Bin Zhu, PhD, moved from KTH, Sweden as a Chief Scientist (Professor Director) of Energy Storage Joint Research Center, Southeast University, China. He has published more than 300 scientific papers in nano-composite ionic conductors and new semiconductor-ionic materials for advanced fuel cells.Rizwan Raza, PhD, is Assistant Professor in the Department of Physics in COMSATS Institute of Information Technology, Pakistan. He has published more than 100 scientific papers.Liangdong Fan, PhD, is Lecturer in the College of Chemistry and Environmental Engineering at Shenzhen University, China. His interests focus on novel nanocomposite functional materials for fuel cells and electro-catalysis.Chunwen Sun is a Professor at Beijing Institute of Nanoenergy and Nanosystems (BINN), Chinese Academy of Sciences (CAS). His research interests include energy storage and conversion, e.g., lithium/sodium-ion batteries, metal-air batteries, all-solid-state batteries, fuel cells and self-power systems.

• Preface xiiiPart I Solid Oxide Fuel Cell with Ionic Conducting Electrolyte 11 Introduction 3Bin Zhu and Peter D. Lund1.1 An Introduction to the Principles of Fuel Cells 31.2 Materials and Technologies 51.3 New Electrolyte Developments on LTSOFC 101.4 Beyond the State of the Art: The Electrolyte-Free Fuel Cell (EFFC) 201.4.1 Fundamental Issues 231.5 Beyond the SOFC 25References 282 Solid-State Electrolytes for SOFC 35Liangdong Fan2.1 Introduction 352.2 Single-Phase SOFC Electrolytes 372.2.1 Oxygen Ionic Conducting Electrolyte 372.2.1.1 Stabilized Zirconia 372.2.1.2 Doped Ceria 392.2.1.3 SrO- and MgO-Doped Lanthanum Gallates (LSGM) 422.2.2 Proton-Conducting Electrolyte and Mixed Ionic Conducting Electrolyte 422.2.3 Alternative New Electrolytes and Research Interests 442.3 Ion Conduction/Transportation in Electrolytes 492.4 Composite Electrolytes 522.4.1 Oxide–Oxide Electrolyte 522.4.2 Oxide–Carbonate Composite 532.4.2.1 Materials Fabrication 542.4.2.2 Performance and Stability Optimization 572.4.3 Other Oxide–Salt Composite Electrolytes 602.4.4 Ionic Conduction Mechanism Studies of Ceria–Carbonate Composite 622.5 NANOCOFC and Material Design Principle 662.6 Concluding Remarks 67Acknowledgments 69References 693 Cathodes for Solid Oxide Fuel Cell 79Tianmin He, Qingjun Zhou, and Fangjun Jin3.1 Introduction 793.2 Overview of Cathode Reaction Mechanism 803.3 Development of Cathode Materials 823.3.1 Perovskite Cathode Materials 823.3.1.1 Mn-Based Perovskite Cathodes 833.3.1.2 Co-Based Perovskite Cathodes 853.3.1.3 Fe-Based Perovskite Cathodes 883.3.1.4 Ni-Based Perovskite Cathodes 893.3.2 Double Perovskite Cathode Materials 893.4 Microstructure Optimization of Cathode Materials 943.4.1 Nanostructured Cathodes 943.4.2 Composite Cathodes 973.5 Summary 102References 1034 Anodes for Solid Oxide Fuel Cell 113Chunwen Sun4.1 Introduction 1134.2 Overview of Anode Reaction Mechanism 1144.2.1 Basic Operating Principles of a SOFC 1144.2.1.1 The Anode Three-Phase Boundary 1154.3 Development of Anode Materials 1174.3.1 Ni–YSZ Cermet Anode Materials 1174.3.2 Alternative Anode Materials 1184.3.2.1 Fluorite Anode Materials 1184.3.2.2 Perovskite Anode Materials 1204.3.3 Sulfur-Tolerant Anode Materials 1244.4 Development of Kinetics, Reaction Mechanism, and Model of the Anode 1264.5 Summary and Outlook 135Acknowledgments 137References 1375 Design and Development of SOFC Stacks 145Wanbing Guan5.1 Introduction 1455.2 Change of Cell Output Performance Under 2D Interface Contact 1455.2.1 Design of 2D Interface Contact Mode 1455.2.2 Variations of Cell Output Performance Under 2D Contact Mode 1475.2.3 2D Interface Structure Improvements and Enhancement of Cell Output Performance 1495.2.4 Contributions of 3D Contact in 2D Interface Contact 1515.2.5 Mechanism of Performance Enhancement After the Transition from 2D to 3D Interface 1535.3 Control Design of Transition from 2D to 3D Interface Contact and Their Quantitative Contribution Differentiation 1565.3.1 Control Design of 2D and 3D Interface Contact 1565.3.2 Quantitative