This timely book explores the latest research results on the physics and materials science of oxide thermoelectrics at all scales. It covers the theory, design and properties of thermoelectric materials as well as fabrication technologies for devices and their applications.
Written by three distinguished materials scientists, Oxide Thermoelectric Materials reviews: the fundamentals of electron and phonon transport; modeling of thermoelectric modules and their optimization; synthetic processes, structures, and properties of thermoelectric materials such as Bi2Te3- and skutterudite-based materials and Si-Ge alloys. In addition, the book provides a detailed description of the construction of thermoelectric devices and their applications.
-Contains fundamentals and applications of thermoelectric materials and devices, and discusses their near-future perspectives
-Introduces new, promising materials and technologies, such as nanostructured materials, perovskites, and composites
-Paves the way for increased conversion efficiencies of oxides
-Authored by well-known experts in the field of thermoelectrics
Oxide Thermoelectric Materials is a well-organized guidebook for graduate students involved in physics, chemistry, or materials science. It is also helpful for researchers who are getting involved in thermoelectric research and development.
Table of Contents
Foreword ix
Part I Theories and Fundamentals 1
1 Electron Transport Model in Nano Bulk Thermoelectrics 3
1.1 History of Conducting Oxides 3
1.2 Structural Characteristics of Oxides 8
1.3 Band Structure of Conventional Oxides 11
1.4 Electrical Properties 11
1.5 Model for Thermoelectric Oxides 15
1.6 Effect of Interface on Electron Transport 17
References 22
2 Controlling the Thermal Conductivity of Bulk Nanomaterials 25
2.1 Bonding and Lattice Vibration 25
2.2 Lattice Distortions in Determining Thermal Properties 25
2.2.1 Point Defects and Dislocations 25
2.2.2 Peierls Distortion 27
2.2.3 Octahedral Distortion in Manganite Perovskites 28
2.3 Callaway Model and the Minimum Thermal Properties 30
2.4 Temperature Relationship in Thermal Properties 32
2.5 Model for Lattice Thermal Conductivity 36
2.5.1 Kinetic Theory 36
2.5.2 Boltzmann Equation 36
2.5.3 Phonon-Phonon Collisions 38
2.6 Interfacial Thermal Conductivity 40
2.7 Model for Nano Bulk Materials 43
2.8 Minimum Value for Oxides 48
References 49
Part II Materials 53
3 Nonoxide Materials 55
3.1 Bi2Te3-Based Materials 55
3.2 Skutterudite-Based Materials 59
3.3 Si-Ge Alloys 62
3.4 Other Alloy Materials 66
References 71
4 Binary Oxides 77
4.1 Introduction for ZnO 77
4.2 Property of ZnO 77
4.2.1 Structure 77
4.2.2 Lattice Parameters 77
4.2.3 Electronic Band Structure 77
4.2.4 Mechanical Properties 79
4.2.5 Thermal Expansion Coefficients 79
4.2.6 Thermal Conductivity 80
4.2.7 Specific Heat 80
4.2.8 Electrical Properties of Undoped ZnO 81
4.3 Doping for ZnO-Based Thermoelectric Materials 81
4.4 ZnO Nanostructures 84
4.5 Introduction for In2O3 87
4.6 Property of In2O3 88
4.6.1 Structure 88
4.6.2 Electronic Band Structure 89
4.6.3 Thermal Properties and Electrical Properties 89
4.7 Doping for In2O3-BasedThermoelectricMaterials 90
4.8 In2O3 Nanostructures 94
4.9 TiO2 and Others 98
References 101
5 Perovskite-Type Oxides 105
5.1 Introduction for Perovskite-Type Oxides 105
5.2 Crystal Structure and Electronic Structure of Perovskite-Type Oxides 106
