DOI: 10.1002/slct.

201600050

Full Papers

z Energy Technology & Environmental Science

Cardanol benzoxazine-Sulfur Copolymers for Li-S batteries:

Symbiosis of Sustainability and Performance
Swapnil Shukla+,[a] Arnab Ghosh+,[b] Uttam Kumar Sen,[b] Prasun Kumar Roy,[c] Sagar Mitra,*[b]
and Bimlesh Lochab*[a]
A sulfur-rich copolymer is synthesized via a sustainable, ecofriendly approach using two major wastes namely, elemental
sulfur (industrial waste) and cardanol (agro waste) and its application as cathode active material in Li S battery. The presence
of chemically bound sulfur (90 wt%) utilising cardanol (10 wt%)
derivative in the copolymer (S90) showed a reduction in the active material dissolution into the electrolyte. In addition, the organic sulfur units get dispersed into the insoluble/insulating Li2
S2/Li2S phase and thus found to suppress their irreversible dep-

osition. Li S battery based on S90/multi-walled carbon nanotubes (MWCNT) (10 wt%) exhibited a reversible capacity of
1302 mAh g 1 at 2nd cycle, maintaining a high reversible capacity of 928 mAh g 1 after 70 cycles at a relatively constant
coulombic efficiency over 99 % at current rate of 200 mA g 1.
At 1000 mA g 1 current rate, the composite cathode delivered
a reversible capacity of 697 mAh g 1 at 2nd cycle and retained
75 % of its initial capacity even after 180 cycles.

1. Introduction

terial but is also directly associated with the irreversible deposition of insoluble Li2S2/Li2S on the electrodes.[8] The deposition
of insoluble/insulating Li2S2/Li2S could block the electronic as
well as ionic transport, which leads to rapid capacity fading and
poor cell performance. One of the most widely explored strategies, amongst others[9] is aimed at resolving dissolution issues
via preparation of nanostructured sulfur/carbon composites[10]
by melt-diffusion strategy, so as to encapsulate the active S as
well as intermediate polysulfides. Physical encapsulation of sulfur has been attempted utilizing various 3-D porous framework
of metal oxides, MOF, PAF, graphene based nanocomposites as
polysulfide reservoirs.[11] However, these strategies demand expensive starting materials, elaborate synthetic procedure, prolonged reaction time with high temperature and sophisticated
cell configuration. All such processes are cost effective, timeconsuming, and associated with environmental issues during
disposal of device after its usage. Moreover, these reservoirs
composed of physically bound sulfur which may leach over
time and thus affect the performance of the device. Therefore,
alternative simplistic methodologies are required to provide
commercially viable solution to chemically bind S in a sustainable manner for Li S batteries. Recently, Pyun and co-workers
synthesized a sulfur-rich copolymer via inverse vulcanization of
S utilising an organic monomer, 1,3-diisopropenylbenzene (DIB)
with promising potential as a polymeric cathode material in Li
S batteries.[12] This sulfur-rich copolymer exhibited the highest
specific capacity (~ 1100 mAh g 1 at 1st cycle and 823 mAh g 1
after 100 cycles) amongst polymer based cathode. Gao et al.
utilized DIB monomer followed by thiol-ene and Menschutkin
quaternization reactions demonstrating solution processable
sulfur copolymers as cathode-active materials.[13] Subsequently,
the work was extended to a similar class of petro-based monomers and polymers, viz. 1,3-diethynylbenzene,[14] 1,4-diphenylbutadiyne,[15]
carbyne-polysulfide
polymers,[16]
poly[17]
thiophenes etc.

Elemental sulfur (S) is one of the major by-products of petroleum refining industries, formed during hydrogen sulfide cleanup processes.[1] The existing usage of S in commodity chemical
production and rubber vulcanization accounts for less than
510 wt% than its annual production. As a result, concerns over
piling-up of unutilized sulfur as a hazardous irrepressible waste
entity has risen recently.
The abundance (~ 70 MT annum 1) and properties like high
electrochemical capacity[2] and high refractive index[3] merits
the exploration of S as a polymeric feedstock, which still remains a challenge[4] despite numerous advances. [1a, 5]
Elemental sulfur appeared as a promising candidate for Li
S energy storage devices due to its high theoretical energy
density (2600 Wh kg 1), appreciable specific capacity (1672
mAh g 1),[6] and relatively low cost ($ 0.57 kg 1). Despite these
advantages, the commercialization of Li S batteries is hindered
due to the problems of low structural integrity and relative
density of reactants, and its simultaneous dissolution in the
electrolyte [7] affecting cyclability and performance. The dissolution of polysulfides not only leads to the loss of active ma[a] S. Shukla,+ Dr. B. Lochab
Department of Chemistry, School of Natural Sciences
Shiv Nadar University, Gautam Budh Nagar, UP 201314, INDIA
E-mail: bimlesh.lochab@snu.edu.in
[b] A. Ghosh,+ Dr. U. K. Sen, Prof. S. Mitra
Electrochemical Energy Storage Laboratory, Department of Energy Science and Engineering, IIT, Bombay, Powai, Mumbai 400076, INDIA
E-mail: sagar.mitra@iitb.ac.in
[c] Dr. P. K. Roy
Centre for Fire, Explosive and Environment Safety, DRDO, Timarpur, New
Delhi 110054, INDIA.
[+] Authors SS and AG are equally contributed to this manuscript
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/slct.201600050

