Electrolytes for Lithium and Lithium-Ion Batteries

488 Pages·2014·18.13 MB·English

by  T. Richard Jow

Modern Aspects of Electrochemistry 58
T. Richard Jow
Kang Xu
Oleg Borodin
Makoto Ue Editors
Electrolytes
for Lithium
and Lithium-
Ion Batteries
MODERN ASPECTS OF
ELECTROCHEMISTRY
No. 58
Series Editors:
Ralph E. White
Department of Chemical Engineering
University of South Carolina
Columbia, SC 29208
Constantinos G. Vayenas
Department of Chemical Engineering
University of Patras
Patras 265 00
Greece
For further volumes:
http://www.springer.com/series/6251
Previously from Modern Aspects of Electrochemistry
Modern Aspects of Electrochemistry No. 56
Applications of Electrochemistry in Medicine
Edited by Mordechay Schlesinger, Professor Emeritus,
Department of Physics, University of Windsor, Canada.
Topics in Number 56 include:
(cid:129) Electrochemistry in the design and development of medical technologies
and devices
(cid:129) Medical devices at the interface of biology and electrochemistry
(cid:129) Sensing by screen printed electrodes for medical diagnosis
(cid:129) Electrochemical glucose sensors
(cid:129) Electrochemistry of adhesion and spreading of lipid vesicles on electrodes
(cid:129) Bio-Electrochemistry and chalcogens
(cid:129) Nanoplasmonics in medicine
(cid:129) Extravascular hemoglobin: aging contusions
(cid:129) Modeling tumor growth and response to radiation
Modern Aspects of Electrochemistry No. 57
Electrodeposition and Surface Finishing
Edited by Stojan S. Djokic´, Professor of Chemical & Materials
Engineering at the University of Alberta
Topics in Number 57 include:
(cid:129) Electrodeposition and the characterization of alloys and composite materials
(cid:129) Mechanistic aspects of lead electrodeposition
(cid:129) Electrophoretic deposition of ceramic materials onto metal surfaces
(cid:129) Metal oxides for energy conversion and storage
(cid:129) Electrochemical aspects of chemical mechanical polishing
(cid:129) Surface treatments prior to metallization of semiconductors, ceramics, and polymers
(cid:129) Anodization of aluminum
T. Richard Jow (cid:129) Kang Xu (cid:129) Oleg Borodin
Makoto Ue
Editors
Electrolytes for Lithium
and Lithium-Ion Batteries
Editors
T. Richard Jow Kang Xu
U.S. Army Research Laboratory U.S. Army Research Laboratory
Adelphi , MD , USA Adelphi , MD , USA
Oleg Borodin Makoto Ue
U.S. Army Research Laboratory Mitsubishi Chemical Corporation
Adelphi , MD , USA Yokohama , Kanagawa , Japan
ISSN 0076-9924 ISSN 2197-7941 (electronic)
ISBN 978-1-4939-0301-6 ISBN 978-1-4939-0302-3 (eBook)
DOI 10.1007/978-1-4939-0302-3
Springer New York Heidelberg Dordrecht London
Library of Congress Control Number: 2014935230
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Pref ace
L ithium-ion (Li-ion) batteries were fi rst introduced into the marketplace by Sony in
1991 to power a video camera. Since then, Li-ion batteries have become part of our
daily lives—powering a wide range of mobile electronic devices and power tools.
The electrolyte is a key component of a Li-ion battery. Current electrolytes are the
result of many years of research and development and play a key role in providing
good performance for applications. New and more challenging battery requirements
for power tools, hybrid electric vehicles, plug-in electric vehicles, and stand-by
power sources for communications and modern airplanes require a signifi cant
advance in battery chemistry. The batteries needed are often of higher voltages and
higher energy content. Furthermore, they will be exposed to extremes of tempera-
ture with the necessity of still providing long cycle and storage life and assured user
safety. A new class of electrolytes is needed to meet these demands. The new elec-
trolytes must not only provide good ionic conduction over a wide range of ambient
temperatures but also provide good chemical stability and compatibility with the
more reactive electrode materials that are required to achieve higher battery-specifi c
energy and power. With the demand for higher energy density Li-ion batteries,
recent development trends favor the use of higher voltage cathodes such as 4.7 V for
LiNi Mn O and 4.8 V LiCoPO , higher capacity cathodes such as layer–layer
0.5 1.5 4 4
composite and layer–spinel composite made of Li[Ni,Mn,Co]O with a capacity in
2
the range of 250–300 mA h/g versus 140 mA h/g for LiCoO cathodes used today
2
in commercial cells, and higher capacity Li alloy-based anodes such as Li–Sn and
Li–Si alloys. Today’s state-of-the-art electrolytes made of lithium hexafl uorophos-
phate (LiPF ) dissolved in cyclic carbonate and linear carbonate solvent mixtures
6
with functional additives are not adequate in these new higher energy density elec-
trochemical pairs without losing capacity or power. Looking beyond the horizon,
many researchers and institutions intend to utilize sulfur or air as an even higher
theoretical capacity cathode and pair with pure Li as an anode pursuing even higher
energy density. The need of compatible electrolytes is also imperative for develop-
ing such systems.
