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Abstract
A novel PVA/TiO2 composite polymer membrane was prepared by a solution casting method. Glutaraldehyde (GA) was used as a cross-linker
for the composite polymer membrane in order to enhance the chemical, thermal and mechanical stabilities. The characteristic properties of the
cross-linked PVA/TiO2 composite polymer membranes were examined by thermal gravimetric analysis (TGA), X-ray diffraction (XRD), scanning
surface microscopy (SEM), and ac impedance method. The novel DMFC, consisting of an air cathode electrode with MnO2 carbon inks, an anode
electrode with PtRu black inks on carbon paper and the PVA/TiO2 composite polymer membrane, was assembled and examined. It was found that
the DMFC using this novel cheap PVA/TiO2 composite polymer membrane showed good electrochemical performance at ambient temperature
and pressure. The maximum peak power density of the alkaline DMFC is about 7.54 mW cm2 at 60 C and 1 atm.
2006 Elsevier B.V. All rights reserved.
Keywords: Direct methanol fuel cell (DMFC); PVA; Composite polymer membrane; TiO2 ; MnO2
1. Introduction
Direct methanol fuel cell (DMFC) [118] and solid polymer electrolyte membranes fuel cell (PEMFC) [1925] have
recently received a lot of attentions due to these power sources
presenting a high-energy efficiency and low emission of pollutants. For PEMFC, hydrogen was used as fuel and delivered
the power density of 300500 W cm2 at 8090 C. While,
using hydrogen as a fuel may cause some problems, such
as production, storage and transportation of hydrogen. Due
to these reasons, the DMFC has attracted much attention
than PEMFC because of using liquid methanol fuel, which is
easy to deliver and store. More importantly, liquid fuel can
use at ambient temperature and pressure, which makes the
DMFC easily be applied on the portable 3C electronic devices
[1318].
However, the development of acidic DMFC has faced several
serious problems: (i) slow methanol oxidation kinetics [13],
(ii) the poisoning of CO intermediate on the Pt surface [6], (iii)
the high methanol cross-over through the polymer membrane
0376-7388/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2006.10.048
[5,7,9,10], and (iv) the high costs of the Nafion membrane and
Pt catalyst.
Presently, the perfluorosulfonate ionomer membranes, such
as Nafion membrane (Dupont), are the primary polymer membranes used on the DMFC. However, the commercial Nafion
polymer membranes showed serious methanol cross-over problem [5,9], which methanol permeates from the anode to the
cathode. The methanol permeation not only cause a loss of fuel
but also a mixed potential being formed at the cathode and leading to a lower electrochemical performance of the DMFC. Thus,
for the liquid methanol fuel cell, it is imperative that the most
important characteristic properties of a solid polymer membrane
on the DMFC must have a lower methanol permeation of liquid
fuel.
Alkaline polymer electrolytes based on PEO have been studied for application on NiCd, NiZn [26,27], and NiMH
secondary battery systems [28,29]. They reported the alkaline
PEOKOH polymer electrolyte exhibiting the ionic conductivity
around 103 S cm1 at room temperature. Yang and Lin [30,31]
studied and prepared the alkaline polymer electrolyte membrane based on PEOPVAKOH for use on secondary NiMH
and primary Zn-air batteries. Lewandowski et al. [32] synthesized PEOKOH polymer electrolyte for electric double layer
capacitors (EDLCs). Yang and Lin [33,34] also reported the
52
PVA composite polymer electrolyte for use in NiMH and Znair batteries. Agel et al. [35,36] prepared an alkaline anionic
exchange membrane for fuel cell by grafting quaternary amines
on the epichlorhydride polymer with the ionic conductivity about
102 S cm1 and with anionic transport number (t ) greater than
0.9.
Recently, Cho et al. [37] prepared the semi-interpenetrating
polymer networks (IPNs) of Nafion and cross-linked
poly(AMPS) for DMFC. The IPNs membrane showed a
reduction of the methanol permeability and increased the
maximum power density as much as 22% (209 mW cm2 )
compared with Nafion (171 mW cm2 ). Song et al. [38]
also prepared Nafion/montmorillonite (MMT) nanocomposite membranes with lower methanol permeability (1.6
107 cm3 cm cm2 s1 ) for DMFC. Those membranes demonstrated that the Nafion/MMT nanocomposite membranes
delivered much higher maximum power density (about
100 mW cm2 ) at concentrated 10 M methanol feed at 70 C.
Li et al. [39] prepared the sulfonated poly(ether ether ketone)
(SPEEK) membranes on the acidic DMFC. The methanol
permeability (1.31.4 107 cm2 s1 ) was about an order of
magnitude lower than that of Nafion 115 membrane (4.9
106 cm2 s1 ).
