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Lithium-Ion Batteries www.small-journal.com

3D Graphene Encapsulated Hollow CoSnO3 Nanoboxes

as a High Initial Coulombic Efficiency and Lithium Storage
Capacity Anode
Jian Huang, Yating Ma, Qingshui Xie,* Hongfei Zheng, Jingren Yang, Laisen Wang,
and Dong-Liang Peng*

and safety is urgently required and of par-

3D Graphene sheets encapsulated amorphous hollow CoSnO3 nanoboxes amount significance.
(H-CoSnO3@reduced graphene oxide [RGO]) are successfully fabricated by Nowadays, transition metal oxides
first preparing 3D graphene oxides encapsulated solid CoSn(OH)6 have received numerous attentions as
nanocubes, followed by an alkaline etching process and subsequent heating promising anode materials for Li-ion bat-
teries.[6–9] Among them, tin oxides have
treatment in Ar. The hollow CoSnO3 nanoboxes with average particle size of
been intensively investigated because of
230 nm are uniformly and tightly encapsulated by RGO sheets. As an anode their higher theoretical capacity and better
material for Li-ion batteries, H-CoSnO3@RGO displays high initial Coulombic safety than graphite anode, low toxicity,
efficiency of 87.1% and large reversible capacity of 1919 mA h g−1 after and moderate operating potential versus
500 cycles at the current density of 500 mA g−1. Moreover, excellent rate Li+. Unfortunately, the huge volume varia-
tion of tin oxides during discharge–charge
capability (1250, 1188, 1141, 1115, 1086, 952, 736, and 528 mA h g−1 at
process will lead to the cracking and
100, 200, 300, 400, 500, 1000, 2000, and 5000 mA g−1, respectively) is acquired. pulverization of active materials, conse-
The reasons for excellent lithium storage properties of H-CoSnO3@RGO are quently resulting in bad structural stability
discussed in detail. and rapid capacity fading.[10,11] And the
electrochemical reaction kinetics is greatly
restricted by the poor electronic conduc-
1. Introduction tivity of tin oxides. Moreover, the poor conversion reaction
reversibility between the Sn nanocrystals and Li2O during del-
Rechargeable Li-ion batteries have been widely used in port- ithiation process, which is mainly caused by the coarsening of
able devices owing to their characteristic merits such as high Sn nanocrystals by means of recrystallization and cyclic stress,
energy density, environmental benignity, light weight, and long results in low Coulombic efficiency in the first several cycles,
service life.[1–5] In recent years, the rapid development of energy especially the initial Coulombic efficiency.[12,13] These problems
industry, such as smart grid and electric vehicle, puts forward have greatly hampered the lithium storage properties of tin
higher requirements for the energy and power density as well oxides anodes. How to effectively circumvent these shortcom-
as safety of Li-ion batteries. It is well known that the perfor- ings has been a prerequisite for their commercial application in
mance of the Li-ion battery is closely relating to the electrode lithium ion batteries, and, thus far, is still a challenge.
materials. And the conventional commercial graphite anode It has been confirmed that constructing hollow structure
shows limited specific capacity (372 mA h g−1) and dendrite electrode materials is helpful to ease the intrinsic strain
crustal problems, which have greatly hampered the application originated from drastic volume expansion of active parti-
of current Li-ion batteries in such high energy consumption cles and facilitate the diffusion of lithium ions, enabling to
areas. Thus, developing new alternative anode materials with improve structural endurance and electrochemical reaction
higher specific capacity, longer lifespan, better rate capability, kinetics.[14–18] In addition, combining metal oxide active mate-
rials with other metal oxides and/or carbonaceous materials
has been demonstrated to be another effective strategy for
J. Huang, Y. Ma, Dr. Q. Xie, H. Zheng, J. Yang, Dr. L. Wang, the improvement of rate properties on account of the syner-
Prof. D.-L. Peng
Department of Materials Science and Engineering getic effect between different components or the better elec-
Collaborative Innovation Center of Chemistry for Energy Materials tronic conductivity of carbonaceous materials.[12,19–21] Taking
College of Materials ternary metal oxide NiCo2O4 as an example, it reveals more
Xiamen University superior electronic conductivity and thus electrochemical
Xiamen 361005, China
E-mail: [email protected]; [email protected]
activity than single nickel oxide and/or cobalt oxide.[22] Gra-
phene, as a member of carbonaceous materials, exhibits not
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smll.201703513. only high electron mobility but also good chemical stability
and excellent flexibility, which make it an ideal additive or
DOI: 10.1002/smll.201703513 support framework for metal oxide anode materials.[23–28]

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In respect to cycling efficiency, especially initial Coulombic 2. Results and Discussion

efficiency, Hu et al. introduced high density interfaces and
grain boundaries into SnO2 in order to suppress the coars- 2.1. Morphology and Structural Investigations
ening of Sn nanocrystals formed during discharge process.[12]
As a result, the conversion reaction reversibility between Sn Figure 1 depicts the schematic illustration for the preparation
and Li2O was enhanced greatly. In our earlier work, we found of H-CoSnO3@RGO. When CoCl2 aqueous solution and SnCl4
that the diffusion and growth of ZnO grains could be effec- ethanol solution were added into suspension containing GO
tively prohibited by the uniform decoration of Ag nanoparti- sheets, Co2+ and Sn4+ ions would adsorb on the surfaces of GO
cles that act as anchors during heating process.[29] Inspired by sheets by means of electrostatic interaction between positive
this result, the uniform incorporation of tin oxides with other metal ions and negative functional groups containing oxygen
electrochemical active/inactive components may be a very species existed on the GO sheets. The chemical reaction between
promising solution to suppress the coarsening of the formed Co2+, Sn4+, and OH− ions takes place during the first addition
Sn nanocrystals and increase the initial Coulombic efficiency. of NaOH solution in the help of citrate ions, leading to the for-
Therefore, bearing in mind the above discussions, it is highly mation of solid CoSn(OH)6 nanocubes which contact with GO
desirable to prepare graphene modified hollow Sn-based ter- sheets tightly. The shell part of solid CoSn(OH)6 nanocubes is
nary metal oxides with uniform compositional distribution, more stable than the inner part.[30,31] So, when secondly adding
which possess the above-mentioned three features simultane- the excess NaOH solution, the inner void room of CoSn(OH)6
ously and consequently deliver fascinating electrochemical nanocubes would form due to further reaction between the inner
properties. CoSn(OH)6 and excess OH− to generate soluble [Sn(OH)6]2− and
In this work, 3D graphene sheets encapsulated amorphous [Co(OH)4]2−. As a result, hollow CoSn(OH)6 nanoboxes could be
hollow CoSnO3 nanoboxes (H-CoSnO3@reduced graphene acquired. By calcination of the 3D graphene oxide (GO) sheets
oxide [RGO]) have been successfully fabricated through a encapsulated hollow CoSn(OH)6 nanoboxes in Ar atmosphere,
simple solution route. When worked as anode materials CoSn(OH)6 would convert to CoSnO3 and the graphene oxides
for Li-ion batteries, the achieved H-CoSnO3@RGO dis- would be reduced to reduced graphene oxides, giving rise to the
plays highest initial Coulombic efficiency (ICE) and revers- successful synthesis of H-CoSnO3@RGO.
ible capacity as well as most remarkable cycling and rate The produced H-CoSn(OH)6@GO precursor is subjected to
performances than CoSnO3 hollow and solid counterparts. X-ray diffraction (XRD) assessment firstly. As shown in Figure 2,
The significantly enhanced lithium storage properties of the obvious and sharp diffraction peaks of the precursor are
H-CoSnO3@RGO are associated with its unique structural consistent well with the standard pattern of perovskite-type
advantages, including unique hollow configuration that can CoSn(OH)6 (JCPDS card No. 13-356), which implies good
provide extra accommodating room, the tight decoration of crystallinity of CoSn(OH)6. The corresponding morphology
3D graphene network that benefits to enhance the overall and microstructure investigations are implemented and exhib-
electronic conductivity effectively and prohibit the pulveriza- ited in Figure S1 in the Supporting Information. The hollow
tion of electrode materials to some extent, and the mutual CoSn(OH)6 nanoboxes and wrinkle GO sheets (Figure S1a,
buffering matrices due to different lithiation potentials of tin Supporting Information) can be seen clearly, which contact
oxide and cobalt oxide are beneficial to suppress the diffu- with each other solidly. The interior void space of nanoboxes
sion and aggregation of Sn nanocrystals during lithium ions can be distinguished from some broken particles indicated by
de-intercalation. black circles. The average particle size of hollow CoSn(OH)6

