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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3

Available online at www.sciencedirect.com

ScienceDirect

journal homepage: www.elsevier.com/locate/he

Review Article

Gas diffusion layers for PEM fuel cells: Materials,

properties and manufacturing e A review

Grigoria Athanasaki a, Arunkumar Jayakumar b, A.M. Kannan a,*

a
Fuel Cell Laboratory, The Polytechnic School, Ira A. Fulton Schools of Engineering, Arizona State University, Mesa,
AZ, 85212, USA
b
Green Vehicle Technology Research Centre, Department of Automobile Engineering, SRM-Institute of Science and
Technology, Kattankulathur, 603203, India

highlights

Focusses on the fundamental mechanism of the diffusion process and evaluates the pros and cons of various GDL materials.

Explores the structural and functional attributes of GDL based on material properties.

Demonstrates the emerging trend through Additive Manufacturing process for GDL.

article info abstract

Article history: The complexity in proton exchange membrane fuel cell (PEMFC) stack stems from the fact
Received 1 June 2022 that numerous physio-chemical processes as well as multi-functional components are
Received in revised form involved in its operation. Among the various components a Gas Diffusion Layer (GDL) being
5 October 2022 an integral component that plays a significant role in determining the performance,
Accepted 9 October 2022 durability, and the dynamic characteristics, when air is used as oxidant. In addition, it
Available online 3 November 2022 serves as an armour to safeguard the membrane (Nafion), which is a delicate as well as one
of the most expensive components of the PEMFC stack. A comprehensive insight on the
Keywords: GDL can help us to assess the fuel cell stack performance and durability. Apparently, the
Gas diffusion layer gas (hydrogen and air/oxygen) being converted to the energy in a PEM fuel cell needs to be
Surface morphology diffused uniformly for which surface attributes and porosity must also be well interpreted.
Hydrophobicity This review is a comprehensive assessment made on the fundamental mechanism of the
Electrical conductivity diffusion process along with the various materials involved and evaluating their pros and
Thermal conductivity cons. Eventually, the various manufacturing techniques involved in the GDL fabrication
Advanced manufacturing process are also reviewed holistically. It is envisaged that the additive manufacturing
process can be a potential option to fabricate a GDL in a cost-effective and simple
manufacturing approach.
© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: amk@asu.edu (A.M. Kannan).
https://doi.org/10.1016/j.ijhydene.2022.10.058
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3 2295

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2295
GDLs for PEMFCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2295
Materials and components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2296
Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2296
Mechanical support . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2296
Mass transport . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2298
Hydrophobicity/hydrophilicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2301
Electrical and thermal conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2301
Surface morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2302
Electrochemical characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2302
Manufacturing methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2303
Casting and blade coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2303
Wet laying technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2304
Spraying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2304
Screen printing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2305
Electrospinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2305
Additive Manufacturing (AM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2305
Heat treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2306
Research, development, and commercialization trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2306
GDL fabrication and characterisation techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2308
Magneto-optical Kerr effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2309
Direct optical visualization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2309
Fluorescence microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2309
Neutron radiography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2309
Role of neural network . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2309
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2309
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2310
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2310

GDL aids in the removal of product water. It anatomically

Introduction
Hydrogen based fuel cells are sustainable energy conversion
systems that convert the chemical energy of the fuel into
electrical energy without any harmful emission. Apparently,
fuel cells are not limited by Carnot's cycle and are highly en-
ergy efficient. Among various types, PEM fuel cells are the
most widely used, and they operate at low temperature
(60e90  C), have good dynamic characteristics and high-
power density [1]. These attributes make them a promising
option in automotive and other applications where space is a
constraint. PEMFCs comprise several key components such as
bipolar plates, electrolytes, electrodes, and gas diffusion
layers (GDLs). Among these components the GDL is an integral
component normally located external to the catalyst layers.
GDLs perform numerous critical tasks in the PEM fuel cell
operation such as gas distribution, water transportation,
thermal and electrical conduction apart from providing me-
chanical integrity for the membrane electrodes assembly
(MEA) [2e5]. Fig. 1 represents the PEM fuel cell stack compo-
nents, reaction as well their functional attributes.
Intrinsically, as represented in Fig. 2, the GDL in-
terconnects the catalyst layer and the bipolar plate thus acting
as a pathway medium to the catalyst layer that facilitates the
reactant transport to the electrocatalyst site. In addition, the
comprises two layers, a hydrophobic agent and a microporous
layer made of carbon paper or cloth that is covered with a
microporous layer. Reactant gases diffuse through the pores
of these layers. The hydrophobic agent provides open pores,
inhibiting the excess water accumulation. Functionally, GDL
also aids to remove the product water or else flooding can
occur where water blocks the GDL site, and this limits the
reactants access to the catalyst site which can severely dete-
riorate fuel cell performance. The membrane, electrocatalyst
and GDLs are assembled into a sandwich structure to form a
MEA.
Although GDL is predominantly carbon-based such as
woven carbon cloth, non-woven carbon paper, carbon felt,
and carbon foam, few carbon-free based GDLs have also been
reported, such as SS and its alloys, Ti and its alloys and copper
and Ni substrate. The classifications are well explained in
Fig. 3 [4e23].
GDLs for PEMFCs
The GDLs initially consisted of a macroporous layer or sub-
strate, which is usually a woven or non-woven sheet, with
pore size between 10 and 30 mm. Since the early 2000s, widely
used substrate materials have been carbon-based (paper, felts
2296 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3

Fig. 1 e Basic components of a Proton Exchange Membrane Fuel Cell and its functional attributes.

To improve electrical conductivity and water manage-

Fig. 2 e Typical structure of Gas Diffusion Layer.
and cloth) with several studies comparing the material and
structural properties among them [8,24].
Materials and components
Carbon papers are clipped carbon fibers prepared by wet-
laying technology followed by thermal bonding, carbonizable
resin impregnation, curing and graphitization [25]. Carbon
felts are manufactured by depositing spun carbon fibers
through carding in a binder suspension and pressurizing to
create a heat insulating material. Carbon cloth comprises of
thin woven carbon fibers [26]. The oxidized fiber cloth is
carbonized under inert atmosphere and turned into a carbon
cloth. For enhanced conductivity and corrosion resistance, the
carbon cloth undergoes graphitization under inert atmo-
sphere [27]. Metal based GDLs were originally investigated due
to thinner diffusion layers and the ability to produce uniform
porous structure. They are structured in the form of a metal
mesh, foam or micro-machined metal substrate, and are
usually used in Direct Methanol Fuel cells (DMFCs) because of
their relatively large pores, enhancing the transport properties
of the liquid fuel and the water product. Fig. 4 shows different
types of GDLs used, both carbon-based and metallic.
ment, newer developments in the GDL fabrication introduced
a Microporous Layer (MPL). MPLs mainly consist of carbon
powder and a hydrophobic agent (e.g. PTFE), applied on the
inner side of carbon substrates towards the catalyst layer,
with pore size 100e500 nm, and are reported to have beneficial
impact on the fuel cell performance, due to the good electrical
properties of carbon powder, and enhance gas transport to the
catalyst layer while the hydrophobic agent expels the excess
water from the system [3,28,29]. The addition of hydrophobic
agents, usually PTFE, has been employed to balance the hy-
drophilic characteristics of carbon, in both the substrate and
MPL. The desired GDL configuration includes hydrophilic
pores to help keep the membrane moist and conductive while
the hydrophobic pores expel the excess water and keep the
pathways open for the reactant gases to reach the catalyst
layers. Hydrophilicity of carbon materials depends on the
different kinds of carbon fibers and powders and whether they
are graphitized. Nonetheless, an excessive amount of hydro-
phobic agent leads to reduced conductivity, porosity, and
permeability, therefore the optimum amount of hydrophobic
agent is directly related to the type of hydrophobic agent and
the type of carbon used.
Properties
There are numerous micro structural properties that are very
essential to validate the properties of GDL. These properties
include porosity, permeability, thermal and electrical con-
ductivity, and surface morphology and subsequently their
effects on fuel cell performance are discussed in this section.
Mechanical support
One of the GDL roles is to provide mechanical strength to
support the membrane and catalyst layers. GDLs are often
subjected to high compression forces as part of the MEA when
assembled, and thus, GDLs need to be rigid and stable enough
 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3 2297

Fig. 3 e Classification of widely used materials for Gas Diffusion Layers.

to withstand these mechanical stresses. The GDL mechanical
stability is usually studied by applying an incremental pres-
sure to it and measuring the changes in thickness. The
clamping pressure decreases electrical and thermal re-
sistances; however, it also affects the reactant flows through
the GDL and causes high intrusion into the flow field channels
for woven GDLs.
Porosity, carbon fiber diameter and thickness determine
the microstructure of the substrate which has a direct effect
on its compressibility [30]. Radhakrishnan et al. mentioned
that the fiber structure plays an important role as it de-
termines properties, such as porosity, permeability, and
electrical conductivity [31], whereas Nazemian et al. indicated
that while the impact of carbon paper thickness and porosity
is significant, the carbon fiber diameter has negligible effect
on the current density [32]. They, also, stated that fuel cell
performance drops when carbon paper thickness or porosity
are increased. Lee et al. performed finite element analysis to
investigate the correlation between the membrane and GDL
deformation. They emphasized the importance of GDL thick-
ness selection, stating that GDLs with low thickness and
inadequate through-plane stiffness will not provide sufficient
support to endure the membrane swelling [33]. Compressive
stress on the GDL results in non-linear irreversible structure
deformation, affecting the surface morphology by smooth-
ening of the rough GDL surface at low compression, or
collapsing GDL pores at higher compression [30]. Non-woven
carbon felts are considered stiffer than woven structures
with much smaller total strain [34].
Carbon fiber paper is the main product of the macroporous
layer for the GDLs. Its brittleness induces higher compressive
strength with better mechanical support and uniform gas flow
throughout the system [35]. On the contrary, carbon cloth
being more porous and less tortuous than carbon paper, is
2298 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3
Fig. 4 e Gas Diffusion Layer substrates with (a) carbon felt, (b) carbon cloth, (c) metal foam and (d) carbon paper.
characterized by higher compressibility, leading to material
intrusion into the flow field channels, causing non uniform
gas flow, which subsequently affects the fuel cell performance
[31]. Ge et al., while testing carbon paper and cloth GDLs,
observed an initial increase in the fuel cell performance when
the compression was increased, however, the performance
decreased after a certain value of compression, concluding
that there is a maximum compression value for optimal fuel
cell performance [36].
To enhance mechanical strength and durability, a variety
of carbon-free materials were examined; Jayakumar et al.
proposed a 3D-printing technique to fabricate metal com-
posite GDLs from alumide (nylon filled with aluminum dust)
and increased the mechanical support and durability,
compared to carbon-based Sigracet™ 39 BC GDL [25,37]. In
addition, to enhance the electrical conductivity and further
increase the mechanical support, they incorporated an opti-
mized amount of titanium powder on the alumide base. The
results showed increased thickness compared to reference
carbon-based GDL (Sigracet™ 39 BC) and the lower conduc-
tivity was attributed to the porous 3D-printed GDL structure
[19]. Choi et al. used titanium foam as GDL and achieved
higher fuel cell performance at 0.7 V in H2/O2 and H2/air and
insignificant weight loss during accelerated stress testing,
compared to commercial carbon GDL (SGL 35BC); however, in
the mass transport region the metal GDL experienced
increased loss, due to small uniform porosity unable to
remove the product water efficiently [20]. Porous copper GDLs
were fabricated by Sima et al. and tested successfully for gas
permeability. The main disadvantage of this technique was
that the copper GDL was oxidized a few hours after being in
contact with air [38], indicating that copper does not have the
appropriate properties to withstand the acidic PEMFC envi-
ronment, as metal corrosion of transition metals was found to
accelerate polymer membrane degradation rate [39]. On the
same subject, fabricated copper GDL by Zhang et al. demon-
strated poor but stable fuel cell performance compared to
Toray TGP-H-060. To increase the performance, they intro-
duced an MPL layer to reduce pore size, and achieved even
better results with the reduction of the contact area by
applying a carbon based GDL between the bipolar plates and
the copper GDL [40]. Hussain et al. stated that the rigidity and
stiffness of stainless steel GDLs is the main contributor to its
superior performance to the commercial carbon paper GDL
(Freudenberg H2315I3C1) because it provides a straightfor-
ward diffusive pathway, eliminating the tortuosity and
compression deformation of the carbon based GDLs [41].
These findings agree with prior findings of Desplobain et al.,
who monitored the H2 flow of a manufactured silicon based
and commercial ceramic GDLs and concluded that the
enhanced hydrogen flow was due to the straight pores of the
silicon GDL [42].
Mass transport
The most important role of the GDL is the ability to transport
the reactant gases to the catalyst layers and remove the
excess water produced during the operation of the fuel cell.
Mass transport refers to the mechanisms by which gases and
 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3 2299

