An innovation in battery science and technology is necessary to build better power sources for our modern lifestyle needs. One of the main fields being explored for the possible breakthrough is the development of metal-air batteries. Metal-Air Batteries: Fundamentals and Applications offers a systematic summary of the fundamentals of the technology and explores the most recent advances in the applications of metal-air batteries. Comprehensive in scope, the text explains the basics in electrochemical batteries and introduces various species of metal-air batteries.
The author-a noted expert in the field-explores the development of metal-air batteries in the order of Li-air battery, sodium-air battery, zinc-air battery and Mg-O2 battery, with the focus on the Li-air battery. The text also addresses topics such as metallic anode, discharge products, parasitic reactions, electrocatalysts, mediator, and X-ray diffraction study in Li-air battery. Metal-Air Batteries provides a summary of future perspectives in the field of the metal-air batteries. This important resource:
-Covers various species of metal-air batteries and their components as well as system designation
-Contains groundbreaking content that reviews recent advances in the field of metal-air batteries
-Focuses on the battery systems which have the greatest potential for renewable energy storage
Written for electrochemists, physical chemists, materials scientists, professionals in the electrotechnical industry, engineers in power technology, Metal-Air Batteries offers a review of the fundamentals and the most recent developments in the area of metal-air batteries.
Table of Contents
Preface xiii
1 Introduction to Metal-Air Batteries: Theory and Basic Principles 1
Zhiwen Chang and Xin-bo Zhang
1.1 Li-O2 Battery 1
1.2 Sodium-O2 Battery 5
References 7
2 Stabilization of Lithium-Metal Anode in Rechargeable Lithium-Air Batteries 11
Bin Liu,Wu Xu, and Ji-Guang Zhang
2.1 Introduction 11
2.2 Recent Progresses in Li Metal Protection for Li-O2 Batteries 13
2.2.1 Design of Composite Protective Layers 13
2.2.2 New Insights on the Use of Electrolyte 18
2.2.3 Functional Separators 25
2.2.4 Solid-State Electrolytes 29
2.2.5 Alternative Anodes 30
2.3 Challenges and Perspectives 30
Acknowledgment 32
References 32
3 Li-Air Batteries: Discharge Products 41
Xuanxuan Bi, RongyueWang, and Jun Lu
3.1 Introduction 41
3.2 Discharge Products in Aprotic Li-O2 Batteries 43
3.2.1 Peroxide-based Li-O2 Batteries 43
3.2.1.1 Electrochemical Reactions 43
3.2.1.2 Crystalline and Electronic Band Structure of Li2O2 44
3.2.1.3 Reaction Mechanism and the Coexistence of Li2O2 and LiO2 47
3.2.2 Superoxide-based Li-O2 Batteries 52
3.2.3 Problems and Challenges in Aprotic Li-O2 Batteries 54
3.2.3.1 Decomposition of the Electrolyte 54
3.2.3.2 Degradation of the Carbon Cathode 55
3.3 Discharge Products in Li-Air Batteries 56
3.3.1 Challenges to Exchanging O2 to Air 56
3.3.2 Effect ofWater on Discharge Products 56
3.3.2.1 Effect of Small Amount ofWater 56
3.3.2.2 Aqueous Li-O2 Batteries 57
3.3.3 Effect of CO2 on Discharge Products 59
3.3.4 Current Li-Air Batteries and Perspectives 60
Acknowledgment 61
References 61
4 Electrolytes for Li-O2 Batteries 65
Alex R. Neale, Peter Goodrich, Christopher Hardacre, and Johan Jacquemin
4.1 General Li-O2 Battery Electrolyte Requirements and Considerations 65
4.1.1 Electrolyte Salts 69
4.1.2 Ethers and Glymes 73
4.1.3 Dimethyl Sulfoxide (DMSO) and Sulfones 76
4.1.4 Nitriles 78
4.1.5 Amides 79
4.1.6 Ionic Liquids 80
4.1.7 Solid-State Electrolytes 86
4.2 Future Outlook 87
References 87
5 Li-Oxygen Battery: Parasitic Reactions 95
Xiahui Yao, Qi Dong, Qingmei Cheng, and DunweiWang
5.1 The Desired and Parasitic Chemical Reactions for Li-Oxygen Batteries 95
5.2 Parasitic Reactions of the Electrolyte 96
