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Xian-guo Yu
a,
*
, Jing-ying Xie
a
, Jun Yang
b
, Hai-jiang Huang
a
,
Ke Wang
a
, Zhong-sheng Wen
a
a
Energy Science and Technology Laboratory, Shanghai Institute of Microsystems and Information Technology, Chinese Academy of Sciences, No. 865,
Changning Road, Shanghai 200050, China
b
Department of Chemical Engineering, Shanghai JiaoTong University, Shanghai 200240, China
Received 8 May 2004; received in revised form 1 July 2004; accepted 1 July 2004
Available online 27 July 2004
Abstract
Conductive sulfur-containing cathode materials for high-capacity lithium secondary batteries have been synthesized by heating a
mixture of polyacrylonitrile and elemental sulfur. The structures and electrochemical properties of the materials depend on the re-
action conditions, particularly synthesis temperatures. FTIR, Raman and XPS measurements show that the fundamental chemical
structure of the materials is composed of a dehydropyridine type matrix with SS bonds in the side-chain. The cycle performances of
the materials synthesized at dierent temperatures have been examined as active cathode materials in lithium cells. Due to the ex-
istence of p-conjugation and the CSSC covalent bond, signicantly improved redox rates and cycleability at room temperature
are achieved. A stable discharge capacity for the material synthesized at 450 C is maintained at about 480 mAh/g and the capacity
retention remains at ca. 92% (referred to the second cycle) after about 240 cycles. The excellent cycle characteristics supply a good
foundation for practical application of this material in rechargeable lithium batteries.
2004 Elsevier B.V. All rights reserved.
Keywords: Conductive polymer; Elemental sulfur; Sulfur-containing oligomer; Cathode material; Rechargeable lithium batteries
1. Introduction
Compounds containing elemental sulfur such as met-
al suldes [13], organosuldes [47] and some compos-
ites [811] have been proposed as promising cathode
active materials for rechargeable lithium batteries. In
particular, elemental sulfur, with the advantages of high
theoretical specic capacity (1672 mAh/g), high theoret-
ical energy density (2600 Wh/kg, lithium as anode) and
low cost as well as non-toxicity, displays great potential
for application in the next generation of lithium batter-
ies. However, Li/S batteries suer from low percentage
utilization of the bulk material and poor reversibility
or cycle life [1214]. The drawbacks can be ascribed to
the electrically insulating nature of sulfur and the Li-in-
sertion product and to the loss of active material in the
form of soluble reaction intermediates of polysuldes.
Even by adding multiwalled carbon nanotubes, which
connes polysuldes inside tubes to prevent them from
further solution, the improved cycle performance of a
sulfur electrode shows only ca. 300 mAh/g discharge ca-
pacity after 50 cycles [15].
Organosuldes are attractive alternatives as cathode
materials for their relatively better cycle properties in
comparison with elemental sulfur. In particular, 2,5-
dimercapto-1,3,4-thiadiazole (DMcT) is one of the most
well-known candidates, with a theoretical specic capac-
ity of 362 mAh/g. However, polymerization and de-po-
lymerization reactions occur during charge and
discharge, respectively, between DMcT and poly-DMcT
as is shown in Scheme 1. In addition, this compound has
disadvantages for battery application, e.g., lack of
0022-0728/$ - see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jelechem.2004.07.004
*
Corresponding author. Tel.: +86-21-62131647; fax: +86-21-
32200534.
E-mail address: yuxg@mail.sim.ac.cn (X. Yu).
www.elsevier.com/locate/jelechem
Journal of Electroanalytical Chemistry 573 (2004) 121128
Journal of
Electroanalytical
Chemistry
electrical conductivity, electrochemically slow redox ki-
netics, and solvent-solubility during discharge [4], etc.
