Advanced Fluoride-Based Materials for Energy Conversion

438 Pages·2015·28.477 MB·English

by  Tsuyoshi Nakajima, Henri Groult

Advanced
Fluoride-Based
Materials for Energy
Conversion
Edited by
Tsuyoshi Nakajima
Department of Applied Chemistry
Aichi Institute of Technology
Yakusa, Toyota, Japan
Henri Groult
Sorbonne Universités, UPMC Univ.
Laboratoire PHENIX
CNRS, Paris, France
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Contributors
Bruno Ameduri Institut Charles Gerhardt, Ingénierie et Architectures
Macromoléculaires, UMR CNRS 5253, Ecole Nationale Supérieure de Chimie de
Montpellier, Montpellier, France
Khalil Amine Chemical Sciences and Engineering Division, Argonne National
Laboratory, Lemont, IL, USA
Ramin Amin-Sanayei Arkema Inc, King of Prussia, PA, USA
Ahmed Bahloul Laboratoire des Matériaux et Systèmes Électroniques, Centre
Universitaire de Bordj Bou Arréridj, Bordj Bou Arréridj, Algeria
T. Böttcher School of Engineering and Science, Jacobs University GmbH, Bremen,
Germany
Emmanuel Briot Sorbonne Universités, UPMC Univ., Laboratoire PHENIX, CNRS,
Paris, France
S. Cadra CEA/DAM, Le Ripault, Monts, France
Benjamin Campagne Institut Charles Gerhardt, Ingénierie et Architectures
Macromoléculaires, UMR CNRS 5253, Ecole Nationale Supérieure de Chimie de
Montpellier, Montpellier, France
Zonghai Chen Chemical Sciences and Engineering Division, Argonne National
Laboratory, Lemont, IL, USA
Mouad Dahbi Department of Applied Chemistry, Tokyo University of Science, Tokyo,
Japan; Elements Strategy Initiative for Catalysts and Batteries, Kyoto University,
Kyoto, Japan
A. Darwiche IPREM-ECP CNRS UMR 5254, Pau, France
Ghislain David Institut Charles Gerhardt, Ingénierie et Architectures
Macromoléculaires, UMR CNRS 5253, Ecole Nationale Supérieure de Chimie de
Montpellier, Montpellier, France
R. Dedryvère ICG-AIME, Université Montpellier 2, Montpellier, France
M. Dubois Institute of Chemistry of Clermont-Ferrand, University of Blaise Pascal,
Aubiere Cedex, France
D. Farhat PCM2E, Université F. Rabelais, Parc de Grandmont, Tours, France
Maximilian Fichtner Helmholtz Institute Ulm for Electrochemical Energy Storage
(HIU), Helmholtzstr, Ulm, Germany
F. Ghamouss PCM2E, Université F. Rabelais, Parc de Grandmont, Tours, France
xiii
xiv Contributors
Henri Groult Sorbonne Universités, UPMC Univ., Laboratoire PHENIX, CNRS,
Paris, France
K. Guérin Institute of Chemistry of Clermont-Ferrand, University of Blaise Pascal,
Aubiere Cedex, France
Rika Hagiwara Department of Fundamental Energy Science, Graduate School of
Energy Science, Kyoto University, Kyoto, Japan
Wensheng He Arkema Inc, King of Prussia, PA, USA
Christian M. Julien Sorbonne Universités, UPMC Univ., Laboratoire PHENIX,
CNRS, Paris, France
N. Kalinovich School of Engineering and Science, Jacobs University GmbH, Bremen,
Germany
O. Kazakova School of Engineering and Science, Jacobs University GmbH, Bremen,
Germany
Jae-Ho Kim Headquarters for Innovative Society-Academia Cooperation, Fukui
University, Fukui, Japan
Shinichi Komaba Department of Applied Chemistry, Tokyo University of Science,
Tokyo, Japan; Elements Strategy Initiative for Catalysts and Batteries, Kyoto
University, Kyoto, Japan
Sandrine Leclerc Sorbonne Universités, UPMC Univ., Laboratoire PHENIX, CNRS,
Paris, France
Young-Seak Lee Department of Applied Chemistry and Biological Engineering,
Chungnam National University, Daejeon, Republic of Korea
D. Lemordant PCM2E, Université F. Rabelais, Parc de Grandmont, Tours, France
B. Lestriez Institut des Matériaux Jean Rouxel (IMN), CNRS UMR 6502, Université
de Nantes, Nantes, France
H. Martinez ICG-AIME, Université Montpellier 2, Montpellier, France
Kazuhiko Matsumoto Department of Fundamental Energy Science, Graduate School
of Energy Science, Kyoto University, Kyoto, Japan
Alain Mauger Sorbonne Universités, UPMC Univ., Laboratoire PHENIX, CNRS,
Paris, France; UPMC Univ. Paris 06, Institut de Minéralogie et Physique de la
Matière Condensée, Paris, France
L. Monconduit IPREM-ECP CNRS UMR 5254, Pau, France
Tsuyoshi Nakajima Department of Applied Chemistry, Aichi Institute of Technology,
Yakusa, Toyota, Japan
Madeleine Odgaard IRD Fuel Cells A/S, Kullinggade, Svendborg, Denmark
