Fast Ion Transport in Solids

NATO ASI Series Advanced Science Institutes Series

A Series presenting the results of activities sponsored by the NA TO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities.

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

A Life Sciences B Physics

C Mathematical and Physical Sciences

D Behavioural and Social Sciences E Applied Sciences

F Computer and Systems Sciences G Ecological Sciences H Cell Biology I Global Environmental Change

NATO-PCO-DATA BASE

Plenum Publishing Corporation London and New York

Kluwer Academic Publishers Dordrecht, Boston and London

Springer-Verlag Berlin, Heidelberg, New York, London, Paris and Tokyo

The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to more than 30000 contributions from international scientists published in all sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible in two ways:

- via online FILE 128 (NATO-PCO-DATA BASE) hosted by ESRIN, Via Galileo Galilei, 1-00044 Frascati, Italy.

- via CD-ROM "NATO-PCO-DATA BASE" with user-friendly retrieval software in English, French and German (© WTV GmbH and DATAWARE Technologies Inc. 1989).

The CD-ROM can be ordered through any member of the Board of Publishers or through NATO-PCO, Overijse, Belgium.

Series E: Applied Sciences - Vol. 250

Fast Ion Transport in Solids

edited by

B. Scrosati Dipartimento di Chimica, Universita La Sapienza, Rome,ltaly

A. Magistris Dipartimento di Chimica Fisica, Universita di Pavia, Pavia, Italy

C. M. Mari Dipartimento di Chimica Fisica ed Elettrochimica, Universita di Milano, Milan, Italy

and

G. Mariotto Dipartimento di Fisica, Universita di Trento, Povo,ltaly

~t'l n~tU1 h~~);1 D '\

Springer Science+Business Media, B.V.

Proceedings of the NATO Advanced Research Workshop on Fast Ion Transport in Solids Belgirate, Italy September 20-26, 1992

Library of Congress Cataloging-in-Publication Data

Fa s t 10 n t r a n s por t 1 n sol 1 d s led 1 te d b Y B. Sc ros a t 1 ... [e taI. J . p. cm. -- (NATO ASI series. Serles E, Applied sClences ; voI.

250) Papers from a workshop held ln Belglrate, Italy, in 1992. "Publ ished ln cooperat ion with NATO SClentific Affairs Dlvlsion." ISBN 978-94-010-4847-7 ISBN 978-94-011-1916-0 (eBook) DOI 10.1007/978-94-011-1916-0 1. Ions--Migratlon and velocity--Congresses. 2. Diffusion­

-Congresses. 3. Elect~olytes--Conductlvlty--Congresses. 4. Sol ids--Electric properties--Congresses. I. Scrosati, Bruno. II. Serles, NATO ASI series. Ser ies E, Appl ied SClences ; no. 250. QD561.F33 1993 541.3'72--dc20 93-20898

ISBN 978-94-010-4847-7

Printed an acid-free paper

AII Rights Reserved © 1993 Springer Science+Business Media Dordrecht

Originally published by Kluwer Academic Publishers in 1993 Softcover reprint of the hardcover 1 st edition 1993 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 information storage and retrieval system, without wriUen permission from the copyright owner.

Contents

List of participants Conference Photograph Preface

Lectures

New routes in the development of chemical sensors: surface devices S. Pizzini

VII XII XIII

3

2 Materials and concepts for solid state electrochemical devices 9 W. Weppner

3 Optical properties of transition-metal and rare earth ions in beta aluminas 41 G. Mariotto

4 Intercalation compounds 69 M. Stanley Whittingham

5 Polymer electrolytes and intercalation electrodes: fundamentals and applications 87 P.G. Bruce

6 Is there a future for lithium-batteries as high energy density source in electrical engine vehicles? Some recent trends 109 C. Delmas, I. Saadoune, H. Auradou, M. Menetrier and P. Hagenmuller

7 Ion mobility in chalcogenide semiconductors; Room temperature creation of bipolar junction transistor 121 D. Cahen, L. Chernyak, G. Dagan and A. Jakubowicz

8 Mixed conductors for negative electrodes 143 R.A. Huggins

9 Surface oxygen exchange kinetics of solid oxide ion conductors 167 B.A. Boukamp, I.C. Vinke, K.J. De Vries and A.J. Burggraaf

10 Ionic conduction in sulphates 181 A. Lunden

11 Copper solid electrolyte-copper(l) halide and alkali halide systems 203 0. Yamamoto

VI

12

13

14

15

16

Ionic conduction in glasses A Magistris

Chemical vapor deposition techniques for thin films of solid electrolytes and electrodes V.E.J van Dieten, JP. Dekker, AA van Zomeren and J Schoonman

