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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