ARTICLE IN PRESS

Materials Science and Engineering B (2016)

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Materials Science and Engineering B

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / m s e b

Boron oxidetin oxide/graphene composite as anode materials for

lithium ion batteries
Lina Wen a, Xue Qin a,b,*, Wei Meng a, Ning Cao a, Zhonghai Song a
a Department of chemistry, School of Science, Tianjin University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin

300072, China
b
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China

A R T I C L E I N F O A B S T R A C T

Article history: B2O3SnO2/graphene (B2O3SnO2/G) composite is fabricated via a chemical heat solvent method and uti-
Received 14 January 2016 lized as anode material for lithium ion batteries. The added B2O3 dramatically improves the electrochemical
Received in revised form 28 April 2016 performance of lithium ion batteries compared to the SnO2/G composite. The B2O3SnO2/G composites
Accepted 3 May 2016
as anode show an outstanding discharge capacity of 1404.9 mAh g1 at 500 mA g1 after 200 cycles and
Available online
an excellent rate capacity, which apparently outperforms the previously reported SnO2-based anode ma-
terial. These improved electrochemical performance characteristics are due to the B2O3 played a buffering
Keywords:
role, which are easily benecial for accommodating the volume change during the lithium ions insertion/
B2O3
SnO2 extraction processes. Furthermore, boron atoms can accept electrons for its electron-decient nature and
Composite boron ions could release electrons, which lead to electrons increased density and conductivity are in-
Anode creased. The results indicate that the B2O3SnO2/G composite is a promising anode material for lithium
Lithium ion batteries ion batteries.
2016 Elsevier B.V. All rights reserved.

1. Introduction for application in LIBs and exhibited increased capacity, including

Lithium ion batteries (LIBs), as the most prominent energy storage
system, have attracted worldwide attention due to their advan-
tages such as high working voltage, high energy density, excellent
cycle life, no memory effect, convenience, and environment-
friendly [13]. However, a considerable lower theoretical capacity
of graphite (372 mAh g1) as an anode material has limited the de-
velopment of LIBs and cannot meet the increasing energy storage
demand. Therefore, it is urgent to explore new selectable anode ma-
terials to promote the electrochemical performances.
In recent years, many efforts have been made in researching
hybrid structural nanomaterials as lithium ion anode materials. These
anode materials have been studied contain core-shell structured
NiO@SiO2 [4], carbon doped materials [5] and graphene compos-
ites and so on. For the material of NiO@SiO 2 , the capacity is
only 700 mAh g 1 after 150 cycles, which is far less than the
demand for energy in modern society. For MoO2/N-doped carbon
heteronanowires, although the cycle life is up to 500 cycles, the ca-
pacity is too low that is only 800 mAh g1. With the development
of science materials, graphene is found to be a material with ex-
cellent performance. Graphene, as a two-dimensional sheet of sp2-
bonded carbon, had been widely investigated as an anode material
* Corresponding author. Tel.: +86 022 27403670; fax: +86 22 27403475.
E-mail address: qinxue@tju.edu.cn (X. Qin).
other allotropic substances such as one-dimensional nanotubes and
zero-dimensional fullerenes. However, LIBs capacity improve-
ment of these carbon materials is limited [6,7]. Besides, metal oxides
or suldes usually have a higher specic capacity, but the struc-
ture is not stable. If they are combined with graphene, it is very
possible to produce more excellent materials. And there are already
many graphene composites including Fe3O4/graphene, CoO/graphene,
V2O3/graphene, Cu2O/graphene, TiO2/graphene, SnO2/graphene, MoS2
RGO, etc [815]. Among the above composite materials, tin dioxide
(SnO2) has been considered to be an excellent candidate as anode
material for LIBs for its high theoretical capacity of 782 mAh g1,
which is much higher than that of graphite [16]. Importantly, SnO2
possesses several advantages as a LIB anode material, such as low
cost, safety, environmental benignity, high abundance, and lower
chargedischarge plateau, which are not contained in other metal
oxide anodes [17,18]. SnO2/graphene (SnO2/G) anode composites
utilize both advantages of graphene and SnO2 to signicantly improve
the electrochemical performance. However, SnO2 anodes suffer the
disadvantage that they exhibit a large volume change of about 300%
during the lithiation and delithiation processes, which results in
severe election materials pulverization and rapid capacity fading
during the charge/discharge processes [16]. In addition, there is a
poor initial Coulombic eciency during the rst cycle, which con-
tributes to Li2O formation in the irreversible conversion reaction.
In order to offset the defects of SnO2, many efforts by doping with
other substances have been made to increase life cycle. For example,

http://dx.doi.org/10.1016/j.mseb.2016.05.004
0921-5107/ 2016 Elsevier B.V. All rights reserved.

