You are on page 1of 10

Journal of Membrane Science 288 (2007) 5160

Synthesis and characterization of the cross-linked PVA/TiO2


composite polymer membrane for alkaline DMFC
Chun-Chen Yang
Department of Chemical Engineering, Mingchi University of Technology, Taipei Hsien 243, Taiwan, ROC
Received 21 June 2006; received in revised form 26 October 2006; accepted 28 October 2006
Available online 11 November 2006

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

Tel.: +886 2 908 4309; fax: +886 2 2904 1914.


E-mail address: ccyang@ccsun.mit.edu.tw.

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

C.-C. Yang / Journal of Membrane Science 288 (2007) 5160

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.

The addition of ceramic filler into polymer matrix is allow to


reduce the glass transition temperature (Tg ) and the crystallinity
of the polymer, and also allow the increase the amorphous
phases of polymer matrix, then increase the ionic conductivity. There are various ceramic filler, such as Al2 O3 , TiO2 [5],
SiO2 [7], have been extensively studied. These experimental
results indicated improvements in the ionic conductivity, thermal and mechanical properties as the different ceramic fillers
were added into the solid polymer electrolyte (SPE). The reason for the increase of ionic conductivity of composite polymer
electrolyte was explained that the ceramic particle fillers in the
polymer matrix created some defects and free volume at interface of between the ceramic particle and the polymer chain. In
this work, we attempted to disperse the nano-sized TiO2 particles into the PVA matrix act as a solid plasticizer capable of
enhancing chemical, thermal and mechanical stabilities of the
PVA-based composite polymer membrane.
TGA was used to analyze the thermal stability properties of
the cross-linked PVA/TiO2 composite polymer membrane. XRD
was used to investigate the crystal structure of the PVA/TiO2
composite polymer membrane. SEM was used to examine
the surface morphology of the composite polymer film. The
ionic conductivity of alkaline PVA/TiO2 composite polymer
membranes was measured by ac impedance spectroscopy. The
characteristic properties of the cross-linked PVA/TiO2 polymer membranes with different weight percents of TiO2 fillers
(120 wt.%) will be examined and discussed in detail.
In this work, the alkaline DMFC, composed of the air cathode
electrode loaded with MnO2 /BP2000 + CNT binary carbon inks,
the PtRu anode electrode (4.00 mg cm2 ) and the cross-linked
PVA/TiO2 composite polymer membrane, was assembled and
examined. The PVA/TiO2 composite polymer membrane was at
first prepared through directly blending PVA polymer with nanosized TiO2 (anatase, 7 nm) fillers under ultrasonic condition.
The obtained composite polymer membrane was then further
immersed in 5 wt.% GA solution for the cross-linking reaction.
For anodic methanol electro-oxidation reaction, cathodic oxygen reduction reaction (ORR) and the overall reaction of the
DMFC in alkaline media can be described as follows:
Anodic reaction : CH3 OH + 6OH CO2 + 5H2 O + 6e ,
Ea0 = 0.810 V (versus SHE),
Cathodic reaction :

(1)

3
O2 + 3H2 O + 6e 6OH ,
2

Ec0 = 0.402 V (versus SHE),

(2)

3
Overall reaction : CH3 OH + O2 CO2 + 2H2 O,
2
0
Ecell
= 1.21 V.

(3)

Additionally, the electrochemical characteristics of the


DMFC with the cross-linked PVA/TiO2 composite polymer
membrane were investigated by the linear polarization and
potentiostatic methods; especially, for the peak power density
of the DMFC.

C.-C. Yang / Journal of Membrane Science 288 (2007) 5160

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)