To improve the redox dynamics of DMcT at room tem-
perature, a conducting polymer of polyaniline (PAn),
which functions as both an eective electrocatalyst and
an active material, has been used to construct a compos-
ite with DMcT. Oyama et al. [8] reported a practical ca-
pacity as high as 184 mAh/g for the PAn/DMcT
composite. Obviously, this low capacity cannot embody
the merit of the high capacity density of sulfur.
So far, neither elemental sulfur nor organosuldes
has been reported to satisfy the requirements of both
high capacity and long cycle life for lithium batteries.
Recently, a novel conductive sulfur-containing material
(CSM) has been synthesized by heating a mixture of
polyacrylonitrile (PAN) and sulfur at 280300 C. Its re-
versible capacity reaches ca. 600 mAh/g and the capacity
fade rate is about 26% after 50 cycles in cells with a gel-
type polymer electrolyte, improving the chargedis-
charge performance of this sulfur-containing material
to a great extent [16,17]. The CSM was assumed previ-
ously to be a composite with a conductive macromolec-
ular polymer and nano-sulfur [16,17]. The polymer is
composed of a p-conjugated co-plane hetero-ring re-
peated structure unit, in which sulfur is embedded.
The polymer structure is similar to active carbon bers
or disordered carbon obtained by pyrolysing pure
PAN [18,19]. The structure and degree of carbonization
of such pyrolysates depend on the synthesis temperature
as is shown in Scheme 2 [20,21]. However, when heating
the mixture of PAN and S, sulfur as the reducer may fa-
cilitate the dehydrogenation and cyclization of PAN.
Meanwhile, as the cleavage of the S
8
ring and the forma-
tion of sulfur free radicals occur at relatively high tem-
peratures, other reactions possibly also take place
between the carbon-matrix of PAN and S. For further
understanding of the structure and electrochemical
properties, in this paper, we characterize chemically
and physically in greater depth the materials of CSM
prepared at dierent temperatures and examine their cy-
cle performance as the active material in lithium cells.
2. Experimental
In a wider temperature range of 200800 C, dierent
CSM samples were synthesized as described previously
[16]. The rate of temperature increase and time of reac-
tion retention were xed as 10 C/min and 8 h, respec-
tively. The samples were designated according to the
temperature of formation. For example, CSM-450 des-
ignates the sample synthesized at 450 C.
Powder X-ray diraction (XRD) patterns of the sam-
ples were obtained using an automated powder dirac-
tometer with Cu Ka radiation (Type: D-max 2550 V).
Fourier-transform infrared spectroscopy (FTIR) data
were recorded from KBr pellets of CSM on a PerkinEl-
mer (L-710) spectrophotometer. Raman spectra were
recorded on a Lab Ram1B system with a HeNe
lamp-house, whose wavelength was 632.8 nm. The X-
ray photoelectron spectroscopy (XPS) analyses were
performed with a surface science instruments spectrom-
eter (Lab M
1
CR
0
MK II) employing focused monochro-
matized Mg Ka radiation (1253.6 eV). Calibration of
the binding energy scale was done with the C
1s
line
(284.6 eV) from the carbon contamination layer. Ele-
mental analysis (EA) of C, N, H, and S was conducted
with a PE2400II analyzer.
CR2025-type Li coin cells were assembled in a glove
box to evaluate the cycle performance of CSM samples.
The composite positive electrodes were fabricated as fol-
lows: CSM active material, acetylene black (AB) and
polytetrauorethylene (PTFE) binder, in a weight ratio
of 7:2:1, were thoroughly mixed in ethanol. The paste
produced after solvent evaporation was shaped into a
thin self-sustainable lm and then it was dried under
vacuum at 80 C for 6 h. The dried lm had a thickness
of ca. 7080 lm and was cut into pellets with a diameter
of 10 mm, which were then pressed onto a nickel foam
current collector. The loaded mass of active material
was about 4.5 mg. The cells, with a negative electrode
of lithium, electrolyte containing 1 M LiPF
6
plus ethyl-
ene carbonate (EC) + dimethyl carbonate (DMC) (1:1,
v/v) (Mitsubishi Chemical), and a separator (Cel-
gard2300), were tested on a LAND electrochemical in-
N N N
N N
N
N N
Ar
Ar
about 700 250~600
Scheme 2.