Please cite this article in press as: Lina Wen, Xue Qin, Wei Meng, Ning Cao, Zhonghai Song, Boron oxidetin oxide/graphene composite as anode materials for lithium ion batteries,
Materials Science and Engineering B (2016), doi: 10.1016/j.mseb.2016.05.004
 ARTICLE IN PRESS
2 L. Wen et al. / Materials Science and Engineering B (2016)
Xia et al. [19] reported a novel core-shell nanocomposite struc-
ture of SnO2B2O3 produced by a modied molten-salt decomposition
method. The electrochemical performances of the prepared mate-
rials were greatly improved because B2O3 limited the SnO2 volume
change. Liu and his co-workers prepared composite anode mate-
rials of hollow SnO2 microspheres covered by B2O3 layers, which
exhibited improved cycling performance and rate capacity com-
pared to that of pristine hollow SnO2 [20]. There are also many other
ternary nanocomposites such as SnO2PANIrGO, grapheneSnO2
carbon and SnO2TiO2/graphene [2123]. Among those methods,
doping boron is deemed as a promising one, for its excellent im-
proving characteristics and simple operation.
In this paper, a one-step chemical heat solvent method was de-
veloped to obtain a nanocomposite of B2O3SnO2/graphene (B2O3
SnO2/G). B2O3, distributed on the SnO2/G surface, resulted in the B2O3
SnO2/G ternary nanocomposites formation. On one hand, as anode
for lithium ion batteries, B2O3 works as a mechanical support in B2O3
SnO2/G to buffer the volume change of SnO2 during the lithium ions
insertion/extraction processes as well as protects the SnO2 crystal
from agglomeration. On the other hand, electrons density and con-
ductivity was increased owing to that boron atoms can accept
electrons for its electron-decient nature, and boron ions could
release electrons, thus facilitate the insertion/de-insertion of Li in
SnO2. Notably, B2O3 made a great contribution to the enhanced elec-
trochemical performance, and the specic improvement was
systematically researched.
2. Experimental
2.1. Sample preparation
The ternary nanocomposites B2O3SnO2/G were synthesized using
a one-step chemical heat solvent method. All raw chemical mate-
rials were of analytical grade and utilized without any further
purication. Graphene oxide (GO) was prepared from natural graph-
ite powder by a modied Hummers method reported previously
[24,25].
In a typical synthesis, 100 mg of dried GO was dispersed in 100 mL
of deionized water. The obtained solution was ultrasonicated for
30 min in the ultrasonic cell crusher to separate the graphene oxide
layer from the layer, followed by centrifugation of 5 min to remove
impurities and produce the supernatant for the next reaction. In ad-
dition, 5 mL of concentrated hydrochloric acid was added dropwise
onto 100 mg of SnCl2 2H2O to dissolve the SnCl2, followed by adding
100 mL of deionized water to make a transparent solution. Then,
the transparent solution and the above supernatant were mixed and
stirred for 10 min. After that, 50 mg of boric acid was added to the
suspension and stirred for another 20 min to get a homogeneous
suspension. The nal suspension was transferred to a three distil-
lation ask of 250 mL. Then, the suspension was reuxed and stirred
at 85 C for 12 h. After the reaction was completed and the reaction
mixture cooling down to room temperature, the precipitate were
rinsed with deionized water until the pH value of the system reached
nearly to 7 and dried at 55 C for 24 h. Then the product was sin-
tered in a tubular furnace at 500 C with a ow of argon for 1 h. Finally,
the B2O3SnO2/G composite was obtained after annealing. Another
sample SnO2/G was also produced in accordance with the above steps
in the absence of boric acid.
2.2. Sample characterization
The as-prepared material of B2O3SnO2/G was investigated by
X-ray diffraction (XRD, D/MAX-2500), Raman spectroscopy (RS, In
Via Rex), thermogravimetric analysis (TGA, STA 409 PC Luxx),
transmission electron microscopy (TEM, Tecnai G2 F20), and
Please cite this article in press as: Lina Wen, Xue Qin, Wei Meng, Ning Cao, Zhonghai Song, Boron oxidetin oxide/graphene composite as anode materials for lithium ion batteries,
