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Thin copper oxide nanowires/carbon nanotubes interpenetrating networks for
lithium ion batteries{
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Hongwen Huang, Qing Yu, Yinghui Ye, Peng Wang, Liqiang Zhang, Mingxia Gao, Xinsheng Peng* and
Zhizhen Ye*
Received 1st June 2012, Accepted 1st August 2012
DOI: 10.1039/c2ce25873k

Thin CuO nanowires with a diameter of 7 3 nm, aspect ratio up to 103104 and specific surface area
of 51.08 m2 g21 were synthesized by shape-reserved transformation from the corresponding thin
copper hydroxide nanowires (CHNs) under an appropriate temperature. A topotactic transition of
the crystal structure between Cu(OH)2 and CuO occurred. CdO nanowires were also successfully
prepared by this synthetic method. Subsequently, thin CuO nanowires/carbon nanotubes (CNTs)
interpenetrating networks were prepared from preformed Cu(OH)2 nanowire/CNT interpenetrating
networks and these demonstrated a much higher electrochemical performance than that of pure CuO
nanowires for lithium ion batteries. When the CNTs were 33.3 wt% of the CuO nanowires/CNTs
interpenetrating networks, they gave the best electrochemical performance, including high
capacitance as well as good stability.

1. Introduction
The term ultrathin nanowires (NWs) is generally used to
describe a type of NW with a diameter less than 10 nm.13
Comparing with other nanostructures, the ultrathin NWs have
several distinct advantages. First, they provide more surface
active sites because of their high surface-to-volume ratio. In
addition, ultrathin NWs are desirable for the transportation of
electrons, phonons, and photons.46 Moreover, when the
diameter of an ultrathin NW is close to the exciton Bohr radius,
which is usually less than 3 nm, numerous fascinating properties
have been explored owing to obvious quantum effects.7,8 For
these reasons, much attention has been paid to this field. For
example, Shen et al.9 reported the synthesis of single-crystal
In2O3 NWs with diameters below 4 nm by a laser-ablation
chemical vapor deposition method. Qian et al.10 synthesized
high-quality luminescent tellurium nanowires with diameters
of 49 nm by a poly(vinylpyrrolidone)-assisted hydrothermal
process. Xu et al.11 synthesized ultrathin InOOH NWs with a
diameter of ca. 2 nm and a length up to ca. 200 nm by a
hydrolysis reaction in a solution system. Although tremendous
progress has been achieved, there is still much space remaining to
be exploited. So far, ultrathin transition metal oxide NWs have
been rarely reported. In this work, a facile and general method
State Key Laboratory of Silicon Materials, Department of Materials
Science and Engineering, Zhejiang University, Hangzhou, 310027,
P. R. China. E-mail: pengxinsheng@zju.edu.cn; yezz@zju.edu.cn;
Fax: 86-571-87952625; Tel: 86-571-87951958
{ Electronic Supplementary Information (ESI) available: DTG, TGA
curves, Diameter distribution of CuO NWs, SEM images of Cu(OH)2
afte heated at 300 uC, CdO NWs and XRD of Cd(OH)2 NWs treated at
different conditions. See DOI: 10.1039/c2ce25873k
was carried out to synthesize copper oxide and cadmium oxide
NWs.
It is well known that ultrathin transition metal oxide NWs are
undoubtedly outstanding candidates for anode materials.12,13
Compared to the commercial anode materials, graphitic carbons,
transition metal oxide materials have much higher specific
capacities. In addition, ultrathin NWs are a good type of
nanostructure for electrochemical reactions, which is ascribed to
their high specific surface area and the extremely short diffusion
length.14,15 Copper oxide (CuO), as a promising anode alter-
native material, has attracted much attention with its theoretical
capacity of 674 mAh g21, which is almost two times that of
commercial graphite materials, and its affordable price.16
However, a serious problem exists in CuO-based anodes, that
is the stability of repetitive cycling. This is a pervasive weakness
in transition metal oxide anodes.17 Consequently, a great many
strategies have been proposed to solve this critical problem by
designing various nanostructures and functional modifications.
