Synthetic Metals 160 (2010) 193199

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Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Alkali doped poly(vinyl alcohol) for potential fuel cell applications

Jing Fu a,c , Jinli Qiao a,b, , Xizhao Wang a , Jianxin Ma a , Tatsuhiro Okada d
a

Clean Energy Automotive Engineering Center, Tongji University, Caoan Road 4800, Shanghai 201804, China
School of Environmental Science and Engineering, Donghua Universtiy, Songjiang University City 2999, Shanghai 201260, China
c
School of Resource and Environmental Engineering, East China University of Science and Technology, Melong Road 130, Shanghai 200237, China
d
National Institute of Advanced Industrial Science and Technology, Higashi 1-1-1, Central 5, Tsukuba, Ibaraki 305-8565, Japan
b

a r t i c l e

i n f o

Article history:
Received 11 September 2009
Received in revised form 18 October 2009
Accepted 6 November 2009
Available online 3 December 2009
Keywords:
Alkaline solid polymer electrolyte
PVAKOH
Chemical stability
Microstructure
Ionic-conductivity
Methanol uptake
ADMFC

a b s t r a c t
Optical transparent, chemically stable alkaline solid polymer electrolyte membranes were prepared by
incorporation KOH in poly(vinyl alcohol) (PVA). The distributions of oxygen and potassium in the membrane were characterized by XRD and SEMEDX. It is demonstrated that combined KOH molecules may
exist in the PVA matrix, which allow it to be an ionic conductor. In particular, the chemical and thermal stabilities were investigated by measuring changes of ionic conductivities after conditioned the membrane
in various alkaline concentrations at elevated temperatures for 24 h for potential use in fuel cells. The
membranes were found very stable even in 10 M KOH solution up to 80 C without losing any membrane
integrity and ionic conductivity due to high dense chemical cross-linking in PVA structure. The measured ionic conductivity of the membrane by AC impedance technique ranged from 2.75 104 S cm1
to 4.73 104 S cm1 at room temperature, which was greatly increased to 9.77 104 S cm1 after high
temperature conditioning at 80 C. Although, a relatively higher water uptake, the methanol uptake of
this membrane was one-half of Nafon 115 at room temperature and 6 times lower than that of Naon
115 after conditioned at 80 C. The membrane electrolyte assembly (MEA) fabricated with PVAKOH in
direct methanol fuel cell (DMFC) mode showed an initial power density of 6.04 mW cm2 at 60 C and
increased to 10.21 mW cm2 at 90 C.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Fuel cell technology has received an increasing interest over
the past few decades, particular to proton-exchange membrane
(PEM) fuel cells. This fuel cell uses an acidic membrane as electrolyte and gives excellent results. To date, the full potential of the
PEM fuel cells has not been realized although they show the excellent chemical, mechanical, and thermal stability as well as high
ionic conductivity. The cost and durability are two major challenges
to fuel cell commercialization. Further, the PEM fuel cells exhibit
several signicant disadvantages including slow electrode-kinetics,
carbon monoxide poisoning of expensive Pt and Pt-based electrocatalysts at low temperatures, the high cost of membranes and high
fuel permeability (methano) [1].
To overcome the drawbacks of the PEM fuel cells, a new concept fuel cell using alkaline anion exchange membranes (AAEMs)
has been evoked great interest. One of the advantages of AAEM
fuel cells is the faster kinetics of oxygen reduction reactions in an
alkaline media, which allows the use of non-precious metal electrocatalysts such as silver catalysts [2] and perovskite-type oxides [3].

