Applied Surface Science 258 (2011) 13171321

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Applied Surface Science
j our nal home page: www. el sevi er . com/ l ocat e/ apsusc
Facile synthesis of CuO hollow nanospheres assembled by nanoparticles and
their electrochemical performance
Mei Kong, Weixin Zhang

, Zeheng Yang, Shaoying Weng, Zhangxian Chen

School of Chemical Engineering, Anhui Key Laboratory of Controllable Chemical Reaction and Material Chemical Engineering, Hefei University of Technology, Hefei 230009, China
a r t i c l e i n f o
Article history:
Received 18 May 2011
Received in revised form29 August 2011
Accepted 30 August 2011
Available online 29 September 2011
Keywords:
CuO
Hollownanospheres
Synthesis
Kirkendall effect
Lithiumion batteries
a b s t r a c t
CuO hollow nanospheres with an average diameter of 400 nm and shell thickness of 40 nm have been
successfully synthesized via a simple thermal oxidation strategy with Cu
2
O solid nanospheres as the
precursor. The products have been characterized by X-ray diffraction, transmission electron microscopy
and eld emission scanning electron microscopy. The formation of CuO hollow nanospheres mainly
results from the Kirkendall effect on the basis of temperature-dependent experiments. Furthermore, the
electrochemical performance of CuO hollow nanospheres as anode materials for lithium ion batteries has
been evaluated by cyclic voltammetry and galvanostatic discharge-charge experiments. The as-prepared
CuO hollow nanospheres assembled by nanoparticles exhibit higher initial discharge capacity and better
cycle performance than the reported CuO nanoparticles. The hierarchical hollow nanospheres have been
demonstrated to take the advantages of nanoparticles and hollow architectures, which could not only
shorten the lithium ion transport distance and increase the kinetics of conversion reactions, but also
provide suitable electrode/electrolyte contact area and accommodate the volume change associated with
lithium ion insertion and extraction.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Hollow nanostructures have been paid much attention due
to their high specic surface area, low density and widespread
potential applications in drug delivery, chemical sensors, photonic
devices and lightweight ller [1,2]. A variety of methods have been
developed for the synthesis of nanostructures with hollow interi-
ors including template methods [3,4], hydrothermal treatment [5]
and ultrasonic treatment [6]. In particularly, the Kirkendall effect-
based methods have attracted great interests for the preparation
of hollow nanomaterials in recent years, such as oxidation, sul-
dation and phosphorization of metal nanoparticles, which results
from the different diffusion rates between two components in a
diffusion couple [7,8].
CuO, an important p-type semiconductor with a narrow band
gap (E
g
=1.2eV), has potential applications in sensors, catalysts,
optical switches, lithium ion batteries and solar cells [9,10]. Con-
sidering its wide applications, various CuO hollowstructures have
been prepared. Liu and Zeng [11] synthesized dandelion-like CuO
hollowmicrospheres with diameters of 48m, assembled by CuO
nanoribbons, using Cu(NO
3
)
2
3H
2
O, NH
3
H
2
O, NaOH and NaNO
3

Corresponding author. Tel.: +86 551 2901450; fax: +86 551 2901450.
E-mail address: wxzhang@hfut.edu.cn (W. Zhang).
as reactants by solvothermal method at 100

C for 24h. Liu and

Xue [12] reported the synthesis of porous CuOhollowarchitectures
with diameters of 11.7mby thermal oxidation of CuS and Cu
2
S
solid precursors at 700

C for 4h, respectively. The precursors were

synthesized by solvothermal method using Cu(NO
3
)
2
3H
2
O and
thiourea as reactants with the assistance of PVP at 120

C for 20h.
Bourret and Lennox [13] synthesized porous CuO hollow micro-
spheres assembled by nanoribbons with diameter of 2.55m by
thermolysis of porous Cu(OH)
2
hollow microspheres at 600

