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Dual coreshell structured sulfur cathode composite


synthesized by a one-pot route for lithium sulfur
Cite this: DOI: 10.1039/c2ta00915c
batteries
Published on 21 November 2012 on http://pubs.rsc.org | doi:10.1039/C2TA00915C

Chao Wang,ab Wang Wan,a Ji-Tao Chen,*a Heng-Hui Zhou,a Xin-Xiang Zhang,a
Li-Xia Yuanb and Yun-Hui Huang*b

Lithiumsulfur batteries are promising electrochemical devices for future energy conversion and storage.
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Its theoretical capacity is 1675 mA h g1, much higher than that of conventional lithium-ion batteries.
However, it suers from rapid capacity decay and low energy eciency. In this work, we introduce a
novel dual coreshell structured sulfur composite with multi-walled carbon nanotubes (MWCNTs) and
polypyrrole (PPy), MWCNTs@S@PPy, as a cathode material for LiS batteries. The composite is
synthesized via a facile one-pot method. In the structure, MWCNTs and PPy work as a combined
conductive framework to provide access to Li+ ingress and egress for reaction with sulfur, and to inhibit
the diusion of polysulde out of the cathode, and hence reduce the capacity decay. Meanwhile, LiNO3
additive is added into the electrolyte to improve the coulombic eciency. The as-designed
Received 31st October 2012
Accepted 20th November 2012
MWCNTs@S@PPy composite shows excellent rate capability and cyclability. The initial discharge specic
capacity is as high as 1517 mA h g1, and remains at 917 mA h g1 after 60 cycles at a current density
DOI: 10.1039/c2ta00915c
of 200 mA g1. Even at a high current density of 1500 mA g1, the composite still shows a good cycle
www.rsc.org/MaterialsA performance with a capacity of 560 mA h g1 after 200 cycles.

Introduction capacity is much higher than those of conventional cathode


materials in LIBs, ca. 100250 mA h g1. Moreover, sulfur
Rechargeable lithium-ion batteries (LIBs) have attracted great exhibits many other impressive characteristics such as abun-
attention over the past two decades since they have high energy dant resources, environmental friendliness, and low cost.810
density for commercial applications such as portable devices.1,2 Therefore, lithiumsulfur batteries have potential for next-
However, traditional intercalation cathode materials used in generation energy storage applications such as in electric
LIBs like LiCoO2 and LiMn2O4 have a limited gravimetric energy vehicles and smart grids.
density of less than 200 W h kg1, which is not sucient to meet The poor electrochemical performance of LiS batteries,
the increasing demand for high energy/power density for elec- however, limits their scale-up application. This could be due to
tric vehicles. Therefore, exploring new electrode materials or several reasons. One is the low electrical conductivity of
new battery systems with higher capacity is of great impor- elemental sulfur (5  1030 S cm1 at room temperature),
tance.37 Lithiumsulfur and lithiumair batteries have received which makes the direct utilization of sulfur impossible. This
more and more attention as new electrochemical devices in problem can be resolved by introducing conductive additives,
recent years. such as carbon nanotubes, graphene, conductive polymers
Elemental sulfur is a very promising cathode material for etc.,1117 but further improvement is still desirable. Another
rechargeable lithium batteries due to its high theoretical issue associated with the LiS system is the high solubility of the
capacity of 1675 mA h g1 and energy density of 2600 W h kg1 lithium polysulde products (Li2Sx, x > 2) in organic electrolyte.
on the basis of the formation of lithium sulphide (Li2S). This This not only leads to the loss of active materials from the
cathode, but also causes serious redox shuttle reactions
a
College of Chemistry and Molecular Engineering, Peking University, Beijing, P. R.
between polysulde (PS) anions in the electrolyte and the Li
China. E-mail: chenjitao@pku.edu.cn; Fax: +86-10-62754680; Tel: +86-10-62754680 metal anode, resulting in low coulombic eciency, high self-
b
State Key Laboratory of Material Processing and Die & Mould Technology, School of discharge rate, and short cycle life.3,7,18,19 In order to reduce the
Materials Science and Engineering, Huazhong University of Science and Technology, redox shuttle eect of PS, most research has focused on
Wuhan, P. R. China. E-mail: huangyh@mail.hust.edu.cn; Fax: +86-27-87558241; reducing the PS diusion away from the cathode by impreg-
Tel: +86-27-87558241
nating sulfur into porous carbon, because its high surface area
Electronic supplementary information (ESI) available. See DOI:
10.1039/c2ta00915c
can physically adsorb the dissolved PS. But the loading of sulfur

