Materials Research Bulletin 42 (2007) 1499–1506

www.elsevier.com/locate/matresbu

Alanine-assisted low-temperature combustion synthesis of

nanocrystalline LiMn2O4 for lithium-ion batteries
M.W. Raja, S. Mahanty, Paromita Ghosh, R.N. Basu *, H.S. Maiti
Fuel Cell and Battery Section, Electroceramics Division, Central Glass and Ceramic Research Institute,
Kolkata 700 032, India
Received 30 August 2006; received in revised form 18 October 2006; accepted 1 November 2006
Available online 6 December 2006

Abstract
Nanocrystalline LiMn2O4 powders have been synthesized by combustion process in a single step using a novel fuel, L-alanine.
Thermogravimetric analysis and differential thermal analysis of the gel indicate a sharp combustion at a temperature as low as
149 8C. Quantitative phase analysis of X-ray diffraction data shows about 97% of phase purity in the as-synthesized powder, which
on further calcination at 700 8C becomes single phase LiMn2O4. High Brunauer, Emmett, and Teller surface area values obtained
for ash (53 m2/g) and calcined powder (23 m2/g) indicate the ultrafine nature of the powder. Average crystallite size is found to be
60–70 nm from X-ray diffraction analysis and transmission electron microscopy. Fourier transformed infra-red spectrum shows
two strong bands at 615 and 511 cm1 originating from asymmetrical stretching of MnO6 octahedra. A nominal composition of
Li0.88 Mn2O4 is calculated from the inductive coupled plasma analysis. From UV–vis spectroscopy, an optical band gap of 1.43 eV
is estimated which is assigned to a transition between t2g and eg bands of Mn 3d. Electrochemical charge–discharge profiles show
typical LiMn2O4 behavior with a specific capacity of 76 mAh/g.
# 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Oxides; B. Sol–gel chemistry; C. X-ray diffraction; D. Optical properties

1. Introduction

In recent years, extensive research is focused on LiMn2O4 as a cathode material for Li-ion secondary batteries to
replace the more expensive and toxic LiCoO2. However, compared to the layered oxides such as LiCoO2 and LiNiO2,
LiMn2O4 has a higher rate of capacity fading and a limited cycleability in the 4 V region. The reason for capacity
fading has not yet been fully understood but some possible mechanisms have been proposed [1–6]. These include (i)
dissolution of manganese into the electrolyte, (ii) decomposition of electrolyte at fully charged state and (iii)
breakdown of the spinel framework due to repeated contraction–expansion. It is shown that particle size and surface
morphology have significant influences on charge–discharge rate capability, safe cell performance and electrode
formulation of the cathode material [5–8]. Wu et al. [9] have observed a higher initial capacity for nanosized LiMn2O4
than the corresponding large grain size materials. This is due to the fact that small particles with large interface area
provide more lithium ions for diffusion resulting in high ionic current and specific capacity [9,10]. Therefore, it is
apparent that the synthesis procedure and material properties are crucial factors in achieving high battery performance.

* Corresponding author. Tel.: +91 33 2473 3469; fax: +91 33 2473 0957.
E-mail address: rnbasu@cgcri.res.in (R.N. Basu).

0025-5408/$ – see front matter # 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2006.11.002
1500 M.W. Raja et al. / Materials Research Bulletin 42 (2007) 1499–1506

Conventionally, LiMn2O4 is prepared by the solid-state reaction of lithium and manganese salts [11–14]. However,
the process is tedious and has several disadvantages such as inhomogeneity, irregular morphology, larger particle size,
poor control of stoichiometry and longer period of calcination. On the other hand, low temperature combustion process
has several advantages such as single step process, low calcination temperature, smaller particle size, high surface area
and better stoichiometry of the prepared spinel [15]. Several authors have synthesized LiMn2O4 by combustion
process using various fuels such as starch [16], cellulose-citric acid [17], citric acid [18], polyethylene glycol (PEG)
[19], urea [20,21] and glycene [22]. Similarly, in author’s laboratory, the conventional LiCoO2 cathode material has
been synthesized using citrate–nitrate gel route and nanocrystalline powders have been obtained [23]. Guan and Liu
[24] have observed that under the same cycling conditions, LiMn2O4 powders synthesized at a lower temperature
exhibit a much higher capacity than those synthesized at higher temperature. Therefore, combustion temperature is a
crucial factor for determining the particle size and consequently, the capacity.
In the present investigation, we have used L-alanine, a common amino acid as a reducing fuel with an aim to achieve
a low combustion temperature. Alanine belongs to the same amino acid series as glycene, but unlike glycene it has an
extra branched methyl group that might cause evolution of a large quantity of gases during combustion resulting in
finer particles. Moreover, alanine undergoes chelation with both monovalent lithium and divalent manganese ions
facilitating the chelation process that precedes the combustion reaction. In this report, we show that indeed by using
alanine as the fuel the combustion reaction occurs at a very low temperature producing nano-LiMn2O4 powders with a
high surface area.