Fig. 5 e Types of mass transport through gas diffusion layer.

liquids move through a porous gas diffusion medium and
depends on the molecule acceleration and environment. The 4
types of flow, as depicted in Fig. 5, are defined by the equation:
l relatively larger pore sizes than the MPLs [4,46].
Kn ¼
d Porosity and pore size distribution have been closely
where Kn is defined as the Knudsen number,
is the mean free
path of flow, and d the flow channel diameter. (a) In free
molecule flow, the collision among the gas molecules is more
frequent than with the containing walls. Kn varies between
0.01 and 0.5 which indicates that the mean free path of the gas
molecules is in the same length scale of the container and flow
and diffusion cannot be distinguished. (b) In molecular flow
Kn > 0.5 and flow dominates over diffusion, as the mean path
is significantly larger than the flow channel diameter. (c) In
viscous flow, the mean free path of the gas molecules is
significantly shorter than the dimensions of the flow channel
and the collisions between gas molecules are more frequent
than with the containing walls. The gas particles remain in the
constantly parallel layers to each other however, if the flow
velocity increases, the layers are destroyed, and the particles
collide onto each other in disorder. (d) In surface diffusion, the
gas molecules are being absorbed and move along a solid
surface [43].
Xu et al. modelled the water transport in compressed GDL
via energy storage analysis and the effects of channel geom-
etry, GDL thickness and clamping force and observed that the
maximum pressure initially decreases and then increases
with the thickness of GDL, because of the combined effect of
through-plane and in-plane mass transport, with an esti-
mated optimum thickness of 0.2 mm for maximum water
transport. They concluded that smaller rib-channel ratio en-
ables better water drainage with less mass transport resis-
tance and stable maximum pressure [44]. Yuan et al. studied
the water distribution in different parts of the fuel cell and
concluded that the area with the highest water content is the
GDLs followed by the flow field channels, the proton exchange
membrane and the catalyst layers [45]. A typical GDL shows
micro, meso and macropores, since carbon substrates have
associated with mass transport [47]. Many studies have
concluded that high GDL porosity improves mass transport,
which leads to increased fuel cell performance [48,49]. It has
been well established throughout the years that the influence
of pore size distribution of GDL on mass transport is stronger
than the influence of the total porosity and that larger porosity
is better for both the reduction of water saturation and in-
crease in limiting current density. Athanasaki et al. reported
higher fuel cell performance and durability while using GDLs
with increased MPL porosity achieved by the implementation
of a pore forming agent [50]. However, high porosity can
decrease the through-plane electrical conductivity and me-
chanically weaken the structure [49]. At high relative humidity
conditions, larger pore diameter volume confirmed that it
decreases flooding at the cathode, so that the reactant gas has
an open path to active sites through the smaller, hydrophobic
pores [51,52].
During the fuel cell operation, liquid water is produced on
the interface between the cathode catalyst layer and the MPL
(Fig. 6). The liquid water can easily move (or transport) mainly
through the larger pores of the MPL and the carbon substrate,
to the flow field channels while the smaller pores of the MPL
inhibit liquid water due to their hydrophobic characteristics,
serving as paths for transporting the reactant gases to the
reaction zone [15]. Xu et al. investigated the water dynamic
phenomena using X-ray tomographic microscopy. They
studied the water transport in different temperatures and
concluded that at low temperatures the water was distributed
from the MPL to the flow field channels, while at high
2300 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3
Fig. 6 e Water transport and diffusion process in the cathode region through GDL.
temperatures the saturation appeared elevated at the in-
terfaces between the MPL-GDL and GDL-flow field channel
and the water distribution was mostly driven by water clus-
ters at the GDL-flow field interface [53]. Nishiyama and Mur-
ahashi showed that the gas transport is enabled through the
hydrophobic micropores while the large pores, depending on
the MPL location and composition, could appear as either
hydrophobic or hydrophilic. Due to its larger viscosity and
poor affinity to micropores, liquid water can only be trans-
ported through the macropores, with a rate dependent on the
surface morphology and inertia forces. In conclusion, gas
transport can occur in both micro- and macropores, assuming
that the channels are not occupied by liquid water [54]. Due to
the inadequate capillary pressure required for the water to
enter the smaller pores, the remaining water is driven to the
anode side through the membrane through diffusion, leading
to reduced flooding of the GDL and the catalyst layer and
improved membrane hydration [55]. Hiramitsu et al. showed
that flooding originates at the interface between the GDL and
the CL and can be reduced by controlling the GDL pore size in
that area [56]. Hence, the role of GDL porosity in determining
two-phase transport in the GDL is crucial.
Due to the random water content within the structure,
GDLs with non-uniform porosity have been examined. Zhao
et al. developed a visualization platform and water balance
model to investigate the water transport mechanisms of a
single cell. The results showed fuel cell performance
increased inlet gas humidity and hydrogen/air stoichiometry
and the water content in the fuel cell increases with the
decreased humidity of the inlet gas [57].
Porosity, pore size distribution and permeability of the GDL
are closely related. In-plane and through-plane permeability
depend on parameters, such as density, hydrophobic agent
content, structure, post-compression thickness and type of
MPL [58,59]. In order to mitigate the complex water flooding
issue during fuel cell operation, graded porosity GDLs have
been reported to demonstrate improved performance by
promoting water removal and gas transport. Ko et al. evalu-
ated GDLs with and without pore gradients at 25 and 100% RH
[60]. The results showed decreased conductivity with
increased porosity gradient, however they concluded that the
GDLs with medium pore gradient performed better in both low
and high RH conditions and emphasized the need of porosity
optimization for maximum fuel cell performance.
The use of pore forming agents on the MPL slurry have
been shown to improve mass transport limitations by
increasing the MPL porosity and facilitate water transport
through the larger hydrophilic pores, leaving the smaller hy-
drophobic pores open for gas transport, avoiding flooding and
ultimately increasing fuel cell performance. The effect of pore
forming agents depends on their type and loading. Liu et al.
investigated the physical pore characteristics of GDLs
designed with different carbon types, PTFE content and pore
forming agents. They concluded, out of all the carbon types
used, graphitized carbon black revealed the greatest perfor-
mance and the optimum amount of PTFE for the specific
carbon was estimated at 30% wt. The performance was further
increased with the use of ammonium oxalate as a pore
forming agent, compared to three other agents, due to the
larger pore diameter and volume which increased the elec-
trode activity [61].
Mathematically, the effective diffusivity of the GDL is
estimated using Fick's law of diffusion, where the effective
diffusion coefficient of gaseous species is used.
dC
J¼  D x A x
dr
where J is the diffusive flux, D the diffusion coefficient, A the
active area and dC/dr the concentration gradient. Zhu et al.
investigated the correlation between the gas diffusivity and
 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3
binder loading in the GDL and developed a numerical model in
the attempt to further comprehend the gas transport and
performance correlation [62]. Yoshimune et al. designed an
experimental device for estimating the through-plane effec-
tive diffusion coefficient in GDLs and after confirming the re-
sults of commercial GDLs with previous reported studies, they
concluded that there is a proportional correlation between
normalized gas diffusivity and porosity [63].
Hydrophobicity/hydrophilicity
The reactant flows through the GDL, both by diffusion and
convection, are dependent upon the geometry, the material
parameters, and the flow field plate design. On the other hand,
hydrophobicity is directly related to water management in the
fuel cell and is an important property of both the surface and
pores of the GDL. As carbon substrates have relatively larger
pore sizes compared to MPLs, in most cases a GDL is a multi-
porous layer. Hydrophilic pores tend to retain water while
hydrophobic pores repel the water out. GDL hydrophobicity
has been manipulated by varying the hydrophobic agents
(binders) contents. The most commonly used binder is PTFE,
however there is extensive literature on other types such as
perfluoropolyether (PFPE) and fluorinated ethylene propylene
(FEP). Consequently, the most commonly reported PTFE con-
tent is 33% by weight. Nevertheless, it is well known that the
optimum PTFE content depends on parameters such as the
carbon type and loading, and that there is an optimum value
for PTFE content at which mass transport limitation are
decreased, and above or below which, the performance de-
creases as a result of decreased porosity and permeability [64].
Permeability governs the reactants flow through GDL and
is a key criterion for PEM fuel cell performance. The values of
in-plane and through-plane permeability are significantly
determined by GDL factors such as density, hydrophobic
agent load, fibre topologies, and the existence of MPL. The in-
plane and through-plane permeability of a GDL material
under steady airflow might well be computed utilizing
experimental measurements and the Darcy-model [65]. In
practice, PTFE loading, and thickness increase the perme-
ability limit, although modest compression of the GDL has
little effect. The GDL porosity has a direct impact on the
‘effective’ diffusion coefficient and permeability, and there-
fore the reactants and water transport through the GDL [9].
Recently, Balzarotti et al. prepared GDLs using PFPE as
hydrophobic agent and reported lower preparation tempera-
ture, and increased durability with less amount PFPE
compared to PTFE [66]. Additionally, Stampino et al. per-
formed testing of GDLs prepared with both PFPE and PFTE and
reported superior fuel cell performance at operating temper-
ature of 60  C, in the high current density region, where the
water generation on the cathode is maximum, attributing this
behaviour in its lower ohmic resistance [67]. Latorrata et al.
synthesised GDLs using PFPE, Hyflon and a mix of the two and
examined the fuel cell performance. They observed that the
