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Article history:
Received 22 July 2010
Received in revised form 15 July 2011
Accepted 18 July 2011
Available online 13 September 2011
Keywords:
Polyvinyl alcohol (PVA)
Sulfonated MWCNT
Fluorinated MMT
Polymer nano composite membrane
DMFC
a b s t r a c t
A new PEM composite membrane comprising of polyvinyl alcohol (PVA), sulfonic acid functionalized CNT and
uorinated MMT has been fabricated. Composite polymer membrane has been prepared by simple solution
casting method. Composite properties have been evaluated by using thermal gravimetric analysis (TGA),
scanning electron microscopy (SEM), and FTIR techniques. The proton conductivity, methanol crossover and
water uptake properties of newly fabricated membrane have been studied. The polymer membrane shows
good thermal properties. The water content is in the range of 3545%. Especially, it has been found that the
uorinated MMT used in this study plays a decisive role in water uptake and acts as a hydrophobic surface for
controlling the swelling. The proton conductivities and the methanol permeabilities of all the membranes are
in the range of 10 3 to 10 2 S/cm and 2.08 10 6 cm 2/s at room temperature, respectively.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Fuel cell technology is a benign process and has the potential to
become future generation green energy for portable electronics and
vehicle propulsion [13]. Now a day, research on the improvement of
polymer membrane for direct methanol fuel cell application is one of the
challenging assignments to resolve the balance between proton
conductivity and methanol crossover [46]. The large-scale commercial
utilization of Naon in DMFC causes some issues such as low power
density which is due to methanol crossover and dehydration at high
temperature [4,7]. Low cost membrane is also required for DMFC
commercial application without sacricing their properties. Reduction
of membrane cost could be achieved by using non-uorinated polymer
electrolytes with a cheaper polymer. From commercial point of view,
PVA is a possible candidate to be used as a membrane for DMFC because
of its low cost, good chemical stability, lm-forming ability, and high
hydrophilicity and availability of cross-linking sites to create a stable
membrane with good mechanical properties and selective permeability
to water [811]. Furthermore, the PVA polymer used is biodegradable,
nonhazardous, and environmentally benign [12]. PVA based composite
membranes if optimized may serve as a potential alternative protonconducting membrane for direct methanol fuel cell applications. Water
uptake is also important in determining the ultimate performance of
proton exchange membrane materials. In essentially all current polymer
based membrane, water is required to facilitate proton conductivity.
However, absorbed water also affects the mechanical properties of the
membrane by acting as a plasticizer, lowering the Tg and modulus of the
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(SSA) (10 wt.%) and the mixture was stirred at room temperature for
24 h. After that, the homogeneous solutions were poured onto a
plastic petridish. The cast polymer solutions were allowed to dry in air
at room temperature for 24 h. The fully dried membranes were peeled
off away from the petridish, and then heated in an oven at 120 C for
1 h to make cross linking reaction. The membranes were stored in DI
water before use. The membrane thickness was in the range of 100
150 m.
2. Experimental
2.1. Materials
Polyvinyl alcohol (PVA) (molecular weight of 31,00050,000),
sulfosuccinic acid (SSA) (70 wt% in water solution), Hexauorophosphoric acid (65 wt.% solution in water), Montmorillonite K10, all the
chemicals were purchased from Aldrich company. Multi walled CNT
was purchased from EM Power, South Korea.
2.5. FTIR
Fourier transform infrared (FT-IR) spectroscopic measurements
were performed using a JASCO FT-IR 300E device.
2.6. Thermogravimetric analysis
Wwet Wdry
X 100:
Wdry
L
RWD
A P
C t to
VBL A
23
24
100
PVA polymer
PVA nano composite
Weight (%)
80
observed for membrane 1 (PVA/S-MWCNT/F-MMT/SSA). The compatibility of membrane 2 (without F- MMT) is still uniform and
homogenous. This indicates that the nano F-MMT was not properly
dispersed within the PVA polymer matrix, as shown in Fig. 3.
However, it is clearly seen that cracks have been generated on the
top of the surface in the both type (with or without MMT) of
membrane. The degree of sulfonation and uorination has been
calculated by EDX measurement as shown in Fig. 4, 0.16 wt.% of the
sulfur is attached to the MWCNT by this method (Fig. 4 a). Indeed the
amount of sulfonation is low and can be systematically varied by
changing the concentration of ammonium sulfate. The degree of
uorination on the MMT is 0.62 wt.% (Fig. 4b).
3.4. Water uptake
60
40
20
0
0
100
200
300
400
500
600
700
800
Temperature (oC)
Fig. 2. TGA plot of PVA and nano composite membrane.
900
25
26