vii
TABLE OF CONTENTS
CHAPTER
1
TITLE
PAGE
ACKNOWLEDGEMENT
iv
ABSTRACT
v
ABSTRAK
vi
TABLE OF CONTENTS
vii
LIST OF TABLES
xviii
LIST OF FIGURES
xxiv
LIST OF PHOTOGRAPH
xxxix
LIST OF SYMBOLS
xl
LIST OF ABBREVIATIONS
xli
LIST OF PUBLICATIONS
xlii
INTRODUCTION
1
1.1
Classification of Polymer Electrolytes
3
1.2
Polymer Electrolytes Background
5
1.3
Why Polymer Electrolytes
6
1.4
The Characteristics of Polymer Electrolytes
6
1.5
Characteristic of the Doping Salt
7
1.6
Preparation of Polymer Electrolytes
7
1.7
Modification of Polymer Host
8
1.8
Applications of Polymer Electrolytes
10
1.9
Problem Statements
11
1.10 Objectives
12
viii
1.11 Research Scope
2
12
1.11.1
Selection of Materials
12
1.11.2
Selection of Material Characterizations
14
1.11.3
Selection of Test cell
15
1.12 Expectations
16
1.13 Technical Challenge and limitations
16
LITERATURE REVIEW
18
2.1
Poly(methyl methacrylate) as a Polymer Host
18
2.2
Epoxidised Natural Rubber
22
2.3
Plasticizers
24
2.4
Structure and Morphology
25
2.5
Polymer-Salt Interaction : Concepts of Ion Solvation by the
30
Polymer
2.6
2.7
Conductivity Studies
32
2.6.1
32
Impedance Spectroscopy
Ionic Conduction Mechanism
37
2.7.1 Arrhenius Behaviour : Solid State Theory
40
2.7.2 Vogel-Tammam –Fulcher Equation : A Free
42
Volume-Based Model
2.7.3
Williams, Landel and Ferry
44
2.8
Dielectric Behaviour Study
45
2.9
Equivalent Circuit Study
47
2.10 Electrochemical Cell Studies
50
2.10.1
Introduction
50
2.10.2
Secondary Lithium Batteries
52
2.10.3
Electrochemical Characteristics and Performance
56
Criteria of Cells and Batteries
ix
3
RESEARCH METHODOLOGY
59
3.1
Samples Preparation
59
3.1.1
59
Materials
3.2
Preparation of Polymer Stock Solution
60
3.3
Preparation of Poly(methyl methacrylate) / 50% Epoxidised
60
Natural Rubber film
3.3.1
To Determine the Effect of 50% Epoxidised Natural
60
Rubber on the Properties of PMMA
3.3.2
To Determine the Effect of Salts on the Conductivity of
61
Poly(methyl methacrylate) / 50% Epoxidised Natural
Rubber Blend
3.3.3
To Determine the Effect of Plasticizer on the
61
Conductivity of doped Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber Films
3.4
Material Characterization
62
3.4.1
Scanning Electron Microscopy
63
3.4.2
Differential Scanning Calorimetry
63
3.4.3
Infrared Spectroscopy
66
3.5
Conductivity Studies
66
3.6
Ion Transport Characterization by Wagner’s Polarization
68
Method
3.7
4
Fabrication of Solid State Secondary Battery
70
/ 50% EPOXIDISED
71
The effect of 50% Epoxidised Natural Rubber on the Formation
71
POLY(METHYL METHACRYLATE)
NATURAL RUBBER BLEND
4.1
of Freestanding Poly(methyl methacrylate)/ 50% Epoxidised
Natural Rubber Films
4.2
Field Emission Scanning Electron Microscopy Study on The
Morphology of Poly(methyl methacrylate) / 50% Epoxidised
Natural Rubber Films
74
x
4.3
Differential Scanning Calorimetry Study on the Poly(methyl
78
methacrylate) / 50% Epoxidised Natural Rubber Films
4.4
Fourier Transform Infra Red Study
81
4.4.1
81
Poly(methyl methacrylate)– 50% Epoxidised Natural
Rubber Interactions
5
4.5
Conductivity Study
85
4.6
Conclusion
89
POLY(METHYL METHACRYLATE)
NATURAL
RUBBER
/
LITHIUM
/ 50% EPOXIDISED
NITRATE
90
BASED
ELECTROLYTES
5.1
The Effect of Lithium Nitrate Salt on the Formation of
90
Poly(methyl methacrylate) / 50% Epoxidised Natural Rubber /
Lithium Nitrate Films
5.2
The Effect of Plasticizer on the Formation of Poly(methyl
91
methacrylate) / 50% Epoxidised Natural Rubber / Lithium
Nitrate Films
5.3
Field Emission Scanning Electron Microscopy Study
91
5.3.1
91
The Effect of Lithium Nitrate Salt on the Morphology
of Poly(methyl methacrylate) / 50% Epoxidised Natural
Rubber Films
5.3.2
The Effect of Dimethyl Carbonate Plasticizer on the
94
Morphology of Poly(methyl methacrylate) / 50%
Epoxidised Natural Rubber / Lithium Nitrate Films
5.4
Fourier Transform Infra Red Study
97
5.4.1
97
Determination of Polymer-Salt Complexation in
Un-plasticized Poly(methyl methacrylate) / 50%
Epoxidised Natural Rubber / Lithium Nitrate Films
5.4.2
Determination of Polymer-Salt Complexation in
102
Plasticized Poly(methyl methacrylate) / 50%
Epoxidised Natural Rubber / Lithium Nitrate Films
5.5
Conductivity Study
104
xi
5.5.1
Concentration Dependence
104
5.5.1.1
104
The Effect of Lithium Nitrate Salt on the
Conductivity of Poly(methyl methacrylate)/
50% Epoxidised Natural Rubber Films
5.5.1.2
The Effect of Dimethyl Carbonate Plasticizer
108
on the Conductivity of Poly(methyl
methacrylate) / 50% Epoxidised Natural
Rubber / Lithium Nitrate Films
5.5.2 Conductivity : Temperature Dependence
5.5.2.1
The Effect of Temperature on the
111
111
Conductivity of Poly(methyl methacrylate)/
50% Epoxidised Natural Rubber / Lithium
Nitrate Films
5.5.2.2
The Effect of Temperature on the
113
Conductivity of Plasticized Poly(methyl
methacrylate)/ 50% Epoxidised Natural
Rubber / Lithium Nitrate / Dimethyl
Carbonate Films
5.6
Dielectric Behaviour Study
115
5.6.1
115
Dielectric Study for Poly(methyl methacrylate) / 50%
Epoxidised Natural Rubber / Lithium Nitrate Films
5.6.2
Dielectric Study for Poly(methyl methacrylate) / 50%
122
Epoxidised Natural Rubber / Lithium Nitrate /
Dimethyl Carbonate Films
5.7
Equivalent Circuit Determination
127
5.7.1
127
Equivalent Circuit for Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber / Lithium Nitrate
Films
5.7.2
Equivalent Circuit for Plasticized Poly(methyl
129
methacrylate)/ 50% Epoxidised Natural Rubber /
Lithium Nitrate Films
5.8
Conclusion
131
xii
6
POLY(METHYL METHACRYLATE)
/ 50% EPOXIDISED
NATURAL
TRIFLATE
RUBBER
/
LITHIUM
133
BASED
ELECTROLYTES
6.1
The Formation of Poly(methyl methacrylate)
/ 50%
133
Epoxidised Natural Rubber / Lithium Triflate Film Based
Electrolyte
6.1.1 The Effect of Lithium Triflate Salt on the Formation of
133
Poly(methyl methacrylate) / 50% Epoxidised Natural
Rubber / Lithium Triflate Films
6.1.2
The Effect of Plasticizer on the Formation of Poly
134
(methyl methacrylate) / 50% Epoxidised Natural
Rubber / Lithium Triflate Films
6.2
Field Emission Scanning Electron Microscopy Study
135
6.2.1 The Effect of LiCF3SO3O3 Salt on the Morphology of
135
Poly(methyl methacrylate) / 50% Epoxidised Natural
Rubber Films
6.2.2
The Effect of Plasticizers on the Morphology of
137
Poly(methyl methacrylate) / 50% Epoxidised Natural
Rubber / Lithium Triflate Films
6.2.2.1
