i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 5 8 5 0 e5 8 6 5

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Review

A review of gas diffusion layer in PEM fuel cells: Materials

and designs

Sehkyu Park 1, Jong-Won Lee 2, Branko N. Popov*

Center for Electrochemical Engineering, Department of Chemical Engineering, University of South Carolina, 301 Main Street,
Columbia, SC 29208, USA

article info abstract

Article history: The gas diffusion layer (GDL) plays a key role on reactant gas diffusion and water
Received 6 September 2011 management in proton exchange membrane (PEM) fuel cells. This paper reviews recent
Received in revised form developments of single- and dual-layer GDLs for PEM fuel cells and various materials and
21 December 2011 approaches used for development of novel GDL. A variety of carbon- and metal-based
Accepted 28 December 2011 macroporous substrates are presented. Hydrophobic treatments using different fluori-
Available online 6 February 2012 nated polymers are addressed. Engineering parameters which control the performance of
microporous layer such as carbon treatment, wettability, thickness, and microstructure are
Keywords: also reviewed. In addition, future prospects for development of new GDL development are
Gas diffusion layer discussed.
Water management Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Proton exchange membrane fuel cell reserved.
Macroporous substrate
Microporous layer

1. Introduction impedes reactants transport through non-reactive region.

The proton exchange membrane (PEM) fuel cell is becoming
center of attention as an alternative power source for auto-
motive and stationary applications, since it is capable of
producing high power densities under rapid change in load
[1,2]. However, effective water management is necessary in
order to meet fast response to power required in a system, i.e.,
deficient water reduces ionic conductivity in the membrane
and the catalyst layer (CL) as well as induces severe contact
resistance between the membrane and the CL, whereas
excessive water in the membrane-electrode-assembly (MEA)
reduces catalytic sites for electrochemical reactions and
Liquid water condensed from the water vapor and produced
by oxygen reduction reaction at the cathode CL moves into the
membrane or the gas diffusion layer (GDL). In the former case,
higher liquid water pressure formed by electro-osmotic drag
and electrochemical reaction at the interface between the
membrane and the CL drives water flow toward the anode. In
the latter, liquid water accumulates at the CL/GDL interface
and then flows toward the gas flow channel when liquid water
pressure exceeds a threshold pressure for water flow through
the GDL determined by its pore geometry and hydrophobicity.
The GDL in PEM fuel cells is sandwiched between the CL
and the gas flow channel and its structure controls the

