Electrochimica Acta 120 (2014) 226230

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Highly dispersed copper nanoparticle modied nano Li4 Ti5 O12 with
high rate performance for lithium ion battery
Chongling Cheng a , Hongjiang Liu b, , Xin Xue b , Hui Cao c , Liyi Shi a,b,
a
b
c

Nano-Science & Technology Research Center, Shanghai University, P. R. China

college of science, Shanghai University, P. R. China
Shanghai Aerospace Power Technology Co. Ltd, P. R. China

a r t i c l e

i n f o

Article history:
Received 27 July 2013
Received in revised form 9 December 2013
Accepted 9 December 2013
Available online 24 December 2013
Keywords:
Lithium ion battery
Lithium titanate
Copper nanoparticles
High electric performance
Agglomeration

a b s t r a c t
We report a simple strategy to prepare Li4 Ti5 O12 /Cu nanoparticles as an anode material for high rate
lithium ion batteries. The copper nanoparticles are highly dispersed on the surface of Li4 Ti5 O12 through
hydrothermal process and a short post -annealing. X-ray diffraction, Field-emission scanning electron
microscopy and transmission electron microscopy are performed to characterize their structures and
morphologies. The cyclic voltammetry, galvanostatic charge/discharge and alternate current impedance
are used to evaluate their electric performance. Compared to pure Li4 Ti5 O12 , the Li4 Ti5 O12 /Cu composites
has high rate capability, capacity retention and excellent cycling performance. The results show that
copper nanoparticles enhance the electric conductivity of Li4 Ti5 O12 /Cu, and prevent agglomeration.
Crown Copyright 2013 Published by Elsevier Ltd. All rights reserved.

1. Introduction
The utilization of conventional energy source such as oil and
coal has caused extensive environment problem, thus the development of clean energy become an essential issue for human beings
[13]. Recently, considerable efforts has been made to develop
high performance lithium ion batteries (LIBs) for new applications including electric vehicles (EVs) and energy storage station
(ESS) because of its long cycle life, high energy density and ecofriendliness[4,5]. However, the stability and safety of LIBs are the
key factors, limiting the lithium ion batteries largely commercially
used in these elds[6,7]. To smooth away obstacles in large scale
applications of LIBs, extensive work has been done to exploit some
novel electrode materials with larger lithium ion storage at high
rate.
The spinel Li4 Ti5 O12 (LTO) is one of the most potential materials
that might solve these problems and broaden its application elds
owing to its inherent advantages. The spinel LTO material with a
theoretical capacity of 175 mAhg1 has excellent lithium ion insertion/deinsertion reversibility within the voltage range from 2.5 V to
1.0 V [8,9]. Compared to other anode materials, LTO has a very at
voltage plateau at around 1.55 V (vs. Li/Li+ ), which is higher than
the reduction potential of most cathode materials. This refrains
LTO electrode from some crucial problems caused by undesirable

Corresponding authors. Tel.: +86 21 66136069; fax: +86 21 66136038.

E-mail addresses: hjliushu@hotmail.com (H. Liu), shiliyi@shu.edu.cn (L. Shi).

electrolyte decomposition that occurs at reductive potentials under

1 V (vs Li/Li+ ) [10]. Therefore, it can avoid forming solid electrolyte
interphase (SEI) lm,which results in low coulombic efciency
especially in the rst formation cycle due to a signicant loss
of lithium ion [11].The exceptional durability owing to negligible volume expansion/contraction <1% is also the distinguishing
performance of the LTO[12]. In contrast, graphite experiences 13%
volume change during full charge/discharge[13]. Thus, the LTO has
better excellent safety and stability than the graphite, which has
been widely used as cathode materials for lithium ion battery[14].
The major disadvantage of LTO is its low electronic conductivity
(<1013 S cm1 )[15]. There have been many reports on improving
the electronic conductivity including surface coating with conductive material[16,17], nanocomposite formation with multi-walled
carbon nanotubes[18,19], metal doping[2022] and nitridation on
the surface[23,24]. The use of nanostructure is another approach to
improve electrical conductivity by signicantly shortening the electronic transportation path. In addition, the nanostructures[2527]
also enable facile transport of the electrolyte to the surfaces
of electrochemical active materials, resulting in rapid charge
transfer reactions due to the high electrode-electrolyte interface area, and short lithium diffusion path[28]. Recently, the
synthesis and electrochemical investigation of nanostructured
LTO materials including 1D nanorods[29], 2D nanosheets[30,31],
hollow spheres[32] and assembled microspheres[32] have been
reported. However, the nano-sized materials also have some disadvantages, such as low packing density[33] and low volumetric
density.

