Journal of

Materials Chemistry A
View Article Online
PAPER View Journal

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.
Downloaded by University of Arizona on 09 December 2012

Received 31st October 2012
Accepted 20th November 2012
DOI: 10.1039/c2ta00915c
www.rsc.org/MaterialsA
Its theoretical capacity is 1675 mA h g
1, 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
MWCNTs@S@PPy composite shows excellent rate capability and cyclability. The initial discharge specic
capacity is as high as 1517 mA h g
1, and remains at 917 mA h g
1 after 60 cycles at a current density
of 200 mA g
1. Even at a high current density of 1500 mA g
1, the composite still shows a good cycle
performance with a capacity of 560 mA h g
1 after 200 cycles.

Introduction capacity is much higher than those of conventional cathode

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

This journal is The Royal Society of Chemistry 2012 J. Mater. Chem. A


Journal of Materials Chemistry A
in porous carbon is limited by the carbon type and pore size,
and therefore needs further investigation.4,9,2025
Unfortunately, these approaches are not ecient enough to
absorb the polysulde intermediates, and oen result in low
sulfur content in the composites. Consequently, the negative PS
anions will be electrically dragged toward the Li anode by the
internal electrical eld force during the discharge process.26
Since the dissolution of lithium PS into the liquid organic
electrolyte is inevitable, some researchers tried to apply suitable
electrolyte additives or solid state electrolytes. It has been
reported that the addition of LiNO3 to organic electrolytes can
signicantly increase the cell's coulombic eciency, because it
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
lithium metal from chemical reaction with the PS anions, but
can also prevent PS anions from electrochemical reduction on
the Li anode, thus reducing the shuttle eect.2731 When a
Downloaded by University of Arizona on 09 December 2012
polyethylene oxide layer is coated on the surface of mesoporous
carbon to trap PS, the S electrode may exhibit improved capacity
and unaected cycling behaviour.9 A monolayer of polymer is
not thick enough to trap most PS, and its insulating nature may
exert an adverse eect on the conductivity. Therefore, the
application of conductive polymers should be more eective.
Regrettably, a uniform coating of conductive polymer has
seldom been achieved.29,3235
In this work, we have developed a dual coreshell structured
sulfur composite cathode material for LiS batteries by a facile
one-pot method. MWCNTs and PPy are introduced into
the sulfur composite to improve the conductivity, inhibit the
diusion of polysulde out of the cathode and relieve the
volumetric expansion of sulfur during chargedischarge
cycling.36,37 As illustrated in Fig. 1, sulfur particles are rst
deposited on the surface of MWCNTs, and then PPy is designed
to wrap around the S particles as an outer layer. Thus the dual
coreshell structure is formed. In such a structure, the inner
MWCNTs are expected to act as a conductive network for S and
to absorb PS to some extent, while the outmost elastic PPy layer
is expected to further enhance the conductivity and to stabilize
the dual structure of the composite during cycling.38,39 More-
over, the PPy layer can restrain the PS from moving out of the
Fig. 1 Schematic illustration for the synthesis and discharge process of the dual
coreshell structured MWCNTs@S@PPy composite.
J. Mater. Chem. A
View Article Online
Paper
cathode and alleviate the volumetric expansion of S. PPy itself is
electrochemically active for lithium intercalation/dein-
tercalation.38 Here, it should be pointed out that PPy has been
used in LiS batteries for a long time and behaves well because
it is stable and moderately rigid in the electrochemical envi-
ronment.12,14,35,4043 This dual coreshell structure can provide
structural stability for Li-ion insertion and extraction, and
hence is expected to exhibit a good chargedischarge perfor-
mance during cycling.
Experimental section
Materials synthesis
Sodium dodecyl sulfate (SDS, CP), ferric chloride (FeCl3$6H2O,
AR) and hydrochloric acid (HCl) were purchased from Sino-
pharm Chemical Reagent and used as received. The monomer
pyrrole (CP, Sinopharm Chemical Reagent Co., Ltd) was
distilled before use. Acid-treated MWCNTs (2030 nm in
diameter) were purchased from Beijing Nachen S&T Ltd.
Sodium thiosulfate (Na2S2O3$5H2O, AR) and sodium p-tolue-
nesulfonate (SDBNa, AR) were used without further
purication.
The dual coreshell structured MWCNTs@S@PPy composite
was prepared by a simple one-pot solution route. The reaction
formula for the sulfur preparation can be expressed as below:
Na2S2O3 + 2HCl / 2NaCl + SY + H2O + SO2[
PPy was synthesized via an in situ chemical oxidative poly-
merization of pyrrole on MWCNTs@S.
In a typical procedure, 4 g SDS was dissolved in 400 ml
distilled water, and then 1 g MWCNTs was dispersed into the
solution and sonicated for 1 h. 32.6 g Na2S2O3 was added to the
mixture and stirred for 10 min. Aer that, 52 g HCl was added
dropwise at a rate of 10 ml min
1 to the solution and stirred for
1 h. Subsequently, 3.763 g BDSNa was added to the mixture and
stirred for 10 min at 0  C, followed by the addition of 0.52 g
pyrrole. Aer the pyrrole was homogeneously dispersed, a
proper amount of FeCl3 (three times the amount of pyrrole) was
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
chemical analysis performed using STEM-EDX with a HAADF
detector on TEM (JEOL, JEM-2100F) operated at 200 kV. The
This journal is The Royal Society of Chemistry 2012
 View Article Online

