Metal-Air Batteries Fundamentals and Applications

Xin-bo Zhang, PhD, is Professor in Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, China. His research interests mainly focus on functional inorganic materials for energy storage and conversion with fuel cells and batteries, especially lithium-air batteries.

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

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