Synthetic Metals 125 (2002) 153±159

Creation of nanospaces by intercalation of alkali metals into

graphite in organic solutions
Y. Mizutania, T. Abeb,*, M. Inabab, Z. Ogumib
a
Institute of Advanced Energy, Kyoto University, Uji, Sakyo-ku, Kyoto 610-0011, Japan
b
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan
Received 22 May 2001; received in revised form 5 June 2001; accepted 25 June 2001

Abstract

Co-intercalation of alkali metals (Li, Na, K, Rb and Cs) with various organic solvents has been utilized for introducing nanospaces in
graphite. The co-intercalation has been conducted by a solution method. Resultant products were studied by X-ray diffraction. For solvents
of cyclic ethers, co-intercalation is likely to occur for heavy alkali metals of Rb and Cs. For linear ethers with one oxygen atom, binary
graphite intercalation compounds (GICs) were mainly obtained, irrespective of alkali metal species. For linear ethers with two oxygen
atoms, light alkali metal, in particular, Li tends to give ternary Li±solvent±GICs. From these results, it is concluded that co-intercalation is
mainly in¯uenced by the interaction between alkali metals and solvents and by the size of solvated alkali metals. # 2001 Elsevier Science
B.V. All rights reserved.

Keywords: Co-intercalation; Alkali metals; Organic solvents; GIC

1. Introduction nanospaces in graphite layers by the decomposition of co-

Intercalation is one of the methods for the creation of
nano-sized spaces in graphite. The created nano-sized
spaces in graphite are dependent on kinds of atoms and
molecules, namely intercalates. The intercalation changes
the chemical and physical properties of graphite [1±4] and
the resultant graphite intercalation compounds (GICs) have
been applied in various application ®elds, in particular, in the
market of Li-ion batteries.
Alkali metal±GICs have been extensively studied [1±4]
because the GICs consist of only two elements, which is
favorable to study the GICs systematically by changing
stage number and the kind of alkali metal. New ternary
GICs with high concentration of alkali metals have also been
reported [5±7]. Recently, alkali metal±GICs have been
received much attention again because of the rapid devel-
opment of Li-ion batteries in which carbonaceous materials
are used as negative electrodes [8±13]. Since the potential of
Li±GIC is well known to be as low as Li metal, most organic
solvents should decompose by electrochemical reactions at
low potentials. However, the suppression of solvent decom-
position is made by the surface ®lm formed on graphite
electrode. The surface ®lm is considered to be created at
*
Corresponding author. Tel.: ‡81-75-753-5542; fax: ‡81-75-753-5889.
E-mail address: abe@elech.kuic.kyoto-u.ac.jp (T. Abe).
intercalated Li‡ ions with solvents [14,15], and hence study
of co-intercalation of alkali metals and solvents into graphite
will give an informative clue for surface ®lm formed on
graphite electrode in Li-ion batteries.
Co-intercalation of alkali metals and organic solvents into
graphite was extensively studied by French groups [16±19].
Studies on co-intercalation of alkali metals and organic
solvents were roughly categorized by two methods: (1)
alkali metal±GICs are ®rst synthesized and then organic
solvents are reacted with the alkali metal±GICs, and (2)
alkali metals are reacted with graphite in organic solutions
(solution method). These studies [16±19] showed that
organic solvents are easily co-intercalated into graphite
due to their strong polarity.
The present authors have found the formation of alkali
metal±GICs in 2-methyltetrahydrofuran (2-MeTHF) and
2,5-dimethyltetrahydrofuran (2,5-diMeTHF) solutions by
a solution method [20,21]. These solvents are polar, but
no co-intercalation took place in some conditions. Solution
method in tetrahydrofuran (THF) gives co-intercalated pro-
ducts of alkali metal±THF±GICs [16,22], and therefore the
formation of alkali metal±GICs in a 2-MeTHF solution is
very interesting because the molecular structures of THF and
2-MeTHF differ only in one methyl group. Similar behavior
can be observed for electrochemical intercalation of lithium
ion into graphite in ethylene carbonate (EC)-based and