PFPE-based GDL achieved higher power densities than PTFE-
based, whereas the addition of Hyflon-based binder created
decreased performance due to higher dielectric constant,
negatively affecting the ohmic resistance [68]. Lastly, Park
et al. used FEP to control hydrophobicity and demonstrated
better fuel cell performance, due to FEP's better physical
2301
characteristics (melting point, contact resistance and
compression strength) [69], while previously, they had
experimented with polyvinylidene fluoride binder and ach-
ieved uniform microstructure without large cracks, unlike the
GDL prepared with PTFE binder, which lead to better electrical
conductivity, platinum catalyst support, resulting in improved
fuel cell performance [70].
Many studies have been focused on determining the effect
of the hydrophobic agent content on the fuel cell performance.
More precisely, Park and Popov investigated the effect of hy-
drophobic agents on water and oxygen gas transport. They
concluded that the ideal PTFE content in the GDL reduced mass
transport limitations and improved oxygen diffusion kinetics.
However, they observed that higher or lower PTFE content re-
sults in poor fuel cell performance due to decrease in perme-
ability and water flooding, respectively [71].
Electrical and thermal conductivity
Another desired property GDLs must possess is adequate
electrical conductivity. Electron transport through the GDL is
affected by the GDL material, thickness, and electrical con-
ductivity. In addition, the transfer of electrons between the
GDL, the catalyst layer and the FFP/BPP affects the transport of
electrons and has a crucial role in PEM fuel cell performance.
Generally, thinner GDLs demonstrate better performance due
to less mass resistance and high electrical conductivity,
although since thickness is material dependent, it needs to be
optimised to meet the researcher's needs. Specifically for the
case of carbon cloth, too thin GDLs will not be able to provide
the adequate mechanical support to the catalyst layers and
intrusion of the material in the flow field channels, disrupting
the gas and water flow of the system, has been observed. Xia
et al. reported performance increase with increased GDL
thickness, associated with gas flow uniformity. However,
when the thickness was further increased, there was a per-
formance decline due to increased ohmic resistance [49].
These findings come into agreement with Truong et al. who
observed a similar response in an Anion Exchange Membrane
Fuel Cell (AEMFC) [72]. Useful observations in past research
are still used to provide significant guidance in recent work,
with Prasanna et al. reporting that there should be an optimal
substrate thickness, at which mass transfer loss, contact
resistance and activation potential would be minimum, while
Zhou et al. confirmed that electrical resistance is material
dependent and as long as the same materials are used,
through and in-plane electronic resistances of the GDL
demonstrate minimum effect on the fuel cell performance
and therefore can be eliminated [73,74]. On the contrary, the
interface contact resistance between the fuel cell components
has a significant effect, as it not only depends on material
properties, but also compression and surface geometry, since
non-uniform compression of the GDL may result in an uneven
current distribution along the MEA [75]. Hamour et al. per-
formed a series of experiments on GDLs and bipolar plates
under load and observed an increase in electrical conductivity
when the compression was increased. Nonetheless, beyond a
certain degree of compression the GDL structure undergoes
plastic deformation, and although the conductivity increases
with material contact improvement, the porous system in the
GDL is collapsed [76].
2302 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3
Heat conduction and temperature control are two aspects
that affect the fuel cell performance. Thermal conductivity in
GDLs is an important property for predicting the temperature
distribution within the MEA. As in the case for electrical
resistance, thermal resistance is also dependent on clamping
pressure; for example, both through-plane thermal and con-
tact resistances decrease with an increase in compression or
clamping pressure. It was shown that the presence of PTFE in
the GDL leads to an increase in thermal conductivity at low
clamping pressures but to a decrease at higher compressions
[77]. During the fuel cell operation, the temperature in the
catalyst layers, where the exothermic reaction takes place,
rises and can cause membrane deterioration and decreased
durability. The thermal conductivity of the GDL, being in
direct contact with the membrane, can play an important role
in controlling these parameters. Specifically, under wet con-
ditions, liquid water formed on the catalyst layers can be
removed via evaporation when the membrane temperature is
high, thus low conductivity GDLs are preferred. On the other
hand, when the fuel cell is operated under dry conditions,
GDLs with inadequate thermal conductivity would promote
membrane dehydration, which leads to reduced electrical
conductivity and fuel cell performance decrease. The addition
of PTFE and MPL affects the thermal conductivity. PTFE as a
polymer, is characterized by low thermal conductivity, hence
the GDL conductivity is dependent on the PTFE loading, and
MPL thickness is also a crucial parameter as the MPL provides
additional resistance to heat transfer [78]. Therefore, the
appropriate GDL materials must be carefully selected by tak-
ing the operational conditions into consideration.
Surface morphology
Many studies demonstrate the correlation between surface
morphology of the GDLs and fuel cell performance. In partic-
ular, Wang et al. studied the difference between carbon paper
and carbon cloth and found that carbon cloth performs better
in wet conditions due to the smaller tortuosity and rougher
surface which facilitates the detachment of the water drop-
lets. However, the higher tortuosity and smoother surface of
carbon paper results in torpidity of water droplets and operate
better in dry conditions [79]. GDLs with MPLs have gained a lot
of research attention, as their presence and structure influ-
ence many parameters, including fuel cell performance. MPL
application usually results in a smoother surface in contact
with the CL which can also be a contributor to the undoubt-
edly enhanced performance on its presence. Finer carbon
particles result in smoother surfaces and smaller pores, hence
MPL morphology depends on the type and loading of the
carbon powder, as well as the coating method.
Several research papers correlate the improved efficiency
of GDL with the carbon type and loading. Antolini et al. studied
the effect of carbon powder characteristics on the PEMFC
performance, using two different types of carbon powder;
acetylene black and VULCAN® (XC-72R), and proved the
enhanced performance of acetylene black [80]. Stuckey et al.
introduced the growth of carbon nanotubes nanoforest (CNT)
on carbon paper substrates and observed excellent perfor-
mance on various RH conditions [81]. Gao et al. used CNT GDLs
for a DMFC and reported improvement in limiting current
density and peak power density of 40% and 27%, respectively,
compared to Toray carbon paper (TGP-H-060). These findings
were attributed to the higher graphitization degree and larger
pore number of CNT [82]. Wei et al. developed a three-step
method to produce CNT GDLs that are characterized by low
thickness and cost and high flexibility and reported dramati-
cally increased performance of ~60% on H2/air, compared to a
commercial GDL, and durability over 500 h [83]. Similarly,
Fontana et al. grew CNTs on carbon fibers as an MPL and
achieved 30% increase in current density at 0.75 V and 100 h of
durability without any major voltage losses; however further
research is encouraged to fully comprehend the reasons for
these improvements [84].
The effect of carbon loading on the surface morphology,
and subsequently on fuel cell performance, was observed in
the 1990s. Specifically, Wilson et al. reported that for a given
carbon loading the electrode performance is a function of its
structure (porosity and surface area) and composition [85].
Park et al. investigated the effect of carbon loading in the MPL
by preparing MPLs of different carbon loading on a carbon
fiber paper and concluded that the improvement on fuel cell
performance highly depends on the carbon loading of the GDL
[86]. Sim et al. investigated the effect of carbon loading on MPL
of 1, 2 and 3 mg/cm2 and showed that 2 mg/cm2 loading
demonstrated the higher performance due to its increased
porosity (compared to 1 mg/cm2) and decreased electrical
resistance (compared to 3 mg/cm2). They also concluded that
there exists an optimum carbon loading for maximum fuel
cell performance [87].
Cracks usually appear on the MPL surface during temper-
ature changes. Although it has been reported that cracks can
act like larger pores and assist the transport of water through
the GDL, their presence on the MPL surface is not desired
because they lead to poor electrical conductivity. Moreover,
the Pt catalyst particles dissociate and fall into the cracks and
pores which results in reduced support for the catalyst and
rapid MPL and membrane degradation by accumulating water
and forming defects around the cracks [51,52]. Swamy et al.
reported that surface roughness of the MPL/CL interface play a
significant part on the polarization losses and more specif-
ically, water pooling in the interfacial gaps due to capillary
flow could significantly impact transport of the MPL/CL
interface [88]. On the contrary, the smooth, crack-free surface
and homogenous nature of MPL could lead to uniform reac-
tant gas transport to the reaction zone and effective water
removal, as the membrane is capable of adhering to the
catalyst layer without any interfacial gaps [50].
Electrochemical characteristics
Electrochemical impedance spectroscopy (EIS) is a
noneinvasive diagnosis tool for in situ measurements of
transport and kinetic properties of PEM fuel cell functional
diffusion layers, as shown in Fig. 7. It is interpreted to repre-
sent the movement of molecules/particles such as the charge/
mass transfer, diffusion, electrochemical double layer, ion
adsorption, coating, electrical resistance, corrosion, conduc-
tivity, and electrochemical reactions [89,90]. Electrochemical
impedance spectroscopy (EIS) is a reliable in situ tool for fuel
cell characterization. Diffusion phenomenon in PEM fuel cell
create an impedance called Warburg impedance, which de-
pends on the frequency of the potential perturbation at high
 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3
Fig. 7 e Impedance Spectra of PEM fuel cell with Equivalent circuit.
frequencies; the Warburg impedance is small since diffusing
reactants do not have to move very far and at low frequencies,
and the reactants have to diffuse farther, increasing the
impedance [5]. The Warburg impedance is defined as:
1
Zw ¼ aðuÞ2 ð1  jÞ
where u is the radial frequency and a is the Warburg coeffi-
cient given by the equation below:




