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Nickel oxide crystalline nano akes: synthesis,
characterization and their use as anode in lithium-ion
batteries
Majid Ahmadi1, Reza Younesi2, Tejs Vegge2 and Maxime J-F Guinel1,3
1
Department of Physics, College of Natural Sciences, University of Puerto Rico, PO Box 70377,
San Juan, PR 00936-8377, USA
2
Department of Energy Conversion and Storage, Technical University of Denmark,
Frederiksborgvej 399, PO Box 49, DK-4000 Roskilde, Denmark
3
Department of Chemistry, College of Natural Sciences, University of Puerto Rico, PO Box
70377, San Juan, PR 00936-8377, USA
E-mail: maxime.guinel@upr.edu

Received 12 January 2014, revised 20 February 2014

Accepted for publication 6 March 2014
Published 2 April 2014
Materials Research Express 1 (2014) 025501
doi:10.1088/2053-1591/1/2/025501

Abstract
Nickel oxide crystalline nano akes (NONFs)only about 10 nm widewere
produced using a simple and inexpensive chemistry method followed by a short
annealing in ambient air. In a rst step, Ni(OH)2 sheets were synthesized by
adding sodium hydroxide (NaOH) drop-wise in a Ni(NO3)2 aqueous solution
that was then sonicated for up to 60 min, washed and vigorously stirred over-
night in deionized water. In a second step, the products of this reaction were
annealed in ambient air in the temperature range 285450 C producing the
desired NONFs. The products were characterized using x-ray diffraction,
scanning electron microscopy and high resolution transmission electron micro-
scopy including electron diffraction and electron energy-loss spectroscopy.
Electrochemical investigations showed that anodes made of these NONFs pro-
vided signicantly higher discharge capacities (70 to 100% higher) compared to
commercial nanometric NiO nanopowder used under the same conditions.
Moreover, these NONFs had higher initial capacity retentions at both low and
high current densities compared to the same NiO nanopowder.

S Online supplementary data available from stacks.iop.org/MRX/1/025501/

mmedia

Keywords: lithium ion battery, electrochemistry, conversion reaction, electron

microscopy

Materials Research Express 1 (2014) 025501

2053-1591/14/025501+12$33.00 2014 IOP Publishing Ltd
Mater. Res. Express 1 (2014) 025501 M Ahmadi et al

1. Introduction

Nickel oxide (NiO) is a p-type semiconductor with a wide band gap (3.64.0 eV) [12] and
good electronic, optical and catalytic properties that may be used in a variety of applications: for
example, in pollutant clean-up [3], p-type dye sensitized solar cells (p-DSCs) [4], drug delivery
and MRI agents [5] because of its superparamagnetism [6] and also as an anode material in
lithium-ion batteries (LIB) [7, 8].
Metal oxides (MO) are widely studied as anode materials in LIB owing to their high
theoretical capacities, high specic energy and high volumetric energy density compared to
graphite anodes [912]. NiO has attracted considerable attention for its high capacity [13, 14],
environmental friendliness, low cost, and high volumetric energy density (at 6.67 g cm3, it has
about 5.8 times the volumetric energy density of graphite). Although NiO crystalline nano-
sheets and mesoporous NiO sheets (about 5 m thickness) have already been tested as anode
materials, they generally suffered from poor electronic conduction and capacity retention
performance [7, 15, 16]. However, two-dimensional (2D) structured materials provide i) larger
active surface areas, and ii) better stability against volume expansion [8]. These two properties
are key parameters for LIB because faster ion/electron transfer speeds and larger contact
interfaces between active materials and electrolyte can be achieved.
In this article, we report on a very simple, low temperature and inexpensive synthesis
method with no use of organic compounds to synthesize NiO nano-akes (NONFs). Our
method can therefore be easily scaled up for commercial production compared to others
[1721]. The intermediate Ni(OH)2 and nal products (NONFs) were characterized using
thermogravimetric analysis (TGA), x-ray diffraction (XRD), scanning electron microscopy
(SEM), high resolution transmission electron microscopy (HRTEM) and ultraviolet/visible
(UV/Vis) spectroscopy. Moreover, the electrochemical performance of our NONFs was also
tested as an anode material in LIB and compared to a commercial NiO nanopowder.

