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Nanostructures

Ultrasmall Fe3O4 Nanoparticle/MoS2 Nanosheet

Composites with Superior Performances for Lithium Ion
Batteries
Yu Chen, Bohang Song, Xiaosheng Tang, Li Lu, and Junmin Xue*

novel composite consisting of graphene-like MoS2 nanosheets and ultrasmall

Fe3O4 nanoparticles (3.5 nm) is synthesized as an anode for lithium ion battery
application. In such composite anode, MoS2 nanosheets provide flexible substrates
for the nanoparticle decoration, accommodating the volume changes of Fe3O4 during
cycling process; while Fe3O4 nanoparticles primarily act as spacers to stabilize the
composite structure, making the active surfaces of MoS2 nanosheets accessible for
electrolyte penetration during charge/discharge processes. Owing to the high reversible
capacity provided by the MoS2 nanosheets and the superior high rate performance
offered by ultrasmall Fe3O4 nanoparticles, superior cyclic and rate performances are
achieved by Fe3O4/MoS2 anode during the subsequent electrochemical tests, delivering
1033 and 224 mAh g1 at current densities of 2000 and 10 000 mA g1, respectively.

1. Introduction
Owing to their high energy densities and environmental
benignity, lithium ion batteries (LIBs) have been recognized
as potential power sources for various applications, ranging
from a tiny music player to a massive sports car.[13] Anode, as
a crucial component, controls every aspect of a LIBs performances. In scientific field, great effort has been concentrated
on improving reversible capacities of anodes. To achieve
this, various new anode materials based on different reaction mechanisms have been proposed to replace the current
commercially available graphite anode, with a theoretical
capacity of 372 mAh g1.[46] Besides, rate capability, namely
the ability of an anode material to be charged/discharged

Y. Chen,[+] X.Tang, Dr. J. Xue

Department of Materials Science and Engineering
National University of Singapore
Singapore, 117576
E-mail: msexuejm@nus.edu.sg
B. Song,[+] Prof. L. Lu
Department of Mechanical Engineering
National University of Singapore
Singapore, 117576
[+] These

authors contributed equally to this work.

DOI: 10.1002/smll.201302879

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in a short period of time, is another crucial criterion when

selecting a potential anode for fast charging applications,
such as electric vehicles.[7,8]
Owing to its high theoretical capacity, natural abundance, and environmental benignity, Fe3O4 has been widely
reported as a potential anode material. Fe3O4 with different
morphologies have been studied as anodes for LIB.[912]
Recently, ultrasmall size of Fe3O4 nanoparticels (5 nm) has
been reported to be a crucial factor in composite electrodes
to achieve satisfactory high rate electrochemical performances.[13,14] Firstly, the ultrasmall size can greatly mitigate
the volume expansion/contraction of Fe3O4 particles during
charge/discharge. Secondly, a high lithium ion flux can be
achieved by the large surface area provided by the ultrasmall
particles.[15] More importantly, due to the extremely short
distance for lithium ions transportation within ultrasmall particles, the rate capability of lithium insertion/removal can be
significantly enhanced.[16] Many works have focused on the
combination of Fe3O4 with 2D materials for enhanced electrochemical performances.[17]
MoS2, a transition metal sulfide with layered structure,
has recently been discovered as a popular anode material
for lithium ion batteries (LIBs).[1820] This material consists
of atomic layers of S-Mo-S stacked together by van der
Waals interactions.[21] Such layered structure allows small
ions, such as lithium ions, to be reversibly intercalated into
the galleries between layers without major volume expansion

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Ultrasmall Fe3O4 Nanoparticle/MoS2 Nanosheet Composites with Superior Performances for Lithium Ion Batteries

in its overall dimension.[22] It has been reported that MoS2

based anodes are able to deliver high reversible capacities
of 900 1200 mAh g1.[20,2224] Owing to the similar layered
structure of MoS2 as graphite, great effort has been put on
the fabrication of few-layered MoS2 nanosheets.[23,2527] With
a large effective surface area resulting from the 2D structures,
and also its much higher capacities compared with that of
graphene (usually in the range of 200 to 500 mAh g1),[2831]
MoS2 nanosheets have great potential to replace graphene,
and become one of the next most popular materials in the
scientific research of LIB materials.
However, as a detrimental weakness from its 2D structure, MoS2 nanosheets are vulnerable to easy restacking.[32]
The adjacent 2D layers can be easily restacked together
under the van der Waals interaction during charge/discharge
processes.[33] As a consequence, the unique 2D structures
and their high active surface will be lost.[34,35] The restacked
surface is hardly accessible to electrolyte which carries
lithium ions, resulting in fast fading of reversible capacities. To combat this problem, particles with various sizes are
introduced as spacers between nanosheets, thus making both
faces of nanosheets accessible to electrolytes.[31,33] However,
large particles are undesirable for high rate applications of
LIB anodes due to the slow lithium transportation within
solid state.[17] Therefore, ultrasmall transition metal oxides
with significantly shortened lithium ion transportation paths,
greatly enhance the rate capability of lithium insertion/
removal.[1517]
In the present work, MoS2 nanosheets decorated with
ultrasmall Fe3O4 nanoparticles were fabricated for LIB
anodes. Instead of the most commonly reported synthetic
methods of MoS2 nanosheets, including sonication in suitable
solvents and ion intercalation,[36,37] MoS2 nanosheets were
synthesized through a facile one-step hydrothermal process in