Materials Science and Engineering B (2016), doi: 10.1016/j.mseb.2016.05.004
BrunauerEmmettTeller (BET) specic surface (NOVA2200e;
Quantachrome).
2.3. Electrochemical measurements
The electrochemical performances of the as-prepared material
were investigated as the anode in the coin-type cell (CR 2032). The
as-prepared material, lithium tablets, and 1 M LiPF6 in a mixture
of ethylene carbonate and dimethyl carbonate in a volume ratio of
1:1 were used as the working electrode, counter electrode, and elec-
trolyte, respectively, and assembled in an argon-lled glove box. The
cells were galvanostatically charged/discharged in the voltage range
of 0.01 to 3.0 V versus Li/Li+ by a battery testing system (LAND CT-
2001A). Cycle voltammetry (CV) curves were carried out using a
Zahner Ennium electrochemical workstation. Electrochemical im-
pedance spectra of the electrodes were recorded from 100 kHz to
100 mHz at 5 mV of the amplitude of the perturbation.
3. Results and discussion
Fig. 1a shows the XRD patterns of the as-prepared SnO2/G and
B2O3SnO2/G composites. For the SnO2/G sample, the main peaks
for SnO2 can be clearly observed according to the tetragonal rutile
structure of SnO2 (JCPDS No. 41-1445). More obvious diffraction
peaks including 2 = 26.5, 33.8, 37.8, 51.8, 54.6, 57.8, 61.7, 65.1,
71.3 and 78.7 can be assigned to the (110), (101), (200), (211), (220),
(002), (310), (112), (202), and (321) planes of SnO2 phase. There are
also another two wide diffraction peaks at 22.5 and 41.5 for the
B2O3SnO2/G structure, which are attributed to the presence of single
crystalline structure B2O3 [20]. The wider peak width of B2O3 is due
to the particles are relatively small. Moreover, no other redundant
peaks are observed, suggesting the reduction of graphene oxide (GO)
and no other crystalline borne phase formed in the reaction.
Boric acid can be divided into H2O and B2O3 at 500 C under a
heated condition, so B2O3 can adhere to the SnO2 and graphene. Fur-
thermore, the crystal SnO2 can be more solid in the surface of
graphene. As is known to all, boron atoms can accept electrons for
its electron-decient nature and boron ions can release electrons,
which increases the electrons density and conductivity. Thus, B2O3
can be an important additive for the processes of charge and dis-
charge. So, the B2O3SnO2/G is expected to be a material that
performs excellent electrochemical properties.
Fig. 1b shows the Raman spectroscopy of B2O3SnO2/G and SnO2/
G. For the two kinds of composites, the peaks around 1588 and
1344 cm1 correspond to the G and D bands of graphene, respec-
tively. The G band results from the in-plane vibration of sp2C bonded
pairs, while the D band originates from the defect sites or disor-
dered carbon. Also, the peaks at 2675 and 2930 cm1 are assigned
to the high reduction of GO and the formation of graphene. In ad-
dition, the intensity ratio of D to G band (ID/IG) is used for estimating
the disorder degree of graphene [26]. The D/G intensity ratio of B2O3
SnO 2 /G sample (I D /I G = 1.18) is larger than that of the SnO 2 /G
nanocomposite (ID/IG = 0.97), suggesting increased structural dis-
order of graphene, and simultaneously that the SnO2 and B2O3
nanocomposites have been loaded in the graphene sheets.
The TG curves in Fig. 1c can clearly quantify the concentration
of SnO2 and B2O3. The two samples were heated from room tem-
perature to 800 C at a rate of 5 C min1. For both nanocomposites,
there is an abrupt weight loss from 250 C to 550 C with the in-
creasing temperature, which is attributed to the combustion and
decomposition of graphene. After 600 C, there is nearly no mass
loss. From analyzing the curves, the calculated concentration of SnO2
and B2O3 in B2O3SnO2/G is 65.02 wt% and SnO2 in SnO2/G is 44.31
wt%. Thus, the B2O3 concentration in B2O3SnO2/G is 20.71 wt%.
Fig. 2 shows the TEM images of the SnO2/G sample (Fig. 2ac)
and the B2O3SnO2/G composite (Fig. 2df). The diameters of SnO2/G
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L. Wen et al. / Materials Science and Engineering B (2016) 3

