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Solid State Ionics 201 (2011) 2126

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Solid State Ionics


j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s s i

PVA nano composite membrane for DMFC application


Jatindranath Maiti, Nitul Kakati, Seok Hee Lee, Seung Hyun Jee, Young Soo Yoon
Energy and Sensor Laboratory, School of Materials Science and Engineering, Yonsei University, 134 Shinchon Dong, Seoul 120-749, South Korea

a r t i c l e

i n f o

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

Corresponding author. Tel.: + 82 2 2123 2847; fax: + 82 2 365 5882.


E-mail address: yoonys@yonsei.ac.kr (Y.S. Yoon).
0167-2738/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2011.07.013

membrane [13]. Careful control of water uptake is critical for reducing


adverse effects of swelling and degradation of the mechanical properties
of the membrane in humid environments, as well as inducing stresses
between the membrane and the electrodes. Both conductivity and water
uptake rely heavily on the concentration of ion conducting units (most
commonly sulfonic acid) in the polymer membrane. Varying the ion
content of the membrane can control both its water uptake and
conductivity. While it is desirable to maximize the proton conductivity
of the membrane by increasing its ion content (decreasing equivalent
weight), other physical properties must be considered. Too many ionic
groups will cause the membrane to swell excessively with water, which
compromises mechanical integrity and durability. Polymer swelling can
be reduced by crosslinking with suitable crosslinking agent, whereas
proton conductivity can be increased by the formation of hybrid
composites by the incorporation of proton conductors such as sulfonic
acids [14]. In the past few decades, nano clay (MMT) [1517] and carbon
nanotubes (CNTs) [18] were studied intensively as typical nano llers to
incorporate into polymer matrices. The dispersion of nano clay in
polymer can result in a reduction of moisture absorption, thermal
stability, barrier properties, and ammability as well as signicant
enhancements of modulus, strength, and hence overall performance of
nanocomposite [16]. Furthermore, clay is inexpensive relative to
traditional reinforcing materials and environmentally friendly. The
sulfonic acid functionalized carbon nano tube based polymer composites
has been revealed a remarkable improvement of proton conductivity
and also capable of increasing the mechanical stability along with a
decrease in methanol permeability [18].
Herein we present a chemical strategy to increase the sulfonic acid
content and better channel like network for proton transport of PVA
membrane by incorporating sulfonic acid functionalized multi walled
carbon nanotubes. The membranes with highly hydrophobic

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J. Maiti et al. / Solid State Ionics 201 (2011) 2126

uorinated surface exhibited improved proton conductivity and


reduced methanol permeability at a relatively low water uptake
[19]. The hydrophobic blocks can serve as matrix for mechanical
strength and limited swelling. We have integrated both hydrophobic
surface and acidic group by using two different nano ller. The
strategy of using both sulfonated CNT and uorinated MMT to enrich
proton conductivity, self humidication, thermal and barrier properties of the membrane might be helpful in alleviating many signicant
difculties associated with fuel cell.
In this work, composite membrane composed of polyvinyl alcohol
(PVA), sulfonic acid functionalized CNT and uorinated MMT have
been prepared by simple solution casting method. This is a new
approach to add two different functionalized nano ller into same
matrix for studying the water uptake, proton conductivity, methanol
permeability and thermal stability of composite membrane.

(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

The membrane thermal stability was evaluated by using a


thermogravimetric analyzer TA Q 50 system TGA. The samples were
scanned at a heating rate of 10 C/min under ow of nitrogen.

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

2.7. Surface morphology and chemical composition characterization


A scanning electron microscope with an energy dispersive X-ray
spectroscopy system (FESEM JSM-6700F, JEOL coupled with INCA
energy dispersive X-ray spectroscopy) was used to evaluate the
membrane microstructure and chemical composition.

2.2. Sulfonation of MWCNT


2.8. Water uptake
First, purication of MWCNT (1 g) was carried out by reuxing the
CNT with 200 ml of 60% HNO3 at 120 C for 4 h to remove the metal
particles. The mixture was diluted, centrifuged and washed with
excess DI water. The puried product was dried at 70 C in vacuum
oven for overnight.
Second, the sulfonation of MWCNT was executed in presence of
(NH4)2SO4 [20]. 0.25 g of ammonium sulfate dissolved in 5 ml DI
water was mixed with 0.25 g MWCNT. After that, the mixture was
well agitated; it was heated at 235 C for as long as 30 min. It is
believed that at 235 C, (NH4)2SO4 decomposes to generate SO3, and
the formed SO3 reacts with carbon via its surface hydrogen atoms to
have SO3H groups linked onto it [21].
NH4 2 SO4 2NH3 + H2 O + SO3