Corresponding author. Tel.: +86 21 6958 9480; fax: +86 21 6958 9355.
E-mail address: qiaojinli@hotmail.com (J. Qiao).
0379-6779/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.synthmet.2009.11.013

In addition, the water management is improved due to the electroosmotic drag transporting water away from the cathode and the
so-called alcohol crossover problem also is highly reduced because
of the opposite movement of the hydroxide ion to the movement
of proton in acidic membrane.
The quaternized polymers based on AAEMs have been proposed as electrolytes in alkali fuel cells such as polysiloxane [4],
poly(oxyethylene) methacrylates [5], polysulfone [6], polyethersulfone cardo [7], poly(phthalazinon ether sulfone ketone) [8],
poly(ether-imide) [9] and radiation-grafted PVDF and FEP [10].
However, the quaternized polymers are unstable in alkaline
medium at temperatures above 60 C. Therefore, the development
of AAEMs for an improved performance is still urgent.
PVA is a polyhydroxy polymer, which is very common
in practical applications because of its easy preparation and
biodegradability [11]. It has been selected as epolymer matrix in
view of its lm-forming capacities, hydrophilic properties and high
density of reactive chemical functions favorable for cross-linking
by irradiation, chemical or thermal treatments [1214]. Due to its
perfect methanol tolerance effect, PVA also has been used to alkaline direct methanol fuel cell (ADMFC) studies with inorganic llers
incorporation [15,16]. However, little is reported on the chemical
stability of PVA-based alkaline solid polymer electrolyte, especially
in alkaline medium conditioned at high KOH concentration in solu-

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J. Fu et al. / Synthetic Metals 160 (2010) 193199

tion at temperatures above 60 C. One of the major challenges with

the development of AAEMs is the availability of suitable ionic conductivity with high chemical stability under fuel cell operating
conditions.
In this article, the alkaline solid polymer electrolyte membrane based on alkaline doped poly(vinyl alcohol) (PVAKOH) was
proposed aiming at a new cost-effective, easier preparing and
chemical stable AAEM. Through chemical cross-linking procedure,
the swelling property of PVA was effectively controlled and the
formed membranes were both exibility and toughness. Particular interest was devoted to the chemical stability, on which the
microstructure of PVAKOH membranes were studied in detail for
further improved performance for potential use in alkali membrane fuel cells. Additionally, the electrochemical characteristics of
KOH doped PVA were investigated in 2MKOH + 2 M CH3 OH solution
by the linear polarization methods, especially, for the peak power
density of the DMFC.
2. Experimental
2.1. Materials and membrane preparation
Chemically cross-linked PVA membranes were prepared by a
simple solution casting method where PVA (99% hydrolyzed, average Mw = 86,00089,000, Aldrich) was fully dissolved in water to
make a 10% solution at 90 C. Appropriate amounts of the above
solution were then mixed with water to get a homogeneous,
transparent and viscous appearance. After removing the air under
vacuum, the solutions were poured into plastic petri dishes and,
the water was evaporated at ambient temperatures. When visually dry, the membrane was peeled off from the plastic substrate
and, samples of square pieces of membranes (ca. 1.5 cm 2 cm)
were soaked in a reaction solution containing 10 mass% glutaraldehyde (GA) (25 wt% solution in water, Shanghai Guoyao) in acetone
at 30 C for one hour [17]. The cross-linking proceeded between
the OH of PVA and the CHO of GA in the membrane due to
an acid-catalyzed reaction by addition of small amount of HCl in
the solution. Transparent, at membranes were obtained with a
thickness of about several tens of micrometers (60100 m). The
thickness of the membranes can be easily controlled by adjusting
the volume of suspension.
The preparation of the PVA alkaline membranes (PVAKOH)
were conducted by immersion the membrane in KOH solution with
various concentrations at least for 24 h. The absorbed KOH on the
surface of the membrane was removed by rinsing the membrane in
deionized (D.I.) water numerous times, then the membranes were
stored in D.I. water for measurements. Fig. 1 illustrates the inner
structure model of PVAKOH and some typical membrane pictures.
2.2. Characterization of PVAKOH membranes
The crystal structures of the composite membranes were examined with an X-ray diffractometer (XRD, PHILIPS PW 3040/60
powder diffractometer) using Cu K radiation ( = 0.15406 nm)
and operating at 40 kV and 100 mA. The membrane samples were
scanned in the reection mode with a 2 angle between 5 and 80
with a scan rate of 2 min1 .
The composite morphology was evaluated using a FEI Sirion
200 eld emission scanning electron microscopy (SEM) operating
at 5 kV. Prior to observations, the membrane samples were fractured in liquid nitrogen and sputtered with gold, then examined
at 2000, 6000 and 40,000 magnications. The element distribution in the cross-section was determined by Oxford Instrument
X-ray Microanalysis INCA, operating at 20 kV with a data collection
time of 10 min.