0013-4686/$ see front matter. Crown Copyright 2013 Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2013.12.049

2. Experimental
2.1. Preparation of pure LTO and LTO/Cu
All the reagents were purchased from China National Medicines
Corp., Ltd without any purication.
LTO/Cu was prepared by hydrothermal method. 0.1010 g TiO2
(anatase), 0.502 g LiOHH2 O were mixed in 30 ml deionized water
and magnetically stirred about 30 min. The mixture was transferred
into a Telfon-lined autoclave and then maintained at 180 C for
24 h. The precipitate collected from the bottom of the autoclave by
centrifugation was the precursor of Li4 Ti5 O12 . After washing and
centrifuging more than 3 times with deionized water and absolute ethyl alcohol, the product was dried in 80 C oven. Then, 1 g
precursor of Li4 Ti5 O12 , 0.05 g ascorbic acid and 0.01 g CuNO3 3H2 O
were mixed in 10 ml ethyl alcohol absolute and magnetically stirred
about 2 h. Finally, the calcination of product was carried out at
750 C for 2 h in a nitrogen atmosphere to obtain the Li4 Ti5 O12 /Cu
material. The pure Li4 Ti5 O12 was prepared in a similar manner.
2.2. Materials characterization
The phase identication was characterized by powder X-ray
radiation
diffraction (XRD) using D/max 2200 with Cu K (1.54 A)
in the 2 range of 10-70 . The structures and morphologies of the
LTO and LTO/Cu compounds were characterized by scanning electron microscopy (SEM) using JSM-6700F (Japan) and transmission
electron microscope (TEM) using JEM-2010F (Japan). The elemental
compositions of these samples (Ti, Li, Cu) were tested by inductively coupled plasma optical emission spectroscopy (ICP) using
iCAP 6300 (Thermo-Fisher Scientic, UK).
The electrochemical properties were measured by a twoelectrode electrochemical cell. The working electrodes were
prepared by mixing 80 wt% active materials, 10 wt% Super P and 10
wt% polyvinylidene uoride dissolved in N-methylpyrrolidinone.
The resultant slurry was spread uniformly on copper foil, and dried
at 120 C under vacuum for 12 h. The coin cells (2016) were assembled in an argon-lled glove box using Li-foil as counter electrode,
Celgary2400 as separator, and 1 M LiPF6 in a 1:1:1 (volume) mixture of ethylene carbonate, dimethyl carbonate and ethylmethyl
carbonate as the electrolyte. The cells were tested at various current densities using a LAND-CT2001A cell test instrument with
voltage window of 1-2.5 V (vs. Li/Li+ ) at room temperature. After
cycles nished, the electrode slices were taken out of the coin,
washed with absolute ethyl alcohol and dried in the glove box.
Cycle voltammograms were recorded from 1.0 v to 2.5 v at
different scanning rates using a CHI660d electrochemical workstation, and the AC impedance spectrum was measured by CHI660d
Impedance Analyzer in the frequency range from 10 mHz to 100
KHz with a potential perturbation at 10 mV. All the LIBs measurements mentioned above are based on the total mass of the active
material.

(200)

Cu

(440)
(531)

(333)

(331)

LTO/Cu

* Cu

* (200)

(222) (311)

(111)

a
Intensity/a.u.

Owing to its high conductivity, copper is one of the most widely

used doping metals for electrode materials. It was reported that
depositing (mixing) copper on (with) electrode materials (e.g.
LiCoO2 , LiMn2 O4 , LiFePO4 ) [3436] could greatly enhance the electronic conductivity as well as improve the high-rate capability.
Many experiments have proved that the addition of copper could
improve the charge/discharge capacity of the LTO and electronic
conductivity without loss of volumetric power density [37,38].
Here we report a facile method to prepare the LTO/Cu which
exhibits high reversible high-rate capability with good cycling performance. In order to understand the effect of additive copper, we
also research the electrode slices.