Silver solid state energy storage devices B. B. Owens

Bismuth-based oxide conductors novel structural and electrical features G. Mairesse

Composite electrolytes with special reference to Copper Chloride-Alumina systems O.S. Finch and JB. Wagner Jr

Student presentations

17

18

19

20

21

22

23

Anisotropy in the ionic conductivity of K3NdSi308(OH)2 S. M. Hale, J Maier, B.J. Wuensch and R.A. Laudise

Peculiarities in the low temperature ion and electron conductivity of solid oxide electrolytes H. Nate

Chemical analysis and structural investigations of sodium­and lanthanide ion-exchanged beta-aluminas F. Tietz and W. Urland

Electrical relaxation in polymer electrolytes I. Albinsson and B.-E. Me/lander

Quadrupole-broadened NMR-MAS spectra of disordered materials: acquisition and analysis P. Mustarelli

Experimental working group report:-What is the experimental status of solid state ionics (SSI)? R. J. Nowak, E. Zanghellini, H. Nate and V. van Dieten

Experimental working group report:What are the major contributions of solid state ionics to technology in the past and future? J.S. Lunsgaard, C. Arbizzani, M. Giua, T. Kawada and J. Lane

Final remarks W. van Gool

213

231

259

271

291

315

327

337

347

353

361

365

373

LIST OF PARTICIPANTS

Dr. I. ALBISSON Department of Physics. Chalmers University of Technology S-412 96 Goteborg SWEDEN Tel: (46) 31 77 23 341 Fax: (46) 31 1651 76

Dr. M. ARMAND LI.E.S-G/ENSEEG Domaine Universitaire B.P.75 38402 SAINT-MARTIN-D'HERES CEDEX FRANCE Tel.: (33) 76 82 65 62 Fax.: (33) 76 82 62 70

Dr. B. A. BOUKAMP Department of Chemfcal Technology Laboratory for Inorganic Chemistry University Twente THE NERTHERLANDS Tel: (31) 53 89 29 90 Fax: (31) 53 35 60 24

Dr. Peter G. BRUCE Department of Chemistry University of S1. Andrews St. ANDREWS, Fife KY 169ST SCOTLAND Tel: (44) 33 47 61 61 Fax: (44) 33 47 82 92

Dr. David CAHEN Department of Materia!s & Interfaces Weizmann Institute of Science Rehovot 76100- ISRAEL Tel: (972)8- 34 22 46. Fax: (972)8- 47 30 39

vii

Dr. L. DESSEMOND L.I.E.S-G/ENSEEG Domaine Universitaire B.P.75 38402 SAINT-MARTIN-D'HERES CEDEX FRANCE Tel.: (33) 76 82 65 62 Fax.: (33) 76 82 62 70

Dr. M.A.K.L. DISSANA YAKE Istitute of Fundamental Studies Hantana Road, Kandy SRI-LANKA Tel: (94) 832002 Fax: (94) 832 131

Dr. G.C. FARRINGTON School of Eng. and Applied Scie. Office of The Dean 220 South 33 Rd Street University Pennsylvania Philadelphia U.S.A. Tel: (1) 215898 72 44 Fax: (1) 2155732018

Dr. D. FAUTEUX Arthur D. Little Inc. Acon Park, Cambridge, Massachussets 02140-2390 U.S.A. Tel: (1) 617 864 57 70 Fax: (1) 617 8641650

Dr. D. S. FINCH Department of Materials Technology Brunei Univ. Uxbridge, Middlesex UB8 3PH U.K.­ENGLAND Tel: (44) 895 20 32 53 Fax: (44) 895 81 2636

viii

Mr. M. GIUA Dipartimento di Chimica Universita di Roma "La Sapienza" P.le A. Moro, 5 00185 ROMA- ITALY Tel: (39) 6 49 91 3530 Fax: (39) 6 49 1769

Dr. P. HAGENMULLER Lab. de Chimie du Solide Du CNRS Universite Bordeaux I 351 , Cou rs de la Liberation 33405 TELENCE CEDEX FRANCE Tel: (33) 56 84 63 24 Fax: (33) 56 84 66 34

Dr. S. HAILE Max-Planck-I nstltute Heisenbergstr. 1 7000 Stuttgart 80 GERMANY Tel: (49) 711-6860-1 Fax: (49) 711-6874371