Fig. 1. Inner structure model of PVAKOH and membrane pictures for (a) pure PVA,
(b) PVA conditioned in 4 M KOH at 25 C, (c) PVA conditioned in 4 M KOH at 80 C.
Condition time: 24 h, followed by complete removal of free KOH prior to testing.

2.3. Water and methanol uptake

The water uptake (WU) of the membranes (g g1 ) was evaluated
from the mass change before and after the complete dryness of the
membrane. A dry membrane was swelled in D.I. water for a day,
then the surface water was wiped carefully with a lter paper, and
it was immediately weighed. After drying the sample overnight in a
vacuum oven at 60 C, the water uptake (WU), was calculated using
the expression:
WU =

Wwet Wdry
Wdry

(1)

where Wwet and Wdry are the mass of fully hydrated membrane,
and of the dry membrane, respectively. The methanol uptake was
measured at the same procedures.
2.4. Ionic conductivity measurements
The OH ionic conductivity of the formed membranes was measured by an AC impedance technique using an electrochemical
impedance analyzer (VMP2/Z, PAR), where the AC frequency was
scanned from 100 kHz to 0.1 Hz at a voltage amplitude of 100 mV.
Fully hydrated membranes were sandwiched in a Teon conductivity cell equipped with Pt foil contacts [18]. The membrane was
in contact with water over the measurements. Ionic conductivity,
(S/cm), was calculated according to the following equation:
=

l
RTW

(2)

where l is the length of the membrane between two potential sensing platinum wires, R is the membrane resistance, W and T are the
width and the thickness of the membrane, respectively.
2.5. Membrane electrode assembly (MEA) fabrication and
single-cell performance measurements
The
cell
conguration:
2M
MeOH + 2 M
KOH|Pt/
C|PVAKOH|Pt/C|O2 , was used in a single-cell of ADMFC. The
catalyst for both anode and cathode was Pt/C on carbon paper
with catalyst loading of 1 mg(Pt) cm2 (ElectroChem). The active
electrode area for a single cell test was 4 cm2 . The MEA was
prepared by hot pressing the PVAKOH membrane with anode and
cathode at 90 C and 100 kg cm2 for 5 min. The MEA was inserted
into a fuel cell hardware, which consisted of graphite block with

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195

Fig. 2. Ionic conductivity of PVA membranes as a function of doping KOH concentration in aqueous solution. The membranes were immersed in various concentration
of KOH solution for 24 h followed by complete removal of free KOH prior to conductivity testing.

machined serpentine ow channel and copper current collectors.

2 M MeOH + 2 M KOH aqueous solution was pumped into the
anode channel of the cell under atmospheric pressure, with a ow
rate 5 mL min1 . Pure oxygen gas was supplied as the cathode fuel
to enter the cathode channel with a gas ow rate 20 mL min1
through a humidier held at 25 C under ambient pressure. The
cell was placed in a temperature-controlled chamber, which was
used to keep the cell at a constant temperature. Polarization curves
were obtained using a fuel cell evaluation system (TFC-2100,
Sokken) over the temperature range of 6090 C.