* Corresponding author. Tel.: þ1 (803) 777 7314; fax: þ1 (803) 777 8265.
E-mail address: popov@cec.sc.edu (B.N. Popov).
1
Present address: Pacific Northwest National Laboratory, Richland, WA 99352, USA.
2
Present address: Korea Institute of Energy Research, Daejeon 305-343, South Korea.
0360-3199/$ e see front matter Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.12.148
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 5 8 5 0 e5 8 6 5
catalyst utilization and the overall cell performance. It allows
gas transport toward the CL while providing a physical
support for the CL. It also aids water vapor to reach the
membrane increasing its ionic conductivity, while causing
liquid water produced at the catalytic active sites to leave the
CL/membrane interface. The GDL is typically wet-proofed so
that the surface and pores in the GDL are not clogged with
liquid water that could impede gas transport to the CL. The
GDL consists of a macroporous substrate (MPS) (i.e., single-
layer GDL) or a thin carbon layer on a sheet of macroporous
carbon cloth or carbon paper (i.e., dual-layer GDL). The
structure of dual-layer GDL is presented in Fig. 1 [3]. As seen,
the first layer in contact with the gas flow channel is the MPS
serving as a gas distributor and a current collector. The second
layer is a thin microporous layer (MPL) which contains carbon
powder and hydrophobic and/or hydrophilic agent, primarily
managing two-phase water flow.
With increasing interests in effective water management
through the GDL in PEM fuel cells, it is necessary to shine light
on the subject of novel materials and lead architecture in the
GDL which could maximize performance and stability in PEM
fuel cells. This review is focused on a variety of strategies in
development of advanced GDLs. First, different MPS materials
such as carbon-based and metal-based substrates are
reviewed, followed by its effective hydrophobic treatment.
Next, MPL materials and water managements using hydro-
phobic and hydrophilic additives are addressed. Various
approaches for an advanced architecture down to micro-
structure are also presented. Finally, future prospects for
a novel GDL development are given and this is followed by
summary.
2. Single-layer gas diffusion layer
A single-layer GDL is typically carbon-based product,
including woven carbon cloth, non-woven carbon paper,
carbon felt, and carbon foam. Carbon-based GDL is widely
used because (i) it is stable in acid environment, (ii) provides
high gas permeability and good electronic conductivity, (iii) is
elastic on compression, and (iv) controls porous structure of
a dual-layer GDL, as depicted in Fig. 2 [4]. Metal-based GDL
such as metal mesh, metal foam, and micromachined metal
Fig. 1 e Schematic diagram of a dual-layer GDL for PEM fuel
cells. Reprinted from Ref. [3] with permission of Elsevier.
5851
Fig. 2 e PSD curves (dV/dlogdp) for single-layer (SGL 10CA,
and carbon cloth A) and dual-layer GDL (SGL 10BB and
ELAT-LT-1400W) by mercury porosimetry. (Inset) PSD
curves (dV/ddp). Reprinted from Ref. [4] with permission of
Elsevier.
substrate has been developed and applied to PEM fuel cells
due to good mechanical strength and high stability over
a wide potential range. Hydrophobic treatment of a single-
layer GDL is necessary to prevent water flooding and facili-
tate oxygen transport at the cathode. Many researchers have
conducted extensive experimental and theoretical works on
the single-layer GDL to investigate effects of the MPS and
hydrophobic treatment on the PEM fuel cell performance.
2.1. Macroporous substrates
Carbon-fiber paper or cloth has been typically employed as
a substrate for the GDL in PEM fuel cells. Conventionally,
carbon fibers are graphitized at high temperature (>2000  C) to
enhance electronic conductivity and mechanical strength,
and impregnated with thermoset resin to manufacture carbon
papers. Carbon cloths are produced by spinning and weaving
of carbon yarns, followed by carbonization or graphitization
[5,6]. More details for carbon-fiber products and processing
can be found in Ref. [5]. Modification of carbon-fiber cloth by
phenolic resin before carbonization [7] improved fuel cell
polarization behavior without significant ohmic and mass
transfer losses. Liu et al. [8] prepared carbon-fiber paper with
different yard weights (70e320 g m2) for the cathode GDL.
Their carbon-fiber paper with a small yard weight which has
smaller thickness and lower permeability led to a better
performance, although its electronic conductivity is relatively
small. Expanded graphite manufactured by perforation
process from flexible graphite sheet was proposed by Yazici
[9]. The performance obtained using expanded graphite at the
cathode was comparable to that of the dual-layer structured
ELAT (E-TEK).
The performance of PEM fuel cells using both carbon paper
and carbon cloth has been reported in Ref. [10e12]. Ralph et al.
5852 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 5 8 5 0 e5 8 6 5
[10] examined commercially available carbon paper (TGP-090,
Toray) and carbon cloth (Panex PWB-3, Zoltek). Their results
showed better performance at high current densities when
carbon cloth was used as a substrate. Fuel cell operation with
air feed showed that the enhancement in oxygen diffusion
across the cathode was primarily due to higher porosity and
water removal rate. Similarly, Frey and Linardi [11] demon-
strated better performance using carbon cloth (0.33 mm, 35 wt
% PTFE, EC-CC1-060T), as compared to that using carbon paper
(0.17 mm, 35 wt% PTFE, EC-TP1-060T), although the thickness
of the carbon cloth is larger. Wang et al. [12] simulated two-
phase transport across both carbon paper and carbon cloth
used as a single-layer GDL in PEM fuel cells. For fully humid-
ified feed, the cathode with carbon cloth facilitated water
removal due to relatively low tortuosity and rough surface,
and reduced oxygen transport limitation toward catalytic
sites. However, carbon paper improved the performance by
mitigating membrane dehydration under low humidity
condition.
Recently, Gao et al. [13] developed a new carbon paper
made up of carbon nanotube (CNT), polyacrylonitrile-based
carbon fiber and PTFE, which showed higher electronic
conductivity due to high degree of graphitization and larger
pore volume at 0.03e3 mm in pore diameter, as compared to
Toray carbon paper (TGP-H-060) with the MPL. Based on the
result that in-plane liquid water saturation is more severe
than through-plane saturation in diffusion media [14], as seen
in Fig. 3, Gerteisen et al. [15,16] made an attempt to drill holes
into the carbon paper along a pattern of gas flow channel by
laser perforation which made clear cut edge within holes
(80 mm in diameter). Their results showed better water
management under change in load, as compared to the
untreated GDL in both single cell and 6-cell stack test. Carbon
cloth typically has low tortuosity and dual pore size distribu-
tion (PSD) resulting from spaces between carbon yarns and
between carbon fibers [4]. Modification of carbon paper by
laser perforations may increase macropore volume, resulting
in dual PSD. It is inferred that the improvement in fuel cell
performance using carbon cloth or carbon paper with perfo-
rations can be mainly ascribed to local flooding mitigation by
macropores with a short drain path.
On the other hand, metal substrate made of stainless steel
mesh [17], titanium mesh [18e23], nickel mesh [24], or
Fig. 3 e (a) SEM micrograph for a hole made by laser perforation. (b) Schematic diagram of perforations in the GDL along the
gas flow channel. Reprinted from Ref. [15] with permission of Elsevier.
nickelechromium alloy foam [25] have been employed as
a liquid fuel diffusion medium or an oxidant diffusion
medium in PEM fuel cells. Oedegaard et al. [17] prepared the
anodes with different diffusion media such as carbon cloth A
(E-TEK), carbon cloth B (E-TEK), carbon paper (TGP-H-090,
Toray), stainless steel wire cloth (Filtertechnik GmbHWilly
Spee) and compared polarization characteristics. They found
that stainless steel wire cloth as an anode diffusion medium
in direct methanol (DM) fuel cells led to a higher performance
due to a higher electronic conductivity and a better two-phase
transport of methanol and carbon dioxide to and from the CL.
Ioroi et al. [26] and Wittstadt et al. [27] applied a titanium
substrate, dipped into the PTFE emulsion and heat-treated, to
bifunctional oxygen electrode in unitized regenerative (UR)
fuel cells and demonstrated stable performance without
severe water flooding in fuel cell mode.
Microfabricated metal GDL has been developed by micro-
machining technology [28,29]. The process of thin metal GDL
consists of (i) mask design, (ii) the photoresist coating onto
metal or sacrificial layer, (iii) photolithographic patterning of
the photoresist, (iv) chemical etching of metal or sacrificial
layer, and (v) photoresist and sacrificial layer removal.
Microfabrication processes and SEM image for thin titanium
GDL are illustrated in Fig. 4. Using this micromachining
technique, Fushinobu et al. [28] attempted to make thin tita-
nium GDL using various design parameters: the pattern of the
current collector, the diameter of microhole, and the thick-
ness of the GDL. A single cell test was conducted to examine
effects of design parameters on the PEM fuel cell performance.
Also, the performance was evaluated at different operating
conditions. Their results exhibited that when the titanium
GDL is used, the humidification of the reactants makes the
cathode flooded at low temperature, resulting in lower
performance. However, it enhances the performance at high
temperature due to the improved membrane conductivity.
They also displayed better performance with smaller micro-
holes and thinner GDL at constant porosity. As a result, the
polarization curve obtained using titanium GDL was compa-
rable to that of a commercially available carbon paper GDL at
low current densities (i.e., <200 mA cm2).
Similarly, Zhang et al. [29] fabricated thin copper GDL using
MEMS (microelectromechanical systems) technology and
placed the copper GDL and the carbon paper (Toray, TGP-H-