0379-6779/01/$ ± see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 9 - 6 7 7 9 ( 0 1 ) 0 0 5 2 5 - 2
154 Y. Mizutani et al. / Synthetic Metals 125 (2002) 153±159
propylene carbonate (PC)-based electrolytes. Molecular
structures of EC and PC differ only in one methyl group.
However, electrochemical lithium intercalation takes place
in an EC-based electrolyte while a PC-based electrolyte does
not give electrochemical lithium intercalation into graphite.
This is because surface ®lm on graphite electrode is not
formed in a PC-based electrolyte [23].
The above results and facts are very interesting, which led
us to further studies on intercalation of alkali metals into
graphite in organic solutions. Here, we summarize the
intercalation of alkali metals into graphite in various
ether-type organic solvents by a solution method and discuss
the co-intercalation phenomena.
2. Experimental
Ether-type solvents of THF, 2-MeTHF, 2,5-diMeTHF,
methoxypropane (MP), methoxybutane (MB), diethyl ether
(Et2O), t-butylmethyl ether (TBME), dimethoxymethane
(DMM), diethoxymethane (DEM), 1,2-dimethoxyethane
(1,2-DME), 1,2-diethoxyethane (1,2-DEE), and 1,2-dibu-
toxyethane (1,2-DBE) were used without further puri®ca-
tion. Natural graphite ¯akes produced in China were used as
host materials. Solution method was applied as follows: an
excess amount of alkali metals were dissolved into 2 ml of
solvents using a dissolving agent of 0.5 mmol of naphtha-
lene, followed by immersing natural graphite ¯akes into the
solutions in a small reaction tube of Pyrex glass. After the
reaction tube was sealed completely, it was stirred for 30 min
to 30 days at ambient temperature. The sample was taken out
from the reaction tube into liquid paraf®n, and it was
immediately wrapped with a thin polyethylene ®lm to pre-
vent the oxidation by atmospheric air and moisture.
Fig. 1. Variation of XRD patterns of GICs prepared in Li±2-MeTHF solution for 1, 6, and 12 h. The symbol P.E. denotes polyethylene film and the numbers
on the peaks correspond to the index 0 0 l.
X-ray diffraction (XRD) of the sample were collected with
Cu Ka radiation monochromatized by highly oriented pyr-
olytic graphite using a scintillation detector. Typical working
conditions were 35 kV and 20 mA, and scanning speed of 28/
min with a time constant of 0.5 s. The XRD pattern of the
polyethylene ®lm was measured in advance and the peaks
were observed at 9.58, 21.48, 28.78 and 36.28 in 2y.
3. Results and discussion
3.1. Formation process of GIC by a solution method
Figs. 1(a) and (b) show XRD patterns in the range 20±288
and 50±588 in 2y, respectively, for GICs prepared in Li±2-
MeTHF solution for 1, 6 and 12 h. Here, the symbol P.E.
denotes peaks due to polyethylene ®lms, and number on
peaks denote the index 0 0 l. Peak positions at 25.38, 25.68
and 25.98 in 2y are observed in Fig. 1(a), which are identi®ed
as binary stage-2, -3 and -4 Li±GICs. The stage number can
be clari®ed with the higher 0 0 l lines as shown in Fig. 1(b).
As is evident from Figs. 1(a) and (b), intercalation of Li into
graphite in the Li±2-MeTHF solution was found to proceed
from binary higher stage Li±GIC to lower stage one. No
ternary Li±MeTHF±GIC is observed under the present
condition.
Fig. 2 shows XRD patterns in the range 0±408 in 2y
for GICs prepared in Li±1,2-DEE solution for 30 min (solid
line) and 1 h (dotted line). Number on peaks denote the
index 0 0 l, and st1 and st2 refer to stage-1 and -2, respec-
tively. From the peak positions, the c-axis repeat distance
is determined to be 1.12 and 1.45 nm, which corresponds to
the stage-1 and -2 Li±1,2-DEE±GICs. Therefore, co-inter-
calation of 1,2-DEE takes place in Li±1,2-DEE solution, and
 Y. Mizutani et al. / Synthetic Metals 125 (2002) 153±159 155

polar solvents do not necessarily co-intercalate into graphite

with alkali metals. In addition, formation of binary GICs is
likely to occur for heavy alkali metal such as Rb and Cs.
Since the reaction of alkali metals with graphite in organic
solutions can be described as follows [24]:
Alkali metal …M† ‡ n solvent ‡ ‰aromaticŠ
! ‰aromaticŠ M‡ …solvent†n (1)

