Electrode Processes in Solid State Ionics

NATO ADVANCED STl1DY INSTITUTES SERIES I

Proceedings of the Advanced Study Institute Programme, which aims at the dissemination of advanced knowledge and the formation of contacts among scientists from different countries

The series is published by an international board of publishers in conjunction with NATO Scientific Affairs Division

A Life Sciences Plenum Publishing Corporation B Physics London and New York

C Mathematical and D. Reidel Publishing Company Physical Sciences Dordrecht and Boston

D Behavioral and Sijthoff International Publishing Company Social Sciences Leiden

E Applied Sciences Noordhoff International Publishing Leiden

Series C - Mathematical and Physical Sciences

Volume 25 - Electrode Processes in Solid State /onics

Electrode Processes in Solid State lonics Theory and Application to Energy Conversion and Storage

Proceedings of the NATO Advanced Study Institute

held at Ajaccio (Corsica), 28 August-9 September 1975

edited by

M. KLEITZ Institut National Poly technique de Grenoble, Grenoble, France

J. DUPUY Universite Claude Bernard, Lyons, France

D. Reidel Publishing Company Dordrecht-Holland / Boston-U.S.A.

Published in cooperation with NATO Scientific Affairs Division

Library of Congress Catalpging in Publication Data

NATO Advanced Study Institute, Ajaccio, Corsica, 1975. Electrode processes in solid state ionics.

(NATO advanced study institutes series: Series C, Mathematical and physical sciences ; v. 25) an Includes bibliographies.

1. Electrodes Congresses. 2. Solid state chemistry Congresses. 3. Ionic crystals Congresses. I. Kleitz, M., 1937- II. Title. III. Series. QD571.N281975 541:3724 75-44113 ISBN-13: 978-94-010-1891-3 e-ISBN-I3: 978-94-010-1889-0 DOl: 10.1007/978-94-010-1889-0

Published by D. Reidel Publishing Company P.O. Box 17, Dordrecht, Holland

Sold and distributed in the U.S.A., Canada, and Mexico by D. Reidel Publishing Company, Inc. Lincoln Building, 160 Old Derby Street, Hingham, Mass. 02043, U.S.A.

All Rights Reserved Copyright © 1976 by D. Reidel Publishing Company, Dordrecht, Holland Softcover reprint of the hardcover I st edition 1976 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording or by any informational storage and retrieval system, without written permission from the copyright owner

CONTENTS

PREFACE

LIST OF PARTICIPANTS

INTRODUCTION - Descriptions of Junctions between Electronic and Solid Ionic Conductors M. KLEITZ, P. FABRY, and E. SCHOULER

Structure and Energetics of the Ionic Surface

VII

IX

P. MARK 19

Adsorption and Catalysis on Ionic Solids B. CLAUDEL 45

Structure and Defects at Ionic Crystal Surfaces J. M. BLAKELY 83

The Electrochemical Double Layer in Solid Electrolytes D. O. RALEIGH 119

Space Charge Polarisation J. R. MACDONALD 149

Polarization Studies on Solid State Electrolytes J. B. WAGNER 185

Electrode Reactions at Electrode-Solid Electrolyte Interfaces. Use of Electroanalytical Techniques J. VEDEL 223

Impedance Diagrams for Solid Electrolyte Cells R. D. ARMSTRONG 261

Ion Transfer at the Interface between an Electronic and Ionic Conductor H. GERISCHER

Contacts on Ionic Solids H. K. HENISCH

Electrochemical Coloration and Redox Reactions in Solid Ionic Conductors P. FABRY and M. KLEITZ

High Temperature Fuel Cells and Electrolysers B. C. H. STEELE

The Application of Solid State Ionics to Batteries R. M. DELL

Rechargeable Solid Electrolyte Traction Batteries R. M. DELL and L. S. EVANS

Various Utilisations of Solid Electrolytes M. VOINOV

277

309

331

367

387

411

431

PREFACE

The idea of an "Advanced Study Institute" on the theme of electrode reactions on solid electrolytes was put forward by Dr. J. Dupuy at the meeting of the International Society for Electrochemistry in Eindhoven in September 1973. Through Dr. Dupuy, the Solid State Physics Department of Lyons University offered the Institute possibilities of accommodation in Corsica that seemed particularly tempting.

