Received: 1 November 2020 Revised: 28 November 2020 Accepted: 2 December 2020

DOI: 10.1002/er.6350

RESEARCH ARTICLE

Effect of pore size distribution in the gas diffusion layer

adjusted by composite carbon black on fuel cell
performance

Guangyi Lin1 | Shouyi Liu1 | Guangkai Qu1 | Yingjie Song1 | Tianya Li2 |
Fumin Liu1 | Yafei Hu1

1
College of Mechanical and Electric
Engineering, Qingdao University of Summary
Science and Technology, Qingdao, China In this paper, the newly prepared gas diffusion layer (GDL) is investigated and
2
College of Mechanical and Electric characterized. The GDL mainly includes the carbon paper layer and micropo-
Engineering, Beijing University of
rous layer (MPL). By the analysis of physical and electrochemical test results,
Chemical Technology, Beijing, China
it is found that the performance of GDL prepared by composite carbon black is
Correspondence obviously improved compared with conventional GDL prepared by single car-
Guangyi Lin, College of Mechanical and
Electric Engineering, Qingdao University
bon black. This new GDL combines the characteristics of two original carbon
of Science and Technology, Qingdao materials and has a more reasonable pore structure, which can meet the good
266042, China. transmission of reaction gas and liquid water. Furthermore, the research
Email: gylin666@163.com
shows that the pore size distribution of GDL can be effectively adjusted by
Funding information changing the proportion of composite carbon black. The GDL with composite
NSFC-Shandong Joint Fund for Marine carbon black consisting of 70 wt.% Acetylene Black carbon and 30 wt.% Vulcan
Science Research Centers, Grant/Award
Number: U1606401 XC-72 is finally confirmed to have the best fuel cell performance.

KEYWORDS
composite carbon black, gas diffusion layer, microporous layer, pore size distribution

1 | INTRODUCTION electrode assembly, is generally composed of gas diffu-

With the aggravation of environmental pollution and
energy shortage, fuel cells have drawn widespread atten-
tion due to their small emissions, high power density,
and abundant fuel sources.1,2 In particular, except advan-
tages of general fuel cells, proton exchange membrane
fuel cells (PEMFC) are considered as the most promising
green energy generating devices because of their low
working temperature, fast start-up, and simple structure.3
The key components of PEMFC mainly include bipolar
plates on both sides, anode gas diffusion layer (GDL),
cathode GDL, anode catalyst layer (CL), cathode CL, and
proton exchange membrane (PEM).4 The porous GDL, as
the core component of water management in membrane-
Guangyi Lin and Shouyi Liu are co-first authors.
sion backing layer and microporous layer (MPL).5-7 The
most significant function of GDL is to discharge the
water generated on the surface of the CL and distribute
the reactant gas brought by the flow channel.8-10 Like
some emerging technologies, PEMFCs must overcome
some cost problems if they are to be commercialized and
popularized.11 The flooding on the cathode side under a
high current region is an important factor restricting the
further improvement of PEMFC performance. Therefore,
improving the water management capabilities of fuel
cells to alleviate flooding is very crucial for reducing the
cost of PEMFC. Some researchers found that a thin MPL
consisted of hydrophobic materials such as poly-
tetrafluoroethylene (PTFE) and carbon black provided a
suitable microporous characteristic and hydrophobicity,
which is advantageous to reduce the saturation of liquid