Dr. R.A. HUGGINS Center of Solar Energy & Hydrogen Research (ZSW) Erich-Rittjnghaus-Str. 2 7913 Senden/l LLE R GERMANY Tel: (49) 7307-6087 Fax: (49) 73076080

Dr. L. JONISSEN Center of Solar Energy & Hydrogen Research (ZSW) Erich-Rittinghaus-Str. 2 7913 Senden/iLLER GERMANY Tel: (49) 7307-6087 Fax: (49) 7307-6080

Dr. T. KAWADA National Chemical Laboratory for Industry Tskuba Research Center, Ibaraki 305 JAPAN Tel (81 ) 298- 544542 Fax (81) 298-54 44 87

Dr. B. KATZ 107 Town 220 South, 33rd Street Univ. Pennsylvania U.SA Tel (1) 215 5732018 Fax (1) 215 898 3455

Dr. M. KLEITZ L.I.E.S-G/ENSEEG Domaine Universitaire B.P.75 38402 SAINT-MARTIN-D'HERES CEDEX-FRANCE Tel: (33) 76 82 65 58 Fax: (33) 76 82 66 30

Dr. J. LANE Dept. of Materials Science Imperial College London SW7 2BP ENGLAND Tel: (44) 71 5895 111 ext 5954 Fax: (44) 71 5843194

Dr. A. LUNDEN Department of Physics, Chalmers University of Technology S-412 96 Goteborg SWEDEN Tel: (46) 31 77 23 341 Fax: (46) 31 1651 76

Dr. J.S. LUNDSGAARD INNOVISION IMIS ERL Lindvedvej 75 DK-5260 Odense 8 Tel: (45) 659591 00 Fax: (45) 65 95 78 00 DENMARK

Dr. S. MAFFI CNR-Centro di Studio suiProcessi Elettrodici - Dipt. Chimica Fisica Applicata Politecnico di Milano P.zza L da Vinci, 32 20133 MILANO-ITALY Tel: (39) 2 2399 31 36 Fax: (39) 2 239931 80

Dr. A. MAGISTRIS Dipartimento di Chimica Fisica Universita di Pavia-ITALY Tel: (39) 382 39 2216

Dr. G. MAIRESSE Lab. Cristallochimie ENS de Chimie B.P. 108 59652 Villeneuve d'Asq Cedex FRANCE Tel: (33) 20 43 65 83 Fax: (33) 20 436814

Dr. C. MARl Dipartimento di Chi mica Fisica ed Elettrochimica Universita degli Studi di Milano Via Golgi, 19 20133 Milano -ITALY Tel: (39) 2 26603204 Fax: (39) 2 706381 29

Dr. G. MARIOTTO Dipartimento di Fisica Universita Trento 38050 POVO- TRENTO-ITALY Tel: (39) 461 881501 Fax (39) 461 88 1696

Dr. Hj. MATZKE Institute for Transurnium Elements Joint Research Center Postfach 2340, D-7500 Karlsruhe GERMANY Tel (49) 7247841 Fax (49) 72474046

Dr. H. NAFE Max -Planck-I nstltute Heisenbergstr. 1 7000 Stuttgart 80 GERMANY Tel (49) 711-6860-1 Fax: (49) 711-6874371

Dr. D. NARDUCCI Dipartimento di Chimica Fisica ed E lettrochi mica Universita degli Studi di Milano Via Golgi, 19 20133 Milano -ITALY Tel: 39 2 26 60 32 04 Fax: (39) 2 706381 29

Dr. R.J. NEAT UKAEA AERE Harwell Applied Electrochemistry 8 552 Harwell Lab. Didcot OXON, OX11 ORA, UK ENGLAND Tel: (44) 235 43 5567 Fax: (44) 235434673

Dr. S. NICOLL Institute for Transurnium Elements Joint Research Center Postfach 2340, D-7500 Karlsru he GERMANY Tel: (49) 7247 841 Fax (49) 7247 4046

Dr. R.J. NOVAK Code 1113ES Office of Naval Research 800 N. Quincy SI Arlington, Virginia 22217-5660 U.S.A. Tel: (1) 703 696 4409 Fax: (1) 7036962611

Dr. B.B. OWENS 4707 Lyndale Avenue North University of Minnesota Minneapolis, MN 55430 U.S.A Tel: (1) 612 3710848 fax: (1) 612 6730040