The subject matter appealed to a number of people for a variety of reasons. A great deal of development work on applications comes up against interface phenomena which appreciably reduce anticipated performances. Numerous potential applications of specific electrodes or gauges appear that would benefit from a more systematic approach. From a more fundamental viewpoint, interface phenomena on ionic crystals are the subject of indepen­dent investigations in quite distinct research fields such as solid state physics and electrochemistry. The choice of an interpretation from among the different models available is very often not a straightforward matter, and an attempt to promote a synthesis by bringing together the proponents of the various "schools" could not fail to be rewarding.

The value of these arguments was recognized by NATO which awarded a substantial grant to the Institute. Further subsidies were awarded by the Mission Interministerielle pour l'Amenagement et l'Equipement de la Corse (Inter-Ministery Body for the Develop­ment of Corsica), Thomson-CSF Company, the Physics Faculty of ClaudeBernard University in Lyons, and the Institut Poly technique in Grenoble. The National Science Foundation granted travelling scholarships to young scientists from the United States taking part in the Institute. The members of the Organizing Committee and all the participants are greatly indebted to these organiza­tions.

The project of the "A.S.I." took shape in the course of later meetings of the European Group for Solid State Electrochemistry (Besan~on February 1974, Bressanone, December 1974), which assembled most of the members of the Scientific Committee.

Dr. D.O. Raleigh took charge of liaising with the United States and was a source of sound advice for the Committee. All these persons must be warmly thanked for their enthusiastic encourage­ment and most efficient help.

A vast bibliographic file was used to publicize the forthcoming meeting and was implemental in contacting many young specialists who had recently obtained valuable results in research fields that are traditionally distinct from Solid State Electrochemistry. The number of applications to attend the Institute far exceeded acceptable limits and almost half these requests had to be regretfully turned down.

This work is a collection of the teaching papers presented over the twelve days of study at the Institute. The courses were followed by fruitful discussions and work sessions on the follow­ing themes : • electrode polarization and mechanisms

electrode materials electrolyte reduction and decomposition electrochemical methods electrode reactions on semiconductors typical applications

During these work sessions original results were presented. Unfortunately, for economic reasons the number of pages of this book is stringently limited. Consequently, it is to be regretted that all this second facet of the Institute is not covered in the proceedings, and in particular the summaries of the discuss­ions which followed the teaching papers and which would have formed a very valuable complement.

In this field where development is so rapid and the number of people concerned so much greater than the actual participants in the Institute, it was felt that a prompt publication of the proceedings was essential. Consequently, some material defects are unavoidable and we trust that the reader will take them in good part.

To conclude, I would like to thank those who, although their names do not appear in any official capacity, made an essential contribution to the success of the Institute :

- the late Pascal Rossini, Mayor of the City of Ajaccio, and Jacques de Rocca Serra, Directeur de la Mission Regionale

for the sightseeing outings they organized and offered to the participants and which delighted us all

- Madame Cavalier and Monsieur Fouletier

for the considerable work they accomplished in the preliminary stages of the organization.

Grenoble October 1975

Michel Kleitz

LIST OF PARTICIPANTS

Directors :

M. KLEITZ, I.N.P. Grenoble, France C.H.S. DUPUY Co-Director, Universite Claude Bernard, Lyons,France J. DUPUY Co-Director, Universite Claude Bernard, Lyons, France

Scientific Committee :

R.D. ARMSTRONG, University of Newcastle-Upon-Tyne, England R.M.DELL, UKEA-Harwell, England C. DEPORTES t Institut National Poly technique, Grenoble, France D.H. COLLINS, Admiralty Engineering Laboratory, England H. GERISCHER, Fritz-Haber-Institut der Max Plank Gesellschaft,