Paper Journal of Materials Chemistry A

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 min
1 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
Downloaded by University of Arizona on 09 December 2012

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 cm
2. CR2032 coin cells
were assembled in an argon-lled glove box (Master 100 Lab,
Braun, Germany) using an electrolyte of 0.6 mol l
1 LiTFSI/DOL
+ DME (1 : 1 by volume) with 0.4 mol l
1 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 s
1 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. min
1 under a N2 atmosphere.

Results and discussion

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

This journal is The Royal Society of Chemistry 2012 J. Mater. Chem. A

 View Article Online

Journal of Materials Chemistry A Paper

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
Downloaded by University of Arizona on 09 December 2012

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 s
1. 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 cm
2. 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 s
1.

J. Mater. Chem. A This journal is The Royal Society of Chemistry 2012


Paper
Published on 21 November 2012 on http://pubs.rsc.org | doi:10.1039/C2TA00915C
rd th rd rd
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 g
1.
Downloaded by University of Arizona on 09 December 2012
charge and discharge voltage proles for the MWCNTs@S@PPy
composite. Two discharge voltage plateaus appear at around
2.35 and 2.1 V, which can be assigned to two-step reactions
during the discharge process. The voltage plateaus do not drop
during cycling, indicative of good retention. On the charge
curve, the voltage plateau at around 2.3 V corresponds to the
oxidation process, which shows a small change during cycling.
The voltage peak (see the red arrow in Fig. 6) can be attributed
to the oxidation of Li2S and Li2S2 to low-order PS, which can be
expressed by the following two equations:
Li2Sx + Li2S / Li2Sx
y + Li2S1+y (1)
Li2Sx + Li2S2 / Li2Sx
y + Li2S2+y (2)
where x
y and 1+y are larger than 2. The two equations are
known to contribute to the reversibility of LiS batteries.26
Fig. 7 presents the cycling performance of the
MWCNTs@S@PPy composite at dierent current densities of
200, 300 and 500 mA g
1. At 200 mA g
1, the initial specic
discharge capacity is as high as 1517 mA h g
1, which is 88% of
Fig. 7 Cycling performance of the MWCNTs@S@PPy composite at various
current densities of 200, 300 and 500 mA g
1. The typical coulombic eciency at
200 mA g
1 is also displayed.
This journal is The Royal Society of Chemistry 2012
View Article Online
Journal of Materials Chemistry A
Fig. 8 Comparison of the rate capability of MWCNTs@S@PPy and MWCNTs@S
at current densities from 200 to 2000 mA g
1.
the theoretical specic capacity. The uncoated sample delivers
an initial capacity of 1131 mA h g
1, much lower than that of
the coated sample. Aer 60 cycles, the capacity of the uncoated
composite decreases to 635 mA h g
1, whereas the PPy-coated
composite still retains a capacity of 917 mA h g
1. This indi-
cates that the PPy coating greatly improves the cycling
performance of the MWCNTs@S composite. In Fig. 7e, the
MWCNTs@S@PPy electrode exhibits a coulombic eciency of
nearly 100% during cycling, indicating that the sulfur shuttle
mechanism is diminished to quite a low level. It is believed
that the uniform coating of the conductive polymer and the
use of LiNO3 can restrain the dissolution of PS into the elec-
trolyte. Notably, the MWCNTs@S@PPy electrode shows
excellent cycling performance even at high current density. For
example, aer 60 cycles, the capacities are still 840 and 771 mA
h g
1 at 300 and 500 mA g
1, respectively, indicating 93% and
91.8% capacity retention. It can be seen in Fig. 7b and c that
the discharge capacity increases gradually with cycle number
during the initial several cycles. This can be explained by the
gradual penetration process of the active composite material
in the cathode into the electrolyte. The reversibility demon-
strates that the dual coreshell structure composite can