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Motivated by these works, here we report the synthesis of
sulfur copolymer by inverse vulcanization from two waste materials: sulfur, a petroleum waste and cardanol, an agro waste.
Cardanol was chemically modified to benzoxazine monomer
(Bzc) via one-pot solventless synthetic route.[18] Inverse vulcanization of sulfur was facilitated by Bzc using bulk polymerization to form random sulfur copolymers, poly(S-r-Bzc). The
sulfur-rich copolymer with 10 wt% Bzc (S90) was used as the
cathode material in Li S batteries. The chemical attachment of
sulfur atoms with the organic part in sulfur copolymer was
found to reduce the active material dissolution into the electrolyte. Since copolymers synthesized are insulating in nature,
therefore incorporation of conducting nano-filler, multi-walled
carbon nanotubes (MWCNT) showed an enhancement in specific capacity with an improved rate performance.

Scheme 1. Schematic illustration of poly(S-r-Bzc) copolymer synthesis.

2. Results and Discussion

Elemental sulfur (S) mainly consists of S8 rings, which melt at
120124 8C followed by ring opening polymerization (ROP) at
159 8C. This leads to the formation of linear polysulfane di-radical chains reaching their maximum chain length at 185 8C and
truncating subsequently with a further increase in temperature.
In literature, S8 has been copolymerized with petro-origin monomers which traps the growing -(S)n- di-radical shifting the
equilibrium in forward direction.[12] Cardanol, an agro-waste
with its reactivity towards free radical reactions, high temperature stability and non-volatility comes up as a viable and sustainable alternative for the replacement of petro-based monomers.[19] However, the presence of phenolic groups have an
inhibitory effect towards the growth of the polymeric chain
due to the formation of resonance stabilized phenoxy radicals.
This has been countered by conversion of phenolic group to
oxazine ring forming benzoxazine (Bzc) monomer using solventless method reported previously by our group (Figure S1).[18, 20] In addition, Bzc owing to its low viscosity (145
mPa s at 43 8C), acts as a reactive diluent preventing viscosity
build up at higher weight percent of sulfur in the feed ratio
allowing higher conversion yields of the copolymers. This work
explores the potential of sulfur, an industrial waste and cardanol, an agro-waste towards the synthesis of sustainable random
copolymers, poly(S-r-Bzc). A schematic illustration for the formation of copolymers is shown in Scheme 1.
In order to ensure the viability of large scale commercial
applications, cardanol which is a mixture of monoene (39 %),
diene (18 %) and triene (25 %), and unidentified product (rest)
was used without any further purification.[20] Elemental sulfur is
initially heated to 185 8C to obtain linear polysulfane di-radicals,
which is subsequently copolymerized with Bzc. Interestingly,
Bzc exhibits excellent miscibility with molten sulfur, under the
experimental conditions employed. The structure of Bzc offers
a multitude of reaction sites. Bzc can react with sulfur radicals
at five probable sites, namely at the double bonds (addition reaction), benzylic, allylic and oxazine ring carbon (substitution
reaction), and ring opening of benzoxazine i. e., via OBERS
(Opening of Benzoxazine Rings by Sulfur radicals) mechanism,
as illustrated in Scheme 2. The devised synthetic strategy for
ChemistrySelect 2016, 3, 594 600

Scheme 2. Proposed mechanisms for the formation of interlinks of polysulfane radicals with Bzc.

both monomer and copolymer formation adapts to the principles of sustainability on numerous counts namely utilization of
waste reserves as feedstock, solventless strategies both in the
case of monomer and copolymer synthesis, one-pot atom
economized reaction, no evolution of toxic waste and the only
by-product of the reaction is water. Copolymer samples designated as S90 and S50 with the different feed ratio of S: Bzc
namely 90:10 and 50:50 were prepared respectively. The yields
of the products were found to be quantitative with appreciable
sustainable content. Cardanol is the sustainable content in Bzc
preparation. Therefore, the conversion of sustainable feedstock
in Bzc and S90 copolymer synthesis is 72 % w/w [(MW of cardanol/ MW of Bzc) * 100] and 97.2 % w/w [90 % S + (10 % of sustainable content in Bzc)] respectively. The copolymer S90 was
subsequently used as an active material for Li S battery due to
its higher sulfur content.
During the S and Bzc reaction, the yellow colour of S
changed to deep-orange colour (185 8C) before the addition of
Bzc. Upon addition of Bzc, the reddish brown biphasic medium
changed to a monophasic syrupy dark brown colour suggesting polymerization. The copolymers were heated at 110 8C in
vacuo for 24 h to sublime any unreacted sulfur.[21] At this temperature, a variation in melting behaviour without any weight
loss is observed. The synthesized copolymers exhibited sol595