5.2.1 Nucleophilic Attack 97
5.2.2 Autoxidation Reaction 99
5.2.3 Acid-Base Reaction 100
5.2.4 Proton-mediated Parasitic Reaction 100
5.2.5 Additional Parasitic Chemical Reactions of the Electrolyte: Reduction Reaction 102
5.3 Parasitic Reactions at the Cathode 102
5.3.1 The Corrosion of Carbon in the Discharge Process 104
5.3.2 The Corrosion of Carbon in the Recharge Process 106
5.3.3 Catalyst-induced Parasitic Chemical Reactions 106
5.3.4 Alternative Cathode Materials and Corresponding Parasitic Chemistries 110
5.3.5 Additives and Binders 111
5.3.6 Contaminations 111
5.4 Parasitic Reactions on the Anode 112
5.4.1 Corrosion of the Li Metal 114
5.4.2 SEI in the Oxygenated Atmosphere 114
5.4.3 Alternative Anodes and Associated Parasitic Chemistries 115
5.5 New Opportunities from the Parasitic Reactions 116
5.6 Summary and Outlook 117
References 118
6 Li-Air Battery: Electrocatalysts 125
Zhiwen Chang and Xin-bo Zhang
6.1 Introduction 125
6.2 Types of Electrocatalyst 126
6.2.1 Carbonaceous Materials 126
6.2.1.1 Commercial Carbon Powders 126
6.2.1.2 Carbon Nanotubes (CNTs) 126
6.2.1.3 Graphene 127
6.2.1.4 Doped Carbonaceous Material 128
6.2.2 Noble Metal and Metal Oxides 129
6.2.3 Transition Metal Oxides 130
6.2.3.1 Perovskite Catalyst 131
6.2.3.2 Redox Mediator 133
6.3 Research of Catalyst 135
6.4 Reaction Mechanism 138
6.5 Summary 141
References 142
7 Lithium-Air BatteryMediator 151
Zhuojian Liang, Guangtao Cong, YuWang, and Yi-Chun Lu
7.1 Redox Mediators in Lithium Batteries 151
7.1.1 Redox Mediators in Li-Air Batteries 151
7.1.2 Redox Mediators in Li-ion and Lithium-flow Batteries 153
7.1.2.1 Overcharge Protection in Li-ion Batteries 153
7.1.2.2 Redox Targeting Reactions in Lithium-flow Batteries 154
7.2 Selection Criteria and Evaluation of Redox Mediators for Li-O2 Batteries 156
7.2.1 Redox Potential 156
7.2.2 Stability 157
7.2.3 Reaction Kinetics and Mass Transport Properties 161
7.2.4 Catalytic Shuttle vs Parasitic Shuttle 163
7.3 Charge Mediators 166
7.3.1 LiI (Lithium Iodide) 170
7.3.2 LiBr (Lithium Bromide) 172
7.3.3 Nitroxides: TEMPO (2,2,6,6-Tetramethylpiperidinyloxyl) and Others 176
7.3.4 TTF (Tetrathiafulvalene) 180
7.3.5 Tris[4-(diethylamino)phenyl]amine (TDPA) 182
7.3.6 Comparison of the Reported Charge Mediators 183
7.4 Discharge Mediator 186
7.4.1 Iron Phthalocyanine (FePc) 190
7.4.2 2,5-Di-tert-butyl-1,4-benzoquinone (DBBQ) 192
7.5 Conclusion and Perspective 194
References 195
8 Spatiotemporal Operando X-ray Diffraction Study on Li-Air Battery 207
Di-Jia Liu and Jiang-Lan Shui
8.1 Microfocused X-ray Diffraction (μ-XRD) and Li-O2 Cell Experimental Setup 207
8.2 Study on Anode: Limited Reversibility of Lithium in Rechargeable LAB 209
8.3 Study on Separator: Impact of Precipitates to LAB Performance 217
8.4 Study on Cathode: Spatiotemporal Growth of Li2O2 During Redox
Reaction 222
References 230
9 Metal-Air Battery: In Situ Spectroelectrochemical Techniques 233
IainM. Aldous, Laurence J. Hardwick, Richard J. Nichols, and J. Padmanabhan Vivek
9.1 Raman Spectroscopy 233
9.1.1 In Situ Raman Spectroscopy for Metal-O2 Batteries 233
9.1.2 BackgroundTheory 233
9.1.3 Practical Considerations 235
9.1.3.1 Electrochemical Roughening 235
9.1.3.2 Addressing Inhomogeneous SERS Enhancement 237
9.1.4 In Situ Raman Setup 238
9.1.5 Determination of Oxygen Reduction and Evolution Reaction MechanismsWithin Metal-O2 Batteries 239
9.2 Infrared Spectroscopy 247
9.2.1 Background 247
9.2.2 IR Studies of Electrochemical Interfaces 247
9.2.3 Infrared Spectroscopy for Metal-O2 Battery Studies 249
9.3 UV/Visible Spectroscopic Studies 253
9.3.1 UV/Vis Spectroscopy 254
9.3.2 UV/Vis Spectroscopy for Metal-O2 Battery Studies 255
9.4 Electron Spin Resonance 257
9.4.1 Cell Setup 259
9.4.2 Deployment of Electrochemical ESR in Battery Research 259
9.5 Summary and Outlook 262
References 262
