Energy Storage – Batteries, Supercapacitors Set, Volume 4: Inorganic Massive Batteries

199 Pages·2018·19.368 MB·English

by  Virginie Viallet, Benoit Fleutot

Inorganic Massive Batteries

Energy Storage – Batteries, Supercapacitors Set
coordinated by
Patrice Simon and Jean-Marie Tarascon
Volume 4
Inorganic Massive Batteries

Virginie Viallet
Benoit Fleutot
First published 2018 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:
ISTE Ltd John Wiley & Sons, Inc.
27-37 St George’s Road 111 River Street
London SW19 4EU Hoboken, NJ 07030
UK USA
www.iste.co.uk www.wiley.com

© ISTE Ltd 2018
The rights of Virginie Viallet and Benoit Fleutot 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: 2018930592

British Library Cataloguing-in-Publication Data
A CIP record for this book is available from the British Library
ISBN 978-1-84821-724-9
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
Chapter 1. Anatomy of an All-Solid-State Battery . . . . . . . . . . . . . 1
1.1. Constituents of an all-solid battery . . . . . . . . . . . . . . . . . . . . . . 3
1.1.1. Nature of solid electrolytes: required qualities . . . . . . . . . . . . . 3
1.1.2. Positive electrode materials . . . . . . . . . . . . . . . . . . . . . . . . 4
1.1.3. Negative electrode materials . . . . . . . . . . . . . . . . . . . . . . . 5
1.1.4. Conductive additive . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.1.5. Formulation of electrodes . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.2. Shaping methods of all-solid batteries . . . . . . . . . . . . . . . . . . . . 8
1.2.1. Assembly by cold pressing . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.2. Design by high temperature sintering . . . . . . . . . . . . . . . . . . 10
Chapter 2. Solid Ionic Conductors . . . . . . . . . . . . . . . . . . . . . . . 13
2.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2. Solid lithium-ion conductors . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.1. The Garnets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.2. The NASICON A MM′(XO ) structure . . . . . . . . . . . . . . . . 17
x 4 3
2.2.3. The compounds LISICON and Thio-LISICON . . . . . . . . . . . . 18
2.2.4. Ion conductive glass and glass-ceramics . . . . . . . . . . . . . . . . 23
2.2.5. The Argyrodites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.2.6. The complex hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.2.7. Phosphorus and lithium oxynitride or LiPON . . . . . . . . . . . . . 36
2.2.8. Anti-perovskite lithium-rich solid electrolytes . . . . . . . . . . . . . 36
2.2.9. Solid polymer electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.3. Solid sodium-ion conductors . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.3.1. NASICON compounds . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.3.2. Na PS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3 4
vi Inorganic Massive Batteries
Chapter 3. All-Solid-State Battery Technology
Using Solid Sulfide Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.1. Monolithic Li-ion “all-solid-state” batteries . . . . . . . . . . . . . . . . . 47
3.1.1. The first “all-solid-state” batteries . . . . . . . . . . . . . . . . . . . . 47
3.1.2. Second generation “all-solid-state” batteries . . . . . . . . . . . . . . 48
3.1.3. Toward High Performance Batteries . . . . . . . . . . . . . . . . . . 53
3.1.4. Batteries using lithium argyrodite electrolytes . . . . . . . . . . . . . 58
3.1.5. Li XP S (X = Ge, Si, Sn) phase in the structure LGPS . . . . . . 66
10 2 12
3.1.6. Understanding stability at the interfaces between the electrolyte and
electrode materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
3.1.7. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3.2. Sodium monolithic “all-solid-state” batteries . . . . . . . . . . . . . . . . 85
3.3. “All-solid-state” Li–S batteries . . . . . . . . . . . . . . . . . . . . . . . . 91
Chapter 4. Monolithic “All-Solid-State” Batteries
Using Solid Oxide Electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.1. Silver “all-solid-state” battery technology . . . . . . . . . . . . . . . . . . 97
4.2. Li-ion “solid-state” battery technology . . . . . . . . . . . . . . . . . . . 100
4.3. Sodium “solid-state” battery technology . . . . . . . . . . . . . . . . . . . 108
4.3.1. Sodium-ion “solid-state” battery technology . . . . . . . . . . . . . . 108
4.3.2. Sodium-sulfur “all-solid-state” battery technology . . . . . . . . . . 116
Chapter 5. LiBH Electrolyte and Polymer Battery Technology . . . 119
4
5.1. “All-solid-state” battery technology: LiBH electrolyte . . . . . . . . . 119
4
5.2. “Solid-state” polymer battery technology . . . . . . . . . . . . . . . . . . 120
Chapter 6. Markets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
6.1. Solid electrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
6.1.1. Ohara . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
6.1.2. NEI . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
6.2. Solid-state batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
6.3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
Introduction
I.1. Energy issues
Originally dedicated to survival and dietary requirements, global energy
consumption had been in equilibrium for over 12,000 years after the
discovery of the first energy source in the form of fire. This balance was
considerably affected by the industrial revolution of 1850. Since then,
energy demands have been increasing steadily due to the exponential
development of new technologies, better standards of living and growth of
the world’s population. All the energy consumed to satisfy our various needs
comes from forms of the so-called primary energies, that are either non-
renewable (fossil fuels such as coal, oil, natural gas, but also uranium) or
renewable (hydro, wind, marine, geothermal and solar energies, including
biomass). The evolution of the global consumption of these different sources
is presented in Figure I.1 [IEO 16].