For instance, numerous CuO nanostructures, such as nano-
wires,18 hollow microspheres,19 hierarchical nanostructures20
and so on, have been synthesized to investigate their electro-
chemical performances. To further improve their electrochemical
performances, graphite coating21 and carbon nanotube (CNTs)
addition22,23 have been applied. However, the graphite coating
process is complex and not appropriate for mass production. The
addition of CNTs is usually fulfilled by mechanical mixing or
dispersing the oxidized CNTs into solution with active materials,
owing to the big difference in density between CNTs and active
materials, the uniformity of the mixture is a nonnegligible issue.
Recently, we have developed a general and simple way to
prepare highly positively charged thin metal hydroxide NWs

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with average diameter of 3 nm and length of tens micrometers in
aqueous solutions.2426 Using these metal hydroxide NWs as the
precursor, after dehydration by an optimum heat treatment, the
nanofibrous morphology could be reserved, and the correspond-
ing metal oxide NWs were achieved. In this work, we took CuO
and CdO as examples to present the generality of our method.
Furthermore, interpenetrating networks of thin CuO NWs and
single-walled CNTs were prepared by mixing highly positively
charged metal hydroxide NWs with negatively charged CNTs.
The prominent advantage of this technique is to achieve an
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excellent uniform CuO NWsSWCNTs composite. These CuO
NWsCNTs interpenetrating networks show a splendid electro-
chemical performance as a lithium ion battery anode.
2. Experimental section
2.1 Materials
Copper nitrate (Cu(NO3)2?2.5H2O), cadmium nitrate
(Cd(NO3)2?4H2O), aminoethanol (NH2CH2CH2OH) (AE) were
purchased from SigmaAldrich. Single-walled carbon nanotubes
produced by a high-pressure CO conversion method were
purchased from Carbon Nanotechnologies. Ethanol and nitric
acid were purchased from SINOPHARM. All chemicals were
used as received. Polycarbonate (PC) membrane (Whatman)
with pore size of 200 nm, and effective diameters of 19 and
47 mm were used for the separation of ultrathin Cu(OH)2 NWs.
Deionized water (18.2 MV) was produced by a Millipore Direct-
Q3 System, and used in all of the experiments.
2.2 Synthesis of thin CuO and CdO NWs
For the CuO NWs, a typical synthetic process was carried out as
follows: first, ultrathin Cu(OH)2 NWs solution was prepared by
mixing a certain volume of aqueous copper nitrate (4 mM) with an
equal volume of 1.6 mM AE solution under vigorous stirring at
room temperature and aging for 2 days, as described elsewhere.24
The preformed ultrathin Cu(OH)2 NWs were collected by filtration
and transferred to a clean quartz boat. This quartz boat was
inserted into a tube furnace for heat treatment. The temperature of
the furnace was raised from room temperature (25 uC) to 160 uC at
the ascending rate of 2 uC min21 in air, and kept at 160 uC for 4 h to
complete the dehydration. To examine the thermal stability of the
ultrathin CuO NWs, the samples were also heated to 300 uC and
kept for 2 h at the same ascending temperature speed.
Similar to the synthesis of CuO NWs, thin CdO NWs were
obtained through the dehydration of ultrathin Cd(OH)2 NWs.
The ultrathin Cd(OH)2 NWs were prepared by mixing an equal
volume of 4 mM aqueous Cd(NO3)2 with 0.8 mM AE solution
under vigorous stirring at room temperature and aging for 1 h, as
described elsewhere.25 With regard to the dehydration process,
the furnace was heated with the ascending rate of 2 uC
min21from room temperature (25 uC) to 250 uC and kept at
that temperature for 2 h. Continuous N2 gas was applied
throughout the dehydration process.
2.3 Preparation of thin CuO NWs/CNTs interpenetrating
networks
First, oxidized water-soluble CNTs were prepared by partial
oxidation using nitric acid.26 A certain amount of single-walled
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CNTs were heated in 6 M nitric acid at 80 uC for 24 h. The
solution was subsequently washed with adequate deionized
water, and the precipitates were collected by centrifuge. The
washing and centrifugation were repeated several times until the
solution reached pH 6.5. The resultant materials were dispersed
in water by sonification to give a concentration of 1 mg mL21.
Then, the CuO NWs/CNTs interpenetrating networks were
prepared by adding different amounts of oxidized CNTs into a
4L thin Cu(OH)2 NWs solution under vigorous stirring.
