Crosslinked inter penetrating network of
sulfonated styrene and sulfonated PVdF-co-HFP as
electrolytic membrane in a single chamber
microbial fuel cell†
Vikash Kumar, Piyush Kumar, Arpita Nandy and Patit Paban Kundu
*
In the present study, semi-IPN membranes of sulfonated styrene (SS) and sulfonated PVdF-co-HFP
membranes have been analyzed as a polymer electrolyte membrane in single chamber microbial fuel
cells (MFCs). 5%, 10%, 20% and 30% sulfonated styrene (SS) with varying concentrations of divinyl
benzene (DVB) have been polymerized in the presence of sulfonated PVdF-co-HFP to prepare SPS-
0 (0% SS), SPS-5 (5% SS), SPS-10 (10% SS), SPS-20 (20% SS) and SPS-30 (30% SS) membranes,
respectively. Progressive improvements in membrane properties were observed with increasing SS and
DVB concentrations, where excess DVB (<0.8 wt% of SS) resulted in increased crosslinks within the
membrane structure. This eventually impeded the membrane properties and altered their rigidity. The
membranes were characterized for their ion exchange capacity (IEC) and proton conductivity; IEC value
of 0.39 meq g
1
, 0.42 meq g
1
, 0.47 meq g
1
, 0.54 meq g
1
and 0.63 meq g
1
and proton conductivity
of 3.23 10
3
, 1.06 10
2
, 1.87 10
2
, 2.47 10
2
and 1.61 10
2
S cm
1
were observed for SPS-
0 (0% SS), SPS-5 (5% SS), SPS-10 (10% SS), SPS-20 (20% SS) and SPS-30 (30% SS) membranes. The
membranes were sandwiched as membrane electrode assemblies (MEA) and employed in single
chamber MFCs with open air cathode to analyze their overall performance outputs. It was observed that
amongst these membranes, the MFC with SPS-20 membrane showed the maximum power and current
density of 447.42 22 mW m
2
and 1729.63 87 mA m
2
with an overall 91.27% COD removal in 28
days of operation, using electrogenic mixed firmicutes as biocatalysts. Overall, this study reveals the
relevance of semi-IPN membranes of sulfonated styrene (SS) and sulfonated PVdF-co-HFP in MFC
applications for harvesting bio-energy.
1. Introduction
The vast majority of the advances made in MFCs have occurred
in the last 5 to 10 years. Bennetto et al. were one of the rst
groups which consistently pursued MFC research in the 1980s
and 1990s.
1,2
In addition several studies on alternative polymer
electrolyte membranes (PEMs) and their optimization have
been conducted. A suitable replacement for the high cost per-
uorinated membranes as PEM has always been a requisite in
fuel cell technology. Some polymeric materials like polystyrene,
polyether ether ketone (PEEK), poly (arylene ether sulfone),
phenylated poly sulfone, polyphosphazenes, polyimides, poly(4-
phenoxybenzoyl-1,4-phenylene), polybenzimidazole (PBI), low
density polyethylene (LDPE), high density polyethylene (HDPE)
and polypropylene (PP) have been widely studied.
3–6
Fundamentally, any ion permeable material can function as a
barrier and serve as a PEM in fuel cells; for comparison, Kim
et al. equated cation-exchange, anion exchange, and ultra
ltration (molecular cut-offs of 0.5, 1, and 3 kilodaltons)
membranes to determine their effects in MFC performance.
7–9
Similarly, other PEMs using different catholytes e.g.; ferricya-
nides have been analyzed in dual chamber MFCs.
10–12
Recently,
a group led by S. Ayyaru developed a sulfonated polystyrene–
ethylene–butylene–polystyrene (SPSEBS) membrane as an
alternative of Naon membrane.
13
SPSEBS membranes were
found to be butylene–polystyrene (SPSEBS) membrane as an
alternative of Naon membrane.
13
SPSEBS membranes were
found to be producing 106.9% higher power density and lower
internal resistance in comparison to Naon 117 in a single
chamber MFC (SCMFC). S. Ayyaru and S. Dharmalingam also
carried out the sulfonation of polyether ether ketone (PEEK)
and used it as a proton exchange membrane (PEM) in a single
chamber MFC (SCMFC).
14
MFC with the SPEEK membrane were
found to produce approximately 55.2% higher power density
than Naon-117. In another study, the performance of an anion
Advanced Polymer Laboratory, Department of Polymer Science & Technology,
University of Calcutta, 92 A. P. C. Road, Kolkata-700009, India. E-mail: ppk923@
yahoo.com; Fax: +91-33-2352-510; Tel: +91-33-2352-510
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c5ra03411f
Cite this: RSC Adv. , 2015, 5, 30758
Received 24th February 2015
Accepted 20th March 2015
DOI: 10.1039/c5ra03411f
www.rsc.org/advances
30758 | RSC Adv. , 2015, 5, 30758–30767 This journal is © The Royal Society of Chemistry 2015
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