Fig. 1. (a) XRD patterns; (b) Raman spectra; and (c) TG curves of B2O3SnO2/G and SnO2/G.

Fig. 2. TEM images for SnO2/G (ac) and B2O3SnO2/G composites (df).

Please cite this article in press as: Lina Wen, Xue Qin, Wei Meng, Ning Cao, Zhonghai Song, Boron oxidetin oxide/graphene composite as anode materials for lithium ion batteries,
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Fig. 3. N2 adsorptiondesorption isotherms of (a) SnO2/G and (b) B2O3SnO2/G nanocomposites. Insert pore size distribution from the adsorption branch through the BJH
method.
nanoparticles exhibited in TEM images in Fig. 2ac are in the range
of 2040 nm. For the B2O3SnO2/G composites, as shown in Fig. 2df,
the nanoparticles diameters are in the range of 3050 nm. This is
a larger dimension compared to the SnO2/G sample, which is due
to the addition of B2O3 during the stirring and calcining processes.
Furthermore, graphene, as a substrate, play a huge role for its lam-
inated structure to the two kinds of material. In addition, Fig. 2c and
f show the measured crystal structures of the two composites. The
interplanar spacing of simplex SnO2 in Fig. 2c is about 0.33 nm, which
corresponds to the (110) SnO2 planes (JCPDS No. 41-1445). However,
the interplanar spacing of SnO2 doped B2O3 in Fig. 2f is about
0.342 nm, which is wider than that of simplex SnO2, which indi-
cates that B2O3 indeed adhere to SnO2 nanoparticles and insert into
different crystal surfaces. There is also a lighter colored edge in Fig. 2f
relative to the uniform color of Fig. 2c, which further suggests that
B2O3 is distributed around the SnO2. All the characterizations are
consistent with the XRD results.
Fig. 3 exhibits the N2 adsorption-desorption isotherms and pore
size distribution of SnO2/G and B2O3SnO2/G nanocomposites. The
concrete surface area of B2O3SnO2/G is calculated by the multi-
point BrunauerEmmettTeller (BET) method, from the isotherm
curves adsorption branch, as 2756.130 m2 g1; which is dramatical-
ly larger than that of SnO2/G (576.742 m2 g1). The expanded surface
area of B2O3SnO2/G is attributed to the B2O3 buffer layers around
the SnO2/G. From the isotherm curves desorption branch, the most
porouse radius calculated through a BarrettJoynerHalenda (BJH)
model for B2O3SnO2/G and SnO2/G is 2.267 and 2.285 nm, respec-
tively, which both in the range of typical mesoporous structure
(insert). In addition, the total pore volume of B 2 O 3 SnO 2 /G
is 4.031 cm 3 g 1 , which is much larger than that of SnO 2 /G
(0.970 cm3 g1). The higher the surface area, the larger pore volume
and mesoporous structure for B2O3SnO2/G can be advantageous to
anode materials. On one hand, the larger pore volume can provide
more space for absorptiondesorption of Li+; on the other hand, the
higher surface area is also helpful for the sucient electrochemi-
cal reaction and diffusion of Li+ during charge/discharge processes.