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ubility in chloroform and tetrahydrofuran (THF) (Figure 1a) and
were found to be insoluble in water, methanol, ethanol and di-

Figure 1. (a) Solutions of copolymers (30  2 mg/mL) in THF after sonication

for 4 minutes. (b) Normalised UV-visible spectra of elemental sulfur (S), Bzc,
and copolymers S50 and S90 in chloroform. (c) Raman spectra of elemental
sulfur and copolymer samples and Bzc. (d) FT-IR spectra of Bzc and copolymers (S90 and S50).

methyl sulfoxide (DMSO). The enhanced solubility of copolymers is attributed to the presence of chemically-linked cardanol
units in between the polymeric sulfur domains. The solubility of
copolymers permitted the structural characterization by ultraviolet-visible (UV-visible) and 1H- and 13C- NMR (proton and carbon nuclear magnetic resonance) spectroscopy studies. UV-visible spectroscopy (Figure 1b) of S showed a maximum at 240,
263 and a shoulder at 275 nm whereas Bzc showed maxima at
242 nm with a shoulder at 268 nm. In addition to these peaks,
the copolymers S90 and S50 revealed an additional shoulder at
~ 340 nm. The different UV-visible characteristics of S90 and
S50 as compared to S and Bzc suggested the formation of polymer architecture. Raman spectra of S, Bzc and copolymers are
shown in Figure 1c. Elemental sulfur showed the characteristic
peaks at 150 (n8: SSS bending), 220 (n2: SSS bending) and
472 cm 1 (n1: SS stretching vibration) accounting for the presence of S S bonds.[2223] On the other hand, Bzc showed absorption peaks in the region 750770, 10001750 and
2800 cm 1. The characteristic peak at 750770 cm 1 is assigned
to the ring breathing mode of benzoxazines.[24] The copolymers
S50 and S90 showed no such peak in 750770 cm 1 but a substantial decrease in the peak intensity in the region
10001750 cm 1 which revealed the participation of Bzc in the
copolymer formation. The Fourier transform-infrared (FT-IR)
spectroscopy spectra of poly(S-r-Bzc) copolymers and Bzc monomer are shown in Figure 1d. In comparison to Bzc, the appearance of a new peak in copolymers at ~ 658 cm 1 support the
formation of the C S bond in the copolymers.[25] The absorption band at 3008 cm 1 (aryl-H and C=C-H stretch), and at
1626 and 623 cm 1 (C=C and vinyl group) in Bzc nearly disChemistrySelect 2016, 3, 594 600

appeared and peaks at 995 cm 1 (out-of-plane bending vibrations of C H bond due to alkylene double bond)[20] also
showed a lowering in intensity suggesting involvement of double bond of alkylene chain in reaction with the polysulfane diradical. Simultaneously, the characteristic bands at 1240, 1030
and 960 cm 1 due to oxazine ring also showed a reduction in
intensity suggesting that the oxazine ring also undergoes ring
opening reaction with polymeric sulfur free radicals forming a
more inter-linked network. The oxazine ring opening was further suggested due to appearance of peak at 3400 cm 1 due to
phenolic OH groups. In literature, ring opening reaction of
benzoxazines with thiols is also reported.[26] Hence, the ring
opening of benzoxazine cardanol based monomer in our case,
is said to be proceeded also via opening of benzoxazine rings
by sulfur radicals (OBERS) mechanism (Scheme 2, V). The 1H NMR of Bzc, S50 and S90 copolymers are shown in Figure S2.
The conversion of cardanol to Bzc resulted in formation of benzoxazine ring as confirmed by the appearance of characteristic
signals at 4.57 ppm (s, ArCH2N, labelled as a) and 5.37 ppm
(olefin, ArOCH2N labelled as b, 79). In addition, Bzc also
showed signals corresponding to the 15-carbon long alkylene
chain (0.8 - 2.9 ppm, labelled as 1 - 6 and 56 ppm labelled as
7 - 9) and aromatic hydrogens (6.6 - 7.3 ppm). 1H - NMR of
both S50 and S90 confirmed the absence of any unreacted Bzc
monomer in the copolymers. As compared to Bzc, the copolymers showed absence of protons due to allylic (labelled as 5
and 6), benzoxazine ring (ArCH2N and ArOCH2N) and double
bonds at 2.15, 2.9, 4.5, and 5.0 - 5.4 ppm, respectively and variation in position of benzylic (2.6 ppm, labelled as 4) and aromatic protons (6.5 7.5 ppm) suggesting reaction of sulfur
radicals at these positions in Bzc. In addition, some new signals
are observed at 2.9-4.4 ppm (inset Figure S2) which corresponds to methylene peaks in the copolymer which are bonded to sulfur co-monomer units.[4b, 27] The signal at 8.8 ppm can
be due to phenolic OH group obtained due to ring opening
of benzoxazine ring via OBERS reaction (Scheme 2, V). In addition, 1H - NMR showed broadening of signals indicating polymerization under the reaction conditions employed. Solution
13
C - NMR spectroscopy (Figure S3) further provide structural
evidence for olefinic and benzoxazine moiety consumption and
formation of C S bonds during copolymerisation. The absence
of benzoxazine resonances at 50.0 and 79.5 ppm (labelled as a
and b respectively) in copolymers confirms the ring opening
reaction. The alkylene hydrogens due to long aliphatic chain in
Bzc i. e. 2538 (labelled as 3 - 6) (Figure S3a), 118 (labelled as
7) and 126133 ppm (labelled as 8) (Figure S3b) showed
variation in copolymers confirming their involvement in copolymerisation reaction. The C S bond formation is confirmed by
appearance of resonances at 56.7, 52, 46 ppm (inset Figure S3a) and 36.3 ppm (Figure S3a). The signal at 56.7 ppm is
assigned to the newly formed N-CH2-S bonds in copolymers.
The N-CH2-S signal is upfield than N-CH2-O (labelled as b in
Bzc) due to lower electronegativity of S as compared to O.
The alkylene C S bond appeared at different resonances 52, 46
and 36.3 ppm may be ascribed due to both their existence in
different environment and association with different chain
lengths of polysulfane units. Aromatic carbons in copolymers
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also showed variation and appeared in different range
113165 ppm (Figure S3b) as compared to Bzc. Based on the
NMR, FT-IR and Raman studies the copolymer structure can be
represented as (a summation of structural changes as depicted
in Scheme 2) shown Figure S4. The molecular weight of synthesized copolymers was found to be dependent on the feed
ratio of the reactants. Gel permeation chromatography (GPC)
traces of S90 and S50 are shown in Figure S5. S90 and S50
showed a weight average molecular weight of 1.81 x 106 and
1.64 x 104 gmol 1 and a polydispersity index (PDI) of 3.7 and 4.1
respectively. A very high molecular weight in S90 without much
variation in PDI as compared to S50 suggested existence of
longer polymer chain lengths in the former. It further demonstrated the capability of higher functionality of Bzc as a linker
to facilitate the growth of sulfur radical polymer chains even at
lower weight percent (10 wt%). Thermal characterization of copolymers and monomers is carried out using differential scanning calorimetry (DSC) (Figure 2a) and thermo-gravimetric anal-

