxide. Nickel rich samples, LixNiyCo1-yO2 (0.7 < y < 0.9), showed cycle
performance
compared
with
LiCoO2
but
substantially
higher
capacity
35
(150~200 mA h/g) than LiCoO2 (140 mA h/g). They also showed the good capacity
retention at high rate (1 C, where C = numerical value of rated capacity of a cell or
battery) (Li and Currie,1997). This opens the possibility of them being used in high
power applications. Additionally, Co substitution in LixNiO2 induces greater thermal
stability. For y = 0.8 (LiNi0.8Co0.2O2), the exothermic peak shifts to higher temperature
(~235 oC) and peak height is reduced significantly (Gao et al.1998).
With the exception of cobalt, substitution of transition metals in LiNiO2 appears
to result in materials characterized by lower capacities and less reversible insertion/
extraction. Furthermore, as a general trend increased concentration of the substitutional
metal appears to have a negative effect on the specific capacity, beyond a certain
optional level of satisfaction. Gao et al., 1998 reported on Ti and Mg substituted nickel
oxide, LiyNi1-xTix/2Mgx/2O2. This material, (at 30 % substitution) showed superior
thermal stability compared to LiNiO2, LiNi0.8Co0.2O2, and LiCoO2. No exotherm was
observed up to 400 oC for this material in its totally charged state (charged up to 4.5 V),
which is mostly unstable state. The price for this improvement in thermal stability in
terms of specific capacity is not significant. LiNi0.75Ti0.125Mg0.125O2, for example, shows
a reversible capacity of 190 mA h/g and stable cycling has been demonstrated in the
voltage window between 3.0 and 4.4 V.
2.2.2 Spinel Manganese Oxide
Considerable work has been focused on characterization and optimization of the
lithiated manganese oxides. Although the reversible specific capacities for the
manganese oxides are lower than the theoretical capacity of the cobalt and nickel
oxides, they have the merit of being the least costly among the commonly available
cathode materials. Additionally, while cobalt and nickel oxides are relatively toxic,
manganese oxides are environmentally benign. Most research has concentrated on the
spinel phase LixMn2O4. This spinel has two different reaction voltages (3 V and 4 V),
36
with large gap (1 V) in between. Significant efforts have been expanded to extend the
capacity of the initial 4 V discharge by including the three plateau without major loss of
the specific capacity (Kang et al., 2000; Sun et al., 2000). The structure of the
delithiated spinel (x < 1) has also been studied (Hunter 1981). Both the 3 V volt plateau
(Baochen et al., 1993; Barboux et al., 1991) and the 4 V plateau (Barker et al., 1995;
Gummow et al., 1994; Hwang et al., 1994) were most extensively investigated
respectively.
LixMn2O4 has a cubic spinel structure that possesses prototypic symmetry. The
ideal spinel structure consists of a cubic closed-packed array of oxygen ions, which are
face-centered. In a unit cell of spinel there are 32 octahedral interstices and 64
tetrahedral interstices. In a binary oxide spinel the general formula is AB2O4. A unit cell
containing 32 oxygen ions, (32e), 16 octahedral cations (16d), and 8 tetrahedral cations
(8a) is constructed by eight of elementary cells (sub-cells). The cations, A and B, in the
spinel structure are placed at different types of sites (interstices), namely, octahedral
interstices and tetrahedral interstices. As shown in the sub cell of Figure 2.2, one eighth
of the tetrahedral and one half of the octahedral interstices are occupied by cations. For
a sub cell of this structure there are four anions, four octahedral interstices, and eight
tetrahedral interstices. This makes, for a total of twelve interstices, to be filled by three
cations, one divalent (A) and two trivalent (B).
In each elementary cell (sub-cell) two octahedral sites and one tetrahedral site
are filled. As octahedral interstices (16d), the interstitial octahedral sites (16c) share six
common edges, among themselves, they also share two common faces having opposite
side with occupied tetrahedral sites (8a), and the other faces with empty interstitial
tetrahedral sites (48f). Finally empty tetrahedral sites (8b) share four faces with
occupied octahedral sites (16d). The diamond type network represented by the
interstitial spaces of the spinel framework, which consists of tetrahedral 8a and
surrounding octahedral 16c sites, offers 3D (3-Dimensional) pathways for Li+ ions. One
may modify the redox potential of an electrode by using various transition-metal ions
which prefer octahedral sites (16d). The 3D structure also allows the electrode to expand
37
and contract isotropically during lithium insertion /extraction processes into or out of the
electrode.
Oxygen
(B) Cation in octahedral
(A) Cation in tetrahedral
Octahedral interstice
(32 per unit cell)
Figure: 2.2:
Tetrahedral interstice
(64 per unit cell)
Structure of spinel unit cell (AB2O4)
In the LixMn2O4 spinel, lithium ions are monovalent only but manganese ions
have two different valences. They are positioned in tetrahedral sites (Li+ ion) and
octahedral sites (Mn3+and Mn+4 ions), respectively in the spinel framework,
Lix[Mn3+Mn+4]O4. The theoretical capacity of LixMn2O4 is 148 mA h/g when 1 mol of
Li is cycled (insertion/extraction). This reaction occurs around 4 V. Around 3 V,
additional lithium (1< x < 2) can be inserted and extracted with corresponding capacity
of 150 mA h/g. The theoretical capacity may be reached at very low rate, but even at
38
these rates extended cycling usually causes a concurrent capacity fade. Normally, about
80 % of theoretical capacity is achieved around 4 V. The utilization of capacity in 3V
range is much lower than at 4 V, and the capacity fading upon extended cycling is
usually faster. Thackeray et al.,1992 proposed that Jahn-Teller distortion is responsible
for the poor cycling behavior of LixMn2O4 in the 3 V range. When additional lithium is
inserted, the average manganese valency is decreased below 3.5+. As soon as the
manganese valency reaches 3.46+, a strong Jahn-Teller distortion occurs that changes
crystal symmetry from cubic of tetragonal. To stabilize the 3 V capacity of LixMn2O4
(1< x < 2), various routes have been explored such as controlling synthesis condition
(Tarascon et al., 1991), conducting different synthesis methods (Kang et al., 2000),
using alternative precursors and doping (Sun et al., 2000) by various elements. The
diffusion coefficient of Li+ in the spinel has been measured by various electrochemical
techniques.
CHAPTER 3
MATERIALS AND METHODS
3.1
Chemicals and Reagents
Metal sources for the cathode raw materials were from manganese nitrate,
Mn(NO3)2.4H2O (98.5 %, Merck, Germany); lithium nitrate, LiNO3 (98 %, Scharlau,
Spain); lithium acetate, CH3COOLi.2H2O (99 %, Fluka); manganese acetate,
(CH3COO)2Mn.4H2O (Merck, Germany); cobalt nitrate, Co(NO3)2.6H2O (97 %, BDH
Limited, Poole, England); aluminium nitrate, Al(NO3)3.9H2O (95 %, Merck, Germany);
chromium nitrate, Cr(NO3)3.9H2O (99 %, Riedel-deHaën, Germany); and lithium
hydroxide, LiOH.H2O (99 %, BDH, England). The reagents used as organic carriers
(chelating agents) were citric acid, C6H8O7.H2O (99.7 %, BDH, England); propionic
acid, C3H6O2 (99 %, Riedel-deHaën, Germany) and ethylene glycol, HOCH2CH2OH
(99.5 %, Merck, Germany). Ammonia solution (25 %, Merck, Germany) used as pH
controlling agent. Lithium hexafluorophosphate, LiPF6 (99.99 %, Aldrich, USA);
ethylene carbonate C3H4O3 (99 %, Fluka, Switzerland); dimethyl carbonate, C3H6O3
(99 %, Fluka, Switzerland) and polyvinylidene fluoride, (-CH2CF2-) n (Aldrich, USA)
used to fabricate the cathode and cell.
40
3.2
Instruments
The instruments used to prepare and characterize cathode raw materials, cathode
and cell were muffle furnace (Carbolite muffle furnace, model: ELF 11/6B, Barloworld
Scientific, England); Pulse Chemisorb 2705 Micromeritics (Micromeritics Instrument
Corporation, USA); Scanning Electron Microscope (SEM) (Philips, model XL 40)
incorporated with energy dispersive X-ray analysis (EDAX) (EDAX Inc. USA); Perkin
Elmer Diamond Thermogravimetric/Differential Thermal Analyzer (Model: Pyris
Diamond TG-DTA, High Temp.11, Japan); Cyber Scan pH/Ion 510 pH meter (Eutech
Instruments); X-ray Diffraction (XRD), (Bruker HR X-ray Diffractometer, Germany)
and Solartron 1470 Battery Testing System
3.3
Research Design and Methodology
The preliminary step is to synthesize the cathode raw materials from various
metal salts and different organic solvents. Prior to the calcination of the raw materials,
the TG-DTA analysis of the gel precursors was first performed. After the calcination
characterizations of the raw materials were carried out using various techniques. The
characterization includes BET surface area, X-ray diffraction (XRD), scanning electron
microscopy (SEM), energy dispersive X-ray analysis (EDAX) and electrochemical
characterizations. The crucial step in this research is to fabricate a cathode from cathode
raw materials. After this step the cathodes were used to fabricate a satisfactory full cell
and then the electrochemical characterizations were performed. Finally, the cathodes
were used to fabricate the Li-ion battery. Figure 3.1 shows the methodology scheme of
overall research.
41
TG-DTA
Metal Salts
Organic Solvents
BET
Cathode Raw Materials
XRD
SEM
Characterizations
EDAX
Cathode Fabrication
Cell Fabrication
Cycleability
Charge Capacity
Discharge Capacity
Figure 3.1:
Charge-Discharge
Cycling
Electrochemical
Characterizations
Battery Fabrication
The methodology scheme of overall research
42
3.4
Preparation of Cathode Raw Materials
At the initial stage, various types of raw materials for cathode were prepared
using the original sol-gel method with various conditions. This technique offers better
homogeneity, preferred surface morphology, reduced heat treatment conditions,
sub-micron sized particles and better crystallinity.
3.4.1
Sol-Gel Method
Metal salts (as a metal source) and different organic acids/solvents used as a
chelating agent for sol-gel synthesis. The general work flow to prepare cathode raw
materials by a sol-gel method is showed in Figure 3.2. The preparation conditions of the
cathode raw materials studied in this work are summarized in Table 3.1.
A stoichiometric amount of the metal salts with appropriate cationic ratio were
dissolved in distilled/de-ionized water and mixed well with an aqueous solution of
organic acid/organic solvents and the optimum pH was also adjusted. After evaporation
at 70-80 oC for 5 to 6 hours, a transparent sol was obtained. This sol was dried in oven at
100 oC for 24 hours. Firstly, it became viscous gel and finally dried solid. This dried
precursors was ground prior to the calcination at different temperatures.
43
Aqueous solution of metal salts
Aqueous solution of organic acids
Mixing and pH control
Aqueous solution of metal salts & organic acid /organic mixture
Evaporation at 70-80 oC
Transparent sol of metal salts & acid mixture /organic mixture
Drying in oven at 100 oC
Gel precursors
Again drying in oven at 100oC
Dried precursors
Grinding
Precursor powders
Calcination at 250-850 oC
Polycrystalline composite
cathode materials
Figure 3.2: A flow diagram of cathode raw materials preparation
44
Table 3.1:
Preparation conditions of various types of cathode raw materials
6-7
Eva.
time
(hrs)
5
250
300
400
450
Res.
time
(hrs.)
5
CA-EG
6-7
5
250
300
400
450
5
1.0
CA-EG
6-7
5
250
300
400
450
5
0.5
CA
6-7
5
300
500
600
700
10
LiMn2O4
1.0
CA
6-7
5
300
500
600
700
10
(CA assisted)
1.5
CA
6-7
5
300
500
600
700
10
0.5
PA
6-7
5
350
450
650
750
5
LiMn2O4
0.83
PA
6-7
5
350
450
650
750
5
(PA assisted)
1.5
PA
6-7
5
350
450
650
750
5
2.0
PA
6-7
5
350
450
650
750
5
0.0
PA
7-8.5
5
400
600
800
-
4
Cr doped
0.01
PA
7-8.5
5
400
600
800
-
4
LiCrxMn2-xO4
0.02
PA
7-8.5
5
400
600
800
-
4
0.05
PA
7-8.5
5
400
600
800
-
4
0.1
PA
7-8.5
5
400
600
800
-
4
0.2
PA
7-8.5
5
400
600
800
-
4
-
CA
1-2
6
350
550
750
5
-
PA
1-2
6
350
550
750
5
Raw materials
M.
ratio
Chela.
agents
pH
LiMn2O4
0.25
CA-EG
(CA-EG
0.5
assisted)
LiCo0.7Al0.3O2
Calcination temperatures
(oC)
(CA assisted)
LiCo0.7Al0.3O2
(PA assisted)
Chela.agents = Chelating agents
Eva.time = Evaporation time
Res. time = Residence time
M. ratio (Molar ratio) : Chelating agent concentration to total metal ions ratio
Evaporation temperature for all samples : 70-80 oC
Drying temperature for all samples : 100 oC
Duration of drying for all samples : 24 hours
Ramping rate for all samples : 5 oC /min
45
3.4.2 CA-EG (Citric Acid-Ethylene Glycol) Mixture Assisted, Sol-Gel Route for
the Preparation of LiMn2O4 Cathode Raw Materials
Polymeric carriers are used for sol-gel methods, and there is little difference in
the process depending on the polymers used. A stoichiometric amount of lithium acetate
and manganese acetate salts with the cationic ratio Li:Mn = 1:2 were dissolved in 50 mL
distilled water separately and then mixed well. Organic mixture (citric acid-ethylene
glycol mixture, 50 mL) was added to the solution with constant stirring to ensure the
homogeneous distribution of metal ions and partially neutralized (pH = 6.00-7.00) to
form a complex of citric acid with metal ions. The mixture solution was heated to
esterify and with the progress of esterification the viscosity increased gradually, and this
ensured the homogeneous distribution of cations in the complex. A subsequent
condensation process removed the additional ethylene glycol to form a bulky glass. This
glass is very stable.
Finally the mixture was dried at 100 oC for 24 hours in a vacuum dryer to yield
gel precursors. For the preparation of the gel precursors with different molar ratio of
citric acid-ethylene glycol mixture to total metal ions, the same procedure was repeated
and organic mixture to total metal ions ratio of 0.25, 0.5, 1.0 samples were prepared
using 0.42 M, 0.84 M, and 1.65 M organic mixture (citric acid-ethylene glycol mixture),
respectively. The gel precursors obtained were decomposed at 250-450 oC for 5 hours in
the furnace to obtain polycrystalline powders and was reserved for characterizations.
3.4.3 CA (Citric Acid) Assisted, Sol-Gel Route for the Preparation of LiMn2O4
Cathode Raw Materials
LiMn2O4 powders were prepared according to the procedure as shown in the
Figure 3.2. A stoichiometric amount of lithium hydroxide and manganese acetate salts
with the cationic ratio Li:Mn = 1:2 were dissolved in 50 mL distilled water separately
46
and mixed well with 50 ml of various concentration of citric acid. Citric acid was used
as a chelating agent in making gel. Ammonia solution was slowly added to this solution
with a constant stirring until a pH of 6.0-7.0 was achieved. Different conditions for the
preparation, such as the pH, the molar ratio of carrier to total metal ions, the amount of
water, the calcination temperatures and the starting materials can affect the purity of this
oxide. In the case of the pH, it can affect the solubility of LiOH, the carrier and Mn2+.
When it is below 6.00, the solubility of the organic carrier will be low, and LiOH will be
soluble in aqueous solution. When it is greater than 10.0, the organic carrier will be
soluble in aqueous solution, Mn2+ and Li+ will be precipitated, and a stable complex will
not be formed. The solution was evaporated at 70-80 oC for 5 hours until a transparent
sol was obtained. To remove water in the sol, the transparent sol was dried at 100 oC for
24 hours in a vacuum dryer to yield gel precursors. For the preparation of the gel
precursors with different molar ratio of citric acid to total metal ions, the same
procedure was repeated and citric acid to total metal ions ratio of 0.5,1.0,1.5 were
prepared using 0.84 M, 1.67 M and 2.51 M citric acid, respectively. The gel precursors
obtained were decomposed at 300-700 oC for 10 hours in the furnace to obtain phasepure polycrystalline powders. After the calcinations, the powders were slightly ground
and were subjected to characterizations.
3.4.4
PA (Propionic Acid) Assisted, Sol-Gel Route for the Preparation of
LiMn2O4 Cathode Raw Materials
A general sol-gel method used to prepare LiMn2O4 cathode raw materials using
propionic acid as an organic carrier. lithium acetate and manganese acetate salts also
used as a metal sources. A stoichiometric amount of lithium acetate and manganese
acetate salts with the cationic ratio Li : Mn = 1:2 were dissolved in 50 mL distilled
water separately and mixed well with 50 mL of various concentration of propionic acid.
Ammonia solution was slowly added to this solution with a constant stirring until a pH
of 6.0-7.0 was achieved. The solution was evaporated at 70-80 oC for 5 hours.
47
To remove water in the sol, the transparent sol was dried at 100 oC for 24 hours in a
vacuum dryer to yield gel precursors. For the preparation of the gel precursors with
different molar ratio of propionic acid to total metal ions, the same procedure was
repeated and propionic acid to total metal ions ratio of 0.5, 0.83, 1.5, 2.0 samples were
prepared using 0.837 M, 1.39 M, 2.5 M, and 3.35 M propionic acid respectively. The gel
precursors obtained were decomposed at 350-750 oC for 5 hours in the furnace to obtain
phase-pure polycrystalline powders. After the calcination the powders were slightly
ground for characterizations.
3.4.5
Preparation of Cr-doped LiCrxMn2-xO4 (x = 0.00, 0.01, 0.02, 0.05, 0.10, 0.20)
Cathode Raw Materials
LiCrxMn2-xO4 (x = 0.00, 0.01, 0.02, 0.05, 0.10, 0.20) powders were prepared by
a sol-gel method using propionic acid as a chelating agent. Stoichiometric amounts of
lithium nitrate, chromium nitrate, and manganese acetate were dissolved in de-ionized
water separately and mixed thoroughly. The solution was stirred continuously with mild
heating to ensure homogeneity. The 50 mL of 1 M propionic acid was added drop wise
to the homogeneous solution and the solution was subsequently adjusted to pH 7.0-8.5
by ammonia solution (25 %). The resultant solution was then evaporated at 70-80 oC for
5 hours and transparent sol was obtained. The sol thus obtained was heated initially in
an oven at 100 oC for 24 hours and dried mass was obtained and then thoroughly ground
prior to the calcination. This precursor powders were calcined in a furnace at 400, 600
and 800 oC for 4 hours to ensure good purity and crystallinity. After calcination the
powders were again ground to make fine powders. Ultimately, the resulting powders
were subjected to characterizations.
48
3.4.6 CA (Citric Acid) and PA (Propionic Acid) Assisted, Sol-Gel Route for the
Preparation of LiCo0.7Al0.3O2 Cathode Raw Materials
The method involves the mixing of aqueous solution of lithium nitrate, cobalt
nitrate and aluminum nitrate with the complexing agent, organic acid (citric acid &
propionic acid) an aqueous medium. Stoichiometric amounts of lithium nitrate, cobalt
nitrate, and aluminum nitrate were dissolved in triple distilled water separately and
thoroughly mixed with aqueous solution of organic acid. In making a gel pH of the
mixture solution was around 1-2. The resultant solution was then evaporated off at
70-80 oC with magnetic stirring for about 6 hours until a sol was formed. Heating the sol
to moderate temperature causes a condensation reaction between – COOH groups via
dehydration with the concurrent formation of water. As most of the excess water was
removed, the sol turned into a gel, and extremely high viscosity resin was formed.
Finally, the products referred to as precursor powders were formed by drying in an oven
at 100 oC for 24 hours. The dried mass was ground into fine particles prior to the
calcination at 350, 550 and 750 oC for 5 hours.
49
3.5
Characterizations of Prepared Cathode Raw Materials
Characterization includes determination of surface area, thermogravimetric-
differential thermal analysis (TG-DTA), surface morphology (scanning electron
microscopy, SEM), energy dispersive X-ray analysis (EDAX), and X-ray diffraction
(XRD) analysis.
3.5.1 Determination of Surface Area
The specific surface area of synthesized cathode raw materials was determined
by using the instrument Pulse Chemisorb 2705 Micromeritics. The maximum surface
area that can be measured by this instrument is about 280 m2 and the minimum is about
0.2 m2. For surface area determination, the accuracy of this instrument is typically better
than ± 2 % and ± 0.5 % reproducibility. Firstly, all of the samples were ground using
mortar to generate the extra small size of solid sample. Then, approximately 0.05 g
sample was taken as representative of the overall sample and was then transferred to the
sample holder. Prior to the adsorption of N2 gases, the sample was degassed at 300 oC
for an hour. The measurement of surface area was accomplished using a 30 % N2 / 70 %
He gas mixture. The data for adsorption and desorption (D) of mixture gases was taken.
After the measurement, sample was weighed to get the final weight of sample (Mf). The
procedure was repeated three rimes. The calculation for determination of specific
surface area is the average value of desorb gas, D (m2) divide by the final weight of
sample, Mf (g). Thus, the unit for specific surface area is m2/g.
50
3.5.2 Thermogravimetric-Differential Thermal Analysis (TG-DTA)
Thermal analysis (TG-DTA) were carried out in a Perkin Elmer Diamond
Thermogravimetric/Differential Thermal Analyzer (Model: Pyris Diamond TG-DTA,
High Temp.11, Japan). The instrument operating conditions were at 5 oC/min or
10 oC/min step from room temperature to 900 oC, using an approximately 10 mg of
samples in a platinum crucible and N2 flow of 200 mL/min. The record of data and
thermogram were assisted by the Pyris software provided by the manufacturer.
3.5.3 Surface Morphology (Scanning Electron Microscopy, SEM)
The surface morphology of prepared cathode materials was investigated from the
magnified images of the samples surface by scanning electron microscopy (SEM). The
SEM was carried out by the bombardment of electrons of 30 keV on target sample
particle which was spread earlier over an aluminum stub with the help of a doubled
edged tape followed by coating the surface with gold film. Electrons that are emitted
from the specimen with an energy of less than 50 eV are defined as secondary electrons
and are used for specimen investigation. Other than scanning electron microscopic
investigation, instrument also imparts the detection of scattered X-ray for the
characteristic radiation of a specific element in an energy dispersive system to identify
the element.
3.5.4 Energy Dispersive X-ray Analysis (EDAX)
EDAX is a chemical microanalysis technique used in conjunction with scanning
electron microscope (SEM). Analytical measurement of the composition by means of
51
EDAX confirm the presence of the elements and EDAX was performed using EDAX
DX-4 coupled to the microscope.
3.5.5 X-ray Diffraction (XRD) Analysis
The crystallinity and the structure of the samples were examined using X-ray
Diffraction (XRD) method (Bruker HR X-ray Diffractometer, Germany). The
pulverized samples were divided finely to permit packing of samples into an XRD
sample holder as a self-supporting window. The X-ray diffraction patterns were
recorded with Cu KĮ radiation with Ȝ = 1.5418 Å at 40 kV and 20 mA in the range of 2ș
= 10o-80o at a scan rate of 0.050o/s.
3.6
Cathode Preparation
After the raw materials successfully produced the composite cathodes were
prepared. The working electrodes for electrochemical testing were prepared by mixing
the cathode materials powders (80 wt %) with a blend of acetylene black and
polyvinylidene fluoride (PVDF) (20 wt %) in an agate mortar. The acetylene black used
to provide good electrical conductivity as well as mechanical toughness between active
grains (Julien et al.,1999). The mixture was spread onto a stainless steel mesh and then
compressed between flat plates. The electrodes were then dried around 120 oC in the
oven overnight before transferred into a glove box filled with argon gas.