2. Experimental methods

2.1. Synthesis
The NONFs were produced using a simple and inexpensive chemistry method followed by a
short annealing in ambient air. In a rst step, sodium hydroxide (NaOH) 0.1 M was added drop-
wise to a 100 cc. nickel nitrate Ni(NO3)2 10 mM solution under vigorous stirring until the
pH reached 7.1. According to the Pourbaix diagram [22] for Ni2+ ions, increasing the pH to
above 7.0 results in Ni(OH)2 being the dominant species. The obtained solution was
ultrasonicated for up to 60 min and then stirred for 1 h. The solution was centrifuged and
washed several times. The product was transferred to 300 cc. deionized water for overnight
stirring (12 h). This solutionlime green in colorwas centrifuged and dried at 50 C in an
oven (in ambient air). Finally, the products were annealed between 285 and 450 C in a furnace
in ambient air, producing the NONFs.

2.2. Characterization
The phase(s) present in each product was determined using XRD (Siemens D5000
diffractometer with a Cu K radiation). TGA curves were recorded (SDTA 851, Mettler

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Mater. Res. Express 1 (2014) 025501 M Ahmadi et al

Toledo 10 C min1) in order to determine the proper heat treatment temperatures. The materials
were examined using a eld emission SEM (JEOL JSM-7500 F) and a HRTEM (JEOL JEM-
2200FS) operated at 200 kV. The compositions of the materials were determined using x-ray
energy-dispersive spectrometry (XEDS) in the SEM and the HRTEM. The electron energy-loss
spectra (EELS) were recorded in the HRTEM using the in-column Omega-type energy lter.
The NONFs were placed on interdigitated Pt/PtO electrode devices (dispersed in ethanol and
then allowed to dry) to record their currentvoltage (IV) and currenttime (It) characteristics.
The electrode separation distance was 20 m with an electrode nger length of 1 mm. A picture
of the actual device is displayed in gure S1 in the supplementary data as an inset. A high
internal resistance Keithley 2401 electrometer was used to record the data. UV/Vis absorption
spectra in aqueous solutions were recorded using a Varian Cary 500 spectrophotometer.

2.3. Electrochemical measurements

A pouch cell construction was used to assemble Li-ion cells in an argon-lled glove box with
oxygen and moisture levels below 2 ppm. A lithium foil was used as the counter electrode,
Whatman glass-ber sheets as the separator, and the NONFs as the working electrode. The
NONFs-based working electrodes were composed of the binders Super P carbon (lithium
battery grade, Erachem Comilog) and Kynar 2801 (Arkema) and NONFs in weight ratios of
80:10:10. For comparison, similar electrodes were made using commercial NiO nano-powder
(Sigma Aldrich) instead of the NONFs. Prior to the tests, the NiO electrodes were dried at
120 C overnight in a vacuum furnace, directly placed inside the glove box. A 1 M LiPF6 salt
was dissolved in ethylene carbonate:diethylene carbonate (EC:DEC) in (1:1) or (2:1) ratios and
used as the electrolyte. EC and DEC were purchased from Ferro, Purolyte, with water contents
10 ppm as measured by Karl Fischer titration. Galvanostatic tests were run by applying
current densities of 71.8 mA g1 or 718 mA g1 (based on the amount of NONFs in the
electrodes), corresponding to 0.1 C or 1.0 C current densities, respectively. The voltage window
was between 0.1 and 3.0 V.

3. Results and discussion

The TGA plot recorded from as-synthesized Ni(OH)2 (sample S1) is displayed in gure 1. Two
mass losses were observed: The rst one (I) occurred at about 50 C, corresponding to the
evaporation of adsorbed water molecules. The second one (II) occurred between 260 and
450 C and was due to the phase transition from Ni(OH)2 to NiO, corresponding to the mass
loss during the dehydration process. It coincided with the observed change in color from lime
green to black (see gure S2 in the supplementary data).
Accordingly, two samples were annealed with a ramp rate of 10 C min1 to T1 = 285 C
(sample S285) and T2 = 450 C (sample S450) for 90 min in air. Samples S285 and S450 were
no different and presented the same exact characteristics. The results obtained from sample
S285 are therefore presented in the supplementary data. The LIB tests were performed using
sample S450.
X-ray diffractograms recorded from samples S1 and S450 are displayed in gure 2. The
only phase present in sample S1 was indexed to hexagonal Ni(OH)2 with the P-3m1 space
group according to the JCPDS card No. 73-1520 with lattice parameters a = 0.3114 nm and

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Mater. Res. Express 1 (2014) 025501 M Ahmadi et al

Figure 1. TGA plot recorded from the as-synthesized material Ni(OH)2.