C for
15h. The Cu(OH)
2
precursor was fabricated by template method at
room temperature for 35min, using CuCl
2
2H
2
O, n-butylamine as
reactants andwater-in-oil emulsionas soft templateinH
2
O/CH
2
Cl
2
system.
Among all those potential applications, CuO as anode materi-
als for lithiumion batteries have attracted much interests because
of their high theoretical capacity (670mAh g
1
), high safety and
low cost. It has been reported that the morphology and size of
CuO could inuence its electrochemical performances [14,15]. For
instance, Zheng et al. [16] synthesized CuO nanoparticles with an
average size of 10nm via thermal decomposition of CuC
2
O
4
pre-
cursor at 400

C for 4h, which could deliver an initial discharge

capacity of 810mAh g
1
at a current density of 0.1mA cm
2
. The
second and third discharge capacities were about 350mAhg
1
and 120mAh g
1
, respectively. The CuO nanoparticles had a poor
cycle performance. Li et al. reported [17] the synthesis of CuO nan-
otubes by heating Cu nanowires at 600

C for 3h, which showed

0169-4332/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2011.08.127
1318 M. Kong et al. / Applied Surface Science 258 (2011) 13171321
an initial discharge capacity of 910mAh g
1
and the 10th dis-
charge capacity of about 100mAh g
1
at a current density of
50mAg
1
.
In this paper, we report a facile route to synthesize CuO hol-
lownanospheres with uniformdiameters in large scale by thermal
oxidation of Cu
2
O solid nanospheres at 400

C for 2h. The uniform

Cu
2
O solid nanospheres as the precursor were prepared in large
scale through a solution-phase method at roomtemperature with-
out any surfactant or organic solvent. The formation mechanismof
CuO hollow nanospheres has been proposed. As anode materials
for lithiumion batteries, the as-prepared CuO hollownanospheres
showhigher initial dischargecapacityandbetter cycleperformance
compared with the reported CuOnanoparticles, which mainly ben-
ets from the hierarchical hollow nanostructures assembled by
nanoparticles.
2. Experimental details
2.1. Synthesis
All the reagents used in the experiments were analytical grade
and used without further purication. The synthesis of Cu
2
O solid
nanospheres as the precursor was referred to our previous report
[18]. The whole reaction was conducted in a beaker at room tem-
perature under constant magnetic stirring. Typically, 0.375g of
CuSO
4
5H
2
O and 2g of glucose were dissolved in 100mL of dis-
tilled water. Then, 25mL of NH
3
H
2
O solution (0.04M) and 25mL
of NaOH solution (0.20M) were added dropwise into the above
solution in turn. 10min later, 50mL of ascorbic acid (0.03M) was
quickly poured into the mixture. After stirring for another 1h, the
yellowprecipitates were collected by centrifugation, washed with
deionized water and ethanol for several times and then dried in air
at 60

C.
The CuO hollownanospheres were prepared by thermal oxida-
tion of Cu
2
O precursor in air at 400

C for 2h at a heating rate of

5

Cmin
1
. After cooling to roomtemperature naturally, the black
product was obtained.
2.2. Characterization
The as-prepared samples were characterized by X-ray powder
diffraction (XRD) in a Rigaku D/max-B X-ray diffractometer with
a CuK radiation source (=0.154178nm) operated at 40kV and
80mA. Field-emissionscanning electronmicroscopy (FESEM) mea-
surement was carried out with a FEI Sirion-200 scanning electron
microscope operated at an acceleration voltage of 5kV. Transmis-
sion electron microscopy (TEM) images and selected area electron
diffraction (SAED) patterns were taken with a Hitachi H-800 trans-
mission electron microscope performed at an accelerating voltage
of 200kV. Fourier TransformInfrared (FTIR) spectra were recorded
on a PerkinElmer Spectrum100 FTIR Spectrometer using the stan-
dard KBr pellet technique in the range of 4004000cm
1
.
2.3. Electrochemical measurements
The electrochemical measurements were carriedout usingcoin-
type cells (CR2032) at room temperature. The working electrodes
werepreparedbymixingtheas-preparedCuOhollownanospheres,
acetylene black and polyvinylidene uoride (PVDF) at a weight
ratio of 80:10:10 in N-methylpyrrolidone (NMP). The resulting
slurry was uniformly spread onto a Cu foil and dried in vacuumat
70