Figure 1. Schematic illustration for the fabrication of H-CoSnO3@RGO.

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XRD pattern (Figure 2) of the annealed product implicates the

amorphous characteristic of CoSnO3. Meanwhile, the raised
broad peaks located at 26° and 42.5°, respectively correspond to
the typical (002) and (100) peaks of RGO, implying the successful
reduction of GO to RGO. The scanning electron microscopy
(SEM) and TEM images of the synthesized H-CoSnO3@RGO are
displayed in Figure 3. The CoSnO3 nanoboxes with good mor-
phology inheritance and wrinkled RGO sheets can be found in
Figure 3a. Figure 3b,c images implicate the hollow construction
of CoSnO3 nanoboxes (marked by arrows) and the tight contact
interfaces between CoSnO3 nanoboxes and RGO sheets (marked
by circles). Figure S2 in the Supporting Information shows the
energy-dispersive X-ray spectroscopy result with the Co/Sn molar
ratio of about 1.0. From the TEM measurements, as shown in
Figure 3d,e, the hollow structure of CoSnO3 particles is certified
again. The high resolution TEM image (Figure 3f) demonstrates
that the hollow CoSnO3 nanoboxes are solidly encapsulated by the
RGO sheets, being in good line with the above SEM results. Fur-
Figure 2. XRD patterns of H-CoSn(OH)6@GO, RGO, H-CoSnO3@RGO, thermore, there are a large number of mesopores (marked with
H-CoSnO3, and S-CoSnO3 samples.
white circles) on the shell of hollow CoSnO3 nanoboxes, indica-
tive of their porous characteristics. And no crystal fringe can
nanoboxes is around 230 nm. From Figure S1b in the Sup- be discerned, validating the amorphous nature of the harvested
porting Information, one can distinctly find that the hollow hollow CoSnO3 nanoboxes. This behavior coincides well with
CoSn(OH)6 nanoboxes are well encapsulated by the 3D gra- the selected area electron diffraction (SAED) pattern manifested
phene oxide sheets. And the transmission electron microscopy in Figure 3g. The STEM image and the corresponding element
(TEM) image (Figure S1c, Supporting Information) further mappings of the H-CoSnO3@RGO are displayed in Figure 3h–l,
confirms the hollow configuration of CoSn(OH)6 nanoboxes, respectively. Undoubtedly, the Co, Sn, and O elements distribute
showing the successful fabrication of 3D graphene oxide sheets evenly within the whole hollow CoSnO3 nanoboxes, and the C
encapsulated hollow CoSn(OH)6 nanoboxes. element results from the RGO sheets.
To obtain the final H-CoSnO3@RGO product, the produced Figure 4a displays the Raman spectrum of H-CoSnO3@
H-CoSn(OH)6@GO precursor is heated in Ar atmosphere. The RGO. Two clear peaks around 1334 and 1595 cm−1, respectively

Figure 3. a–c) SEM, d,e) TEM, and f) HRTEM images of H-CoSnO3@RGO. g) SAED pattern and h) STEM image of H-CoSnO3@RGO. The
corresponding element mapping of i) Co, j) Sn, k) O, and l) C elements.

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Figure 4. a) Raman spectrum of the H-CoSnO3@RGO. b) Survey XPS spectrum of H-CoSnO3@RGO. The high-resolution XPS spectra of c) Co 2p,
d) Sn 3d, e) O 1s, and f) C 1s.

correspond to the D and G bands of carbon, further con- (metal–oxygen bonds) from CoSnO3 and the latter one nearby
firming the presence of RGO. And the intensity ratio of the 532.0 eV relates to the surface adsorbed oxygen species, such as
D and G bands is 1.03, indicating of a moderate disorder water or other surface contaminates.[36,37] Figure 4f displays the
degree of RGO.[32] The X-ray photoelectron spectroscopy (XPS) high-resolution C 1s XPS spectrum, which can be fitted into
measurements are carried out to verify the element valence three peaks. The peaks at 284.4, 285.5, and 288.6 eV relate to the
of H-CoSnO3@RGO. The full XPS spectrum is showed in CC, CO, and CO bonds, respectively. The weak intensity of
Figure 4b, which indicates the presence of Co, Sn, O, and CO and CO bond suggests the successful reduction of GO
C elements. In the high-resolution Co 2p XPS spectrum to RGO. In order to further investigate the weight percentage
(Figure 4c), two peaks at 781.0 and 796.8 eV, together with two of RGO in the H-CoSnO3@RGO, the TG test is performed
satellite peaks (assigned as S) nearby 786.5 and 802.5 eV, are in air from 30 to 600 °C and the corresponding TG curve is
ascribed to the Co 2p3/2 and Co 2p1/2 of Co2+.[33,34] As shown in exhibited in Figure S3a in the Supporting Information. Except
Figure 4d, two peaks centered at 486.6 and 495.0 eV are attrib- the gradual weight loss before 200 °C which can be ascribed to
uted to Sn 3d5/2 and Sn 3d3/2, implying the presence of Sn4+ in the removal of absorbed water, the following large weight loss
H-CoSnO3@RGO.[35] Figure 4e depicts the high-resolution O 1s is due to the combustion of graphene in air. Accordingly, the
spectrum, which can be fitted into two peaks. The former peak content of graphene in H-CoSnO3@RGO is determined to be
located at 530.4 eV corresponds to the lattice oxygen species 6.03 wt%.

