The CRC handbook of solid state electrochemistry

목차 (Table of Contents)

• CONTENTS
• Chapter 1. INTRODUCTION / Henny J. M. Bouwmeester ; Paul J. Gellings = 1
• Ⅰ. Introduction = 1
• Ⅱ. General Scope = 1
• Ⅲ. Elementary Defect Chemistry = 2
• A. Types of Defects = 2
• B. Defect Notation = 5
• C. Defect Eauilibria = 5
• Ⅳ. Elementary Considerations of the Kinetics of Electrode Reactions = 6
• References = 8
• Chapter 2. PRINCIPLES OF ELECTROCHEMISTRY / Heinz Gerischer = 9
• Ⅰ. The Subject of Electrochemistry = 10
• Ⅱ. Faraday's Law and Electrolytic Conductivity = 10
• Ⅲ. The Galvanic Cell at Thermodynamic Equilibrium = 11
• Ⅳ. Electrostatic Potentials : Galvani Potential, Volta Potential, Surface Potential = 13
• Ⅴ. Electrochemical Equilibrium at Interfaces = 16
• Ⅵ. Standard Potentials and Electromotive Series = 19
• A. Reference Electrodes = 19
• B. Electromotive Series = 21
• Ⅶ. The Electric Double Layer at Interfaces = 24
• A. Metal／Electrolyte Interfaces = 24
• B. Semiconductor／Electrolyte Interfaces = 30
• C. Membrane／Electrolyte Interfaces = 34
• Ⅷ. Kinetics of Electron Transfer Reactions at Interfaces = 35
• A. General Concepts of Electron Transfer = 36
• B. Electron Transfer at Metal Electrodes = 40
• C. Electron Transfer at Semiconductor Electrodes = 45
• Ⅸ. Kinetics of Ion Transfer Reactions at Interfaces = 50
• A. Liquid Metals = 50
• B. Solid Metals = 53
• C. Semiconductors = 57
• Ⅹ. Techniques for the Investigation of Electrode Reaction Kinetics = 60
• A. Current and Potential Step = 60
• B. Impedance Spectroscopy = 63
• XI. Mechanisms of Electrode Reactions and Electrocatalysis = 66
• A. Hydrogen Electrode = 67
• B. Oxygen Electrode = 70
• C. General Remarks = 71
• Acknowledgment = 72
• References = 72
• Chapter 3. SOLID STATE BACKGROUND / Isaac Abrahams ; Peter G. Bruce = 75
• Ⅰ. Introduction = 76
• Ⅱ. The Solid State = 76
• A. Amorphous Solids = 76
• 1. Glasses = 76
• B. Crystalline Solids = 79
• 1. Molecular Solids = 79
• 2. Nonmolecular Solids = 81
• a. Metallic Solids = 81
• b. Covalent Solids = 81
• c. Ionic Solids = 81
• Ⅲ. Lattice Energy = 83
• Ⅳ. The Crystal Lattice and Unit Cells = 87
• Ⅴ. Close Packing = 88
• A. Interstitial Sites = 91
• B. Polyhedral Representations of Close Packing = 92
• C. Structures Based on Close Packing = 94
• 1. Structures Based on hcp = 94
• a. NiAs = 94
• b. ZnS （Wurtzite） = 95
• 2. Structures Based on ccp = 96
• a. NaCI （Rock Salt） = 96
• b. CaF₂ （Fluorite） = 97
• c. ZnS （Zinc Blende or Sphalerite） = 98
• 3. Layered Structures Based on Close Packing = 98
• a. CdCl₂ and CdI₂ = 98
• b. CrCl₃ and BiI₃ = 100
• 4. Other Important Structures = 100
• a. TiO₂ （Rutile） = 100
• b. α­Al₂O₃（Corundum） = 100
• c. ReO₃ = 100
• d. CaTiO₃ （Perovskite） = 101
• e. MgAl₂P₄ （Spinel） = 101
• Ⅵ. Crystal Defects = 102
• A. Energetics of Defect Formation = 103
• B. Classification of Crystal Defects = 104
• 1. Lattice Vacancies／Interstitials = 105
• a. Intrinsic Defects = 105
• b. Extrinsic Defects = 107
• 2. Defect Clusters = 108
• 3. Dislocations = 109
• 4. Stacking Faults = 110
• 5. Grain Boundaries = 111
• C. Movement of Defects = 112
• Ⅶ. Solid Solutions = 114
