Lithium Batteries and other Electrochemical Storage Systems E-Book

Christian Glaize

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

Seitenzahl: 456

Veröffentlichungsjahr: 2013

Beschreibung

Lithium batteries were introduced relatively recently in comparison to lead- or nickel-based batteries, which have been around for over 100 years. Nevertheless, in the space of 20 years, they have acquired a considerable market share - particularly for the supply of mobile devices. We are still a long way from exhausting the possibilities that they offer. Numerous projects will undoubtedly further improve their performances in the years to come. For large-scale storage systems, other types of batteries are also worthy of consideration: hot batteries and redox flow systems, for example. This book begins by showing the diversity of applications for secondary batteries and the main characteristics required of them in terms of storage. After a chapter presenting the definitions and measuring methods used in the world of electrochemical storage, and another that gives examples of the applications of batteries, the remainder of this book is given over to describing the batteries developed recently (end of the 20th Century) which are now being commercialized, as well as those with a bright future. The authors also touch upon the increasingly rapid evolution of the technologies, particularly regarding lithium batteries, for which the avenues of research are extremely varied. Contents Part 1. Storage Requirements Characteristics of Secondary Batteries Examples of Use 1. Breakdown of Storage Requirements. 2. Definitions and Measuring Methods. 3. Practical Examples Using Electrochemical Storage. Part 2. Lithium Batteries 4. Introduction to Lithium Batteries. 5. The Basic Elements in Lithium-ion Batteries: Electrodes, Electrolytes and Collectors. 6. Usual Lithium-ion Batteries. 7. Present and Future Developments Regarding Lithium-ion Batteries. 8. Lithium-Metal Polymer Batteries. 9. Lithium-Sulfur Batteries. 10. Lithium-Air Batteries. 11. Lithium Resources. Part 3. Other Types of Batteries 12. Other Types of Batteries. About the Authors Christian Glaize is Professor at the University of Montpellier, France. He is also Researcher in the Materials and Energy Group (GEM) of the Institute for Electronics (IES), France. Sylvie Geniès is a project manager at the French Alternative Energies and Atomic Energy Commission (Commissariat à l'Energie Atomique et aux Energies Alternatives) in Grenoble, France.

Leseprobe

Contents

Preface

Acknowledgements

Introduction

PART 1: Storage Requirements Characteristics of Secondary Batteries Examples of Use

Chapter 1: Breakdown of Storage Requirements

1.1. Introduction

1.2. Domains of application for energy storage

1.3. Review of storage requirements and appropriate technologies

1.4. Conclusion

Chapter 2: Definitions and Measuring Methods

2.1. Introduction

2.2. Terminology

2.3. Definitions of the characteristics

2.4. States of the battery

2.5. Faradaic efficiency

2.6. Self-discharge

2.7. Acceptance current

2.8. Conclusion

2.9. Appendix 1: Nernst’s law

2.10. Appendix 2: Double layer48

2.11. Appendix 3: Warburg impedance37

2.12. Solutions to the exercises in Chapter 2

Chapter 3: Practical Examples Using Electrochemical Storage

3.1. Introduction

3.2. Conclusion

3.3. Solution to the exercises in Chapter 3

PART 2: Lithium Batteries

Chapter 4: Introduction to Lithium Batteries

4.1. History of lithium batteries

4.2. Categories of lithium batteries

4.3. The different operational mechanisms for lithium batteries

4.4. Appendices

Chapter 5: The Basic Elements in Lithium-ion Batteries: Electrodes, Electrolytes and Collectors