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 5 8 5 0 e5 8 6 5
Fig. 4 e (a) Flow chart of microfabrication processes for titanium GDL. (b) SEM micrograph of titanium GDL with microholes.
Reprinted from Ref. [28] with permission of Elsevier.
060) onto each cathode CL. The carbon paper led to better fuel
cell performance at high stoichiometry (i.e., lH2 ¼ 4 and
lair ¼ 4), while the copper GDL improved water management,
resulting in better oxygen diffusion at low stoichiometry (i.e.,
lH2 ¼ 2 and lair ¼ 2) due to relatively small thickness and
straight-pore feature with different diameters. Although
a thin metal substrate was successfully used as a GDL, its
competence under oxidizing condition in aqueous solution of
low pH is still in issue. Thus, durability of these metal
substrates has to be examined in a long-term or an acceler-
ated corrosion condition.
2.2. Hydrophobic treatment
The wettability of carbon-fiber paper or cloth is typically
controlled by hydrophobic treatment to effectively remove the
liquid water saturated at the cathode [30,31]. In order to
provide hydrophobicity to the carbon paper or cloth, various
hydrophobic agents have been employed: polytetrafluoro-
ethylene (PTFE) [32e35], polyvinylidene fluoride (PVDF) [36],
and fluorinated ethylene propylene (FEP) [37e39]. The hydro-
phobic agent is applied to the GDL in various ways: dipping,
spraying, brushing, etc. A representing hydrophobic treat-
ment is dipping a GDL into a suspension which contains
hydrophobic polymers, followed by drying and heating above
350  C to remove surfactants and uniformly distribute
hydrophobic polymer. The amount of hydrophobic agent
throughout the GDL is controlled by dipping time and
concentration of the suspension.
Bevers et al. [34] examined carbon paper loaded with
different PTFE contents and sintered at various temperatures.
The carbon papers were characterized, in terms of gas
permeability, wettability, and electronic conductivity. Their
results demonstrated that the carbon paper with higher PTFE
content reduces water saturation in the GDL, while it causes
poor gas transport and high electronic resistance. Park et al.
[35] studied how the PTFE concentration in the carbon paper at
the cathode influences the polarization behavior at various
5853
relative humidities (RHs). The results showed that the carbon
paper loaded with 15 wt% PTFE resulted in better fuel cell
performance due to high air permeability and fast water
removal. Prasanna et al. [40] studied commercially available
carbon papers with different PTFE contents (10e40 wt%) using
scanning electron microscopy, gas permeability measure-
ment, electrochemical impedance spectroscopy, and polari-
zation technique. Poor fuel cell performance was observed for
the cathode GDL loaded with 30 wt% or higher PTFE mainly
due to the decreased porosity. The gas permeability
measurement and ac-impedance study indicated the opti-
mized PTFE content in the GDL (20 wt% PTFE in their study) led
to better gaseous oxygen diffusion and liquid water transport,
thereby reducing charge transfer resistance in the CL.
Lim and Wang [38] treated a commercially available GDL
(Toray, TGP-H-090) with 10 or 30 wt% FEP and examined the
dependency of polarization characteristics on the hydro-
phobic agent concentration. They showed that 10 wt% FEP
provides sufficient hydrophobicity to avoid water flooding
inside the GDL, resulting in better fuel cell performance,
especially at high operating temperature (90  C in their study).
The enhancement in performance resulted from better mass
transfer of reactants and products owing to less blockage of
the GDL surface. The hydrophobic property of the carbon cloth
woven from active carbon fibers (Beam Associate Co., Ltd) was
enhanced by CF4 plasma treatment [41]. CF4 plasma treatment
of active carbon fibers slightly reduced electronic resistivity
and made hydrophobic materials (i.e., fluorine molecules and
CFþ3 hydrophobic functional groups) uniformly distributed on
the carbon fibers without reducing void space between active
carbon fibers. Comparing the power density data at the back
pressure of 20 psi for the cathode GDL, the GDL treated with
CF4 plasma resulted in ca. 1.5 times higher performance than
the GDL without CF4 treatment (10 wt% PTFE).
In order to understand the effect of hydrophobic treatment
into the cathode GDL on liquid water transport, Benziger et al.
[42] measured the minimum pressure necessary to penetrate
liquid water across the GDL using a pressurized membrane
5854 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 5 8 5 0 e5 8 6 5
filtration cell. They showed that initial water flow for
a hydrophobized GDL (20e60 wt% PTFE) was observed beyond
5 kPa, which was fivefold higher than the pressure applied to
the GDL during fuel cell operation. Under the assumption that
liquid water flows across a cylindrical hydrophobic pore, they
calculated the largest pores for liquid water flow and the
fraction of pore volume filled with liquid water at a constant
water flux. The largest pores for liquid water flow in the
carbon paper and the carbon cloth were ca. 21 mm and ca.
135 mm, respectively. The volume fraction of the pores occu-
pied by liquid water did not exceed ca. 0.31. The authors
supposed that the PTFE treatment makes more pores liquid
water free due to high surface energy of the water/PTFE
interface in the pore, resulting in better reactant transport.
Park and Popov [43] characterized commercial carbon cloth
(Carbon Cloth A, E-TEK) with different PTFE contents and
applied each GDL to the cathode compartment to scrutinize
the effect of hydrophobic agent on mass transfer in PEM fuel
cells. From mercury intrusion experiment and polarization
curve analysis, they found that liquid water saturation in the
GDL derived from limiting current is governed by the trade-off
between contact angle and absolute water permeability. They
also quantified the effect of hydrophobic property and pore
geometry of the cathode GDL on water management and fuel
cell performance using an analytical model [44]. Fig. 5 illus-
trates average saturation savg in a single-layer GDL at various
gradients of hydrophilic surface fraction fHI with respect to
average pore diameter davg. In the absence of the gradient of
fHI with respect to davg, savg decreased with larger pore diam-
eter in a single layer. However, a minimum value of average
saturation in a GDL appeared when there existed a gradient of
fHI with respect to davg. As seen in Fig. 5, this minimum value
shifted negatively with higher gradient. The results helped to
explain that a minimum savg arises from the interplay
between hydrophilic surface fraction, which characterizes
surface energy within the pores, and average pore diameter,
coupled with the liquid water permeability.
Fig. 5 e Average saturation in the MPS with gradient of
fraction of hydrophilic surface with respect to average pore
diameter. Reprinted from Ref. [44] with permission of
Elsevier.
3. Dual-layer gas diffusion layer
Various approaches have been developed to reduce mass
transfer limitation in PEM fuel cells by tailoring the
membrane-electrode-assembly (MEA) structure. One of the
most effective approaches is to use a dual-layer GDL e (i)
a carbon-fiber woven cloth or non-woven paper substrate that
functions as a gas diffuser and as a mechanical support for the
electrode, and (ii) a thin MPL that comprises carbon black
powder and hydrophobic agent, typically PTFE [3,30,35,45e61].
The MPL reduces contact resistance between the CL and the
macroporous carbon substrate by forming flat and uniform
layer that is not permeable to the catalyst particles. More
importantly, it has been widely reported that the MPL
enhances water management in the MEA, resulting in the
improvement in fuel cell performance.
From a simulation study based on the water formation
rate, the evaporation/condensation kinetics, and the capillary
motion of the condensate in a hydrophobic GDL, Nam and
Kaviany [55] demonstrated that the MPL lowers liquid water
saturation at the interfaces between the MPL and the MPS and
between the CL and the MPL, thereby suppressing severe
water flooding at the cathode. Weber and Newman [57] sug-
gested that the MPL functions as a valve that pushes water
away from the CL to the flow field to control water saturation
level. Assuming more hydrophobic MPL can be entrenched
into the MPS, which changes pore volume and hydrophobicity
in the MPS [3], Park and Popov [44] showed that deposition of
more hydrophobic MPL reduces the fraction of hydrophilic
surface in the MPS, thus allowing faster water removal from
the cathode CL.
In general, carbon powder is mixed with PTFE-dispersed
water, organic solvent and additives to prepare carbon ink
for the MPL. The resulting carbon ink is deposited onto one side
of the carbon-fiber paper or cloth pre-treated with PTFE
suspension. The dual-layer GDL is heat-treated to evaporate all
remaining surfactants and to evenly melt PTFE throughout the
MPL. Extensive work has been carried out to investigate how
the MPL properties such as (i) carbon powder, (ii) wettability,
(iii) carbon loading (or thickness), and (iv) porous structure
make an impact on the water management in PEM fuel cells.
3.1. Carbon materials
A variety of carbon-based materials [49,53,59,60,62e66] have
been used to effectively modify pore structure and wettability
for improved mass transfer and electronic conductivity at the
cathode. Recently, using chemical vapor deposition process,
PTFE-free MPL [67e69] has been fabricated.
Jordan et al. [59,62] studied polarization characteristics for
the MEA with different carbon powders (Vulcan XC-72 and
acetylene black) in the cathode MPL (10 wt% PTFE) with an
oxygen or an air feed at various operating conditions. The MPL
which contains acetylene black led to higher power density
than that with Vulcan XC-72 due to less porous structure in
the MPL. Furthermore, when the MPL was heat-treated at
350  C for 30 min, the enhancement in performance was
observed. They claimed that uniform distribution of the PTFE
throughout the MPL by sintering makes the MPL more
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 5 8 5 0 e5 8 6 5 5855