M. Ponomarenko School of Engineering and Science, Jacobs University GmbH,
Bremen, Germany
Ana-Gabriela Porras-Gutierrez Sorbonne Universités, UPMC Univ., Laboratoire
PHENIX, CNRS, Paris, France
Contributors xv
Munnangi Anji Reddy Helmholtz Institute Ulm for Electrochemical Energy Storage
(HIU), Helmholtzstr, Ulm, Germany
G.-V. Röschenthaler School of Engineering and Science, Jacobs University GmbH,
Bremen, Germany
Soshi Shiraishi Graduate School of Science and Technology, Gunma University,
Kiryu, Japan
Masayuki Takashima Department of Materials Science & Engineering, Faculty of
Engineering, University of Fukui, Fukui, Japan
Osamu Tanaike Research Center for Compact Chemical System, National Institute of
Advanced Industrial Science and Technology, Sendai, Japan
K. Vlasov School of Engineering and Science, Jacobs University GmbH, Bremen,
Germany
M. Winter MEET—Münster Electrochemical Energy Technology, Westfälische
Wilhelms-Universität, Münster, Germany
Susumu Yonezawa Headquarters for Innovative Society-Academia Cooperation, Fukui
University, Fukui, Japan; Department of Materials Science & Engineering, Faculty
of Engineering, University of Fukui, Fukui, Japan
Zhengcheng Zhang Chemical Sciences and Engineering Division, Argonne National
Laboratory, Lemont, IL, USA
W. Zhang ICG-AIME, Université Montpellier 2, Montpellier, France
Preface
The present book summarizes recent progress of fluoride-based materials for
lithium and sodium batteries, fuel cells, and capacitors. These electric energy-
generating devices have been widely used for many objectives. In particular,
they are important energy sources not only for hybrid and electric vehicles, but
also for our daily lives. To save petroleum resources and suppress CO genera-
2
tion, the social demand for electrochemical devices generating electric energy
has been increasing. Hybrid cars are now popular in our society and fuel cell
cars will be soon sold. Fuel and solar cells are also found in many buildings
and houses. Lithium batteries are of course important energy sources for many
kinds of electronic devices. Among various materials used as electrodes, elec-
trolytes, membranes, and so on for lithium and sodium batteries, fuel cells
and capacitors, fluorine-containing compounds have exhibited high functions
not found in other materials. Fluorine atom with a small size has the highest
electronegativity and small polarizability, making strong and stable chemical
bonds with other elements. Since fluorine gas (F ) has a small dissociation
2
energy (155 kJ mol−1), the reactivity of F with other compounds and single
2
substances is very high. Not only F , but also NF and ClF are important fluo-
2 3 3
rinating agents used for the preparation of many kinds of fluorine compounds.
Because of these properties of fluorine, inorganic and organic fluorine com-
pounds and fluoropolymers are now employed for lithium batteries, fuel cells,
and capacitors. The use of graphite fluoride as a cathode material of primary
lithium battery was realized about 40 years ago. Since then, graphite fluoride
has been used for primary lithium battery as an excellent cathode. Commer-
cialization of Li/(CF) battery revealed the usefulness of fluorine compounds
n
as energy materials. Polytetrafluoroethylene (PTFE) has been also used for
fuel cells to control the surface property of electrodes. Recently, many kinds
of fluorine-containing materials are being examined as new electrodes, elec-
trolytes, additives, membranes, and binders. Surface modification is one of the
convenient methods to improve the functions of electrode materials because
F and other fluorinating agents have high reactivity and can easily modify
2
the surface structures and composition of solid materials. Nowadays many
inorganic, organic, and polymer fluorine chemists are working to develop new
materials for batteries and capacitors. “Energy” is now one of the important
discussion themes at international fluorine symposiums and conferences. The
present book provides advanced information on fluorinated materials used as
xvii
xviii Preface
energy conversion materials, being quite useful for researchers, graduate stu-
dents, and engineers in universities, research institutes, and industries.