The ionic transport numbers of the cross-linked PVA/TiO2


composite polymer membranes were examined using a dynamic
Hittorfs method [52] at 25 C.
2.3. Crystal structure, morphology, and thermal analysis
The crystal structures of the PVA/TiO2 composite polymer membranes were examined using a Philips XPert X-ray
diffractometer (XRD) with Cu K radiation of wavelength
for 2 angles between 10 and 80 . The sur = 1.54056 A
face morphology and microstructure of the PVA/TiO2 composite
polymer membrane was examined by a Hitachi S-2600H scanning electron microscope (SEM).
TGA thermal analysis was carried out using a Perkim-Elmer
Pyris 7 TGA system. Measurements were carried out by heating
from 25 to 500 C, under N2 atmosphere at a heating rate of
10 C min1 with about 10 mg sample.
2.4. Preparation of the anode and cathode electrodes
The preparation of the catalyst slurry ink for the anode electrode was prepared by mixing 70 wt.% PtRu black powders
(Alfa, HiSPEC 6000, PtRu black with Pt:Ru = 1:1 molar ratio),
30 wt.% PTFE binder solution (Dupont, 30 wt.% base solution),
and a suitable amount of distilled water and alcohol. The resulting PtRu black mixtures were ultrasonicated for 2 h. The PtRu
black inks were loaded onto the carbon paper (Sigracet GDL
10BC, Germany) by a paint-brush method to achieve a loading of PtRu black of 4.0 mg cm2 . The as-prepared PtRu anode
electrode was dried in a vacuum oven at 100 C for 2 h.
The carbon slurry for the gas diffusion layer of the air cathode
was prepared with a mixture of 70 wt.% Shawinigan acetylene black (AB50) with specific surface area of 80 m2 g1 and
30 wt.% PTFE (Teflon-30 suspension) as a wet-proofing agent
and binder. The carbon slurry was coated on the Ni-foam as a current collector and then pressed at a pressure of 120 kg cm2 . The
gas diffusion layer was then sintered at temperature of 360 C,
30 min. The catalyst layer of the air electrode was then prepared
by spraying a mixture of a 15 wt.% of PTFE solution binder and
85 wt.% of mixed powders consisting of -MnO2 (electrolytic
manganese oxide, EMD) catalyst supported on binary carbons
(i.e., BP2000:CNT = 1:1). The Ni-foam current collector was
cut from 1 cm 1 cm or 2 cm 4 cm. Both BP2000 and CNTs
carbons were used as the supporting materials for the cathode
electrode (so-called a binary carbon system). The preparation

54

C.-C. Yang / Journal of Membrane Science 288 (2007) 5160

methods of the air cathode electrodes have been reported in


detailed [53,54].
2.5. Electrochemical measurements
The cross-linked PVA/TiO2 composite polymer membrane
was sandwiched between the sheets of the anode electrode
and the cathode electrode, and then hot-pressed at 60 C for
120 kgf cm2 for 10 min to obtain a membrane electrode assembly (MEA). The electrode area of the MEA was about 1 or
8 cm2 .
The electrochemical measurements were carried out in a
two-electrode cell. The Et curves of the alkaline DMFC with
the PVA/TiO2 composite polymer membrane were recorded at
a constant current density of 20 mA cm2 . All electrochemical measurements were performed on an Autolab PGSTAT-30
electrochemical system with GPES 4.8 package software (Eco
Chemie, The Netherlands). The electrochemical performances
of the alkaline DMFC with the cross-linked PVA/TiO2 composite polymer membrane and the cathode electrode open to
the atmospheric air were studied in 2 M KOH + 2 M methanol
solutions at different temperatures.
3. Results and discussion

large peak at a 2 angle of 20 [33,34]. As can be seen clearly in


Fig. 1, a large peak at 2 of 20 for the PVA/TiO2 (10 wt.%) composite polymer membrane was seen. But, it was also clearly seen
that the peak intensity of the PVA/TiO2 composite polymer film
greatly reduced when the membranes were further cross-linked
by GA for the time between 6 and 48 h. It is well known that the
hydroxyl groups of PVA chemically react with aldehydes to form
acetal or semi-acteal linkages. Indeed, this chemically crosslinking reaction on the PVA/TiO2 polymer membrane provides
greater chemical, thermal and mechanical stabilities for DMFC
applications. It was observed that the cross-linked PVA/TiO2
composite polymer membrane greatly augmented the domain of
amorphous region (i.e., the degree of crystallinity is decreased).
This indicates that the cross-linked PVA/TiO2 polymer membrane becomes more amorphous. Notably, it was found that the
degree of amorphous of the composite membranes increases as
both the TiO2 ceramic fillers and the cross-linking reaction were
added into and treated on the PVA polymer, respectively.
SEM photographs for the PVA/TiO2 (20 wt.%) composite
polymer membrane at different magnifications, as shown in
Fig. 2(a) and (b), respectively. It was found that the surface
morphology of the PVA/TiO2 composite polymer sample shows
many different sizes of PVATiO2 aggregates or chunks that are
randomly distributed on the top surface. It was found that the