‰aromaticŠ M‡ …solvent†n ‡ xC ! MCx …solvent†n

Fig. 2. Variation of XRD patterns of GICs prepared in Li±1,2-DEE
solution for 30 min and 1 h. The symbols st1 and st2 denote to stage-1 and
stage-2, respectively.
‡‰aromaticŠ…MCx ‡ n solvent ‡ ‰aromaticŠ† (2)
Thus, the interaction between alkali metal and solvent,
namely ion±dipole interaction should play an important role
on the formation of GICs. Further, the sizes of solvated alkali
metal should also be considered. Hereafter, those two factors
are mainly focused in the discussion of the formation of
binary or ternary GICs in a solution method.
Solvents in this study were classi®ed to three groups: (1)
cyclic ethers of THF, 2-MeTHF, and 2,5-diMeTHF, (2)
linear ethers with one oxygen atom of MP, MB, Et2O,
and TBME, and (3) linear ethers with two oxygen atoms
of DMM, DEM, 1,2-DME, 1,2-DEE, and 1,2-DBE. Results
of each group are presented in the following sections.

co-intercalation of Li with 1,2-DEE into graphite in the 3.3. Cyclic ethers

solution also proceeded from higher stage to lower one.
The above results were given only for Li±solvent systems. Co-intercalation of THF was observed irrespective of
The other alkali metals±solvent systems also gave the alkali metals, which is in good agreement with the previous
similar behavior for the formation of binary or ternary GICs. literatures [16]. As is mentioned above, heavy alkali metals
The mixture of binary and ternary GICs was obtained in tend to give binary GICs by a solution method. However,
limited combinations of alkali metal and solvents, and their exceptional results were observed for heavy alkali metals
formation mechanism will be discussed later. and 2-MeTHF systems. Mixture of binary and ternary GICs
were obtained for Rb and Cs.
3.2. Type of GICs obtained by a solution method Burley and Young [25] reported ion pairing in alkali metal
salts in 1,3-diphenylbut-1-ene. According to their results,
In Table 1, types of GICs prepared in organic solvents by a interaction between alkali metal and 2-MeTHF is in the
solution method were given. The symbols T and B denote the order of Li‡ > Na‡ ˆ K‡ > Cs‡ , indicating that co-inter-
ternary and binary GICs, respectively. As a whole, more than calation of 2-MeTHF should take place more easily for Li‡
half of the resultant products are binary GICs, indicating that because of the strong interaction between Li and 2-MeTHF.
However, Li±2-MeTHF system gives binary Li±GIC as
mentioned in Section 3.1. These phenomena observed by
Table 1 use of the 2-MeTHF solutions can be explained by the steric
Types of GICs prepared in organic solvents by solution method hindrance. Although ionic radius of Li‡ is smaller than that
Solvents Li Na K Rb Cs of Cs‡, c-axis repeat distance of stage-1 Li±THF±GIC is
much larger that of Cs±THF±GIC [22]. The difference of the
THF T T T T T
2-MeTHF B B B B, T B, T distance is due to the different con®guration in graphite
2,5-diMeTHF B B B B layers. The THF molecules coordinated with Li‡ by a
MP B B B B
tetrahedral-type of arrangement in Li±THF±GIC [26] while
MB B B B B THF molecules lies parallel to the graphite plane in Cs±
Et2O B B, T B, T B THF±GIC [19]. If the same arrangement in graphite layers is
TBME B B, T applied to Li±2-MeTHF system, the size of solvated Li‡ ion
DMM T B B B by 2-MeTHF would become very large due to the methyl
DEM T B B B group. For Cs±2-MeTHF system, the size of solvated Cs‡
1,2-DME T T T T B ion by 2-MeTHF should be as same as that by THF due to the
1,2-DEE T T B, T B B
parallel con®guration. In fact, Cs±2-MeTHF±GIC showed
1,2-DBE B B B B
the c-axis repeat distance of Ic as 0.718 nm, which is almost
156 Y. Mizutani et al. / Synthetic Metals 125 (2002) 153±159
