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Author:   Vladislav V. Kharton (CICECO, Department of Ceramic Engineering, University of Aveiro, 3810 Aveiro, Portugal)
Publisher:   Wiley-VCH Verlag GmbH
Imprint:   Blackwell Verlag GmbH
Dimensions:   Width: 17.50cm , Height: 3.30cm , Length: 24.40cm
Weight:   0.998kg
ISBN:  

9783527323180

ISBN 10:   352732318
Pages:   527
Publication Date:   15 July 2009
Audience:   Professional and scholarly ,  Professional & Vocational
Format:   Hardback
Publisher's Status:   Out of Print
Availability:   Awaiting stock  

Table of Contents

Preface xv List of Contributors xix 1 Fundamentals, Applications, and Perspectives of Solid-State Electrochemistry: A Synopsis 1 Joachim Maier 1.1 Introduction 1 1.2 Solid versus Liquid State 2 1.3 Thermodynamics and Kinetics of Charge Carriers 4 1.4 Usefulness of Electrochemical Cells 6 1.5 Materials Research Strategies: Bulk Defect Chemistry 9 1.6 Materials Research Strategy: Boundary Defect Chemistry 11 1.7 Nanoionics 11 References 12 2 Superionic Materials: Structural Aspects 15 Stephen Hull 2.1 Overview 15 2.2 Techniques 16 2.2.1 X-Ray and Neutron Diffraction 16 2.2.2 Extended X-Ray Absorption Fine Structure 17 2.2.3 Nuclear Magnetic Resonance 18 2.2.4 Computational Methods 18 2.3 Families of Superionic Conductors 19 2.3.1 Silver and Copper Ion Conductors 19 2.3.1.1 Silver Iodide (AgI) 20 2.3.1.2 Copper Iodide (CuI) 21 2.3.1.3 Other Ag+ and Cu+ Halides 21 2.3.1.4 Ag+ Chalcogenides 22 2.3.1.5 Cu+ Chalcogenides 23 2.3.1.6 Silver Sulfur Iodide (Ag3SI) 23 2.3.1.7 Ternary AgI-MI2 Compounds 24 2.3.1.8 Ternary AgI-MI Compounds 24 2.3.1.9 Ternary Derivatives of Ag2S 24 2.3.2 Fluorite-Structured Compounds 24 2.3.2.1 The Fluorite Structure 25 2.3.2.2 Halide Fluorites 25 2.3.2.3 Lead Tin Fluoride (PbSnF4) 26 2.3.2.4 Anion-Excess Fluorites 26 2.3.2.5 Oxide Fluorites 27 2.3.2.6 Anion-Deficient Fluorites 28 2.3.2.7 Bi2O3 29 2.3.2.8 Antifluorites 29 2.3.2.9 The ‘‘Rotator’’ Phases 30 2.3.3 Pyrochlore and Spinel-Structured Compounds 30 2.3.3.1 The Pyrochlore Structure 30 2.3.3.2 Oxide Pyrochlores 30 2.3.3.3 The Spinel Structure 31 2.3.3.4 Halide Spinels (LiM2Cl4, etc.) 31 2.3.3.5 Oxide Spinels: Li2MnO4 32 2.3.4 Perovskite-Structured Compounds 32 2.3.4.1 The Perovskite Structure 32 2.3.4.2 Halide Perovskites 33 2.3.4.3 Cryolite (Na3AlF6) 33 2.3.4.4 Oxide Perovskites 34 2.3.4.5 Brownmillerites (Ba2In2O5) 35 2.3.4.6 BIMEVOXs 35 2.4 Current Status and Future Prospects 35 2.5 Conclusions 36 References 37 3 Defect Equilibria in Solids and Related Properties: An Introduction 43 Vladimir A. Cherepanov, Alexander N. Petrov, and Andrey Yu. Zuev Editorial Preface 43 Vladislav Kharton 3.1 Introduction 44 3.2 Defect Structure of Solids: Thermodynamic Approach 44 3.2.1 Selected Definitions, Classification, and Notation of Defects 44 3.2.2 Defect Formation and Equilibria 46 3.2.3 Formation of Stoichiometric (Inherent) Defects 47 3.2.3.1 Schottky Defects 47 3.2.3.2 Frenkel Defects 47 3.2.3.3 Intrinsic Electronic Disordering 47 3.2.3.4 Ionization of Defects 48 3.2.4 Influence of Temperature 48 3.2.5 Nonstoichiometry: Equilibria with Gaseous Phase 51 3.2.6 Impurities and their Effects on Defect Equilibria 54 3.2.7 Crystallographic Aspects of Defect Interaction: Examples of Defect Ordering Phenomena 