3.1. Crystalline structure and surface morphology


The X-ray diffraction measurement was performed to examine the crystallinity of the PVA/TiO2 composite polymer
membrane. Fig. 1 shows the diffraction pattern of the PVA/TiO2
composite polymer membranes that were cross-linked by 5 wt.%
GA solutions at 40 C for different times. It is well known that
the PVA polymer exhibits a semi-crystalline structure with a

Fig. 1. XRD spectra of PVA/TiO2 (10 wt.%) composite polymer membranes.

Fig. 2. SEM photographs for PVA/TiO2 (20 wt.%) composite polymer membrane at: (a) 500; (b) 5k.

C.-C. Yang / Journal of Membrane Science 288 (2007) 5160

dimension of these TiO2 embedded in PVA chunks is about


120 m. This indicates that the nano-TiO2 particles were not
dispersed well within the PVA polymer matrix, as shown in
Fig. 2(b).
As a whole, the compatibility of the PVA polymer and TiO2
particles is still uniform and homogenous when the weight percent of nano-TiO2 fillers is less than 20 wt.%. As we know, the
higher the content of TiO2 (as a methanol permeation barrier) in
the PVA network matrix may help reduce the methanol crossover through the polymer membranes. However, it will become
another important issue how to obtain a uniform PVA/TiO2
composite membrane without nano-sized TiO2 chunks or aggregates.
3.2. TGA thermal analysis
Fig. 3 shows TGA and differential gravimetric analysis
(DTG) thermographs of the PVA polymer membrane alone,
the PVA/TiO2 (15 wt.%) composite polymer membrane (without GA) and the cross-linked PVA/TiO2 (15 wt.%) composite
polymer membrane (with GA) in this work, respectively. TGA
and DTG curves of the pure PVA polymer film reveal three
main weight loss regions, which appear as three peaks in the
DTG curves. The first region at a temperature of 80100 C
is due to the evaporation of physical weakly and chemically
strongly bound water; the weight loss of the membrane is about
7.39 wt.%. The second transition region at around 250350 C
is due to the degradation of PVA polymer membrane; the total
weight loss corresponds to this stage about 76.67 wt.%. The peak
of third stage at 425 C is due to the cleavage backbone of PVA
polymer membrane (or so-called carbonation); the total weight
loss is 91.30 wt.% at 500 C, as listed in Table 1.
Moreover, the TGA and DTG curves of the PVA/TiO2 composite polymer film without cross-linked display three main
weight losses, which also appear as three peaks in the DTG
curves. The first stage at a temperature range of 80100 C is

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

PVA film (%)


PVA/TiO2 (15 wt.%) SPE
(without cross-linked) (%)
PVA/TiO2 (15 wt.%) SPE
(cross-linked by GA) (%)

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:

Fig. 3. TGA thermograph of the cross-linked PVA/TiO2 (15 wt.%) composite


polymer membranes.

L
Rb A

(5)

56

C.-C. Yang / Journal of Membrane Science 288 (2007) 5160


Table 3
The conductivity values of cross-linked PVA/TiO2 (2 wt.%) (under 5 wt.% GA
at 40 C, 12 h) composites polymer membranes (SPE was dipped in 8 M KOH
for 24 h) at different temperatures
T ( C)