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in porous carbon is limited by the carbon type and pore size, cathode and alleviate the volumetric expansion of S. PPy itself is
and therefore needs further investigation.4,9,2025 electrochemically active for lithium intercalation/dein-
Unfortunately, these approaches are not ecient enough to tercalation.38 Here, it should be pointed out that PPy has been
absorb the polysulde intermediates, and oen result in low used in LiS batteries for a long time and behaves well because
sulfur content in the composites. Consequently, the negative PS it is stable and moderately rigid in the electrochemical envi-
anions will be electrically dragged toward the Li anode by the ronment.12,14,35,4043 This dual coreshell structure can provide
internal electrical eld force during the discharge process.26 structural stability for Li-ion insertion and extraction, and
Since the dissolution of lithium PS into the liquid organic hence is expected to exhibit a good chargedischarge perfor-
electrolyte is inevitable, some researchers tried to apply suitable mance during cycling.
electrolyte additives or solid state electrolytes. It has been
reported that the addition of LiNO3 to organic electrolytes can Experimental section
signicantly increase the cell's coulombic eciency, because it
Materials synthesis
Published on 21 November 2012 on http://pubs.rsc.org | doi:10.1039/C2TA00915C

can facilitate the formation of a highly protective passive lm on


the lithium anode. The passive lm can not only protect the Sodium dodecyl sulfate (SDS, CP), ferric chloride (FeCl3$6H2O,
lithium metal from chemical reaction with the PS anions, but AR) and hydrochloric acid (HCl) were purchased from Sino-
can also prevent PS anions from electrochemical reduction on pharm Chemical Reagent and used as received. The monomer
the Li anode, thus reducing the shuttle eect.2731 When a pyrrole (CP, Sinopharm Chemical Reagent Co., Ltd) was
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polyethylene oxide layer is coated on the surface of mesoporous distilled before use. Acid-treated MWCNTs (2030 nm in
carbon to trap PS, the S electrode may exhibit improved capacity diameter) were purchased from Beijing Nachen S&T Ltd.
and unaected cycling behaviour.9 A monolayer of polymer is Sodium thiosulfate (Na2S2O3$5H2O, AR) and sodium p-tolue-
not thick enough to trap most PS, and its insulating nature may nesulfonate (SDBNa, AR) were used without further
exert an adverse eect on the conductivity. Therefore, the purication.
application of conductive polymers should be more eective. The dual coreshell structured MWCNTs@S@PPy composite
Regrettably, a uniform coating of conductive polymer has was prepared by a simple one-pot solution route. The reaction
seldom been achieved.29,3235 formula for the sulfur preparation can be expressed as below:
In this work, we have developed a dual coreshell structured
sulfur composite cathode material for LiS batteries by a facile Na2S2O3 + 2HCl / 2NaCl + SY + H2O + SO2[
one-pot method. MWCNTs and PPy are introduced into
the sulfur composite to improve the conductivity, inhibit the
PPy was synthesized via an in situ chemical oxidative poly-
diusion of polysulde out of the cathode and relieve the
merization of pyrrole on MWCNTs@S.
volumetric expansion of sulfur during chargedischarge
In a typical procedure, 4 g SDS was dissolved in 400 ml
cycling.36,37 As illustrated in Fig. 1, sulfur particles are rst
distilled water, and then 1 g MWCNTs was dispersed into the
deposited on the surface of MWCNTs, and then PPy is designed
solution and sonicated for 1 h. 32.6 g Na2S2O3 was added to the
to wrap around the S particles as an outer layer. Thus the dual
mixture and stirred for 10 min. Aer that, 52 g HCl was added
coreshell structure is formed. In such a structure, the inner
dropwise at a rate of 10 ml min1 to the solution and stirred for
MWCNTs are expected to act as a conductive network for S and
1 h. Subsequently, 3.763 g BDSNa was added to the mixture and
to absorb PS to some extent, while the outmost elastic PPy layer
stirred for 10 min at 0  C, followed by the addition of 0.52 g
is expected to further enhance the conductivity and to stabilize
pyrrole. Aer the pyrrole was homogeneously dispersed, a
the dual structure of the composite during cycling.38,39 More-
proper amount of FeCl3 (three times the amount of pyrrole) was
over, the PPy layer can restrain the PS from moving out of the
added and stirred overnight at 0  C. Aer vacuum ltration, the
precipitated MWCNTs@S@PPy material was washed repeatedly
with distilled water, and the resulting composite was nally
obtained by drying at 60  C for 12 h.
A reference S@MWCNTs sample without PPy was also
synthesized by the same precipitation method.

