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 7 ( 2 0 2 2 ) 4 0 1 8 e4 0 3 2

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Optimization of graded catalyst layer to enhance

uniformity of current density and performance of
high temperature-polymer electrolyte membrane
fuel cell

Venkatesh Babu K.P a, Geethu Varghese a, Thadathil Varghese Joseph a,

Purushothama Chippar b,*
a
CHRIST (Deemed to Be University), Bengaluru, 560 029, India
b
Applied Engineering and Computational Analysis Laboratory, St Joseph Engineering College (Affiliated to
Visvesvaraya Technological University, Belagavi), Vamanjoor, Mangaluru, 575 028, India

highlights

Performance of HT-PEMFC comprising a graded cathode catalyst structure is studied.

Multiple graded CLs improve performance but leads to uneven current distribution.

High Pt loading downstream greatly improves uniformity in current distribution.

Proposed hybrid CL structures improve both performance and current distribution.

Study shows the importance of a rational design of CL based on cell application.

article info abstract

Article history: The optimal use of catalyst materials is essential to improve the performance, durability
Received 21 September 2021 and reduce the overall cost of the fuel cell. The present study is related to spatial distri-
Received in revised form butions of current and overpotential for various graded catalyst structures in a high
30 October 2021 temperature-polymer electrolyte membrane fuel cell (HT-PEMFC). The effect of catalyst
Accepted 2 November 2021 gradient across the catalytic layer (CL) thickness and along the channel and their combi-
Available online 26 November 2021 nation on cell performance and catalyst utilization is investigated. The graded catalytic
structure comprises two, three, or multiple layers of catalyst distribution. For a total
Keywords: cathode catalyst loading of 0.35 mg/cm2, higher loading near the membrane presents
High temperature-polymer improved cell performance and catalyst utilization due to reduced limitations caused by
electrolyte membrane fuel cell oxygen and ion diffusions. However, non-uniformity in the current distribution is signifi-
Catalyst grading cantly increased. The increase in the catalyst loading along the reactant flow provides a
Mathematical functions substantially uniform current density but lower cell performance. The synergy of varying
Current distribution catalytic profiles across the CL thickness and along the cathode flow direction is investi-
Numerical modeling gated. The results emphasize the importance of a rational design of cathode structure and
mathematical functions as a strategic tool for functional grading of a CL towards improved
uniform current distribution and catalyst utilization.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author. Applied Engineering and Computational Analysis Laboratory, St. Joseph Engineering College, Vamanjoor,
Mangaluru, 575028, India.
E-mail address: purushothama@sjec.ac.in (P. Chippar).
https://doi.org/10.1016/j.ijhydene.2021.11.006
0360-3199/© 2021 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 7 ( 2 0 2 2 ) 4 0 1 8 e4 0 3 2
Introduction
The ubiquitous adoption of fuel cells, be it in the automotive
sector or stationary applications, is primarily impeded due to
its high cost per kW, durability, and cost of hydrogen produc-
tion, transportation, and storage. Another major challenge in
its commercialization is tailoring fuel cell components to suit
desired applications as required kinetic activities, reactant and
product transport, and heat and water management vary with
the operational load conditions. One of the primary contrib-
uting factors of overall cost of the fuel cell is the use of noble
Platinum Group Metal (PGM) in the electrodes. A recent study
on the price breakdown of the polymer electrolyte membrane
fuel cell (PEMFC) stack analysis shows that 34% of the overall
cost of the fuel cell system is contributed by catalysts, which
are made up of PGM supported carbons [1]. The significant
advancements in the fabrication technologies of catalysts and
electrodes resulted in the drop of platinum (Pt) loading from
28 mg/cm2 in 1960 to the present 0.2e0.6 mg/cm2. The recent
targets for electrocatalyst of PEMFC by the Department of En-
ergy [2] were: fuel cell system cost of $40/kW, Pt usage-8 kW/g
and 0.125 mg/cm2, and durability of 5000 h with less than 10%
loss in performance. Indeed, a special attention is needed to
improve the catalyst utilization while optimizing the electrode
structure to achieve high catalyst specific power density.
Recent advancements in catalyst technology have achieved
very low Pt loading [3,4]. However, historically the price of noble
metals is very sensitive to their demand. The extensive
commercialization of the fuel cells would drive up the Pt demand
and hence the costs. Therefore, a strategy must be developed to
address the Pt usage without negatively impacting the fuel cell
durability and performance. The catalyst layer (CL) of a PEMFC is
a porous structure of carbon-supported catalyst and ionomer.
The reactants and products of the electrochemical reactions
enter and exit from the reaction sites through the pores, whereas
the electrons and protons are transported through the carbon
