Materials Letters 96 (2013) 158161

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

SnO2/NiO core-shell nanobelts and their high reversible lithium storage

capacity arising from synergistic effect
Li-Li Xing, Chun-Xiao Cui, Bin He, Yu-Xin Nie, Ping Deng, Xin-Yu Xue n
College of Sciences, Northeastern University, Shenyang 110004, China

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 31 October 2012
Accepted 9 January 2013
Available online 20 January 2013

SnO2/NiO core-shell nanobelts have been synthesized simply by coating NiO nanobelts with a thin layer
of SnO2 nanoparticles. As the anode material of lithium-ion battery, SnO2/NiO core-shell nanobelts
exhibit higher reversible capacity (  900 mAh/g at C/20 rate) and better cycling performance than
individual NiO or SnO2 materials. The excellent performance can be attributed to the synergistic effect
between SnO2 and NiO. Our results demonstrate the potential applications of SnO2/NiO core-shell
nanobelts in high-performance lithium-ion batteries.
& 2013 Elsevier B.V. All rights reserved.

Keywords:
Nanomaterials
Nanocomposites
Energy storage
Lithium-ion battery

1. Introduction
Lithium-ion batteries (LIBs) have attracted great attention in
the scientic and industrial elds because of their high energy
density and long service life. In the most recent years, the
development of solar-LIB power pack and self-charging power
cell has raised new demands on the performance of LIBs [1,2].
Although graphite as anodes shows excellent cyclability, their low
capacity (372 mAh/g) limits their applications [3]. Nowadays,
nanostructured metal oxides have been regarded as good candidates in fabricating high-capacity/cyclability anodes [48]. However, irreversible capacity loss of metal oxide nanostructures
resulted from the formation of Li2O (e.g. SnO2) is too large [9].
In this paper, synergistic effect is introduced in SnO2/NiO coreshell nanobelts, which exhibit both high reversible lithium
storage capacity and excellent cycling performance. The irreversible capacity loss is much smaller than traditional metal oxides.
Ni nano-clusters make extra Li2O from SnO2 reversibly convert to
Li . These results can provoke a new direction on fabricating
high-performance LIB anodes.

2. Experiments
0.251 g NiCl2.6H2O and 0.065 g Na2C2O4 were put into a
mixture of 9.0 mL H2O and 16 mL ethylene glycol (EG). After
stirring for 10 min, the solution was transferred into a 50 mL
Teon lined stainless steel autoclave and kept at 220 1C for 12 h.
n

Corresponding author. Tel.: 86 024 83687658; fax: 86 010 83676883.

E-mail address: xuexinyu@mail.neu.edu.cn (X.-Y. Xue).

0167-577X/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2013.01.030

NiC2O4.2H2O nanobelts were collected, washed and dried. Then,

as-synthesized NiC2O4.2H2O (0.4 g) and SnCl2.2H2O (2.408 g)
were added into 80 mL distilled water and ultrasonically
dispersed for 30 min. 1.33 mL of concentrated HCl was slowly
added and continually stirred for 24 h. The precipitation was
washed and dried. Finally, SnO2/NiO core-shell nanobelts were
obtained by annealing at 400 1C. The fabrication process of coincells was similar to our previous report [10,11].

3. Results and discussion

Fig. 1a is typical X-ray diffraction (XRD) patterns of SnO2/NiO
core-shell nanobelts (red) and bare NiO nanobelts (black). Sharp
diffraction peaks can be observed in both of the patterns,
indicating good crystallization. All the diffraction peaks in the
black curve can be indexed to cubic NiO (JCPDS card no. 47-1049).
In the red curve, the three asterisked peaks can be indexed to
(110), (101), (211) planes of tetragonal SnO2 crystal (JCPDS card
no. 41-1445). EDS spectrum in Fig. 1b reveals that the structure
consists of Ni, Sn and O elements, and no other impurities are
observed in our products. EDS analysis has been performed on ten
other different areas, and the average mass percentage of SnO2 in
the composites is about 20%.
Fig. 2a is a typical scanning electron microscope (SEM) image
of NiC2O4.2H2O nanobelts. NiC2O4.2H2O nanobelts have the
length of 1030 mm and the width of 90 nm. Fig. 2b is a
transmission electron microscope (TEM) image of NiO nanobelts
and their polycrystalline structure can be conrmed from the
selected area electron diffraction (SAED) pattern in the inset of
Fig. 2b. The diffraction rings in the inset can be indexed to (111),
(200) and (220) planes of cubic NiO crystal. As shown in Fig. 2c,

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159

Fig. 1. (a) XRD patterns of SnO2/NiO core-shell nanobelts (red) and NiO nanobelts (black). and (b) energy dispersive X-ray spectrometer (EDS) spectrum of SnO2/NiO coreshell nanobelts. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

Fig. 2. (a) SEM image of NiC2O4.2H2O nanobelts. (b) and (c) are low resolution (the inset is SAED pattern) and high resolution TEM images of NiO nanobelts, respectively.
(d) SEM image of SnO2/NiC2O4.2H2O core-shell nanobelts. (e) and (f) are low resolution (the inset is SAED pattern) and high resolution TEM images of SnO2/NiO core-shell
nanobelts, respectively.