• A. Substitutional Solid Solutions = 114
• B. Interstitial／Vacancy Solid Solutions = 114
• 1. Cation Vacancies = 115
• 2. Cation Interstitials = 115
• 3. Anion Vacancies = 115
• 4. Anion Interstitials = 116
• C. Monitoring of Solid Solution Formation = 116
• References = 118
• Chapter 4. INTERFACE ELECTRICAL PHENOMENA IN IONIC SOLIDS / Janusz Nowotny = 121
• List of Symbols and Abbreviations = 122
• Abstract = 123
• Ⅰ. Introduction = 124
• Ⅱ. Definition of Terms = 125
• A. Interface = 125
• 1. Interphase and Interface = 125
• 2. Surface = 125
• 3. Adsorption Layer = 125
• 4. Interface Layer = 125
• 5. Near­Surface Layer = 126
• 6. Surface Layer = 126
• 7. Space Charge Layer = 126
• 8. Boundary Layer = 126
• 9. Grain Boundary = 126
• 10. Grain Boundary Layer = 127
• 11. Structural Deformation Layer （Bidimensional Interface Structure） = 127
• B. Segregation = 127
• C. Defect Structure = 127
• Ⅲ. Basic Electrical Methods and Procedures in Studies of Ionic Solids at Elevated Temperatures = 128
• A. Work Function = 128
• B. Thermopower = 132
• C. Electrical Conductivity = 134
• D. The Jonker Analysis = 137
• E. Conclusions = 138
• Ⅳ. Electrical Effects at the Metal Oxide／Oxygen Interface = 139
• A. Physical Adsorption = 139
• B. lonosorption = 139
• C. Incorporation of Oxygen into the Boundary Layer = 140
• D. Bulk Equilibration Kinetics = 142
• E. Conclusions = 145
• Ⅴ. Segregation = 145
• A. Effect of Segregation on Interface Composition = 145
• 1. Segregation of Foreign Elements = 145
• 2. Segregation of Host Elements = 149
• 3. Polycrystals vs. Single Crystals = 150
• B. Segregation­Induced Bidimensional Interface Structures = 150
• C. Effect of Impurities on the Surface State in Equilibrium = 151
• D. Conclusions = 152
• Ⅵ. Effect of Interfaces on Transport = 153
• A. Transport along Interfaces = 153
• B. Transport across Interfaces = 153
• C. Conclusions = 154
• Ⅶ. Applied Aspects = 155
• Ⅷ. Future Prospects = 157
• A. Interface Properties = 157
• B. Engineering of Interfaces = 157
• Ⅸ. Summary and Final Conclusions = 157
• Acknowledgments = 157
• References = 158
• Chapter5 DEFECT CHEMISTRY IN SOLID STATE ELECTROCHEMISTRY / Joop Schoonman = 161
• Ⅰ. Introduction = 161
• Ⅱ. Defect Chemistry of Binary and Ternary Compounds = 163
• A. Defects and Nonstoichiometry in Binary Compounds = 163
• 1. Metal Halides = 165
• 2. Transition Metal Oxides = 169
• B. Generalized Approach to the Defect Chemistry of Ternary Compounds = 172
• 1. Variation of Defect Concentrations with $$a_0$$ and $$P_X₂$$ = 173
• 2. Composition and Defect Chemistry = 175
• 3. Defect Diagrams = 178
• 4. Application to Several Ternary Compounds = 180
• C. Multinary Compounds = 184
• D. Multicomponent Materials = 187
• Ⅲ. Concluding Remarks = 189
• References = 190
• Chapter 6 SURVEY OF TYPES OF SOLID ELECTROLYTES / Tetsuichi Kudo = 195
• Ⅰ. Introduction = 195
• Ⅱ. Oxide Ion Conductors = 195
• Ⅲ. Fluoride Ion Conductors = 199
• Ⅳ. Silver and Copper Ion Conductors = 201
• Ⅴ. Sodium and Potassium Ion Conductors = 203
• Ⅵ. Lithium Ion Conductors = 207
• Ⅶ. Proton Conductors = 213
• Ⅷ. Polymer Solid Electrolytes = 217
• References = 219