C for 4h. The cells were assembled in an argon-lled glove box

with lithium disk as counter electrode, microporous polypropy-
lene membrane (Celgard-2400) as separator and 1M LiPF
6
in a
mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC)
10 20 30 40 50 60 70
1

1

1 |
(b)
1

1

0
2

2

0
2

0

0
1

1

1
1

1

0 R
e
l
a
t
i
v
e

I
n
t
e
n
s
i
t
y
2 / degree
| |
|
2

2

0
3

1

1
1

1

3
2

0

2
0

2

0
2

0

2
1

1

1
1

1

1
(a)
Fig. 1. XRD patterns of (a) the precursor and (b) the nal product after thermal
treatment at 400

C for 2h in air.
(1:1involume) as electrolyte. Galvanostatic chargedischarge tests
were conducted on a BTS battery test system (Shenzhen Neware
Co., China) at a current density of 67mAg
1
in a potential range
of 0.0013.0V. Cyclic voltammetry (CV) measurements were per-
formed on a CHI604C electrochemical analyzer (Shanghai Chenhua
Instrument Co., China) at a scan rate of 0.1mV s
1
in the potential
range of 03.0V.
3. Results and discussion
The composition and phase purity of the products were deter-
mined by X-ray powder diffraction (XRD). Fig. 1a shows the XRD
pattern of the precursor precipitated in the solution at roomtem-
perature. All the diffraction peaks can be indexed to cubic Cu
2
O
(JCPDS No. 05-0667). Fig. 1b displays the XRD pattern of the nal
product obtained by thermal oxidation of Cu
2
Oprecursor at 400

C
for 2h, inwhichall the diffractionpeaks canbe indexedto the mon-
oclinic CuO (JCPDS No. 48-1548). No impurities could be obviously
detected in the XRD patterns.
Typical FESEM images of the as-prepared products are shown
in Fig. 2. As can be seen in Fig. 2a, the Cu
2
O precursor con-
sists of nanospheres with an average diameter of 400nm in large
scale. The high-magnication FESEMimage in Fig. 2b displays the
rough surface of these nanospheres. Fig. 2c and d shows the mor-
phology of CuO prepared through thermal oxidation of the Cu
2
O
nanospheres. The average diameter and shell thickness are about
400nm and 40nm, respectively, without any obvious changes of
diameters compared with Cu
2
O precursor. Many broken hollow
spheres shown in Fig. 2c reveal the existence of hollow nano-
structure. Fromthe high-magnication FESEMimage displayed in
Fig. 2d, it can be seen that the shell of the CuO hollownanospheres
is rough and some small nanoparticles can be clearly observed.
The TEMinvestigation was used to provide further insight into
the CuO hollow structure. Fig. 3a shows the TEM image of the
Cu
2
O precursor, indicating that the Cu
2
O nanospheres have a solid
structure with a diameter of 400nm. The TEM image of CuO is
shown in Fig. 3b. The contrast in brightness between the dark
edges and bright centers conrms the hollowstructure of CuOwith
shell thickness of about 40nm, which is consistent with FESEM
images. The corresponding SAED patterns in Fig. S1a and b (Sup-
porting information) display the characteristic diffraction rings of
cubic Cu
2
O and monoclinic CuO, respectively, indicating the poly-
crystalline nature of the products.
To study the formation mechanism of CuO hollow structure,
samples were collected after heating the Cu
2
O precursor in air at
250

C and 300

C for 2h, respectively. After 2h of thermal treat-

ment inair at 250

C, a core-shell structure witha little voidstarts to

M. Kong et al. / Applied Surface Science 258 (2011) 13171321 1319
Fig. 2. FESEMimages of (a, b) Cu
2
O nanospheres and (c, d) CuO hollownanospheres.
form, indicating condensation of abundant vacancies (Supporting
information, Fig. S2a). When heated at 300

C for 2h, the voids

become larger (Supporting information, Fig. S2b).
Similar phenomena were also observed when the samples were
collected through thermal oxidation of the Cu
2
Osolid nanospheres
at 400

Cfor different time. The TEMimages of the morphologyevo-

lution after heating the samples at 400

C for different time were

shown in Fig. S3 (Supporting information). It can be seen that after
heating at 400

