Physical Chemistry of Ionic Materials E-Book

Joachim Maier

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1301

Veröffentlichungsjahr: 2023

Beschreibung

Physical Chemistry of Ionic Materials Discover the physical chemistry of charge carriers in the second edition of this popular textbook Ionic and electronic charge carriers are critical to the kinetic and electrochemical properties of ionic solids. These charge carriers are point defects and are decisive for electrical conductivity, mass transport, and storage phenomena. Generally, defects are deviations from the perfect structure, and if higher-dimensional, also crucial for the mechanical properties. The study of materials science and energy research therefore requires a thorough understanding of defects, in particular the charged point defects, their mobilities, and formation mechanisms. Physical Chemistry of Ionic Materials is a comprehensive introduction to these charge carrier particles and the processes that produce, move, and activate them. Covering both core principles and practical applications, it discusses subjects ranging from chemical bonding and thermodynamics to solid-state kinetics and electrochemical techniques. Now in an updated edition with numerous added features, it promises to be the essential textbook on this subject for a new generation of materials scientists. Readers of the 2nd Edition of Physical Chemistry of Ionic Materials will also find: * Two new chapters on solid state electrochemistry and another on nanoionics * Novel brief sections on photoelectrochemistry, bioelectrochemistry, and atomistic modelling put the treatment into a broader context * Discussion of the working principles required to understand electrochemical devices like sensors, batteries, and fuel cells * Real laboratory measurements to ground basic principles in practical experimentation Physical Chemistry of Ionic Materials is a valuable reference for chemists, physicists, and any working researchers or advanced students in the materials sciences.

Leseprobe

Physical Chemistry of Ionic Materials

Ions and Electrons in Solids

Joachim MaierMax Planck Institute for Solid State Research, Stuttgart, Germany

Second Edition

This second edition first published 2023© 2023 John Wiley & Sons Ltd

Edition HistoryJohn Wiley & Sons Ltd (1e, 2004)

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Library of Congress Cataloging‐in‐Publication Data

Names: Maier, Joachim, author. | John Wiley & Sons, publisher.Title: Physical chemistry of ionic materials: ions and electrons in solids / Joachim Maier.Description: Second edition. | Hoboken, NJ: Wiley, 2023. | Includes bibliographical references and index.Identifiers: LCCN 2022034910 (print) | LCCN 2022034911 (ebook) | ISBN 9781119799108 (hardback) | ISBN 9781119799115 (adobe pdf) | ISBN 9781119799122 (epub)Subjects: LCSH: Solid state chemistry.Classification: LCC QD478.M35 2023 (print) | LCC QD478 (ebook) | DDC 541/.042–dc23/eng20221021LC record available at https://lccn.loc.gov/2022034910LC ebook record available at https://lccn.loc.gov/2022034911

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Preface to the Second Edition

This second edition is a substantially reworked version of the first. First of all, textual defects in the presentation have been removed. Although it would be easy to justify their presence in a book in which the defects are the major players*, it is advisable to refrain from using such cheap argument. Fortunately, most of the defects have been local and easily identifiable as imperfections. The justification for leaving major parts unchanged is based on Dyson's dictum, which the reader finds** in footnote 31 in Chapter 8 and hence because of the fact that the conceptual parts do not lose their validity. Consequentially, the major new additions refer to applied aspects. In particular, the field of batteries has experienced a boost and many new materials surfaced. In fact, the chapter about solid‐state electrochemistry now turned into two, the first on fundamentals and the second on applications. Moreover, sections on photo‐ and bio‐electrochemistry have been included, as well as a small paragraph on atomistic modeling. Last but not least, a chapter on nanoionics has been added, not only because it is a favorite subject of the author but also because it wonderfully criss‐crosses all the various topics, ranging from bonding properties to electrochemistry via thermodynamics and kinetics, and forms an (almost) perfect ending. It equally affects the fundamentals and applications and beyond that may foster synergies between various disciplines. In addition to the persons that I had acknowledged in the first edition, let me thank Eugene Kotomin, Bettina Lotsch, Jochen Mannhart, Davide Moia, and Rob Usiskin for scientific discussions; Madeleine Burkhardt for her great help in getting the new text written; and finally Angelika simply for being around. Annette Fuchs, Maximilian Hödl, Markus Joos, Rotraut Merkle, Davide Moia, Chuanlian Xiao, and Yue Zhu have kindly read the new sections.

