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DOI: 10.1002/fuce.201000172
Department of Mechanical Engineering, Rochester Institute of Technology, 76 Lomb Memorial Drive, Rochester, NY 14623, USA
Abstract
It has now been well recognized that both the performance
and durability of proton exchange membrane fuel cells
(PEMFCs) are closely related to the water accumulation and
transport inside its porous components, particularly in the
gas diffusion layer (GDL), and microporous layer (MPL). In
this paper, the key GDL and MPL properties that affect
water transport through them are first discussed and a
review of GDL degradation mechanisms is presented. An
intermittent water drainage mechanism across the GDL is
discussed. The capillary breakthrough pressure (CBP) and
the dynamic capillary pressure (DCP), or recurrent breakthrough dynamics, have been identified as key GDL properties that affect its water management performance and func-
1 Introduction
Polymer electrolyte membrane fuel cells (PEMFCs)
directly convert the chemical energy of the reactants into electrical energy and usually consist of a proton exchange membrane (PEM) sandwiched between two catalyst layers (CLs),
two porous gas diffusion layers (GDLs) often coated with a
microporous layer (MPL) on the CL side, and two bipolar
plates with embedded gas channels. Protons and electrons
produced by a hydrogen oxidation reaction in the anode CL
flow through the membrane and the external circuit, respectively, and participate in the oxygen reduction reaction in the
cathode CL producing water and waste heat.
814
Despite considerable progress in the overall cell performance made in the past decade, a pivotal performance, and
durability limitation centers on the water management of the
PEMFC, namely the transport of product water (both liquid
and vapor) and the resulting drying and/or flooding in the
constituent components. In current PEMFC technologies,
water content of the membrane determines the membrane
performance and its durability. Although sufficient water
content is required to maintain high proton conductivity of
the membrane, excessive liquid water in the fuel cell can
flood, and block the pores of the CLs, GDLs, and gas channels. Both a dry membrane and flooded electrode hinder the
performance and lead to an accelerated degradation of the
fuel cell.
Kandlikar et al.: Water Management in A PEMFC: Water Transport Mechanism and Material Degradation
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Kandlikar et al.: Water Management in A PEMFC: Water Transport Mechanism and Material Degradation
change in porosity could be detected for GDLs aged at various conditions [2426].
2.1.2 Permeability
The permeability of the GDL is one of the major intrinsic
properties influencing reactants and water transport as well
as thermal management in PEMFCs [9]. Higher permeability
is often related to larger pores, which aid in oxygen transport
by enhancing bulk diffusion and pressure driven hydraulic
permeation through the GDL. Williams et al. [9] reported that
a GDL with higher gas permeability had the ability to avoid
water flooding under nearly saturated operating conditions.
Ahmed et al. [27, 28] found that the cell performance deteriorated due to the reduced water removal from a cathode GDL
with low permeability. Due to the anisotropic orientation of
carbon fibers as well as the addition of an MPL, the permeability of a GDL is also highly anisotropic, with much higher
in-plane permeability than through-plane permeability [9, 29,
30]. The water and thermal management in PEMFCs depend
on both the in-plane and through-plane permeability characteristics of the GDL, especially under the land region [27,28].
Attempts have been made to measure the in-plane [5, 31]
and through-plane permeabilities of GDLs with different
PTFE loadings [32], with and without an MPL [30, 32, 33] and
with varying thicknesses [33]. Moreover, Gostick et al. [30]
showed experimentally that the compression of a GDL to half
of its initial thickness causes its permeability to decrease by
an order of magnitude. Water and air relative permeabilities
in a partially saturated GDL have also been experimentally
determined [34].
The gas permeability is likely to change as the GDL is
degraded. Lee and Merida [22] observed an increase in the
in-plane and through-plane permeabilities in the GDLs subjected to freezethaw cycles between 35 and 20 C and attributed the effect to the material (mainly MPL and PTFE)
loss. It was believed that aging under freezing conditions
weakened the MPL structurally such that it was prone to
material loss from air flow through the GDL, resulting in
increased permeability. A much bigger influence of the material (PTFE) loss on liquid (relative) permeability would be
expected for a degraded GDL. However, the experimental
data on this topic is rare in literature. This is one of the motivations for the current degradation study reported in the
present paper.
2.1.3 Capillary Breakthrough Pressure (CBP) and Dynamic
Capillary Pressure (DCP)
The CBP is an important transport parameter of the GDL.
It corresponds to the first appearance of a non-wetting phase
(e.g., water in hydrophobic GDL) on the outlet face of a sample. The physical meaning of the CBP corresponds to the incipient formation of a continuum of the non-wetting phase
through a pore network of arbitrarily large size. The CBP provides a direct indicator on the liquid water transport through a
GDL.
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Kandlikar et al.: Water Management in A PEMFC: Water Transport Mechanism and Material Degradation
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Antolini et al. [56] found that the polymer coats the pores
of sizes smaller than 1 lm (carbon inter-agglomerate pores),
while the pores larger than 1 lm are not influenced by the
presence of PTFE. Above 40 wt.% PTFE, a further supply of
polymer does not fill the pores, but increases the thickness of
the layer. Qi and Kaufman [6] recommended an optimal loading of 35% PTFE and 2.0 mg cm2 carbon, based on their
study.
