Electrochimica Acta 45 (1999) 322

www.elsevier.nl/locate/electacta

Lithium insertion into host materials: the key to success

for Li ion batteries
M. Broussely a,*, P. Biensan b, B. Simon b
a
SAFT, Advanced and Industrial Battery Group, BP 1039, 86060 Poitiers, France
SAFT, Direction de la Recherche, 111, Boulevard A.Daney, 33074 Bordeaux, France

Received 7 February 1999; received in revised form 28 April 1999

Abstract
The aim of this paper is to summarise the present situation in Li ion batteries, from a short historical perspective
of the concepts and materials, to the present trends. It aims also at giving the scientists working in this eld some
picture of the impact of the insertion material properties on the nal cell characteristics. The market and
applications of lithium ion batteries, present and future, are also briey discussed. # 1999 Elsevier Science Ltd. All
rights reserved.
Keywords: Lithium insertion; Li ion batteries; Final cell characteristics

1. Introduction
In 1990, Sony [1] surprised the `battery world' by
abandoning rechargeable lithium metal battery development, in which they had been deeply involved for
several years with a Li/MnO2 couple, to introduce a
new concept, which they named `Li ion'. Based on previous scientic studies and some early prototype results
[2], engineers from Sony were able to demonstrate that
disordered non-graphitisable carbons (hard carbons)
can also insert lithium, using an appropriate electrolytic solution and a suitable electrode technology.
Since this time, a lot of research and development
work has been increasingly carried on worldwide, and
very rapid and signicant improvements were made to
the insertion materials used in these batteries. For

example, crystallised carbons can now be used without

exfoliation, bringing useful improvements to cell voltage and energy. Considerable economic incentives
linked to the huge development of portable electronic
devices such as cellular phones or notebook computers,
greatly stimulated this R&D activity, in both the technology aspects and the fundamentals.
Much progress can be still anticipated for the future,
and this type of battery, up to now limited to small
sizes, will nd other applications in the business for
larger batteries. Low material cost is one of the key
issues to make Li ion become a true multipurpose battery system in the next decade.
2. From lithium to `lithium ion', a long story
2.1. The early days

* Corresponding author. Tel.: +33-5-4955-4829; fax: +335-4955-5630.

E-mail address: michel.broussely@saft.alcatel.fr (M.
Broussely)

When the lithium battery concept began to stimulate

the brains of a few battery engineers early in the
sixties, the rechargeable system was already uppermost

0013-4686/99/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 3 - 4 6 8 6 ( 9 9 ) 0 0 1 8 9 - 9

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

in their minds. In 1962, at the Electrochemical Society

fall meeting in Boston, Chilton Jr. and Cook [3] from
Lockheed Missile and Space Co. gave a presentation
entitled `Lithium Nonaqueous Secondary Batteries',
which was probably the rst paper ever presented in
this meeting on a lithium battery. The goal was a high
energy density and long cycle life battery to increase
the mission lifetime of satellites . . . which is now
becoming a reality, about 40 years later. Since that
time, a lot of research would follow, on a long journey
that would go through many dierent steps.
Many diculties had to be overcome at that time,
from to nd a stable electrolyte medium with lithium,
to dening a reversible positive electrode material.
Based on experience with aqueous systems, the aim
was to nd an `second kind' electrode, using a low
solubility metallic salt. Halides like AgCl, CuCl2 [4],
CuCl [5] or CuF2, NiF2 were mostly investigated,
forming LiCl or LiF and the corresponding metallic
phase during discharge. In their work, Chilton and
Cook used a metallic positive (Ag, Cu or Ni), and
formed lithium deposited in situ on Ni during the rst
charge, from the LiClAlCl3 electrolyte dissolved in
propylene carbonate.
The main drawbacks were the formation of soluble
complexes, like CuCl2, leading to irreversible self-discharge phenomena, and the large volume changes of
the electrode during cycling. In addition, the electrical
insulating properties of the materials required a large
addition of a conductive agent like carbon to the electrode.
2.2. An insertion material as reversible positive
A decisive step was passed when the development of
insertion compounds chemistry in several research laboratories [6] brought about a solution in the early seventies. These materials could at the same time host
lithium ions inside their crystalline structure, while
reducing transition metals from their higher oxidation
state. This so-called `topotactical' electrochemical reaction would occur reversibly, without major phase
change, and should be made easier by a signicant
conductivity or semi-conductivity. From that time, a
new electrochemistry for energy storage would spring
up, involving more and more solid state chemistry. In
the last two decades, the signicant improvement of
scientic equipment for the investigation of crystalline
structure has been a decisive factor in the understanding and development of new materials.
2.3. A rechargeable lithium electrode?
Beside the problem of the positive electrode, lithium
corrosion and dendrite formation on the negative side