this work. The morphology of the obtained MoS2 nanosheets

was similar to that of graphene. Subsequently, the obtained
MoS2 nanosheets were used as substrates for the decoration
of ultrasmall Fe3O4 nanpoarticles via another hydrothermal
method.[13,38] In the final product of MoS2 nanosheets decorated by ultrasmall Fe3O4 nanoparticles (Fe3O4/MoS2), the
2D MoS2 nanosheets not only accommodated the large
volume changes of Fe3O4 during charge/discharge, but also
provided substrates for Fe3O4 nanoparticles to be attached
on, thus preventing their agglomeration and fast fading in
capacity. On the other hand, Fe3O4 nanoparticles primarily
acted as spacers between the MoS2 nanosheets, preventing
the anode composites from collapsing after long-term charge/
discharge process. Such effect was proven to be crucial in
later comparison of electrochemical performances between
anodes fabricated from Fe3O4/MoS2 and pristine MoS2. Furthermore, the potential of ultrasmall Fe3O4 nanoparticles to
reach excellent high rate performance is also crucial for the
resultant rate capability of Fe3O4/MoS2 composites.[14]

2. Results and Discussion

To synthesize MoS2 nanosheets, sodium molybdate was
chosen as the precursor for molybdenum and thioacetamide
was used as the sulfur source. These two chemicals were
mixed in appropriate ratio and sealed in a Teflon-lined stainless steel autoclave. During the subsequent hydrothermal
condition, MoO42 anions were reduced under high temperature condition, forming MoS2.[32,39] Without adding any 2D
substrate, pristine MoS2 nanosheets were obtained through a
simple hydrothermal reaction. Figure 1a shows a low magnification scanning electron microscope (SEM) image of MoS2
nanosheets spreading on a silicon substrate, indicating large

Figure 1. (a) Low and (b) high magnification SEM images of MoS2 nanosheets. (c-e) TEM images of MoS2 nanosheets. (f) High resolution TEM image
of MoS2. Inset: SAED pattern of MoS2 nanosheets.
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amount of uniform MoS2 nanosheets can be easily fabricated

by such hydrothermal method. A magnified SEM image of
MoS2 nanosheets is shown in Figure 1b. The nanosheets show
a certain level of transparency under SEM beam, indicating
their small thickness. Figure 1c shows a transmission electron
microscope (TEM) image of a single MoS2 nanosheet. Under
the examination of TEM, the nanosheet is fully transparent,
showing the extremely small thickness of this 2D structure. The size of the nanosheet shown in Figure 1c is about
300 nm in width. Figure 1d and 1e are two magnified TEM
images of the boxed areas from Figure 1c. With the wrinkles and scrolling, the morphology of the MoS2 nanosheet
mimics exactly that of a single graphene nanosheet. The high
resolution TEM image of the MoS2 nanosheets is shown
in Figure 1f. The cross-sections of MoS2 nanosheets can be
observed. As shown in Figure 1f, the distance between two
adjacent atomic planes were calculated to be around 0.61 nm,
corresponding to the interplanar distance of (002) plane of
hexagonal MoS2 crystalline structure. As shown in TEM
images, the stacking of MoS2 in the (002) direction is not significant. Such observation was further proven by missing of
(002) peak in the X-ray diffraction (XRD) pattern (Figure
S1) of MoS2, indicating the successful synthesis of few-layers
MoS2 nanosheets.[40,41] The selected area electron diffraction (SAED) pattern of MoS2 nanosheets is shown in the
inset of Figure 1f. The two diffraction rings can be observed,
corresponding to the hexagonal MoS2 crystalline structure
(JCPDS: 371492).

The as-synthesized MoS2 nanosheets were further decorated with ultrasmall Fe3O4 nanoparticles via another
hydrothermal process. Figure 2a shows the large scale morphological characterization of the obtained Fe3O4/MoS2
under SEM, demonstrating its great uniformity in morphology. The boxed area in Figure 2a was magnified as is
shown in Figure 2b. Compared with the SEM image of pristine MoS2 nanosheets with the same magnification shown in
Figure 1b, Fe3O4/MoS2 shows different contrasts due to the
decoration of Fe3O4 nanoparticles. As shown in the TEM
image of Fe3O4/MoS2 in Figure 2c, uniform decoration of
Fe3O4 nanoparticles on MoS2 nanosheets can be clearly
observed, proving the successful formation of the Fe3O4/
MoS2 composite structure. To further investigate the morphologies of Fe3O4/MoS2, three TEM images with increasing
magnifications on the same sample area were taken and
shown in Figure 2d-f, respectively. Figure 2d shows a low
magnification TEM image of Fe3O4/MoS2. By comparing
with the pristine MoS2 nanosheets shown in Figure 1c, the
dark cloudy patterns indicate the decoration of untrasmall
Fe3O4 nanoparticles. The boxed area of Figure 1d is magnified and shown in Figure 2e. Under a higher magnification,
the ultrasmall Fe3O4 particles attached on MoS2 nanosheets
can be well observed. The average size of Fe3O4 is around
3.5 nm (size distribution bar chart shown in Figure S2). Such
small size is beneficial for the subsequent high rate battery
performances.[16] The boxed area of Figure 2e is shown as a
high resolution TEM image in Figure 2f. The lattices of Fe3O4

Figure 2. (a, b) SEM images, (cf) TEM images, and (g) EDX mappings with corresponding TEM image of Fe3O4/MoS2 composite.