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

obtained, as shown in Fig. 4(b). Notice that, the cross-linked


polymer membrane was immersed in 8 M KOH solutions for at
least 24 h before measurement. As a result, the Rb values for the
cross-linked PVA/TiO2 composite membranes are of the order of
less than 3.50  and are dependent on the contents of TiO2 fillers
and the cross-linking conditions ( in the order of 103 S cm2 ).
Table 3 shows the ionic conductivity values for the cross-linked
PVA/TiO2 (2 wt.%) composite polymer membrane at different
temperatures. Notably, the corresponding value of ionic conductivity at 30 C is about 0.0056 S cm1 . It was found that
the highest ionic conductivity value of alkaline cross-linked
PVA/TiO2 (20 wt.%) composite polymer membrane reaches
about 0.0120 S cm1 at 30 C. It can be seen clearly that the ionic
conductivity of the cross-linked PVA/TiO2 SPE decreases some
extent after the PVA/TiO2 polymer membrane is cross-linked by
gultaraldehyde.
As a matter fact, the cross-linked PVA/TiO2 composite membrane may have less accessible free volume for the KOH
electrolyte; therefore, the ionic conductivity is in the order of
103 S cm1 at ambient temperature. However, the cross-linked
PVA/TiO2 composite membranes show greater thermal properties (as indicated in TGAs results) and chemical stability
properties (as indicated in liquid uptakes results later). The temperature dependence of the ionic conductivity is of the Arrhenius
type:


Ea
= 0 exp
(6)
RT
where 0 is a pre-exponential factor, Ea the activation energy,
and T is the temperature in Kelvins. The log10 () versus 1/T
plots, as shown in Fig. 5, obtains the activation energy (Ea ) of the
PVA composite SPE, which is highly dependent on the contents
of TiO2 fillers and the cross-linking conditions. The Ea value for
alkaline cross-linked PVA/TiO2 composite polymer membrane
is in the order of 11 kJ mol1 (normally cross-linked SPE shows
Ea value over 20 kJ mol1 ).
Fig. 6 shows the variation of the ionic conductivity values
versus the weight percents of TiO2 fillers for the cross-linked
PVA/TiO2 composite polymer membranes at 30 and 60 C. The
improvement ionic conductivity for the cross-linked PVA/TiO2
composite polymer electrolyte exhibited when the content of
nano-TiO2 filler is over 10 wt.%. In contrast with, Yang and Lin
[33,34] reported the ionic conductivity values of the blend PVA
polymer electrolyte (free of TiO2 fillers) are about 0.0471 and

C.-C. Yang / Journal of Membrane Science 288 (2007) 5160

57

Table 4
The liquid uptake (%) results for the PVA/TiO2 composite polymer membranes
at 25 C
Types of membranes

PVA + 2 wt.% TiO2


PVA + 5 wt.% TiO2
PVA + 10 wt.% TiO2
PVA + 2 wt.% TiO2 + 5 wt.% GA
PVA + 5 wt.% TiO2 + 5 wt.% GA
PVA + 10 wt.% TiO2 + 5 wt.% GA

Fig. 5. Arrehenius plot of PVA/TiO2 (2 wt.%) composite polymer membranes:


(a) PVA direct blend KOH without cross-linked; (b) the PVA/TiO2 composite
polymer film cross-linked with GA.

0.0528 S cm1 , at 20 and 60 C, respectively. It can be concluded


that the optimum content of TiO2 ceramic filler in the PVAbased composite polymer membrane must keep around 10 wt.%
in order to obtain a uniform composite SPE film.
Moreover, we found that the anionic transport number value
(t ) of alkaline cross-linked PVA/TiO2 (2 and 15 wt.%) composite polymer membrane is about 0.80 and 0.70, respectively, by
Hittorfs method. Comparatively, the anionic transport number
of alkaline blend PVA polymer electrolyte at ambient temperature is about 0.940.95 [52]. The lower value of anion transport
number value for the cross-linked PVA/TiO2 SPE indicates that
the OH ions (function as major charge carriers) are not easily
to transport in the matrix of cross-linked PVA/TiO2 SPE.