Dr. L. PERALDO BICELLI CNR-Centro di Studio suiProcessi Elettrodici - Dipt. Chi mica Fisica Applicata Politecnico di Milano P.zza L. da Vinci, 32 20133 MILANO-ITALY Tel: (39) 2 23 99 31 36 Fax: (39) 2 23 99 31 80

ix

x

Dr. S. PIZZINI Dipartimento di Chim~ca Fisica ed Elettrochimica Universita degli Studi di Milano Via Golgi, 19 20133 Milano -ITALY Tel: (39) 2 26 60 32 04 Fax: (39) 2 70 63 81 29

Dr. M. POUCHARD L.I.E.S-G/ENSEEG Damaine Universitaire B.P.75 38402 SAINT-MARTIND'HERES CEDEX FRANCE Tel (33) 76 82 65 62 Fax.: (33) 76 82 62 70

Dr. N. RAO INNOVISION 1M IS ERL Lindvedvej 75 DK-5260 Odense 8 DENMARK Tel (45) 659591 00 Fax (45) 65957800

Dr. J. M. ROSOLEN Dipartimento di Chimica Universita di Roma "La Sapienza" P.le A. Mora, 5 00 185 ROMA- ITALY Tel: (39) 6 4991 3530 Fax: (39) 6 491769

Dr. J. SCHOON MANN Faculty of Chemical Tech. and Materials Sci. Delf University of Technology Julianalaan 136, 2628 DELFT THE NETHERLANDS Tel: (31) 15782647 Fax: (31) 15782655

Dr. B. SCROSATI Dipartimento di Chi mica Universita di Roma "La Sapienza" P.le A. Moro, 5 00185 ROMA- ITALY Tel: (39) 6 49 91 3530 Fax: (39) 6 49 1769

Dr. B.C.H. STEELE Department of Materials Imperial College Prince Consort Road, London SW7 2BP ENGLAND Tel: (44) 71 5895 111 Fax: (44) 71 5843 194

Dr. J.B. THOMPSON Department of Chemistry University of St. Andrews St. ANDREWS, Fife KY 169ST SCOTLAND Tel (44) 334761 61 Fax (44) 33478292

Dr. F. TIETZ Institut f. Anorg Chemie Hannover University Callin Str. 9, 3000 Hannover GERMANY Tel: (49) 511 7623554 Fax: (49) 511 7623006

Dr. V. van DIETEN Faculty of Chemical Tech. and Materials.Sci. Delf University of Technology Julianalaan 136, 2628 DELFT THE NETHERLANDS Tel: (31) 15782647 Fax: (31) 15782655

Dr. W. van GOOl Faculty of Chemical Tech. and Materials Sci. Delf University of Technology Julianalaan 136. 2628 BL DELFT THE NETHERLANDS Tel: (31) 3438 18972 Fax: (31) 343821935

Dr. O. YAMAMOTO Faculty of Engineering Department of Chemistry Mie University 514 JAPAN Tel: (81) 592-321211 Fax: (81) 592-31-22 52

Dr. B. WAGNER Center for Solid State Science Arizona State University Temple,AZ 85287-1704 U.sA Tel: (1) 602 965 6959 Fax: (1) 602 965 900

Dr. W. WEPPNER Max -Planck-I n st Itute Heisenbergstr. 1 7000 Stuttgart 80 GERMANY Tel: (49) 711-6860-1 Fax: (49) 711-68 74 371

Dr. M. S. WHITTINGHAM Chemistry Dept. and Materials Research Center SUNY at Binghamton Binghamton, NY 13902-6000 U.S.A. Tel: (1) 607 777 4623 Fax: (1) 607777 4478

Dr. W.L. WORREll 113 Towne Building Engineering & Applied Sci. University of Pennsylvania PA 19104 U.S.A. Tel: (1) 2158988241 Fax: (1) 215898 1130

Dr. WYNN-JONES Chloride Silent Power Davy Road Astmoor, Runcorn -Cheshire ENGLAND Fax: (44) 9285695 17

