Electrochemistry Communications 17 (2012) 1–5

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Electrochemistry Communications
journal homepage: www.elsevier.com/locate/elecom

Porous carbon-sulfur composite cathode for lithium/sulfur cells

Mumin Rao a, b, c, 1, Weishan Li a, Elton J. Cairns b, c,⁎
a
College of Materials Science and Engineering, South China University of Technology, Guangzhou 510641, China
b
Department of Chemical & Biomolecular Engineering, University of California, Berkeley, CA 94720, USA
c
Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA

a r t i c l e i n f o a b s t r a c t

Article history: A unique porous carbon was prepared using a polymer mixture of polyacrylonitrile and poly(methylmetha-
Received 8 December 2011 crylate). Sulfur was incorporated into this porous carbon via a new simple solution chemical deposition
Received in revised form 23 December 2011 method. This novel porous carbon–sulfur composite showed high reversible capacity, good capacity retention
Accepted 30 December 2011
and good rate capability when used as the cathode in rechargeable Li/S cells. The electrochemical results
Available online 12 January 2012
show that porous carbon–sulfur composite with 53.7 wt.% S maintains a stable discharge capacity of more
Keywords:
than 740 mA h g− 1-sulfur after 100 cycles.
Porous carbon © 2012 Elsevier B.V. All rights reserved.
Sulfur composite
Cathode
Lithium/sulfur cell

1. Introduction Porous carbon was prepared by the carbonization of a polymer

The rechargeable lithium/sulfur cell has received a great deal of
attention recently as the high specific energy (theoretical specific
energy = 2600 W h kg − 1) makes it very attractive as a power source
for electric vehicles and energy storage systems. Sulfur with its high
theoretical specific capacity of 1675 mA h g − 1 makes it an attractive
electrode material for Li secondary cells [1–3]. In addition, sulfur
has the advantages of being inexpensive, abundant, non-toxic and en-
vironmentally benign. Unfortunately, the Li/S cell still faces several
serious challenges, including low utilization of sulfur because of its
poor electrical conductivity, and rapid capacity loss on repeated cy-
cling because of the dissolution of polysulfides into the electrolyte
[4,5]. The main approaches to enhance Li/S cell performance have
been focused on fabricating porous carbon–S nanocomposites
[3,6–8] and conductive polymer/sulfur composites [2,9–11], and find-
ing an appropriate electrolyte to replace the traditional organic liquid
electrolyte systems that are composed of carbonates and a lithium
salt [12–14]. In this work the porous carbon acts as an electronic con-
ductor and absorbing agent to improve the electrical conductivity and
to restrict the dissolution of polysulfides in the electrolyte.
⁎ Corresponding author at: Department of Chemical & Biomolecular Engineering,
University of California, Berkeley, CA 94720, USA. Tel.: + 1 510 486 5028; fax: + 1
510 486 7303.
E-mail addresses: liwsh@scnu.edu.cn (W. Li), ejcairns@lbl.gov (E.J. Cairns).
1
Visiting researcher in University of California at Berkeley from South China
University of Technology, China.
mixture of polyacrylonitrile (PAN) and poly(methyl methacrylate)
(PMMA). Sulfur is uniformly incorporated into the porous carbon
via a new simple chemical deposition strategy using a sulfur precur-
sor with a one-step procedure, which is more convenient and simpler
than our previous report with a two-step procedure [15,16]. The po-
rous carbon not only can provide stable electrical and ionic transfer
channels, but also can play the role of strong absorbent to retain poly-
sulfides and reduce their dissolution into the electrolyte during the
discharge/charge process.
2. Experimental procedures
2.1. Preparation of porous carbon
PAN-PMMA blends were prepared by dissolving 10 wt% total PAN
+ PMMA polymers with a mass ratio of 1:3 in DMF at 60 °C under
constant stirring to obtain a homogeneous PAN-PMMA solution,
then immersed in deionized water drop by drop at room tempera-
ture. After the exchange of DMF and water by phase inversion, a sub-
stantial number of pores were formed in the PAN-PMMA mixture.
After the water was evaporated, the PAN-PMMA mixture was heated
to 280 °C in Ar at a rate of 3 °C min − 1, and then the mixture was fur-
ther heated to 900 °C at a rate of 3 °C min − 1, and finally held at this
temperature for 2 h. During this heat treatment a large amount of
small micropores inside the pores of the PAN-PMMA mixture were
formed. In the PAN-PMMA mixture, the PAN acts as the carbon pre-
cursor and the PMMA acts as the small micropore generator [16,17].