created numerous problems, resulting in poor cycling

eciency and cell shorting.
Electrolytes have been extensively studied to try to
solve this problem, showing the major role of additives
and impurities in lm formation. Many solutions were
proposed, from well known cyclic carbonates PC and
EC to ether-based solutions, using for example 1,3dioxolane [4], or 3-MeTHF [7]. The cell design, by
using a microporous polypropylene separator and spirally wound electrodes with sucient mechanical stress
to reduce dendrite formation, proved also to be a critical parameter and led to a very signicant breakthrough in the mid-eighties, with the rst commercial
rechargeable lithium products [8]. However, this technology still suered from relatively limited cycle life
(currently less than 200), and more importantly poor
safety associated with the formation of nely divided
lithium powder upon cycling.
2.4. Replacing the lithium metal: `the rocking chair'
Li alloys with other metals (like aluminum) appeared
naturally as the rst solution to replace Li metal, but
they suer from severe morphological changes upon
cycling due to large volume changes [9]. Li diusion
into the alloys is also a limiting factor, especially at
ambient temperature. Except for special use at low
rate and very limited depth of discharge (coin cells),
the use of Li alloys with metals (mainly Al) has been
unsuccessful.
Insertion of lithium into graphite via a chemical
route had been known since 1955 [10], and the electrochemical insertion of lithium into graphite was investigated in 1976 by Besenhard [11]. It was proposed as a
reversible negative material in secondary lithium batteries by Armand in 1978 [12]. However, severe problems of exfoliation were experienced in organic
electrolytes, limiting the apparent viability of this concept to polymer electrolyte cells [13]. Later, following
rst investigations in molten salt batteries [14] Basu
described in 1982 a battery using LiC6 anode and organic electrolyte, more specically Dioxolane, in a US
patent [15]. However, the positive material did not
contain lithium ions at the initial state (NbSe3, V6O13,
TiS2 were proposed), and carbon was chemically prelithiated before cell assembly. In 1980, the `rocking
chair concept', using two insertion compounds based
on metallic oxides or suldes was proposed by Lazzari
and Scrosati [16]. A LixWO2/LiyTiS2 cell was
described, working at an average voltage of 1.8 V.
However, while this system could solve the lithium
electrode problems, it was unable to provide the practical energy density required to make it attractive compared to existing rechargeable systems, and very far
from the numbers which could be expected from a true
`lithium battery.' Assuming exchange of 1 Li/mol, the

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

Fig. 1. First cycle of the three usual candidates as positive materials for Lithium-ion cells. Results obtained in coin cells versus
lithium, at C/20 rate and ambient temperature. Electrolyte was PC/EC/DMC (1/1/3) LiPF6. EOCV is 4.2 V except for LiMn2O4
(4.3 V).

theoretical energy density (active materials only) is

about 150 Wh/kg compared to 520 Wh/kg for a
Li/TiS2 cell. These comparative numbers may also
explain why eorts were so much focused on the
rechargeability of lithium metal, instead of insertion
compounds.
2.5. The `Li ion'
Finally, the discovery in the mid-eighties of the
unexpected property of disordered carbon to insert
lithium [2] with a stable protective passivating layer,
and the successful association with the high voltage
positive material LiCoO2 [1], led to what can now be
considered as the major breakthrough in new practical
battery systems in the second half of the twentieth century.
3. The positive material
When insertion materials were proposed [12,17] as
the best solution for rechargeable non-aqueous batteries, the rst materials which captured attention was
the chalcogenides. The layered TiS2 was undoubtedly
the most popular [18,19], and has been extensively studied for years. Thanks to its stable layered structure
and electronic conductivity, it provided high drain
capability and good reversibility. It was used as the
positive electrode material in the rst marketed
rechargeable lithium battery, by Exxon, which was a

coin cell for watches, using a LiAl negative electrode.

TiS2 stood for a long time as the standard positive
electrode material, and was used in the development
stage of cylindrical spirally wound cells [20]. A lot of
other di- and tri-chalcogenides were studied, including
amorphous structures; see for example the review by
Abraham [21]. Layered thiophosphates, like NiPS3,
were also proposed [22]. From this array of materials,
NbSe3 [23] was used at the development stage of
lithium batteries, and MoS2 [8] was used up until the
beginning of mass production.
Utilisation of metal oxides as reversible insertion
electrodes was proposed quite early, for example
MoO3 in 1971 [24] or WO3. A large number of materials were investigated, including chromium oxides
[25] and vanadium oxides [26], which 10 years ago
were probably the most studied of the oxides.
Manganese oxide MnO2 and V2O5 are used in commercial rechargeable coin cells using LiAl as the negative electrode. A vanadium oxide `VOx' is also the
positive material in the polymer electrolyte Li battery
developed by Hydro Quebec and 3 M.
Although Mizushima and Goodenough published
quite early the possible use of LixCoO2 or LixNiO2 in
1980 [27], relatively little attention was paid at the time
to these materials, probably because the high working
voltage was considered as a drawback for stability in
organic electrolytes. Some work was, however, performed [28], leading to the development of suitable
electrolytes using pure carbonate solvent mixtures. At
the same time, studies on spinel materials led to the

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

Fig. 2. DSC behaviour of LiCoO2 for dierent EOCV from 4.2 V up to 4.7 V. Electrolyte is PC/EC/DMC (1/1/3)+LiPF6(1 M).
Scanning rate is 108C/min. Curves are shifted for a better legibility (each starting point=0 mW).