55 3.2.8 Thermal and Defects-Induced (Chemical) Expansion of Solids 57 3.3 Basic Relationships Between the Defect Equilibria and Charge Transfer in Solids 59 3.3.1 Phenomenological Equations 59 3.3.2 Mass Transfer in Crystals 60 3.3.3 Electrical Conductivity. Transport under a Temperature Gradient 62 3.3.4 Electrochemical Transport 63 3.3.4.1 Mass and Charge Transport under the Chemical Potential Gradient: Electrolytic Permeation 63 3.3.4.2 Charge Transfer under Temperature Gradient and Seebeck Coefficient: Selected Definitions 66 3.4 Examples of Functional Materials with Different Defect Structures 69 3.4.1 Solid Electrolytes 70 3.4.2 Examples of Defect Chemistry in Electronic and Mixed Conductors 75 References 77 4 Ion-Conducting Nanocrystals: Theory, Methods, and Applications 79 Alan V. Chadwick and Shelley L.P. Savin 4.1 Introduction 79 4.2 Theoretical Aspects 82 4.2.1 Space-Charge Layer 82 4.2.2 Surface Texture and Mismatch at Surfaces 85 4.3 Applications and Perspectives 85 4.3.1 Nanoionic Materials as Gas Sensors 86 4.3.2 Nanoionics as Battery Materials 90 4.3.3 Nanoionic Materials in Fuel Cells 92 4.4 Experimental Methods 94 4.4.1 Preparation of Nanoionic Materials 94 4.4.2 Determination of Particle Size and Dispersion 96 4.4.2.1 Transmission Electron Microscopy 96 4.4.2.2 X-Ray Based Methods 97 4.4.3 Characterization of Microstructure 98 4.4.4 Transport Measurements 102 4.4.4.1 Tracer Diffusion 103 4.4.4.2 NMR Spectroscopy Methods 104 4.4.4.2.1 Relaxation Time Experiments 105 4.4.4.2.2 Field Gradient Methods 107 4.4.4.2.3 Creep Measurements 108 4.5 Review of the Current Experimental Data and their Agreement with Theory 110 4.5.1 Microstructure 110 4.5.2 Transport 111 4.5.2.1 Simple Halides 112 4.5.2.1.1 Calcium Fluoride 112 4.5.2.1.2 Calcium Fluoride-Barium Fluoride 113 4.5.2.2 Oxides 114 4.5.2.2.1 Lithium Niobate 114 4.5.2.2.2 Zirconia 115 4.5.2.2.3 Ceria 119 4.5.2.2.4 Titania 121 4.6 Overview and Areas for Future Development 122 References 124 5 The Fundamentals and Advances of Solid-State Electrochemistry: Intercalation (Insertion) and Deintercalation (Extraction) in Solid-State Electrodes 133 Sung-Woo Kim, Seung-Bok Lee, and Su-Il Pyun 5.1 Introduction 133 5.2 Thermodynamics of Intercalation and Deintercalation 135 5.2.1 Simple Lattice Gas Model 136 5.2.2 Consideration of Ionic Interaction Using the Lattice Gas Model 137 5.2.3 Application to Lithium Intercalation/Deintercalation 138 5.2.3.1 Application of Lattice Gas Model with Mean Field Approximation 138 5.2.3.2 Application of Lattice Gas Model with Monte Carlo Simulation 142 5.2.3.3 Application of Ab Initio (First Principles) Method 149 5.3 Kinetics of Intercalation and Deintercalation 149 5.3.1 Diffusion-Controlled Transport 150 5.3.2 Cell-Impedance-Controlled Transport 151 5.3.2.1 Non-Cottrell Behavior 151 5.3.2.2 (Quasi-) Current Plateau 152 5.3.2.3 Linear Relationship Between Current and Electrode Potential 155 5.3.3 Numerical Calculations 159 5.3.3.1 Governing Equation and Boundary Conditions 159 5.3.3.2 Calculation Procedure of Cell-Impedance-Controlled Current Transients 159 5.3.3.3 Theoretical Current Transients and their Comparison with Experimental Values 160 5.3.3.4 Extension of Cell-Impedance-Controlled Lithium Transport Concept to the Disordered Carbon Electrode 