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

C.-C. Yang / Journal of Membrane Science 288 (2007) 5160

Fig. 7. The Et curves for the DMFC in 2 M KOH + 15 M CH3 OH solutions


at 20 mA cm2 at 60 C at ambient pressure.

solutions at 20 mA cm2 at 60 C. In spite of a tendency to


fall at the beginning of the test, the cell potential are stabilized
and remain constant after 1 h, it shows the good electrochemical stability of the DMFC. Table 5 shows the cell potentials
of the DMFC in different CH3 OH concentrations at 60 C at
1 atm. The results indicate that the highest cell working potential (Ecell = 0.320 V) of the DMFC is in 2 M KOH + 2 M CH3 OH
solutions.
Fig. 8 shows the potentialcurrent density curves and
power densitycurrent density curves of the alkaline DMFC
(A = 8 cm2 ) at the temperature between 30 and 60 C in
2 M KOH + 2 M CH3 OH solution at ambient pressure. In
fact, the peak power density of 3.86 mW cm2 was achieved
at Ep,max = 0.238 V with a peak current density (ip,max ) of
16.17 mA cm2 at ambient temperature and pressure. On the
other hand, the maximum power density of 7.54 mW cm2 was
obtained at Ep,max = 0.258 V with a peak current density of
29.18 mA cm2 at 60 C. Moreover, Table 6 lists some electrochemical parameters, such as the open circuit potential (Eocp ),
the maximum peak power density (PDmax ), the peak potential (Ep,max ) and the peak current density (ip,max ) at different
temperatures for the alkaline DMFC. It was found that the values of open circuit potential of the alkaline DMFC are about

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

0.770.84 V. As a result, the maximum peak powder density


of the alkaline DMFC increases as the operation temperature
increases. Finally, it is important to study the durability of
cross-linked PVA/SiO2 composite membrane on DMFC under
long-term operation. Fig. 9 demonstrates the result of long-term

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).

C.-C. Yang / Journal of Membrane Science 288 (2007) 5160

stability test for the alkaline DMFC at 25 C and 1 atm for 50 h


operation. The measurement of cell potential versus time was
recorded at 20 mA cm2 (the load current density is higher than
the ip,max = 16.17 mA cm2 with a mean PD = 3.41 mW cm2 )
under ambient conditions for a total time of 50 h. During the
stability test, the measurement was carried out for a continuous operation of 10 h plus 30 min off-period. It was found that
the cell working potential of 0.17 V for alkaline DMFC was flat
and stable at 20 mA cm2 ; in contrast, the cell potential was
immediately from 0.17 V back to OCP (about 0.77 V) during
off-period.
Scrosati et al. [7] studied the cross-linked PVA/SiO2 composite polymer membrane for a lab-type acidic DMFC using
2 M H2 SO4 + 2 M CH3 OH solutions, the cell with a maximum
peak power density of only about 2.0 mW cm2 at ambient temperature and pressure. Furthermore, according to their results,
it was found that the stability of MEA with Nafion polymer membrane seems not stable for their lab-type DMFC. By
contrast, the electrochemical performance of alkaline DMFC
system with the cross-linked PVA/TiO2 composite membrane
(PD = 3.86 mW cm2 ) shows better than that of acidic DMFC
cell with the cross-linked PVA/SiO2 composite membrane
(PD = 2.00 mW cm2 ) at ambient conditions. It was demonstrated that the alkaline DMFC system exhibits some advantages
over than that of the acidic DMFC system. In particular, the alkaline DMFC with the air electrode is allowed to use non-precious
metal catalyst (i.e., with MnO2 catalyst inks instead of with
Pt/C inks) and also choose the cross-linked PVA/TiO2 composite polymer membrane (i.e., not perfluorosulfonated cheap
polymer membrane instead of Nafion).
4. Conclusions
A novel cross-linked PVA/TiO2 composite polymer membrane was prepared by a solution casting method. Alkaline
direct methanol fuel cell (DMFC) consisting of this novel crosslinked PVA/TiO2 composite polymer membrane was assembled
and examined. The novel alkaline DMFC cell is comprised of
the air cathode electrode with MnO2 catalyst inks, the PtRu
anode electrode and the novel cross-linked PVA/TiO2 composite
polymer membrane. It was demonstrated that alkaline DMFCs
with these cross-linked PVA/TiO2 composite polymer membranes show good electrochemical performances at ambient
temperatures and pressure. The maximum peak power density of the DMFC is about 7.54 mW cm2 at 60 C and 1 atm.
From the economic and application point of view, the crosslinked PVA/TiO2 composite polymer membranes are easily
prepared for the mass production and PVA is also a cheap polymer material. These cross-linked PVA/TiO2 composite polymer
membranes show a highly potential candidate for the DMFC
applications.
Acknowledgement
Financial support from the National Science Council, Taiwan
(Project no: NSC-94-2214-131-002) is gratefully acknowledged.