S
N N
HS SH
S
N N
S
S
n
Oxidation or Charge
Reduction or Discharge
Scheme 1.
122 X. Yu et al. / Journal of Electroanalytical Chemistry 573 (2004) 121128
strument at room temperature. Unless stated otherwise,
the chargedischarge current density was 0.2 mA/cm
2
and the cuto voltage was from 3.0 to 1.0 V vs. LijLi
+
.
3. Results and discussion
3.1. Material characterization
The existence of a CS bond is the key to judge
whether S is incorporated into the PAN-based polymer
due to the chemical reactions between the carbon-ma-
trix of PAN and S. Using the standard solid
13
C
NMR technique for characterization of CSM-300,
CC and CN bonds can be assigned denitively, al-
though their peak bands are relatively wide [17]. How-
ever it is dicult to conrm the presence of the CS
bond, because the gap of the chemical shift between
CC and CS bonds is only about 13 ppm. FTIR
and Raman spectrophotometers are sensitive to some
functional groups or bonds and suitable for insoluble
powders, so some useful information may be observed.
Fig. 1 shows the FTIR spectra of PAN and the CSM
synthesized at dierent temperatures. The group of
peaks in the region of 16001200 cm
1
and the charac-
teristic peak at 802 cm
1
for CSM do indicate the for-
mation of a hexahydric-ring containing CC and
CN bonds, based on the vibration modes for the py-
rolysate of PAN, pyridine and pyrrole [22,23]. The as-
signments for the peaks in the low frequency region
have not been considered important because of their
weak signals [17]. Although the peaks at ca. 943, 670
and 513 cm
1
are weak, they are characteristic because
they do not appear in the FTIR spectra of either the
pyrolysate of PAN or elemental sulfur. The peak at
513 cm
1
can be ascribed to the SS stretching, based
on assignments for organodisuldes [4,24]. Because el-
emental sulfur is inactive in IR, the vibration at 513
cm
1
can be caused only by stretching of SS bonds
in the compound-state. Generally, the CS stretching
appears at ca. 800600 cm
1
[25]. However, some re-
ports have also assigned the peaks at 1080 and 670
cm
1
to the CS stretching [26,27]. Based on the anal-
ysis above, we assign the peak at 943 cm
1
to ring
breathing, in which a CS bond is contained, and that
at 670 cm
1
to CS stretching. Possibly due to the in-
uence of the six-member ring coupling with the S at-
om, the peak for CS ring breathing shifts greatly to
low frequency. The detailed assignments for the dier-
ent samples are summarized in Table 1.
The signals of the CS and SS bonds can also be
clearly seen in the Raman spectra shown in Fig. 2. The
three strong characteristic peaks of elemental sulfur, S
8
,
are still sharp in the Raman spectrum of CSM-250 be-
cause it contains elemental sulfur or poly(sulfur) due to
the low synthesis temperature. Also, peaks located at
305, 374, 927 and 1142 cm
1
, which cannot be observed
in the pyrolysate of pure PAN, are now present, a further
indication that chemical reactions have occurred be-
tween elemental sulfur and the matrix of cyclized PAN.
For CSM synthesized at higher temperatures, the
2800 2400 2000 1600 1200 800 400
(b)
(c)
(d)
(e)
(a)
Wavenumber / cm
-1
Fig. 1. FTIR spectra for (a) PAN and for the sulfur-containing
materials synthesized at temperatures of (b) 250 C; (c) 300 C; (d) 450
C; (e) 800 C.