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To assess the specific surface area and pore size distribu- noticed and is attributed to the reduction reaction of CoSnO3
tion of the H-CoSnO3@RGO, N2 absorption–desorption iso- with Li+ ions to form CoO and Sn nanocrystals in Li2O matrix
therm measurements are carried out. Type-IV isotherms can as well as the formation of solid electrolyte interface (SEI)
be observed in Figure S3b in the Supporting Information, film that results from the decomposition of electrolyte.[38–40]
which implies the mesoporous structure of the sample. The The conspicuous peaks located at 0.65 and 0.05 V are due to
Brunauer−Emmett−Teller (BET) specific surface area of the the further reduction of CoO into Co nanocrystals and the
H-CoSnO3@RGO is calculated to be 131.4 m2 g−1. On the basis alloying reaction between Sn and Li+ to generate LixSn alloys,
of Barrett–Joyner–Halenda method, the pore size distribu- respectively. In the anodic sweep, the distinct oxidation peak
tion is depicted in the inset in Figure S3b in the Supporting centered at 0.56 V relates to the dealloying reaction of LixSn
Information. In the micropore range, the pore size mainly alloys.[41,42] The peaks located at 1.09 and 1.73 V correspond
centers at 1.7 nm, and in the mesopore range it exhibits a to the oxidation reactions of Sn to SnO2 and the one nearby
wide pore size distribution from 6 to 50 nm. The contact 2.06 V relates to the oxidation reaction of Co to CoO.[43,44] This
interfaces between hollow CoSnO3 nanoboxes and graphene suggests that CoSnO3 cannot be achieved during delithiation
sheets would form plenty of mesopores with different sizes, process. In the following three scans, the CV profiles show
giving rise to the wide pore size distribution of H-CoSnO3@ excellent registration, which implies high reversibility of the
RGO. electrode reactions and good cycling stability. In comparison
In order to better display the advantages of the obtained with H-CoSnO3@RGO, the similar CV curves in shape can be
H-CoSnO3@RGO, the hollow CoSnO3 (H-CoSnO3) nano- found for H-CoSnO3 and S-CoSnO3 (Figure S6a,b, Supporting
boxes and solid CoSnO3 (S-CoSnO3) nanocubes are also Information), indicating the same electrochemical reactions
fabricated. The amorphous features of both H-CoSnO3 and during discharge–charge process. However, the curve areas of
S-CoSnO3 can be observed clearly from Figure 2, coinciding both H-CoSnO3 and S-CoSnO3 in the following cycles reduce
well with H-CoSnO3@RGO. As illustrated in Figure S4 in gradually with cycle number, which has implication that the
the Supporting Information, the dispersed CoSnO3 particles reversible capacity and cycling stability of H-CoSnO3 and
with hollow and solid structures can be seen distinctly. The S-CoSnO3 fade rapidly in the initial four cycles. This behavior
SAED patterns (the insets in Figure S4b,d, Supporting Infor- is quite different with that of H-CoSnO3@RGO. All in all, the
mation) of H-CoSnO3 and S-CoSnO3 further evidence their electrochemical reactions during cycling can be concluded as
amorphous nature, agreeing well with the XRD results. And follows
the porous structure of H-CoSnO3 can be carefully discerned
from the TEM image showed in Figure S4b in the Sup- CoSnO 3 + 4Li + + 4e − → Sn + CoO + 2Li 2 O (1)
porting Information. Moreover, as demonstrated in Figure S5
in the Supporting Information, the specific surface areas of
CoO + 2Li + + 2e − ↔ Co + Li 2 O (2)
the H-CoSnO3 and S-CoSnO3 are determined to be 83.9 and
60.1 m2 g−1, respectively. Both H-CoSnO3 and S-CoSnO3
show the mesoporous structure and the pores mainly center Sn + xLi + + xe − ↔ Li x Sn ( 0 ≤ x ≤ 4.4 ) (3)
nearby 11.2 nm, which is different to H-CoSnO3@RGO.
Undoubtedly, H-CoSnO3@RGO reveals largest specific sur-
Sn + 2Li 2 O ↔ SnO 2 + 4Li + 4e − (4)
face area than H-CoSnO3 and S-CoSnO3. The higher specific
surface area can provide larger contact area between elec- Figure 5b demonstrates the initial three galvanostatic
trode materials and electrolyte, benefitting the improvement discharge–charge curves of H-CoSnO3@RGO exam-
of reversible capacity. And the porous feature of active par- ined at a current density of 100 mA g−1 between 0.01 and
ticles is helpful for the diffusion of electrolyte and lithium 3.0 V. Clearly, there are three plateaus around 1.33, 0.68, and
ions within the electrode, which is beneficial to enhance the 0.06 V in the first discharge profile, relating to the reduc-
rate performance. These merits make H-CoSnO3@RGO a tion of CoSnO3 and the formation of SEI layer, the further
very promising anode material for next-generation lithium reduction of the formed CoO to Co nanocrystal, and the
ion batteries. alloying reaction between Sn and Li+ ions, respectively. In
the first charge profile, the weak plateaus located at 0.52,
1.15, and 2.1 V are associated with the dealloying reaction
2.2. Electrochemical Measurements of LixSn alloys, the oxidation reactions of Sn to SnO2 and
of Co to CoO, respectively.[45] These results are consistent
The electrochemical performances of the as-prepared well with the above CV measurements. It is noteworthy
H-CoSnO3@RGO, H-CoSnO3, and S-CoSnO3 samples are that H-CoSnO3@RGO delivers the discharge and charge
investigated, using as anode materials for lithium ion bat- capacities of 1465 and 1276 mA h g−1 in the first cycle, corre-
teries. Firstly, cyclic voltammograms (CV) measurements sponding to a very high ICE of 87.1%. By contrast, the initial
were performed to explore the electrochemical reactions of three galvanostatic discharge–charge curves of H-CoSnO3
the synthesized various anode materials during lithiation– and S-CoSnO3 examined at 100 mA g−1 are exhibited in
delithiation process at a scan rate of 0.1 mV s−1 in the voltage Figure S6c,d, respectively in the Supporting Information.
range of 0.01–3.0 V. The CV profiles of H-CoSnO3@RGO for The first discharge/charge capacities of the H-CoSnO3 and
the initial four cycles are manifested in Figure 5a. In the first S-CoSnO3 are about 1692/873 mA h g−1 and 1562/667 mA h g−1,
cathodic sweep, a clear reduction peak around 1.26 V can be leading to the initial Coulombic efficiencies of 51.6%

