Preface xiii
1 Introduction 1
Jinqiang Gao, Wentao Deng, Guoqiang Zou, Hongshuai Hou, and Xiaobo Ji
1.1 Overview 1
1.2 The Birth and Development of Sodium-ion Batteries 4
References 8
2 Characteristics of Sodium-ion Batteries 11
Haoji Wang, Wentao Deng, Hongshuai Hou, Guoqiang Zou, and Xiaobo Ji
2.1 Basic Features 11
2.2 Working Principle 14
2.3 Concepts and Equations 15
2.3.1 Cell Voltage 16
2.3.1.1 Electromotive Potential 16
2.3.1.2 Theoretical Voltage EΘ 16
2.3.1.3 Open Circuit Voltage Eocv 16
2.3.1.4 Operating Voltage Ecc 16
2.3.1.5 Cutoff Voltage 16
2.3.2 Cell Capacity and Specific Capacity 17
2.3.2.1 Theoretical Capacity (Co) 17
2.3.2.2 Actual Capacity (C) 17
2.3.2.3 Rated Capacity (Cr) 18
2.3.2.4 Specific Capacity (Cm or CV) 18
2.3.3 Cell Energy and Specific Energy 18
2.3.3.1 Theoretical Energy (Wo) 18
2.3.3.2 Actual Capacity (W) 18
2.3.3.3 Specific Capacity (w>M Or WV) 18
2.3.4 Cell Power and Specific Power 19
2.3.5 Charge and Discharge Rate 19
2.3.6 Constant Current Charge and Discharge 19
2.3.7 Constant Voltage Charge 19
2.3.8 Coulombic Efficiency 19
2.3.9 Energy Conversion Efficiency 20
2.3.10 Cell Internal Resistance 20
2.3.11 Cell Life 20
2.3.12 State of Charge (SOC) 20
2.3.13 Depth of Discharge (DOD) 20
2.4 Structural Composition 20
2.4.1 Cathode Materials 21
2.4.2 Anode Materials 23
2.4.3 Electrolytes 24
2.4.4 Separators, Binders, Conductive Agents, and Current Collectors 25
References 26
3 Cathode Materials of SIBs 29
Xu Gao, Wentao Deng, Guoqiang Zou, Hongshuai Hou, and Xiaobo Ji
3.1 Polyanion Cathode 30
3.1.1 Phosphates 31
3.1.1.1 Olivine-type Phosphates (NaMPO4, M=Fe, Mn, etc.) 31
3.1.1.2 NASICON-type Phosphates (Na3 M2 (PO4)3, M=Ti, V, Ni, Fe, Mn, etc.) 33
3.1.1.3 Pyrophosphate Na2 MP2 O735
3.1.2 Sulfates/Borates/Silicates 36
3.1.2.1 Sulfates 36
3.1.2.2 Borates 37
3.1.2.3 Silicate 37
3.1.3 Mixed Polyanions 38
3.1.3.1 Fluorophosphates 38
3.1.3.2 Mixed Phosphates 42
3.2 Oxide Cathode 43
3.2.1 Layered Transition Metal Oxides 43
3.2.1.1 Structural Classification 43
3.2.1.2 Key Issues of Layered Oxides 46
3.2.1.3 P2-type Layered Oxides 56
3.2.1.4 O3-type Layered Oxides 60
3.2.1.5 P3-type Layered Oxides 64
3.2.1.6 Mixed-phase Layered Oxides 64
3.2.2 Tunnel-type Oxides 67
3.2.2.1 NaX Mno2 67
3.2.2.2 NaX [mnm]o2 (m=ti,fe,co,etc.) 69
3.2.2.3 Tunnel Oxides for Aqueous SIBs 70
3.3 Prussian Blue and their Analogues 70
3.3.1 Prussian Blue in Non-Aqueous SIBs 72
3.3.1.1 Iron Hexacyanoferrate (FeHCF) 72
3.3.1.2 Manganese Hexacyanoferrate (MnHCF) 73
3.3.1.3 Cobalt Hexacyanoferrate (CoHCF) 75
3.3.1.4 Nickle Hexacyanoferrate (NiHCF) 75
3.3.1.5 Other Hexacyanoferrates 77
3.3.1.6 Other Metal Hexacyanometallic Compounds 77
3.3.2 Prussian Blue in Aqueous SIBs 79
