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Lithium Ion Batteries

Facile Synthesis of Ultrasmall CoS2 Nanoparticles within

Thin N-Doped Porous Carbon Shell for High Performance
Lithium-Ion Batteries
Qingfei Wang, Ruqiang Zou,* Wei Xia, Jin Ma, Bin Qiu, Asif Mahmood, Ruo Zhao,
Yangyuchen Yang, Dingguo Xia, and Qiang Xu

Cobalt sulfide (CoS2) is considered one of the most promising alternative anode
materials for high-performance lithium-ion batteries (LIBs) by virtue of its
remarkable electrical conductivity, high theoretical capacity, and low cost. However,
it suffers from a poor cycling stability and low rate capability because of its volume
expansion and dissolution of the polysulfide intermediates in the organic electrolytes
during the battery charge/discharge process. In this study, a novel porous carbon/CoS2
composite is prepared by using nano metal–organic framework (MOF) templates for
high-preformance LIBs. The as-made ultrasmall CoS2 (15 nm) nanoparticles in N-rich
carbon exhibit promising lithium storage properties with negligible loss of capacity at
high charge/discharge rate. At a current density of 100 mA g−1, a capacity of 560 mA
h g−1 is maintained after 50 cycles. Even at a current density as high as 2500 mA g−1, a
reversible capacity of 410 mA h g−1 is obtained. The excellent and highly stable battery
performance should be attributed to the synergism of the ultrasmall CoS2 particles
and the thin N-rich porous carbon shells derieved from nanosized MOF precusors.

1. Introduction
Lithium-ion batteries (LIBs) are creating great changes in
modern life, and have been widely used in portable electronic
devices due to their high energy density and long cycle life.
However, their performance is still far from meeting the
requirements of the mass, growing electric vehicles’ market.[1]
Graphite is the prevailing commercial anode material and
has nearly approached its theoretical limit (372 mA h g−1).[2]
Among the available alternative anode materials, cobalt
Q. Wang, Prof. R. Zou, W. Xia, J. Ma, B. Qiu,
A. Mahmood, R. Zhao, Y. Yang, Prof. D. Xia
Department of Materials Science and Engineering
College of Engineering
Peking University
Beijing 100871, China
E-mail: rzou@pku.edu.cn
Prof. Q. Xu
National Institute of Advanced Industrial
Science and Technology (AIST)
Ikeda, Osaka 563-8577, Japan
DOI: 10.1002/smll.201403579
sulfide (CoS2) has attracted much attention due to its remark-
able electrical conductivity and high theoretical capacity.[3]
However, its practical application suffers from several prob-
lems. For example, the pulverization problem caused by the
huge volume change during charge/discharge process could
cause a rapid capacity fading during cycling. This problem is
further aggravated by the dissolution of the polysulfide inter-
mediates in the organic electrolytes. Moreover, the poor rate
performance of CoS2 also limits its practical application.
So far, considerable efforts have been devoted for better
cycling stability and higher rate performance. Previous works
have shown that reducing the particle size of the anode mate-
rial into nano-range could weaken the mechanical stress
generated during the charge/discharge process, and conse-
quently inhibit the pulverization problem.[4] In addition,
the short diffusion path of lithium ions in the nanoparticles
would be helpful to the rate performance. Besides reducing
the particle size, using porous carbons[5] or graphene[6] as a
host structure for the CoS2 could offer spare space for the
volume expansion and prevent the pulverization effectively.
More importantly, the host structure could adsorb and trap
the polysulfide intermediates, consequently help to extend

