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E-mail: cxw31@psu.edu
using the streaming potential method. Ren et al.8,9 developed a measurement for fully hydrated Nafion 117 membranes in DMFC and
found that the EOD strongly increased with temperature from 2.0 at
15C to 5.1 at 130C. Ise et al.10 applied electrophoretic NMR
!ENMR" method to measure the EOD of Nafion and polyetheretherketone !PEEK" membranes and attained the values equal to 2.6 for
Nafion $! = 20% and 3.1 for PEEK membranes $! = 40%. Motupally
et al.11 utilized a HCl gas electrolyzer to measure EOD of Nafion
membranes with one side contact with liquid water and the other
side with gaseous anhydrous HCl. They fitted the EOD from a
model that is equal to 3.84 at 80C and 3.50 at 60C, respectively.
The reported EOD values of the membranes equilibrated with
water vapor are much smaller than those of the same membranes
equilibrated with liquid water. Fuller and Newman12 experimentally
determined the EOD of Nafion 117 membrane using a concentration
cell. They concluded that its value at 25C decreased from 1.4 toward zero as the activity of water in the vapor phase dropped from
unity to zero. Zawodzinski et al.13 adopted Fuller and Newmans
method and observed that the EOD values were closely equal to 1.0
for Nafion and other PFSA membranes equilibrated with water vapor over a large range of activities. Weng et al.14 utilized a specially
designed cell consisting of a large gas reservoir and a small gas
chamber and determined the EOD of the membranes from the gas
chambers partial pressure change. They reported that the EOD for
Nafion/H3PO4 membrane varied from 0.2 to 0.6, but was essentially
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JEOD = EOD
I
F
"1#
"2#
where Ja,in, Ja,out, Jc,in, and Jc,out $mol/m s% are the water fluxes of
the gas streams on the anode and cathode side and at the inlet and
outlet, respectively. If a linear relationship exists between JEOD
" F and current density, the value of EOD can then be obtained
from the slope of the line.
One advantage of using the hydrogen pumping mode to measure
EOD lies in that the hydrogen pumping cell does not generate net
water as opposed to a H2/air fuel cell so that water buildup on the
cathode and hence water back diffusion through the membrane is
minimized. This enables more accurate determination of EOD values.
In contrast, measurement of water diffusion coefficient in GoreSelect membranes was performed in an operating H2/air fuel cell
using relatively thin membranes. A schematic of the water concentration profile through the MEA is shown in Fig. 2. Due to the EOD
and water production from oxygen reduction reaction, water builds
up at the interface between the membrane and CCL forming a concentration profile shaped like a watershed. The water concentration
at the membrane/CCL interface, which is higher than that in the
cathode gas channel, must be known in order to determine the water
diffusion coefficient through the membrane. As the binary water
diffusion coefficient in hydrogen is about four times that in air,30,31
and the water flux through the anode side $Ja,w% is much smaller
than that through the cathode side $Jc,w% due to additional water
production at the cathode, the water concentration gradient through
the anode catalyst layer is believed to be much smaller than that
through the cathode. Thus, it is assumed that the membrane on the
anode side is equilibrated with water vapor in the anode gas channels as controlled through a fuel cell test station.
It has been reported in literature24,32 that the water concentration
profile within a thin membrane is approximately linear. Thus, the
water concentration at the membrane/CCL can be obtained from the
following equations
! = f 1$a%
! = !a,m + $!c,m !a,m%
"3#
x
lm
"4#
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"5#
# = #$!%
R =
m
&
lm
dx
lm
=
#$!% !c,m !a,m
&
!c,m
!a,m
d!
!
#$!%
"6#
"7#
and
Jnet = Jc,out Jc,in Jprod
"8#
where Jnet is the net water flux through the membrane, which is the
sum of the EOD and back diffusion terms, i.e.
Jnet = JEOD + JD
"9#
I
2F
"10#
I
lm
&
Cc,m
DmdC!
"11#
Ca,m
$m
EWmlm
&
!c,m
Dmd!!
"12#
!a,m
where $m and EWm are the membranes density $kg/m3% and equivalent weight !kg/mol", respectively. The water diffusion coefficients
of the membrane can then be experimentally obtained when the
EOD and !c,m become available.
Experimental
Materials. Thick MEAs with multilayer Gore-Select membranes !200 %m thick" and multilayer Nafion 115 membranes
!250 %m thick" were used in the hydrogen pumping cell to measure
the EOD of these membranes. These MEAs were self-prepared from
8 layers of 25 %m Gore-Select membranes and two layers of Nafion
115 membranes, respectively. The multilayer membranes were made
by hot pressing at 125C and 100 kgf/cm2 for 3 min. Great care was
taken to ensure that no air bubbles were formed between layers and
that the whole membrane had an excellent integrity. The catalystcoated membranes !CCM" were fabricated by a decal technique.35,36
The catalyst ink was prepared by mixing carbon supported catalyst
!40% Pt/Vulcan XC72, E-TEK, Inc., Somerset, NJ" with an appropriate amount of Nafion solution !5 wt % in alcohols/water, Aldrich". The ink mixture was first coated onto a Telfon substrate and
then was transferred onto both sides of the membrane by hot pressing. The catalyst loading for both the anode and cathode is
0.4 mg/cm2. Commercially available MEAs, 5 cm2 GorePRIMEA-18 and -25 !12 %m catalyst layer, 0.4 mg/cm2 loading,
and 18 and 25 %m membrane thickness, respectively" were used in
the fuel cell to determine water diffusion coefficient through GoreSelect membranes. The gas diffusion layers !GDL" in both hydrogen
pumping cell and fuel cell were self-fabricated from TGPH-60
Toray carbon paper by a paste casting process. The paste was prepared by dispersing a certain amount of poly!tetrafluoroethylene"
!PTFE" powder into an appropriate carbon powder solution.
