Journal of Materials Science: Materials in Electronics

https://doi.org/10.1007/s10854-018-9895-1

Synthesis and characterization of lithium titanate ­(Li4Ti5O12)

nanopowder for battery applications
M. Selvamurugan1 · C. Natarajan2 · Y. Andou3 · S. Karuppuchamy1 

Received: 9 March 2018 / Accepted: 17 August 2018

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
Nanostructured lithium titanate ­(Li4Ti5O12) nanopowder was successfully synthesized by simple peroxide route using titanium
oxysulphate and lithium hydroxide. The structural properties of the as-prepared and sintered powders were characterized
by using powder X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy. Surface morphological
property was studied by scanning electron microscope. Compositional analysis was studied using X-ray photo electron
spectroscopy. The thermal degradation behavior of the as-synthesized materials was analyzed by thermo gravimetric analy-
sis (TG–DTA). The electrochemical properties of the ­Li4Ti5O12 nanopowders were examined using galvanostatic charge/
discharge test. The effect of sintering temperature on its various physical properties and the electrochemical performances
of ­Li4Ti5O12 was investigated. The storage capacity value obtained for ­Li4Ti5O12 and L ­ i4Ti5O12/graphite composite anode
was 83.52 and 91.33 mAhg−1 in 1 M ­LiPF6 at 0.1 mA.

1 Introduction direction of the discharge. Li-ion battery has three main

In recent years, worldwide researchers are mainly focus-
ing the research work on alternative and sustainable energy
storage systems for the use in near future due to fossil fuel
depletion. The batteries are attracting much attention com-
pared with other energy storage systems because it is cost
effective and easily accessible. Lithium ion batteries are
rapidly gaining much attention among the researchers since
they offer a number of advantages over other energy storage
systems. Fundamentally, lithium ion batteries are classified
in to two categories such as primary and secondary bat-
teries. The primary batteries are non-rechargeable because
of their electrochemical reaction cannot be reversed. But
in the case of secondary batteries, it is rechargeable for the
reason that their electrochemical reaction can be overturned
by applying a certain voltage to the battery in the opposite
* S. Karuppuchamy
skchamy@gmail.com; skchamy@alagappauniversity.ac.in
1
Department of Energy Science, Alagappa University,
Karaikudi, Tamilnadu 630 003, India
2
Research and Development Centre, Himadri Chemicals &
Industries Ltd, Kolkata 700001, India
3
Graduate School of Science and Systems Engineering,
Kyushu Institute of Technology, 2‑4 Hibikino, Kitakyushu,
Fukuoka 808‑0196, Japan
components: such as positive electrode (cathode), negative
electrode (anode) and electrolyte. Rechargeable lithium-ion
batteries with a high power energy density and long lifetime
have been regarded as one of the important energy storage
devices for application in electric vehicles and portable
devices. A number of different cathode materials used in
lithium ion batteries, such as lithium cobalt oxide ­(LiCoO2),
lithium manganese oxide (­ LiMn2O4), lithium iron phosphate
­(LiFePO4). Recently, researchers have been trying to develop
a cost effective materials such as vanadium pentoxide ­(V2O5)
[1–3], manganese oxide ­(MnO 2) [4–7], titanium oxide
­(TiO2) [8–14] and graphite to use as anode materials in Li-
ion batteries. However, carbons have been most commonly
used anode material in lithium ion batteries. This material
has good performance, but it is expensive. In recent years,
extensive research has been started on the development of
spinel lithium titanate as an alternative anode material for
Li-ion batteries because of their excellent safety features and
longer lifetime.
Lithium titanate anode provides a number of major
advantages more than its carbon counterpart, for e.g. lithium
titanate based batteries can be charged quickly (≈ 10 min),
because of its negligible change in its volume during charge/
discharge process. Lithium titanate exhibits a flat and rela-
tively high lithium insertion-extraction potential plateau
at around 1.55 V, its theoretical capacity is 175 mAhg−1