• Chapter 7 = 223
• Chapter 8 ELECTRODICS / Ilan Riess ; Joop Schoonman = 269
• List of Symbols = 270
• Abstract = 271
• Ⅰ. Introduction = 271
• Ⅱ. Electrodes = 273
• A. Current­Carrying Electrodes = 273
• 1. Cathodes in Solid Oxide Fuel Cells = 273
• 2. Anodes in SOFCs = 275
• 3. Insertion Electrodes = 276
• 4. Solid／Solid Interfaces at Electrodes = 276
• 5. Reversible Electrodes = 277
• 6. Ion­Blocking Electrodes = 277
• 7. Electron­Blocking Electrodes = 277
• 8. Reference Electrodes = 279
• 9. Electrodes as Catalysts = 279
• 10. Using Differences in Catalytic Properties of Electrodes to Drive Fuel Cells = 280
• B. Voltage Probes = 280
• 1. General = 280
• 2. Probes for Measuring △$$\tilde \mu$$_e = 281
• 3. Probes for Measuring △$$\tilde \mu$$_i = 281
• 4. Use of MIECs as Intermediate Contacts = 282
• Ⅲ. Grain Boundaries = 282
• A. Introduction, Single Crystals = 282
• B. Single­Phase Polycrystalline Materials = 283
• C. Two­Phase Materials = 283
• D. Effect of Electric Fields Applied Perpendicular to the Grain Boundary = 284
• Ⅳ. Experimental Methods for Characterizing Electrodes and Grain Boundaries = 284
• A. General = 284
• B. Direct Measurement of the Electrode Overpotential = 285
• 1. General = 285
• 2. Four­Point Method = 285
• 3. Current Interruption Method = 286
• 4. Use of High dc Voltages = 286
• 5. Overpotential at Ion­Blocking Electrodes = 287
• 6. Overpotential at Electron­Blocking Electrodes = 288
• 7. Overpotential at Nonblocking Electrodes = 288
• C. ac Impedance Measurements = 288
• D. Ⅰ­Ⅴ Relations = 291
• E. Diffusion in Intercalation Electrodes = 292
• F. Determining the Grain Boundary Properties = 293
• Ⅴ. Summary = 293
• Acknowledgment = 293
• References = 293
• Chapter 9 PRINCIPLES OF MAIN EXPERIMENTAL METHODS / Werner Weppner = 295
• Ⅰ. Introduction = 295
• Ⅱ. Fundamental Aspects = 296
• A. Formation of Galvanic Cell Voltages = 296
• B. Galvanic Cell Currents = 297
• Ⅲ. Thermodynamic Properties = 300
• A. Determination of Phase Equilibria = 300
• B. Determination of Gibbs Energies of Formation = 305
• Ⅳ. Kinetic Properties = 308
• A. Solid Ionic Conductors = 308
• 1. Conductivity of Majority Charge Carriers （Ions） = 308
• 2. Conductivity of Minority Charge Carriers （Electrons, Holes） = 310
• 3. Mobility and Concentration of Minority Charge Carriers （Electrons, Holes） = 312
• a. Voltage Relaxation Method = 313
• b. Charge Transfer Technique = 314
• B. Solid Mixed Conductors = 314
• 1. Partial Ionic Conductivity = 315
• 2. Partial Electronic Conductivity = 316
• 3. Chemical Diffusion = 317
• a. Galvanostatic Intermittent Titration Technique （GITT） = 318
• b. Potential Step Technique = 320
• c. Short Pulse Technique = 321
• 4. Ionic Diffusivity, Mobility, and Conductivity = 322
• C. Kinetics of Solid State Reactions = 322
• Ⅴ. Summary = 324
• References = 326
• Chapter 10 ELECTROCHEMICAL SENSORS / Pierre Fabry ; Elisabeth Siebert = 329
• List of Abbreviations = 330
• List of Symbols = 330
• Ⅰ. Introduction = 331
• A. Brief History = 332
• B. Current Trends = 332
• C. Prefatory Note = 332
• Ⅱ. Different Kinds of Sensors = 332
• A. Potentiometric Sensors = 332