Table 1 e Characteristics of the GDLs with different types of carbon in the MPL [49].
Carbon in MPL V (cm3 g1) APR (mm) VP (cm3 g1) VS (cm3 g1) APRP (mm) APRS (mm)

Asbury 850 0.346 3.5 0.212 0.134 0.29 8.6

Mogul L 0.276 6.0 0.157 0.119 0.20 13.6
Vulcan XC-72 0.489 1.8 0.319 0.170 0.24 4.9
Shawinigan Acetylene Black 0.594 1.7 0.368 0.226 0.27 4.3

V is pore volume; APR is Average Pore Radius; Subscripts P and S mean primary and secondary, respectively.

hydrophobic, resulting in better water management at the
cathode. In order to investigate the effect of porous carbon
structure on the fuel cell performance, Passalacqua et al. [49]
prepared the MPLs by using different types of carbon blacks:
Asbury graphite 850 (13 m2 g1 in surface area), Mogul L
(140 m2 g1), Vulcan XC-72 (250 m2 g1), and Shawinigan
acetylene black (70 m2 g1). The GDL properties measured
using mercury intrusion technique are listed in Table 1 [49].
They showed that the MPL prepared with Shawinigan acety-
lene black resulted in better fuel cell performance. The
observed performance improvement was attributed to higher
pore volume and smaller pore size of acetylene black which
facilitates gas diffusion and also reduces the amount of water
accumulation inside the MPL. Antolini et al. [60] fabricated
a triple-layer GDL (i.e., MPL/MPS/MPL) to examine carbon
powder characteristics on the polarization behavior. Simi-
larly, they obtained higher fuel cell performance with the MPL
loaded with 3.0 mg cm2 Shawinigan acetylene black. In
addition, they constructed a GDL with different combinations
of carbon powders in the MPL to measure MEA performance:
Shawinigan acetylene black (or Vulcan XC-72)/carbon cloth/
Shawinigan acetylene black (or Vulcan XC-72). The cathode
GDL with two MPLs made up of Shawinigan acetylene black
resulted in a higher limiting current and lower total resistance
at various cathode back pressures.
Chen et al. [53] measured RH of the air passing through
a dual-layer GDL at various flow rates (0.5e5.0 L min1). When
the MPL prepared with Vulcan XC-72 was utilized, higher RH
was obtained over the whole flow rates, as compared to the
MPL containing Ketjenblack EC-600JD. The authors supposed
that Ketjenblack EC-600JD keeps more water vapor in the MPL
due to its five times larger surface area and micropores in its
primary particles, resulting in lower protonic conductivity
through the membrane. Kannan and co-workers [70e72]
adopted a partially ordered graphtized carbon (Pureblack
205-110 Carbon, Superior Graphite Co.) which provides high
hydrophobicity and mechanical integrity with vapor-grown
nanofiber carbon (VGCF-H, Showa Denko America Inc.) for
the MPL applied to the carbon paper, which leads to better
mass transfer inside the MEA when compared to Vulcan XC-
72 as an MPL material. Furthermore, adding a dispersion
agent (Novec-7300) to the carbon slurry further improved fuel
cell performance at mass transfer limited regions. Kannan
et al. [67] implemented chemical vapor deposition (CVD)
technology to grow multi-walled CNT as an MPL on the carbon
paper, which leads to high and stable fuel cell performance at
70e100% RH in the absence of hydrophobic agent in the MPL.
Similarly, Du et al. [68] prepared CNT-based MPL without
hydrophobic agent and deposited Pt nanoparticles by physical
vapor deposition. As represented in Fig. 6, CNT-based MPL
served as a support for a thin CL and enhanced electronic
conductivity, resulting in higher catalyst utilization during
fuel cell operation. Tang et al. [69] fabricated in-situ grown CNT
layer onto a commercial carbon paper (TGP-H-090, Toray) and

Fig. 6 e Schematic diagram of conventional MPL (Pt/PTFE-MPL-CB) and CNT grown and PTFE-free cathode (Pt-MPL-CNT).
Reprinted from Ref. [68] with permission of Royal Society of chemistry.
5856 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 5 8 5 0 e5 8 6 5

effectively tailored its structure and morphology at various

a 1.2
C2H4 flow rates during CVD process.

iR-Corrected Cell Potential, EiR-corrteced / V

3.2. Hydrophobic and hydrophilic treatment 1.0

It is well known that capillary-driven flow arises from the

pressure difference between liquid and vapor phases [73,74]. 0.8

Since change in vapor pressure is assumed to be constant or

relatively small at a given temperature in the fuel cell, liquid 0.6
pressure building up at the CL/MPL interface mainly functions
as driving force for water flow at the cathode [30,31,57,75,76].
So, hydrophobic treatment of the MPL alleviates liquid water 0.4
PTFE content in the MPL
saturation in both the MPL and the MPS, resulting in better 10 wt%
oxygen counter flow in the GDL. One might expect that high 20 wt%
0.2
capillary pressure at the CL/MPL interface reduces catalytic 30 wt%
o
40 wt% H2 / air, 75 C
active area, leading to poor performance. However, it was
found that oxygen diffusion benefit in the MPS dominates 0 0.2 0.4 0.6 0.8 1.0 1.2
polarization characteristics in mass transfer-controlled -2
Current Density, i / A cm
regions [75].
Hydrophobic MPL for effective water management in PEM
b 1.4 160
fuel cells has been extensively studied. Giorgi et al. [47]
investigated how the PTFE content in the microporous layer -2