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nanoparticles can be clearly observed with the interplanar

distance of 0.25 nm, matching the (311) plane of cubic Fe3O4
crystalline structure (JCPDS: 653107). Energy dispersive
X-ray spectroscopy (EDX) elemental mapping was also performed on a single piece of Fe3O4/MoS2 composite. As shown
in Figure 2g, all three elements of Iron, Molybdenum, and
Sulfur were uniformly distributed in the sample area, suggesting the uniform decoration of Fe3O4 nanoparticles. For
comparison, MoS2 nanosheets decorated with twice amount
of Fe3O4 nanoparticles (H-Fe3O4/MoS2) was also synthesized
via a similar hydrothermal method, with their morphologies
shown in Figure S3. According to ICP measurements, the
atomic ratio of Fe : Mo for Fe3O4/MoS2 composite is 2.5 : 1
while it is around 5 : 1 for H-Fe3O4/MoS2. It agrees well with
the relative precursor ratios during the synthesis of the two
composites. The XRD patterns of MoS2 nanosheets, Fe3O4/
MoS2, H-Fe3O4/MoS2, and pristine Fe3O4 nanoparticles were
also shown in Figure S1.
The first cycle charge/discharge curves of pristine MoS2
nanosheets, Fe3O4/MoS2, H-Fe3O4/MoS2 composites, and ultrasmall Fe3O4 nanoparticles at a current density of 100 mA g1
are shown in Figure 3a. As indicated in the first cycle charge
profiles, the reversible capacities of MoS2 nanosheets,

Fe3O4/MoS2, H-Fe3O4/MoS2, and ultrasmall Fe3O4 nanoparticles are 1122, 1079, 990, and 809 mAh g1, respectively,
suggesting that the reversible capacity of MoS2 is almost
40% higher than that of Fe3O4. Therefore, observed from
the first reversible capacity of Fe3O4/MoS2 and H-Fe3O4/
MoS2, the higher the Fe3O4 percentage the lower the reversible capacity. Besides, Fe3O4 comprised the majority part of
both composite anodes (Fe3O4/MoS2 and H-Fe3O4/MoS2),
thus leading to large proportion of the reversible capacities
contributed from Fe3O4 content. The corresponding dQ/dV
curves of these four anodes are shown in Figure S4. For the
pristine MoS2 nanosheets, the reduction peak around 0.6 V in
the first discharge process is due to the conversion reaction
of MoS2 into Mo nanoparticles and Li2S.[42,43] The two oxidation peaks in the reverse charge process at 1.75 and 2.25 V
can be attributed to the partial oxidation of Mo to MoS2 and
the oxidation of Li2S to S, respectively.[43]
The cycling performances of all anode materials are
shown in Figure 3b. During the initial low rate cycles, the
electrode structure tended to form stable SEI layers from
electrolyte-closing side to electrolyte-distant side due to the
activation process, leading to quick capacity fade because of
the continuous consumption of Li for SEI layer formation.