Stuttgart, November 2022

Joachim Maier

Notes

*

There is a crack in everything, that's how the light gets in

. (Leonard Cohen)

**

A brief statement on the extensive use of footnotes (like this one) shall be added. In spite of a certain loss of elegancy, I consider them extremely helpful as they provide in‐depth information such as proofs or advanced information without disrupting the reading flow. They are highly recommended to be visited if the reader wants to dive into a special topic, but they are not necessary for the understanding of the major text. The alternative, to put such information in an isolated appendix, might be aesthetically preferable but is – as experience shows – not really helpful.

Preface to the First Edition

The book that you are about to read is, in a broad sense, concerned with the physical chemistry of solids. More specifically, it deals with the ionic and electronic charge carriers in ionic solids. The latter species are the major players in the game when one attempts a detailed understanding or deliberate tuning of kinetic properties. The charge carriers that we refer to are not necessarily identical with the charged particles that constitute the solid but rather with the effective particles that transport charge, i.e. in the case of ionic crystals the ionic point defects, in addition to excess electrons and holes. These ionic and electronic charge carriers constitute the redox and acid–base chemistry in the same way as is the case for aqueous solutions; they permit charge and matter transport to occur and are also reactive centers in the sense of chemical kinetics. This explains the central role of defect chemistry in this book. The more classical introductory chapters on chemical bonding, phonons, and thermodynamics of the perfect solid may, on the one hand, be considered as preparation for the key chapters that deal with thermodynamics of the real solid, as well as with kinetics and electrochemistry – both being unthinkable without the existence of defects; on the other hand, they provide the complement necessary for the book to serve as a textbook of physical chemistry of solids. (In fact, the different chapters correspond to classical fields of physical chemistry but referred to the solid state.) The structure of the book is expected to be helpful in view of the heterogeneity of the potential readership: This addresses chemists who traditionally consider solids from a static, structural point of view and often ignore the “internal life” enabled by defect chemistry, physicists who traditionally do not take pertinent account of composition as a state parameter, and materials scientists who traditionally concentrate on materials properties and may not adequately appreciate the basic role of electrochemistry. Of course, the book cannot fully cover the materials space or the world of properties. If the reader is a chemist, he or she may miss special chapters on covalent and disordered solids (e.g. polymers); the physicist will certainly find electronic properties under‐represented (e.g. metals), and the materials scientist may have expected a detailed consideration of mechanical and thermal properties. Nonetheless the author is convinced – and this is based on the lectures on Physical Chemistry and Materials Science given to very different audiences in Cambridge (USA), Tübingen and Stuttgart (Germany) and Graz (Austria) – that he made a germane selection to highlight the physical chemistry of charge carriers in solids. A certain preference for examples stemming from the working group of the author is not the result of slothfulness or vanity; rather, it is based on the endeavor to concentrate on a few model materials. The many cross‐references are meant to facilitate reading; proofs or remarks that would disturb the flow of reading and belong to a different level are put into footnotes, and they should be considered when reading the text a second time. Compared to the German version, which appeared earlier (Festkörper – Fehler und Funktion, Prinzipien der Physikalischen Festkörperchemie; B. G. Teubner Stuttgart, 2000), the English text is – apart from a few modifications and hopefully a smaller concentration of “defects” – essentially a 1: 1 translation. I am indebted to D. Bonnell, W. B. Eberhardt, K. Funke, O. Kienzle, M. Martin, M. Rühle, E. Schönherr, and A. Simon for the discussions and the courtesy of providing valuable figures. I would like to thank my co‐workers and colleagues for critical remarks. In particular, I appreciate helpful discussion with Jürgen Fleig, Janez Jamnik, Klaus–Dieter Kreuer, Rotraut Merkle, and Roger de Souza. I am also indebted to Dr de Souza for his great help in the process of translating the German version into English. I would like to thank Barbara Reichert for the unremitting editorial assistance. Sofia Weiglein and M. Trieloff deserve thanks for their help as regards many tiny things (infinity times zero might be a very significant number). Harry Tuller (MIT Cambridge) and Werner Sitte (TU Graz) provided the hospitality and my wife Eva the additional free time, without which this book would have never been completed. Many thanks to them.

