Table Of ContentAdvances in Lithium-Ion Batteries
Advances in Lithium-Ion Batteries
Edited by
Walter A. van Schalkwijk
SelfCHARGE,Inc.
Redmond, Washington
Department of Chemical Engineering
University of Washington
Seattle, Washington, U.S.A.
and
Bruno Scrosati
Department of Chemistry
University of Rome
“La Sapienza”
Rome, Italy
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Acknowledgment
Dr. Scrosati would like to acknowledge his wife, Etta Voso, for her patience and continuous
support of his work. The many exchanges with chapter authors were appreciated, as were
the helpful suggestions of Mark Salomon. The contribution on fuzzy logic battery manage-
ment from Professor Pritpal Singh of Villanova University and the rapid turn of some
artwork by Liann Yi from his lab was greatly appreciated. Thank you also to Brad Taylor
and Kevin Talbot for reworking some of the more complicated figures. Lastly, Dr. van
Schalkwijk wishes to acknowledge the support of his co-editor, and the hospitality of his
institution and research group during his visit to Rome.
Walter van Schalkwijk
Seattle, Washington
Bruno Scrosati
Rome, Italy
v
Contributors
Caria Arbizzani University of Bologna, Dip. Chimica “G. Ciamician”, Via F. Selmi 2,
40126 Bologna, Italy
Doron Aurbach Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900,
Israel
George F. Blomgren Blomgren Consulting Services Ltd., 1554 Clarence Ave., Lake-
wood, Ohio 44107, U.S.A.
Ralph J. Brodd Broddarp of Nevada, Inc., 2151 Fountain Springs Drive, Henderson,
Nevada 89074, U.S.A.
Michael Broussely SAFT, F-86060 Poitiers, France
Robert M. Darling International Fuel Cells, South Windsor, Connecticut, U.S.A.
John B. Goodenough Texas Materials Institute, ETC 9.102, University of Texas at
Austin, Austin, Texas, U.S.A.
Mary Hendrickson U.S. Army CECOM RDEC, Army Power Division, AMSEL-R2-
AP-BA, Ft. Monmouth, New Jersey 07703-5601, U.S.A.
H. Ikuta Department of Applied Chemistry, Tokyo Institute of Technology, 2-12-1
Ookayama, Meguro-ku Tokyo 152-8552, Japan
Minoru Inaba Department of Energy & Hydrocarbon Chemistry, Graduate School of
Engineering, Kyoto University, Sakyo-ku, Kyoto 606-01, Japan
Hsiu-ping Lin MaxPower, Inc., 220 Stahl Road, Harleysville, Pennsylvania 19438,
U.S.A.
Marina Mastragostino University of Bologna, UCA Scienze Chimiche, Via San Donato
15, 40127 Bologna, Italy
John Newman Department of Chemical Engineering, University of California at Berke-
ley; and Lawrence Berkeley National Labs, Berkeley, California, U.S.A.
Yoshio Nishi Sony Corporation, 1-11-1 Osaki, Shinagawa-ku, 141-0032 Tokyo, Japan
Zempachi Ogumi Department of Energy & Hydrocarbon Chemistry, Graduate School
of Engineering, Kyoto University, Sakyo-ku, Kyoto 606-01, Japan
vii
Contributors
viii
Edward J. Plichta U.S. Army CECOM RDEC, Army Power Division, AMSEL-R2-AP-
BA, Ft. Monmouth, New Jersey 07703-5601, U.S.A.
Mark Salomon MaxPower, Inc., 220 Stahl Road, Harleysville, Pennsylvania 19438,
U.S.A.
Bruno Scrosati Department of Chemistry, University of Rome “La Sapienza”, 00185
Rome, Italy
Francesca Soavi Univeristy of Bologna, UCI Scienze Chimiche, Via San Donato 15,
40127 Bologna, Italy
Robert Spotnitz Battery Design Company, Pleasanton, California, U.S.A.
Kazuo Tagawa Hoshen Corporation, 10-4-601 Minami Senba 4-chome, Chuo-ku, Osaka
542-0081, Japan
Karen E. Thomas Department of Chemical Engineering, University of California at
Berkeley; and Lawrence Berkeley National Labs, Berkeley, California, U.S.A.
Y. Uchimoto Department of Applied Chemistry, Tokyo Institute of Technology, 2-12-1
Ookayama, Meguro-ku Tokyo 152-8552, Japan
Walter A. van Schalkwijk SelfCHARGE, Inc., Redmond, Washington; and Department
of Chemical Engineering, University of Washington, Seattle, Washington, U.S.A.
M. Wakihara Department of Applied Chemistry, Tokyo Institute of Technology, 2-12-1
Ookayama, Meguro-ku Tokyo 152-8552, Japan
Andrew Webber Energizer, 23225 Detroit Rd., P.O. Box 450777, Westlake, Ohio 44145,
U.S.A.