a ¼ RT Fn2 A√2 ÷ ð1 = Co √Do Þ þ 1 CR √DR
where Do is the diffusion coefficient of the oxidant, DR the
diffusion coefficient of the reductant, A the surface area of the
electrode and n the number of electrons involved.
Manzo and Greenwood used EIS parameters derived from
PEMFCs at various oxygen levels and developed a mathe-
matical simulation of a gas diffusion layer (GDL) and air
channel, separating the impedance caused by oxygen deple-
tion in the channel/GDL interface [91]. EIS is a powerful tool
which allows a deep in situ kinetic analysis of not only the
catalytic phenomena but also on the diffusion process. Spe-
cifically, EIS, reveals the behaviour of GDL which is likely to be
attributed to diffusion resistance that occurs at various over-
potential and is illustrated in Fig. 7. Crucial parameters for the
evaluation of fuel cell performance, such as Ohmic resistance,
charge transfer, and mass transfer resistance, whose trends
have been studied as a function of the power density and
performance [92].
Manufacturing methods
A variety of manufacturing methods for the MPLs have been
reported in the literature. Yet, the MPL properties affected by
these methods need further examination and understanding.
The manufacturing method has a direct effect on the MPL
2303
thickness, surface morphology, porosity and evidently fuel
cell performance, as those parameters are directly related to
electrical and thermal conductivity and mass transport. There
are numerous techniques for slurry deposition, the use of
which depend on the reproducibility, scalability, application,
and time. The techniques often used for the fabrication of
MPLs are categorised into coating and printing. Both tech-
niques describe the method of transferring a layer of ink to a
substrate, however the difference between the two mainly lies
in the complexity of the pattern formed. Depending on the
substrate type and coating methods, the manufacturing could
be either continuous (e.g., roll to roll (R2R)) or batch process
(e.g., spray coating).
Casting and blade coating
The most conventional methods are casting and blade coating.
Casting is the simplest coating technique as no equipment is
required. The solution is simply casted on the substrate laid on
a flat surface, followed by drying. This method has been used
successfully in production of film and coatings, although the
main disadvantage is that there is no control over the film
thickness and appropriate solvents must be used to avoid
precipitation or crystallization and/or inhomogeneous drying.
Glacigen Materials, Inc. recently presented freeze tape casting
as a novel method to develop high structured GDLs, addressing
the water removal issue with the presence of capillary pore
structures, by performing improvements to render this tech-
nique cost effective for large GDL production [93]. Blade coating
(doctor blade) technique includes deposition of coating mate-
rial in front of a sharp blade which is in fixed distance from the
surface with a substrate on top of it. As the blade moves, the
coating is uniformly deposited on the top of the substrate,
typically between 10 and 500 mm, and the dry thickness can be
estimated by the following equation:
2304 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3

Fig. 8 e Manufacturing process of Gas Diffusion Layer by wet-layer technique.

suspended in water and filtered onto interwoven fibre mat.

1 c The process is as follows: the chopped PAN based carbon fi-
d¼ g
2 r bres are processed to a primary carbon fibre. The raw paper is
then impregnated with carbonizable resins (carbonizable
where g is the distance between the blade and the substrate, c
resins with the optional addition of carbon fillers), cured and
the concentration of the solid material in the ink (g.cm3), and
recarbonized/graphitized. This procedure serves to adjust the
r the final film density (g.cm3) [94]. This technique has a well-
porosity and enhance the electrical and thermal conductivity.
defined thickness control, compared to casting, however, to
In addition, sintering or thermal annealing is applied to bond
increase reproducibility, it requires viscous inks prepared
the substrate/MPL and to develop the full hydrophobic prop-
with a higher binder composition. Sim et al. reported MPL
erties of the GDL. Proper selection of raw materials and ad-
fabrication using doctor blade method and reported that as
ditives guarantees the material is virtually free from the heavy
the PTFE content increased on the MPL, the drying time was
metals that are detrimental to fuel cell applications. Fig. 8 is an
decreased leading to the formation of larger cracks during
illustration of SIGRACET® grade GDL 39 BC (325-mm thickness)
sintering [87]. Doctor blade is a relatively slow technique and
as a baseline material. The chopped PAN based carbon fibre
similarly to casting, there is a possibility of material aggrega-
GDL are the preferred solutions since they can be fabricated at
tion or crystallisation during the process.
high volume (scalability) and low thickness [25].
Ideally, a coating process should combine high speed and
cost effectiveness, as well as solvents and substrate flexibility.
Spraying
The R2R manufacturing process is commonly used to produce
Spray coating is the most popular technique for MPL deposi-
fuel cell membranes, nevertheless its use on gas diffusion
tion, where a dispersion of carbon powder and hydrophobic
layer fabrication at high precision and rate, has been reported.
agent are mixed in a solvent (usually water or IPA) via soni-
The process utilizes several rollers as a web path in which a
cation and the mixture is deposited on the substrate in the
substrate material is navigated through and additives or
form of an aerosol through a nozzle. It does not produce high
coatings are added onto it, as it moves along, which makes it
volume products as it is a time consuming process with limited
suitable for large production. NREL (National Renewable En-
focus area and surface uniformity as the aerosol particles do
ergy Laboratory), in an annual report, presented a modifica-
not align when they reach the substrate [94]. Nonetheless, a
tion of R2R manufacturing method for multilayer coatings
variety of studies have used spraying deposition for MPL
[95]. Recently, Chen et al. developed a method incorporating
fabrication due to its feasibility, ease of use and variety of
roll-to-roll method to fabricate five layer MEAs with high
viscosities and thickness range. Electrospray methods are
precision [96].
characterized by uniform coating due to the fine droplets
created by the atomization and the fast evaporated solvents.
Wet laying technology However, parameters such as flow rate, voltage onset and
Wet-laying is predominantly used in the traditional textile working distance have to be controlled by case. Chingthamai
and paper-making industry in which cellulose fibres are et al. considered air permeability, low resistance, and coating
 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3
adhesion and fabricated optimized MPL using electrospraying
technique at working distance of 1.5e2.0 cm and the flow rate
of 0.4e0.6 ml/h [97]. Ultrasonic spraying creates standing
waves by converting high frequency sound waves into me-
chanical energy and transferring it into a liquid and while
exiting the nozzle surface, it is dispersed into micro-droplets in
the form of a uniform fine mist. The median droplet size de-
pends on the specific resonance frequency that the nozzle
operates. Reportedly, spraying has demonstrated the largest
Gurley numbers for air permeability, however the lack of
reproducibility and scalability limits this technique to lab scale
applications [98,99].
Screen printing
Screen printing requires fluids with high viscosity and the
thickness of the coating is controlled by the thickness of the
solution and the screen, with numerous parameters
involved (the speed of the squeegee, applied force, distance
and position) increasing the complexity of the technique.
The screen-printing ink is deposited on a substrate, which is
located underneath a meshed screen fixed into a frame with
openings positioned in such a way to form the desired
image. The coating solution is then drawn across the frame
with squeegee, pushing the solution through the screen onto
the substrate according to the mesh pattern. Li et al.
compared MPL properties prepared with screen printing and
spraying techniques. They observed cracked surfaces on the
MPL prepared with screen printing, while the MPL showed
smooth surfaces with various pore diameters on the spray-
ing method. Evidently, the fuel cell demonstrated higher
performance at low relative humidity conditions on the
screen-printing method attributed to binder precipitation
causing a more hydrophilic MPL, as revealed from contact
angle measurements. On the other hand, on high relative
humidity conditions the MPL deposited by the spraying
method performed better [100]. Same observation has been
reported by Zeis while comparing spraying and doctor blade
methods, concluding that the association of the
Fig. 9 e Additive Manufacturing through selective laser sintering process.
2305
manufacturing process with the GDL properties need further
evaluation [101].
Electrospinning
Electrospinning is a technique often used for carbon nanofiber
fabrication where a polymer solution is projected through a jet
by applying a voltage difference of 10 kV between the opening
and the collector. This process produces very thin fibre with
diameter of 0.5e5 mm with controllable pore structures. Li
et al. used electrospinning for MPL fabrication, followed by
heat treatment. They reported that the final product demon-
strated high performance due to decreased mass transport
resistance, attributed to the improved pore structure, at high
RH conditions compared to a commercial GDL [102]. Addi-
tionally, Balakrishnan et al. designed a GDL with graded
porosity used electrospinning technique and observed supe-
rior performance under relatively low and high RH conditions,
when compared to two GDL structures with uniform porosity,
also fabricated using electrospinning method [103]. The single
jet limits the scalability of this method and therefore the use
of multiple jets is investigated to increase productivity [104].
Additive Manufacturing (AM)
Additive manufacturing is a transformative 3D process during
which materials are deposited layer by layer according to a
CAD design. The approach is a promising option that enables
the creation of lighter, functional parts such as that of GDL in
PEM fuel cell application. The most used types of additive
manufacturing in the fabrication of GDLs are the Selective
Laser Sintering (SLS) and Selective Laser Melting (SLM), where
a high-power laser is used to combine small particles of ma-
terials into one 3D shape, as shown in Fig. 9.
The SLS operating parameters predominantly determine
the quality end product attribute which includes the laser
power and scanning speed and can be easily controlled. Ad-
ditive manufacturing is the most common GDL fabrication
method nowadays due to the cost effectiveness, automation
and high productivity it offers. In the PEMFCs, AM finds
2306 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3
Fig. 10 e Illustration of hydrogen diffusion from the bared Co25Pd75 to ZnO/Co25Pd75, monitored through magneto-optical
Kerr effect.
numerous applications in material fabrication, including
GDLs, MEAs and bipolar plates [105e107]. Specifically, for GDLs,
Jayakumar et al. proposed a 3D printing for large scale GDL
synthesis using alumide as substrate, incorporating porosity
and achieving small thickness, decreasing the resistance [108].
Also, Tai et al. inferred that additive manufacturing has gained
a lot of research attention lately, as it can be used to produce
multiple critical fuel cell components with great performance
and cost efficiency [109] (see Fig. 10).
Heat treatment
Heat treatment plays a very important role in the fabrication of
GDLs. As mentioned above, the microporous layer is a very
critical component of the fuel cell, as it controls parameters
that facilitate the water management of the system. One of the
commonly used heat treatment processes on the MPLs is solid
state sintering and the main reason is to control the hydro-
phobicity, since for optimum hydrophobic agent distribution
with the carbon powder high temperatures are required (PTFE
~360  C, FEP ~270  C). Although the hydrophobic agent content
plays a crucial role on the surface structure and degree of hy-
drophobicity, the sintering temperature has a great impact as
well. Rohendi et al. studied the effects of PTFE content and
sintering temperatures on the MPL and concluded that
increased sintering temperature had a negative effect on
electrical conductivity [110]. Borisov et al. mentioned that the
time and temperature of sintering has a direct effect on the
MPL pore structure and hydrophobicity [111]. Orogbemi et al.
evaluated MPLs before and after sintering and confirmed that
regardless of the carbon type sintering decreased the air
permeability of the GDL, due to better hydrophobic agent dis-
tribution when the temperature reached close to its melting
point, sealing some of the cracks and increasing mass resis-
tance [112]. However, it has been reported that high tempera-
ture sintering accelerates degradation of GDLs grafted with
combined hydrophobic and hydrophilic patterns around
200e250  C, therefore alternative heat treatment techniques,
such as local heating using infrared, should be considered [113]
(see Tables 1 and 2, Figs. 11e13).
Research, development, and commercialization
trends
The need of PEMFC for transportation is undoubtedly crucial,
directing the recent research attention on approaches to dim
this technology vital in order to substitute the internal com-
bustion engine vehicles. However, there are still many issues
to be addressed before this can become reality. Nevertheless,
Clean Energy Ministerial Hydrogen Initiative (CEM H2I), a
multi-governmental initiative launched in Vancouver in 2019,
aims to assist with hydrogen deployment in industrial and
transportation applications, in order to accelerate the use and
commercialization of hydrogen and fuel cell technologies
[114]. There are many attempts for commercialization and
automation of fuel cell parts, including GDLs. The main
challenge is clearly the cost, since fuel cell materials, and
especially the platinum catalyst, are still very costly compared
to other vehicle technologies such as internal combustion and
hybrids, therefore manufacturers have to reduce the produc-
tion cost to make the market more accessible. This issue be-
comes very complicated as the fuel cell technology is still
evolving and new approaches are developed daily. Research
facilities along with industrial organizations are developing
new protocols to establish lower cost on the material fabri-
cation. In 2020, NREL and other research facilities presented
their plan to reduce the cost on manufacturing GDLs by
replacing the expensive materials, such as PAN fibers, which
are made from costly raw materials and require high tem-
peratures (1700e2000  C) carbonization process, and PTFE,
with less costly fibers and super-hydrophobic gas phase
techniques that will possibly eliminate the need of MPLs [115].
 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3 2307

Table 1 e GDL manufacturing methods.

