Volume 10 Number 12 December 2017 Pages 2483–2654

Energy &
Environmental
Science
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ISSN 1754-5706

PAPER
A. S. Gago et al.
Comprehensive investigation of novel pore-graded gas diffusion layers
for high-performance and cost-effective proton exchange membrane
electrolyzers
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Environmental
Science
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Comprehensive investigation of novel pore-graded

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gas diffusion layers for high-performance and cost-

Cite this: Energy Environ. Sci.,
effective proton exchange membrane electrolyzers†
Open Access Article. Published on 24 July 2017. Downloaded on 5/2/2025 11:40:36 AM.

2017, 10, 2521

P. Lettenmeier, a S. Kolb,a N. Sata,a A. Fallisch,b L. Zielke,c S. Thiele,cde

A. S. Gago *a and K. A. Friedrich af

Hydrogen produced by water electrolysis is a promising storage medium for renewable energy. Reducing
the capital cost of proton exchange membrane (PEM) electrolyzers without losing efficiency is one of its
most pressing challenges. Gas diffusion layers (GDL), such as felts, foams, meshes and sintered plates, are
key stack components, but these are either inefficient or expensive. This study presents a new type of GDL
produced via vacuum plasma spraying (VPS), which offers a large potential for cost reduction. With this
technology, it is possible to introduce a gradient in the pore-size distribution along the thickness of the
GDL by varying the plasma parameters and titanium powder particle sizes. This feature was confirmed by
cross-section scanning electron microscopy (SEM). X-ray computed tomography (CT) and mercury
intrusion porosimetry allowed determining the porosity, pore radii distribution, and pore entry distribution.
Pore radii of ca. 10 mm could be achieved in the layers of the GDL close to the bipolar plate, while those in
Received 7th May 2017, contact with the electrodes were in the range of 5 mm. The thermally sprayed Ti-GDLs allowed achieving
Accepted 24th July 2017 PEM electrolyzer performances comparable to those of the state-of-the-art sintered plates and far superior
DOI: 10.1039/c7ee01240c than those of meshes. Moreover, a numerical model showed that the reduced capillary pressure and
tortuosity eliminates mass transport limitations at 2 A cm 2. The results presented herein demonstrate a
rsc.li/ees promising solution to reduce the cost of one of the most expensive components of the stack.

Broader context
One of the dominating topics of the 21st century is climate change and indeed, the question of how to reduce greenhouse gases is still unanswered. The rapid
increase in the use of renewable energy (RE) sources, such as wind and solar energy, is one promising solution; however, new challenges still emerge. The
discrepancy between renewable electricity production and demand still has to be addressed in order to guarantee a stable power-line frequency. This task has to
be performed not only during sunny and windy days, but also during those periods of the year with diminished RE sources. Large-scale hydrogen generation via
polymer electrolyte membrane (PEM) electrolysis can solve this issue and provide a sustainable conversion of electricity to chemical energy. Moreover,
hydrogen can be used as well for seasonal energy storage in the chemical industry and mobility sector, which together are responsible for a large proportion of
CO2 emissions. However, despite all the advantages of hydrogen, PEM electrolysis technology is expensive, with the anode gas diffusion layer (GDL) being one
of the most expensive components of the stack. Herein, we present an innovative and cost-effective manufacturing process for the GDL that could potentially
change the investment costs of PEM electrolyzers for large-scale energy storage applications.

a
Institute of Engineering Thermodynamics, German Aerospace Center,
Pfaffenwaldring 38-40, Stuttgart, 70569, Germany. E-mail: [email protected];
Fax: +49 711 6862-747; Tel: +49 711 6862-8090
1. Introduction
b
Fraunhofer-Institut für Solare Energiesysteme ISE Heidenhofstrasse 2, Freiburg,
The progressive increase in greenhouse gases requires the
79110, Germany
c
Laboratory for MEMS Applications, IMTEK Department of Microsystems
utilization of sustainable energy carriers.1 Hydrogen produced
Engineering, University of Freiburg, Georges-Koehler-Allee 103, 79110 Freiburg, by electrolysis can provide the main resource of almost all
Germany synthetic fluidic energy carriers by means of renewable energy
d
Hahn-Schickard, Wilhelm-Schickard-Straße 10, 78052 Villingen-Schwenningen, and water. Proton exchange membrane (PEM) water electrolysis is
Germany
e
a very promising technology for sustainable hydrogen production.2
FIT, University of Freiburg, Georges-Koehler-Allee 105, 79110 Freiburg, Germany
f
Institute for Energy Storage, University of Stuttgart, Keplerstraße 7,
One main challenge regarding the large-scale penetration of this
70550, Stuttgart, Germany technology is the high specific cost of the generated hydrogen
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c7ee01240c compared to that produced by steam reforming and hydrocarbons.

