Modeling Electrochemical Energy Storage at the Atomic Scale (eBook)

Contents 6
Preface 7
Fundamental Challenges for Modeling Electrochemical Energy Storage Systems at the Atomic Scale 9
Abstract 9
1 Introduction 9
2 Basic Principles of Battery Operation 11
3 Computational Methods 13
4 Descriptors 14
5 Dendrite Growth in Batteries 14
6 Structure of Interfaces in Electrochemical Storage Devices 17
6.1 Grand-Canonical Approach to Consider the Presence of Electrolytes at Interfaces 17
6.2 Description of Electrolytes in Implicit Solvent Models 19
6.3 Explicit Atomistic Modeling of ElectrodeElectrolyte Interfaces 22
7 Atomistic Modeling of Bulk Electrode Properties 24
8 Conclusions 26
Acknowledgements 26
References 26
Interfaces and Materials in Lithium Ion Batteries: Challenges for Theoretical Electrochemistry 31
Abstract 31
1 Terminology 32
2 Introduction to Electrochemical Energy Storage Devices 33
3 Introduction to Lithium Ion Cell Chemistry 36
4 Anode Materials for LIBs 38
4.1 Lithium Metal, the Ancestor Anode of LIB Electrodes 38
4.2 Classification of Anode Materials 38
4.3 Graphitic and Non-Graphitic Carbon Anodes 39
4.4 Lithium Titanate 41
5 Cathode Materials for Lithium Ion Batteries 41
6 Electrolytes for LIBs 46
7 Conclusion 53
References 53
Assessment of Simple Models for Molecular Simulation of Ethylene Carbonate and Propylene Carbonate as Solvents for Electrolyte Solutions 60
Abstract 60
1 Introduction 61
1.1 Methods and Force Fields 63
1.2 Plan of this Report 64
2 Ethylene Carbonate and Propylene Carbonate Liquids 64
2.1 Molecular Mobilities 66
2.2 Dielectric Constants and Relaxation Times 69
2.3 Non-linear Polarization Response 70
2.4 Electrochemical Double-Layer Capacitor Based on CNT Forests 70
3 Empirically Scaled Partial Charges for Li...Carbonate Interactions 73
3.1 Free Energy Results and Quasi-Chemical Theory (QCT) 73
3.2 Radial Distribution Function 75
3.3 Ion Mobilities 75
4 Model solid electrolyte interphase layer 77
5 Conclusions 78
Acknowledgements 79
References 79
Elucidating Solvation Structures for Rational Design of Multivalent Electrolytes—A Review 85
Abstract 85
1 Introduction 86
2 Magnesium Electrolytes 89
2.1 Simple Inorganic Mg Salts 90
2.2 Organometallic Compounds (Complex Salts) 101
2.3 Aqueous Mg Electrolytes 108
2.4 Mg Polymer Electrolytes 109
3 Zinc Electrolytes 114
4 Calcium Electrolytes 119
5 Rational Design of Electrolytes 120
6 Conclusions 121
Acknowledgements 123
References 123
Towards Synergistic Electrode–Electrolyte Design Principles for Nonaqueous Li–O batteries 131
Abstract 131
1 Introduction 132
2 Electrolyte Design 133
2.1 Electrochemical Stability 133
2.2 Chemical Stability 135
2.3 Ionic Solubility 137
2.4 Stringent Limitations and Fundamental Trade-Offs 138
3 Cathode Electrocatalyst Design 139
3.1 Discharge Pathways 139
3.2 Discharge Product Nucleation Thermodynamics 141
3.3 Lithium Peroxide Nucleation 142
3.4 Lithium Oxide Nucleation and Trends in Discharge-Product Selectivity 142
3.5 Cathode Stability 143
4 Conclusions 147
Acknowledgements 147
References 147