2. Experimental

LiMn2O4 powder was synthesized by a single step combustion process. LiNO3 (SRL, 99.5%), Mn(Ac)24H2O
(Merck, 99.5%) and L-alanine (Merck, 99.5%) were used as the starting materials. First, a saturated aqueous solution
of manganese acetate and lithium nitrate (Li:Mn = 1:2) were mixed and stirred on a hot plate at about 120 8C. Then, a
saturated aqueous solution of L-alanine (alanine:nitrate = 1:1) was added to it. A dilute nitric acid (70 vol.%) was
added slowly to this solution. After vigorous stirring, the whole solution turned into a viscous gel. Thereafter, an
instantaneous burning occurred to produce a blackish ash. The reaction was carried out inside a fume-hood for safety
reasons. The as-synthesized powder (ash) was then calcined at 300, 500 and 700 8C in air.
The concentrations of lithium and manganese in the samples were determined by inductively coupled plasma (ICP)
analysis. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were carried out by a Shimadzu
TA-50 thermal analyzer from room temperature to 600 8C in air at a heating rate of 10 8C/min. X-ray diffractograms
were recorded by a Philips X’pert X-ray diffractometer with a Cu Ka radiation at 40 kV and 40 mA. The X-ray data
were collected in the 2u range 10–708 with a scan rate of 0.58/min and a dwell time of 0.02 s. Rietveld refinement of the
powder diffraction profiles and quantitative phase analysis were done using a pseudovoight function by PANalytical
Highscore Plus software. Size-strain analysis was performed by comparing the particle width of a standard silicon scan
to account for the instrument broadening. Amorphous content of the as-synthesized powder was determined by taking
the sample calcined at 700 8C as reference with 100% crystallinity.
Fourier transform infrared (FT-IR) spectroscopy has been done to study the structure co-ordination of as-
synthesized and calcined powders with the BOMEN infrared spectrophotometer. For FT-IR, each sample was mixed
with KBr and examined in the wavenumber range from 4000 to 400 cm1. UV–vis absorption spectra were recorded
by a Shimadzu (UV3100) spectrophotometer in the wavelength range 2000–200 nm for information about the optical
transitions. Surface areas of the ash and calcined powders were determined by a Sorpty 1750 surface area analyzer. To
investigate the microstructure of LiMn2O4 powder, scanning electron micrographs (SEM) were taken with a Leo
(S430i) microscope. Transmission electron microscopy (TEM) measurements were done with a Philips CM200
Microscope operating at 100 kV.
The electrochemical performance was studied by assembling 2016 coin-type cells. A typical cathode was
fabricated from a slurry of the synthesized LiMn2O4 powder (80 wt%), acetylene black (15 wt%) and PVDF
binder (5 wt%) using NMP as solvent. After casting the slurry on aluminium foil (current collector) and drying at
110 8C in an oven for 10 h, a circular disk of 18 mm in diameter was cut and pressed. The cells were assembled using
lithium metal as an anode and LiPF6 in EC:DMC (1:1 vol.%) as electrolyte within an argon filled glove box.
Galvanostatic charge–discharge cycles were performed with Autolab PGSTAT30 between 2.9 and 4.1 V at a constant
current of 0.03 mA.
 M.W. Raja et al. / Materials Research Bulletin 42 (2007) 1499–1506 1501