Sun et al. [40] synthesized characterized the sulfonated
poly(phthalazinone ether ketone) (SPPEK) membranes with
lower methanol permeability for DMFC. The maximum power
density of a single cell DMFC was 55 mW cm2 at optimal
methanol concentration (3 M) at 70 C. Shen et al. [41] reported
the performance of DMFC with radiation grafted polymer electrolyte membranes. Three base polymer films (polyethylene
tetrafluoroethylene (ETFE), polyvinyl fluoride (PVDF), lowdensity polyethylene (LDPE)) were grafted with polystyrene
sulfonic acid (PSSA). The DMFC with PSSA grafted-PVDF
membrane showed the maximum peak power density about
58 mW cm2 at 80 C.
For comparison, Yu and Scott [4244] studied the electrochemical performance of the alkaline DMFC with anion
exchange membranes. The DMFC performance with maximum power density of about 10 mW cm2 was obtained in
a commercial quaternary-ammonium anion-exchange membrane (Morgane-ADP, Solvay SA, Belgium). In addition, the
PVA/PWA based [45,46] membranes have been prepared and
applied on DMFC. Varcoe et al. [4750] developed and characterized the quaternary ammonium (as the counter ions bund
to the polymer backbone) radiation grafted ETFC [47], PVDF
and FEP [50] alkaline anion exchange membrane (AAEM).
They [48] prepared the AAEM-MEAs that do not contain any
metal-cation Mn+ (i.e., K+ , Na+ ) ions to avoid the carbonate
precipitation problem and to improve the long-term operation stability. It is a breakthrough for alkaline anion-exchange
membranes on fuel cell application. The peak power density
of 130 mW cm2 for the H2 /O2 fuel cell with AAEM membrane was obtained. While the maximum power density of
8.5 mW cm2 was obtained in a metal-cation-free methanol/O2
fuel cell with 22.5 bar back pressure at 80 C. Recently, Yang
et al. [51] prepared the alkaline PVA/PAA IPNs membranes and
can be applied on the fuel cells.
(1)
3
O2 + 3H2 O + 6e 6OH ,
2
(2)
3
Overall reaction : CH3 OH + O2 CO2 + 2H2 O,
2
0
Ecell
= 1.21 V.
(3)
2. Experimental
2.1. Preparation of the cross-linked PVA/TiO2 composite
polymer membranes
PVA (Aldrich), nano-sized TiO2 fillers (7 nm, 338 m2 g1 ,
Aldrich), and KOH (Merck) were used as received without
further purification. Degree of polymerization and saponification of PVA were 1700 and 9899%, respectively. The alkaline
PVA/TiO2 composite polymer membranes were prepared by
a solution casting method. The appropriate weight ratios of
PVA:TiO2 = 1:120 wt.% were dissolved in distilled water under
stirring, respectively. The above resulting solution was stirred
continuously until the solution mixture became a homogeneous
viscous appearance at 85 C for 2 h. The addition sequence of
powders and the time of blending in the vessel were well controlled. The resulting mixture solution was poured out into a
Teflon container or Petri dish. The thickness of wet composite
polymer membrane is between 0.20 and 0.40 mm. The container with viscous PVA/TiO2 composite polymer sample was
weighed again and then the excess water was allowed to evaporate slowly at 25 C with a relative humidity of 30%. After
water solvent evaporation, the container with the composite solid
polymer membrane was weighed again. The composition of the
PVA/TiO2 composite polymer membrane was determined from
the mass balance. The thickness of the composite polymer membrane was controlled at between 0.10 and 0.30 mm. The PVA
composite polymer membrane was cross-linked by immersing
in a solution of 5 wt.% glutaraldehyde (GA, 75% content in distilled water, Merck), 0.20.5 vol.% HCl (used as a catalyst) and
acetone for the cross-linking reaction at 40 C for different times
of 648 h. The preparation methods of the PVA-based polymer
electrolyte membranes by the solution casting method have been
reported in detailed [33,34,51].
2.2. Ionic conductivity, liquid uptake and ionic transport
property measurements
Conductivity measurements were made for alkaline
PVA/TiO2 composite polymer membrane by an ac impedance
method. The cross-linked PVA/TiO2 composite samples were
immersed in 32 wt.% KOH solutions for at least 24 h before test.
The alkaline PVA/TiO2 composite polymer membranes were
sandwiched between SS304 stainless steel, ion-blocking electrodes, each of surface area 0.785 cm2 , in a spring-loaded glass
holder. A thermocouple was kept in close to the composite polymer membrane for temperature measurement. Each sample was
equilibrated at the experimental temperature for at least 30 min
before measurement. The ac impedance measurements were carried out using an Autolab PGSTAT-30 equipment (Eco Chemie
B.V., The Netherlands). The ac frequency range from 300 kHz
to 1 Hz at an excitation signal of 10 mV was recorded. The
impedance of the composite polymer membrane was recorded
at a temperature range between 30 and 70 C. Experimental
temperatures were maintained within 0.2 C by a convection
oven. All alkaline PVA/TiO2 composite polymer membranes
were studied at least three times.