Cfor 5min, a sphere withvoids betweenthe surface

layer and the inside core can be observed (Fig. S3a). When the heat-
ing time at 400

C is prolonged to 8min, the voids become larger

and the core-shell structure becomes more obvious (Fig. S3b). After
15min of heating at 400

C, the core almost disappears and a hol-

lowsphere gradually forms (Fig. S3c). Finally the solid nanospheres
Fig. 3. TEMimages of (a) Cu
2
O nanospheres and (b) CuO hollownanospheres.
are completely transformed into hollow nanospheres after 2h of
heating at 400

C (Fig. 3d).
Onthe basis of above observations, the formationprocess of CuO
hollowstructure is much related with the Kirkendall effect [7,8]. At
the beginning of the thermal oxidation, Cu
2
O reacts with O
2
in air
and a thin CuO layer would be formed on the surface of Cu
2
O solid
nanospheres. Subsequently, the Cu
+
in the core diffuse outward
through the CuO shell, meanwhile the O
2
in air diffuse inward.
Because of the different diffusion rates, Cu
+
diffuse much faster
outward than O
2
inward and the hollow interior forms [19]. Con-
sequently, excess vacancies occur in the core and hollowstructure
appears.
Interestingly, theresult hereis quitedifferent fromthat reported
by Lis group [20], who used a solution-phase method in N,N-
dimethylformamide at 8595

C to get Cu
2
Osolid nanospheres and
transformedthemintoCuOsolidnanospheres bythermal oxidation
in air at 500

C for 2h, without any obvious change of morphology.

The possible reason may be that the Cu
2
O nanosphere precursor
in our work, synthesized at room temperature in the presence of
glucose, is different from the one reported in the literature [20].
To further characterize the as-prepared Cu
2
O nanospheres, FTIR
spectra of the as-prepared Cu
2
O nanospheres and glucose were
investigated, respectively, as shown in Fig. S4 (Supporting infor-
mation). Fig. S4a shows the FTIR spectra of the as-prepared Cu
2
O
nanospheres. The characteristic absorption band at 629cm
1
cor-
responds to the CuOvibrationof the Cu
2
Onanocrystals. The bands
due to adsorptions of water molecules are observed at 3300cm
1
and1610cm
1
, whichare attributedtothe OHstretchingandOH
bending, respectively. Besides, the bands in the 28003000cm
1
region correspond to the CH stretching. The bands located at
1460cm
1
and 1270cm
1
are assigned to the vibrations associ-
ated with the CH
2
group, and typically the band near 1050cm
1
conrms the existence of carbohydrate [21]. Compared with the
FTIR spectra of glucose in Fig. S4b, the result clearly suggests that
there still exist some glucose molecules in the Cu
2
O spheres even
1320 M. Kong et al. / Applied Surface Science 258 (2011) 13171321
0.0 0.5 1.0 1.5 2.0 2.5 3.0
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
0.83 V
1.01 V
2.36 V
0.73 V
3rd
2nd
1st
C
u
r
r
e
n
t

/

m
A
Potential / V vs. Li
+
/Li
1.15 V
Fig. 4. Cyclic voltammograms of the CuO/Li cell in the rst, second and third cycles
at a scan rate of 0.1mV s
1
.
after washing the samples with water and ethanol several times
[22,23]. Thus, the aggregates of Cu
2
O nanoparticles with the mod-
ication of the glucose molecules may play an important role in
the facile formation of CuO hollow nanostructures [24,25]. Mean-
while, during the thermal oxidation process, the remnant glucose
molecules inthe Cu
2
Ospheres were decomposed into CO
2
and H
2
O
gases, which would emit out of the spheres and were benecial to
the formation of the CuO hollownanostructures [26].
The electrochemical performances of the as-prepared CuO hol-
low nanospheres have been evaluated as anode materials for
lithiumion batteries. Fig. 4 shows the rst three cyclic voltammo-
grams of the CuO/Li cell at a scan rate of 0.1mV s
1
. In the rst
cycle, two cathodic peaks located at 1.01 and 0.83V (vs. Li
+
/Li)
are attributed to the electrode reaction and growth of solid elec-
trolyte interface, respectively [27,28]. Meanwhile, the anodic peak
at 2.36V is corresponding to the Li extraction fromthe crystal lat-
tice of CuO [29]. In the following cycle, two cathodic peaks shift to
0.73V and 1.15V along with the decrease of each peak intensity,
indicating that the reversible capacity greatly loses. In the third
cycle, the peak potentials remain similar and the peak intensity
decreases slightly.
Fig. 5 displays the dischargecharge curves of the CuO/Li cell
at a current density of 67mAg
1
. During the rst discharge pro-
cess, there are two obvious plateaus at the potential of 1.221.0V
and 0.80.01V (vs. Li
+
/Li), which is consistent with the results of
CV measurement. The rst discharge capacity is 1134mAh g
1
,
0 1 2 3 4 5 6 7 8 9 10
0
200
400
600
800
1000
1200
S
p
e
c
i
f
i
c