3.3.2.1 Single-Redox-Center PBAs 79
3.3.2.2 Two-Redox-Center PBAs 80
3.3.2.3 All-PBA Aqueous Batteries 81
3.4 Perovskite Transition Metal Fluorides 82
3.4.1 Metal Fluorides 82
3.4.2 Sodium Metal Fluorides 84
3.5 Organic Cathode 85
3.5.1 Working Mechanism 86
3.5.2 Carbonyl Small Molecules 88
3.5.3 Conductive Polymers 89
References 90
4 Anode Materials of Sodium-ion Batteries 109
Peng Ge, Shaohui Yuan, Guoqiang Zou, Hongshuai Hou, Yue Yang, and Xiaobo Ji
4.1 Carbon-based Anode 109
4.1.1 Graphite Anode 110
4.1.2 Soft Carbon 111
4.1.3 Hard Carbon 112
4.1.3.1 The Doping of Heteroatoms 112
4.1.3.2 Structure and Morphology Designing 114
4.2 Titanium-based Anode 116
4.2.1 The Exploring of TiO2 Samples 116
4.2.2 The Exploring of TiS2 and TiSe2 Samples 117
4.2.3 The Exploring of Other Ti-based Samples 118
4.3 Conversion Anode 118
4.3.1 Co-based Samples 118
4.3.1.1 The Exploring of Co-based Oxides 118
4.3.1.2 The Exploring of Co-based Sulfides and Selenides 119
4.3.1.3 The Exploring of Co-based Phosphide 120
4.3.2 Ni-based Samples 121
4.3.2.1 The Exploring of Ni-based Oxides/Sulfides 122
4.3.2.2 The Exploring of Ni-based Selenium, Phosphide, and Other Samples 122
4.3.3 Fe-based Samples 123
4.3.3.1 The Exploring of Fe-based Oxides 124
4.3.3.2 The Exploring of Fe-based Sulfides and Selenides 124
4.3.3.3 The Exploring of Fe-based Phosphides 126
4.3.3.4 The Exploring of Other Fe-based Composites 127
4.3.4 Mo-based Samples 128
4.3.4.1 The Exploring of Mo-based Oxides 128
4.3.4.2 The Exploring of Mo-based Sulfide and Selenides 129
4.3.4.3 The Exploring of Other Mo-based Composites 130
4.3.5 Other Metal-based Samples 130
4.3.5.1 The Exploring of Zn-based Samples 130
4.3.5.2 The Exploring of Cu-based Samples 131
4.3.5.3 The Exploring of Mn-based Samples 132
4.3.5.4 The Exploring of Cr-based Composites 133
4.3.5.5 The Exploring of W-based Composites 133
4.3.5.6 The Exploring of V-based Composites 133
4.3.5.7 The Exploring of Nb-based Composites 134
4.3.5.8 The Exploring of In-based Samples 135
4.4 Metal/Alloy Anode 135
4.4.1 Sb-based Samples 135
4.4.1.1 The Exploring of Sb and Sb-based Alloy Samples 135
4.4.1.2 The Exploring of Sb-based Oxide, Sulfides, Selenium 137
4.4.2 Sn-based Samples 138
4.4.2.1 The Exploring of Sn-based Alloys and Sn@Carbon Materials 139
4.4.2.2 The Exploring of Sn-based Oxides 141
4.4.2.3 The Exploring of Sn-based Sulfides 142
4.4.2.4 The Exploring of Sn-based Selenide, Phosphide 142
4.4.3 Bi-based Samples 143
4.4.4 Ge-based Samples 145
4.4.4.1 The Exploring of Ge and the Relative Alloying Materials 145
4.4.4.2 The Exploring of Ge-based Oxides Samples 145
4.4.4.3 The Exploring of Other Ge-based Samples (GeX, X=Se, S, OH, P) 146
References 146