support and ionomer, respectively. The presence of three phases
of transport - species, electron, and proton, simultaneously poses
a competitive environment [5], and altering the ratio of PGM,
ionomer [6,7], carbon support, and porosity of the electrode [8]
will defer the cell performance. The reactant concentrations vary
spatially, with a higher concentration under the channel region,
better electron transport under the rib region, and high Hþ ions
at the CL/membrane interface. The spatial variation of the above
and the non-uniformity in the reaction rates will be a strong
function of the operating conditions. Therefore, there is a need to
optimize the CL composition based on the operational re-
quirements of the PEMFC. To ensure this, intensive research
works, which could be experimental or simulated, are necessary
to optimize the catalyst loading, porosity, and ionomer content
and their distribution in the electrode. The catalyst loading being
the one prominent component in the electrode is not only a cost
concern but also has a significant effect on the electrochemical
reaction activity and durability. The homogeneous distribution of
the catalyst in the porous electrode increases the cost as the
electrochemical activity is not uniform in the electrode. The ki-
netics of oxygen reduction reaction at catalyst and electrolyte
interface has been studied for several decades to improve the
efficiency of catalyst and minimize the voltage losses. The main
4019
challenge in the present scenario in fuel cells is enhancing per-
formance and durability. The performance and durability are
mainly affected by the local current distribution. A considerable
variation in the distribution of current can exist along the flow
field leading to faster degradation of the Membrane Electrode
Assembly (MEA) during operation. A local current density is pri-
marily caused due to electrochemical reactions and species
transport, leading to non-uniform current density over the
membrane, which arises due to consumption of reactant gasses
along the channel. The local current density gradient can be
made uniform by modifying the electrochemical reactions that
are occurring in the fuel cell. One such efficient method is the use
of functional grading for cost reduction and optimization of the
cell performance and to achieve uniform current density within
the MEA [9].
Recently, several researchers investigated the effect of
variation of CL constituents in the in-plane [6,10,11], along-the-
channel [12,13], and through-plane [14e17] directions, and all
the researches pronounced the significance of optimizing the
design parameters of the CL based on the operating conditions
to achieve maximum cell performance. Cetinbas et al. [18,19]
studied the effect of bi-directionally-graded CL compositions,
i.e., Nafion content and Pt and carbon loadings, on cell perfor-
mance using a two-dimensional cathode model and reported
superior performance compared to the unidirectional grading.
The simulation results assert that the effectiveness of the CL
can be maximized by rationally matching the distribution of
constituents to the reaction rates. Santis et al. [20] and Pra-
sanna et al. [21] showed that in a low temperature-PEMFC (LT-
PEMFC), an increase in catalyst loading along the cathode flow
direction improves the cell performance due to its counter-
acting with the depletion of oxygen and water flooding along
the channel. Wei et al. [22] prepared PEMFC with gradient Pt
indicating that the catalytic kinetic performance can be
enhanced by increasing the Pt loading and suggested that the
higher the Pt loading increases the aggregation leading to low
utilization of the catalyst. The optimal performance of the
cathode CL can be achieved by modifying the Pt loading
gradient and particle size gradient, which attains a more uni-
form distribution of electrochemical active surface area (ECSA)
for enhancing the performance as well as the durability [14].
Xing et al. [10] numerically investigated the effect of variation of
catalyst loading and GDL porosity simultaneously along the
cathode flow direction and concluded that a systematic design
is necessary to achieve higher uniform current distributions in
the membrane. The results show the importance of optimizing
the design parameters of multiple components of the fuel cell
simultaneously. Higher catalyst loading is recommended at the
membrane and cathode CL interface due to the higher con-
centration of Hþ ions [23]. In contrast, with considering the
influence of liquid water, Srinivasrao et al. [24], Xing et al. [25],
and Zheng et al. [14] studied the effect of Pt particle size and
loading gradients on cell performance and degradation of CL. It
was reported that employing larger size Pt particles near the CL/
membrane interface significantly mitigate the loss of ECSA and
Pt mass, but smaller particles at the CL/gas diffusion layer (GDL)
interface accelerates the dissolution, which can be alleviated by
using higher Pt loading at the region close to the GDL. The effect
of varying the catalyst particle size along with the through
plane is also investigated [14,17], and it is observed that larger
4020 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 7 ( 2 0 2 2 ) 4 0 1 8 e4 0 3 2