59

References
[1] W.H. Lizcano-Valbuena, V.A. Paganin, E.R. Gonzalez, Methanol electrooxidation on gas diffusion electrodes prepared with PtRu/C catalysts,
Electrochim. Acta 47 (2002) 3715.
[2] N. Nakagawa, Y. Xiu, Performance of a direct methanol fuel cell operated
at atmospheric pressure, J. Power Sources 118 (2003) 248.
[3] G.-G. Park, T.-H. Yang, Y.-G. Yoon, W.-Y. Lee, C.-S. Kim, Pore size effect
of the DMFC catalyst supported on porous materials, Int. J. Hydrogen
Energy 28 (2003) 645.
[4] H. Fukunaga, T. Ishida, N. Teranishi, C. Arai, K. Yamada, Impedance of
vapor feed direct methanol fuel cells-polarization dependence of elementary processes at the anode, Electrochim. Acta 49 (2004) 2123.
[5] V. Baglio, A.S. Arico, A.D. Blasi, V. Antonucci, P.L. Antonucci, S. Licoccia, E. Traversa, F.S. Fiory, Nifion-TiO2 composite DMFC membranes:
physico-chemical properties of the filler versus electrochemical performance, Electrochim. Acta 50 (2005) 1241.
[6] T.C. Deivaraj, J.Y. Lee, Preparation of carbon-supported PtRu nanoparticles
for direct methanol fuel cell applicationsa comparative study, J. Power
Sources 142 (2005) 43.
[7] S. Panero, P. Fiorenza, M.A. Navarra, J. Romanowska, B. Scrosati, Sillcaadded, composite poly(vinyl alcohol) membranes for fuel cell application,
J. Electrochem. Soc. 152 (12) (2005) A2400.
[8] K. Furukawa, K. Okajima, M. Sudoh, Structural control and impedance
analysis of cathode for direct methanol fuel cell, J. Power Sources 139
(2005) 9.
[9] J.H. Choi, Y.M. Kim, J.S. Lee, K.Y. Cho, H.Y. Jung, J.K. Park, I.S. Park,
Y.E. Sung, A polyaniline supported PtRu nanocompsite anode and a Pdimpregnated nanocomposite Nafion membrane for DMFCs, Solid State
Ionics 176 (2005) 3031.
[10] V.S. Silva, S. Weisshaar, R. Reissner, B. Ruffmann, S. Vetter, A. Mendes,
L.M. Madeirs, S. Nunes, Performance and efficiency of a DMFC using nonflourinated composite membranes operating at low/medium temperatures,
J. Power Sources 145 (2005) 485.
[11] B.E. Hayden, D.V. Malevich, D. Pletcher, Platinum catalysed nanoporous
titanium dioxide electrodes in H2 SO4 solutions, Electrochem. Commun. 3
(2001) 395.
[12] E. Antolini, Formation of carbon-supported PtM alloys for low temperature
fuel cells: a review, Mater. Chem. Phys. 78 (2003) 563.
[13] G.Q. Lu, C.Y. Wang, Development of micro direct methanol fuel cells for
high power applications, J. Power Sources 144 (2005) 141.
[14] C.Y. Chen, P. Yang, Performance of an air-breathing direct methanol fuel
cell, J. Power Sources 123 (2003) 37.
[15] T. Shimizu, T. Momma, M. Mohamedi, T. Osaka, S. Sarangapani, Design
and fabrication of pumpless small direct methanol fuel cells for portable
applications, J. Power Sources 137 (2004) 277.
[16] K. Kordesch, V. Hacker, U. Bachhiesl, Direct methanol-air fuel cells
with membranes plus circulating electrolyte, J. Power Sources 96 (2001)
200.
[17] J.G. Liu, T.S. Zhao, R. Chen, C.W. Wong, The effect of methanol concentration on the performance of a passive DMFC, Electrochem. Commun. 7
(2005) 288.
[18] B.K. Kho, I.H. Oh, S.A. Hong, H.Y. Ha, The effect of pretreatment methods
on the performance of passive DMFCs, Electrochim. Acta 50 (2004) 781.
[19] P. Costamagna, S. Srinivasan, Quantum jumps in the PEMFC science and
technology from the 1960s to the year 2000, J. Power Sources 102 (2001)
242.
[20] C. Wang, Z.X. Liu, Z.Q. Mao, J.M. Xu, K.Y. Ge, Preparation and evaluation
of a novel self-humidifying Pt/PFSA composite membrane for PEM fuel
cell, Chem. Eng. J. 112 (2005) 87.
[21] H. Chang, J.R. Kim, J.H. Cho, H.K. Kim, K.H. Choi, Materials and processes for small fuel cells, Solid State Ionics 148 (2002) 601.
[22] R. Benitez, J. Soler, L. Daza, Novel method for preparation of PEMFC
electrodes by the electrospray technique, J. Power Sources 151 (2005)
108.
[23] R. Fernandez, P. Ferreira-Apericro, L. Daza, PEMFC electrode preparation:
influence of the solvent composition and evaporation rate on the catalytic
layer microstructure, J. Power Sources 151 (2005) 18.