Flocculent precipitate quickly appeared in solution in a few
minutes. After filtrating the flocculent precipitate, the Cu(OH)2
NWs/CNTs interpenetrating networks was obtained. Then, the
same procedure of transforming the Cu(OH)2 NWs to CuO NWs
was undertaken to gain CuO NWs/CNTs interpenetrating
networks. In this work, 10 mg, 20 mg, and 40 mg of oxidized
CNTs were chosen to add into the 4L Cu(OH)2 NWs solution, to
investigate the effect of a different amount of CNTs on the
electrochemical performances. A 4L Cu(OH)2 NWs solution will
produce 80 mg CuO NWs after transformation.
2.4 Characterization
The morphology and the structure of the as-synthesized samples
were characterized by scanning electron microscopy (SEM,
Hitachi S-4800), transmission electron microscopy (TEM,
Philips CM200) with an accelerating voltage of 160 kV, high
resolution transmission electron microscopy (HRTEM, FEI
TECNAI F20), and using an X-ray diffractometer (XRD,
PANalytical XPERT-PRO). The Raman spectra were conducted
on the Labor Raman HR-800 equipment (Jobin Yvon, France)
under the excitation length of 514 nm. The thermal-gravimetric
analysis (TGA) and derivative-thermo-gravimetry (DTG) were
performed on a TGA-4000 (PerkinElmer) in an air atmosphere
and with a heating rate of 5 uC min21 from room temperature to
300 uC. The specific surface area of the ultrathin CuO NWs was
measured on an ASIC-2 (Quantachrome Instruments) by multi-
point Brunauer-Emmett-Teller (BET) analysis of the nitrogen
adsorption isotherms at 77 K.
2.5 Electrochemical performances
The electrochemical measurements were conducted using three-
electrodes Swagelok-type coin cells with lithium metal as both
counter and reference electrode. The working electrodes consist
of 80 wt% of the active materials (our prepared materials),
10 wt% of conductivity agent (carbon black, Super-P), and
10 wt % of binder (polyvinylidene fluoride, PVDF, Aldrich). The
electrolyte employed in the cell was 1 M LiPF6 in a 50 : 50 (w/w)
mixture of ethylene carbonate and diethyl carbonate. Cell
assembly was carried out in an argon-filled glove box. The
surface area of the foamed nickel current collector was 1.33 cm2.
The active material loading on the current collector was around
5 mg. Note that the mass of CNTs was considered when the
specific capacity was calculated. The galvanostatic charge-
discharge performances of the cells were tested in the voltage
range of 0.013.0 V under a constant current density of
67 mAg21 by LAND battery-test system. The high rate specific
capacities of the cells were tested under a constant charge current
density of 67 mAg21 with various discharge rates by LAND
battery-test system.
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3. Results and discussions
3.1 Synthesis and characterization of thin CuO NWs
The synthesis and characterization of ultrathin Cu(OH)2 NWs
have been described previously.24 The preformed Cu(OH)2 NWs
were shape-reserved transformed to CuO NWs through a
thermal dehydration process. The proper dehydration tempera-
ture was determined by TGA (see Fig. S1 in the ESI{), the TGA
curve demonstrates there is an abrupt weight loss in the
temperature range of 120240 uC, and around 160 uC the loss
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of the weight is maximal. This is associated with the dehydration
of Cu(OH)2. Therefore, the dehydration temperature was fixed
at 160 uC in the following text, if not mentioned specifically.
The XRD pattern of the as-prepared products displayed in
Fig. 1a can be indexed to a pure monoclinic phase of CuO (space
group C2/c; a = 4.685 A, b = 3.426 A, c = 5.13 A, b = 99.549u.
JCPDS Card No. 45-0937). The grain size was calculated to be
6.6 nm according to the Scherrer equation. Moreover, Fig. 1b,
the Raman spectrum also indicates that the as-prepared products
are CuO phase.27 It is observed that these Raman peaks of the
as-synthesized CuO are broad and weak. This further demon-
strates the crystal size of the as-prepared CuO NWs is fine. All
the XRD and Raman results show that CuO is really formed in
very fine crystal size. This is further confirmed by the following
SEM and TEM observation.