Coating method Material input Material output Scalability Controllability Limitations Section
Casting Ink/slurry wet film/coating Low No control over film Use of specific solvents C(i)
thickness
Blade coating Ink/slurry wet film/coating Low Well defined thickness Use of viscous inks with C(i)
control binders
Spray coating Ink/slurry Aerosol Low Low surface area Limited focus, time C(iii)
uniformity, large variety consuming
of solvent viscosities,
large thickness range
Screen printing Ink/slurry Low Controllable thickness High viscosity fluids C(iv)
Electro spray Ink/slurry Fine droplet aerosol Low Uniform coating Use of fast evaporating C(iii)
solvents
Ultrasonic spraying Ink/slurry Fine mist Low Uniform coating, C(iii)
controllable droplets
Electro-spinning Ink/slurry Medium Controllable pore Single jet limits C(v)
structures scalability
R2R Ink/slurry wet film/coating High High precision C(i)
SLM Metal powder 3D complex geometry High Laser speed determines C(vi)
structure final properties, high
controllability

Table 2 e Main GDL manufacturers and their FCEV contribution.

Manufacturer Country Product FCEV
Toray Japan Carbon paper substrates, GDLs, CCM, MEAs Toyota Mirai
Honda Clarity Fuel Cell
Ballard Canada FC engines, Bipolar plates, MEAs, Catalysts Heavy duty trucks, light rail, buses
Audi (research prototype)
SGL Germany Carbon paper substrates, GDLs, MPLs Hyundai NEXO

Fig. 11 e Schematic illustration of the fluorescence microscopy for visualizing water transport in GDL.

The major GDL manufacturers are Toray, Ballard, and SGL,
specializing in carbon fiber production for batteries and fuel
cell applications. In 2017, Toray announced their decision to
initiate a large-scale manufacturing facility for the mass
production of carbon paper used as substrates for the con-
struction of the GDLs, to meet the increasing material demand
and contribute to the establishment of hydrogen technology
[116]. Toray has been contributing to hydrogen technology for
decades, providing the carbon paper for the first fuel cell ve-
hicles by large automotive companies Toyota (Mirai,
December 2014) and Honda (Clarity, March 2016). In Europe,
SGL joined the project INSPIRE, in 2017, as a GDL component
2308 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3

Fig. 12 e Neutron radiography to visualize water distribution inside the GDL.

Fig. 13 e Novel neural network model to identify the optimized output performance.