Int J Energy Res. 2021;45:7689–7702. wileyonlinelibrary.com/journal/er © 2020 John Wiley & Sons Ltd 7689
7690
water in GDL and the electrical contact resistance near
the catalyst layer.12-14
The MPL has a positive influence in the water man-
agement of PEMFC, which can effectively reduce
flooding and improve fuel cell performance. Therefore, it
is of great meaning to study the reasonable structural
characteristics of MPL to ensure the high performance of
PEMFC. Recently, some scientists have studied the influ-
ences of the MPL composition and properties,15-17 espe-
cially porosity and pore size distribution.18-20 Zhan et al21
investigated the influence of GDL porosity distribution
variation on the flux of liquid water. Research demon-
strated that with the increase of MPL porosity, the satura-
tion of liquid water in GDL substrate decreases, which
promoted the removal of water on the CL surface and
enhanced the oxygen transmission from GDL to the cata-
lyst layer. Therefore, they believed that the effective gas
diffusion coefficient increases by an increase in MPL
porosity. Turkmen et al22 simulated the effect of porosity
of the cathode side GDL on the PEMFC performance.
They uncovered that the change of porosity has different
influences on fuel cells at low and high voltage. Espe-
cially, the GDL with high porosity obviously improves
fuel cell performance. Some researchers have revealed
that pore size of MPL is also an important factor that
affects its water management capabilities.23,24 Chun
et al25 examined the influence of MPL pore size distribu-
tion on fuel cell performance using pore formers under
different drying conditions. They revealed that under
high external humidification, MPL with more micro-
pores can more effectively remove water, which is condu-
cive to mass transfer. On the contrary, under low external
humidification conditions, MPL containing several
macro-pores contributes to the supply of reactant gas,
thereby promoting a further increase in PEMFC perfor-
mance. Wang et al26 prepared a novel MPL including
20 wt.% Black Pearls 2000 and 80 wt.% Acetylene Black.
Besides, they uncovered that the wettability and pore size
distribution are two vital factors affecting GDL water/gas
transportation. In addition, some scientists have pres-
ented that porosity gradient in MPL also helps to improve
its water removal properties, thereby enhancing cell's
performance.27-29 For example, Chun et al28 used thermal
expansibility to produce pores in MPL and the porosity of
each layer was controlled by adopting thermal expand-
able graphite, thereby preparing a porosity-graded MPL.
Compared with the conventional single-layer MPL, this
new porosity-graded MPL enhanced the water manage-
ment capacity of GDL and reduced the polarization loss
caused by the flooding problem.
In previous studies, more researchers usually
employed a single type of carbon powder to prepare the
MPL and the pore size formed was in a single
LIN ET AL.
distribution.30-32 This single-distributed pore structure is
not conducive to the two-phase transmission of liquid
water and gas inside the fuel cell. On the one hand, if the
GDL contains only single large pores, PEMFC will be
unfavorable to the discharge of liquid water because of the
lack of capillary pressure, which will lead to flooding. On
the other hand, the GDL containing a single type of
micro-pores is not advantageous for the supply of air or
hydrogen on the surface of the catalyst layer, which will
cause serious concentration polarization. Therefore, the
reasonable pore size distribution that maintains a suitable
balance between water removal and gas supply is very nec-
essary for the performance of PEMFC.
In this paper, MPLs composed of composite carbon
black were fabricated and added on the carbon paper
near the catalyst layer. By employing the different char-
acteristics of the two carbon black, Acetylene Black car-
bon and Vulcan XC-72, a GDL with multi-level pore size
distribution was designed and tested by mercury injection
experiment. Further, we controlled pore size distribution
in GDL by adjusting the ratio of composite carbon black.
We expected that the GDL adjusted by this method will
exhibit a more reasonable pore structure, which can
simultaneously satisfy the good transmission of electrode
liquid water and reactant gas. In addition, the single-cell
performance of GDL was characterized at two external
humidification conditions (60% RH and 100% RH).