• 1. Fundamental Principles = 332
• a. Ionic Junction of the First Kind = 333
• b. Ionic Junction of the Second Kind = 333
• c. Electrode Reaction of the First Kind = 336
• d. Electrode Reaction of the Second Kind = 337
• e. Ionic Exchange at Interfaces = 338
• f. Electrochemical Chain = 339
• 2. Ionic Sensors = 340
• a. Solid Internal Reference Systems = 340
• b. Interfering Phenomena = 343
• c. Influence of Electronic Conductivity = 345
• d. Limit of Detection = 345
• 3. Gas Sensors （Electrochemical Gauges） = 346
• a. Working Temperature = 346
• b. Reference Systems = 349
• c. Influence of Electronic Conductivity = 350
• d. Interfering Phenomena = 353
• B. Amperometric Sensors = 354
• 1. Principle = 354
• 2. Experimental Cells = 356
• 3. Different Species Analyzed by Amperometry = 356
• C. Coulometric Sensors = 357
• 1. Principle = 357
• 2. Different Kinds of Measurement = 358
• a. Electrochemical Purge Devices = 358
• b. Electrochemical Enrichment Devices = 358
• D. Pump­Gauge Devices = 359
• 1. Direct Current Mode = 359
• 2. Alternating Current Mode = 359
• E. Conductometric Sensors = 360
• 1. Principle = 360
• 2. Achievements = 362
• Ⅲ. Measurement Characteristics = 362
• A. Impedance = 362
• B. Response Time = 363
• C. Sensitivity = 364
• Ⅳ. Conclusion and Prospects = 365
• References = 365
• Chapter 11 SOLID STATE BATTERIES / Christian Julien = 371
• List of Symbols and Abbreviations = 372
• Ⅰ. Introduction = 372
• A. Advantages of Solid State Battery Technology = 373
• B. Potential Effects on Energy Conservation = 374
• C. Requirements of Solid State Battery Technology = 375
• D. Advanced Projects = 377
• Ⅱ. Applications of Solid State Ionic Materials to Batteries = 379
• A. High­Temperature Cells = 379
• 1. Sodium Sulfur Batteries = 380
• 2. Lithium Iron Sulfide Batteries = 381
• 3. Sodium Chloride Batteries = 382
• 4. Lithium Chloride Batteries = 382
• 5. Sodium­Sulfur­Glass Batteries = 383
• B. Polymeric and Glass Batteries = 383
• 1. Lithium­Polymer Intercalation Compound Batteries = 383
• 2. Solid Redox Polymerized Electrode Batteries = 385
• 3. Alkali Glass Batteries = 385
• C. Solid State Primary Lithium Batteries = 386
• 1. Lithium­Iodine Cells = 386
• 2. Li／LiI­Al₂O₃ ／Pbl₂ Cells = 387
• 3. Li／LiI （SiO₂, H₂O）／Me₄ $$NI_5$$ + C Cells = 387
• 4. Lithium Bromine Trifluoride Battery = 387
• D. Solid State Secondary Lithium Batteries = 388
• E. Secondary Insertion Cathode Lithium Batteries = 388
• 1. Li／TiS₂ Battery = 390
• 2. Li／MoS₂ Battery = 390
• 3. Li／NbSe₃ Battery = 391
• 4. Li／V₂ $$O_5$$ Battery = 391
• 5. Li／MnO₂ Battery = 392
• 6. Other Items = 393
• F. Liquid Electrolyte Primary Lithium Batteries = 393
• 1. Lithium­Polycarbon Fluorides Cell = 394
• 2. Lithium Oxide­Compounds Cell = 394
• G. Silver and Copper Batteries = 395
• 1. Silver Cells = 395
• 2. Copper Cells = 396
• Ⅲ. Lithium Metal­Free Rechargeable Batteries = 397
• A. Principle = 397
• B. Electrodes for Rocking­Chair Batteries = 397
• C. Rocking­Chair Batteries = 398
• Ⅳ. Microbatteries = 399
• A. Silver and Copper Microbatteries = 400
• B. Lithium Microbatteries = 400
• 1. Lithium Electrode Thin Films = 400