the same value as that of Cs±THF±GIC obtained by a
solution method in this work.
Formation mechanism of binary and ternary GICs for Rb±
2-MeTHF and Cs±2-MeTHF systems can be explained as
follows. The electrochemical potential of Rb±GICs and Cs±
GICs should be very low as can be easily deduced by the
potential of Li±GIC and the redox potentials of Li, Rb, and
Cs. This means that Rb±GICs and Cs±GICs are highly
reductive to decompose 2-MeTHF. Therefore, mixture of
binary and ternary GICs can be obtained only in condition
that co-intercalation of 2-MeTHF occurs before the forma-
tion of binary Rb±GICs and Cs±GICs. Electrochemical
intercalation of Li‡ ions into graphite takes place below
the potential of 0.25 V (vs. Li/Li‡) [10]. In contrast, inter-
calation of solvated Li‡ ions occurs at more positive poten-
tial around 1.0±1.5 V (vs. Li/Li‡) [27]. Therefore, co-
intercalation of Li‡ ions and solvent is thermodynamically
more stable than intercalation of Li into graphite [13]. With
an analogy of electrochemical Li intercalation, co-intercala-
tion can take place in the Rb±2-MeTHF and Cs±2-MeTHF
systems before the formation of binary Rb±GICs and Cs±
GICs. These explanations were con®rmed by the XRD
results.
The variation of XRD patterns of GICs prepared in Rb±2-
MeTHF solution for 12 h, 3 days, and 30 days are given in
Fig. 3. As is readily observed, peaks identi®ed as ternary
GICs are ®rstly observed and then the peaks due to binary
GICs grow with increment of reaction time. These XRD
patterns directly indicate that co-intercalation take place ®rst
before the formation of binary GICs. However, there still
remains a question why ternary GICs can exist when binary
Fig. 3. Variation of XRD patterns of GICs prepared in Rb±2-MeTHF
solution for 12 h, 3 days and 30 days. The symbols t1, t2, and b1
correspond to stage-1 and -2 ternary Rb±2-MeTHF±GICs, and stage-1
binary Rb±GIC, respectively.
GICs are formed. Therefore, more complicated competitive
reactions may occur in Rb±2-MeTHF and Cs±2-MeTHF
systems, but the detail cannot be studied by the present
solution method.
In alkali metal±2,5-diMeTHF solutions, only binary GICs
were obtained. Burley and Young [25] also reported the
solvating ability of 2,5-diMeTHF; the interaction between
alkali metal and 2,5-diMeTHF is smaller than that between
alkali metal and 2-MeTHF. In addition, steric hindrance of
2,5-diMeTHF is larger than 2-MeTHF, which should lead to
the formation of only binary GICs.
3.4. Linear ethers with one oxygen atom
Fig. 4 shows resultant products obtained in alkali metal±
MB solutions except for Na. Only binary GICs are obtained
and no co-intercalation takes place. For the other ethers in
this group, most of the products are binary GICs. This is due
to the weak solvation ability of linear ethers with one oxygen
atom. According to Burley and Young [25], various linear
ethers with one oxygen showed weak solvation ability. As is
clear from Fig. 4, alkali metal±MB systems gave stage-1
GICs (XRD patterns show mixture of stage-1 and stage-2
binary GICs, but most of the resultant products were colored
to be gold, and therefore stage-2 GICs were the decomposed
products from stage-1 GICs), while stage-2 binary GICs
were mainly obtained in alkali metal±2,5-diMeTHF sys-
tems. The difference of stage number cannot be explained by
diffusion coef®cient of Li‡ ion in graphite layers because the
reaction temperatures were kept constant, leading to the
same diffusion coef®cient. Hence, mass transport in the
Fig. 4. XRD patterns of products obtained in alkali metal±MB solutions.
All the resultant products are mixture of stage-1 and stage-2 binary alkali
metal±GICs.
 Y. Mizutani et al. / Synthetic Metals 125 (2002) 153±159 157