5.1. Introduction

5.2. Operation of lithium-ion technology

5.3. Positive electrodes

5.4. Negative electrodes

5.5. Electrolyte

5.6. Current collectors

5.7. Conclusion

5.8. Solution to exercises in Chapter 5

Chapter 6: Usual Lithium-ion Batteries

6.1. Principle of operation of conventional assemblies of electrodes

6.2. Major characteristics

6.3. Solution to exercises from Chapter 6

Chapter 7: Present and Future Developments Regarding Lithium-ion Batteries1

7.1. Improvement of the operation and safety of current technologies

7.2. Improvement of the intrinsic performances (energy, power)

7.3. New formats of batteries

7.4. Conclusion

Chapter 8: Lithium-Metal Polymer Batteries1

8.1. Principle of operation

8.2. Manufacturing process

8.3. Main characteristics

Chapter 9: Lithium-Sulfur Batteries1

9.1. Introduction

9.2. The element sulfur

9.3. Principle of operation

9.4. Discharge curve

9.5. Advantages to Li-S

9.6. Limitations and disadvantages of a Li-S battery

9.7. Conclusion

Chapter 10: Lithium-Air Batteries1

10.1. Introduction

10.2. Operational principle

10.3. Electrolytes

10.4. Main limitations

10.5. Main actors

10.6. Conclusion

10.7. Appendix: calculation of theoretical gravimetric energy densities

Chapter 11: Lithium Resources1

11.1. State of the art in terms of availability of lithium resources

11.2. Comparison of resources with the needs of the electrical industry

11.3. State of the art of extraction techniques and known production reserves

11.4. Nature and geological origin of all potential lithium resources

11.5. Global geographic distribution of raw lithium resources

11.6. Evolution of the cost of lithium

11.7. Summary

PART 3: Other Types of Batteries

Chapter 12: Other Types of Batteries1

12.1. Introduction

12.2. Sodium–sulfur technology

12.3. Nickel chloride batteries

12.4. Conclusions about high-temperature batteries

12.5. Redox flow systems

Conclusion

Index

First published 2013 in Great Britain and the United States by ISTE Ltd and John Wiley & Sons, Inc.

Apart from any fair dealing for the purposes of research or private study, or criticism or review, as permitted under the Copyright, Designs and Patents Act 1988, this publication may only be reproduced, stored or transmitted, in any form or by any means, with the prior permission in writing of the publishers, or in the case of reprographic reproduction in accordance with the terms and licenses issued by the CLA. Enquiries concerning reproduction outside these terms should be sent to the publishers at the undermentioned address:

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John Wiley & Sons, Inc.

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© ISTE Ltd 2013

The rights of Christian Glaize and Sylvie Geniès to be identified as the authors of this work have been asserted by them in accordance with the Copyright, Designs and Patents Act 1988.

Library of Congress Control Number: 2013941764

British Library Cataloguing-in-Publication Data A CIP record for this book is available from the British Library ISBN: 978-1-84821-496-5

Preface

Whether for mobile, on-board or stationary applications, it is of crucial importance to have high-performing storage systems, whose manufacturing, use and recycling costs are reasonable and which offer good operational safety. In view of the extent of application domains, and of the diversity of usage profiles and technical/economic criteria which need to be satisfied, it is undeniable that no single technology can serve all these needs. The first part of this book (Chapters 1–3) outlines the storage requirements and the most widely-used technologies for each of these, the definitions used to characterize accumulators, and gives examples of the usage of electrochemical storage. The rest of the book describes the most recently introduced electrochemical secondary batteries1: lithium technologies and the most recent accumulators (redox-flow batteries, high-temperature batteries, etc.).

This book will show the reader that batteries are complex systems, whose successful commercialization has been the fruit of a great many projects in scientific research, empiricism and industrial know-how. The design of electrochemical accumulators has been the focus of a great deal of work, and sometimes compromise with a view to keeping them competitive and economically viable. Their design is not set in stone. Quite the opposite, in fact – it is constantly changing, thanks to feedback from experience on the ground, but at the cost of lengthy and painstaking validation testing, because the lifetimes are increasingly long and the laws of accelerated aging are not always usable or representative of real-life operation. We also wished to demonstrate that it is not possible to consider a group of batteries as having fixed characteristics which are applicable regardless of the application and the technology used to manufacture them. For this reason, we made a quite deliberate choice to outline the fundamental electrochemical and chemical phenomena involved, as simply and clearly as possible, sometimes “by hand”. Indeed, we feel it is essential to have knowledge of these mechanisms in order to develop appropriate theoretical models and understand the possible applications for each technology.

The challenge for us was to explain how to choose and properly use an secondary battery for a given usage, without falling into the trap of merely giving a list of “recipes”. For this purpose, the reader needs to be given a detailed understanding of the function of secondary batteries and a description of their different (and often numerous) technological variants. This is not something which can be done in merely a few pages. Also, it is no easy task to give a pedagogical explanation of the electrochemical processes and the industrial constraints to readers with a background in electrical engineering, but who are not specialists in electrochemistry.