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the cycle life of the materials. Notwith-

standing these advantages, the rational
design and controllable synthesis of nano-
structured CoS2 composite still face great
challenges.
Metal–organic frameworks (MOFs),
as a new category of porous materials,
have been widely used in areas like gas
storage,[7] catalysis,[8] biomedicine,[9] and
electrochemistry.[10] Recently, there is an
increasing tendency to use MOFs as pre-
cursor to synthesize nanostructured func-
tional materials, like porous carbon[11]
and porous carbon/metal or metal oxide
composites.[12] Under properly controlled
carbonization condition, perfect nano-
structures could be obtained with ultras-
mall nanoparticles uniformly dispersed
in porous carbon matrix. Moreover,
by choosing proper MOFs with N-rich
organic ligands, the incorporation of
nitrogen species in resultant carbon matrix
could be easily achieved, which could
enhance the energy storage capacity.[13]
Several recent works have revealed the
significant advantage of using this strategy
to prepare ideal nanostructured composite
as electrode materials for LIBs.[14]
Herein, we expanded the applica-
tion of this strategy to synthesize porous
carbon/cobalt sulfide composite (C/CoS2)
for the first time. ZIF-67, which has a soda-
lite (SOD) topological structure with Co
(II) metal ions and N-containing methyl-
imidazole ligand, was chosen as the MOF
precursor.[15] After a simple low tempera-
ture postvulcanizing step, we got ultras-
mall CoS2 nanoparticles finely dispersed in
Scheme 1. Schematic illustration of the synthesis process of ultrasmall CoS2 nanoparticles
N-rich porous carbon matrix. Compared
in N-rich carbon.
with the other methods, this strategy is
quite convenient. Moreover, different
from the previous work using bulk crystals, we chose ZIF-67 of highly uniform rhombic dodecahedron particles with an
nanocrystals (NanoZIF-67) as the precursor, which reduced average size of 300 nm (Figure 1b).
the particle size of the carbon matrix to several hundred Pyrolysis of NanoZIF-67 at 650 °C under Ar atmos-
nanometers. Such ideal nanostructure endues the composite phere gave the C/Co composite, denoted as NC/Co-650.
with excellent battery performance. Additionally, by tai- PXRD patterns of NC/Co-650 show that all the diffraction
loring the sizes of CoS2 particles and carbon matrices, we peaks can be assigned to metallic cobalt (Figure 1a). The
studied the relationship between the particle size and battery low peak intensities and broad peak indicate the nanosized
performance. feature of cobalt particles. From the transmission electron
microscopy (TEM) image (Figure 1c), it is clearly observed
that NC/Co-650 retains the pristine rhombic dodecahedron
2. Results and Discussion structure, and the black dots are uniformly distributed in
the carbon matrix. High-resolution TEM (HRTEM) image
Synthesis of the C/CoS2 composite is illustrated in Scheme 1. further reveals that the grain size of the Co nanoparticles is
The NanoZIF-67 were well-controlled synthesized according ≈10 nm (Figure 1d). The lattice fringes of Co can be found
to our previous research.[16] The sample purity was confirmed clearly in Figure S1, Supporting Information. Notedly, the
by the powder X-ray diffraction (PXRD) patterns, as shown organic ligands were transferred into N-rich porous carbon
in Figure 1a. Scanning electron microscopy (SEM) images matrix during the carbonization process, while the Co2+ was
clearly show that the NanoZIF-67 precursor is composed reduced to Co nanoparticle with average grain size of ≈10 nm

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8.53 wt% N species. High-resolution

