This book is the completely revised and extended version of the German edition "Einfiihrung in die Elektrochemie fester Stoffe" which appeared in 1973. Since then, the subject of the electro chemistry of solids has developed further and a large number of new solid electrolytes have been discovered. With the help of solid electrolytes, i. e. solid ionic conductors, galvanic cells are constantly being built for thermodynamic or kinetic investigations and for technical applications. Though the book takes these new develop ments into consideration, its main aim is to provide an introduction to the electrochemistry of solids, emphasizing the principles of the subject but not attempting to present a complete account of the existing literature. The latter can be found in handbooks and specialists' reports of conferences in this field; these are referred to in the text. This book is written for scientists and graduate stu dents who require an approach that will familiarize them with this field. It is assumed that the reader will be acquainted with the fundamentals of physical chemistry. The various chapters have been written so that most of them can be read independently of each other. Parts which may be omitted during a first reading are printed in small type. Of vital importance for the publication of this English edition have been the comments, suggestions and the help of colleagues and co-workers. I would particularly like to express my thanks to Dr. Holzapfel, Dl'. Lohmar, Professor Mitchell, Dr.
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ISBN-13
978-3-540-11116-0 (9783540111160)
DOI
10.1007/978-3-642-68312-1
Schweitzer Klassifikation
1 Introduction.- 1.1 References.- 2 Disorder in Solids.- 2.1 General Considerations Regarding Lattice Defects and Their Significance.- 2.2 Point Defects.- 2.3 Disorder Equilibria.- 2.4 The Chemical Potentials of Defects.- 2.5 Internal Disorder Equilibria.- 2.6 Kinetic Derivation of Disorder Equilibria.- 2.7 Disorder Equilibria Involving Neighbouring Phases.- 2.8 Disorder Equilibria Involving Surfaces.- 2.9 References.- 3 Examples of Bisorder in Solids.- 3.1 Disorder in Doped Zirconium Dioxide and Thorium Dioxide.- 3.2 Disorder in ZnO, Cu2O and CuO.- 3.3 Structural Disorder.- 3.4 References.- 4 Thermodynamie Quantities of Quasi-Free Electrons and Electron Defects in Semiconductors.- 4.1 General Considerations.- 4.2 Electrochemical Potential $$\tilde\eta_{\rm e}$$ of Electrons.- 4.3 The Fermi Distribution Function f (?).- 4.4 The Density of States D(?).- 4.5 Relation Between the Concentration of Electrons or Electron Defects and Their Electrochemical Potential.- 4.6 Chemical Potential of Electrons and Standard States.- 4.7 The Activity Coefficient of Electrons and Electron Defects in the Case of Degeneracy.- 4.8 The Phase Boundary Solid/Vacuum. The Work Function W.- 4.9 The Volta Potential or Contact Potential.- 4.10 The Phase Boundary Solid I/Solid II. The Galvani Voltage.- 4.11 References.- 5 An Example of Electronic Disorder. Electrons and Electron Defects in ?-Ag2S.- 5.1 Disorder in ?-Ag2S and Coulometric Titration Curve.- 5.2 Quantitative Evaluation of Coulometric Titration Curves of ?-Ag2S.- 5.3 Entropy and Enthalpy of the Electrons in Ag2S.- 5.4 References.- 6 Mobility, Diffusion and Partial Conductivity of Ions and Electrons.- 6.1 Phenomenological Treatment of Transport Processes.- 6.1.1 Diffusion Equations.- 6.1.2 The Mechanical Mobility Bm.- 6.1.3 The Nernst-Einstein Equation.- 6.1.4 The Component Diffusion Coefficient DK.- 6.1.5 Relationship Between D and DK.- 6.1.6 Relationship Between the Component Diffusion Coefficient DK and the Tracer Diffusion Coefficient DTr.- 6.1.7 Particle Flux in an Electrical Field.- 6.1.8 Particle Flux in the Presence of a Concentration or Activity Gradient and an Electrical Field.