160 5.3.4 Statistical Approach with Kinetic Monte Carlo Simulation 166 5.3.4.1 Calculation Procedure of Cell-Impedance-Controlled Current Transients with Kinetic Monte Carlo Method 166 5.3.4.2 Theoretical Current Transients and their Comparison with Experimental Data 168 5.4 Methodological Overview 171 5.4.1 Galvanostatic Intermittent Titration Technique (GITT) in Combination with EMF-Temperature Measurement 171 5.4.2 Electrochemical AC-Impedance Spectroscopy 172 5.4.3 Potentiostatic Current Transient Technique 172 5.5 Concluding Remarks 173 References 174 6 Solid-State Electrochemical Reactions of Electroactive Microparticles and Nanoparticles in a Liquid Electrolyte Environment 179 Michael Hermes and Fritz Scholz 6.1 Introduction 179 6.2 Methodological Aspects 181 6.3 Theory 182 6.3.1 General Theoretical Treatment 182 6.3.2 Voltammetry of Microparticle-Modified Electrodes 187 6.3.2.1 Adsorbed (Surface-)Electroactive Microparticles on Solid Electrodes 187 6.3.2.2 Voltammetry at Random Microparticle Arrays 192 6.3.2.2.1 The Diffusion Domain Approach 193 6.3.2.2.2 The Diffusion Categories 194 6.3.2.2.3 Voltammetric Sizing 200 6.3.2.3 Voltammetry at Regularly Distributed Microelectrode Arrays (Microarrays, Microbands) 201 6.3.2.4 The Role of Dissolution in Voltammetry of Microparticles 202 6.3.3 Voltammetric Stripping of Electroactive Microparticles from a Solid Electrode 204 6.3.3.1 Microparticles Within a Carbon Paste Electrode 204 6.3.3.2 Microparticles on a Solid Electrode Surface 205 6.3.4 Voltammetry of Single Microparticles (Microcrystals, Nanocrystals) on Solid Electrodes 209 6.3.4.1 Voltammetric Sizing of a Microparticle Sphere 211 6.4 Examples and Applications 212 6.4.1 Analytical Studies of Objects of Art 212 6.4.2 Metal Oxide and Hydroxide Systems with Poorly Crystalline Phases 213 6.4.3 Electrochemical Reactions of Organometallic Microparticles 215 6.4.4 Selected Other Applications 219 References 221 7 Alkali Metal Cation and Proton Conductors: Relationships between Composition, Crystal Structure, and Properties 227 Maxim Avdeev, Vladimir B. Nalbandyan, and Igor L. Shukaev 7.1 Principles of Classification, and General Comments 227 7.1.1 Physical State 227 7.1.2 Type of Disorder 228 7.1.3 Type of Charge Carrier 231 7.1.4 Connectivity of the Rigid Lattice 231 7.1.5 Connectivity of the Migration Paths 232 7.1.6 Stability to Oxidation and Reduction 232 7.1.7 A Comment on the Activation Energy 233 7.2 Crystal-Chemistry Factors Affecting Cationic Conductivity 233 7.2.1 Structure Type 233 7.2.2 Bottleneck Concept and Size Effects 235 7.2.3 Site Occupation Factors 238 7.2.4 Electronegativity, Bond Ionicity, and Polarizability 238 7.3 Crystal Structural Screening and Studies of Conduction Paths 239 7.3.1 Topological Analysis with Voronoi Tessellation 239 7.3.2 Topological Analysis with Bond-Valence Maps 241 7.3.3 Static First-Principles Calculations and Molecular Dynamics Modeling 242 7.3.4 Analysis of Diffraction Data with Maximum Entropy Method 245 7.4 Conductors with Large Alkali Ions 247 7.4.1 β/β”-Alumina, β/β”-Gallates and β/β”-Ferrites 247 7.4.2 Nasicon Family 248 7.4.3 Sodium Rare-Earth Silicates 251 7.4.4 Structures Based on Brucite-Like Octahedral Layers 251 7.4.5 Cristobalite-Related Tetrahedral Frameworks 252 7.4.6 Other Materials 