selection of LiMn2O4 as a competitive material, which

was especially attractive for its potential low cost.
Studies on positive materials moved then almost completely from suldes to oxides and these three families
of oxides are now the most used or studied. Their
main features and trends for the future are described
hereafter.
3.1. LiCoO2 and derivatives
The reason for the choice of LiCoO2, which is now
the most prevalent positive electrode material, is based
on several considerations. Initially, as Sony decided to
move from Li metal to lithiated carbon, the positive
material had to have a sucient working voltage to
compensate for the voltage loss on the negative side.
Also, the material had to be fully lithiated at the discharged state, to build the cell with pure carbon.
Already studied in the frame of lithium metal batteries,
LiCoO2 was available and tted the needs completely.
LiNiO2, with potentially a higher specic capacity [29],
was more dicult to prepare, because of the tendency
to form a Ni-rich nonstoichiometric phase. Many
industrial makers now propose LiCoO2 materials not
just in Japan (NCI, SEIMI, Tanaka, Santoku . . .), but
also in Europe (Union Miniere, Sogemet, . . . ) and in
north America (FMC, Union Miniere (previously
Westaim)).
Good electrochemical performance is obtained up to
4.2 V versus Li/Li+, providing 150 A h/kg on rst
delithiation, and generally 140145 A h/kg reversible
capacity on cycling (Fig. 1). From the experience accumulated over several years in consumer cells, LiCoO2
does not appear to present any strong technical draw-

back, compared with LiNiO2 (lower safety) and

LiMn2O4 (fading, hot temperature behaviour). The
thermal stability is lower than with LiMn2O4 [30,31]
but safe cells can be designed with 4.14.2 V end of
charge voltage. However, a small overcharge of the
material leads readily to higher reactivity, as the material is more oxidizing and thermal stability is lower.
In fact, the material reactivity is strongly dependent on
state of charge, as shown on Fig. 2 which describes
dierential scanning calorimetry (DSC) spectra of
LiCoO2 as a function of end of charge voltage
(EOCV).
Much research work on LiCoO2 has involved structural aspects of the material and its delithiated phases
and the optimisation of the synthesis process [3234].
A lot of work worldwide has also been dedicated to
partial substitution of cobalt by other metals like
nickel, iron and manganese [3539]. More recently substitution with aluminum [40,41] has shown an increase
of the average discharge voltage which was predicted
by the theory involving the participation of oxygen
ions bonding in the oxidation-reduction process. It was
also demonstrated that a very small amount of magnesium has an impact on fading behaviour during
cycling [42].
Up to now, however, these materials have not found
a practical application, as they have no signicant
positive impact on the cost, which is the main drawback of LiCoO2. The elevated price of cobalt forbids
any practical use in large batteries (E.V., H.E.V, . . . ).
Industrial research is now concentrated more on
energy density improvement based on the electrode
formulation and the physical properties of the material
powder.

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

Fig. 3. Fading behaviour at 608C of LiNiO2 and LiNi(1M)MMO2 positive materials for M=Ti, Co or Co+Mg in coin cells with
lithium counter electrode. Cycling was performed between 4.1 and 3 V in PC/EC/DMC(1/1/3)+LiPF6(1 M).

3.2. LiNiO2 and derivatives

LiNiO2 is almost not used in commercial cells
despite its excellent, probably the best, specic capacity
(185 to 210 A h/kg at 4.1 or 4.2 V, respectively), and
lower cost than LiCoO2. Practically, however, this material did not have great success for dierent reasons: a
tighter synthesis process, a tendency to give higher fading with cycling and a lower thermal stability.
First, the synthesis of the material is more dicult
than that of LiCoO2, as illustrated by the number of
publications dedicated to this subject. The main pro-

blem is linked to the formation of a nickel over-stoichiometric phase [4345] with general formulation
Li(1z )Ni(1+z )O2. These extra nickel ions with respect
to stoichiometry lead to a low electrochemical performance: a low amount of lithium extracted and poor
reversibility of electrochemical process. A phenomenological explanation was given by Delmas et al. [46] by
the formation of non-accessible sites around the nickel
in the lithium site after its oxidation during the rst
cycle. Optimisation of the synthesis process can lead to
materials with low z values of z = 12%, but not less
up to now.

Fig. 4. Capacity fading during cycling of a 4/5A size prototype cells using magnesium substituted LiNi0.86Co0.09Mg0.05O2 material
and graphite negative electrode. Electrolyte=PC/EC/DMC(1/1/3), 1 MliPF6. Cycling at 258C and 608C, at C rate.

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

Fig. 5. Incremental capacity of LiNiO2 (- - - -) and LiNi0.86Co0.09Mg0.05O2 (() at C/20 rate, in coin cells vs. Li. Electrolyte is PC/
EC/DMC(1/1/3)+LiPF6(1 M).

The second point, which limited extensive development of LiNiO2, is the problem of capacity fading with
cycling. High losses in cycling have been reported for
pure LiNiO2, but these results might have been greatly
inuenced by the way the material was produced. If
properly synthesised, the cycle life can be quite acceptable, and no evolution of the structure of the material
is observed, even with tools like Rietveld renements,
after as much as 1200 cycles [47]. However, this some-

what unreliable behaviour can be very much improved

by substituting other cationic elements for nickel.
Cobalt or magnesium demonstrates high eciency, as
shown on Fig. 3. These results were obtained at 608C
in small coin cells with lithium metal, which are good
test vehicles for comparison by greatly accelerating capacity fading on cycling. Even low amounts of magnesium, close to 5%, are sucient to suppress
completely the fading of the material up to 4.3 V

Fig. 6. DSC behaviour of LiNiO2+electrolyte, for dierent EOCV from 3.8 V up to 4.7 V. Electrolyte is PC/EC/DMC (1/1/
3)+LiPF6 (1 M). Scanning rate is 108C/min.

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

Fig. 7. DSC measurements on LiNiO2, LiCoO2, LiMn2O4 compared to new multi doped LiNi(1M)MMO2 material with improved
safety (M=0.25). Scanning rate is 108C/min. Electrolyte is PC/EC/DMC (1/1/3)+LiPF6 (1 M).