solution should be the rate-determining step, since the

viscosity of 2,5-diMeTHF solution is larger than that of
MB solution.

3.5. Linear ethers with two oxygen atoms

Since molecular structures of 1,2-DME, 1,2-DEE, and

1,2-DBE are very similar, size effect of solvated alkali
metal ions on co-intercalation can be easily studied. For
alkali metals of Li, Na and K, formation of ternary alkali
metal±1,2-DME±GICs has been known [28,29]. Formation
of Rb±1,2-DME±GIC is also found in the present work.
However, Cs±1,2-DME system only gives binary Cs±GIC
as shown in Fig. 5. Here, the symbols St1 and St2 denote to
the stage-1 and -2 Cs±GICs, respectively. In Fig. 6, c-axis
repeat distances of Ic for alkali metal±1,2-DME±GICs were
plotted against ionic radii of alkali metals [30]. Fig. 6
shows a linear correlation between Ic and ionic radii except
for Li±1,2-DME±GIC, indicating that structures of solvated
alkali metal ions in alkali metal±1,2-DME±GICs should be Fig. 5. XRD pattern of GIC prepared in Cs±1,2-DME solution. Obtained
GICs are mixture of stage-1 and -2 binary Cs±GICs.
very similar with each other. When Cs±1,2-DME±GIC is
formed, the Ic value will be about 1.21 nm as is easily
expected from Fig. 6. This value is less than Ic value of
1.24 nm for Li±THF±GIC [26]. Hence, the value of between Cs and 1,2-DME is the weakest among alkali
1.21 nm must be acceptable for expansion of graphite metal ion. Therefore, it is concluded that degree of inter-
layers for formation of Cs±1,2-DME±GIC, indicating that action between alkali metal and 1,2-DME plays an impor-
another factor other than size of solvated alkali metal tant role on co-intercalation in alkali metal±1,2-DME
should be considered. The degree of interaction between systems.
alkali metal ion and 1,2-DME [25] was reported by the ratio For resultant products using alkali metal±1,2-DEE solu-
of the concentration of solvent-separated ion pairs to that tions as given in Table 1, similar explanation mentioned
of solvent-contacted ion pairs. In the literature [25], the above is applicable because the respective Ic values for Li±
interaction of alkali metal and 1,2-DME is in the order of 1,2-DEE±GICs and Na±1,2-DEE±GICs are almost the same
Li‡ ˆ Na‡ > K‡ > Cs‡ . This means that the interaction with those for Li±1,2-DME±GICs and Na±1,2-DME±GICs.