The Effect of Single Plasticizer on the
138
Morphology of Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber / Lithium
Triflate Films
6.2.2.2
The Effect of Mix Plasticizers on the
145
Morphology of Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber / Lithium
Triflate Films
6.3
Fourier Transform Infra Red Study
150
6.3.1
150
Determination of Polymer-Ion Complexation in
Poly(methyl methacrylate)/ 50% Epoxidised Natural
Rubber / Lithium Triflate Films
xiii
6.3.2
Determination of Polymer-Ion Complexation in Single
153
Plasticized Poly(methyl methacrylate) / 50%
Epoxidised Natural Rubber / Lithium Triflate Films
6.3.3
Determination of Polymer-Ion Complexation in Mix
159
Plasticized Poly(methyl methacrylate) / 50%
Epoxidised Natural Rubber / Lithium Triflate Films
6.4
Differential Scanning Calorimetry Studies of Poly(methyl
165
methacrylate) / 50% Epoxidised Natural Rubber / Lithium
Triflate Films
6.5
Conductivity Study
166
6.5.1
Concentration Dependence
166
6.5.1.1 The Effect of Salt Concentration on The
166
Conductivity of Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber /
Lithium Triflate Films
6.5.1.2
The Effect of Single Plasticizer on the
172
Conductivity of Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber / Lithium
Triflate Electrolytes
6.5.1.3
The Effect of Mix Plasticizers on the
178
Conductivity of Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber / Lithium
Triflate Electrolytes
6.5.2
Conductivity Study : Temperature Dependence
6.5.2.1
185
The Effect of Temperature on the
Conductivity of Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber /
Lithium Triflate Electrolytes
6.5.2.2
The Effect of Temperature on the
Conductivity of Plasticized Poly(methyl
methacrylate)/ 50% Epoxidised Natural
Rubber/ Lithium Triflate Films
187
xiv
6.5.2.3
The Effect of Temperature on the
195
Conductivity of Mix Plasticized
Poly(methyl methacrylate)/ 50%
Epoxidised Natural Rubber / Lithium
Triflate Films
6.6
Dielectric Behaviour Study
199
6.6.1
199
Dielectric Behaviour for Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber / Lithium Triflate
Electrolytes
6.6.2
Dielectric Behaviour for Single Plasticized
204
Poly(methyl
methacrylate)/ 50% Epoxidised Natural Rubber /
Lithium Triflate Electrolytes
6.6.3
212
Dielectric Behaviour for Mix Plasticizer System of
Poly(methyl methacrylate) / 50% Epoxidised Natural
Rubber / Lithium Triflate Electrolytes
220
6.7
Transference Number
222
6.8
Equivalent Circuit Study
227
6.9
Battery Fabrication and Characterization
227
6.9.1
Characterization of the Lithium Nickel Cobalt Oxide /
Poly(methyl methacrylate) / 50% Epoxidised Natural
Rubber / Lithium Triflate / Mesocarbon Microbeads
Cell
6.9.2
230
Characterization of the Lithium Nickel Cobalt Oxide /
Poly(methyl methacrylate) / 50% Epoxidised Natural
Rubber / Lithium Triflate / Propylene Carbonate /
Mesocarbon Microbeads Cell
6.9.3
232
Characterization of the Lithium Nickel Cobalt Oxide /
Poly(methyl methacrylate) / 50% Epoxidised Natural
Rubber / Lithium Triflate / Ethylene Carbonate /
Dimethyl Carbonate / Mesocarbon Microbeads Cell
6.10
Conclusion
235
xv
7
POLY(METHYL METHACRYLATE)
NATURAL
RUBBER
/
/ 50% EPOXIDISED
LITHIUM
IMIDES
BASED
The Formation of Poly(methyl methacrylate)
/ 50%
236
ELECTROLYTES
7.1.1
236
Epoxidised Natural Rubber / Lithium Imides Film Based
Electrolyte
7.1.1 The Effect of Lithium Imides Salt on the Formation of
236
Poly(methyl methacrylate) / 50% Epoxidised Natural
Rubber / Lithium Imides Films
7.1.2 The Effect of Plasticizer on the Formation of
237
Poly(methyl methacrylate) / 50% Epoxidised Natural
Rubber / Lithium Imides Films
7.2
Optical Microscope Study
237
7.2.1 The Effect of Lithium Imides Salt on the Morphology
237
of Poly(methyl methacrylate) / 50% Epoxidised Natural
Rubber Films
7.2.2
The Effect of Plasticizers on the Morphology of
242
Poly(methyl methacrylate) / 50% Epoxidised Natural
Rubber / Lithium Imides Films
7.2.2.1
The Effect of Single Plasticizer on the
242
Morphology of Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber /
Lithium Imides Films
7.2.2.2
The Effect of Mix Plasticizers on the
250
Morphology of Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber / Lithium
Imides Films
7.3
Fourier Transform Infra Red Study
256
7.3.1
256
Determination of Polymer-Ion Complexation in
Poly(methyl methacrylate)/ 50% Epoxidised Natural
Rubber / Lithium Imides Films
xvi
7.3.2
Determination of Polymer-Ion Complexation in Single
260
Plasticized Poly(methyl methacrylate) / 50%
Epoxidised Natural Rubber / Lithium Imides Films
7.3.3
Determination of Polymer-Ion Complexation in Mixed
269
Plasticized Poly(methyl methacrylate) / 50%
Epoxidised Natural Rubber / Lithium Imides Films
7.4
Conductivity Study
7.4.1
276
Concentration Dependence
276
7.4.1.1
276
The Effect of Sal Concentration on the
Conductivity of Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber / Lithium
Imides Films
7.4.1.2
The Effect of Single Plasticizer on
280
the Conductivity of Poly(methyl
methacrylate) / 50% Epoxidised Natural
Rubber / Lithium Imides Electrolytes
7.4.1.3 The Effect of Mix Plasticizers on the
286
Conductivity of Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber / Lithium
Imides Electrolytes
7.4.2 Conductivity Study : Temperature Dependence
7.4.2.1
The Effect of Temperature on the
290
290
Conductivity of Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber / Lithium
Imides Electrolytes
7.4.2.2
The Effect of Temperature on the
Conductivity of Single Plasticized
Poly(methyl methacrylate)/ 50%
Epoxidised Natural Rubber / Lithium
Imides Films
292
xvii
7.4.2.3
The Effect of Temperature on the
295
Conductivity of Mix Plasticized
Poly(methyl methacrylate)/ 50%
Epoxidised Natural Rubber / Lithium
Imides Films
7.5
Dielectric Behaviour Study
298
7.5.1
298
Dielectric Behaviour for Poly(methyl methacrylate) /
50% Epoxidised Natural Rubber / Lithium Imides
Electrolytes
7.5.2
Dielectric Behaviour for Single Plasticized
303
Poly(methyl
methacrylate)/ 50% Epoxidised Natural Rubber /
Lithium Imides Electrolytes
7.5.3
309
Dielectric Behaviour for Mix Plasticizer System of
Poly(methyl methacrylate) / 50% Epoxidised Natural
Rubber / Lithium Imides Electrolytes
8
7.6
Equivalent Circuit
7.7
Conclusion
CONCLUSIONS
REFERENCES
317
321
322
325
xviii
LIST OF TABLES
TABLE NO.