developer, aiming to design the next generation of fuel cells
with increased performance and durability, achieving a
150 kW stack with performance of 1.3 W/cm2. SGL's collabo-
ration with Hyundai developed the FCEV Hyundai NEXO,
which was demonstrated in February 2018 and released later
that year [117,118]. Ballard Power Systems, the largest PEM
manufacturer globally, provides manufacturing solutions
including CCM and films with R2R process, bipolar plates as-
sembly and fuel cell stack and system assembly, and has
partnered with large automotive companies to accelerate the
development of FC passenger vehicles. In 2020, Ballard pre-
sented a fuel cell stack of maximum power of 140 kW and
power density of 4.3 kW/L in cooperation with Audi. They
have, also, developed a wide variety of fuel cell modules for
heavy duty trucks, buses and light rail applications, and their
platforms include the FC velocity of net power of 30, 85 and
100 kW for small buses and trucks and the FC move of net
power of 70 and 100 kW and freeze start 25  C, suitable for
buses and heavy-duty trucks and vehicles [119,120].
Although the availability of fuel cell vehicles will not increase
until such time that there are enough hydrogen fuelling stations
to meet the public demand, more and more automobile manu-
facturers are initiating design and development plans for fuel cell
powered passenger cars, most of whom have been experiment-
ing for decades. BMW, in cooperation with Toyota, will release
the BMW iX5, with an estimated maximum power output at
125 kW when operating in hydrogen and refuelling time 3e4 min.
The third generation Honda Clarity FCV is expected to return to
the market in 2023 with improved durability and reduced price.
Finally, Hyundai plans to return with a new Hyundai Nexo, with a
production of 11,000 units, and Hyundai Staria with maximum
power of 100 and 200 kW, respectively [121].
GDL fabrication and characterisation techniques
Despite issues with voltage oxidation [19], the conventional
GDLs are predominantly made from carbon fibres which are
preferentially oriented along the in-plane [122].
C þ 2H2O / CO2 þ 4Hþ þ 4e, Eo ¼ 0.207 V vs. Standard
Hydrogen Electrode
Fu et al. [123] proposed a simple one-step method to pre-
pare a GDL with three different functional layers, based on the
different sedimentation rates and filtration rates of short
 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3
carbon fibre (CF) and carbon nanotube (CNT). The GDL with
20% CNT, 50% CF and 22% PTFE exhibited a power density of
365 mW cm2, which is higher than the Sigracet GDL
(205 mW cm2). Investigation by Okereke et al., validate that
the GDL with anisotropic transport properties in the in-plane
direction will enhance the performance of the PEMFC [124].
In addition, GDL samples with aligned fibres generally display
the highest anisotropy and their in-plane permeability values
could be higher by a factor of 2 in contrast to through-plane.
Benchmarking the GDL with an advanced measurement
tool can potentially provide a comprehensive insight into the
broad process by which a material's structural and functional
properties are measured and subsequently ascertained. The
advanced characterization of GDL techniques includes,
magneto-optical Kerr effect, Direct optical visualization,
Fluorescence microscopy, Neutron radiography, X-ray
computed tomography, Stochastic method, Pore network
model, and Volume of the fluid model (VOF).
Magneto-optical Kerr effect
Chang et al. [125] used the Magneto-optical Kerr effect to
investigate hydrogen diffusion in a cobalt-palladium alloy film
where light is reflected from a magnetized surface. The
spatially resolved images provide a non-invasive technique to
monitor hydrogen transport.
Direct optical visualization
Direct optical visualization is a technique employed to visualize
liquid water flow in transparent PEM fuel cells. Yin et al., 2021
[126] proposed a method with a CCD camera placed over the
transparent plate for direct optical investigation of liquid flow
phenomena during PEM fuel cell operation. However, due to
carbon fibres being non-transparent; this technique can only
observe liquid water at the GDL surface or within a couple of
pores below the surface.
Fluorescence microscopy
Fluorescence microscopy is a tool to visualize micro-scale
liquid water inside GDLs near the surface, using the fluores-
cent dye as flow indicator. Litster et al. [127], used the fluo-
rescence microscopy method to have a visualised insight
liquid water behaviour in GDL. They mentioned that water
transport does not take place based on the accepted hypoth-
esis of branching. Their physical observation showed that
water does not pass through a convergent capillary tree.
Neutron radiography
Neutron radiography is a technique that uses a collimated
beam of neutrons to generate an image in the beam. Nasu
et al. [128] used neutron radiography to observe the distribu-
tion of liquid water during power generation at current den-
sity of 1e3 Acm2. In the anode channel, liquid water spread
more throughout the cell using the water-repellent GDL than
using the basic GDL. This indicates that the water generated at
the cathode efficiently back-diffused (at 2.0 A cm2) to the
anode side via the electrolyte without staying in the cathode
2309
GFCs. In addition, the heat generated by the cathode over-
voltage contributed to the suppression of dew condensation
both at the cathode and the anode.
Role of neural network
Neural network can provide a reliable and robust operation
especially when numerous operational parameters are
involved [129]. For instance, porosity is the integral parameter
that is correlated to other physical parameters such as elec-
trical conductivity, thermal conductivity, permeability and
hydrophilicity. Neural network can be one potential compu-
tational algorithm that can optimise the PEM fuel cell perfor-
mance based on the weighted sum of the parameters.
Figure 13 illustrates a neural network model to identify the
optimized fuel cell output performance .
Summary
GDLs play a crucial role in PEMFCs performance, hence un-
derstanding the effect of their properties is a necessity for
enhancing three important aspects pertaining to commer-
cialization: performance, durability, and cost. Materials and
properties suitable for GDLs have been investigated for years,
in numerous publications and studies, however, main issues
seem to persist due to the intense fuel cell environment that
causes physical and chemical degradation to the internal fuel
cell parts. Thus, continuous research and material develop-
ment is necessary to mitigate the durability aspect. Further-
more, properties such as mass transport, porosity and
electrical/thermal conductivity, are being constantly investi-
gated to overcome the performance barrier and escalate
hydrogen to commercially viable technologies. Nevertheless,
the underlying properties and their impact in performance
(e.g., permeability, capillarity, diffusivity etc.) seem to be
incoherent and studies are limited. Considering the GDL ma-
terials, carbon appears to be the predominant choice despite
its limitations, (e.g., carbon corrosion, material wash-off,
flooding effects etc.) as a result of the intense fuel cell envi-
ronment. New research focus on carbon-free alternatives,
mainly metals, due to superior material properties and high-
volume manufacturing capability and automation.
A wide range of studies have been conducted on the GDLs
materials combined with a variety of manufacturing processes
to improve GDLs material properties for research purposes
with spray coating being the most frequent due to its feasibility
and ease of use; however, the literature focused on large scale
fabrication capabilities, such as roll-to-roll and additive
manufacturing is limited. Both mass production processes are
characterized by high volume production, cost effectiveness
and high precision, however AM can utilize automation, which
increases the process efficiency, applicability, and renders it a
potential long-term solution for mass production of GDLs. The
need of alternative energy solutions is crucial, accounting for
the recent increase of fossil fuel costs, and fortunately, major
research facilities and automotive manufacturers have been on
the search for ways to successfully implement hydrogen
technology to public transportation and personal vehicles and
competitively replace internal combustion engines.
2310 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
references
[1] Madheswaran DK, Jayakumar Arunkumar, Varuvel EG.
Recent advancement on thermal management strategies in
PEM fuel cell stack: a technical assessment from the context
of fuel cell electric vehicle application. Energy Sources
2022;44:3100e25. https://doi.org/10.1080/
15567036.2022.2058122.
[2] Okonkwo PC, Otor C. A review of gas diffusion layer
properties and water management in proton exchange
membrane fuel cell system. Int J Energy Res 2020:1e21.
https://doi.org/10.1002/er.6227.
[3] Martı́n-Alca  ntara A, Gonza lez-Mora
 n L, Pino J, Guerra J,
Iranzo A. Effect of the gas diffusion layer design on the
water management and cell performance of a PEM fuel cell.
Processes 2022;10:1395. https://doi.org/10.3390/pr10071395.
[4] Cindrella L, Kannan AM, Lin JF, Saminathan K, Ho Y,
Lin CW, et al. Gas diffusion layer for proton exchange
membrane fuel cells-A review. J Power Sources
2009;194:146e60. https://doi.org/10.1016/
j.jpowsour.2009.04.005.
[5] Jayakumar A, Sethu SP, Ramos M, Robertson J, Al-Jumaily A.
A technical review on gas diffusion, mechanism and
medium of PEM fuel cell. Ionics 2015;21:1e18. https://
doi.org/10.1007/s11581-014-1322-x.
[6] Omrani R, Shabani B. Review of gas diffusion layer for
proton exchange membrane-based technologies with a
focus on unitised regenerative fuel cells. Int J Hydrogen
Energy 2019;44:3834e60. https://doi.org/10.1016/
j.ijhydene.2018.12.120.
[7] Park S, Lee JW, Popov BN. A review of gas diffusion layer in
PEM fuel cells: materials and designs. Int J Hydrogen Energy
2012;37:5850e65. https://doi.org/10.1016/
j.ijhydene.2011.12.148.
[8] Park S, Popov BN. Effect of a GDL based on carbon paper or
carbon cloth on PEM fuel cell performance. Fuel
2011;90:436e40. https://doi.org/10.1016/j.fuel.2010.09.003.
[9] Zamel N, Li X, Shen J. Correlation for the effective gas
diffusion coefficient in carbon paper diffusion media.
Energy Fuel 2009;23:6070e8. https://doi.org/10.1021/
ef900653x.
[10] Salahuddin M, Uddin MN, Hwang G, Asmatulu R.
Superhydrophobic PAN nanofibers for gas diffusion layers
of proton exchange membrane fuel cells for cathodic water
management. Int J Hydrogen Energy 2018;43:11530e8.
https://doi.org/10.1016/j.ijhydene.2017.07.229.
[11] Liu X, Xi J, Xu B Bin, Fang B, Wang Y, Bayati M, et al. A high-
performance direct methanol fuel cell technology enabled
by mediating high-concentration methanol through a
graphene aerogel. Small Methods 2018;2:7e12. https://
doi.org/10.1002/smtd.201800138.
€
[12] Oner €
E, Oztürk A, Yurtcan AB. Utilization of the graphene
aerogel as PEM fuel cell catalyst support: effect of
polypyrrole (PPy) and polydimethylsiloxane (PDMS)
addition. Int J Hydrogen Energy 2020;45:34818e36. https://
doi.org/10.1016/j.ijhydene.2020.05.053.
[13] Yi P, Peng L, Lai X, Li M, Ni J. Investigation of sintered
stainless steel fiber felt as gas diffusion layer in proton
exchange membrane fuel cells. Int J Hydrogen Energy 2012;
37:11334e44. https://doi.org/10.1016/j.ijhydene.2012.04.161.
[14] Kariya T, Yanagimoto K, Funakubo H, Shudo T. Effects of
porous flow field type separators using sintered Ni-based
alloy powders on interfacial contact resistances and fuel
cell performances. Energy 2015;87:134e41. https://doi.org/
10.1016/j.energy.2015.04.060.
[15] Omrani R, Shabani B. Gas diffusion layer modifications and
treatments for improving the performance of proton
exchange membrane fuel cells and electrolysers: a review.
