Solid State Electrochemistry I: Fundamentals, Materials and their Applications

Solid State Electrochemistry I: Fundamentals, Materials and their Applications......Page 5
Contents......Page 7
Preface......Page 17
List of Contributors......Page 21
1.1 Introduction......Page 25
1.2 Solid versus Liquid State......Page 26
1.3 Thermodynamics and Kinetics of Charge Carriers......Page 28
1.4 Usefulness of Electrochemical Cells......Page 30
1.5 Materials Research Strategies: Bulk Defect Chemistry......Page 33
1.7 Nanoionics......Page 35
References......Page 36
2.1 Overview......Page 39
2.2.1 X-Ray and Neutron Diffraction......Page 40
2.2.2 Extended X-Ray Absorption Fine Structure......Page 41
2.2.4 Computational Methods......Page 42
2.3.1 Silver and Copper Ion Conductors......Page 43
2.3.1.1 Silver Iodide (AgI)......Page 44
2.3.1.3 Other Ag+ and Cu+ Halides......Page 45
2.3.1.4 Ag+ Chalcogenides......Page 46
2.3.1.6 Silver Sulfur Iodide (Ag3SI)......Page 47
2.3.2 Fluorite-Structured Compounds......Page 48
2.3.2.2 Halide Fluorites......Page 49
2.3.2.4 Anion-Excess Fluorites......Page 50
2.3.2.5 Oxide Fluorites......Page 51
2.3.2.6 Anion-Deficient Fluorites......Page 52
2.3.2.8 Antifluorites......Page 53
2.3.3.2 Oxide Pyrochlores......Page 54
2.3.3.4 Halide Spinels (LiM2Cl4, etc.)......Page 55
2.3.4.1 The Perovskite Structure......Page 56
2.3.4.3 Cryolite (Na3AlF6)......Page 57
2.3.4.4 Oxide Perovskites......Page 58
2.4 Current Status and Future Prospects......Page 59
2.5 Conclusions......Page 60
References......Page 61
3 Defect Equilibria in Solids and Related Properties: An Introduction......Page 67
3.2.1 Selected Definitions, Classification, and Notation of Defects......Page 68
3.2.2 Defect Formation and Equilibria......Page 70
3.2.3.3 Intrinsic Electronic Disordering......Page 71
3.2.4 Influence of Temperature......Page 72
3.2.5 Nonstoichiometry: Equilibria with Gaseous Phase......Page 75
3.2.6 Impurities and their Effects on Defect Equilibria......Page 78
3.2.7 Crystallographic Aspects of Defect Interaction: Examples of Defect Ordering Phenomena......Page 79
3.2.8 Thermal and Defects-Induced (Chemical) Expansion of Solids......Page 81
3.3.1 Phenomenological Equations......Page 83
3.3.2 Mass Transfer in Crystals......Page 84
3.3.3 Electrical Conductivity. Transport under a Temperature Gradient......Page 86
3.3.4.1 Mass and Charge Transport under the Chemical Potential Gradient: Electrolytic Permeation......Page 87
3.3.4.2 Charge Transfer under Temperature Gradient and Seebeck Coefficient: Selected Definitions......Page 90
3.4 Examples of Functional Materials with Different Defect Structures......Page 93
3.4.1 Solid Electrolytes......Page 94
3.4.2 Examples of Defect Chemistry in Electronic and Mixed Conductors......Page 99
References......Page 101
4.1 Introduction......Page 103
4.2.1 Space-Charge Layer......Page 106
4.3 Applications and Perspectives......Page 109
4.3.1 Nanoionic Materials as Gas Sensors......Page 110
4.3.2 Nanoionics as Battery Materials......Page 114
4.3.3 Nanoionic Materials in Fuel Cells......Page 116
4.4.1 Preparation of Nanoionic Materials......Page 118
4.4.2.1 Transmission Electron Microscopy......Page 120
4.4.2.2 X-Ray Based Methods......Page 121
4.4.3 Characterization of Microstructure......Page 122
4.4.4 Transport Measurements......Page 126
4.4.4.1 Tracer Diffusion......Page 127
4.4.4.2 NMR Spectroscopy Methods......Page 128
4.4.4.2.1 Relaxation Time Experiments......Page 129
4.4.4.2.2 Field Gradient Methods......Page 131
4.4.4.2.3 Creep Measurements......Page 132
4.5.1 Microstructure......Page 134
4.5.2 Transport......Page 135
4.5.2.1.1 Calcium Fluoride......Page 136
4.5.2.1.2 Calcium Fluoride-Barium Fluoride......Page 137
4.5.2.2.1 Lithium Niobate......Page 138
4.5.2.2.2 Zirconia......Page 139
4.5.2.2.3 Ceria......Page 143
4.5.2.2.4 Titania......Page 145
4.6 Overview and Areas for Future Development......Page 146
References......Page 148
5.1 Introduction......Page 157
5.2 Thermodynamics of Intercalation and Deintercalation......Page 159
5.2.1 Simple Lattice Gas Model......Page 160
5.2.2 Consideration of Ionic Interaction Using the Lattice Gas Model......Page 161
5.2.3.1 Application of Lattice Gas Model with Mean Field Approximation......Page 162