Figure 3. (a) First cycle charge/discharge curves of MoS2, Fe3O4/MoS2, H-Fe3O4/MoS2, and Fe3O4. (b) Cycling performances of MoS2, Fe3O4/MoS2,
and H-Fe3O4/MoS2 from cycle number 1 to 560. (c) Polymeric gel-like film formed on composite of Fe3O4/MoS2 after cycling. Charge/discharge
and dQ/dV curves of (d) Fe3O4/MoS2 and (e) H-Fe3O4/MoS2 at 12th, 260th, and 510th cycles under the current density of 2000 mA g1, respectively.
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This could be supported by relatively low coulombic effi- Figure 3d and 3e. As shown in Figure 3d, there was no new
ciency for initial cycles (Figure S5). To examine the high plateau/peaks appearance from 12th to 510th cycle during the
rate battery performances of these electrodes, the current charge/discharge processes of Fe3O4/MoS2 at 2000 mA g1,
densities for Fe3O4/MoS2, H-Fe3O4/MoS2, and MoS2 anodes indicating that no new mechanism occurred. The gradual
were increased to 2000 mA g1 starting from the 11th cycle increment of whole region areas enclosed by the dQ/dV
to 510th cycle. As shown in Figure 3b, the starting revers- curves shown in Figure 3d highly supports our assumption
ible capacity is still low because of only surface of Fe3O4/ that more and more available sites on both MoS2 and Fe3O4
MoS2 electrode contributed at such a high rate. However, inside electrode were activated, in addition to reversible forthe condition has been gradually changed by the presence mation of polymeric film over these cycles. Fe3O4 plays a
of Fe3O4 nanoparticles, since the continuous expansion/con- critical role in opening MoS2 nanosheets to make it further
traction of Fe3O4 at surface parts of electrode during lithi- electrolyte accessible, which will be confirmed in a later secation/delithiation may further open the graphene-like MoS2 tion. Similar behaviors were also observed in the charge/
nanosheets structure, and thus forming nano-sized channels discharge and dQ/dV curves for H-Fe3O4/MoS2. Due to its
for electrolyte penetration. As a result, more and more avail- higher percentage of Fe3O4 content, a distinct reduction peak
able sites from both MoS2 and Fe3O4 inside electrode par- around 0.7 V (Figure 3e) was observed in the dQ/dV curves
ticipated into the reversible reaction to contribute capacity, of H-Fe3O4/MoS2, which can be attributed to the reduction of
leading to a continuous increasing of capacity from 11th to Fe3O4 to Fe.[7] Subsequently, the current density was reduced
510th cycles, as shown in Figure 3b. When the current density to 500 mA g1 for the following 50 cycles (Figure 3b). The
was reduced to 500 mA g1, the capacity has been further reversible capacities of Fe3O4/MoS2 and H-Fe3O4/MoS2 conincreased to almost 1200 mAh g1 at 560th cycle for Fe3O4/ tinued to increase to 1240 and 1100 mAh g1, respectively.
MoS2 composite, which exceeds the initial reversible capacity The corresponding charge/discharge and dQ/dV curves at
of either Fe3O4 or MoS2. It must be related to a formation different stages in this process are shown in Figure S6.
Same cells fabricated from Fe3O4/MoS2, H-Fe3O4/MoS2,
of polymeric gel-like film on top of stable SEI layer, which
is believed to be a reversible process. [31,4446] In fact, except and MoS2 were subjected to further electrochemical tests
for those switching cycles which have unstable values, the with cycling performances shown in Figure 4a. The stabiaverage coulombic efficiency for the increasing part from 11th lized reversible capacities of Fe3O4/MoS2 were 1189, 943,
to 510th cycles is as high as 99.4% (Figure S5). It strongly sug- 569, 362, 270, and 224 mAh g1 at current densities of 1000,
gests the high reversibility of lithiation/delithiation process of 2000, 4000, 6000, 8000, and 10000 mA g1, respectively. The
the composite structure during these cycles. The huge incre- charge/discharge curves of Fe3O4/MoS2 at the first cycles of
ments in capacities over cycles have been previously reported each current density are shown in Figure S7. With a higher
in many composite structures containing both nanosheets percentage of incorporated Fe3O4 nanoparticles, H-Fe3O4/
and conversion reaction-based particles.[24,4749] On the con- MoS2 delivered lower reversible capacities under relatively
trary, the MoS2 anode is not able to exhibit comparable low current densities (1000 to 4000 mA g1), but showed
electrochemical performances at a same testing condition. It slightly better rate capabilities when the current density
could be understood by three reasons. The first one is that increased beyond 6000 mA g1. This observation implies
compared to semiconducting MoS2,[50,51] metallic Fe3O4 pos- a better electrochemical performance of ultrasmall Fe3O4
sesses a higher conductivity.[52,53] Thus higher capacity was nanoparticles over that of MoS2 nanosheets under high
provided by Fe3O4-contained electrodes at a current density current densities.[14] Subsequently, the three anodes were
of 2000 mA g1. The second reason is that the prerequisite for cycled at 2000 mA g1 for another 500 cycles. Fe3O4/MoS2
polymeric film formation is a stable SEI layer on surface of and H-Fe3O4/MoS2 both showed stable reversible capacinguyn cht
MoS2 nanosheets and/or Fe3O4 nanoparticles. However, neat ties, delivering 1033 and 782 mAh g1 at the 1180th cycle,
b li
MoS2 failed to form such SEI layer which will be discussed respectively. Although the initial reversible capacity of MoS2
in a later section. The third reason is that neat MoS2 is easy anodes was compromised by incorporating with Fe3O4, at
to be restacked, leading to reduced effective surface areas to subsequent higher current densities up to 10000 mA g1, the
form any polymeric films. Figure 3c shows the low magnifica- electrochemical performances of anodes containing Fe3O4
tion TEM image of Fe3O4/MoS2 after 1180 cycles of charge/ are much better than those of pristine MoS2 anodes as shown
discharge. The polymeric gel-like film can be observed, which in Figures 3b and 4a.The anode containing pristine MoS2 was
disappeared after 60 seconds exposure under energetic elec- tested under the same condition and showed extremely low
trons in TEM.[46] The formation of polymeric gel-like film capacities, delivering reversible capacities around 50 mAh g1
consumes the electrolyte because the decomposition prod- throughout the entire testing period. Such huge difference
ucts are required to compose this film. Besides, it is also rose from the presence of ultrasmall Fe3O4 nanoparticles on
accepted that thick SEI film formation upon cycling tends to the MoS2 nanosheets.[33] The morphologies of pristine MoS2
in tr ca in cc
increase an internal resistance of electrode, thus leading to an nanosheets after 1180 cycles are shown in Figure 4b and 4c,
enhanced polarization upon charge/discharge.[54] Therefore, whereas the morphologies of Fe3O4/MoS2 composite are
the amount of electrolyte inside our cells is in excess com- shown in Figure 4e and 4f. Figure 4d schematically represents
pared to normal industrial level. The charge/discharge and the restacking of bare MoS2 anodes. After prolonged charge/
corresponding dQ/dV curves of Fe3O4/MoS2 and H-Fe3O4/ discharge process, the 2D MoS2 nanosheets crumpled and
MoS2 at different stages (12th, 260th, and 510th cycle) of agglomerated into a denser structure, so that large proportion
cycling under 2000 mA g1 were also plotted and shown in of active MoS2 surface was hardly accessible to electrolyte.