5.2.1 Crystal Structure 106
5.2.2 Electronic Structure 107
5.3 A- and B-Sites Doping for Perovskite-Type Oxides 108
5.3.1 SrTiO3 108
5.3.2 CaMnO3 109
5.3.3 LaCoO3 111
5.4 Double Perovskites 112
5.4.1 Structure of Double Perovskites 112
5.4.2 Thermoelectric Properties of A′A′′B2O5+𝛿 113
5.4.3 Thermoelectric Properties of A2B′B′′O6 113
5.4.4 Doping Modulation 115
5.4.5 Composite Ceramics 118
5.5 Nanostructure Property Relationships in Perovskite-Type Oxides 120
References 124
6 Oxide Cobaltites 133
6.1 Introduction 133
6.2 NaxCoO2 133
6.3 Ca3Co4O9 138
6.3.1 Single Dopants of Ca3Co4O9 139
6.3.2 Dual Dopants of Ca3Co4O9 144
6.3.3 Texture for Ca3Co4O9 147
6.3.4 Nanocomposites for Ca3Co4O9 147
6.4 New Concepts for Oxide Cobaltites 150
References 151
7 Promising Complex Oxides for High Performance 155
7.1 Crystal Structure-Property Relationships 155
7.2 History of Complex Superconductors 156
7.3 Ternary Oxyselenides 158
7.3.1 Donor Doping on [Bi2O2]2+ Layers 158
7.3.2 Donor Doping on [Se]2− Layers 160
7.3.3 The Solid Solution of Bi2O2Se and Bi2O2Te 160
7.4 Quaternary Oxyselenides 164
7.4.1 Thermoelectric Properties 166
7.4.2 Band Gap Tuning 168
7.4.3 Texturing 168
7.4.4 Modulation Doping 169
7.4.5 Nanocompositing 171
7.5 Complexity Through Disorder in the Unit Cell 173
7.6 Complex Unit Cells 174
References 176
8 New Thermoelectric Materials and Nanocomposites 179
8.1 Nanocomposite Design 180
8.1.1 Energy-filtering Design 180
8.1.2 All-Scale Hierarchical Architectures 181
8.1.3 Quantum Nanostructured Bulk Materials 183
8.2 Organic Thermoelectric Materials 183
8.2.1 p-Type Organic Thermoelectric Materials 184
8.2.2 PEDOT 184
8.2.3 PANI 187
8.2.3.1 The Molecular Structure of PANI 188
8.2.3.2 Conductive Mechanism of PANI 188
8.2.3.3 Synthesis of PANI 188
8.2.3.4 Electrochemical Method 189
8.2.4 Doping of PANI 189
8.2.5 Tuning the Work Function of Polyaniline 190
8.2.6 n-Type Thermoelectric Materials 192
8.3 Organic/Inorganic Thermoelectric Nanocomposites 192
8.3.1 0D Nanoparticles/Polymer 192
8.3.2 1D Nanowires or Nanotubes/Polymer 193
8.3.3 2D Nanosheets/Polymer 197
References 201
Part III Devices and Application 207
9 Oxide Materials Preparation 209
9.1 Synthesis Method of Nanopowder 209
9.1.1 Solid-State Reaction 209
9.1.2 Solution Preparation 210
9.1.2.1 Sol-Gel Method 211
9.1.2.2 Precipitation and Coprecipitation Method 211
9.1.2.3 Hydrothermal Method 213
9.1.3 Gas-Phase Reaction 214
9.2 Advanced Bulk Technology 214
9.2.1 Spark Plasma Sintering 215
9.2.2 Hot-Press Sintering 215
9.2.3 Microwave Sintering 217
9.2.4 Two-Step Sintering 218
9.2.5 Phase-Transformation Sintering 219
9.3 Sintering Conditions on the Properties of Bulk 219
9.3.1 Effect of Sintering Temperature 219
9.3.2 Effect of Sintering Atmosphere 220
9.3.3 Effect of the Addition for Sintering 220
References 221
10 Modeling and Optimizing of Thermoelectric Devices 229
10.1 Introduction to Thermoelectric Devices 229
10.2 The Theoretical Analysis 230
10.3 The Model Design 232
10.4 The Interfaces in Thermoelectric Modules 236
10.5 The Simulation and the Optimization 238
10.6 The Measurement Theories and Systems 241
10.7 All-oxide Thermoelectric Device 242
References 245
11 Photovoltaic Application of Thermoelectric Materials and Devices 247
11.1 Introduction 247
11.2 Photovoltaic-Thermoelectric Integration Devices 248
11.3 Photoelectric-Thermoelectric Composite Materials 253
References 260
Index 263