Experimental setup and apparatus. A schematic diagram of
the experimental setup for the hydrogen pumping cell is illustrated
in Fig. 3. A single cell fixture of 5 cm2 with serpentine flow channels was used as a differential cell. Arbin 12-channel integrated
FCTS Fuel Cell Testing System !Arbin Corporation, College Station, TX" was used as a dc power source. Teledyne MEDUSATM
RD 890C 50 W Fuel Cell Test Station !Teledyne Energy Systems,
Inc. Hunt Valley, MA" was employed for gas supply, humidification,
and electronic load !for the fuel cell mode". Solatron 1255B frequency response analyzer !FRA, Solartron Inc., Houston, TX" and
the Teledyne Test Station were combined for HFR measurements at
various current densities. ZView softare !Scribner Associates, Inc.,
Southern pines, NC" was used to analyze the collected ac impedance
data.
The MEAs were sandwiched between GDLs, and the cell was
assembled by application of a uniform torque of 20 in. lbs between
the two copper plates on either side. Two silicon rubber gaskets
were used to ensure good sealing. The cell, pressure gauges, and
tubing connections were all carefully checked to ensure a leak-free
system. Water flux measurements at the inlet and outlet on the both
sides of the fuel cell were carried out by trapping water in the gas
streams into two laboratory gas-drying columns filled with Drierite
desiccants !W. A. Hammond Drierite Co. Ltd, Xenia, OH". A 100%
water trapping efficiency was attained within the period of each
experiment. A mass balance with 0.01 g accuracy was used to weigh
the amount of the water trapped.
Experimental procedure. The success of the experiments for
measuring EOD in the hydrogen pumping cell and determination of
water diffusion coefficient in an operating fuel cell hinges on the
accuracy of water flux measurement and on the stability of the humidifiers performance. Special care was taken to improve the experiments reliability. Before the initiation of measurements with
both hydrogen pumping cell and fuel cell operation, the MEAs were
sufficiently activated by preconditioning for over 10 h until a stable
performance was achieved so that the measurements were obtained
at the MEAs steady state. Two gas streams !H2 /H2 and H2/air for
hydrogen pumping and fuel cell operation, respectively" with a sufficiently large stoichiometry rate and roughly equal relative humidity !RH" were passed on the both sides of the cell. A good compro-
B679
mise was made between the uniform RH level along the gas
channels and the reliable measurement of water flux through the
membrane. To eliminate the effect of hydraulic pressure difference
across the membrane on water transport, the pressures on the anode
and cathode side were kept equal using the backpressure regulators
during each measurement. To reduce the influence of the humidifiers unstable performance and improve the measurement accuracy,
the amount of the trapped water from the gas streams was usually
more than 10 g. The water flux measurement for the inlet gas
streams was carried out immediately after that for the outlet gas
streams, and the readings of the pressure gauges were kept identical
in the whole measurement process such that the possible effect of
pressure on the actual performance of the humidifiers was eliminated. In the operational fuel cell, the measurement of HFR values
under various conditions was continuously carried out within the
possibly shortest time in order to minimize the effect of performance
degradation, if any.
rent density for both membranes. The EOD values as obtained from
the slope of the lines are 1.07 and 1.10 for Gore-Select and Nafion
membranes, respectively.
Note that the present method of measuring EOD critically depends on the membrane thickness. Too thin a membrane will give
rise to the influence of back diffusion and hence erroneous EOD
coefficient. Our experimental data showed that the EOD value so
obtained for a 25 %m Gore-Select membrane was only 0.51, as
shown in Fig. 6. In addition, deviation from the linearity is clearly
seen for higher current densities at 95% RH.
We validated the methodology of hydrogen pumping cell with
the measurement of Nafion membranes. A summary of the results
reported in the literature for EOD values of Nafion membranes is
shown in Fig. 7. If not mentioned, they were for Nafion 117 membrane at ambient temperatures. Note that the EOD value we obtained for Nafion 115 membrane at 80C agrees well with that reported by Zawondzinski et al. for Nafion 117 at 30C,13 which has
been widely used in the literature !see Ref. 4 and references therein".
They are all closely equal to 1.0 over a large range of water content
albeit at different temperatures. The EOD value of Gore-Select
membranes, measured for the first time to the best of our knowl-
Figure 6. Net flux of water vs current density for Gore-Select 25 %m membrane in a hydrogen pumping cell.
B680
than that of the membrane at open circuit under the same conditions,
and this tendency became stronger with increasing current density.
Therefore, for a thin membrane as we used in this study EOD does
not dehydrate the membrane at the anode. Instead, the net effect of
current load is that the membrane becomes wetter due to the production of water at the cathode and the strong back diffusion sufficiently compensating for EOD. This observation is in agreement
with those reported in the literature. Buchi and Scherer39,40 reported
that the resistance decreased with current density for the thin Nafion
112 membrane but increased for thick membranes.
Water diffusion coefficient of Gore membranes. To characterize water diffusion coefficient of the membrane, we need to obtain
accurately the water concentration at the membrane/CCL interface
from HFR measurements via the membranes proton conductivity as
a function of water activity such as the following
# = 0.12a2.80
"13#
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Figure 10. Scattering of the scaling factor for the water diffusion coefficient
of Gore-Select membranes relative to that of Nafion membranes.
D!&4
' (
1
1
)*
"14#
Acknowledgments
We acknowledge ECEC industrial sponsors for their financial
support of this work and W. L. Gore & Associates for donation of
various fuel cell materials.
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