Materials characterization
The phase of the MWCNTs@S@PPy composite was checked by
X-ray diraction (XRD) on a Rigaku D/MAX-2000 diractometer
(Japan) using Cu Ka radiation (l 0.15406 nm) from 10 to 70 .
The morphology and microstructure were observed by eld-
emission scanning electron microscopy (SEM, S4800, Hitachi)
and transmission electron microscopy (TEM, Tecnai F20). The
elemental composition and mapping were conducted via local
Fig. 1 Schematic illustration for the synthesis and discharge process of the dual chemical analysis performed using STEM-EDX with a HAADF
coreshell structured MWCNTs@S@PPy composite. detector on TEM (JEOL, JEM-2100F) operated at 200 kV. The

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component ratio of the composite was determined by ther-


mogravimetric analysis (Mettler Toledo) in the temperature
range of 25400  C at a heating rate of 10  C min1 under a N2
atmosphere. The chemical transformation of the composite
during the preparation process was investigated by Fourier
transform infrared spectroscopy (FTIR, Bruker VECTOR22) with
KBr pellets. The N content in the composite was determined by
chemical elemental analysis (CHNS, Vario EL, Elementar).

Electrochemical measurements
The electrochemical properties of the composite were evaluated
Published on 21 November 2012 on http://pubs.rsc.org | doi:10.1039/C2TA00915C

using coin cells with lithium metal as the anode and Celgard
2400 lm as a separator. The cathode was prepared by mixing
the active material, acetylene black and polyvinylidene uoride
(PVDF) binder in a weight ratio of 70 : 20 : 10 in N-methyl-
pyrrolidone to form a homogeneous slurry. The slurry was
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uniformly spread onto pure aluminium foil using a doctor blade


cast and dried for 12 h in a vacuum at 60  C. The electrode was
punched into circular disks with a diameter of 12 mm and an
active material loading of about 2 mg cm2. CR2032 coin cells
were assembled in an argon-lled glove box (Master 100 Lab,
Braun, Germany) using an electrolyte of 0.6 mol l1 LiTFSI/DOL
+ DME (1 : 1 by volume) with 0.4 mol l1 LiNO3 as an additive.
Cells were galvanostatically charged and discharged between
1.7 and 2.8 V versus Li+/Li on a Land CT2001A battery tester. The
specic capacities and current rates were calculated according
to the mass of S in the cathode. Cyclic voltammetry was carried
out on a CHI660D electrochemical workstation (CH Instru-
ments, China) at a scan rate of 0.1 mV s1 ranging from 1.5 to
3 V versus Li+/Li. Electrochemical impedance spectroscopy (EIS)
was performed on the coin cell with an electrochemical work-
Fig. 2 (a) FTIR spectra of PPy and the MWCNTs@S@PPy composite; (b) XRD
station (Autolab PG302N, Netherlands) with an applied sinu- patterns of S, PPy and MWCNTs@S@PPy; (c) TG curves for PPy and
soidal excitation voltage of 5 mV in the frequency range from MWCNTs@S@PPy from room temperature to 400  C at a heating rate of 10  C
100 kHz to 0.01 Hz. min1 under a N2 atmosphere.