Berlin, Germany S. PIZZINI, University of Milano, Italy B.C.H. STEELE, Imperial College, London, England D.O. RALEIGH, Science Center, Rockwell Int. California, U.S.A. H. RICKERT, University Dortmund, Germany H. TANNENBERGER, Institut Battelle, Geneva, Switzerland

Organization Committee :

C. CHASSAGNE t Secretary General, Universite Claude Bernard, Lyons M. DUCLOT, Treasurer, I.N.P. Grenoble, France

Secretarial and Technical staff :

P. BELL, Translator Interpreter, Bureau de traduction, Grenoble M. BONNAT, I.N.P. Grenoble, France.

Australia :

L.B. HARRIS - School of Physics, University of New South Wales, P.O. Box 1, Kensington NSW 2033.

Canada :

T.H. ETSELL - Department of Metallurgy and Materials Science, University of Toronto, 184 College Street, Toronto M5S lA4.

M. GAUTHIER - Institut de Recherche de l'Hydro-Quebec, 1800 montee Ste Julie, Varennes, Quebec.

Denmark :

S.A. MARKLAND - Vicking Chemicals, P.O. Box 226, 4000 Roskilde

France :

M. ARMAND - Laboratoire de Cinetique Electrochimique Minerale, ENSEEG, Domaine Universitaire, 38401 St Martin d'Heres.

J. BERT - Dept. Physique des Materiaux, Universite Claude Bernard 43 Bd du 11 Novembre, 69100 Villeurbanne.

G. CHASSAGNE - Dept. Physique des Materiaux, Universite Claude Bernard, 43 Bd du 11 Novembre, 69100 Villeurbanne.

B. CLAUDEL - Institut de Recherches sur la Catalyse, 39 Bd du 11 Novembre 1918, 69100 Villeurbanne.

M. COULON - Laboratoire d'Adsorption et Reaction de gaz sur solides, ENSEEG, Domaine Universitaire, 38401 St Martin d'Heres.

M. CROSET - Thomson CSF, Laboratoire Central de Recherche, BP 10 Corbeville/Orsay 91401.

M. DUCLOT - Laboratoire de Cinetique Electrochimique Minerale, ENSEEG , Domaine Universitaire, 38401 St Martin d'Heres.

C.H.S. DUPUY - Dept. Physique des Materiaux, Universite Claude Bernard, 43 Bd du 11 Novembre, 69100 Villeurbanne.

J. DUPUY - Dept. Physique des Materiaux, Universite Claude Bernard, 43 Bd du 11 Novembre, 69100 Villeurbanne.

P. FABRY - Laboratoire de Cinetique Electrochimique Minerale, ENSEEG, Domaine Universitaire, 38401 St Martin d'Heres.

J. FOULETIER - Laboratoire de Cinetique Electrochimique Minerale, ENSEEG, Domaine Universitaire, 38401 St Martin d'Heres.

C.G. GABRIELLI - Physique des Liquides et Electrochimie, Univer­site Pierre et Marie Curie, Tour 22, 4 Place Jussieu, 75230 Paris Cedex 05.

M. GOUET - U.E.R. Sciences, Departement de Physique, Universite de Paris Val de Marne, 94000 Creteil.

M.H. GUENIN - Institut de Recherches sur la Catalyse, 39 Bd du 11 Novembre 1918, 69100 Villeurbanne.

M. KLEITZ - Laboratoire de Cinetique Electrochimique Minerale, ENSEEG, Domaine Universitaire, 38401 St Martin d'Heres.

G. LETISSE - U.E.R. Sciences, Universite de Paris Val de Marne, 94000 Creteil.

G. ROBERT - Laboratoire d'Electrochimie, Universite de Besan~on, Faculte des Sciences, La Bouloie, Route de Gray, 25030 Besan~on Cedex.