Figure I.1. Global energy consumption between 1990 and 2040 (quadrillion Btu) by
energy source [IEO 16]. The dotted lines show projections of the effects of the US Clean
Energy Plan. For a color version of this figure, see www.iste.co.uk/viallet/batteries.zip
viii Inorganic Massive Batteries
Fossil fuels still account for this demand, and in 2014, 78.3% of the
energy consumed was still from coal and oil and only 19.2% from alternative
energy sources (Figure I.2) [REN 16]. Although extremely weak, these
results are encouraging considering that in 1973, renewable energies
accounted for only 0.1% of global energy consumption [WEO 12].

Figure I.2. Estimated share of renewable energy in overall
global energy consumption, 2014 [REN 16]. For a color version of
this figure, see www.iste.co.uk/viallet/batteries.zip
The replacement of these fossil resources is the major challenge of the
21st Century. The consumption of these resources has caught up with their
production and their exhaustion is only a matter of decades away.
Nevertheless, it appears that new sources of oil are possible, but at much
higher costs than today. Moreover, even if fossil energy resources were not
an issue, they should be limited because they are harmful to the environment
mainly due to the gases emitted upon their combustion. It is imperative to
turn to renewable energies.
The main disadvantage of renewable energies is that they are intermittent
and that their production fluctuates during the day and according to the
weather (i.e. for solar and wind in particular). They cannot power a power
grid on demand. It is therefore necessary to develop new systems capable of
reversibly storing the energy produced by these alternative resources. To
fulfill this function, electrochemical cells appear to be the ideal storage
system. The latter allow reversible storage of the electrical energy in the
form of chemical energy and have the advantage of being adaptable with
regard to their size.
Introduction ix
The storage of electrical energy involves, on the one hand, stationary
systems and, on the other hand, embedded systems. Stationary installations
are dedicated sites, usually high capacity storage systems (> a few megawatt
hours), medium or high power storage systems (from 100 kW to GW),
which support the (continuous) power grids and production of renewable
energies (wind and photovoltaics). On-board installations are small capacity
storage devices integrated into a mobile system, in particular in rechargeable
electric and hybrid vehicles, multimedia and equipment [LAR 15, POI 11].
I.2. Lithium Ion cells
As shown in Figure I.3 [TAR 01], lithium ion cells are the most efficient
of electrochemical storage batteries, both in terms of volume and mass
density, despite a higher price than their competitors, nickel-cadmium and
nickel-metal hydride.
After a quick overview of the operating principle and of the characteristic
features of a lithium battery, the means of increasing the energy density of
these batteries will be discussed.
I.2.1. Operating principle of a battery
The operation of these batteries is based on an intercalation chemistry
demonstrated in the 1970s, improved over the years with the use of lamellar
oxides of transition metals proposed by Goodenough [MIZ 80].

Figure I.3. Comparison of mass and volume energy
densities of the main electrochemical cell [REN 16]. For a color
version of this figure, see www.iste.co.uk/viallet/batteries.zip