CarbonH + SO3 CarbonSO3 H:

2.3. Fluorination of MMT


MMT (1.2 g) was dispersed in 100 ml of deionized water using an
ultrasonic bath. The suspension was stirred with 1 N H2SO4 (20 ml) at
room temperature for 2 h in order to increase its surface activity and to
remove impurities. The mixture was washed with excess deionized
water and dried in vacuum oven at 70 C for 12 h. 2 ml hexauorophosphoric acid (60 wt.% solution in water) and MMT (1 g) in 5 ml water
were mixed and the mixture was stirred using a Teon beaker at room
temperature for 24 h [22]. The product was washed in a mixture of
isopropyl alcohol and water (1:1) for preventing agglomeration of MMT
particle resulting in higher surface area product. Finally the material was
dried in vacuum oven at 70 C for 12 h.

The water uptake of the membranes was determined by


measuring the change in the weight before and after the hydration.
Pre-dried membranes were immersed in deionized water for 24 h,
and then surface attached water onto the membrane was removed
with lter paper. After that, the wetted membrane weight (Wwet) was
determined as quickly as possible. The weight of dry membrane
(Wdry) was determined after completely drying it in vacuum at 60 C
for 24 h. The water uptake (%) value of the membranes was calculated
by using the following equation
Water uptake % =

Wwet Wdry
X 100:
Wdry

2.9. Proton conductivity measurements


Proton conductivity measurements were carried out at ambient
temperature after equilibrating the membrane in de-ionized water for
1 day. The proton conductivity cell was composed of two 5 mm
diameter platinum electrodes. The membrane sample was sandwiched between the platinum electrodes. Proton conductivity of the
membranes was measured by an impedance spectroscopy using a
Solartron 1260 gain phase analyzer, interfaced to a Solartron 1480
multistat. The measurement was carried out in a potentiostatic mode
in the frequency range of 0.1 Hz to 10 MHz with 5 mV of oscillating
voltage. The laboratory made four probe conductivity cell was used.
The conductivity cell was placed in the head-space of a temperature
controlled sealed vessel which was maintained at 100% relative
humidity. Proton conductivity () of the samples was calculated from
impedance data using the following equation [23]:

2.4. Membrane preparation


10 wt.% of PVA in water was stirred continuously at 90 C for 6 h
until the solution mixture reached a homogeneous solution. Then the
PVA solutions were mixed with sulfonated MWCNT (1wt.%),
uorinated MMT (1 wt.%) and cross linking agent sulfosuccinic acid

L
RWD

where R is the membrane resistance derived from the impedance


value at zero phase angle, L is the distance between two potential

J. Maiti et al. / Solid State Ionics 201 (2011) 2126

sensing platinum electrodes, W and D are the width and thickness of


the membrane respectively.
2.10. Methanol crossover
Methanol permeability measurement was carried out with a
home-made permeation measuring cell that had two compartments.
Compartment A was lled with 150 ml 20% (v/v) methanol solution in
de-ionized water, and compartment B was lled with 150 ml deionized water. The membrane was mounted between the two
compartments, and the diameter of the diffusion area was 3.0 cm.
The solutions in both compartments were magnetically stirred. The
methanol concentration in compartment B was monitored using a
refractive index detector (RI BT600, Younglin Instrument Co., Korea)
through a 1-mm diameter silicon tube with a 1.0 ml min 1 constant
ow driven by a Master ex pump. The output signal was converted
by a data module (Autochro, Younglin Instrument Co., Korea) and
recorded by a personal computer. Methanol permeability (P) was
obtained by means of the following relationship [24]:
CB t

A P
C t  to
VBL A

where CA is the initial methanol concentration in compartment A;


CB(t) the methanol concentration in compartment B at diffusion
time t; VB the volume of de-ionized water in compartment B; L the
thickness of the membrane; and A is the effective permeating area.
3. Results and discussion
3.1. FTIR
The membrane was prepared by solution casting method as shown
in scheme 1. FTIR studies have been carried out on samples containing
PVA and sulfonated MWCNT, and composite membrane (Fig. 1). In

