SUPERJ:ONJ:C CONDUCTORS

PHYSICS OF SOLIDS AND LIQUIDS

Editorial Board: Jozef T. Devreese • University of Antwerp, Belgium Roger Evrard· University of Liege, Belgium Stig Lundqvist • Chalmers University of Technology, Sweden Gerald D. Mahan. Indiana University, Bloomington, Indiana Norman H. March· Imperial College, London, England

SUPERIONIC CONDUCTORS Edited by Gerald D. Mahan and Walter L. Roth. 1976

SUPERJ:ONJ:C CONDUCTORS

Edited by

Gerald D. Mahan Indiana University

Bloomington, Indiana

and

Walter L. Roth General Electric Research and Development Center

Schenectady, New York

PLENUM PRESS· NEW YORK AND LONDON

Library of Congress Cataloging in Publication Data

Conference on SuperionicConductors-Chemistry, Physics, and Applications, General Electric Research and Development Center, 1976. Superionic conductors.

(physics of solids and liquids) 1. Ions-Migration and velocity-Congresses. 2. Superionic conductors-Congresses.

I. Mahan, Gerald D. II. Roth, Walter L. III. Title. QD561.C641976 537.6'23 76-28538 ISBN-13: 978-1-4615-8791-0 e-ISBN-13: 978-1-4615-8789-7 DOl: 10.1007/978-1-4615-8789-7

Proceedings of a Conference on Superionic Conductors: Chemistry, Physics, and Applications held at the General Electric Research and Development

Center, Schenectady, New York, May 10-12, 1976

© 1976 Plenum Press, New York Softcover reprint ofthe hardcover 1st edition 1976 A Division of Plenum Publishing Corporation 227 West 17th Street, New York, N. Y. 10011

All rights reserved

No part of this book may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, microfilming,

recording, or otherwise, without written permission from the Publisher

Preface

A hundred and eighty five chemists, physicists, and engineers met in Schenectady, New York, for the three days May 10-12, 1976, to discuss the subject of Superionic Conductors. This International Conference was held at the Research and Development Center of the General Electric Company.

The subject of the Conference was fast ion transport in solids. These materials have potential application in new types of batteries, fuel cells, and sensors. Some like beta alumina are under active development in nov'el new systems. Their study has also become a popular area of scientific investigation. One objective of the Conference was to provide a forum for interdisciplinary communication between chemists, physicists, and engineers. The Conference was an attempt to bring these groups together, in order to listen to each others problems and progress.

We began organizing the Conference in the spring of 1975. It was suggested to General Electric managers Drs. Craig S. Tedmon, Jr. and Roland W. Schmitt. They provided immediate and enthusiastic support. They also provided the advice, staff, and backup which were necessary at all points in the planning and duration of the Conference. We were also pleased that they could participate in the Conference: Dr. Tedmon welcomed the participants and officially opened the Conference, and Dr. Schmitt gave the after banquet address. We thank them. Additional and invaluable help, and advice, were also provided by Drs. D. Chatterji, J. B. Bush, G. W. Ludwig, and J. B. Comly.

We were joined on the program committee by Drs. B. A. Huberman (Xerox), R. A. Huggins (Stanford), J. T. Kummer (Ford), M. O'Keeffe (Arizona State), and D. B. McWhan (Bell). This committee worked hard, not only in selecting the invited and contributed papers, but also

v

PREFACE

in arranging the schedule. The chapters in this book are the talks given by the invited speakers. Each speaker was as~ed to survey his area, and the composite picture should provide an up-to-date view of this rapidly evolving field. Papers on applications and needs were scheduled early in the Conference in order to place the entire field in perspective, and to stimulate awareness of the significance of each investigator's work to the whole. These were followed by papers on theory, the physical properties of single crystals, and the properties of polycrystalline ceramic materials used in practical systems. The program committee decided to represent the contributed papers by just their abstract. These results are invariably published in complete form elsewhere, and it was felt unnecessary to republish them here.

The contributed papers were divided into two classes. Some were presented on the program as ten minute talks with five minutes of discussion. Due to lack of time, since there were no parallel sessions, others were presented in poster sessions: results were pinned on posters which were on view in a seminar room adjacent to the main Conference lounge. The division between these two classes was made chronologically--those abstracts submitted before the official January 5, 1976 deadline were nearly all accomo­dated into the main program. Abstracts submitted late were put into the poster sessions. Before the meeting, some authors of poster papers complained that they were receiving second class treatment. But during the meeting it became apparent that the poster papers were a more successful format for presenting the contributed papers. They could be viewed at leisure, and discussed in depth. After the meeting, many felt that next time, if we hold another meeting, all contributed papers should be presented in the poster sessions. Then more leisure time could be scheduled into the program to encourage their viewing and discussion. They also have the advantage that one can be flexible in accepting later papers for poster sessions since no scheduling is involved. We were still accepting papers ten days before the Conference, when the program booklet finally went to press. All contributed papers have been treated equally in preparing the abstracts for publi­cation. We also permitted author~ to revise them at the meeting, and these contributed abstracts are often quite different than those in the program booklet.