Tsuyoshi Nakajima (Aichi Institute of Technology, Japan)
Henri Groult (University of Pierre and Marie Curie, CNRS, France)
Chapter 1
High Performance Lithium-Ion
Batteries Using Fluorinated
Compounds
Zonghai Chen, Zhengcheng Zhang and Khalil Amine
Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA
Chapter Outline
1.1 Introduction 1 1.3 F luorinated Redox Shuttles 13
1.2 Stabilization of Lithiated 1.4 H igh Voltage Electrolytes 19
Anodes 2 1.5 C losing Remarks 29
1.2.1 Modification of Acknowledgments 29
SEI Layer 5 References 30
1.2.2 Artificial SEI Layer 7
1.1 INTRODUCTION
Lithium-ion batteries have been the dominant energy storage technology for
powering modern portable electronics. There is also a global effort on R&D
of advanced lithium-ion batteries for propulsion and stationary applications in
smart grids. The major technological barriers that hinder the realization of these
emerging applications include (1) high cost, (2) insufficient life, (3) insufficient
energy density, and (4) intrinsically poor safety characteristics. These barriers
can be partially tackled by developing advanced electrode materials with a bet-
ter structural stability, developing materials with higher energy density, and/or
using low-cost starting materials and manufacturing processes. High energy-
density materials are of great interest since they can lead to an overall reduction
in the battery size, resulting in a large saving on other materials like the elec-
trolyte and separator. These barriers can also be addressed by developing func-
tionalized electrolytes that suppress the side reactions between the electrode
materials and the electrolytes; these side reactions are the major contributors to
the degradation of battery performance.
The current lithium-ion batteries generally use graphitic carbons as the anode
material, a lithium transition metal oxide as the cathode material, and a solution
Advanced Fluoride-Based Materials for Energy Conversion. http://dx.doi.org/10.1016/B978-0-12-800679-5.00001-4
Copyright © 2015 Elsevier Inc. All rights reserved. 1
2 Advanced Fluoride-Based Materials for Energy Conversion
of LiPF in a blend solvent of alkyl carbonates as the electrolyte. The electrolyte
6
in the battery is used as the lithium-ion conducting medium to transport lithium
ions between the anode and cathode. The chemical–electrochemical reactions
leading to performance degradation, as well as a potential safety hazard, mostly
occur at the interface between the electrode material and the nonaqueous elec-
trolyte, where the electrolyte components can act as either the reactant or the
dilution medium that promotes detrimental reactions [1,2]. In an ideal system,
the solvent should have a combination of several physical–chemical properties.
First, it should be able to dissolve a fairly high concentration of lithium salts for
high lithium-ion conductivity. Second, the energy level of the highest occupied
molecular orbital (HOMO) of the solvents should be low enough for good resis-
tance to oxidation by the delithiated cathode. Third, the energy level of the lowest
unoccupied molecular orbital (LUMO) of the solvents should be high enough to
prevent the reduction by lithiated anode materials. So far, an electrolyte that meets
the above three requirements has not been identified. For instance, the LUMOs
of currently used carbonates are substantially lower than the Fermi energy level
of lithium, and hence, they are thermodynamically incompatible with lithium
metal and lithiated graphite. The long-term stability of lithiated graphite with the
presence of nonaqueous electrolytes can only be kinetically achieved with the
presence of the solid-electrolyte interphase (SEI) [3–5], which is a thin layer of
an organic–inorganic composite deposited on the surface of a graphitic electrode
and acts as a kinetic barrier to protect the lithiated graphite from rapid reaction
with the nonaqueous electrolyte. Recently, a massive effort has been devoted
to developing cathode materials with high specific capacity and high voltage to
meet the energy requirements for plug-in hybrid electric vehicles and full electric
vehicles [6–10]. These R&D efforts have pushed the working potential of the
cathode materials beyond the thermodynamic limit of the carbonate solvents, and
an advanced electrolyte is highly desired to enable high-voltage cathodes [11,12].
