The CRC handbook of solid state electrochemistry

618 Pages·1997·7.582 MB·English

by  P.J. Gellings, H.J.M. Bouwmeester

The CRC Handbook
of Solid State
Electrochemistry
Edited by
P.J. Gellings
and
H.J.M. Bouwmeester
University of Twente
Laboratory for Inorganic
Materials Science
Enschede, The Netherlands
CRC Press
Boca Raton New York London Tokyo
Acquiring Editor: Felicia Shapiro
Project Editor: Gail Renard
Marketing Manager: Arline Massey
Direct Marketing Manager: Becky McEldowney
Cover design: Denise Craig
PrePress: Kevin Luong
Manufacturing: Sheri Schwartz
Library of Congress Cataloging-in-Publication Data
The CRC handbook of solid state electrochemistry / edited by P.J. Gellings
and H.J.M. Bouwmeester.
p. cm.
Includes bibliographical references and index.
ISBN 0-8493-8956-9
1. Solid state chemistry—Handbooks, manuals, etc. I. Gellings, P.J. II. Bouwmeester, H.J.M.
QD478.C74 1996
541.3′7—dc20
96-31466
CIP
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Copyright © 1997 by CRC Press, Inc.
ABOUT THE EDITORS
Prof. Dr. P.J. Gellings. After studying chemistry at the University of Leiden (the Neth-
erlands), Prof. Gellings received his degree in physical chemistry in 1952. Subsequently he
worked as research scientist in the Laboratory of Materials Research of Werkspoor N.V.
(Amsterdam, the Netherlands). He obtained his Ph.D. degree from the University of Amster-
dam in 1963 on the basis of a dissertation titled: “Theoretical considerations on the kinetics
of electrode reactions.”
In 1964 Prof. Gellings was appointed professor of Inorganic Chemistry and Materials
Science at the University of Twente. His main research interests were coordination chemistry
and spectroscopy of transition metal compounds, corrosion and corrosion prevention, and
catalysis. In 1991 he received the Cavallaro Medal of the European Federation Corrosion for
his contributions to corrosion research. In 1992 he retired from his post at the University, but
has remained active as supervisor of graduate students in the field of high temperature
corrosion.
Dr. H.J.M. Bouwmeester. After studying chemistry at the University of Groningen (the
Netherlands), Dr. Bouwmeester received his degree in inorganic chemistry in 1982. He
received his Ph.D. degree at the same university on the basis of a dissertation titled: “Studies
in Intercalation Chemistry of Some Transition Metal Dichalcogenides.” For three years he
was involved with industrial research in the development of the ion sensitive field effect
transistor (ISFET) for medical application at Sentron V.O.F. in the Netherlands.
In 1988 Dr. Bouwmeester was appointed assistant professor at the University of Twente,
where he heads the research team on Dense Membranes and Defect Chemistry in the Labo-
ratory of Inorganic Materials Science. His research interests include defect chemistry, order-
disorder phenomena, solid state thermodynamics and electrochemistry, ceramic surfaces and
interfaces, membranes, and catalysis. He is involved in several international projects in these
fields.
Copyright © 1997 by CRC Press, Inc.