13
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[15–19] which is higher reduction potential of most organic
electrolytes, showing good capacity preservation potential
compared with other graphite based anode materials. How-
ever, owing to its low electrical conductivity, the lithium
titanate anodes exhibit a poor rate capability. The invention
of ­Li4Ti5O12 anode material is inexpensive environment-
friendly to the society [20–26]. The lithium titanate have
been prepared by several methods such as hydrothermal,
electrospinning, sol–gel process [27–29], spray pyrolysis
water burning [30], microwave synthesis [31–33], solid sate
reaction [34, 35], solvothermal process [36] and computa-
tional methods [37, 38]. In this study, we report the prepara-
tion of lithium titanate nanopowder by peroxide route. The
reported method is promising alternate to prepare materials
for large scale applications.
2 Experimental section
2.1 Material preparation
All chemicals were of analytical grade and used without any
further purification. The chemicals used during synthesis
were titanium oxysulfate ­(TiOSO4·xH2O, > 29% Sigma-
Aldrich, USA), lithium hydroxide monohydrate (LiOH·H2O,
99% Himedia, Mumbai, India), hydrogen peroxide ­[H2O2,
30–32% Nice Chemical (P) Ltd, Kerala, India]. The lithium
titanate was prepared by solution growth technique. Firstly,
the titanium oxysulfate ­(TiOSO4·xH2O) was dissolved in 1:1
ratio (20 ml) double distilled water and ethanol solution.
The lithium hydroxide monohydrate (LiOH·H2O) solution
was prepared by dissolving it in the similar ratio of water
and ethanol. Then, the lithium hydroxide solution was added
into the prepared titanium oxysulfate solution. The reaction
mixture was continuously stirred for 2 h and subsequently
a white color colloidal mixture was obtained. Further, one
drop of assay 30% ­H2O2 was added into the colloidal mix-
ture and it ultimately end up with a formation of yellow
color precipitate. Then, the obtained yellow precipitate was
washed with deionized water for several times to remove the
unreacted chemical species in the mixture. The precipitate
was collected and dried at 80 °C for 6 h in hot air oven.
Finally, synthesized powders were sintered at 700 °C for 1 h,
2 h, 3 h, and 4 h and the samples are denoted as LT1, LT2,
LT3 and LT4, respectively.
2.2 Materials characterization
The X-ray diffraction (XRD) studies of all the samples were
analysed using (Xpert-PRO PANalytical) X-ray diffractom-
eter with monochromatic CuKα—radiation (λ = 1.5406 Å).
FT-IR spectra of the sample was recorded on a (Thermo
Nicolet 380, USA) spectrometer using a KBr pellet
13
Journal of Materials Science: Materials in Electronics
technique in the range of 4000–400 cm−1. The particle size
was measured by Microtrac S3500 particle size analyzer.
Micro Raman analysis of our samples was carried out using
the Princeton Acton SP250, Raman spectrometer wave
length 532 nm. Thermogravimetric analysis (TG/DTA) was
carried out using a Rigaku Thermo plus TG8120 analyzer
under air flow condition with a ramping rate of 10 °C min−1.
The SEM–EDX was observed using JEOL JSM-6360LV at
an accelerating voltage of 30.0 kV. X-ray photoelectron
spectroscopic analysis (XPS) (VG Scientific ESCALAB
210; Mg-Ka, 15 kV, 18 mA) was also carried out for the
sintered samples.
2.3 Fabrication of electrodes
1.3504 g of lithium titanate and 0.9079 g of carboxyme-
thyl cellulose (CMC) were taken in the porcelain dish and
mixed well with few drops of distilled water. 0.0966 g of
polyvinyldene fluoride (PVDF) binder was also added into
the above mixer and then the mixture was homogeneously
mixed manually with the aid of spatula. The paste is coated
on the aluminum foil substrate using the doctor blade tech-
nique. Then the electrode was dried in oven at 75 °C for 1 h.
Lithium foil was used as counter electrode and polypropyl-
ene was used as the separator. 1 mol l−1 ­LiPF6 was dissolved
in a mixture of ethylene carbonate, dimethyl carbonate and
diethyl carbonate (EC: DMC: DC = 1:1:1 v/v) and used as
the electrolyte. The cell was assembled inside the glove box
under the argon atmosphere. Galvanostatic charge/discharge
cycle test was carried out for all the assembled cells at ambi-
ent temperature with constant current mode (0.1 mA) up to
1.5 V for charging and up to 2 V for discharging.
3 Results and discussion
3.1 Thermogravimetric analysis
The dehydration process of the lithium titanate nanopow-
der was monitored by Thermogravimetric analysis. Figure 1
shows TG/DTA curve of as prepared sample. From the TG
curve, the first weight loss about 15.8% occurred between
room temperature and 185 °C, presenting endothermic peak
at 72.47% (DTA). The weight loss was mainly attributed due
to the removal of moisture/water molecules from the sample.
In the temperature range from 185 °C to 345 °C, a further
weight loss about 11% corresponding to the exothermic peak
at 120 °C in the DTA curve, is due to the volatilization of
carbon present in the ethanol. Further, progressive phase
transformation from orthorhombic to cubic spinel LTO was
accompanied by 5% of weight loss which is associated with
an exothermic peak at 440 °C in the DTA curve. A weight
loss (6%) of L
­ i4Ti5O12 by solid state reactions was observed
Journal of Materials Science: Materials in Electronics
Fig. 1  TG/DTA of as-prepared sample
at 440–645 °C in TG curve. There is no decay or any further
phase transformation when the temperature is raised upto
800 °C. Instead, there is a straight line which clearly dem-
onstrates the good stability of lithium titanate. Hence, it is
decided that the optimum annealing temperature is 700 °C
and the as prepared sample were annealed at 700 °C for vari-
ous time period (1 h to 4 h).
3.2 XRD analysis
Figure 2 shows the XRD patterns of the synthesized pow-
der. The XRD pattern of the sintered sample at 700  °C
for 1 h is shown Fig. 2a. The XRD pattern shows peaks
belong to L
­ i4Ti5O12, along with anatase T
­ iO2 (*). The pres-
ence of ­TiO2 may be due to the composite nature of the
Fig. 2  XRD patterns of samples calcined at 700  °C for (a) 1  h, (b)
2 h, (c) 3 h and (d) 4 h
obtained nanopowder. Further on increasing the time period,
(Fig. 2b–d) the pure L ­ i4Ti5O12 is obtained and the impurity
phase of ­TiO2 disappears. The peaks at 18.42, 35.63, 43.29,
47.40, 57.28, 62.86, 66.11 and 79.34 was observed and those
peaks are appeared owing to the crystalline planes of face-
centered cubic phase ­(Li4Ti5O12) assigned to (111), (311),
(400), (331), (333), (440), (531), and (444) crystalline planes
with Fd3m space group in accordance with JCPDS card no:
49-0207 suggesting the pure phase of the synthesized prod-
uct [39]. The time dependant peak intensity was gradually
increased, it is clearly indicated the pure ­Li4Ti5O12 crystal-
line nanopowder was achieved in 4 h. The average crystallite
size of the sintered samples was calculated by using Scher-
rer’s equation and the sizes are ca. 36, 43, 46 and 56 nm for
1 h, 2 h, 3 h and 4 h calcined samples, respectively. Thus,
it is inferred that the sintering temperature as well as the
sintering hours plays an important role for obtaining desired
crystallinity.
3.3 FT‑IR analysis
Figure 3a–d shows FT-IR spectra of LT1, LT2, LT3 and LT4
nanopowder and the peaks were observed at 491, 665 and
870 cm−1. The appeared peaks are attributed to the sym-
metric stretching vibration of octahedron groups. The peaks
located in the range of 400–900 cm−1 reveal the symmetric
stretching vibration of octahedron groups [­ TiO6] [40–42].
The peaks at 1432 and 1503 cm−1 represents antisymmetric
stretching vibration of ­CO32− anions, due to absorbance of
­CO2 molecules on the surface of the samples. Further, the
peak at 1123 cm−1 can be attributed to the C–O absorption
stretching vibration band (zhu et al). A small absorption
peak at 1621 cm−1 is corresponding to the bending mode
of water which indicates the presence of hydroxyl groups
Fig. 3  FT-IR spectra of samples calcined at 700  °C for (a) 1  h, (b)
2 h, (c) 3 h and (d) 4 h
13