5.2.3.2 Application of Lattice Gas Model with Monte Carlo Simulation......Page 166
5.3 Kinetics of Intercalation and Deintercalation......Page 173
5.3.1 Diffusion-Controlled Transport......Page 174
5.3.2.1 Non-Cottrell Behavior......Page 175
5.3.2.2 (Quasi-) Current Plateau......Page 176
5.3.2.3 Linear Relationship Between Current and Electrode Potential......Page 179
5.3.3.2 Calculation Procedure of Cell-Impedance-Controlled Current Transients......Page 183
5.3.3.4 Extension of Cell-Impedance-Controlled Lithium Transport Concept to the Disordered Carbon Electrode......Page 184
5.3.4.1 Calculation Procedure of Cell-Impedance-Controlled Current Transients with Kinetic Monte Carlo Method......Page 190
5.3.4.2 Theoretical Current Transients and their Comparison with Experimental Data......Page 192
5.4.1 Galvanostatic Intermittent Titration Technique (GITT) in Combination with EMF-Temperature Measurement......Page 195
5.4.3 Potentiostatic Current Transient Technique......Page 196
5.5 Concluding Remarks......Page 197
References......Page 198
6.1 Introduction......Page 203
6.2 Methodological Aspects......Page 205
6.3.1 General Theoretical Treatment......Page 206
6.3.2.1 Adsorbed (Surface-)Electroactive Microparticles on Solid Electrodes......Page 211
6.3.2.2 Voltammetry at Random Microparticle Arrays......Page 216
6.3.2.2.1 The Diffusion Domain Approach......Page 217
6.3.2.2.2 The Diffusion Categories......Page 218
6.3.2.2.3 Voltammetric Sizing......Page 224
6.3.2.3 Voltammetry at Regularly Distributed Microelectrode Arrays (Microarrays, Microbands)......Page 225
6.3.2.4 The Role of Dissolution in Voltammetry of Microparticles......Page 226
6.3.3.1 Microparticles Within a Carbon Paste Electrode......Page 228
6.3.3.2 Microparticles on a Solid Electrode Surface......Page 229
6.3.4 Voltammetry of Single Microparticles (Microcrystals, Nanocrystals) on Solid Electrodes......Page 233
6.3.4.1 Voltammetric Sizing of a Microparticle Sphere......Page 235
6.4.1 Analytical Studies of Objects of Art......Page 236
6.4.2 Metal Oxide and Hydroxide Systems with Poorly Crystalline Phases......Page 237
6.4.3 Electrochemical Reactions of Organometallic Microparticles......Page 239
6.4.4 Selected Other Applications......Page 243
References......Page 245
7.1.1 Physical State......Page 251
7.1.2 Type of Disorder......Page 252
7.1.4 Connectivity of the Rigid Lattice......Page 255
7.1.6 Stability to Oxidation and Reduction......Page 256
7.2.1 Structure Type......Page 257
7.2.2 Bottleneck Concept and Size Effects......Page 259
7.2.4 Electronegativity, Bond Ionicity, and Polarizability......Page 262
7.3.1 Topological Analysis with Voronoi Tessellation......Page 263
7.3.2 Topological Analysis with Bond-Valence Maps......Page 265
7.3.3 Static First-Principles Calculations and Molecular Dynamics Modeling......Page 266
7.3.4 Analysis of Diffraction Data with Maximum Entropy Method......Page 269
7.4.1 β/β\"-Alumina, β/β\"-Gallates and β/β\"-Ferrites......Page 271
7.4.2 Nasicon Family......Page 272
7.4.4 Structures Based on Brucite-Like Octahedral Layers......Page 275
7.4.5 Cristobalite-Related Tetrahedral Frameworks......Page 276
7.4.6 Other Materials......Page 277
7.5.2 Garnet-Related Mixed Frameworks of Oxygen Octahedra and Twisted Cubes......Page 279
7.5.3 Mixed Frameworks of Oxygen Octahedra and Tetrahedra......Page 281
7.5.4 Octahedral Framework and Layered Structures......Page 282
7.5.5 Structures Based on Isolated Tetrahedral Anions......Page 283
7.5.6 Structures with Isolated Monatomic Anions......Page 284
7.6.1 General Remarks......Page 286
7.6.2 Low-Temperature Proton Conductors: Acids and Acid Salts......Page 289
7.6.3 High-Temperature Proton Conductors: Ceramic Oxides......Page 290
7.6.4 Intermediate-Temperature Proton Conductors......Page 292
References......Page 294
8 Conducting Solids: In the Search for Multivalent Cation Transport......Page 303
8.1 Introduction......Page 304
8.2 Analysis of Trivalent Cation Transport......Page 305
8.2.1 β/β\"-Alumina......Page 306
8.2.2 β-Alumina-Related Materials......Page 309
8.2.3 Perovskite-Type Structures......Page 310
8.2.4 Sc2(WO4)3-Type Structures......Page 311
8.2.5 NASICON-Type Structures......Page 317
8.3 Search for Tetravalent Cation Conductors......Page 319