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 g
1 is shown in
Fig. 8. The composite exhibits an excellent rate performance,
with specic capacities of 1210, 1060, 860, 735 and 665 mA h
g
1 at 200, 500, 1000, 1500 and 2000 mA g
1, 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
g
1 if the current density is higher than 1000 mA g
1. 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 g
1 is
recovered if the current density is decreased back to 200 mA
g
1 aer cycling at various current densities from 200 to
2000 mA g
1.
J. Mater. Chem. A

Journal of Materials Chemistry A
We further studied the cycling performance of the
MWCNTs@S@PPy composite at high current densities of 1000,
1500 and 2000 mA g
1. The battery was charged and discharged
for 200 cycles. As shown in Fig. 9, at 1000, 1500 and 2000 mA
g
1, the corresponding specic capacities are 970, 867 and
810 mA h g
1 for the rst cycle, and decrease to 603, 560 and
465 mA h g
1 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
reported for similar sulfur composites modied by carbon or
conductive polymers.13,33,35,37,5356 For example, Yang et al. repor-
ted that coating conductive poly(3,4-ethylenedioxythiophene)
Downloaded by University of Arizona on 09 December 2012
poly(styrene sulfonate) (PEDOT:PSS) onto mesoporous carbon/
sulfur particles achieved a capacity of 600 mA h g
1 aer 60
cycles at 0.2 C.37 Chen et al. obtained a reversible capacity as
high as 1000 mA h g
1 aer 100 cycles at 300 mA g
1 in a
hierarchical S/MWCNT nanomicrosphere, but the sulfur load
and rate capability were lower as compared with the present
MWCNTs@S@PPy.55 In our case, the dual coreshell structure
based on MWCNTs and PPy plays an important part in the
superior performance.
Fig. 10 shows the EIS spectra of the MWCNTs@S@PPy and
MWCNTs@S cathodes before cycling. The depressed semi-
circle in the high frequency region relates to the constant
resistance and charge transfer resistance, and the oblique
inclined line in the low frequency region corresponds to the ion
diusion within the cathodes. It is obvious that the
MWCNTs@S@PPy composite electrode exhibited a much lower
charge transfer resistance than that of the MWCNTs@S, which
could be attributed to the enhanced conductivity of the
MWCNTs@S@PPy composite.57 Moreover the charge transfer
resistance reduced by half aer cycling for 60 cycles, as seen
in Fig. S3.
The morphology of the MWCNTs@S@PPy composite elec-
trode before and aer 200 cycles at 2000 mA g
1 is shown in
Fig. 9 Cycling performance of the MWCNTs@S@PPy composite at current
densities of 1000, 1500 and 2000 mA g
1.
J. Mater. Chem. A
View Article Online
Paper
Fig. 10 Electrochemical impedance spectroscopy for MWCNTs@S and
MWCNTs@S@PPy composites.
Fig. S4. It can be seen that the composite shows well-dispersed
primary particles except for a few agglomerates in the original
MWCNTs@S@PPy electrode. Aer 200 cycles, the sulfur blocks
almost disappear, no obvious change occurs in the morphology,
and no sulfur or lithium suldes reduction products are
observed on the surface of the electrode. In addition, aer 200
cycles, the electrodes of MWCNTs@S and MWCNTs@S@PPy
dier greatly in appearance. The MWCNTs@S lm is easily
separated from the Al foil, whereas the MWCNTs@S@PPy lm
still strongly adheres to the Al foil (see Fig. S5). This observa-
tion demonstrates that PPy is helpful for achieving a uniform
coating of the cathode lm and for inhibiting PS from being
dissolved out of the electrode, and can alleviate the volume
expansion during the cycling process.48,51,58,59 However, side
reactions of the cathode material with the electrolyte and
the dissolution of the PS products into the electrolyte may
inevitably lead to the degradation of capacity upon cycling.
Optimization of the MWCNTs@S@PPy hierarchical structure
is desirable to further diminish the PS loss and the
capacity fading.
Conclusions
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-
trochemical performance can be attributed to the novel dual
coreshell structure supported by MWCNTs and PPy. We believe
This journal is The Royal Society of Chemistry 2012