3. Results and discussion

Fig. 1(a) shows that TGA curve for lithium manganese alanine precursor and the corresponding DTA curve is
shown in the inset. A gradual weight loss is observed up to about 140 8C followed by an abrupt large weight loss of
about 75% between 140 and 150 8C. While the first weight loss is attributed to the removal of trapped water that
corresponds to an endothermic peak at 143 8C in the DTA curve, a sharp drastic weight loss at 149 8C is associated
with the decomposition of nitrates and evolution of gases like N2 and CO2. This is manifested as a strong exothermic
peak at 149 8C in the DTA curve. No further significant weight loss is observed up to 600 8C. In order to understand
thermal decomposition behavior thoroughly, lithium alanine and manganese alanine precursor were synthesized
individually and their TGA curves are shown in Fig. 1(b) and (c), respectively. The decomposition behavior of these
two precursors is found to vary significantly. In case of lithium alanine precursor, the weight loss occurs in several
successive stages. An initial gradual weight loss continues up to about 170 8C (removal of residual water), followed by
a sharp weight loss at 193 8C (decomposition of lithium alanine complex), and a sluggish gradual weight loss up to
around 363 8C. Complete decomposition occurs only after about 500 8C. In contrast, the TGA curve of manganese
alanine precursor follows the trend similar to that of lithium manganese alanine precursor—an initial gradual weight
loss occurs up to 120 8C followed by a huge abrupt weight loss at about 143 8C with no further weight loss up to
600 8C. The overall reaction during combustion can be written as

2MnðAcÞ2 4H2 O þ 4HNO3 þ LiNO3 þ 2C3 H7 NO2 ! LiMn2 O4 þ 23H2 O þ 7=2N2 " þ 12CO2 " . . . (1)

ICP analysis of the sample calcined at 700 8C shows that the respective weight percent of Li and Mn are 3.2 and
56.7, which correspond to a nominal composition of Li0.88Mn2O4. The corresponding BET surface area of the sample
has been found to be 23 m2/g.
Fig. 2 shows the X-ray diffractograms for LiMn2O4 powders calcined in air at three different temperatures, i.e., 300,
500 and 700 8C together with the as-synthesized powder (ash). It reveals that even in the ash form, all the peaks for
cubic LiMn2O4 clearly appear together with oxides of manganese as impurity phases and quantitative phase analysis
indicates formation of about 97% of the spinel phase. This suggests that alanine having more carbon in the chain
increases the combustion temperature momentarily to a high value inducing near complete phase formation. The
amorphous content of the as-synthesized powder has been determined by PANalytical HighScorePlus program using
the sample calcined at 700 8C as reference assuming a crystallinity of 100%. It is found that the ash contains about
16% of amorphous content. The crystalline size as determined by XRD analysis is found to be 14 nm. As shown in
Eq. (1), the presence of extra branched methyl group evolutes more gaseous species during combustion making the
powder highly porous. These, together with the momentarily high combustion temperature are the major factors for
producing such fine nanocrystalline LiMn2O4 powder. For a comparison, the combustion temperature for synthesis of

Fig. 1. TGA curves for (a) lithium manganese alanine, (b) lithium alanine and (c) manganese alanine precursor. The inset shows the DTA curve for
lithium manganese alanine.
1502 M.W. Raja et al. / Materials Research Bulletin 42 (2007) 1499–1506

Fig. 2. X-ray diffractograms for LiMn2O4 powders calcined at 300, 500 and 700 8C for 10 h in air (*stands for Mn3O4 and Mn2O3 phases).

Table 1
Decomposition temperature, phase purity, crystallite size and surface area of as-synthesized LiMn2O4 using different fuels
Fuel Decomposition LiMn2O4 Crystallite Surface Reference
temperature (8C) phase (%) size (nm) area (m2/g)
Citric acid 408 75 200–500 14 [25]
Citric acid 350 – Agglomerates 2.5 [26]
Glycine 170 80 100–150 26 [25]
Tartaric acid 350 – 21–50 55 [27]
Alanine 149 95 14–20 53 This work