Effects of 2D Contact on the Transient Output Performance of a Cell 1585.3.3 Quantitative Effects of 2D Contact on the Steady-State Output Performance of the Cell 1615.3.4 Quantitative Effects of 3D Contact on Cell Transient Performance 1635.3.5 Quantitative Effects of 3D Contact on the Steady-State Performance of a Cell 1665.3.6 Differences Between 2D and 3D Interface Contacts 1695.4 Conclusions 171References 172Part II Electrolyte-Free Fuel Cells: Materials, Technologies, and Working Principles 1736 Electrolyte-Free SOFCs: Materials, Technologies, and Working Principles 175Bin Zhu, Liangdong Fan, Jung-Sik Kim, and Peter D. Lund6.1 Concept of the Electrolyte-Free Fuel Cell 1756.2 SLFC Using the Ionic Conductor-based Electrolyte 1776.3 Developments on Advanced SLFC 1796.4 From SLFCs to Semiconductor–Ionic Fuel Cells (SIFCs) 1846.5 The SLFC Working Principle 1966.6 Remarks 204Acknowledgments 207References 2077 Ceria Fluorite Electrolytes from Ionic to Mixed Electronic and Ionic Membranes 213Baoyuan Wang, Liangdong Fan, Yanyan Liu, and Bin Zhu7.1 Introduction 2137.2 Doped Ceria as the Electrolyte for Intermediate Temperature SOFCs 2147.3 Surface Doping for Low Temperature SOFCs 2167.4 Non-doped Ceria for Advanced Low Temperature SOFCs 222References 2358 Charge Transfer in Oxide Solid Fuel Cells 239Jing Shi and Sining Yun8.1 Oxygen Diffusion in Perovskite Oxides 2398.1.1 Oxygen Vacancy Formation 2398.1.2 Oxygen Diffusion Mechanisms 2428.1.3 Anisotropy Oxygen Transport in Layered Perovskites 2448.1.3.1 Oxygen Transport in Ruddlesden–Popper (RP) Perovskites 2448.1.3.2 Oxygen Transport in A-Site Ordered Double Perovskites 2448.1.4 Oxygen Ion Diffusion at Grain Boundary 2468.1.5 Factors Controlling Oxygen Migration Barriers in Perovskites 2488.2 Proton Diffusion in Perovskite-Type Oxides 2498.2.1 Proton Diffusion Mechanisms 2498.2.2 Proton–Dopant Interaction 2538.2.2.1 Influence of Dopants in A-site 2538.2.2.2 Influence of Dopants in B-Site 2548.2.3 Long-range Proton Conduction Pathways in Perovskites 2558.2.4 Hydrogen-Induced Insulation 2568.3 Enhanced Ion Conductivity in Oxide Heterostructures 2598.3.1 Enhanced Ionic Conduction by Strain 2598.3.2 Enhanced Ionic Conductivity by Band Bending 2638.3.2.1 Surface State-induced Band Bending 2638.3.2.2 Band Bending in p–n Heterojunctions 2658.3.2.3 p–n Heterojunction Structures in SOFC 2658.4 Summary 266Acknowledgments 267References 2679 Material Development II: Natural Material-based Composites for Electrolyte Layer-free Fuel Cells 275Chen Xia and Yanyan Liu9.1 Introduction 2759.1.1 Materials Development for EFFCs 2759.1.2 Natural Materials as Potential Electrolytes 2769.2 Industrial-grade Rare Earth for EFFCs 2799.2.1 Rare-earth Oxide LCP 2809.2.2 Semiconducting–Ionic Composite Based on LCP 2819.2.2.1 LCP–LSCF 2829.2.2.2 LCP–ZnO 2849.2.3 Stability Operation and Schottky Junction of EFFC 2889.2.3.1 Performance Stability 2889.2.3.2 In Situ Schottky Junction Effect 2889.2.4 Summary 2909.3 Natural Hematite for EFFCs 2919.3.1 Natural Hematite 2929.3.2 Semiconducting–Ionic Composite Based on Hematite 2959.3.2.1 Hematite–LSCF 2959.3.2.2 Hematite/LCP–LSCF 2979.3.3 Summary 3009.4 Natural CuFe Oxide Minerals for EFFCs 3029.4.1 Natural CuFe2O4 Mineral for EFFC 3029.4.2 Natural Delafossite CuFeO2 for EFFC 3059.4.3 Summary 3089.5 Bio-derived Calcite for EFFC 3089.5.1 Bio-derived Calcite for EFFC 3099.5.2 Summary 312References 31410 Charge Transfer, Transportation, and Simulation 319Muhammad Afzal, Mustafa Anwar, Muhammad I. Asghar, Peter D. Lund, Naveed Jhamat, Rizwan Raza, and Bin Zhu10.1 Physical Aspects 31910.2 Electrochemical Aspects 32010.3 Ionic Conduction Enhancement in Heterostructure Composites 32110.4 Charge Transportation Mechanism and Coupling Effects 32610.5 Surface and Interfacial State-Induced Superionic Conduction and Transportation 33010.6 Ionic Transport Number Measurements 33110.7 Determination of Electron and Ionic Conductivities in EFFCs 33210.8 EIS Analysis 33410.9 Semiconductor Band Effects on the Ionic Conduction Device