EOCV. This improvement is also illustrated in Fig. 4,

relating 400 cycles at 608C in complete prototype Li
ion cells with no particular fading observed. This
strong improvement of the cycling ability probably
originates in the suppression of the phase transitions
usually observed for LiNiO2 which disappear with
magnesium substitution as demonstrated in Fig. 5.
Improvement of reversibility and fading behaviour is
also observed by co-substitution of cobalt and manganese of up to 40% of the nickel [48].
Last but not least, the thermal stability of LiNiO2 is
signicantly lower than the two other materials [30].
This is partially due to the instability of nickel in the
oxidation state of 4, but it can also be seen as a drawback of its very high capacity: the charged state at 4.1
V corresponds to composition close to Li0.33NiO2, far
more delithiated than for LiCoO2, for example. The
delithiation state of the material is a rst order parameter of its thermal stability [31] as illustrated in Fig.
6. Thermal stability of delithiated nickel-rich phases
can be modied by substitution. Substitution by aluminum of 25% of the nickel cations for example was studied by Ohzuku et al. [49] while researchers from
FMC [50,51] obtain very nice thermal stability up to
4008C with titanium and magnesium co-substitution,
but higher charge voltage than usual is needed in both
cases. Moreover, eciency of the rst cycle is signicantly reduced. Conservation of electrochemical performance associated with good thermal stability needs
multiple substitution, as illustrated in Fig. 7. The thermal stability of the doped material is similar to that of

LiMn2O4 in terms of temperature of reaction with electrolyte, and the heat power related to electrochemical
energy of the material (W h) is signicantly lower.
Substituted nickel-rich materials are therefore the
subject of increasing interest. Substituting other cations
for nickel had produced a large and increasing number
of papers and patents. Almost half the periodic table
of elements has been investigated, including Ti, V, Cr,
Fe, Co, Mn, Cu, Zn, Cd, Sn, Al, B, Mg, Ga, Ca, Na,
. . .. Research is now oriented on multiple substitution,
with each element bringing some peculiar advantage
on reversibility, fading or thermal stability for safety.
Some material can be produced now on an industrial
scale, and utilisation in commercial cells can be anticipated soon.
3.3. LiMn2O4 and derivatives
For many years, the three-dimensional spinel
LiMn2O4 has been the object of intense worldwide
research to improve its behaviour (see for example
Ref. [52]). This is motivated by four advantages of this
material: a potential lower cost of Mn than Ni or Co,
a larger thermal stability domain especially when overcharged, a higher discharge voltage useful for telecom
appliance and a more friendly impact on environment.
However, in spite of signicant improvements from the
beginning of this research work, it still suers from
some major diculties: rst of all a low specic capacity associated with a low density compared to other
candidates, secondly a potentially lower power than

10

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

Fig. 8. Cycling behaviour with lithium counter electrode of various Li1+dMn2-dO4 (4.3 V) compared to LiCoO2 (4.2 V) typical materials. Electrolyte is PC/EC/DMC (1/1/3)+LiPF6 (1 M). C/20 charge and discharge rates.

the layered materials (LiNiO2, LiCoO2), nally fading

and losses on storage are very high, especially with
increasing temperature.
Capacity improvement of cells using LiMn2O4 active
material may be improved through pre-reduction
methods. These procedures aim at compensating the irreversible losses of the negative electrode, so increasing
the overall cell energy. Dierent methods have been
proposed including reaction with LiI in organic solvent
at 808C [53] or recently by reaction with n-buthyllithium [54]. However, these treatments do not improve
cycling performance.
A lot of work was done in the early 90's to improve
electrochemical performances of the spinel. Capacity
fading has been attributed to the JahnTeller eect
[55], structural instability at high potentials [56] or to
manganese dissolution [57]. Research was mainly dedicated to substitution for manganese by other elements
like iron [58,59], cobalt [55,6062], nickel [58,59] or
more exotic ones like magnesium, titanium, silver, copper and some others [58,63]. Generally, all these materials exhibit lower performance than the pristine
spinel in terms of capacity (100110 A h/kg), although
fading improvement is observed with cobalt and magnesium [63]. Improvement of fading by cobalt substitution was conrmed recently by Arora et al., and
both the amount and rate of capacity loss are
decreased [64]. These results are explained by a specic

surface diminution and higher crystal size for one part,

and easier lithium charge transfer reaction and lithium
diusion into the structure for a second part.
A main breakthrough in this eld are the overlithiated
phases
of
general
formulation
Li(1+d )Mn(2d )O4 [63], presenting strongly reduced
fading, albeit with some reduction in capacity. This is
illustrated in Fig. 8, with comparison to typical behaviour of LiCoO2 industrial materials. It shows clearly
the lower capacity of manganese compounds and the
reduction of fading at 608C thanks to over lithiation of
the material, with lower capacities as the ratio of Li/
Mn increases.
Elevated temperature is a more crucial problem for
the LiMn2O4 positive material. Mn3+ dismutation and
dissolution of the Mn2+ produced, is a severe problem
of the spinel. It appears to contribute greatly to the
occurrence of irreversible losses during storage at elevated temperature: for which partial improvement is
obtained by using low surface area materials (<0.5
m2/g), or surface modication by encapsulating material into a solid inorganic lithiated borate glass [65].
In this latter case, the surface lm also helps to reduce
the catalytic eect of the surface on electrolyte decomposition, and the detrimental eect of HF impurities on the material.
A lot of research work is still going on to understand and improve the behaviour of LiMn2O4.