LiMn2O4 using some other fuels are given in Table 1 [25–27]. While the impurity phase present in the as-synthesized
powder is mainly Mn2O3, the diffractogram for the sample calcined at 300 8C shows presence of both Mn2O3 and
Mn3O4 (Fig. 2). However, as the calcination temperature is further increased to 500 8C, the intensity of the impurity
peaks diminishes and at 700 8C, a single phase LiMn2O4 is obtained. All the peaks could be identified and indexed
with a cubic spinel structure conforming to the JCPDS Data File No. 88-1026. The lattice parameter, a0, has been
found to be 8.2304 which is in good agreement with the literature value [27]. The variation in crystallite size, lattice
strain and the lattice parameter, a0, with calcination temperature is shown in Fig. 3. It is found that as the temperature

Fig. 3. Variation in crystallite size and lattice strain with temperature. The inset shows the variation in the lattice parameter, a0.
 M.W. Raja et al. / Materials Research Bulletin 42 (2007) 1499–1506 1503

of calcination increases, the crystallite size increases, while the lattice strain decreases. In line with these results, the
lattice parameter is also found to increase almost linearly with increasing calcination temperature. Thus, the results of
thermal analysis and XRD highlights the superiority of alanine as a fuel for combustion synthesis compared to other
commonly used fuels such as citric acid [18], polyethyleneglycol [19], urea [20,21], glycene [22], etc., in the sense that
pure spinel LiMn2O4 powder can be prepared at a much lower temperature (149 8C) for combustion with nanosized
crystallites (60 nm).
Fig. 4 shows the transmission electron (TEM) micrograph of the powder calcined at 700 8C. It indicates that the
synthesized powder consists of some agglomerates that are formed due to the small particle size. The particle size as
estimated from the micrograph is around 70 nm. The scanning electron micrograph (SEM) of the same sample (not
shown here) also reveals the agglomerated nature of the particles with an average particle size of 70 nm. These
results are in good agreement with the crystallite size as determined by XRD.
Fig. 5(a)[i–iii] shows the FT-IR spectra in the wavelength range 4000–400 cm1 recorded at room temperature for
the lithium manganese alanine precursor gel, the as-synthesized LiMn2O4 powder (ash) and the calcined powder,
respectively. For clarity, the spectra for the as-synthesized and calcined powder are also shown in the range 800–
400 cm1 in Fig. 5(b)[ii and iii]. In the spectrum of the gel, several peaks are observed which may be identified as due
to OH stretching (1650 cm1), CO3 ions (1460 cm1) and NO3 stretching (1382 cm1) [28,29]. Julien and Massot [30]
have observed the strong low frequency bands of LiMn2O4 (belonging to F1u species) at 615 and 513 cm1 and
assigned these to the asymmetric stretching of MnO6 groups. Fig. 5(b)[ii] shows that even in the as-synthesized
powder, the characteristics bands of LiMn2O4 are clearly observed at 615 and 509 cm1. No other bands are found
except for a spike at 1382 cm1 which is due to NO3 stretching. These results support the findings of XRD that nearly
phase pure LiMn2O4 is obtained even in the ash form. When calcined at 700 8C, the positions of the low frequency
bands remain nearly the same at 615 and 511 cm1.
In order to understand the optical transition processes in the Mn 3d bands of LiMn2O4, UV–vis absorption spectra
have been recorded. Fig. 6(a) shows the absorption spectrum for the calcined sample and Fig. 6(b) shows the
differential plot (dA versus l). The absorption spectrum is marked by three regions: (i) weak lower energy transitions at
0.70 eV (I) and at 0.88 eV (II), (ii) strong higher energy transitions at 1.43 eV (III) and at energies higher than 3.18 eV
(V) and (iii) relatively weak transitions around 1.90 eV (IV). The origin of the lower energy transitions (I) and (II) may
be assigned to some defect levels or more probably may be related to Jahn–Teller lattice distortion arising from the
longer and shorter Mn–O bonds [31]. The theoretical density of states (DOS) as calculated from the work of Liu et al.

Fig. 4. TEM micrograph of LiMn2O4.

1504 M.W. Raja et al. / Materials Research Bulletin 42 (2007) 1499–1506

Fig. 5. FT-IR spectra of the (i) gel, (ii) as-synthesized ash, and (iii) the powder calcined at 700 8C.