227

(400)

C. Cheng et al. / Electrochimica Acta 120 (2014) 226230

LTO

10

20

30

40

2/degree

50

60

70

49

50
51
2/degree

52

Fig. 1. (a) XRD patterns of pure LTO and LTO/Cu composites, (b) local view of LTO/Cu
in the 2 rang of 49-52 .

3. Results and Discussion

The XRD spectra of LTO and LTO/Cu composite were shown
in Fig. 1a. The pure LTO had several sharp diffraction peaks at
2 = 18.4 , 35.6 , 43.3 , 47.4 , 57.2 , 62.8 and 66.1 , corresponding to (111), (311), (400), (331), (333), (440), and (531) planes of
a face-centered cubic spinel Li4 Ti5 O12 with the Fd3 m space group
(JCPDS Card No.049-0207), respectively. The diffraction peaks of
LTO/Cu were almost the same as the pure LTO, except that the
peak at 2 = 50.43 , which could be ascribed to the reection of copper (JCPDS Card No.04-0836) in the magnied prole (Fig. 1b).The
result proved that we successfully synthesized LTO after adding
cooper .And the ICP result shows that the ratio of Cu to LTO was
only 1:100.
The typical TEM and HRTEM images of the LTO/Cu were shown
in Fig. 2. The nano-sized copper nanparticles with average diameter of 15 nm were uniformly dispersed on the surface of the LTO
nanoparticles, which was agree with the result that calculated by
Scherrers formula. Fig. 2b showed that the lattice fringe of copper
and LTO were interlaced. The copper nanoparticles highly dispersed
and closely bonded on the surface of LTO instead of adhesion, may
owing to the effect of hydrothermal and post-annealing, The SEM
images of pure LTO and LTO/Cu were shown in Fig. 3a and Fig. 3b.
Their morphologies were almost the same. The particle diameters
of the LTO/Cu and pure LTO were both in the range of 100 200 nm.
These results demonstrated that additive copper had little inuence
on the crystal structure and morphology of spinel LTO.
Fig. 3c and Fig. 3d showed the SEM images of the electrode slices
after cycling. It could be seen that the dispersion of LTO/Cu was
better than pure LTO. And the LTO particles had an obvious agglomeration after cycling, which would lead to the decrease of surface
area contacted with the electrode, affecting electrical conductivity.
These results indicated that addition of copper could prevent the
agglomeration of the LTO particles and improve the LTO stability.
The reason why LTO/Cu was more stable maybe that the surface
energy of the LTO was reduced through the copper dispersed on
the surface of the LTO nanoparticles. Therefore, the contact angels
test was done to prove this assumption. As showed in Fig. S1, the
contact angels of the LTO electrode(less than 90 ) was larger than
the LTO/Cu electrode (more than 90 ), which proved the surface
energy of LTO/Cu was lower than LTO.
LTO/Cu composite and pure LTO were subjected to cycling at different charge/discharge rates. Cycle performances of LTO/Cu and
pure LTO were shown in Fig. 4. The capacity of LTO/Cu was 167,
155, 148,133 and 117 mAhg1 at 1 C, 2 C, 5 C, 10 C and 20 C, and the
capacity of LTO was 139, 132, 124,118 and 99 mAhg1 at 1 C, 2 C, 5 C,
10 C and 20 C, respectively. All of them showed excellent cycle performance and nearly 100% coulomb efciency. As expected, with
the increase of discharge currents, the capacities of both electrodes
decreased. However, the LTO/Cu electrode exhibited better cycle

228

C. Cheng et al. / Electrochimica Acta 120 (2014) 226230

Fig. 2. TEM and HRTEM images for LTO/Cu.

performance and capacity retention than the pure LTO electrode.