-1
Limiting Current Density, ilim / A cm

Empirical Tafel Slope / mV dec

affects the fuel cell performance. They suggested that 10 wt% 1.2
PTFE as a binder in the MPL was required to avoid water 150

flooding and to improve the gas transport. Lufrano et al. [48]

showed that the optimum PTFE loading was around 20 wt%
in a pressurized system.
Popov and his co-workers [77] studied the effect of hydro-
phobic agent concentration in the MPL on the performance
using mercury porosimetry, water permeation experiment,
and electrochemical polarization technique. The mercury
intrusion data showed that the pore volume of the dual-layer
GDL decreased with increasing PTFE content in the MPL. The
total porosity of the dual-layer GDL was measured to be 80.8%
for 10 wt% PTFE, 80.5% for 20 wt%, 80.0% for 30 wt%, and 77.9%
for 40 wt%. The microstructural observation indicated that
part of the MPL was entrenched into the carbon-fiber
substrate during the deposition of carbon ink, which made it
difficult to determine the individual porosities of the MPL and
the MPS in the dual-layer GDL. Their ex-situ water permeation
experiment indicated that the resistance to water flow
through the dual-layer GDL rises with PTFE content in the
MPL, which is due to increased MPL hydrophobicity and
decreased MPL porosity. When air was used as an oxidant, as
shown in Fig. 7(a), the MPL loaded with 20 wt% PTFE led to the
best fuel cell performance. The experimental polarization
curves were analyzed to determine the empirical Tafel slope
and the limiting current density which characterize the
concentration polarizations resulting from oxygen diffusion
limitation in the CL and the GDL, respectively. Here, the
empirical Tafel slope represents the Tafel slope determined in
the intermediate current densities, and it is distinguished
from the kinetic Tafel slope in the low current densities. The
kinetic Tafel slope characterizes the oxygen reduction kinetics
in the absence of oxygen transport limitation in the catalyst
layer. In the intermediate current range, on the other hand,
the oxygen concentration polarization is significant in the
catalyst layer, and the empirical Tafel slope becomes two
times larger than the kinetic Tafel slope, as demonstrated by
the simulation study [78e81]. Popov et al. also confirmed that
1.0
140
0.8
130
0.6
o
H2 / air, 75 C
0.4 120
10 20 30 40
PTFE content in MPL / wt%
Fig. 7 e (a) Polarization curves of the PEM fuel cells
measured using the MPLs with different PTFE loadings.
The curves were corrected for ohmic losses (iR). (b)
Dependencies on the PTFE content in the MPL of the
limiting current density and the empirical Tafel slope.
Reprinted from Ref. [77] with permission of Elsevier.
the empirical Tafel slope was approximately two times higher
than the kinetic Tafel slope, which was consistent with the
theoretical prediction.
As illustrated in Fig. 7(b), the MPL loaded with 20 wt% PTFE
resulted in lower empirical Tafel slope (i.e., effective oxygen
transport in the CL) and higher limiting current (i.e., effective
oxygen transport in the dual-layer GDL) [78e81]. The effective
porosity of the GDL, which represents the pore volume frac-
tion available for oxygen transport, was also calculated from
the measured limiting current. The effective porosity was
determined to be ca. 0.19. This indicates that most of pores in
the dual-layer GDL were occupied by liquid water, and only ca.
19% of the total porosity was available for oxygen diffusion in
the GDL. Besides the fact that the dual-layer GDL consists of
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 5 8 5 0 e5 8 6 5
two layers with different porous structures, it is practically
impossible to determine experimentally the limiting currents
in the MPL and the MPS from the polarization curves, thus
making it difficult to quantify the effective porosity of each
layer. Note that the limiting current density in Fig. 7(b)
represents a measure of oxygen diffusion limitation across
the whole GDL, neither the MPL nor the MPS. It is thus
reasonable that the measured limiting current can be used to
calculate the effective porosity of the dual-layer GDL. In
addition to the experimental study, the mathematical simu-
lations will be necessary to determine the water saturation
profiles and the effective porosities in the MPL and the MPS.
Chun et al. [82] designed a dual-layer MPL with hydro-
phobicity gradient: more hydrophobic MPL (MHMPL) using
PTFE as a binder and less hydrophobic MPL (LHMPL) which
contains a hydrophobic agent with less fluorine. They claimed
a dual-layer MPL (i.e., CL/LHMPL/MHMPL/MPS) reduces liquid
water content in the CL and increases humidity of the air
toward the CL so that it leads to better proton and oxidant
transport in the CL at 65  C and RH ¼ 50%.
On the other hand, the actual fuel cell may not be in
isothermal condition due to heat generation in the CL and
high flow rate of oxidants which is not completely heated
Fig. 8 e SEM micrographs of an MPL incorporated with
hydrophilic and cylindrical aluminosilicate fibers. Top
image is in low magnification and bottom one is in high
magnification. Reprinted from Ref. [95] with permission of
John Wiley & Sons.
5857
before reaching the inlet. Specifically, when a temperature
gradient exists between the CL and the gas flow channel at the
cathode, the evaporated water in the CL moves toward the gas
flow channel and it condenses due to lower vapor pressure at
a given temperature. Thus, hydrophilic channel could help to
transport liquid water condensed in the GDL toward the gas
flow channel. In line with this mechanism (called as phase-
change-induced flow) [83e89], several research groups have
introduced a variety of hydrophilic materials into a hydro-
phobic GDL to reduce water saturation level in the CL. Cin-
drella et al. [90] coated a hydrophilic layer using several
inorganic oxides (i.e., TiO2, SiO2, Aerosil, Al2O3, and
Al2O3 þ SiO2) onto a dual-layer GDL in-house fabricated [72]
and compared each polarization curve at various RH condi-
tions. The GDL coated with titanium dioxide leads to better
performance at high RHs (80e100%), while the GDL which
contains aluminum oxide or silicon dioxide layer shows
enhanced oxygen diffusion characteristics at low RHs
(50e70%). Wang et al. [91] inserted a composite layer of silica
nanoparticles and poly(dimethysiloxane) (PDMS) between the
CL and the macroporous substrate. An interesting feature of
this layer was superhydrophobic (qc,app ¼ 162 ) surface and
hydrophilic pores inside due to hydroxyl groups [92,93] on
silica surface. Their results suggested that superhydrophobic
surface on the composite layer readily removes water droplet
at CL/MPL interface and internal hydrophilic pores facilitate
uniform liquid water distribution throughout the GDL. Based
on the results [86,94] that most of excess water in the CL
transports in vapor phase down the temperature gradient
toward the gas flow channel and water nucleation appears at
each MPL interface, Schweiss et al. [95] added hydrophilic and
cylindrical aluminosilicate fibers (type ALTRA B97 LA C25,
Rath GmbH) to hydrophobic carbon ink for the MPL in order to
remove liquid water condensed at the interfaces (see Fig. 8). In
Fig. 9 e Nyquist plots of the ac-impedance spectrum
measured at different carbon loadings in the MPL. The
experiments were performed at 0.6 V. Reprinted from Ref.
[3] with permission Elsevier.
5858 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 5 8 5 0 e5 8 6 5