2 | EXPERIMENTAL
2.1 | Preparation of MPL
MPL preparation process is carried out in the following
three steps, which include the mixing of solution, the
addition of MPL, and the sintering of MPL. Figure 1 is
the preparation process of MPL. In the first step, anhy-
drous ethanol (Dezhou Runxin Experimental Instrument
Co., Ltd. China. Purity ≥99.7%) suspension with a certain
ratio of Acetylene Black carbon (Japan Denka) and Vul-
can XC-72 (Cabot Corp.) was ultra-sonicated by an ultra-
sonic machine for 40 minutes and then stirred by a
magnetic stirrer for 40 minutes, and the above ultrasonic
and stirring processes were repeated four times. Next, the
PTFE (a polytetrafluoroethylene emulsion, Japan Denka,
60 wt.%) was added to the beaker and then stirred for
20 minutes, and its content in the mixture was 30 wt.%.
In the second step, to form the MPL, the prepared solu-
tion was sprayed on carbon paper (TGP-H-060, Japan
Toray Group) by a spray gun. The MPL thickness was
measured by a digital thickness gauge which has a preci-
sion of 1 μm, and the thickness of MPL was maintained
at 60 μm. In the last step, the prepared MPL was baked
LIN ET AL.
FIGURE 1 Preparation process of MPL sample [Colour figure can be viewed at wileyonlinelibrary.com]
TABLE 1 Parameters of different GDL samples
Samples Composition of carbon powders
AB Acetylene Black carbon
VXC Vulcan XC-72
AV73 70% Acetylene Black carbon + 30% Vulcan XC-72
AV55 50% Acetylene Black carbon + 50% Vulcan XC-72
AV37 30% Acetylene Black carbon + 70% Vulcan XC-72
in a tube furnace at 250
C for 40 minutes and then
sintered at 350
C for 40 minutes. Finally, we obtained
the GDL with MPL prepared by composite carbon black
and examined its electrochemical and physical proper-
ties. The naming and detailed parameters of different
GDL samples are shown in Table 1.
2.2 | Test conditions of single cell
The prepared GDL was tested at a cell temperature of
80
C (±0.2
C) without back pressure. The catalyst coated
membrane (CCM) used had an active area of 4 cm2 and
7691
MPL thickness (μm) Carbon powders: PTFE (wt.%)
60 ± 2.0 7:3
60 ± 1.6 7:3
60 ± 2.5 7:3
60 ± 1.8 7:3
60 ± 2.8 7:3
was manufactured by Wuhan Himalaya Optoelectronics
Technology Co., Ltd. In addition, the Pt loading of the
cathode and anode of the catalyst layer was 0.3 and
0.2 mg cm−2, respectively. The single-cell test was per-
formed under two external humidification conditions:
60% humidification (cathode and anode temperature:
68
C [±0.2
C]) and 100% humidification (cathode and
anode temperature: 80
C [±0.2
C]). Before the single cell
was tested, it needed to be activated at constant current
and low current for 40 minutes. At the same time, H2
and O2 should be introduced for 15 seconds before each
test. During the experiment, the flow rates of the constant
reactant gases at the cathode and anode were both
7692
TABLE 2 Physical parameters of carbon powders
Particle Surface
Samples size (nm) area (m2 g−1)
AB 40 62.5
VXC 30 230.6
AV73 - 116.9
AV55 - 134.5
AV37 - 184.6
a
t-Plot micro-pore volume.
b
BJH adsorption cumulative pore volume (pores within 1.7000 and 300.0000 nm).
50 sccm and both maintained an excess factor of 2. In
addition, the electrochemical reaction on the cathode
side occurred under pure oxygen conditions. Finally, the
voltage, current density, and power density of single-cell
test were obtained by data acquisition system. In addi-
tion, we tested the electrochemical impedance spectros-
copy (EIS) at the current density of I = 3 A cm−2.
Moreover, the cell temperature during EIS test was 80
C
and the frequency range was 0.1 to 10 000 Hz. Each GDL
sample was examined under the same conditions to study
the impact of composite carbon black on GDL. Finally,
the Nyquist image was obtained by fitting EIS test data
with Zview software.
2.3 | Physical characterization of GDL
Mesoporous physical adsorption system (Micromeritics
ASAP-2460) was applied to test the Brunauer-Emmett-
Teller surface areas and pore volumes of different compos-
ite carbon black. Furthermore, the test took place at a tem-
perature of 77.3 K with N2 as the analytical adsorbent. The
surface topography of the MPL was characterized by scan-
ning electron microscopy (SEM; Hitachi S-4700, Japan).
The surface roughness of the MPL was measured by 3D
topography instrument (Olympus LEXT OLS4500, Japan).
The porosity and pore size distribution inside the GDL
was characterized by a mercury intrusion porosimetry