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Figure 5. a) CV curves at 0.1 mV s−1 in 0.01–3.0 V and b) galvanostatic discharge–charge curves at 100 mA g−1 of H-CoSnO3@RGO. c) Cycling
performance of H-CoSnO3@RGO at 100 and 500 mA g−1. d) The galvanostatic discharge–charge curves at 200th, 300th, and 400th cycles of H-CoSnO3@
RGO. e) The rate capability of H-CoSnO3@RGO.

and 42.7%, respectively. The coarsening of the formed Sn lead to irreversible capacity loss during first cycle.[29] And
nanocrystals by means of cyclic stress during Li+ extrac- the tight encapsulation of hollow CoSnO3 nanoboxes by gra-
tion process results in the poor conversion reaction reversi­ phene sheets benefits to inhibit the detrimental chemical
bility between Sn and Li2O, consequently giving rise to low reaction and enhance the interface stability between CoSnO3
cycling efficiency, especially initial Coulombic efficiency of and the electrolyte by prohibiting their direct contact, con-
H-CoSnO3 and S-CoSnO3 anodes.[12,13] This behavior is cer- sequently giving rise to the formation of thin and stable
tified by the acutely decreasing peak areas nearby 1.09 and SEI layer on the surface of graphene instead of CoSnO3
1.73 V, representing the oxidation reactions between Sn (Figure 6a). This may be another reason for the significantly
and Li2O, at the second and third cycles in the CV curves enhanced initial Coulombic efficiency of H-CoSnO3@RGO
(Figure S6a,b, Supporting Information). The significantly compared to H-CoSnO3 and S-CoSnO3.
increased conversion reaction reversibility between Sn and For comparison, the discharge–charge capacities of other
Li2O for H-CoSnO3@RGO results in higher initial Cou- Sn-based oxide electrode materials during first cycle and the
lombic efficiency than H-CoSnO3 and S-CoSnO3 counter- corresponding initial Coulombic efficiency are summarized
parts. Additionally, the formation of SEI layer on the surface and showed in Table 1.[35,38–40,43,44,46–48] For example, SnO2@
of electrode materials would consume extra lithium ions and Co3O4 hollow nanospheres illustrated the initial discharge

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and charge capacities of 2208 and 1280 mA h g−1, relating to olution Sn 3d spectrum (Figure 6c) of H-CoSnO3@RGO
a first Coulombic efficiency of 58.0%.[39] Co2SnO4 hollow cubes electrode materials collected after 300th cycles, the fitted
encapsulated in graphene delivered the initial discharge and peaks around 485.6 and 493.9 eV are respectively assigned
charge capacities of 2220 and 1547 mA h g−1, leading to the first to Sn 3d5/2 and Sn 3d3/2 of Sn2+, and the fitted peaks around
Coulombic efficiency of 69.7%.[47] Silver nanoparticle-decorated 486.5 and 495.2 eV are respectively assigned to Sn 3d5/2 and
SnO2/NiO nanotubes were synthesized by Kim’s group and Sn 3d3/2 of Sn4+. Furthermore, the differential charge capacity
exhibited an initial Coulombic efficiency of 77.4%.[38] It is worth plots of H-CoSnO3@RGO anode from 100th to 500th cycles
pointing out that the as-achieved H-CoSnO3@RGO anode dis- are demonstrated in Figure 7a. The peak in the potential range
plays one of the highest initial Coulombic efficiency, which of 0.01–0.85 V corresponds to the dealloying reaction of LixSn
exerts significant effect on its practical application in lithium alloys and the one in the potential range of 0.85–1.88 V is due
ion batteries. to the conversion reaction between Sn and Li2O. Distinctly, the
In order to clearly interpret the high initial Coulombic effi- shape and position of these two peaks keep almost unchanged
ciency of H-CoSnO3@RGO anode, the schematic illustration of from 300th to 500th cycles, being in support of the out-
the structure and phase evolution of H-CoSnO3@RGO electrode standing reversibility of the conversion reaction between Sn
during initial discharge and charge is displayed in Figure 6a. and Li2O, and the durable anchor effect of Co nanoparticles.
It is worth pointing out that the reversed conversion (oxida- Taking these into account, it is feasible to effectively prohibit
tion) potential of metal Co to CoO (2.06 V) during lithium the diffusion and coarsening of Sn nanoparticles, enhance
ions extraction process is higher than the dealloying potential the conversion reaction reversibility between Sn and Li2O
of LixSn to Sn (0.56 V) and the conversion oxidation poten- during cycling and thus the cycling efficiency, especially initial
tial of metal Sn to SnO2 (1.09 and 1.73 V). In other words, Coulombic efficiency, by means of the anchor effect of well-
the formed well-dispersed Co nanoparticles in LixSn/Li2O or dispersed Co nanoparticles in LixSn/Li2O or Sn/Li2O matrices
Sn/Li2O matrices after full lithiation of H-CoSnO3@RGO due to its higher conversion oxidation potential.
can work as anchors to effectively prohibit the diffusion and The cycling performances of H-CoSnO3@RGO are tested at
coarsening of Sn nanocrystals during the dealloying and different current density in the potential range of 0.01–3.0 V
reversed conversion reactions of Sn. And the resulting high and the corresponding results are displayed in Figure 5c.
dispersion state of Sn in Li2O matrix benefits to increase Clearly, H-CoSnO3@RGO anode delivers very stable cycling
the conversion reaction reversibility between Sn and Li2O stability when discharged/charged at a current density of
during delithiation process, giving rise to the obviously 100 mA g−1, which is quite different with H-CoSnO3 and
enhanced cycling efficiency, especially the initial Coulombic S-CoSnO3 electrodes. As illustrated in Figure S6e in the Sup-
efficiency.[12] In an effort to validate this point more clearly, porting Information, the specific capacities for both samples
the H-CoSnO3@RGO active materials are collected after 1st deteriorate quickly with cyclic number, demonstrating infe-
and 300th cycles, and subjected to XPS measurements. As rior cyclability. The reversible capacity of H-CoSnO3@RGO
shown in Figure 6b, there are two peaks at 486.7 and 495.2 eV anode maintains at 1280 mA h g−1 after 50 cycles, which
in the high-resolution Sn 3d spectrum of H-CoSnO3@RGO is far higher than those of H-CoSnO3 (355 mA h g−1) and
collected after 1st cycle, which can be ascribed to Sn 3d5/2 S-CoSnO3 (93 mA h g−1) after cycling 50 times. In order to
and Sn 3d3/2 of Sn4+, respectively.[35] This suggests that the further show the structural advantages, the H-CoSnO3@RGO
formed Sn nanoparticles after dealloying of LixSn alloys can anode is subjected to discharge/charge at a larger current
further react with Li2O and be reoxidized to form SnO2, well density of 500 mA g−1 after 50 cycles. The specific capacity of
confirming the obviously strengthened conversion reaction H-CoSnO3@RGO anode maintains very stable from 50th to
reversibility between Sn and Li2O, and the expected anchor 200th cycles, gradually increases from 200th to 400th cycles
effect of Co nanoparticles. In addition, from the high-res- and then keeps almost unchanged in the following cycles.