References......Page 321
9.1 Introduction......Page 325
9.2 Oxygen Ionic Transport in Acceptor-Doped Oxide Phases: Relevant Trends......Page 326
9.3 Stabilized Zirconia Electrolytes......Page 331
9.4 Doped Ceria......Page 333
9.5 Anion Conductors Based on Bi2O3......Page 334
9.6 Transport Properties of Other Fluorite-Related Phases: Selected Examples......Page 337
9.7 Perovskite-Type LnBO3 (B = Ga, AI, In, Sc, Y) and their Derivatives......Page 338
9.8 Perovskite-Related Mixed Conductors: A Short Overview......Page 342
9.10 Solid Electrolytes with Apatite Structure......Page 348
References......Page 350
10.1 Introduction......Page 359
10.2.1 The Proton-Exchange Membrane Fuel Cell (PEMFC)......Page 360
10.2.2 Proton-Exchange Membranes for Fuel Cells......Page 361
10.2.3.3 Evaluation of Durability......Page 362
10.3.1 Perfluorosulfonate Membranes......Page 363
10.3.2 Partially Fluorosulfonated Membranes......Page 365
10.3.3.1 PFSA/PTFE Composite Membranes......Page 366
10.3.3.2 PFSA/CNT Composite Membranes......Page 367
10.3.4 Hybrid Organic–Inorganic Membranes......Page 368
10.3.4.2 Catalyst Material/PFSA Composite Membranes......Page 369
10.3.4.4 Self-Humidifying Reinforced Composite Membranes......Page 370
10.4.1.1 Post-Sulfonated Polymers......Page 371
10.4.1.2 Direct Polymerization from the Sulfonated Monomers......Page 373
10.4.1.4 Durability Issues......Page 375
10.4.2 Reinforced Composite Membranes......Page 376
10.4.3 Hybrid Organic–Inorganic Membranes......Page 377
10.5.1 Acid-Doped Polybenzimidazole......Page 378
10.5.2 Nitrogen-Containing Heterocycles......Page 380
10.5.3 Room-Temperature Ionic Liquids......Page 381
10.6 Conclusions......Page 382
References......Page 383
11.1 Introduction......Page 389
11.2.1 Molecular, Low-Dimensional CT Complexes and π-Conjugated Organic Oligomers......Page 390
11.2.2.1 Inorganic π-Conjugated Polymers and Polymer-Like Carbonaceous Materials......Page 393
11.2.2.4 Inorganic Ion-Insertion (Intercalation) Compounds......Page 394
11.3.1 The Electronic Band Diagram of ECP as a Function of Doping Level......Page 395
11.3.2 The Effect of Morphology on the Conductivity of the Polymeric Films......Page 397
11.3.3.1 Selection of Suitable Electrolyte Solutions......Page 398
11.3.3.2 A Short Survey on In Situ Techniques used for Studies of Mechanisms of Electrochemical Doping of π-Conjugated Polymers......Page 399
11.3.3.3 Mechanisms of Electrochemical Synthesis of Conducting Polymer Films......Page 401
11.3.3.4 Dynamics of the Micromorphological Changes in ECP Films as a Function of their Doping Level......Page 403
11.3.3.5 The Maximum Attainable Doping Levels and the Conductivity Windows......Page 404
11.3.3.6 Charge Trapping in n-Doped Conducting Polymers......Page 409
11.4 The Thermodynamics and Kinetics of Electrochemical Doping of Organic Polymers and Ion-Insertion into Inorganic Host Materials......Page 411
11.5 Concluding Remarks......Page 417
References......Page 418
12.1 Introduction......Page 421
12.2 Characteristics of a Current-Carrying Electrode on an Oxide Electrolyte......Page 423
12.3 Operating Modes......Page 426
12.3.2 Fuel Cell Mode......Page 427
12.3.3 The NEMCA Effect......Page 430
12.3.4 Electrolyte Reduction......Page 431
12.4.1.1 Oxide Electrolytes......Page 432
12.4.1.2 Proton-Conducting Electrolytes......Page 433
12.4.2.1 Cathode......Page 434
12.5 Cell Designs......Page 435
12.6 Examples of Applications......Page 437
12.6.2.1 Open System: Oxygen Monitoring in a Flowing Gas......Page 438
12.6.2.2 Closed Systems......Page 441
12.6.3 HT- and IT-SOFC......Page 442
References......Page 447
13.1 Introduction......Page 451
13.2.1.1 Potentiometric Sensors: Equilibrium......Page 452
13.2.1.2 Potentiometric: Nonequilibrium......Page 455
13.2.2 Current-Based Sensors......Page 458
13.2.2.2 Amperometric Sensors......Page 459
13.3.1 Electrolytes......Page 461
13.3.2.1 Reference Electrodes......Page 465
13.3.2.2 Auxiliary Electrodes......Page 468
13.3.2.3 Electrocatalytic Electrodes......Page 476
13.3.2.4 Electrodes for Current-Based Sensors......Page 483
13.4.1 Gaseous Medium......Page 486
13.4.2 Molten Metals......Page 488
13.5 Summary and Conclusions......Page 491
References......Page 492
Index......Page 517