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

11

Industrial materials are beginning to be available with

reduced SSA and lithium-rich compositions leading to
improved performance in terms of capacity fading.
However, fading, particularly at elevated temperature,
is still far worse than that observed with nickel or
cobalt-rich materials. Despite this, a range of lithiumion cells using LiMn2O4 spinel as positive active material are now available from Moli Energy Limited for
portable equipment.
3.4. Other `4 V' materials
Two other materials have been mainly studied to
replace the three main candidates: LiMnO2 and
LiFeO2.
Orthorhombic LiMnO2 may be an excellent material
for lithium-ion batteries [66], even better than
LiMn2O4 because its higher Li/Mn ratio: theoretical
capacity is close to LiNiO2 and LiCoO2 ones (285 A
h/kg). Several laboratories have been studying its
structural or electrochemical properties [6773].
Besides the optimisation of the synthesis process, a
main problem is the gradual structural transformation
of the material during cycling. After few cycles, the
material behaves very much like LiMn2O4 spinel: the
capacity is split in two dierent electrochemical mechanisms at 3 and 4 V, respectively [72,73]. However the
cycling behaviour is much better than for LiMn2O4,
when cycling on both voltage plateaus. This partition
of the capacity in two voltage plateaus of 1 V dierence makes this material useless in practical cells.
The electrochemical performances of both orthorhombic and ramsdellite LiFeO2 phases was described
in a few papers [7476]. Properties were studied up to
4.5 V, some authors claiming electrochemical reversible
activity around 4 V. However, it seems rather that irreversible reactions occur at high potential: main problem seems the instability of Fe4+ species in
Li1xFeO2 with the electrolyte. Reversible intercalation
may be obtained only at about 3 V, as evidenced in a
recent work to be published on these materials [77,78].
3.5. Towards 5 V
A recent trend in the positive material eld is the
appearance of a new family of materials having an
average working voltage of 5 V or so. First studied
were the inverse spinel vanadates like LiNiVO4
[79].These are also generally spinel materials close to
LiMn2O4 with levels of substitution up to 50% with elements like copper [80,81], cobalt [82,83], nickel [59,84]
iron [85] or chromium [86]. Specic capacities are in
the range of 80120 A h/kg maximum at the moment.
Explanation of the very high working voltage is still
not clear. According to Ohzuku et al. [87] this is a
result of the very high solid state redox potential of

Fig. 9. OCV of fully lithiated carbons (short cut with lithium

counter electrode 48 h) as a function of discharge capacity.
(a) and (b) are the same gures at dierent scales, to highlight
the usable range (1b). Electrolyte: EC/DMC 1 MliPF6.

the substituting cations in the compact crystal eld of

the spinel framework structure. Redox potentials
would rely between 4.8 and 5 V for the metals already
listed plus nickel and zinc in spinel of composition
LiMe1/2Mn3/2O4.
This new eld of research may be very promising
providing stable electrolytes may be found at these
very high potentials. Fading behaviour and also safety
of such materials is still an open question.
4. The negative material
As opposed to the study of insertion compounds for
positive electrodes, such materials for the negative
were much less investigated before the emergence of Li
ion. One must recognise that the exceptional behaviour
of carbon as an insertion material of lithium in organic
solvents is quite surprising: few battery specialists
would have predicted that the necessary passivation
layer built on the (large) surface area of the lithiated
carbon would have sucient stability and reversibility

12

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

to insure a high cycle life of thousands of cycles without irreversible lithium corrosion, as we can foresee
today.
As mentioned above, the rst attempts to use graphites as the negative host structure for lithium ion failed
because of electrode disintegration. Only intercalation
via solid polymer electrolyte at high temperature was
reported as successful [13]. The situation changed with
the nding that poorly crystalline carbons are less sensitive to that electrolyte decomposition. The feasibility
was demonstrated but with modest capacities compared to that expected with graphite [88]. Sony was the
rst company to achieve a commercial battery based
on such a non-crystalline carbon negative [1]. It
appeared later from patent literature that several
Japanese battery makers had been working on that
eld few years before [2]. Crystalline carbon materials
then regained interest when LiC6 stoichiometry was
actually achieved with a careful design of electrolyte
composition [8991] mainly based on ethylene carbonate (EC).
4.1. The carbon properties
4.1.1. Specic energy
The basic requirement is a high quantity of reversible lithium ion inserted per unit of volume or mass, at
a potential range close to that of metallic lithium. This
property appears to be very dependent on the carbon
crystalline structure (Fig. 9):
4.1.1.1. Crystalline carbons. The mechanism of lithium
intercalation in crystalline carbons is well known,
thanks to X-ray spectroscopy methods [90,91]. It is
very similar to that proposed for vapor phase intercalation, as it proceeds through well-identied stages,
apparent as potential plateaus on the O.C.V. curve
(Fig. 9). LiC6 (372 mA h/g) in the 0300 mV range vs.
a Li/Li+ reference electrode is achieved only for carbons with a low degree of turbostatic disorder (interlayer space d002 < 0.336 nm), generally referred as
graphites. For graphitised carbons, higher values of
interlayer space result from the presence of structural
defects that decreases the capacity. Several theories
have been proposed to account for this capacity
decrease [9294].
4.1.1.2. Non crystalline carbons. For this kind of carbon that exhibits large undened peaks on X-ray spectra, two dierent qualitative behaviours are observed:
The `coke' type behaviour shows no evidence of staging and a sloppy evolution of potential as a function
of Li content. For carbons synthesised at low temperature, an `extra capacity' is discharged with large hysteresis at high potential (>1 V/Li), that can reach values
as high as 1000 mA h/g [95]. However, this is not of