52
3.7
Cell Fabrication
The cells were assembled in an argon-filled glove-box. Standard coin cells were
assembled using lithium foil as the reference and counter electrode and 1 M LiPF6
dissolved in ethylenecarbonate, EC: dimethylcarbonate, DMC (1:1) as the electrolyte in
a teflon cell casing. Li/1 M LiPF6-EC/DMC/LiMn2O4 (CA-EG) (A cell); Li/1 M LiPF6EC/DMC/LiMn2O4 (CA) (B cell); Li/1 M LiPF6-EC/DMC/LiMn2O4 (PA) (C cell);
Li/1 M LiPF6-EC/DMC/LiCrxMn2-xO4 (D cell); Li/1 M LiPF6-EC/DMC/LiCo0.7Al0.3O2
(CA) (E cell) and Li/1 M LiPF6-EC/DMC/LiCo0.7Al0.3O2 (PA) (F cell) cells were
fabricated. A photograph of fabricated coin cell sample is shown in the Figure 3.3.
Figure 3.3 :
A photograph of fabricated coin cell sample
Model: CR2032, Diameter 20 mm, Thickness: 3.2 mm
53
3.8
Electrochemical Characterization of Fabricated Cells
Cathode preparation, cell fabrication and their electrochemical investigations
were done by the Advanced Materials Research Centre (AMREC), SIRIM Berhad,
09000 Kulim, Kedah, Malaysia. The cells were cycled using a Solartron 1470 Battery
Testing System in the suitable voltage range (3.0 to 4.3 V) and suitable current density
(0.20 mA/cm2). Electrochemical investigations include cut-off voltage, applied current,
number of cycles, charge capacity, discharge capacity, capacity fading, capacity
retention and coulombic efficiency. Finally data recorded with an automated battery
cycle life tester and sent to our laboratory for manipulation. From the recorded data we
separated 1st cycle, 2nd cycle and 3rd cycle charge-discharge capacity data, respectively
and plotted it [cell voltage vs.Li (V)] to investigate about the charge-discharge capacity
curve of the cells. Cycleability and coulombic efficiency study curves for all cells were
done with the number of cycles using charge-discharge capacity data. Capacity
retention, capacity fading and coulombic efficiency were calculated from the data
according to the given example below.
Capacity retention: The fraction of the full capacity available from a battery or
a cell under specified conditions of discharge after it has been stored for a period of
time. Capacity retention is calculated in percentage
Capacity fading: Gradual loss of capacity of a secondary battery with cycling
and it is calculated in percentage
Coulombic efficiency: The ratio of the output of a secondary cell or battery on
discharge to the input required to store it to the initial state of charge under specified
conditions. Coulombic efficiency is calculated in percentage
Let,
1st cycle charge capacity of a cell = C mA h/g
1st cycle discharge capacity = D mA h/g
54
2nd cycle charge capacity
= E mA h/g
nd
2 cycle discharge capacity = F mA h/g
3rd cycle charge capacity
= G mA h/g
rd
3 cycle discharge capacity = H mA h/g
e.g. cell was runed up to 3rd cycle.
Calculation:
Capacity retention, (%)
H mA h/g
u 100
D mA h/g
(a)
Capacity fading, (%)
D mA h/g - H mA h/g
u 100
D mA h/g
(b)
Coulombic efficiency for the 1st cycle, (%)
D mA h/g
u 100
C mA h/g
(C)
Coulombic efficiency for the 2nd cycle, (%)
F mA h/g
u 100
E mA h/g
(d)
Coulombic efficiency for the 3rd cycle, (%)
H mA h/g
u 100
G mA h/g
(e)
CHAPTER 4
RESULTS AND DISCUSSION
4.1
Characterization of Prepared Cathode Raw Materials
Prior to their utilization in cathode fabrication, cathode raw materials were
characterized by thermogravimetriy-differential thermal analysis (TG-DTA), X-ray
diffraction (XRD), BET surface area, scanning electron microscopy (SEM) and energy
dispersive X-ray analysis (EDAX) to ensure the applicability for fabrication of positive
electrodes. Fabricated cathodes were also characterized using various electrochemical
techniques.
4.2
Characterizations
4.2.1
Thermogravimetry-Diffrential Thermal Analysis (TG-DTA)
LiMn2O4 (CA-EG Mixture Assisted) Cathode Raw Materials:
The gel precursors were synthesized at various molar ratios of citric acidethylene glycol (CA-EG) mixture to total metal ions. The milky color of the gel
56
precursors indicated that the composition of the precursors was very homogeneous. It is
believed that carboxylic groups in the citric acid and hydroxyl groups in the ethylene
glycol form a chemical bonding with the metal ions so that they become extremely
viscous gelled polymeric resins (Liu et al., 1996). Due to the complex chemical route of
LiMn2O4 preparation the TG-DTA analysis were first performed. Figure 4.1 presents the
TG-DTA curves for the gel precursors of LiMn2O4 pretreated in vacuum dryer at 100 oC
for 24 hours.
Observing the TG curve it was found that three discrete weight loss regions were
detected at the temperatures range of 50-150 oC, 150-270 oC, and 270-450 oC, and the
weight loss of the precursors terminated after 450 oC. The weight loss in the temperature
range of 50-150 oC revealed a continuous water loss. In this cases, the mass loss is a
result of desorption of moisture or water molecules located in the precursors cavities, or
other volatile species that may be present.
TG Curve
DTA Curve
Figure 4.1: TG-DTA curves for the gel precursors pretreated in vacuum dryer at 100 oC
for 24 hours prior to calcination. Heating rate: 10 oC/min and N2 flow 200 mL/min
The weight loss in the temperature range of 150-270 oC was associated with the
decomposition of citric acid-ethylene glycol and acetate ions which results from the
pyrolysis of citric acid-ethylene glycol and metal acetates mixture. The weight loss in
the temperature range of 270-450 oC was attributed to the combustion of the remaining
57
organic constituents. About 25-30 wt % of the weight loss occurred during this stage
because of violent oxidation-decomposition reaction. It appeared that citric
acid-ethylene glycol mixture functioned as a fuel in the decomposition of the acetate
ions and heat evolved from the decomposition of acetate ions accelerated the
decomposition of the remaining organic constituents. This argument was supported by
the observation that the gel precursors turned into fluffy dark powders after being
calcined at this stage. Similar behavior was observed in previous work (Lee et al.,
1998). Water loss continued at very slow rate up to 450 oC and achieved almost total
removal of moisture. From the DTA curve, the endothermic peak appeared in the
temperature range of 240-280 oC. Such endothermic effect corresponds to water release
from the precursor and the size of its area speaks about the amount of water loss and
temperature limits in which release take place. It is well known that the endothermic
effect in the heating process of the precursors is a consequence of the consumption of
the heat or energy for dehydration.
LiMn2O4 (CA Assisted) Cathode Raw Materials:
The gel precursors were synthesized at various molar ratios of citric acid (CA) to
total metal ions. The greenish color (like transparent glass) of the precursors indicated
that the composition of the precursors was highly homogeneous. Figure 4.2 shows the
TG-DTA curves for the gel precursors of LiMn2O4 pretreated in the vacuum dryer at
100 oC for 24 hours.
The result display three discrete weight loss regions in the temperature range of
50-200 oC, 200-300 oC, and 300-600 oC. The DTA curve shows several distinguishable
transformation enthalpies. Endothermic peaks are observed in 130 oC and 250 oC. The
first endothermic peak in the temperature 130 oC reveals a continuous water loss and
minimum weight loss is observed here. In this case, the mass loss is a result of
desorption of moisture or water molecules located in the precursors cavities or other
volatile species that may be present. The rest endothermic effect in the temperature
250 oC is accompanied by a noticeable weight loss in the TG curve. It indicates the
58
consumption of the heat or energy of the decomposition and or the soft oxidation of the
molecular precursors.
Figure 4.2: TG-DTA curves for the gel precursors pretreated in a vacuum dryer at
100 oC for 24 hours prior to calcination. Heating rate: 10 oC/min and N2 flow 200
mL/min
The weight loss in the temperature range of 200-300 oC is associated with the
decomposition of citric acid and metal ions which result from the pyrolysis of citric
acid, metal hydroxide and metal acetate mixture. Maximum weight loss occurred during
this stage because of violent oxidation-decomposition reaction. The weight loss in the
temperature range of 300-600 oC is attributed to the combustion of the remaining
organic constituents.
LiMn2O4 (PA Assisted) Cathode Raw Materials:
Figure 4.3 shows the results and the behavior of the starting precursor. The
results display three discrete weight loss regions in the temperature range of 30-260 oC,
260-380
o
C, and 380-730
o
C. The DTA curve shows several distinguishable
transformation enthalpies. Endothermic peaks are observed at about 60 oC, 200 oC, and
59
300 oC. The first endothermic effect associated with a weight loss of about 10 % are
attributed to departure of moisture or residual water and the rest endothermic effect is
accompanied by a noticeable weight loss in the TG curve. This is attributed to the
superficial water loss due to the hygroscopic nature of the precursor complex. After the
departure of the remaining water molecules, a strong exothermic peak appeared at about
260 oC indicating the onset of the decomposition and/or the soft oxidation of the
Figure: 4.3 TG-DTA curves for the gel precursors pretreated in a vacuum dryer at
100 oC prior to thermal analysis in the air. Heating rate: 10 oC/min and N2 flow 200
mL/min
The huge exothermic reaction indicates the decomposition of organic species
present in the precursor complex. A weight loss of about 50 % occurred during this
stage because of the violent oxidation-decomposition reaction. The gel precursor was
burning because the decomposed acetate ions acted as an oxidizer. The weight loss of
5 % in the temperature range of 380-730 oC corresponds to the decomposition of the
remaining organic constituents. This process leaded to the formation of fluffy dark
powders when the precursor was heated in the temperature range of 350-750 oC.
60
Cr-doped LiCrxMn2-xO4 Cathode Raw Materials:
We performed thermogravimetric and differential thermal analysis of the
precursor gels dried at 100 oC for 24 hours to study the thermal stability of the samples
and to optimize the calcination temperatures for the gel precursors. Figure 4.4 shows the
TG-DTA curves, which display the formation temperature of the oxide LiCrxMn2-xO4
grown by the carboxylic acid assisted aqueous method. A strong exothermic peak
appears in the temperature range of 190-230 oC after the departure of the remaining
water molecules at 50-180 oC.
Figure 4.4: TG-DTA curves of the LiCrxMn2-xO4 (x = 0.05) grown by propionic acid
assisted sol-gel technique. This measurement was carried out at a heating rate
of 10 oC/min with N2 flow rate of 200 mL/min.
The exothermic effect corresponds to the combustion of carboxylic acid and
nitrate/acetate ions. More than half of the weight loss occurs during this stage because of
violent oxidation-decomposition reaction. During the combustion process, the gel
precursors turned into brownish black powders. Assuming that complexing agent
provides combustion heat for calcination in the synthesis of oxide powders.
61
LiCo0.7Al0.3O2 (CA and PA Assisted) Cathode Raw Materials:
Figure 4.5 shows the TG-DTA curves, which display the formation temperature
of the LiCo0.7Al0.3O2 oxide grown by the carboxylic acid assisted aqueous method.
Figure 4.5: TG-DTA curves for the gel precursors pretreated in a vacuum dryer at
100 oC for 24 hours prior to calcination. Heating rate: 10 oC/min and N2 flow
200 mL/min.
The TG curve display three discrete weight loss regions in the temperatures
range of 90-240 oC, 240-290 oC, and 290-490 oC and weight loss of the precursors
terminated after 500 oC. The weight loss in the temperature range of 90-240 oC revealed
a continuous water loss and minimum weight loss is observed here. The first
endothermic effect associated with a weight loss of about 20 % is attributed to the
departure of moisture or residual water. The rest endothermic effect is attributed to the
superficial water loss due to the hygroscopic nature of the precursors complex. A strong
exothermic peak appeared at ca. 240 oC that corresponds to the decomposition of
carboxylic acid and nitrate ions. Maximum weight loss occurred during this stage
because of oxidation-decomposition reaction. It appeared that carboxylic acid acts as a
fuel in the pyrolysis of the gel precursor, favoring the decomposition of nitrate ions. It
was reported that chelating agent (carboxylic-based acid) provokes decomposition
62
during the synthesis oxide powders. The gel precursor was burning because the
decomposed nitrate ions acted as an oxidizer. The weight loss of about 20 % in the
temperature range of 290-490 oC corresponds to the decomposition of the remaining
organic constituents. Even though the crystallization starts around 500 oC, thus wellcrystallized and single phases have been obtained at 550 oC. While the pyrolysis at this
stage was very complicated, it could be presumed that the weak exothermic peak feature
at ca. 380-390
o
C in the DTA curve correspond to the crystallization of the
LiCo0.7Al0.3O2 phases.
4.2.2 BET surface area
Specific surface area of the materials was analyzed by 30 % N2 / 70 % He gas
adsorption-desorption using the instrument Pulse Chemisorb 2705 Micromeritics and
surface area was measured by a single point physisorption determination. Figure 4.6
shows the dependence of specific surface area of the same materials on the calcination
temperature and Figure 4.7 shows the dependence of specific surface area of the same
materials on the molar ratio of chelating agents to total metal ions and on the dopant
concentrations respectively. Figure 4.6 a, b, c, d and e show that the specific surface
area for the LiMn2O4 powders (CA-EG mixture assisted), LiMn2O4 powders
(CA assisted), LiMn2O4 powders (PA assisted), LiCo0.7Al0.3O2 powders (CA assisted)
and LiCo0.7Al0.3O2 powders (PA assisted), respectively. In general, all specific surface
areas decrease with increasing the calcination temperatures, due to the growth of
crystallites. The specific surface area of 24.59, 22.63, 20.06 and 19.55 m2/g for the
LiMn2O4 powders (CA-EG mixture assisted) calcined at 250, 300, 400 and 450 oC;
14.85, 12.19, 6.25 and 4.01 m2/g for the LiMn2O4 powders (CA assisted) calcined at
300, 500, 600 and 700 oC; 5.66, 4.58, 4.17 and 3.05 m2/g for the LiMn2O4 powders (PA
assisted) calcined at 350, 450, 650 and 750 oC; 56.22, 40.12 and 29.90 m2/g for the
LiCo0.7Al0.3O2 powders (CA assisted) calcined at 350, 550 and 750 oC; 42.15, 31.60 and
63
22.30 m2/g for the LiCo0.7Al0.3O2 powders (PA assisted) calcined at 350, 550 and
30
28
Specific surface area (m 2/g)
2
Specific surface area (m /g)
750 oC, respectively.
(a)
26
24
22
20
18
16
14
200
250
300
350
400
450
20
18
16
14
12
10
8
6
4
2
0
(b)
200
500
300
o
Specific surface area (m /g)
2
2
Specific surface area (m /g)
(c)
4
3
2
400
500
600
700
60
55
50
45
40
35
30
25
20
800
200
300
800
400
500
600
700
800
o
Calcination temperature ( C)
2
700
(d)
o
Specific surface area (m /g)
600
Calcination temperature ( C)
6
300
500
o
Calcination temperature ( C)
5
400
Calcination temperature ( C)
45
(e)
40
35
30
25
20
15
10
200
300
400
500
600
700
800
o
Calcination temperature ( C)
Figure 4.6:
Dependence of the specific surface area for the (a) LiMn2O4 powders
(CA-EG mixture assisted), (b) LiMn2O4 powders (CA assisted), (c) LiMn2O4 powders
(PA assisted), (d) LiCo0.7Al0.3O2 powders (CA assisted) and (e) LiCo0.7Al0.3O2 powders
(PA assisted) on the calcination temperatures.
64
The variations in BET surface area by the different calcination temperatures are
summarized in Table 4.1.
Table 4.1: The BET surface area of the materials prepared from different calcination
temperatures
Materials
Chelating agents
Calcination
Specific surface area
to total metal
temperatures
(BET) m2/g
ions ratio
(oC)
250
24.59
300
22.63
400
20.06
450
19.55
300
14.85
500
12.19
600
6.25
700
4.01
350
5.66
450
4.58
650
4.17
750
3.05
-
350
56.22
LiCo0.7Al0.3O2
-
550
40.12
(CA assisted)
-
750
29.90
-
350
42.15
LiCo0.7Al0.3O2
-
550
31.60
(PA assisted)
-
750
22.30
LiMn2O4
(CA-EG mixture
1.0
assisted )
LiMn2O4
( CA assisted )
1.0
LiMn2O4
( PA assisted )
1.5
65
Figure 4.7 shows the dependence of specific surface area of the respective
prepared cathode raw materials on the molar ratio of its chelating agents to the total
metal ions and on the dopant concentrations. The specific surface area was seen to
increase as the molar ratio of chelating agents to total metal ions increases, but remain
20
16
12
8
(a)
4
0
0.2
0.4
0.6
0.8
1
1.2
Molar ratio of citric acid-ethylene
glycolmixture to tot al metal ions
7
9
8
7
6
5
4
3
2
1
0
(b)
0.25 0.5 0.75
1
1.25 1.5 1.75
M olar ratio of citric acid to total metal ions
3
2
Specific surface area (m 2/g)
Specific surface area (m 2/g)
24
Specific surface area (m /g)
Specific surface area (m 2 /g)
constant upon dopant concentrations.
6
5
4
(c)
3
2
0
1
2
3
M olar ratio of p rop ionic acid to total metal ions
Figure 4.7:
1.5
(d)
0
0
0.05
0.1
0.15
0.2
Dopant concentrations (x)
Dependence of the specific surface area for the (a) LiMn2O4 powders
(CA-EG mixture assisted), (b) LiMn2O4 powders (CA assisted), (c) LiMn2O4 powders
(PA assisted), and d) Cr doped LiCrxMn2-xO4 powders on the molar ratios and dopant
concentrations respectively
The specific surface area for the LiMn2O4 (CA-EG mixture assisted) materials of
the molar ratio of citric acid-ethylene glycol (CA-EG) mixture to total metal ions of
0.25, 0.5 and 1.0 was 3.436 , 5.75 and 19.55 m2/g; for the LiMn2O4 (CA assisted)
materials of the molar ratio of citric acid (CA) to total metal ions of 0.5, 1.0 and 1.5 was
3.02, 6.25 and 7.92 m2/g; for the LiMn2O4 (PA assisted) materials of the molar ratio of
66
propionic acid (PA) to total metal ions of 0.5, 0.83, 1.5 and 2.0 was 2.49, 4.76, 5.66 and
6.52 m2/g respectively. On the other hand, the specific surface area for the Cr doped
LiCrxMn2-xO4 materials of the dopant concentrations of x = 0.00, 0.01, 0.02, 0.05, 0.10
and 0.20 was 2.23, 2.04, 2.08, 2.13, 2.22 and 2.08 m2/g respectively. The specific
surface area of Cr doped LiCrxMn2-xO4 powders remained constant at around 2 m2/g
with the increase of dopant concentrations. The variations in specific surface area for the
same materials by the different molar concentrations of the chelating agents to total
metal ions and different dopant concentrations are showed in Table 4.2
The reason why the crystallinity and the specific surface area of the LiMn2O4
powders increase with the content of chelating agents used in preparing gel precursors
can be explained as follows:
Chelating agents (especially carboxylic acid) not only work as a chelating agents
but also provide the combustion heat requires for synthesis of LiMn2O4 powders. The
less chelating agents used in preparing gel precursors, the shorter Li-Mn cations distance
and thus the higher probability of the crystallization between the cations, but the less
combustion heat required for synthesis of LiMn2O4 phase is generated from chelating
agents. On the contrary, the more chelating agents used, the more cross-linked gel
precursors suppressed cations mobility, the less segregation of the cations occurred
during calcination and thus the cations are trapped. But, the greater the combustion heat
is generated from the chelating agents with increasing calcination temperatures, yielding
the LiMn2O4 phase together with fluffy powders which result from much void volumes
formed by the evolution of CO and CO2 gases during the thermal decomposition of
chelating agents. This is supported by the observation that the materials swell much
when the amount of chelating agents increases though the gel precursors are calcinated
at the same temperature.
67
Table 4.2: The BET surface area for LiMn2O4 and Cr doped LiCrxMn2-xO4 powders
prepared from different molar ratios of chelating agents to total metal ions and different
dopant concentrations respectively.
Materials
Calcination
Chelating agents to
Specific surface area
temperature
total metal ions
(BET) m2/g
(oC)
ratio
LiMn2O4
0.25
3.44
0.5
5.75
assisted )
1.0
19.55
LiMn2O4
0.5
3.02
1.0
6.25
1.5
7.92
0.5
2.49
0.83
4.76
1.5
5.66
2.0
6.52
(CA-EG mixture
( CA assisted )
450
600
LiMn2O4
( PA assisted )
350
Dopant
concentrations
LiCrxMn2-xO4
400
x = 0.00
2.23
x = 0.01
2.04
x = 0.02
2.08
x = 0.05
2.13
x = 0.10
2.22
x = 0.20
2.08
Therefore, the increased chelating agents quantity might be thought to increase
the crystallinity and the specific surface area of the powders. If too much chealting
agents are used, it can have a negative effect by raising the temperature too high in a
short period of time and by decreasing the partial pressure of near LiMn2O4 resulted
68
from the increase amount of CO or CO2 during the decomposition of chelating agents.
The high temperature tends to make large crystallities that are not agglomerated.
However, if the chelating agents quantity used is too small, the more segregation of
cation occurred and the combustion heat for synthesis of LiMn2O4 phase generated from
chelating agents becomes insufficient.
4.2.3
X-ray Diffraction Analysis (XRD)
In order to investigate the effect of calcination temperatures and the quantity of
chelating agents on the formation mechanism and structural difference of the powdered
materials, the precursors LiMn2O4 (CA-EG mixture assisted) materials calcined at 250,
300, 400 and 450 oC; LiMn2O4 (CA assisted) materials calcined at 300, 500, 600 and
700 oC; LiMn2O4 (PA assisted) materials calcined at 350, 450, 650 and 750 oC; Cr doped
LiCrxMn2-xO4 materials calcined at 800 oC; LiCo0.7Al0.3O2 (CA assisted) materials
calcined at 350, 550 and 750 oC and LiCo0.7Al0.3O2 (PA assisted) materials calcined at
350, 550 and 750 oC were analyzed with XRD. In the preliminary attempts of synthesis
of LiMn2O4, Cr doped LiCrxMn2-xO4 and LiCo0.7Al0.3O2 cathode raw materials from
metal salts and organic carrier have been produced. These results are incomplete
agreement with previous reports (Lee et al., 1998; Sun, 1997).
Identification and purity of the products were determined by matching the
diffractogram of the prepared samples with the diffractogram of good-quality singlephase pattern of powder data file (PDF, Compiled by the International Centre for
Diffraction Data, ICDD) with the assist of Diffraction of EVA software. The obtained
product can be considered pure and highly crystalline as proven by the high intense and
narrow peaks without elevated baseline and extra peaks. The XRD peaks of the
LiMn2O4 powders and LiCo0.7Al0.3O2 powders are well matched with the PDF 35-0782
(Lithium Manganese Oxide) and PDF 89-0912 (Lithium Aluminum Cobalt Oxide),
respectively. The XRD peaks with PDF file for the LiMn2O4 (CA-EG mixture assisted)
69
materials and LiCo0.7Al0.3O2 (PA assisted) materials are shown in the Figures 4.8 a and
Lin (Counts)
4.8 b, respectively.
Figure 4.8 a: XRD pattern for gel derived LiMn2O4 (CA-EG mixture assisted)
materials calcined at 450 oC temperature for 5 hours in air, where the molar ratio of
citric acid-ethylene glycol (CA-EG) mixture to total metal ions was 1.0
Figure 4.8 b: XRD pattern for gel derived LiCo0.7Al0.3O2 (PA assisted) materials
calcined at 550 oC temperature for 5 hours in air, where chelating agent concentration
was 1 molar.
70
Figures 4.9 a, 4.9 b, 4.9 c, 4.9 d, and 4.9 e show the stacking form of XRD
patterns for the LiMn2O4 (CA-EG mixture assisted) materials, LiMn2O4 (CA assisted)
materials, LiMn2O4 (PA assisted), LiCo0.7Al0.3O2 (CA assisted) materials and
LiCo0.7Al0.3O2 (PA assisted) materials on the calcination temperatures, respectively.