1388-2481/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2011.12.022
2 M. Rao et al. / Electrochemistry Communications 17 (2012) 1–5
2.2. Preparation of the porous carbon-sulfur composite
The porous carbon-sulfur composite was synthesized by a chemi-
cal deposition method in an aqueous solution. The preparation reac-
tion formula is as follows:
2− þ
S2 O3 þ 2H →S þ SO2 þ H2 O
The as-prepared porous carbon was ground to small particles. So-
dium thiosulphate (purity: 99.9%, Aldrich) was dissolved in double
distilled water and then the as-prepared porous carbon was added.
The mixture was mixed ultrasonically until the porous carbon was
homogenously dispersed in the solution. The solution was then
titrated into 2 mol L − 1 HCOOH solution containing 5 mM L − 1 cetyl-
trimethylammoniumbromide (CTAB, purity: 99.9%, Aldrich) at a rate
of 30–40 drop min − 1. The precipitate was filtered and washed with
acetone and deionized water several times to eliminate salts and im-
purities, and dried at 50 °C for 24 h in a vacuum oven. The as-
synthesized porous carbon–S composite was thermally treated in an
Ar environment at 160 °C for 12 h. This heat treatment allows the
(liquid) sulfur to penetrate into the pores of the carbon.
2.3. Cell assembly and testing
The porous carbon–S electrode was prepared from a mixture of
80 wt.% of porous carbon–S composite, 8 wt.% of carbon nanofibers,
2 wt.% of carbon black particles, 10 wt.% of binder carboxy methyl cel-
lulose (CMC) and styrene butadiene rubber (SBR) (CMC:SBR = 2:3, by
weight). Water served as dispersant. Firstly, CMC solution was added
to the mixture of the porous carbon–S composite and the conductive
carbon and mixed for about 1 h, and then the SBR solution was added
to the above solution and stirred for 1 h to obtain a homogenous slur-
ry. The resultant slurry was uniformly spread onto carbon-coated alu-
minum foil using a doctor blade, and dried at 50 °C for 72 h. The
resulting cathode film (ca. 50 μm thick) was used to prepare the cath-
odes by punching circular disks having an area of 0.9 cm 2. One molar
per kilogram LiTFSI in PYR14TFSI + PEGDME (1:1 by weight) was used
as electrolyte [18,19]. Cyclic voltammogram (CV) measurement was
performed on an AQ4 Gamry Reference 600 electrochemical worksta-
tion using a voltage range of 1.0 to 3.0 V vs. Li/Li + at a scan rate of
0.05 mV s − 1. Galvanostatic discharge and charge cycling of the Li/S
cells was conducted using a Maccor cycle life tester at several differ-
ent rates between cut-off potentials of 1.5 and 2.8 V, and all of the ca-
pacity values in this article are calculated according to the mass of
active material S. The morphology of the samples was investigated
by using a scanning electron microscope (SEM-JEOL JSM 7500F) and
transmission electron microscopy (TEM: JEOL 2100F). The sulfur con-
tent of the composites was ascertained by thermogravimetric analysis
(NETZSCH STA 409 PC/PG). The BET surface area and pore volume of
porous carbon were evaluated by Micromeritics ASAP2020 apparatus.
3. Results and discussion
Fig. 1a, c, and e show SEM images of the porous carbon and the po-
rous carbon–S composite. The porous carbon (Fig. 1a) has a porous
structure with a large amount of small micropores which can be ob-
served in the corresponding TEM image in Fig. 1b. N2 adsorption/
desorption isotherms (Fig. 2a) for porous carbon show a BET surface
area of 738 m 2 g − 1 and pore size less than 2 nm. The porous structure
is beneficial for the deposition of nano-sulfur and access of electrolyte
throughout the porous structure of the carbon. The small micropores
inside the porous carbon structure are beneficial for the migration of
the melted sulfur during the thermal treatment process and can re-
strict the dissolution of lithium polysulfides into the electrolyte.
After the simple chemical deposition reaction between S2O32−
and HCOOH in the porous carbon system, sulfur nanoparticles de-
posited in the pores of the carbon. Because of the large amount of
sulfur present, there is some significant surface deposition and ag-
gregation of sulfur attached to the outer surface of the porous car-
bon, as shown in the SEM image in Fig. 1c and the TEM image in
Fig. 1d. The sulfur content of about 69.8 wt.% is determined by TGA
as shown in Fig. 2b. In order to increase the sulfur incorporation
into the micropores and evaporate the sulfur attached to the porous
carbon surface, the as-prepared porous carbon–S composite was
thermally treated at 160 °C for 12 h under the flow of Ar. During
the thermal treatment process, part of the bulk sulfur on the exter-
nal surface of the porous carbon can melt and diffuse into the
micropores of the carbon, as shown in Fig. 1e and f. There is an indis-
tinguishable difference between the surface morphology of Fig. 1a
and e, because the sulfur exists inside the micropores [3,7,20]. Al-
though the micropores are filled with sulfur, open pore mouths
also can be observed from the TEM image in Fig. 1f. STEM images
of porous carbon–S composites thermally treated at 160 °C for 12 h
(Fig. 1g), and the corresponding carbon (Fig. 1h) and sulfur
(Fig. 1i) elemental maps show the homogeneous distribution of sul-
fur. The TGA results indicate that these thermally treated samples
contain about 53.7 wt.% S (Fig. 2b).
Fig. 3a presents the CV curves of the porous carbon–S composite
with 53.7 wt.% S thermally treated at 160 °C for 12 h. The CV shows
two main cathodic peaks at about 2.4 and 2.0 V, which are related
to the change from elemental sulfur to the higher-order lithium
polysulfides (Li2Sn, n ≥ 4), and the reduction of higher-order
lithium polysulfides to lower-order lithium polysulfides (Li2Sn,
n b 4) [21–23]. In the first anodic scan, the two expected oxidation
peaks overlap and form one large peak at about 2.55 V. In the sub-
sequent scans, the main reduction peaks are shifted to higher po-
tentials and the oxidation peaks to lower potentials, indicating an
improvement of reversibility of the electrode with cycling. The an-
odic peak current and potential are stable, confirming the stable
existence of lower-molecular weight elemental sulfur and lithium
polysulfides in the micropores of the carbon, which is crucial for
stabilizing the electrochemical performance of the cathode. The
CV results indicate that the porous carbon not only has an excellent
conductive structure in which the sulfur is well dispersed, but
also has a strong adsorbing ability to suppress the dissolution of
the polysulfides into the electrolyte during the discharge/charge
process.
In order to further investigate the electrochemical performance
of the porous carbon–S composite, galvanostatic cycling perfor-
mance and rate capability evaluations were carried out. Fig. 3b pre-
sents typical discharge/charge profiles for the initial two cycles at
the 0.02C rate (1C = 1675 mA g − 1) between 1.5 and 2.8 V. The dis-
charge curves show two discharge plateaus, which correspond to
the two reduction peaks as depicted in Fig. 3a. Further cycling
shows that the porous carbon–S composite also exhibits stable cy-
cling, as shown in Fig. 3c. The porous carbon–S composite electrode
can deliver a discharge capacity of about 1300 mA h g − 1-sulfur for
the first cycle at 0.02C (96.9% coulombic efficiency). After the two
initial cycles, the porous carbon–S composite electrode displays a
discharge capacity of 1080 mA h g − 1-sulfur at 0.05C, maintaining
more than 740 mA h g − 1-sulfur even after 100 cycles. In addition,
the coulombic efficiency was maintained in the range of 97.9–
98.5%. This suggests that porous carbon not only can provide an ef-
fective electron conduction path for the sulfur electrode, but also
can successfully accommodate the volume change associated with
the Li/S electrochemical reaction. The microporous channels in the
composite can restrict the diffusion of the polysulfides during the
charge/discharge process. The rate capability of the porous carbon–
S electrode is demonstrated in Fig. 3d. The reversible capacity at a
low rate of 0.02C is about 1300 mA h g − 1-sulfur. This cell shows a
 M. Rao et al. / Electrochemistry Communications 17 (2012) 1–5 3