Fig. 3. Typical impedance spectra of PVA doped in 6 M KOH at 25 C. The free KOH on
membrane surface was completely removed by rinsed the membrane in D.I. water
prior to conductivity testing.

tional contribution to the conductivity. The membrane samples are

found to be supernatant at high doping KOH concentration (>8 M)
in solution. It seems that more OH could not be taken into the
polymer at high KOH doping solution due to the weak ionic mobility (such as formed ion-pairs or increased viscosity), thus a decrease
in ionic conductivity.
3.2. Chemical stability of alkaline PVA

3. Results and discussions

3.1. Ionic conductivity of alkaline PVA
The alkaline PVA membranes appeared transparent and homogeneous with mechanical exibility. When immersed in KOH
solutions, the PVA membrane became orange in color but it almost
decolored completely by rinsing the membrane in D.I. water. Fig. 2
shows the ionic conductivities of the PVAKOH membranes. The
PVAKOH membrane preparation was conducted by immersion
the PVA membranes in KOH aqueous solution with various concentrations at least for 24 h. The absorbed KOH on the surface of the
membrane was removed by rinsing the membrane in D.I. water
numerous times, then the membranes were stored in D.I. water
for ionic conductivity measurement. Fig. 3 illustrates the typical
AC impedance spectra, which are related to the ionic conduction
process in the bulk properties of the membrane. The intercept of
the semicircular arc with the Z (ReZ) axis was taken as the bulk
resistance, R, of the polymer electrolyte membrane. It can be seen
that the ionic conductivity measured at 25 C reached a maximum
value of 4.73 104 S cm1 for PVA in doping KOH concentration of
24 mol L1 in solution. This is in the same order of the ionic conductivity obtained by directly mixing a viscous PVA solution with
concentrated KOH aqueous solution as reported elsewhere [19].
This result suggests that some of KOH molecules are taken into
the polymer by water molecules. The chemical interaction, such as
dipoledipole interaction including hydrogen bonding and induction forces, may take place between CO and OH groups on PVA and
KOH during alkali doping, which is helpful for the ionic conductivity
of PVA. However, the ionic conductivity decreased with additional
doping KOH concentration in solution, for example, when KOH concentration in solution is larger than 4 M. That is, additional higher
doping KOH concentration in solution does not simply make addi-

The chemical stability of AAEMs is recognized as a key factor

that affects fuel cell performances, especially, in alkaline medium at
temperatures above 60 C and high KOH concentration. The chemical stability of alkaline PVA was tracked by immersing the PVA
membranes in different concentrations of KOH at elevated temperatures for at least 24 h. This was an experiment designed to
test the tolerance of the membrane to base treatments at elevated temperatures [9]. After complete removal of the free KOH,
the conductivity of the membrane was measured at room temperature. Shown in Fig. 4 are the results of the typical candidates
with four concentrations (1, 4, 6, and 10 M) of KOH for PVA applied.
The conductivity values from the tested membranes ranged from
1.36 104 S cm1 to 4.51 104 S cm1 at 25 C. Generally speaking, AAEMs are frequently less stable since the basic groups are
inherently less stable than the acidic groups [11]. Because of the
fact, the purely quaternized polymers can be just subjected to 0.5
or 1.0 M KOH at 80 C but deteriorated only in 2.0 M KOH at 60 C
[9] or even in pure water at 80 C [8]. The ionic conductivity is
greatly decreased and even cannot be measured thereby [9]. To
our interest, however, no decrease in conductivity was found for
PVAKOH membranes. Inversely, all tested membranes showed
an increased conductivity with increasing KOH concentration in
solution at elevated treating temperatures. The PVA soaked in 6
and 10 M KOH showed the rapid increase in ionic conductivity
and, exhibited the highest conductivities of 8.74 104 S cm1 and
9.77 104 S cm1 after temperature conditioned at 80 C, respectively. It seems that PVA has a remarkable absorbent capacity to
KOH after temperature treatment, thus an increased ionic conductivity due to much increased charge carriers. On the other hand,
the results suggest the tough tolerance of the PVA membranes to
base treatments even in 10 M KOH at 80 C due to the high dense
chemical cross-linkage in PVA polymer matrix.