water vapor permeation test, its diffusion rate is mainly
dependent on the thickness of each GDL, irrespective of
wettability in the GDL, whereas liquid water permeability for
the GDL treated with inorganic fiber (SGL 25BL, SGL group) is
ca. 5 times higher than that for a hydrophobic GDL (SGL 25BC,
SGL group) due to more liquid flow channels created by
wicking effect. Ahn et al. [96] blended a carbon black (Vulcan-
XC-72) with different amount of a perfluorosulfonated acid
polymer (5 wt% Nafion solution) for a hydrophilic MPL (no
PTFE). Their cathode containing 10 wt% hydrophilic polymer
in the MPL results in faster water removal from the CL.
3.3. MPL thickness
In terms of MPL thickness, one of the first studies was done by
Paganin et al. [46] who fabricated triple-layer GDL (i.e., MPL/
MPS/MPL) and examined MPLs (Vulcan XC-72 and 10 wt%
PTFE) with different thickness from 15 to 65 mm. Their results
showed that the fuel cell performance reaches a maximum
when total thickness of MPL is 50 mm and then the
performance decays with thicker MPLs. They surmised that
a very thin MPL does not provide smooth surface on the
carbon cloth, resulting in higher ohmic resistance, while
a thick MPL causes mass transfer limitation due to lengthened
diffusion path. Other research groups [51,62,97,98] did similar
experiments with dual-layer GDLs and also observed the same
trends in fuel cell performance. Lin and Nguyen [54] tested
three commercially available GDL: bare SGL SIGRACET, Toray
TGPH carbon-fiber papers and SGL SIGRACET carbon-fiber
papers coated with the MPL. They showed that higher fuel
cell performance was obtained using the MPL-coated carbon
paper when compared to the bare carbon papers even at lower
air stoichiometry. The authors claimed that the MPL facilitates
the back diffusion of water from the cathode through the
membrane to the anode.
In theoretical approaches [30,31,55,57,99], Nam and
Kaviany [55] suggested the optimal thickness ratio of the MPL
and the MPS to minimize mass transfer limitation at the
cathode is 3:7. Pasaogullari and Wang [30] calculated average
liquid water saturation in a cathode dual-layer GDL with

Fig. 10 e Experimental and simulated impedance spectra of the PEM fuel cell at different O2 concentrations: (L) 20% O2 and
80% N2, (D) 10% O2 and 90% N2, (3) 5% O2 and 95% N2. The experiments were performed at 60  C and 300 mA cmL2. The
frequency values in the figure indicate some characteristic frequencies on the top point of the high-frequency or low-
frequency arcs. Reprinted from Ref. [108] with permission of Elsevier.
Table 2 e Materials, approaches, and properties for GDLs.
Component Materials Approaches Properties Ref.
3
MPS Carbon cloth Addition of 0.5 wt% phenolic resin 0.49 mm in thickness, 1.6664 g cm in density, [7]
116.5% in water uptake, 82.3% in porosity, 124.3
in contact angle
MPS Carbon paper Carbon paper with small yard weight (70 g m2) with 0.55 mm in thickness, 465 cm3 cm2 s1 in air [8]
carbonizations at 1000  C and 1400  C, respectively permeability
MPS Expanded graphite Expanded graphite with perforations 0.20 mm in thickness, 200 Wm1 K1 in in-plane [9]
thermal conductivity, ca. 1.2  103 U-cm in in-plane

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 5 8 5 0 e5 8 6 5
electrical resistivity
MPS Carbon paper Carbon paper fabricated with carbon nanotube, 4.16  1012 m2 in gas permeability [13]
polyacrylonitrile, and PTFE
MPS Carbon paper Drilling microholes (ca. 80 mm) along the gas flow channel [15,16]
by laser perforation
MPS Stainless steel mesh Stainless steel wire cloth for the anode in DM fuel cells 0.45 mm in thickness, 0.10 g cm2 in weight [17]
MPS Titanium mesh Catalyzed titanium mesh for DM alkaline fuel cells [18e23]
MPS Nickel mesh Gold-plated nickel mesh for DM fuel cells 0.80 mm in thickness, 0.125 U-cm in through-plane [24]
electrical resistivity
MPS Nickelechromium alloy foam Gold-sputtered nickelechromium alloy foam for DM fuel cells 1.0 mm in thickness, 95.0% in porosity, ca. 0.40 mm in [25]
average pore diameter
MPS Titanium Sintered titanium fiber substrate treated with PTFE 0.50 mm in thickness, 75.0% in porosity [26,27]
MPS Titanium Micromachined thin titanium substrate 0.0050 mm in thickness, 33.9% in porosity [28]
MPS Copper Micromachined thin copper substrate with MPL and carbon 0.0125 mm in thickness, 21.0% in porosity, 152.0 in [29]
paper (CP/Cu/MPL) contact angle on the MPL
MPS Carbon paper Hydrophobic treatment with PTFE 3 mg H2O cm2 in water uptake and 1.4 Pa at 20 SLPM in [34,35]
pressure drop for GDL with 180 wt.% PTFE sintered at 190  C.
MPS Carbon fiber Hydrophobic treatment with PVDF [36]
MPS Carbon paper Hydrophobic treatment with 10 wt.% FEP 77.0% in porosity calculated and 98.0 and 80.0 in contact [38]
angle at 25  C and 80  C, respectively
MPS Active carbon-fiber CF4 plasma treatment of active carbon fiber to provide 132.8  0.2 in contact angle [41]
hydrophobicity
MPL Acetylene black, PTFE Control of porous structure using acetylene black [59,62]
MPL Shawinigan acetylene Improvement of mass transfer using Shawinigan [49,50]
black, PTFE acetylene black
MPL Partially ordered graphitized Enhancement of hydrophobicity and mechanical integrity. 150.0 in contact angle, 47 mm in GDL average pore [70e72]
carbon, vapor-grown carbon Addition of a dispersion agent (Novec-7300) diameter for Ref. [72]
nanofiber, PTFE
MPL PTFE-free CNT In-situ grown CNT onto the MPS using CVD processes 0.002e0.005 mm in CL-MPL thickness, 122.9 m2 g1 in MPL [67e69]
surface area, 120.8 in contact angle for Ref. [68]
MPL Vulcan XC-72, PTFE 10 wt% PTFE treatment ca. 94.0% in GDL porosity [47]
MPL Vulcan XC-72, PTFE 20 wt% PTFE treatment and pressurized fuel cell operating [48]
system
MPL Acetylene black, PTFE 20 wt% PTFE treatment 80.5% in GDL porosity, 0.9 mm in GDL average pore diameter, [77]
MPL Vulcan XC-72, less fluorinated Hydrophobicity-graded MPLs (CL/More hydrophobic MPL ca. 440 g m2 h1 in GDL vapor permeability, ca. 0.019 kg m2 in [82]
polymer, PTFE containing PTFE/Less hydrophobic MPL containing less GDL water retention, 138.2 in contact angle
fluorinated polymer/MPS)

5859
(continued on next page)
5860 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 5 8 5 0 e5 8 6 5

different MPL thickness and its minimum value was found ca.
38 mm. Weber and Newman [57] conducted the theoretical
Ref.