2.2.2 MPL Pore Structure
The MPL pores range from 0.1 to 0.5 lm in diameter, making them much smaller than the pores in the GDL, which
range from 10 to 30 lm in diameter. This fact indicates that
the influence of capillary effects on water balance is more
pronounced in the MPL [5759]. The MPL causes a sharp
increase in capillary pressure and, for a given saturation, the
capillary pressure increases with an increase in the PTFE content [58]. Lin and Nguyen [33] concluded that the hydrophobic pores are used for gas transport while the hydrophilic
pores are used for liquid water transport within the MPL.
Park et al. [60] suggested that the capillary driving force
might be the dominant water transport mechanism in the
MPL. In addition, Gostick et al. [40] found that the pore-size
distribution for the hydrophilic pores was similar in shape to
the overall distribution for standard substrate materials. Their
work indicates that proper hydrophobic and hydrophilic pore
distributions are very important for liquid water removal and
the transport of reactant gases.
Different types of carbon particles [6163] and carbon
loading [6] in the MPL have been investigated. The MPL
thickness was also investigated by Qi and Kaufman [6] and
Pasaogullari and Wang [47]. The latter concluded that an
MPL thickness of approximately 50 lm would offset the positive effects.
2.3 Summary of Desirable GDL Properties
Table 1 gives a summary of the various GDL and MPL
properties, how they are characterized, their optimal values,
and how degradation has an effect on them. Optimal values
are taken from [64] while the characterization and property
degradation sections are proposed from knowledge of the
authors group.
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Kandlikar et al.: Water Management in A PEMFC: Water Transport Mechanism and Material Degradation
Table 1 Summary of carbon paper GDL intrinsic properties related to water management, degradation, and cell performance.
Properties
Characterizations
Optimal value
GDL properties
Porosity and poresize distribution
Pore structure
7090% [812]
Permeability
TP = 10141012 m2 [32]
Both depend on PTFE
content and compression
515 kPa [3538] for most
commercial GDLs
PTFE coating
530 wt.%
0.10.5 lm
MPL properties
PTFE loading
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Kandlikar et al.: Water Management in A PEMFC: Water Transport Mechanism and Material Degradation
GDL
Structure
Baseline-A
Baseline-B
SGL 25BA
SGL 25BC
No MPL
w/MPL
No MPL
w/MPL
200
208
183
225
a)
b)
3
3
3
3
7.0
7.0
5.0
5.0
Porosity (%)
Vpore (lL)
Pb (kPa)
Sw,b (%)
87
80
88
80
29
28
27
30
7.4 1.1
12.7 1.4
1.7 0.5
6.7 1.2
4.712.2
2.4 0.2
2.67.1
0.8 0.2
New break
locations
Yes
No
Yes
No
Rc (lm)
19.5
11.3
80.9
21.5
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Quantity
Unit
Current density
Water flow rate
Compression
Temperature
2
36.4
1.4
80
A cm2
lL min1
MPa
C
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Table 2 GDL properties, water breakthrough pressures (Pb), water saturation at breakthrough (Sw,b), equivalent capillary radius corresponding to breakthrough (Rc), and information about the emergence of new break sites in different GDLs.
Kandlikar et al.: Water Management in A PEMFC: Water Transport Mechanism and Material Degradation
MPL and then the GDL substrate just as it does at the cathode
side of a PEMFC. To prevent corrosion during the AST, each
CC was gold plated at a 1.27 lm thickness. Each CC also features a 25 mm 25 mm array of 13.1 mm wide through
channels and 12.1 mm wide lands for passing water and current through the GDL, respectively. Four aluminum blocks
sandwich the two CCs and both supply water to and heat the
GDL. The water heating loop is driven by a recirculating bath
(VWR Industries 1196D). The GDL water supply is driven by
a syringe pump (Kent Scientific Co. GENIE). Data acquisition
equipment included a load cell (Omega Engineering LC3041K) and a differential pressure transducer (Honeywell
FDW2AR) for compression and CBP measurement, respectively. Finally a screw driven clamping device compresses
the entire system at the arrowed locations specified in
Figure 2.
820
9
8
7
Pressure / kPa
The AST consisted of initially taking a fresh GDL and compressing and sealing it in the test section. The syringe pump
was filled with de-ionized water produced by a water purification system (Millipore Direct-Q 3) and was 18.2 MX cm at
25 C. The water was then delivered at 70 lL min1 to measure the initial CBP and observe the dynamics through the
fresh GDL. Subsequently, the AST conditions were set and
the system was run until the degradation time reached 500 h.
At that point, the GDL was purged with purified air at less
than 2 ppm of water content for 1 hour at 1 SLPM and then
left to dry for 1 week while still in the test section. The DCP
was, in turn, observed again at 70 lL min1 and the test section was disassembled to remove the GDL for further investigation.