60

C.-C. Yang / Journal of Membrane Science 288 (2007) 5160

[24] A. Ayed, J. Bouet, F.J. Fauvarque, Comparative study of protonic conducting polymers incorporated in the oxygen electrode of the PEMFC, J. Power
Sources 149 (2005) 66.
[25] R. Thangamuthu, C.W. Lin, Membrane electrode assemblies based on
solgel hybrid membranesa preliminary investigation on fabrication
aspects, J. Power Sources 150 (2005) 48.
[26] J.F. Fauvarque, S. Guinot, N. Bouzir, E. Salmon, J.F. Penneau, Alkaline poly(ethylene oxide) solid polymer electrolyte, Electrochim. Acta 40
(1995) 2449.
[27] S. Guinot, E. Salmon, J.F. Penneau, F. Fauvarque, A new class of PEObased SPEs: structure, conductivity and application to alkaline secondary
batteries, Electrochim. Acta 43 (1998) 1163.
[28] N. Vassal, E. Salmon, F. Fauvarque, Electrochemical properties of an alkaline solid polymer electrolyte based on P(ECH-co-EO), Electrochim. Acta
45 (2000) 1527.
[29] N. Vassal, E. Salmon, J.F. Fauvarque, Nickel/metal hydride secondary batteries using an alkaline solid polymer electrolyte, J. Electrochem. Soc. 146
(1999) 20.
[30] C.C. Yang, Polymer NiMH battery based on PEOPVAKOH polymer
electrolyte, J. Power Sources 109 (2002) 22.
[31] C.C. Yang, S.J. Lin, Alkaline composite PEOPVA-glass-fibre-mat
polymer electrolyte for Zn-air battery, J. Power Sources 112 (2002)
497.
[32] A. Lewandowski, M. Zajder, E. Frackowiak, F. Beguin, Supercapacitor
based on activated carbon and polyethylene oxide-KOH-H2 O polymer
electrolyte, Electrochim. Acta 46 (2001) 2777.
[33] C.C. Yang, S.J. Lin, Preparation of composite alkaline polymer electrolyte,
Mater. Lett. 57 (2002) 873.
[34] C.C. Yang, S.J. Lin, Preparation of alkaline PVA-based polymer electrolytes for NiMH and Zn-air batteries, J. Appl. Electrochem. 33 (2003)
777.
[35] E. Agel, J. Bouet, J.F. Fauvarque, H. Yassir, Utilisation d electrolyte solide
polymere dans les piles a combustibles alcalines, Ann. Chim. Sci. Mater.
26 (2001) 59.
[36] E. Agel, J. Bouet, J.F. Fauvarque, Characterization and use of anionic
membranes for alkaline fuel cells, J. Power Sources 101 (2001) 267.
[37] K.Y. Cho, H.Y. Jung, S.S. Shin, N.S. Choi, S.J. Sung, J.K. Park, J.H. Choi,
K.W. Park, Y.E. Sung, Proton conducting semi-IPN based on Nafion and
crosslinked poly(AMPS) for direct methanol fuel cell, Electrochim. Acta
50 (2004) 589.
[38] M.K. Song, S.B. Park, Y.T. Kim, K.H. Kim, S.K. Min, H.W. Rhee, Characterization of polymer-layered silicate nanocomposite membranes for direct
methanol fuel cells, Electrochim. Acta 50 (2004) 639.