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The two main cost drivers for sustainable hydrogen production as high as with the sintered structures or felts. Sintered Ti
are the electricity and capital expenditure (CAPEX).3,4 The plates are limited in area and thickness but allow achieving high
scientific community and industry are working intensively to performances.34 Foams have also been tested in PEM electro-
decrease the stack cost, which is what predominately governs lyzers,35 though they may face mechanical stability issues with
the CAPEX. The high amount of required noble metals, such increasing contact pressure. Zielke and co-workers performed an
as Ir and Pt, are often mentioned as the bottleneck for the X-ray tomography-based screening study, reporting the morphol-
commercialization of PEM technology and indeed, the scarcity ogical and transport parameters of different felts and sintered
of these catalysts could limit the expansion of this technology plates for their use in a tandem solar cell coupled with a PEM
to the gigawatt scale.5 Reduction of the precious metal content electrolyzer.22
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by improving the activity of the electrocatalytic properties is a Unfortunately, the relation of GDL engineering properties,
high priority and is in the focus of our research efforts as well as such as thickness, porosity, pore size and surface finishing with
Open Access Article. Published on 24 July 2017. Downloaded on 5/2/2025 11:40:36 AM.

several other groups.6–15 However, the catalysts currently have a phenomena such as the interfacial contact, gas diffusion and
relatively small influence on the capital cost. mass transport, is hitherto not well understood.19 Ito et al.
The most expensive stack components are the interconnectors, reported that high porosity enables the effective transport of the
chiefly consisting of titanium bipolar plates (BPP) and gas gas and water from the GDL but increases the through-plane
diffusion layers (GDL).3,16 Two main cell designs are currently electrical resistivity and contact resistance.21 Gas transport in
used in the industry. In the first design, the BPP is mainly porous structures is highly dominated by capillary forces, even
responsible for managing the water distribution and gas collec- at high gas evolution rates (high current density).30 Thus,
tion across the electrode active area.2 This task usually requires the optimum pore radii should be between 5 and 6.5 mm to
a complex flow field geometry, which increases the manu- maintain a balance between the contact to the electrode and the
facturing cost of the titanium BPPs.17,18 The BPPs are often mass transport properties.34 Recently, we developed a macro
combined with very thin GDLs to maintain a uniform electrical porous layer (MPL) for PEM electrolyzer GDLs that showed
connection with the electrode.19 The second cell design focuses improved electrical properties for the contact surface and the
on the GDL, while the BPP is simply regarded as a separator mitigation of mass transport issues at high current densities.32
and can be a flat metal sheet without a flow field.3,20 These Our findings suggested that the internal distribution of porosity
separators require more functional GDLs to manage the water and pore sizes within the GDL as well as the contact area to the
distribution and gas collection.21,22 However, an optimized and electrode play important roles in the effective design of this
highly efficient GDL design is not yet fully envisaged for either component. Lee et al. confirmed the positive impact on the
the first or second cell design. water saturation of GDLs having the limiting throat close to the
In terms of material properties, the GDL needs to be cost electrode layer, which needs to be breached for the break-
effective, highly conductive, and chemically stable under the through to occur.36
operating conditions of a PEM electrolyzer. Herein, the use of The challenge of developing cost-effective PEM electrolyzer
platinum-group metal (PGM) coatings can guarantee the latter GDLs with optimal porosity, pore size, thickness, and surface
two points but fails in keeping the cost low. Titanium is used as properties still persists. In this study, we introduce the develop-
the anode side GDL, which is often coated with precious metals ment of novel freestanding pore-graded titanium layers for
to reduce the contact resistance and reduce oxidation;23–26 their use as GDLs of a PEM electrolyzer. Via extensive physical,
however, the step of coating the anode side GDL with precious electrochemical, and numerical modeling characterizations,
metals to reduce the contact resistance is not strictly necessary. we deliver deep insights into the mass transport phenomena
Recently, we found that, in fact, the protective PGM coating of the multifunctional GDLs and discuss the role of the
on Ti is more useful at the cathode, which is in contact with different properties of the contact porous layers for the anode
carbon GDL, than in the anode.24 Alternatively, stainless steel and BPP.
interconnectors, coated with Ti only on the anode side, may be
used, since austenitic stainless steel is highly resistant to H2
embrittlement.27,28 Furthermore, the use of Nb as a protective 2. Experimental
coating instead of a PGM may be a promising solution29 and
also has the benefit that it can be applied by thermal spraying. 2.1. Vacuum plasma spraying
The complete removal of PGM coatings in the stack inter- Porous titanium layers (PTL) were produced by vacuum plasma
connectors to decrease the cost of megawatt PEM electrolyzer spraying on mild steel. The feedstock powders were grade 1
facilities is still a pressing challenge. titanium (TLS Technik Spezialpulver) with grain sizes of
In addition to the material requirements, the GDL must ca. 45 and 125 mm, which are referred to in this study as Ti45
provide optimized water distribution over the electrode and and Ti125, respectively. Table 1 summarizes the samples that
remove the produced gas. Different types of porous titanium were produced with these powders. The numbers ‘‘8’’, ‘‘16’’, and
structures such as felts,21,30 meshes,21,31 foams30 and porous ‘‘32’’ in the sample nomenclature correspond to the iterative
sintered plates21,30,32,33 are often used as GDLs in the anode number of coating runs or plasma torch sweeps, in which the
side of PEM electrolyzers. While meshes are the cheapest GDLs, spraying nozzle moves over the mild steel substrates during the
the performance of the electrolyzer with this type of GDL is not coating process. In general, the labels of the samples are given