Fig. 10. End of charge of carbon electrodes at a rate of 20

mA/g of carbon. Electrolyte: EC/DMC 1 M LiPF6.

practical interest in a battery if high average voltage is

required. This behaviour has been associated with covalent Li bonding in large hydrogen content carbons
[96], with the presence of microcavities [93] and the
occurrence of Li2 molecules [97].
The `hard carbon ' behaviour shows an additional
`pseudo' potential plateau (Fig. 9) with no hysteresis at
high lithium content [98]. There is still some controversy about the actual mechanism for such a behaviour
[99101]. From 7Li RMN measurements, the lithium
absorbed at high lithium content do not present a metallic character [102] and seems to result in a schematic
way from dense absorption of Li in microcavities.
Therefore high porosity of this structure is a basic
requirement, and the volumetric energy density is consequently limited. A concern remains about the electrochemical behaviour at high charging rate, as a large
part of the capacity is obtained at potential very close
to that of metallic lithium (Fig. 10). When polarisation
increases at high current density, it appears dicult to
ensure lithium ion absorption throughout the electrode
thickness without metallic lithium deposition on the
outer electrode surface.
4.1.2. Reversibility
4.1.2.1. Passivation losses. All carbon types experience
irreversible side reactions during the rst electrochemical absorption of lithium ions. A generally recognised
source of irreversibility is the electrolyte instability at
low potential yielding insoluble products [13,103,104].
As no thermodynamically stable electrolyte of interest
have been found up to now, the quality of the resulting
passivating layer is fundamental for the further intercalation of Li ion and explains the large work involved
for its characterisation by dierent techniques [105
108]. A major contribution came from the work of
Aurbach's team [107,109,110] mainly based on FTIR
technique. This explained why the cyclic carbonates

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

Fig. 11. Irreversible losses at the rst cycle of teon bonded

electrodes, at 20 mA/g, in the range 02 V. EC based electrolyte (EC/DMC LiTFSI 1 M), as a function of specic surface
area (BET).

like propylene carbonate or ethylene carbonate were

the best-suited solvents, as they yield double lithium
alkyl carbonates with a good passivating ability. The
exceptional physical properties of the layer formed,
itself greatly dependent on the electrolyte composition,
and the small variations of molar volume between the
charged and discharged states, are actually the key
points which allow the Li ion battery to exist.
The carbon characteristic which should be linked to
this phenomenon is the electrochemically active surface
area, and a relationship with the amount of faradic
losses has indeed been reported [89,111,112], in the
absence of any additional source of irreversibility (Fig.
11).
For this purpose, materials having special morphology like carbon spheres grown from mesophase or
bers [92,113] are attractive for surface area optimisation.

Fig. 12. Inuence of PC on graphite exfoliation: First cycle

(20 mA/g) of synthetic graphite teon bonded electrode. EC
based=EC/DMC 1 M LiPF6, PC based=PC/EC/DMC (1/1/
3), 1 M LiPF6.

13

Fig. 13. Irreversible faradic losses at the rst cycle of teonbinded graphite electrodes, at 20 mA/g in the range 0 to 2 V.
The losses are expressed per m2 of carbon material (estimated
from the BET surface area) to eliminates the dierences due
to passivation. Electrolytes: EC based=EC/DMC 1 M LiPF6,
PC based=PC/EC/DMC (1/1/3), 1 M LiPF6.

4.1.2.2. Exfoliation. With crystalline carbons, a large

irreversible capacity loss can occur during the rst
intercalation step, regardless of their surface area.
Exfoliation of graphene layers can explain such a low
faradic eciency [89]. It results from intercalation of
solvated lithium ion followed by gas release in the carbon structure [11], causing the exfoliation to occur and
resulting in newly created surface area needing `extra
passivation'. This has been conrmed by dierent techniques [114116].
As discussed earlier, crystalline materials are highly
desirable to achieve high energy density, but they had
remained discarded because of this exfoliation occurrence. Improvement of their electrochemical behaviour
allowing their utilisation in actual batteries has been
the subject of many studies. Propylene carbonate (PC),
a solvent otherwise interesting for its physical properties, has been pointed as the main culprit in the exfoliation of crystalline carbons, whereas ethylene
carbonate EC or other carbonates would prevent it
[89,90]. Although graphites can be exfoliated even in
EC based electrolyte without PC [112], it is true that
the sensitivity of crystalline carbon to PC is markedly
higher (Fig. 12). The dierence of behaviour of such
close molecules like PC and EC is not yet fully understood.
Another way to reduce the risks of exfoliation is to
choose graphite grades with a high content of rhombohedral phase [117]. This phase is generally introduced
in commercial samples from the normal hexagonal
structure by a grinding operation. High rhombohedral
phase content are more resistant to exfoliation and can
withstand large amount of propylene carbonate [113]
(Fig. 13).
A third method eective in hindering crystalline carbon exfoliation consists of the addition to the electrolyte compounds able to passivate the carbon at high

14

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

Table 1
Average values for main cell design parameters
Constant parameters (unless used as variables)
Negative mat. Specic capacity
Negative material specic gravity
Positive mat. Specic capacity
Positive material specic gravity
Negative excess over positive
Negative rst charge eciency
Electrode porosity
Separator thickness
Collectors total thickness
Total cell stack thickness (2 electrodes coated both sides, 2 separators)
Average cell working voltage during complete discharge at medium rate.