dation, with a sharp mass loss at 200 8C, due to sublimation of

sulfur. PBzc exhibited simultaneous two-step decomposition at
280420 8C and 420800 8C, respectively. The copolymer samples containing lower percentage of Bzc i. e. S90, exhibited athree step decomposition viz. 240360 8C, 360500 8C and
500680 8C, respectively. S50 exhibited a slightly higher thermal
stability than S90 and is comparable to PBzc which may be due
to higher weight percent of Bzc. Figure S8 represents the
powder X-ray diffraction (PXRD) pattern of the copolymers and
S to demonstrate the incorporation of sulfur in the as synthesized copolymers. Energy dispersive X-ray (EDX) spectra and elemental mapping of S90 copolymer (Figure S9) confirmed a
uniform distribution of sulfur throughout the copolymer. Elemental analysis of S50 and S90 copolymer showed a sulfur content of 53.3 and 92.1 wt% respectively.
The cyclic voltammetry (CV) curve of S90 electrode (electrode-A) showed three reduction peaks and one oxidation peak
(Figure 3a) in scan range of 1.2-2.8 V. The reduction peaks at

Figure 2. Thermal behaviours (a) DSC traces of S, Bzc and copolymers and
(b) TGA traces of S, copolymers and polybenzoxazine (PBzc).

ysis (TGA) (Figure 2b). DSC analysis of S and Bzc were

compared with the copolymers to understand the effect of sulfur on the curing exotherm of Bzc. The curing behaviour of cardanol derived benzoxazines has been discussed in our previous
papers.[18, 20]
The dynamic DSC trace of Bzc clearly revealed a single curing exotherm, with an onset and peak temperature as 242 and
263 8C respectively (Figure S6). Elemental sulfur exhibited two
melting transitions at 109 8C and 119 8C, which can be attributed to the existence of different phases (Figure 2a). The copolymers S50 and S90 exhibited melting transitions confirming
the existence of crystalline domains. The melting transition of
S50 is broad as compared to S90 with a peak maximum at
102 8C whereas S90 showed two sharp endotherm transitions
at 104 and 116 8C. It is reported that DIB (10 wt%) copolymerized S (90 wt%) showed a melting transition at 113.6 8C.[12a]
Our studies clearly confirmed that curing temperature of benzoxazine is lowered in the presence of sulfur, which presumably
takes place during copolymer formation at 185 8C. This is further confirmed by NMR studies (Figure S2 and S3) where the
signals associated with the benzoxazine rings were not observed. DSC thermogram of second cycle of S90 copolymer is
also shown in Figure S7.The thermal stability of copolymers
S50 and S90 was compared with S and neat polybenzoxazine
(PBzc) (Figure 2b). Pristine sulfur exhibited a single-step degraChemistrySelect 2016, 3, 594 600

Figure 3. (a) Cyclic voltammetry (1st cycle) of S90 copolymer [electrode-A] at

a scan rate of 20 mV s 1 and within the potential range 1.2-2.9 V. (b) Illustration of first discharge profile for electrode-A at 200 mA g 1 current rate. (c)
Chargedischarge profile of electrode-A at 200 mA g 1 current rate. (d) Cycling experiment of S90 copolymer (green) and elemental sulfur (orange) at
200 mA g 1 current rate.

