Metal-Air Batteries

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 MetalAir Batteries: Theory and Basic Principles 1 Zhiwen Chang and Xin-bo Zhang 1.1 LiO2 Battery 1 1.2 SodiumO2 Battery 5 References 7 2 Stabilization of Lithium-Metal Anode in Rechargeable LithiumAir Batteries 11 Bin Liu,Wu Xu, and Ji-Guang Zhang 2.1 Introduction 11 2.2 Recent Progresses in Li Metal Protection for LiO2 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 LiAir Batteries: Discharge Products 41 Xuanxuan Bi, RongyueWang, and Jun Lu 3.1 Introduction 41 3.2 Discharge Products in Aprotic LiO2 Batteries 43 3.2.1 Peroxide-based LiO2 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 LiO2 Batteries 52 3.2.3 Problems and Challenges in Aprotic LiO2 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 LiAir 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 LiO2 Batteries 57 3.3.3 Effect of CO2 on Discharge Products 59 3.3.4 Current LiAir Batteries and Perspectives 60 Acknowledgment 61 References 61 4 Electrolytes for LiO2 Batteries 65 Alex R. Neale, Peter Goodrich, Christopher Hardacre, and Johan Jacquemin 4.1 General LiO2 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 LiOxygen Battery: Parasitic Reactions 95 Xiahui Yao, Qi Dong, Qingmei Cheng, and DunweiWang 5.1 The Desired and Parasitic Chemical Reactions for LiOxygen 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 AcidBase 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 LiAir 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 LithiumAir 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 LiAir Batteries 151 7.1.2 Redox Mediators in Li-ion and Lithium-flow Batteries 153 7.1.2.1 Overcharge Pr