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Table 1 Sample composition of sprayed porous titanium layers (PTL), removed using outlier filters. ImageJ was used for analyzing the
where ‘‘S’’ and ‘‘L’’ stand for small or large titanium particle size, respectively. images of all the steps.37 Finally, the images were cropped to
The samples labeled with ‘‘+’’ contain layers sprayed with two different
avoid edge effects. For samples 32L + 8S and 16L + 8S, the
plasma enthalpies (fourth column)
background on the rough side was masked and removed from
No. of coating No. of coating Enthalpy/ all the calculations. The mask was determined by segmenting
PTL runs, Ti (125 mm) runs, Ti (45 mm) MJ kg 1
the pores and applying a broad Gaussian blur filter to the whole
16S — 16 12.5 dataset, followed by a global threshold in order to mark the
32S — 32 12.5
background on the rough side. For the tortuosity calculations,
16L + 8S 16 8 21.3/12.5
the reconstructions were shrunk by a factor of two to decrease
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32L + 8S 32 8 21.3/12.5
the computational time. The calculations were done using the
commercial solver GeoDict. The capillary pressure curves were
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as follows: ‘‘S’’ and ‘‘L’’ stand for small or large titanium calculated using the pore-morphology method, implemented in
particle size, respectively, samples labeled with ‘‘+’’ contain GeoDict.38 Both local and global pore-size distributions were
layers sprayed with different plasma enthalpies; for example, made using self-programmed Matlab functions, implementing
the PTL labeled as 32L + 8S has been produced in two steps: the method of Delerue et al.39
(i) 32 layers of large size (L) Ti particles were sprayed on the MIP is a powerful technique for calculating the pore radii of
substrate with a plasma enthalpy of 21.3 MJ kg 1; (ii) sub- porous structures with throat-like voids. However, the techni-
sequently, 8 layers of small size (S) Ti particles were sprayed on top que allows observing only the size of the pore opening due to
of the previous ones with a plasma enthalpy of 12.5 MJ kg 1. The the so-called ink-bottle effect.40 The measured pore radius can
gas flow rates of Ar, N2 and H2 were carefully chosen to achieve the be significantly smaller compared to the one obtained by X-ray
desired plasma enthalpies. For all the samples, the torch sweep CT, which is calculated by tightly fitting spheres into the pore
rates were 350 mm s 1. The substrates were pre-heated up to space.39 However, the pore radius from MIP corresponds to the
250 1C before deposition. The chamber pressure was 50 mbar to average size of the throat that the generated gas has to over-
avoid titanium oxidation during the coating process. Finally, the come for efficient transport out of the electrode. Therefore,
PTLs were removed from the mild steel substrates by immersing both parameters are relevant for our study. In the next sections,
the samples in 0.5 M H2SO4 for approx. 1 h to produce the GDLs the pore size obtained by MIP is termed the pore entry radius,
for testing in PEM electrolyzers. while the pore size calculated by X-ray CT is simply referred to
as the pore radius.
2.2. SEM, porosimetry, and X-ray computer tomography
The morphology of the PTLs was investigated by analyzing the 2.3. PEM electrolyzer tests
pore variation along the thickness of the samples via SEM The GDLs were measured in in-house-produced PEM electro-
and X-ray CT, thereby determining the pore-size distribution, lyzers. Fig. 1 shows a scheme of the cell configurations used for
tortuosity, bubble points, and connectivity. The tomography the tests. Commercially available MEAs (Greenerity E300) with
results on the porosity and global pore sizes were compared to an Ir-based anode, Pt-based cathode, and Nafion 212 membrane
the results of mercury intrusion porosimetry (MIP). were used for all the measurements. The first electrochemical
Cross-section images were recorded for all the produced characterization of the GDLs was performed in configuration 1,
samples with an FE-SEM Zeiss ULTRA plus in secondary which consisted of a 4 cm2 active area 2-cell device (Fig. 1,
electrons mode with charge compensation. The working distance configuration 1) having BPPs without a flow field. The developed
and accelerating potential were 8.4 mm and 15 kV, respectively. GDLs were placed on top of the anode LAS mesh and were in
Porosity measurements of the samples were performed by the contact with the Ir-electrodes. Small aperture size (SAS) Ti mesh
mercury intrusion technique (Pascal 140/240, Thermo Scientific) and sintered Ti plates (SIKA-T 10, GKN Sinter Metals), which
up to a pressure of 200 MPa. The tested sample volume was in the are state-of-the-art GDLs, were tested as well for comparison
range of 100–200 mm3. Prior to the measurements, the samples purposes. The cells were characterized by recoding polarization
were kept in an oven at 100 1C overnight. The pore entry radii curves up to 2 A cm 2, specifically after one day of MEA activa-
were determined by applying Gaussian fittings to the pore-size- tion period at 38 1C and constant 1 A cm 2. The scan rate was
distribution profiles. 4 mA cm 2 s 1, which was sufficiently slow for analyzing the
The X-ray computer tomography (CT) analysis was performed phenomena of interest. Electrochemical impedance spectro-
with a Multiscale X-ray nanotomograph (Skyscan 2211, Bruker). scopy (EIS) was performed from 50 kHz to 100 mHz at 0.25
The tested sample volume was in the range of 1 mm3. An and 1 A cm 2 with an amplitude of 50 mA and 100 mA,
acceleration potential of 70 kV was used and a voxel size of respectively, using a potentiostat/galvanostat (Zahner Elektrik
1 mm3 was achieved. The reconstructed images were prepared IM6) and booster (Module PP240). All the GDLs were character-
for segmentation by removing artifacts using outlier filters, ized at least three times on new assemblies to ensure reliable
followed by normalization of the image contrast and applying a data and generate proper error bars.
3D median filter. Subsequently, a global threshold was found The second electrochemical characterization was performed
by visual judgment. Features smaller or equal to 2  2  2 in a 25 cm2 active area 2-cell device (Fig. 1, configuration 2) with
voxels were considered most likely to be noise and were thus BPPs having a parallel flow field. The BPPs were manufactured