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J. Fu et al. / Synthetic Metals 160 (2010) 193199

Fig. 4. Ionic conductivity of PVA membranes after conditioned with KOH at elevated
temperatures. The membranes were conditioned in 1, 4, 6 and 10 M KOH at 25, 40, 60
and 80 C for 24 h, followed by complete removal of free KOH prior to conductivity
testing. The conductivity was measured at 25 C.

Fig. 5 shows the temperature dependence of the ionic conductivity of PVAKOH membranes. Here the PVA membranes doping
in 4 M KOH, and then conditioned at r.t. and at 80 C as typical candidates, respectively. After complete removal of the free KOH on
the membrane surface, the conductivity was measured at elevated
temperatures. It can be seen that the ionic conductivity was almost
no change with the temperature up to 80 C after membrane being
conditioned in 4 M KOH at r.t., but linearly increased with temperature after the membrane being conditioned in 4 M KOH at 80 C,
which reached the highest ionic conductivity of 9.51 104 S cm1 .
This is in well agreement with the results obtained from Fig. 4, that
is, the dynamic properties seems to be greatly improved after conditioned at high temperature of 80 C, due to an increased charge
carriers.
It should be mentioned that alkaline doped PVA, i.e., with a couple of additives such as PEO [20], SSA [21] and TiO2 ller [15] gives
high ionic conductivities ranged from 103 102 S cm1 and even
101 S cm1 for PVAHEMASiO2 so-gel membranes [22]. Lower
ionic conductivity in this work stems from the different membrane
preparation procedure. KOH was directly added into PVA solution,
thus high KOH content in the polymer, but an obvious phase separation produced [19,20,15] or immersed the membrane in KOH
concentration in solution, then directly conduct the ionic conduc-

Fig. 6. XRD patterns for PVAKOH membranes: (a) pure PVA, (b) PVA conditioned
in 4 M KOH at 25 C, (c) PVA conditioned in 4 M KOH at 80 C. Condition time: 24 h,
followed by complete removal of free KOH prior to testing.

tivity measurement [21,22] without any treatment such as rinsing.

However, in this work PVAKOH membranes were conducted by
immersion the PVA membranes in KOH solution, then, the membranes were rinsed in D.I. water numerous times for completely
removing the absorbed KOH on the surface of the membrane, then
the membranes were stored in D.I. water for nal ionic conductivity measurements. Therefore, the high ionic conductivity values
reported in the literature were mainly from the contribution of
free KOH absorbed on membrane surface. Contrary to this, in
this work the ionic conductivity merely comes from the bonded
KOH through chemical interaction such as dipoledipole interaction including hydrogen bonding and induction forces between CO
and OH groups on PVA and KOH as Fig. 1 shows. Additionally, high
cross-linking in PVA network may also contribute to the lower ionic
conductivity of the resulting membrane.
3.3. XRD analysis
The X-ray diffraction measurements were performed to examine the crystallinity of the composite membranes. XRD pattern
of wet PVA doping in 4 M KOH concentration with surface KOH
removed was obtained as shown in Fig. 6. PVA membrane exhibits a
semi-crystalline structure with a large peak at a 2 angle of 19 20
and a small peak of 39 40 [23]. From the outline of XRD pattern
of PVAKOH, no abroad lump between 20 and 40 was observed
from KOH crystal as reported elsewhere [24]. However, as can be
seen clearly in Fig. 6, the peak intensity at 20 of PVAKOH was
decreased when in comparison with pure PVA. This implies that the
domain of amorphous region into PVA polymer matrix augmented
due to doped in KOH. Usually, the ionic conductivity of the polymer electrolyte could be attributed to the transport of cation and
anion in a polymer matrix by hopping between coordinate sites,
local structural relaxation and segmental motions of the polymer
in amorphous domain, as well as ion transport in solvent. Thus, it
can be conclude that KOH simultaneously act as a plasticizer here,
thus the PVA polymer electrolyte becomes more exible and more
amorphous phase (as XRD results indicated), which makes for the
ionic conductivity of PVAKOH membranes.
3.4. SEM and EDX characterization

Fig. 5. Ionic conductivity of PVA/KOH membranes as a function of temperature: (a)

conditioned in 4 M KOH at 25 C, (b) conditioned in 4 M KOH at 80 C. Condition
time: 24 h, followed by complete removal of free KOH prior to testing.