Paper
that such a structure can be also applicable for other electrode
materials with poor electronic conductivity and high volume
expansion, such as silicon or tin-based materials.
Acknowledgements
The authors gratefully acknowledge the nancial support by the
National High-Tech Research and Development Program of
China (863 program, Grant no. 2009AA035201), and the Natural
Science Foundation of China (Grant no. 50825203). They are
also grateful to Dr. Jiangfeng Ni in Soochow University for
valuable discussion.
Published on 21 November 2012 on http://pubs.rsc.org | doi:10.1039/C2TA00915C
Notes and references
1 B. Scrosati, Nature, 1995, 373, 557558.
2 G. Ceder, Y. M. Chiang, D. R. Sadoway, M. K. Aydinol,
Downloaded by University of Arizona on 09 December 2012
Y. I. Jang and B. Huang, Nature, 1998, 392, 694696.
3 F. Zhang, X. Zhang, Y. Dong and L. Wang, J. Mater. Chem.,
2012, 22, 1145211454.
4 C. Lai, X. P. Gao, B. Zhang, T. Y. Yan and Z. Zhou, J. Phys.
Chem. C, 2009, 113, 47124716.
5 M. Armand and J. M. Tarascon, Nature, 2008, 451, 652657.
6 P. G. Bruce, S. A. Freunberger, L. J. Hardwick and
J.-M. Tarascon, Nat. Mater., 2012, 11, 1929.
7 Y. Wang, L. Huang, L. Sun, S. Xie, G. Xu, S. Chen, Y. Xu, J. Li,
S. Chou, S. Dou and S. Sun, J. Mater. Chem., 2012, 22, 4744
4750.
8 P. Novak, K. Muller, K. S. V. Santhanam and O. Haas, Chem.
Rev., 1997, 97, 207282.
9 X. Ji, K. T. Lee and L. F. Nazar, Nat. Mater., 2009, 8, 500506.
10 X. Ji and L. F. Nazar, J. Mater. Chem., 2010, 20, 98219826.
11 L. Ji, M. Rao, S. Aloni, L. Wang, E. J. Cairns and Y. Zhang,
Energy Environ. Sci., 2011, 4, 50535059.
12 J. Wang, J. Chen, K. Konstantinov, L. Zhao, S. Ng, G. Wang,
Z. Guo and H. Liu, Electrochim. Acta, 2006, 51, 46344638.
13 W. Wei, J. Wang, L. Zhou, J. Yang, B. Schumann and Y. NuLi,
Electrochem. Commun., 2011, 13, 399402.
14 X. Liang, Y. Liu, Z. Wen, L. Huang, X. Wang and H. Zhang,
J. Power Sources, 2011, 196, 69516955.
15 S. Evers and L. F. Nazar, Chem. Commun., 2012, 48, 1233
1235.
16 M. Park, J. Yu, K. J. Kim, G. Jeong, J. Kim, Y. Jo, U. Hwang,
S. Kang, T. Woo and Y. Kim, Phys. Chem. Chem. Phys.,
2012, 14, 67966804.
17 N. Li, M. Zheng, H. Lu, Z. Hu, C. Shen, X. Chang, G. Ji, J. Cao
and Y. Shi, Chem. Commun., 2012, 48, 41064108.
18 S. S. Zhang and J. A. Read, J. Power Sources, 2012, 200, 7782.
19 Y. V. Mikhaylik and J. R. Akridge, J. Electrochem. Soc., 2004,
151, A1969A1976.
20 X. Li, Y. Cao, W. Qi, L. V. Saraf, J. Xiao, Z. Nie, J. Mietek,
J.-G. Zhang, B. Schwenzer and J. Liu, J. Mater. Chem., 2011,
21, 1660316610.
21 N. Jayaprakash, J. Shen, S. S. Moganty, A. Corona and
L. A. Archer, Angew. Chem., Int. Ed., 2011, 50, 59045908.
22 J. Schuster, G. He, B. Mandlmeier, T. Yim, K. T. Lee, T. Bein