The morphology of ultrathin Cu(OH)2 NWs is shown in
Fig. 2a. Fig. 2b reveals the SEM image of the as-prepared CuO
sample from ultrathin Cu(OH)2 NWs by heating at 160 uC in air
for 4 h. Similar thin fibrous structures with lengths of tens of
micrometers are exhibited in Fig. 2a and 2b, which indicates that
Fig. 1 (a) XRD pattern and (b) Raman spectrum of the as-prepared
products by heat treatment of ultrathin Cu(OH)2 NWs at 160 uC in air
for 4 h.
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Fig. 2 SEM images of (a) ultrathin Cu(OH)2 NWs, (b) the products
after heat treatment of the Cu(OH)2 NWs at 160 uC for 4 h, (c) and (d)
TEM images of the as-prepared CuO NWs at low magnification and high
magnification, respectively. The inset in (c) shows the corresponding
SAED patterns, (e) HRTEM image of a single NW.
the fibrous nanostructures were reserved during the dehydration
process. TEM images, Fig. 2c and 2d, further demonstrate one
dimensional CuO NWs, and the diameter of the thinnest single
NWs is about 3 nm. However, many of them are larger than
3 nm because of aggregation and bundle formation from single
CuO NWs during the filtering concentration process and the
heat treatment process. After measuring the diameter of more
than 100 CuO NWs from the TEM image (Fig. 2c), the diameter
distribution of the obtained CuO NWs is shown in Fig. S2 (see
ESI{), which presents the average diameter of CuO NWs, as 7
3 nm. This value is also consistent with that evaluated from the
XRD results by Scherrer equation. The SAED pattern (inset of
Fig. 2c) recorded from the NWs is shown in Fig. 2c. The
concentric diffraction rings are assigned to the (002), (111) and
(-311) planes of the CuO phase, respectively. These are consistent
with the XRD pattern in Fig. 1a. The HRTEM image shown in
Fig. 2e exhibits a regular lattice spacing of 0.246 nm, which is
assigned to the (002) plane of monoclinic CuO. This means that
these ultrathin NWs are crystalline. Furthermore, to clarify the
thermal stability of such thin CuO NWs, a procedure of heating
treatment of Cu(OH)2 NWs at 300 uC in air for 2 h was
undertaken. As seen in Fig. S3 (see ESI{), this demonstrates that
the fibrous morphology of ultrathin Cu(OH)2 NWs is retained in
a large measure, and a minority of them are destroyed. This
result verifies that the ultrathin NWs have a good thermal
stability even at a higher temperature up to 300 uC. But
considering the more excellent uniformity of products prepared
at 160 uC for 4 h, we choose 160 uC as an optimum temperature
to carry out all experiments. It is surprising that the ultrathin,
tens of micrometers long metal hydroxide NWs with aspect
ratios reaching up to 103104 can be reserved after transforming
to their corresponding metal oxide NWs.
The specific surface area of the as-prepared thin CuO NWs
was determined by BET technique. The BET surface area of
these CuO NWs is 51.08 m2 g21 with a correlation coefficient of
0.9985. This value is a desired data as compared with the other
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Fig. 3 (a) Crystal structures of Cu(OH)2. (b) When the temperature
rises, long CuO bonds break and HO bonds break. The structure of
Cu(OH)2 changes to a layered Cu(OH)4 structure. (c) Projection along
the a-axis for (b). (d) and (e) The dehydration process in the b,c plane of
Cu(OH)2. (f) Crystal structure of CuO.29
CuO nanostructures that have been reported.16,28 It means these
ultrathin CuO NWs are promising for the applications as anode
materials in Li-ion batteries.
3.2 Mechanism of shape-reserved transformation between thin
Cu(OH)2 NWs and CuO NWs
The above results demonstrate that the NWs morphology of
ultrathin Cu(OH)2 NWs can be retained after heat treatment.