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Fig. 1 Scheme of the PEM electrolyzer cell configurations: configuration 1: cell with bipolar plates (BPP) without a flow field. Configuration 2: cell with
BPPs having a flow field. GDL: gas diffusion layer. LAS: large aperture size. The LAS mesh was used to take over the function of a flow field for distributing
water and releasing bubbles from the tested GDLs.
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in stainless steel and protected on the anode side with a dense charge transfer resistance accompanied with double layer effects
Ti coating, based on a procedure reported elsewhere.24,25 The in the electrode,43–46 or the first charge transfer of the two-
cathode side was left uncoated. Straight after the MEA break-in electron process of the oxygen evolution reaction (OER).47 The
procedure described in the previous paragraph, the polariza- red and green arcs in the Nyquist plot in Fig. 2b represent the
tion curves were recorded up to 2 A cm 2 with a scanning rate charge transfer of the rate determining step of the OER and
of 4 mA cm 2 s 1. EIS was performed at 0.5 A cm 2 with an the mass transport phenomena, respectively.43,45,47
amplitude of 2 A at frequencies between 100 kHz and 100 mHz
at 80 1C. The equivalent circuit shown in Fig. 2a was used to
quantify the EIS measurements. An example of the impact of
3. Results
the individual impedances is shown in the Nyquist diagram in 3.1. Physical properties
Fig. 2b, which can be translated to the corresponding over- Cross-sectional SEM analysis was performed on the freestanding
potentials for a typical polarization curve (Fig. 2c). The Ohmic PTLs to observe the pore variation along the thickness of the
resistance is represented by the high frequency (HF) interception samples. The SEM images in Fig. 3a and b depict samples 16S
of the EIS (gray). The high frequency arc is represented in blue and 32S, respectively, which were produced with small particle
and is attributed to the hydrogen evolution reaction (HER),41,42 size Ti powder (Ti45). Fig. 3c and d show the pore-graded PTLs
produced by spraying 8 layers of Ti45 on top of 16 and 32 layers,
respectively. The bottom layers were realized with large particle
size Ti powder (Ti125). The dual pore size PTLs of Fig. 3c and d
were labeled as 16L + 8S and 32L + 8S, respectively.
The thickness of the Ti45 layers in samples 16S and 32S was
approx. 300 and 550 mm, respectively, while the thickness of the
Ti45 layers in samples 16L + 8S and 32L + 8S was approx. 120 mm.
The differences in thickness were confirmed with the height-
dependent pore-size distribution calculated from the X-ray CT
reconstructions, see Fig. 3f, where the approximate position of
the boundary between the Ti45 region and the Ti125 region are
shown with a dashed line. Below the line, the Ti45 structure is
located, yielding considerably smaller pore sizes in both cases.
Interestingly, the thickness of the Ti125 layer is 180 mm for
sample 16L + 8S and 280 mm for sample 32L + 8S. This result
indicates that the enthalpy of the plasma is not sufficiently high
to form the splat structure of the Ti125 particles, leading to low
deposition efficiency. In this regard, the plasma deposition
parameters with Ti125 powder are yet to be optimized.
One interesting observation was the fact that the Ti45 layers in
samples 16L + 8S and 32L + 8S had larger pore radii than in the
16S and 32S PTLs. The compactness of the Ti45 layers increased
with the number of torch sweeps during the plasma spraying
process due to a sintering effect. The temperature history during
the thermal spray process and subsequent residual stress distri-
Fig. 2 (a) Equivalent circuit for analysis of the EIS; (b) example of a Nyquist
bution within the sample also had an impact on the pore
plot with the analyzed arcs (time constants), and (c) the corresponding properties. The temperature of the sample rose as the number
overpotentials for a typical PEM electrolyzer polarization curve. of deposited layers increased.48,49 The temperature increase,