particle size and higher ionomer content [26] at the CL/mem- provide a promising strategy for grading the CL, which would
brane interface helps to improve the cell performance. The expedite the commercialization of the HT-PEMFC.
ionomer dispersion state in the catalyst ink has a substantial
effect on the catalyst particle size and hence the cell perfor-
mance [27]. Park et al. [28] studied the effect of solvents in Mathematical model
ionomer dispersions on CL performance and durability of the
PEMFC. It should be noted that the use of conventional carbon A three-dimensional, non-isothermal HT-PEMFC model used in
supports, which has numerous micropores, can trap the Pt the present study is based on the previous publications [36,37].
particles and thus resulting in reduced Pt utilization. Therefore, The computational domain presented in Fig. 1a encompasses
carbon nanotubes and nanofibers catalyst supports are the bipolar plates (BP), gas channels (GC), gas diffusion layers
considered due to their large specific area and high conduc- (GDL), CLs, and membrane. The associated physiochemical,
tivity [29,30]. The functionalization of carbon supports with transport and geometrical properties are listed in Table 1. This
NHx group is found to redistribute the ionomer and phosphoric section presents the governing equations, relevant source/sink
acid (PA) in the CL. Pimperl et al. [31] discussed the use of terms, constitutive equations, a spherical agglomerate model
nitrogen-modified CLs in HT-PEMFC and observed that high for the CLs, and electrochemical properties of the model.
degree of functionalization results in inhomogeneous acid
distribution whereas low degree functionalization improves Governing equations
the acid distribution and mass transport in the CL. Xing et al.
[32] developed a segmented fuel cell unit to evaluate the effect Conservation of mass and momentum
of catalyst grading and temperature on cell performance and The Navier-Stokes equations presented in Eqs (1) and (2) are
homogeneity in the distribution of current density and heat. used to calculate the flow variables in the gas channels,
The study indicated that temperature variation in the cell must whereas equations (1) and (3) are used to calculate the velocity
be considered to optimize the profile of Pt loading in the CL. in the porous medium, i.e., GDL and CL [35]. The velocity of the
Especially in high temperature-PEMFC (HT-PEMFC), where the species is assumed to be zero in the membrane.
operating temperature has a significant effect on the perfor-
mance, and current distributions, designing the CL by inte- V:ðr!
uÞ¼0 (1)
grating the effects of catalyst loading and local temperature will
V:ðr!
u!u Þ ¼  Vp þ V:ðmðV!
u þ V!
T
be an attractive solution, and it may reduce the catalyst loading u ÞÞ (2)
remarkably. Aiming to reduce the MEA degradation rate in a
V:ðr!
u!u Þ ¼  Vp þ V:ðmðV! u ÞÞ  !
u þ V!
direct methanol fuel cell by homogenizing the current density T m
u (3)
distribution, Rabissi et al. [33] developed a gradient MEA by K
locally tuning the catalyst and ionomer loadings. The test where the dynamic viscosity m, is:
demonstrated a 70% reduction in the degradation and 55%
more homogeneous current distribution in the MEA. Samris ma ¼ 9:88  106 xH2 þ 1:12  105 xH2 O þ 2:01  105 xN2
et al. [34] numerically studied the effect of Pt loading and its
dispersity on the cell performance. The study showed that the mC ¼ 2:3  105 xO2 þ 1:12  105 xH2 O þ 2:01  105 xN2
optimization of Pt dispersity is essential to achieve better per-
formance and reduction in its cost. The literature results Conservation of species
demonstrate that controlling the local magnitude of the cata- Eq. (4) presents the general transport equation for the species
lyst based on the local condition is a promising solution to H2, O2, and H2O [38]. The first, second, and third terms repre-
reduce its consumption and improve cell performance. This sent convective, diffusion, and source/sink, respectively. The
also helps to mitigate spatial variation of heat, current and corresponding source/sink terms for the species are provided
overpotential, and therefore, possibly improve cell durability. in Eq. (5).
However, understanding the location of higher/lower reaction