potential, prior to solvated lithium intercalation. SO2

[118], vinylene carbonate [119] and chloroethylene carbonate [120] have revealed eciency in that purpose.
4.2. Non-carbon anodes
As mentioned above, the use of insertion materials
other than carbons was suggested quite a long time
ago. Metal oxides like WO2 or Fe203 [121], and more
recently Li4Ti5O12 [122], were proposed for rocking
chair batteries, but they present a high average voltage
versus metallic lithium and limited reversible capacity,
resulting in low energy density for complete cells (see
Section 5). The problem was similar with metal suldes
that decompose to metal and lithium sulde at low potential [123]. Conducting polymers like polyacetylene
are stable at low potential, but present low volumetric
capacity for lithium doping [124].
A new class of materials, based on amorphous oxides, is now being investigated. This originates from
Fuji Photo Film company, which announced the use
of tin-based amorphous oxides in a commercial product [125]. Controversy remains concerning the exact
mechanism [126,127], but it seems that, at least for the
crystalline forms, the functioning is based on the formation of metal clusters which further alloy with
lithium. Beside the fact that reduction to metal from
oxide is an irreversible reaction causing high capacity
loss, this principle rises questions about its sensitivity
to temperature and charging condition [128]. Indeed,
the commercial launching of batteries with such a
negative material has been delayed.
The mention of metal cluster occurrence in the former systems revived some interest in lithium alloys
with special characteristics, as for example nanometricsized particles [129].
Metal vanadates have also been investigated at low
potential, and although the mechanism proposed is

350 A h/kg
2.2 g/cm3
140 A h/kg
5 g/cm3
10%
90%
30%
25 mm
30 mm
500 mm
3.5 V

dierent, they share with tin based oxides high values

of both irreversible and reversible capacities [130].
Finally, some promising work has been published
concerning lithiated metal nitrides [131,132] with both
high capacity (up to 800 mA h/g) and low average voltage (0.5 V vs. Li). The fact that they are available
only in a lithiated (=charged) state rules out problems
of irreversibility on rst charge encountered with other
materials, but on the other hand eliminates conventional positive lithiated (=discharged) metal oxides
which allow high voltage. Indeed, these highly oxidizing positive materials cannot be handled in their
charged state for cell manufacturing.
4.3. Trends
The use of carbon seems to be well established, at
least for the medium term. Within this class of products, things are still moving rapidly. In fact, the
choice of a particular grade of carbon results from
compromises, including electrode processing, and especially the cost, because of very tough competition.
After the initial interest in non-crystalline carbons even
though they could be further improved, the general
trend of battery makers is to use crystalline carbons
with carefully designed electrolyte composition.
Because of their low price and higher capacity, natural
or synthetic graphites seem still to be preferred by
some manufacturers, whereas others use variable
amounts of spherical or ber shape materials.

5. Impact of the main properties of insertion compounds

on battery characteristics
While battery designers can rapidly calculate the
impact of the introduction of a new material in a particular technology, many scientists often lack the tools

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

15

Fig. 14. Inuence of the specic capacity of materials on complete cell specic energy.

to evaluate the characteristics of actual cells using that

material. The purpose of this section is to give some
gures, which would help in this evaluation.
The easiest way is to calculate the volume and

weight of the complete cell stack, including the active

materials, conductive and binder additives, current collectors, separator and electrolyte.
Then construction derating factors of 0.8 for the

Fig. 15. Inuence of the volumetric capacity of the materials on the cell energy density.

16

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

Fig. 16. Inuence of non-crystalline carbon specic capacity and rst charge eciency on cell energy density. (Carbon specic gravity 2 g/cm2, cell average voltage=3 V).

weight and 0.75 for the volume are applied to determine actual cell characteristics (large batteries).
The main parameters used in these calculations can
be considered as an optimised Li ion cells using conventional separators, assuming that the negative is
carbon, as described in Table 1. This design would
provide an energy density of 400 W h/l and a specic
energy of 160 W h/kg. The `hybrid' or `plastic' polymer technology, using roughly the same type of electrodes, would dier mainly from these numbers by
the thickness of the electrolyte-separator, presently
about 2 to 3 times thicker than the conventional
ones. This would give, for a 60 m thick polymer
separator, comparative values of 335 W h/l, and 145
W h/kg. Both construction factors should be
increased to close to 0.9 to come back to the same
nal values as conventional technology. This technology is especially more favorable for small thin batteries (<1 A h), where the construction factor are
more important.
5.1. Specic capacity, A h/kg
The rst characteristic evaluated is the cell specic
energy, as a function of the material's specic capacity.
Fig. 14 describes the results obtained. As expected
from the density, the positive material has a greater inuence. A 50% increase in A h/kg of the positive compound results in an overall 28% improvement of cell
W h/kg, while the same change in the negative produces only a 13% gain.

5.2. Capacity density, A h/l

Fig. 15 describes the energy density as a function
of `capacity density', in A h/l of the materials. Here
we can see that the positive and negative materials,
occupying about same volume in the cell, have a
very similar inuence on the nal results. A 50%
increase of any of each in A h/l results in an increase
of about 25% W h/l at the cell level. This last
characteristic is the most important for small portable cells, while the specic energy will be of prime
interest for large cells, used for example in EVs or
satellites.
5.3. First charge eciency and voltage of carbons
In recent years, many new negative materials
have been proposed, including some carbonaceous
compounds exhibiting quite large specic capacity,
up to 0.8 A h/kg or more. However, compared to
graphitised materials, they also had higher irreversible capacities, lower density, as well as much
higher working voltage versus lithium, reducing to
about 3 V the average cell voltage, when used
with a positive material like LiCoO2. Fig. 16 shows
the calculated cell energy density as a function of irreversible capacity, and specic capacity for such carbons. A material specic gravity of 2 g/cm3 has been
taken for these calculations, with an average voltage of
3 V.