Performance 33510.10 Simulations 339Acknowledgments 343References 34311 Electrolyte-Free Fuel Cell: Principles and Crosslink Research 347Yan Wu, Liangdong Fan, Naveed Mushtaq, Bin Zhu, Muhammad Afzal, Muhammad Sajid, Rizwan Raza, Jung-Sik Kim, Wen-Feng Lin, and Peter D. Lund11.1 Introduction 34711.2 Fundamental Considerations of Fuel Cell Semiconductor Electrochemistry 35311.2.1 Physics and Electrochemistry at Interfaces 35311.2.2 Electrochemistry vs. Semiconductor Physics 35511.3 Working Principle of Semiconductor-Based Fuel Cells and Crossing Link Sciences 35611.4 Extending Applications by Coupling Devices 36711.5 Final Remarks 368Acknowledgments 372References 373Part III Fuel Cells: From Technology to Applications 37712 Scaling Up Materials and Technology for SLFC 379Kang Yuan, Zhigang Zhu, Muhammad Afzal, and Bin Zhu12.1 Single-Layer Fuel Cell (SLFC) Engineering Materials 37912.2 Scaling Up Single-Layer Fuel Cell Devices: Tape Casting and Hot Pressing 38312.3 Scaling Up Single-Layer Fuel Cell Devices: Thermal Spray Coating Technology 38612.3.1 Traditional Plasma Spray Coating Technology 38712.3.2 New Developed Low-Pressure Plasma Spray (LPPS) Coating Technology 38812.4 Short Stack 39512.4.1 SLFC Cells 39512.4.2 Bipolar Plate Design 39612.4.3 Sealing and Sealant-Free Short Stack 39612.5 Tests and Evaluations 39712.6 Durability Testing 39912.7 A Case Study for the Cell Degradation Mechanism 40012.8 Continuous Efforts and Future Developments 40412.9 Concluding Remarks 409References 41113 Planar SOFC Stack Design and Development 415Shaorong Wang, Yixiang Shi, Naveed Mushtaq, and Bin Zhu13.1 Internal Manifold and External Manifold 41513.2 Interface Between an Interconnect Plate and a Single Cell 41613.3 Antioxidation Coating of the Interconnect Plate 41813.4 Design the Flow Field of Interconnect Plate 41913.4.1 Mathematical Simulation 42013.4.2 Effect of Co-flow, Crossflow, and Counterflow 42213.4.3 Air Flow Distribution Between Layers in a Stack 42413.5 The Importance of Sealing 42413.5.1 Thermal Cycling of the Sealing 42813.5.2 Durability of Sealing 42813.6 The Life of the Stack: The Chemical Problems on the Interface 42913.7 Toward Market Products 43113.8 Concluding Remarks 443References 44314 Energy System Integration and Future Perspectives 447Ghazanfar Abbas, Muhammad Ali Babar, Fida Hussain, and Rizwan Raza14.1 Solar Cell and Fuel Cell 44714.2 Fuel Cell–Solar Cell Integration 45014.3 Solar Electrolysis–Fuel Cell Integration 45214.4 Fuel Cell–Biomass Integration 45314.5 The Fuel Cell System Modeling Using Biogas 45414.5.1 Activation Loss 45714.5.2 Ohmic Loss 45714.5.3 Concentration Voltage Loss 45814.6 The Fuel Cell System Efficiency (Heating and Electrical) 45814.6.1 The Effect of Different Temperatures on System Efficiency 45814.6.2 The Fuel Utilization Factor and Efficiencies of the System 45814.6.3 The System Efficiencies and Operating Pressure 46014.7 Integrated New Clean Energy System 46014.8 Summary 462References 462Index 465

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Bin Zhu, PhD, moved from KTH, Sweden as a Chief Scientist (Professor Director) of Energy Storage Joint Research Center, Southeast University, China. He has published more than 300 scientific papers in nano-composite ionic conductors and new semiconductor-ionic materials for advanced fuel cells.Rizwan Raza, PhD, is Assistant Professor in the Department of Physics in COMSATS Institute of Information Technology, Pakistan. He has published more than 100 scientific papers.Liangdong Fan, PhD, is Lecturer in the College of Chemistry and Environmental Engineering at Shenzhen University, China. His interests focus on novel nanocomposite functional materials for fuel cells and electro-catalysis.Chunwen Sun is a Professor at Beijing Institute of Nanoenergy and Nanosystems (BINN), Chinese Academy of Sciences (CAS). His research interests include energy storage and conversion, e.g., lithium/sodium-ion batteries, metal-air batteries, all-solid-state batteries, fuel cells and self-power systems.