PREFACE

The trick to organizing a successful conference is to start a bandwagon effect, whereby everybody thinks it is going to be a success and wants to participate. Special thanks must go to Dr. J. R. Birk, who was the first person to join the bandwagon. His early and generous support, from the Electric Power Research Institute, was crucial in the early days of proposing the Conference. It gave concrete backing to the Conference proposal. Soon after­wards we received additional support from the Air Force Office of Scientific Research and the National Science Foundation. Cosponsorship and valuable publicity were provided by the American Physical Society and the Electro­chemical Society.

A special thanks must also go to those who did the work. Foremost we thank Elizabeth Allen, who came out of retirement to help us with the local details. She is the conference and publication expert at the General Electric Corporate Research and Development Center. She was invaluable in organizing buses, motels, meals, and printing. Her efforts in overseeing the preparation and printing of the Conference Program were crucial: thanks to her they were available on time. She also ran the registration and information table, organized the travel reimbursing, and helped everybody. We also thank the secretaries who did the endless typing: Mrs. Karen Gibson at Indiana University, and Mrs. Mary Sammler and Stephenie Smaldone at General Electric. We also thank Professor Harold Story at SUNY­Albany, for helping arrange the Conference banquet at his beautiful campus.

Schenectady, New York May, 1976

G. D. Mahan W. L. Roth

Contents

A: ELECTROCHEMICAL SYSTEMS

Energy Storage, Batteries, and Solid Electrolytes: Prospects and Problems . • • • . • . • • • • 1

J. R. Birk

High Temperature Solid Electrolyte Fuel Cells T. L. Markin, R. J. Bones, and R. M. Dell

Applications of Beta Alumina in the Energy Field N. Weber

Properties and Applications of Solid Solution Electrodes •.....•..•...

B. C. H. Steele

The Electrochemical Properties of Some Solid E1ectro1yte~ • . . . .

R. D. Armstrong and T. Dickinson

Interpretation of AC Impedance Measurements in Solids • . . . . . . . . . . .

J. R. Macdonald

Use of Pulse Methods in the Study of Solid E1ectro1ytes* . . . . . .

P. H. Botte1berghs

A Study of the Electrical Properties of Single Crystal and Po1ycrysta11ine S-A1umina Using Complex Plane Methods* . • . . .

A. Hooper, P. McGeehin, and A. E. Hughes

* Articles marked with an asterisk appear in the form of abstracts only.

ix

15

37

47

65

81

99

99

x CONTENTS

B: THEORY

Phase Transitions and Translational Freedom in Solid Electrolytes . . • • • . . .• •• • • 101

M. O'Keeffe

Theoretical Issues in Superionic Conductors . . • • . . 115 G. D. Mahan

Path Probability Method as Applied to Problems of Super ionic Conduction • • . • • • • • . 135

H. Sa to and R. Kikuchi

Domain Model for 'Superionic Conductors • . • . • . • • 143 W. van Goo1

Remarks on Phase Transitions and Dynamics in Super ionic Conductors • • • • . .• •...• 151

B. A. Huberman

Vibration Effect in the Order-Disorder Transition Theory of RbAg4I 5 • . • . . . • • • • . • . . • . 157

S. Choi and W. M. Lee

Super ionic Conductivity and Order-Disorder Transition* . . •. ...••....••••• 167

R. Kikuchi and H. Sato

A Microscopic Model for Sub1attice Disorder in Ionic Crysta1s* • . . . . • . . • .• •.•. 167

D. o. Welch and G. J. Dienes

Minimum Energy Path Model Calculation for Several Fast Ionic Conductors* . . •. • • • 168

o. B. Ajayi, I. D. Raistrick, L. E. Nagel, and R. A. Huggins

One-Dimensional Models for Super ionic Conductors* . • . 168 J. C. Wang and D. F. Pickett

A Quantum Mechanical Theory of Ionic Diffusion* • • . • 169 E. Gorham-Bergeron

CONTENTS xi

C: SILVER CONDUCTORS

Crystal Structure and Conductivity of AgI-Based Solid Electrolytes II • . • . . • • . • • . • • . 171