E. SCHOULER - Laboratoire de Cinetique Electrochimique Minerale, ENSEEG, Domaine Universitaire, 38401 St Martin d'Heres.

J. SIEJKA - Groupe de Physique des Solides de l'ENS, Tour 23, 2 Place Jussieu, 75005 Paris.

J. VEDEL - Laboratoire d'Electrochimie Analytique et Appliquee, 11, rue Pierre et Marie Curie, 75231 Paris Cedex 05.

Germany :

H. DOEBRICH - Battelle Institut e.V. 6000 Frankfurt am Main 90, Am ROmerhof 35, Postfach 900 160.

P. BINDRA - Fritz Haber Institut der Max Planck Gesellschaft, Faradayweg 4-6, 1 Berlin 33.

L. CONTRERAS-VENEGAS - Universitat Dortmund, Lehrstuhl fur Physikalische Chemie, 46 Dortmund 50, Postfach 50 05 00.

G. EICHINGER - Technische Universitat 8 Munchen 2, Arcisstrasse 21, Postfach 20 24 20.

H. GERISCHER - Fritz Haber Institut der Max Planck Gesellschaft, Dl Berlin 3/Dahlem, Faradayweg 4-6.

J. GROBRECHT - Fritz-Haber-Institut der Max Planck Gesellschaft, D.lOOO Berlin 33, Faradayweg 4-6.

B. HARTMANN - University of Dortmund, Lehrstuhl fur Physikalische Chemie, 46 Dortmund Hombruch, Postfach 500.

G. HOLZAPFEL - Universitat Dortmund, Lehrstuhl fur Phys~kalische Chemie, 46 Dortmund 50, Postfach 50 05 00.

P.J. MESCHTER - Max-Planck Institut fur Eisenforschung, 4000 DUsseldorf, Max Planck Strasse 1, Postfach 14 01 40.

B. PETTINGER - Fritz-Haber-Institut der Max Planck Gesellschaft, Faradayweg 4-6, 1 Berlin 33.

Great Britain :

R.D. ARMSTRONG - The University of Newcastle-Upon-Tyne, School of Chemistry, Newcastle-Upon-Tyne NEI 7RU.

N. BONANOS - Applied Sciences, Stage II, University of Sussex, Falmer Brighton, Sussex BNl 9QT.

D.H. COLLINS - Admiralty Engineering Laboratory, West Drayton, Middx, UB7 9BZ.

R.M. DELL - Atomic Energy Research Establishement, Applied Chemistry, Division, Building 220.23 Harwell, Didcot OXll ORA Oxon.

T. DICKINSON - Electrochemistry Research Laboratories, University of Newcastle-Upon-Tyne, Newcastle-Upon-Tyne NEI 7RU.

G.J. DUDLEY - Dept. Metallurgy, Materials Science, Imperial College, Prince Consort Rd, London SW7.

M. GREEN - Imperial College of Science and Technology! Department of Electrical Engineering, Exhibition Road, London SW7, 2BT U.K.

A.H. HARKER - Theoretical Physics Division, AERE Harwell OXll ORA. D.A. HOOPER - Building 552, Materials Development Division,

AERE Harwell, DIDCOT. Oxon. J.M. POLLOCK - School of Chemistry, Leicester Polytechnic,

Leicester. B.C.H. STEELE - Imperial College of Science and Technology, Dept.

of Metallurgy, Royal School of Mines, Prince Consort Road, London SW7 2BP.

J.E. STRUTT - Applied Sciences, Stage II, University of Sussex, Falmer. Brighton, Sussex BNl gOT.

K. TAYLOR - Electrochemistry Research Laboratories, University of Newcastle-Upon-Tyne, Newcastle-Upon-Tyne NEI 7RU.

Israel :

M. STEINBERG - The Hebrew University of Jerusalem, Department of Inorganic and Analytical Chemistry, Jerusalem.

Italy :

G.B. BARBI - Euratom, Casella Postale 1, Ispra, Varese. C. CALANDRA - Istituto Di Fisica, Via Universita 4, 41100 Modena. F. COLOMBO - Universita di Milano, Istituto di Elettrochimica e

Metallurgia, Via Venezian 21, Milano. A. GENNARO - Institute of Physical Chemistry, University of Padua,

Via Loredan 2, 35100 Padua. C.L. MARl - Istit'uto di Elettrochimica dell 'Universita di Milano,

Via Venezian 21, 20133 Milano. A. MASSERINI - Istituto di Elettrochimica del Politecnico,

Piazza Leonardo da Vinci 32, 20133 Milano. L. OSCAR - Universita di Milano, Istituto di Elettrochimica e

Metallurgia, Via Venezian 21, Milano 20133. S. PIZZINI - Universita di Milano, Istituto di Elettrochimica e

Metallurgia, Via Venezian 21, 20133 Milano.