2.35-2.4 and 2.0-2.05 V are related to the conversion of sulfur to

higher order linear polysulfides and their subsequent reduction
to Li2S2 or Li2S respectively. The third reduction peak in the potential range of 1.65-1.7 V could be attributed to the irreversible decomposition of LiNO3 in the electrolyte.[28] One intense
oxidation peak at 2.3-2.35 V in the subsequent charge process
corresponded to the oxidation of the discharged products. The
cathodic and anodic peak position differences were observed
between the initial CV curves of S and S90 (Figure S10). This
indicates a distinctly different electrochemical behaviour of S90
from chemically unbound sulfur i. e. S. This initial electrochemical difference of S from S90 can be explained by the
presence of C S covalent bonds in addition to the existing S-S
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framework in the latter. Figure 3b depicts the 1st discharge profile of S90 (electrode-A) from open circuit voltage (OCV) to
1.5 V vs. Li/Li + at 200 mA g 1 rate. The 1st discharge profile exhibited three discharge plateaus at around 2.28, 2.0 and 1.7 V
which is in good agreement with the three reduction peaks observed in the 1st cycle of CV curve (Figure 3a). The charge-discharge profiles corresponding to 1st, 2nd, 10th and 20th cycles of
electrode-A at 200 mA g 1 are shown in Figure 3c. It can be observed (Figure 3c) that there is a third plateau at around 1.7 V
in 1st discharge profile (corresponding to the extra peak at
same voltage range in 1st cycle of CV curve) which gets reduced from the 2nd cycle onwards. The plateau at 1.6-1.7 V is
attributed to an irreversible electrochemical decomposition of
LiNO3 to form a solid electrolyte interphase (SEI), resulting in
low coulombic efficiency of the first cycle (ca. 85 %). However,
from 2nd cycle onwards the coulombic efficiency was found to
be > 98.5 %. The cycling performance of electrode-A and S
electrode at 200 mA g 1 is shown in Figure 3d. The electrode-A
showed a reversible discharge capacity of 892 mAh g 1 at 2nd
cycle and 528 mAh g 1after 50 cycles. A sharp capacity fading
for both the electrodes based on S90 and S (Figure 3d) was observed in the initial cycles. However, the S90 cathode showed
better stability in later cycles as compared to S cathode. The
better cycling performance of S90 cathode could be due to
chemical attachment of sulfur atoms with organic moiety (i. e.
Bzc). In addition, it can be observed that the S90 cathode retained greater degree of structural/mechanical integrity after
cycling, as compared to S-cathode (Figure S11). The retention
of mechanical integrity of the cathode fabricated from S90 copolymer, during cycling also may be one reason for its better
cycling performance in comparison to S cathode.
The initial capacity fading in electrode-A could be due to
the poor electronic conductivity and polymeric nature of
S90 active material. This may prevent the uniform distribution
of conductive carbon additive throughout the electrode. Subsequently the percolation network required to connect the
bulk of the material to the current collector for easy flow of
electrons may be affected. In order to address this fallacy,
MWCNTs were dispersed in S90 before electrode fabrication.
Electrodes were prepared using S90 with different wt% of
MWCNT, 5 wt% (electrode-B) and 10 wt% (electrode-C) respectively. Due to excellent electronic conductivity of carbon
nanotubes, an improved cycling stability and specific capacity
were observed for both the electrodes (Figure 4a). Electrode-B
showed a reversible discharge capacity of 970 mAh g 1 at 2nd
cycle and 720 mAh g 1 after 75 cycles. On the other hand, electrode-C showed a reversible capacity of 1310 mAh g 1 at 2nd cycle and 900 mAh g 1 after 75 cycles. From Figure 4a, it can be
seen that MWCNTs showed no contribution towards the capacity in the voltage range 1.5-2.6 V. Therefore, incorporation
of MWCNTs into the copolymer not only assisted in improving
the cycling stability and specific energy density, but also contributed towards the volume of the material in the circuit, that
was hitherto not exhibiting any lithium storage capacity.
In order to further interrogate the improved electrochemical properties of S90/MWCNT composite as active electrode material, additional electrochemical experiments were
ChemistrySelect 2016, 3, 594 600

Figure 4. (a) Cycling performance of electrode-B (violet), electrode-C (red)

and MWCNT (olive) at 200 mA g 1 within the voltage range 1.5-2.6 V. (b) Long
term cycling performance of electrode-B (violet) and electrode-C (red) at
1000 mA g 1 current rate. (c) Rate performances of electrode-A (green), electrode-B (violet) and electrode-C (red) at different current rates. (d) Ragone
plots (specific power density vs. specific energy density) of electrode-A
(green), electrode-B (violet) and electrode-C (red).

