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Nanostructures
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
DOI: 10.1002/smll.201302879
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Ultrasmall Fe3O4 Nanoparticle/MoS2 Nanosheet Composites with Superior Performances for Lithium Ion Batteries
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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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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Ultrasmall Fe3O4 Nanoparticle/MoS2 Nanosheet Composites with Superior Performances for Lithium Ion Batteries
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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4. Experimental Section
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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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.
Ultrasmall Fe3O4 Nanoparticle/MoS2 Nanosheet Composites with Superior Performances for Lithium Ion Batteries
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