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Fig. 3 (a–e) SEM images of the PTLs: (a) 16S, (b) 32S, (c) 16L + 8S, (d) 32L + 8S, and (e) sintered Ti. The scale bar represents 100 mm. (f) Height-dependent
pore diameters of the samples from a–e. When used as GDLs, the MEA electrode would be located on the top of the images and the BPP on the bottom.
The boundary between the Ti45 region and the Ti125 region is shown with a dashed line.

along with the pressure from the impinging hot Ti particles, radius near the electrode, which can be explained by boundary
resulted in a sintering effect, which was more prominent for effects and roughness. These boundary effects originate from
sample 32S than for 16S. Consequently, the pore entry radius of the symmetric boundary condition, which was chosen for the
the former sample was slightly smaller than the latter. calculation of the local pore radii. The boundary effects when
Moreover, the 16S and 32S specimens showed similar sintering calculating pore-size distributions is most easily explained with
morphology as the sintered titanium sample, see Fig. 3e, with the image shown in Fig. S1 in the ESI,† where a cross-section
the three of them having a homogeneous pore diameter along of the X-ray CT of sample 16S is shown. When quantifying
their thickness. The different nature of the surface on which the local sizes of the pore space, the question of the chosen
the Ti45 layers were deposited, dense mild steel for 16S and 32S boundary condition rises. There are two options: (i) treat the
and porous Ti125 layers for 16L + 8S and 32L + 8S, also played a pores at the border as if they were mirrored (symmetric boundary
role in the resulting pore radii of the PTLs. One can clearly condition) or (ii) treat the pores to immediately stop at the crop-
observe in the SEM images of Fig. 3c and d that some of the out border. It makes sense to take option (i), as water will
Ti45 particles partially fill the large pores of the 16L and 32L experience pressure originating from the local radius, rather
layers, respectively. However, there are still empty pores visible than from a smaller radius resulting from option (ii). However,
in the 32L layers of sample 32L + 8S, which the Ti45 particles this results in a tendency to calculate higher local radii at the
did not fill, resulting in an overall increase in pore entry radii of border of the volume.
the 32L region compared to 16L. Fig. 4a–f present 3D reconstruction images of the free
Lastly, except for sample 32L + 8S, the pore radii of all the standing PTLs from the X-ray CT analysis of the X-ray CT cross-
thermally sprayed samples showed a slight increase in pore section images (Fig. S2, ESI†), providing optical impressions of

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Fig. 4 3D reconstruction of the PTLs from the X-ray CT analysis.

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the roughness of the top and bottom surfaces. For comparison,