All those characterizations are benecial to the improvement of elec-
trochemical performance.
In order to analyze the lithium ions insertion/extraction pro-
cesses in the SnO2/G and B2O3SnO2/G composites, CV curves were
carried out in the 0.013.0 V potential range at a scan rate of
0.2 mV s1, as shown in Fig. 4a. Both the SnO2/G and B2O3SnO2/G
Please cite this article in press as: Lina Wen, Xue Qin, Wei Meng, Ning Cao, Zhonghai Song, Boron oxidetin oxide/graphene composite as anode materials for lithium ion batteries,
Materials Science and Engineering B (2016), doi: 10.1016/j.mseb.2016.05.004
show the oxido-reduction peaks at the similar potential position.
During the cathodic processes, for example, the peaks around 0.5
1.25 V are assigned to the reduction of SnO2 to Sn, as well as the
formation of Li2O (Eq. (1)). Meanwhile, the LixC forms with the Li
insertion in graphene nanosheets in this process, as exhibited in Eq.
(2). In the anodic curves, the oxidation peaks around 0.50.75 V can
be described as the Li extraction from graphene and the Li de-
alloying from LixSn (Eq. (3)). The peaks around 1.251.5 V are
attributed to the reversible formation/decomposition of Li2O and
partially the reversible reaction of the Eq. (1) [27,28]. There are no
other peaks regarding boron except for that of Sn, suggesting that
B2O3 did not participate in the charge/discharge processes. However,
the scanned area of B2O3SnO2/G is larger than that of SnO2/G, which
indicates that boron atoms contributed toward accepting and re-
leasing electrons. Thus, the boron atoms increased the free electron
density and enhanced the electrochemical performance.
4Li+ + SnO2 + 4e Sn + 2Li2O (1)
xLi+ + C ( graphene) + xe  Lix C (2)
xLi+ + Sn + xe  Lix Sn (3)
Li2O + Sn  SnO + 2Li+ + 2e (4)
Fig. 4b shows the typical charge/discharge proles of the B2O3
SnO2/G composite for the 1st, 2nd, 50th, 100th, 150th and 200th
at the current densities of 500 mA g1 with a voltage range from
0.01 V to 3.0 V. For the rst cycle, there is an obvious plateau from
0.6 to 0.9 V, which corresponds to the irreversible reduction
from SnO2 to Sn and Li2O. The rst discharge and charge capaci-
ties are 2283.3 and 1396.3 mAh g1 with a lower coulombic eciency
of 61.2% due to the formation of the solid electrolyte interphase (SEI)
layers [29]. For the rest of the charge/discharge proles, there are
plateaus around 0.51.25 V in the discharge proles as well as 0.5
0.75 V and 1.251.5 V plateaus in the charge curves, which is in
accordance with the CV analysis.
Fig. 4c shows the electrochemical cycling performance of the
B 2 O 3 SnO 2 /G and SnO 2 /G composites at a current density of
500 mA g1 between 0.01 and 3.0 V. The B2O3SnO2/G composite ex-
hibits a higher initial discharge capacity of 2283.3 mAh g1. The initial
charge capacity is 1396.3 mAh g1, which is reduced to be about
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L. Wen et al. / Materials Science and Engineering B (2016) 5