• Preface xiiiPart I Solid Oxide Fuel Cell with Ionic Conducting Electrolyte 11 Introduction 3Bin Zhu and Peter D. Lund1.1 An Introduction to the Principles of Fuel Cells 31.2 Materials and Technologies 51.3 New Electrolyte Developments on LTSOFC 101.4 Beyond the State of the Art: The Electrolyte-Free Fuel Cell (EFFC) 201.4.1 Fundamental Issues 231.5 Beyond the SOFC 25References 282 Solid-State Electrolytes for SOFC 35Liangdong Fan2.1 Introduction 352.2 Single-Phase SOFC Electrolytes 372.2.1 Oxygen Ionic Conducting Electrolyte 372.2.1.1 Stabilized Zirconia 372.2.1.2 Doped Ceria 392.2.1.3 SrO- and MgO-Doped Lanthanum Gallates (LSGM) 422.2.2 Proton-Conducting Electrolyte and Mixed Ionic Conducting Electrolyte 422.2.3 Alternative New Electrolytes and Research Interests 442.3 Ion Conduction/Transportation in Electrolytes 492.4 Composite Electrolytes 522.4.1 Oxide–Oxide Electrolyte 522.4.2 Oxide–Carbonate Composite 532.4.2.1 Materials Fabrication 542.4.2.2 Performance and Stability Optimization 572.4.3 Other Oxide–Salt Composite Electrolytes 602.4.4 Ionic Conduction Mechanism Studies of Ceria–Carbonate Composite 622.5 NANOCOFC and Material Design Principle 662.6 Concluding Remarks 67Acknowledgments 69References 693 Cathodes for Solid Oxide Fuel Cell 79Tianmin He, Qingjun Zhou, and Fangjun Jin3.1 Introduction 793.2 Overview of Cathode Reaction Mechanism 803.3 Development of Cathode Materials 823.3.1 Perovskite Cathode Materials 823.3.1.1 Mn-Based Perovskite Cathodes 833.3.1.2 Co-Based Perovskite Cathodes 853.3.1.3 Fe-Based Perovskite Cathodes 883.3.1.4 Ni-Based Perovskite Cathodes 893.3.2 Double Perovskite Cathode Materials 893.4 Microstructure Optimization of Cathode Materials 943.4.1 Nanostructured Cathodes 943.4.2 Composite Cathodes 973.5 Summary 102References 1034 Anodes for Solid Oxide Fuel Cell 113Chunwen Sun4.1 Introduction 1134.2 Overview of Anode Reaction Mechanism 1144.2.1 Basic Operating Principles of a SOFC 1144.2.1.1 The Anode Three-Phase Boundary 1154.3 Development of Anode Materials 1174.3.1 Ni–YSZ Cermet Anode Materials 1174.3.2 Alternative Anode Materials 1184.3.2.1 Fluorite Anode Materials 1184.3.2.2 Perovskite Anode Materials 1204.3.3 Sulfur-Tolerant Anode Materials 1244.4 Development of Kinetics, Reaction Mechanism, and Model of the Anode 1264.5 Summary and Outlook 135Acknowledgments 137References 1375 Design and Development of SOFC Stacks 145Wanbing Guan5.1 Introduction 1455.2 Change of Cell Output Performance Under 2D Interface Contact 1455.2.1 Design of 2D Interface Contact Mode 1455.2.2 Variations of Cell Output Performance Under 2D Contact Mode 1475.2.3 2D Interface Structure Improvements and Enhancement of Cell Output Performance 1495.2.4 Contributions of 3D Contact in 2D Interface Contact 1515.2.5 Mechanism of Performance Enhancement After the Transition from 2D to 3D Interface 1535.3 Control Design of Transition from 2D to 3D Interface Contact and Their Quantitative Contribution Differentiation 1565.3.1 Control Design of 2D and 3D Interface Contact 1565.3.2 Quantitative Effects of 2D Contact on the Transient Output Performance of a Cell 1585.3.3 Quantitative Effects of 2D Contact on the Steady-State Output Performance of the Cell 1615.3.4 Quantitative Effects of 3D Contact on Cell Transient Performance 1635.3.5 Quantitative Effects of 3D Contact on the Steady-State Performance of a Cell 1665.3.6 Differences Between 2D and 3D Interface Contacts 1695.4 Conclusions 171References 172Part II Electrolyte-Free Fuel Cells: Materials, Technologies, and Working Principles 1736 Electrolyte-Free SOFCs: Materials, Technologies, and Working Principles 175Bin Zhu, Liangdong Fan, Jung-Sik Kim, and Peter D. Lund6.1 Concept of the Electrolyte-Free Fuel Cell 1756.2 SLFC Using the Ionic Conductor-based Electrolyte 1776.3 Developments on Advanced SLFC 1796.4 From SLFCs to Semiconductor–Ionic Fuel Cells (SIFCs) 1846.5 The SLFC Working Principle 1966.6 Remarks 204Acknowledgments 207References 2077 Ceria Fluorite Electrolytes from Ionic to Mixed Electronic and Ionic Membranes 213Baoyuan Wang, Liangdong Fan, Yanyan Liu, and Bin Zhu7.1 Introduction 2137.2 Doped Ceria as the Electrolyte for Intermediate Temperature SOFCs 2147.3 Surface Doping for Low Temperature SOFCs 2167.4 Non-doped