Table 1
FTIR wavenumbers (cm
1
) and assignments for sulfur-containing materials
CSM-250 CSM-450 CSM-800 Assignment
1554 w
a
1549 vw CC asymmetric stretch
1550 s 1502 s 1541 s CC symmetric stretch
1452 vw CH
2
symmetric stretch
1425 w 1431 w CN asymmetric stretch
1363 w 1363 m CC deformation
1252 m 1250 s 1281 s CN symmetric stretch
1092 w CC stretch
939 w 943 m 952 vw Ring breath (side-chain containing SS)
804 w 804 m 802 w Ring breath (main-chain hexahydric-ring)
660 vw 671 vw 679 vw CS stretch
472 w 513 w 513 vw SS stretch
a
s, Strong; m, medium; w, weak; vw, very weak.
X. Yu et al. / Journal of Electroanalytical Chemistry 573 (2004) 121128 123
characteristic peaks for elemental sulfur are very weak,
as for CSM-300, or even disappear, as for CSM-450
and CSM-800. The detailed assignments for the peaks
of the dierent samples are listed in Table 2. In the higher
frequency region above 1200 cm
1
, there are two diuse
peaks related to carbon-like materials obtained by pyro-
lysing the polymer. The mode at ca. 1513 cm
1
, often re-
ferred to as the G peak, is due to a graphite-like
structure, whereas that near ca. 1325 cm
1
is due to a dis-
ordered structure or D mode [28].
The C
1s
and S
2p
X-ray photoelectron spectra for CSM-
450 and CSM-800 are deconvoluted into separate spec-
tra, each of which is associated with a specic binding
energy, as shown in Fig. 3. The typical binding energy
values of carbon atoms in polyacetylene [29], phenylthi-
olate attached to S [30] and carbon nitride containing a
CN bond [31] are 284.6, 285.6 and 286.6 eV, respec-
tively. Consequently, we assign the C
1s
peak in CSM-
0 400 800 1200 1600 2000
Wavenumber / cm
-1
(e)
(d)
(c)
(b)
(a)
Fig. 2. Raman spectra for (a) sulfur and for the sulfur-containing
materials synthesized at temperatures of (b) 250 C; (c) 300 C; (d) 450
C; (e) 800 C.
Table 2
Raman shifts (cm
1
) and assignments for sulfur-containing materials and sulfur
CSM-300 CSM-450 CSM-800 Sulfur Assignments
150 s Characteristic peak of S
8
182 s
a
176 m 161 w CS
219 w 217 s Characteristic peak of S
8
308 w 298 m CS in plane bending
378 s 370 m CS deformation
472 s 471 s Characteristic peak of S
8
460 m 460 w SS
805 vw 798 vw 797 vw CS stretch
932 m 926 m 919 w Ring (containing SS bond) stretch
1151 w 1143 vw 1052 vw Ring (containing SS bond) stretch
a
s, Strong; m, medium; w, weak; vw, very weak.
290 288 286 284 282
Binding energy/eV
(a)
(c) (d)
(b)
290 288 286 284 282
Binding energy/eV
168 166 164 162 160 158
Binding energy /eV
168 166 164 162 160 158
Binding energy/eV
Fig. 3. XPS spectra of (a) C
1s
and (b) S
2p
in CSM-450 and of (c) C
1s
and (d) S
2p
in CSM-800.
124 X. Yu et al. / Journal of Electroanalytical Chemistry 573 (2004) 121128
450 at 284.6 eV to the sp
2
-type CC bonds, the peak at
285.7 eV to the CS bonds and the peak at 286.5 eV to
the sp
2
-type CN bonds. Besides the change in relative
intensities, the positions of the three simulated peaks in
CSM-800 shift hardly at all compared with those in
CSM-450, indicating that three fundamental chemical
bonding states involving carbon atoms still exist in
CSM-800. The S
2p
peak prole for CSM-450 actually
consists of three components located at 162.2, 163.5
and 164.6 eV. The main peak with 163.5 eV binding
energy, consistent with that of anthracene-based organo-
disulde (163.5 eV) [27] or close to that of poly(1,4-phen-
ylene sulde) [32] and poly(benzenethiol) [33] (163.6 eV),
corresponds to SS bonds or S attached to C. The contri-
bution at 164.6 eV also originates primarily from the SS
bond according to the S
2p
binding energy value of diphe-
nyl disulde (164.6 eV) [34], but the attribution of the
peak at 162.2 eV is not clear. No cyclic octa-atomic ele-
mental sulfur peak (ca. 164.2 eV) [34] was found. The po-
sitions of the peaks move towards higher energy levels
with ca. 0.3 eV for CSM-800. Moreover, the shoulder be-
tween 162.5 and 161.0 eV in CSM-450 disappears for
CSM-800.