253 7.5 Lithium Ion Conductors 255 7.5.1 General Comments 255 7.5.2 Garnet-Related Mixed Frameworks of Oxygen Octahedra and Twisted Cubes 255 7.5.3 Mixed Frameworks of Oxygen Octahedra and Tetrahedra 257 7.5.4 Octahedral Framework and Layered Structures 258 7.5.5 Structures Based on Isolated Tetrahedral Anions 259 7.5.6 Structures with Isolated Monatomic Anions 260 7.5.7 Other Structures 262 7.6 Proton Conductors 262 7.6.1 General Remarks 262 7.6.2 Low-Temperature Proton Conductors: Acids and Acid Salts 265 7.6.3 High-Temperature Proton Conductors: Ceramic Oxides 266 7.6.4 Intermediate-Temperature Proton Conductors 268 References 270 8 Conducting Solids: In the Search for Multivalent Cation Transport 279 Nobuhito Imanaka and Shinji Tamura Editorial Preface 279 Vladislav Kharton 8.1 Introduction 280 8.2 Analysis of Trivalent Cation Transport 281 8.2.1 β/β”-Alumina 282 8.2.2 β-Alumina-Related Materials 285 8.2.3 Perovskite-Type Structures 286 8.2.4 Sc2(WO4)3-Type Structures 287 8.2.5 NASICON-Type Structures 293 8.3 Search for Tetravalent Cation Conductors 295 References 297 9 Oxygen Ion-Conducting Materials 301 Vladislav V. Kharton, Fernando M.B. Marques, John A. Kilner,and Alan Atkinson 9.1 Introduction 301 9.2 Oxygen Ionic Transport in Acceptor-Doped Oxide Phases: Relevant Trends 302 9.3 Stabilized Zirconia Electrolytes 307 9.4 Doped Ceria 309 9.5 Anion Conductors Based on Bi2O3 310 9.6 Transport Properties of Other Fluorite-Related Phases: Selected Examples 313 9.7 Perovskite-Type LnBO3 (B = Ga, Al, In, Sc, Y) and their Derivatives 314 9.8 Perovskite-Related Mixed Conductors: A Short Overview 318 9.9 La2Mo2O9-Based Electrolytes 324 9.10 Solid Electrolytes with Apatite Structure 324 References 326 10 Polymer and Hybrid Materials: Electrochemistry and Applications 335 Danmin Xing and Baolian Yi 10.1 Introduction 335 10.2 Fundamentals 336 10.2.1 The Proton-Exchange Membrane Fuel Cell (PEMFC) 336 10.2.2 Proton-Exchange Membranes for Fuel Cells 337 10.2.3 Membrane Characterization 338 10.2.3.1 Electrochemical Parameters 338 10.2.3.2 Physical Properties 338 10.2.3.3 Evaluation of Durability 338 10.3 Fluorinated Ionomer Membranes 339 10.3.1 Perfluorosulfonate Membranes 339 10.3.2 Partially Fluorosulfonated Membranes 341 10.3.3 Reinforced Composite Membranes 342 10.3.3.1 PFSA/PTFE Composite Membranes 342 10.3.3.2 PFSA/CNT Composite Membranes 343 10.3.4 Hybrid Organic–Inorganic Membranes 344 10.3.4.1 Hygroscopic Material/PFSA Composite Membranes 345 10.3.4.2 Catalyst Material/PFSA Composite Membranes 345 10.3.4.3 Heteropolyacid/PFSA Composite Membranes 346 10.3.4.4 Self-Humidifying Reinforced Composite Membranes 346 10.4 Non-Fluorinated Ionomer Membranes 347 10.4.1 Materials, Membranes, and Characterization 347 10.4.1.1 Post-Sulfonated Polymers 347 10.4.1.2 Direct Polymerization from the Sulfonated Monomers 349 10.4.1.3 Microstructures and Proton Transportation 351 10.4.1.4 Durability Issues 351 10.4.2 Reinforced Composite Membranes 352 10.4.3 Hybrid Organic–Inorganic Membranes 353 10.5 High-Temperature PEMs 354 10.5.1 Acid-Doped Polybenzimidazole 354 10.5.2 Nitrogen-Containing Heterocycles 356 10.5.3 Room-Temperature Ionic Liquids 357 10.5.4 Inorganic Membranes: A Brief Comparison 358 10.6 Conclusions 358 References 359 11 Electrochemistry of