Results and discussion


TG measurement and chemical elemental analysis were used
FTIR spectroscopy was used to determine the presence of PPy in to determine the S content in the composite. The TG curves
the composite. Fig. 2a shows the FTIR spectra of PPy powder obtained in N2 are displayed in Fig. 2c. The pure S shows a
and the MWCNTs@S@PPy composite. It can be seen that both weight loss from 170  C, which is complete at 300  C. PPy
of the two samples display almost identical spectra, indicating undergoes continuous weight loss up to 400  C. The
that the composite is fully covered by PPy. The spectrum of the MWCNTs@S composite shows a similar thermal behaviour to
PPy sample agrees well with that reported.43 The bands at 1545 sulfur, since MWCNTs are quite stable in N2. Incorporation of
and 1458 cm1 correspond to the fundamental vibration of the MWCNTs slightly accelerates the evaporation of sulfur due to
pyrrole ring; the band at 1291 cm1 can be ascribed to the ] the enhanced heat transfer rate. The sulfur content of
CH in-plane vibration of the PPy chain. MWCNTs@S is then calculated to be about 81 wt%. Since PPy is
Fig. 2b shows the XRD patterns of the sublimed sulfur, PPy continuously decomposed during the heating process, it is
and MWCNTs@S@PPy. For S, the peaks centred at 2q 23.4 dicult to directly calculate the S content in MWCNTs@S@PPy
and 28.0 match well with the (222) and (040) reections of the by TG analysis alone. Determined by elemental analysis, the N
Fddd orthorhombic phase (JCPSD no. 08-0247).44 The sharp and content in this composite is 1.78 wt%, and therefore the PPy
strong diractions indicate a well-dened crystal structure. content is 8.28 wt%. Combined with the TG analysis, the
However, PPy only has a broad, weak diraction centred at S content in the MWCNTs@S@PPy composite is 68.3 wt%,
2q 23 , suggesting a poorly crystalline state. For which is quite reasonable as compared with MWCNTs@S.
MWCNTs@S@PPy, the diractions are almost same as those of SEM and TEM were used to investigate the morphology and
S but only their intensities are lower, demonstrating that PPy microstructure of the MWCNTs@S@PPy composite. The
is incorporated to dilute the S content in the composite. images are shown in Fig. 3. It can be seen that the composite

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appears to have a tubular shape, and no massive or agglomer-


ated S particles can be observed. From the TEM images (Fig. 3c
and d), we can see that S and PPy are uniformly coated onto the
surface of the MWCNTs. However, it is dicult to distinguish S
and PPy from each other. The coated MWCNTs show a diameter
of about 25 nm, and a coating layer with a thickness of 1015
nm. It is clear that the composite has a coreshell structure.
In order to identify the microstructure of the
MWCNTs@S@PPy composite, high-angle annular dark-eld
scanning transmission electron microscopy (HAADF-STEM)
and the corresponding EDS mapping were used, as shown in
Fig. 4. The HAADF-STEM image (Fig. 4a) further illustrates the
Published on 21 November 2012 on http://pubs.rsc.org | doi:10.1039/C2TA00915C

coreshell structure of the composite, which is consistent with


our design. The elemental maps of C, S and N clearly demon-
strate that they are homogeneously distributed in the frame-
work of the MWCNTs.
For comparison, the single coreshell structured
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MWCNTs@S containing 81 wt% S was investigated. As depicted