23

pure PVA, we observe a doublet peak around 10001300 cm 1 and a


broad region around 30003500 cm 1. They are characteristic of PVA
and have been assigned to CO stretching and OH stretching,
respectively. In sulfonated MWCNT, two peaks at 1030 cm 1 and
around 700 cm 1 have been assigned to S_O and SO symmetric
stretching, respectively. Upon blending sulfonated MWCNT and SSA
with PVA, the S_O and SO stretching characteristics of membrane
grow up while the CO stretching characteristic of PVA decreases.
More direct evidence of the percentage of sulfur and uorine comes
from EDX studies, as will be discussed later.
3.2. Thermal properties
The thermal stability of the PVA nano composite membrane was
evaluated through the TGA experiments. The thermogravimetric
analysis (TGA) results for the PVA and composite membranes are
shown in Fig. 2. Pure PVA sample exhibited two thermal decomposition stages. The rst occurred at 285 C and the second at 400
450 C. These two stages reect the breakage of the side and main
backbone polymer chains, respectively [25]. At the end of the analysis,
at 800 C, the PVA had 5% residue. The TGA curve of the PVA
membrane showed three consecutive weight losses arising from the
processes of thermal solvation, thermal desulfonation, and thermo
oxidation and degradation of the polymer matrix. The rst weight loss
of about 5 wt.% at 100 C is closely associated with the loss of absorbed
water molecules. Most of these absorbed water molecules are
supposed to be in a bound state, rather than in the free molecular
state [26]. The second weight loss of about 35 wt.% at around 150
380 C corresponds to the loss of sulfonic acid group by the
desulfonation and a breakage of some portion of polymer chains as
well as breakage of the ester bonds. In the third weight loss of about
40 wt.% at temperatures N400 C is due to the decomposition of the
main chains of the PVA [27]. The decomposition temperature of PVA
was 285 C. That temperature increased to 410 C with chemical
crosslinking and inorganic nano ller addition. Many researchers have

Scheme 1. Membrane preparation.

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J. Maiti et al. / Solid State Ionics 201 (2011) 2126

Fig. 1. FTIR spectra of PVA, sulfonated MWCNT and membrane.

pointed out that incorporation of nanoparticles into a polymer matrix


enhanced the membranes thermal stability for PVA. Mbhele et al. [28]
claimed that the thermal degradation occurs from free radical
formations at weak bonds and/or chain ends, followed by their
transfer to adjacent chains via interchain reaction. The presence of the
nanoller restricted the mobility of the polymer chains, prohibited the
free radical transfer and, therefore, suppressed the thermal degradation. It could therefore be concluded that the thermal stability was
improved due to the additive effect of the MMT and CNT llers and the
chemical crosslinking reaction between the OH group on the PVA and
the COOH group on the SSA.
3.3. SEM and EDX
The morphology and composition of composite membranes
have been analyzed by a SEM microscope. SEM photographs for the
PVA/S-MWCNT/F-MMT/SSA (membrane 1) and PVA/S-MWCNT/SSA
(membrane 2) composite polymer membrane are shown in Fig. 3 (a)
and (b), respectively. The basic difference between these membranes
is that membrane 1 contains F-MMT and membrane 2 does not
contain F-MMT except this all other compositions are same for both.
No relevant morphological features have been noticed in these
membranes although some difference on the surface morphology
for membrane 1 has been detected. Many different sizes of aggregates
or chunks that are randomly distributed on the top surface have been

100

PVA polymer
PVA nano composite

Weight (%)

80

Fig. 3. (a) SEM photograph of the PVA/S-MWCNT/F-MMT/SSA (membrane 1) and


(b) PVA/S-MWCNT/SSA (membrane 2).

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

The water uptake of the PVA nano composite membranes is


37 wt.%. While the water uptake of pure PVA membrane (24.4 wt%) is
comparable to that of Naon117 membrane, the PVA nano
composite membrane exhibited a remarkably higher water uptake
owing to the high hydrophilic nature of cross linking agent and the
disruption of the highly ordered arrangement of pristine PVA chain
individually [29]. We have prepared PVA nano composite membrane
without uorinated MMT to study the positive effect of the addition of
hydrophilic SSA as well as sulfonated CNT and the negative effect of
hydrophobic uorinated MMT function on the water uptake. The
water uptake of PVA nano composite without uorinated MMT is

J. Maiti et al. / Solid State Ionics 201 (2011) 2126

25

Fig. 4. (a) EDX analysis of S-MWCNT, (b) EDX analysis of F-MMT.