v
vi Preface
W hat we need are better electrolyte materials that are compatible with the chosen
electrode materials. The development of better electrolyte materials will require a
much better understanding of electrolytes and how they interact with electrode
materials. This book provides an overview of electrolyte research and development
in the past 10 years as a foundation for thinking about future directions.
A number of books have been devoted to the science and technology of Li-ion
batteries in recent years. However, there is no single book giving a comprehensive
overview of electrolytes for Li-ion batteries. With the high demand for more robust
electrolytes for the improvement of performance and energy density of Li and
Li-ion batteries, it is time for a book that covers the electrolyte materials and the
understanding of electrolyte and electrode interactions that have been developed in
the past 10 years. This book covers the materials’ aspects of the electrolytes, the
state of the understanding of the electrolyte and electrode interactions, and basic
understandings of the electrolytes and electrode/electrolyte interaction through
computation. We are pleased to provide a ten-chapter book divided in three parts to
cover subjects that we believed would make a good reference for researchers and
technologists in the fi eld and also for those who are not working in the fi eld but are
interested in understanding the basics, challenges, and progress that have been made
in the fi eld.
The fi rst part of the book comprises four chapters focusing on electrolyte materials.
In Chap. 1 , Professor Wesley A. Pacifi c Northwest National Laboratory focuses on the
various lithium salts that have been developed and compares these salts with LiPF ,
6
which is the salt used in today’s Li-ion batteries. A comprehensive review of the physi-
cochemical properties of these salts in nonaqueous solvents is also provided. The
developed alternative salts have potential to be useful as additives or substitute for
LiPF in new Li battery chemistry. Dr. Makoto Ue of Mitsubishi Chemicals together
6
with Emeritus Professor Yukio Sasaki of Tokyo Polytechnic University, Professor
Yasutaka Tanaka of Shizuoka University, and Professor Masayuki Morita of Yamaguchi
University contribute Chap. 2 , which provides a solid review of heteroatom-containing
organic solvents—including sulfur, fl uorine, boron, and phosphorous—applied to lith-
ium cells in recent years. Dr. Koji Abe of Ube Industries reviews work on additives for
Li-ion electrolytes since 1990. Given that the properties of additives vary widely with
battery test conditions, Dr. Abe selected additives that were utilized in practical appli-
cations and tried to replace those that were less successful; he then organized the addi-
tives chronologically. As a result, the cited references are mostly patents. He left the
concepts, chemistry, and mechanism for each additive to the cited references as he
explained in the Background of his chapter. In Chap. 4 , Dr. Hajime Matsumoto of
National Institute of Advanced Industrial Science and Technology, Japan, reviews the
recent progress on ionic liquids for rechargeable lithium batteries.
The second part of the book focuses on interfacial chemistry at the electrodes
and the methods of characterizing the interphases. Dr. Mengqing Xu, Dr. Lidan
Xing, and Professor Weishan Li of South China Normal University, China, contrib-
ute Chap. 5 , a review of the understanding of the interphases between the electro-
lyte and the anodes including graphite anode and Li–Sn and Li–Si alloy anodes in
Li-ion batteries. Dr. Francis Amalraj Susai, Dr. Ronit Sharabi, Dr. Hadar Sclar, and
Preface vii
Professor Doron Aurbach of Bar-Ilan University, Israel, contribute Chap. 6 , which
provides a review of the surface chemistry of cathode materials including transi-
tion metal spinel, transition metal layer, transition metal phosphate, and oxygen
cathode materials in nonaqueous electrolytes. Dr. Jordi Cabana of Lawrence
Berkeley National Laboratory wrote Chap. 7 , which provides an overview of the
experimental tools and the kind of information they can offer with representative
examples in the literature. It is important to recognize that no single technique can
currently provide the answers to these complex interfacial phenomena in Li and
Li-ion batteries.
