DOI: 10.1002/chem.

201200086

Mesoporous Nickel Oxide Nanowires: Hydrothermal Synthesis,

Characterisation and Applications for Lithium-Ion Batteries and
Supercapacitors with Superior Performance

Dawei Su,[a] Hyun-Soo Kim,[b] Woo-Seong Kim,[c] and Guoxiu Wang*[a]

Abstract: Mesoporous nickel oxide nanowires were synthesized by a hydrothermal

reaction and subsequent annealing at 400 8C. The porous one-dimensional nano-
structures were analysed by field-emission SEM, high-resolution TEM and N2 ad- Keywords: hydrothermal synthesis ·
sorption/desorption isotherm measurements. When applied as the anode material lithium-ion batteries · mesoporous
in lithium-ion batteries, the as-prepared mesoporous nickel oxide nanowires dem- materials · nanostructures · nickel
onstrated outstanding electrochemical performance with high lithium storage ca- oxide
pacity, satisfactory cyclability and an excellent rate capacity. They also exhibited
a high specific capacitance of 348 F g1 as electrodes in supercapacitors.

Introduction higher specific capacity and volumetric energy density than

commercial graphite anode materials.[6, 19–21] The electro-
Lithium-ion batteries and supercapacitors are important chemical performance of metal oxide anodes depends on
electrochemical energy storage and conversion devices. Cur- their composition, morphology and crystal structure. The
rently, lithium-ion batteries are the most advanced power lithiation and de-lithiation process of transition metal oxide
sources for portable electronic devices.[1–3] The combination anode materials is usually associated with significant varia-
of lithium-ion batteries and supercapacitors is being consid- tions thereof which induce pulverization of the electrode.
ered as a state-of-the-art energy source to power electric ve- A porous structure can provide voids to cushion electrode
hicles and hybrid electric vehicles.[4] The intrinsic diffusivity materials from pulverization in lithium-ion batteries.[22–25]
of the lithium ions in the solid-state electrodes limits the Recently, many mesoporous structured materials have been
rate of lithium intercalation/de-intercalation. High-energy developed as electrode materials for lithium ion batteries,
applications urgently require the development of new elec- including cathode materials such as LiCoO2, LiMn2O4,
trode materials with high capacity (in particular, high rate LiFePO4 and LiTiO2[26–30] and anode materials like Co3O4,
capacity) and high energy density. Therefore, extensive stud- SnO2, MoO2 and TiO2 based materials.[31–36] Porous materials
ies have been devoted to improving the intercalation rate can provide high surface area, large surface-to-volume ratio
performance of electrode materials for high-energy lithium- and favourable structural stability against volume expan-
ion batteries.[5–18] sion/contraction. These characteristics improve electrochem-
Transition metal oxides have been widely investigated as ical performance because they can lead to fast ion/electron
anode materials for lithium-ion batteries because they have transfer and sufficient contact interface between active ma-
terials and electrolyte.
Here we report a facile synthesis of high-quality, polycrys-
[a] D. Su, Prof. Dr. G. Wang
talline, mesoporous NiO nanowires by a hydrothermal
Centre for Clean Energy Technology method. The as-prepared mesoporous NiO nanowires exhib-
School of Chemistry and Forensic Science ited superior electrochemical performance for reversible
University of Technology lithium storage in lithium-ion batteries and high charge-stor-
Sydney, NSW 2007 (Australia)
age performance in supercapacitors.
Fax: (+ 61) 295141460
E-mail: [email protected]
[b] H.-S. Kim
Battery Research Centre Results and Discussion
Korea Electrotechnology
Research Institute Structure and morphological analysis: The morphologies of
Changwon, 641-120 (Republic of Korea)
the NiC2O4·2 H2O precursor nanowires and the annealed
[c] W.-S. Kim
Daejung Energy Materials Co. Ltd.
NiO final product were analysed by field-emission (FE)
Namdong-gu, Incheon 405-820 (Republic of Korea) SEM (Figure 1). The precursor consists entirely of
Supporting information for this article is available on the WWW NiC2O4·2 H2O nanowires with lengths extending to a few
under http://dx.doi.org/10.1002/chem.201200086. tens micrometers (Figure 1 a). Annealing converted the

8224  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2012, 18, 8224 – 8229
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FULL PAPER

Figure 1. FESEM images of a) the as-prepared NiC2O4·2 H2O precursor

nanowires, and b) NiO nanowires.