CONTRIBUTORS
Isaac Abrahams Heinz Gerischer‡
Department of Chemistry Scientific Member Emeritus of the Fritz Haber
Queen Mary and Westfield College Institute
University of London Department of Physical Chemistry
London, United Kingdom Fritz-Haber-Institut der Max-Planck-
Gesellschaft
Symeon I. Bebelis Berlin, Germany
Department of Chemical Engineering
University of Patras Claes G. Granqvist
Patras, Greece Department of Technology
Uppsala University
Henny J.M. Bouwmeester Uppsala, Sweden
Laboratory for Inorganic Materials Science
Faculty of Chemical Technology Jacques Guindet
University of Twente Université Joseph Fourier
Enschede, The Netherlands Laboratoire d’Electrochimie et de
Physicochimie des Matériaux et Interfaces
Peter G. Bruce (LEPMI)
School of Chemistry Domaine Universitaire
University of St. Andrews Saint Martin d’Hères,
St. Andrews, Fife, United Kingdom France
Anthonie J. Burggraaf Abdelkader Hammou
Laboratory for Inorganic Materials Science Université Joseph Fourier
Faculty of Chemical Technology Laboratoire d’Electrochimie et de
University of Twente Physicochimie des Matériaux et Interfaces
Enschede, The Netherlands (LEPMI)
Domaine Universitaire
Hans de Wit Saint Martin d’Hères,
Materials Institute Delft France
Delft University of Technology
Faculty of Chemical Technology and Materials Christian Julien
Science Laboratoire de Physique des Solides
Delft, The Netherlands Université Pierre et Marie Curie
Paris, France
Pierre Fabry
Université Joseph Fourier Tetsuichi Kudo
Laboratoire d’Electrochimie et de Institute of Industrial Science
Physicochimie des Matériaux et Interfaces University of Tokyo
(LEPMI) Tokyo, Japan
Domaine Universitaire
Saint Martin d’Hères, France Janusz Nowotny
Australian Nuclear Science & Technology
Thijs Fransen Organisation
Laboratory for Inorganic Materials Science Advanced Materials Program
University of Twente Lucas Heights Research Laboratories
Enschede, The Netherlands Menai, Australia
Paul J. Gellings Ilan Riess
Laboratory for Inorganic Materials Science Physics Department
Faculty of Chemical Technology Technion — Israel Institute of
University of Twente Technology
Enschede, The Netherlands Haifa, Israel
‡ Deceased
Copyright © 1997 by CRC Press, Inc.
Joop Schoonman Constantinos G. Vayenas
Laboratory for Applied Inorganic Chemistry Department of Chemical Engineering
Delft University of Technology University of Patras
Faculty of Chemical Technology and Materials Patras, Greece
Science
Delft, The Netherlands Werner Weppner
Chair for Sensors and Solid State Ionics
Technical Faculty, Christian-Albrechts
Elisabeth Siebert University
Université Joseph Fourier Kiel, Germany
Laboratoire d’Electrochimie et de
Physicochimie des Matériaux et Interfaces
(LEPMI)
Domaine Universitaire
Saint Martin d’Hères, (France)
Copyright © 1997 by CRC Press, Inc.
IN MEMORIAM
Heinz Gerischer
1919–1994
On September 14, 1994, Professor Heinz Gerischer died from heart failure. With his
death, the international community of electrochemistry lost the man who most probably was
its most eminent representative. Professor Gerischer was one of the founders of modern
electrochemistry, having contributed to nearly all modern extensions and improvements of
this science.
He was born in 1919 and studied chemistry at the University of Leipzig from 1937 to
1944, presenting his Ph.D. thesis, under the supervision of Professor Bonhoeffer, in 1946.
He worked throughout Germany, was professor of physical chemistry at the Technical
University–Munich, and director of the Fritz-Haber-Institut der Max-Planck-Gesellschaft in
Berlin. He made great contributions to the kinetics of electrode reactions and to the electro-
chemistry at semiconductor surfaces. He also initiated the application of a wide range of
modern experimental methods to the study of electrochemical reactions, including nonelec-
trochemical techniques such as optical and electron spin resonance spectroscopy, and advo-
cated the use of synchroton radiation in surface research. His scientific work was published
in more than 300 publications and was notable for its great originality, clarity of exposition,
and high quality.
We are grateful that we can publish as Chapter 2 of this handbook, what may be Professor
Gerischer’s last publication, in which he again shows his ability to give a very clear exposition
of the basic principles of modern electrochemistry.
Copyright © 1997 by CRC Press, Inc.
PREFACE
The idea for this book arose out of the realization that, although excellent surveys and
handbooks of electrochemistry and of solid state chemistry are available, there is no single
source covering the field of solid state electrochemistry. Moreover, as this field gets only
limited attention in most general books on electrochemistry and solid state chemistry, there
is a clear need for a handbook in which attention is specifically directed toward this rapidly
growing field and its many applications.
This handbook is meant to provide guidance through the multidisciplinary field of solid
state electrochemistry for scientists and engineers from universities, research organizations,
and industries. In order to make it useful for a wide audience, both fundamentals and
applications are discussed, together with a state-of-the-art review of selected applications.