• 2. Lithium Microbatteries with Chalcogenide Cathode = 401
• 3. Lithium Microbatteries with Oxide Cathode = 403
• References = 404
• Chapter 12 SOLID OXIDE FUEL CELLS / Abdelkader Hammou ; Jacques Guindet = 407
• Ⅰ. Foreword = 407
• Ⅱ. Introduction = 407
• Ⅲ. Advantages and Drawbacks of Solid Oxide Fuel Cells = 408
• Ⅳ. Electrolytes = 409
• Ⅴ. Cathode Materials and Interfacial Reactions = 413
• Ⅵ. Anode Materials = 419
• Ⅶ. Interconnection Materials （Interconnects） = 422
• Ⅷ. Solid Oxide Fuel Cell Configurations and Performance = 424
• A. The Tubular Configuration = 424
• B. Monolithic Solid Oxide Fuel Cells （MSOFCs） = 429
• C. The Planar （Bipolar） Plate Design = 431
• Ⅸ. Comparative Performance Evaluation = 435
• Ⅹ. Manufacturing Processes = 435
• XI. Conclusion = 438
• Acknowledgment = 438
• References = 438
• Chapter 13 ELECTROCATALYSIS AND ELECTROCHEMICAL REACTORS / Constantinos G. Vayenas ; Symeon I. Bebelis ; I.V. Yentekakis, ; S.N. Neophytides = 445
• List of Abbreviations and Symbols = 446
• Ⅰ. Charge Transfer and the Nature of Overpotentials in Solid State Electrochemistry = 447
• A. General Considerations = 447
• B. Thermodynamic Considerations = 449
• C. Types of Overpotential = 450
• D. Exchange Current Density and Electrocatalytic Activity = 452
• Ⅱ. Electrocatalytic Operation of Solid Electrolyte Cells = 456
• A. Electrocatalysis for the Production of Chemicals = 456
• B. Electrochemical Reactor Analysis and Design = 458
• Ⅲ. Catalysis on the Electrodes of Solid Electrolyte Cells = 459
• A. Potentiometric Investigations = 459
• B. Electrochemical Activation of Catalyzed Reactions = 464
• 1. Introduction = 466
• 2. Experimental Setup = 467
• 3. Catalytic Rate Modification = 468
• 4. Effect of Gaseous Composition on Regular （Open­Circuit） and NEMCA­Induced Reaction Rate = 470
• 5. Definitions and the Role of the Exchange Current $$I_0$$ = 470
• 6. Selectivity Modification = 474
• 7. Work Function Measurements : an Additional Meaning of the emf of Solid Electrolyte Cells with Metal Electrodes = 474
• 8. Dependence of Catalytic Rates and Activation Energies on eΦ = 475
• 9. XPS Spectroscopic and Voltammetric Identification of Back­Spillover Ions as the Cause of NEMCA = 476
• Ⅳ. Concluding Remarks = 477
• Acknowledgment = 477
• References = 477
• Chapter 14 DENSE CERAMIC MEMBRANES FOR OXYGEN SEPARATION / Henny J.M. Bouwmeester ; Anthonie J. Burggraaf = 481
• List of Abbreviations and Symbols = 482
• Ⅰ. Introduction = 484
• Ⅱ. General Survey = 485
• A. Major Membrane Concepts = 486
• B. Data : Oxygen Permeability of Solid Oxide Membranes = 488
• C. Factors Controlling Oxygen Permeation = 488
• D. Scope of this Chapter = 496
• Ⅲ. Fundamentals = 496
• A. Bulk Transport = 496
• 1. Wagner Equation = 496
• 2. Chemical Diffusion Coefficient = 498
• 3. Trapping of Electronic and Ionic Defects = 499
• 4. Empirical Equations = 500
• B. Surface Oxygen Exchange = 501
• 1. Characteristic Membrane Thickness = 502
• 2. Measuring $$L_c$$ = 504
• 3. Effect of Surface Roughness and Porosity = 507
• Ⅳ. Solid Oxide Electrolytes = 507
• A. Introduction = 507
• B. Oxygen Semipermeability of Oxide Electrolytes = 508