(Autopore IV 9500 V1.09, China). In addition, the water
contact angle meter (TBU 90E, Germany) and four-probe
conductivity tester (RTS-4, China) were used to test the
water contact angle and conductivity of GDLs.
3 | R ES U L T S A N D D I S C U S S I O N
3.1 | Pore structure of different carbon
powders
Table 2 summarized the physical characteristics of sin-
gle carbon powder and composite carbon powder in this
LIN ET AL.
Micro-pore volumea Meso-pore and macro-pore
(cm3 g−1) volumeb (cm3 g−1)
0.0019 0.1878
0.0358 0.7546
0.0126 0.3636
0.0163 0.3886
0.0261 0.5101
study. The particle sizes of the two single carbon powder
materials were 40 and 30 nm, respectively, and the sur-
face area is distributed in a large range, from
230.6 m2 g−1 of Vulcan XC-72 to 62.5 m2 g−1 of Acety-
lene Black carbon. At the same time, the pore volumes
of the micro-pore and meso-pore (macro-pore) of the
two single carbon powder materials also showed signifi-
cant differences. This obvious difference was reflected in
the cumulative pore volume and pore size distribution
shown in Figure 2. Vulcan XC-72 had abundant pores of
various sizes and possessed the largest number of pore
volumes. On the contrary, Acetylene Black carbon pos-
sessed the lowest number of pore volume and the lowest
peak in all-size range. For the composite of the two car-
bon blacks, we can observe from Table 2 that it indi-
cated the intermediate properties of the two carbon
materials. In addition, the surface area, micro-pore vol-
ume and meso-pore (macro-pore) volume of composite
carbon black all increased with the increase of the ratio
of Vulcan XC-72, and we can also observe this phenom-
enon from Figure 2. The addition of Vulcan XC-72 to
Acetylene Black carbon increased the pore volume in
the range of 0 to 5 nm compared with Acetylene Black
carbon and showed similar peaks to Vulcan XC-72 in
the range of 30 to 40 nm. Furthermore, the cumulative
pore volume and pore size distribution were obviously
different due to the difference in the ratio of the two
original carbon black materials, and their distribution
tended to the larger one of the two carbon blacks. This
phenomenon indicated that the pore volume and pore
size distribution can be effectively interfered adjusting
the ratio of composite carbon powder.
3.2 | The surface hydrophobicity and
resistivity of GDLs
Figure 3 demonstrates the measurement results of the
water contact angle and resistivity. Without any treat-
ment, the water contact angle of the original carbon
paper surface was 78.5
, showing a certain degree of
LIN ET AL.
(A)
(C)
F I G U R E 2 Comparison of pore diameter distribution of different carbon materials, A, BJH desorption cumulative pore volume; B, BJH
desorption dV/dD pore volume; C, 1 to 10 nm local enlarged view of BJH desorption dV/dD pore volume [Colour figure can be viewed at
wileyonlinelibrary.com]
hydrophilicity. The GDL with an MPL exhibited hydro-
phobicity compared with the original carbon paper
because of the addition of a hydrophobic agent. From
Figure 3A, we can see that the MPL prepared by the com-
posite carbon powder and the MPL prepared by the sin-
gle carbon powder both had good hydrophobicity, and
there was little difference between them. From
Figure 3B, we can see that compared to carbon paper, the
resistivity of GDL with MPL was significantly increased.
This was because: on the one hand, the resistance tested
in the article was in-plane resistance. On the other hand,
carbon paper was composed of conductive carbon fibers
interwoven with each other, and its in-plane resistance
value was low. While the surface of GDL prepared in the
laboratory was MPL composed of carbon black and
7693
(B)
30 wt.% PTFE. PTFE was an insulating material, which
led to an increase in the resistance of GDL sprayed with
MPL. In addition, Figure 3B showed that the resistivity of
the MPL made of composite carbon powder and the MPL
made of single carbon powder were basically the same,
and the distribution varied in a smaller range from 40.2
to 42.3 mΩ cm. The above phenomenon indicated that
when the total amount of PTFE and all relevant factors
including CCMs, total thickness, and operating condi-
tions were consistent, composite carbon powder had little
effect on the surface water contact angle and resistivity of
MPL. In addition, the water contact angle of VXC was
relatively small (the water contact angle of VXC was
139.75
), which may be caused by higher surface defects
of VXC.
7694 LIN ET AL.