As is true for nearly all fields of modern science and technology, it is impossible to treat
all subjects related to solid state electrochemistry in a single textbook, and choices therefore
had to be made. In the present case, the solids considered are mainly confined to inorganic
compounds, giving only limited attention to fields like polymer electrolytes and organic
sensors.
The editors thank all those who cooperated in bringing this project to a successful close.
In the first place, of course, we thank the authors of the various chapters, but also those who
advised us in finding these authors. We are also grateful to the staff of CRC Press — in
particular associate editor Felicia Shapiro and project editor Gail Renard, who were of great
assistance to us with their help and experience in solving all kinds of technical problems.
It is a great loss for the whole electrochemical community that Professor Heinz Gerischer
died suddenly in September 1994 and we remember with gratitude his great services to
electrochemistry. We consider ourselves fortunate to be able to present as Chapter 2 of this
handbook one of his last important contributions to this field.
P.J. Gellings
H.J.M. Bouwmeester
Copyright © 1997 by CRC Press, Inc.
TABLE OF CONTENTS
Chapter 1
Introduction
Henny J.M. Bouwmeester and Paul J. Gellings
Chapter 2
Principles of Electrochemistry
Heinz Gerischer
Chapter 3
Solid State Background
Isaac Abrahams and Peter G. Bruce
Chapter 4
Interface Electrical Phenomena in Ionic Solids
Janusz Nowotny
Chapter 5
Defect Chemistry in Solid State Electrochemistry
Joop Schoonman
Chapter 6
Survey of Types of Solid Electrolytes
Tetsuichi Kudo
Chapter 7
Electrochemistry of Mixed Ionic–Electronic Conductors
Ilan Riess
Chapter 8
Electrodics
Ilan Riess and Joop Schoonman
Chapter 9
Principles of Main Experimental Methods
Werner Weppner
Chapter 10
Electrochemical Sensors
Pierre Fabry and Elisabeth Siebert
Chapter 11
Solid State Batteries
Christian Julien
Chapter 12
Solid Oxide Fuel Cells
Abdelkader Hammou and Jacques Guindet
Copyright © 1997 by CRC Press, Inc.
Chapter 13
Electrocatalysis and Electrochemical Reactors
Constantinos G. Vayenas and Symeon I. Bebelis
Chapter 14
Dense Ceramic Membranes for Oxygen Separation
Henny J.M. Bouwmeester and Anthonie J. Burggraaf
Chapter 15
Corrosion Studies
Hans de Wit and Thijs Fransen
Chapter 16
Electrochromism and Electrochromic Devices
Claes G. Granqvist
Copyright © 1997 by CRC Press, Inc.
Chapter 1
INTRODUCTION
Henny J. M. Bouwmeester and Paul J. Gellings
I. Introduction
II. General Scope
III. Elementary Defect Chemistry
A. Types of Defects
B. Defect Notation
C. Defect Equilibria
IV. Elementary Considerations of the Kinetics of Electrode Reactions
References
I. INTRODUCTION
As in aqueous electrochemistry, research interest in the field of solid state electrochemistry
can be split into two main subjects:
Ionics: in which the properties of electrolytes have the central attention
Electrodics: in which the reactions at electrodes are considered.
Both fields are treated in this handbook. This first chapter gives a brief survey of the scope
and contents of the handbook. Some elementary ideas about these topics, which are often
unfamiliar to those entering this field, are introduced, but only briefly. In general, textbooks
and general chemical education give only minor attention to elementary issues such as defect
chemistry and kinetics of electrode reactions. Ionics in solid state electrochemistry is inher-
ently connected with the chemistry of defects in solids, and some elementary considerations
about this are given in Section III. Electrodics is inherently concerned with the kinetics of
electrode reactions, and therefore some elementary considerations about this subject are
presented in Section IV. In an attempt to lead into more professional discussions as provided
in subsequent chapters, some of these considerations are presented in this first chapter.
II. GENERAL SCOPE
The distinction made between ionics and electrodics is translated into detailed discussions
in various chapters on the following topics:
• electrochemical properties of solids such as oxides, halides, cation conductors, etc.,
including ionic, electronic, and mixed conductors
• electrochemical kinetics and mechanisms of reactions occurring on solid electrolytes,
including gas-phase electrocatalysis.
Copyright © 1997 by CRC Press, Inc.