Physical Multiscale Modeling and Numerical Simulation of Electrochemical Devices for Energy Conversion and Storage (eBook)

Preface 6
Contents 8
1 Atomistic Modeling of Electrode Materials for Li-Ion Batteries: From Bulk to Interfaces 9
Abstract 9
1 Introduction 9
2 Macroscopic Picture of an Electrochemical Reaction 11
2.1 Microscopic Picture of an Electrochemical Reaction 13
2.2 Beyond the Thermodynamic Equilibrium 14
2.3 First-Principles Approach to Condensed Matter 15
3 Modelization of Bulk Materials 18
3.1 Equilibrium Crystal Structures 18
3.2 Finite Temperature Effects 21
3.3 Electrochemical Properties 24
4 Modelization of Interfaces 30
4.1 Surface/Interface Thermodynamics 30
4.2 First-Principles Approach to Charged Surfaces 33
4.3 Application to Solid/Liquid Interfaces 35
4.4 Application to Solid/Solid Interfaces 36
5 Perspectives 39
References 40
2 Multi-scale Simulation Study of Pt-Alloys Degradation for Fuel Cells Applications 45
Abstract 45
1 Introduction 45
2 Time Evolution by Molecular Dynamics and DFT Simulations 48
3 Time Evolution of PtM Alloys by KMC Methods 51
4 Degradation of PtCo Skin 57
5 Concluding Remarks 64
References 65
3 Molecular Dynamics Simulations of Electrochemical Energy Storage Devices 68
Abstract 68
1 Introduction 69
2 Molecular Dynamics 71
2.1 Principle 71
2.2 All-Atom Force Fields 71
2.3 Modelling Metallic Electrodes at Constant Potential 72
2.4 Coarse-Grained Force Fields 73
3 Li-Ion Batteries 74
3.1 A Polarizable Force Field Based on First-Principles Calculations 75
3.2 Conduction Mechanism in Stoichiometric LiMgSO4F 76
3.3 Effect of Li+ Vacancies 80
3.4 On the Importance of Finite-Size Effects 82
4 Supercapacitors 83
4.1 Increase of the Capacitance in Nanoporous Carbons 83
4.2 Effect of the Local Structure 86
4.3 Dynamics of Charging: Coarse-Graining Further 88
5 Perspectives 89
References 90
4 Continuum, Macroscopic Modeling of Polymer-Electrolyte Fuel Cells 97
Abstract 97
1 Introduction 97
1.1 Modeling Dimension 101
2 Basic Governing Equations 103
2.1 Material 104
2.1.1 Charge 106
2.1.2 Momentum 109
2.1.3 Energy 110
3 Membrane 112
3.1 Membrane Uptake, Morphology, and Function 114
3.1.1 Calculating Water Uptake 116
3.2 Transport Equations 119
3.2.1 General Governing Equations 119
3.2.2 Choice of Water Driving Force and Transport Parameters 121
3.2.3 Gas Crossover 123
3.3 Membrane Swelling 124
3.4 Contamination and Multi-ion Transport 125
4 Gas-Diffusion Media 128
4.1 Modeling Equations 128
4.1.1 Gas Phase 129
4.1.2 Liquid Phase 130
4.1.3 Heat Transport 131
4.1.4 Liquid/Vapor/Heat Interactions 132
4.2 Microporous Layers and Pore-Network Modeling 133
4.3 Transport in the Gas Channel 134
4.3.1 Droplet Movement 136
5 Catalyst Layer 137
5.1 Kinetics 138
5.2 Transport Phenomena 143
5.2.1 Agglomerate Length Scale and Ionomer Films 144
5.3 Electrochemical Impedance Spectroscopy 146
6 Summary and Future Outlook 149
References 150
5 Mathematical Modeling of Aging of Li-Ion Batteries 156
Abstract 156
1 Introduction 156
2 Brief Overview of the Degradation Phenomena in Li-Ion Batteries 160
2.1 Aging at the Anode 160
2.2 Aging at the Cathode 163
3 Mathematical Models 166
3.1 Performance (Aging-Free) Models 166
3.1.1 Model of the Elementary Sandwich (``Dualfoil'') 166
3.1.2 Single-Particle Model 169
3.2 Modeling of Aging Phenomena 170
4 Model-Aided Analysis of Battery Aging 177
4.1 Typical Aging Experiments and Characterization 177
4.1.1 Aging protocols 177
4.1.2 Nonintrusive Cell Characterization Techniques 178
4.1.3 Intrusive Analysis 182
4.2 ``Snapshot'' Analysis with the Aging-Free Model 185
4.3 Analysis with the Aging Model 189
5 Outlook of Physics-Based Aging Modeling 191
References 192
6 Fuel Cells and Batteries In Silico Experimentation Through Integrative Multiscale Modeling 196
Abstract 196
1 Introduction 197
1.1 The Role of Computational Electrochemistry 198
2 Integrative Multiscale Modeling Methods 200
3 Application Examples 206
3.1 Microstructurally Resolved Performance Models 206
3.2 Performance Models with Detailed Electrochemistry 219
4 Conclusions and Open Challenges 229
References 233
7 Cost Modeling and Valuation of Grid-Scale Electrochemical Energy Storage Technologies 239
Abstract 239
1 Introduction 240
2 Methodology 241
3 Performance Matrix 242
4 Techno-Economic Cost Modeling 244
4.1 Analytics Framework 245
4.2 Determining Storage Benefits 245
5 Databases 249
5.1 Database of Storage Technologies 249
5.2 Database of Storage Applications 250
6 Storage Valuation 250
7 Summary and Conclusion 252
References 252