Electronically Conducting Polymers 365 Mikhael Levi and Doron Aurbach 11.1 Introduction 365 11.2 Solid Organic and Inorganic Electrochemically Active Materials for Galvanic Cells Operating at Moderate Temperatures 366 11.2.1 Molecular, Low-Dimensional CT Complexes and π-Conjugated Organic Oligomers 366 11.2.2 Electroactive Solids and Polymeric Films with Mixed Electronic–Ionic Conductivity 369 11.2.2.1 Inorganic π-Conjugated Polymers and Polymer-Like Carbonaceous Materials 369 11.2.2.2 Organic π-Conjugated Polymers 370 11.2.2.3 Conventional Redox-Polymers 370 11.2.2.4 Inorganic Ion-Insertion (Intercalation) Compounds 370 11.3 General Features of Doping-Induced Changes in π-Conjugated Polymers 371 11.3.1 The Electronic Band Diagram of ECP as a Function of Doping Level 371 11.3.2 The Effect of Morphology on the Conductivity of the Polymeric Films 373 11.3.3 Electrochemical Synthesis and Doping 374 11.3.3.1 Selection of Suitable Electrolyte Solutions 374 11.3.3.2 A Short Survey on In Situ Techniques used for Studies of Mechanisms of Electrochemical Doping of π-Conjugated Polymers 375 11.3.3.3 Mechanisms of Electrochemical Synthesis of Conducting Polymer Films 377 11.3.3.4 Dynamics of the Micromorphological Changes in ECP Films as a Function of their Doping Level 379 11.3.3.5 The Maximum Attainable Doping Levels and the Conductivity Windows 380 11.3.3.6 Charge Trapping in n-Doped Conducting Polymers 385 11.4 The Thermodynamics and Kinetics of Electrochemical Doping of Organic Polymers and Ion-Insertion into Inorganic Host Materials 387 11.5 Concluding Remarks 393 References 394 12 High-Temperature Applications of Solid Electrolytes: Fuel Cells, Pumping, and Conversion 397 Jacques Fouletier and Véronique Ghetta 12.1 Introduction 397 12.2 Characteristics of a Current-Carrying Electrode on an Oxide Electrolyte 399 12.3 Operating Modes 402 12.3.1 Electrochemical Pumping 403 12.3.2 Fuel Cell Mode 403 12.3.3 The NEMCA Effect 406 12.3.4 Electrolyte Reduction 407 12.4 Cell Materials 408 12.4.1 Electrolytes 408 12.4.1.1 Oxide Electrolytes 408 12.4.1.2 Proton-Conducting Electrolytes 409 12.4.2 Electrodes 410 12.4.2.1 Cathode 410 12.4.2.2 Anode 411 12.5 Cell Designs 411 12.6 Examples of Applications 413 12.6.1 Oxygen and Hydrogen Pumping, Water Vapor Electrolysis 414 12.6.2 Pump–Sensor Devices 414 12.6.2.1 Open System: Oxygen Monitoring in a Flowing Gas 414 12.6.2.2 Closed Systems 417 12.6.2.3 Amperometric and Coulometric Sensors 418 12.6.3 HT- and IT-SOFC 418 12.6.4 Catalytic Membrane Reactors 423 References 423 13 Electrochemical Sensors: Fundamentals, Key Materials, and Applications 427 Jeffrey W. Fergus 13.1 Introduction 427 13.2 Operation Principles 428 13.2.1 Voltage-Based Sensors 428 13.2.1.1 Potentiometric Sensors: Equilibrium 428 13.2.1.2 Potentiometric: Nonequilibrium 431 13.2.2 Current-Based Sensors 434 13.2.2.1 Sensors Based on Impedance Measurements 435 13.2.2.2 Amperometric Sensors 435 13.3 Materials Challenges 437 13.3.1 Electrolytes 437 13.3.2 Electrodes 441 13.3.2.1 Reference Electrodes 441 13.3.2.2 Auxiliary Electrodes 444 13.3.2.3 Electrocatalytic Electrodes 452 13.3.2.4 Electrodes for Current-Based Sensors 459 13.4 Applications 462 13.4.1 Gaseous Medium 462 13.4.2 Molten Metals 464 13.5 Summary and Conclusions 467 References 468 Index 493