V:ðr!
eff
rates depending on the operating current and parameters is u Ci Þ ¼ V: Di VCi þ Si (4)
crucial for the successful grading of the CL. To the authors' best
knowledge, there is no much work carried out on designing a ja jc jc
Anode CL : SH2 ¼  ; Cathode CL : SO2 ¼ ; SH2 0 ¼ (5)
graded CL for HT-PEMFC. In the present study, the HT-PEMFC 2F 4F 2F
model developed earlier [35,36] is modified to consider the
Conservation of charge
functionally graded cathode CL and applied to a single straight-
channel fuel cell geometry. The cell performance and key dis-
The charge transport equations expressed in Eqs (6) and (7) are
tributions such as current and cathode overpotential were
used to solve proton transport in the CLs and membrane and
compared with various catalyst grading along the CL thickness,
electron transport in the BPs, GDLs, and CLs, respectively [35].
along the oxidant flow direction and also simultaneously in the
above directions. The synergetic effect of bi-directional loading Proton transport V:ðsV∅e Þ þ S∅ ¼ 0 (6)
of Pt is explored. In which, one of the overall objective is to
achieve higher catalyst utilization at the electrodes without Electron transport V:ðkV∅s Þ þ S∅ ¼ 0 (7)
compensating the cell performance, and homogeneous distri-
bution of current and overpotential which will result in high
at the Anode CL : S∅ ¼ ja ; Cathode CL : S∅ ¼ jc :
power output and longer service life. The present study aims to
 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 7 ( 2 0 2 2 ) 4 0 1 8 e4 0 3 2 4021

Fig. 1 e i) Computational domain for CFD simulation and ii) Agglomerate modeling of the CL.

Table 1 e Geometrical, Transport and physiochemical properties.

Description Value Ref.
Phosphoric acid doping level 10 [35]
Porosity of GDL 0.6 [35]
Permeability of GDL and CL 1.0  1012 and 1.0  1013 m2 [35]
Electronic conductivity in the GDL, CL, BP 1250, 300, 14,000 S m1 [35]
Specific heat capacities of GDL, CL, membrane, and BP 568, 3300, 1650, 2930 J kg1 K1 [35]
Specific heat capacities of species (H2, O2, N2, H2O) 14,430, 929,1042, 1968 J kg1 K1 [35]
Thermal conductivities of GDL, CL, membrane, BP 1.2, 1.5, 0.95, 20 W m1 K1 [44]
Thermal conductivities of species (H2, O2, N2, H2O) 0.2040, 0.0296, 0.0293, 0.02378 W m1 K1 [44]
Anode transfer coefficient, aa 1.0 [36]
Cathode transfer coefficient, ac 0.5 [36]
0.2  109A m3
ref
Volumetric reference exchange current density in anode, i0;a [36]
0.2  104A m3
ref
Volumetric reference exchange current density in cathode, i0;c [36]
Thickness of GC, GDL, CL, MEM 1,0.35, 0.05, 0.05  103 m [36]
Cell length 0.1 m
Radius of the Pt particle 5  109 m [40]
Diameter of the carbon particle 2.25  106 m [40]
Density of Pt particle 21,450 kg m3 [40]
Density of carbon 1800 kg m3 [40]
Density of ionomer 1300 kg m3 [40]

The proton conductivity in the ionomer, s, is estimated

using the expression given by Cheddie et al. [39] as presented 3Lpt
apt ¼ (10)
in Eq. (8), which is highly dependent on the acid doping level X, dCL rpt rpt
and temperature. The doping level is defined as the number of
The volume fractions of Pt (εPt ), carbon (εC ) and ionomer
acid molecules per repeating unit of polybenzimidazole (PBI)
(εmem ) in the agglomerate are calculated as [32,40]:
polymer and can be written as a function of the molar con-
centration of acid, M, as below: Lpt
εPt ¼ (11)
   rpt dCL
100 2605:6  70:1X
s¼ exp 8:0219  (8)
T T
Lpt
εC ¼  (12)
rC wt%Pt=C dCL
X ¼ 0:012M3  0:2111M2 þ 1:2363M þ 0:7119 (9)

Agglomerate model at the CL rC

The electrochemical activities in the anode and cathode CLs
are modeled using a simple agglomerate approach as
described below. The shape and size of the agglomerate are
assumed to be constant, and its effective surface area is
dependent only on the catalyst loading as expressed in eq.
(10).
εmem ¼ I C εC (13)
rmem
where I/C is the ionomer to carbon ratio, which is assumed to
be 1.0 [41]. The void fraction available in the CL for species
transport is calculated from the weight fractions of the
different constituents as given in Eq. (14). A constant CL
thickness is considered for all the calculations.
4022 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 7 ( 2 0 2 2 ) 4 0 1 8 e4 0 3 2

spontaneously consumed in the electrochemical reaction.