Fig. 3 presents the topotactic transformation between these two
solids.29,30 The crystal structure of Cu(OH)2 belongs to an
orthorhombic type with the cell parameters a = 2.951 A, b =
10.592 A, c = 5.273 A, space group Cmcm, as is drawn in Fig. 3a.
It was reported by Y. Cudennec et al.29 When the temperature
was raised to 50 uC, the long CuO bond would be breaking as
illustrated in Fig. 3b. As the temperature was increased, the
dehydration process occurred in the b,c plane of Cu(OH)2. In
order to simplify the analytic process, we project the stereo-
structure along the a-axis into the b,c plane and just need to
figure out the transformation in the b,c plane, owing to the
symmetrical characteristic of the crystalline structure. Fig. 3(ce)
clearly show the dehydration process (these clearly show how
water is lost during this process in the dotted ellipse), through an
oxolation mechanism. In the course of the oxolation in the b,c
plane, the CuO bonds are established. The shifts along the three
axes are adjusted according to the basic bond making principle.
Meanwhile, owing to the ability of coordination of the CuO
bond, the crossing bonds of CuO4 are obtained finally. Through
the transformation of the oxolation process, the structure of the
monoclinic CuO is conducted as shown in Fig. 3f. Because of the
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topotactic transformation existing during the dehydration
process, the morphology can be reserved well during Cu(OH)2
transforming to CuO.
3.3 The generality of the synthesis method for thin metal oxide
NWs
In order to test the generality of the above method for metal
oxide NWs, we further extended it to synthesize the thin CdO
NWs. Nevertheless, it is different from the dehydration of
Cu(OH)2 NWs to CuO NWs. It was found that mixtures of
CdCO3 and CdO were formed when Cd(OH)2 NWs were treated
at 250 uC for 2 h in the air (See Fig. S4 in the ESI{). Therefore,
the thermal treatment process was arranged with the protection
of N2. The XRD patterns of the samples treated in N2 at 250 uC
for 2 h are shown in Fig. S5c,{ which clearly demonstrate the
final products are cadmium oxide (JCPDS card: 05-0640) and no
other impurities could be found. The SEM images demonstrate
that the morphology of ultrathin Cd(OH)2 NWs (Fig. S5a{) and
ultrathin CdO NWs (Fig. S5b{) are very similar. All the above
indicates that our synthetic technique can be expanded to
prepare other ultrathin functional metal oxide NWs.
3.4 Application of the thin CuO NWs-based materials as anodes in
Li-ion batteries
Very recently, ultrathin NWs have been deemed as promising
nanostructures for application in Li-ion batteries because of their
high surface-to-volume ratio and very short diffusion length.28
Owing to pervasive issues in Li-ion batteries, which include the
stability of nanostructures during the Li+ intercalation and
extraction, and the electroconductivity of electrode materials,
hereby, we incorporated CNTs into thin CuO NWs to obtain
thin CuO NWs/CNTs interpenetrating networks. These CuO
NWs/CNTs interpenetrating networks show superior electro-
chemical performance as anodes for Li-ion batteries.
3.4.1 Synthesis and characterization of thin CuO NWs/CNTs
interpenetrating networks. The formation process of the thin
CuO NWs/CNTs interpenetrating networks is schematically
illustrated in Fig. 4.
Based on the above discussion, shape-reserved transformation
will occur between Cu(OH)2 NWs and CuO NWs when
dehydration is employed. In this process, we prepared uniform
CuO NWs/CNTs interpenetrating networks with the aid of
electrostatic interactions between the positively-charged
Cu(OH)2 NWs24 and negatively-charged CNTs (oxidized
CNTs). That the electrostatic interaction occurred in solution
is a characteristic advantage in our process. It is beneficial to the
uniformity of the CuO NWs/CNTs interpenetrating networks,
which is very important for the application in Li-ion batteries.
Although many publications have reported the method of
adding CNTs into active materials to enhance the performance
of the electrochemistry, very rare reports have discussed the role
that the quantity of CNTs played. In this paper, we investigated
the effect of different amounts of CNTs on the specific capacity
of Li-ion batteries. The mass ratios of the thin CuO NWs to
CNTs, including 8 : 1, 8 : 2, and 8 : 4, were taken to understand
the role that the quantity of CNTs played, and referred to 8 CuO
NWs1 CNTs, 8 CuO NWs2 CNTs, 8 CuO NWs4 CNTs,
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Fig. 4 Schematic illustration of the preparation process of the thin CuO NWsCNTs interpenetrating networks.
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respectively. The phase and morphology characterization of the
as-prepared final products was conducted by Raman spectro-
scopy, SEM and TEM.