Even within a well-characterized lithium-ion chemistry, the working potential of
electrode materials can be driven beyond the electrochemically stable window of
solvents during overcharge abuse, which can occur during the normal operation
of an off-balance lithium-ion battery pack [13–16].
In this chapter, emphasis will be placed on advanced electrolytes with fluo-
rinated components, including (1) advanced electrolyte additives that stabilize
lithiated anodes; (2) fluorinated redox shuttles for overcharge protection and
automatic capacity balance of the lithium-ion battery pack; and (3) advanced
high-voltage electrolytes comprising fluorinated solvents.
1.2 STABILIZATION OF LITHIATED ANODES
Graphitic materials have been the dominant anode material for state-of-the-art
lithium-ion technology. However, it is also well known that the lower cutoff
potential of lithiated graphite can be as low as 0.1 V versus Li+/Li, which is far
below the standard redox potential of carbonates used for lithium-ion batteries.
High Performance Lithium-Ion Batteries Chapter | 1 3
The long-term compatibility between the lithiated graphite and the electrolyte
solvents is kinetically achieved with the presence of an SEI layer that acts as a
physical barrier to prevent the direct exposure of the lithiated graphite to non-
aqueous electrolytes. Figure 1.1 schematically shows the SEI formation mecha-
nism during the initial lithiation of a graphitic anode. In general, the open circuit
potential of the anode in a freshly prepared lithium-ion cell is about 3.0 V versus
Li+/Li. During the initial charge (also called the formation stage) of a fresh
lithium-ion cell, the potential of the graphitic anode decreases with the lithia-
tion process. The lithium salt, typically LiPF , starts to decompose at a potential
6
below 1.5 V versus Li+/Li [17,18]. Part of the decomposition product, mostly
inorganic components, deposits on the graphite surface while other components
like PF promote the electrically triggered polymerization reaction of ethylene
5
carbonate (EC) that forms a flexible layer, mostly organic components, on top
of the inorganic layer. This layer of organic–inorganic thin film, or SEI layer,
gives a long life to lithium-ion batteries using graphitic anodes. The thermal and
electrochemical stability of this SEI layer will determine the electrochemical
performance of the batteries using graphitic anodes. Zheng et al. [5] investigated
the capacity loss of half cells comprising mesocarbon microbeads (MCMB)
electrodes during storage experiments at various temperatures, and found that
the capacity loss increased exponentially with the storage temperature. Kinet-
ics study revealed that the process leading to the capacity loss had a fairly low
activation energy of 39.7 kJ mol−1. It was concluded that the thermal instability
of the SEI layer was a contributor to the capacity loss in lithium-ion cells stored
or operated at elevated temperatures. Alternatively, Levi et al. [19] investigated
the same issue by tracing the self-discharge process of the graphitic anodes; this
process was attributed to the continuous reaction between the lithiated graphite
(cid:19)(cid:17)(cid:19)
(cid:16)(cid:19)(cid:17)(cid:20)
(cid:47)(cid:76) (cid:38)
(cid:91) (cid:25)
(cid:57)
(cid:75)(cid:18)(cid:16)(cid:19)(cid:17)(cid:21)
(cid:36)
(cid:80)
(cid:57)(cid:15)(cid:3)(cid:16)(cid:19)(cid:17)(cid:22)
(cid:71) (cid:54)(cid:40)(cid:44)
(cid:52)(cid:18)
(cid:71)
(cid:16)(cid:19)(cid:17)(cid:23)
(cid:16)(cid:19)(cid:17)(cid:24)
(cid:19)(cid:17)(cid:19) (cid:19)(cid:17)(cid:24) (cid:20)(cid:17)(cid:19) (cid:20)(cid:17)(cid:24) (cid:21)(cid:17)(cid:19) (cid:21)(cid:17)(cid:24)
(cid:38)(cid:72)(cid:79)(cid:79)(cid:3)(cid:83)(cid:82)(cid:87)(cid:72)(cid:81)(cid:87)(cid:76)(cid:68)(cid:79)(cid:3)(cid:89)(cid:86)(cid:17)(cid:3)(cid:47)(cid:76)(cid:14)(cid:18)(cid:47)(cid:76)(cid:15)(cid:3)(cid:57)
FIGURE 1.1 Schematic showing the formation of solid electrolyte interphase during the initial
lithiation of a graphitic anode. SEI, solid-electrolyte interphase.