45 wt.% which is higher than that of the uorinated MMT based


membrane. The uorinated MMT decreases the water content by
increasing the hydrophobic surface property. This result shows that
water uptake can be controlled by using hydrophobichydrophilic
interaction to reach a balance.

crosslinking agent present in the membrane. Water uptake plays a


critical role in proton conduction because it is the major carrier of
protons. However, excess swelling in water reduces the membrane's
mechanical strength. Typically, many polymer electrolyte membranes
swell or even become soluble in water when the sulfonation level

3.5. Proton conductivity and methanol permeability


The proton conductivity of the membrane is a key property that
directly affects operational fuel cell voltage. The proton conductivity
measurements of the membrane were run at RH 100% at room
temperature in the longitudinal direction by AC impedance spectroscopy. The proton conductivities of the hybrid membranes measured at
a temperature range between 25 and 80 C. The proton conductivity
value of membrane 1 (PVA/S-MWCNT/F-MMT/SSA) and membrane 2
(PVA/S-MWCNT/SSA) is 0.006 S/cm and 0.004 S/cm at 30 C, respectively. We have added same amount of sulfonic acid source (1 wt.%
sulfonated MWCNT and 10 wt.% crosslinking agent with respect to
PVA) in both type of membrane. Both type of membrane show more
or less same order of proton conductivity. Proton conductivity
increases with increasing temperature in both cases (Fig. 5). It was
reported that proton conductivity of PVA based membrane increased
with increasing the content of crosslinking agent (SSA) [30,31]. In
our case, observed proton conductivity is low compared to other
membranes (reported proton conductivity in the order of 10 2 S/cm)
[31,32] due to low level of sulfonic group in MWCNT as well as

Fig. 5. Proton conductivity of membrane 1 (PVA/S-MWCNT/F-MMT/SSA) and


membrane 2 (PVA/S-MWCNT/SSA) in the temperature range from 25 to 80 C under
100% RH conditions.

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J. Maiti et al. / Solid State Ionics 201 (2011) 2126

increases in order to obtain high proton conductivity [30]. In our case,


crosslinked as well as hydrophobichydrophilic interaction both
approach are applied to balance water uptake and proton conductivity.
The methanol permeability of the membranes 1 and 2 has been
calculated as 2.08 10 6 cm 2/s and 4.13 10 6 cm 2/s, respectively. It
is known that methanol permeates through hydrophilic ionic
channels; especially free water molecules and that proton are
transported by hopping between ionic sites due to hydrogen bonding
between bound water molecules as well as through ionic channels.
Therefore, it is expected that the methanol permeability should be
decreased due to the MMT particles acting as materials for blocking
the methanol transport and/or for reducing free water. However
methanol permeability of our membrane is high compared to other
type of PVA membranes (methanol permeability in the range of
10 810 7 cm 2 /s) [31,32]. This is possibly due to the crack
generation on the surface of the membrane. MMT does not act as a
blocking material for methanol transport in our study owing to their
agglomerate structure.
For comparison purposes, methanol permeability and proton
conductivity of Naon 115 membranes were also measured using the
same apparatus and testing conditions. The values of methanol
permeability and proton conductivity obtained were 1.78 106 cm 2/s
and 0.112 S/cm at 30 C, respectively. In relation to this study, most of the
membranes prepared herein have similar methanol permeability
compared to Naon 115 membrane. Proton conductivity values are,
however, lower than that of the Naon115. Further attempts have yet to
be made to improve the proton conductivity as well as methanol
permeability of the PVA nanocomposite membrane. This might be
achieved by optimizing the degree of sulfonation and the degree of
crosslinking of the membrane.
4. Conclusions
In the present work, crosslinked PVA nanocomposite membrane
containing sulfonic acid and uorine group has been prepared by
simple solution techniques and also evaluated as a potential polymer
electrolyte membrane in direct fuel cell application. Especially,
sulfonic acid functionalized MWCNT and uorine functionalized
MMT have been effectively introduced into the PVA matrix with
sulfosuccinic acid as a crosslinked agent. The proton conductivity of
the membrane is in the range of 0.004 to 0.01 S/cm. The low proton
conductivity is due to low level of sulfonic acid group present in the
membrane. The methanol permeability of the membrane is
2.08 10 6 cm 2/s. It has been found that the water uptake of the
membrane can be controlled by using uorine functionalized MMT.
Our future attempt is to obtain a uniform, improved property and to

demonstrate the practical applicability of using this PVA composite


membrane without cracks and nano-sized chunks or aggregate in
DMFC.
Acknowledgments
This research was supported by the Pioneer Research Center
Program through the National Research Foundation of Korea funded
by the Ministry of Education, Science and Technology (20110001676).
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