NiC2O4·2 H2O precursor nanowires to NiO nanowires with-

out any by-products such as nanoparticles and broken frag-
ments (Figure 1 b). A high-magnification FESEM image of
Figure 2. XRD patterns of a) the NiC2O4·2 H2O precursor nanowires and
an NiO nanowire is shown in Figure S1 (Supporting Infor-
b) NiO nanowires obtained by annealing.
mation). Figure 2 shows powder XRD patterns of the pre-
cursor and product nanowires. In Figure 2 a, the diffraction
peaks at 18.8, 22.7, 30.4, 35.5 and 37.68 can be assigned to
(
202), (002), ( 402) and (021) lines of monoclinic
NiC2O4·2 H2O (JCPDS 25-0581). Figure 2 b shows a well-
crystallised cubic NiO phase (JCPDS 47-1049). All diffrac-
tion peaks can be indexed to the cubic unit cell with space
group Fm 3m. The lattice parameter a was calculated to be
4.1667 . The absence of peaks for any impurity phase in
Figure 2 b confirms that the NiC2O4·2 H2O precursor was
completely converted to NiO after annealing.
The crystal structures of the precursor NiC2O4·2 H2O
nanowires and NiO nanowires were further characterised by
TEM and high-resolution (HR) TEM analysis. Figure 3 a
shows a TEM image of the precursor nanowires, from which
the diameters of individual nanowires can be determined to
be around 30–50 nm. The surfaces of the precursor
NiC2O4·2 H2O nanowires are very smooth. During the TEM
observation, we found that the precursor nanowires were
unstable and very sensitive to electron-beam irradiation, Figure 3. a) Low-magnification TEM image of NiC2O4·2 H2O precursor
which is associated with the decomposition of NiC2O4·2 H2O nanowires. b) An NiO nanowire. c) High magnification TEM image of an
to NiO. An HRTEM image and the corresponding selected- NiO nanowire. Inset: SAED pattern. d) Lattice-resolved HRTEM image
of NiO nanocrystals.
area electron diffraction pattern (SAED), shown in Fig-
ure S2 (Supporting Information), further confirm the crystal
structure of NiC2O4·2H2O precursor nanowires. Figure 3 b clear that individual NiO nanocrystals (a few nanometres)
shows a TEM image of an NiO nanowire. The diameters of aggregated together to form the nanowire shape, and meso-
NiO nanowires expanded to 40–60 nm; they are polycrystal- pores exist between the NiO nanocrystals. In the inset
line and consist of small nanoparticles. Figure 3 c shows SAED pattern in Figure 3 c, the diffraction rings can be in-
a high-magnification TEM image of an NiO nanowire. It is dexed to the cubic NiO phase. The lattice-resolved HRTEM

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G. Wang et al.

image of an NiO nanowire is presented in Figure 3 d. The in-

terplanar distance of the (111) crystal plane was measured
to be 0.242 nm.
The NiO nanowires were formed in two steps. In the first
step, nickel chloride salts reacted with K2C2O4 and H2O to
form NiC2O4·2H2O nanowires through the influence of eth-
ylene glycol under hydrothermal conditions. In the second
step, the NiC2O4·2 H2O precursors were converted to NiO
nanowires by heat treatment. During this process, NiC2O4
decomposed to NiO, accompanied by evaporation of H2O
and release of CO2. Simultaneously, mesopores also formed
during this process. The reactions are formulated as follows
[Eqs. (1)–(3)]

NiCl2 þ K2 C2 O4 þ 2 H2 O ! NiC2 O4  2 H2 O þ 2 KCl ð1Þ

Figure 5. N2 sorption isotherms of mesoporous NiO nanowires. Inset: cor-
NiC2 O4  2 H2 O ! NiC2 O4 þ 2 H2 O ð2Þ responding pore size distributions.

2 NiC2 O4 þ O2 ! 2 NiO þ 4 CO2 " ð3Þ

size of 12.5 nm. The specific surface area of NiO nanowires
To study the conversion process, thermogravimetric/differ- was calculated to be 85.18 m2 g1, and the total pore volume
ential thermal analysis (TG/DTA) was performed on the as- is 0.18 cm3 g1.
prepared NiC2O4·2 H2O nanowire precursor. As shown in
Figure 4, a two-step weight-loss process was observed from Electrochemical performance of mesoporous NiO nano-
wires: The electrochemical reactivity of porous NiO nano-
wires for lithium storage was evaluated by cyclic voltamme-
try (CV) measurement. Figure 6 shows the CV curves of an