Int J Hydrogen Energy 2017;42:28515e36. https://doi.org/
10.1016/j.ijhydene.2017.09.132.
[16] Jiao K, Xuan J, Du Q, Bao Z, Xie B, Wang B, et al. Designing
the next generation of proton-exchange membrane fuel
cells. Nature 2021;595:361e9. https://doi.org/10.1038/
s41586-021-03482-7.
[17] Ito H, Abe K, Ishida M, Hwang CM, Nakano A. Effect of
through-plane polytetrafluoroethylene distribution in a gas
diffusion layer on a polymer electrolyte unitized reversible
fuel cell. Int J Hydrogen Energy 2015;40:16556e65. https://
doi.org/10.1016/j.ijhydene.2015.09.102.
[18] Chen G, Zhang H, Zhong H, Ma H. Gas diffusion layer with
titanium carbide for a unitized regenerative fuel cell.
Electrochim Acta 2010;55:8801e7. https://doi.org/10.1016/
j.electacta.2010.07.103.
[19] Jayakumar A, Singamneni S, Ramos M, Al-Jumaily AM,
Pethaiah SS. Manufacturing the gas diffusion layer for PEM
fuel cell using a novel 3D printing technique and critical
assessment of the challenges encountered. Materials
2017;10:1e9. https://doi.org/10.3390/ma10070796.
[20] Choi H, Kim OH, Kim M, Choe H, Cho YH, Sung YE. Next-
generation polymer-electrolyte-membrane fuel cells using
titanium foam as gas diffusion layer. ACS Appl Mater
Interfaces 2014;6:7665e71. https://doi.org/10.1021/
am500962h.
[21] Steen SM, Mo J, Kang Z, Yang G, Zhang FY. Investigation of
titanium liquid/gas diffusion layers in proton exchange
membrane electrolyzer cells. Int J Green Energy 2017;
14:162e70. https://doi.org/10.1080/15435075.2016.1253582.
[22] Abraham BG, Chetty R. Design and fabrication of a quick-fit
architecture air breathing direct methanol fuel cell. Int J
Hydrogen Energy 2021;46:6845e56. https://doi.org/10.1016/
j.ijhydene.2020.11.184.
[23] Miura T, Hatakaeyama T, Fushinobu K, Okazaki K. An
investigation of effect of micro-structure on current
collector for polymer electrolyte fuel cells. Therm Sci Eng
2009;17:75e81.
[24] Stampino P, Omati L, Dotelli G. Electrical performance of
PEM fuel cells with different gas diffusion layers. J Fuel Cell
Sci Technol 2013;8:1e5. https://doi.org/10.1115/1.4003630.
[25] Schweiss R, Meiser C, Damjanovic T, Galbiati I, Haak N.
White paper SIGRACET ® gas diffusion layers for PEM fuel
cells , electrolyzers and batteries. SGL Group 2016;1e10.
[26] Shu C, Wang E, Jiang L, Sun G. High performance cathode
based on carbon fiber felt for magnesium-air fuel cells. Int J
Hydrogen Energy 2013;38:5885e93. https://doi.org/10.1016/
j.ijhydene.2013.02.093.
[27] Yang H, Tu HC, Chiang IL. Carbon cloth based on PAN
carbon fiber practicability for PEMFC applications. Int J
Hydrogen Energy 2010;35:2791e5. https://doi.org/10.1016/
j.ijhydene.2009.05.019.
[28] Chu H, Yeh C, Chen F. Effects of porosity change of gas
diffuser on performance of proton exchange membrane
fuel cell. J Power Sources 2003;123:1e9.
[29] Gostick JT, Ioannidis MA, Fowler MW, Pritzker MD. On the
role of the microporous layer in PEMFC operation.
Electrochem Commun 2009;11:576e9. https://doi.org/
10.1016/j.elecom.2008.12.053.
 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3
[30] Zhang Z, He P, Dai YJ, Jin PH, Tao WQ. Study of the
mechanical behavior of paper-type GDL in PEMFC based on
microstructure morphology. Int J Hydrogen Energy
2020;45:29379e94. https://doi.org/10.1016/
j.ijhydene.2020.07.240.
[31] Radhakrishnan V, Haridoss P. Effect of cyclic compression
on structure and properties of a Gas Diffusion Layer used in
PEM fuel cells. Int J Hydrogen Energy 2010;35:11107e18.
https://doi.org/10.1016/j.ijhydene.2010.07.009.
[32] Nazemian M, Molaeimanesh GR. Impact of carbon paper
structural parameters on the performance of a polymer
electrolyte fuel cell cathode via lattice Boltzmann method.
Acta Mechanica Sinica/Lixue Xuebao 2020;36:367e80.
https://doi.org/10.1007/s10409-019-00919-1.
[33] Lee T, Yang C. A parametric study on the deformation of gas
diffusion layer in PEM fuel cell. J Mech Sci Technol
2020;34:259e68. https://doi.org/10.1007/s12206-019-1227-8.
[34] Bouziane K, Khetabi EM, Lachat R, Zamel N, Meyer Y,
Candusso D. Impact of cyclic mechanical compression on
the electrical contact resistance between the gas diffusion
layer and the bipolar plate of a polymer electrolyte
membrane fuel cell. Renew Energy 2020;153:349e61. https://
doi.org/10.1016/j.renene.2020.02.033.
[35] Sun X, Wang Z. Understanding of the role of carbon fiber
paper in proton exchange membrane fuel cells. J
Electrochem Energy Conv Storage 2022;19:1e7. https://
doi.org/10.1115/1.4050043.
[36] Ge J, Higier A, Liu H. Effect of gas diffusion layer
compression on PEM fuel cell performance. J Power Sources
2006;159:922e7. https://doi.org/10.1016/
j.jpowsour.2005.11.069.
[37] Jayakumar A, Ramos M, Al-Jumaily A. A novel 3D printing
technique to synthesise gas diffusion Layer for PEM fuel cell
application. ASME Int Mech Eng Congress Exp Proc (IMECE)
2016. https://doi.org/10.1115/IMECE2016-65554. 6B-2016:3-8.
[38] Sima CM, Ciupina V, Prodan G. Application of porous copper for
GDL in PEM fuel cells. J Optoelectron Adv Mater 2015;17:602e7.
[39] El-Kharouf A, Chandan A, Hattenberger M, Pollet BG. Proton
exchange membrane fuel cell degradation and testing:
Review. J Energy Inst 2012;85:188e200. https://doi.org/
10.1179/1743967112Z.00000000036.
[40] Zhang F, Advani SG, Prasad AK. Performance of a metallic
gas diffusion layer for PEM fuel cells. J Power Sources
2008;176:293e8. https://doi.org/10.1016/
j.jpowsour.2007.10.055.
[41] Hussain N, Van Steen E, Tanaka S, Levecque P. Metal based
gas diffusion layers for enhanced fuel cell performance at
high current densities. J Power Sources 2017;337:18e24.
https://doi.org/10.1016/j.jpowsour.2016.11.001.
[42] Desplobain S, Gautier G, Ventura L, Bouillon P. Macroporous
silicon hydrogen diffusion layers for micro-fuel cells. Phys
Status Solidi (A) Appl Mater Sci 2009;206:1282e5. https://
doi.org/10.1002/pssa.200881081.
[43] Spiegel C. PEM fuel cell modeling and simulation using
MATLAB. Elsevier; 2011.
[44] Xu Y, Qiu D, Yi P, Lan S, Peng L. An integrated model of the
water transport in nonuniform compressed gas diffusion
layers for PEMFC. Int J Hydrogen Energy 2019;26:13777e85.
https://doi.org/10.1016/j.ijhydene.2019.03.222.
[45] Yuan W, Li J, Xia Z, Chen S, Zhang X, Wang Z, et al. Study of
water transport mechanism based on the single straight
channel of proton exchange membrane fuel cell. AIP Adv
2020;10. https://doi.org/10.1063/5.0023383.
[46] Arvay A, Yli-Rantala E, Liu CH, Peng XH, Koski P, Cindrella L,
et al. Characterization techniques for gas diffusion layers
for proton exchange membrane fuel cells - a review. J Power
Sources 2012;213:317e37. https://doi.org/10.1016/
j.jpowsour.2012.04.026.
2311
[47] Fishman Z, Bazylak A. Heterogeneous through-plane
porosity distributions for treated heterogeneous through-
plane porosity distributions for treated PEMFC GDLs. J
Electrochem Soc 2011;158:B841e5. https://doi.org/10.1149/
1.3594578.
[48] Turkmen AC, Celik C. The effect of different gas diffusion
layer porosity on proton exchange membrane fuel cells.
Fuel 2018;222:465e74. https://doi.org/10.1016/
j.fuel.2018.02.058.
[49] Xia L, Ni M, He Q, Xu Q, Cheng C. Optimization of gas
diffusion layer in high temperature PEMFC with the focuses
on thickness and porosity. Appl Energy 2021;300:117357.
https://doi.org/10.1016/j.apenergy.2021.117357.
[50] Athanasaki G, Wang Q, Shi X, Chauhan N, Vimala V,
Cindrella L, et al. Design and development of gas diffusion
layers with pore forming agent for proton exchange
membrane fuel cells at various relative humidity
conditions. Int J Hydrogen Energy 2021;46:6835e44. https://
doi.org/10.1016/j.ijhydene.2020.11.187.
[51] Simon C, Hasche  F, Gasteiger HA. Influence of the gas
diffusion layer compression on the oxygen transport in PEM
fuel cells at high water saturation levels. J Electrochem Soc
2017;164:F591e9. https://doi.org/10.1149/2.0691706jes.
[52] Tanuma T, Kawamoto M, Kinoshita S. Effect of properties of
hydrophilic microporous layer (MPL) on PEFC performance. J
Electrochem Soc 2017;164:F499e503. https://doi.org/10.1149/
2.0371706jes.
[53] Xu H, Nagashima S, Nguyen HP, Kishita K, Marone F,
Büchi FN, Eller J. Temperature dependent water transport
mechanism in gas diffusion layers revealed by subsecond
operando X-ray tomographic microscopy. J Power Sources
2021;490:229492. https://doi.org/10.1016/
j.jpowsour.2021.229492.
[54] Nishiyama E, Murahashi T. Water transport characteristics
in the gas diffusion media of proton exchange membrane
fuel cell - role of the microporous layer. J Power Sources
2011;196:1847e54. https://doi.org/10.1016/
j.jpowsour.2010.09.055.
[55] Wargo EA, Schulz VP, Çeçen A, Kalidindi SR, Kumbur EC.
Resolving macro- and micro-porous layer interaction in
polymer electrolyte fuel cells using focused ion beam and
X-ray computed tomography. Electrochim Acta
2013;87:201e12. https://doi.org/10.1016/
j.electacta.2012.09.008.
[56] Hiramitsu Y, Sato H, Hosomi H, Aoki Y, Harada T,
Sakiyama Y, et al. Influence of humidification on
deterioration of gas diffusivity in catalyst layer on polymer
electrolyte fuel cell. J Power Sources 2010;195:435e44.
https://doi.org/10.1016/j.jpowsour.2009.07.035.
[57] Zhao X, Wang R, Zhang Y, Hao D, Yang Z. Study on water
transport mechanisms of the PEMFC based on a
visualization platform and water balance model. Int J Chem
Eng 2021;2021:1e12.
[58] Hussaini IS, Wang CY. Measurement of relative
permeability of fuel cell diffusion media. J Power Sources
2010;195:3830e40. https://doi.org/10.1016/
j.jpowsour.2009.12.105.
[59] Ismail MS, Hughes KJ, Ingham DB, Ma L, Pourkashanian M.
Effect of PTFE loading of gas diffusion layers on the
performance of proton exchange membrane fuel cells
running at high-ef fi ciency operating conditions. Int J
Energy Res 2013;37:1592e9. https://doi.org/10.1002/er.
[60] Ko D, Doh S, Park HS, Kim MH. The effect of through plane
pore gradient GDL on the water distribution of PEMFC. Int J
Hydrogen Energy 2018;43:2369e80. https://doi.org/10.1016/
j.ijhydene.2017.12.007.
[61] Liu J, Yang C, Liu C, Wang F, Song Y. Design of pore
structure in gas diffusion layers for oxygen depolarized
2312 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3
cathode and their effect on activity for oxygen reduction
reaction. 2014.
[62] Zhu L, Yang W, Xiao L, Zhang H, Gao X, Sui PC.
Stochastically modeled gas diffusion layers: effects of
binder and polytetrafluoroethylene on effective gas
diffusivity. J Electrochem Soc 2021;168:014514.
[63] Yoshimune W, Kato S, Inagaki M, Yamaguchi S. A simple
method to measure through-plane effective gas diffusivity
of a gas diffusion layer for polymer electrolyte fuel cells. Int
J Heat Mass Tran 2022;191:122887.
[64] Chen T, Liu S, Zhang J, Tang M. Study on the characteristics
of GDL with different PTFE content and its effect on the
performance of PEMFC. Int J Heat Mass Tran
2019;128:1168e74. https://doi.org/10.1016/
j.ijheatmasstransfer.2018.09.097.
[65] El-kharouf A, Pollet BG. Gas diffusion media and their
degradation. Elsevier Inc.. n.d, https://doi.org/10.1016/B978-
0-12-386936-4.10004-1.
[66] Balzarotti R, Latorrata S, Mariani M, Stampino PG, Dotelli G.
Optimization of perfluoropolyether-based gas diffusion
media preparation for PEM fuel cells. Energies 2020;13:1e14.
https://doi.org/10.3390/en13071831.
[67] Stampino PG, Balzarotti R, Cristiani C, Dotelli G,
Guilizzoni M, Latorrata S. Effect of different hydrophobic
agents onto the surface of gas diffusion layers for PEMFC.
Chem Eng Trans 2013;32:1603e8. https://doi.org/10.3303/
CET1332268.
[68] Latorrata S, Sansotera M, Gola M, Stampino PG,
Navarrini W, Dotelli G. Innovative perfluoropolyether-
functionalized gas diffusion layers with enhanced
performance in polymer electrolyte membrane fuel cells.
Fuel Cell 2020;20:166e75. https://doi.org/10.1002/
fuce.201900169.
[69] Park SB, Park Y il. Fabrication of gas diffusion layer (GDL)
containing microporous layer using flourinated ethylene
prophylene (FEP) for proton exchange membrane fuel cell
(PEMFC). Int J Precis Eng Manuf 2012;13:1145e51. https://