Ceria for Advanced Low Temperature SOFCs 222References 2358 Charge Transfer in Oxide Solid Fuel Cells 239Jing Shi and Sining Yun8.1 Oxygen Diffusion in Perovskite Oxides 2398.1.1 Oxygen Vacancy Formation 2398.1.2 Oxygen Diffusion Mechanisms 2428.1.3 Anisotropy Oxygen Transport in Layered Perovskites 2448.1.3.1 Oxygen Transport in Ruddlesden–Popper (RP) Perovskites 2448.1.3.2 Oxygen Transport in A-Site Ordered Double Perovskites 2448.1.4 Oxygen Ion Diffusion at Grain Boundary 2468.1.5 Factors Controlling Oxygen Migration Barriers in Perovskites 2488.2 Proton Diffusion in Perovskite-Type Oxides 2498.2.1 Proton Diffusion Mechanisms 2498.2.2 Proton–Dopant Interaction 2538.2.2.1 Influence of Dopants in A-site 2538.2.2.2 Influence of Dopants in B-Site 2548.2.3 Long-range Proton Conduction Pathways in Perovskites 2558.2.4 Hydrogen-Induced Insulation 2568.3 Enhanced Ion Conductivity in Oxide Heterostructures 2598.3.1 Enhanced Ionic Conduction by Strain 2598.3.2 Enhanced Ionic Conductivity by Band Bending 2638.3.2.1 Surface State-induced Band Bending 2638.3.2.2 Band Bending in p–n Heterojunctions 2658.3.2.3 p–n Heterojunction Structures in SOFC 2658.4 Summary 266Acknowledgments 267References 2679 Material Development II: Natural Material-based Composites for Electrolyte Layer-free Fuel Cells 275Chen Xia and Yanyan Liu9.1 Introduction 2759.1.1 Materials Development for EFFCs 2759.1.2 Natural Materials as Potential Electrolytes 2769.2 Industrial-grade Rare Earth for EFFCs 2799.2.1 Rare-earth Oxide LCP 2809.2.2 Semiconducting–Ionic Composite Based on LCP 2819.2.2.1 LCP–LSCF 2829.2.2.2 LCP–ZnO 2849.2.3 Stability Operation and Schottky Junction of EFFC 2889.2.3.1 Performance Stability 2889.2.3.2 In Situ Schottky Junction Effect 2889.2.4 Summary 2909.3 Natural Hematite for EFFCs 2919.3.1 Natural Hematite 2929.3.2 Semiconducting–Ionic Composite Based on Hematite 2959.3.2.1 Hematite–LSCF 2959.3.2.2 Hematite/LCP–LSCF 2979.3.3 Summary 3009.4 Natural CuFe Oxide Minerals for EFFCs 3029.4.1 Natural CuFe2O4 Mineral for EFFC 3029.4.2 Natural Delafossite CuFeO2 for EFFC 3059.4.3 Summary 3089.5 Bio-derived Calcite for EFFC 3089.5.1 Bio-derived Calcite for EFFC 3099.5.2 Summary 312References 31410 Charge Transfer, Transportation, and Simulation 319Muhammad Afzal, Mustafa Anwar, Muhammad I. Asghar, Peter D. Lund, Naveed Jhamat, Rizwan Raza, and Bin Zhu10.1 Physical Aspects 31910.2 Electrochemical Aspects 32010.3 Ionic Conduction Enhancement in Heterostructure Composites 32110.4 Charge Transportation Mechanism and Coupling Effects 32610.5 Surface and Interfacial State-Induced Superionic Conduction and Transportation 33010.6 Ionic Transport Number Measurements 33110.7 Determination of Electron and Ionic Conductivities in EFFCs 33210.8 EIS Analysis 33410.9 Semiconductor Band Effects on the Ionic Conduction Device Performance 33510.10 Simulations 339Acknowledgments 343References 34311 Electrolyte-Free Fuel Cell: Principles and Crosslink Research 347Yan Wu, Liangdong Fan, Naveed Mushtaq, Bin Zhu, Muhammad Afzal, Muhammad Sajid, Rizwan Raza, Jung-Sik Kim, Wen-Feng Lin, and Peter D. Lund11.1 Introduction 34711.2 Fundamental Considerations of Fuel Cell Semiconductor Electrochemistry 35311.2.1 Physics and Electrochemistry at Interfaces 35311.2.2 Electrochemistry vs. Semiconductor Physics 35511.3 Working Principle of Semiconductor-Based Fuel Cells and Crossing Link Sciences 35611.4 Extending Applications by Coupling Devices 36711.5 Final Remarks 368Acknowledgments 372References 373Part III Fuel Cells: From Technology to Applications 37712 Scaling Up Materials and Technology for SLFC 379Kang Yuan, Zhigang Zhu, Muhammad Afzal, and Bin Zhu12.1 Single-Layer Fuel Cell (SLFC) Engineering Materials 37912.2 Scaling Up Single-Layer Fuel Cell Devices: Tape Casting and Hot Pressing 38312.3 Scaling Up Single-Layer Fuel Cell Devices: Thermal Spray Coating Technology 38612.3.1 Traditional Plasma Spray Coating Technology 38712.3.2 New Developed Low-Pressure Plasma Spray (LPPS) Coating Technology 38812.4 Short Stack 39512.4.1 SLFC Cells 39512.4.2 Bipolar Plate Design 39612.4.3 Sealing and Sealant-Free Short Stack 39612.5 Tests and Evaluations 39712.6 Durability Testing 39912.7 A Case Study for the Cell Degradation Mechanism 