Figure 2. X-ray diffractograms recorded from samples S1 and S450. The inset shows a
picture of sample S1 diluted in water taken 30 d after the solution was last stirred.

c = 0.4617 nm. The inset shows a picture of sample S1 diluted in deionized water taken 30 days
after the solution was last stirred. After this long period, the materials did not yet settle.
The broadening of the (001), (011) and (012) peaks for Ni(OH)2 is due to the small grain
sizes. On the other hand, the (100) and (110) peaks were relatively sharp suggesting a growth in
the (xy) plane. This structure results in turbostratic disorder and large space between sheets. The
sheets are held together by non-covalent interactions allowing for the movement and trapping of
water between the sheets [23]. According to the Pourbaix diagram for Ni2+ in aqueous solution
[22], increasing the pH to 8 and then 12.5 results in the stable species changing from Ni2+ to
Ni(OH)2 and then [Ni(OH)3]1, respectively (see equation (1)). By adding NaOH (0.1 M) drop-
wise to a highly diluted nickel nitrate Ni(NO3)2 solution, Ni2+ ions slowly form Ni(OH)2
crystals coinciding with a reduction of the pH. The rate of growth of the Ni(OH)2 crystals in
solution is very slow leading to the formation of large area sheet-like structures (see gure 3(a)).
For sample S450, the XRD results showed it to be cubic NiO according to the JCPDS card
No. 78-0429 with lattice parameter a = 0.4177 nm and Fm-3 m space group. The broadness of
the peaks indicates small crystallite sizes. A typical crystallite size of about 9.3 nm was

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Mater. Res. Express 1 (2014) 025501 M Ahmadi et al

Figure 3. SEM images showing (a) as-synthesized Ni(OH)2 (Sample S1) and (b)
NONFs (Sample S450).

Table 1. Sizes of the NiO crystallites in sample S450, calculated using x-ray
diffractograms.
Normalized intensity
JCPDS card No. 78- Calculated (Scherrer) crystallite
(hkl)NiO Measured 0429 size (nm)
(111) 0.695 0.678 10.5
(200) 1.000 0.999 9.3
(220) 0.571 0.438 11.3
(311) 0.213 0.144 13.3

determined from the Scherrer equation using the (200) peak. The mean size of the crystal
domains was on average 11.1 nm when all peaks were considered. Note that the akes do not
have specic shapes. These results are all summarized in table 1. The change in the slope at
310 C in the TGA plot corresponded to a change in the rate of phase transition reaction from Ni
(OH)2 to NiO. XRD were similar for the sample annealed at 285 C (gure S3 in the
supplementary data).
Nickel hydroxide is formed according to the following reaction:
pH > 7
2NaOH (aq) + Ni ( NO3)2(aq) 2Na ( NO3)(aq) + Ni ( OH)2(s) (1)

and when annealed, dehydrates to nickel oxide according to:

Heating
Ni ( OH)2 NiO + H 2O (2)

SEM images recorded from the as-synthesized (sample S1) and the sample annealed at
450 C (sample S450) are displayed in gure 3. The image recorded from sample S1 (Ni(OH)2),
shown in gure 3(a), demonstrates the thinness of the sheets, which is in agreement with the
XRD. However, the NONFs samples were very ne akes and were difcult to image because
of its high band-gap (charging). XEDS recorded in the SEM (also conrmed in the HRTEM)
showed that the samples were pure, consisting of only O and Ni.

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Mater. Res. Express 1 (2014) 025501 M Ahmadi et al

Figure 4. (a) TEM image recorded from sample S1. The inset is a SAED recorded from
the area delimited by the red circle and indexed to hexagonal Ni(OH)2. (b), (c) HRTEM
images recorded from sample S2 (i.e. NONFs), with structure corresponding to cubic
NiO. Crystallographic directions are indicated. The inset in (c) is a FFT calculated from
the highlighted area (actually a Moir pattern) and indexed to the {100} family planes
of three distinct hexagonal Ni(OH)2 layers.