[105]

[106]
[90]

[91]

[95]

[96]
[46]

[62]

[52]
[3]
simulations to study the effect of MPL thickness on the fuel
cell performance. The mathematical model for a fuel cell
sandwich (the membrane, an anode gas channel, CL, and
single-layer GDL, and a cathode gas channel, CL, dual-layer
GDL) was developed using (i) porous electrode theory
combined with embedded macrohomogeneous model for the

3.2 mm in GDL average pore diameter, 3.1 cm3 g1

CL and (ii) porous medium model for the GDL. Under the
simulation conditions used, a maximum power was observed
with a relatively thin MPL (ca. 20 mm). The authors claimed
0.18 g m2 h1 in GDL vapor permeability

that a maximum power at the optimum MPL thickness results

Properties

from the interplay between having an MPL thick enough to

affect the water balance and having an MPL thin enough to
facilitate oxygen transport.
The MPL thickness can be regarded as the carbon loading.
162  2 in contact angle

In study done by Park et al. [3], the effect of carbon (acetelyne

55.2% in GDL porosity

51.5% in GDL porosity

145 in contact angle

in GDL pore volume

black, Alfa Aesar) loading in the MPL on the fuel cell perfor-
mance was examined. They demonstrated that carbon
loading of 0.5 mg cm2 at 75  C and at ambient pressure leads
to a maximum limiting current density. The impedance
spectra measured at various cell potentials and air flow rates
were analyzed in terms of the thin film/flooded-agglomerate
dynamics in the CL and oxygen diffusion in the GDL. Fig. 9
10 wt% perfluorosulfuric acid polymer treatment without PTFE

presents the Nyquist plots of the ac-impedance spectrum

Porosity-graded MPLs (CL/MPL with 10 wt% NH4Cl/MPL with
Modification of microstructure using 140 wt% pore-forming
Insertion of hydrophilic layer between CL and hydrophobic

Addition of hydrophilic fiber into hydrophobic MPL to wick

measured for various carbon loadings in the MPL. The

MPL. Enhancement of oxygen diffusion using TiO2 at high

1.25 mg cm2 carbon for the MPL, MPL sintering at 350  C

nanoparticles and PDMS. Superhydrophobic surface and

0.5 mg cm2 carbon for the MPL, MPL sintering at 350  C

Triple-layer GDL (MPL/MPS/MPL). 25 mm in thickness for

Drilling microholes through dual-layer GDL (ca. 300 mm)

impedance measurement was performed over the frequency

RHs (>80%), and Al2O3 and SiO2 at low RHs (50e70%)

range from 10 mHz to 10 kHz. All of the ac-impedance spectra

Sandwich wettability structure composed of silica

consist of two separated arcs: the high-frequency arc is due to

electrode kinetics in the CL and the low-frequency arc is
condensed water from the CL and the MPS

ascribed to oxygen diffusion in the GDL. As shown in Fig. 9, the

MPL loaded with 0.5 mg cm2 carbon results in a minimum
Approaches

value of total resistance, indicating that the optimized carbon

agent, followed by heat-treatment

loading effectively controls water saturations in the CL and

the GDL, thereby facilitating oxygen transport at the cathode.
This experimental result agrees qualitatively with the simu-
hydrophilic pores inside

lation results that there exists an optimum carbon loading

50 wt% NH4CL/MPS).

by laser perforation

(MPL thickness) for enhanced fuel cell performance [31,58].

3.4. Microstructure modification

each MPL

Several researchers added various pore-formers which are

different in diameter to the CL [100e102] or the MPL
[52,101,103,104], thereby controlling gas-phase pore volume at
nanofiber, PTFE, Inorganic oxides

the cathode. Kong et al. [52] made an attempt to modify the

Carbon-free oxide and polymer

porous structure of the MPL by using Li2CO3 as a pore-forming

Partially ordered graphitized
carbon, vapor-grown carbon

Vulcan XC-72, Li2CO3, PTFE

Vulcan XC-72, NH4Cl, PTFE

agent. Their results exhibited that when the pore-forming

agent was removed by acid treatment, the volume of macro-
Acetylene black, PTFE,
Materials

Acetylene black, PTFE

Acetylene black, PTFE
aluminosilicate fibers
Vulcan XC-72, Nafion

pores (5e10 mm) increased, resulting in better fuel cell

Vulcan XC-72, PTFE

performance both in H2/O2 and in H2/air operation due to less

diffusion limitation in the MPL. Tang et al. [105] added
composite

different amount of ammonium chloride (NH4Cl) as a pore-

SGL10BB
Table 2 e (continued )

forming agent to carbon ink for the MPL and made porosity-
graded MPL (i.e., CL/MPL I with 10 wt% NH4Cl/MPL II with
50 wt% NH4Cl/MPS). The porosity-graded MPL resulted in
Component