1500
: LiMn2O4
1400
1300
1200
450 oC
1100
1000
Lin (Counts)
900
400 oC
800
700
600
300 oC
500
400
300
250 oC
200
100
0
10
20
30
40
50
60
70
80
2-Theta - Scale
Figure 4.9 a: Stacking of X-ray diffraction patterns of LiMn2O4 (CA-EG mixture
assisted) materials calcined at various temperatures on the molar ratio of citric acidethylene glycol (CA-EG) mixture to total metal ions of 1.0.
71
1200
:
LiMn2O4
: Mn2O3
1100
1000
900
700 oC
800
Lin (Cps)
700
600 oC
600
500
500 oC
400
300
200
300 oC
100
0
10
20
30
40
50
60
70
80
2-Theta - Scale
Figure 4.9 b: Stacking of X-ray diffraction patterns of LiMn2O4 (CA assisted) materials
calcined at various temperatures on the molar ratio of citric acid to total metal ions of
1.0
1100
1000
: LiMn2O4
: Li2CO3
: MnO
: Unknown
900
800
750 oC
Lin (Counts)
700
600
650 oC
500
400
300
450 oC
200
350 oC
100
0
10
20
30
40
50
60
70
80
2-Theta - Scale
Figure 4.9 c: Stacking of XRD patterns of LiMn2O4 (PA assisted) materials calcined at
various temperatures on the molar ratio of propionic acid to total metal ions of 1.5
72
1500
: LiCo0.7Al0.3O2
1400
1300
750 oC
1200
1100
Lin (Cps)
1000
900
550 oC
800
700
600
350 oC
500
400
300
200
100
0
10
20
30
50
40
60
70
80
2-Theta - Scale
Figure 4.9 d: Stacking of XRD patterns of LiCo0.7Al0.3O2 (CA assisted) materials
calcined at 350, 550 and 750 oC
: LiCo0.7Al0.3O2
1300
1200
1100
750 oC
1000
900
800
550 oC
700
600
500
350 oC
400
300
200
100
0
10
20
30
40
50
60
70
80
2-Theta - Scale
Figure 4.9 e: Stacking of XRD patterns of LiCo0.7Al0.3O2 (PA assisted) materials
calcined at 350, 550 and 750 oC
73
The X-ray diffraction patterns for the materials of LiMn2O4 (CA-EG mixture
assisted), LiMn2O4 (CA assisted), LiMn2O4 (PA assisted), LiCo0.7Al0.3O2 (CA assisted)
and LiCo0.7Al0.3O2 (PA assisted) calcined at 250, 300, 350, 350 and 350 oC show no
diffraction sharp peaks respectively, which indicates an amorphous phase. The x-ray
diffraction pattern for the materials of LiMn2O4 (PA assisted) calcined at 350oC, the
crystallinity of LiMn2O4 phase is very poor and the peaks of impurities such as Li2CO3
and MnO are observed. When the materials of LiMn2O4 (CA-EG mixture assisted),
LiMn2O4 (CA assisted), LiMn2O4 (PA assisted), LiCo0.7Al0.3O2 (CA assisted) and
LiCo0.7Al0.3O2 (PA assisted) calcined at 300, 500, 450, 550 and 550 oC respectively, the
crystalline LiMn2O4 and LiCo0.7Al0.3O2 begin to appear and impurity peaks are also not
observed, which are often found in other low temperature techniques. For all materials,
there is a gradual increase in the peak intensities accompanied by sharpening of the
peaks with increasing the calcination temperatures, which indicates an increase of
crystallinity. The precursors were crystallized into a phase pure LiMn2O4 and
LiCo0.7Al0.3O2 powders without any development of minor phase throughout the
calcination temperature range. This result strongly suggests that a sol-gel method
requires much lower calcination temperature and shorter calcination time than the solidstate reaction. It is inferred from the above results that since the cross-linked gel
precursors may provide more homogeneous mixing of cations and less tendency for
segregation during calcination though the chemical bonding is destroyed, the use of
chelating agents greatly suppresses the formation of precipitates from which the
heterogeneity stems.
Figures 4.10 a, 4.10 b, 4.10 c and 4.10 d show the stacking of X-ray diffraction
patterns for the materials of LiMn2O4 (CA-EG mixture assisted), LiMn2O4
(CA assisted), LiMn2O4 (PA assisted) and Cr doped LiCrxMn2-xO4 calcined at 450, 600,
350 and 800 oC in terms of the quantity of chelating agents and dopant concentrations
respectively. It is confirmed from the XRD patterns that the LiMn2O4 phase could be
formed regardless of the molar ratio of chelating agents to total metal ions due to higher
calcination temperatures. However, the comparison of peak intensities at each 2ș shows
74
that the crystallinity of the materials is improved with increasing molar ratio of chelating
agents to total metal ions
1500
: LiMn2O4
1400
1300
1200
(c)
1100
Lin (Counts)
1000
900
800
700
(b)
600
500
400
(a)
300
200
100
0
10
20
30
40
50
60
70
80
2-Theta - Scale
Figure 4.10 a : Stacking of X-ray diffraction patterns of LiMn2O4 (CA-EG mixture
assisted) materials calcined at 450 oC for 5 hours at the molar ratio of citric acidethylene glycol mixture to total metal ions of (a) 0.25, (b) 0.5 and (c) 1.0.
800
: LiMn2O4
: Mn2O3
700
600
(c)
Lin (Cps)
500
400
(b)
300
200
(a)
100
0
10
20
30
40
50
60
70
80
2-Theta - Scale
Figure 4.10 b : Stacking of X-ray diffraction patterns of LiMn2O4 (CA assisted)
materials calcined at 600 oC for 10 hours at the molar ratio of citric acid to total metal
ions of (a) 0.5, (b) 1.0 and (c) 1.5.
75
: : LiMn2O4
800
: MnO
: Li2CO3
700
(d)
Lin (counts)
600
(c)
500
400
(b)
300
200
(a)
100
10
20
30
40
50
60
70
80
2-Theta - Scale
Figure 4.10 c:
Stacking of X-ray diffraction patterns of LiMn2O4 (PA assisted)
materials calcined at 350 oC for 5 hours at the molar ratio of propionic acid to total
metal ions of ( a) 0.5, (b) 0.83, (c) 1.5, and (d) 2.0
3400
3300
: LiCrxMn2-xO4
3200
3100
3000
2900
x = 0.20
2800
2700
2600
2500
2400
x = 0.10
2300
2200
2100
Lin (Cps)
2000
1900
1800
x = 0.05
1700
1600
1500
1400
x = 0.02
1300
1200
1100
1000
900
800
x = 0.01
700
600
500
400
x = 0.00
300
200
100
0
10
20
30
40
50
60
70
80
2-Theta - Scale
Figure 4.10 d: Stacking of XRD patterns for Cr doped LiCrxMn2-xO4 materials calcined
at 800oC for 4 hours at the dopant concentrations of x = 0.00, 0.01, 0.02, 0.05, 0.10, 0.20
76
Figure 4.10 c shows the results for different molar ratio of propionic acid to total
metal ions. It was expected that the peak intensities increase with increase in molar
ratios. But that was not observed in this case. The reason why the peaks intensities don’t
increase gradually with the increase of content of propionic acid used in preparing gel
precursors can be explained as follows:
It is well known that propionic acid not only works as chelating agent but also
provides the combustion heat required for the synthesis of LiMn2O4 powders. The
materials with the much quantity of propionic acid (mole ratio of propionic acid to total
metal ions of 1.5) was amorphous at the lower calcination temperature range (350 oC).
The less propionic acid (mole ratio 0.5 and 0.83) used in preparing gel precursors, the
shorter Li-Mn cation distance and thus the higher probability of the crystallization
between the cations, hence less combustion heat would be required for the formation of
LiMn2O4 phase generated from propionic acid. On the contrary, as more propionic acid
used (mole ratio:2.00) to prepare gel precursors, more cross-linked gel precursors would
be created that may suppress cation mobility with less segregation. However, these
cations will be trapped and LiMn2O4 phase would be formed clearly. But it hasn’t
occurred actually because may be of insufficient calcination temperature (350 oC).
From the above results we could conclude that crystallinity of LiMn2O4 powders
not only depends on the molar ratio but also depends on the calcination temperatures.
The X-ray diffraction patterns for the Cr doped LiCrxMn2-xO4 materials calcined at
800 oC for 4 hours showed no impurity peaks (Figure 4.10 d ), even though it is often
found in other low temperature techniques. There is no gradual increase in the peak
intensities with increasing the dopant concentration. This is because, peak intensities
increase with increasing the calcination temperatures as well as chelating agent
concentrations and that already have been discussed. In this case, calcination
temperatures (800 oC) and chelating agent concentration (50 mL 1 M propionic acid) are
the same for all specimens. Dopant concentration doesn’t affect the feature of the peak
intensities.
77
4.2.4
Structure Analysis
LiMn2O4 materials:
From Table 4.3, LiMn2O4 (CA-EG mixture assisted) materials with the molar
ratio of CA-EG mixture to total metal ions of 1.0 calcined at 300 oC shows peaks at 2ș =
18.641, 36.145, 43.884 and 63.471 with the d-value (Å) of 4.75622, 2.48304, 2.06144
and 1.46446 respectively. These peaks are similar with the d-value (Å) of 4.76279,
2.48695, 2.06224 and 1.45817 from the PDF (35-0782) data file. From the reference dvalues (Å), it is known that LiMn2O4 form is cubic unit cell. Sample with the ratio of 1.0
calcined at 400 oC shows peaks at 2ș = 18.657, 36.194, 37.817, 44.093, 58.028 and
63.920 with the d-value (Å) of 4.75206, 2.47982, 2.37705, 2.05216, 1.58817 and
1.45524 respectively. These d-values are similar with reference d-values (Å) from the
PDF data file. It is shown that the structure still remain in the cubic unit cell. For the
sample with the ratio of 1.0 calcined at 450 oC shows peaks at 2ș = 18.622, 30.844,
36.176, 44.039, 58.522, and 63.859 with the d-values (Å) of 4.76089, 2.89669, 2.48099,
2.05458, 1.57594 and 1.45648 respectively. These d-values are similar with the PDF
data file and remained the cubic unit cell structure.
Similarly LiMn2O4 (CA assisted) materials and LiMn2O4 (PA assisted) materials
show cubic unit cell structure. From the diffractogram, it is known that LiMn2O4 is
originally in crystal form. Analysis has been done with different chelating agent
concentrations as well as different calcination temperatures but no changes obtained
towards the structure and LiMn2O4 still remained in cubic unit cell structure.
78
Table 4.3: XRD results obtained on LiMn2O4 (CA-EG mixture assisted) materials
calcined at 300, 400 and 450 oC with the molar ratio of CA-EG mixture to total metal
ions of 1.0
Calcination
Angle, 2ș (o)
d-value (Å)
temperature (oC)
300
400
450
Intensity
(%)
18.641
4.75622
100.0
36.145
2.48304
88.8
43.884
2.06144
67.1
63.471
1.46446
62.6
18.657
4.75206
100.0
36.194
2.47982
53.1
37.817
2.37705
40.7
44.093
2.05216
45.6
58.028
1.58817
39.3
63.920
1.45524
41.7
18.622
4.76089
100.0
30.844
2.89669
32.7
36.176
2.48099
48.1
44.039
2.05458
43.4
58.522
1.57594
33.9
63.859
1.45648
34.8
79
LiCo0.7Al0.3O2 materials:
LiCo0.7Al0.3O2 (PA assisted) materials calcined at 550 oC shows peaks at 2ș =
18.823, 37.289, 45.305, 65.417, and 66.633 with the d-value (Å) of 4.71053, 2.40949,
2.00005, 1.42553 and 1.40242 respectively (Table 4.4).
Table 4.4: XRD results obtained on LiCo0.7Al0.3O2 (PA assisted) materials calcined at
350, 550 and 750 oC, where chelating agent concentration was 1 M.
Calcination
Angle, 2ș (o)
d-value (Å)
temperature (oC)
350
550
750
Intensity
(%)
36.887
2.4348
100.0
44.863
2.01874
89.2
65.325
1.4273
90
18.823
4.71053
100.0
37.289
2.40949
72.1
45.305
2.00005
82.8
65.417
1.42553
67.6
66.633
1.40242
65.7
18.902
4.691
100.0
37.493
2.39686
72.2
45.275
2.00129
84.2
52.747
1.73404
62.8
65.369
1.42645
67.9
68.803
1.36339
63.2
80
These peaks are similar with the reference d-value (Å) of 4.69187, 2.40094,
2.00294, 1.426618 and 1.40659 from the PDF (89-0912) data file. From the reference dvalues (Å), it is known that LiCo0.7Al0.3O2 materials belong to the rhombohedral system.
The crystal chemistry of these Al doped samples was carefully investigated. In all cases
the materials are single phase from the lowest temperature and all diffraction lines can
be indexed assuming a hexagonal (hex) lattice, which corresponds to the quasi-layered
Į-NaFeO2 type structure (R3m space group) in which Li+, M+ (M = Al, Co) and O2occupy 3a, 3b, and 6c sites (Wyckoff notations), respectively. As the calcinations
temperature gets higher, the diffraction peaks get sharper and the width of the peaks
narrower due to an increase in the sample crystallinity and a gradual growth of the
average particle size.
Cr doped LiCrxMn2-xO4 materials:
The X-ray diffraction patterns of Cr+3 doped samples show striking similarity to
that of pure LiMn2O4 ( space group Fd3m) in which the manganese ions occupy the 16d
sites and O-2 ions occupy the 32c sites. That the Cr doped compounds have been
demonstrated to have cubic spinel structure by several workers (Pistoia et al.,1992;
Baochen et al.,1993). In facts the lattice parameters of LiCrxMn2-xO4 are very closed to
those of LiMn2O4 (Thackeray et al.,1983; David et al.,1984). Substitution of Mn by Cr
showed result in a shrinkage of the unit-cell volume. This is because, in the same
oxidation state, chromium ions have smaller radii than manganese ions, i.e., Cr+3 (0.615
Å), Mn+3 (0.68 Å), Cr+4 (0.58 Å) and Mn+4 (0.60 Å) (Borchardt-Ott, 1993). The decrease
in the cell volume should increase the stability of the structure during intercalation and
de-intercalation of the lithium (Sigala et al., 1995; Zhang et al., 1998; Iwata et al.,1999).
The stronger Cr-O bonds in the delithiated state (compare the binding energy of 1142
kJ/mol for CrO2 with 946 kJ/mol for Į-MnO2) may also be expected to contribute to
stabilization of the octahedral sites. The higher stabilization energy of Cr+3 ions for
octahedral coordination is well known. Sigala et al.,1995 have demonstrated the
structural stability imparted by Cr+3 ions to LiMn2O4 spinel, and a similar effect by
chemically modified Cr+5…Cr+6 oxide has been observed by Zhang et al.,1998. It has
81
also been found (Iwata et al., 1999) that incorporation of Cr+3 greatly suppresses the
dissolution of manganese ions in the electrolyte, which one of the failure mechanisms of
LiMn2O4 cathodes.
4.2.5 Surface morphology
Surface morphology, one of the prime factors that govern the physical as well as
the electrochemical properties of synthesized cathode raw materials, has been studied by
means of SEM analysis. The micrographs for the materials of LiMn2O4 (CA-EG mixture
assisted), LiMn2O4 (CA assisted), LiMn2O4 (PA assisted), Cr doped LiCrxMn2-xO4,
and LiCo0.7Al0.3O2 (CA and PA assisted) are given in the Figures 4.11 a, 4.11 b, 4.12,
4.13, 4.14 and 4.15 respectively.
LiMn2O4 (CA-EG mixture assisted) materials:
Figure 4.11 a shows scanning electron micrographs (SEM) for the powders
calcined the gel precursors of the molar ratio of citric acid-ethylene glycol mixture to
total metal ions of 1.0 at various temperatures for 5 hours in air. When the gel
precursors are calcined at 250 oC, the average particle size of the powders was around
9.5 µm with fairly narrow size distribution. The presence of agglomerated particles was
also observed. As calcination temperature increased, slight growth kinetics was favored
and particles were changed to a slight larger particulate. When the gel precursors were
heated at 400 oC, the average particle size of the powders increased to 11 µm. For the
materials calcined at 450 oC, it was observed that agglomerated particles were changed
and the average particle size of the powders increased to about 13 µm with narrow
particle size distribution.
82
In order to investigate the effect of morphological features of LiMn2O4 powders
on citric acid-ethylene glycol mixture quantity, scanning electron microscopy (SEM)
was used for the powders with the gel precursors of the molar ratio of citric acidethylene glycol mixture to total metal ions of 0.25 and 0.5 calcined at 450 oC for 5 hours
in air as shown in Figure 4.11 b. The surface of the powders of the molar ratio of citric
acid-ethylene glycol mixture to total metal ions of 0.25 contained monodispersed fine
particulates with an average particle size of about 0.12 mm. For the materials prepared
by the molar ratio of citric acid-ethylene glycol mixture to total metal ions of 0.5, it was
observed that the particle size of the particulates was seen to be 0.18 mm which is larger
than that of the ratio of 0.25 at same calcination temperature.
(a)
(b)
(c)
Figure 4.11 a: Scanning electron micrographs of LiMn2O4 (CA-EG mixture assisted)
powders calcined at (a) 250 oC, (b) 400 oC and (c) 450 oC where citric acid-ethylene
glycol mixture to total metal ions was 1.0
83
(e)
(d)
Figure 4.11 b: Scanning electron micrographs for LiMn2O4 (CA-EG mixture assisted)
powders calcined the gel precursors of the molar ratio of citric acid-ethylene glycol
mixture to total metal ions of (d) 0.25 and (e) 0.5 at 450 oC.
From the above result, it was concluded that LiMn2O4 powders with a wide
variety of the physicochemical property such as particle size, crystallinity and specific
surface area could be controlled by simply varying the processing condition of pyrolysis
and chelating agent quantity.
LiMn2O4 (CA assisted) materials:
Figure 4.12 shows scanning electron micrographs for LiMn2O4 powders calcined
the gel precursors at 300 and 700 oC.
(a)
1000 x
(b)
1000 x
Figure 4.12: Scanning electron micrographs of LiMn2O4 (CA assisted) powders
calcined at (a) 300 oC and (b) 700 oC where citric acid to total metal ions was 1.0
84
When the gel precursors were calcined at 300 oC, the average particle size of the
powders was found around 4.603 µm with fairly narrow size distribution. The presence
of slightly agglomerated particles was also observed. As calcination temperature
increased, slight growth kinetics were favored and particles were changed to a slight
larger particulate. When the gel precursor were heated at 700 oC, the average particles
size of the powders increased to about 6.75 µm with a narrow size distribution.
LiMn2O4 (PA assisted) materials:
Figure 4.13 shows scanning electron micrographs for LiMn2O4 powders calcined
the gel precursors at 350 and 750 oC. When the gel precursors are calcined at 350 oC, the
average particle size of the powders was found around 4.66 µm with fairly narrow size
distribution. The presence of slightly agglomerated particles was also observed. As
calcination temperature increased, slight growth kinetics were favored and particles
were changed to a slight larger particulate. When the gel precursors were heated at
750 oC, the average particles size of the powders increased to about 5.87 µm with a
narrow size distribution.
(a)
(b)
Figure 4.13 : Scanning electron micrographs of LiMn2O4 (PA assisted) powders
calcined at (a) 350 oC and (b) 750 oC where propionic acid to total metal ions was 1.5
85
Cr-doped LiCrxMn2-xO4 Materials:
SEM imaging was employed to show the surface morphology and texture as well
as particle sizes at different dopant concentrations and same calcination temperature
(Figure 4.14). It is found that the particle morphology of the materials prepared at
800 oC is almost the same. Slightly agglomerated particles are formed at lower dopant
concentrations. The presence of spherical grains of an independent nature are obtained
up to a dopant level of about x = 0.20. It is interesting to note that the effect of a high
calcination temperature results in the formation of highly sintered particles, as
demonstrated by the micrographs. Nevertheless, particles of nanometer size are present
throughout the series of LiCrxMn2-xO4 (x = 0.00-0.20). The particles size distribution is
not significantly influenced by the dopant concentrations. Since extremely fine (<1 µm)
and extremely course (> 20 µm) particle fractions are absent, the materials are suitable
for usual electrode preparation techniques (Arnold et al., 2003).
LiCo0.7Al0.3O2 (CA and PA assisted) materials:
The micrographs for the materials of LiCo0.7Al0.3O2 (CA assisted) and
LiCo0.7Al0.3O2 (PA assisted) are given in the Figure 4.15. Figure 4.15 (a) and 4.15 (b)
show scanning electron micrographs (SEM) for the materials of LiCo0.7Al0.3O2 (CA
assisted) calcined at 350 and 550 oC, respectively. Whereas, Figure 4.15 (c) and 4.15 (d)
show scanning electron micrographs (SEM) for the materials of LiCo0.7Al0.3O2 (PA
assisted) calcined at 350 and 550 oC, respectively. When the gel precursors are calcined
at 350 oC, the average particle sizes are found around 1.15 µm and 1.9 µm for the
materials of LiCo0.7Al0.3O2 (CA assisted) and LiCo0.7Al0.3O2 (PA assisted), respectively
with fairly narrow size distribution. The presence of agglomerated particles was also
observed. As calcination temperature increased, slight growth kinetics was favored and
particles were changed to a slight larger particulate. When the gel precursors are
calcined at 550 oC, the average particle size of the powders increased to 1.67 µm and
2.34 µm, respectively with narrow particle size distribution.
86
(a)
(b)
(c)
(d)
(e)
Figure 4.14: Scanning electron micrographs for LiCrxMn2-xO4 materials calcined at
800 oC for 4 hours: (a) x = 0.00, (b) x = 0.01, (c) x = 0.02, (d) x = 0.05 and (e) x = 0.20
87
(a)
(c)
(b)
(d)
Figure 4.15: Scanning electron micrographs for the materials of LiCo0.7Al0.3O2
(CA assisted) calcined at (a) 250 oC and (b) 550 oC and for the materials of
LiCo0.7Al0.3O2 (PA assisted) calcined at (c) 250 oC and (d) 550 oC, respectively.
4.2.6 Energy Dispersive X-ray Analysis (EDAX)
EDAX is a chemical microanalysis technique used in conjunction with scanning
electron microscope (SEM). Analytical measurement of the composition by means of
EDAX confirm the presence of the elements. EDAX analysis is done to determine the
composition of elements of the prepared raw materials. Figures 4.16 a, 4.16 b, 4.17, 4.18
4.19, 4.20 and 4.21 show the spectrum of the materials LiMn2O4 (CA-EG mixture
assisted), LiMn2O4 (CA assisted), LiMn2O4 (PA assisted), Cr doped LiCrxMn2-xO4,
LiCo0.7Al0.3O2 (CA assisted) and LiCo0.7Al0.3O2 (PA assisted), respectively. Materials
88
LiMn2O4 (CA-EG mixture assisted) calcined at 250, 400 and 450 oC with the molar ratio
of citric acid-ethylene glycol (CA-EG) mixture to total ions of 1.0; materials LiMn2O4
(CA assisted) calcined at 300 and 700 oC with the molar ratio of propionic acid to total
metal ions of 1.0; materials LiMn2O4 (PA assisted) calcined at 350 and 750 oC with the
molar ratio of 1.5; materials Cr doped LiCrxMn2-xO4 calcined at 800 oC with the dopant
concentrations of x = 0.00, 0.01, 0.02, 0.05 and 0.20; materials LiCo0.7Al0.3O2 (CA
assisted) calcined at 350 and 750 oC with the chelating agent concentration of 1 M citric
acid, and materials LiCo0.7Al0.3O2 (PA assisted) calcined at 350 and 750 oC with the
chelating agent concentration of 1 M propionic acid. On the other hand, Figure 4.16 b
represents the spectrum of the LiMn2O4 (CA-EG mixture assisted) materials calcined at
450 oC with molar ratios of 0.25, 0.5 and 1.0.
Based on the spectrum in the Figures 4.16 a, 4.17 and 4.18 show that the
composition percentage (wt %) of oxygen decrease and manganese increase with
increasing the calcination temperature where as Figure 4.16 b shows that the
composition percentage (wt %) of oxygen increase and manganese decrease with
increasing the chelating agent concentration. Figures 4.20 and 4.21 also show that the
composition percentage (wt %) of oxygen decrease with increasing the calcination
temperatures. This is because; the lower particle size gives higher surface area.