Table 1. The discharge and charge capacities during first cycle and initial Coulombic efficiency (ICE) of various Sn-based electrode materials for
lithium ion batteries.

Materials Morphology Discharge–charge capacity [mAh g−1] ICE Ref.

CoSnO3–graphene–carbon Nanocubes 1830.1–1363.9 74.5% [35]
SnO2/NiO–Ag Nanotubes 1635.5–1266.0 77.4% [38]
SnO2@Co3O4 Hollow nanospheres 2208–1280 58% [39]
Polydopamine-coated SnO2 Nanocrystals 1542–945 61.3% [40]
CoSnO3@C Nanoboxes 1410–480 34.0% [43]
CoO⊙CoSnO3@C Nanotubes 1162.1–1007.5 86.7% [44]
Carbon-Coated ZnSnO3 Porous nanocubes 1633–1180 72% [46]
Co2SnO4–graphene Hollow cubes 2219.8–1546.8 69.7% [47]
N-Doped SnO2 Nanoparticles 1899–1158 61% [48]
CoSnO3–graphene Nanoboxes 1465–1275 87.1% This work

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Figure 6. a) The schematic illustration of the structure and phase evolution of CoSnO3-RGO electrode during initial discharge and charge along with
the following cycling. The high-resolution Sn 3d XPS spectra of the H-CoSnO3@RGO after b) 1st and c) 300th cycles.

A very high reversible capacity of 1919 mA h g−1 is achieved curve gradually shifts to higher voltage and the charge curve
after total 500 cycles, hinting the greatly strengthened gradually moves to lower voltage (indicated by black arrows)
reversible capacity and cycling stability of H-CoSnO3@RGO. as cyclic number increasing from 200th to 300th and 400th
According to the weight ratio and the theoretical capacity of cycles. This phenomenon suggests the gradually reduced elec-
CoSnO3 (93.97 wt% and 1238 mA h g−1) and RGO (6.03 wt% trode polarization, which is beneficial for the enhancement of
and 744 mA h g−1), the theoretical capacity of the H-CoSnO3@ reversible capacity.[51] On the other hand, the charge capacity
RGO is calculated to be about 1208.2 mA h g−1. The observed of H-CoSnO3@RGO electrode can be divided into three parts
specific capacity of H-CoSnO3@RGO anode is higher than its on the basis of the different electrochemical reaction voltages.
theoretical value. The differential charge capacity versus poten- Namely, the charge capacities in the voltage ranges of 0.01–0.85,
tial curves of H-CoSnO3@RGO from 300th to 500th cycles are 0.85–1.88, and 1.88–3.0 V correspond to the dealloying reaction
demonstrated in Figure 7a, wherein an obvious and broad peak of LixSn alloys, the oxidation reactions of Sn to SnO2 and of
indicated by a circle emerges in the potential range of 2.5–3.0 V, Co to CoO, respectively. From Figure 7b–d, one can observe
indicating the decomposition of electrolyte due to the elec- that the increased reversible capacity mainly originates from
trochemical catalysis of the formed Co nanocrystals.[49] This the voltage ranges of 0.85–1.88 and 1.88–3.0 V. The formed Co
behavior can offer extra lithium storage capacity, giving rise to nanocrystals after lithiation possess catalytic activity to promote
higher reversible capacity of H-CoSnO3@RGO than its theoret- the decomposition of Li2O and thus the reversible formation of
ical value. Additionally, the reversible (pseudocapacitive) inter- SnO2, accounting for the increased reversible capacity in the
facial lithium storage between CoSnO3 and graphene sheets voltage range of 0.85–1.88 V.[52,53] The high-resolution Co 2p
may be another reason for this phenomenon.[50] XPS spectra of H-CoSnO3@RGO after 1st and 300th cycles are
The gradually increased specific capacity of manifested in Figure 7e,f. As showed in Figure 7e, the peaks
H-CoSnO3@RGO electrode can be attributed to the following around 781.4 and 797.2 eV are respectively ascribed to Co 2p3/2
aspects. On one hand, the galvanostatic discharge–charge and Co 2p1/2 of Co2+, and the peaks nearby 779.5 and 794.9 eV
curves of H-CoSnO3@RGO electrode at 200th, 300th, and 400th are respectively assigned to Co 2p3/2 and Co 2p1/2 of Co3+.[54]
cycles are depicted in Figure 5d. It is clear that the discharge These phenomena evidence the simultaneous presence of

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Figure 7. a) The differential charge capacity versus potential curves from100th to 500th cycles for CoSnO3-RGO. Reversible capacities versus cycle
number of the H-CoSnO3@RGO separated into potential ranges of b) 0.01–0.85, c) 0.85–1.88, and d) 1.88–3.0 V. The high-resolution Co 2p XPS spectra
of H-CoSnO3@RGO active material after e) 300th and f) 1st cycles.