TITLE
PAGE
2.1
PMMA Based Electrolytes
21
2.2
Some Physical Properties of EC, PC and DMC plasticizers
25
3.1
Dilution Procedure for PC and DMC
62
4.1
Tg for PMMA / ENR 50 Blend
81
4.2
-C=O, -OCH3, -C-O, -CH3 Bands of PMMA and -C-O-C –
83
Band of ENR 50 Obtained from Previous Studies
4.3
-C=O, -OCH3, -CH3, -C-O-C – and C=C Bands Obtained
83
from Present Study
4.4
Average Thickness and Conductivity of Un-doped PMMA /
87
ENR 50 Blend
5.1
The Shift of C=O Band After Complexation in PMMA /
101
ENR 50 / LiNO3 Electrolyte
5.2
The Average Conductivity Value for PMMA / ENR 50 /
107
LiNO3 Films at Various Amounts of Salt and Temperatures
5.3
The Average Conductivities for PMMA / ENR 50 / LiNO3
109
Electrolyte Films at Various Amounts of DMC and
Temperatures
5.4
Conductivity Relaxation Times For Various Concentration
120
of LiNO3 Salt in PMMA / ENR 50 Blend
5.5
Conductivity Relaxation Times For Various Concentration
of DMC Plasticizer in PMMA / ENR 50 / LiNO3
Electrolytes
126
xix
5.6
The Fitted Values for the Equivalent Circuit for The
129
Highest Conducting PMMA / ENR 50 / LiNO3 Electrolyte,
PE1N2
5.7
The Fitted Values for the Equivalent Circuit for The
131
Highest Conducting Plasticized PMMA / ENR 50 / LiNO3
Electrolyte, PE1ND1
6.1
Bands Shift in PMMA / ENR 50 / LiCF3SO3 Electrolytes
152
6.2
Bands Shift in PMMA / ENR 50 / LiCF3SO3 / DMC
155
Electrolytes
6.3
Bands Shift in PMMA / ENR 50 / LiCF3SO3 / EC
157
Electrolytes
6.4
Bands Shift in PMMA / ENR 50 / LiCF3SO3 / PC
159
Electrolytes
6.5
Bands Shift in PMMA / ENR 50 / LiCF3SO3 / EC/ DMC
161
Electrolytes
6.6
Bands Shift in PMMA / ENR 50 / LiCF3SO3 / EC/ PC
163
Electrolytes
6.7
Bands Shift in PMMA / ENR 50 / LiCF3SO3 / PC/ DMC
164
Electrolytes
6.8
The Average Conductivity of PMMA / ENR 50 / LiCF3SO3
169
at Various Amount of Salt and Temperatures
6.9
The Average Conductivity of PMMA / ENR 50 / LiCF3SO3
175
/ DMC Electrolytes at Various Amount of DMC and
Temperatures
6.10
The Average Conductivity of PMMA / ENR 50 / LiCF3SO3
175
/ EC Electrolytes at Various Amount of EC and
Temperatures
6.11
The Average Conductivity of PMMA / ENR 50 / LiCF3SO3
177
/ PC Electrolytes at Various Amount of PC and
Temperatures
6.12
The Average Conductivity of PMMA / ENR 50 / LiCF3SO3
/ EC / DMC Electrolytes at Various Amount of EC:DMC
and Temperatures
181
xx
6.13
The Average Conductivity of PMMA / ENR 50 / LiCF3SO3
182
/ EC / PC Electrolytes at Various Amount of EC:PC and
Temperatures
6.14
The Average Conductivity of PMMA / ENR 50 / LiCF3SO3
183
/ PC / DMC Electrolytes at Various Amount of PC:DMC
and Temperatures
6.15
The Activation Energy, Ea for PMMA / ENR 50 /
187
LiCF3SO3 Electrolytes
6.16
The Activation Energy, Ea for PMMA / ENR 50 Blend/
190
LiCF3SO3 / DMC Electrolytes
6.17
The Activation Energy, Ea for PMMA / ENR 50 Blend/
192
LiCF3SO3 / EC Electrolytes
6.18
The Activation Energy, Ea for PMMA / ENR 50 Blend/
195
LiCF3SO3 / PC Electrolytes
6.19
The Activation Energy, Ea for PMMA / ENR 50 Blend/
196
LiCF3SO3 / EC / DMC Electrolytes
6.20
Conductivity Relaxation Times For Various Concentration
203
of LiCF3SO3 Salt in PMMA / ENR 50 Blend at Room
Temperature
6.21
Dielectric Constant Value for Various Concentration of
205
Plasticizer in PMMA / ENR 50 / LiCF3SO3 Electrolytes at
100 Hz
6.22
Dielectric Loss Value for Various Concentration of
206
Plasticizer in PMMA / ENR 50 / LiCF3SO3 Electrolytes
6.23
Dielectric Constant and Dielectric Loss at 100 Hz for
208
Plasticized PMMA / ENR 50 / LiCF3SO3 Electrolytes at
Various Temperature
6.24
Conductivity Relaxation Times For Various Concentration
210
of EC and DMC Plasticizer in PMMA / ENR 50 /
LiCF3SO3 at Room Temperature
6.25
Dielectric Constant Value for Various Concentration of
Plasticizer Mixture in PMMA / ENR 50 / LiCF3SO3
Electrolytes at 100 Hz
214
xxi
6.26
Dielectric Loss Value for Various Concentration of
214
Plasticizers Mixture in PMMA / ENR 50 / LiCF3SO3
Electrolytes at 100 Hz
6.27
Dielectric Constant and Dielectric Loss at 100 Hz for
215
Plasticized PMMA / ENR 50 / LiCF3SO3 Electrolytes at
Various Temperature
6.28
Conductivity Relaxation Times For Various Concentration
218
of EC / PC and PC / DMC Plasticizer in PMMA / ENR 50 /
LiCF3SO3 at Room Temperature
6.29
Transference Number for the Highest Conducting Sample
222
6.30
The Fitted Values for the Equivalent Circuit for PE1T3,
226
PE1TP2 and PE1TE2D1
7.1
Bands Shift in PMMA / ENR 50 / LiN(CF3SO2)2
259
Electrolytes
7.2
Bands Shift in PMMA / ENR 50 / LiN(CF3SO2)2 / DMC
263
Electrolytes
7.3
Bands Shift in PMMA / ENR 50 / LiN(CF3SO2)2 / EC
266
Electrolytes
7.4
Bands Shift in PMMA / ENR 50 / LiN(CF3SO2)2 / PC
269
Electrolytes
7.5
Bands Shift in PMMA / ENR 50 / LiN(CF3SO2)2 / EC/
272
DMC Electrolytes
7.6
Bands Shift in PMMA / ENR 50 / LiN(CF3SO2)2 / EC/ PC
274
Electrolytes
7.7
Bands Shift in PMMA / ENR 50 / LiN(CF3SO2)2 / PC/
276
DMC Electrolytes
7.8
The Average Conductivity of PMMA / ENR 50 /
LiN(CF3SO2)2
280
at Various Composition of Salt and
Temperatures
7.9
The Average Conductivity of PMMA / ENR 50 /
284
LiN(CF3SO2)2 / DMC Electrolytes at Various Amounts of
DMC and Temperatures
7.10
The Average Conductivity of PMMA / ENR 50 /
285
xxii
LiN(CF3SO2)2 / EC Electrolytes at Various Amounts of EC
and Temperatures
7.11
The Average Conductivity of PMMA / ENR 50 /
285
LiN(CF3SO2)2 / PC Electrolytes at Various Amount of PC
and Temperatures
7.12
The Average Conductivity of PMMA / ENR 50 /
289
LiN(CF3SO2)2 / EC / DMC Electrolytes at Various
Compositions of EC:DMC and Temperatures
7.13
The Average Conductivity of PMMA / ENR 50 /
289
LiN(CF3SO2)2 / EC / PC Electrolytes at Various
Compositions of EC:PC and Temperatures
7.14
The Average Conductivity of PMMA / ENR 50 /
290
LiN(CF3SO2)2/ PC / DMC Electrolytes at Various
Compositions of PC:DMC and Temperatures
7.15
The Activation Energy, Ea for PMMA / ENR 50 /
291
LiN(CF3SO2)2 Electrolytes
7.16
The Activation Energy, Ea for PMMA / ENR 50 Blend/
294
LiN(CF3SO2)2 / DMC Electrolytes
7.17
The Activation Energy, Ea for PMMA / ENR 50 Blend/
294
LiN(CF3SO2)2 / EC Electrolytes
7.18
The Activation Energy, Ea for PMMA / ENR 50 Blend/
296
LiN(CF3SO2)2 / EC / DMC Electrolytes
7.19
Conductivity Relaxation Times For Various Concentration
301
of LiN(CF3SO2)2 Salt in PMMA / ENR 50 Blend at Room
Temperature
7.20
Conductivity Relaxation Times For Various Concentration
303
of LiN(CF3SO2)2 Salt in PMMA / ENR 50 Blend at
Different Temperatures
7.21
Conductivity Relaxation Times For Various Concentration
307
of EC and DMC Plasticizer in PMMA / ENR 50 /
LiN(CF3SO2)2 at Room Temperature
7.22
Conductivity Relaxation Times For EC Plasticized in
PMMA / ENR 50 / LiN(CF3SO2)2 at Elevated Temperature
309
xxiii
7.23
Conductivity Relaxation Times For Various Concentration
316
of Mix Plasticizer in PMMA / ENR 50 / LiN(CF3SO2)2 at
Elevated Temperature
7.24
The Fitted Values for the Equivalent Circuit for PMMA /
318
ENR 50 / LiN(CF3SO2)2 Electrolyte
7.25
The Fitted Values for the Equivalent Circuit for Plasticized
PMMA / ENR 50 / LiN(CF3SO2)2 Electrolyte
320
xxiv
LIST OF FIGURES
FIGURE NO.