40012.8 Continuous Efforts and Future Developments 40412.9 Concluding Remarks 409References 41113 Planar SOFC Stack Design and Development 415Shaorong Wang, Yixiang Shi, Naveed Mushtaq, and Bin Zhu13.1 Internal Manifold and External Manifold 41513.2 Interface Between an Interconnect Plate and a Single Cell 41613.3 Antioxidation Coating of the Interconnect Plate 41813.4 Design the Flow Field of Interconnect Plate 41913.4.1 Mathematical Simulation 42013.4.2 Effect of Co-flow, Crossflow, and Counterflow 42213.4.3 Air Flow Distribution Between Layers in a Stack 42413.5 The Importance of Sealing 42413.5.1 Thermal Cycling of the Sealing 42813.5.2 Durability of Sealing 42813.6 The Life of the Stack: The Chemical Problems on the Interface 42913.7 Toward Market Products 43113.8 Concluding Remarks 443References 44314 Energy System Integration and Future Perspectives 447Ghazanfar Abbas, Muhammad Ali Babar, Fida Hussain, and Rizwan Raza14.1 Solar Cell and Fuel Cell 44714.2 Fuel Cell–Solar Cell Integration 45014.3 Solar Electrolysis–Fuel Cell Integration 45214.4 Fuel Cell–Biomass Integration 45314.5 The Fuel Cell System Modeling Using Biogas 45414.5.1 Activation Loss 45714.5.2 Ohmic Loss 45714.5.3 Concentration Voltage Loss 45814.6 The Fuel Cell System Efficiency (Heating and Electrical) 45814.6.1 The Effect of Different Temperatures on System Efficiency 45814.6.2 The Fuel Utilization Factor and Efficiencies of the System 45814.6.3 The System Efficiencies and Operating Pressure 46014.7 Integrated New Clean Energy System 46014.8 Summary 462References 462Index 465

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Bin Zhu, PhD, moved from KTH, Sweden as a Chief Scientist (Professor Director) of Energy Storage Joint Research Center, Southeast University, China. He has published more than 300 scientific papers in nano-composite ionic conductors and new semiconductor-ionic materials for advanced fuel cells.Rizwan Raza, PhD, is Assistant Professor in the Department of Physics in COMSATS Institute of Information Technology, Pakistan. He has published more than 100 scientific papers.Liangdong Fan, PhD, is Lecturer in the College of Chemistry and Environmental Engineering at Shenzhen University, China. His interests focus on novel nanocomposite functional materials for fuel cells and electro-catalysis.Chunwen Sun is a Professor at Beijing Institute of Nanoenergy and Nanosystems (BINN), Chinese Academy of Sciences (CAS). His research interests include energy storage and conversion, e.g., lithium/sodium-ion batteries, metal-air batteries, all-solid-state batteries, fuel cells and self-power systems.

• Preface xiiiPart I Solid Oxide Fuel Cell with Ionic Conducting Electrolyte 11 Introduction 3Bin Zhu and Peter D. Lund1.1 An Introduction to the Principles of Fuel Cells 31.2 Materials and Technologies 51.3 New Electrolyte Developments on LTSOFC 101.4 Beyond the State of the Art: The Electrolyte-Free Fuel Cell (EFFC) 201.4.1 Fundamental Issues 231.5 Beyond the SOFC 25References 282 Solid-State Electrolytes for SOFC 35Liangdong Fan2.1 Introduction 352.2 Single-Phase SOFC Electrolytes 372.2.1 Oxygen Ionic Conducting Electrolyte 372.2.1.1 Stabilized Zirconia 372.2.1.2 Doped Ceria 392.2.1.3 SrO- and MgO-Doped Lanthanum Gallates (LSGM) 422.2.2 Proton-Conducting Electrolyte and Mixed Ionic Conducting Electrolyte 422.2.3 Alternative New Electrolytes and Research Interests 442.3 Ion Conduction/Transportation in Electrolytes 492.4 Composite Electrolytes 522.4.1 Oxide–Oxide Electrolyte 522.4.2 Oxide–Carbonate Composite 532.4.2.1 Materials Fabrication 542.4.2.2 Performance and Stability Optimization 572.4.3 Other Oxide–Salt Composite Electrolytes 602.4.4 Ionic Conduction Mechanism Studies of Ceria–Carbonate Composite 622.5 NANOCOFC and Material Design Principle 662.6 Concluding Remarks 67Acknowledgments 69References 693 Cathodes for Solid Oxide Fuel Cell 79Tianmin He, Qingjun Zhou, and Fangjun Jin3.1 Introduction 793.2 Overview of Cathode Reaction Mechanism 803.3 Development of Cathode Materials 823.3.1 Perovskite Cathode Materials 823.3.1.1 Mn-Based Perovskite Cathodes 833.3.1.2 Co-Based Perovskite Cathodes 853.3.1.3 Fe-Based Perovskite Cathodes 883.3.1.4 Ni-Based Perovskite Cathodes 893.3.2 Double Perovskite