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PAPER

www.rsc.org/materials | Journal of Materials Chemistry

Synthesis of CuO/graphene nanocomposite as a high-performance anode

material for lithium-ion batteries
Bao Wang,ab Xing-Long Wu,ab Chun-Ying Shu,a Yu-Guo Guo*a and Chun-Ru Wang*a

Downloaded by Institute of Chemistry, CAS on 26 April 2012

Published on 11 October 2010 on http://pubs.rsc.org | doi:10.1039/C0JM01941K

Received 18th June 2010, Accepted 23rd August 2010

DOI: 10.1039/c0jm01941k
An optimized nanostructure design for electrode materials for high-performance lithium-ion batteries
was realized by introducing three-dimensional (3D) graphene networks into transition metal oxide
nanomicrostructures. A CuO/graphene composite was selected as a typical example of the optimized
design. Self-assembled CuO and CuO/graphene urchin-like structures have been successfully
synthesized by a simple solution method and investigated with SEM, TEM, XRD, and
electrochemical measurements. The CuO/graphene nanocomposite exhibits a remarkably enhanced
cycling performance and rate performance compared with pure CuO urchin-like structure when being
used as anode materials in lithium-ion batteries. During all the 100 discharge-charge cycles under
a current density of 65 mA g1, the CuO/graphene electrode can stably deliver a reversible capacity of
ca. 600 mA h g1. At a high current density of 6400 mA g1, the specific charge capacity of the CuO/
graphene nanocomposite is still as high as 150 mA h g1, which is three times larger than that of
graphene (48 mA h g1), while that of CuO is nearly null under the same current density. The
enhancement of the electrochemical performance could be attributed to the 3D electrically
conductive networks of graphene as well as the unique nanomicrostructure of the CuO/graphene
nanocomposite in which the CuO nanomicroflowers are enwrapped by a thin layer of graphene as an
elastic buffer.

Introduction
Lithium-ion batteries (LIBs) have been widely used in daily life
such as the powers of computers, mobile telephones, watches and
toys etc., however, it is still a challenge to extend the applications
of LIBs into electrical vehicles and hybrid electrical vehicles
because they require higher energy density, higher rate capability
and longer cycle life.13 For getting a better performance of LIBs,
every components of the LIBs, including cathode materials,
anode materials, electrolyte, separator etc., should be improved,
in which we have special interests on the anode materials.
Copper oxide (CuO), as one of the promising anode materials for LIBs, has been recently widely investigated due to its
high theoretical capacity, high safety, environmental benignity
and low cost,414 but a shortage of this electrode material is its
large volume variation during Li+ insertion/extraction
processes, which would lead to severe mechanical strains and
rapid capacity decay. It is obvious that the CuO anode always

a
Key Laboratory of Molecular Nanostructure and Nanotechnology, Beijing
National Laboratory for Molecular Sciences, Institute of Chemistry,
Chinese Academy of Sciences, Beijing, 100190, China. E-mail: crwang@
iccas.ac.cn; ygguo@iccas.ac.cn
b
Graduate School of the Chinese Academy of Sciences, Beijing, 100064,
China
Electronic supplementary information (ESI) available: SEM, TEM,
XRD and XPS analysis of the graphene. XPS analysis of the
CuO/graphene. SEM and TEM images of the as-prepared CuO and
CuO/graphene after use in lithium ion batteries. Comparison of the
electrochemical performance of the CuO/graphene composite,
CuO/CNTs composite, CuO/graphite composite and CuO-graphene
mixture used as anode materials in batteries. See DOI:
10.1039/c0jm01941k

This journal is The Royal Society of Chemistry 2010

lapses after only several discharge/charge cycles if no structural

modification is used. Recently, there have some techniques
been reported to improve the CuO anode performances. For
example, by combining the metal oxides with graphite, the
nanocomposites exhibit both high capacity and capacity
retention as anode materials in LIBs.15,16 The reason why
graphite improves the CuO anode properties is because the
graphite not only possesses excellent electronic conductivity,
but also it prevents the breakdown of anode materials during
Li+ insertion/extraction. Another example is our recent work
combining CuO with carbon nanotubes (CNTs) to form
composite nanomicrospheres and then obtain high capacity
and excellent cycling performance.14,17 The high performance
of the CuO/CNT hybrid anode benefits from the as-prepared
three-dimensional (3D) CNT network, which acts both as a 3D
current collector network and an elastic buffer in LIBs. Since
graphene exhibits superior electrical conductivity, large
surface-to-volume ratio, and excellent chemical tolerance, it is
expected to improve the CuO anode performance better than
graphite and CNTs.1721 Herein we report the construction of
CuO/graphene composite structures and the characterizations
of these materials in LIBs.