6
5
4
3
2
1
0
100
200
300
400
500
600
700
800
900
1000
Time / s
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Kandlikar et al.: Water Management in A PEMFC: Water Transport Mechanism and Material Degradation
Specimen
Static
Advancing
Receding
Fresh
Degraded
147
140
145
142
144
137
Pressure / kPa
7
6
5
Specimen
0 min
15 min
30 min
45 min
Fresh
Degraded
144
142
141
134
143
123
144
104
4
3
2
1
0
0
100
200
300
400
500
600
700
800
900
1000
Time / s
Fig. 4 Plot of DCP through degraded GDL sample.
coupled with the shorter linear fall off time can also be
coupled with the GDL becoming more saturated.
4.5 GDL Hydrophobicity Investigation
The effect of the AST on the GDLs hydrophobicity was
investigated through measuring the surface contact angle on
a fresh GDL and on the degraded GDL. The measurement
system used was an AST Products, Inc. VCA Optima. The
degraded GDL as well as a separate fresh GDL cut from the
same sheet were both investigated and the surface contact
angle on the MPL side of both GDLs was measured. Table 4
outlines the averaged results for static, advancing, and receding contact angles that were taken at three different locations
on each GDL sample. It can be drawn from the table that,
with respect to the degraded GDL, a decrease in all three
angles occurred and, in turn, a decrease in hydrophobicity of
the MPL surface occurred.
The areas where water was passed through the GDL during the AST were found to be much less hydrophobic than
the areas where current was passed. When dispensing the
droplets onto the narrow strips of MPL surface where current
was applied during the AST, the droplet would move to the
areas of the MPL where water was passed. This was consistent throughout the contact angle measurement process and,
in turn, forced all the contact angles measured on the
degraded MPL surface to be at the areas where the water was
passed through.
A time study was also conducted to further investigate the
hydrophobicity change of the degraded MPL surface. Identical sized water droplets were dispensed onto the both the
fresh and degraded MPL surfaces and the static contact angle
was measured every 15 min over the course of 45 min.
Images of the water droplets taken for both MPL surfaces
during the time study are pictured in Figure 5. Table 5 lists
the static contact angles measured over time for both specimens.
It can be seen that the degraded sample had a much smaller contact angle after 45 min and showed a steady decrease in
contact angle over time while the fresh MPL surface maintained approximately the same contact angle throughout the
study.
It should also be noted that after dispensing a water droplet on the degraded MPL surface, it was impossible to withdraw it completely back into the syringe. On the contrary, the
droplet on the fresh MPL surface was able to be entirely withdrawn back into the syringe after the time study was completed. This along with the marked
decrease in contact angle ensures that the
degraded MPL surface did indeed
become less hydrophobic due to the AST
it was subjected to.
4.6 Degradation Study Summary
Fig. 5 Images of water droplet contact angle time study on both fresh and degraded MPL surfaces
of GDL samples.
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Kandlikar et al.: Water Management in A PEMFC: Water Transport Mechanism and Material Degradation
by the authors group and applied it in a novel ex situ setup
to further investigate the phenomenon as well as how it
affects GDL degradation. It is proposed that the MPL area
where water was passed during the AST became much less
hydrophobic. This caused the DCP of the GDL to change and
the water to be absorbed more easily into the GDL and thus
made it more susceptible to flooding. The contact angle measurement time study showed that the surface area of the MPL
became much less hydrophobic while the areas where current
was passed did not. Thus it can be concluded that the water
flow degraded the hydrophobicity of the MPL surface more
than the current flow. Further work is being continued by the
authors group to investigate other GDLs without MPLs or
PTFE loading in the substrate using the same procedure.
5 Conclusion
The GDL was successfully degraded as a result of the AST
and in turn both the CBP and DCP changed. The CBP
dropped by approximately 1.6 kPa and the spikes fell to a
pressure approximately 2.75 kPa lower than before. Also the
period of the spikes became much shorter and the spikes
became much steadier. A surface contact angle study
revealed a decrease in the hydrophobicity of the MPL surface
especially when the droplet was left on the surface over time.
The contact angle decreased about 40 over the course of
45 min on the degraded MPL surface while the contact angle
remained the same on the fresh MPL surface. It also showed
that the area of the MPL surface where water was passed
showed a larger decrease in hydrophobicity than the area
where the current was applied. From this study, it was concluded that the changes observed show that the degradation
mechanism caused by the AST is the loss of hydrophobicity
of the MPL. A more detailed and extended test plan is recommended under higher current loading and water flow rate
conditions to provide useful information for developing more
durable GDL and MPL materials.
The GDL is a complex component of PEMFCs and it has
been shown that its degradation can affect the CBP and DCP
which in turn affects water management in the cell. Degradation studies that pertain to the CBP are warranted as well as
visuals of how the morphology of the MPL changes with degradation time. These types of experiments can broaden the
spectrum of knowledge of the GDL and MPL and in turn
allow for the design of more robust GDLs.
Acknowledgements
The authors would like to acknowledge the US Department of Energy for the financial support under award No.
DE-EE0000470.
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