TITLE
2.1
Structure of PMMA
2.2
Free
Radical
Vinyl
PAGE
18
Polymerization
of
Methyl
19
Methacrylate
2.3
1,4 cis-polyisoprene
22
2.4
Structure of ENR 50
23
2.5
Structure of Crystalline PEO-NaClO4
26
2.6
Schematic Representation of Polymer Spherullite
26
2.7
DSC Scans for Pure PMAAM-co-PMMA Copolymers
28
2.8
DSC Curve for ABS / PMMA Blend Based Electrolytes
29
2.9
Electron Micrograph of Polymer Electrolytes Based on
29
PVC / PMMA
2.10
Surface Morphology of ENR 50
30
2.11
FTIR plots for PVC / PMMA / LiBF4 / DBP Complexes
32
2.12
Complex Impedance Plot of a Typical Polymer
34
Electrolyte
2.13
Complex Impedance Plot in Li/P(VDF-HFP)-g-PMMA
34
2.14
Impedance Plots of Salt-Doped Modified Natural Rubber
35
Based Gel Electrolytes
2.15
Impedance Plot of PMMA-PVdF-LiCF3SO3-DMP
35
2.16
Complex Impedance Plot and its Respective admittance
36
Plot
2.17
Complex Impedance Plot at Various Temperature
37
2.18
Cation Transport Mechanism in PEO-Based Polymer
38
Electrolyte
xxv
2.19
Log of σ vs. 1000/T that Obeys Arrhenius Equation in
39
PMMA / LiN(CF3SO2)2 / EC / PC Systems
2.20
Log of σ vs. 1000/T that Obeys VTF Equation in PVC /
39
PMMA / LiAsF6 / DBP Systems
2.21
The Master Curve of the WLF Plots of Ionic Conductivity
40
for Various PEO-Alkali Metal Salt Complexes
2.22 (a)
The Vacancy mechanism
40
2.22 (b)
The Interstitial Mechanism
41
2.22 (c)
The Interstitialcy Mechanism
41
2.23 (a)
Cationic Motion in Polymer Electrolyte Assisted by
43
Polymer Chain Motion
2.23 (b)
Cationic Motion in Polymer Electrolyte by Contribution
43
of Ionic Cluster
2.24
Dispersion of the (a) Real and (b) Imaginary Part of
47
Dielectric for Chitosan Doped with Different Amounts of
Lithium Acetate
2.25
Dispersion of the (a) Real and (b) Imaginary Part of
47
Electrical Modulus for Chitosan Doped with Different
Amounts of Lithium Acetate
2.26
Complex
Impedance
Plots
and
Their
Respective
48
Equivalent Circuit
2.27
Equivalent Circuit Consisting of R and Q
49
2.28
Equivalent Circuit Consisting of R, C and W
49
2.29
Cole-Cole Plot that Contain W Element
49
2.30
The Schematic Diagram of the Electrochemical Process in
53
a Rocking Chair Lithium Battery
2.31
A Typical Current Voltage Curve with Superimposed Cell
57
Power as a Function of Load Current
3.1
Schematic Diagram in DSC Technique
64
3.2
Schematic DSC Plot Diagram
65
3.3
Determination of τ from the Plot of Electrical Modulus,
67
(M) Versus Log Frequency (f)
xxvi
3.4
Experimental
Arrangements
for
Measuring
Ionic
68
Transference Number by d.c Polarization Technique
3.5
Normalized Current vs. Time Plot
69
3.6
The (a) Aerial and (b) Cross-Section View of the
70
Fabricated Cell
4.1
Distribution of ENR 50 in PMMA Matrix
72
4.2
Possible Hydrogen Bonds Between PMMA and ENR 50
73
4.3
Hydrogen Bonding in (a) PMMA and (b) ENR 50 Chains
74
4.4
FESEM Micrograph for Pure PMMA
75
4.5
FESEM Micrograph for Pure ENR 50
75
4.6
FESEM Micrograph for PMMA Blend with (a) 10%, (b)
77
20%, (c) 30%, (d) 40% and (e) 50% ENR 50
4.7
DSC Scans for (a) Pure PMMA and (b) Pure ENR 50
79
4.8
DSC Scans for (a) 10% ENR 50 blend and (b) 50% ENR
80
50 blend
4.9
FTIR Spectra for (a) Pure PMMA and (b) Pure ENR 50
82
4.10
FTIR Spectra for (a) 10% and (b) 50% ENR 50 blend
85
4.11
Cole-Cole Plots for (a) Pure PMMA and (b) Pure ENR 50
86
Films
4.12
The Effect of ENR 50 on the Conductivity of PMMA /
88
ENR 50 Blends
4.13
Cole-Cole Plot for 10% ENR 50 Blend Film at Room
88
Temperature
5.1
FESEM Micrograph of 10% ENR 50 Blend Doped with
92
(a) 0.1 g , (b) 0.2 g and (c) 0.3 g of LiNO3 Salt
5.2
FESEM Micrograph of 20% ENR 50 Blend Doped with
93
(a) 0.1 g , (b) 0.2 g and (c) 0.3 g of LiNO3 Salt
5.3
FESEM Micrograph for Doped LiNO3 in 10% ENR 50
95
Blend when Plasticized with (a) 0.1 g , (b) 0.2 g and (c)
0.3 g of DMC
5.4
FESEM Micrograph for Doped LiNO3 in 20% ENR 50
Blend when Plasticized with (a) 0.1 g , (b) 0.2 g and (c)
0.3 g of DMC
96
xxvii
5.5
The IR Spectrum for Pure LiNO3 Salt
98
5.6
FTIR Spectra for (a) 10% and (b) 20% ENR 50 Blend
99
Doped with 0.2 g LiNO3
5.7
FTIR Spectra for (a) 10% and (b) 20% ENR 50 Blend
100
Doped with 0.3 g LiNO3
5.8
Polymer-Salt Complex at C=O and O-CH3 Groups
100
5.9
The IR Spectra for DMC Plasticizer
102
5.10
FTIR Spectra for 0.2 g Doped LiNO3 in (a) 10% and (b)
103
20% ENR 50 Plasticized with 0.3 g DMC
5.11
Cole-Cole Plots for (a) PMMA, (b) ENR 50 and (c)
105
PMMA / ENR 50 Blend Films Doped with 0.2 g of
LiNO3 Salt
5.12
The Effect of LiNO3 Salt on the Conductivity of PMMA
106
/ ENR 50 / LiNO3 Films at Room Temperature
Cole-Cole Plots for PMMA / ENR 50 / LiNO3 Films
5.13
Electrolyte when Plasticized with 0.2 g of DMC
108
Plasticizer
5.14
The Effect of DMC on the Conductivity of PMMA / ENR
109
50 / LiNO3 / DMC
5.15
Transport of Lithium Ion Along a Convoluted Path
110
5.16
Illustration of Lithium Ion Trapped in ENR 50 Coil
111
5.17
Cole-Cole Plot for the Highest Conducting Sample of
112
PMMA / ENR 50 / LiNO3 : PE1N2 at Various
Temperatures
5.18
Plot ln (σ) Vs. 1000/T for Various Amount of LiNO3 in
113
PMMA / ENR 50 / LiNO3 Electrolyte
5.19
Cole-Cole Plot for PMMA / ENR 50 / LiNO3 / DMC :
114
PE1D1 at Various Temperatures
5.20
Plot ln (σ) Vs. 1000/T for Various Amount of DMC in
115
PMMA / ENR 50 / LiNO3 / DMC electrolyte
5.21
Dielectric Constant (εr) Versus Log Frequency (log f) for
PMMA / ENR 50 / LiNO3 electrolytes at Room
Temperature
116
xxviii
5.22
Dielectric Constant (εr) Versus Log Frequency (log f) for
117
PMMA / ENR 50 / LiNO3 : PE1N2 at Different
Temperatures
5.23
Dielectric Loss (εi) Versus Log Frequency (log f) for
118
PMMA / ENR 50 / LiNO3 electrolytes at Room
Temperature
5.24
Dielectric Loss (εi) Versus Log Frequency (log f) for
118
PMMA / ENR 50 / LiNO3 : PE1N2 at Different
Temperatures
5.25
(a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical
120