performed to examine rate performances of all three electrodes

(A, B and C) and extended cycling of electrode-B and electrodeC. At a higher current density of 1000 mA g 1, electrode-C delivered an initial 2nd cycle reversible capacity of 697 mAh g 1
and maintained a reversible capacity of 520 mAh g 1 after 180
cycles with capacity fading of 0.13 % per cycle (Figure 4b). The
nanocomposites of S90 with MWCNT also exhibited improved
rate performances as shown in Figure 4c and 4d.
Electrochemical impedance spectroscopy (EIS) characterizations of S electrode and electrode-A were carried out after
cycling to investigate the effect of organosulfur units in the copolymer. The EIS spectra (Figure 5a and 5b) of both the electro-

Figure 5. Nyquist plot of elemental sulfur and S90 copolymer electrodes (a)
before cycling and (b) after cycling (after 50 cycles at 200 mA g 1).

des after cycling were comprised of a high-frequency semicircle

related to the charge-transfer process[29] and a low frequency
straight-line corresponding to a semi-infinite Warburg diffusion
process.[30] The electrode-A showed a lower charge-transfer resistance and Warburg diffusion resistance after 50 cycles, which
can be accounted due to the presence of organosulfur units.[12b]
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Such units may get dispersed into the insoluble/insulating end
discharge product (Li2S2/Li2S) phase thus preventing their irreversible deposition on the electrodes.
Other major shortcoming associated with sulfur based cathode is its high self-discharge due to rapid dissolution of active
sulfur into electrolyte. To investigate the active material dissolution rate, for S electrode and S90 electrode (electrode-A),
charge-discharge cycling was performed after a rest time of
120 h (5 days). An electrolyte without LiNO3 additive was used
in this study to interrogate the effect of chemical confinement
strategy on active sulfur dissolution. From Figure S12, it can
be observed that the S90 electrode exhibited two distinct discharge plateaus while, S electrode showed only lower discharge plateau as OCV was less than the potential at which upper discharge plateau was observed. This demonstrates that in
S electrode, the unbound sulfur dissolved into electrolyte during rest time, resulting in a loss of the upper discharge plateau.
On other hand, S90 electrode showed a lower rate of active
material dissolution in same electrolyte which could be due to
chemical confinement of sulfur via inverse vulcanization. Therefore, the chemical attachment/confinement of sulfur in S90 copolymer has significantly lowered the self-discharge rate of Li
S batteries by reducing the active material dissolution into the
electrolyte.

3. Conclusions
In summary, a facile, scalable and sustainable approach for the
preparation of a chemically stable sulfur based polymer using
low utility resources namely, elemental sulfur and cardanol via
inverse vulcanization process has been demonstrated. The copolymer showed its utility as an active material for cathode in
Li S battery. The chemical confinement of sulfur in the copolymer by virtue of its organo-sulfur units has countered the irreversible deposition of moieties onto the electrodes and
showed a lower self-discharge rate of Li S batteries. Such advantageous characteristics permit the utility of poly(S-r-Bzc) as
available active material for a relatively low-cost, sustainable
and high performing cathodic material in Li S batteries. Therefore, the synthetic approach hence demonstrated may open
new-avenues for the waste materials utilization in sustainable
energy storage technology. A new class of monomer as a potential candidate for polymeric sulfur cathode was unearthed in
the current paper.
Supporting information for this article is given via a link at
the end of the document: Synthetic procedure and scheme of
Bzc. 1H- and 13C-NMR spectra of Bzc and copolymers (S90, S50).
Proposed structure of copolymer. GPC trace of Bzc and copolymers (S90, S50). DSC trace of Bzc and second scan of S90. Powder XRD pattern of elemental sulfur, S50 and S90 copolymers.
FE-SEM image, EDX spectra and elemental mapping of S90 copolymer. CV performances of both elemental sulfur and S90 copolymer electrodes. FE-SEM images of electrode surfaces for
both S and S90 copolymer cathodes before and after cycling.
First discharge profile for both S90 copolymer and S cathodes
after 120 h rest time. Performances comparison table of our

ChemistrySelect 2016, 3, 594 600

cathode material with recently reported sulfur-MWCNT composites.

Acknowledgements
The authors (SS, BL) would like to acknowledge the financial
support from Shiv Nadar University and DST/BL/2014/15 and
are thankful to AIRF, JNU for providing assistance in characterization facility and SCCPL, India for providing cardanol. The
authors (AG, UKS and SM) are thankful to the National Centre
for Photovoltaics Research and Education (NCPRE) Ministry of
New and Renewable Energy, Govt. of India and the project
DST/RCUK/SGES/2012/13 for providing financial and instrumental supports. The authors acknowledge the IRCC, IIT
Bombay for infrastructure facilities.
Keywords: cardanol benzoxazines
sustainability inverse vulcanization