[32] is shown in the inset of Fig. 6. The band structure of LiMn2O4 is strongly influenced by hybridization between Mn
3d orbitals and O 2p orbitals, while Li remains in ionic form. In the DOS, the Fermi level, EF lies within the non-
bonding t2g. Below the Fermi level, a strong hybridization of O 2p orbital and 3s, 3p and 3d states of Mn gives rise to
the filled Mn–O bonding. Thus, the t2g states of Mn are filled while the eg bands are vacant. Liu et al. [32] have
calculated the theoretical density of states for LiMn2O4 by discrete variational Xa (DV-Xa) molecular orbital method
(represented in the inset of Fig. 6) and the calculated values for the transitions from t2g to lower and upper eg are 1.2 and
2.1 eV, respectively. In the present study, the corresponding transition energies are found to be 1.43 and 1.90 eV
respectively which are in good agreement. Somewhat higher t2g to eg transition energies (1.63 and 2.0 eV, respectively)
have been observed by Kushida and Kuriyama [33] for LiMn2O4 thin films on silica glass. However, thin films are
always known to show a higher band gap than the corresponding bulk compound. The transitions observed at the
higher energy region-V can be attributed to the transitions coming from oxygen 2p levels to the metal t2g or eg orbitals.
Li/LiMn2O4 2016 coin cells prepared wtih nano-crystalline LiMn2O4 powder shows an open circuit voltage (OCV)
of 2.9 V. Fig. 7(a) represents a typical charge discharge profile cycled between 2.9 and 4.1 V. Two distinct plateaus are

Fig. 6. UV–vis absorption spectra and differential plot for LiMn2O4. The inset shows the calculated DOS [32].
 M.W. Raja et al. / Materials Research Bulletin 42 (2007) 1499–1506 1505

Fig. 7. Charge–discharge profiles of Li/LiMn2O4 coin cells prepared by (a) alanine assisted combustion [present work], (b) emulsion drying [36] and
(c) triethanolamine (TEA)-starch-induced combustion [37].

observed in the regions 4.1–4.0 and 4.0–3.9 V which is characteristic behavior of LiMn2O4 and are associated with the
two-step mechanism of electrochemical lithium intercalation as reported earlier [34,35]. For comparison, typical
charge–discharge profiles of Li/LiMn2O4 coin cells prepared by different chemical route – emulsion drying [36] and
triethanolamine (TEA)-starch-induced combustion [37] are also presented in Fig. 7(b) and (c) respectively along with
the present results. The ratio of charge/discharge capacity as calculated from Fig. 7(a) is found to be 0.95 with a
discharge capacity of 76 mAh/g. It has been reported earlier that calcination at a lower temperature results in reduced
number of Mn3+—the capacity enhancing species in the 4 V region [36,37]. Presence of structural disorder due to non-
stoichiometry may also lead to a reduction in capacity. As the sample in the present study was calcined at a lower
temperature of 700 8C, a somewhat lower specific capacity is obtained.

4. Conclusions

L-Alanine, a common amino acid, has been used for the first time, as a fuel for combustion synthesis of LiMn2O4
cathode materials for lithium ion batteries. Sharp single-step combustion triggers at 149 8C, the lowest temperature
ever reported. The as-synthesized powder consists of 97% of the LiMn2O4 with some lower-valent manganese oxides
as impurities that are removed when calcined at 700 8C. The nominal composition of the powder has been found to be
Li0.88Mn2O4 with an average crystallite size of 60–70 nm and a surface area of 23 m2/g. From UV–vis spectroscopy,
an optical band gap of 1.43 eV has been observed which has been assigned to d–d transitions in Mn involving t2g and eg
orbitals. These nanocrystalline cathodes show charge discharge profiles characteristic of LiMn2O4 but with a
discharge capacity 76 mAh/g.

Acknowledgements

The authors wish to thank Director, CGCRI, Kolkata for his kind permission to publish this paper. Kind help from
Dr. S. Gopukumar, Central Electrochemical Research Institute, India in the electrochemical work is acknowledged.
Thanks are also due to Dr. A.K. Tyagi, BARC, Mumbai for extending the FT-IR facilities.

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