doi.org/10.1007/s12541-012-0152-x.
[70] Park SB, Kim S, Park Y Il, Oh MH. Fabrication of GDL
microporous layer using PVDF for PEMFCs. J Phys Conf
2009;165:1e4. https://doi.org/10.1088/1742-6596/165/1/
012046.
[71] Park G, Sohn Y, Yang T, Yoon Y, Lee W, Kim C. Effect of PTFE
contents in the gas diffusion media on the performance of.
PEMFC 2004;131:182e7. https://doi.org/10.1016/
j.jpowsour.2003.12.037.
[72] Truong M, Duong N, Yang H. Effect of gas diffusion layer
thickness on the performance of anion exchange
membrane fuel cells. Processes 2021;9:718e27. https://
doi.org/10.3390/pr9040718.
[73] Prasanna M, Ha HY, Cho EA, Hong S, Oh I. Influence of
cathode gas diffusion media on the performance of the
PEMFCs. J Power Sources 2004;131:147e54. https://doi.org/
10.1016/j.jpowsour.2004.01.030.
[74] Zhou T, Liu H. Effects of the electrical resistances of the GDL
in a PEM fuel cell. J Power Sources 2006;161:444e53. https://
doi.org/10.1016/j.jpowsour.2006.04.106.
[75] Mishra V, Yang F, Pitchumani R. Measurement and
prediction of electrical contact resistance between gas
diffusion layers and bipolar plate for applications to PEM
fuel cells. Trans ASME 2004;1:2e9. https://doi.org/10.1115/
1.1782917.
[76] Hamour M, Grandidier JC, Ouibrahim A, Martemianov S.
Electrical conductivity of PEMFC under loading. J Power
Sources 2015;289:160e7. https://doi.org/10.1016/
j.jpowsour.2015.04.145.
[77] Bock R, Shum AD, Xiao X, Karoliussen H, Seland F,
Zenyuk IV, et al. Thermal conductivity and compaction of
GDL-MPL interfacial composite material. J Electrochem Soc
2018;165:F514e25. https://doi.org/10.1149/2.0751807jes.
[78] Sadeghifar H, Djilali N, Bahrami M. Effect of
Polytetrafluoroethylene (PTFE) and micro porous layer (MPL)
on thermal conductivity of fuel cell gas diffusion layers:
modeling and experiments. J Power Sources 2014;248:632e41.
https://doi.org/10.1016/j.jpowsour.2013.09.136.
[79] Wang Y, Wang C, Chen KS. Elucidating differences between
carbon paper and carbon cloth in polymer electrolyte fuel
cells. Electrochim Acta 2007;52:3965e75. https://doi.org/
10.1016/j.electacta.2006.11.012.
[80] Antolini E, Passos RR, Ticianelli EA. Effects of the carbon
powder characteristics in the cathode gas diffusion layer on
the performance of polymer electrolyte fuel cells. J Power
Sources 2002;109:477e82.
[81] Stuckey PA, Lin JF, Kannan AM, Ghasemi-Nejhad MN. Gas
diffusion layers for proton exchange membrane fuel cells
using in situ modified carbon papers with multi-walled
carbon nanotubes nanoforest. Fuel Cell 2010;10:369e74.
https://doi.org/10.1002/fuce.200900141.
[82] Gao Y, Sun GQ, Wang SL, Zhu S. Carbon nanotubes based
gas diffusion layers in direct methanol fuel cells. Energy
2010;35:1455e9. https://doi.org/10.1016/
j.energy.2009.11.031.
[83] Wei J, Ning F, Bai C, Zhang T, Lu G, Wang H, et al. An ultra-
thin, flexible, low-cost and scalable gas diffusion layer
composed of carbon nanotubes for high-performance fuel
cells. J Mater Chem 2020;8:5986e94. https://doi.org/10.1039/
c9ta13944c.
[84] Fontana M, Ramos R, Morin A, Dijon J. Direct growth of
carbon nanotubes forests on carbon fibers to replace
microporous layers in proton exchange membrane fuel
cells. Carbon 2021;172:762e71. https://doi.org/10.1016/
j.carbon.2020.10.049.
[85] Wilson M, Gottesfeld S. Thin-film catalyst layers for
polymer electrolyte fuel cell electrodes. J Appl Electrochem
1992;22:1e7.
[86] Park S, Lee J, Popov BN. Effect of carbon loading in microporous
layer on PEM fuel cell performance. 2006. p. 357e63. https://
doi.org/10.1016/j.jpowsour.2006.09.020. 163.
[87] Sim J, Kang M, Min K. Effects of basic gas diffusion layer
components on PEMFC performance with capillary pressure
gradient. Int J Hydrogen Energy 2021;46:27731e48. https://
doi.org/10.1016/j.ijhydene.2021.05.205.
[88] Swamy T, Kumbur EC, Mench MM. Characterization of
interfacial structure in PEFCs: water storage and contact
resistance model. J Electrochem Soc 2010;157:B77. https://
doi.org/10.1149/1.3247585.
[89] Kulikovsky A. Ananlytical impendance of PEM fuel cell
cathode including oxygen transport in the channel, gas
diffusion and catalyst layers. J Electrochem Soc
2022;169(3):034527.
[90] Syarif N, Rohendi D, Nanda AD, Sandi MT, Sihombing DSW.
Gas diffusion layer from binchotan carbon and its
electrochemical properties for supporting electrocatalyst in
fuel cell. AIMS Energy 2022;10(2):292e305. https://doi.org/
10.3934/energy.2022016.
[91] Cruz-Manzo S, Greenwood P. Analytical Warburg
impedance model for EIS analysis of the gas diffusion layer
with oxygen depletion in the air channel of a PEMFC. J
Electrochem Soc 2021;168:1e39.
[92] Latorrata S, Pelosato R, Gallo Stampino P, Dotelli G. Use of
electrochemical impedance spectroscopy for the evaluation
of performance of PEM fuel cells based on carbon cloth gas
diffusion electrodes. J Spectrosc 2018.
[93] Driscoll D, Pessoa Guttenberg AC, Anderson R, Sofie S.
Advanced manufacturing of gas diffusion layers with highly
engineered porosity. 2019.
 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 4 8 ( 2 0 2 3 ) 2 2 9 4 e2 3 1 3
[94] Cherrington R, Liang J. Materials and deposition processes
for multifunctionality. Elsevier Inc.; 2016. https://doi.org/
10.1016/B978-0-323-34061-8.00002-8.
[95] Wood D. Roll-to-Roll advanced materials manufacturing lab
collaboration. 2020.
[96] Chen J, Jiang X, Tang W, Ma L, Li Y, Huang YA, et al. Roll-to-
roll stack and lamination of gas diffusion layer in multilayer
structured membrane electrode assembly. Proc IME B J Eng
Manufact 2020;234:66e74. https://doi.org/10.1177/
0954405419862090.
[97] Chingthamai N, Sombatmankhong K, Laoonual Y.
Experimental investigation of electrospray coating
technique for electrode fabrication in PEMFCs. In: Energy
Proc. Elsevier Ltd; 2017. p. 1806e12. https://doi.org/10.1016/
j.egypro.2017.03.523. 105.
[98] Koraishy B, Meyers JP, Wood KL. Manufacturing of
membrane electrode assemblies for fuel cells, vols. 1e13;
2009.
[99] Vatanatham M, Song Y, Bonville L, Kunz HR, Fenton JM,
Smirnova A, et al. Methods for manufacturing diffusion
layers for PEMFCs. 2002.
[100] Li T, Zhou K, Lin G. Study on preparation process and
durability of gas diffusion layer of proton exchange
membrane fuel cell. Ionics 2022. https://doi.org/10.1007/
s11581-022-04439-0.
[101] Zeis R. Materials and characterization techniques for high-
temperature polymer electrolyte membrane fuel cells.
Beilstein J Nanotechnol 2015;6:68e83. https://doi.org/
10.3762/bjnano.6.8.
[102] Li C, Si D, Liu Y, Zhang J, Liu Y. Water management
characteristics of electrospun micro-porous layer in PEMFC
under normal temperature and cold start conditions. Int J
Hydrogen Energy 2021;46:11150e9. https://doi.org/10.1016/
j.ijhydene.2020.05.271.
[103] Balakrishnan M, Shrestha P, Ge N, Lee C, Fahy KF, Zeis R,
et al. Designing tailored gas diffusion layers with pore size
gradients via electrospinning for polymer electrolyte
membrane fuel cells. ACS Appl Energy Mater
2020;3:2695e707. https://doi.org/10.1021/acsaem.9b02371.
[104] Wei L, Liu C, Mao X, Dong J, Fan W, Zhi C, et al. Multiple-jet
needleless electrospinning approach via a linear flume
spinneret. Polymers 2019;11:1e9. https://doi.org/10.3390/
polym11122052.
[105] Mo J, Dehoff RR, Peter WH, Toops TJ, Green JB, Zhang FY.
Additive manufacturing of liquid/gas diffusion layers for
low-cost and high-efficiency hydrogen production. Int J
Hydrogen Energy 2016;41:3128e35. https://doi.org/10.1016/
j.ijhydene.2015.12.111.
[106] Sassin MB, Garsany Y, Gould BD, Swider-lyons KE.
Fabrication method for laboratory-scale high-performance
membrane electrode assemblies for fuel cells. 2017. https://
doi.org/10.1021/acs.analchem.6b03005.
[107] Svendby J, Bjelland Ø, Bokach D, Solheim BGB. The use of
additive manufactured inconel 625 as bipolar plate for the
high temperature proton electrolyte membrane fuel cell.
Procedia Struct Integr 2021;34:51e8. https://doi.org/10.1016/
j.prostr.2021.12.008.
[108] Jayakumar A. An assessment on additive manufacturing
technique to fabricate integral PEM fuel cell/electrolyser
component. MATEC Web Conf 2018;172. https://doi.org/
10.1051/matecconf/201817204005.
[109] Tai XY, Zhakeyev A, Wang H, Jiao K, Zhang H, Xuan J.
Accelerating fuel cell development with additive
manufacturing technologies : state of the art , opportunities
and challenges, vols. 1e15; 2019. https://doi.org/10.1002/
fuce.201900164.
[110] Rohendi D, Majlan EH, Mohamad AB, Daud WRW,
Kadhum AAH, Shyuan LK. Effect of PTFE content and
2313
sintering temperature on the properties of a fuel cell
electrode backing layer. J Fuel Cell Sci Technol 2014;11:1e6.
https://doi.org/10.1115/1.4026932.
[111] Borisov G, Avramov S, Petkucheva E, Lefterova E,
Slavcheva E, Lehnert W. Effect of sintering temperature on
performance and durability of HT-PEFC cathodes49; 2017.
p. 179e85.
[112] Orogbemi OM, Ingham DB, Ismail MS, Hughes KJ, Ma L,
Pourkashanian M. Through-plane gas permeability of gas
diffusion layers and microporous layer: effects of carbon
loading and sintering. J Energy Inst 2018;91:270e8. https://
doi.org/10.1016/j.joei.2016.11.008.
[113] Forner-Cuenca A, Manzi-Orezzoli V, Biesdorf J, Kazzi M El,
Streich D, Gubler L, et al. Advanced water management in
PEFCs: diffusion layers with patterned wettability. J
Electrochem Soc 2016;163:F788e801. https://doi.org/
10.1149/2.0271608jes.
[114] Clean Energy Ministerial. Clean energy ministerial-
hydrogen initiative (H2I) work plan 2021-22. 2021.
[115] Borup R, Leonard D, Neyerlin KC, Kabir S, Cullen D. Low cost
gas diffusion layer materials and treatments for durable
high performance PEM fuel cells. 2020.
[116] Abe K. Toray innovation by chemistry. 2021.
[117] SGL Group. SGL group is development partner for high-
performance fuel cells in the automotive sector, vols. 1e3;
2016.
[118] SGL Group. SGL, Hyundai expand cooperation in fuel cell
components for NEXO. Fuel Cell Bull 2018;2018:15. https://
doi.org/10.1016/s1464-2859(18)30182-2. 15.
[119] Ballard Power Systems. FCmove fuel cell products solutions
for zero-emission heavy-duty mobility. 2021.
[120] Ballard Power Systems. High performance fuel cell stack -
innovations in proton exchange membrane fuel cell stack
design. 2021.
[121] Huyndai. Nexo fuel cell 2022. 2022. https://www.
hyundaiusa.com/us/en/vehicles/nexo.
[122] Son J, Um S, Kim Y.B. Numerical analysis of the effect of
anisotropic gas diffusion layer permeability on polymer
electrolyte membrane fuel cell performance with various
channel types. Fuel, 289, p.119888.
[123] Fu X, Wen Q, Han J, Wei J, Li Y, Ning F, Zhou X. One-step to
prepare high-performance gas diffusion layer (GDL) with
three different functional layers for proton exchange
membrane fuel cells (PEMFCs). Int J Hydrogen Energy,
47(61), pp.25769-25779.
[124] Okereke IC, Ismail MS, Ingham D, Hughes KJ, Ma L,
Pourkashanian M. The effects of GDL anisotropic transport
properties on the PEFC performance. Int J Numer Methods
Heat Fluid Flow 2022 (in press).
[125] Chang PC, Chang Y., Wang W., Lo FY, Lin WC. Visualizing
hydrogen diffusion in magnetic film through magneto-
optical Kerr effect. Commun Chem, 2(1), pp.1-8.
[126] Yin Y, Qu Z, Zhu C, Zhang J. Visualizing gas diffusion
behaviors in three-dimensional nanoporous media. Energy
Fuel, 35(3), pp.2075-2086.
[127] Litster S, Sinton D, Djilali N. Ex situ visualization of liquid
water transport in PEM fuel cell gas diffusion layers. J Power
Sources, 154(1), pp.95-105.
[128] Nasu M, Yanai H, Hirayama N, Adachi H, Kakizawa Y,
Shirase Y, Nishiyama H, Kawamoto T, Inukai J, Shinohara T,
Hayashida H. Neutron imaging of generated water inside
polymer electrolyte fuel cell using newly-developed gas
diffusion layer with gas flow channels during power
generation. J Power Sources 2022;530:231251. https://
doi.org/10.1016/j.jpowsour.2022.231251.
[129] Pang Y, Liang H, Yun W. Convolutional neural network
analysis of radiography images for rapid water
quantification in PEM fuel cell. Appl Energy 2022;321:119352.