Modulus Versus Log Frequency (log f) for PMMA /
ENR 50 / LiNO3 electrolytes at Room Temperature
5.26
(a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical
121
Modulus Versus Log Frequency (log f) for PMMA / ENR
50 / LiNO3 : PE1N2 at Different Temperatures
5.27
(a) Dielectric Constant (εr) and (b) Dielectric Loss (εi)
123
Versus Log Frequency (log f) for PMMA / ENR 50 /
LiNO3 / DMC at Room Temperature
5.28
(a) Dielectric Constant (εr) and (b) Dielectric Loss (εi)
124
Versus Log Frequency (log f) for the Highest Conducting
Plasticized PMMA / ENR 50 / LiNO3 : PE1ND1 at
Different Temperatures
5.29
(a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical
125
Modulus Versus Log Frequency (log f) for PMMA / ENR
50 / LiNO3 /DMC at Room Temperature
5.30
(a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical
127
Modulus Versus Log Frequency (log f) for PMMA / ENR
50 / LiNO3 / DMC : PE1ND1 at Different Temperatures
5.31
The Fitting Conductivity Plot for the Highest Conducting
128
PMMA / ENR 50 / LiNO3 Electrolyte, PE1N2
5.32
The Equivalent Circuit for the Highest Conducting
128
PMMA / ENR 50 / LiNO3 Electrolyte, PE1N2
5.33
The Fitting Conductivity Plot for the Highest Conducting
130
xxix
Plasticized PMMA / ENR 50 / LiNO3 Electrolyte,
PE1ND1
5.34
The Equivalent Circuit for the Highest Conducting
130
Plasticized PMMA / ENR 50 / LiNO3 Electrolyte,
PE1ND1
6.1
ENR 50 Chains in PMMA phase (a) without Plasticizer
134
and (b) With Plasticizer
6.2
FESEM Micrograph of 10% ENR 50 Films Doped with
136
(a) 0.1 g , (b) 0.2 g and (c) 0.3 g of LiCF3SO3 Salt
6.3
FESEM Micrograph of 20% ENR 50 Films Doped with
137
(a) 0.1 g , (b) 0.2 g and (c) 0.3 g of LiCF3SO3 Salt
6.4
FESEM Micrographs for 10% ENR 50 Blend Electrolytes
139
Plasticized with (a) 0.1 g , (b) 0.2 g and (c) 0.3 g of
DMC
6.5
FESEM Micrographs for 20% ENR 50 Blend Electrolytes
140
Plasticized with (a) 0.1 g , (b) 0.2 g and (c) 0.3 g of
DMC
6.6
FESEM Micrographs for 10% ENR 50 Blend Electrolytes
141
Plasticized with (a) 0.1 g , (b) 0.2 g and (c) 0.3 g of EC
6.7
FESEM Micrographs for 20% ENR 50 Blend Electrolytes
143
Plasticized with (a) 0.1 g , (b) 0.2 g and (c) 0.3 g of EC
6.8
FESEM Micrographs for 10% ENR 50 Blend Electrolytes
144
Plasticized with (a) 0.1 g , (b) 0.2 g and (c) 0.3 g of PC
6.9
FESEM Micrographs for 20% ENR 50 Blend Electrolytes
145
Plasticized with (a) 0.1 g , (b) 0.2 g and (c) 0.3 g of PC
6.10
FESEM Micrographs for 10% ENR 50 Blend Electrolytes
146
Plasticized with EC:DMC (g:g) (a) 0.1:0.2 and (b)
0.2 :0.1
6.11
FESEM Micrographs for 20% ENR 50 Blend Electrolytes
Plasticized with EC:DMC (g:g)
147
(a) 0.1:0.2 and (b)
0.2 :0.1
6.12
FESEM Micrographs for 10% ENR 50 Blend Electrolytes
Plasticized with EC:PC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1
148
xxx
6.13
FESEM Micrographs for 20% ENR 50 Blend Electrolytes
148
Plasticized with EC:PC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1
6.14
FESEM Micrographs for 10% ENR 50 Blend Electrolytes
149
Plasticized with PC:DMC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1
6.15
FESEM Micrographs for 20% ENR 50 Blend Electrolytes
150
Plasticized with PC:DMC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1
6.16
The FTIR Spectrum for LiCF3SO3 Salt
151
6.17
FTIR Spectra for 10% ENR 50 Blend when Doped with
152
(a) 0.1 g and (b) 0.3 g of LiCF3SO3
6.18
Polymer-Salt Complex in PMMA
153
6.19
FTIR Spectra for 10% ENR 50 Blend when Plasticized
154
with (a) 0.1 g and (b) 0.3 g of DMC
6.20
The FTIR Spectra for EC Plasticizer
156
6.21
FTIR Spectra for 10% ENR 50 Blend when Plasticized
156
with (a) 0.1 g and (b) 0.3 g of EC
6.22
The FTIR Spectra for PC Plasticizer
158
6.23
FTIR Spectra for 10% ENR 50 Blend when Plasticized
158
with (a) 0.1 g and (b) 0.3 g of PC
6.24
FTIR Spectra for EC:DMC (0.2 g:0.1 g) System in
160
(a)10% ENR 50 Blend and (b) 20% ENR 50 Blend
6.25
FTIR Spectra for EC:PC (0.2 g:0.1 g) System in (a)10%
162
ENR 50 Blend and (b) 20% ENR 50 Blend
6.26
FTIR Spectra for PC:DMC (0.2 g:0.1 g) System in
164
(a)10% ENR 50 Blend and (b) 20% ENR 50 Blend
6.27
DSC Scan for 10% ENR 50 Blend Doped with (a) 0.1 g
166
and (b) 0.3 g LiCF3SO3
6.28
Cole-Cole Plots for (a) PMMA, (b) ENR 50, (c) 10%
168
ENR 50 Blend and (d) 20% ENR 50 Blend Films when
Doped with 0.2 g of LiCF3SO3 Salt
6.29
The Effect of LiCF3SO3 Addition in 10% and 20% ENR
170
50 Blend
6.30
Illustration of Ion Transport in (a) Different Metal and (b)
Un-homogeneous Films
171
xxxi
6.31
Cole-Cole Plots for 0.2 g of LiCF3SO3 Doped in 10%
173
ENR 50 Films when Plasticized with 0.3 g of (a) DMC,
(b) EC and (c) PC
6.32
The Effect of (a) DMC and (b) EC Plasticizer in 10%
173
ENR 50 Blend and (c) DMC and (d) EC Plasticizer in
20% ENR 50 Blend
6.33
The Effect of PC Plasticizer in PMMA / ENR 50 /
176
LiCF3SO3 / PC Electrolytes
6.34
Cole-Cole Plot for PMMA / ENR 50 / LiCF3SO3 / EC /
179
DMC (0.1 g:0.2 g) in (a) 10% and (b) 20% ENR 50
Blend
6.35
Cole-Cole Plot for PMMA / ENR 50 / LiCF3SO3 / EC /
180
PC (0.1 g:0.2 g) in (a) 10% and (b) 20% ENR 50 Blend
6.36
The Effect of EC Plasticizer in PMMA / ENR 50 /
181
LiCF3SO3 / EC/DMC Electrolytes
6.37
The Effect of EC Plasticizer in PMMA / ENR 50 /
182
LiCF3SO3 / EC/PC Electrolytes
6.38
Cole-Cole Plot for PMMA / ENR 50 / LiCF3SO3 / PC /
184
DMC (0.1 g:0.2 g) in (a) 10% and (b) 20% ENR 50
Blend
6.39
Cole-Cole Plot for the Highest Conducting Sample of
185
PMMA / ENR 50 / LiCF3SO3 : PE1T3 at Elevated
Temperature
6.40
Arrhenius Plot for Different Amount of LiCF3SO3 Dopant
186
in PMMA / ENR 50 / LiCF3SO3 Electrolyte
6.41
Activation Energy Variations with LiCF3SO3 in PMMA /
187
ENR 50 Blend
6.42
Impedance Plot for the Highest Conducting Sample of
188
PMMA / ENR 50 / LiCF3SO3 when Plasticized with 0.3 g
of DMC at Elevated Temperature
6.43
Arrhenius Plot for Different Amount of DMC Plasticizer