Experimental section
Preparation of CuO/graphene and CuO nanomicrostructures
The graphene was synthesized by an arc discharge method.22,23
The CuO/graphene composite and CuO nanomicrostructures
were prepared by a simple liquid method.10,14 In a typical
synthesis, 0.005 mol Cu(CH3COO)2$5H2O was dissolved in 50 mL
of deionized water with violent magnetic stirring, then 80 mg
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of graphene dispersed in 10 mL of ethanol (95%) was added to

the above solution. Ammonia solution (10 mL, 25 wt%) was
added to the resulting suspension last. After being stirred for 1 h,
the resulting mixture was refluxed for 2 h. Vigorous stirring was
maintained throughout the entire process. After the reaction, the
solution was cooled to room temperature. The product was
separated by centrifugation, washed with deionized water and
absolute alcohol three times, and then dried in a vacuum oven at
80  C for 10 h. CuO material was prepared by a similar process
for comparison without added graphene. The CuO/CNTs
composite and CuO/graphite composite were also prepared using
a similar process while replacing the graphene with CNTs and
graphite, respectively. A CuO-graphene mixture was also
prepared by simply grinding CuO and graphene with weight ratio
of 74 : 26.
Structure and morphology characterization
The XRD patterns were obtained by a Rigaku D/max 2000
spectrometer using a Cu-Ka radiation. For the XPS analysis,
a Kratos AXIS 165 multitechnique electron spectrometer was
used. And Elementar Vario EL (Germany) was employed to
quantify the element components. The morphology of the final
products was characterized by scanning electron microscopy
(SEM) (JEOL JSM-6700). Transmission electron microscopy
(TEM) and corresponding high resolution TEM images were
obtained by a JEOL 2010 TEM with an accelerating voltage of
200 kV. The samples were ultrasonically dispersed in ethanol and
dropped onto the TEM grids, and allowed subsequent solvent
evaporation in air at room temperature.
Electrochemical characterization
Electrochemical experiments were performed using Swageloktype cells assembled in an argon-filled glovebox. To prepare
working electrodes, a mixture of active material, super-P acetylene black, and poly(vinyl difluoride) (PVDF) at a weight ratio of
80 : 10 : 10 was pasted on a Cu foil. A glass fiber (GF/D) from
Whatman was used as a separator. The loading mass of active
materials is about 10 mg cm2. Lithium foil was used as the
counter electrode. The electrolyte consisted of a solution of 1 M
LiPF6 in ethylene carbonate (EC)/dimethyl carbonate (DMC)/
diethyl carbonate (DEC) (1 : 1 : 1, in wt%) obtained from
Tianjin Jinniu Power Sources Materials Co., Ltd. Galvanostatic
cycling tests of the assembled cells were carried out on an Arbin
BT2000 system in the voltage range of 0.01 3.0 V (vs. Li+/Li)
under different current densities. Note that the mass of graphene
was included when the specific capacity of CuO/graphene
composite were calculated. For measuring the electrical
conductivity (s) of the synthesized samples, the pellets of CuO
or CuO/graphene with a thickness of about 1 mm were first
prepared by pressing the powder uniaxially at 5 MPa into columniform molds with a diameter of 14 mm. Then, the electrochemical impedance spectroscopy (EIS) recorded on
a PARSTAT 2273 advanced electrochemical system in the
frequency range from 10.0 Hz to 1.0 MHz were used to calculate
s based on s L/(RA), where L and A is the thickness and area
of the pellets, and R is the fitted resistances from EIS. The EIS
were also used to measure the electronic conductivities of the
10662 | J. Mater. Chem., 2010, 20, 1066110664

assembled cells using lithium foil as both counter electrode and

reference electrode.