SEM photographs for the cross-sectional views of PVAKOH

and its corresponding EDX mappings for potassium and oxygen
elements are shown in Figs. 7 and 8, respectively. Prior to the exper-

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197

Fig. 7. SEM pictures of the cutview of the PVA/KOH membranes: (a) conditioned in 4 M KOH at r.t (2000), (b) conditioned in 10 M KOH at r.t. (2000), (c) conditioned in
4 M KOH at 80 C (6000), (d) conditioned in 10 M KOH at 80 C (6000), (e) conditioned in 4 M KOH at 80 C (40,000), (f) conditioned in 10 M KOH at 80 C (40,000).
Condition time: 24 h, followed by complete removal of free KOH prior to testing.

iment, the sample was rinsed with D.I. water to remove KOH on
its surface, and then it was freeze-fractured in the liquid nitrogen.
SEM observations of the sections of a membrane (Fig. 7a and b at
2,000 magnication) showed a homogeneous and dense material.
It should be mentioned that by increasing doping KOH concentration in solution and/or conditioned at temperature above room
temperature induced an orange color on the membranes as Fig. 1c
shows. But not any surface degradation or membrane modication,
such as holes or phase separation phenomena, could be detected.
The structure is very compact on the SEM pictures (Fig. 7c and d at
6000 magnication) either being conditioned at high KOH concentration (10 M KOH) or conditioned at 80 C. This is very different
from PEOPVAKOH blend polymer, on which many small pores
with different size are produced on the surface of the lm [20].
In this work, the KOH particles are discernable as light dots and
evenly dispersed in the PVA polymer matrix at 40,000 magnication (Fig. 7e and f). There were neither gaps nor cracks between the
particles and polymer matrix, which proves the excellent chemical
stability due to the cross-linkage in PVA matrix.
In the EDX mapping image, the highlighted bright dots revealed
high element concentration. It can be seen that distributions
of potassium and oxygen elements were homogeneous, which
implied that KOH was well dispersed throughout PVA membrane.

An intriguing result was revealed from EDX mapping that no obvious change in potassium element before and after conditioned in
alkaline concentration (4 M KOH) and temperature, but a much
higher concentration in oxygen element particular to conditioned
at 80 C. This may be due to the fact that OH in KOH may react with
acetal group in PVA matrix to generate OH and water, although
this reaction may take place incompletely. This result suggests further that combined KOH molecules by long-distance interaction
may exist in the PVA matrix, which was helpful for the ionic conductivity just as described previously.
3.5. Water/methanol uptake
The importance of the ionic conductivity and fuel permeability is
well known, particular to ADMFC. Furthermore, the swelling property of the conducting membranes is also an important parameter,
which is highly correlative to the cell performance. The presence
of water in the membranes is a prerequisite for reaching high ionic
conductivity. On the other hand, excessively high water uptake will
affect other performances of the membranes such as the dimensional and thermal stability. Table 1 gives the changes in both
the water uptake and the methanol uptake values of PVAKOH
membrane before and after conditioned in 4 M KOH at r.t. and at

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J. Fu et al. / Synthetic Metals 160 (2010) 193199

Fig. 8. EDX mapping of (a), (d) potassium element and (b), (c) oxygen element within PVA/KOH, respectively. Doping KOH concentration in solution: 4 M; (a and b):
conditioned at r.t., (c and d): conditioned at 80 C. Condition time: 24 h, followed by complete removal of free KOH prior to testing.
Table 1
Physico-chemical properties of alkaline PVA based on chemical cross-linking and Naon 115 membranes.
Membrane Membrane thickness
(mm)

KOH doping
concentration (M)

Liquid uptake (%)

r.t.