189
in PMMA / ENR 50 / LiCF3SO3 / DMC Electrolyte
6.44
Activation Energy Variations with DMC Plasticizer in
190
xxxii
PMMA / ENR 50 / LiCF3SO3 / DMC Electrolyte
6.45
Arrhenius Plot for Different Amount of EC Plasticizer in
191
PMMA / ENR 50 / LiCF3SO3 / EC Electrolyte
6.46
Activation Energy Variations with EC Plasticizer in
191
PMMA / ENR 50 / LiCF3SO3 / EC Electrolyte
6.47
Arrhenius Plot for Different Amount of PC Plasticizer in
193
(a) 10% ENR 50 Blend and (b) 20% ENR 50 Blend
6.48
Activation Energy Variations with PC Plasticizer in 10%
194
ENR 50 Blend
6.49
Arrhenius Plot for Different Amount of EC Plasticizer in
196
PMMA / ENR 50 / LiCF3SO3 / EC / DMC Electrolyte
6.50
Activation Energy Variations with EC Plasticizer in
197
PMMA / ENR 50 / LiCF3SO3 / EC / DMC Electrolyte
6.51
Arrhenius Plot for Different Amount of EC Plasticizer in
198
PMMA / ENR 50 / LiCF3SO3 / EC/ PC Electrolyte
6.52
Arrhenius Plot for Different Amount of PC Plasticizer in
198
PMMA / ENR 50 / LiCF3SO3 / PC / DMC Electrolyte
6.53
(a) Dielectric Constant (εr) and (b) Dielectric Loss (εi)
200
Versus Log Frequency (log f) for PMMA / ENR 50 /
LiCF3SO3 at Room Temperature
6.54
(a) Dielectric Constant (εr) and (b) Dielectric Loss (εi)
201
Versus Log Frequency (log f) for the Highest Conducting
Sample of PMMA / ENR 50 / LiCF3SO3 : PE1T3 at
Different Temperatures
6.55
(a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical
202
Modulus Versus Log Frequency (log f) for PMMA / ENR
50 / LiCF3SO3 at Room Temperature
6.56
(a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical
204
Modulus Versus Log Frequency (log f) for PMMA / ENR
50 / LiCF3SO3 : PE1T3 at Different Temperatures
6.57
(a) Dielectric Constant (εr) and (b) Dielectric Loss (εi)
Versus Log Frequency (log f) for Plasticized PMMA /
ENR 50 / LiCF3SO3 at Room Temperature
205
xxxiii
6.58
Dielectric Constant (εr) Versus Log Frequency (log f) for
208
the Highest Conducting Sample of PMMA / ENR 50 /
LiCF3SO3 plasticized with (a) DMC: PE2TD3; (b) EC:
PE2TE3 and (c) PC: PE1TP2 at elevated Temperature
6.59
The Imaginary Part of Electrical Modulus (Mi) Versus
210
Log Frequency (log f) for Various Concentration of (a)
DMC, (b) EC and (c) PC in
PMMA / ENR 50 /
LiCF3SO3 Electrolyte at Room Temperature
6.60
The Imaginary Part of Electrical Modulus (Mi) Versus
212
Log Frequency (log f) for the Highest Conducting Sample
of PMMA / ENR 50 / LiCF3SO3 Plasticized with (a)
DMC: PE2TD3, (b) EC:PE2TE3 and (c) PC:PE1TP2 at
Elevated Temperature
6.61
(a) Dielectric Constant (εr) and (b) Dielectric Loss (εi)
213
Versus Log Frequency (log f) for mix plasticized PMMA
/ ENR 50 / LiCF3SO3 at Room Temperature
6.62
Dielectric Constant (εr) Versus Log Frequency (log f) for
216
(a) PE1TE2D1, (b) PE1TE1P2 and (c) PE1TP1D2 at
Elevated Temperature
6.63
The Imaginary Part of Electrical Modulus (Mi) Versus
218
Log Frequency (log f) for Various Concentration of (a)
EC:DMC, (b) EC:PC and (c) PC:DMC in PMMA / ENR
50 / LiCF3SO3 Electrolyte at Room Temperature
6.64
The Imaginary Part of Electrical Modulus (Mi) Versus
220
Log Frequency (log f) for (a) PE1TE2D1, (b) PE1TE1P2
and (c) PE1TP1D2 at Elevated Temperature
6.65
Normalized Current Versus Time Plot for (a) PE1T3, (b)
222
PE1TP2 and (c) PE1TE2D1
6.66
(a) The Fitting Conductivity Plot and (b) The Equivalent
223
Circuit for PE1T3
6.67
(a) The Fitting Conductivity Plot and (b) The Equivalent
224
Circuit for PE1TP2
6.68
(a) The Fitting Conductivity Plot and (b) The Equivalent
225
xxxiv
Circuit for PE1TE2D1
6.69
The Charging Curve for LiNiCoO2 / PMMA / ENR 50 /
227
LiCF3SO3 / MCMB Cell at 10 mA Charging Current
6.70
The Charging Capacity Curve for LiNiCoO2 / PMMA /
228
ENR 50 / LiCF3SO3 / MCMB Cell at 10 mA Charging
Current
6.71
The Discharge Curve for LiNiCoO2 / PMMA / ENR 50 /
229
LiCF3SO3 / MCMB Cell at 10 mA
6.72
The Discharge Rate for LiNiCoO2 / PMMA / ENR 50 /
229
LiCF3SO3 / MCMB Cell at 10 mA
6.73
The Charging Curve for LiNiCoO2 / PMMA / ENR 50 /
231
LiCF3SO3 / PC / MCMB Cell at 10 mA Charging Current
during (a) 1st Cycle and (b) 2nd Cycle
6.74
The OCV Versus Time Plot for LiNiCoO2 / PMMA /
231
ENR 50 / LiCF3SO3 / PC / MCMB Cell
6.75
The Charging Curve for LiNiCoO2 / PMMA / ENR 50 /
232
LiCF3SO3 / EC / DMC / MCMB Cell at 10 mA Charging
Current
6.76
The Charging Capacity Curve for LiNiCoO2 / PMMA /
233
ENR 50 / LiCF3SO3 /EC / DMC / MCMB Cell at 10 mA
Charging Current
6.77
The Discharge Curve for LiNiCoO2 / PMMA / ENR 50 /
234
LiCF3SO3 / EC / DMC / MCMB Cell at 10 mA
6.78
The Discharge Rate for LiNiCoO2 / PMMA / ENR 50 /
234
LiCF3SO3 / EC / DMC / MCMB Cell at 10 mA
7.1
Optical Micrograph for (a) Pure PMMA and (b) Pure
238
ENR 50 Films
7.2
Optical Micrograph for (a) 10% ENR 50 Blend and (b)
239
20% ENR 50 Blend Films
7.3
Optical Micrographs for 10% ENR 50 Blend Films
Doped with
240
(a) 0.1 g , (b) 0.2 g and (c) 0.3 g of
LiN(CF3SO2)2
7.4
Optical Micrographs for 20% ENR 50 Blend Films
241
xxxv
Doped with
(a) 0.1 g , (b) 0.2 g and (c) 0.3 g of
LiN(CF3SO2)2
7.5
Optical Micrographs for 10% ENR 50 Blend Films
243
Plasticized with (a) 0.1 g , (b) 0.2 g and (c) 0.3 g of
DMC
7.6
Optical Micrographs for 20% ENR 50 Blend Electrolytes
244
Plasticized with (a) 0.1 g , (b) 0.2 g and (c) 0.3 g of
DMC
7.7
Optical Micrographs for 10% ENR 50 Blend Electrolytes
245
Plasticized with (a) 0.1 g , (b) 0.2 g and (c) 0.3 g of EC
7.8
Optical Micrographs for 20% ENR 50 Blend Electrolytes
247
Plasticized with (a) 0.1 g , (b) 0.2 g and (c) 0.3 g of EC
7.9
Optical Micrographs for 10% ENR 50 Blend Electrolytes
248
Plasticized with (a) 0.1 g , (b) 0.2 g and (c) 0.3 g of PC
7.10
Optical Micrographs for 20% ENR 50 Blend Electrolytes
249
Plasticized with (a) 0.1 g , (b) 0.2 g and (c) 0.3 g of PC
7.11
Optical Micrographs for 10% ENR 50 Blend Electrolytes
251