Dr. E. ZANGHElLiNI Dipartimento di Fisica Universita Trento 38050 POVO-TRENTO ITALY Tel: (39) 461881501 Fax: (39) 461 88 1696

xi

PREFACE

The main motivation for the organization of the Advanced Research Workshop in Belgirate was the promotion of discussions on the most recent issues and the future perspectives in the field of Solid State lonics. The location was chosen on purpose since Belgirate was the place were twenty years ago, also then under the sponsorship of NATO, the very first international meeting on this important and interdisciplinary field took place. That meeting was named "Fast Ion Transport in Solids" and gathered virtually everybody at that time having been active in any aspect of motion of ions in solids. The original Belgirate Meeting made for the first time visible the technological potential related to the phenomenon of the fast ionic transport in solids and, accordingly, the field was given the name "Solid State lonics". This field is now expanded to cover a wide range of technologies which includes chemical sensors for environmental and process control, electrochromic windows, mirrors and displays, fuel cells, high performance rechargeable batteries for stationary applications and electrotraction, chemotronics, semiconductor ionics, water electrolysis cells for hydrogen economy and other applications. The main idea for holding an anniversary meeting was that of discussing the most recent issues and the future perspectives of Solid State lonics just twenty years after it has started at the same location on the lake Maggiore in North Italy. It appeared of relevance to take advantage of this occasion for settli ng a forum where to compare the today achievements with the goals set at the first meeting and to reach conclusions valid for directing the future research and development in the field in view of the importance of the related applications. With this in mind, the Belgirate 2 Workshop was organized by inviting a group of lecturers to present and discuss the above mentioned points and a group of students and/or young researchers to listen and evaluate the presentations. Priority in the selection of the lecturers was given to the participants of the first NATO meeting in 1992; in addition some leading experts in Solid State lonics were also invited. The students were selected on the basis of recommendations received from the invited speakers. The response was excellent and the workshop could benefit by the participation and the contribution of the top scientists in the field. The total attendance was 52 persons. The scientific programme was structured in nine sessions over a period of six days. In order to favour discussions and interactions, long afternoon brakes were allowed between sessions. Furthermore, to promote active participation and to obtain the maximum advantage from such an outstanding forum, five working groups, each formed by an average number of five students, were settled. A task was assigned to each group, consisting in the joint discussion and in the evaluation of a selected topic. The students were encouraged to discuss the assigned topic with the lecturers and to present their results at the end of the Workshop. The topics assigned were: i) Theory: among the various topics of Solid State lonics where do you believe the theory is most needed?; ii) Crystals versus non-crystal: what are the pros and cons of crystalline and non­crystalline materials?'; iii) Technology: what are the major contributions of

xiii

xiv

Solid State lonics to technology in the past and in the future?; iv)Experimental: what is the experimental status of Solid State lonics?; and v)Understanding: what would we like to understand more? In the course of the Workshop all the most relevant aspects of Solid State lonics were covered by the invited speakers. The lectures of the first day included presentations on 'materials and concepts for electrochemical devices'; 'oxygen intercalation electrodes"; multivalent cations in polymers and in beta aluminas' and 'optical properties on transition-metal and rare­earth ions in beta aluminas'. The second day was devoted to intercalation compounds and oxides, with lectures on 'intercalation compounds'; 'from intercalation compounds to polymer ionics'; 'oxygen intercalation in oxide lattices'; "unusual oxidation states of transition element oxides' and 'ionic mobility in semiconductors'. The third day of the workshop was focused on fuel cells and on solid electrolytes with lectures on 'application of fast ion conductors to solid oxide fuel cells'; 'electronic and partial conductivity in solids'; 'mixed conductors for negative electrodes'; Ionic conduction in sulphates'; 'composite electrolytes' and 'copper solid electrolytes'. The morning of the fourth day was devoted to glasses and thin films with two lectures on 'Ionic glasses' and 'thin film ionics', respectively, and in the afternoon, free from scientific sessions, all the participants enjoyed a relaxing trip on the lake resorts. In the fifth day, applications and future trends were discussed. In the morning, lectures on 'silver solid state energy storage devices'; 'sodium sulphur batteries' and 'bismuth-based oxide conductors' were presented. In the afternoon, Prof. W. van Gool, who was the Director of the first Belgirate meeting, gave an overall evaluation of the Worshop with final remarks and conclusions. After Prof. van Gool's presentation, the students reported the results obtained within the respective working groups, as well as some relevant aspects of their research work in the field of Solid State lonics. All the student presentations were remarkably good, especially considering the challenging nature of the assigned topics. All the participants agreed in giving the best evaluation to the work elaborated by the students and in concluding that the idea of settling working groups was a very successful initiative to be continued in future workshops and that the students contributions should be included in these Proceedings. Finally, the ARW was concluded by a social dinner attended by all the participants and their accompanying persons, which served to strengthen the friendship and the personal contacts among scientists who arrived in Belgirate from many countries in the world. On behalf of the Scientific and the Organizing Committees, I would like to express my thanks and gratitude to the NATO Science Committee for the financial support which gave us the possibility of organizing such an important event.

Bru no Scrosati Director of the ARW