Therefore, they will absorb a lot of oxygen molecules to the particles pores resulting to
the higher oxygen percentage. Decreasing of the manganese percentage doesn’t mean
that the manganese element was terminated. This was due to the increasing of acid
concentration which has increased the composition percentage of oxygen, thus reduced
the composition percentage of manganese. The ratio of manganese must be compared
with all the elements in manganese oxide. Based on the spectrum in the Figure 4.19
shows that the composition percentage (wt %) of oxygen and manganese decrease along
with increasing the dopant concentrations.
89
450 oC
400 oC
250 oC
Figure 4.16 a:
EDAX spectrum of LiMn2O4 (CA-EG mixture assisted) materials
calcined at 250, 400 and 450 oC with citric acid-ethylene glycol mixture to total metal
ions of 1.0
90
1.0
0.5
0.25
Figure 4.16 b: EDAX spectrum of LiMn2O4 (CA-EG mixture assisted) materials
calcined at 450 oC with citric acid-ethylene glycol mixture to total metal ions of 0.25,
0.5 and 1.0
91
700 oC
300 oC
Figure 4.17: EDAX spectrum of LiMn2O4 (CA assisted) materials calcined at 300 and
700 oC with citric acid to total metal ions of 1.0
(b)
(a)
Figure 4.18: EDAX spectrum of LiMn2O4 (PA assisted) materials calcined at (a) 350 oC
and (b) 750 oC with propionic acid to total metal ions of 1.5
92
x = 0.20
x = 0.05
x = 0.02
x = 0.01
x = 0.00
Figure 4.19: EDAX spectrum of Cr doped LiCrxMn2-xO4 materials calcined at 800 oC
where dopant concentrations of x = 0.00, 0.01, 0.02, 0.05, 0.20
93
(b)
(a)
Figure 4.20: EDAX spectrum of LiCo0.7Al0.3O2 (CA assisted) materials calcined at (a)
350 oC and (b) 750 oC
(b)
(a)
Figure 4.21: EDAX spectrum of LiCo0.7Al0.3O2 (PA assisted) materials calcined at (a)
350 oC and (b) 750 oC
94
Composition variations by the different calcination temperatures and different
molar concentrations for the materials LiMn2O4 (CA-EG mixture assisted), LiMn2O4
(CA assisted), LiMn2O4 (PA assisted), Cr doped LiCrxMn2-xO4, LiCo0.7Al0.3O2 (CA and
PA assisted) are shown in the Tables 4.5, 4.6, 4.7, 4.8, and 4.9 respectively. In the
earlier section, we observed that specific surface area of the particles decreases with
increasing the calcination temperatures and increases with increasing the chelating agent
concentration that is well matched with the XRD patterns.
Table 4.5: Composition analysis of LiMn2O4 (CA-EG mixture assisted) materials
Calcination
mixture to
temperature
total metal
(oC)
Wt.
%
ions ratio
1.0
1.0
1.0
CA-EG
Calcination
mixture to
temperature
total metal
(oC)
Element
CA-EG
Element
calcined at 250, 400 and 450 oC.
Wt.
%
ions ratio
250
400
450
O
26.39
O
26.63
Mn
73.61
Mn
73.37
Total
100
Total
100
O
21.71
O
27.16
Mn
78.29
Mn
72.84
Total
100
Total
100
O
21.10
O
27.66
Mn
78.90
Mn
72.34
Total
100
Total
100
0.25
0.5
1.0
450
450
450
95
Table 4.6: Composition analysis of LiMn2O4 (CA assisted) materials calcined at 300
and 700 oC.
Citric acid to total metal ions
ratio
Calcination
temperature (oC )
1.0
Element
Wt %
O
16.0
Mn
84.0
Total
100
O
12.38
Mn
87.62
Total
100
300
1.0
700
Table 4.7: Composition analysis of LiMn2O4 (PA assisted) materials calcined at 350
and 750 oC.
Propionic acid to total
metal ions ratio
1.5
1.5
Calcination
temperature (oC)
350
750
Element
Wt %
O
23.74
Mn
76.26
Total
100
O
21.46
Mn
78.54
Total
100
96
Table 4.8: Composition analysis of Cr doped LiCrxMn2-xO4 materials calcined at 800 oC
Dopant concentrations (x)
x = 0.00
x = 0.01
x = 0.02
x = 0.05
x = 0.20
Elements
Wt %
Cr
-
O
20.77
Mn
79.23
Total
100
Cr
2.02
O
21.19
Mn
76.79
Total
100
Cr
2.54
O
20.87
Mn
76.58
Total
100
Cr
4.63
O
20.12
Mn
75.25
Total
100
Cr
15.44
O
15.46
Mn
69.10
Total
100
97
Table 4.9: Composition analysis of LiCo0.7Al0.3O2 (CA and PA assisted) materials
LiCo0.7Al0.3O2
(PA assisted)
LiCo0.7Al0.3O2
(CA assisted)
Materials
calcined at 350 and 750 oC
Calcination
temperature
(oC)
350
350
Elements
Wt.
%
C
Calcination
temperature
(oC)
Elements
Wt.
%
30.86
C
41.52
O
35.84
O
28.80
Al
4.85
Al
2.53
Co
28.45
Co
27.15
Total
100
Total
100
C
33.35
C
41.06
O
35.60
O
30.07
Al
4.70
Al
2.43
Co
26.35
Co
26.45
Total
100
Total
100
750
750
98
4.3
Electrochemical Characterizations
4.3.1
Charge-Discharge Studies
Charge/discharge cycling has been performed at a current density of 0.2 mA/cm2
between the cut-off voltage of 3.0 to 4.3 V. Figure 4.22 shows charge-discharge
behavior with the number of cycles for the (a) A cell, (b) B cell, (c) C cell and (d) D cell
where the raw materials calcined at 400, 700, 750 and 800 oC, respectively. Figure 4.23
shows charge-discharge behavior with the number of cycles for the (e) E cell and (f) F
cell where the raw materials for the both cells calcined at 550 oC respectively and
chelating agent concentration was same (1 M). The molar ratios of citric acid-ethylene
glycol (CA-EG) mixture to total metal ions, citric acid (CA) to total metal ions and
propionic acid (PA) to total metal ions of 1.0, 1.0 and 1.5 were for the A cell, B cell and
C cell, respectively. Dopant concentration for the D cell was x = 0.20
The voltage profiles of the first three charge-discharge cycles for the compounds
of A cell, B cell and C cell have two distinct plateaus in 3.9 and 4.1 volt; 3.8 and 4.1
volt; 4.8 and 4.16 volt regions, respectively which means a well defined spinel LiMn2O4
structure and which is characteristic of manganese oxide spinel structure (Liu et al.,
1996; Thackery et al., 1983). It was reported that each plateaus delivers half of the total
capacity, which confirmed the hypothesis that there were two binary equilibrium
systems during Li+ intercalation, i.e., Ȝ-MnO2-Li0.5Mn2O4 and Li0.5Mn2O4-LiMn2O4 (Liu
et al.,1996). The shape of the charge-discharge curves for the E cell and F cell shows
good reversibility and capacity retention during the cycling.
A cell, B cell and C cell initially deliver discharge capacity of 29.66, 20.94, and
41.65 mA h/g, respectively. Discharge capacity slowly decreases with the cycle
numbers and remains 21.18, 19.63, and 37.72 mA h/g at the 3rd cycle respectively. This
shows 28.6, 6.3 and 9.43 % capacity fading for the A cell, B cell and C cell respectively.
Capacity fade for the B cell is lower than that of others. The poor crystallinity of
LiMn2O4 powders calcined at low temperature (400 oC) is well consistent with the
99
results of XRD patterns. It is inferred from the above results that the LiMn2O4 powders
calcined at higher temperatures have higher crystallinity and thus higher initial capacity.
The main problem of LiMn2O4 cathode materials for lithium batteries is it weak
cycleability at elevated temperatures displaying significant capcity fades. LiPF6 is the
common electrolyte solution of lithium ion batteries (widely employed in commercial
batteries). The battery designed also loses about 50 % of its capacity after 50 cycles at
55 oC. Whereas, employing the electrolyte solution of LiBF4, Ali Eftekhari, 2003
observed significant improvement for cycleability of lithium-ion battery. Although,
reporting such improvement is satisfactory from an applied research point of view,
further investigations on the source of such capacity fade are needed to clarify the
problem. It should be emphasized that it can not be claimed that using LiBF4 could
completely satisfy the problem related to instability of electrolyte solution at high
voltage operation, however, their results suggest LiBF4 as a promising alternative to
LiPF6. It is known that the main reason for the appearance of capacity fades in LiMn2O4
particularly at elevated temperatures is due to the Mn dissolution. Sun et at., 2002 have
assumed that this also the main reason for capacity fading of LiNi0.5Mn1.5O4 spinel as a
5 V cathode material at elevated temperature. Mn dissolution is possible due to the
existence of trivalent Mn. As all of Mn in the spinel is oxidized to tetravalent Mn at the
4.1 V redox system, Mn dissolution-based capacity fading should be related to chargedischarging during 4 volt performance.
For the D cell i.e., (x = 0.20) 0.20 Cr-doped material gives 49.50, 47.44 and
45.36 mA h/g discharge capacity for the 1st , 2nd, and 3rd cycle respectively. Specific
capacity is higher than the others and capacity fading only 8.4 % after three cycles.
Replacement of Mn3+ ion by Cr3+ and the oxidation of a similar amount of Mn3+ to the
Mn4+ state leads to an increase in the average oxidation state of manganese. The
diminished Mn3+ ion concentration causes a reduction in the unit-cell volume of the
spinel, which results in increased structural stability. The capacities obtained correspond
to oxidation of Mn3+ to Mn4+.
4.4
4.4
4.2
4.2
Cell voltage (Li /Li),v
Cell voltage (Li /Li),v
100
4
+
+
4
3.8
3.6
3.4
3.2
3.8
3.6
3.4
3.2
3
3
0.00
10.00
20.00
30.00
Specific capacity (mAh/g)
1st cycle charge
2nd cycle charge
3rd cycle charge
40.00
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00
Specific capacity (mAh/g)
1st cycle discharge
2nd cycle discharge
3rd cycle discharge
1st cycle charge
2nd cycle charge
3rd cycle cjharge
(c) C cell
(a) A cell
4.6
4.4
4
4.2
Cell voltage (Li /Li),v
4.2
+
Cell voltage (Li /Li),v
4.4
+
3.8
3.6
3.4
4
3.8
3.6
3.4
3.2
3.2
3
0.00
1st cycle discharge
2nd cycle discharge
3rd cycle discharge
5.00
10.00 15.00 20.00 25.00
Specific capacity (mAh/g)
3rd cycle charge
2nd cycle charge
1st cycle charge
(b) B cell
30.00
3rd cycle discharge
2nd cycle discharge
1st cycle discharge
3
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00
Specific capacity (mAh/g)
1st cycle charge
2nd cycle charge
3rd cycle charge
1st cycle discharge
2nd cycle discharge
3rd cycle discharge
(d) D cell
Figure 4.22: Charge-discharge characteristics with the number of cycles for the (a) A
cell, (b) B cell, (c) C cell and (d) D cell where the raw materials calcined at 400, 700,
750 and 800 oC respectively. Cycling was carried out galvanostatically at constant
charge-discharge current density of 0.2 mA/cm2 (200 µA) between voltage region
3.0 to 4.3 V
101
On the other hand, E cell and F cell initially deliver discharge capacity of 97.34
mA h/g and 74.43 mA h/g, respectively and discharge capacity slowly decreases with
the number of cycle and remains 88.37 and 73.21 mA h/g at the 3rd cycle respectively.
This shows 9.2 % and 1.6 % capacity fading for the E cell and F cell, respectively.
Comparing to the others, E cell delivers the highest specific capacity whereas capacity
4.6
4.6
4.4
4.4
4.2
Cell voltage (Li /Li),V
4
+
+
Cell voltage (Li /Li),V
fade for the F cell is the lowest of all and this shows very good capacity retention.
3.8
3.6
3.4
3.2
4.2
4
3.8
3.6
3.4
3.2
3
0
10 20 30 40 50 60 70 80 90 100 110
3
0
10
20
Specific capacity (mAh/g)
1st cycle charge
2nd cycle charge
3rd cycle charge
1st cycle discharge
2nd cycle discharge
3rd cycle discharge
30 40 50 60 70
Specific capacity (mAh/g)
80
90
1st cycle charge
1st cycle discharge
2nd cycle charge
2nd cycle discharge
3rd cycle charge
3rd cycle discharge
(e) E Cell
100
(f) F Cell
Figure 4.23: Charge-discharge characteristics with the number of cycles for the (e) E
cell and (f) F cell where the raw materials calcined at 550 oC respectively. Cycling was
carried out galvanostatically at constant charge-discharge current density of
0.2 mA/cm2 (200 µA) between voltage region 3.0 to 4.3 V
The voltage profile of the cell with CA assisted cathode exhibited a potential
slightly lower than for propionic acid assisted (PA assisted) compound. This was due to
the different crystallographic texture and morphology of these two materials. It was
observed that the fully intercalated phase was not recovered during the first discharge.
102
This was mainly due to the irreversible capacity loss because this capacity retention
occurred also when the applied current density was decreased.
4.3.2
Cycleability Studies
The cycleability curves for the A cell, B cell, C cell, D cell, E cell and F cell are
shown in the Figure 4.24.
120
Discharge capacity
(mAh/g)
100
80
60
40
20
0
0
1
2
3
Number of cycles
4
A cell
B cell
C cell
D cell
E cell
F cell
Figure 4.24: Cycleability for the A cell, B cell, C cell, D cell, E cell and F cell with a
0.2 mA/cm2 current density at the voltage range of 3.0 to 4.3 V
It shows the capacity response vs. cycle number for the first three cycles and
cycleability data obtained from charge-discharge profile are summarized in Table 4.10.
Cells were charged and discharged at the current density of 0.20 mA/cm2 in the voltage
window of 3.0 to 4.3 V. For the first cycle the initial discharge capacities of 29.66,
20.94, 41.65, 49.50, 97.34 and 74.43 mA h/g for the A cell, B cell, C cell, D cell, E cell
and F cell respectively.
103
Capacity decreases slowly and after three cycles the discharge capacities are 21.18,
19.63, 37.72, 45.36, 88.37 and 73.21 mA h/g respectively. The capacities retention over
three cycles are about 71.4, 93.7, 90.6, 91.6, 90.8 and 98.4 % for the A cell, B cell, C
cell, D cell, E cell and F cell respectively.
Table 4.10: Cycleability data for the three cycles obtained from charge/discharge
characterization of the A cell, B cell, C cell, D cell, E cell and F cell
Cells
A
B
C
D
E
F
Charge
Discharge
Capacity
Capacity
Coulombic
capacity
capacity
retention
fading
Efficiency
(mA h/g)
(mA h/g)
(%)
(%)
(%)
36.57
29.66
25.13
23.84
22.02
21.18
96.2
27.04
20.94
77.0
22.03
20.33
22.01
19.63
89.1
84.92
41.65
49.0
49.49
39.72
50.42
37.72
74.8
78.21
49.50
63.3
49.33
47.44
46.46
45.36
97.6
207.51
97.34
46.9
103.70
92.87
95.25
88.37
92.8
105.31
74.43
70.7
82.38
71.90
77.27
73.21
81.1
71.4
93.7
90.6
91.6
90.8
98.4
28.6
6.3
9.4
8.4
9.2
1.6
94.8
92.2
80.2
96.2
89.5
87.3
94.7
104
It is seen that among the spinel structure materials (A cell, B cell, C cell and D
cell), only D cell i.e., 0.20 Cr-doped Li/1M LiPF6-EC/DMC/LiCrxMn2-xO4 cell exhibits
a higher specific capacity and capacity retention also good up to three cycles. The
superior cycleabilty of the doped variety is due to increased stability caused by the
higher octahedral site stabilization energy of Cr3+. The effect of Cr is more pronounced
in reducing the capacity fade. On the other hand, E cell exhibits the highest initial
discharge capcity whereas F cell exhibits the best capcity retention and less capacity
fading among all. The highest capacity retention and less capacity fading during cycling
tests suggests that Al-doping assists maintenance of the original layered crystal structure
during deintercalation of Li-ions (Guilmard et al., 2003). Generally, good capacity
retention is attributed to smaller volume change of the cathode material crystal lattice
upon Li+ intercalation and deintercalation process.
4.3.3 Coulombic Efficiency
The coulombic efficiencies of the cells were also measured and are summarized in
Table 4.10. The Figure 4.25 shows coulombic efficiency upon cycling. In the first cycle,
the efficiency differs for all specimens. However, after cycling for three or four runs, the
coulombic efficiency is increased to a nearly constant value. The coulombic efficiencies
of A cell, B cell, C cell, D cell, E cell and F cell are 81.1, 94.8 and 96.2 %; 77.0, 92.2
and 89.1 %; 49.0, 80.2 and 74.8 %; 63.3, 96.2 and 97.6 %; 46.9, 89.5 and 92.8 %;
70.7, 87.3 and 94.7 % for the 1st, 2nd and 3rd cycles respectively. The highest coulombic
efficiecy was observed 97.6 % for 3rd cycle of D cell (Li/1M LiPF6-EC/DMC/LiCrxMn2xO4).
The above results reveal that the smallest powders with average 1.0 µm particle
size (LiCrxMn2-xO4, x = 0.20 cathode) exhibits the best coulombic efficiency.
105
When the particle size is reduced, the overall surface area is increased. Thus, cathode
consisting of small particles with large surface area can provide more lithium ions for
diffusion, leading to the high ionic current and specific capacity
Coulombic efficiency
(Percent)
120
100
80
60
40
20
0
0
1
2
3
4
Number of cycles
A cel
B cell
C cell
D cell
E cell
F cell
Figure 4.25: Coulombic efficiency for the A cell, B cell, C cell, D cell, E cell and F cell
with the number of cycles.
In addition, during the discharge process, small particles can provide more
interfacial area for contact within the liquid electrolyte and hence can increase the
opportunity for lithium ions to intercalate back into the host structure, thereby resulting
in the high coulomb efficiency (Lu et al., 2001).
106
4.4
Overall Performance of the Fabricated Cells
A number of criterial specific parameters of the fabricated cells have been
investigated using a Solartron 1470 Battery Testing System in the suitable voltage range
and suitable current density. The impact of these parameters on performance of the cells
is analyzed. Electrochemical parameters of the fabricated cells revealed many
similarities between them, e.g., similar anode materials, similar electrolyte, same current
collector foils, similar separator materials and same size.
Nevertheless, there are quite many differences in some of the electrochemical
parameters and the performances of the cells with respect to specific capacity, capacity
retention, capacity fading and coulombic efficiency. Fabricated A cell, B cell, C cell,
D cell, E cell and F cell deliver specific capacity of 21.18, 19.63, 37.72, 45.36, 88.37
and 73.21 mA h/g at the 3rd cycle respectively. Capacity fading of 28.6, 6.3, 9.4, 8.4, 9.2
and 1.6 % ; capacity retention of 71.4, 93.7, 90.6, 91.6, 90.8 and 98.4 % ; coulombic
efficiency of 96.2, 89.1, 74.8, 97.6, 92.8 and 94.7 % for the A cell, B cell, C cell, D cell,
E cell and F cell respectively.
The most widely used commercial positive electrode materials are LiMn2O4 and
LiCoO2. 100-120 mA h/g and 150 mA h/g are the maximum practical attainable
capacity for the LiMn2O4 and LiCoO2 cathode materials respectively and maximum
efficiency of the battery is 93 % (Mizushim et al., 1980). Presently some companies are
fabricating Li-ion batteries using LiCoO2 as cathode materials. Maximum practical
attainable capacity of Sony, Moli, A&T, Sanyo and Matsushita are 102, 123, 158, 135,
and 155 mA h/g respectively. The capacity losses (capacity fading) of the Matsushita,
Sony, and A&T cells of 9.5, 12.31, and 15.7 % are quite remarkable (Moshtev et al.,
2000). Comparing to the commercial cathode materials, our fabricated materials exhibit
lower specific capacity than the commercial one but some other parameters e.g.,
coulombic efficiency, capacity retention and capacity fading are better.
CHAPTER 5
CONCLUSIONS AND FUTURE INVESTIGATIONS
5.1
Conclusions
Sol-gel synthesis has been demonstrated as versatile route to produce spinel
LiMn2O4 (CA-EG mixture assisted), LiMn2O4 (CA assisted), LiMn2O4, (PA assisted),
Cr-doped LiCrxMn2-xO4 (x = 0.0-0.20) cathode materials and layered LiCo0.7Al0.3O2
(CA and PA assisted) cathode materials using organic acid as chelating agent. In this
report it was demonstrated how, with the slight change of molar ratio of chelating agent
to total metal ions and calcination temperatures, the above products were formed. This
technique offers some advantages. Electrochemical behaviors of the prepared powder
materials were analyzed using galvanostatic charge-discharge cycling studies in the
voltage range 3.0-4.3 V (vs. Li metal) using 1 M LiPF6-EC/DMC as electrolyte. A cell,
B cell, C cell and D cell initially (materials having a spinel structure) deliver discharge
capacity of 29.66, 20.94, 41.65, and 49.50 mA h/g respectively. Specific capacity for
the materials of D cell [Cr-doped LiCrxMn2-xO4 (x = 0.20)] is higher than the others.
Capacity fading 28.6, 6.3, 9.4 and 8.4 % for the A cell, B cell, C cell and D cell
respectively. Capacity fade for the B cell is lower than that of others. The poor
crystallinity of the materials calcined at low temperature (400 oC) is well consistent with
the results of XRD patterns. It is inferred from the above results that the materials
calcined at higher temperatures have higher crystallinity and thus higher initial capacity.
108
Replacement of Mn3+ ion by Cr3+ and the oxidation of a similar amount of Mn3+ to the
Mn4+ state leads to an increase in the average oxidation state of manganese. The
diminished Mn3+ ion concentration causes a reduction in the unit-cell volume of the
spinel, which results in increased structural stability. The higher stabilization energy of
Cr+3 ions for octahedral coordination is well known. Sigala et al.,1995 have
demonstrated the structural stability imparted by Cr+3 ions to LiMn2O4 spinel, and a
similar effect by chemically modified Cr+5…Cr+6 oxide has been observed by Zhang et
al.,1998. It has also been found (Iwata et al.,1999) that incorporation of Cr+3 greatly
suppresses the dissolution of manganese ions in the electrolyte, which one of the failure
mechanisms of LiMn2O4 cathodes. On the other hand, E cell and F cell initially deliver
discharge capacity of 97.34 and 74.43 mA h/g, respectively and this shows 9.2 % and
1.6 % capacity fading respectively. Comparing to the others, the materials
(LiCo0.7Al0.3O2) of E cell and F cell delivers the highest specific capacity and the lowest
capacity fading.
LiCo0.7Al0.3O2 materials have a single phase and Į-NaFeO2 structure. Aluminum
doping increases the interval of thermal stability favoring the formation of well
crystallized LiCo0.7Al0.3O2 powders at lower temperature and preventing the loss of
lithium from the structure. The structural and electrochemical properties are investigated
to examine the effect of Al-doping on specific capacity and its retention. Comparing to
the commercial one, the overall capacity decreases due to the Al doping. On the other
hand, more stable charge-discharge cycling performances have been observed when
electrodes are charged up to 4.3 volt. The rechargeability of the Li/LiCo0.7Al0.3O2 cells
appears better than the all because the lack of the two phase behavior in the high voltage
region. At the cut off voltage of 4.3 V (end of the charge process), the specific capacity
of the Li/ LiCo0.7Al0.3O2 cells is strongly dependent on Al substitution. The superior
cycleability of the doped variety is due to increased stability caused by the higher
octahedral site stabilization energy of Al+3. Replacement of Co by Al results in slight
changes of the lattice parameters and reduces the unit cell volume which in turn
influences the chemical diffusion coefficients of Li-ions due to an increase of the
Vander Waals interlayer spacing.
109
5.2
Scope and Limitations
The prepared cathode materials show the potential to overcome its fast capacity
fading with charge/discharge cycling as well as show very good capacity retention and
good coulombic efficiency over a wide range of calcination temperatures and chelating
agent to total metal ions ratio.