the 3D model of the commercial Ti sintered plate is shown in
Fig. 4g. The top area of the PTLs contacts the electrode of the
MEA when used as GDLs, as the surface is rougher on the top
than on the bottom. The roughness of the contact layer to the
electrode may have a positive impact as long as the difference
of the peaks and the valleys are not damaging the MEA. Sample
16S PTL had, on an average, an arithmetic absolute roughness
(Ra) of 9  1 mm. In contrast, samples 16L + 8S and 32L + 8S had
Ra values of 11.8  0.3 mm and 15  2 mm, respectively, due to
the high rugosity of the Ti125 bottom layer. The sintered Ti
plate on the other hand had a rather even surface with an Ra of
7.7  0.3 mm.
Fig. 5a presents the porosity and pore entry radius of 16S,
16L + 8S, 32S, 32L + 8S, and the sintered Ti plate, obtained from
the MIP (Fig. S4, ESI†). Sample 32S had the smallest porosity,
pore radius, and pore entry radius among all the samples corre-
sponding to 17%, 2.6 mm and 1.5 mm, respectively. In contrast,
the porosity analysis of sample 16S revealed a porosity of 24%, a
pore radius of about 3 mm, and a pore entry radius of 2.1 mm.
Evidently, on increasing the number of torch sweeps, the incident
plasma compresses the layer reducing the porosity. The two pore-
graded samples 16L + 8S and 32L + 8S showed two main peaks
in the MIP characteristics (Fig. S3, ESI†). The first peak (from
left to right) corresponded to the 8S layer, having a pore radii of
5 mm and 5.5 mm for 16L + 8S and 32L + 8S, respectively. The
corresponding pore entry radii were 3 and 3.6 mm. The estimated
pore entry radii of the 16L and 32L layers were 6.5 mm and Fig. 5 (a) Porosity in % (left y-axis) and pore entry radius in mm (right
y-axis) of the PTLs. (b) Complementary pore size distributions calculated
10.5 mm, respectively. These values are comparable to the pore
from the X-ray CT reconstructions of the samples.
radii observed via the X-ray CT analysis (Fig. 3f). The porosities
of the pore-graded samples ranged between 20% and 30%,
which were not significantly larger compared to that of sample with the MIP curves, allowing one to quantify the smaller pores,
16S. The sintered Ti had the highest porosity and the largest as can be seen in Fig. 5b.
pore diameters of all the measured samples.
Fig. 5b shows the pore-size distributions calculated by the 3.2. Electrochemical characterization
X-ray CT analysis. One can observe that all the distributions The produced PTLs were used as PEM electrolyzer GDLs and were
show high phase fractions close to the left end of the x-axis. electrochemically evaluated in the cell designs schematized in
This suggests that there are numerous pores below the resolu- Fig. 1. The average current–potential characteristics of the GDLs
tion limit of B2.5 mm, which cannot be captured by the X-ray in a 4 cm2 active area 2-cell device without a flow field are presented
tomographic reconstruction, but these can be observed in the in Fig. 6a. The LAS mesh was placed between the BPP and the GDL,
SEM images (Fig. 3a–e). Multiscale correlative tomography taking over the function of the flow field for water distribution and
approaches using FIB coupled with SEM as the imaging gas removal. For clarity, these curves are presented separately in
method for smaller pores would be needed to complete the Fig. S4 in the ESI.† The cell voltage (Ecell) measured at 2 A cm 2 is
picture.50 This lack of information due to the resolution limits shown in the histogram of Fig. 6b. One representative EIS,
can be compensated by combining the image-based results which cannot be related directly to the average polarization

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Fig. 6 Electrochemical characterization of the PEM electrolyzer GDLs (4 cm2 active area): (a) polarization curves; (b) Ecell at 2 A cm 2. The tests were
carried out at 38 1C and ambient pressure. (c and d) Nyquist plots from the EIS measurements (from 50 kHz to 100 mHz) at 0.25 (amplitude 50 mA) and
1 A cm 2 (amplitude: 100 mA).

curves in Fig. 6a, is shown in Fig. 6c and d. Furthermore, it needs As can be seen in Fig. 6a and b, the cell with the SAS mesh in
to be mentioned that all the EIS measurements of each individual contact with the electrode, which represents the most economic
GDL maintained their shape as well as number and frequency of state-of-the-art GDL solution for large-area PEM electrolyzes,
processes, but showed changes in the absolute values. shows the highest Ecell. Compared to the cell with the 16S GDL,

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the Ecell of the electrolyzer with the SAS mesh GDL is 185 mV and 32L + 8S GDLs, no LF arc can be observed. However, for the
higher. This increase corresponds to an efficiency drop of approx. sintered Ti, the presence of a small LF arc may indicate that the
7%, which in Megawatt PEM electrolyzers can have a relevant pore radius in contact with the electrode is already too large
impact on the operational expenditure (OPEX). Another commer- for an optimized management of liquid and gas.32 The EIS
cially available GDL is a sintered Ti structure. The Ecell of cells with measurements are in good agreement with the polarization
the 32S, 16L + 8S, 32L + 8S GDLs is higher than the Ecell achieved curve in terms of the performance (D slope vs. D impedance)
with the sintered Ti, but considerably lower than the SAS mesh and mass transport limitations.
GDL. The performances of the electrolyzers with the 16S and To confirm the improved characteristics and benefits of the
sintered Ti GDLs are comparable. Among all the thermally thermally sprayed GDLs, tests in a cell with an active area of
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sprayed GDLs, the 32S GDL produced the worst performance, 25 cm2 and using BPPs with a flow field were performed. The
but it was still higher than the SAS mesh GDL. results obtained with the thermally sprayed GDLs were com-
Open Access Article. Published on 24 July 2017. Downloaded on 5/2/2025 11:40:36 AM.