Li S

battery

[1] a) M. Ksiazek, Compos. Part B: Eng. 2014, 62, 137142; b) A. N. Zagoruiko, Y. S. Matros, Chem. Eng. J. 2002, 87, 7388.
[2] a) X. Ji, K. - T. Lee, L. F. Nazar, Nat. Mater. 2009, 8, 500506; b) N. Jayaprakash, J. Shen, S. S. Moganty, A. Corona, L. A. Archer, Angew. Chem.
Int. Ed. 2011, 50, 59045908.
[3] J. J. Griebel, S. Namnabat, E. T. Kim, R. Himmelhuber, D. H. Moronta,
W. J. Chung, A. G. Simmonds, K.-J. Kim, J. V. D. Laan, N. A. Nguyen, E.
L. Dereniak, M. E. Mackay, K. Char, R. S. Glass, R. A. Norwood, J. Pyun,
Adv. Mater. 2014, 26, 30143018.
[4] a) L. B. Blight, B. R. Currell, B. J. Nash, R. T. M. Scott, C. Stillo, Brit.
Polym. J. 1980, 12, 511; b) Y. Ding, A. S. Hay, J. Polym. Sci. Part A: Poly.
Chem. 1997, 35, 29612968; c) S. Penczek, R. Slazak, A. Duda, Nature
1978, 273, 738739; d) T. Tsuda, A. Takeda, Chem. Commun. 1996,
13171318.
[5] a) K. Amine, R. Kanno, Y. Tzeng, MRS Bull. 2014, 39, 395401; b) J. Lim,
J. Pyun, K. Char, Angew. Chem. Int. Ed. 2015, 54, 212.
[6] a) D. Peramunage, S. Licht, Science 1993, 261, 10291032; b) G. Jeong,
Y. U. Kim, H. Kim, Y. J. Kim, H. J. Sohn, Energy Environ. Sci. 2011, 4,
19862002.
[7] A. Manthiram, Y. Fu, S.-H. Chung, C. Zu, Y. S. Su, Chem. Rev. 2014,
114, 1175111787.
[8] W. Cai, J. Li, G. Xu, H. Cheng, ChemElectroChem 2014, 1, 16621666.
[9] a) X. Liang, C. Hart, Q. Pang, A. Garsuch, T. Weis, L. F. Nazar, Nat.
Commun. 2015, 6, 56825688; b) A. Vizintin, M. U. M. Patel, B. Genorio,
R. Dominko, ChemElectroChem 2014, 1, 10401045; c) H. Chen, C.
Wang, Y. Dai, S. Qiu, J. Yang, W. Lu, L. Chen, Nano Lett. 2015, 15,
54435448; d) S. Chen, Q. Tang, X. Chen, A. Hu, W. Deng, Z. Liu, RSC
Adv. 2015, 5, 7413874143; e) C. Zhang, Y. Lin, J. Liu, J. Mater. Chem. A
2015, 3, 1076010766; f) X. Zhou, F. Chen, J. Yang , L. Ma, T. Bai, B.
Long, Q. Liao, C. Liu, Electroanal. Chem. 2015, 747, 5967.
[10] B. Zhang, X. Qin, G. R. Li, X. P. Gao, Energy Environ. Sci. 2010, 3,
15311537; b) C. Zhang, H. B. Wu, C. Yuan, Z. Guo, X. W. D. Lou,
Angew. Chem. Int. Ed. 2012, 51, 95929595.; c) S. Thieme, J. Brckner, I.
Bauer, M. Oschatz, L. Borchardt, H. Althues, S. Kaskel, J. Mater. Chem.
2013, 1, 92259234; d) D. W. Wang, Q. Zeng, G. Zhou, L. Yin, F. Li and
H. M. Cheng, I. R. Gentle, G. Q. M. Lu, J. Mater. Chem. 2013, 1,
93829394; e) B. Li, S. Li, J. Liu, W. Bo, S. Yang, Nano Lett. 2015, 15,
30733079.
[11] a) X. Ji, S. Evers, R. Black, L. F. Nazar, Nat. Commun. 2011, 2, 325331;
b) J. Zheng, J. Tian, D. Wu, M. Gu, W. Xu, C. Wang, F. Gao, M. H.
Engelhard, J. G. Zhang, J. Liu, J. Xiao, ACS Nano Lett. 2014, 14,
23452352; c) W. Cai, J. Li, Y. Zhang, G. Xu, H. Cheng, ChemElectroChem 2014, 1, 16621666; d) W. Chen, Z. Zhang, Q. Li, Y. Lai, J. Li
ChemElectroChem 2014, 2, 246252; e) G. Salitra, E. Markevich, A.
Rosenman, Y. Talyosef, D. Aurbach, A. Garsuch, ChemElectroChem 2014,
1, 14921496; f) F. Han, W. C. Li, D. Li, A. H. Lu, ChemElectroChem
2014, 1, 733740; g) B. Guo, T. Ben, Z. Bi, G. M. Veith, X. G. Sun, S.