the lattice spacing is about 0.20 nm, corresponding with (200)

plane of NiO crystal. A typical SEM image of SnO2/NiC2O4.2H2O
core-shell nanobelts is shown in Fig. 2d. The width of SnO2/
NiC2O4.2H2O core-shell nanobelts is  200 nm, larger than that of
bare NiC2O4  2H2O nanobelts. Fig. 2e is TEM image of SnO2/NiO
core-shell nanobelts, showing their width of larger than 200 nm.
The inset is the SAED pattern of SnO2/NiO core-shell nanobelts,
showing two different natures of crystals. The diffraction pattern
can be indexed to NiO and SnO2, and their crystal face information has been marked. The lattice spacing of the nanoparticles on
the surface is 0.32 nm and 0.27 nm (Fig. 2f), corresponding with
(110) and (101) plane of SnO2, respectively.
The electrochemical performance of SnO2/NiO core-shell nanobelts and NiO nanobelts is shown in Fig. 3. The rst discharge
capacity of SnO2/NiO core-shell nanobelts is 1133 mAh/g and
maintains at 888 mAh/g after 30 cycles, as shown in Fig. 3a. The
reversible capacity of SnO2/NiO core-shell nanobelts is
900 mAh/g, higher than that of NiO nanobelts ( 770 mAh/g)
shown in Fig. 3b. Such a reversible capacity of SnO2/NiO core-

shell nanobelts is also higher than that of SnO2 materials

(theoretical capacity: 782 mAh/g) [5]. Fig. 3c and d are differential
capacity curves (dC/dV vs. voltage) of SnO2/NiO core-shell nanobelts and NiO nanobelts, respectively. In the rst discharge
process of bare NiO nanobelts, the peak around 0.3 V corresponds
with the conversion of NiO to Ni [12]. In the following discharge
processes, the peaks around 0.3 and 1.3 V correspond with the
reduction of NiO and the formation of solid electrolyte interface
(SEI), respectively [6,12]. During the delithiation processes, the
peaks around 1.5 and 2.0 V correspond with the decomposition of
Li2O and the electrolyte, respectively [6]. In the rst discharge
process of SnO2/NiO core-shell nanobelts, the new peak appearing
around 0.5 V corresponds with the formation of LixSn [13]. And in
the following delithiation processes, the new peak around 0.6 V
corresponds with the decomposition of LixSn [13]. Fig. 3e and f
show the cycling performance of SnO2/NiO core-shell nanobelts and
NiO nanobelts at C/5 rate, respectively. The discharge capacity of
SnO2/NiO core-shell nanobelts after 30 cycles is 798 mAh/g,
while the discharge capacity of NiO nanobelts is 587 mAh/g.

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Fig. 3. Galvanostatic chargedischarge curves of (a) SnO2/NiO core-shell nanobelts and (b) NiO nanobelts at the 1st, 2nd, 5th, 10th, 30th cycle between 3.0 and 0.001 V at
C/20 rate. Differential capacity curves of (c) SnO2/NiO core-shell nanobelts and (d) NiO nanobelts. Cycling performance of (e) SnO2/NiO core-shell nanobelts and (f) NiO
nanobelts at C/5 rate.

Interestingly, a gradual increase of capacity can be observed in SnO2/

NiO core-shell nanobelts, which is well-documented in many
literatures, being attributed to the reversible growth of a polymeric
gel-like lm resulting from kinetically activated electrolyte degradation [1416].
Based on the traditional theory, the reversible capacity of
SnO2/NiO composites should be calculated as follows [17]:
CSnO2 =NiO C SnO2  mass%SnO2 CNiO  mass%NiO

As the value of mass% ranges from 0 to 1, the reversible capacity

of SnO2/NiO should be between 718 and 782 mAh/g. According to
the results presented above, the experimental capacity is higher
than the theoretical capacity. This higher reversible capacity can be
attributed to the synergistic effect between SnO2 and NiO nanostructures. In the rst discharge process, the lithiation reaction of NiO
nanostructures is as follows [6]:
NiO2Li 2e  2NiLi2O

(2)

This reaction yields nano-dispersed Ni metal particles. The

small size effect of Ni nanoparticles can greatly increase the
electrochemical reactivity and make the conversion between Li
and Li2O reversible. Moreover, rst-principle molecular dynamics
calculations in previous reports show that nanostructured metal
oxides contain more oxygen atoms than bulk materials in order to
passivate the surface dangling [10,11]. Therefore, Ni nano-clusters
obtained in this process can make extra Li2O reversibly convert to
Li . And the initial lithiation reaction of SnO2 can just provide
extra Li2O in this system as follows [13]:
SnO2 4Li 4e  -2Li2OSn

(3)

SnxLi xe  2LixSn

(4)

Thus, the synergistic effect between SnO2 and NiO leads to

higher reversible capacity by converting Li2O to Li . The Li
insertion/extraction mechanism of SnO2/NiO core-shell nanobelts
is schematically shown in Fig. 4. And the total reaction between

Fig. 4. Schematic illustration of Li insertion/extraction mechanism for SnO2/NiO

nanobelts.

Li and SnO2/NiO core-shell nanobelts can be roughly written as

follows:
NiO1 2x xSn(28.4x)Li (28.4x)e 
2Ni (12x) Li2O(NiO SnO2) xLi4.4Sn

(5)

The reversible capacity should be calculated as follows:

CSno2 =Nio C Sn  mass%Sn C NiO1 x  mass%NiO1 x

Therefore, based on the experimental data, the mass percentage of SnO2 in the composites can be calculated to be  24%,
agreeing with the EDS results.

4. Conclusions
SnO2/NiO core-shell nanobelts were synthesized via a twostep route. They exhibited high reversible lithium storage capacity and excellent cycling performance. Such a high performance
could be attributed to the synergistic effect of SnO2 and NiO.
Our results could provoke a new direction to fabricate highperformance LIB anodes.

L.-L. Xing et al. / Materials Letters 96 (2013) 158161

Acknowledgment
This work was partly supported from the National Natural
Science Foundation of China (51102041 and 11104025).
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