Solid State electrochemistry

Transcription

1 Solid State electrochemistry edited by Peter G. Bruce Department of Chemistry, University of St Andrews, Scotland IH CAMBRIDGE ^pf UNIVERSITY PRESS

2 Preface Introduction P. G. BRUCE A brief history of solid State electrochemistry Crystalline electrolytes Glass electrolytes Polymer electrolytes Intercalation electrodes Interfaces References page xv Crystalline solid electrolytes I: General considerations and the major materials 7 A. R. WEST 2.1 Introduction Conduction mechanisms Mobile ion concentrations: doping effects Materials with disordered sublattices: a-agl Ion trapping effects Potential energy profiles The activation energy for conduction Hopping rates The ac conductivity spectrum: local motions and long ränge conduction Survey of solid electrolytes: general comments The beta-aluminas Stoichiometry Structure Properties Other alkali ion conductors NASICON LISICON 33 ix

3 Li 4 Si0 4 derivatives Li 3 N Miscellaneous materials Oxide ion conductors Fluoride ion conductors Proton conductors 40 References 41 3 Crystalline solid electrolytes II: Material design 43 J. B. GOODENOUGH 3.1 Quality criteria Electronic energies lonic energies Intrinsic energy gap AH g Motional enthalpy AH m Trapping energy AH, lonic conductivity Phenomenology Correlated ionic movements Proton movements Examples Stoichiometric Compounds Doping strategies Proton conductors 69 References 72 4 Ionic transport in glassy electrolytes 74 j. L. SOUQUET 4.1 Ionic transport: experimental facts Chemical composition of ionically conductive glasses Kinetic and thermodynamic characteristics of glassy 79 electrolytes 4.4 A microscopic approach to ionic transport in glasses Thermodynamics of Charge carriers: weak electrolyte theory Conductivity measurements and the thermodynamics of glass A microscopic model for ionic transport above the vitreous 90 transition temperature References 93 5 Polymer electrolytes I: General principles 95 D. F. SHRIVER AND P. G. BRUCE 5.1 Background Polymer-salt complexes Early developments 96

4 5.2.2 Polymer segment motion and ion transport Formation Structure Host polymers Proton conductors Polyelectrolytes Influence of complexing agents and solvents Summary 116 References Polymer electrolytes II: Physical principles 119 P. G. BRUCE AND F. M. GRAY 6.1 Introduction Why do salts dissolve in polymers? Thermodynamics of dissolution Which salts dissolve in which polymers Evidence for cation solvation Ion association Negative entropy of dissolution Mechanisms of ionic conduction Temperature and pressure dependence of ionic conductivity The dynamic response of polymer electrolytes Ion association and ion transport Ion association Transport Summary 158 Appendix 158 References Insertion electrodes I: Atomic and electronic structure 163 of the hosts and their insertion Compounds W. R. MCKINNON 7.1 Important aspects of ionic and electronic structure Sites for ions 'Sites' for electrons (electronic structure) Examples of host Compounds One-dimensional host, three-dimensional network of sites Three-dimensional structure, with one-dimensional tunnels Two-dimensional Systems: layered host, layers of sites for 170 guests Three-dimensional Systems Thermodynamics of insertion, AG, AS, AH Relation of voltage to chemical potential Measuring the partial entropy 178 xi

5 7.4 Lattice-gas modeis Entropy of ions Entropy of electrons Li x Mo 6 Se 8 as an example of a lattice gas Site energies in lattice-gas modeis Interaction energies in lattice-gas modeis Role of disorder Hysteresis Microstructure - Staging and cointercalation Staging Cointercalation Future prospects 196 References Electrode Performance 199 w. WEPPNER 8.1 Electrodes: Ionic sources and sinks Transport of ions and electrons in mixed conductors Kinetics of electrodes and the role of electrons in atomic 208 transport 8.4 Thermodynamics of electrodes Measurement of kinetic and thermodynamic electrode 219 Parameters References Polymer electrodes 229 B. SCROSATI 9.1 Introduction The case of polyacetylene Electrochemical doping processes Heterocyclic polymers The electrochemical doping of heterocyclic polymers Polyaniline Mechanism of the doping processes in conducting polymers Methods for monitoring the doping processes in conducting 244 polymers Optical adsorption Microbalance studies 9.9 Kinetics of the electrochemical doping processes Kinetics of polyacetylene electrodes Kinetics of heterocyclic polymers 9.10 Methods for enhancing diffusion processes in polymer electrodes 9.11 Applications of polymer electrodes 9.12 Lithium rechargeable batteries Charge-discharge rate xu

6 Self-discharge Energy content The future of the lithium/polymer battery Optical displays The future of polymer displays 261 Acknowledgements 262 References Interfacial electrochemistry 264 R. D. ARMSTRONG AND M. TODD 10.1 The double layer at blocking interfaces Non-blocking metal electrodes - one mobile Charge in the 277 electrolyte 10.3 Non-blocking metal electrodes with more than one mobile 283 Charge in the electrolyte 10.4 The effect of surface films on interfacial measurements The effect of surface roughness on interfacial measurements Other non-blocking interfaces Two step charge transfer reactions 290 References Applications 292 O. YAMAMOTO 11.1 Introduction Solid electrolyte batteries Intercalation electrodes for batteries Solid oxide fuel cells Solid electrolyte sensors Electrochromic devices (ECDs) Electrochemical potential memory device 327 References 329 Index 333 xm