(A) (B)

F I G U R E 3 The water contact angle and resistivity test results of GDLs (Sample 1-3 are AB, VXC, and AV73, respectively. Sample 4-6
are AV55, AV37, and carbon paper, respectively) [Colour figure can be viewed at wileyonlinelibrary.com]

(A) (B)

(C)

FIGURE 4 The pore size distribution of GDLs [Colour figure can be viewed at wileyonlinelibrary.com]
LIN ET AL.
3.3 | Pore size distribution of GDLs
The measurement results of the pore size distribution of
commercial carbon paper and self-made GDL were
shown in Figure 4. Generally speaking, carbon paper was
a porous material with porosity greater than 70%, and
more than 90% of the holes were larger than 20 μm. As
shown in Figure 4A, the pore size of carbon paper was
mostly distributed in a wide range of 20 to 100 μm and its
peak value appeared in 60 to 80 μm. For improving the
water transmission of GDL, an MPL made of PTFE and
carbon black was added to the carbon paper surface, and
it was sandwiched between the carbon paper and the cat-
alyst layer. MPLs usually contained a large number of
micro-pores with pore size distribution ranging from tens
of nanometers to hundreds of nanometers. The addition
of MPL on the carbon paper surface will affect the overall
pore size distribution of the GDL. As shown in
Figure 4A, compared with the carbon paper, the spraying
of MPL made the GDL pore size distribution curve shift
to the left obviously, and the overall pore size decreased
accordingly. In addition, it can be seen from Figure 4A
that sample AB and sample VXC had peaks in the range
of 20 to 40 μm and the peak value of sample AB was
higher than that of sample VXC. Figure 4B,C showed the
comparison of the pore size distribution between MPL
made from composite carbon powder and MPL made
from single carbon powder. It can be seen that both types
of MPL had peaks in the pore range of 20 to 40 μm and
the peak value of sample VXC was the lowest. To better
identify the influence of different pore sizes on the per-
formance of PEMFC, Figure 8 demonstrated the compari-
son of different pore size distribution ranges of GDL
prepared in the laboratory.
3.4 | Porosity distribution of GDLs
Figure 5 showed the porosity distribution of GDL pre-
pared in the laboratory. The difference in porosity of
samples 1 to 5 was small, which indicated that the com-
posite carbon black had no obvious effect on the overall
porosity of GDL when the thickness of MPL, PTFE con-
tent, and other related parameters including CCMs and
cell operating conditions were consistent. However, we
can see that the porosity of sample 2 was relatively small
(the porosity of sample 2 was 56.2%), which may be due
to the addition of Vulcan XC-72 with the highest content.
Due to the small particle size of Vulcan XC-72, more
loading of Vulcan XC-72 was needed to ensure that the
thickness of sprayed MPL reached 60 μm, which led to
the compact structure of sample 2 and the slightly
decreased porosity of sample 2.
7695
F I G U R E 5 The porosity distribution of GDLs [Colour figure
can be viewed at wileyonlinelibrary.com]
3.5 | SEM images of GDLs
The SEM images of MPLs and carbon paper were shown
in Figure 6. As a porous material, carbon paper was
formed by interweaving carbon fibers. From Figure 6, we
can see that there were a lot of pores on the carbon paper
surface and the pore formed was the largest. The sample
AB prepared with Acetylene Black carbon showed the
highest compactness of the carbon structure and some
smaller pores, while the surface of the sample VXC using
Vulcan XC-72 was mostly blocked because of its smaller
pore size, and some larger pores were left. As for the
MPL prepared from composite carbon black, the MPL
surface presented a rough porous surface, and a large
number of small aggregates of PTFE and composite car-
bon black were attached to the surface. From the par-
tially enlarged view of AV55 shown in Figure 6, it can see
that the MPL using composite carbon powder exhibited a
surface with moderate characteristics, which looked
more uniform and had holes of different sizes.
3.6 | Measurement of surface roughness
The measurement of surface roughness is meant to
reflect the effective contact area of GDL and CL. GDL
with small surface roughness can reduce the ohmic loss
caused by contact resistance and improve PEMFC perfor-
mance. For the purpose of better characterizing the sur-
face structure of the self-made MPL, we tested the 3D
surface morphology of the MPL, and the results were
shown in Figure 7. We can see from Figure 7 that the sur-
face of sample AB was the flattest with the smallest aver-
age roughness, while the sample VXC had obvious
7696 LIN ET AL.