(–OH) in the samples [42]. It should be indicated that the
appearance of peak corresponds to OH group may be due to
the presence of moisture in the sample.
3.4 Raman spectra
Figure  4 shows the Raman spectra of the synthesized
­Li4Ti5O12 (LTO) samples sintered at 700 °C for 1 h, 2 h, 3 h
and 4 h. The Raman intensity was gradually increased while
increasing the sintering time from 1 to 4 h. There are four
vibration peaks observed in the Raman spectrum of lithium
titanate at 672, 423, 235 and 353 cm−1. The first three strong
bands are 672, 423 and 235 cm−1 could be assigned to the
characteristics of ­A1g, ­Eg and ­F2g modes, respectively. The
fourth weak intensity peak at 353 cm−1 could be assigned
to the characteristics of F­ 2g mode. It can be concluded from
the above results that the synthesized ­Li4Ti5O12 is exist in
the form of spinel structure ­(A1g + Eg + 2F2g). The charac-
teristic peak appears at 672 cm−1 indicates the presence of
the vibrations of Ti–O bonds in octahedral T ­ iO6. The peak
at 423 cm−1 indicates the presence of Li–O bonds in the
tetrahedral unit of ­LiO4 and octahedral unit of ­LiO6. The
characteristic peaks at 353 and 235 cm−1 could be assigned
to the O–Ti–O bending vibration in octahedron ­TiO6 and
Li–O stretching vibration in ­LiO6 octahedron unit [43–48].
3.5 SEM and EDX
Figure  5 shows SEM micrographs of the synthesized
­Li4Ti5O12 samples. Figure 5a shows the SEM micrograph of
LT1. Figure 3b shows the SEM image of LT2 and it reveals
the formation of nanospheres with agglomerateted particles.
The sample sintered for 1 h does not show the formation of
nanospheres. Figure 5c shows the SEM image of LT3 and
it is clearly shows the nanoporous morphologies. Figure 5d
Fig. 4  Raman spectra of samples calcined at 700  °C for (a) 1  h, (b)
2 h, (c) 3 h and (d) 4 h
13
Journal of Materials Science: Materials in Electronics
shows that the particles are arranged homogeneously. Fig-
ure 5b–d shows the SEM micrographs of LT2, LT3and LT4
samples and it clearly evinces the formation of nanospheres
morphologies. EDX spectra of lithium titanate nanopowder
were shown in Fig. 6. It clearly point out the presence of
titanium (Ti) and oxygen in an appreciable percentage. The
element of lithium (Li) was not observed, because lithium
is light weight metal and it is not possible to detect the pres-
ence by EDX spectra. However, the XPS studies clearly
demonstrate the presence of all elements including lithium
metal shown as shown in Fig. 7.
3.6 XPS spectroscopy
Figure 7 shows the XPS spectrum of ­Li4Ti5O12 nanopowder
sintered at 700 °C for 4 h. The XPS peaks were observed
at 60.0, 288.3, 462.4, 467.8 and 535.7 eV which are cor-
respond to the Li 1 s, Ti 2p, C 1 s and O 1 s, respectively.
XPS result clearly indicates the presence of Li, Ti, C and
Oxygen elements in LT4 sample. The previous reports
clearly pointed out the binding energy of Li 1 s, C 1 s cor-
responds to the peaks at 60.0 eV, 288.3 eV respectively [48,
49]. The peak for Ti 2p doublet was observed in the range of
462.4–467.8 eV with a spin orbit splitting of 5.4 eV, which
is in excellent concurrence with the results expected for
the ­Ti4+ oxidation state. The spin orbit splitting is 5.5 eV
because Ti 2p doublet peak was observed in the range of
458.2–467.7 eV which is one of the conformation for the
­Ti4+ oxidation state [50, 51]. The presence of oxygen-con-
taining groups on the surface of lithium titanate sample was
confirmed from the appearance of peak at 535.7 eV which
corresponds to the oxygen. The all elements including Li
were detected from XPS analysis. Hence, it can be con-
cluded that the formation of lithium titanate is possible from
the simple peroxo solution growth route.
3.7 Cyclic voltammetry
The electrochemical performance of the lithium titanate was
studied by cyclic voltammograms (cv) with potential win-
dow of 0.9–2.0 V (vs Li/Li+) and is shown in Fig. 8. There
is one pair of redox peaks, which is attributed to the redox
of ­Ti4+ / T
­ i3+ which is connected with lithium insertion/
deinsertion in the spinel ­Li4Ti5O12 lattice [51]. The well-
defined cathode and anode centered at 1.889 V and 1.284 V
respectively indicates a high crystallinity which agrees with
the result of XRD. The electrochemical reaction kinetics of
­Li+ insertion/deinsertion occurred between the electrode and
electrolyte. The shape of the voltammetry curve confirms
that the electrode maintains high reversibility and fast kinet-
ics in the ionic liquid medium.
Journal of Materials Science: Materials in Electronics