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Ultrasmall Fe3O4 Nanoparticle/MoS2 Nanosheet Composites with Superior Performances for Lithium Ion Batteries

results of bare Fe3O4 nanoparticles were

tested and shown in Figure S10. Under a
current density of 500 mA g1, the reversible capacity of bare Fe3O4 nanoparticles
dropped quickly to around 300 mAh g1,
showing a much inferior electrochemical
performances compared with Fe3O4/
MoS2 composites (Figure 3b). Such difference indicates the crucial effect of MoS2
nanosheets in enhancing the electrochemical performances of Fe3O4 nanoparticles.
As indicated in Figure S11, the rate
capability at various current densities for
our Fe3O4/MoS2 composite is superior than
most of the reported results from MoS2-C
systems. It is likely that the initial cycles
with continuous increasing capacity effectively activated the whole composite structure, thereby leading to fast transportation
ability for both Li and electron in this composite structure. Regarding the cycling performance, In addition, Table S1 compares
the applied current density, cycle times,
last charge capacity, and capacity retention in different works. It is interesting to
note that several works have reported the
Figure 4. (a) Cyclic performances of Fe3O4/MoS2, H-Fe3O4/MoS2, and MoS2 from cycle anomalous capacity increment during longnumber 561 to 1180. TEM images of (b, c) MoS2 and (e, f) Fe3O4/MoS2 after 1180 cycles of term cycling, resulting in more than 100%
charge/discharge. Schematic representation of (d) MoS2 nanosheets restacking and (g) effect capacity retention. In our work, ascribing
of Fe3O4 particles in preserving the morphologies of composite electrodes during cycling.
to the crucial role of Fe3O4 nanoparticles
in Fe3O4/MoS2 composite structure along
Therefore, fast capacity fading and low reversible capacities with polymeric film contribution to capacity, we observed the
were observed for the bare MoS2 anodes. Figure 4g graphi- highest charge capacity at a moderate current density of 2000
cally shows the effect of Fe3O4 nanoparticles in preserving mA g1 with superior capacity retention.
Ex-situ XRD, X-ray photoelectron spectroscopy (XPS),
the overall 3D structure. By preventing the restacking of 2D
MoS2 nanosheets, the active surface of MoS2 is kept available and Fourier-transform infrared (FTIR) spectra were perfor electrolyte penetration during the charge/discharge pro- formed on both electrodes containing pristine MoS2 and
cess, which is crucial to the satisfactory cycling performances Fe3O4/MoS2 composite which were cycled more than
of Fe3O4/MoS2 anodes. Similarly, due to the presence of 1000 times. The XRD patterns are shown in Figure 5, while
Fe3O4 nanoparticles, H-Fe3O4/MoS2 also did not show severe XPS and FTIR spectra are shown in Figures S12 and S13.
restacking of the 2D MoS2 nanosheets (Figure S8). The SEM As can be seen from Figure 5, clear peaks related to Li2CO3
images of Fe3O4/MoS2, H-Fe3O4/MoS2, and MoS2 before and (JCPDS: 221141) phase could be identified in Fe3O4/MoS2
after 1180-cycle electrochemical tests are shown in Figure electrode, while Li2CO3 is not apparent in case of MoS2.
S9. For the morphologies of Fe3O4/MoS2 (Figure S9b) and Therefore, more stable SEI layer is reasonably formed in
H-Fe3O4/MoS2 (Figure S9d), with the incorporation of Fe3O4 Fe3O4/MoS2 electrode. In fact, this conclusion is also supnanoparticles, the anodes became much more expanded and ported by XPS result. In addition, XPS results also suggest
porous after cycling tests, which is beneficial to the electro- bigger amount of polymer components contributing to stable
lyte penetration.[55] Such phenomenon can be ascribed to the SEI layers formation during cycling in Fe3O4/MoS2 electrode.
presence of Fe3O4 content, because morphological change Furthermore, there are several interesting observations to
was absent in the pristine MoS2 anode (Figure S9f). Besides assist understanding why Fe3O4/MoS2 composite owns better
as the spacers that prevent the restacking of MoS2 nanosheets, electrochemical performance than pristine MoS2. Firstly,
Fe3O4 content is also a primary capacity contributor. In such sulfur phase is easy to be identified in Fe3O4/MoS2 electrode
consideration, MoS2 nanosheets also played crucial roles in as it is absence in MoS2 electrode according to Figure 5. It
enhancing the electrochemical performance of Fe3O4 nano- is well known that the original MoS2 sheets will be electroparticles: the large volume changes of Fe3O4 during charge/ chemically transformed to a mixture of Mo and S after a first
discharge can be accommodated by the 2D MoS2 nanosheets; lithiation/delithiation. [56] Consequently, the elemental S will
and the 2D structure of MoS2 nanosheets provided substrates be responsible for further intercalation of Li to form Li2S
for Fe3O4 nanoparticles to be attached on, thus preventing and thus reversible capacity. It seems that our ex-situ XRD
their agglomeration and fast fading in capacity. The cycling result in case of Fe3O4/MoS2 composite agrees well with
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XPS, and FTIR on cycled electrodes. The reported novel