Co2+ and Co3+ ions in the collected H-CoSnO3@RGO active still delivers higher reversible capacity (528 mA h g−1) than the
materials after 300th cycles, being quite different with that theoretical value (372 mA h g−1) of commercialized graphite
of H-CoSnO3@RGO collected after 1st cycle which only pos- anode. After that, the specific capacity can recover to original
sesses the Co2+ ions (Figure 7f). Namely, some Co2+ ions (CoO) level (1201 mA h g−1) when the current density is set back to
would further react with Li2O to generate Co3+ ions (Co3O4/ 100 mA g−1, indicating the impressive rate performance. The
Co2O3) with cycle number and contribute to extra specific rate properties of H-CoSnO3 and S-CoSnO3 electrodes have also
capacity, being responsible for the increased reversible capacity been investigated and shown in Figure S6f in the Supporting
in the voltage range of 1.88–3.0 V.[55] Additionally, as discussed Information. The reversible capacities for both two samples
above (Figure 7a), the decomposition of electrolyte due to the fade rapidly as increasing the current density, illustrating poor
electrochemical catalytic activity of the formed Co nanocrystals rate capability. For comparison, the lithium storage properties
is capable of providing lithium storage capacity and is another of other Sn-based oxide electrodes are summarized and illus-
reason for the gradually increased specific capacity. trated in Table S1 in the Supporting Information. For instance,
The rate capability of electrode materials is another important carbon-coated SnO2 submicroboxes were produced and showed
parameter for their practical application in lithium ion batteries. a reversible capacity of 372 mA h g−1 when tested at a large
Figure 7e shows the reversible capacity of H-CoSnO3@RGO current density of 5000 mA g−1.[56] Distinctly, the produced
anode tested at various current densities. The average spe- H-CoSnO3@RGO electrode displays one of the most excellent
cific capacities are 1250, 1188, 1141, 1115, 1086, 952, 736, and cycling and rate performances among other Sn-based electrode
528 mA h g−1 at the progressively increased current density materials reported previously.
of 100, 200, 300, 400, 500, 1000, 2000, and 5000 mA g−1. It is The notable electrochemical properties of the harvested
worth mentioning that, even discharged/charged at a very large H-CoSnO3@RGO can be ascribed to its unique structural
current density of 5000 mA g−1, H-CoSnO3@RGO electrode features, including the incorporation of 3D graphene sheets,

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the hollow and porous configuration of nanoboxes, the mutual annealing treatment in Ar atmosphere. When acted as the
buffering matrices between tin oxide and cobalt oxide together anode materials, the as-produced H-CoSnO3@RGO exhibits
with the amorphous characteristics. The tight encapsulation of a very high initial Coulombic efficiency of 87.1% and large
hollow CoSnO3 nanoboxes by graphene sheets results in a 3D reversible capacity of 1919 mA h g−1 at the current density of
interconnected conductive network. The resultant continuous 500 mA g−1 after total 500 cycles. Even tested at a very large
conductive paths are beneficial for the electron transport on current density of 5000 mA g−1, a higher reversible capacity of
the surfaces of active particles and between different active 528 mA h g−1 than the theoretical value of commercialized
particles, giving rise to the enhanced overall electron conduc- graphite anode is obtained. Compared to the H-CoSnO3 and
tivity. In order to interpret this point more clearly, the electro- S-CoSnO3 counterparts, the outstanding electrochemical per-
chemical impedance spectroscopy (EIS) examinations of all formances of H-CoSnO3@RGO are associated with its special
three samples are carried out before cycling from 0.01 Hz to structural merits, inclusive of the modification of RGO sheets,
100 kHz and displayed in Figure S7 in the Supporting Infor- the hollow configuration and porous structure, the mutual
mation. Similarly, all three curves comprise of a semicircle buffering matrices between tin oxide and cobalt oxide, and the
in the high-medium frequency region, the diameter of which amorphous feature. This facile route can be extended to fabri-
represents the charge transfer resistance.[57] It is conspicuous cate other graphene encapsulated oxide-based electrode mate-
that the electronic conductivity of H-CoSnO3@RGO has been rials, which may deliver the greatly enhanced lithium storage
greatly improved compared to H-CoSnO3 and S-CoSnO3, which properties and hold great promising as advanced anode mate-
benefits to increase the electrochemical reaction kinetics and rials for next-generation lithium ion batteries.
thus the reversible capacity and rate capability. The hollow con-
figuration of CoSnO3 nanoboxs can offer extra cushion space
to alleviate the huge volume expansion of electrode materials 4. Experimental Section
and the tight encapsulation of H-CoSnO3 nanoboxes by gra-
phene sheets can also effectively prohibit the cracking and pul- Materials Preparation: The GO were prepared through a modified
Hummer’s method.[60] Firstly, 20 mL of GO suspension (2 mg mL−1)
verization of electrode materials, both of which are beneficial
was pumped into 15 mL of the mixed aqueous solution of CoCl2
to maintain the structural integrity of H-CoSnO3@RGO elec- (1 mmol) and Na3C6H5O7·2H2O (1 mmol) under stirring. Afterward,
trode. Moreover, the amorphous feature guarantees the active 5 mL of SnCl4 (1 mmol) ethanol solution was added into the above
materials with better structure endurance than crystalline one solution drop by drop, followed by adding 5 mL of NaOH (2 m) aqueous
on account of its more homogeneous volume change.[58,59] After solution with continuous stirring for 1 h. Then, 20 mL of NaOH (8 m)
150 cycles, all three samples are collected and subjected to SEM aqueous solution was added into the above brown suspension again and
investigations. As shown in Figure S8a in the Supporting Infor- reacted for another 30 min. After that, the products were separated by
configuration and successively washed for several times with deionized
mation, the nanobox morphology of H-CoSnO3@RGO is well water and ethanol. The H-CoSn(OH)6@GO precursor could be
maintained (marked with black arrows) after cycling, indicating harvested after freeze drying for 12 h and was subjected to consecutively
the brilliant structural stability. While a large part of H-CoSnO3 calcine at 150, 300, and 450 °C with a heating rate of 1°C min−1 in
nanoboxes (Figure S8b, Supporting Information) and almost all Ar and maintain for 2 h at each temperature to obtain amorphous
the S-CoSnO3 nanocubes (Figure S8c, Supporting Information) H-CoSnO3@RGO. The corresponding hollow CoSnO3 (H-CoSnO3)
have cracked and pulverized, evidencing the inferior structural nanoboxes were fabricated by the same method but without addition of
GO. And for the synthesis of solid CoSnO3(S-CoSnO3) nanocubes, the
stability. Benefitting from the extraordinary structural stability,
procedures of addition of GO and the further alkaline etching step were
the resultant well-dispersed Co nanocrystals in Li2O matrix after omissible.[61]
lithiation can work as anchors to effectively prohibit the diffu- Materials Characterization: The crystal phase components of the
sion and coarsening of Sn nanocrystals during cycling due to its products were characterized by X-ray diffraction analysis (PANalytical
higher conversion reaction potential than Sn, which is capable X’pert PRO X-ray diffractometer, Cu Kα radiation 40 kV, 40 mA).
of increasing the conversion reaction reversibility between Sn SEM (Hitachi SU-70) and TEM (JEM-2100, 200 kV) were applied to
and Li2O, and thus the cycling efficiency, especially the initial examine the structures and morphologies of the samples. Thermo-
gravimetric analysis was performed using SDT-Q600 thermal analyzer
Coulombic efficiency. Finally, the largest specific surface area at a heating rate of 10 °C min−1 in air. XPS analysis was carried out on
of H-CoSnO3@RGO than H-CoSnO3 and S-CoSnO3 can pro- PHI QUANTUM 2000 (monochromatic Al K X-ray source). The Raman
vide most electrochemical active sites for lithium storage, and measurement was implemented on LabRam I confocal microprobe
the pores in H-CoSnO3@RGO can function as the diffusion Raman system (Jobin-Yvon) with a 632.8 nm argon ion laser. N2
channels for electrolyte and lithium ions, benefitting to the absorption–desorption examinations were performed on TriStar 3020
improvement of reversible capacity and rate performance. As system.
Electrochemical Measurements: The electrochemical performances of
a result, the achieved 3D graphene sheets encapsulated amor- the fabricated products, using as anode materials, were investigated for
phous CoSnO3 hollow nanoboxes deliver best lithium storage assembling CR2025-type coin cells in a glove box filled with argon gas,
properties. with lithium foil as the counter electrode. 70 wt% of active materials
(the harvested products), 20 wt% of acetylene black, and 10 wt% of
polyvinylidene difluoride were dissolved in an 1-methyl-2-pyrrolidinone
(NMP) solution in a small beaker and stirred for 12 h. Then, black and
3. Conclusions uniform slurry formed, was pasted on a copper foil and dried at 80 °C
for 12 h under vacuum condition to prepare the working electrode. The
In summary, we have successfully fabricated 3D graphene weight loading of H-CoSnO3@RGO ranges from 1.0 to 1.1 mg cm−2 and
sheets encapsulated amorphous CoSnO3 hollow nanoboxes the geometrical area of the electrode is about 2.01 cm2. The specific
through a facile chemical solution method combined with the capacity of the acquired H-CoSnO3@RGO is determined on the basis of