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

17

Fig. 17. Inuence of electrodes porosity on the cell energy density and specic energy.

5.4. Physical properties

The usual electrode manufacturing process consists
of coating thin metallic foils with an `ink' containing
the active material dispersed in an appropriate liquid
medium, including a binder and eventually carbon conductive agent. Up to now, the most used binder has
been PVDF, dissolved in NMP, but other non-uorinated binders may be used, dispersed in water. After
drying, the electrode is laminated to the desired thickness and porosity. The physical properties of the active
materials, including the shape and size of particles and

the taped density (apparent density of the powder after

taping), will also have a signicant impact on the ability of the electrode to be compressed, and consequently
on the achievement of low porosity and good conductivity. Good adhesion to the collector and coating
robustness are also very dependent on the powder
properties. Each battery manufacturer will have its
own requested specications, depending on its electrode process. However, the general trends are low surface area dense particles (in the order of a few m2/g or
less), in the range of 530 mm sizes, having a high
taped density.

Fig. 18. Cell energy density as a function of capacity density (A h/l) of non-carbon negative material, for dierent rst charge eciency.

18

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

Fig. 19. Volume of Portable cells produced world-wide (from H. Takeshita, Nomura Research Institute 1998 report).

As an example, Fig. 17 shows the evolution of the

cell energy density with the electrodes porosity, assuming that negative and positive are the same.
5.5. Properties of non-carbon anodes
The nano-dispersed alloy-forming metals, like those
originating from amorphous oxides, have recently been
extensively investigated since the introduction of this
new class of negative by Fuji-lm in Japan. However,
the usually large irreversible capacity consumption

during the rst charge to reduce the oxides to metals

and build a passivating layer reduces their interest considerably (see Section 4.2). Fig. 18 shows how high this
initial charge eciency (as rst charge eciency), must
be to obtain a sucient energy density.
In this model, the capacity of the negative is
expressed as `capacity density', in A h/l. 6 g/cm3 as
been taken as the negative material specic gravity,
and the calculations are made for specic capacities
from 300 to 750 A h/kg. The average voltage is supposed to be 0.3 V lower than graphite, i.e. 3.2 V.

Fig. 20. Portable cell energy (MW h) produced/year (from H. Takeshita, NRI 1998 report).

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

19

Fig. 21. Sale value of portbale cells (from H. Takeshita, NRI 1998 report).

6. Applications and market of Li ion batteries

The considerable success of small Li ion batteries is
largely due to the very rapid growth of cellular phones
and portable computers. The high energy density, very
high specic energy and high voltage of this battery
type make it very attractive.
Fig. 19 shows the volume of Li ion cells produced
between 1993 and 1999 (projected), compared with the
other competitive new product, NiMH. Quoted in W h
in Fig. 20 (the average energy of a Li ion cell is about

3.7 W h with a tendency to decrease), one can see that

Li ion and NiMH have now reached about the same
production level.
Due to the higher selling price of Li ion, its turnover
is now the most important of the small rechargeable
cells representing about 40% of the total, as shown in
Fig. 21. The unit cell prices have drastically decreased
for both NiMH and Li ion, and at the same time the
size of the cells is diminishing. There is also an increasing demand for prismatic shape vs. cylindrical (Fig.
22). From market experts, the level of manufacturing

Fig. 22. Evolution of Li ion cell type, percentage between cylindrical and prismatic shape (from H. Takeshita, NRI 1998 report).

20

M. Broussely et al. / Electrochimica Acta 45 (1999) 322

capability worldwide is close to exceeding the demand

of the portable market.
The next expected evolution, which could change
this situation is the introduction of polymer Li ion batteries, where the conventional polypropylene/polyethylene microporous separator is replaced by a PVDFbased polymer swelled by electrolyte, sticking together
the two thin electrodes. Presently under development
or pre-industrialisation, these cells will oer the possibility of making very attractive thin cells for small portable devices, providing the required power is
available.
Beside small portable electronic devices, Li ion technology is also very suitable for large batteries, in application where energy density or specic energy is of
prime importance. Electric vehicles and satellites are
presently the most representative applications.
Excellent specic power, which can reach values as
high as 1500 W/kg with still more than 60 W h/kg
specic energy is an interesting additional feature of
this technology, mainly related to thin electrodes technology. Thanks to these outstanding properties, the Li
ion concept is expected to be applied in a near term to
many other utilisations.

7. Conclusions
The future of Li ion batteries appears to be very
bright, when considering their outstanding performance. Insertion materials, especially carbon electrodes,
have been the key of success for this new type of
electrochemical power sources, and these compounds
will be improved again in the coming years A lot of
new applications will use this battery system in a
near future, with both smaller and larger batteries
than today. However, a very wide spreading of this
technology is linked to a drastic cost reduction and
improvement of safety on abuse conditions. Each of
these stakes can be addressed not only by design consideration, but also by working on new materials, especially on the positive electrode. Due to the innite
number of solutions oered by solid state chemistry
in building mixed materials, very promising results
are already obtained and further discoveries can be
expected.

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