53
The pre-weighted, dried PVA/TiO2 composite polymer membrane (W0 ) was immersed in distilled (DI) water, 8 M KOH,
10 M CH3 OH aqueous solutions, respectively, and maintained
for 24 h at 25 C until the equilibrium was established. The composite polymer membrane was taken out from the immersion
bath and the excess surface water was carefully removed. The
weight of the wet composite polymer membrane (W1 ) was then
determined. The liquid uptake was calculated from the following
equation:
Liquid uptake (%) =
W1 W0
100%
W0
(4)
54
Fig. 2. SEM photographs for PVA/TiO2 (20 wt.%) composite polymer membrane at: (a) 500; (b) 5k.
55
Table 1
The weight loss of the PVA polymer membrane, the PVA/TiO2 (15 wt.%) composite polymer membrane without cross-linked and the PVA/TiO2 (15 wt.%)
with GA cross-linked at different temperatures by TGA analysis
T ( C)
Types
100
250
350
500
7.39
6.03
13.94
9.50
76.67
69.47
91.30
84.54
5.43
24.74
35.19
77.97
also due to the removal of bound water; the weight loss is about
6.03%. In fact, the second transition at around 250350 C is due
to the degradation of PVA composite membrane; the total weight
loss corresponds to this stage about 69.47 wt.%. Obviously, the
second main weight loss is much less intense, compared with
the pure PVA polymer film. The third peak at 420 C is due to
the breaking main chain of PVA polymer membrane; there is a
total weight loss of 84.54 wt.% at 500 C.
Furthermore, the TGA and DTG curves for the cross-linked
PVA/TiO2 composite polymer film exhibit three main weight
loss regions, which appear as three peaks in the DTG curves,
as shown in Fig. 3. The first stage at a range of 80100 C is
also due to the evaporation of bounding water; the weight loss is
about 5.43 wt.%. The second transition at around 120300 C is
due to the degradation of GA and PVA in the composite polymer
membrane; the total weight loss corresponds to this stage about
35.19 wt.% at 350 C. Consequently, the second main weight
loss for the cross-linked PVA/TiO2 composite polymer membrane greatly reduces, compared with that of pure PVA polymer
film. The third peak at 450 C is due to the degradation backbone
of cross-linked PVA/TiO2 polymer membrane; however, there
is only a total weight loss of 77.97 wt.% at 500 C.
Overall, the degradation peaks of the cross-linked PVA/TiO2
composite polymer samples are less intense and shift towards
higher temperatures. It can be concluded that the improved thermal stability is probably due to the additive effect of the TiO2
filler and the chemical cross-linking reaction of between PVA
and GA.
3.3. Ionic conductivities and transport numbers
The typical ac impedance spectra for alkaline blend PVA/
TiO2 composite polymer membrane by directly blending PVA
polymer with TiO2 (2 wt.%) and KOH (without cross-linking
treatment) at different temperatures are shown in Fig. 4(a). The
ac spectra are typically non-vertical spikes for stainless steel
(SS) blocking electrodes, i.e., SS|PVA/TiO2 SPE|SS cell. Analysis of the spectra yields information about the properties of the
PVA/TiO2 polymer electrolyte, such as bulk resistance, Rb . Taking into account the thickness of the composite electrolyte films,
the Rb value was converted into the ionic conductivity value, ,
according to the following equation:
L
Rb A
(5)
56
30
40
50
60
70
Fig. 4. Nyquiest plot of PVA/TiO2 SPE: (a) without cross-linked; (b) crosslinked by GA.
where L is the thickness (cm) of the PVA/TiO2 polymer membrane, A the area of the blocking electrode (cm2 ), and Rb is the
bulk resistance () of alkaline composite polymer membrane.
Typically, the Rb values for the blend PVA/TiO2 composite
polymer membranes are of the order of less than 1 and are
dependent on the contents of TiO2 fillers and KOH in the membrane. Table 2 shows the ionic conductivity values of the alkaline
blend PVA/TiO2 composite polymer membrane (without GA) at
different temperatures. As a result, the ionic conductivity value
is 0.0181 S cm1 ( in the order of 102 S cm2 ) at 30 C.