We have not neglected always keeping sight of the economic approach which is important when choosing between different storage possibilities. In addition, although we have tried to make this book as complete as possible and present the maximum possible number of examples, we of course make no pretense of exhaustivity, and no claim of having flawless understanding (the secondary reactions that take place in the oldest accumulators are not all completely elucidated and therefore a fortiori, neither are those of the most recent technologies, which are still subject to diverse and sometimes contradictory explanations). We have cited a great many academic publications, because development has never ceased, even on the commercialized lithium secondary batteries, and the more recently introduced technologies are far from finished. Finally, the data presented (particularly technical-economic data) are those which were available at the time of writing, commenced in 2010 and completed in early 2013. With the advancement of research and development in the field of storage, compounded by the performance requirements for electric vehicles and the storage of electricity – be it of renewable or non-renewable origin – batteries will certainly continue to evolve rapidly in years to come. Hence, this point must be borne in mind.

Christian GLAIZE and Sylvie GENIÈSJune 2013

1 Lead and nickel-based electrochemical secondary batteries are described in detail in: C. Glaize and S. Geniès – Lead and Nickel Electrochemical Batteries, ISTE, London, John Wiley & Sons, New York, 2012.

Acknowledgements

The writing of this book was punctuated by numerous and enriching scientific discussions – between ourselves but also and above all the discussions we have had with fellow researching university professors, researchers, doctoral candidates and industrial partners. In naming all these people (listed below in alphabetical order), we wish to extend to them our heartfelt thanks for their availability and the time which they have given us. Their knowledge, experience and skills have greatly enriched this book and have advanced our own knowledge of accumulators.

Thanks go, therefore, to Jean-Jacques Huselstein, Thierry Martiré, Laure Monconduit, Lorenzo Stievano and Yaël Thiaux, who are researchers and teaching researchers at the Université Montpellier II; to Loïc Goemaere and Adrien Soares, who at the time were doctoral candidates at the Université Montpellier II; to Yann Bultel, Professor at the Institut National Polytechnique de Grenoble; and to Bernard Multon, Professor at the Ecole Normale Supérieure de Cachan and the commissioning editor of this series of books. At CEA-Liten, thanks go to the researchers Mélanie Alias, Philippe Azaïs, Céline Barchasz, Florence Fusalba, Frédéric Le Cras, Sébastien Patoux and Marion Perrin, and to Charles Gayot, Camille Grosjean, Jérémie Jousse, and Mathieu Quenard, who were doctoral candidates and some of whom have now obtained their doctorates. Our thanks to Benoît Connes and Matthieu Prigent from Phaesun France, and to Jean-Pierre Belliard at Novéa Energies.

To those to whom we owe thanks but who are not explicitly thanked above, we beg forgiveness for this unintentional oversight. These people know who they are.

Christian GLAIZE and Sylvie GENIÈS

On a personal note, I would like to express my gratitude to Jean Alzieu, who is a fount of scientific knowledge and innovative ideas, who introduced me to the world of electrochemistry. Further thanks go to Josette Fourcade, Jean-Claude Jumas, Laure Monconduit and Lorenzo Stievano, who then introduced me to the domain of lithium accumulators.

Christian GLAIZE

And now to you, the reader: enjoy this book!

Introduction

Since the presentation of the lead-acid electrochemical accumulator by Gaston Planté at the French Académie des Sciences in 1859, many other material couples for the purpose have emerged. Some have been abandoned or are very underdeveloped, because a number of disadvantages have not been completely resolved, rendering the technology insufficiently viable.1 Others have endured, such as nickel-cadmium (NiCd), introduced in 1899 by the Swede Waldemar Jungner (1869–1924) and developed primarily by Edison. Yet it was not until 1947 that Neumann succeeded in making the battery completely sealed, giving us the modern nickel-cadmium battery. The new generations of batteries are mostly sealed, either by obligation (lithium, NaS, chlorides, redox flow batteries, etc.) or to limit the need for maintenance.