εCL ¼ 1:0  εPt  εC  εmem (14) Finally, the effective oxygen diffusivity in the CL can be writ-
ten as below:
The effective reactant diffusivity in the CL is obtained by
combining both the gas phase transport in the void space and CL;eff
DO 2
g;eff
¼ DO2 þ DPBI PBI
O2 HO2 Ru T (23)
dissolution followed by diffusion in the membrane phase with
respect to the void and ionomer fractions. The Bruggemann The electrochemical reaction rate per unit volume at the
correlation accounting for porosity and tortuosity in the anode and cathode CLs are calculated using the following
porous medium is used to calculate the effective diffusivities equations:
of species concentration as given in Eq (15) [42]. !12  
=

CH2 aa þ ac
g;eff g ja ¼ apt ia Fh (24)
DO2 ¼ DO2 εtCL : (15) ref
CH Ru T
2

The dissolution and subsequent diffusion of oxygen in the

!32 =
 
electrolyte phase at the cathode are elaborated in terms of CO2 ac
temperature, T and weight percentage of PA, mPA as below jc ¼  apt ic ref
exp  Fh (25)
CO2 Ru T
[43,44]:
The temperature dependency of the exchange current

"
2


2
#
257:13ðmPA Þ þ 431:08ðmPA Þ þ 178:45 þ  93500ðmPA Þ þ 156646ðmPA Þ þ 64288
HPA
O2 ¼ 0:1 exp (16)
T

"
2


2
#
 192:55ðmPA Þ þ 323:55ðmPA Þ  125:61 þ 62010ðmPA Þ  105503ðmPA Þ þ 40929
9
DPA
O2 ¼ 10 exp (17)
T

The Henry's constant for dissolved oxygen in the PA doped density [35] at the anode and cathode are expressed as
PBI can be obtained as a function of volume fraction of PA in follows:
the membrane, εPA as [43,44] below:   
ref 1 1
 PA h
 PA i ia ¼ i0;a;393:15 :exp  1400  (26)
1:945 1:8 T 393:15
O2 ¼ ε
HPBI O2 þ 5:79 1  ε
HPA (18)
  
1  ref 1 1
4:81 ic ¼ i0;c;393:15 :exp  7900  (27)
Where εPA ¼ þ1 (19) T 393:15
X2
Boundary conditions and numerical procedure
By using Bruggemann's relation, the diffusion coefficient of
oxygen in the PA doped PBI membrane can be written as
The HT-PEMFC model is numerically implemented and solved
 PA 1:8 using the commercial CFD tool, ANSYS FLUENT 17.2. All the
DPBI
O2 ¼ DPA
O2 ε : (20)
equations, inlet flow variables, physical properties, and source
Due to the absence of data on hydrogen dissolution in the terms of the governing equation were implemented using
PA, based on Cheddie et al. [43] observation, the solubility and user-defined functions (UDF). The convergence criteria for all
diffusivity of hydrogen are assumed to be four and two times species, flow, and energy calculation residuals are set to 108.
higher than those for oxygen, respectively. The oxygen The anode and cathode walls are set to be isothermal, and all
diffusion flux in the PA doped PBI membrane can be written as the other walls in the domain were set to adiabatic for tem-
perature calculation, and no flux condition is applied to the
O2 ¼ DO2 :VCO2 :
JPBI PBI PBI
(21)
outer faces for species transport and flow equations. Whereas
The concentration of oxygen dissolved at the interface of top and bottom surfaces are assumed symmetry boundary
gas and membrane phase can be determined from the partial conditions. The anode and cathode gas channels inlet veloc-
pressure of oxygen using Henry's constant as follows: ities can be expressed as a function of operating current
density, stoichiometric ratios, the cross-sectional area of the
g
O2 ¼ HO2 pO2 ¼ HO2 CO2 Ru T
CPBI PBI PBI
(22) gas channel, and the concentrations of hydrogen and oxygen
It is assumed that the oxygen dissolved in the electrolyte is (Eq. (28)). The hydrogen and oxygen concentrations were
 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 7 ( 2 0 2 2 ) 4 0 1 8 e4 0 3 2 4023