• 1. Diffusion of Electronic Charge Carriers = 508
• 2. Modeling Equations = 510
• 3. Examples = 511
• a. Calcia­Stabilized Zirconia = 511
• b. Erbia­Stabilized Bismuth Oxide = 512
• 4. emf Measurements = 514
• C. Electrochemical Oxygen Separation = 516
• 1. Oxygen Pump = 516
• 2. Dual­Phase Composites = 517
• Ⅴ. Acceptor­Doped Perovskite and Perovskite­Related Oxides = 519
• A. Introduction = 519
• B. Structure and Defect Chemistry = 520
• 1. Perovskite Structure = 520
• 2. Nonstoichiometry = 521
• 3. Localized vs. Delocalized Electrons = 523
• C. Oxygen Desorption and Perovskite Stability = 526
• D. Equations for Oxygen Transport = 527
• E. Electronic Conductivity = 529
• F. Extended Defects and Vacancy Ordering = 531
• 1. Static Lattice Simulation = 531
• 2. Vacancy Ordering = 533
• 3. Microdomain Formation = 533
• 4. Brownmillerite Structure = 534
• 5. High­Temperature NMR = 535
• G. Observations from Permeability Measurements = 536
• 1. $$SrCo_{0.8} Fe_{0.2} O{₃-δ}$$ = 537
• 2. Experimental Difficulties = 537
• 3. Surface Exchange Kinetics = 540
• 4. Behavior in Large $$P_{o₂}$$ ­Gradients = 540
• 5. Grain Boundary Diffusivity = 541
• Ⅵ. Final Remarks = 542
• Acknowledgment = 544
• References = 544
• Chapter 15 CORROSION STUDIES / Hans de Wit ; Th$$\ddot y$$s Fransen = 555
• List of Symbols = 555
• Ⅰ. Introduction = 556
• Ⅱ. Layer Growth of Oxides and Sulfides = 557
• A. Introduction = 557
• B. The Oxidation of Metals and Alloys at High Temperatures = 557
• C. Wagner's Oxidation Theory = 558
• D. The Sulfidation of Metals and Alloys = 565
• 1. Defect Structure of Sulfides = 566
• 2. Stability of the Sulfides = 566
• 3. Melting Points of the Sulfides = 568
• 4. Morphology of the Sulfides = 568
• 5. Complications = 568
• Ⅲ. The Metal／Oxide／Gas System as an Electrochemical Cell = 569
• A. Introduction = 569
• B. The Influence of an Electric Field on the Growth Rate = 571
• C. Electrochemical Kinetic Studies Regarding the Formation of Sulfide Layers = 573
• 1. Potentiostatic Measurement = 574
• 2. Galvanostatic Measurement = 575
• D. High­Temperature Cyclic Voltammetry, a Fingerprint of Initial Oxidation = 576
• 1. Introduction to Cyclic Voltammetry = 576
• 2. Mass Transfer, Initial, and Boundary Conditions = 577
• 3. Cyclic Voltammetry as a Tool for High­Temperature Corrosion = 579
• a. The High­Temperature Oxidation of Ni = 580
• b. The High­Temperature Oxidation of Cu = 583
• c. The High­Temperature Oxidation of Co = 584
• d. The High­Temperature Oxidation of Fe = 585
• 4. General Conclusions on the Application of High­Temperature Voltammetry = 585
• References = 585
• Chapter 16 ELECTROCHROMISM AND ELECTRO CHROMIC DEVICES / Claes G. Granqvist = 587
• Ⅰ. Introduction = 587
• Ⅱ. Some Properties of W Oxide Films : Case Study = 589
• Ⅲ. Survey of Electrochromism Among the Oxides = 594
• A. Defect Perovskite Structure = 596
• B. Rutile and Rutile­Like Structures = 598
• C. Layer Structures = 598
• Ⅳ. Devices with Different Types of Electrolytes = 599
• A. Liquid Electrolytes = 599
• B. Solid Inorganic Ion Conductors = 603
• C. Polymer Electrolytes = 606
• Ⅴ. Conclusions = 611
• References = 612
• INDEX = 617