5 Electrolyte, Separator, Binder and Other Devices of Sodium Ion Batteries 171
Mingguang Yi, Mingjun Jing, Wentao Deng, Guoqiang Zou, Hongshuai Hou, Tianjing Wu, and Xiaobo Ji
5.1 Introduction 171
5.2 Organic Liquid Electrolytes 173
5.2.1 Physical and Chemical Properties 173
5.2.2 Organic Solvents 175
5.2.2.1 Ester-based Solvents 175
5.2.2.2 Ether-based Solvents 177
5.2.3 Electrolyte Salt 180
5.2.4 Electrolyte Additives 183
5.2.4.1 Film Formation Additives 185
5.2.4.2 Flame Retardant Additives 186
5.2.4.3 Overcharge Protection Additives 187
5.2.4.4 Additives with Other Functions 187
5.2.5 New Electrolyte Systems 188
5.3 Solid State Electrolytes 191
5.3.1 Physical and Chemical Properties 191
5.3.2 Inorganic Solid Electrolyte 192
5.3.2.1 β-alumina 192
5.3.2.2 Nasicon 193
5.3.2.3 Sulfides 194
5.3.3 Polymer Electrolyte 197
5.3.3.1 Solid Polymer Electrolytes (SPEs) 197
5.3.3.2 Gel Polymer Electrolytes (GPEs) 200
5.3.4 Composite Solid Electrolyte 203
5.3.4.1 CSEs with Passive Fillers 204
5.3.4.2 CSEs with Active Fillers 208
5.3.5 Phase Interface Between Electrode and Electrolyte 210
5.3.5.1 Solid Electrolyte Interphase (SEI) 211
5.3.5.2 Cathode Electrolyte Interphase (CEI) 214
5.4 Separator 217
5.4.1 Glass Fiber 218
5.4.2 Polyolefin Separator 218
5.4.3 Nonwoven Separator 219
5.5 Binder 220
5.5.1 Poly(vinylidene fluoride) (PVDF) 220
5.5.2 Polyacrylic Acid (PAA) 221
5.5.3 Sodium Alginate (SA) 222
5.5.4 Sodium Carboxymethyl Cellulose (CMC) 222
5.5.5 Crosslinked Binders 223
5.5.6 Conductive Binders 224
5.5.7 Self-healing Binders 225
5.6 Conductive Agent 225
5.6.1 Carbon Black 225
5.6.1.1 Acetylene Black (AB) 226
5.6.1.2 Super-P (SP) 226
5.6.1.3 Ketjen Black (KB) 227
5.6.2 Graphene 228
5.6.3 Carbon Nanofibers (CNFs) 230
5.6.4 Carbon Nanotubes (CNTs) 231
5.7 Current Collector 232
5.7.1 Metal-based Current Collector 232
5.7.2 Carbon-based Current Collector 234
5.8 Conclusion and Perspectives 236
References 238
6 Advanced Characterization Techniques and Theoretical Calculation 247
Cheng Yang, Libao Chen, Hongshuai Hou, Guoqiang Zou, Xiaobo Ji, and Zhibin Wu
6.1 Imaging and Microscopy 248
6.1.1 Fundamentals of Imaging and Microscopy 248
6.1.2 Electron Microscopy Studies of SIBs 249
6.1.3 Synchrotron X-Ray Imaging Studies of SIBs 250
6.1.4 Neutron Imaging Studies of SIBs 251
6.1.5 Scanning Probe Microscopy Studies of SIBs 254
6.1.6 Optical Microscopy Studies of SIBs 255
6.2 Synchrotron Radiation X-Ray Diffraction Technique 256
6.2.1 Principles of XRD 256
6.2.2 Characteristics of XRD 257
6.2.3 XRD studies of SIBs 259
6.2.4 Challenges and Opportunities 262
6.3 Synchrotron Radiation X-ray Absorption Spectroscopy Technique 263
6.3.1 Principles of XAS 264
6.3.2 Characteristics of XAS 266