operating conditions. The total Pt loading at the anode is

maintained constant at 0.350 mg/cm2. As shown in Fig. 2, the
predicted results are in good agreement with the experi-
mental results. The current density increases with the cata-
lyst loading at the cathode, however beyond a certain loading,
the concomitant decrease in porosity in the CL results in mass
transportation loss, and therefore drop in the current density
is observed. This is more pronounced in higher current den-
sity (>1.0 A/cm2) regions. The porosity value decreases from
53% to 4.4% when the catalyst loading is increased from
0.35 mg/cm2 to 0.712 mg/cm2.

Description of the gradient cathode CL structure

The MEA of the fuel cell used in the present work consisted of
uniformly distributed Pt loading of 0.35 mg/cm2 on the anode
Fig. 2 e Comparison of predicted polarization curves with side, a relatively high loading such that the cell performance is
the experimental data [39] for different Pt loadings at the controlled mainly by the cathode kinetics and oxygen con-
cathode. centration polarization. This will enable evaluating the
effectiveness of the various catalyst grading in the cathode
calculated using ideal gas law using inlet pressure and and thus optimizing the distribution. The variation of CL
temperature. porosity and ionomer fractions is calculated using Eqs. (11)
and (13), respectively. The effect of Pt loading on effective
xa IAmem xc IAmem interface area between the solid and membrane phases,
uin;a ¼ ; uin;c ¼ (28)
2FCH2 Aa;chan 4FCO2 Ac;chan therefore on electrochemical activity are mentioned in Eqs.
(24) and (25). The cathode CL structures are obtained with
uniform Pt loading (A), by varying the Pt loading distribution
Results and discussion
using two-step layers of equal thickness (B), three-step layers
of equal thickness (C), and smooth gradient (D) across the
Validation of the model
thickness, increasing (E) and decreasing (F) Pt distribution
along the cathode channel, and combination of B and E, and C
The above described HT-PEMFC model incorporating the
and E. The representative diagrams of various cathode CL
agglomerate approach in the CL is validated against experi-
structures used in the study are presented in Fig. 3. Tables 2
mental data for polarization curves presented by Su et al. [45]
and 3 provide the complete overview of different simulation
for different Pt loadings in the cathode CL under the same
cases and cell performance data at operating voltages 0.6 V

Fig. 3 e Graded cathode CL structures: i) across the thickness, ii) along the cathode channel, and iii) hybrid CL.
 4024
Table 2 e Cell performance for various cathode CL structures (A to D).
Pt Loading (total Lpt: 0.35 mg/cm2) CL/MEM (Max) - CL/GDL (Min) Operating cell voltage ¼ 0.6 V Operating cell voltage ¼ 0.3 V
Current Catalyst Change in Current Catalyst Change in
density A/cm2 utilization g performance density A/cm2 utilization g performance