The description of these different types of batteries is important, because the criteria for choosing a technology appropriate for a given application do not depend solely on the mass energy or the cost per kWh stored, as we might be led to think on the basis of the most commonplace analyses. There are other factors to be considered, such as the lifetime, the type of cycling, safety, etc. Therefore, this book will begin with a chapter which will show the diversity of applications for batteries and the main characteristics required of them in terms of storage. This first chapter will also demonstrate the diversity of the levels of current summed and energy stored (from the few mWh of a lithium battery in a wristwatch to the tens of MWh electricity storage for grid support), and also the diversity of the durations of discharge (which can range from a few minutes for emergency supply for computers to hundreds of hours to preserve data in an electronic device). Thus, it is clear that no single type of accumulator can serve for such diverse applications. Already, with lead and then nickel accumulators, there were different technologies to choose from, but the elements introduced recently – particularly lithium-based solutions – offer a far broader range of different technologies.

After a second chapter which presents the definitions and measuring methods used in the world of electrochemical storage, and a third which gives examples of the applications of batteries, in the rest of this book we propose to describe the electrochemical cells developed recently (end of the 20th Century) which are now being commercialized, as well as those whose future looks bright. We shall begin with lithium secondary batteries (Chapters 4–10). Then, in Chapter 12, we shall describe high-temperature technologies (sodium/sulfur (NaS), ZEBRA and chlorides) and redox flow systems.

We shall also touch upon the increasing rapid evolution of the technologies, particularly as regards lithium batteries, for which the avenues of research are extremely varied. The substance couples used in tomorrow’s world will probably be different to those widely used today. These advances will be discussed in Chapter 7 for lithium-ion elements. Then we shall go on to describe the promising lithium-sulfur batteries (Chapter 9) and lithium-air cells (Chapter 10).

1 For instance, the nickel-iron battery, invented almost at the same time (Edison, 1901) as the nickel-cadmium battery, has a poor charge efficiency, which causes excessive heating and hydrogen release. Another example is nickel-zinc technology, for which further study seems necessary, because it is subject to the formation of dendrites which limit its lifetime.

PART 1

Storage Requirements Characteristics of Secondary Batteries Examples of Use

Chapter 1

Breakdown of Storage Requirements

1.1. Introduction

Electrochemical electricity storage has been in use for as long as electricity has been industrially used. The earliest secondary battery was introduced by Gaston Planté in 1859, i.e. between the first laboratory primary battery created by Alessandro Volta in 1800 and the industrial dynamo from Zénobe Gramme in 1869.

1.2. Domains of application for energy storage

Energy storage systems are used in many fields of application. Each of these domains is characterized by specific operational profiles and, consequently, different types and technologies of secondary batteries. They are described below.

Of the major domains of application, we might cite:

– starter batteries;

– traction batteries and on-board batteries;

– stationary deep cycle batteries (batteries for storage in decentralized microgrids with photovoltaic generation, for grid support, etc.);

– standby power batteries (batteries for uninterruptible power supply, for safeguarding information, etc.);

– and, more recently, batteries for mobile devices: portable computers and mobile telephones – in billions of units produced each year – digital cameras, audio and video players, camcorders, PDAs (Personal Digital Assistants), etc.

1.2.1. Starter batteries

Better known as “SLI” batteries (for “Start, Lighting and Ignition”), these batteries are used to fire up internal combustion engines (in cars and trucks but also tractors, electrogen groups, or even boats or airplanes, etc.) as well as to provide lighting and many other functions. These batteries have an average specific energy1 and a low cost.

The profile of the current entering2 into an SLI battery, and the evolution of the state of charge (SOC, defined in section 2.4.2) are shown qualitatively below (Figure 1.1). Typically, car batteries have a nominal voltage of 12 V. Their capacity is usually between 40 and 80 Ah. Start currents can reach up to several hundred amperes.3 Measured values are given in section 3.1.1.

In a car with a combustion engine, the battery only supplies energy when the engine is not running, or is running at a slowed speed. When the vehicle is moving, it is the alternator which supplies the demands. When the battery is supplying energy, it is usually quickly recharged by the alternator, and is therefore subjected only to a microcycle. Conversely, in certain trucks, the battery may have to supply certain functions such as the raising/lowering of an unloading tailgate, a refrigeration group, a crane, etc. The battery is then subject to deeper discharges (Figure 1.2).

Figure 1.1.Car SLI battery: profile of the current flowing into the battery and change in its SOC

Figure 1.2.SLI battery for a truck with auxiliary functions: profile of current entering into the battery and evolution of its SOC