(a) (b)

(c) (d)

(e) (f)

(g) (h) (i)

Fig. 1. SEM and TEM images of porous carbon (a, b), and porous carbon–S composite before (c, d) and after being thermally treated at 160 °C for 12 h (e, f). STEM images of porous
carbon–S composite thermally treated at 160 °C for 12 h (g), the corresponding carbon (h) and sulfur (i) elemental maps.

reversible capacity of 600 mA h g − 1-sulfur at a rate of 0.5C after 4. Conclusions

being continuously cycled for 20 cycles at various rates, owing to
the good electrical conductivity of the porous carbon as a matrix Porous carbon–S composites were prepared through a simple car-
for the insulating sulfur. bonization of a PAN + PMMA mixture and the subsequent simple
4 M. Rao et al. / Electrochemistry Communications 17 (2012) 1–5
(a)
Fig. 2. (a) N2 adsorption and desorption isotherms of porous carbon, the inset shows corresponding BJH pore-size distribution; (b) TGA curves of porous carbon–S composites and
pure sulfur.
chemical deposition reaction strategy. The small micropores of the
porous carbon can trap elemental sulfur and lithium polysulfides dur-
ing cycling, preventing the dissolution of lithium polysulfides into the
electrolyte and the formation of a Li2S insulating layer on the compos-
ite surface. The porous carbon–S composite with 53.7 wt.% S can re-
tain a discharge capacity of more than mA h g − 1-sulfur at the 0.05C
rate after 100 cycles, reflecting a relatively stable reversible capacity
and improved capacity retention. In addition, when measured at a
higher rate of 0.5C, the composite electrode also exhibits a discharge
capacity of about 600 mA h g − 1-sulfur.
Acknowledgements
M.R. was partially supported by the China Scholarship Council
while visiting the Department of Chemical & Biomolecular Engineer-
ing at UC Berkeley.
(a)
(c)
Fig. 3. (a) Cyclic voltammograms at 0.05 mV s− 1, (b) galvanostatic discharge/charge profiles at 0.02C, (c) cycling performance at 0.05C, and (d) rate performance of porous carbon–S
composite thermally treated in Ar at 160 °C for 12 h.
(b)
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