The decrease in the capacity of LTO after cycling several times, may
be due to the electric conductivity of the electrode decreased, serious polarization and easily slipping from the copper foil resulting
from its agglomeration. In order to test the stability of the LTO/Cu,
the lithium ion battery was cycled 50 times at each stage to carry
out cycle testing. The discharge capacity stayed very stable in each
stage. After cycling 250 varying charge/discharge cycles, the capacity was still 165.2 mAhg1 with a negligible discharging capacity
loss when it was discharged at 1 C again. On the contrast, the stability of LTO was not as well as LTO/Cu, when they charged/discharged
at 10 C and 20 C. In other words, the LTO/Cu electrode exhibited better cycle performance than the pure LTO electrode. The improved
cycling stability may be attributed to higher electronic conductivity

and better ionic conductivity owing to the stability of the LTO/Cu

particles by adding copper. In a word, the copper could ameliorate
the electric performance of the LTO/Cu during the charging and
discharging stages.
The charge/discharge curves of the LTO/Cu electrode cycled
under different current densities between the voltages limits of 12.5 V were shown in Fig. 5. Flat charge/discharge plateaus at about
1.55 V were observed, suggesting that the copper had no inuence
on the charge/discharge plateaus.
To understand the improved high-rate performance after
introducing copper, LTO and LTO/Cu electrodes were also characterized by cyclic voltammograms (CV) within a potential window
of 1.0-2.5 V (vs. Li/Li+ ). It was widely known that the shapes
of redox peaks in a CV curve could reect the electrochemical

Fig. 3. SEM images for (a) LTO, (b) LTO/Cu, and (c) LTO after cycles, (d) LTO/Cu after cycles. The inset shows the high magnication (5) images of the electrodes after cycles.

C. Cheng et al. / Electrochimica Acta 120 (2014) 226230

229

300
LTO/Cu
LTO

Capacity/mAhg-1

250
200

1C

2C

150

5C

1C
10 C

20 C

100
50
0
0

50

100 150 200

Cycle number

250

300

Fig. 4. Cycle performances for the LTO and LTO/Cu. Both batteries are cycled at 1, 2,
5, 10 and 20 C for both electrodes.

2.4

Cell potential/V

2.2
2.0
1.8
1.6
1.4
1.2

20 C

1C

1.0
0

20 40 60 80 100 120 140 160 180

Capacity/mAhg-1

Fig. 5. Discharg/charge curves of the LTO/Cu samples. Charged/discharged rates

range from 1, 2, 5, 10 C and 20 C.

reaction kinetics of lithium ion insertion/deinsertion. Together

with the transfer of electron, the diffusion rate of lithium ions
also played an important role in accelerating lithium ion insertion/extraction during the charging/discharging process. Generally,
sharp and well-resolved peaks implied that lithium ions insertion/deinsertion was accelerated, whereas a broad peak suggested
a sluggish process, as shown in Fig. 6. The CV curves of LTO/Cu
were broadened along with increasing scan rate. The distance
between oxidation and reduction peaks became large, meaning
that polarization became more serious at the same time. For the

0.008

LTO
LTO/Cu

Current/A

0.004
0.000

-0.004
-0.008
-0.012
-0.016
1.0

1.2

1.4

1.6 1.8 2.0

Cell potential/V

2.2

2.4

Fig. 6. Cycle voltammograms of cells using the LTO and LTO/Cu sample as electrode
at 0.2, 0.5, 1, 2, 5, 10 mvs1 .

Fig. 7. Electrochemical impedance spectra of pure LTO and LTO/Cu nanocomposite

electrodes at the voltage of 1.55 V.