Fig. 6. Plots of Ic values for alkali metal±1,2-DME±GICs against ionic radii of alkali metal. Line was drawn by the least-squares method except for the value
of Li±1,2-DME±GIC: (&) observed value; (&) extrapolated value.
158 Y. Mizutani et al. / Synthetic Metals 125 (2002) 153±159
Fig. 7. Variation of XRD patterns of GICs prepared in K±1,2-DEE
solution for 1 h, 1 day and 3 days. The symbols t1, St1 and St2 correspond
to stage-1 ternary K±1,2-DEE±GIC and stage-1 and -2 binary K±GICs,
respectively.
Although solvating power of 1,2-DEE has not been repor-
ted, it should be weaker than that of 1,2-DME due to the
steric hindrance. Hence, interaction between Rb or Cs and
1,2-DEE may be weak, leading to the formation of binary
Rb±GICs and Cs±GICs.
Similar to Rb±2-MeTHF and Cs±2-MeTHF systems,
mixture of binary and ternary GICs were obtained in K±
1,2-DEE solution. As mentioned above in Section 3.3, co-
intercalation should take place ®rst for the formation of
mixture of binary and ternary GICs. Fig. 7 shows XRD
patterns for GICs prepared in K±1,2-DEE solution for 1 h, 1
day, and 3 days. XRD pattern obtained for 1 h gives a peak of
stage-1 K±1,2-DEE±GIC labeled as t1. Increase of reaction
time gave peaks for binary stage-1 and 2 K±GICs labeled
as St1 and St2, respectively. These XRD patterns show that
co-intercalation of K±1,2-DEE takes place before the for-
mation of binary K±GICs. These results are in good agree-
ment with those obtained for Rb±2-MeTHF system.
The strength of interactions between an alkali metal ion
and solvents may be classi®ed by the hard/soft acid base
theory. According to the theory, strong solvation is expected
with the hard alkali metal ion as Li‡. Hence, combination of
Li‡ ion and the present linear ethers with two oxygen atoms
is likely to give ternary Li±solvent±GICs. Only exception is
Li±1,2-DBE system. In Li±1,2-DBE solution, binary Li±
GIC was obtained. In this case, steric hindrance of 1,2-DBE
due to the large butyl group should not be ignored, but the
detail is still under investigation.
As is shown in Table 1, binary GICs were mainly obtained
for alkali metal±DMM and metal±DEM systems. If the
coordination number is the same, sizes of solvated alkali
metal ion in DMM and DEM solutions are assumed to be
smaller than those in 1,2-DME by considering the molecular
sizes of DMM and DEM. However, only Li±DMM and Li±
DEM systems give ternary GICs. Hence, the interaction of
alkali metal ion and DMM (DEM) should be responsible for
the co-intercalation of these solvents.
3.6. Factors for co-intercalation
Co-intercalation of ether solvents in this study was dis-
cussed mainly by (1) the interaction between alkali metal ion
and solvent molecules and (2) the size of solvated alkali
metal ion. As is mentioned above, the strongest solvation is
expected with Li‡ ion, and therefore co-intercalation of
solvents with Li‡ is likely to occur. However, the co-inter-
calation cannot be explained only by the degree of interac-
tion between alkali metal and solvent, in particular, for alkali
metal±2-MeTHF systems.
For Li±solvent systems, we roughly evaluated the order
for the size of solvated Li‡ ion by using the molecular sizes
of solvents. In the organic solvents, four oxygen atoms tend
to coordinate with Li‡ ion [31,32], and therefore, we
estimated the order by multiplying 4 by molecular volumes
for the solvents with one oxygen atom in the molecule and 2
for the solvents with two oxygen atoms. As a result, the sizes
are in the order of DMM < 1; 2-DME < DEM < 1; 2-DEE <
THF < MP < 2-MeTHF < Et2 O < 1; 2-DBE < MB < 2; 5-
diMeTHF. It is clear from this order and Table 1 that there is a
border between THF and MP for the co-intercalation of solvents.
Therefore, it should be concluded that the sizes of solvated alkali
metal ions also play an important role on the co-intercalation of
solvents.
Factors for co-intercalation will be more complicated for
carbonaceous materials other than graphite, which can be
referred to the recent reports by Tanaike and Inagaki [33±
38].
4. Conclusions
Co-intercalation of ether solvents with alkali metal ions
into graphite is summarized. Co-intercalation phenomena
depend on the combination of alkali metal and solvents. It is
very likely that co-intercalation takes place in the presence
of solvents which possess high solvating ability. Further, the
size of solvated alkali metal ion plays an important role on
co-intercalation. The present work will be correlated and
give an informative clue with surface ®lm formation
mechanism on graphite electrode in Li-ion batteries.
Acknowledgements
The authors are grateful to ``Research for the Future
Program of the Japan Society for the Promotion of Science''
for ®nancial support of this research.
 Y. Mizutani et al. / Synthetic Metals 125 (2002) 153±159
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