Figure 4. TG/DTA curves of NiC2O4·2 H2O precursor nanowires.

the TG and DTA curves. The first measured weight loss is

Figure 6. CV curves of the as-prepared NiO nanowires as anode for a lith-
about 17.7 wt % from 182 to 227 8C with the feature of an ium-ion cell. During the anodic scanning process, the generated Ni0 was
endothermic peak at 217 8C, corresponding to dehydration oxidised, corresponding to the anodic peak at 2.25 V. After the first
of NiC2O4·2 H2O. The second weight loss of about 40.0 % cycle, the positions of the cathodic peak and anodic peak remain un-
from 325 to 345 8C is associated with decomposition of changed. This result is consistent with our recent report on the ex situ
XRD analysis of mesoporous NiO, which clearly confirmed the above
NiC2O4 to NiO. FTIR spectra further confirmed the conver- mechanism.[37]
sion from NiC2O4·2 H2O precursor nanowires to NiO nano-
wires (Figure S3, Supporting Information). The mesoporous
nanostructure of NiO nanowires was investigated by nitro- NiO nanowire electrode in the first, second and tenth scan-
gen adsorption/desorption measurements at 77 K, which re- ning cycles, which revealed the electrochemical reaction
vealed a typical type IV isotherm with an H1-type loop hys- mechanism. In the first scanning cycle, the major cathodic
teresis (Figure 5). The pore size distribution curve (inset in peak is located at 0.375 V versus Li + /Li, which can be as-
Figure 5) shows that the as-prepared NiO nanowires have cribed to reduction of Ni2 + to Ni0. This cathodic process
a mesopore distribution from 5 to 40 nm with a mean pore could also be associated with the electrolyte decomposition

8226 www.chemeurj.org  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eur. J. 2012, 18, 8224 – 8229
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Mesoporous Nickel Oxide Nanowires
FULL PAPER
and lithiation reaction to form Li2O. In the first scanning maintained a stable capacity (as shown in Figure 7 b). After
cycle, the major cathodic peak is located at 0.375 V versus 100 cycles, the electrode still showed a lithium storage ca-
Li/Li + , while in the subsequent scanning cycles, the major pacity of 1280 mAh g1, which is much higher than the previ-
cathodic peak shifted to 1.0 V. This indicates different lithi- ously reported result.[6] The excess discharge capacity could
um reaction mechanisms between the first cycle and the be ascribed to interfacial charging at the metal/Li2O inter-
subsequent cycles. In the first cycle, lithium ions react with face.[38, 39] Materials that have high surface area can yield
NiO nanowires and form Ni0 and Li2O [Eq. (4)].[6] high discharge capacities, that is, high surface area enhances
interfacial charge storage. To investigate the rate capability
2 Liþ þ NiO ! Li2 O þ Ni0 ð4Þ of mesoporous NiO nanowires, the electrodes were cycled at
different current densities (Figure 8). When the current den-

The lithium storage capacity of NiO nanowires was tested

by constant-current charge/discharge cycling. Figure 7 a
shows the discharge and charge profiles of the NiO nano-

Figure 8. Rate performance of the NiO nanowire electrode at different

current densities.

sity was increased to 2000 mA g1, the electrode still deliv-

ered a capacity of 435 mAh g1. As long as the current densi-
ty reverts back to low current density, the cell capacity can
recover to a high value, that is, as-prepared NiO nanowires
can tolerate high current charge/discharge cycling. The high
lithium storage capacity of NiO nanowires should be credit-
ed to the unique nanostructure of the as-prepared mesopo-
rous nanowires. As identified by TEM and HRTEM analy-
sis, NiO nanowires are polycrystalline and consist of small
nanocrystals with a size of less than 10 nm, in which nano/
mesopores exist between individual nanocrystals. During the
BET measurement, some nano/mesopores and nanocrystal
boundaries may be not accessible for gas adsorption, and
a lower value of the BET surface area is indicated. Howev-
Figure 7. a) Discharge and charge profiles of NiO nanowire electrodes. er, Li + ions would be able to diffuse and form a monolayer
b) Cycling performance and coulombic efficiency at 100 mA g1 current of Li + per boundary on the surfaces of all individual NiO
density.
nanocrystals, leading to extra lithium storage capacity.[38]
Figure 9 shows the Nyquist plots of the a.c. impedance
spectra of the as-prepared porous NiO nanowire electrode
wire electrode at a current density of 100 mA g1. In the first before cycling and after three cycles. The a.c. impedance
discharge, the NiO nanowire electrode showed a high specif- spectra exhibit a semicircle in the high-frequency region and
ic capacity of 3200 mAh g1. The extra capacity could be at- a straight line in the low-frequency region. The latter repre-
tributed to formation of the solid electrolyte interface (SEI) sents typical Warburg behaviour, which is related to diffu-
layer. Formation of the SEI layer can effectively protect the sion of lithium ions in the active anode materials. The de-
electrode from intercalation of solvent during subsequent pressed semicircle in the medium-frequency region is attrib-
cycles. From the second cycle, the NiO nanowire electrode uted to the charge-transfer process. The numerical value of