In this study, the first step is to prepare cathode raw materials that is too much
time consuming. One of the major parts is the physical characterization of the prepared
raw materials and electrochemical characterization of the synthesized cathode. Such
characterization demands frequent use of instruments as stated in the earlier. Timely
utilization of instruments are important to evaluate and verify the product systematically
but the problems arise when a long queue in using the instruments.
The main limitation is the cathode preparation. To prepare the cathode it is
needed to provide commercial paint applicator, two roller, cathode frame with standard
diameter- thickness-length and hydraulic press. Due to the lack of these instruments we
are fully dependent on the battery manufacturer industry to fabricate the cathode and
cell and also to examine their electrochemical characterization.
5.3
Recommendations for Future Study
Since preliminary investigations show the feasibility of doped metal oxides as a
cathode, further studies are needed to evaluate full-scale treatment. Charge-discharge
examination at various current densities of 0.1, 0.5 and 1.0 mA/cm2; variation of specific
discharge capacity with number of cycles at various current densities of 0.1, 0.5 and 1.0
mA/cm2; cyclic voltammetry; kinetics studies and electrochemical impedance
spectroscopic studies (EIS) in full charged and partially charged conditions will focus
110
on breakthrough capacity as well as on chelating agent and metal ions ratio. So that
these operation can easily be tailored according to the demand of markets.
To improve the better electrochemical performance (practical voltage, chargedischarge capacity, cycle life) of the cathode, a control amount of surface modifier
(various metal oxides) can be used and special attention can also be paid on how the
morphology and structure of the resultant raw materials reflect those of the parent’s
materials.
Therefore, still a lot of works remaining have to be done to manufacture a active
cathode materials. Overall goal will be to contribute to a comprehensive insight in the
factors controlling Li-ion cathode performance, from the synthesis of cathode materials
to the details of phase related electrochemical behavior.
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APPENDIX
APPENDIX A 1
In details Report of Li/1M LiPF6-EC/DMC/LiCo0.7Al0.3O2 (CA assisted)
[E cell] Cell Test Data for the First Cycle Charge
Experiment start time: 11.21.31 AM, Date: 6/14/2005
Sample rate: 0.01 (Hz)
Unit number for each result number: 2
Channel number for each result number: 2
Step number for each result no: 1
Step repeat: 1
Schedule repeat: 1
Result
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
Time
Voltage (V)
Current (A)
Charge (Ah)
Charge (mA h/g)
01:40.0
03:20.0
05:00.0
06:40.0
08:20.0
10:00.0
11:40.0
13:20.0
15:00.0
16:40.0
18:20.0
20:00.0
21:40.0
23:20.0
25:00.0
26:40.0
28:20.0
30:00.0
31:40.0
33:20.0
35:00.0
36:40.0
38:20.0
40:00.0
41:40.0
43:20.0
45:00.0
46:40.0
3.17956543
3.533203125
3.620727539
3.665893555
3.691772461
3.705444336
3.718505859
3.722900391
3.733520508
3.735351563
3.738525391
3.739746094
3.747924805
3.74987793
3.75012207
3.750854492
3.751098633
3.751708984
3.753662109
3.754150391
3.754394531
3.755126953
3.755371094
3.756347656
3.762695313
3.765258789
3.765625
3.76574707
0.000199661
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000199653
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
5.54613E-06
1.10918E-05
1.66376E-05
2.21833E-05
2.7729E-05
3.32747E-05
3.88204E-05
4.43661E-05
4.99119E-05
5.54576E-05
6.10033E-05
6.6549E-05
7.20947E-05
7.76406E-05
8.31866E-05
8.87323E-05
9.4278E-05
9.98237E-05
0.000105369
0.000110915
0.000116461
0.000122007
0.000127552
0.000133098
0.000138644
0.000144189
0.000149735
0.000155281
0.27
0.53
0.80
1.07
1.33
1.60
1.87
2.13
2.40
2.67
2.93
3.20
3.47
3.73
4.00
4.27
4.53
4.80
5.07
5.33
5.60
5.87
6.13
6.40
6.67
6.93
7.20
7.47
123
29
48:20.0
3.76574707
0.000199646
0.000160827
7.73
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
50:00.0
51:40.0
53:20.0
55:00.0
56:40.0
58:20.0
00:00.0
01:40.0
03:20.0
05:00.0
06:40.0
08:20.0
10:00.0
11:40.0
13:20.0
15:00.0
16:40.0
18:20.0
20:00.0
21:40.0
23:20.0
25:00.0
26:40.0
28:20.0
30:00.0
31:40.0
33:20.0
35:00.0
36:40.0
38:20.0
40:00.0
41:40.0
43:20.0
45:00.0
46:40.0
48:20.0
50:00.0
51:40.0
53:20.0
55:00.0
56:40.0
58:20.0
00:00.0
01:40.0
03:20.0
05:00.0
06:40.0
08:20.0
3.766113281
3.766479492
3.766601563
3.766723633
3.766967773
3.767944336
3.76940918
3.769775391
3.769775391
3.769897461
3.770019531
3.770263672
3.770507813
3.770629883
3.770874023
3.770996094
3.770996094
3.770996094
3.771118164
3.771240234
3.771362305
3.771728516
3.773925781
3.77746582
3.779663086
3.780761719
3.780883789
3.781005859
3.780883789
3.780761719
3.780273438
3.779541016
3.779907227
3.780517578
3.780639648
3.780883789
3.780883789
3.780883789
3.780883789
3.781005859
3.781005859
3.781005859
3.781005859
3.78112793
3.78137207
3.781494141
3.781860352
3.781982422
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000199646
0.000199653
0.000199653
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000199653
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000166372
0.000171918
0.000177464
0.000183009
0.000188555
0.000194101
0.000199647
0.000205192
0.000210738
0.000216284
0.000221829
0.000227375
0.000232921
0.000238467
0.000244012
0.000249558
0.000255104
0.00026065
0.000266196
0.000271741
0.000277287
0.000282833
0.000288379
0.000293924
0.00029947
0.000305016
0.000310562
0.000316107
0.000321653
0.000327199
0.000332745
0.00033829
0.000343836
0.000349382
0.000354928
0.000360473
0.000366019
0.000371565
0.00037711
0.000382656
0.000388202
0.000393748
0.000399293
0.000404839
0.000410385
0.00041593
0.000421476
0.000427022
8.00
8.27
8.53
8.80
9.07
9.33
9.60
9.87
10.13
10.40
10.66
10.93
11.20
11.46
11.73
12.00
12.26
12.53
12.80
13.06
13.33
13.60
13.86
14.13
14.40
14.66
14.93
15.20
15.46
15.73
16.00
16.26
16.53
16.80
17.06
17.33
17.60
17.86
18.13
18.40
18.66
18.93
19.20
19.46
19.73
20.00
20.26
20.53
124
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
10:00.0
11:40.0
13:20.0
15:00.0
16:40.0
18:20.0
20:00.0
21:40.0
23:20.0
25:00.0
26:40.0
28:20.0
30:00.0
31:40.0
33:20.0
35:00.0
36:40.0
38:20.0
40:00.0
41:40.0
43:20.0
45:00.0
46:40.0
48:20.0
50:00.0
51:40.0
53:20.0
55:00.0
56:40.0
58:20.0
00:00.0
01:40.0
03:20.0
05:00.0
06:40.0
08:20.0
10:00.0
11:40.0
13:20.0
15:00.0
16:40.0
18:20.0
20:00.0
21:40.0
23:20.0
25:00.0
26:40.0
28:20.0
30:00.0
3.782104492
3.782104492
3.782226563
3.782348633
3.782348633
3.782592773
3.783081055
3.784301758
3.78503418
3.78527832
3.785400391
3.785400391
3.785522461
3.785522461
3.785522461
3.785644531
3.785644531
3.785766602
3.785888672
3.786132813
3.786254883
3.786376953
3.786376953
3.786376953
3.786621094
3.786621094
3.786743164
3.786865234
3.787231445
3.788208008
3.789672852
3.791137695
3.792602539
3.794677734
3.795776367
3.796264648
3.796508789
3.796508789
3.796630859
3.796630859
3.796630859
3.79675293
3.79675293
3.796875
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125
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31:40.0
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126
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128
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0.004037348
0.004042894
0.004048439
0.004053985
0.004059531
0.004065076
0.004070622
0.004076167
0.004081713
0.004087259
0.004092804
0.00409835
0.004103896
0.004109441
0.004114987
0.004120532
0.004126078
0.004131624
0.00413717
0.004142716
0.004148261
0.004153807
0.004159353
0.004164899
0.004170445
0.004175991
0.004181537
0.004187083
0.004192629
0.004198175
0.004203721
0.004209267
0.004214813
0.004220359
0.004225905
0.004231452
0.004236998
0.004242544
0.00424809
0.004253636
0.004259182
0.004264728
0.004270274
0.004275821
0.004281367
0.004286913
0.004292459
0.004298005
0.004303551
193.84
194.10
194.37
194.64
194.90
195.17
195.44
195.70
195.97
196.24
196.50
196.77
197.04
197.30
197.57
197.84
198.10
198.37
198.64
198.90
199.17
199.44
199.70
199.97
200.24
200.50
200.77
201.04
201.30
201.57
201.84
202.10
202.37
202.64
202.90
203.17
203.44
203.70
203.97
204.24
204.50
204.77
205.04
205.30
205.57
205.83
206.10
206.37
206.63
206.90
138
777
778
779
35:00.0
36:40.0
37:09.5
4.487548828
4.487792969
4.495849609
0.000199661
0.000199661
0.000199944
0.004309097
0.004314643
0.004316282
207.17
207.43
207.51
139
APPENDIX A 2
In details Report of Li/1M LiPF6-EC/DMC/LiCo0.7Al0.3O2 (CA assisted)
[E cell] Cell Test Data for the First Cycle Discharge
Experiment start time: 11.21.31 AM, Date: 6/14/2005
Sample rate: 0.01 (Hz)
Unit number for each result number: 2
Channel number for each result number: 2
Step number for each result no: 2
Step repeat: 1
Schedule repeat: 1
Result
Number
780
781
782
783
784
785
786
787
788
789
790
791
792
793
794
795
796
797
798
799
800
801
802
803
804
805
806
807
808
809
810
811
Time
Voltage (V)
Current (A)
Charge (Ah)
38:49.5
40:29.5
42:09.5
43:49.5
45:29.5
47:09.5
48:49.5
50:29.5
52:09.5
53:49.5
55:29.5
57:09.5
58:49.5
00:29.5
02:09.5
03:49.5
05:29.5
07:09.5
08:49.5
10:29.5
12:09.5
13:49.5
15:29.5
17:09.5
18:49.5
20:29.5
22:09.5
23:49.5
25:29.5
27:09.5
28:49.5
30:29.5
4.430419922
4.418701172
4.41015625
4.397949219
4.393798828
4.388916016
4.379638672
4.376464844
4.367919922
4.363037109
4.359863281
4.352539063
4.348144531
4.345458984
4.341308594
4.332275391
4.331298828
4.328125
4.319580078
4.316894531
4.314453125
4.312988281
4.301513672
4.300537109
4.297607422
4.295898438
4.285888672
4.28515625
4.282470703
4.281005859
4.270263672
4.269287109
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
0.00431072
0.004305158
0.004299597
0.004294035
0.004288474
0.004282912
0.004277351
0.004271789
0.004266228
0.004260666
0.004255105
0.004249543
0.004243982
0.00423842
0.004232859
0.004227297
0.004221736
0.004216174
0.004210613
0.004205051
0.00419949
0.004193928
0.004188367
0.004182805
0.004177244
0.004171682
0.004166121
0.004160559
0.004154998
0.004149436
0.004143875
0.004138313
Discharge
(mA h/g)
0.27
0.53
0.80
1.07
1.34
1.60
1.87
2.14
2.41
2.67
2.94
3.21
3.48
3.74
4.01
4.28
4.55
4.81
5.08
5.35
5.61
5.88
6.15
6.42
6.68
6.95
7.22
7.49
7.75
8.02
8.29
8.56
140
812
813
814
815
816
817
818
819
820
821
822
823
824
825
826
827
828
829
830
831
832
833
834
835
836
837
838
839
840
841
842
843
844
845
846
847
848
849
850
851
852
853
854
855
856
857
858
859
860
861
862
32:09.5
33:49.5
35:29.5
37:09.5
38:49.5
40:29.5
42:09.5
43:49.5
45:29.5
47:09.5
48:49.5
50:29.5
52:09.5
53:49.5
55:29.5
57:09.5
58:49.5
00:29.5
02:09.5
03:49.5
05:29.5
07:09.5
08:49.5
10:29.5
12:09.5
13:49.5
15:29.5
17:09.5
18:49.5
20:29.5
22:09.5
23:49.5
25:29.5
27:09.5
28:49.5
30:29.5
32:09.5
33:49.5
35:29.5
37:09.5
38:49.5
40:29.5
42:09.5
43:49.5
45:29.5
47:09.5
48:49.5
50:29.5
52:09.5
53:49.5
55:29.5
4.267089844
4.265869141
4.256591797
4.254394531
4.253417969
4.250732422
4.245117188
4.238769531
4.238037109
4.235351563
4.234375
4.224365234
4.223388672
4.222167969
4.219726563
4.217529297
4.208007813
4.207519531
4.205810547
4.203857422
4.200683594
4.192382813
4.191894531
4.189453125
4.188232422
4.18359375
4.176757813
4.176025391
4.174072266
4.172607422
4.169433594
4.161132813
4.160644531
4.159423828
4.156982422
4.156005859
4.145996094
4.145263672
4.14453125
4.141601563
4.140869141
4.132568359
4.129882813
4.129150391
4.126708984
4.125976563
4.124023438
4.114501953
4.114013672
4.11328125
4.110351563
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200197
-0.000200197
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
0.004132752
0.00412719
0.004121629
0.004116067
0.004110506
0.004104945
0.004099383
0.004093822
0.004088261
0.004082699
0.004077137
0.004071576
0.004066015
0.004060453
0.004054891
0.00404933
0.004043769
0.004038207
0.004032645
0.004027084
0.004021523
0.004015961
0.004010399
0.004004838
0.003999277
0.003993715
0.003988153
0.003982592
0.003977031
0.003971469
0.003965907
0.003960346
0.003954784
0.003949223
0.003943661
0.0039381
0.003932538
0.003926977
0.003921415
0.003915854
0.003910292
0.003904731
0.003899169
0.003893608
0.003888046
0.003882485
0.003876923
0.003871362
0.0038658
0.003860239
0.003854677
8.82
9.09
9.36
9.63
9.89
10.16
10.43
10.70
10.96
11.23
11.50
11.76
12.03
12.30
12.57
12.83
13.10
13.37
13.64
13.90
14.17
14.44
14.71
14.97
15.24
15.51
15.78
16.04
16.31
16.58
16.84
17.11
17.38
17.65
17.91
18.18
18.45
18.72
18.98
19.25
19.52
19.79
20.05
20.32
20.59
20.86
21.12
21.39
21.66
21.93
22.19
141
863
864
865
866
867
868
869
870
871
872
873
874
875
876
877
878
879
880
881
882
883
884
885
886
887
888
889
890
891
892
893
894
895
896
897
898
899
900
901
902
903
904
905
906
907
908
909
910
911
912
57:09.5
58:49.5
00:29.5
02:09.5
03:49.5
05:29.5
07:09.5
08:49.5
10:29.5
12:09.5
13:49.5
15:29.5
17:09.5
18:49.5
20:29.5
22:09.5
23:49.5
25:29.5
27:09.5
28:49.5
30:29.5
32:09.5
33:49.5
35:29.5
37:09.5
38:49.5
40:29.5
42:09.5
43:49.5
45:29.5
47:09.5
48:49.5
50:29.5
52:09.5
53:49.5
55:29.5
57:09.5
58:49.5
00:29.5
02:09.5
03:49.5
05:29.5
07:09.5
08:49.5
10:29.5
12:09.5
13:49.5
15:29.5
17:09.5
18:49.5
4.109863281
4.103759766
4.098632813
4.097900391
4.096923828
4.094726563
4.09375
4.084472656
4.083007813
4.08203125
4.079345703
4.078857422
4.075927734
4.067626953
4.067138672
4.06640625
4.063476563
4.062988281
4.05859375
4.052001953
4.051513672
4.05078125
4.047851563
4.047607422
4.045166016
4.036621094
4.036132813
4.03515625
4.032714844
4.031982422
4.030761719
4.021240234
4.020751953
4.019775391
4.018066406
4.016601563
4.015869141
4.009277344
4.005126953
4.004638672
4.00390625
4.000976563
4.000732422
3.999023438
3.989868164
3.989257813
3.988525391
3.986694336
3.985351563
3.98449707
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200197
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200197
-0.000200212
-0.000200212
-0.000200197
-0.000200197
-0.000200197
-0.000200197
-0.000200197
-0.000200197
-0.000200197
-0.000200197
-0.000200197
-0.000200197
-0.000200197
-0.000200197
-0.000200197
-0.000200197
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
0.003849116
0.003843554
0.003837993
0.003832431
0.00382687
0.003821308
0.003815747
0.003810185
0.003804624
0.003799062
0.003793501
0.003787939
0.003782378
0.003776816
0.003771255
0.003765694
0.003760132
0.003754571
0.00374901
0.003743449
0.003737888
0.003732327
0.003726766
0.003721205
0.003715644
0.003710083
0.003704522
0.003698961
0.0036934
0.003687839
0.003682278
0.003676717
0.003671156
0.003665594
0.003660033
0.003654471
0.00364891
0.003643348
0.003637787
0.003632225
0.003626664
0.003621102
0.003615541
0.003609979
0.003604418
0.003598856
0.003593295
0.003587733
0.003582172
0.00357661
22.46
22.73
22.99
23.26
23.53
23.80
24.06
24.33
24.60
24.87
25.13
25.40
25.67
25.94
26.20
26.47
26.74
27.01
27.27
27.54
27.81
28.07
28.34
28.61
28.88
29.14
29.41
29.68
29.95
30.21
30.48
30.75
31.02
31.28
31.55
31.82
32.09
32.35
32.62
32.89
33.15
33.42
33.69
33.96
34.22
34.49
34.76
35.03
35.29
35.56
142
913
914
915
916
917
918
919
920
921
922
923
924
925
926
927
928
929
930
931
932
933
934
935
936
937
938
939
940
941
942
943
944
945
946
947
948
949
950
951
952
953
954
955
956
957
958
959
960
961
962
963
20:29.5
22:09.5
23:49.5
25:29.5
27:09.5
28:49.5
30:29.5
32:09.5
33:49.5
35:29.5
37:09.5
38:49.5
40:29.5
42:09.5
43:49.5
45:29.5
47:09.5
48:49.5
50:29.5
52:09.5
53:49.5
55:29.5
57:09.5
58:49.5
00:29.5
02:09.5
03:49.5
05:29.5
07:09.5
08:49.5
10:29.5
12:09.5
13:49.5
15:29.5
17:09.5
18:49.5
20:29.5
22:09.5
23:49.5
25:29.5
27:09.5
28:49.5
30:29.5
32:09.5
33:49.5
35:29.5
37:09.5
38:49.5
40:29.5
42:09.5
43:49.5
3.977050781
3.973999023
3.973266602
3.97277832
3.969848633
3.969604492
3.96875
3.959960938
3.958374023
3.957519531
3.95703125
3.954223633
3.953979492
3.953125
3.944458008
3.942626953
3.942016602
3.94152832
3.938720703
3.938354492
3.93762207
3.931762695
3.927124023
3.926635742
3.926025391
3.923461914
3.922851563
3.922119141
3.920043945
3.911743164
3.911376953
3.910644531
3.91015625
3.907470703
3.907104492
3.90637207
3.903442383
3.895996094
3.895751953
3.895019531
3.89453125
3.891967773
3.891479492
3.890991211
3.890380859
3.881835938
3.880249023
3.880004883
3.879272461
3.87902832
3.876464844
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
0.003571049
0.003565487
0.003559926
0.003554364
0.003548803
0.003543241
0.00353768
0.003532118
0.003526557
0.003520995
0.003515434
0.003509872
0.003504311
0.003498749
0.003493187
0.003487626
0.003482064
0.003476503
0.003470941
0.00346538
0.003459818
0.003454257
0.003448695
0.003443134
0.003437572
0.003432011
0.003426449
0.003420888
0.003415326
0.003409765
0.003404203
0.003398642
0.00339308
0.003387519
0.003381957
0.003376396
0.003370834
0.003365273
0.003359711
0.00335415
0.003348588
0.003343027
0.003337465
0.003331904
0.003326342
0.003320781
0.003315219
0.003309658
0.003304096
0.003298535
0.003292973
35.83
36.10
36.36
36.63
36.90
37.17
37.43
37.70
37.97
38.23
38.50
38.77
39.04
39.30
39.57
39.84
40.11
40.37
40.64
40.91
41.18
41.44
41.71
41.98
42.25
42.51
42.78
43.05
43.32
43.58
43.85
44.12
44.38
44.65
44.92
45.19
45.45
45.72
45.99
46.26
46.52
46.79
47.06
47.33
47.59
47.86
48.13
48.40
48.66
48.93
49.20
143
964
965
966
967
968
969
970
971
972
973
974
975
976
977
978
979
980
981
982
983
984
985
986
987
988
989
990
991
992
993
994
995
996
997
998
999
1000
1001
1002
1003
1004
1005
1006
1007
1008
1009
1010
1011
1012
1013
45:29.5
47:09.5
48:49.5
50:29.5
52:09.5
53:49.5
55:29.5
57:09.5
58:49.5
00:29.5
02:09.5
03:49.5
05:29.5
07:09.5
08:49.5
10:29.5
12:09.5
13:49.5
15:29.5
17:09.5
18:49.5
20:29.5
22:09.5
23:49.5
25:29.5
27:09.5
28:49.5
30:29.5
32:09.5
33:49.5
35:29.5
37:09.5
38:49.5
40:29.5
42:09.5
43:49.5
45:29.5
47:09.5
48:49.5
50:29.5
52:09.5
53:49.5
55:29.5
57:09.5
58:49.5
00:29.5
02:09.5
03:49.5
05:29.5
07:09.5
3.875854492
3.875366211
3.875
3.872436523
3.865112305
3.864624023
3.864501953
3.863891602
3.863647461
3.86340332
3.860961914
3.860473633
3.860229492
3.859741211
3.859375
3.858642578
3.850830078
3.849121094
3.848876953
3.848510742
3.848022461
3.847900391
3.845703125
3.844848633
3.844726563
3.843994141
3.84362793
3.839111328
3.833618164
3.833251953
3.832885742
3.832397461
3.83190918
3.829345703
3.829101563
3.82824707
3.824584961
3.817993164
3.817626953
3.816894531
3.816162109
3.813720703
3.813232422
3.811157227
3.802490234
3.802001953
3.801147461