Fig. 5d gives a typical Raman spectrum of the as-prepared 8
CuO NWs4 CNTs. As seen in it, all 8 peaks have been assigned
to CuO and CNTS according to previous reports,27,3133 and no
other surplus peaks existed, indicating the high purity of the
samples. In addition, according to the relationship between
radial breathing mode (RBM) frequency (v) and the diameter
of CNTs (d): v = 248 cm21 nm/d,33 the diameter of the CNTs
was estimated to 1.3 nm, which is in accordance with the
diameter measured by TEM as shown in Fig. 5c. The
morphology of the as-fabricated ultrathin Cu(OH)2 NWs-
CNTs interpenetrating networks was displayed in Fig. 5a. The
CuO NWsCNTs interpenetrating networks were obtained after
thermal treatment of ultrathin Cu(OH)2 NWsCNTs interpene-
trating networks at 160 uC for 4 h, as illustrated in Fig. 5b and
5c. From Fig. 5c, SWCNTs with diameters less than 2 nm and
the thin CuO NWs could be unambiguously distinguished.
Thus, the thin CuO NWsCNTs interpenetrating networks were
successfully fabricated, which is promising for electrochemical
applications.
Fig. 5 Morphology and phase characterization. (a) SEM images of
Cu(OH)2 NWsCNTs interpenetrating networks. (b) and (c) SEM
images and TEM images, respectively, of products prepared by thermal
treatment of Cu(OH)2 NWsCNTs at 160 uC for 4 h. (d) Raman
spectrum of the as-prepared final products, as shown in (b).
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3.4.2 Electrochemical performances of the thin CuO NWs
CNTs interpenetrating networks. As described in the above, three
kinds of CuO NWsCNTs interpenetrating network, with
different mass ratios of the thin CuO NWs to CNTs, were
prepared and assembled into Li-ion batteries as anodes. Their
electrochemical performances were evaluated by galvanostatic
discharge/charge test. As displayed in Fig. 6, all these anode
materials exhibited very high initial discharge specific capacity
(about 1100 mAh g21), which is usually ascribed to the
electrolyte being reduced to form a solid electrolyte interface
(SEI) layer, the reduction of adsorbed impurities on CuO
surfaces and so on.23 High initial discharge specific capacity
means large specific surface area and more sites for hosting Li+,
this feature will benefit the specific capacity of the cell. After
50 cycles, the discharge specific capacity of pure CuO NWs is
360.7 mAh g21 at a rate of C/10, which is much higher than the
CuO nanomicrospheres (296 mAh g21 after 25 cycles) fabricated
by simple solution method.22 This should be due to the large
surface area and short diffusion length in the CuO NWs during
the discharge/charge process. However, owing to a huge volume
expansion of CuO during Li+ insertion (about 174%) and poor
electronic conductivity of CuO, CuO nanostructures usually
have poor cycling performance. After adding CNTs into the thin
CuO NWs, Fig. 6 clearly shows that the CNTs significantly
improve the stability of the cycling performance. It was found
that with an increasing amount of CNTs a better cycling
performance could be achieved. It is commonly deemed that
Fig. 6 The cycling performances of half-cells with anode materials with
different compositions of the thin CuO NWsCNTs interpenetrating
networks at a constant current density of 67 mA g21 (C/10).
This journal is The Royal Society of Chemistry 2012

CNTs play dual functions in improving the electrochemical
properties, including enhancing electronic conductivity and
similar to elastic buffer absorbing stress induced by volume
expansion. Nevertheless, it is not always a positive relationship
between the amount of CNTs and cycling performance because
of the relatively low specific capacity of CNTs (in the range of
400600 mAh g21).22,34,35 According to a coarse estimate, the
theoretic specific capacity of 8 CuO NWs4 CNTs is in the range
of 580647 mAh g21, which is close to our tested results.
Therefore, a 33.3 wt% is the highest addition that was chosen in
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this work. After 50 cycles, the sample of 8 CuO NWs4 CNTs
obtained the best cycling performance up to 576 mAh g21, which
is 1.6 times that of pure CuO NWs and commercial graphite.