FIGURE 6 Surface topography of carbon paper and self-made GDLs [Colour figure can be viewed at wileyonlinelibrary.com]

protrusions and depressions and the average roughness composite carbon powder ratios. For sample AV73, there
was relatively large, which was 4.2 μm. Samples AV73, were a large number of concave holes on the surface but
AV55, and AV37 were MPL prepared with different its average roughness did not increase significantly (the
LIN ET AL.
average roughness of sample AV73 was 4.125 μm), which
showed the intermediate characteristics of both Acety-
lene Black carbon and Vulcan XC-72. In addition, we also
found that as the ratio of Vulcan XC-72 in the composite
carbon powder increased, the average roughness of MPL
increased significantly. This phenomenon may be due to
more aggregate particles brought by Vulcan XC-72.
3.7 | Single-cell performances
The reaction product of PEMFC is water. The accumula-
tion of cathode water which is generated on the catalyst
layer surface and supplied through external humidifiers
will cause the partial pressure of water vapor and the sat-
uration of liquid water to increase. The mass transfer of
FIGURE 7 The surface roughness test results of laboratory-prepared GDL [Colour figure can be viewed at wileyonlinelibrary.com]
7697
water vapor is mainly through diffusion, and the driving
force of mass transfer of liquid water is capillary pressure.
Since the operating temperature of PEMFC is relatively
low, generally not exceeding 90
C, the product water
formed in the cathode electrode is mostly liquid water
and the capillary pressure-driven liquid mass transfer is
dominant. As the key component of the mass transfer of
liquid water in cell electrode, GDL is generally composed
of carbon fiber and PTFE. Carbon fiber is a hydrophilic
material and PTFE is used as a hydrophobic agent, which
makes the pores in GDL include both hydrophilic pores
and hydrophobic pores.33
As indicated by Young-Laplace formula, the capillary
pressure can be connected with the radius and wettability
of pores by the Equation (1). In addition, the capillary
pressure in GDL is also affected by the gas-phase pressure
7698
and the liquid-phase pressure in electrode,34 as shown in
Equation (2).
2γcosθ
PC = − ð1Þ
r of molecular diffusion is three orders of magnitude
PC = Pl −Pg ð2Þ
where r is the radius of pores; Pc is the capillary pressure;
γ is the surface energy of water; θ is the contact angle of
water with the surface of pore; Pl is the liquid-phase pres-
sure, and Pg is the gas-phase pressure.25
When the fuel cell is in the initial stage of operation
or working at a smaller current density, less liquid water
is produced and the reaction gas pressure is higher,
which results in Pl < Pg or Pc < 0. From formula (1), the
contact angle is 0
≤ θ < 90
. Liquid water can easily
enter hydrophilic pores. Besides, the smaller the pore
size, the greater the capillary pressure, which is more
favorable to the discharge of product water. Therefore,
the hydrophilic micro-pores are beneficial to the drainage
of product water. When PEMFC runs for a long time or
at a high current density, the amount of liquid water pro-
duced is large and the pressure of reaction gas is rela-
tively low. From formula (2), we can get Pl > Pg or
Pc > 0. At this time, the hydrophilic pores can no longer
meet the demand for drainage, and product water will
also enter the hydrophobic pores. In this case, liquid
water will preferentially penetrate the larger hydrophobic
pores because the critical Pc for entering the larger pores
is lower than the critical Pc for entering the smaller pores.
In particular, the transport of liquid water usually takes
place in pores larger than 20 μm.20 At the same time, the
hydrophobic micro-pores will also be occupied by prod-
uct water because of its higher capillary pressure. In this