S. Geller

AgI-Type Solid Electrolytes: Properties at Frequencies Between 109 and 1013 Hz • • . • . • . 183

K. Funke

Lattice Dynamics and Ionic Motion in Super ionic Conduc tor s •.••••....•. •••• 201

H. R. Zeller, P. Bruesch, L. Pietronero, and S. Str~ssler

Properties of the 208K Phase Transition in Single Crystals of RbAg4IS*' . • • . • • . •. • •• 217

M. B. Salamon, R. Vargas, F. L. Lederman, and A. Schultz

The Distribution of Silver Ions in a-AgI* . • . • . . • 217 R. J. Cava and B. J. Wuensch

Raman Spectra of the Super ionic Conductors AgI and RbAg4IS*' •••.•..•...••••.•. 218

M. J. Delaney and S. Ushioda

Raman Measurements of AgI and RbAg4I S*' .•••••.. 218 G. Burns, F. H. Dacol and M. W. Shafer

Raman Scattering from RbAg4IS*' • • . . • • • . . . . • 219 D. Gallagher and M.V. Klein

Ion-Ion Correlations in Superionic Conductors RbAg4IS*' ••••••••••••••••••.• 220

T. Kaneda and T. Hattori

Raman Spectra of Some Ionic Conductors* • • . . • 220 D. F. Shriver, D. Greig, G. Joy, and M. B. Leal

Local Order in the Solid Electrolyte a-HgAg214* ••.• 221 T. Hibma and H. U. Beyeler

xii CONTENTS

The Gradual Order-Disorder Transition in PyAg516* •.. 221 T. Hibma

Studies of Ionic Conduction and Diffusion in Solid Silver Halides* ....• •...• 222

R. J. Friauf

D: BETA ALUMINA

Studies of Stabilization and Transport Mechanisms in Beta and Beta" Alumina by Neutron Diffraction . . . • . . . . . . . • . • . . 223

W. L. Roth, F. Reidinger, and S. LaPlaca

X-Ray Diffuse Scattering from B Alumina J. P. Boilot, G. Collin, R. Comes, J. Thery, R. Collongues, A. Guinier

. . . . . . 243

Neutron Scattering Studies of Solid Electrolytes . • . 261 S. M. Shapiro

Experimental Probes of Microscopic Interactions Controlling Diffusion in Cation Substituted B-Alumina . . . . . . • . • . . . . . • • . . . . 279

S. J. Allen, Jr., L. C. Feldman, D. B. McWhan, J. P. Remeika, and R. E. Walstedt

Light Scattering Measurements in Solid Ionic Conductors .............•..... 299

L. L. Chase

NMR Studies of Superionic Conductors, Primarily Beta-Alumina. . . .. • ....•.. 317

H. S. Story, W. C. Bailey, I. Chung, and W. L. Roth

Additives and Resistivity in Beta-Alumina . . . . . . . 335 J. H. Kennedy

The Inter- and Intra-Granular Resistivity of Beta-Alumina . . . . . 351

R. W. Powers

CONTENTS

Nuclear Relaxation and Barrier Height Distribution in Na S-Alumina* ••••••

R. E. Walstedt, R. Dupree, and J.P. Remeika

NMR Study of Sodium Ion Motion in S"-Alumina*. W. C. Bailey, H. S. Story, and W. L. Roth

Sodium NMR Study of the Effects of Additives in Sodium Beta-Alumina Ceramic Samples*

I. Chung, H. S. Story, and W. L. Roth

Calculation of the Phonon Spectra of S-Alumina* W. Y. Hsu

The Thermal Conductivity of S-Alumina* P. J. Anthony and A. C. Anderson

A Collective Ionic Model for Na S-Alumina -Evidence from Conductivity Measurements Between 107 - 1013 Hz* • • . • • •

U. Strom, P. C. Taylor, S. G. Bishop, T. L. Reinecke, and K. L. Ngai

Far Infrared+Spectra of Sodium-S-Alumina and Its K+, Rb , Cs+, Ag+ and Tl+ Analogs*

W. M. Risen, Jr. and W. M. Butler

The Lattice Location of Conducting Atoms in Ag, K S-Alumina by Particle Channeling*.