and L. F. Nazar, Angew. Chem., Int. Ed., 2012, 51, 35913595.
This journal is The Royal Society of Chemistry 2012
View Article Online
Journal of Materials Chemistry A
23 B. Zhang, X. Qin, G. R. Li and X. P. Gao, Energy Environ. Sci.,
2010, 3, 15311537.
24 C. Liang, N. J. Dudney and J. Y. Howe, Chem. Mater., 2009,
21, 47244730.
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
8710.
26 S. S. Zhang and D. T. Tran, J. Power Sources, 2012, 211, 169
172.
27 D. Aurbach, E. Pollak, R. Elazari, G. Salitra, C. S. Kelley and
J. Anito, J. Electrochem. Soc., 2009, 156, A694A702.
28 H. Ryu, H. Ahn, K. Kim, J. Ahn and J. Lee, J. Power Sources,
2006, 153, 360364.
29 L. X. Yuan, H. P. Yuan, X. P. Qiu, L. Q. Chen and W. T. Zhu,
J. Power Sources, 2009, 189, 11411146.
30 A. Hayashi, T. Ohtomo, F. Mizuno, K. Tadanaga and
M. Tatsumisago, Electrochem. Commun., 2003, 5, 701705.
31 J. L. Wang, J. Yang, J. Y. Xie, N. X. Xu and Y. Li, Electrochem.
Commun., 2002, 4, 499502.
32 L. Yin, J. Wang, F. Lin, J. Yang and Y. Nuli, Energy Environ.
Sci., 2012, 5, 69666972.
33 F. Wu, J. Chen, L. Li, T. Zhao and R. Chen, J. Phys. Chem. C,
2011, 115, 2441124417.
34 Y. Cao, X. Li, I. A. Aksay, J. Lemmon, Z. Nie, Z. Yang and
J. Liu, Phys. Chem. Chem. Phys., 2011, 13, 76607665.
35 X. Liang, Z. Wen, Y. Liu, H. Zhang, J. Jin, M. Wu and X. Wu,
J. Power Sources, 2012, 206, 409413.
36 X. He, J. Ren, L. Wang, W. Pu, C. Jiang and C. Wan, J. Power
Sources, 2009, 190, 154156.
37 Y. Yang, G. H. Yu, J. J. Cha, H. Wu, M. Vosgueritchian, Y. Yao,
Z. A. Bao and Y. Cui, ACS Nano, 2011, 5, 91879193.
38 L. Qie, L. X. Yuan, W. X. Zhang, W. M. Chen and Y. H. Huang,
J. Electrochem. Soc., 2012, 159, A1624A1629.
39 Q. G. Shao, W. M. Chen, Z. H. Wang, L. Qie, L. X. Yuan,
W. X. Zhang, X. L. Hu and Y. H. Huang, Electrochem.
Commun., 2011, 13, 14311434.
40 Y. Fu and A. Manthiram, J. Phys. Chem. C, 2012, 116, 8910
8915.
41 Y. Zhang, Z. Bakenov, Y. Zhao, A. Konarov, T. N. L. Doan,
M. Malik, T. Paron and P. Chen, J. Power Sources, 2012,
208, 18.
42 L. Qiu, S. Zhang, L. Zhang, M. Sun and W. Wang,
Electrochim. Acta, 2010, 55, 46324636.
43 M. Sun, S. Zhang, T. Jiang, L. Zhang and J. Yu, Electrochem.
Commun., 2008, 10, 18191822.
44 J. Choi, J. Kim, G. Cheruvally, J. Ahn, H. Ahn and K. Kim,
Electrochim. Acta, 2007, 52, 20752082.
45 R. G. Chaudhuri and S. Paria, J. Colloid Interface Sci., 2010,
343, 439446.
46 M. Omastova, M. Trchova, J. Kovarova and J. Stejskal, Synth.
Met., 2003, 138, 447455.
47 J. Stejskal, M. Omastova, S. Fedorova, J. Prokes and
M. Trchova, Polymer, 2003, 44, 13531358.
48 J. Shim, K. A. Striebel and E. J. Cairns, J. Electrochem. Soc.,
2002, 149, A1321A1325.
49 R. Elazari, G. Salitra, A. Garsuch, A. Panchenko and
D. Aurbach, Adv. Mater., 2011, 23, 56415644.
J. Mater. Chem. A