One TEM image and three HRTEM images recorded from sample S1 are shown in
gure 4. The TEM image shown in gure 4(a) demonstrates the thinness of the sheets.
The corresponding selected area electron diffraction (SAED) pattern was indexed to hexagonal
Ni(OH)2 which was in agreement with XRD patterns.
An HRTEM image is shown in gure 4(b), where two directions ([100] and [110]) are
indicated, corresponding to lengths of 0.270 nm and 0.156 nm, respectively. The electron beam
was along the [001] direction. It conrmed that the NONFs grew in the (xy) plane. A fast
Fourier transform (FFT) calculated from the selected area in the image of gure 4(c) was
indexed to the {100} family planes of three individual overlapping sheets, resulting in a Moir
pattern. They were each rotated by 30 around the z axis.

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Mater. Res. Express 1 (2014) 025501 M Ahmadi et al

Figure 5. Micrographs recorded from sample S450. (a) and (b) TEM images. The inset
in (a) is the corresponding SAED, indexed to cubic NiO. The inset in (b) shows one
NONF. (c) and (d) HRTEM images with directions and planes indicated. The inset in
(d) is an FFT calculated from the highlighted area and indexed to three sets of {220}
planes along the zone axis [111].

Two TEM and four HRTEM images recorded from sample S450 are shown in gure 5.
TEM and HRTEM images recorded from sample S285 are presented in gure S4 in the
supplementary data (results show that samples appeared similar).
The TEM images (gures 5(a) and (b)) and corresponding SAED pattern (see inset in
gure 5(a)) corresponded to the cubic NiO structure, in agreement with XRD. Two directions
([111] and [220]) are shown in the HRTEM image of gure 5(c) with d-spacing of 0.240 and
0.150 nm, respectively. The {111} (0.240 nm), {220} (0.150 nm) and {222} (0.120 nm) planes
are indicated on the image of gure 5(d). The inset is an FFT calculated from the highlighted
area. It was indexed to the {220} planes of three NiO crystals rotated by 10.5 around the
[111] axis. It formed Moir patterns in the images and conrmed that the dominant exposed
facets in NONFs were the {111} facets.
EEL spectra were recorded from few NONFs around the O K-edge and the Ni L2,3 edge
and are displayed in gures 6(a) and (b), respectively. EELS recorded from sample S285 were
the same and are presented in gure S5 in the supplementary data. Multiple scattering effects
can be ignored because the NONFs are very thin (on the order of several nm) and have little
effect on the energy loss near-edge structure (ELNES).

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Mater. Res. Express 1 (2014) 025501 M Ahmadi et al

Figure 6. EELS showing the O K-edge (a) and Ni L2,3 (b) recorded from NONFs
(sample S450).

The Ni L edge is split in 2p3/2 (L3) and 2p1/2 (L2) with their ratio expected to be 2:1
because of the statistical ratio of the 2p3/2(4 electrons) and 2p1/2(2 electrons). However, here the
ratio measured for our NONFs was 4:1. Leapman et al reported that this ratio can change
according to the atomic number and the d band occupancy and may vary between 1:1 and 4:1
[24]. In order to estimate the 3d occupancy number for the NONFs, the intensities of the L3 and
L2 were measured following the Pearson method [25]. Our calculations showed that the 3d
occupancy for Ni in NONFs is 8 (7.96). The O K-edge may also be affected by several factors
including the ejection of electrons into the continuum producing a saw-tooth shape, as well as
solid-state effects and transitions to unoccupied bound states creating ne structures in the edge
[26, 27]. The ELNES of the O K edge in transition MO is due to the crystal eld splitting of the
metallic orbitals into eg and t2g components, resulting in the EELS double-peak signature
[2830]. The positions of the peaks in the O K edge were 1.7, 7.3, 10.2, 16.5 and 32.1 eV (with
respect to 532.0 eV) as shown in gure 6(a). The rst two peaks are associated with the crystal
eld splitting (eg and t2g) and their separation (about 5.67 eV or 45 700 cm1) is related to the
crystal eld parameter.

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Mater. Res. Express 1 (2014) 025501 M Ahmadi et al

Figure 7. UV/Vis absorption spectra recorded from Ni(OH)2 (S1) and NONFs (S450)
dispersed in water.