Cathode Materials 893.4 Microstructure Optimization of Cathode Materials 943.4.1 Nanostructured Cathodes 943.4.2 Composite Cathodes 973.5 Summary 102References 1034 Anodes for Solid Oxide Fuel Cell 113Chunwen Sun4.1 Introduction 1134.2 Overview of Anode Reaction Mechanism 1144.2.1 Basic Operating Principles of a SOFC 1144.2.1.1 The Anode Three-Phase Boundary 1154.3 Development of Anode Materials 1174.3.1 Ni–YSZ Cermet Anode Materials 1174.3.2 Alternative Anode Materials 1184.3.2.1 Fluorite Anode Materials 1184.3.2.2 Perovskite Anode Materials 1204.3.3 Sulfur-Tolerant Anode Materials 1244.4 Development of Kinetics, Reaction Mechanism, and Model of the Anode 1264.5 Summary and Outlook 135Acknowledgments 137References 1375 Design and Development of SOFC Stacks 145Wanbing Guan5.1 Introduction 1455.2 Change of Cell Output Performance Under 2D Interface Contact 1455.2.1 Design of 2D Interface Contact Mode 1455.2.2 Variations of Cell Output Performance Under 2D Contact Mode 1475.2.3 2D Interface Structure Improvements and Enhancement of Cell Output Performance 1495.2.4 Contributions of 3D Contact in 2D Interface Contact 1515.2.5 Mechanism of Performance Enhancement After the Transition from 2D to 3D Interface 1535.3 Control Design of Transition from 2D to 3D Interface Contact and Their Quantitative Contribution Differentiation 1565.3.1 Control Design of 2D and 3D Interface Contact 1565.3.2 Quantitative Effects of 2D Contact on the Transient Output Performance of a Cell 1585.3.3 Quantitative Effects of 2D Contact on the Steady-State Output Performance of the Cell 1615.3.4 Quantitative Effects of 3D Contact on Cell Transient Performance 1635.3.5 Quantitative Effects of 3D Contact on the Steady-State Performance of a Cell 1665.3.6 Differences Between 2D and 3D Interface Contacts 1695.4 Conclusions 171References 172Part II Electrolyte-Free Fuel Cells: Materials, Technologies, and Working Principles 1736 Electrolyte-Free SOFCs: Materials, Technologies, and Working Principles 175Bin Zhu, Liangdong Fan, Jung-Sik Kim, and Peter D. Lund6.1 Concept of the Electrolyte-Free Fuel Cell 1756.2 SLFC Using the Ionic Conductor-based Electrolyte 1776.3 Developments on Advanced SLFC 1796.4 From SLFCs to Semiconductor–Ionic Fuel Cells (SIFCs) 1846.5 The SLFC Working Principle 1966.6 Remarks 204Acknowledgments 207References 2077 Ceria Fluorite Electrolytes from Ionic to Mixed Electronic and Ionic Membranes 213Baoyuan Wang, Liangdong Fan, Yanyan Liu, and Bin Zhu7.1 Introduction 2137.2 Doped Ceria as the Electrolyte for Intermediate Temperature SOFCs 2147.3 Surface Doping for Low Temperature SOFCs 2167.4 Non-doped Ceria for Advanced Low Temperature SOFCs 222References 2358 Charge Transfer in Oxide Solid Fuel Cells 239Jing Shi and Sining Yun8.1 Oxygen Diffusion in Perovskite Oxides 2398.1.1 Oxygen Vacancy Formation 2398.1.2 Oxygen Diffusion Mechanisms 2428.1.3 Anisotropy Oxygen Transport in Layered Perovskites 2448.1.3.1 Oxygen Transport in Ruddlesden–Popper (RP) Perovskites 2448.1.3.2 Oxygen Transport in A-Site Ordered Double Perovskites 2448.1.4 Oxygen Ion Diffusion at Grain Boundary 2468.1.5 Factors Controlling Oxygen Migration Barriers in Perovskites 2488.2 Proton Diffusion in Perovskite-Type Oxides 2498.2.1 Proton Diffusion Mechanisms 2498.2.2 Proton–Dopant Interaction 2538.2.2.1 Influence of Dopants in A-site 2538.2.2.2 Influence of Dopants in B-Site 2548.2.3 Long-range Proton Conduction Pathways in Perovskites 2558.2.4 Hydrogen-Induced Insulation 2568.3 Enhanced Ion Conductivity in Oxide Heterostructures 2598.3.1 Enhanced Ionic Conduction by Strain 2598.3.2 Enhanced Ionic Conductivity by Band Bending 2638.3.2.1 Surface State-induced Band Bending 2638.3.2.2 Band Bending in p–n Heterojunctions 2658.3.2.3 p–n Heterojunction Structures in SOFC 2658.4 Summary 266Acknowledgments 267References 2679 Material Development II: Natural Material-based Composites for Electrolyte Layer-free Fuel Cells 275Chen Xia and Yanyan Liu9.1 Introduction 2759.1.1 Materials Development for EFFCs 2759.1.2 Natural Materials as Potential Electrolytes 2769.2 Industrial-grade Rare Earth for EFFCs 2799.2.1 Rare-earth Oxide LCP 2809.2.2 Semiconducting–Ionic Composite Based on LCP 2819.2.2.1 LCP–LSCF 2829.2.2.2 LCP–ZnO 2849.2.3 Stability