Fig. 4 (a) HAADF-STEM image and corresponding EDS mapping for the distri-
in Fig. S1, MWCNTs@S shows a coreshell structure, but
bution in the MWCNTs@S@PPy composite: (b) C, (c) S, and (d) N.
the coating layer is not as homogeneous as that of
MWCNTs@S@PPy. The discrepancy in morphology between
MWCNTs@S@PPy and MWCNTs@S indicates that PPy plays an
anodic peak at about 2.52.6 V is observed, which can be
important role in achieving a uniform microstructure during
attributed to the oxidation of Li2S2 and Li2S to Li2S8.11,20,34,4852
the one-pot synthesis process. The use of a large amount of
Higher oxidation potential in the CV is due to the polarization
surfactant will reduce the S particles to a nanoscale size. In
caused by the phase transition from insoluble Li2S/Li2S2 to
addition, the surfactant can mediate the polymerization process
soluble low-order PS, which corresponds to the voltage peak
in the presence of sodium p-toluenesulfonate, which helps to
observed at the beginning of the charge in Fig. 6. The variation
obtain high-quality PPy and ne S spheres.4547
of current and peak potential for the oxidation process in the
Fig. 5 shows the CV curves of the MWCNTs@S@PPy elec-
following scans implies a possible structural rearrangement,
trode during the rst 4 cycles. Two cathodic peaks are observed
which may result in capacity fading over the cycles. It is
due to the multiple reduction of sulfur in the presence of Li+
common for the capacity of LiS batteries to fade greatly in the
ions. The peak at 2.2 V is related to the reduction of S8 to long
rst cycle. However, the reduction peak increases due to the
chain lithium PS (Li2Sx, 4 < x < 8). The following peak at about
maximum accessible sulfur utilization at the applied scan rate
1.9 V is associated with the further reduction of the long chain
of 0.5 mV s1. In the successive cycles, the reduction and
PS to Li2S2 or Li2S. In the subsequent anodic scan, only one
oxidation peaks change little; the system tends to reach a
balanced state and hence the capacity fading is slow.
The chargedischarge performance was tested in a coin cell
using a constant-current chargedischarge protocol, and the
capacity was calculated on the basis of sulfur mass. Typically,
the sulfur loading was about 1 mg cm2. Fig. 6 shows typical

Fig. 3 Microstructure of MWCNTs@S@PPy: (a and b) SEM images, and (c and d) Fig. 5 Cyclic voltammograms of the MWCNTs@S@PPy composite electrode
TEM images. between 1.5 and 3 V vs. Li+/Li, recorded at a potential scanning rate of 0.5 mV s1.

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Published on 21 November 2012 on http://pubs.rsc.org | doi:10.1039/C2TA00915C

Fig. 8 Comparison of the rate capability of MWCNTs@S@PPy and MWCNTs@S


rd th rd rd at current densities from 200 to 2000 mA g1.
Fig. 6 Typical charge and discharge curves at the 3 , 13 , 23 , and 33
cycle and the 1st discharge curve for MWCNTs@S@PPy at a current density
of 200 mA g1.
the theoretical specic capacity. The uncoated sample delivers
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an initial capacity of 1131 mA h g1, much lower than that of