The current versus voltage (IV) curves for the NONFs from sample S450 were recorded
and showed ohmic behavior with a slope of 4 106 V A1 (see gure S6 in the supplementary
data). The work function of this p-type semiconductor (NiO = 5.05.6 eV) [31] should be lower
than the work function of platinum (Pt 5.3 eV). The ohmic behavior in a Pt-NiO junction
allows for the easy transfer of electrons between Pt and NiO and can therefore be used in gas
sensing devices [32].
The UV/Vis absorption spectra recorded from samples S1 and S450 are shown in gure 7.
One peak was observed around 215 nm for as-synthesized Ni(OH)2 (sample S1). Annealing
resulted in the appearance of a peak at 285 nm. This peak has already been reported for NiO
around 260295 nm [33].
Figure 8 shows the rst and the second galvanostatic discharge-charge curves recorded
using our NONFs and commercial NiO nanopowder cells at 0.1 C and 1.0 C current rates using
1 M LiPF6 in EC:DEC (1:1) electrolyte. The cell with the NONFs displayed discharge and
charge capacities during the rst cycle (at a rate of 0.1 C) of 1400 mA h g1 and 950
mA h g1, respectively. This irreversible capacity in the rst cycle is due to the formation of a
solid electrolyte interphase (SEI) on the NONFs anode. In addition, the initial reduction of NiO
to Ni occurs via the well-known conversion reaction mechanism for NiO anodes [10]:
NiO + 2Li+ + 2e Ni + Li 2O
Subsequently, during the charging step, the in situ formed Li2O decomposes and NiO
forms:
Ni + Li 2O NiO + 2Li+ + 2e
The cell fabricated using the purchased NiO powder showed the same capacity loss in the
rst cycle. However, the discharge capacity of NONFs cell was signicantly higher. During the
second cycle (at a rate of 0.1 C), the discharge capacity of NONFs reached 70% of its rst
cycle (1400 mA h g1 versus 970 mA h g1). The commercial NiO powder retained only
50% of its initial capacity in the second discharge. A similar behavior was observed when
cycling identical cells at higher current density of 1.0 C (see gure 8).
Figure 9 shows the dischargecharge capacities recorded from NONFs cells for the rst 15
cycles at the rates of 0.1 C and 1.0 C. The NONFs cells had coulombic efciencies above 85%,

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Mater. Res. Express 1 (2014) 025501 M Ahmadi et al

Figure 8. Voltage proles recorded between 0.1 and 3.0 V for the rst and the second
cycles of the galvanostatic discharge/charge for our NONFs and commercial NiO
powder versus Li/Li+ at current densities of 71.8 mA g1 (i.e., 0.1 C) and 718 mA g1
(i.e., 1.0 C) using 1 M LiPF6 in EC:DEC (1:1) electrolyte.

for both rates. The capacity fading is more noticable in the cell with higher current rate (1.0 C),
which is in agreement with previously published results [34]. The capacity fading is a common
issue observed for anodes based on the conversion reaction [10] that can be improved using a
more suitable binder, more appropriate electrolyte additives, etc.
The electrolyte chemistry can also signicantly inuence the performance of conversion
anodes [18]. The NONFs cells were also assembled using a 2:1 ratio of EC:DEC solvents,
(results shown in gure S6 in the supplementary data). Compared to the cells with a 1:1 ratio,
they displayed higher capacity fading indicating that tuning is possible. It should be noted that
the rst discharge capacity was higher than the theoretical capacity of NiO, because of the
formation of a polymer-based layer on the surface of the NONFs, and the interfacial storage of
Li in the Ni/Li2O matrix [35, 36].

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Mater. Res. Express 1 (2014) 025501 M Ahmadi et al

Figure 9. Discharge and charge capacities for NONFs cells at current densities of
71.8 mA g1 (i.e., 0.1 C) and 718 mA g1 (i.e., 1.0 C) using 1 M LiPF6 in EC:DEC (1:1)
electrolyte.

4. Conclusions

Nickel oxide crystalline nano-akes were synthesized using a very simple chemistry method
followed with a short and low temperature annealing in ambient air. Their average size was
determined to be 10 nm. Our method can easily be scaled up for commercial production.
When used as an anode in lithium-ion batteries, these nano-akes provided an initial discharge
capacity of 1400 mA h g1 and 1300 mA h g1 at 0.1 C and 1.0 C rates, respectively, which was
a better performance when compared to a commercial NiO nano-powder used under the same
conditions which delivered capacities of 800 mA h g1 and 750 mA h g1 at 0.1 C and 1.0 C
rates, respectively.

Acknowledgements

The partial support from NSEC Center for Hierarchical Manufacturing at the University of
Massassuchets (National Science Foundation award 1025020). NSF for its support (award
0701525) to the Nanoscopy Facility, an electron microscopy facility at UPR.

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Mater. Res. Express 1 (2014) 025501 M Ahmadi et al

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