Operation and Schottky Junction of EFFC 2889.2.3.1 Performance Stability 2889.2.3.2 In Situ Schottky Junction Effect 2889.2.4 Summary 2909.3 Natural Hematite for EFFCs 2919.3.1 Natural Hematite 2929.3.2 Semiconducting–Ionic Composite Based on Hematite 2959.3.2.1 Hematite–LSCF 2959.3.2.2 Hematite/LCP–LSCF 2979.3.3 Summary 3009.4 Natural CuFe Oxide Minerals for EFFCs 3029.4.1 Natural CuFe2O4 Mineral for EFFC 3029.4.2 Natural Delafossite CuFeO2 for EFFC 3059.4.3 Summary 3089.5 Bio-derived Calcite for EFFC 3089.5.1 Bio-derived Calcite for EFFC 3099.5.2 Summary 312References 31410 Charge Transfer, Transportation, and Simulation 319Muhammad Afzal, Mustafa Anwar, Muhammad I. Asghar, Peter D. Lund, Naveed Jhamat, Rizwan Raza, and Bin Zhu10.1 Physical Aspects 31910.2 Electrochemical Aspects 32010.3 Ionic Conduction Enhancement in Heterostructure Composites 32110.4 Charge Transportation Mechanism and Coupling Effects 32610.5 Surface and Interfacial State-Induced Superionic Conduction and Transportation 33010.6 Ionic Transport Number Measurements 33110.7 Determination of Electron and Ionic Conductivities in EFFCs 33210.8 EIS Analysis 33410.9 Semiconductor Band Effects on the Ionic Conduction Device Performance 33510.10 Simulations 339Acknowledgments 343References 34311 Electrolyte-Free Fuel Cell: Principles and Crosslink Research 347Yan Wu, Liangdong Fan, Naveed Mushtaq, Bin Zhu, Muhammad Afzal, Muhammad Sajid, Rizwan Raza, Jung-Sik Kim, Wen-Feng Lin, and Peter D. Lund11.1 Introduction 34711.2 Fundamental Considerations of Fuel Cell Semiconductor Electrochemistry 35311.2.1 Physics and Electrochemistry at Interfaces 35311.2.2 Electrochemistry vs. Semiconductor Physics 35511.3 Working Principle of Semiconductor-Based Fuel Cells and Crossing Link Sciences 35611.4 Extending Applications by Coupling Devices 36711.5 Final Remarks 368Acknowledgments 372References 373Part III Fuel Cells: From Technology to Applications 37712 Scaling Up Materials and Technology for SLFC 379Kang Yuan, Zhigang Zhu, Muhammad Afzal, and Bin Zhu12.1 Single-Layer Fuel Cell (SLFC) Engineering Materials 37912.2 Scaling Up Single-Layer Fuel Cell Devices: Tape Casting and Hot Pressing 38312.3 Scaling Up Single-Layer Fuel Cell Devices: Thermal Spray Coating Technology 38612.3.1 Traditional Plasma Spray Coating Technology 38712.3.2 New Developed Low-Pressure Plasma Spray (LPPS) Coating Technology 38812.4 Short Stack 39512.4.1 SLFC Cells 39512.4.2 Bipolar Plate Design 39612.4.3 Sealing and Sealant-Free Short Stack 39612.5 Tests and Evaluations 39712.6 Durability Testing 39912.7 A Case Study for the Cell Degradation Mechanism 40012.8 Continuous Efforts and Future Developments 40412.9 Concluding Remarks 409References 41113 Planar SOFC Stack Design and Development 415Shaorong Wang, Yixiang Shi, Naveed Mushtaq, and Bin Zhu13.1 Internal Manifold and External Manifold 41513.2 Interface Between an Interconnect Plate and a Single Cell 41613.3 Antioxidation Coating of the Interconnect Plate 41813.4 Design the Flow Field of Interconnect Plate 41913.4.1 Mathematical Simulation 42013.4.2 Effect of Co-flow, Crossflow, and Counterflow 42213.4.3 Air Flow Distribution Between Layers in a Stack 42413.5 The Importance of Sealing 42413.5.1 Thermal Cycling of the Sealing 42813.5.2 Durability of Sealing 42813.6 The Life of the Stack: The Chemical Problems on the Interface 42913.7 Toward Market Products 43113.8 Concluding Remarks 443References 44314 Energy System Integration and Future Perspectives 447Ghazanfar Abbas, Muhammad Ali Babar, Fida Hussain, and Rizwan Raza14.1 Solar Cell and Fuel Cell 44714.2 Fuel Cell–Solar Cell Integration 45014.3 Solar Electrolysis–Fuel Cell Integration 45214.4 Fuel Cell–Biomass Integration 45314.5 The Fuel Cell System Modeling Using Biogas 45414.5.1 Activation Loss 45714.5.2 Ohmic Loss 45714.5.3 Concentration Voltage Loss 45814.6 The Fuel Cell System Efficiency (Heating and Electrical) 45814.6.1 The Effect of Different Temperatures on System Efficiency 45814.6.2 The Fuel Utilization Factor and Efficiencies of the System 45814.6.3 The System Efficiencies and Operating Pressure 46014.7 Integrated New Clean Energy System 46014.8 Summary 462References 462Index 465

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