It should be noted that the forward and backward polariza- pared with those generated when using the sintered Ti plate.
tion curves of the SAS mesh and 32S GDLs in Fig. 6a deviate There were difficulties in assembling the 2-cell device with the
slightly. This difference between the positive and negative sweeps SAS mesh as it is quite thin and the flow field deformed its
corresponds to a non-steady state condition like with capacitive flatness. No further efforts were employed in solving these issues
currents or mass transport issues. Capacitive currents by means since the performance of the cell in the previous configuration
of charging the double layer occur due to high step rates. This was rather low. The current–potential characteristics of the
argument is correct up to certain extent for all the GDLs but it 25 cm2 2-cell device having the sintered Ti plate and the thermally
cannot explain the slight difference of the Ecell at any current sprayed GDLs are presented in Fig. 7a. The results are in good
density for the 32S and SAS mesh GDLs. Consequently, the agreement with the previous tests, although some differences
hysteresis is attributed to mass transport limitations, which can can be observed. Cells with the 16S and 32S GDLs showed a
be confirmed by the Nyquist plots of EIS, as shown in Fig. 6c lower performance than expected. The main reason for this can
(at 0.25 A cm 2) and 6d (at 1 A cm 2). Due to the high be elucidated by means of EIS (inset of Fig. 7a) and is attributed
impedance, the Ohmic resistance and the behavior of the to the mass transport limitations, as indicated by the LF arc,
charge transfer arc can be clearly distinguished from each which did not appear for the 16S GDL in cell configuration 1.
other at low current densities. However, the mass transport A plausible explanation for this is that the BPP blocks the direct
limitations are easily distinguished from the low frequency (LF) through-plane pathways of water to the electrode, as it covers a
arc at high current densities. In both diagrams, the cell with the significant area of the top of the GDL. An efficient water supply
sintered Ti GDL shows the lowest Ohmic resistance, calculated to every point on the electrode thus makes in-plane transport
from the horizontal axis interception at high frequencies (left and therefore longer pathways necessary. With the 16S GDL,
interception), and this result can explain the high performance which is the thinnest GDL, the time for water to distribute
of the cell with this GDL. effectively in-plane was the shortest. Sample 16S had the
It can be concluded that, with the exception of the SAS mesh second smallest pore radius (B3 mm), which might be already
GDL, the charge transfer arc for all the thermally sprayed and too small if it is intended to be in contact with a BPP having a
sintered Ti GDLs are comparable. In the case of the SAS mesh flow field. Fig. 7b displays a graphical scheme to illustrate the
GDL, the arc appears to be slightly wider, which is most prob- differences in the through-plane pathways for the two cell con-
ably due to the low contact area with the electrode, leading to figurations with the 16S GDL. The transversal pathway is signifi-
an increased contact resistance and activation overpotential.21 cantly longer for configuration 2 than for configuration 1. The
Mass transport limitations for the cells with the SAS mesh and long transversal pathway of water and gases caused by the use of a
32S GDLs are noticeable in the LF arc of the Nyquist diagram in flow field may lead to mass transport limitations.
Fig. 6d. Yet, it is obvious that the mechanisms of mass trans- The cell with 32S shows a marked increased cell potential at
port limitations are different for these two GDLs. In the case high current densities, which produces an LF arc in the Nyquist
of the 32S GDLs, water cannot reach the active electrode fast diagram. The low porosity and the small pore size of the 32S
enough since the Ti structure is too packed. The pressure GDL prevent efficient removal of the gas from the electrode,
between the electrode and the packed GDL increases since it is thus generating backpressure. The backpressure needs to be
not efficiently removed from the electrode. This negative effect overcome by water driven by capillary pressure and this process
can lead to the partial blocking of electrode active centers, can lead to mass transport issues. In addition, the interception
inhibiting them from further reactions. Still, water can reach of the HF arc of the 32S GDL with the x-axis is shifted positively,
the active surfaces via secondary paths, for example, via thin i.e., higher Ohmic resistance, which can also be related to the
films or through the ionomer in the catalyst layer, producing increased backpressure, which then reduces the contact between
efficiency losses. A gas pillow formed between the electrode and the electrode and the GDL. Clearly, the HF arc is affected by the
the GDL can also explain the increased Ohmic resistance of the nature of the GDL, yet further investigations are necessary to
cell with the 32S GDL. clarify the electrochemical processes taking place in this range of
On the other hand, in the SAS mesh GDL, the bubbles are frequencies.
not released from the electrode without capillary force until a Lastly, the multifunctional coatings 16L + 8S and 32L + 8S
certain bubble diameter is achieved.51,52 For the 16S, 16L + 8S show an Ecell comparable to the sintered Ti GDL with porosities

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Fig. 7 (a) Polarization curves with 25 cm2 active area 2-cell PEM electrolyzer having BPPs with a flow field. Scanning rate: 4 mA cm 2 s 1. The inset
shows the Nyquist diagrams of the corresponding EIS measurements at 0.5 A cm 2. Amplitude of 2 A at frequencies between 100 kHz and 100 mHz. The
measurements were carried out at 80 1C and ambient pressure. (b) Scheme used for explaining the differences in performance of the cells with 16S GDL
when tested in cell configurations 1 (left) and 2 (right).