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the whole weight of H-CoSnO3@RGO (CoSnO3 and RGO). The Celgard [15] W. Wei, Z. Wang, Z. Liu, Y. Liu, L. He, D. Chen, A. Umar, L. Guo,
2400 porous polypropylene film was used as separator. The organic J. Li, J. Power Sources 2013, 238, 376.
electrolyte was 1 m LiPF6 dissolved in the mixture of ethylene carbonate [16] L. Ji, Z. Lin, M. Alcoutlabi, X. Zhang, Energy Environ. Sci. 2011, 4,
and diethyl carbonate (1:1 by volume). The galvanostatic discharge/ 2682.
charge measurements were implemented on a Neware multiple [17] X. Wang, J. Feng, Y. Bai, Q. Zhang, Y. Yin, Chem. Rev. 2016, 116,
battery tester. Both CV and EIS tests were carried out on an Autolab 10983.
electrochemical workstation (NOVA 1.9). [18] S. H. Choi, Y. C. Kang, ACS Appl. Mater. Interfaces 2014, 6, 2312.
[19] B. Lu, R. Hu, J. Liu, J. Liu, H. Wang, M. Zhu, RSC Adv. 2016, 6,
13384.
[20] Y. L. Wang, J. J. Xu, H. Wu, M. Xu, Z. Peng, G. F. Zheng, J. Mater.
Supporting Information Chem. 2012, 22, 21923.
Supporting Information is available from the Wiley Online Library or [21] C. R. Zhu, X. H. Xia, J. L. Liu, Z. X. Fan, D. L. Chao, H. Zhang,
from the author. H. J. Fan, Nano Energy 2014, 4, 105.
[22] C. Yuan, J. Li, L. Hou, X. Zhang, L. Shen, X. W. D. Lou, Adv. Funct.
Mater. 2012, 22, 4592.
[23] X. Huang, X. Qi, F. Boey, H. Zhang, Chem. Soc. Rev. 2012, 41, 666.
Acknowledgements [24] L. Ji, P. Meduri, V. Agubra, X. Xiao, M. Alcoutlabi, Adv. Energy Mater.
This study was financially supported by the National Key R&D Program of 2016, 6, 1502159.
China (No. 2016YFA0202602), the National Natural Science Foundation [25] G. Zhou, D.-W. Wang, F. Li, L. Zhang, N. Li, Z.-S. Wu, L. Wen,
of China (Nos. 51371154, 51571167, and 51701169), the Natural Science G. Q. Lu, H.-M. Cheng, Chem. Mater. 2010, 22, 5306.
Foundation of Fujian Province of China (No. 2017J05087), and the Young [26] J. Luo, J. Liu, Z. Zeng, C. F. Ng, L. Ma, H. Zhang, J. Lin, Z. Shen,
and Middle-aged Scholars Education Research Project of the Education H. J. Fan, Nano Lett. 2013, 13, 6136.
Department of Fujian Province of China (No. JAT160017). [27] S. Ding, D. Luan, F. Y. Boey, J. S. Chen, X. W. Lou, Chem. Commun.
2011, 47, 7155.
[28] X. Zhou, L. J. Wan, Y. G. Guo, Adv. Mater. 2013, 25, 2152.
[29] Q. Xie, Y. Ma, X. Wang, D. Zeng, L. Wang, L. Mai, D. L. Peng, ACS
Conflict of Interest
Nano 2016, 10, 1283.
The authors declare no conflict of interest. [30] L. L. Wang, K. B. Tang, Z. P. Liu, D. K. Wang, J. Sheng, W. Cheng, J.
Mater. Chem. 2011, 21, 4352.
[31] Y. Ma, Q. Xie, X. Liu, Y. Zhao, D. Zeng, L. Wang, Y. Zheng,
D.-L. Peng, Electrochim. Acta 2015, 182, 327.
Keywords [32] D. Pan, S. Wang, B. Zhao, M. Wu, H. Zhang, Y. Wang, Z. Jiao,
amorphous features, CoSnO3, graphene decorations, hollow structures, Chem. Mater. 2009, 21, 3136.
lithium ion battery anodes [33] Q. Guan, J. Cheng, X. Li, B. Wang, L. Huang, F. Nie, W. Ni, Sci. Rep.
2015, 5, 10017.
Received: October 9, 2017 [34] F. Wu, X. Ma, J. Feng, Y. Qian, S. Xiong, J. Mater. Chem. A 2014, 2,
Revised: November 2, 2017 11597.
Published online: [35] X. J. Zhao, G. Wang, Y. X. Zhou, H. Wang, Energy 2017, 118, 172.
[36] L. Zhang, K. Zhao, R. Yu, M. Yan, W. Xu, Y. Dong, W. Ren, X. Xu,
C. Tang, L. Mai, Small 2017, 13, 1603973.
[37] P. Shi, X. Dai, H. Zheng, D. Li, W. Yao, C. Hu, Chem. Eng. J. 2014,
[1] J. B. Goodenough, K. S. Park, J. Am. Chem. Soc. 2013, 135, 1167. 240, 264.
[2] J. M. Tarascon, M. Armand, Nature 2001, 414, 359. [38] J. Lin, Z. W. Peng, C. S. Xiang, G. D. Ruan, Z. Yan, D. Natelson,
[3] M. Armand, J. M. Tarascon, Nature 2008, 451, 652. J. M. Tour, ACS Nano 2013, 7, 6001.
[4] V. Etacheri, R. Marom, R. Elazari, G. Salitra, D. Aurbach, Energy [39] W. H. Xie, L. L. Gu, F. Y. Xia, B. L. Liu, X. Y. Hou, Q. Wang,
Environ. Sci. 2011, 4, 3243. D. Q. Liu, D. Y. He, J. Power Sources 2016, 327, 21.
[5] Z. Yang, J. Zhang, M. C. Kintner-Meyer, X. Lu, D. Choi, [40] M. Zhang, Y. Wang, M. Q. Jia, Electrochim. Acta 2014, 129, 425.
J. P. Lemmon, J. Liu, Chem. Rev. 2011, 111, 3577. [41] F. Huang, Z. Yuan, H. Zhan, Y. Zhou, J. Sun, Mater. Lett. 2003, 57,
[6] M. V. Reddy, G. V. Subba Rao, B. V. Chowdari, Chem. Rev. 2013, 113, 3341.
5364. [42] G. Wang, X. P. Gao, P. W. Shen, J. Power Sources 2009, 192, 719.
[7] Y.-M. Kang, M.-S. Song, J.-H. Kim, H.-S. Kim, M.-S. Park, J.-Y. Lee, [43] C. Guan, X. L. Li, H. Yu, L. Mao, L. H. Wong, Q. Y. Yan, J. Wang,
H. K. Liu, S. X. Dou, Electrochim. Acta 2005, 50, 3667. Nanoscale 2014, 6, 13824.
[8] H. Liu, G. Wang, J. Park, J. Wang, H. Liu, C. Zhang, Electrochim. [44] Y. Cao, L. Zhang, D. Tao, D. Huo, K. Su, Electrochim. Acta 2014,
Acta 2009, 54, 1733. 132, 483.
[9] Y. J. Feng, R. Q. Zou, D. G. Xia, L. L. Liu, X. D. Wang, J. Mater. [45] R. B. Lewis, A. Timmons, R. E. Mar, J. R. Dahn, J. Electrochem. Soc.
Chem. A 2013, 1, 9654. 2007, 154, A213.
[10] C. Wu, J. Maier, Y. Yu, Adv. Funct. Mater. 2015, 25, 3488. [46] R. M. Thankachan, M. M. Rahman, I. Sultana, A. M. Glushenkov,
[11] Q. He, J. Liu, Z. Li, Q. Li, L. Xu, B. Zhang, J. Meng, Y. Wu, L. Mai, S. Thomas, N. Kalarikkal, Y. Chen, J. Power Sources 2015, 282,
Small 2017, 13, 1701504. 462.
[12] R. Hu, D. Chen, G. Waller, Y. Ouyang, Y. Chen, B. Zhao, [47] J. Zhang, J. Liang, Y. Zhu, D. Wei, L. Fan, Y. Qian, J. Mater. Chem. A
B. Rainwater, C. Yang, M. Zhu, M. Liu, Energy Environ. Sci. 2016, 9, 2014, 2, 2728.
595. [48] L. P. Wang, Y. Leconte, Z. Feng, C. Wei, Y. Zhao, Q. Ma, W. Xu,
[13] R. Hu, Y. Ouyang, D. Chen, H. Wang, Y. Chen, M. Zhu, M. Liu, Acta S. Bourrioux, P. Azais, M. Srinivasan, Z. Xu, Adv. Mater. 2017, 29,
Mater. 2016, 109, 248. 1603286.
[14] Z. Wang, L. Zhou, X. W. David Lou, Adv. Mater. 2012, 24, 1903. [49] L. Su, Y. Zhong, Z. Zhou, J. Mater. Chem. A 2013, 1, 15158.