6.3.3 XAS Studies of SIBs 266
6.3.4 Challenges and Opportunities 268
6.4 Solid-state Nuclear Magnetic Resonance Spectroscopy 270
6.4.1 Principles of ssNMR 271
6.4.2 NMR Interactions and Shift Ranges for Battery Materials 272
6.4.2.1 Shift Interactions (Nuclear Spin−Electron Spin) 272
6.4.2.2 Dipolar Coupling (Nuclear Spin−Nuclear Spin) 273
6.4.2.3 Quadrupolar Coupling 273
6.4.3 ssNMR Studies of SIBs 273
6.4.4 The Challenge of NMR Detection 278
6.5 Electrochemical Test Techniques 279
6.5.1 Cyclic Voltammetry 279
6.5.2 Galvanostatic Charge–Discharge 281
6.5.3 Electrochemical Impedance Spectroscopy 282
6.5.4 Other Electrochemical Testing Techniques 285
6.5.5 Electrochemical Analysis of SIBs 286
6.6 Other Characterization Techniques 287
6.6.1 Neutron Diffraction Technique 287
6.6.2 Fourier Transform Infrared Spectrometry 290
6.6.3 Raman 292
6.7 Theoretical Calculation 293
6.7.1 Classical Molecular Dynamics 296
6.7.2 Ab Initio Molecular Dynamics 297
6.7.3 Machine-learning Molecular Dynamics 298
6.7.4 Applications of Theoretical Calculations 300
References 304
7 Practical Application of SIBs 311
Huanqing Liu, Wentao Deng, Hongshuai Hou, Guoqiang Zou, and Xiaobo Ji
7.1 Introduction 311
7.2 Commercial Sodium Battery 311
7.2.1 High-Temperature Na–S Battery 312
7.2.2 Sodium–Nickel Chloride Battery 313
7.3 Design and Manufacture Process of SIBs 314
7.3.1 Laboratory Button Battery Assembly 314
7.3.1.1 Metal Na Anode Materials 314
7.3.1.2 Button Cell Assembly Order 315
7.3.1.3 The Matching of Positive and Negative Electrodes 315
7.3.2 Type of Cell for SIBs 316
7.3.2.1 Cylindrical Battery 316
7.3.2.2 Soft-pack Battery 317
7.3.2.3 Prismatic Battery 317
7.3.3 Design Requirements for Cell 317
7.3.3.1 Basic Design Principles 318
7.3.3.2 Safety Design 318
7.3.4 Manufacturing Process of SIBs 319
7.3.4.1 Front-end Electrode Fabrication Process 319
7.3.4.2 Back-end Assembly Process 320
7.3.4.3 Formation and Sorting Process 321
7.3.4.4 Design of SIBs Pack 321
7.3.4.5 Battery Management System 321
7.4 Presodiation Techniques 322
7.4.1 EC/Chemical Methods 323
7.4.1.1 Ec 323
7.4.1.2 Chemical Methods 323
7.4.2 Self-sacrificial Additive 324
7.4.3 Other Novel Methods of Presodiation 324
7.4.4 Factors Need to be Improved 325
7.5 Performance Tests and Failure Analysis 325
7.5.1 Electrochemical Performances Test 326
7.5.2 Safety Performances Test 326
7.5.3 Failure Phenomenon 327
7.5.4 Failure Analysis Method 328
7.5.5 Cost Estimation 330
7.6 Commercial Application and Future Perspectives 332
7.6.1 Current State of Commercialization of SIBs 332
7.6.2 Application Prospect 333
7.6.2.1 Low-Speed Electric Vehicle Market 333
7.6.2.2 Large-scale ESSs 334
References 334
Index 337