Results and discussion

The purities of the as-prepared CuO and CuO/graphene were
confirmed by X-ray diffraction (XRD) spectrometry. As shown
in Fig. 1, all the peaks in spectrum can be assigned to CuO and
graphene, in which CuO shows a monoclinic symmetry (space
 b0 3.425 A,
 c0 5.129 A,
 b
group C2/c; a0 4.684 A,
99.47 , JCPDS Card No. 05 0661), and the graphene peak at 25
is attributed to the (002) plane of hexagonal graphite structure
(see Fig. S1c in ESI). Moreover, the X-ray photoelectron
spectroscopy (XPS) shows only C, O, and Cu (Fig. S2), further
confirming the purity of the as-prepared CuO/graphene material.
A detailed quantitative analysis of XPS spectrometry reveals that
the precise chemical composition of the composites is ca. 74%
CuO and 26% graphene in weight.
The morphology of as-prepared CuO and CuO/graphene was
examined by SEM and TEM. Fig. 2a and 2c show the typical
SEM and TEM images of the as-prepared CuO sample. It is
revealed that the as-prepared CuO has an urchin-like feature
with an average diameter of about 1.5 mm, and the structure are
composed of many CuO nanosheets/nanoplates with a thickness
of ca. 25 nm. In comparison, Fig. 2b and 2d present the typical
SEM and TEM images of the as-prepared CuO/graphene
nanocomposite. Obviously, the basic urchin-like CuO cluster
with CuO nanosheet substructure is little affected after the
addition of graphene material, but all these CuO flowers were
uniformly separated by the surrounding graphene sheets, which
can be clearly observed in the high resolution TEM image
(Fig. 2f).
In view of the high electronic conductivity of graphene, the asobtained CuO/graphene nanocomposite is expected to maintain
the excellent electronic conductivities, which is favorable for
electrode material in LIBs. Electrochemical impedance spectroscopy (EIS) of the CuO material and the CuO/graphene
nanocomposite is performed (Fig. 3a). The results reveal that the
electrical conductivity (s) of the CuO/graphene composite (ca.
0.16 S cm1) is enhanced by as much as 5 orders of magnitude
compared with that of pure CuO material (ca. 1  106 S cm1).
Fig. 3a shows the conductivity measurements of these materials
in the assembled half batteries which give also analogous results.
It can be observed that the conductivity of CuO/graphene
nanocomposite is very close to that of pure graphene material,
but much higher than that of pure CuO.

Fig. 1 XRD pattern of the as-prepared CuO/graphene (a) and CuO (b).

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Fig. 2 SEM and TEM images of the as-prepared CuO (a, c, e) and CuO/
graphene (b, d, f).

To demonstrate the potential use of the CuO/graphene

nanocomposite as a LIBs anode, we carried out a preliminary
investigation on the electrochemical performance of this material
toward Li uptake-release comparing with that of the pristine
CuO. As shown in Fig. 3, the first and the second discharge/
charge voltage file for CuO/graphene electrode are very similar to
that of CuO (Fig. 3b and 3c), implying that the introduction of
graphene does not change the nature of CuO. However, since the
second cycle, the discharge/charge voltage profile for CuO/graphene
electrode has maintained, indicating an excellent capacity retention
capability. For comparison, the capacity retention for CuO electrode has monotonously decreased cycle by cycle. The results
indicate that CuO/graphene nanocomposite is electrochemical
stable which makes it a promising anode material for LIBs.
One surprising enhancement for the CuO/graphene nanocomposite electrode is its remarkable rate capability. As shown in
Fig. 3d, the CuO electrode exhibits poor rate performance
because of its low electronic conductivity and large volume
variations during Li uptake-release cycles. After introducing the
graphene material, the CuO/graphene composite electrode is
observed to show high specific capacity at all discharge/charge
rates. Briefly, the battery was first cycled under 65 mA g1 for 10
cycles, and then the current density was gradually increased in
stages to 6400 mA g1. It can be observed that a specific charge
capacity of ca. 600 mA h g1 was obtained under 65 mA g1 after
This journal is The Royal Society of Chemistry 2010