Reviews

"""It will soon be definitely acclaimed as the only comprehensive handbook on this important and rapidly developing topic combining fundamental information with a brief overview of recent advances and intriguing problems in solid state electrochemistry, primarily targeting specialists working in this scientific field."" (Current Engineering Practice, 2010) ""In summary, the book succeeds in providing the reader with a concise introduction to a broad and diverse research area. The discussion and references can be used expand any topic of interest with the advantages and disadvantages of synthetic methods, materials, and approaches for many solid-state electrochemical systems."" (JACS, 2010)   CHEMICAL & ENGINEERING NEWS CHEMICAL ABSTRACTS SERVICE CHOICE JOURNAL OF AMERICAN CHEMICAL SOCIETY JOURNAL OF THE ELECTROCHEMICAL SOCIETY Current Engineering Practice"

It will soon be definitely acclaimed as the only comprehensive handbook on this important and rapidly developing topic combining fundamental information with a brief overview of recent advances and intriguing problems in solid state electrochemistry, primarily targeting specialists working in this scientific field. (Current Engineering Practice, 2010) In summary, the book succeeds in providing the reader with a concise introduction to a broad and diverse research area. The discussion and references can be used expand any topic of interest with the advantages and disadvantages of synthetic methods, materials, and approaches for many solid-state electrochemical systems. (JACS, 2010) CHEMICAL & ENGINEERING NEWS CHEMICAL ABSTRACTS SERVICE CHOICE JOURNAL OF AMERICAN CHEMICAL SOCIETY JOURNAL OF THE ELECTROCHEMICAL SOCIETY Current Engineering Practice

CHEMICAL & ENGINEERING NEWS CHEMICAL ABSTRACTS SERVICE CHOICE JOURNAL OF AMERICAN CHEMICAL SOCIETY JOURNAL OF THE ELECTROCHEMICAL SOCIETY Current Engineering Practice

Author Information

Vladislav Kharton is a principal investigator at the Department of Ceramics and Glass Engineering, University of Aveiro (Portugal). Having received his doctoral degree in physical chemistry from the Belarus State University in 1993, he has published over 260 scientifi c papers in international SCI journals, including 10 reviews, and coauthored over 40 papers in other refereed journals and volumes, 2 books and 2 patents. He is a topical editor of the Journal of Solid State Electrochemistry, and member of the editorial boards of Materials Letters, The Open Electrochemistry Journal, The Open Condensed Matter Physics Journal, and Processing and Application of Ceramics. In 2004, he received the Portuguese Science Foundation prize for Scientific Excellence.

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