CONTENTS
CHAPTER – I
Page No.
1.0 INTRODUCTION 1
1.1 CLASSIFICATION OF BATTERIES 1
1.1.1 Primary batteries 2
1.1.2 Secondary batteries 2
1.1.2.1 Lead acid battery 4
1.1.2.2 Nickel-Cadmium battery 4
1.1.2.3 Nickel-Metal hydride battery 4
1.1.2.4 Lithium-ion batteries 5
1.1.3 Fuel cells 5
1.1.4 Reserve batteries 6
1.2 LITHIUM BATTERY – AN ALTERNATIVE POWER SOURCE 6
1.3 CLASSIFICATION OF LITHIUM BATTERIES 7
1.3.1 Primary Lithium batteries 7
1.3.2 Secondary (or) Rechargeable Lithium batteries 9
1.3.3 Classification of Secondary Lithium batteries 11
1.4 PRINCIPLES OF LI-ION BATTERIES 16
1.4.1 Lithium intercalating compounds 22
1.4.2 Historical developments in Li-battery research 24
1.4.3 Lithium-ion batteries as energy storage systems 27
1.5 CATHODE MATERIALS 29
1.6 ANODE MATERIALS 32
1.7 ELECTROLYTES 33
1.8 SEPARATORS 34
REFERENCES 35
CHAPTER – II
2.0 LITERATURE SURVEY AND SCOPE OF
THE PRESENT RESEARCH WORK 40
2.1 LOW VOLTAGE CATHODE MATERIALS 43
2.1.1 Transition-Metal Trichalcogenides 43
2.1.2 Layered-Type Transition-Metal Dichalcogenides 44
2.2 HIGH VOLTAGE CATHODE MATERIALS 45
2.2.1 Layered-Type Transition-Metal Dioxides 45
2.2.1.1 LiCoO2 and its derivatives 46
2.2.1.2 LiNiO2 and its derivatives 52
2.2.1.3 Layered Manganese Oxides 60
2.2.2 Three Dimensional Spinel Lithium Manganese Oxides 61
2.3 SCOPE OF THE PRESENT RESEARCH WORK 75
REFERENCES 78
CHAPTER – III
3.0 EXPERIMENTAL DETAILS 92
3.1 CHEMICALS USED 92
3.2 EXPERIMENTAL DETAILS FOR THE SYNTHESIS OF
SUBSTITUTED AND SURFACE MODIFIED LAYERED
LiNiO2 CATHODE MATERIALS 94
3.2.1 Synthesis of Samarium, Lanthanum and Lithium substituted LiNiO2 94
3.2.2 Synthesis of SiO2, La2O3-coated LiNiO2 cathode materials 94
3.3 EXPERIMENTAL DETAILS FOR THE SYNTHESIS OF
SUBSTITUTED AND SURFACE MODIFIED LiMn2O4
CATHODE MATERIALS 96
3.3.1 Synthesis of Vanadium, Cobalt and Lithium substituted LiMn2O4 96
3.3.2 Synthesis of LaPO4, CePO4-coated LiMn2O4 cathode materials 98
3.4 CHARACTERIZATIONS OF THE
SYNTHESIZED METAL OXIDES 100
3.4.1 Thermal Analysis 100
3. 4.2 X-ray diffraction analysis (XRD) 105
3.4.3 X-ray Photoelectron spectroscopy (XPS) 108
3.4.4 Scanning Electron Microscope (SEM) 110
3.4.5 Transmission Electron Microscope (TEM) 111
3.3.6 Electrode Preparation 113
3. 3.7 Galvanostatic Charge/discharge 113
3. 3.8 Cyclic Voltammetry (CV) study 115
3.3.9 Electrochemical Impedance Spectroscopy (EIS) 115
REFERENCES 118
CHAPTER – IV
4.0 RESULTS AND DISCUSSION 119
SYNTHESIS AND ELECTROCHEMICAL CHARACTERIZATIONS OF
SAMARIUM, LANTHANUM AND LITHIUM SUBSTITUTED
NANOSTRUCTURED Li-Ni-O LAYERED CATHODE MATERIALS FOR
RECHARGEABLE LITHIUM ION BATTERIES
4.1 Preparation and electrochemical performances of samarium
substituted LiSm1-xNixO2 (0.00≤x≤0.20) cathode materials for
rechargeable lithium-ion batteries 119
4.1.1 Thermo Gravimetric and DTA analysis 119
4.1.2 X-ray Diffraction analysis 120
4.1.3 Scanning Electron Microscopy with EDAX analysis 125
4.1.4 Transmission Electron Microscopy 127
4.1.5 Cyclic Voltammetric study 127
4.1.6 Galvanostatic Charge/discharge studies 132
4.1.7 Electrochemical Impedance Spectroscopy Measurements 141
REFERENCES 146