- 6.1.9 Description of Particle Fluxes Using the General Transport Equations of Irreversible Thermodynamics.- 6.1.10 Chemical Diffusion.- 6.2 Statistical Treatment of Transport Quantities.- 6.3 Experimental Determination of Partial Conductivities.- 6.3.1 Transference Measurements.- 6.3.2 Measurements of Transference Numbers by Means of Emf Measurements Using Galvanic Cells.- 6.3.3 Determination of Partial Conductivities by Means of Stationary Polarization Measurements.- 6.4 Alternating Current Measurements. Complex Impedance Diagrams.- 6.5 References.- 7 Solid Ionic Conductors, Solid Electrolytes and Solid-Solution Electrodes.- 7.1 Solid Ionic Conductors, Solid Electrolytes.- 7.1.1 Oxygen Ion Conductors.- 7.1.2 Sodium Ion Conductors.- 7.1.3 Silver Ion Conductors.- 7.1.4 Copper Ion Conductors.- 7.1.5 Lithium Ion Conductors.- 7.1.6 Fluorine Ion Conductors.- 7.2 Solid-Solution Electrodes.- 7.3 References.- 8 Galvanic Cells with Solid Electrolytes for Thermodynamic Investigations.- 8.1 Determination of Gibbs Reaction Energies.- 8.2 Determination of Chemical Potentials, Thermodynamic Activities or Partial Pressures.- 8.2.1 Galvanic Cells of the First Kind.- 8.2.2 Galvanic Cells of the Second Kind.- 8.3 Determination of ?S and ?H from the Temperature-Dependence of the Electromotive Force of Galvanic Cells.- 8.4 References.- 9 Technical Applications of Solid Electrolytes --Solid-State Ionics.- 9.1 Sensors.- 9.2 Fuel Cells and Electrolyzers.- 9.3 Batteries with Solid Electrolytes. The Sodium-Sulfur Battery.- 9.4 Chemotronic Building Units.- 9.4.1 Coulometers and Time Switches.- 9.4.2 Analog Memories.- 9.4.3 Capacitors Containing Solid Electrolytes.- 9.5 References.- 10 Solid-State Reactions.- 10.1 Theory of the Formation of Tarnishing Layers on Metal Surfaces.- 10.1.1 Rate Laws Describing the Formation of Tarnishing Layers.- 10.1.2 Calculation of the Parabolic Rate Law Constant Using the Method of C. Wagner.- 10.2 Examples of the Formation of Tarnishing Layers on Metals and Other Solid-State Reactions.- 10.2.1 Oxidation of Copper to Cu2O at 1000°C.- 10.2.2 Oxidation of Zinc at 400°C.- 10.2.3 Reaction of Silver with Liquid Sulfur at 400°C.- 10.2.4 Formation of Double Salts and Double Oxides via Solid-State Reactions.- 10.3 References.- 11 Galvanic Cells with Solid Electrolytes for Kinetic Investigations.- 11.1 Electrochemical Measurements of Oxygen Diffusion in Metals at Higher Temperatures Using Zirconium Dioxide as Solid Electrolyte.- 11.1.1 The Principle of Electrochemical Measurements of Oxygen Diffusion in Metals.- 11.1.2 The Potentiostatic Method.- 11.1.2.1 The Linear Geometry.- 11.1.2.2 The Cylindrical Geometry.- 11.1.3 The Galvanostatic Method.- 11.2 Electrochemical Investigations on the Formation of Nickel Sulfide in the Solid-State at Higher Temperatures.- 11.2.1 Potentiostatic Measurements.- 11.2.2 Galvanostatic Measurements.- 11.3 Electrochemical Investigations of the Transfer of Silver, Silver Ions and Electrons Across the Phase Boundary Solid Silver/Solid Silver Sulfide.- 11.3.1 Simplified Experimental Arrangement.- 11.3.2 Extended Experimental Arrangement.- 11.3.3 Results and Discussion of Polarization Measurements at the Phase Boundary Ag(s)/Ag2S(s)..- 11.4 Electrochemical Studies of Evaporation and Condensation.- 11.5 An Electrochemical Knudsen Cell for the Investigation of the Thermodynamics of Gases.- 11.6 Electrochemical Measurements of the Chemical Diffusion Coefficient of Wüstite and Silver Sulfide.- 11.7 References.- 12 Non-Isothermal Systems. Soret Effect, Transport Processes, and Thermopowers.- 12.1 Basic Equations of Irreversible Thermodynamics.- 12.2 The Soret Effect.- 12.3 Stationary Transport Processes in Solids Subjected to a Temperature Gradient.- 12.4 Thermoelectric Powers.- 12.5 References.- Author Index.