combinations of MoS2 nanosheets and ultrasmall Fe3O4 nanoparticles should inspire the design and fabrication of next
generation of LIB anodes based on 2D MoS2 nanosheets.

4. Experimental Section

Figure 5. Ex situ XRD patterns of MoS2 and Fe3O4/MoS2 electrodes

which were cycled 1180 times.

elemental S formation. And XPS results strongly support this

observation. Secondly, a Li2MoO4 phase (JCPDS: 12763) can
be found only in MoS2 electrode (Figure 5). The formation of
Li-containing compound in neat MoS2 electrode may further
explain the trapping mechanism of Li during initial cycles,
leading to drastic loss of reversible Li to host structure. In
fact, two Mo6+ peaks of 3d5/2 (232.5 eV) and 3d3/2 (235.6 eV)
orbital[57] are observed in Mo 3d spectra, which also supports the formation of Li2MoO4 phase (Figure S12). Thirdly,
according to Fe 2p spectra (Figure S12), Fe2+ (710.5 eV)
and Fe3+ (712.5 eV) [58] are still the dominant elements at a
fully charged state of Fe3O4/MoS2 electrode even after 1000
cycles. It implies a reversible process of lithiation/delithiation
of Fe3O4 particles, which is a consequence of their ultrasmall
sizes. Such observation is also supported by the charge/discharge profiles and dQ/dV curves shown in Figure 3e.

3. Conclusion
In summary, MoS2 nanosheets with an initial reversible
capacity of 1122 mAh g1 were synthesized through a facile
hydrothermal reaction. Two composites, namely Fe3O4/MoS2
and H-Fe3O4/MoS2, were fabricated by decorating ultrasmall Fe3O4 nanoparticles on the surface of MoS2 nanosheets
to prevent the restacking of 2D MoS2 nanosheets and thus
improving the cyclic performance of the composites. The
2D MoS2 nanosheets effectively accommodated the volume
change of Fe3O4 during charge/discharge process. Besides,
the ultrasmall Fe3O4 nanoparticale were beneficial to the
high rate performance of the composites. Increasing capacities during cycling observed from these two composites can
be attributed to increasing activated sites of MoS2 and Fe3O4
inside electrode as well as the reversible formation of polymeric gel-like film resulting from the sustained surface area
of composite structure. This has been confirmed by various
characterization techniques, including TEM, SEM, XRD,

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Synthesis of MoS2 Nanosheets: sodium molybdate (Na2MoO4,

0.3 g) and thioacetamide C2H5NS, 0.6 g) were dissolved in DI
water (30 mL), transferred into a Telfon-lined stainless steel autoclave (125 mL), and hydrothermally treated in an air-flow electric
oven at 220 C for 24 hours. The black precipitates were collected
by centrifuge, washed with DI water, and freeze dried for subsequent experiments.
Synthesis of Fe3O4/MoS2 Composite: the decoration of ultrasmall Fe3O4 nanoparticles followed previously reported method. In
a typical synthesis, appropriate amount of MoS2 nanosheets, iron
chloride hexahydrate (FeCl36H2O, 0.7095 g), sodium bicarbonate
(NaHCO3, 0.6616 g), and L-ascorbic acid (0.088 g) were added
accordingly into DI water (30 mL). The mixture was transferred to a
Telfon-lined stainless steel autoclave (125 mL), sealed and heated
at150 C for 6 hours. The obtained black precipitates were collected using centrifuge, washed several times with DI water, and
freeze dried in vacuum environment.
Characterization: Scanning electron microscopy (SEM) images
were recorded on a Zeiss Supra 40 FESEM. Transmission electron
microscopy (TEM) images, high-resolution transmission electron
microscopy (HRTEM) images, selected area electron diffraction
(SAED) patterns, and energy x-ray dispersive (EDX) mapping were
collected on a JEOL 100CX instrument, using a 300 kV accelerating voltage. Powder X-ray diffraction (XRD) pattern was obtained
on a powder diffractometer (Bruker D8 Advanced Diffractometer
System) with Cu K (1.5418 A) source. X-ray photoelectron spectroscopy (XPS) data were obtained by an Axis Ultra DLD X-ray
photoelectron spectrometer equipped with an Al Ka X-ray source
(1486.6 eV). Fourier-transform infrared (FTIR) spectra of purified
and dried nanoparticles were recorded using an attenuated total
reflection FTIR (Varian 3100 FT-IR).
Electrochemical Measurements: The electrochemical performance for all samples were tested using CR2016 coin-type cells.
The working electrodes were firstly prepared by mixing 70 wt%
active materials, 15 wt% carbon black (Super P), and 15 wt% Polyvinylidene Fluoride (PVDF) in n-methyl-2-pyrrolidone (NMP) solution,
followed by drying it before usage. The typical loading density for
as-prepared electrodes is approximately 1 mgcm2. All cells were
carefully assembly using as-prepared electrodes, pure Li foil, separators (Celgard 2500), and electrolyte (1 M LiPF6 in EC : DEC : DMC
= 1 : 1 : 1 organic solutions) in an argon-filled glovebox. A same
voltage window of 0.01 3 V vs. Li0/Li+ was applied for all tests.