10 Zn-Air Batteries 265
Tongwen Yu, Rui Cai, and Zhongwei Chen
10.1 Introduction 265
10.2 Zinc Electrode 266
10.3 Electrolyte 268
10.4 Separator 270
10.5 Air Electrode 271
10.5.1 Structure of Air Electrode 271
10.5.2 Oxygen Reduction Reaction 271
10.5.3 Oxygen Evolution Reaction 272
10.5.4 Electrocatalyst 273
10.5.4.1 Noble Metals and Alloys 274
10.5.4.2 Transition Metal Oxides 275
10.5.4.3 Inorganic-Organic Hybrid Materials 278
10.5.4.4 Metal-free Materials 282
10.6 Conclusions and Outlook 288
References 288
11 Experimental and Computational Investigation of Nonaqueous Mg/O2 Batteries 293
Jeffrey G. Smith, Gülin Vardar, CharlesW. Monroe, and Donald J. Siegel
11.1 Introduction 293
11.2 Experimental Studies of Magnesium/Air Batteries and Electrolytes 295
11.2.1 Ionic Liquids as Candidate Electrolytes for Mg/O2 Batteries 295
11.2.2 Modified Grignard Electrolytes for Mg/O2 Batteries 299
11.2.3 All-inorganic Electrolytes for Mg/O2 Batteries 303
11.2.4 Electrochemical Impedance Spectroscopy 307
11.3 Computational Studies of Mg/O2 Batteries 310
11.3.1 Calculation of Thermodynamic Overpotentials 310
11.3.2 Charge Transport in Mg/O2 Discharge Products 315
11.4 Concluding Remarks 320
References 321
12 Novel Methodologies to Model Charge Transport in Metal-Air Batteries 331
Nicolai RaskMathiesen,Marko Melander,Mikael Kuisma, Pablo García-Fernández, and JuanMaria García Lastra
12.1 Introduction 331
12.2 Modeling Electrochemical Systems with GPAW 333
12.2.1 Density FunctionalTheory 333
12.2.2 Conductivity from DFT Data 335
12.2.3 The GPAWCode 337
12.2.4 Charge Transfer Rates with Constrained DFT 338
12.2.4.1 MarcusTheory of Charge Transfer 338
12.2.4.2 Constrained DFT 339
12.2.4.3 Polaronic Charge Transport at the Cathode 341
12.2.5 Electrochemistry at Solid-Liquid Interfaces 342
12.2.5.1 Modeling the Electrochemical Interface 342
12.2.5.2 Implicit Solvation at the Electrochemical Interface 343
12.2.5.3 Generalized Poisson-Boltzmann Equation for the Electric Double Layer 344
12.2.5.4 Electrode PotentialWithin the Poisson-Boltzmann Model 345
12.2.6 Calculations at Constant Electrode Potential 346
12.2.6.1 The Need for a Constant Potential Presentation 346
12.2.6.2 Grand Canonical Ensemble for Electrons 347
12.2.6.3 Fictitious Charge Dynamics 349
12.2.6.4 Model in Practice 350
12.2.7 Conclusions 351
12.3 Second Principles for MaterialModeling 351
12.3.1 The Energy in SP-DFT 352
12.3.2 The Lattice Term (E(0)) 353
12.3.3 Electronic Degrees of Freedom 354
12.3.4 Model Construction 357
12.3.5 Perspectives on SP-DFT 358
Acknowledgments 359
References 359
13 Flexible Metal-Air Batteries 367
Huisheng Peng, Yifan Xu, Jian Pan, Yang Zhao, LieWang, and Xiang Shi
13.1 Introduction 367
13.2 Flexible Electrolytes 368
13.2.1 Aqueous Electrolytes 368
13.2.1.1 PAA-based Gel Polymer Electrolyte 369
13.2.1.2 PEO-based Gel Polymer Electrolyte 369
13.2.1.3 PVA-based Gel Polymer Electrolyte 371
13.2.2 Nonaqueous Electrolytes 373
13.2.2.1 PEO-based Polymer Electrolyte 373
13.2.2.2 PVDF-HFP-based Polymer Electrolyte 377
13.2.2.3 Ionic Liquid Electrolyte 377
13.3 Flexible Anodes 378
13.4 Flexible Cathodes 381
13.4.1 Modified Stainless Steel Mesh 381
13.4.2 Modified Carbon Textile 382
13.4.3 Carbon Nanotube 384
13.4.4 Graphene-based Cathode 385
13.4.5 Other Composite Electrode 386
13.5 Prototype Devices 386
13.5.1 Sandwich Structure 387
13.5.2 Fiber Structure 390
13.6 Summary 394
References 394
14 Perspectives on the Development of Metal-Air Batteries 397
Zhiwen Chang and Xin-bo Zhang
14.1 Li-O2 Battery 397
14.1.1 Lithium Anode 397
14.1.2 Electrolyte 398
14.1.3 Cathode 398
14.1.4 The Reaction Mechanisms 399
14.1.5 The Development of Solid-state Li-O2 Battery 399
14.1.6 The Development of Flexible Li-O2 Battery 400
14.2 Na-O2 Battery 401
14.3 Zn-air Battery 402
References 403
Index 407