Stuttgart, January 2004

Joachim Maier

1Introduction

1.1 Motivation

It may seem odd to ask the reader in the first sentence of the book he or she has just opened to put it down for a moment (naturally with the intention of picking it up and reading it again with greater motivation). Consider, however, your environment objectively for a moment. The bulk of it is (as we ourselves are to a large degree) made up of solid matter. This does not just apply to the materials, from which the house in which you live is built or the chair in which you may be seated is made, it also applies to the many technical products which make your life easier, and in particular to the key components that are hidden from your eyes, such as the silicon chip in the television set, the electrodes in lithium‐based batteries powering mobile phones or enabling electrotraction and the oxide ceramics in the oxygen sensors of automobiles. It is the rigidity of solids which endows them with characteristic, advantageous properties: The enduring structure of our world is inconceivable without solid matter, with its low diffusion coefficients at least for one component (the reader may like to consider for a moment his or her surroundings being in spatial equilibrium, i.e. with all diffusion barriers having been removed). In addition and beyond the mere mechanical functionality, solids offer the possibility of subtly and reproducibly tailoring chemical, electric, magnetic and thermal functions.

The proportion of functional materials and, in particular, electrical ceramics in daily life is going to increase enormously in the future: Chemical, optical or acoustic sensors will analyse the environment for us, actuators will help us influence it. More or less autonomous systems perceiving the environment by sensors and influencing it by actuators, controlled by computers and powered by an autarchic energy supply (battery) or by an ‘electrochemical metabolism’ (fuel cell) are by no means visions for the distant future. Wherever it is possible, attempts are being made to replace fluid systems by solid ones, for instance, liquid electrolytes by solid ion conductors. In short: The importance of (inorganic or organic) solids can hardly be overestimated (even if we ignore the crowning functionality of biopolymers, as (almost)1 done in this book). Furthermore, solid state reactions were not only of importance for and during the creation of our planet, but also constitute a large portion of processes taking place, nowadays, in nature and in the laboratory.

Perhaps you are a chemistry student in the midst of your degree course or a chemistry graduate already with a complete overview of the syllabus. You will then certainly agree that the greater part of a chemist's education is concerned with liquids and, in particular, with water and aqueous solutions. Solids, when they are considered, are almost always considered from a naive ‘outer’ point of view, i.e. as chemically invariant entities: Interest is chiefly concerned with the perfect structure and chemical bonding; in aqueous solutions it either precipitates or dissolves. Only the surface is considered as a site of chemical reactions. The concept of a solid having an ‘internal chemical life’, which makes it possible for us to tailor the properties of a solid, in the same manner that we can those properties of aqueous solutions, sounds – even now – somewhat adventurous.

On the other hand, solid state physicists have influenced the properties of semiconductors such as silicon, germanium or gallium arsenide by defined doping in a very subtle way. If the reader is a physicist, I believe he or she would agree that the role of composition as a parameter is not sufficiently appreciated in physics. Even though internal chemical equilibria are sometimes considered and doping effects are generally taken into account, concentration is still too strongly focused on singular compositions and electronic carriers. In fact, a large number of functional materials are based on binary or multinary compounds, for which stoichiometric effects play an enormous role.

Lastly this text is addressed to materials scientists for whom the mechanical properties frequently and traditionally are of prime interest. Electrochemical aspects are generally not sufficiently considered with respect to their importance for the preparation and durability of the material and optimization of its function. Thus, the fields of electroceramics and more generally of solids for energy applications are addressed.

The chemistry and physics of defects play a key role in the following text [1, 2]. After all, in the classical examples of water in chemistry and silicon in physics, it is not so much the knowledge of the structure or of the chemical bonding that has made it possible to carry out subtle and controllable tuning of properties, but rather the phenomenological knowledge of the nature of relevant particles, such as ions, ions or foreign ions in water that determine its acid‐base and redox chemistry. In the case of silicon the relevant particles are conduction electrons and electron holes, which, on account of their properties, determine the (redox) chemistry and the electronic properties.

Focusing on such relevant particles leads to the generalized concept of defect chemistry that permits the treatment of internal chemical processes within the solid state (in this context Figure 1.1 is illustrative). In processes, in which the structure of the phase does not alter, the perfect state can be regarded as invariant and all the chemical occurrences can then be reduced to the behaviour of the defects, that is, the deviations from the perfect state. The foundation stone of defect chemistry was laid by Frenkel, Schottky and Wagner [1, 2] as early as the 1930s; there is an extensive technical literature covering the field [3–14], but in chemistry and physics it has not yet become an adequate and generally accepted component of our training. In this sense this text is intended to motivate the chemist to deal with the internal chemistry of solid bodies. I hope that the effort will