Solid State Electrochemistry I

The only comprehensive handbook on this important and rapidly developing topic combines fundamental information with a brief overview of recent advances in solid state electrochemistry, primarily targeting specialists working in this scientific field. Particular attention is focused on the most important developments performed during the last decade, methodological and theoretical aspects of solid state electrochemistry, as well as practical applications. The highly experienced editor has included chapters with critical reviews of theoretical approaches, experimental methods and modeling techniques, providing definitions and explaining relevant terminology as necessary. Several other chapters cover all the key groups of the ion-conducting solids important for practice, namely cationic, protonic, oxygen-anionic and mixed conductors, but also conducting polymer and hybrid materials. Finally, the whole is rounded off by brief surveys of advances in the fields of fuel cells, solid-state batteries, electrochemical sensors, and other applications of ion-conducting solids. Due to the very interdisciplinary nature of this topic, this is of great interest to material scientists, polymer chemists, physicists, and industrial scientists, too.

Auteur
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.

Texte du rabat
The one-stop reference source for fundamentals, advances and intriguing problems of solid-state electrochemistry. This important and rapidly developing scientifi c fi eld integrates many aspects of the classical electrochemical science and engineering, materials science, solid-state chemistry and physics, heterogeneous catalysis and other areas of physical chemistry. The range of practical applications includes many types of batteries, fuel cells, analytical appliances, electrochemical pumps and compressors, solid-state electrolyzers and electrocatalyticreactors, synthesis of new materials with improved properties and corrosion protection, supercapacitors, electrochromic and memory devices.
The first volume contains brief reviews dealing with the general methodology of solid state electrochemistry, the major groups of solid electrolytes, mixed ionic-electronic conductors, and selected applications of the electrochemical cells. Particular attention is focused on the nanostructured solids, superionics, polymer and hybrid materials, insertion electrodes, electroanalysis and electrochemical sensors. Due to the highly interdisciplinary nature of the topic, this ready reference is of great interest to industrial and academic researchers, engineers and postgraduate students specializing in all related areas of science and technology.

Contenu

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 ...