4.2 Preparation and electrochemical performances of co-substituted
(La and Li) LiLax-yLiyNi1-xO2 cathode materials for rechargeable
lithium-ion batteries 148
4.2.1 X-ray Diffraction analysis 148
4.2.2 Scanning Electron Microscopy with EDAX analysis 152
4.2.3 Transmission Electron Microscopy 155
4.2.4 Cyclic Voltammetry study 155
4.2.5 Galvanostatic Charge/discharge studies 159
4.2.6 Electrochemical Impedance Spectroscopy Measurements 168
REFERENCES 174
SYNTHESIS AND ELECTROCHEMICAL CHARACTERIZATIONS OF SILICA,
LANTHANUM OXIDE COATED NANOSTRUCTURED Li-Ni-O LAYERED
CATHODE MATERIALS FOR RECHARGEABLE LITHIUM
BATTERIES
4.3 Preparation and electrochemical performances of silica coated
LiNiO2 cathode materials for rechargeable lithium-ion batteries 176
4.3.1 X-ray Diffraction analysis 176
4.3.2 Scanning Electron Microscopy 177
4.3.3 Cyclic Voltammetry study 180
4.3.4 Galvanostatic Charge/discharge studies 182
REFERENCES 188
4.4 Preparation and electrochemical performances of La2O3 coated
LiNiO2 cathode materials for rechargeable lithium-ion batteries 189
4.4.1 X-ray Diffraction analysis 189
4.4.2 Scanning Electron Microscopy 190
4.4.3 Cyclic Voltammetry study 193
4.4.4 Galvanostatic Charge/discharge studies 195
REFERENCES 202
SYNTHESIS AND ELECTROCHEMICAL CHARACTERIZATIONS OF
VANADIUM, COBALT AND LITHIUM SUBSTITUTED NANOSTRUCTURED
Li-Mn-O SPINEL CATHODE MATERIALS FOR RECHARGEABLE LITHIUM
BATTERIES
4.5 Preparation and electrochemical performances of vanadium substituted
LiMn2O4 cathode materials for rechargeable lithium-ion batteries 203
4.5.1 Thermo Gravimetric and DTA analysis 203
4.5.2 X-ray Diffraction studies 204
4.5.3 Scanning Electron Microscopy 207
4.5.4 Transmission Electron Microscopy 209
4.5.4 Galvanostatic Charge/discharge studies 209
REFERENCES 216
4.6 Preparation and electrochemical performances of co-substituted
LiCoxLix-yMn2-xO4 cathode materials for the rechargeable
Lithium-ion batteries 217
4.6.1 X- ray Diffraction studies 217
4.6.2 Scanning Electron Microscopy 220
4.6.3 Transmission Electron Microscopy 222
4.6.4 Galvanostatic Charge/discharge studies 222
4.6.5 Electrochemical Impedance Spectroscopy 229
REFERENCES 233
SYNTHESIS AND ELECTROCHEMICAL CHARACTERIZATIONS OF
SURFACE MODIFIED LaPO4, CePO4 COATED NANOSTRUCTURED Li-Mn-O
SPINEL CATHODE MATERIALS FOR RECHARGEABLE LITHIUM
BATTERIES
4.7 Structure and electrochemical performance of surface modified LaPO4
coated LiMn2O4 cathode materials for rechargeable lithium batteries 234
4.7.1 X-ray Diffraction analysis 235
4.7.2 Scanning Electron Microscopy 235
4.7.3 X-ray Photoelectron Spectroscopy 238
4.7.4 Cyclic Voltammetry study 240
4.7.5 Galvanostatic Charge/discharge studies 242
REFERENCES 249
4.8 Preparation and electrochemical performances of CePO4 coated
LiMn2O4 cathode materials for rechargeable lithium-ion batteries 251
4.8.1 X-ray Diffraction analysis 251
4.8.2 Scanning Electron Microscopy 253
4.8.3 Transmission Electron Microscopy 253
4.8.4 X-ray Photoelectron Spectroscopy analysis 256
4.8.5 Cyclic Voltammetry study 256
4.8.6 Galvanostatic Charge/discharge studies 260
REFERENCES 268
CHAPTER – V
5.0 CONCLUSIONS 270
FUTURE WORK 278
ACHIEVEMENTS 279