c
a
p
a
c
i
t
y

/

m
A

h

g
1
Cycle number
0 200 400 600 800 1000 1200
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
3rd
2nd 3rd
2nd
1st
P
o
t
e
n
t
i
a
l

/

V

v
s
.

L
i
+
/
L
i
Specific capacity / mAh g
1
1st
Fig. 5. The dischargecharge curves of the CuO/Li cell at a current density of
67 mA g
1
in a potential range of 0.0013.0V. The inset is the corresponding cyclic
performance of the cell.
which is higher than the theoretical capacity of CuO(670mAh g
1
).
The extra discharge capacity is mainly attributed to the formation
of a solid electrolyte interface (SEI) lm during the rst dis-
charge/charge process [27,30]. The capacity fades to 425mAh g
1
in the second discharge cycle and after 10 cycles the discharge
capacity gradually decreased to 190mAh g
1
(inset in Fig. 5). The
CuO hollownanospheres assembled by nanoparticles showhigher
initial discharge capacity and better cycle performance than the
previous report of CuOnanoparticles with size of 10nm, which can
only deliver an initial discharge capacity of 810mAhg
1
at a cur-
rent densityof 0.1mA cm
2
andthedischargecapacitydecreasedto
120mAh g
1
after 3 cycles [16]. The results indicate that the hierar-
chical hollownanospheres cantaketheadvantages of nanoparticles
and hollow architectures. The high initial discharge capacity may
result from the nanoparticles, which could shorten the lithium
ion transport distance and increase the kinetics of conversion
reactions. The good cycle performance is much related with the
hierarchical hollow nanostructures, which could provide suitable
electrode/electrolyte contact area and accommodate the volume
change associated with lithiumion insertion and extraction.
4. Conclusions
This work demonstrates the synthesis of CuO hollow
nanospheres with diameters of about 400nm by thermal oxi-
dation of Cu
2
O solid nanospheres as the precursor in air at 400

C
for 2h. The morphology of CuO does not change obviously in
comparison with Cu
2
O precursor and the as-prepared CuO hollow
nanospheres are assembled by nanoparticles. The formation of
CuO hollow nanospheres from Cu
2
O solid nanospheres mainly
results from the Kirkendall effect. The whole process can be
easily achieved without any surfactant, organic solvent or etching
process. This facile, green and low-cost synthesis route may be of
great signicance to prepare other metal oxide hollow structures.
Besides, the as-prepared CuO hollow nanospheres as anode mate-
rials for lithiumion batteries showhigher initial discharge capacity
of 1134mAh g
1
and better cycle performance than the reported
CuO nanoparticles. It is attributed to the hierarchical hollow
nanostructures which could provide enhanced accommodation of
the strain energy associated with lithium insertion/removal and
offer a suitable electrode/electrolyte contact area. Furthermore,
the nanoparticles assembling the hierarchical nanospheres could
reduce the transport or diffusion distances of electrons and lithium
ions and increase the kinetics of conversion reactions.
Acknowledgements
The authors are grateful to the nancial supports of the National
Natural Science Foundation of China (NSFC Grants 20871038,
20976033 and 21176054), the Fundamental Research Funds for the
Central Universities (2010HGZY0012) and the Education Depart-
ment of Anhui Provincial Government (TD200702).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.apsusc.2011.08.127.
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