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G. Wang et al.

Figure 9. Alternating-current impedance spectra of the as-prepared meso-

porous NiO nanowire electrode before cycling and after three cycles. The
a.c. impedance spectra were measured in the discharged state of 0.01 V
in the frequency range from 0.01 Hz to 100 kHz.

the diameter of the semicircle on the Zre axis gives an ap-

proximate indication of the charge transfer resistance Rct,
which decreases substantially after three cycles. This sug-
gests that a few cycles are necessary for the electrolyte to
diffuse into the mesopores of NiO nanowires, and facilitate
facile charge transfer at the nanoscale particles/electrolyte
Figure 10. a) Cyclic voltammetry of the as-prepared mesoporous NiO
interface. The electrochemical enhancement of the as-pre- nanowires as electrodes in supercapacitors at different scanning rates.
pared one-dimensional NiO nanowires as an anode material b) Specific capacitance of NiO electrodes at different scanning rates.
may be ascribed to the high surface area and high reactivity
of mesoporous nanostructures, which maximises contact
areas between electrolyte and active electrode materials. Conclusions
Consequently, the high contact area of electrolyte/electrode
can provide more reaction sites for intercalation/de-interca- One-dimensional mesoporous nickel oxide nanowires were
lation of lithium ions.[40] synthesised by a hydrothermal reaction and subsequent an-
Since the as-prepared NiO nanowires have a large specific nealing at 400 8C in air. FESEM, HRTEM and N2 adsorp-
surface area, they are ideal electrode materials for superca- tion analysis revealed that the as-prepared individual NiO
pacitors. The capacitances of as-prepared NiO nanowires nanowire consist of aggregated nanocrystals and have a mes-
were evaluated by cyclic voltammetry. Figure 10 a shows the oporous structure, which lead a high specific surface area
CV curves obtained at scanning rates of 5, 10, 20, 50 and and allows mesoporous NiO nanowires in lithium ion cells
100 mV s1. All CV curves exhibited a broad oxidation peak to deliver a high lithium storage capacity, high rate capacity
and a sharp reduction peak rather than the ideal rectangular and good cycle life as anodes in lithium ion cells. Mesopo-
shape. This characteristic indicates that the supercapacitance rous NiO nanowires also demonstrated a high specific ca-
was not double-layer capacitance, but originated from fara- pacitance of 348 F g1 as electrode materials in supercapaci-
daic pseudocapacitance. Figure 10 b shows the relationship tors.
between specific capacitance and scanning rate. A maximum
specific capacitance of 348 F g1 was achieved at 10 mV s1.
The as-prepared mesoporous NiO nanowires exhibited
a much higher capacitance than previously reported nanopo-
Experimental Section
rous NiO nanorods.[41, 42] This improvement is related to the
Materials preparation: Mesoporous NiO nanowires were synthesized by
intrinsic properties of the as-synthesised mesoporous NiO the combination of a hydrothermal method and annealing. In a typical
nanowires, NiO nanowires are polycrystalline and consist of synthesis, 0.5 mmol of NiCl2·6 H2O (Sigma-Aldrich,  97 %) was dissolved
small nanocrystals with sizes less than 10 nm. Furthermore, in 20 mL of distilled water. Then 0.03 g of K2C2O4 (Sigma-Aldrich, 98 %)
the nano/mesopores between individual nanocrystals lead to and 8.0 mL of ethylene glycol (Sigma-Aldrich, 99 %) were added under
vigorous stirring. A clear transparent solution was formed gradually. The
extra charge storage at the boundaries of NiO nanocrystals. mixture was then transferred into a Teflon-lined stainless steel autoclave
and heated to 220 8C for 12 h. After cooling to room temperature, the
product was collected by centrifugation and washed thoroughly with dis-

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Mesoporous Nickel Oxide Nanowires
FULL PAPER
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