charge and discharge voltage proles for the MWCNTs@S@PPy the coated sample. Aer 60 cycles, the capacity of the uncoated
composite. Two discharge voltage plateaus appear at around composite decreases to 635 mA h g1, whereas the PPy-coated
2.35 and 2.1 V, which can be assigned to two-step reactions composite still retains a capacity of 917 mA h g1. This indi-
during the discharge process. The voltage plateaus do not drop cates that the PPy coating greatly improves the cycling
during cycling, indicative of good retention. On the charge performance of the MWCNTs@S composite. In Fig. 7e, the
curve, the voltage plateau at around 2.3 V corresponds to the MWCNTs@S@PPy electrode exhibits a coulombic eciency of
oxidation process, which shows a small change during cycling. nearly 100% during cycling, indicating that the sulfur shuttle
The voltage peak (see the red arrow in Fig. 6) can be attributed mechanism is diminished to quite a low level. It is believed
to the oxidation of Li2S and Li2S2 to low-order PS, which can be that the uniform coating of the conductive polymer and the
expressed by the following two equations: use of LiNO3 can restrain the dissolution of PS into the elec-
trolyte. Notably, the MWCNTs@S@PPy electrode shows
Li2Sx + Li2S / Li2Sxy + Li2S1+y (1) excellent cycling performance even at high current density. For
example, aer 60 cycles, the capacities are still 840 and 771 mA
Li2Sx + Li2S2 / Li2Sxy + Li2S2+y (2) h g1 at 300 and 500 mA g1, respectively, indicating 93% and
91.8% capacity retention. It can be seen in Fig. 7b and c that
where xy and 1+y are larger than 2. The two equations are the discharge capacity increases gradually with cycle number
known to contribute to the reversibility of LiS batteries.26 during the initial several cycles. This can be explained by the
Fig. 7 presents the cycling performance of the gradual penetration process of the active composite material
MWCNTs@S@PPy composite at dierent current densities of in the cathode into the electrolyte. The reversibility demon-
200, 300 and 500 mA g1. At 200 mA g1, the initial specic strates that the dual coreshell structure composite can
discharge capacity is as high as 1517 mA h g1, which is 88% of provide an eective electron conducting network and an
eective coating layer to restrain PS, indicating that the novel
dual coreshell structure can form a stable system for the
sulfur electrode.
The rate capability of the MWCNTs@S@PPy composite at
various current densities from 200 to 2000 mA g1 is shown in
Fig. 8. The composite exhibits an excellent rate performance,
with specic capacities of 1210, 1060, 860, 735 and 665 mA h
g1 at 200, 500, 1000, 1500 and 2000 mA g1, respectively.
Compared with the uncoated composite, the dual coreshell
structured composite shows a much higher capacity. We can
see that the capacity of the MWCNTs@S is less than 200 mA h
g1 if the current density is higher than 1000 mA g1. More-
over, the superior performance of MWCNTs@S@PPy is
also evidenced by the easy recovery of the capacity aer
cycling. As seen in Fig. 9, a capacity of up to 1168 mA h g1 is
Fig. 7 Cycling performance of the MWCNTs@S@PPy composite at various
recovered if the current density is decreased back to 200 mA
current densities of 200, 300 and 500 mA g1. The typical coulombic eciency at g1 aer cycling at various current densities from 200 to
200 mA g1 is also displayed. 2000 mA g1.

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We further studied the cycling performance of the


MWCNTs@S@PPy composite at high current densities of 1000,
1500 and 2000 mA g1. The battery was charged and discharged
for 200 cycles. As shown in Fig. 9, at 1000, 1500 and 2000 mA
g1, the corresponding specic capacities are 970, 867 and
810 mA h g1 for the rst cycle, and decrease to 603, 560 and
465 mA h g1 aer 200 cycles. Their capacity retentions are 62%,
65% and 58%, respectively. The coulombic eciency remains
near 100%. The remarkable capacity, columbic eciency and
cyclability at high current density indicate that the dual core
shell structure is quite stable. As a comparison, MWCNTs@S
exhibits a lower capacity and poorer coulombic eciency
Published on 21 November 2012 on http://pubs.rsc.org | doi:10.1039/C2TA00915C