[39] L. Li, J. Zhang, Y. Wang, Sulfonated poly(ether ether ketone) membranes


for direct methanol fuel cell, J. Membr. Sci. 226 (2003) 159.
[40] Y.M. Sun, T.C. Wu, H.C. Lee, G.B. Jung, M.D. Guiver, Y. Gao, Y.L. Liu,
J.Y. Lai, Sulfonated poly(phthalazinone ether ketone) for proton exchange
membranes in direct methanol fuel cell, J. Membr. Sci. 265 (2005) 108.
[41] M. Shen, S. Roy, J.W. Kuhlmann, K. Scott, K. Lovell, J.A. Horsfall, Grafted
polymer electrolyte membrane for direct methanol fuel cells, J. Membr. Sci.
251 (2005) 121.
[42] E.H. Yu, K. Scott, Development of direct methanol alkaline fuel cells using
anion exchange membranes, J. Power Sources 137 (2004) 248.
[43] E.H. Yu, K. Scott, Direct methanol alkaline fuel cell with catalysed metal
mesh anodes, Electrochem. Commun. 6 (2004) 361.
[44] E.H. Yu, K. Scott, R.W. Reeve, A study of the anodic oxidation methanol
on Pt in alkaline solutions, J. Electroanal. Chem. 571 (2003) 17.
[45] J.W. Rhim, H.B. Park, C.S. Lee, J.H. Jun, D.S. Kim, Y.M. Lee, Crosslinked
poly(vinyl alcohol) membranes containing sulfonic acid group: proton and
methanol transport through membranes, J. Membr. Sci. 238 (2004) 143.
[46] C.W. Lin, R. Thangamuthu, C.J. Yang, Proton-conducting membranes with
high selectivity from phosphotungstic acid-doped poly(vinyl alcohol) for
DMFC applications, J. Membr. Sci. 253 (2005) 23.
[47] J.R. Varcoe, R.C.T. Slade, An electron-beam-grafted ETFE alkaline anionexchange membrane in metal-cation-free solid-state alkaline fuel cells,
Electrochem. Commun. 8 (2006) 839.
[48] J.R. Varcoe, R.C.T. Slade, E.L.H. Yee, An alkaline polymer electrochemical interface: a breakthrough in application of alkaline anion-exchange
membranes in fuel cells, Chem. Commun. (2006) 1428.
[49] J.R. Varcoe, R.C.T. Slade, Prospects for alkaline anion-exchange membranes in low temperature fuel cells, Fuel Cells 5 (2005) 187.
[50] T.N. Danks, R.C.T. Slade, J.R. Varcoe, Comparison of PVDF- and FEPbased radiation-grafted alkaline anion-exchange membranes for use in low
temperature portable DMFCs, J. Mater. Chem. 12 (2002) 3371.
[51] G.M. Wu, S.J. Lin, C.C. Yang, Preparation and characterization of
PVA/PAA membranes for solid polymer electrolytes, J. Membr. Sci. 275
(2006) 127.
[52] C.C. Yang, S.J. Lin, G.M. Wu, Study of ionic transport properties of alkaline
poly(vinyl) alcohol-based polymer electrolytes, Mater. Chem. Phys. 92
(2005) 251.
[53] C.C. Yang, Preparation and characterization of electrochemical properties
of air cathode electrode, Int. J. Hydrogen Energy 29 (2004) 135.
[54] C.C. Yang, S.T. Hsu, W.C. Chien, M.C. Shih, S.J. Chiu, K.T. Lee, C.L.
Wang, Electrochemical properties of air electrodes based on MnO2 catalysts supported on binary carbons, Int. J. Hydrogen Energy 31 (2006)
2076.