Recent advances in molecular modeling using molecular simulations—and espe-
cially density functional theory—show promise of accurate prediction of the elec-
trolyte’s electrochemical, structural, and transport properties. The third part of this
book is devoted to the understanding of electrolytes and electrolyte/electrode inter-
actions through computational and molecular modeling. In Chap. 8 , Dr. Oleg
Borodin of the U.S. Army Research Laboratory discusses the applications of quan-
tum chemistry to determine electrolyte oxidative stability and oxidation-induced
decomposition reactions. He uses molecular dynamics simulations and density
functional theory to predict the structural and transport properties of liquid electro-
lytes and solid electrolyte interphase (SEI) model compounds; free energy profi les
for lithium desolvation from electrolytes; and the behavior of electrolytes at charged
electrodes and the electrolyte–SEI interface.
In Chap. 9 , Dr. Johan Scheers and Prof. Patrik Johansson of Chalmers University
of Technology, Sweden, provide a thorough, historical perspective on the prediction
of electrolyte and additive electrochemical stabilities from DFT calculations, a
description of the simultaneous computational modeling methods, and materials
evolutions. The materials put into reduction and oxidation stability prediction inves-
tigation include carbonate solvents, salts with different anions, and additives. In
Chap. 1 0 , the fi nal chapter, Dr. Kah Chun Lau, Dr. Rajeev Assary, and Dr. Larry
Curtiss of Argonne National Laboratory review the recent progress towards under-
standing of aprotic electrolytes stability and decomposition mechanisms in Li-Air
battery obtained from quantum chemistry calculations that were corroborated with
experimental data. They also review the research that has been done on the develop-
ment of stable aprotic liquid electrolytes for Li-air batteries. One of the key prob-
lems is the electrochemical stability of the presently known carbonate- and
ether-based nonaqueous electrolyte systems. The Li-air battery is a relatively new
system and thus there are great challenges in developing stable electrolytes that are
resistant to attack by reduced O species.
2
The development of higher energy density Li-based batteries, whether they are
made of higher voltage cathodes, high capacity cathodes, carbonaceous anodes,
higher capacity Li alloy anodes, pure Li anode, or air cathode, all require stable and
compatible electrolytes. We need better electrolytes to match the new electrochemi-
cal pairs. This cannot be achieved without a good understanding of the electrolyte
and electrode interactions in relation to the electrolyte itself. In addition to electro-
chemical methods, many in situ and ex situ analytical tools need to be applied to the
systems. Basic understanding of the stability of the electrolytes—including
viii Preface
electrochemical and chemical interactions with the electrodes through molecular
modeling—is much needed. Experimental techniques for the validation of the mod-
eling are also very much in need for advancing the modeling. Research and devel-
opment of Li and Li-ion batteries are on the rise. New knowledge and new
understanding are increasing daily. To advance effectively, synthetic scientists, ana-
lytical scientists, and computational scientists need to work together to develop
higher energy density electrochemical energy storage systems.
Adelphi, MD, USA T. Richard Jow
Adelphi, MD, USA Kang X u
Adelphi, MD, USA Oleg Borodin
Yokohama, Japan Makoto Ue
Contents
1 Nonaqueous Electrolytes: Advances in Lithium Salts ......................... 1
Wesley A. Henderson
1.1 Introduction .................................................................................... 1
1.2 Electrolyte Salt Properties .............................................................. 5
1.3 Established Salts ............................................................................ 7
1.4 Electrolyte Characterization Tools ................................................. 9
1.5 Advanced Salts—Fluoroborates and -Phosphates ......................... 19
1.6 Advanced Salts—Perfl uoroalkylacetates, -Sulfonates,
and -Phosphates ............................................................................. 26
1.7 Advanced Salts—Imides, Methides,
and Phosphorylimides .................................................................... 29
1.8 Advanced Salts—Organoborates, -Phosphates,
and -Aluminates ............................................................................. 36
1.9 Advanced Salts—Other Anions ..................................................... 47
1.10 Adoption Criterion for New Salts .................................................. 55
1.11 Summary ........................................................................................ 57
References ................................................................................................. 58
2 Nonaqueous Electrolytes with Advances in Solvents ........................... 93
Makoto Ue, Yukio Sasaki, Yasutaka Tanaka, and Masayuki Morita
2.1 General Remarks (Makoto Ue) ........................................................ 94
2.2 Fluorine-Containing Organic Solvents (Yukio Sasaki) .................... 100
2.2.1 Introduction .......................................................................... 100
2.2.2 Fluorinated Lactones ............................................................ 100
2.2.3 Fluorinated Linear Carboxylates .......................................... 103
2.2.4 Fluorinated Cyclic Carbonates ............................................. 105
2.2.5 Fluorinated Linear Carbonates ............................................. 108
2.2.6 Fluorinated Monoethers ....................................................... 116
2.2.7 Fluorinated Diethers ............................................................. 117
ix