Fig. 5  SEM images of samples

calcined at 700 °C for a 1 h, b
2 h, c 3 h and d 4 h

3.8 Conductivity studies

Electrochemical impedance spectroscopy is a powerful

method of characterizing many electrical properties of
materials and interface with the electronically conducting
electrodes. It has become a well established technique to
study the electrode kinetics of anode and cathode materials
in lithium ion batteries. Figure 9 shows the AC impedance
spectrum of the coin cells with the ­Li4Ti5O12 anode. The
intercept impedance on the Z’ real axis represents the solu-
tion resistance. The impedance spectrum consists of semi-
circle region at high-frequency and slope region at lower
frequency. The semicircle in the high-frequency region is
associated with the electron transfer and L ­ i+-ion intercala-
tion/de-intercalation process. The slope in the low-frequency
region can correspond to the Warburg resistance (W) reflect-
ing the ­Li+ ion diffusion within the solid matrix [52]. The
high frequency intercept of the semi-circle on the real axis
yields the internal resistance ­(Rs). An increase of ­Rs and ­Rct
can be observed after the cell being cycled. The former is
most probably caused by the increasing electrode/electrolyte
contact resistance, while the latter is due to the decrease in
Fig. 6  EDX spectra of samples calcined at 700 °C for 1 h and 4 h