better fuel cell performance than the MPLs which contain 10

or 50 wt% NH4Cl as a pore-forming agent, especially at high
MPS/MPL

current densities. Their result suggested that thickening pores

MPL

MPL

MPL

MPL
MPL

MPL
MPL

MPL

MPL

by porosity gradient in the MPL creates higher driving force

(i.e., higher capillary pressure) for water flow when compared
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 5 8 5 0 e5 8 6 5
with straight pores across the MPL, resulting in improved
water management at the cathode.
Similarly to previous studies in terms of GDL modification
by laser perforation [15,16], Manahan et al. [106] applied
a dual-layer GDL (SGL 10BB, SGL group) with 300 mm laser-cut
holes to the cathode compartment and quantitatively
analyzed water mass through the MEA using neutron radi-
ography testing. They found that the perforated GDL is subject
to water retention due to water pooling at the perforations,
resulting in better polarization characteristics at intermediate
current densities and serious performance drop at high
current densities. For a dual-layer GDL, it is believed that
a high fraction of perforations in the GDL eliminates a benefit
of the MPL which creates a higher capillary pressure at the
interface between the MPL and the CL, resulting in severe
water saturation in both the MPL and the MPS. From these
results [15,16,106], a dual-layer GDL made up of an MPL and
a perforated MPS is expected to lower in-plane water satura-
tion in the macroporous substrate, still maintaining driving
force for water removal from the CL.
4. Future prospects
Actual water transport within a multi-layered porous medium
could be significantly complicated, although representative
two mechanisms for water flow (i.e., capillary-driven flow and
phase-change-induced flow) across the GDL have been
proposed by many research groups. According to the experi-
mental results presented in hydrophobic/hydrophilic treat-
ment for a dual-layer GDL, hydrophobic MPL mitigates water
saturation in the GDL, whereas hydrophilic MPL wicks water
from the CL. Which mechanism prevails may rely on the
operating conditions, e.g., at low operating temperatures,
capillary-driven flow can be dominant because of small
change in vapor pressure, while phase-change-induced flow
may predominate water transport at high temperatures.
Operating current (or power) related to heat generated at the
CL also can determine main driving force for water flow.
Therefore, the GDL engineering parameters in terms of water
management have to be optimized with two perspectives,
taking into account fuel cell operating conditions and its
maximum power demanded. Specifically, since a MPS in
contact with a well-defined MPL results in larger liquid satu-
ration drop at the MPL/MPS interface in comparison with
a MPS incorporated with an MPL, the MPL applied to the
catalyst-coated membrane, instead of being coated on the
MPS [107] can form better multi-layered structure that
enhances capillary-driven flow at the cathode. In addition,
selection of the MPL and the MPS material in terms of wetta-
bility and thermal conductivity can affect polarization char-
acteristics in high current densities and adding insulating
materials into the MPL increases temperature gradient in the
GDL, possibly enhancing phase-change-induced flow.
The PEM fuel cell performs poorly when air is used as an
oxidant instead of pure oxygen. Besides the fact that oxygen
reduction kinetics is first-order in oxygen concentration,
significant oxygen depletion occurs across the cathode and
creates large diffusion resistance during fuel cell operation
with diluted oxygen gas. This causes the limiting current
5861
density to appear at higher potentials (lower current densi-
ties). Bultel et al. [108] carried out a combined experimental
and modeling analysis of ac-impedance behavior of the
cathode at different oxygen concentrations (5e20% O2). As
shown in the experimental and simulated impedance spectra
of Fig. 10, oxygen diffusion through the GDL leads to
a ‘restricted’ Warburg impedance that appears at low
frequency and becomes more predominant for lower oxygen
concentration. The results indicated that slow oxygen diffu-
sion in the GDL is mainly responsible for oxygen depletion
across the cathode and it is the crucial factor which holds back
the oxygen reduction reaction at the cathode. Since oxygen
depletion in the GDL would become more significant at higher
current densities, the GDL should be engineered to minimize
the performance loss due to the diffusion resistance of oxygen
over a wide current range.
It is well known that at the cathode inlet, high oxidant
concentration may cause hot spots due to higher oxygen
reduction activity, resulting in the ionomer and membrane
failure, while accumulated water near the cathode outlet
readily causes water flooding in the CL [109]. These issues
along the gas flow channel lead to decreased peak power and
cell reliability. It is thus believed that an optimized gradient
with content of additives in the GDL from inlet to outlet will
improve catalyst utilization, current distribution, and thermal
and water management. Interestingly, digital fabrication such
as inkjet printing has received attention as a method for
printing the MPL onto various substrates [110,111]. Rieke and
co-workers [112] have fabricated electrode for PEM fuel cells
employing inkjet print technique capable of submilli- and
submicro-resolution in the x, y, and z direction. The MPL
prepared by digital fabrication which ensures the precise
location of carbon and additives is expected to cope with non-
uniformities both through the thickness and from gas inlet
and outlet in PEM fuel cells.
5. Summary
For nearly two decades, the GDL demonstrated great influence
on the performance and stability of PEM fuel cells. The recent
research and development of advanced gas diffusion layer
materials and structures exhibiting promising performance
were reviewed. Various materials and approaches used for
novel GDL development and the GDL properties were
summarized in Table 2.
Carbon-based GDL such as carbon paper and carbon cloth
has been commonly used as a MPS due to its high porosity,
electronic conductivity, and flexibility. Carbon cloth exhibited
fast water removal with fully humidified oxidant due to its
unique woven structure, while carbon paper enhanced
membrane hydration at low RHs, resulting in improved
performance. Metal GDL were developed for various fuel cells
including gas- and liquid-feed PEM fuel cells and UR fuel cells
and showed high stability in a wide potential window. Thin
metal GDL prepared by micromachining technology also was
applied to the cathodes and led to comparable performance to
carbon-based GDL. To prevent the cathode from flooding, the
MPS were hydrophobized with various fluorinated polymers
including polytetrafluoroethylene (PTFE), polyvinylidene
5862 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 5 8 5 0 e5 8 6 5
fluoride (PVDF), and fluorinated ethylene propylene (FEP). It
was found that an optimal content of different hydrophobic
agents in the MPS was dependent on the interplay between
MPS wettability and its porous structure.
According to experimental and theoretical studies, MPL
deposition onto the MPS led to reduced ohmic and concen-
tration polarization at the cathode. A variety of carbon
powders such as carbon black, carbon nanofiber, CNT, and
ordered graphitized carbon were adopted at various operating
conditions and showed significant impact on water manage-
ment. Recently, in-situ grown CNT onto carbon substrate was
used as an MPL without any hydrophobic component, result-
ing in better performance than the MPL prepared by roll-to-
roll coating techniques. For a dual-layer GDL, fluorinated
polymer as a binder and hydrophobic agent has been used to
facilitate liquid water transport to the gas flow channel. In
contrast to more common hydrophobic MPL fabrication,
several research groups added hydrophilic materials to
hydrophobic MPL to wick water from the CL. Various
approaches to design and optimize MPL architecture from
thickness to microstructure have been carried out. MPLs that
are thin and have uniform layered-structure improved peak
power. Microstructure of the MPL was modified using pore
former, laser perforation technique, etc. The results indicated
that small macropores (<10 mm) in the MPL and the porosity
gradient to the CL help gaseous oxygen flow at the cathode,
while large macropores (>100 mm) increase water saturation
level in the GDL.
Since it is supposed that water transport in both liquid and
vapor phase through the GDL depends on the operating
conditions, proper material selection and GDL architecture is
necessary to promote water management in PEM fuel cells. In
addition, novel designs and methods (e.g., digital fabrication)
for high performance and stable GDL have to be developed to
overcome non-uniformities along the gas flow channel.
Acknowledgments
The financial support from National Science Foundation
(CBET e966956) and DOE (DE-EE0000460) are gratefully
acknowledged.
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