Small 2017, 1703513 1703513 (11 of 12) © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 small
NANO MICRO

www.advancedsciencenews.com www.small-journal.com

[50] Y. Dou, J. Xu, B. Ruan, Q. Liu, Y. Pan, Z. Sun, S. X. Dou, Adv. Energy [56] L.-F. Cui, R. Ruffo, C. K. Chan, H. Peng, Y. Cui, Nano Lett. 2009, 9,
Mater. 2016, 6, 1501835. 491.
[51] F. Geng, A. Yuan, J. Xu, Electrochim. Acta 2016, 216, 376. [57] R. M. Thankachan, M. M. Rahman, I. Sultana, A. M. Glushenkov,
[52] W.-S. Kim, Y. Hwa, H.-C. Kim, J.-H. Choi, H.-J. Sohn, S.-H. Hong, S. Thomas, N. Kalarikkal, Y. Chen, J. Power Sources 2015, 282, 462.
Nano Res. 2014, 7, 1128. [58] F. F. Cao, J. W. Deng, S. Xin, H. X. Ji, O. G. Schmidt, L. J. Wan,
[53] B. Lu, R. Hu, J. Liu, J. Liu, H. Wang, M. Zhu, RSC Adv. 2016, 6, Y. G. Guo, Adv. Mater. 2011, 23, 4415.
13384. [59] X. Zhou, L. Yu, X. W. Lou, Adv. Energy Mater. 2016, 6, 1600451.
[54] J.-J. Zhang, H.-H. Wang, T.-J. Zhao, K.-X. Zhang, X. Wei, Z.-D. Jiang, [60] D. C. Marcano, D. V. Kosynkin, J. M. Berlin, A. Sinitskii, Z. Z. Sun,
S.-I. Hirano, X.-H. Li, J.-S. Chen, ChemSusChem 2017, 10, 2875. A. Slesarev, L. B. Alemany, W. Lu, J. M. Tour, ACS Nano 2010, 4,
[55] X. J. Zhu, Z. P. Guo, P. Zhang, G. D. Du, R. Zeng, Z. X. Chen, S. Li, 4806.
H. K. Liu, J. Mater. Chem. 2009, 19, 8360. [61] Z. Y. Wang, Z. C. Wang, H. B. Wu, X. W. Lou, Sci. Rep. 2013, 3. 1391.

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