10 cycles; and this value was slowly lowered to 530 mA h g1,

480 mA h g1, 410 mA h g1, 320 mA h g1, 230 mA h g1, and
150 mA h g1 under 160 mA g1, 320 mA g1, 640 mA g1,
1600 mA g1, 3200 mA g1, and 6400 mA g1, respectively. Under
6400 mA g1, the specific charge capacity of the CuO/graphene
nanocomposite is still as high as 150 mA h g1, which is three
times larger than that of graphene (48 mA h g1), while that of
CuO is nearly null under the same current density. That is to say,
the electrochemical performance of the CuO/graphene nanocomposite is excellent compared with either pure graphene
material or CuO material.
Another excellent advantage of the CuO/graphene nanocomposite is its highly improved cycling performance. Fig. 3e
shows the cycling behavior for the CuO/graphene electrode
under 65 mA g1. During all the 100 cycles, the specific capacity
of the composite is stabilized at ca. 600 mA h g1. The selected
discharge/charge voltage profiles for the 2nd, 50th, and 100th
cycles are shown in Fig. 3e. The essential identical discharge/
charge curves under different cycles indicate that the CuO/graphene nanocomposite must own a high structural stability. SEM
and TEM study of the CuO/graphene nanocomposite after 100
discharge/charge cycles are then performed. The images reveal
that the morphology of CuO/graphene composite is only a little
changed after use (Fig. S3), confirming the high structure stability
of the CuO/graphene composite in electrochemical processes.
To further attest the superiority of graphene to CNTs and
graphite in improving electrochemical performance of CuO,
CuO/CNTs composite, CuO/graphite composite, and CuO-graphene mixture were also synthesized and tested. It is found that
the CuO/graphene nanocomposite shows a very high reversible
capacity and much enhanced cycling performance (600 mA h
g1 after 10 cycles), as well as significantly improved high rate
capability (230 mA h g1 under 3200 mA g1), compared with
CuO/CNTs composite (520 mA h g1 after 10 cycles; 140 mA
h g1 under 3200 mA g1) and CuO/graphite composite (226
mA h g1 after 10 cycles; 5 mA h g1 under 3200 mA g1). In
addition, the CuO/graphene nanocomposite also exhibits higher
reversible capacity than the simply mixed one under all current
densities (see Fig. S4). The improvements can be attributed to
the well dispersed graphene between CuO nanoparticles as well
as the graphene nanocoating layer surrounding CuO in the
nanocomposite compared with those in the mixture. The results
give clear evidence of the superiority of graphene to CNTs and
graphite in improving electrochemical performance of electrode
materials like CuO, as well as the efficiency of the 3D graphene
networks in the present CuO/graphene nanocomposite for high
performance lithium storage.

Conclusions
Based on above electrochemical studies, obviously, the CuO/
graphene nanocomposite is never a simple mixture of CuO and
graphene but a brand new anode material with high specific
capacity, high rate performance, high stability and long cycling
life. In fact, the excellent feature of this CuO/graphene nanocomposite could be attributed to its unique hybrid structure. On
one hand, the 3D network of graphene in the composite material
can be taken as a 3D current collector network, which provides
a high conductivity of electrode and permits rapid exchange of
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Fig. 3 (a) Impedance measurement of graphene, CuO, and CuO/graphene, (b) and (c) discharge/charge profiles for CuO and CuO/graphene under 65
mA g1, respectively, (d) specific capacity of CuO/graphene, graphene, and CuO under different current density. (e) Discharge-charge capacity of the
CuO/graphene up to 100 cycles under 65 mA g1 and the corresponding 2nd, 50th, and 100th discharge-charge voltage profiles.

electrons between CuO and current collector. On the other hand, the
CuO material maintains an urchin-like structure with a nanosheet
substructure, so the excellent Li ion coordination ability of CuO is
maintained. Moreover, the CuO flowers are enwrapped by a thin
layer of graphene as an elastic buffer, which is beneficial for relieving
the strain associated with the volume variations of CuO during Li
uptake-release process and prevent the pulverization of CuO, so the
CuO/graphene nanocomposite is highly stable and has excellent
cycling performance. The construction of the CuO/graphene
composite material highly improves the electrochemical performance of CuO as electrode materials in LIBs, and it is a promising
anode material for high-performance LIBs towards future applications in electrical vehicles and hybrid electrical vehicles.

Acknowledgements
This work is supported by the National Natural Science Foundation of China (Grant Nos., 20821003, 20702053 and
50730005), National Key Project on Basic Research (Grant No.
2009CB930400), the 973 Program (2006CB300402), Ministry of
Science and Technology (2008ZX05013-004), and the Chinese
Academy of Sciences.

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This journal is The Royal Society of Chemistry 2010