diffusion-limited process, the peak current was proportional to

the square roots of the scan rate (v1/2 ) as the following equation:
ip = (2.69 105 )n3/2 AD1/2 Cv1/2 . Where ip was the peak current; n
was the number of transfer electrons; A was the surface of the electrode; D was the diffusion coefcient, C was concentration of the
reactant and v was the scan rate. It was obvious that the slope of the
ip vs. v1/2 curve presents the lithium ion diffusion coefcient. If the
slope was higher, the diffusion coefcient would be higher, which
proved that the insertion/extraction process was accelerated[39].
Fig. 6 showed the CV curves of the LTO and LTO/Cu sample as electrode at scan of 0.2, 0.5, 1.0, 2.0, 5.0 and 10 mvs1 . The LTO/Cu
showed sharper peak and higher slope than the LTO in both images,
indicating that the lithium ions were better transported in this electrode and the lithium diffusion coefcient was faster than the pure
LTO electrode. The distance between the oxidation peak and reduction peak of the LTO/Cu was closer than the LTO, which meant that
LTO/Cu was less polarized than LTO. It was also the reasons why
the LTO/Cu had better high rate performance.
The EIS spectra and impedance data analyzed on the basis of
the equivalent circuit were shown in Fig. 7, in which Rs was the
resistance of the electrolyte and the charge transfer resistance
(Rct ) represented the kinetic resistance of charge transfer at the
electrode/electrolyte interface or intrinsic charge transfer resistance of the electrodes. Table 1 presented parameters tted by
Zview software[40]. The charge transfer resistance of the LTO/Cu
electrode (Rct = 132 ) was signicantly lower than the pure LTO
electrode (Rct = 259 ), and the same for the exchange current density (i0 = RT/nFRct ). The faradaic reaction was controlled by transfer
of both the electronic conductivity and the lithium ion diffusion
coefcient. As shown in Table 1, the LTO/Cu had higher i0 than
LTO, which proved that it had better performance, likely because
of better electric conductive and lower polarization. The LTO/Cu
with smaller interface charge transfer resistance and great high rate
performance would draw our attention to nd out the reasons.
The electrodes of the lithium ion battery stored/released electrical energy by insertion/deinsertion of lithium ions when electrons
went through the electrode material. Therefore, the diffusion rate
of lithium ions could be evaluated based on a diffusion equation
relating to achieving high rate charge/discharge reaction. The diffusion rate for lithium ion can be estimated based on a diffusion
equation relating to two-dimensional Brownian motion, r= (Dt)
Table 1
Impedance parameters calculated from equivalent circuits.
Electrodes

Rs /

Rct /

i0 /mA cm2

LTO/Cu
LTO

4.3
13.3

132
259

0.19
0.10

230

C. Cheng et al. / Electrochimica Acta 120 (2014) 226230

1/2 ,

where r was the diffusion distance, D was the diffusion coefcient, and t was the time. Apparently, the lithium ion diffusion
length depended on the particles size. The large particles tended to
decrease diffusion rate. As a result, polarization was increased during charge/discharge rate, which led to poor charge/discharge-rate
capability. In contrast, smaller particles could shorten the lithiumion diffusion path as well as increase active electrode area, thus
improving the rate capability[41].It was also well known that the
LTO was a semiconductor, the conductivity of LTO was one of main
factors determining its electric performance. In summary, the size
of the nanoparticles was important to the electric performance of
the LTO, which would not only affect the lithium ion diffusion, but
also electric conductivity of the LTO. In this work, the agglomeration of LTO was adequately prevented by adding copper to form
LTO/Cu composites, which resulted in faster lithium ion diffusion
coefcient and better electric conductivity. Moreover, more surface area of LTO/Cu provided a less electrode/electrolyte resistance
during the cycling process. And the electric conductivity of LTO/Cu
improved also owing to the copper nanoparticles with high inherent electric conductivity, which was highly disappeared on the
surface of LTO. This result strongly indicated that the copper was
the important factor that would affect the performance of LTO.
4. Conclusions
A simple hydrothermal method combined with calcination was
used to synthesize nanostructure LTO/Cu composites. When evaluated as anode materials for lithium ion battery, the LTO/Cu
exhibited excellent high rate capacity and high stability for lithium
storage. The capacity of the LTO/Cu composite was about 167
mAhg1 at 1 C and 117 mAhg1 at 20 C. Its alternating current
impedance reduced from 259  to 132 . The superior electrochemical performance of the LTO/Cu electrode was due to the
copper improving the electric conductivity and structure stability.
Such nanosized LTO/Cu could be a promising anode material for
high-rate lithium ion batteries.
Acknowledgements
This work was nancially supported by Shanghai Science and
Technology Committee (11160704000 and 12nm0500100). The
authors also thank Professor Xueguang Wang for discussion and
Professor Weijun Yu for his help in TEM characterization.
Appendix A. Supplementary data
Supplementary material related to this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.electacta.2013.
12.049.
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