Journal of Materials Chemistry A
50 H. Yamin, A. Gorenshtein, J. Penciner, Y. Sternberg and
E. Peled, J. Electrochem. Soc., 1988, 135, 10451048.
51 S.-E. Cheon, K.-S. Ko, J.-H. Cho, S.-W. Kim, E.-Y. Chin and
H.-T. Kim, J. Electrochem. Soc., 2003, 150, A796A799.
52 J. Akridge, Solid State Ionics, 2004, 175, 243245.
53 Y. Fu and A. Manthiram, Chem. Mater., 2012, 24, 30813087.
54 L. Wang, X. He, J. Li, J. Gao, J. Guo, C. Jiang and C. Wan,
J. Mater. Chem., 2012, 22, 2207722081.
Published on 21 November 2012 on http://pubs.rsc.org | doi:10.1039/C2TA00915C
Downloaded by University of Arizona on 09 December 2012
J. Mater. Chem. A
View Article Online
Paper
55 J. Chen, Q. Zhang, Y. Shi, L. Qin, Y. Cao, M. Zheng and
Q. Dong, Phys. Chem. Chem. Phys., 2012, 14, 53765382.
56 Y. Fu and A. Manthiram, RSC Adv., 2012, 2, 59275929.
57 X. Gao and H. Yang, Energy Environ. Sci., 2010, 3, 174189.
58 S. Cheon, S. Choi, J. Han, Y. Choi, B. Jung and H. S. Lim,
J. Electrochem. Soc., 2004, 151, A2067A2073.
59 Y. Diao, K. Xie, S. Xiong and X. Hong, J. Electrochem. Soc.,
2012, 159, A421A425.
This journal is The Royal Society of Chemistry 2012