Plasticized with EC:DMC (g:g) (a) 0.1:0.2 and (b)
0.2 :0.1
7.12
Optical Micrographs for 20% ENR 50 Blend Electrolytes
Plasticized with EC:DMC (g:g)
252
(a) 0.1:0.2 and (b)
0.2 :0.1
7.13
Optical Micrographs for 10% ENR 50 Blend Electrolytes
253
Plasticized with EC:PC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1
7.14
Optical Micrographs for 20% ENR 50 Blend Electrolytes
254
Plasticized with EC:PC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1
7.15
Optical Micrographs for 10% ENR 50 Blend Electrolytes
255
Plasticized with PC:DMC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1
7.16
Optical Micrographs for 20% ENR 50 Blend Electrolytes
256
Plasticized with PC:DMC (g:g) (a) 0.1:0.2 and (b) 0.2 :0.1
7.17
The FTIR Spectrum for LiN(CF3SO2)2 Salt
257
7.18
FTIR Spectra for 10% ENR 50 Blend when Doped with
258
(a) 0.1 g and (b) 0.3 g of LiN(CF3SO2)2
xxxvi
7.19
Polymer-Salt Complex in PMMA
259
7.20
FTIR Spectra for 10% ENR 50 Blend when Plasticized
261
with (a) 0.1 g and (b) 0.3 g of DMC
7.21
FTIR Spectra for 20% ENR 50 Blend when Plasticized
262
with (a) 0.1 g and (b) 0.3 g of DMC
7.22
FTIR Spectra for 10% ENR 50 Blend when Plasticized
264
with (a) 0.1 g , (b) 0.2 g and (c) 0.3 g of EC
7.23
FTIR Spectra for 20% ENR 50 Blend when Plasticized
265
with (a) 0.1 g and (b) 0.3 g of EC
7.24
FTIR Spectra for 10% ENR 50 Blend when Plasticized
268
with (a) 0.1 g , (b) 0.2 g and (c) 0.3 g of PC
7.25
Proposed Interaction Between PC-Salt Complex Via
268
Hydrogen Bonding
7.26
FTIR Spectra for 10% ENR 50 Blend when Plasticized
270
with EC:DMC (a) 0.1 g: 0.2 g and (b) 0.2 g:0.1 g
7.27
FTIR Spectra for 20% ENR 50 Blend when Plasticized
271
with EC:DMC (a) 0.1 g: 0.2 g and (b) 0.2 g:0.1 g
7.28
FTIR Spectra for EC:PC (0.1 g:0.2 g) System in (a)10%
273
ENR 50 Blend and (b) 20% ENR 50 Blend
7.29
FTIR Spectra for 10% ENR 50 Blend Electrolyte when
275
Plasticized with PC:DMC (a) 0.1 g: 0.2 g and (b) 0.2
g:0.1 g
7.30
Cole-Cole Plots for (a) PMMA, (b) ENR 50, (c) 10%
278
ENR 50 Blend and (d) 20% ENR 50 Blend Films when
Doped with 0.2 g of LiN(CF3SO2)2 Salt
7.31
The Effect of LiN(CF3SO2)2 Addition in 10% and 20%
279
ENR 50 Blend
7.32
Cole-Cole Plots for 0.2 g of LiN(CF3SO2)2 Doped in 10%
282
ENR 50 Blend Films when Plasticized with 0.3 g of (a)
DMC, (b) EC and (c) PC
7.33
The Effect of Plasticizers in (a) 10% ENR 50 Blend and
(b) 20% ENR 50 Blend when Doped with LiN(CF3SO2)2
Salt
283
xxxvii
7.34
The Cole-Cole Plots for PMMA / ENR 50 /
287
LiN(CF3SO2)2 plasticized with (0.1 g:0.2 g) (a) EC /
DMC, (b) EC / PC and (c) PC / DMC in 10% ENR 50
Blend
7.35
Arrhenius Plot for Different Amount of LiN(CF3SO2)2
291
Dopant in PMMA / ENR 50 / LiN(CF3SO2)2 Electrolyte
7.36
Plot ln (σ) Vs. 1000/T for Different Amount of (a) DMC,
293
(b) EC and (c) PC Plasticizer in PMMA / ENR 50 /
LiN(CF3SO2)2 Electrolyte
7.37
Arrhenius Plot for Different Amount of EC Plasticizer in
295
PMMA / ENR 50 / LiN(CF3SO2)2 / EC / DMC
Electrolyte
7.38
Arrhenius Plot for Different Amount of EC Plasticizer in
296
PMMA / ENR 50 / LiN(CF3SO2)2 / EC / PC Electrolyte
7.39
Arrhenius Plot for Different Amount of PC Plasticizer in
297
PMMA / ENR 50 / LiN(CF3SO2)2 / PC / DMC Electrolyte
7.40
(a) Dielectric Constant (εr) and (b) Dielectric Loss (εi)
299
Versus Log Frequency (log f) for PMMA / ENR 50 /
LiN(CF3SO2)2 Electrolytes at Room Temperature
7.41
(a) Dielectric Constant (εr) and (b) Dielectric Loss (εi)
300
Versus Log Frequency (log f) for the Highest Conducting
Sample of PMMA / ENR 50 / LiN(CF3SO2)2 : PE2I3 at
Different Temperatures
7.42
(a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical
301
Modulus Versus Log Frequency (log f) for PMMA / ENR
50 / LiN(CF3SO2)2 Electrolytes at Room Temperature
7.43
(a) Real (Mr) and (b) Imaginary (Mi) Part of Electrical
302
Modulus Versus Log Frequency (log f) for PMMA / ENR
50 / LiN(CF3SO2)2 : PE2I3 at Different Temperatures
7.44
(a) Dielectric Constant (εr) and (b) Dielectric Loss (εi)
304
Versus Log Frequency (log f) for Plasticized PMMA /
ENR 50 / LiN(CF3SO2)2 at Room Temperature
7.45
The Dielectric Constant (εr) Versus Log Frequency (log f)
305
xxxviii
for the Highest Conducting Sample of Plasticized PMMA
/ ENR 50 / LiN(CF3SO2)2 with (a) DMC:PE2ID3, (b) EC:
PE2IE1 and (c) PC:PE1IP2 at Elevated Temperature
7.46
The Imaginary Part of Electrical Modulus (Mi) Versus
307
Log Frequency (log f) for Various Concentration of (a)
DMC, (b) EC and (c) PC in
PMMA / ENR 50 /
LiN(CF3SO2)2 Electrolyte at Room Temperature
7.47
The Imaginary Part of Electrical Modulus (Mi) Versus
308
Log Frequency (log f) for (a) DMC:PE2ID3, (b)
EC:PE2IE1 and (c) PC:PE1IP2 in Plasticized PMMA /
ENR 50 / LiN(CF3SO2)2 at Elevated Temperature
7.48
(a) Dielectric Constant (εr) and (b) Dielectric Loss (εi)
310
Versus Log Frequency (log f) for Mix Plasticized PMMA
/ ENR 50 / LiN(CF3SO2)2 at Room Temperature
7.49
The Dielectric Constant (εr) Versus Log Frequency (log f)
312
for PMMA / ENR 50 / LiN(CF3SO2)2 plasticized with (a)
EC / DMC : PE1IE2D1, (b) EC / PC : PE1IE2P1 and (c)
PC / DMC : PE1IP2D1 at Elevated Temperature
7.50
The Imaginary Part of Electrical Modulus (Mi) Versus
314
Log Frequency (log f) for Various Concentration of (a)
EC:DMC, (b) EC:PC and (c) PC:DMC in PMMA / ENR
50 / LiN(CF3SO2)2 Electrolyte at Room Temperature
7.51
The Imaginary Part of Electrical Modulus (Mi) Versus
316
Log Frequency (log f) for PMMA / ENR 50 /
LiN(CF3SO2)2 Plasticized with (a) EC/DMC : PE1IE2D1 ,
(b) EC/PC : PE1IE2P1 and (c) PC/DMC : PE1IP2D1 at
Elevated Temperature
7.52
(a) The Fitting Conductivity Plot and (b) The Equivalent
318
Circuit for PE2I3
7.53
(a) The Fitting Conductivity Plot and (b) The Equivalent
319
Circuit for PE2IE3
7.54
(a) The Fitting Conductivity Plot and (b) The Equivalent
Circuit for PE1IE2D1
320
xxxix
LIST OF PHOTOGRAPHS
PHOTOGRAPH
NO.