Jun-ichi Yamaki Institute of Advanced Material Study, Kyushu University, Kasuga
816-8580, Japan
Contents
Introduction 1
B. Sacrosati and W.A. van Schalkwijk
1. The Role of Surface Films on Electrodes in Li-Ion Batteries 7
D. Aurbach
2. Carbon Anodes 79
Z. Ogumi and M. Inaba
3. Manganese Vanadates and Molybdates as Anode Materials for Lithium-
Ion Batteries 103
M. Wakihara, H. Ikuta, and Y. Uchimoto
4. Oxide Cathodes 135
J.B. Goodenough
5. Liquid Electrolytes 155
J-i. Yamaki
6. Ionic Liquids for Lithium-Ion and Related Batteries 185
A. Webber and G. E. Blomgren
7. Lithium-Ion Secondary Batteries with Gelled Polymer Electrolytes 233
Y. Nishi
8. Lithium Polymer Electrolytes 251
B. Scrosati
9. Lithium-Ion Cell Production Processess 267
R.J. Brodd and K. Tagawa
10. Low-Voltage Lithium-Ion Cells 289
B. Scrosati
ix
x Contents
11. Temperature Effects on Li-Ion Cell Performance 309
M. Salomon, H-p. Lin, E.J. Plichta and M. Hendrickson
12. Mathematical Modeling of Lithium Batteries 345
K.E. Thomas, J. Newman, and R.M. Darling
13. Aging Mechanisms and Calendar-Life Predictions 393
M. Broussely
14. Scale-Up of Lithium-Ion Cells and Batteries 433
R. Spotnitz
15. Charging, Monitoring and Control 459
W.A. van Schlakwijk
16. Advances in Electrochemical Supercapacitors 481
M. Mastragostino, F. Soavi and C. Arbizzani
Index 507
Advances in Lithium Ion Batteries
Introduction
Walter van Schalkwijk Bruno Scrosati
SelfCHARGE Inc., Redmond, WA Universita "La Sapienza"
Department of Chemical Engineering, Dipartimento di Chimica
University of Washington, Seattle, WA Opiazza Aldo Moro 5, 00185 Rome
USA Italy
Portable power applications continue to drive research and development of
advanced battery systems. Often, the extra energy content and considerations
of portability have outweighed economics when a system is considered. This
has been true of lithium battery technologies for the past thirty years and for
lithium ion battery systems, which evolved from the early lithium battery
development. In recent years, the need for portable power has accelerated due
to the miniaturization of electronic appliances where in some cases the battery
system is as much as half the weight and volume of the powered device.
Lithium has the lightest weight, highest voltage, and greatest energy
density of all metals. The first published interest in lithium batteries began
with the work of Harris in 1958 [1]. The work eventually led to the
development and commercialization of a variety of primary lithium cells
during the 1970s. The more prominent systems included lithium/sulfurdi-
oxide lithium-thionylchloride lithium-sulfurylchloride
lithium-polycarbon monofluoride lithium-manganese
dioxide and lithium-iodine Apologies
to any chemistries that were not mentioned, but were studied and
developed by the legions of scientists and engineers who worked on the
many lithium battery couples during those early days.
The 1980s brought many attempts to develop a rechargeable lithium
battery; an effort that was inhibited by difficulties recharging the metallic
lithium anode. There were occasional unfortunate events pertaining to safety
(often an audible with venting and flame). These events were often due to
the reactivity of metallic lithium (especially electrodeposited lithium with
electrolyte solutions, but events were also attributed to a variety of other
reactive conditions. Primary and secondary lithium batteries use non-aqueous
electrolytes, which are inherently orders of magnitude less conductive than
aqueous electrolytes. The reactions of the lithium electrode were studied
extensively and this included a number of strategies to modify the reactivity of
the Li-solution interface and thus improve its utility and safety [2].
2 Introduction
Studies of fast ion conduction in solids demonstrated that alkali metal ions
could move rapidly in an electronically conducting lattice containing transition
metal atoms in a mixed valence state. When the host structure is fully
populated with alkali metal atoms - lithium ions in the most common context
– the transition metal atom is in the reduced state. The structure is fully
lithiated. As lithium ions are removed from the host, the transition metal (and
host structure) is oxidized. A host structure is a good candidate for an
electrode if (1) it is a mixed ionic-electronic conductor, (2) the removal of
lithium (or other alkali metal ion) does not change the structure over a large
range of the solid solution, (3) the lithiated (reduced) structure and partially
lithiated (partially oxidized) exhibit a suitable potential difference versus
lithium, (4) the host lattice dimension changes on insertion/removal of lithium
are not too large, and (5) have an operational voltage range that is compatible
with the redox range of stability for an accompanying electrolyte.
This led to the development of rechargeable lithium batteries during the
late 1970s and 1980s using lithium insertion compounds as positive
electrodes. The first cells of this type appeared when Exxon and Moli Energy
tried to commercialize the and systems, respectively. These
were low voltage systems operating near 2 volts. In a large compilation of
early research, Whittingham [3] reviewed the properties and preparation of
many insertion compounds and discussed the intercalation reaction. The most
prominent of these to find their way into batteries were and
All of these systems continued to use metallic lithium anodes. The
safety problems, real or perceived, limited the commercial application of
rechargeable batteries using metallic lithium anodes.
During that era Steele considered insertion compounds as battery
electrodes and suggested graphite and the layered sulfide as potential
candidates for electrodes of a lithium-ion battery based on a non-aqueous
liquid electrolyte [4].
After the era of the transition metal chalcogenides came the higher
voltage metal oxides (where M = Ni, Co, or Mn) [5,6]. These
materials are the basis for the most commonly used cathodes in commercial
lithium-ion cells. At about that time the concept of a lithium-ion cell was
tested in the laboratory with two insertion electrodes cycling lithium ions
between them, thus eliminating the use of a metallic lithium anode [7,8].
The next decade saw substantial research and development on advanced
battery systems based upon the insertion and removal of lithium ions into
host compounds serving as both electrodes. Much of the work was
associated with finding a suitable material to host lithium ions as a battery
negative. As mentioned before, the concept is not new: Steele and Armand
suggested it in the 1970s [4,9,10]. Eventually, in 1991, Sony introduced the
first commercial lithium-ion cell based on The cells had an open
circuit potential of 4.2 V and an operational voltage of 3.6 V.