The powder X-ray diraction pattern of CSM synthe-
sized above 300 C in Fig. 4 reveals only one distinct
broad 002 peak at around 25.0, similar to that of the
pyrolysates of pure PAN, indicating that the major
structural ordering is related to a graphite-like pstacking
of the hexahydric-ring layer, analogous to disordered
carbon [35,36]. Thus structurally, CSM can be divided
mainly into graphite-like microcrystal phase and amor-
phous phases. The crystallite size L
c
for CSM estimated
using the Scherrer equation [37] ranges from 1.18 nm to
1.99 nm. Previously, elemental sulfur had always been
supposed to be embedded on the nano-sized scale in
the hexagonal ring formed by the cyclization of poly-
acrylonitrile [16,17]. Since the diameter of a sulfur atom
(0.204 nm) is larger than that of a carbon atom (0.154
nm) and sulfur usually exists as an S
8
-ring, the sulfur
possibly is too large to be embedded in the hexahy-
dric-ring. It seems reasonable that elemental sulfur dis-
perses uniformly as nano-sized particles in the
interlayers of the graphite-like microcrystal or the nano-
pores formed by disordered stacking of the microcrystal
sheets or adsorbs on the surface of particles.
Based on the above material characterization, the re-
actions of PAN with S during the heating process in-
clude not only the dedydrogenation and cyclization of
PAN, but also the bonding of sulfur with carbon. As a
good reducer, sulfur accelerates the dehydrogenation
of PAN. At the same time, the sulfur free radical, pro-
duced by the cleavage of the S
8
-ring at a certain temper-
ature, can combine chemically with the positively
polarized carbon atoms in the polymer matrix. The de-
tailed reaction mechanisms between PAN and S are un-
der investigation. We have evaluated carefully the
chemical reaction from the point of view of the stoichi-
ometry at 450 C When xing the weight of PAN pow-
der at 0.8 or 2.0 g and changing the weight ratio of
sulfur to PAN from 2:1 to 10:1, the product weights -
nally obtained are always ca. 1.23 g and ca. 3.02 g, re-
spectively, which suggests that, at 450 C, the reaction
product of PAN and S ts approximately with a special
stoichiometric ratio. Elemental analysis shows that the
atom ratio of C/N and C/S is always 3, as is shown in
Table 3. Therefore, we deduce the predominant compo-
nent of CSM-450 is a novel sulfur-containing oligomer.
A possible thermo-reaction and the molecular structure
of such an oligomer is shown in Scheme 3.
3.2. Cycle performance of CSM
Control of fast capacity fade of sulfur or sulde is one
of the most important aspects for their application in re-
chargeable lithium batteries. The structure and compo-
nents of CSM formation have a great eect on its
cycle performance. The samples prepared below 250
C have no electrochemical activity in lithium cells
0 10 20 30 40 50 60 70 80
(d)
(c)
(b)
(a)
2 / degree
Fig. 4. XRD patterns for the sulfur-containing materials synthesized
at the temperatures of (a) 250 C; (b) 300 C; (c) 450 C; (d) 800 C.
Table 3
Results of elemental analysis and XRD of the composites
Sample Relative content
of C/wt%
Relative content
of N/wt%
Relative content
of S/wt%
Atomic ratio
of C/N
Atomic ratio
of C/S
d
002
/A
L
c
/A