case, if the reactant gas wants to maintain free transmis-
sion, it can only pass through the hydrophobic meso-
pores. Therefore, we believe that the hydrophobic meso-
pores in GDL are very important, especially for gas
transmission.34
The reactant of the PEMFC cathode is oxygen or air.
The main mass transfer mode of the reactant in the cath-
ode GDL is diffusion. Generally, the diffusion of gas in
porous media is mainly carried out in two ways: molecu-
lar diffusion and Knudsen diffusion.26 Molecular diffu-
sion usually occurs in pores with a pore diameter greater
than 100 times the molecular mean free path. When the
pore size is smaller than 1/10 of the molecular mean free
path, Knudsen diffusion plays a major role. Furthermore,
the diffusion of pores with pore diameters in between
these two limits is caused by the mixing effect of Knud-
sen diffusion and molecular diffusion. Since the mean
free path of air is about 70 nm, molecular diffusion
LIN ET AL.
mainly occurs in pores larger than 7 μm, Knudsen diffu-
sion mainly occurs in pores smaller than 7 nm, and
mixed diffusion is mainly carried out in pores of 7 nm to
7 μm. Besides, considering that the diffusion coefficient
higher than that of Knudsen diffusion, we finally believe
that the pores larger than 7 μm in GDL are more condu-
cive to the mass transfer of the reactant gas.
According to the above analysis, to further under-
stand the role of pores in different size ranges in the mass
transfer of reactant gas and product water, we artificially
divided the pores in GDL into four categories according
to their sizes: the micro-pores in the range of 7 nm to
0.5 μm, the small-pores in the range of 0.5 to 7 μm, the
meso-pores of 7 to 20 μm, and the macro-pores of 20 to
100 μm. Figure 8 presented the comparison of the pore
volume of the above four size pores in self-made GDL. It
was worth noting that the definition of the pore range
was according to the above analysis and was different
from the general standard. As shown in Figure 8A, AB
prepared with Acetylene Black carbon possessed more
meso-pores and small-pores than VXC prepared with
Vulcan XC-72, which provided a large number of chan-
nels for gas diffusion. Besides, more macro-pores in AB
promoted the occupation of liquid water in GDL, thereby
reducing the water coverage on the catalyst layer surface.
But the fewest micro-pores in the sample AB hindered
the removal of liquid water in the GDL, which was an
important factor limiting the improvement of cell perfor-
mance. While most micro-pores of sample VXC promoted
the discharge of liquid water, the least number of meso-
and small-pores severely weakened the diffusion of the
reactant gas and the least macro-pores also hindered the
flow of liquid water. Therefore, we speculated VXC was
more prone to flooding and had worse performance. As
for the sample AV55 prepared by composite carbon pow-
der, on the one hand, the addition of Vulcan XC-72
appropriately increased the number of micro-pores for
drainage; on the other hand, the existence of Acetylene
Black carbon ensured the number of meso-pores and
small-pores as gas transmission paths in AV55. Figure 8B
showed the comparison results of different pore size
ranges under different ratios of composite carbon pow-
der. It can be seen that the adjustment of the composite
carbon powder ratio had an impact on the pore size dis-
tribution of GDL. Especially AV73, which had the largest
number of meso-pores.
Figure 9 were the single-cell test results of self-made
GDLs under different relative humidity. The tests were
conducted under two different humidity conditions: 60%
humidification and 100% humidification. As shown in
Figure 9A,B, under two different humidity conditions,
AB exhibited higher limiting current density and limiting
LIN ET AL. 7699