X-ray photoelectron spectrometer (XPS)
provides insight into the nitrogen spe-
cies. As shown in Figure S2, Supporting
Information, the spectra can be decon-
voluted into three peaks, which corre-
spond to the pyridinic (398.9 eV), pyrrolic
(400.4 eV), and graphitic (401.3 eV)
nitrogen species, respectively.[17] The
porous structure of the amorphous carbon
matrix is further investigated by meas-
uring the nitrogen adsorption isotherm at
77 K (Figure S3, Supporting Informa-
tion). The pore size distribution calcu-
lated using the quenched solid density
functional theory (QSDFT) equilibrium
model reveals a hierarchical porosity of
the carbon matrix (Figure S3 inset, Sup-
porting Information). The content of
CoS2 in the composite could be estimated
by the inductive coupled plasma (ICP)
analysis. According to the result, the Co
content reaches 24.27 wt%, equivalent to
50.69 wt% CoS2 in the composite.
As mentioned above, the application
of cobalt sulfide in LIBs is plagued by
pulverization of electrode, dissolution of
intermediates, and poor rate performance.
Figure 1. a) Comparison of PXRD patterns of NanoZIF-67 with the simulated one from single Given that the ideal nanostructure and
crystal structures (upper), and NC/Co-650 with metallic Co (JCPDS Card No. 15-0806) (lower).
high nitrogen content of NC/CoS2-650
b) SEM images of NanoZIF-67. c) Transmission electron microscopy (TEM). d) High-resolution
TEM (HRTEM) images of NC/Co-650. may help to overcome these challenges,
we examined its potential application as
anode material in LIBs.
highly dispersed in the rhombic dodecahedron carbon Figure 3a shows the typical galvanostatic charge/dis-
matrix. charge curves for NC/CoS2-650 in different cycles between
Due to the high reactivity of the Co nanoparticles in NC/ 0.1 and 3.0 V at a current density of 100 mA g−1. It should
Co-650, the C/CoS2 composite was synthesized by a simple be noted that all the current densities and specific capacities
reaction of NC/Co-650 with sulfur at 300 °C in a sealed glass here are calculated based on the total mass of the composite
tube. The final product was denoted as NC/CoS2-650. Figure 2a to avoid the overestimate (Figure S4, Supporting Informa-
reveals that the NC/CoS2-650 maintains the ideal nanostruc- tion). As shown in Figure 3a, the first discharge curve is dif-
ture of its precursor, and the nanoparticles are well-dispersed ferent from the subsequent cycles with three plateaus during
in the carbon matrix. The typical size of the small particles is the lithiation process. In the first cycle, NC/CoS2-650 dis-
around 15 nm according to the HRTEM image (Figure 2b). plays a high discharge capacity of 1100 mA h g−1. The large
The in situ transformation of Co into CoS2 is revealed by initial capacity may benefit from the full utilization of CoS2
the lattice fringes with a spacing of 0.276 nm for the [200] nanoparticles and the irreversible formation of a solid–elec-
plane of CoS2 in Figure 2b. Furthermore, the HRTEM trolyte interphase (SEI) on the surface of the composite.
image shows the amorphous nature of the obtained carbon During the second cycle, the discharge capacity decreases
matrices. The highly distributed structure is also proven to 701 mA h g−1 with a corresponding charge capacity of
by the uniform distribution of C, Co, and S elements from 670 mA h g−1, leading to a high Coulombic efficiency (CE)
energy dispersive spectrometer (EDS) mapping (Figure 2c). of 96%. This high CE indicates the good reversibility of the
Figure 2d presents the PXRD pattern for NC/CoS2-650, in lithiation/delithiation processes. Different from the first cycle,
which most of the peaks correspond to CoS2 (JCPDS Card the subsequent discharge curves display two plateaus in the
No. 41-1471). Similar to the C/Co precursor, CoS2 exhibits potential ranges of 1.8–1.6 and 1.5–1.3 V, which correspond
PXRD peak broadening due to the small size. The amor- to the insertion of a small amount of lithium and displace-
phous nature of the obtained carbon matrix is also supported ment reaction of Li2S + Co, respectively.[18] The charge/dis-
by the Raman spectrum of NC/CoS2-650 (Figure 2e), in which charge behavior of the composite was further investigated
the two broad bands at 1338 and 1590 cm−1 are assigned to by the cyclic voltammetry (CV) experiment with a scan rate
typical D and G bands of amorphous carbon, respectively. of 0.2 mV s−1 in the potential range of 0.1–3.0 V. As shown
Elemental analysis illustrates that NC/CoS2-650 possesses in Figure 3b, three reduction peaks centered at 1.3, 0.9, and

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current densities of 100, 200, 1000, and