3.798095703
3.797607422
3.789916992
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
0.003287412
0.00328185
0.003276289
0.003270727
0.003265165
0.003259604
0.003254042
0.003248481
0.003242919
0.003237358
0.003231796
0.003226235
0.003220673
0.003215112
0.00320955
0.003203989
0.003198427
0.003192866
0.003187304
0.003181743
0.003176181
0.00317062
0.003165058
0.003159497
0.003153935
0.003148374
0.003142812
0.003137251
0.003131689
0.003126128
0.003120566
0.003115005
0.003109443
0.003103882
0.00309832
0.003092759
0.003087197
0.003081636
0.003076074
0.003070513
0.003064951
0.00305939
0.003053828
0.003048267
0.003042705
0.003037143
0.003031582
0.00302602
0.003020459
0.003014897
49.46
49.73
50.00
50.27
50.53
50.80
51.07
51.34
51.60
51.87
52.14
52.41
52.67
52.94
53.21
53.48
53.74
54.01
54.28
54.55
54.81
55.08
55.35
55.61
55.88
56.15
56.42
56.68
56.95
57.22
57.49
57.75
58.02
58.29
58.56
58.82
59.09
59.36
59.63
59.89
60.16
60.43
60.69
60.96
61.23
61.50
61.76
62.03
62.30
62.57
144
1014
1015
1016
1017
1018
1019
1020
1021
1022
1023
1024
1025
1026
1027
1028
1029
1030
1031
1032
1033
1034
1035
1036
1037
1038
1039
1040
1041
1042
1043
1044
1045
1046
1047
1048
1049
1050
1051
1052
1053
1054
1055
1056
1057
1058
1059
1060
1061
1062
1063
08:49.5
10:29.5
12:09.5
13:49.5
15:29.5
17:09.5
18:49.5
20:29.5
22:09.5
23:49.5
25:29.5
27:09.5
28:49.5
30:29.5
32:09.5
33:49.5
35:29.5
37:09.5
38:49.5
40:29.5
42:09.5
43:49.5
45:29.5
47:09.5
48:49.5
50:29.5
52:09.5
53:49.5
55:29.5
57:09.5
58:49.5
00:29.5
02:09.5
03:49.5
05:29.5
07:09.5
08:49.5
10:29.5
12:09.5
13:49.5
15:29.5
17:09.5
18:49.5
20:29.5
22:09.5
23:49.5
25:29.5
27:09.5
28:49.5
30:29.5
3.786621094
3.785644531
3.782470703
3.78112793
3.771362305
3.770385742
3.766967773
3.76574707
3.755737305
3.754516602
3.751220703
3.748046875
3.739990234
3.738769531
3.735473633
3.729248047
3.724243164
3.72253418
3.719604492
3.709472656
3.708007813
3.704467773
3.702270508
3.693115234
3.692016602
3.688598633
3.68347168
3.677490234
3.676269531
3.672729492
3.662109375
3.660522461
3.657104492
3.646850586
3.645263672
3.641845703
3.637207031
3.630615234
3.629516602
3.626220703
3.623901367
3.615234375
3.614135742
3.611450195
3.610351563
3.603881836
3.599609375
3.598510742
3.596191406
3.594848633
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
0.003009336
0.003003774
0.002998213
0.002992651
0.00298709
0.002981528
0.002975967
0.002970405
0.002964844
0.002959282
0.002953721
0.002948159
0.002942598
0.002937036
0.002931475
0.002925913
0.002920352
0.00291479
0.002909229
0.002903667
0.002898106
0.002892544
0.002886983
0.002881421
0.00287586
0.002870298
0.002864737
0.002859175
0.002853614
0.002848052
0.002842491
0.002836929
0.002831367
0.002825806
0.002820244
0.002814682
0.00280912
0.002803558
0.002797997
0.002792435
0.002786873
0.002781312
0.00277575
0.002770188
0.002764626
0.002759064
0.002753502
0.002747941
0.002742379
0.002736817
62.83
63.10
63.37
63.64
63.90
64.17
64.44
64.71
64.97
65.24
65.51
65.78
66.04
66.31
66.58
66.84
67.11
67.38
67.65
67.91
68.18
68.45
68.72
68.98
69.25
69.52
69.79
70.05
70.32
70.59
70.86
71.12
71.39
71.66
71.92
72.19
72.46
72.73
72.99
73.26
73.53
73.80
74.06
74.33
74.60
74.87
75.13
75.40
75.67
75.94
145
1064
1065
1066
1067
1068
1069
1070
1071
1072
1073
1074
1075
1076
1077
1078
1079
1080
1081
1082
1083
1084
1085
1086
1087
1088
1089
1090
1091
1092
1093
1094
1095
1096
1097
1098
1099
1100
1101
1102
1103
1104
1105
1106
1107
1108
1109
1110
1111
1112
1113
32:09.5
33:49.5
35:29.5
37:09.5
38:49.5
40:29.5
42:09.5
43:49.5
45:29.5
47:09.5
48:49.5
50:29.5
52:09.5
53:49.5
55:29.5
57:09.5
58:49.5
00:29.5
02:09.5
03:49.5
05:29.5
07:09.5
08:49.5
10:29.5
12:09.5
13:49.5
15:29.5
17:09.5
18:49.5
20:29.5
22:09.5
23:49.5
25:29.5
27:09.5
28:49.5
30:29.5
32:09.5
33:49.5
35:29.5
37:09.5
38:49.5
40:29.5
42:09.5
43:49.5
45:29.5
47:09.5
48:49.5
50:29.5
52:09.5
53:49.5
3.59387207
3.585571289
3.583862305
3.582885742
3.582275391
3.579345703
3.578979492
3.576416016
3.568481445
3.568115234
3.567138672
3.564331055
3.563476563
3.562011719
3.552978516
3.552490234
3.551147461
3.548095703
3.54675293
3.537353516
3.536499023
3.533813477
3.532226563
3.52331543
3.521240234
3.518066406
3.516235352
3.506103516
3.504760742
3.500854492
3.490478516
3.48828125
3.483276367
3.474731445
3.470703125
3.461669922
3.458129883
3.452636719
3.443481445
3.438964844
3.428344727
3.423950195
3.413696289
3.409545898
3.399169922
3.394287109
3.3828125
3.377441406
3.366088867
3.360351563
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200219
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200219
-0.000200227
-0.000200227
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200219
-0.000200219
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
0.002731255
0.002725694
0.002720132
0.00271457
0.002709008
0.002703447
0.002697885
0.002692323
0.002686761
0.002681199
0.002675638
0.002670076
0.002664514
0.002658952
0.002653391
0.002647829
0.002642267
0.002636705
0.002631143
0.002625582
0.00262002
0.002614458
0.002608896
0.002603335
0.002597773
0.002592211
0.002586649
0.002581087
0.002575526
0.002569964
0.002564402
0.00255884
0.002553279
0.002547717
0.002542155
0.002536593
0.002531032
0.00252547
0.002519908
0.002514346
0.002508784
0.002503223
0.002497661
0.002492099
0.002486537
0.002480976
0.002475414
0.002469852
0.00246429
0.002458728
76.20
76.47
76.74
77.01
77.27
77.54
77.81
78.07
78.34
78.61
78.88
79.14
79.41
79.68
79.95
80.21
80.48
80.75
81.02
81.28
81.55
81.82
82.09
82.35
82.62
82.89
83.16
83.42
83.69
83.96
84.22
84.49
84.76
85.03
85.29
85.56
85.83
86.10
86.36
86.63
86.90
87.17
87.43
87.70
87.97
88.24
88.50
88.77
89.04
89.31
146
1114
1115
1116
1117
1118
1119
1120
1121
1122
1123
1124
1125
1126
1127
1128
1129
1130
1131
1132
1133
1134
1135
1136
1137
1138
1139
1140
1141
1142
1143
1144
55:29.5
57:09.5
58:49.5
00:29.5
02:09.5
03:49.5
05:29.5
07:09.5
08:49.5
10:29.5
12:09.5
13:49.5
15:29.5
17:09.5
18:49.5
20:29.5
22:09.5
23:49.5
25:29.5
27:09.5
28:49.5
30:29.5
32:09.5
33:49.5
35:29.5
37:09.5
38:49.5
40:29.5
42:09.5
43:49.5
43:55.5
3.349975586
3.33972168
3.33190918
3.319458008
3.311035156
3.302001953
3.288818359
3.278442383
3.26940918
3.256835938
3.244628906
3.236450195
3.224975586
3.21081543
3.19921875
3.189575195
3.177734375
3.16394043
3.154418945
3.144897461
3.132080078
3.118652344
3.106201172
3.094482422
3.08215332
3.068115234
3.053466797
3.038452148
3.023071289
3.007202148
3.001586914
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200041
0.002453167
0.002447605
0.002442043
0.002436481
0.00243092
0.002425358
0.002419796
0.002414234
0.002408672
0.002403111
0.002397549
0.002391987
0.002386425
0.002380864
0.002375302
0.00236974
0.002364178
0.002358617
0.002353055
0.002347493
0.002341931
0.002336369
0.002330808
0.002325246
0.002319684
0.002314122
0.002308561
0.002302999
0.002297437
0.002291875
0.002291542
89.57
89.84
90.11
90.38
90.64
90.91
91.18
91.44
91.71
91.98
92.25
92.51
92.78
93.05
93.32
93.58
93.85
94.12
94.39
94.65
94.92
95.19
95.46
95.72
95.99
96.26
96.53
96.79
97.06
97.33
97.34
147
APPENDIX A 3
In details Report of Li/1M LiPF6-EC/DMC/LiCo0.7Al0.3O2 (CA assisted)
[E cell] Cell Test Data for the 2nd Cycle Charge
Experiment start time: 11.21.31 AM, Date: 6/14/2005
Sample rate: 0.01 (Hz)
Unit number for each result number: 2
Channel number for each result number: 2
Step number for each result no: 1
Step repeat: 2
Schedule repeat: 1
Result
Number
Time
Voltage (V)
Current (A)
Charge (Ah)
Charge
(mA h/g)
1145
1146
1147
1148
1149
1150
1151
1152
1153
1154
1155
1156
1157
1158
1159
1160
1161
1162
1163
1164
1165
1166
1167
1168
1169
1170
1171
1172
1173
1174
1175
1176
1177
45:35.5
47:15.5
48:55.5
50:35.5
52:15.5
53:55.5
55:35.5
57:15.5
58:55.5
00:35.5
02:15.5
03:55.5
05:35.5
07:15.5
08:55.5
10:35.5
12:15.5
13:55.5
15:35.5
17:15.5
18:55.5
20:35.5
22:15.5
23:55.5
25:35.5
27:15.5
28:55.5
30:35.5
32:15.5
33:55.5
35:35.5
37:15.5
38:55.5
3.190063
3.320068
3.399414
3.461914
3.51355
3.557739
3.595215
3.626709
3.652344
3.671021
3.686768
3.698853
3.70459
3.714966
3.71936
3.7229
3.732056
3.734497
3.737183
3.73877
3.746826
3.75
3.750977
3.75415
3.755127
3.764526
3.765747
3.766724
3.769775
3.770874
3.780151
3.781128
3.782227
0.000199653
0.000199653
0.000199653
0.000199646
0.000199653
0.000199646
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199646
0.000199653
0.000199646
0.000199653
0.000199653
0.000199646
0.000199646
0.002297088
0.002302634
0.00230818
0.002313725
0.002319271
0.002324817
0.002330363
0.002335909
0.002341455
0.002347
0.002352546
0.002358092
0.002363638
0.002369184
0.00237473
0.002380276
0.002385822
0.002391367
0.002396913
0.002402459
0.002408005
0.002413551
0.002419097
0.002424643
0.002430189
0.002435734
0.00244128
0.002446826
0.002452372
0.002457917
0.002463463
0.002469009
0.002474555
0.27
0.53
0.80
1.07
1.33
1.60
1.87
2.13
2.40
2.67
2.93
3.20
3.47
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148
1178
1179
1180
1181
1182
1183
1184
1185
1186
1187
1188
1189
1190
1191
1192
1193
1194
1195
1196
1197
1198
1199
1200
1201
1202
1203
1204
1205
1206
1207
1208
1209
1210
1211
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1213
1214
1215
1216
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1218
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1220
1221
1222
1223
1224
1225
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40:35.5
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149
1228
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1230
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1232
1233
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1235
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03:55.5
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150
1279
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1281
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1283
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1291
1292
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1321
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1324
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1328
28:55.5
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35:35.5
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40:35.5
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49.06
151
1329
1330
1331
1332
1333
1334
1335
1336
1337
1338
1339
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1341
1342
1343
1344
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1353
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1355
1356
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1366
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1371
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1375
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1377
1378
52:15.5
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152
1379
1380
1381
1382
1383
1384
1385
1386
1387
1388
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15:35.5
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4.218506
4.21875
4.219482
4.221191
4.222412
4.2229
4.224854
4.233887
4.234131
4.234863
4.235352
4.237793
4.238037
4.23877
4.247559
4.25
4.250732
4.250732
4.253418
4.253662
4.254395
4.260498
4.264893
4.265137
4.266113
4.267578
4.268799
4.269287
4.271484
4.280518
4.281006
4.281982
4.282227
4.284668
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.003594777
0.003600323
0.003605869
0.003611414
0.00361696
0.003622505
0.003628051
0.003633597
0.003639142
0.003644688
0.003650233
0.003655779
0.003661325
0.00366687
0.003672416
0.003677962
0.003683507
0.003689053
0.003694598
0.003700144
0.00370569
0.003711235
0.003716781
0.003722327
0.003727872
0.003733418
0.003738963
0.003744509
0.003750055
0.0037556
0.003761146
0.003766691
0.003772237
0.003777783
0.003783328
0.003788874
0.00379442
0.003799965
0.003805511
0.003811056
0.003816602
0.003822148
0.003827693
0.003833239
0.003838785
0.00384433
0.003849876
0.003855421
0.003860967
0.003866513
62.66
62.92
63.19
63.46
63.72
63.99
64.26
64.52
64.79
65.06
65.32
65.59
65.85
66.12
66.39
66.65
66.92
67.19
67.45
67.72
67.99
68.25
68.52
68.79
69.05
69.32
69.59
69.85
70.12
70.39
70.65
70.92
71.19
71.45
71.72
71.99
72.25
72.52
72.79
73.05
73.32
73.59
73.85
74.12
74.39
74.65
74.92
75.19
75.45
75.72
153
1429
1430
1431
1432
1433
1434
1435
1436
1437
1438
1439
1440
1441
1442
1443
1444
1445
1446
1447
1448
1449
1450
1451
1452
1453
1454
1455
1456
1457
1458
1459
1460
1461
1462
1463
1464
1465
1466
1467
1468
1469
1470
1471
1472
1473
1474
1475
1476
1477
1478
38:55.5
40:35.5
42:15.5
43:55.5
45:35.5
47:15.5
48:55.5
50:35.5
52:15.5
53:55.5
55:35.5
57:15.5
58:55.5
00:35.5
02:15.5
03:55.5
05:35.5
07:15.5
08:55.5
10:35.5
12:15.5
13:55.5
15:35.5
17:15.5
18:55.5
20:35.5
22:15.5
23:55.5
25:35.5
27:15.5
28:55.5
30:35.5
32:15.5
33:55.5
35:35.5
37:15.5
38:55.5
40:35.5
42:15.5
43:55.5
45:35.5
47:15.5
48:55.5
50:35.5
52:15.5
53:55.5
55:35.5
57:15.5
58:55.5
00:35.5
4.284912
4.285645
4.293457
4.296143
4.296631
4.297363
4.299316
4.300049
4.300781
4.307129
4.312012
4.312256
4.313232
4.314697
4.315918
4.316406
4.317627
4.326904
4.327393
4.328125
4.328369
4.331055
4.331299
4.332031
4.340088
4.343506
4.34375
4.344238
4.346436
4.347412
4.3479
4.349854
4.358154
4.358643
4.359375
4.360107
4.362305
4.362549
4.363281
4.373291
4.374756
4.375244
4.375488
4.37793
4.378418
4.37915
4.380859
4.389404
4.389648
4.390381
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.003872058
0.003877604
0.003883149
0.003888695
0.003894241
0.003899786
0.003905332
0.003910877
0.003916423
0.003921969
0.003927514
0.00393306
0.003938606
0.003944151
0.003949697
0.003955242
0.003960788
0.003966334
0.003971879
0.003977425
0.00398297
0.003988516
0.003994062
0.003999607
0.004005153
0.004010699
0.004016244
0.00402179
0.004027335
0.004032881
0.004038427
0.004043972
0.004049518
0.004055063
0.004060609
0.004066155
0.0040717
0.004077246
0.004082792
0.004088337
0.004093883
0.004099428
0.004104974
0.00411052
0.004116065
0.004121611
0.004127156
0.004132702
0.004138248
0.004143793
75.99
76.25
76.52
76.79
77.05
77.32
77.59
77.85
78.12
78.39
78.65
78.92
79.19
79.45
79.72
79.99
80.25
80.52
80.79
81.05
81.32
81.59
81.85
82.12
82.39
82.65
82.92
83.18
83.45
83.72
83.98
84.25
84.52
84.78
85.05
85.32
85.58
85.85
86.12
86.38
86.65
86.92
87.18
87.45
87.72
87.98
88.25
88.52
88.78
89.05
154
1479
1480
1481
1482
1483
1484
1485
1486
1487
1488
1489
1490
1491
1492
1493
1494
1495
1496
1497
1498
1499
1500
1501
1502
1503
1504
1505
1506
1507
1508
1509
1510
1511
1512
1513
1514
1515
1516
1517
1518
1519
1520
1521
1522
1523
1524
1525
1526
1527
1528
02:15.5
03:55.5
05:35.5
07:15.5
08:55.5
10:35.5
12:15.5
13:55.5
15:35.5
17:15.5
18:55.5
20:35.5
22:15.5
23:55.5
25:35.5
27:15.5
28:55.5
30:35.5
32:15.5
33:55.5
35:35.5
37:15.5
38:55.5
40:35.5
42:15.5
43:55.5
45:35.5
47:15.5
48:55.5
50:35.5
52:15.5
53:55.5
55:35.5
57:15.5
58:55.5
00:35.5
02:15.5
03:55.5
05:35.5
07:15.5
08:55.5
10:35.5
12:15.5
13:55.5
15:35.5
17:15.5
18:55.5
20:35.5
22:15.5
23:55.5
4.390625
4.393311
4.393555
4.394287
4.399414
4.405762
4.406006
4.406738
4.407227
4.409668
4.409912
4.410645
4.419434
4.420654
4.421143
4.421631
4.422363
4.424561
4.424805
4.425293
4.432129
4.437256
4.437256
4.437988
4.438232
4.440918
4.441162
4.44165
4.442871
4.451416
4.452148
4.452637
4.452881
4.454346
4.455811
4.456055
4.456543
4.462891
4.468506
4.46875
4.469238
4.469482
4.472168
4.472168
4.472656
4.473145
4.480469
4.483154
4.483398
4.483887
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.004149339
0.004154885
0.00416043
0.004165976
0.004171521
0.004177067
0.004182613
0.004188158
0.004193704
0.00419925
0.004204795
0.004210341
0.004215886
0.004221432
0.004226977
0.004232523
0.004238069
0.004243615
0.00424916
0.004254706
0.004260251
0.004265797
0.004271342
0.004276888
0.004282434
0.00428798
0.004293525
0.004299071
0.004304616
0.004310162
0.004315707
0.004321253
0.004326798
0.004332344
0.00433789
0.004343436
0.004348981
0.004354527
0.004360072
0.004365618
0.004371163
0.004376709
0.004382255
0.004387801
0.004393346
0.004398892
0.004404437
0.004409983
0.004415528
0.004421074
89.32
89.58
89.85
90.12
90.38
90.65
90.92
91.18
91.45
91.72
91.98
92.25
92.52
92.78
93.05
93.32
93.58
93.85
94.12
94.38
94.65
94.92
95.18
95.45
95.72
95.98
96.25
96.52
96.78
97.05
97.32
97.58
97.85
98.12
98.38
98.65
98.92
99.18
99.45
99.72
99.98
100.25
100.52
100.78
101.05
101.31
101.58
101.85
102.11
102.38
155
1529
1530
1531
1532
1533
25:35.5
27:15.5
28:55.5
30:35.5
32:10.0
4.484131
4.486084
4.486572
4.487061
4.489014
0.000199646
0.000199646
0.000199646
0.000199646
0.000199668
0.00442662
0.004432166
0.004437711
0.004443257
0.004448501
102.65
102.91
103.18
103.45
103.70
156
APPENDIX A 4
In details Report of Li/1M LiPF6-EC/DMC/LiCo0.7Al0.3O2 (CA assisted)
[E cell] Cell Test Data for the 2nd Cycle Discharge
Experiment start time: 11.21.31 AM, Date: 6/14/2005
Sample rate: 0.01 (Hz)
Unit number for each result number: 2
Channel number for each result number: 2
Step number for each result no: 2
Step repeat: 2
Schedule repeat: 1
Result
Number
1534
1535
1536
1537
1538
1539
1540
1541
1542
1543
1544
1545
1546
1547
1548
1549
1550
1551
1552
1553
1554
1555
1556
1557
1558
1559
1560
1561
1562
1563
1564
1565
Time
Voltage (V)
Current (A)
Charge (Ah)
Discharge
(mA h/g)
33:50.0
35:30.0
37:10.0
38:50.0
40:30.0
42:10.0
43:50.0
45:30.0
47:10.0
48:50.0
50:30.0
52:10.0
53:50.0
55:30.0
57:10.0
58:50.0
00:30.0
02:10.0
03:50.0
05:30.0
07:10.0
08:50.0
10:30.0
12:10.0
13:50.0
15:30.0
17:10.0
18:50.0
20:30.0
22:10.0
23:50.0
25:30.0
4.442383
4.425781
4.415771
4.409912
4.398193
4.393799
4.389404
4.379639
4.376465
4.367188
4.363037
4.359619
4.350098
4.347656
4.344727
4.335205
4.332031
4.328857
4.324951
4.317139
4.315918
4.313232
4.30249
4.300781
4.297607
4.294678
4.285889
4.284912
4.282227
4.276123
4.269775
4.269043
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
0.00444294
0.004437378
0.004431816
0.004426254
0.004420693
0.004415131
0.004409569
0.004404007
0.004398445
0.004392884
0.004387322
0.00438176
0.004376198
0.004370636
0.004365074
0.004359513
0.004353951
0.004348389
0.004342827
0.004337266
0.004331704
0.004326142
0.004320581
0.004315019
0.004309457
0.004303895
0.004298334
0.004292772
0.00428721
0.004281648
0.004276086
0.004270524
0.27
0.53
0.80
1.07
1.34
1.60
1.87
2.14
2.41
2.67
2.94
3.21
3.48
3.74
4.01
4.28
4.55
4.81
5.08
5.35
5.62
5.88
6.15
6.42
6.68
6.95
7.22
7.49
7.75
8.02
8.29
8.56
157
1566
1567
1568
1569
1570
1571
1572
1573
1574
