Oxide Thermoelectric Materials from Basic Principles to Applications

Yuan-Hua Lin, PhD, is Dean of the School of Materials Science and Engineering at Tsinghua University, China. His research interests are focused on functional oxide-based ceramics and thin films.

Jinle Lan, PhD, is Associate Professor of the College of Materials Science and Engineering at Beijing University of Chemical Technology, China. His research focuses on functional oxides and composites for energy conversion and storage.

Cewen Nan, PhD, is Professor of the School of Materials Science and Engineering at Tsinghua University, China. His research focuses on functional materials, including multiferroic magnetoelectric materials, thermoelectric oxides, functional polymer-based composites, and solid state electrolytes.

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 Na_xCoO₂ 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

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