L. C. Feldman, J. P. Remeika, P. J. Silverman, and K. Komaki

Structural Characteristics and Non-Stoichiometry of S-Alumina Type Compounds* • • • • • • •

H. Sato, Y. Hirotsu, and J. K. MCCoy

Planar [00.1] Disorder in Sodium Beta Alumina* L. C. DeJonghe

Latest Reults of "Laboratoire de Chimie Appliquee de l'etat solide de l'ENSCP" on Compounds

xiii

369

369

370

370

371

372

372

373

374

374

of S Alumina Type* • • • . • • • • • • • • • 374 J. Antoine, J. P. Boilot, G. Collin, R. Collongues, D. Gratias, A. Kahn, J. Livage, J. Thery, and D. Vivien

xiv CONTENTS

Power Neutron Diffraction Analysis of Sodium Silver and Deuterium Beta Aluminas*. • • • • • • 375

B. C. Tofield, A. J. Jacobson, and W. A. England

Ammonium Ion Reorientation in NH4+ S-Alumina* J. D. Axe, L. M. Corliss, J. M. Hastings, O. Muller, and W. L. Roth

X-Ray Diffuse Scattering from Alkali and Europium S-Aluminas* • • • •

D. B. McWhan, P. D. Dernier, C. Vettier, and J. P. Remeika

Surface Studies of Na-S-Alumina* M. L. Knotek

Transport Properties of Single Crystal Beta Alumina*. • • • • • • •

N. Choudhury, J. N. Mundy, and S. Puri

E: OTHER SUPERIONIC CONDUCTORS

376

376

377

378

Some Super Ionic Conductors and Their Applications 379 T. Takahashi

Fluorite-Type Oxygen Conductors A. S. Nowick and D. S. Park

395

Ion Dynamics and Defect Structure of Cubic PbF2* • • • 413 J. B. Boyce and J. C. Mikkelsen

NMR Studies of F Ion Motion in Doped S-PbF2* • • • • • 413 T. Y. Hwang, I. J. Lowe, K. F. Lau, and R. W. Vaughan

E. S. R. of Mn2+ in Zirconia-Calcia Solid Solutions* • • • • 414

G. Bacquet, J. Dugas, and C. Escribe

Composition and Electrical Properties of R. F. Sputtered Stabilized Zirconia Thin Films* 414

M. Croset, G. Velasco, and J. Siejka

CONTENTS xv

Influence of Dopant and Dopant Concentration on Ionic Conduction and Stoichiometry in Solid Ceria Electrolytes*. • • • . • • • • • . • • . • 415

H. L. Tuller and D. S. Tannhauser

New Fluor Ion Conductors* • • • •• .••••••• 416 J. M. Reau, C. Lucat, G. Campet, J. Claverie, J. Portier, and P. Hagenmuller

New Lithium Ion Conductors* • • . • .• .• 417 B. A. Boukamp, I. D. Raistrick, C. Ho. Y-W. Hu, and R. A. Huggins

Ionic Conductivity in Lithium Aluminosilicate Solid Electrolyte Materials* . . • • • • • 418

R. M. Biefeld and R. T. Johnson, Jr.

Li+ Conduction in the Beta Alumina Structure* ••.•. 418 G. C. Farrington and W. L. Roth

Mechanism of Formation of the Sodium Gallate Super ionic Conductors* • . • . • • . 419

B. M. Foxman, S. J. LaPlaca, and L. M. Foster

Reaction of S"-Sodium Gallate with Water*. • • • • • . 420 L. M. Foster and G. V. Arbach

Electron Paramagnetic Detection of the Liquid­Like Motion of Divalent Ions in Solid S-Sodium Gallate*. • • • • • . ••• 421

R. S. Title and G. V. Chandrashekhar

New Solid Electrolytes* • . • . . . • . . • . 421 H. Y-P. Hong, J. A. Kafalas, K. Dwight, and G. B. Goodenough

Anomalous Properties of CU3VS4* ••••••••••.• 422 N. LeNagard, G. Collin, o. Gorochov, H. Arribart, A. Willig, and B. Sapoval

On the Transport Mechanism in Sulfate-Based Solid Electrolytes*

A. Lunden, E. Bowling, B. Heed, B. E. Melander, L. Nilsson, K. Schroeder, and C. A. Sjoblom

• • 423

xvi

Structural Aspects and High Partial Cu+-ionic Conductivity in Compounds of CuTeX (X=Cl, Br, I) * . . . . . . • . . . . •

U. v.Alpen, J. Fenner, J. Marcoll, and A. Rabenau

The State of Order of the Conducting Ions in Hollandites* . . • • • • . . • •

H. U. Beyeler, T. Hibma, and C. Schuler

Diffusion in the Intercalation Compounds of Layered Disulfides* . . • . • .

R. R. Chianelli, B. G. Silbernagel, and M. S. Whittingham

Single Crystal Studies of Cubic Phases of VOx by Neutron Diffraction*.

F. Reidinger, J. J. Reilly, and R. R. Stoenner

Author Index

Formula Index

Subject Index

the

CONTENTS

424

425

426

427

429

432

436