599

 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Papers

[12]

[13]
[14]
[15]

[16]
[17]

[18]

Qui, S. Dai, Chem. Commun. 2013, 49, 49054907.; h) Y.-L. Ding, P. Kopold, K. Hahn, P. A. van Aken, J. Maier, Y. Yu, Adv. Funct. Mater. 2015,
26, 11121119; i) Z. W. Seh, W. Li, J. J. Cha, G. Zheng, Y. Yang, M. T.
McDowell, P. C. Hsu, Y. Cui, Nat. Commun. 2013, 4, 13311337; j) Y.
Huang, M. Zheng, Z. Lin, B. Zhao, S. Zhang, J. Yang, C. Zhu, H.
Zhang, D. Sun, Y. Shi, J. Mater. Chem. A 2015, 3, 1091010918; k) G.
Zhou, E. Paek, G. S. Hwang, A. Manthiram, Nat. Commun. 2015, 6,
77607771.
a) W. J. Chung, J. J. Griebel, E. T. Kim, H. Yoon, A. G. Simmonds, H. J.
Ji, P. T. Dirlam, R. S. Glass, J. J. Wie, N. A. Nguyen, B. W. Guralnick, J.
Park, A. Somogyi, P. Theato, M. E. Mackay, Y.-E. Sung, K. Char, J. Pyun,
Nat. Chem. 2013, 5, 518524; b) A. G. Simmonds, J. J. Griebel, J. Park, K.
R. Kim, W. J. Chung, V. P. Oleshko, J. Kim, E. T. Kim, R. S. Glass, C. L.
Soles, Y. E. Sung, K. Char, J. Pyun, ACS Macro Lett. 2014, 3, 229232.
Y. Wei, X. Li, Z. Xu, H. Sun, Y. Zheng, L. Peng, Z. Liu, C. Gao, M. Gao,
Polym. Chem. 2015, 6, 973982.
Z. Sun, M. Xiao, S. Wang, D. Han, S. Song, G. Chen, Y. Meng, J. Mater.
Chem. A 2014, 2, 92809286.
P. T. Dirlam, A. G. Simmonds, T. S. Kleine, N. A. Nguyen, L. E. Anderson, A. O. Klever, A. Florian, P. J. Costanzo, P. Theato, M. E. Mackay, R.
S. Glass, K. Char, J. Pyun, RSC Adv. 2015, 5, 2471824722.
B. Duan, W. Wang, A. Wang, Z. Yu, H. Zhao, Y. Yang, J. Mater. Chem. A
2014, 2, 308314.
P. T. Dirlam, A. G. Simmonds, R. C. Shallcross, K. J. Arrington, W.J.
Chung, J. J. Griebel, L. J. Hill, R. S. Glass, K. Char, J. Pyun, ACS Macro
Lett. 2015, 4, 111114.
B. Lochab, I. K. Varma, J. Bijwe, J. Therm. Anal. Calorim. 2010, 102,
769774.

ChemistrySelect 2016, 3, 594 600

[19] B. Lochab, S. Shukla, I. K. Varma, RSC Adv. 2014, 4, 2171221752.

[20] S. Shukla, A. Mahata, B. Pathak, B. Lochab, RSC Adv. 2015, 5,
7807178080.
[21] W. J. Chung, A. G. Simmonds, J. J. Griebel, E. T. Kim, H. S. Suh, I. - B.
Shim, R. S. Glass, D. A. Loy, P. Theato, Y. -E. Sung, K. Char, J. Pyun,
Angew. Chem. Int. Ed. 2011, 50, 1140911412.
[22] a) A. G. Kalampounias, K. S. Andrikopoulos, S. N. Yannopoulos, J. Chem.
Phys., 2003, 118, 84608467.
[23] R. Steudeland, B. Eckert, J. Chem. Phys. 2004, 121, 65736574.
[24] H. Ishida, T. Agag, Handbook of benzoxazine resins. Elsevier, Amsterdam,
2011.
[25] E. T. Kim, W. J. Chung, J. Lim, P. Johe, R. S. Glass, J. Pyun, K. Char,
Polym. Chem. 2014, 5, 36173623.
[26] a) Z. Beyazkilic, M. U. Kahveci, B. Aydogan, B. Kiskan, Y. Yagci, J. Polym. Sci. Part A: Polym. Chem. 2012, 50, 40294036; b) J. Narayanan, M. J.
Jungman, D. L. Patton, React. Func. Polym. 2012, 72, 799806.
[27] A. W. Kawaguchi, A. Sudo, T. Endo, ACS Macro Lett. 2012, 2, 14.
[28] a) S. S. Zhang, Electrochim. Acta 2012, 70, 344348; b) A. Rosenman, R.
Elazari, G. Salitra, E. Markevich, D. Aurbach, A. Garsuch, J. Electrochem.
Soc. 2015, 162, A470-A473.
[29] L. X. Yuan, X. P. Qiu, L. Q. Chen and W. T. Zhu, J. Power Sources 2009,
189, 127132.
[30] G. C. Li, G. R. Li, S. H. Ye, X. P. Gao, Adv. Energy Mater. 2012, 2, 1238
1245.

Submitted: January 22, 2016

Accepted: March 10, 2016

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