Moreover, this value is comparable with those of CuO
nanostructures in the range of 300627 mAh g21.22,23,3639 The
result indicates the excellent electrochemical stability of the thin
CuO NWsCNTs interpenetrating network with 33.3 wt% of
CNTs. The possible explanation is the specific structure,
including the ultrathin CuO NWs and the interpenetrating
networks of the thin CuO NWs and CNTs. These interpenetrat-
ing networks fully take use of CNTs as a three-dimensional
current collector and a stress buffer. Furthermore, the ultrathin
CuO NWs provide a very short diffusion length.
Fig. 7 (a) and (b) The 1st, 2nd and 10th charge/discharge voltage
profiles of the pure CuO NWs and 8 CuO4CNTS at a constant current
density of 67 mA g21, respectively.
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Fig. 8 Rate capacity of 8 CuO4 CNTS under room temperature with
the same charge current density of 67 mA g21.
Fig. 7a and 7b show the 1st, 2nd and 10th charge/discharge
voltage profiles of the pure CuO NWs and 8 CuO4 CNTs at a
rate of C/10. They have three similar plateaus, implying the
addition of CNTs does not change the nature of CuO in the Li-
ion battery. These three plateaus indicate the process of reductive
reaction from CuO to an intermediate composite copper oxide
phase, and further to Cu and Li2O.40 While in the second
discharge curve, the three plateaus all shift upward. This is
possible due to the irreversible reaction after the first process of
discharge. But the potential plateaus keep stable later. The
charge curves from the first to the tenth cycle are very similar
with two plateaus at 2.52.2 V, and 1.51.2 V, respectively. These
two potential plateaus correspond to the decomposition of Li2O.
In Fig. 7b, the 2nd discharge curve nearly coincides with 10th
discharge curve, this demonstrates its good capacity retention.
These results indicate that the 8 CuO4 CNTs is more stable
than the pure CuO NWs.
Furthermore, we investigate the relation of different discharge
rates with specific capacity for 8 CuO NWs4 CNTs under the
same charge rate of C/10. As shown in Fig. 8, after 15 cycles at a
rate of C/5 (C = 670 mA g21), the discharge specific capacity is
still maintained at 407 mAh g21, and this value lowers with
increasing discharge rate. However, when the discharge rate
recovers to C/10, the discharge specific capacity still exceeds
450 mAh g21. The excellent reversibility reflects its preeminent
stability during electrochemical reaction. And this also proves
that introducing CNTs into CuO NWs to form interpenetrating
networks is an effective way to improve its cycling performance.
4. Conclusions
In summary, the thin CuO NWs were synthesized by shape-
reserved thermal dehydration of Cu(OH)2 NWs with average
diameters of 7 3 nm and lengths of up to tens of micrometers at
relatively low temperature. These thin CuO NWs have a high
aspect ratio of 103104 and BET area of 51.08 m2 g21. The
topotactic transformation between the Cu(OH)2 phase and CuO
phase is proposed and responsible for this shape-reserved
transformation. This method was generally applied for synthesis
of the thin CdO NWs. Our synthetic technique holds promise for
CrystEngComm, 2012, 14, 72947300 | 7299

preparing other ultrathin metal oxide NWs. Pure CuO NWs
display relatively poor cycling performance as anodes for Li-ion
batteries. However, with the aid of electrostatic interaction induced
by surface charge in aqueous solution, uniform CuO NWsCNTs
interpenetrating networks were achieved and these demonstrated
superior cycling stability and capacitances. It was found that 33.3
wt% CNTs addition is the optimal quantity of CNTs for obtaining
excellent battery performance. After 50 cycles, 33.3 wt% CNTs and
66.7 wt% CuO composites sustain 576 mAh g21 at a constant
current density of 67 mA g21. This result is 1.6 times that of pure
Published on 02 August 2012. Downloaded by University of York on 23/08/2013 12:49:28.
CuO NWs and commercial graphite anode materials. It further
exhibits the good reversibility capacity after 60 high rate discharge
cycles. The formation of thin CuO NWsCNTs interpenetrating
networks is a simple and effective way to achieve a superior
electrochemical performance. This proposal would be expanded to
other transition metal oxides as anodes for Li-ion batteries.
Acknowledgements
This work was supported in part by NSFC (21003105), New
Century Excellent Talents Program, and the Fundamental
Research Funds for Central Universities.
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This journal is The Royal Society of Chemistry 2012