13
 Journal of Materials Science: Materials in Electronics

Fig. 7  XPS spectrum of L
­ i4Ti5O12 (i) survey scan (ii) core spectra of (a) Li 1s, (b) Ti 2p, (c) O 1s and (d) C 1s

0.3

0.2

0.1
Current / mA

0.0

-0.1

-0.2

-0.3

-0.4
1.0 1.2 1.4 1.6 1.8 2.0
Potential / V

Fig. 8  Cyclic voltagrametric curve of lithium titanate nanopowder Fig. 9  AC impedance spectrum of lithium titanate nanopowder cal-
calcined at 700 °C for 4 h cined at 700 °C for 4 h

the area of electrodes induced by constant expansion and
contraction during the cycles. It is seen that the increase of
both ­Rs and ­Rct is not severe through the cycling process.
The conductivity of the L ­ i4Ti5O12 can be calculated from
the following Eq. (1):
l
𝜎=
Rba
l is the thickness of the electrode, a is the area of the
electrode, Rb is the bulk resistance of the electrode. The
conductivity of 2.62 × 10−8 S cm−1 was achieved for the
­Li4Ti5O12 electrode. This is acceptable value; it may pos-
sible to achieve the better storage capacity for ­Li4Ti5O12
electrode in ­LiPF6 medium.
(1)

13
Journal of Materials Science: Materials in Electronics

a b
2.1 2.2

2.0
2.0 th
----- 4 Cycle
rd
1.9 th ----- 3 Cycle

Voltage (V)
----- 4 Cycle
Voltage (V)

nd
rd
----- 3 Cycle 1.8 ----- 2 Cycle
st
1.8 nd
----- 2 Cycle ----- 1 Cycle
st
----- 1 Cycle
1.7 1.6

1.6
1.4

1.5
0 20 40 -1
60 80 0 20 40 60 80 100
Capacity (mAh g ) Capacity (mAh g )
-1

Fig. 10  Charge –discharge curves of a lithium titanate (calcined at 700 °C for 4 h), b Lithium titanate/graphite modified anodes in ­LiPF6 electro-
lyte

3.9 Electrochemical studies ­Li4Ti5O12 has nanosphere like morphology. FT-IR spectros-

Galvanostatic charging/discharging cycle test was carried out
for the anodes obtained from L­ i4Ti5O12 (LT4) and L
­ i4Ti5O12/
graphite composite materials at ambient temperature with
constant current mode (0.1 mA) up to 1.5 V for charging
and up to 2 V for discharging. The charge/discharge curves
of LT4 and LT4/graphite composite anodes are shown in
Fig. 10a, b. The LT4 anode have shown the reversible dis-
charge capacities of 83.52, 74.21, 72.92 and 71.9 mAhg−1
in the 1st, 2nd, 3rd and 4th cycles, respectively. The LT4/
graphite composite anode have shown the discharge capaci-
ties of 91.33, 87.64, 87.64 and 87.47 mAhg−1 in the 1st,
2nd, 3rd and 4th cycles, respectively. Furthermore, we could
observe the ­Li4Ti5O12 material retained low columbic effi-
ciency of 87% after 4th cycle and this may due to the dis-
solution of Ti ions in electrolyte. The composite materials
have shown higher columbic efficiency i.e. 100% at the 4th
cycle. From these results higher electronic conductivity,
enhanced columbic efficiency, excellent specific capacity
of the ­Li4Ti5O12/graphite material was observed [53, 54].
Therefore, excellent ­Li4Ti5O12/graphite electrode materials
can deliver excellent performance in Li ions storage and it
assure as a potential low cost anode materials for for Li-ion
batteries.
4 Conclusions
We have successfully synthesized novel bimetal oxide com-
posite of ­Li4Ti5O12 by peroxo route. Crystallite sizes were
in the range of 36, 43, 46 and 56 nm for LT1, LT2, LT3 and
LT4 samples, respectively. SEM observation revealed that
copy confirms the presence of symmetric stretching vibra-
tions of Ti–O bond. The oxidation state of L­ i4Ti5O12 was
determined from XPS studies. The storage capacity values
obtained for ­Li4Ti5O12 anode and ­Li4Ti5O12/graphite com-
posite anode were 83.52 and 91.33 mAhg−1, respectively in
1 M ­LiPF6.
Acknowledgements  The authors express their thanks to Himadri
Chemicals & Industries Ltd, Kolkata, India for financial support.
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