2500 mA g−1, respectively. This result is
remarkable, compared with the previously
reported CoS2 electrodes.[3,18,19] Moreover,
after changing the current density back to
100 mA g−1, the capacity of NC/CoS2-650
reverted to the original values, implying its
good reversibility.
The excellent battery performance of
NC/CoS2-650 originates from the ideal
nanostructure of the composite. The good
cycling stability of NC/CoS2-650 should be
attributed to the following aspects. First,
the inside CoS2 nanoparticles have better
adaptability to the strain arising from the
lithiation/delithiation processes, and could
avoid the pulverization problem effec-
tively. Second, the carbon matrix is able
to confine the CoS2 nanoparticles in small
cages, which offer sufficient space for the
volume expansion of CoS2 nanoparticles
during discharge/charge process, thus
keeping the structural integrity. TEM
images of the electrode after 50 charge/
discharge cycles at 100 and 2500 mA g−1
clearly show that the composite still main-
tains its original structure (Figure 4), fur-
ther verifying the stability of the unique
structure and the generation of the long
cycle stability.[20] Finally, the N-rich hier-
archical porous carbon not only offers
electrolyte pathways to the inside CoS2
Figure 2. View of a) TEM images, b) HRTEM images, c) energy dispersive spectrometer (EDS) particles, but also adsorbs the polysulfide
mapping, d) PXRD patterns, and e) Raman spectrum of NC/CoS2-650. intermide, which consequently help to
extend the cycle life of the material. The
superior rate capability of NC/CoS2-650
0.7 V are observed in the first cathodic sweep. However, should be attributed to the large surface area for increased
from the second cycle onward, only two distinct peaks cen- Li-ion flux and the shorter path lengths for electronic and
tered at 1.3 and 1.7 V are observed, which are in good agree- ionic transport, provided by the CoS2 nanoparticles and small
ment with the plateaus in the galvanostatic discharge curves. carbon matrices.[21] Most importantly, the hierarchical porous
As mentioned above, the peaks should be originated from structure of the carbon shells derived from nanosized MOF
the decomposition of CoS2 into Li2S and Co. In the anodic precursors fascinates the diffusion of lithium ions and elec-
sweep, oxidation peaks between 2.0 and 2.3 V are observed, trolyte through the carbon matrix.
which are related to the formation of CoS2. Different from To further understand the excellent battery performance
the previous literature,[3,18] the peaks are stable after first of NC/CoS2-650 and gain a deep insight into the relationship
cycle, implying the good cycling stability of NC/CoS2-650. between the particle size and battery performance, other two
The cycle performances of NC/CoS2-650 at different cur- C/CoS2 composites were prepared for comparison. The cor-
rent densities are shown in Figure 3c. NC/CoS2-650 exhibits responding PXRD patterns of the samples are provided in
quite good cycling stability at a current density of 100 mA g−1. Figures S5–S7, Supporting Information.
After 50 cycles, the sample maintains a reversible capacity of C/CoS2 composite with large carbon matrix (denoted
about 560 mA h g−1. More importantly, the good cycle sta- as BC/CoS2-650, in which “B” represents its bulk carbon
bility is maintained at high current density. It is shown that matrix) was synthesized by replacing NanoZIF-67 precur-
at 2500 mA g−1 the composite still gives a reversible capacity sors with bulk crystals. Even though the size of carbon matrix
of about 410 mA h g−1 after 50 cycles. The high rate perfor- increased, the inside CoS2 particles are still as small as that in
mance of NC/CoS2-650 is further demonstrated by cycling the NC/CoS2-650 (Figure S8a,b, Supporting Information). Raman
battery at various current densities from 100 to 2500 mA g−1 and nitrogen sorption experiments were conducted to char-
as shown in Figure 3d. The capacity drops moderately acterize the structure of BC/CoS2-650 (Figures S9 and S10,
with the increase of current density. NC/CoS2-650 delivers Supporting Information). Elemental analysis reveals that BC/
reversible capacities of 710, 570, 490, and 340 mA h g−1 at CoS2-650 has a close nitrogen content of 9%. High-resolution