Acknowledgements
Acknowledgements, general annotations, funding. Other references to the title/authors can also appear here, such as AuthorOne and Author-Two contributed equally to this work.

2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

small 2014, 10, No. 8, 15361543

Ultrasmall Fe3O4 Nanoparticle/MoS2 Nanosheet Composites with Superior Performances for Lithium Ion Batteries

[1]
[2]
[3]
[4]
[5]

[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]

J. B. Goodenough, Y. Kim, Chem. Mater. 2009, 22, 587.

M. Armand, J. M. Tarascon, Nature 2008, 451, 652.
J. M. Tarascon, M. Armand, Nature 2001, 414, 359.
J. Cabana, L. Monconduit, D. Larcher, M. R. Palacn, Adv. Mater.
2010, 22, E170.
B. P. N. Nguyen, N. A. Kumar, J. Gaubicher, F. Duclairoir,
T. Brousse, O. Crosnier, L. Dubois, G. Bidan, D. Guyomard,
B. Lestriez, Adv. Energy Mater. 2013, 3, 1351.
K. H. Seng, M.-h. Park, Z. P. Guo, H. K. Liu, J. Cho, Nano Lett.
2013, 13, 1230.
C. He, S. Wu, N. Zhao, C. Shi, E. Liu, J. Li, ACS Nano 2013, 7,
4459.
N. Li, G. Zhou, F. Li, L. Wen, H.-M. Cheng, Adv. Funct. Mater. 2013,
10.1002/adfm.201300495.
J. Liu, D. Xue, Adv. Mater. 2008, 20, 2622.
R. Liu, J. Duay, S. B. Lee, Chem Commun (Camb) 2011, 47, 1384.
X. W. Lou, L. A. Archer, Z. Yang, Adv. Mater. 2008, 20, 3987.
P. L. Taberna, S. Mitra, P. Poizot, P. Simon, J. M. Tarascon, Nat.
Mater. 2006, 5, 567.
Y. Chen, B. Song, L. Lu, J. Xue, Nanoscale 2013, 5, 6797.
Y. Chen, B. Song, M. Li, L. Lu, J. Xue, Adv. Funct. Mater. 2013,
10.1002/adfm.201300872.
Y. Wang, H. Li, P. He, E. Hosono, H. Zhou, Nanoscale 2010, 2,
1294.
P. G. Bruce, B. Scrosati, J.-M. Tarascon, Angew. Chem. Int. Ed.
2008, 47, 2930.
Y.-G. Guo, J.-S. Hu, L.-J. Wan, Adv. Mater. 2008, 20, 2878.
L. Yang, S. Wang, J. Mao, J. Deng, Q. Gao, Y. Tang, O. G. Schmidt,
Adv. Mater. 2013, 25, 1180.
H. Hwang, H. Kim, J. Cho, Nano Lett. 2011, 11, 4826.
G. Huang, T. Chen, W. Chen, Z. Wang, K. Chang, L. Ma, F. Huang,
D. Chen, J. Y. Lee, Small 2013, 10.1002/smll.201300415.
Y. Yao, L. Tolentino, Z. Yang, X. Song, W. Zhang, Y. Chen,
C.-P. Wong, Adv. Funct. Mater. 2013, 23, 3577.
K. Chang, D. Geng, X. Li, J. Yang, Y. Tang, M. Cai, R. Li, X. Sun, Adv.
Energy Mater. 2013, 3, 839.
Y. Gong, S. Yang, L. Zhan, L. Ma, R. Vajtai, P. M. Ajayan, Adv.
Funct. Mater. 2013, 10.1002/adfm.201300844.
J. Xiao, X. Wang, X.-Q. Yang, S. Xun, G. Liu, P. K. Koech, J. Liu,
J. P. Lemmon, Adv. Funct. Mater. 2011, 21, 2840.
H. Li, X. Qi, J. Wu, Z. Zeng, J. Wei, H. Zhang, ACS Nano 2013, 7,
2842.
Y. Liang, R. Feng, S. Yang, H. Ma, J. Liang, J. Chen, Adv. Mater.
2011, 23, 640.
P. Miro, M. Ghorbani-Asl, T. Heine, Adv. Mater. 2013, 25, 5473.
X. Zhao, C. M. Hayner, M. C. Kung, H. H. Kung, ACS Nano 2011, 5,
8739.
X.-C. Chen, W. Wei, W. Lv, F.-Y. Su, Y.-B. He, B. Li, F. Kang,
Q.-H. Yang, Chem. Commun. 2012, 48, 5904.
R. Mukherjee, A. V. Thomas, A. Krishnamurthy, N. Koratkar, ACS
Nano 2012, 6, 7867.
Y. Chen, B. Song, X. Tang, L. Lu, J. Xue, J. Mater. Chem. 2012, 22,
17656.
K. Chang, W. Chen, Chem. Commun. 2011, 47, 4252.

small 2014, 10, No. 8, 15361543

[33] Y. Si, E. T. Samulski, Chem. Mater. 2008, 20, 6792.