(A) (B)

F I G U R E 8 Comparison of different pore size range distributions of laboratory-prepared GDLs [Colour figure can be viewed at
wileyonlinelibrary.com]

(A) (B)

(C) (D)

F I G U R E 9 Performance comparison of GDLs with different MPLs, A and C, 60% humidification, B and D, 100% humidification [Colour
figure can be viewed at wileyonlinelibrary.com]
7700
power density than VXC. We believed that at a relatively
low current density, since the fuel cell produced less
water, the effect of micro-pores in GDL was not signifi-
cant, and more macro-pores in AB ensured sufficient
reaction gas in the electrode. In the high current area,
the larger number of meso-pores and small-pores in AB
facilitated gas diffusion and reduced polarization loss.
However, the smaller number of micro-pores in AB hin-
dered liquid water discharge by capillary-driven forces,
which was a potential factor limiting the further
improvement of cell performance under high current
density. The advantage of VXC was that it had more
micro-pores, which we hoped can make up for the prob-
lem of insufficient micro-pores in AB. For this reason, we
prepared sample AV55 with composite carbon black by
mixing Vulcan XC-72 and Acetylene Black carbon. From
Figure 9A,B, we can see that AV55 had the best perfor-
mance under 60% humidity and 100% humidity. Espe-
cially at high current density, the performance was
obviously better than AB. As guessed, the MPL made of
(A)
(C)
F I G U R E 1 0 EIS test of samples AB, VXC, and AV55, A, 60%RH, B, 100%RH (test current density is 3 A cm−2) [Colour figure can be
viewed at wileyonlinelibrary.com]
LIN ET AL.
composite carbon powder combined the two advantages
of the original carbon powder, and had a more reason-
able pore structure, which can simultaneously meet the
transmission of reactants and liquid water. Figure 9C,D
was performance comparisons of MPL prepared with dif-
ferent proportions of composite carbon powder. We can
see that AV73 showed the best cell performance in both
low humidity and high humidity. From the comparison
of different pore size range distributions of the three
GDLs in Figure 8B, we can see that AV73 had more
meso-pores, which was more beneficial to the supply of
reactant gas and reduced mass transport polarization at
high current density.
3.8 | Electrochemical impedance
spectroscopy tests
From the analysis of the polarization curve in Figure 9,
we can see that the cell performance of AV55 was better
(B)
(D)
LIN ET AL.
than AB and VXC at high current density. We believed
that AV55 had better water vapor management capabili-
ties than AB and VXC under a high current region. To
verify our conjecture, we measured the EIS of AB, VXC,
and AV55, respectively. Under high current density, the
gas transmission channel will be blocked because of the
large accumulation of product water in GDL, and
PEMFC will have obvious concentration loss. In addition,
the size of the arc measured by EIS in the high current
density and low-frequency range reflects the concentra-
tion loss of the fuel cell. Therefore, we tested the EIS of
AB, VXC, and AV55 at current condition of
I = 3 A cm−2. From Figure 10, we can see that under the
current density of I = 3 A cm−2, whether it was low
humidity or high humidity, the arc of AV55 at low fre-
quency was smaller than that of AB and VXC, which
showed that AV55 had better materials transport capac-
ity. The reason was that AV55 had a more reasonable
pore size distribution than AB and VXC, so AV55 had
better fuel cell performance than AB and VXC. At the
same time, we tested EIS of samples AV37, AV55, and
AV73 to verify the validity of the pore size distribution
optimization. From Figure 10C,D, it can be seen that the
arc of AV73 was the smallest under the two humidity
conditions, which indicated that the optimized sample
AV73 had better material transportability due to its more
meso-pores for gas transmission.
4 | C ON C L U S I ON S
In this paper, MPL composed of composite carbon black
was fabricated, and its effect on PEMFC performance was
studied. GDL using Acetylene Black carbon had more
meso-pores and small-pores, which was conducive to gas
diffusion, but its smaller number of micro-pores hindered
the removal of liquid water. On the contrary, GDL with
Vulcan XC-72 had more micro-pores, but the smallest
number of meso-pores and small-pores severely weakened
the diffusion of the reactant gas, resulting in serious mass
polarization losses. To make up for the problem of insuffi-
cient micro-pores in AB, we prepared MPL with composite
carbon powder. Just as guessed, the MPL made of compos-
ite carbon powder combined the two advantages of the
original carbon powder and had a more reasonable pore
structure. Furthermore, we optimized the pore size distri-
bution of GDL by adjusting the ratio of composite carbon
powder. In the end, MPL with 70 wt.% Acetylene Black
carbon and 30 wt.% Vulcan XC-72 showed the best cell
performance, and its limiting power density can reach
1.544 W cm−2 under 60% humidification and
1.778 W cm−2 under 100% humidification.
7701
ACKNOWLEDGEMENTS
The accomplishment of this item is supported by the
NSFC-Shandong Joint Fund for Marine Science Research
Centers (U1606401).
CONFLICT OF INTEREST
None.
DATA AVAILABILITY STATEMENT
The data that support the findings of this study are avail-
able from the corresponding author upon reasonable
request.
ORCID
Shouyi Liu https://orcid.org/0000-0002-1684-0413
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How to cite this article: Lin G, Liu S, Qu G, et al.
Effect of pore size distribution in the gas diffusion
layer adjusted by composite carbon black on fuel
cell performance. Int J Energy Res. 2021;45:
7689–7702. https://doi.org/10.1002/er.6350