Fig. 4. CV curves (a) of B2O3SnO2/G and SnO2/G at a scan rate of 0.2 mV s1, charge-discharge proles (b) of the B2O3SnO2/G, cycling performance (c), rate capability (d),
Nyquist plots (e) and equivalent circuit (f) of B2O3SnO2/G and SnO2/G.

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1116.9 mAh g1 up to the 46th cycle. However, there is an upward
tendency for the capacities of S B2O3SnO2/G composite after 46
cycles. And even after 200 cycles, the reversible discharge and charge
capacities are still maintained at 1404.9 and 1400.8 mAh g1, re-
spectively. The reason why the B2O3SnO2/G composite showed
an excellent cycling performance is because the B2O3 buffer layer
formation hindering the pulverization of the electrode during
the charge/discharge process. More importantly, B2O3 can accept elec-
trons during the electrons transfer as well as lithium insertion.
On the other hand, boron ion releases free electrons, increasing the
electron density [20]. For SnO2/G composites, there is a down-
ward trend of capacities from beginning to end, showing a poorer
cycling performance compared to that of B2O3SnO2/G compos-
ites. The rst charge and discharge capacities of 814.8 and
905.0 mAh g1 are reduce to 511.9 and 514.9 mAh g1 after 200 cycles,
respectively.
The charge/discharge rate capability of the B2O3SnO2/G and
SnO2/G composites between 0.01 and 3.0 V was evaluated by in-
creasing the galvanostatic current density from 50 to 1,000 mA g1
(50, 100, 150, 200, 500, 1,000, 50 mA g1) and then returning to
50 mA g1 as shown in Fig. 4d. The specic capacities of the B2O3
SnO2/G are obviously superior to that of SnO2/G composites at all
charge/discharge rates. For example, at a current density of
1,000 mA g1, the discharge capacity of B2O3SnO2/G is 988.7 mAh g1,
which is much greater than that of SnO2/G composites. When the
current density is reduced to 50 mA g1, the discharge capacity is
recovered to 2206 mAh g1, suggesting excellent reversible capac-
ity retention due to the B2O3 played a buffering role.
In order to determine the electrochemical performance of the
B2O3SnO2/G and SnO2/G composites, electrochemical impedance
spectroscopy measurements were investigated. Fig. 4e shows the
electrochemical impedance spectra of B2O3SnO2/G and SnO2/G
composites electrodes after 5 charge/discharge cycles as well as
their simulated spectra. The two Nyquist plots of both B2O3
SnO2/G and SnO2/G composites consist of one semicircle and a
straight slope. The semicircle in the high-frequency region is bound
up with charge-transfer process occurring at the electrode/
electrolyte interface, and the straight slope in the low-frequency
area can be assigned to the Warburg impedance. The diameter of
the semicircle of B2O3SnO2/G electrode is smaller than that of
SnO2/G electrode, indicating that the charge-transfer resistance is
lower for B2O3SnO2/G, which leads to a higher electrochemical
activity of the B2O3SnO2/G composite electrode. The equivalent
circuit of the electrodes is exhibited in Fig. 4f where R1, R2, R3,
and W1 are indicated as solution resistance, SEI lm resistance,
reaction resistance, and the Warburg impedance, respectively. A
constant phase element is expressed as CPEi (CPEi = {Yi(jw)})1. A
nonlinear, least-square tting calculation is performed using the
equivalent circuit shown in Fig. 4f. The electrochemical imped-
ance value (R3) and CPE2 value (T) are 39.66 cm 2 and
264.87 F cm2 for the B2O3SnO2/G composite electrode, while
67.22 cm2 and 117.04 F cm2 for the SnO2/G composite elec-
trode. The CPE2 value (T) is suggested to be the value of the
double-layer capacitance of the electrode and related to the true
reaction areas of the electrode. Therefore, the true reaction area
of B2O3SnO2/G composite electrode is larger than that of the
SnO2/G composite electrode. Furthermore, the lower electrochemi-
cal impedance (R3) of the B2O3SnO2/G composite electrode indicates
higher electrochemical activity than the SnO2/G composite elec-
trode. All the analysis above strongly conrms that the added
B2O3 largely enhanced the electrochemical activity of SnO2/G com-
posite during the cycle processes.
Please cite this article in press as: Lina Wen, Xue Qin, Wei Meng, Ning Cao, Zhonghai Song, Boron oxidetin oxide/graphene composite as anode materials for lithium ion batteries,
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4. Conclusions
B2O3SnO2/G composite anode material is fabricated via a chem-
ical heat solvent method, which led to an improved cycling
performance and rate capability for lithium ion batteries com-
pared to SnO2/G composite. This improvement is primarily ascribed
to the added B2O3 for its electron-decient nature and the buffer-
ing role. This work indicates that B2O3SnO2/G composite can provide
new insights into producing high-capacity and long-life anode ma-
terials for LIBs and inspire further research on their practical
application.
Acknowledgements
The authors gratefully acknowledge the partial nancial support
from the Open Project of Key Lab Adv. Energy Mat. Chem. (Nankai
University) (KLAEMC-OP201201).
Appendix: Supplementary material
Supplementary data to this article can be found online at
doi:10.1016/j.mseb.2016.05.004.
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