between 20% and 30% and pore radii contacting the active of the GDLs are shown in Fig. 8a and b, respectively. For the
layer between 5 and 10 mm. The advantages of having a gradient sake of clarity, the curves are presented separately in Fig. S5
pore size are put in evidence when demonstrating the potential in the ESI.† The calculated tortuosities and bubble points are
of these multifunctional GDLs for PEM electrolyzers with BPPs presented in Fig. 8c.
with flow fields. The multifunctional GDLs, with pore radii in Concerning water extrusion (drainage), one can see that the
the range of the recommended size of 5 to 6.5 mm34 in contact cells with the 16S and the 32S GDLs show significantly steeper
with the electrode, decrease contact resistance. Moreover, the slopes compared to the other GDLs, meaning that more pres-
large pores and high porosity in contact with the BPP help sure is needed to press water out in the case of gas penetration
reduce the mass transport limitations. from the electrode side. These observations explain the lower
performance of the cell with 32S GDL, which shows increased
3.3. Numerical simulations Ohmic resistance and mass transport limitation. The later is
Possible explanations for the mass transport behavior of the related to the high pressure necessary for transporting gases
GDLs may be found in a comparison of the morphology of through the small pores. Regarding the imbibition, the results
these through-plane paths. Therefore, the capillary pressure also show steeper slopes, meaning that water is more efficiently
curves and bubble points were calculated. These parameters taken up. However, the capillary pressure is lower than the
depend strongly on the pore properties. The ‘‘bubble point’’ backpressure produced by blocked pores in the case of drainage.
refers to the pressure needed to press the wetting phase (water) From these results, one can conclude that indeed an optimal
out of the largest pore along a certain direction. In addition, the pore size and thickness of the GDL exists, as has been reported by
tortuosity of the through-plane pore pathways was calculated Grigoriev et al.34 In the case of the cells with 16L + 8S, 32L + 8S,
using the commercial solver GeoDict. Tortuosity can be con- and sintered Ti GDLs, the flat slopes of the calculated imbibition
sidered as a measure of the complexity of a pore space in a curves do not seem to play an important role, in contrast to the
certain direction and is calculated as t = esintseff 1, where t is flat slopes of the drainage curves, which all three samples have in
the tortuosity, e is the volume fraction of the conducting phase, common. These results can explain the high performance of the
sint is the intrinsic transport parameter, and seff is the effective cells with these GDLs.
transport parameter, calculated in the actual microstructure.53 The Concerning complexity of through-plane pathways, the cells
results of the simulated drainage and imbibition (water uptake) with 16S and the 32S GDLs show exceptionally high tortuosities

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4. Conclusions
Pore-graded gas diffusion layers (GDLs) for proton exchange
membrane (PEM) electrolyzers have been developed via vacuum
plasma spraying (VPS). The coating technique allowed control-
ling important functionalities of the GDL design, such as pore
size, pore distribution, porosity, roughness, and thickness.
Scanning electron microscopy (SEM), mercury intrusion poro-
simetry (MIP), and X-ray computed tomography (CT) were used
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to generate the data necessary for calculating the capillary

pressure, bubble points, and tortuosity. The produced GDLs
Open Access Article. Published on 24 July 2017. Downloaded on 5/2/2025 11:40:36 AM.

were electrochemically tested in two typical PEM electrolyzer

cell designs with and without a bipolar plate (BPP) flow field.
The polarization curves demonstrated high performance and a
significant decrease in mass transport limitations. The optimal
pore diameter in contact with the electrode was found to be
between 6 and 11 mm, with the porosity higher than 22%.
Moreover, depending on the cell design, the complexity of the
through-plane pathways and capillary pressure had an impact
on the electrolyzer performance. Therefore, it was possible to
reduce the tortuosity, capillary pressure, and bubble points by
combining different pore sizes in contact with the electrode and
BPP. The cost of thermal spraying of GDLs to reach the bench-
mark in terms of performance and cost for large-scale m2-size
production has been estimated as 20–100 USD m 2.25 Overall,
the results suggest the possibility of using thermal spraying for
manufacturing the entire stack interconnector on a stainless
steel BPP, including for the protective Ti coating,18,24,25,29 to the
large/medium pore-size GDLs (this work) and backing layer.32
All of them could be produced in one manufacturing step,
representing a significant cost reduction for the interconnectors,
which account for almost 70% of the total stack value.16

Conflicts of interest
There are no conflicts of interest to declare.

Acknowledgements
The authors acknowledge Riko Moroni for providing the Matlab
code on pore-size distributions. We are also grateful to Ina
Plock and Günther Roth for performing the SEM measurements
and the production of the PTLs via VPS, respectively. We thank
Asif Ansar for the fruitful discussions on plasma spraying.
Fig. 8 Simulation of (a) drainage and (b) imbibition for the investigated
GDLs: 16S, 32S, 16L + 8S, 32L + 8S, and sintered Ti. (c) Calculated bubble
point and tortuosity. References
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