4.1
TITLE
PMMA Films Blend with (a) 10% and (b) 20% ENR 50
PAGE
72
xl
LIST OF SYMBOLS
π
-
Pie
Z
-
Impedance
R
-
Resistance
Rb
-
Bulk Resistance
σ
-
Conductivity
Ea
-
Activation Energy
ε’
-
Dielectric Constant
ε”
-
Dielectric Loss
M
-
Electrical Modulus Formalism
τ
-
Conductivity Relaxation Time
C
-
Capacitor
Q
-
Constant Phase Element
W
-
Warburg Impedance
xli
LIST OF ABBREVIATIONS
PMMA
-
Poly(methyl methacrylate)
ENR 50
-
50% Epoxidized Natural Rubber
PVC
-
Poly(vinyl chloride)
PEO
-
Poly(ethylene oxide)
PAN
-
Polyacrylonitrile
PVdF
-
Poly(vinylidene difluoride)
PPO
-
Poly(propylene oxide)
EC
-
Ethylene Carbonate
PC
-
Propylene Carbonate
DMC
-
Dimethyl Carbonate
DBP
-
Dibutyl Phthalate
PEM
-
Proton Exchange Membrane
SPE
-
Solid Polymer Electrolyte
SPEFC
-
Solid Polymer Electrolyte Fuel Cell
FESEM
-
Field Emission Scanning Electron Microscope
FTIR
-
Fourier Transform Infrared
DSC
-
Differential Scanning Calorimetry
VTF
-
Vogel-Tammam-Fulcher
WLT
-
Williams-Landel and Ferry
MCMB
-
Mesocarbon Microbeads
OCV
-
Open Circuit Voltage
UNIPEM
Unit Perkhidmatan Makmal
xlii
LIST OF PUBLICATIONS
No
1
Journal /
Proceedings
Journal of Power
Sources
Place/Date
2006
Paper Published
Page
Authors
Article Famiza Latif,
THE ROLE AND
IMPACT OF RUBBER in
Madzlan
Press
IN POLY(METHYL
METHACRYLATE) /
Aziz, Nasir
LITHIUM TRIFLATE
ELECTROLYTE
Katun, Ab
Malik
Marwan Ali,
Muhd
Zuazhan
Yahya
2
Solid State
Phenomena.
Volume 3
2006
3
Journal Of solid
State Science
And Technology
Letters. Volume
10, No.2
(Abstract)
The XX Regional
Conference On
Solid State
Science And
Technology.
The
Orient
Star
Resort,
Lumut,
Perak.
(12-14
Disember
2003)
THE IMPEDANCE
SPECTROSCOPY
STUDIES OF PVC/
ENR 50 / LICF3SO3
AND PMMA / ENR 50
/ LICF3SO3
ELECTROLYTES
CONDUCTIVITY
STUDY FOR
PMMA/ENR 50
BASED
ELECTROLYTES
67-70
61
M. Aziz, F.
Latif, C.L.
Chew and N.
Katun,
Famiza
Latif and
Madzlan
Aziz
xliii
4
5
Proceedings
Regional
Symposium On
Membrane
Science And
Technology.
Proceedings
International
Conference And
Exhibition On
Macromolecular
Science And Its
Impact On
Industries.
6
Proceedings
International
Conference And
Exhibition On
Macromolecular
Science And Its
Impact On
Industries.
7
Journal Of solid
State Science
And Technology
Letters. Volume
11, No.2
(Abstract)
The XXI
Regional
Conference On
Solid State
Science And
Technology.
Journal Of solid
State Science
And Technology
Letters. Volume
11, No.2
(Abstract)
The XXI
Regional
Conference On
Solid State
Science And
Technology.
8
Putri Pan
Pacific Hotel,
Johor Bahru,
Johor. (21-25
April 2004)
THIN FILM PMMA /
ENR 50 BASED
ELECTROLYTE
FOR LITHIUM ION
CONDUCTOR
-
Famiza
Latif,
Madzlan
Aziz and
Nasir
Katun
Famiza
Latif,
Madzlan
Aziz and
Nasir
Katun
Sunway
Pyramid
Convention
Centre,
Bandar
Sunway,
Petaling Jaya,
Selangor.
(27-29 Sept
2004).
Sunway
Pyramid
Convention
Centre,
Bandar
Sunway,
Petaling Jaya,
Selangor.
(27-29 Sept
2004).
Hyatt
Regency
Kinabalu,
Kota
Kinabalu,
sabah,
Malaysia.
(10-13
October
2004)
THE EFFECT OF
DIMETHYL
CARBONATE
PLASTICIZER ON
POLY (METHYL
METHACRYLATE)/
ENR 50 / LITHIUM
TRIFLATE
ELECTROLYTE
-
PREPARATION OF
THIN FILM
ELECTROLYTE
BASED ON POLY
(METHYL
METHACRYLATE) /
ENR 50 BLEND BY
CASTING METHOD
-
Famiza
Latif,
Madzlan
Aziz and
Nasir
Katun
THE
CONDUCTIVITY OF
ENR 50-POLY
(METHYL
METHACRYLATE)LITHIUM TRIFLATE
SEMI SOLID
ELECTROLYTE
FOR LITHIUM ION
BATTERY
97
Famiza
Latif,
Madzlan
Aziz and
Nasir
Katun
Hyatt
Regency
Kinabalu,
Kota
Kinabalu,
sabah,
Malaysia.
(10-13
October
2004)
PREPARATION OF
THIN FILM
ELECTROLYTE
BASED ON POLY
(METHYL
METHACRYLATE) /
ENR 50 BLEND BY
CASTING METHOD
131
Madzlan
Aziz,
Famiza
Latif, and
Nasir
Katun