Solid Electrolytes

List of Contributors

Preface


1 Introduction

References

Part I Theory and Experimental Method


2 Introduction to the Theory of Solid Electrolytes

I. Introduction

II. Macroscopic Evidence for Liquid Nature

III. Structural Models

IV. Kinetic Models

Appendix I: Theories of Liquids

Appendix II: Experimental Techniques

References


3 Crystal Structures and Fast Ionic Conduction

I. Introduction

II. Interstitial Motion in Body-Centered Cubic Structures

III. Interstitial Motion in the Rutile Structure

IV. Other Materials with Unidirectional Tunnels

V. Materials with the Fluorite and Antifluorite Structures

VI. Materials with Layer Structures

VII. Materials with Three-Dimensional Arrays of Tunnels

VIIL Structures with Isolated Tetrahedra

IX. General Comments

References


4 Diffraction Studies of Superionic Conductors

I. Introduction

II. Diffractional Fundamentals

III. Polycrystalline Materials

IV. Single Crystals

V. Defects and Disorder

References


5 Transport Mechanisms and Lattice Defects

I. General

II. Diffusion and Ionic Conductivity Equations

III. Defects and Split Configurations

IV. Activation Process and Transmission Coefficient

V. Random Walk and Correlation Effects

VI. Application to j8-Alumina

VII. Liquidlike Transport? Conclusions

References


6 High-Frequency Measurements and Interpretations

I. Introduction and Survey

II. Quasi-Elastic Neutron Scattering

III. Electromagnetic Spectra

References


7 NMR Techniques for Studying Ionic Diffusion

I. Introduction

IL Basic Principles of NMR Observations

III. Survey of Selected Systems

References


8 Electron Spin Resonance Application to Solid Electrolytes

Introduction


1. General Considerations about Electron Spin Resonance


9 The Influence of Crystal Structure and of Microstructure on Some Properties of Polycrystalline β-Alumina

I. Introduction

II. Analysis of the Electrical Properties of Polycrystalline β-Alumina

III. The Effects of Fabrication Details on Microstructure and Properties

IV. Summary and Concluding Remarks

References


10 Low-Frequency Measurements on Solid Electrolytes and Their Interpretations

I. Introduction

II. General Impedance Behavior of Solid Cell System

III. Electrical Measurement Techniques

IV. Determination of Bulk Properties

V. Determination of Interfacial Properties

Appendix I. Complex Impedance and Admittances: Argand Diagrams

Appendix II. Relationship between Complex and Transient

Impedances: Laplace Transforms

References


11 Interface Phenomena

I. Introduction

II. Qualitative Theory of Solid Electrolyte Interfaces

References

Part II Materials


12 Solid Electrolytes as a Materials Problem

I. Introduction

II. Ionic Conductivity and Lattice Defects

III. Macroscopic Aspects of Ionic Conductivity

References


13 Organic Ion Conductors

I. Introduction

II. Silver Ion Conductors

III. Copper(I) Ion Conductors

IV. Protonic Conductors

V. Summary

References


14 Inorganic Silver Ion Conductors

I. Introduction

II. The Structure of α-Agl

III. Other Structures with a Body-Centered Cubic Anion Arrangement

IV. Structures with a Cubic Close-Packed Anion Arrangement

V. Structures of β-Mn Type-M Ag4I5

VI. Structural Basis for Silver Ion Conductors

VII. Ionic Conduction and Diffusion

VIII. Thermodynamic Properties

IX. Special Studies

X. Uniqueness of Ag+ as a Mobile Ion

References


15 Inorganic Copper Ion Conductors

I. Introduction

II. Ionic Conductivity

III. Thermoelectric Power

IV. Electronic Conductivity

V. Other Aspects

VI. New Compounds with High Ionic Conductivity

VII. Summary

References


16 β-Aluminas

I. Introduction

II. Elaboration of Materials

III. Crystal Structure of β - and β"-Phases

IV. Relations between Layer Structure and Electrical Properties of β-Aluminas

V. Additional Ions in β-Aluminas

References


17 Ionic Conductive Glasses

I. General Introduction

II. Methods of Measurement of Electrical Conductivity in Vitreous Materials

III. Main Experimental Results and Their Interpretation

References


18 Oxygen Ion Conductors

I. Introduction

II. Theory

III. Experimental Methods

IV. Fluorite-Type Oxides

V. Perovskites and Other Oxides

VI. Interfacial Processes

VII. Oxides as Useful Electrolytes

References


19 Fluorine Ion Conductors

I. Introduction

II. General Principles

III. Materials with Tysonite and YFg Structures

IV. Fluorites

V. Applications

References


20 AnBXm Solid Electrolytes

I. Introduction

II. A2BO4 Compounds

III. A4BO4, A5BO4, and AA'BO4 Compounds

IV. ABX4, A2BX5, and A3BX6 Compounds

V. Concluding Remarks

References


21 Mixed One- and Two-Dimensional Conductors

I. Introduction

II. Structural Types

III. Ionic Conductivity


22 Electronic Insulators with Tunnel and Sheet Structures

I. Introduction

II. Materials of Hollandite Type

III. Materials of LiNb6O15F Type

IV. Materials of NaxFexTi2-xO4 Type

V. Sheet Materials of Ax(LxM1-x)O2 Type

References


23 Skeleton Structures

I. Design Constraints

II. Examples

References


24 Zeolites

I. Introduction

II. Zeolite Structures

III. Ion Exchange Equilibria

IV. Ion Diffusion in Zeolite Channels

References

Part III Applications


25 High-Temperature Fuel Cells

I. Introduction

II. Principles and Fundamentals of the High-Temperature Fuel Cell

III. Present State and Problems of Development

IV. Technical and Economic Aspects

References


26 Application of Solid Electrolytes in Galvanic Cells

Part 1 Low-Energy-Density Cells

I. Introduction

II. Low-Energy-Density Cells

References

IV. Role in Battery Cathodes and Anodes

References


27 Application of Solid Electrolytes in Galvanic Cells

I. Introduction

II. The Sodium-Sulfur Cell

III. The Lithium-Sulfur Cell

IV. Other Developments

V. Concluding Remarks

References


28 Thermodynamic Measurements with Solid Electrolytes

I. Introduction

II. Thermodynamic Treatment of Electromotive Force Data

III. Thermodynamic Equilibrium at Electrodes

IV. Applications of Solid Electrolytes

V. Recent Developments

References


29 Solid-State Potentiometric Gauges for Gaseous Species

I. Introduction

II. Oxygen Gauges

III. Other Gauges

References


30 High-Temperature Heating Elements in Oxidizing Atmosphere

I. Materials Used

II. Heating Elements for Laboratory Furnaces

III. Heating Elements for Industrial Furnaces

References


31 Use of Crystalline Solid Electrolytes as Membranes in Ion-Selective Electrodes

I. Introduction

II. Membrane Requirements in an Ion-Specific Electrode

III. Influence of Solid Electrolyte Solubility

IV. Ion Size, Ion Charge, and Selectivity

V. Interface Double Layer and Rate of Exchange between a Solid and a Liquid Electrolyte


32 Application Prospects of Solid Electrolytes

I. Introduction

II. The Energy-Supply System and Solid Electrolytes

III. Applications of Solid Electrolytes

References

Index