1575
1576
1577
1578
1579
1580
1581
1582
1583
1584
1585
1586
1587
1588
1589
1590
1591
1592
1593
1594
1595
1596
1597
1598
1599
1600
1601
1602
1603
1604
1605
1606
1607
1608
1609
1610
1611
1612
1613
1614
1615
27:10.0
28:50.0
30:30.0
32:10.0
33:50.0
35:30.0
37:10.0
38:50.0
40:30.0
42:10.0
43:50.0
45:30.0
47:10.0
48:50.0
50:30.0
52:10.0
53:50.0
55:30.0
57:10.0
58:50.0
00:30.0
02:10.0
03:50.0
05:30.0
07:10.0
08:50.0
10:30.0
12:10.0
13:50.0
15:30.0
17:10.0
18:50.0
20:30.0
22:10.0
23:50.0
25:30.0
27:10.0
28:50.0
30:30.0
32:10.0
33:50.0
35:30.0
37:10.0
38:50.0
40:30.0
42:10.0
43:50.0
45:30.0
47:10.0
48:50.0
4.266113
4.259521
4.254639
4.253662
4.250977
4.244385
4.23877
4.238037
4.235107
4.232666
4.223633
4.222656
4.219971
4.218994
4.208496
4.20752
4.205566
4.203857
4.197266
4.192383
4.191406
4.188477
4.187012
4.177002
4.17627
4.174316
4.172607
4.16626
4.161133
4.160156
4.157471
4.156738
4.147949
4.145508
4.144531
4.141602
4.140625
4.130859
4.129639
4.128906
4.125977
4.125244
4.118652
4.114258
4.11377
4.113281
4.110352
4.109863
4.103516
4.098633
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200219
-0.000200219
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200219
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200219
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200212
0.004264963
0.004259401
0.004253839
0.004248277
0.004242715
0.004237154
0.004231592
0.00422603
0.004220468
0.004214907
0.004209345
0.004203783
0.004198221
0.00419266
0.004187098
0.004181536
0.004175974
0.004170413
0.004164851
0.004159289
0.004153727
0.004148165
0.004142604
0.004137042
0.00413148
0.004125918
0.004120356
0.004114795
0.004109233
0.004103671
0.004098109
0.004092548
0.004086986
0.004081424
0.004075862
0.004070301
0.004064739
0.004059177
0.004053615
0.004048054
0.004042492
0.00403693
0.004031368
0.004025806
0.004020244
0.004014683
0.004009121
0.004003559
0.003997997
0.003992436
8.82
9.09
9.36
9.63
9.89
10.16
10.43
10.70
10.96
11.23
11.50
11.77
12.03
12.30
12.57
12.83
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07:10.0
08:50.0
10:30.0
12:10.0
13:50.0
15:30.0
17:10.0
18:50.0
20:30.0
22:10.0
23:50.0
25:30.0
27:10.0
28:50.0
30:30.0
32:10.0
33:50.0
35:30.0
37:10.0
38:50.0
40:30.0
42:10.0
43:50.0
45:30.0
47:10.0
3.568359
3.567871
3.566895
3.563721
3.562988
3.555054
3.552612
3.551392
3.548096
3.54541
3.537231
3.535889
3.532471
3.526733
3.521362
3.518555
3.514404
3.505859
3.502319
3.49353
3.489624
3.485229
3.474731
3.470459
3.460083
3.456055
3.445923
3.441284
3.430786
3.426025
3.415039
3.409912
3.398315
3.392822
3.381348
3.373047
3.364868
3.352051
3.344849
3.334106
3.320557
3.310913
3.30127
3.288208
3.275269
3.265259
3.254639
3.241211
3.228027
3.215698
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
0.002869009
0.002863447
0.002857886
0.002852324
0.002846763
0.002841201
0.00283564
0.002830078
0.002824517
0.002818955
0.002813393
0.002807832
0.00280227
0.002796709
0.002791147
0.002785586
0.002780024
0.002774463
0.002768901
0.00276334
0.002757778
0.002752217
0.002746655
0.002741094
0.002735532
0.002729971
0.002724409
0.002718848
0.002713286
0.002707725
0.002702163
0.002696602
0.00269104
0.002685479
0.002679917
0.002674356
0.002668794
0.002663233
0.002657671
0.00265211
0.002646548
0.002640987
0.002635425
0.002629864
0.002624302
0.002618741
0.002613179
0.002607618
0.002602056
0.002596495
75.94
76.20
76.47
76.74
77.01
77.27
77.54
77.81
78.08
78.34
78.61
78.88
79.15
79.41
79.68
79.95
80.22
80.48
80.75
81.02
81.28
81.55
81.82
82.09
82.35
82.62
82.89
83.16
83.42
83.69
83.96
84.23
84.49
84.76
85.03
85.30
85.56
85.83
86.10
86.36
86.63
86.90
87.17
87.43
87.70
87.97
88.24
88.50
88.77
89.04
163
1867
1868
1869
1870
1871
1872
1873
1874
1875
1876
1877
1878
1879
1880
1881
48:50.0
50:30.0
52:10.0
53:50.0
55:30.0
57:10.0
58:50.0
00:30.0
02:10.0
03:50.0
05:30.0
07:10.0
08:50.0
10:30.0
10:54.6
3.2052
3.193115
3.178955
3.164551
3.151123
3.138184
3.125122
3.109253
3.092163
3.075317
3.05896
3.042847
3.026611
3.009766
3.002319
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200093
0.002590933
0.002585371
0.00257981
0.002574248
0.002568687
0.002563125
0.002557564
0.002552002
0.002546441
0.002540879
0.002535318
0.002529756
0.002524194
0.002518632
0.00251727
89.31
89.57
89.84
90.11
90.38
90.64
90.91
91.18
91.45
91.71
91.98
92.25
92.51
92.78
92.85
164
APPENDIX A 5
In details Report of Li/1M LiPF6-EC/DMC/LiCo0.7Al0.3O2 (CA assisted)
[E cell] Cell Test Data for the 3rd Cycle Charge
Experiment start time: 11.21.31 AM, Date: 6/14/2005
Sample rate: 0.01 (Hz)
Unit number for each result number: 2
Channel number for each result number: 2
Step number for each result no: 1
Step repeat: 3
Schedule repeat: 1
Result
Number
1882
1883
1884
1885
1886
1887
1888
1889
1890
1891
1892
1893
1894
1895
1896
1897
1898
1899
1900
1901
1902
1903
1904
1905
1906
1907
1908
1909
1910
1911
Time
Voltage (V)
Current (A)
Charge (Ah)
12:34.6
14:14.6
15:54.6
17:34.6
19:14.6
20:54.6
22:34.6
24:14.6
25:54.6
27:34.6
29:14.6
30:54.6
32:34.6
34:14.6
35:54.6
37:34.6
39:14.6
40:54.6
42:34.6
44:14.6
45:54.6
47:34.6
49:14.6
50:54.6
52:34.6
54:14.6
55:54.6
57:34.6
59:14.6
00:54.6
3.184814
3.315674
3.396851
3.46106
3.513794
3.559082
3.597534
3.629517
3.653809
3.671753
3.687012
3.698364
3.704102
3.712891
3.718872
3.722778
3.729614
3.734253
3.735962
3.738647
3.745361
3.75
3.750977
3.75415
3.755249
3.764893
3.765869
3.767578
3.769897
3.776367
0.000199653
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.002522816
0.002528362
0.002533907
0.002539453
0.002544998
0.002550544
0.00255609
0.002561635
0.002567181
0.002572727
0.002578272
0.002583818
0.002589364
0.002594909
0.002600455
0.002606
0.002611546
0.002617092
0.002622637
0.002628183
0.002633729
0.002639274
0.00264482
0.002650365
0.002655911
0.002661457
0.002667002
0.002672548
0.002678093
0.002683639
Charge
(mA h/g)
0.27
0.53
0.80
1.07
1.33
1.60
1.87
2.13
2.40
2.67
2.93
3.20
3.47
3.73
4.00
4.27
4.53
4.80
5.07
5.33
5.60
5.87
6.13
6.40
6.67
6.93
7.20
7.47
7.73
8.00
165
1912
1913
1914
1915
1916
1917
1918
1919
1920
1921
1922
1923
1924
1925
1926
1927
1928
1929
1930
1931
1932
1933
1934
1935
1936
1937
1938
1939
1940
1941
1942
1943
1944
1945
1946
1947
1948
1949
1950
1951
1952
1953
1954
1955
1956
1957
1958
1959
1960
1961
02:34.6
04:14.6
05:54.6
07:34.6
09:14.6
10:54.6
12:34.6
14:14.6
15:54.6
17:34.6
19:14.6
20:54.6
22:34.6
24:14.6
25:54.6
27:34.6
29:14.6
30:54.6
32:34.6
34:14.6
35:54.6
37:34.6
39:14.6
40:54.6
42:34.6
44:14.6
45:54.6
47:34.6
49:14.6
50:54.6
52:34.6
54:14.6
55:54.6
57:34.6
59:14.6
00:54.6
02:34.6
04:14.6
05:54.6
07:34.6
09:14.6
10:54.6
12:34.6
14:14.6
15:54.6
17:34.6
19:14.6
20:54.6
22:34.6
24:14.6
3.781006
3.782104
3.785034
3.785645
3.791626
3.796631
3.797607
3.799072
3.801147
3.802124
3.811646
3.8125
3.813477
3.816406
3.817017
3.821411
3.827881
3.828857
3.830078
3.832275
3.833252
3.842529
3.843628
3.844482
3.847412
3.848022
3.849976
3.859009
3.859375
3.860229
3.863403
3.86377
3.867065
3.874756
3.875244
3.876343
3.879028
3.879761
3.885986
3.890381
3.891113
3.891724
3.894531
3.89502
3.896729
3.905884
3.90625
3.906982
3.907959
3.910156
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.002689185
0.00269473
0.002700276
0.002705822
0.002711367
0.002716913
0.002722458
0.002728004
0.00273355
0.002739095
0.002744641
0.002750186
0.002755732
0.002761278
0.002766823
0.002772369
0.002777915
0.00278346
0.002789006
0.002794551
0.002800097
0.002805643
0.002811188
0.002816734
0.002822279
0.002827825
0.002833371
0.002838916
0.002844462
0.002850007
0.002855553
0.002861099
0.002866644
0.00287219
0.002877736
0.002883281
0.002888827
0.002894372
0.002899918
0.002905464
0.002911009
0.002916555
0.0029221
0.002927646
0.002933192
0.002938737
0.002944283
0.002949829
0.002955374
0.00296092
8.27
8.53
8.80
9.06
9.33
9.60
9.86
10.13
10.40
10.66
10.93
11.20
11.46
11.73
12.00
12.26
12.53
12.80
13.06
13.33
13.60
13.86
14.13
14.40
14.66
14.93
15.20
15.46
15.73
16.00
16.26
16.53
16.80
17.06
17.33
17.60
17.86
18.13
18.40
18.66
18.93
19.20
19.46
19.73
20.00
20.26
20.53
20.80
21.06
21.33
166
1962
1963
1964
1965
1966
1967
1968
1969
1970
1971
1972
1973
1974
1975
1976
1977
1978
1979
1980
1981
1982
1983
1984
1985
1986
1987
1988
1989
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010
2011
25:54.6
27:34.6
29:14.6
30:54.6
32:34.6
34:14.6
35:54.6
37:34.6
39:14.6
40:54.6
42:34.6
44:14.6
45:54.6
47:34.6
49:14.6
50:54.6
52:34.6
54:14.6
55:54.6
57:34.6
59:14.6
00:54.6
02:34.6
04:14.6
05:54.6
07:34.6
09:14.6
10:54.6
12:34.6
14:14.6
15:54.6
17:34.6
19:14.6
20:54.6
22:34.6
24:14.6
25:54.6
27:34.6
29:14.6
30:54.6
32:34.6
34:14.6
35:54.6
37:34.6
39:14.6
40:54.6
42:34.6
44:14.6
45:54.6
47:34.6
3.910645
3.911377
3.918945
3.921753
3.921997
3.922607
3.922974
3.925293
3.925903
3.926025
3.92688
3.92749
3.935059
3.937256
3.937378
3.937622
3.938232
3.938354
3.938599
3.940308
3.941406
3.941528
3.94165
3.942261
3.942505
3.942993
3.949341
3.952881
3.953003
3.953247
3.953857
3.953979
3.95459
3.956909
3.957153
3.957275
3.957764
3.95813
3.959229
3.967529
3.968628
3.968872
3.969482
3.969727
3.97168
3.972656
3.9729
3.973633
3.977417
3.984009
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.002966465
0.002972011
0.002977557
0.002983102
0.002988648
0.002994193
0.002999739
0.003005285
0.00301083
0.003016376
0.003021921
0.003027467
0.003033013
0.003038558
0.003044104
0.00304965
0.003055195
0.003060741
0.003066286
0.003071832
0.003077378
0.003082923
0.003088469
0.003094014
0.00309956
0.003105106
0.003110651
0.003116197
0.003121743
0.003127288
0.003132834
0.003138379
0.003143925
0.003149471
0.003155016
0.003160562
0.003166108
0.003171653
0.003177199
0.003182745
0.003188291
0.003193837
0.003199383
0.003204928
0.003210474
0.00321602
0.003221566
0.003227112
0.003232658
0.003238204
21.60
21.86
22.13
22.40
22.66
22.93
23.20
23.46
23.73
24.00
24.26
24.53
24.80
25.06
25.33
25.60
25.86
26.13
26.40
26.66
26.93
27.19
27.46
27.73
27.99
28.26
28.53
28.79
29.06
29.33
29.59
29.86
30.13
30.39
30.66
30.93
31.19
31.46
31.73
31.99
32.26
32.53
32.79
33.06
33.33
33.59
33.86
34.13
34.39
34.66
167
2012
2013
2014
2015
2016
2017
2018
2019
2020
2021
2022
2023
2024
2025
2026
2027
2028
2029
2030
2031
2032
2033
2034
2035
2036
2037
2038
2039
2040
2041
2042
2043
2044
2045
2046
2047
2048
2049
2050
2051
2052
2053
2054
2055
2056
2057
2058
2059
2060
2061
49:14.6
50:54.6
52:34.6
54:14.6
55:54.6
57:34.6
59:14.6
00:54.6
02:34.6
04:14.6
05:54.6
07:34.6
09:14.6
10:54.6
12:34.6
14:14.6
15:54.6
17:34.6
19:14.6
20:54.6
22:34.6
24:14.6
25:54.6
27:34.6
29:14.6
30:54.6
32:34.6
34:14.6
35:54.6
37:34.6
39:14.6
40:54.6
42:34.6
44:14.6
45:54.6
47:34.6
49:14.6
50:54.6
52:34.6
54:14.6
55:54.6
57:34.6
59:14.6
00:54.6
02:34.6
04:14.6
05:54.6
07:34.6
09:14.6
10:54.6
3.984253
3.984985
3.985352
3.988037
3.988403
3.989136
3.990356
3.999268
3.999878
4.000488
4.000977
4.003418
4.003906
4.004639
4.006348
4.015137
4.015625
4.016357
4.016602
4.019287
4.019531
4.020508
4.02417
4.031006
4.03125
4.031982
4.033691
4.035156
4.035645
4.037109
4.046387
4.046875
4.047607
4.047852
4.050537
4.051025
4.051758
4.060059
4.0625
4.062744
4.063477
4.066162
4.066406
4.067139
4.074463
4.077881
4.078369
4.079102
4.081543
4.082031
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199646
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199646
0.000199646
0.000199653
0.000199653
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199646
0.000199646
0.000199646
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199646
0.000199653
0.000199653
0.00324375
0.003249296
0.003254842
0.003260387
0.003265933
0.003271479
0.003277025
0.003282571
0.003288117
0.003293662
0.003299208
0.003304754
0.0033103
0.003315846
0.003321391
0.003326937
0.003332483
0.003338029
0.003343574
0.00334912
0.003354665
0.003360211
0.003365757
0.003371303
0.003376849
0.003382395
0.00338794
0.003393486
0.003399032
0.003404578
0.003410124
0.00341567
0.003421216
0.003426762
0.003432307
0.003437853
0.003443399
0.003448945
0.003454491
0.003460037
0.003465582
0.003471128
0.003476674
0.00348222
0.003487766
0.003493311
0.003498857
0.003504403
0.003509949
0.003515495
34.93
35.19
35.46
35.73
35.99
36.26
36.53
36.79
37.06
37.33
37.59
37.86
38.13
38.39
38.66
38.93
39.19
39.46
39.73
39.99
40.26
40.53
40.79
41.06
41.33
41.59
41.86
42.13
42.39
42.66
42.93
43.19
43.46
43.73
43.99
44.26
44.53
44.79
45.06
45.33
45.59
45.86
46.13
46.39
46.66
46.93
47.19
47.46
47.72
47.99
168
2062
2063
12:34.6
14:14.6
4.082764
4.091064
0.000199653
0.000199653
0.003521041
0.003526586
48.26
48.52
2064
2065
2066
2067
2068
2069
2070
2071
2072
2073
2074
2075
2076
2077
2078
2079
2080
2081
2082
2083
2084
2085
2086
2087
2088
2089
2090
2091
2092
2093
2094
2095
2096
2097
2098
2099
2100
2101
2102
2103
2104
2105
2106
2107
2108
2109
2110
15:54.6
17:34.6
19:14.6
20:54.6
22:34.6
24:14.6
25:54.6
27:34.6
29:14.6
30:54.6
32:34.6
34:14.6
35:54.6
37:34.6
39:14.6
40:54.6
42:34.6
44:14.6
45:54.6
47:34.6
49:14.6
50:54.6
52:34.6
54:14.6
55:54.6
57:34.6
59:14.6
00:54.6
02:34.6
04:14.6
05:54.6
07:34.6
09:14.6
10:54.6
12:34.6
14:14.6
15:54.6
17:34.6
19:14.6
20:54.6
22:34.6
24:14.6
25:54.6
27:34.6
29:14.6
30:54.6
32:34.6
4.093506
4.094238
4.094727
4.097412
4.097656
4.098389
4.105957
4.109131
4.109863
4.110352
4.113037
4.113281
4.114014
4.122314
4.124756
4.125488
4.125977
4.128662
4.12915
4.130371
4.139893
4.140625
4.141357
4.143555
4.144531
4.145264
4.152588
4.156006
4.156494
4.156982
4.159912
4.160156
4.161621
4.171387
4.171875
4.172607
4.174072
4.175781
4.176514
4.182861
4.187256
4.187744
4.188477
4.190918
4.19165
4.192627
4.202393
0.000199646
0.000199653
0.000199653
0.000199653
0.000199653
0.000199646
0.000199653
0.000199646
0.000199646
0.000199653
0.000199653
0.000199653
0.000199653
0.000199646
0.000199646
0.000199653
0.000199653
0.000199646
0.000199646
0.000199646
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199646
0.000199653
0.000199653
0.000199653
0.000199653
0.000199646
0.000199653
0.000199653
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000199653
0.000199653
0.003532132
0.003537678
0.003543224
0.00354877
0.003554316
0.003559861
0.003565407
0.003570953
0.003576498
0.003582044
0.00358759
0.003593136
0.003598682
0.003604227
0.003609773
0.003615319
0.003620865
0.00362641
0.003631956
0.003637502
0.003643048
0.003648593
0.003654139
0.003659685
0.003665231
0.003670777
0.003676323
0.003681869
0.003687414
0.00369296
0.003698506
0.003704052
0.003709598
0.003715144
0.003720689
0.003726235
0.00373178
0.003737326
0.003742872
0.003748417
0.003753963
0.003759508
0.003765054
0.0037706
0.003776145
0.003781691
0.003787237
48.79
49.06
49.32
49.59
49.86
50.12
50.39
50.66
50.92
51.19
51.46
51.72
51.99
52.26
52.52
52.79
53.06
53.32
53.59
53.86
54.12
54.39
54.66
54.92
55.19
55.46
55.72
55.99
56.26
56.52
56.79
57.06
57.32
57.59
57.86
58.12
58.39
58.66
58.92
59.19
59.46
59.72
59.99
60.26
60.52
60.79
61.06
169
2111
2112
34:14.6
35:54.6
4.203125
4.203857
0.000199653
0.000199653
0.003792783
0.003798329
61.32
61.59
2113
2114
2115
2116
2117
2118
2119
2120
2121
2122
2123
2124
2125
2126
2127
2128
2129
2130
2131
2132
2133
2134
2135
2136
2137
2138
2139
2140
2141
2142
2143
2144
2145
2146
2147
2148
2149
2150
2151
2152
2153
2154
2155
2156
2157
2158
2159
37:34.6
39:14.6
40:54.6
42:34.6
44:14.6
45:54.6
47:34.6
49:14.6
50:54.6
52:34.6
54:14.6
55:54.6
57:34.6
59:14.6
00:54.6
02:34.6
04:14.6
05:54.6
07:34.6
09:14.6
10:54.6
12:34.6
14:14.6
15:54.6
17:34.6
19:14.6
20:54.6
22:34.6
24:14.6
25:54.6
27:34.6
29:14.6
30:54.6
32:34.6
34:14.6
35:54.6
37:34.6
39:14.6
40:54.6
42:34.6
44:14.6
45:54.6
47:34.6
49:14.6
50:54.6
52:34.6
54:14.6
4.20459
4.206543
4.207031
4.210449
4.218506
4.21875
4.219482
4.221436
4.222412
4.223389
4.230713
4.234131
4.234619
4.235107
4.237793
4.238037
4.239502
4.249268
4.25
4.250732
4.252686
4.253662
4.254395
4.261963
4.264893
4.265625
4.266357
4.268799
4.269043
4.270752
4.280518
4.281006
4.281982
4.282959
4.284912
4.2854
4.290527
4.296143
4.296387
4.297363
4.299805
4.300293
4.301758
4.311768
4.312256
4.313232
4.314453
0.000199653
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000199653
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199646
0.000199653
0.000199653
0.000199653
0.000199646
0.000199646
0.000199646
0.000199653
0.000199653
0.000199646
0.000199646
0.000199646
0.000199653
0.000199653
0.000199653
0.000199653
0.000199646
0.003803875
0.003809421
0.003814966
0.003820512
0.003826057
0.003831603
0.003837149
0.003842694
0.00384824
0.003853786
0.003859331
0.003864877
0.003870422
0.003875969
0.003881514
0.00388706
0.003892606
0.003898151
0.003903697
0.003909243
0.003914788
0.003920334
0.00392588
0.003931426
0.003936972
0.003942518
0.003948064
0.00395361
0.003959156
0.003964702
0.003970247
0.003975793
0.003981339
0.003986885
0.00399243
0.003997976
0.004003522
0.004009068
0.004014614
0.004020159
0.004025705
0.00403125
0.004036796
0.004042342
0.004047888
0.004053434
0.004058979
61.86
62.12
62.39
62.66
62.92
63.19
63.46
63.72
63.99
64.26
64.52
64.79
65.06
65.32
65.59
65.86
66.12
66.39
66.66
66.92
67.19
67.46
67.72
67.99
68.25
68.52
68.79
69.05
69.32
69.59
69.85
70.12
70.39
70.65
70.92
71.19
71.45
71.72
71.99
72.25
72.52
72.79
73.05
73.32
73.59
73.85
74.12
170
2160
2161
55:54.6
57:34.6
4.315918
4.31665
0.000199646
0.000199653
0.004064525
0.004070071
74.39
74.65
2162
2163
2164
2165
2166
2167
2168
2169
2170
2171
2172
2173
2174
2175
2176
2177
2178
2179
2180
2181
2182
2183
2184
2185
2186
2187
2188
2189
2190
2191
2192
2193
2194
2195
2196
2197
2198
2199
2200
2201
2202
2203
2204
2205
2206
2207
2208
2209
59:14.6
00:54.6
02:34.6
04:14.6
05:54.6
07:34.6
09:14.6
10:54.6
12:34.6
14:14.6
15:54.6
17:34.6
19:14.6
20:54.6
22:34.6
24:14.6
25:54.6
27:34.6
29:14.6
30:54.6
32:34.6
34:14.6
35:54.6
37:34.6
39:14.6
40:54.6
42:34.6
44:14.6
45:54.6
47:34.6
49:14.6
50:54.6
52:34.6
54:14.6
55:54.6
57:34.6
59:14.6
00:54.6
02:34.6
04:14.6
05:54.6
07:34.6
09:14.6
10:54.6
12:34.6
14:14.6
15:54.6
17:34.6
4.322021
4.327393
4.327637
4.328125
4.330811
4.331299
4.332275
4.342285
4.343506
4.344238
4.345215
4.347168
4.347656
4.351074
4.358398
4.358887
4.359375
4.362061
4.362549
4.363281
4.373535
4.374756
4.375488
4.375977
4.378418
4.378906
4.380371
4.389404
4.389893
4.390381
4.391602
4.393555
4.394043
4.398438
4.405762
4.40625
4.406738
4.408936
4.409912
4.410645
4.418701
4.420654
4.421143
4.421631
4.424316
4.424561
4.425293
4.432861
0.000199653
0.000199646
0.000199653
0.000199646
0.000199646
0.000199653
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000199653