(Fig. S2). In addition, the performance of the present


MWCNTs@S@PPy composite is higher than those previously Fig. 10 Electrochemical impedance spectroscopy for MWCNTs@S and
reported for similar sulfur composites modied by carbon or MWCNTs@S@PPy composites.
conductive polymers.13,33,35,37,5356 For example, Yang et al. repor-
ted that coating conductive poly(3,4-ethylenedioxythiophene)
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poly(styrene sulfonate) (PEDOT:PSS) onto mesoporous carbon/ Fig. S4. It can be seen that the composite shows well-dispersed
sulfur particles achieved a capacity of 600 mA h g1 aer 60 primary particles except for a few agglomerates in the original
cycles at 0.2 C.37 Chen et al. obtained a reversible capacity as MWCNTs@S@PPy electrode. Aer 200 cycles, the sulfur blocks
high as 1000 mA h g1 aer 100 cycles at 300 mA g1 in a almost disappear, no obvious change occurs in the morphology,
hierarchical S/MWCNT nanomicrosphere, but the sulfur load and no sulfur or lithium suldes reduction products are
and rate capability were lower as compared with the present observed on the surface of the electrode. In addition, aer 200
MWCNTs@S@PPy.55 In our case, the dual coreshell structure cycles, the electrodes of MWCNTs@S and MWCNTs@S@PPy
based on MWCNTs and PPy plays an important part in the dier greatly in appearance. The MWCNTs@S lm is easily
superior performance. separated from the Al foil, whereas the MWCNTs@S@PPy lm
Fig. 10 shows the EIS spectra of the MWCNTs@S@PPy and still strongly adheres to the Al foil (see Fig. S5). This observa-
MWCNTs@S cathodes before cycling. The depressed semi- tion demonstrates that PPy is helpful for achieving a uniform
circle in the high frequency region relates to the constant coating of the cathode lm and for inhibiting PS from being
resistance and charge transfer resistance, and the oblique dissolved out of the electrode, and can alleviate the volume
inclined line in the low frequency region corresponds to the ion expansion during the cycling process.48,51,58,59 However, side
diusion within the cathodes. It is obvious that the reactions of the cathode material with the electrolyte and
MWCNTs@S@PPy composite electrode exhibited a much lower the dissolution of the PS products into the electrolyte may
charge transfer resistance than that of the MWCNTs@S, which inevitably lead to the degradation of capacity upon cycling.
could be attributed to the enhanced conductivity of the Optimization of the MWCNTs@S@PPy hierarchical structure
MWCNTs@S@PPy composite.57 Moreover the charge transfer is desirable to further diminish the PS loss and the
resistance reduced by half aer cycling for 60 cycles, as seen capacity fading.
in Fig. S3.
The morphology of the MWCNTs@S@PPy composite elec- Conclusions
trode before and aer 200 cycles at 2000 mA g1 is shown in
A novel MWCNTs@S@PPy composite with a dual coreshell
structure has been designed as a cathode material for LiS
batteries, and was synthesized via a facile one-pot method.
Sulfur was rstly deposited onto the surface of MWCNTs, and
then PPy was coated in situ onto the outer surface of the
MWCNTs@S by chemical oxidation polymerization. Such a
hierarchical structure is eective to improve the electro-
chemical performance of the S-based cathode material.
MWCNTs provide a pathway for electron transport, while PPy
acts as an elastic layer to restrain the volume expansion of sulfur
with lithium intercalation. The synergistic eects of MWCNTs
and PPy result in a good electronic conductivity and alleviation
of PS dissolution into the electrolyte. Very high specic capacity,
and impressive cyclability and rate capability are obtained in
MWCNTs@S@PPy. The signicant improvement in the elec-
Fig. 9 Cycling performance of the MWCNTs@S@PPy composite at current trochemical performance can be attributed to the novel dual
densities of 1000, 1500 and 2000 mA g1. coreshell structure supported by MWCNTs and PPy. We believe

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that such a structure can be also applicable for other electrode 23 B. Zhang, X. Qin, G. R. Li and X. P. Gao, Energy Environ. Sci.,
materials with poor electronic conductivity and high volume 2010, 3, 15311537.
expansion, such as silicon or tin-based materials. 24 C. Liang, N. J. Dudney and J. Y. Howe, Chem. Mater., 2009,
21, 47244730.
Acknowledgements 25 D. Wang, G. Zhou, F. Li, K. Wu, G. Q. Lu, H. Cheng and
I. R. Gentle, Phys. Chem. Chem. Phys., 2012, 14, 8703
The authors gratefully acknowledge the nancial support by the 8710.
National High-Tech Research and Development Program of 26 S. S. Zhang and D. T. Tran, J. Power Sources, 2012, 211, 169
China (863 program, Grant no. 2009AA035201), and the Natural 172.
Science Foundation of China (Grant no. 50825203). They are 27 D. Aurbach, E. Pollak, R. Elazari, G. Salitra, C. S. Kelley and
also grateful to Dr. Jiangfeng Ni in Soochow University for J. Anito, J. Electrochem. Soc., 2009, 156, A694A702.
valuable discussion. 28 H. Ryu, H. Ahn, K. Kim, J. Ahn and J. Lee, J. Power Sources,
Published on 21 November 2012 on http://pubs.rsc.org | doi:10.1039/C2TA00915C

2006, 153, 360364.


Notes and references 29 L. X. Yuan, H. P. Yuan, X. P. Qiu, L. Q. Chen and W. T. Zhu,
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