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DOI: 10.1002/smll.201403579
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Figure 3. View of a) voltage profile, b) cyclic voltammograms, c) cycle-life performance at 100 and 2500 mA g−1, and d) charge/discharge capacity
at various current densities of NC/CoS2-650.
N 1s XPS spectrum was collected to obtain insight into the
nitrogen species (Figure S11, Supporting Information). Com-
paring the cycling performance of NC/CoS2-650 and BC/
CoS2-650 at 500 mA g−1 between 0.1 and 3.0 V (Figure 5a),
similar stabilities could be obtained, but the average capacity
of BC/CoS2-650 is lower than that of NC/CoS2-650. Given
that BC/CoS2-650 has the similar ultrasmall CoS2 particles,
the difference should be originated from the particle size
and porous structure of the carbon matrix. The thick carbon
matrix of BC/CoS2-650 may hinder the transfer of lithium
ions into its core side, leading to insufficient utilization of all
the CoS2 nanoparticles in the composite. According to the
pore size distribution results (Figure S10 inset, Supporting
Information), the lack of larger mesopores in BC/CoS2-650
will aggravate the condition, thus resulting in the low specific
capacity.
Another C/CoS2 composite with larger CoS2 particles
was prepared by increasing the carbonization temperature
to 1000 °C (denoted as NC/CoS2-1000). During the high
temperature carbonization process at 1000 °C, the cobalt
particles aggregated and formed to large particles of CoS2
without uniform shape in the final C/CoS2 composite
(Figure S8c,d, Supporting Information). Moreover, the mor-
phology of the rhombic dodecahedron carbon matrix was
also changed by the high temperature processing. Besides
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DOI: 10.1002/smll.201403579
the morphology of the carbon matrix, the nitrogen content
of NC/CoS2-1000 decreases sharply compared with NC/
CoS2-650 (Table S1, Supporting Information), due to the loss
of pyridinic and pyrrolic nitrogen atoms (Figure S12, Sup-
porting Information). As shown in Figure 5a, the capacity
of NC/CoS2-1000 falls dramatically after the initial several
cycles. Given that NC/CoS2 has similar hierarchical porosity
to NC/CoS2-650 (Figure S10 inset, Supporting Information),
the larger particle size of CoS2 and lower nitrogen content
in NC/CoS2-1000 should be the vital reasons for the worse
performance. The huge volume change of large CoS2 par-
ticles may cause the protective carbon matrix to crack and
fracture.[22] Without the protection, some small pieces from
the decomposed large CoS2 particles flee into the electrolyte,
resulting in “dead materials.” Furthermore, the low content
of nitrogen may weaken the adsorption ability of the carbon
host toward the polysulfide.[23] Figure 5b shows the Nyquist
plots for NC/CoS2-650 and NC/CoS2-1000. The impedance
associated with the charge transfer resistance in NC/CoS2-
1000 is much lower than that in NC/CoS2-650, leading to
the conclusion that the battery performance mainly depends
on the particle size of CoS2 and the nitrogen content of the
carbon matrix, as well as the thickness of the carbon shell.
Consequently, the comparisons have illustrated the superi-
ority of the ideal nanostructure of NC/CoS2-650.
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NanoZIF-67: 1.43 g of Co(NO3)2·6H2O and