However, the ac impedance spectra for the cross-linked
PVA/TiO2 (2 wt.%) composite polymer membrane were also
Table 2
The conductivity values of PVA/TiO2 (2 wt.%) composite polymer membrane
(PVA direct blended with TiO2 and KOH) at different temperatures (without
cross-linked)
T ( C)
30
40
50
60
70
Parameters
L (cm)
Rb ()
(S cm1 )
0.005
0.005
0.005
0.005
0.005
0.351
0.286
0.243
0.218
0.205
0.0181
0.0222
0.0262
0.0292
0.0310
Parameters
L (cm)
Rb ()
(S cm1 )
0.025
0.025
0.025
0.025
0.025
3.34
2.72
2.06
1.62
1.41
0.0056
0.0069
0.0091
0.0116
0.0134
57
Table 4
The liquid uptake (%) results for the PVA/TiO2 composite polymer membranes
at 25 C
Types of membranes
Solutions
DI water
8 M KOH
97 wt.% CH3 OH
94.71
93.21
95.50
89.20
83.50
87.20
82.70
74.80
65.42
48.18
53.65
50.20
71.41
62.80
54.35
21.70
15.20
8.60
It is well known that the ionic transport property of polymer electrolyte significantly influences the conductivity of
polymer electrolyte membrane. It was found that the conductivity value of alkaline cross-linked PVA/TiO2 (20 wt.%)
composite polymer membrane ( = 0.0120 S cm1 ) is much
lower than that of alkaline blend PVAKOH polymer electrolyte ( = 0.0472 S cm1 ) at ambient temperature. As a result,
the ionic conductivity of alkaline cross-linked PVA/TiO2 composite polymer membrane indeed decreases some extent when
the PVA/TiO2 polymer membrane was further cross-linked by
gultaraldehyde (GA). Nevertheless, the thermal and mechanical properties of the cross-linked PVA/TiO2 composite polymer
membrane are greatly enhanced.
Besides, the liquid uptake (%) for DI water, 8 M KOH
and 97% CH3 OH solutions shows in Table 4. As shown in
Table 4, the percent of DI uptake slightly decreased for both
the blend PVA/TiO2 and the cross-linked PVA/TiO2 composite
polymer membranes; the uptake results also indicate independent of TiO2 content in PVA polymer membrane. However, the
percent of KOH uptake decreases about 2030% for the crosslinked PVA/TiO2 composite polymer membrane. The chain
motion of cross-linked SPEs becomes less flexible (due to
the cross-linking). The free volume in the 3D PVA network
structure reduces, it may cause decrease the amount of KOH
solutions uptake [7]. Furthermore, the percent of CH3 OH solution uptake significantly reduces when the PVA/TiO2 composite
polymer membrane is cross-linked by GA cross-linking treatment.
Clearly, the cross-linked PVA/TiO2 composite polymer membrane becomes rigid and less free volume; it is due to the duel
effects of TiO2 particle filler and GA. As it can be seen, the asprepared cross-linked composite polymer membrane becomes
excellent barrier for methanol cross-over. On the other hand,
it was found that the amount of 97 wt.% CH3 OH solutions
uptake for the cross-linked PVA/TiO2 (10 wt.%) SPE is around
8.60 wt.%.
3.4. Electrochemical characterization of a single DMFC
Fig. 6. The conductivities values vs. the contents of TiO2 fillers for the alkaline
cross-linked PVA/TiO2 composite polymer membranes: (a) 30 C; (b) 60 C.
Fig. 7 shows the Et curves of the alkaline DMFC consisting of the anode electrode with a loading of PtRu black of
4.0 mg cm2 , the cathode electrode with MnO2 carbon inks
of 3.63 mg cm2 and the cross-linked PVA/TiO2 (10 wt.%)
composite polymer membrane in 2 M KOH + 15 M CH3 OH
58
Fig. 8. PD vs. current density curves for the alkaline DMFC (8 cm2 ) at different
temperatures in 2 M KOH + 2 M CH3 OH solutions at ambient pressure.
Table 6
The electrochemical parameters for the alkaline DMFC with the cross-linked
PVA/TiO2 (10 wt.%) composite membrane in 2 M KOH + 2 M CH3 OH solutions
at 1 atm at different temperatures
Parameters
Eocp (V)
Ep,max (V)
ip,max (mA cm2 )
PDmax (mW cm2 )
T ( C)
25
30
40
50
60
0.779
0.238
16.17
3.86
0.810
0.226
17.62
4.00
0.776
0.226
18.96
4.29
0.788
0.240
23.31
5.59
0.845
0.258
29.18
7.54
Table 5
The chronopotentiostatic (Et) curves of the alkaline DMFC in 2 M
KOH + 15 M CH3 OH solutions at i = 20 mA cm2 at ambient temperature and
pressure
Concentration (M)
1
2
3
4
5
Parameter
Ecell (V)
0.308
0.320
0.286
0.283
0.283
Fig. 9. The long-term stability curves (for 50 h) of alkaline DMFC with the
PVA/TiO2 composite membrane at a constant load of 20 mA cm2 in 2 M
KOH + 2 M CH3 OH solution under ambient condition operation (25 C and
1 atm).
59
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