Ionic conductivity 103 (S cm1 )

Conditioned at 80 C

r.t.

Conditioned at 80 C

D.I. water (%) 99.8 wt% MeOH D.I. water (%) 99.8 wt% MeOH D.I. water (%)
PVA
Naon115

80100
135

39.4
34

20.5
41.8

80 C, respectively. For a comparison, water and methanol uptake

of Naon 115 was measured under the same experimental conditions. As seen in Table 1, the water uptake of PVAKOH membrane
decreased from 39.4% when being conditioned at r.t. to 36.1% when
being conditioned at 80 C, while the methanol uptake increased
from 20.5% to 21.4% correspondingly. In other words, no obvious
changes occurred both in water uptake and in methanol uptake
for alkaline PVA even after conditioned at 80 C if the experimental errors are ignored. Conversely, although the lower water
uptake of Naon 115 under the same measuring conditions, it
showed a much higher methanol uptake especially conditioned at
80 C, where the methanol uptake rapidly increased from 41.8%
to 128.7%, i.e., 6-fold of alkaline PVA membrane. Although this
measurement is not a direct consequence of methanol permeability in contact with aqueous solution, these initial results are
promising for future AAEMs fabrications in potential fuel cell applications.

36.1

21.4
128.7

0.47

0.75

and 90 C, respectively. It can be seen that an initial peak power

density of 6.04 mW cm2 was achieved at cell voltage = 0.47 V
with a peak current density of 14.9 mA cm2 at temperature
of 60 C. An increase in fuel cell temperature leads to a dramatic improvement in the cell performance. The open circuit
potential of the alkaline DMFC are about 0.870.91 V. In spite

3.6. Single-cell performance test

Fig. 9 shows IV characteristics of the DMFC using KOH
doped PVA as alkaline solid polymer electrolyte membrane in
2 M KOH + 2 M CH3 OH solution at the temperature between 60

Fig. 9. IV curves of the DMFC using KOH doped PVA as alkaline solid polymer
electrolyte membrane in 2 M KOH + 2 M CH3 OH solution at different temperatures.

J. Fu et al. / Synthetic Metals 160 (2010) 193199

199

of a low catalyst loading (1 mg cm2 both on the anode and

on the cathode), the MEA showed a good performance and,
the power density increased from 6.04 mW cm2 at 60 C to
10.21 mW cm2 at 90 C. However, we did not conclude that
the PVAKOH is comparable to the PVATiO2 KOH [15] or the
PVAPSSAKOH [21] at this stage, since the air cathode is not
considered and the Pt/C cathode electrode was used in this
work.

Acknowledgements

4. Conclusions

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In short, the chemically stable anion exchange membranes

that can conduct OH were prepared by incorporation KOH in
PVA. The SEMEDX results demonstrated a dense structure of
PVAKOH membranes, where the bonded KOH contributes the
ionic conductivity through chemical interaction between CO
and OH groups on PVA and KOH. This is different from the
usual doped one, where the ionic conductivities were mainly
from the free KOH absorbed on membrane surface. In particular, the perfect tolerance of the PVAKOH membranes was
found to base treatments even conditioned in 10 M KOH at 80 C
without losing any membrane integrity and ionic conductivity due to high dense chemical cross-linking in PVA structure.
DMFC test using PVAKOH fabricated MEA showed an initial power density of 6.04 mW cm2 at 60 C and increased to
10.21 mW cm2 at 90 C. These initial results are very promising for further improved AAEMs performance in potential fuel
cell applications, considering the PVA superior methanol barrier
properties and its easy preparation and cost-effective material.

This work is nancially supported by Project Pujiang Foundation (grant no. 08PJ14096) and Natural Science Fundation (grant no.
09ZR1433300) of Science and Technology Commission of Shanghai
Municipality of China. Thanks also to Liuxue Guiguo Foundation of
China Ministry of Education (grant no. 2009(1001)).
References