3.24 g of 2-methylimidazole were dissolved in
100 mL methanol, respectively. The two solu-
tions were mixed at room temperature under
magnetic stirring for 15 min, and stood for
24 h. Solid product was separated by centrifu-
gation and washed with methanol for three
times, followed by vacuum drying at 150 °C
for 8 h.
Synthesis of C/Co Composite: The as-
prepared ZIF precursors were carbonized
at 650 and 1000 °C, respectively. Usually,
the carbonization process was kept for 1 h
under Ar atmosphere with a heating rate of
5 °C min−1 and cooled down to room tempera-
ture naturally. The products were denoted as
NC/Co-650, BC/Co-650, and NC/Co-1000
in which “N” or “B” indicate their “nano” or
“bulk” crystal precursor, and the number rep-
resents their carbonization temperature.
Synthesis of C/CoS2 Composite: The
C/Co composite and sulfur were grounded
together with a mass ration of 2:1, and sealed
in a glass tube. Then the tube was heated at
300 °C for one day. The denotations of the
final products were similar with their C/Co
precursors, except that “Co” was changed into
“CoS2.”
Figure 4. TEM images of NC/CoS2-650 after 50 charge/discharge cycles at a,b) 100 and c,d)
−1 Materials Characterizations: PXRD pat-
2500 mA g , respectively.
terns were recorded on a Bruker D8 Advanced
diffractometer using Cu Kα radiation
3. Conclusion (λ = 1.54050 Å) and operating at 40 kV and
100 mA. SEM images were obtained on a Hitachi S-4800 electron
In summary, we employed a nanoMOF-derived synthesis microscope and equipped with a Bruker Quantax EDS. Elemental
strategy to prepare C/CoS2 composite with ultrasmall CoS2 analysis was performed on a Vario EL Elemental Analyzer. TEM
nanoparticles finely embedded in thin N-rich porous carbon. images were taken on a FEI Tecnai F20 microscope. XPS measure-
The composite exhibits promising Li storage properties. At a ments were performed on a Kratos Axis Ultra Imaging Photoelec-
current density of 100 mA g−1, a capacity of 560 mA h g−1 tron Spectrometer using monochromatic Al Kα line (1486.7 eV).
was maintained after 50 cycles. Increasing the current den- Raman spectra were recorded on a RENISHAW Raman spectrum
sity to 2500 mA g−1, a reversible capacity of 410 mA h g−1 equipment. To determine the quantity of cobalt in the sample,
was still obtained. Moreover, by tailoring the particle size a Leeman prodigy inductively coupled plasma optical emission
of the CoS2 and carbon matrix, we found that the excellent spectrometer (ICP-OES) was used. N2 adsorption isotherms were
battery performance originated from the small size of the measured on an Autosorb-iQ automatic volumetric instrument
CoS2 particles and the carbon matrix. The novel and facile within the pressure range 0–1 atm at 77 K.
synthesis introduced here could be expanded to prepare Electrochemical Measurements: The as-prepared C/CoS2
other ultrasmall metal sulfide particles. These results may composites were mixed with acetylene black, and polyvinylidene
help in the development of new concepts for the design fluoride (PVDF) binder at a weight ratio of 70:20:10 in N-methyl-
and synthesis of electrode materials for next generation pyrrolidone (NMP) to form a slurry. The working electrodes were
LIBs. prepared by coating the slurry onto stainless steel foils and dried in
vacuum at 80 °C for 24 h. The half cells were assembled in a glove
box filled with high pure Ar, using lithium metal as the counter
electrode, and a glass fiber (GF/D) from Whatman as the sepa-
4. Experimental Section rator. The electrolyte was 1 mol L−1 LiPF6 in 1:1 ethylene carbonate
Synthesis of ZIF-67: BulkZIF-67: 3.32 g of Co(Ac)2·4H2O and (EC)/dimethyl carbonate (DMC). The cells were cycled between
3.28 g of 2-methylimidazole were dissolved in 100 mL methanol. 3.0 and 0.1 V on a Neware battery instrument at room tempera-
The mixed solution was sealed in a 125 mL teflon-lined steel auto- ture. The specific capacity was calculated on the total mass of the
clave, and heated at 120 °C for three days. The as-prepared crys- composite. The CV measurements were conducted with a Zahner
tals were filtered out and washed by methanol, finally dried under Zennium Electrochemical Workstation in the potential range
vacuum at 150 °C for 8 h. 0.1–3.0 V at a scan rate of 0.2 mV s−1. The electrochemical

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of Education Program for New Century Excellent Talents of China

(NCET-11-0027).

[1] a) J. B. Goodenough, K.-S. Park, J. Am. Chem. Soc. 2013, 135,

Figure 5. a) Cycle-life performances of NC/CoS2-650, NC/CoS2-1000,
and BC/CoS2-650 at 500 mA g−1 and b) Nyquist plots of NC/CoS2-650
and NC/CoS2-1000.
impedance spectra were measured using the same instrument
with the frequency range from 0.01 to 100 000 Hz with a sine wave
with amplitude of 5.0 mV.
Supporting Information
Supporting Information is available from the Wiley Online Library
or from the author.
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Received: December 2, 2014

This work is supported by National Natural Science Foundation Revised: December 29, 2014
of China (11175006, 51322205, and 21371014), the Ministry Published online:

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DOI: 10.1002/smll.201403579