0.000199653
0.000199646
0.000199646
0.000199646
0.000199653
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000199646
0.000199646
0.000199653
0.000199646
0.000199646
0.000199646
0.004075617
0.004081162
0.004086708
0.004092254
0.004097799
0.004103345
0.004108891
0.004114436
0.004119982
0.004125528
0.004131074
0.004136619
0.004142165
0.00414771
0.004153256
0.004158801
0.004164347
0.004169893
0.004175439
0.004180985
0.004186531
0.004192076
0.004197622
0.004203167
0.004208713
0.004214259
0.004219804
0.00422535
0.004230896
0.004236442
0.004241987
0.004247533
0.004253078
0.004258624
0.004264169
0.004269715
0.004275261
0.004280807
0.004286352
0.004291898
0.004297443
0.004302989
0.004308535
0.00431408
0.004319626
0.004325172
0.004330717
0.004336263
74.92
75.19
75.45
75.72
75.99
76.25
76.52
76.79
77.05
77.32
77.59
77.85
78.12
78.39
78.65
78.92
79.19
79.45
79.72
79.99
80.25
80.52
80.79
81.05
81.32
81.59
81.85
82.12
82.39
82.65
82.92
83.19
83.45
83.72
83.99
84.25
84.52
84.79
85.05
85.32
85.59
85.85
86.12
86.39
86.65
86.92
87.18
87.45
171
2210
19:14.6
4.437256
0.000199646
0.004341809
87.72
2211
2212
2213
2214
2215
2216
2217
2218
2219
2220
2221
2222
2223
2224
2225
2226
2227
2228
2229
2230
2231
2232
2233
2234
2235
2236
2237
2238
2239
20:54.6
22:34.6
24:14.6
25:54.6
27:34.6
29:14.6
30:54.6
32:34.6
34:14.6
35:54.6
37:34.6
39:14.6
40:54.6
42:34.6
44:14.6
45:54.6
47:34.6
49:14.6
50:54.6
52:34.6
54:14.6
55:54.6
57:34.6
59:14.6
00:54.6
02:34.6
04:14.6
05:54.6
06:18.7
4.4375
4.438232
4.44043
4.441162
4.44165
4.444824
4.451904
4.452148
4.452881
4.453613
4.455811
4.456055
4.456787
4.467041
4.468506
4.469238
4.469482
4.472168
4.472412
4.4729
4.475586
4.48291
4.483154
4.483887
4.484131
4.486328
4.486572
4.487549
4.496338
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199646
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199653
0.000199646
0.000199653
0.000199653
0.000199653
0.000199929
0.004347354
0.0043529
0.004358446
0.004363991
0.004369537
0.004375082
0.004380628
0.004386174
0.004391719
0.004397265
0.00440281
0.004408356
0.004413902
0.004419447
0.004424993
0.004430539
0.004436084
0.00444163
0.004447176
0.004452722
0.004458268
0.004463814
0.00446936
0.004474906
0.004480452
0.004485998
0.004491544
0.00449709
0.004498431
87.98
88.25
88.52
88.78
89.05
89.32
89.58
89.85
90.12
90.38
90.65
90.92
91.18
91.45
91.72
91.98
92.25
92.52
92.78
93.05
93.32
93.58
93.85
94.12
94.38
94.65
94.92
95.18
95.25
172
APPENDIX A 6
In details Report of Li/1M LiPF6-EC/DMC/LiCo0.7Al0.3O2 (CA assisted)
[E cell] Cell Test Data for the 3rd Cycle Discharge
Experiment start time: 11.21.31 AM, Date: 6/14/2005
Sample rate: 0.01 (Hz)
Unit number for each result number: 2
Channel number for each result number: 2
Step number for each result no: 2
Step repeat: 3
Schedule repeat: 1
Result
Number
2240
2241
2242
2243
2244
2245
2246
2247
2248
2249
2250
2251
2252
2253
2254
2255
2256
2257
2258
2259
2260
2261
2262
2263
2264
2265
2266
2267
2268
2269
2270
2271
Time
Voltage (V)
Current (A)
Charge (Ah)
07:58.7
09:38.7
11:18.7
12:58.7
14:38.7
16:18.7
17:58.7
19:38.7
21:18.7
22:58.7
24:38.7
26:18.7
27:58.7
29:38.7
31:18.7
32:58.7
34:38.7
36:18.7
37:58.7
39:38.7
41:18.7
42:58.7
44:38.7
46:18.7
47:58.7
49:38.7
51:18.7
52:58.7
54:38.7
56:18.7
57:58.7
59:38.7
4.441406
4.425537
4.412842
4.407471
4.394775
4.391113
4.380371
4.37793
4.368652
4.363037
4.359619
4.348877
4.347412
4.34375
4.332275
4.331055
4.328125
4.317139
4.316162
4.313232
4.302002
4.300293
4.297607
4.289307
4.285645
4.282959
4.280762
4.27002
4.269043
4.266357
4.260254
4.254395
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
0.004492868
0.004487307
0.004481745
0.004476184
0.004470622
0.00446506
0.004459499
0.004453937
0.004448376
0.004442814
0.004437252
0.004431691
0.004426129
0.004420567
0.004415005
0.004409443
0.004403882
0.00439832
0.004392758
0.004387196
0.004381634
0.004376072
0.004370511
0.004364949
0.004359387
0.004353825
0.004348264
0.004342702
0.00433714
0.004331579
0.004326017
0.004320455
Discharge
(mA h/g)
0.27
0.53
0.80
1.07
1.34
1.60
1.87
2.14
2.41
2.67
2.94
3.21
3.48
3.74
4.01
4.28
4.55
4.81
5.08
5.35
5.62
5.88
6.15
6.42
6.68
6.95
7.22
7.49
7.75
8.02
8.29
8.56
173
2272
2273
2274
2275
2276
2277
2278
2279
2280
2281
2282
2283
2284
2285
2286
2287
2288
2289
2290
2291
2292
2293
2294
2295
2296
2297
2298
2299
2300
2301
2302
2303
2304
2305
2306
2307
2308
2309
2310
2311
2312
2313
2314
2315
2316
2317
2318
2319
2320
2321
01:18.7
02:58.7
04:38.7
06:18.7
07:58.7
09:38.7
11:18.7
12:58.7
14:38.7
16:18.7
17:58.7
19:38.7
21:18.7
22:58.7
24:38.7
26:18.7
27:58.7
29:38.7
31:18.7
32:58.7
34:38.7
36:18.7
37:58.7
39:38.7
41:18.7
42:58.7
44:38.7
46:18.7
47:58.7
49:38.7
51:18.7
52:58.7
54:38.7
56:18.7
57:58.7
59:38.7
01:18.7
02:58.7
04:38.7
06:18.7
07:58.7
09:38.7
11:18.7
12:58.7
14:38.7
16:18.7
17:58.7
19:38.7
21:18.7
22:58.7
4.253418
4.250732
4.240234
4.238525
4.23584
4.234619
4.224121
4.2229
4.220215
4.218994
4.208496
4.20752
4.204834
4.203613
4.193604
4.192139
4.189697
4.188232
4.178955
4.176514
4.175293
4.172607
4.167236
4.161133
4.160156
4.157227
4.15625
4.145996
4.145264
4.143555
4.141357
4.134521
4.129883
4.128906
4.126221
4.125244
4.115479
4.114014
4.113037
4.110352
4.108398
4.098877
4.098145
4.096191
4.094482
4.0896
4.083008
4.082275
4.079346
4.078613
-0.000200219
-0.000200219
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
0.004314893
0.004309332
0.00430377
0.004298208
0.004292646
0.004287084
0.004281522
0.004275961
0.004270399
0.004264837
0.004259275
0.004253713
0.004248152
0.00424259
0.004237028
0.004231466
0.004225905
0.004220343
0.004214781
0.004209219
0.004203658
0.004198096
0.004192534
0.004186972
0.004181411
0.004175849
0.004170287
0.004164725
0.004159163
0.004153602
0.00414804
0.004142478
0.004136916
0.004131354
0.004125793
0.004120231
0.004114669
0.004109107
0.004103546
0.004097984
0.004092422
0.00408686
0.004081299
0.004075737
0.004070175
0.004064613
0.004059052
0.00405349
0.004047928
0.004042366
8.82
9.09
9.36
9.63
9.89
10.16
10.43
10.70
10.96
11.23
11.50
11.77
12.03
12.30
12.57
12.83
13.10
13.37
13.64
13.90
14.17
14.44
14.71
14.97
15.24
15.51
15.78
16.04
16.31
16.58
16.85
17.11
17.38
17.65
17.92
18.18
18.45
18.72
18.98
19.25
19.52
19.79
20.05
20.32
20.59
20.86
21.12
21.39
21.66
21.93
174
2322
2323
2324
2325
2326
2327
2328
2329
2330
2331
2332
2333
2334
2335
2336
2337
2338
2339
2340
2341
2342
2343
2344
2345
2346
2347
2348
2349
2350
2351
2352
2353
2354
2355
2356
2357
2358
2359
2360
2361
2362
2363
2364
2365
2366
2367
2368
2369
2370
2371
24:38.7
26:18.7
27:58.7
29:38.7
31:18.7
32:58.7
34:38.7
36:18.7
37:58.7
39:38.7
41:18.7
42:58.7
44:38.7
46:18.7
47:58.7
49:38.7
51:18.7
52:58.7
54:38.7
56:18.7
57:58.7
59:38.7
01:18.7
02:58.7
04:38.7
06:18.7
07:58.7
09:38.7
11:18.7
12:58.7
14:38.7
16:18.7
17:58.7
19:38.7
21:18.7
22:58.7
24:38.7
26:18.7
27:58.7
29:38.7
31:18.7
32:58.7
34:38.7
36:18.7
37:58.7
39:38.7
41:18.7
42:58.7
44:38.7
46:18.7
4.070557
4.067627
4.066406
4.063721
4.062988
4.05542
4.052002
4.051025
4.048584
4.047607
4.044189
4.036377
4.035645
4.034912
4.032227
4.03125
4.02124
4.020508
4.019775
4.016846
4.016357
4.012451
4.005127
4.004639
4.003662
4.000977
4.000244
3.992188
3.98938
3.988525
3.986938
3.985352
3.984131
3.974487
3.973755
3.9729
3.970337
3.969604
3.96875
3.959351
3.958252
3.957275
3.955566
3.954102
3.953247
3.945313
3.942627
3.941772
3.941162
3.938599
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200219
-0.000200227
-0.000200227
-0.000200227
-0.000200219
-0.000200227
-0.000200227
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200219
-0.000200227
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200227
0.004036804
0.004031242
0.004025681
0.004020119
0.004014557
0.004008995
0.004003434
0.003997872
0.00399231
0.003986748
0.003981187
0.003975625
0.003970063
0.003964501
0.00395894
0.003953378
0.003947816
0.003942254
0.003936692
0.003931131
0.003925569
0.003920007
0.003914445
0.003908883
0.003903322
0.00389776
0.003892198
0.003886636
0.003881074
0.003875513
0.003869951
0.003864389
0.003858828
0.003853266
0.003847704
0.003842142
0.00383658
0.003831019
0.003825457
0.003819895
0.003814333
0.003808771
0.00380321
0.003797648
0.003792086
0.003786524
0.003780963
0.003775401
0.003769839
0.003764277
22.19
22.46
22.73
23.00
23.26
23.53
23.80
24.07
24.33
24.60
24.87
25.13
25.40
25.67
25.94
26.20
26.47
26.74
27.01
27.27
27.54
27.81
28.08
28.34
28.61
28.88
29.15
29.41
29.68
29.95
30.22
30.48
30.75
31.02
31.28
31.55
31.82
32.09
32.35
32.62
32.89
33.16
33.42
33.69
33.96
34.23
34.49
34.76
35.03
35.30
175
2372
2373
2374
2375
2376
2377
2378
2379
2380
2381
2382
2383
2384
2385
2386
2387
2388
2389
2390
2391
2392
2393
2394
2395
2396
2397
2398
2399
2400
2401
2402
2403
2404
2405
2406
2407
2408
2409
2410
2411
2412
2413
2414
2415
2416
2417
2418
2419
2420
2421
47:58.7
49:38.7
51:18.7
52:58.7
54:38.7
56:18.7
57:58.7
59:38.7
01:18.7
02:58.7
04:38.7
06:18.7
07:58.7
09:38.7
11:18.7
12:58.7
14:38.7
16:18.7
17:58.7
19:38.7
21:18.7
22:58.7
24:38.7
26:18.7
27:58.7
29:38.7
31:18.7
32:58.7
34:38.7
36:18.7
37:58.7
39:38.7
41:18.7
42:58.7
44:38.7
46:18.7
47:58.7
49:38.7
51:18.7
52:58.7
54:38.7
56:18.7
57:58.7
59:38.7
01:18.7
02:58.7
04:38.7
06:18.7
07:58.7
09:38.7
3.93811
3.935303
3.927246
3.926758
3.926025
3.923218
3.922729
3.921997
3.914185
3.911499
3.911011
3.910278
3.907471
3.907104
3.906372
3.899414
3.895874
3.895508
3.894897
3.892822
3.891602
3.891113
3.890259
3.881104
3.880249
3.879761
3.879272
3.878174
3.876099
3.875732
3.875122
3.874634
3.866699
3.864746
3.864502
3.864014
3.863647
3.863403
3.86084
3.860474
3.860107
3.859497
3.859253
3.853271
3.849121
3.848877
3.848389
3.848022
3.846558
3.844849
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200227
-0.000200227
-0.000200219
-0.000200219
-0.000200227
-0.000200219
-0.000200227
-0.000200227
-0.000200227
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200227
-0.000200219
-0.000200227
-0.000200219
-0.000200227
-0.000200219
-0.000200219
0.003758715
0.003753154
0.003747592
0.00374203
0.003736468
0.003730907
0.003725345
0.003719783
0.003714221
0.003708659
0.003703098
0.003697536
0.003691974
0.003686412
0.003680851
0.003675289
0.003669727
0.003664165
0.003658604
0.003653042
0.00364748
0.003641918
0.003636356
0.003630795
0.003625233
0.003619671
0.003614109
0.003608548
0.003602986
0.003597424
0.003591862
0.0035863
0.003580739
0.003575177
0.003569615
0.003564053
0.003558492
0.00355293
0.003547368
0.003541806
0.003536244
0.003530683
0.003525121
0.003519559
0.003513997
0.003508436
0.003502874
0.003497312
0.00349175
0.003486189
35.56
35.83
36.10
36.37
36.63
36.90
37.17
37.43
37.70
37.97
38.24
38.50
38.77
39.04
39.31
39.57
39.84
40.11
40.38
40.64
40.91
41.18
41.45
41.71
41.98
42.25
42.52
42.78
43.05
43.32
43.59
43.85
44.12
44.39
44.65
44.92
45.19
45.46
45.72
45.99
46.26
46.53
46.79
47.06
47.33
47.60
47.86
48.13
48.40
48.67
176
2422
2423
2424
2425
2426
2427
2428
2429
2430
2431
2432
2433
2434
2435
2436
2437
2438
2439
2440
2441
2442
2443
2444
2445
2446
2447
2448
2449
2450
2451
2452
2453
2454
2455
2456
2457
2458
2459
2460
2461
2462
2463
2464
2465
2466
2467
2468
2469
2470
2471
11:18.7
12:58.7
14:38.7
16:18.7
17:58.7
19:38.7
21:18.7
22:58.7
24:38.7
26:18.7
27:58.7
29:38.7
31:18.7
32:58.7
34:38.7
36:18.7
37:58.7
39:38.7
41:18.7
42:58.7
44:38.7
46:18.7
47:58.7
49:38.7
51:18.7
52:58.7
54:38.7
56:18.7
57:58.7
59:38.7
01:18.7
02:58.7
04:38.7
06:18.7
07:58.7
09:38.7
11:18.7
12:58.7
14:38.7
16:18.7
17:58.7
19:38.7
21:18.7
22:58.7
24:38.7
26:18.7
27:58.7
29:38.7
31:18.7
32:58.7
3.844482
3.84375
3.835449
3.833374
3.832764
3.832031
3.829224
3.828369
3.819092
3.817749
3.816772
3.813721
3.812256
3.802612
3.801636
3.799072
3.797729
3.788574
3.786377
3.783203
3.781372
3.77124
3.77002
3.766724
3.757446
3.755127
3.751465
3.747437
3.73999
3.738403
3.735352
3.725342
3.723633
3.720093
3.714355
3.70874
3.706787
3.703979
3.69397
3.692505
3.689087
3.68689
3.677612
3.676514
3.672974
3.666992
3.661743
3.660156
3.657227
3.64917
-0.000200227
-0.000200227
-0.000200219
-0.000200219
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200227
-0.000200227
-0.000200219
-0.000200227
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-0.000200219
-0.000200227
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
0.003480627
0.003475065
0.003469503
0.003463941
0.00345838
0.003452818
0.003447256
0.003441694
0.003436133
0.003430571
0.003425009
0.003419447
0.003413885
0.003408324
0.003402762
0.0033972
0.003391638
0.003386077
0.003380515
0.003374953
0.003369391
0.003363829
0.003358268
0.003352706
0.003347144
0.003341582
0.003336021
0.003330459
0.003324897
0.003319335
0.003313774
0.003308212
0.00330265
0.003297088
0.003291526
0.003285964
0.003280403
0.003274841
0.003269279
0.003263718
0.003258156
0.003252594
0.003247032
0.00324147
0.003235909
0.003230347
0.003224785
0.003219223
0.003213661
0.0032081
48.93
49.20
49.47
49.74
50.00
50.27
50.54
50.80
51.07
51.34
51.61
51.87
52.14
52.41
52.68
52.94
53.21
53.48
53.75
54.01
54.28
54.55
54.82
55.08
55.35
55.62
55.89
56.15
56.42
56.69
56.95
57.22
57.49
57.76
58.02
58.29
58.56
58.83
59.09
59.36
59.63
59.90
60.16
60.43
60.70
60.97
61.23
61.50
61.77
62.04
177
2472
2473
2474
2475
2476
2477
2478
2479
2480
2481
2482
2483
2484
2485
2486
2487
2488
2489
2490
2491
2492
2493
2494
2495
2496
2497
2498
2499
2500
2501
2502
2503
2504
2505
2506
2507
2508
2509
2510
2511
2512
2513
2514
2515
2516
2517
2518
2519
2520
2521
34:38.7
36:18.7
37:58.7
39:38.7
41:18.7
42:58.7
44:38.7
46:18.7
47:58.7
49:38.7
51:18.7
52:58.7
54:38.7
56:18.7
57:58.7
59:38.7
01:18.7
02:58.7
04:38.7
06:18.7
07:58.7
09:38.7
11:18.7
12:58.7
14:38.7
16:18.7
17:58.7
19:38.7
21:18.7
22:58.7
24:38.7
26:18.7
27:58.7
29:38.7
31:18.7
32:58.7
34:38.7
36:18.7
37:58.7
39:38.7
41:18.7
42:58.7
44:38.7
46:18.7
47:58.7
49:38.7
51:18.7
52:58.7
54:38.7
56:18.7
3.646118
3.644897
3.641846
3.637817
3.630615
3.629761
3.626831
3.625977
3.619873
3.61499
3.614014
3.611694
3.610474
3.609497
3.608032
3.600098
3.599487
3.598999
3.598389
3.598145
3.595825
3.594971
3.594482
3.593628
3.585571
3.583984
3.583374
3.582642
3.579956
3.579224
3.578369
3.571045
3.568237
3.567261
3.566406
3.563721
3.562988
3.55542
3.552612
3.551514
3.548218
3.547363
3.538208
3.536865
3.53418
3.532104
3.522095
3.52063
3.516968
3.509766
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200219
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
0.003202538
0.003196976
0.003191415
0.003185853
0.003180291
0.003174729
0.003169167
0.003163605
0.003158044
0.003152482
0.00314692
0.003141358
0.003135797
0.003130235
0.003124673
0.003119111
0.003113549
0.003107988
0.003102426
0.003096865
0.003091303
0.003085742
0.00308018
0.003074619
0.003069057
0.003063496
0.003057934
0.003052373
0.003046811
0.00304125
0.003035688
0.003030127
0.003024565
0.003019004
0.003013442
0.003007881
0.003002319
0.002996758
0.002991196
0.002985635
0.002980073
0.002974512
0.00296895
0.002963389
0.002957827
0.002952266
0.002946704
0.002941143
0.002935581
0.00293002
62.30
62.57
62.84
63.10
63.37
63.64
63.91
64.17
64.44
64.71
64.98
65.24
65.51
65.78
66.05
66.31
66.58
66.85
67.12
67.38
67.65
67.92
68.19
68.45
68.72
68.99
69.25
69.52
69.79
70.06
70.32
70.59
70.86
71.13
71.39
71.66
71.93
72.20
72.46
72.73
73.00
73.27
73.53
73.80
74.07
74.33
74.60
74.87
75.14
75.40
178
2522
2523
2524
2525
2526
2527
2528
2529
2530
2531
2532
2533
2534
2535
2536
2537
2538
2539
2540
2541
2542
2543
2544
2545
2546
2547
2548
2549
2550
2551
2552
2553
2554
2555
2556
2557
2558
2559
2560
2561
2562
2563
2564
2565
2566
2567
2568
2569
2570
57:58.7
59:38.7
01:18.7
02:58.7
04:38.7
06:18.7
07:58.7
09:38.7
11:18.7
12:58.7
14:38.7
16:18.7
17:58.7
19:38.7
21:18.7
22:58.7
24:38.7
26:18.7
27:58.7
29:38.7
31:18.7
32:58.7
34:38.7
36:18.7
37:58.7
39:38.7
41:18.7
42:58.7
44:38.7
46:18.7
47:58.7
49:38.7
51:18.7
52:58.7
54:38.7
56:18.7
57:58.7
59:38.7
01:18.7
02:58.7
04:38.7
06:18.7
07:58.7
09:38.7
11:18.7
12:58.7
14:38.7
16:18.7
17:06.6
3.505615
3.501343
3.492065
3.489258
3.483521
3.474731
3.470215
3.459717
3.455444
3.445313
3.440552
3.430054
3.425537
3.414551
3.409668
3.398315
3.392944
3.38147
3.37439
3.365356
3.353149
3.346558
3.334595
3.322754
3.314941
3.303223
3.289551
3.278442
3.268799
3.256592
3.242065
3.22937
3.217651
3.206909
3.194092
3.179443
3.165527
3.152588
3.140625
3.128662
3.115112
3.10083
3.085938
3.071411
3.056885
3.042236
3.027466
3.011841
3.003784
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200212
-0.000200152
0.002924458
0.002918897
0.002913335
0.002907774
0.002902212
0.002896651
0.002891089
0.002885528
0.002879966
0.002874405
0.002868843
0.002863282
0.00285772
0.002852159
0.002846597
0.002841036
0.002835474
0.002829913
0.002824351
0.00281879
0.002813228
0.002807667
0.002802105
0.002796544
0.002790982
0.002785421
0.002779859
0.002774297
0.002768736
0.002763174
0.002757613
0.002752051
0.00274649
0.002740928
0.002735367
0.002729805
0.002724244
0.002718682
0.002713121
0.002707559
0.002701998
0.002696436
0.002690875
0.002685313
0.002679752
0.00267419
0.002668629
0.002663067
0.002660401
75.67
75.94
76.21
76.47
76.74
77.01
77.28
77.54
77.81
78.08
78.35
78.61
78.88
79.15
79.42
79.68
79.95
80.22
80.48
80.75
81.02
81.29
81.55
81.82
82.09
82.36
82.62
82.89
83.16
83.43
83.69
83.96
84.23
84.50
84.76
85.03
85.30
85.56
85.83
86.10
86.37
86.63
86.90
87.17
87.44
87.70
87.97
88.24
88.37
179
APPENDIXB
Perfom
an
ceDataofSy
d
en
th
siz
Positve Electrod Materials (LiCoO
Man
u
factres
Po
vesit
Eled
ortc
Ma
terials
a
Th
eo.
Ca
typ
aci
A )h
(m
/g
Cath
od
eMaterialsan
dCom
ercial
2)
Pralcit
Ca
typ
aci
A )h
(m
/g
150
Sony: 102
Commercial
LiCoO2
Moli:123
274
A&T: 158
Sanyo:135
Synthesized
LiMn2O4 (CAEG assisted)
Matsushita:
155
1st cycle:29.66
148
2nd cycle:23.84
Ca
typ
aci
Ren
tioe
)(%
-
Used yb Difern
t
Ca
typ
aci
Fa
gd
in
)(%
Co
cib
m
olu
Efycn
eif
)(%
93
-
-
71.4
28.6
96.2
93.7
6.3
89.1
90.6
9.4
74.8
91.6
8.4
97.6
90.8
9.2
92.8
98.4
1.6
94.7
rd
3 cycle:21.18
Synthesized
LiMn2O4 (CA
assisted)
1st cycle:20.94
148
2nd cycle:20.33
rd
3 cycle:19.63
Synthesized
LiMn2O4 (PA
assisted)
1st cycle:41.65
148
2nd cycle:39.72
rd
3 cycle:37.72
Cr-doped
LiCrxMn2-xO4
1st cycle:49.50
148
2nd cycle:47.44
rd
3 cycle:45.36
Synthesized
LiCo0.7Al0.3O2
(CA assisted)
1st cycle:29.66
120
2nd cycle:23.84
rd
3 cycle:21.18
Synthesized
LiCo0.7Al0.3O2
(CA assisted)
1st cycle:29.66
120
2nd cycle:23.84
rd
3 cycle:21.18
a
Theo. = Theoretical
Ren
cefr
Mizushima
et al., 1980
&
Moshtev
et al., 2000