The Netherlands :

R.W. BONNE - Solid State Department, State University of Utrecht, Sorbonnelaan 4, Utrecht, De Uithof.

D. den ENGELSEN - Philips Research Lab. Eindhoven. L. HEYNE - Philips Research Laboratories, Eindhoven. J. SCHOONMAN - Solid State Department, State University of Utrecht,

Sorbennelaan 4, Utrecht, De Uithof.

Norway :

S. STUEFLOTTEN - University of Trondheim, Norwegian Institute of Technology, Division of Physical Electronics, N 7034, Trondheim NTH.

Romania :

V.M. LAZARESCU - Centre de Chimie Physique, Rue Galati 31, Bucarest. S. TANASESCU - Centre de Chimie Physique, Rue Galati 31, Bucarest. N. TOTIR - Centre de Chimie Physique, Rue Galati 31, Bucarest.

Spain :

F. JAQUE - Departamento de Fisica, Universidad Autonoma de Madrid, Cantoblanco, Madrid.

M.T. MONTOJO - Centro de Investigacion y Desarrollo de la Armada, Arturo Soria 289, Madrid 33.

Sweden :

B. HEED - Chalmers University of Technology Fack S.402-20 GOteborg 5.

K. SCHROEDER - Chalmers University of Technology Fack S-402 20 Goteborg 5.

Switzerland

M. VOINOV - Battelle, Centre de Recherche de Geneve, 7 Route de Drize, 1227 Carouge, Geneve.

U.S.A:

J.M. BLAKELY - Dept. of Materials Science and Eng.College of Engineering, Cornell University, Bard Hall, Ithaca, New York 14853.

T.R. BRUMLEVE - Dept. of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27 514.

R.L. DOTY - Medtronic Inc. 3055 Old Highway 8, Minneapolis, Minnesota 55418.

G.C. FARRINGTON - General Electric Corporate Research & Development Center, Building K-l, Room 3B2, P.O. Box 8, Schenectady NY 12301.

D.L. FOSTER - Clemson University, Clemson, South Carolina 29631. H.K. HENISCH - The Pennsylvania State University, University Park,

Pennsylvania 16802. R.A. HUGGINS - Center for Materials Research, Stanford University,

Stanford California 94305. T.G. JOW - Department of Materials Science Tech. Institute, North­

western University, 2145 Sheridan Road, Evanston, Illinois 60201.

F.A. KROGER - Department Materials Science, Univ. Southern Califor­nia, University Park, Los Angeles, Calif. 90007.

J.R. MACDONALD - Department of Physics and Astronomy, The Universi­ty of North Carolina, At Chapel Hill, North Carolina 27514.

P. MARK - Department of Electrical Engineering, Brackett Hall, Engineering Quadrangle, Princeton, New Jersey 08540.

I.D. RAISTRICK - Center for Materials Research, Stanford University, Stanford California 94305.

D.O. RALEIGH - Science Center, Rockwell International, P.O. Box 1085,1049 Camino Dos Rios, Thousand Oaks, California 91360.

R.D. SHANNON - Central Research Dept. Experimental Station, E.I. du Pont de Nemours, Wilmington, DEI 19898.

R.J. SOJKA - 132 Larsen Hall, Dept. of Electrical Engineering, University of Florida, Gainesville Flo. 32601.

J.B. WAGNER - Materials Research Center, Technological Institute, Northwestern University, Evanston, Illinois 60201.

D.H. WHITMORE - Dept. of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60201.