[34] G. X. Wang, B. Wang, X. L. Wang, J. Park, S. X. Dou, H. Ahn, K. Kim,
J. Mater. Chem. 2009, 19, 8378.
[35] J. Yao, X. P. Shen, B. Wang, H. K. Liu, G. X. Wang, Electrochem.
Commun. 2009, 11, 1849.
[36] V. Nicolosi, M. Chhowalla, M. G. Kanatzidis, M. S. Strano,
J. N. Coleman, Science 2013, 340, 1420.
[37] H. S. S. Ramakrishna Matte, A. Gomathi, A. K. Manna, D. J. Late,
R. Datta, S. K. Pati, C. N. R. Rao, Angew. Chem. Int. Ed. 2010, 49,
4059.
[38] L. Xiao, J. Li, D. F. Brougham, E. K. Fox, N. Feliu, A. Bushmelev,
A. Schmidt, N. Mertens, F. Kiessling, M. Valldor, B. Fadeel,
S. Mathur, ACS Nano 2011, 5, 6315.
[39] S. Ding, D. Zhang, J. S. Chen, X. W. Lou, Nanoscale 2012, 4,
95.
[40] K. Chang, W. Chen, J. Mater. Chem. 2011, 21, 17175.
[41] Z. Wang, T. Chen, W. Chen, K. Chang, L. Ma, G. Huang,
D. Chen, J. Y. Lee, J. Mater. Chem. A 2013, 1, 2202.
[42] K. Bindumadhavan, S. K. Srivastava, S. Mahanty, Chem. Commun.
2013, 49, 1823.
[43] X. P. Fang, X. Q. Yu, S. F. Liao, Y. F. Shi, Y. S. Hu, Z. X. Wang,
G. D. Stucky, L. Q. Chen, Micropor. Mesopor. Mat. 2012, 151,
418.
[44] J. Liu, Y. Li, H. Fan, Z. Zhu, J. Jiang, R. Ding, Y. Hu, X. Huang, Chem.
Mater. 2010, 22, 212.
[45] S. Grugeon, S. Laruelle, L. Dupont, J. M. Tarascon, Solid State Sci.
2003, 5, 895.
[46] L. W. Su, Z. Zhou, P. W. Shen, Electrochim. Acta 2013, 87, 180.
[47] X. Huang, X. Zhou, K. Qian, D. Zhao, Z. Liu, C. Yu, J. Alloys Compd.
2012, 514, 76.
[48] G. Zhou, D.-W. Wang, F. Li, L. Zhang, N. Li, Z.-S. Wu, L. Wen,
G. Q. Lu, H.-M. Cheng, Chem. Mater. 2010, 22, 5306.
[49] Z.-S. Wu, W. Ren, L. Wen, L. Gao, J. Zhao, Z. Chen, G. Zhou, F. Li,
H.-M. Cheng, ACS Nano 2010, 4, 3187.
[50] Y. F. Li, D. H. Wu, Z. Zhou, C. R. Cabrera, Z. F. Chen, J. Phys. Chem.
Lett. 2012, 3, 2221.
[51] Y. F. Li, Z. Zhou, S. B. Zhang, Z. F. Chen, J. Am. Chem. Soc. 2008,
130, 16739.
[52] S. Yuan, Z. Zhou, G. Li, Crystengcomm 2011, 13, 4709.
[53] S. M. Yuan, J. X. Li, L. T. Yang, L. W. Su, L. Liu, Z. Zhou, ACS Appl.
Mater. Interfaces 2011, 3, 705.
[54] D. Aurbach, J. Power Sources 2000, 89, 206.
[55] W. Ai, L. Xie, Z. Du, Z. Zeng, J. Liu, H. Zhang, Y. Huang, W. Huang,
T. Yu, Sci. Rep. 2013, 3, 2341.
[56] J. Z. Wang, L. Lu, M. Lotya, J. N. Coleman, S. L. Chou, H. K. Liu,
A. I. Minett, J. Chen, Adv. Energy Mater. 2013, 3, 798.
[57] T. Weber, J. C. Muijsers, H. van Wolput, C. P. J. Verhagen, J. W. Niemantsverdriet, J. Phys. Chem. 1996, 100,
14144.
[58] J. S. Zhou, H. H. Song, L. L. Ma, X. H. Chen, RSC Adv. 2011, 1,
782.
Received: July 4, 2013
Revised: October 30, 2013
Published online: December 21, 2013

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