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 7 ( 2 0 2 2 ) 4 0 1 8 e4 0 3 2
(Imin, Imax, Iavg) (Pt)/kW (Imin, Imax, Iavg) (Pt)/Kw
A Uniform εCL ¼ 0.53 0.1656, 0.2291, 2.945 0.8736, 1.3009, 1.047
εm ¼ 0.27 0.1981 1.1139
B - Step gradient e
two-step layer cathode CL
B1 60%e40% εCL ¼ 0.44e0.62 0.1668, 0.2337, 2.902 1.46% 0.8729, 1.3464, 1.021 2.55%
εm ¼ 0.32e0.22 0.201 1.1423
B2 70%e30% εCL ¼ 0.34e0.72 0.1676, 0.2371, 2.871 2.57% 0.8689, 1.3802, 1.003 4.38%
εm ¼ 0.38e0.16 0.2032 1.1627
B3 80%e20% εCL ¼ 0.25e0.81 εm ¼ 0.43e0.11 0.1682, 0.2397, 2.848 3.38% 0.8634, 1.4055, 0.991 5.71%
0.2048 1.1775
B4 90%e10% εCL ¼ 0.15e0.91 εm ¼ 0.49e0.054 0.1658, 0.2416, 2.832 3.99% 0.8577, 1.4235, 0.983 6.60%
0.206 1.1874
C - Step gradient e
three-step layer cathode CL
C1 40%e30% - 30% εCL ¼ 0.44e0.58 - 0.58 0.1665, 0.2327, 2.909 1.21% 0.8729, 1.3408, 1.025 2.20%
εm ¼ 0.32e0.24 - 0.24 0.2005 1.1384
C2 40%e40% - 20% εCL ¼ 0.44e0.44 - 0.72 0.1669, 0.2342, 2.896 1.67% 0.8734, 1.3464, 1.020 2.64%
εm ¼ 0.32e032e0.16 0.2014 1.1433
C3 50%e30% - 20% εCL ¼ 0.30e0.58 - 0.72 0.1677, 0.2376, 2.867 2.73% 0.8673, 1.3878, 1.000 4.76%
εm ¼ 0.40e0.24 - 0.16 0.2035 1.1669
C4 60%e20% - 20% εCL ¼ 0.15e0.72 - 0.72 0.1681, 0.2396, 2.848 3.38% 0.8605, 1.4148, 0.988 6.05%
εm ¼ 0.49e0.16 - 0.16 0.2048 1.1813
C5 70%e20% - 10% εCL ¼ 0.013e0.72e0.86 0.1671, 0.2392, 2.861 2.93% 0.8497, 1.3736, 1.025 2.14%
εm ¼ 0.57e0.16 - 0.08 0.2039 1.1377
D - Smooth gradient cathode CL
D1 Pt(X) ¼ 5.7459e-3 - 2.3334 X εCL ¼ 0.48 to 0.58 εm ¼ 0.30 to 0.24 0.166, 0.2309, 2.927 0.61% 0.8739, 1.3187, 1.037 1.01%
(1.1 LPT - 0.9 LPT) 0.1993 1.1252
D2 Pt(X) ¼ 1.1200e-2 - 4.6668 X εCL ¼ 0.44 to 0.62 εm ¼ 0.32 to 0.22 0.1664, 0.2323, 2.914 1.06% 0.8736, 1.3343, 1.028 1.89%
(1.2 LPT - 0.8 LPT) 0.2002 1.135
D3 Pt(X) ¼ 1.6654e-2 - 7.0 X εCL ¼ 0.39 to 0.67 εm ¼ 0.35 to 0.19 0.1669, 0.2339, 2.899 1.56% 0.8727, 1.349, 1.020 2.71%
(1.3 LPT - 0.7 LPT) 0.2012 1.1441
D4 Pt(X) ¼ 2.2109e-2 - 9.3334 X εCL ¼ 0.34 to 0.72 εm ¼ 0.38 to 0.16 0.1672, 0.2353, 2.886 2.02% 0.8715, 1.3619, 1.013 3.43%
(1.4 LPT - 0.6 LPT) 0.2021 1.1521
D5 Pt(X) ¼ 2.7563e-2 - 11.6668 X εCL ¼ 0.34 to 0.72 εm ¼ 0.38 to 0.16 0.1675, 0.2365, 2.876 2.37% 0.8699, 1.3736, 1.007 4.06%
(1.5 LPT - 0.5 LPT) 0.2028 1.1591
Table 3 e Cell performance for various cathode CL structures (E and F).
Pt Loading (total Lpt: 0.35 mg/cm2) Operating cell voltage ¼ 0.6 V Operating cell voltage ¼ 0.3 V

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 7 ( 2 0 2 2 ) 4 0 1 8 e4 0 3 2
2
Current density A/cm Catalyst utilization Change in Current density A/cm2 Catalyst utilization Change in
(Imin, Imax, Iavg) g (Pt)/kW) performance (Imin, Imax, Iavg) g (Pt)/kW) performance
E  increasing catalyst gradient from cathode inlet to outlet
E1 Pt(X) ¼ 0.00315 þ 0.007Z εCL ¼ 0.58 to 0.48 εm ¼ 0.1771, 0.2122, 0.1980 2.946 0.05% 0.9005, 1.2418, 1.1126 1.049 0.12%
(0.9 LPT - 1.1 LPT) 0.24 to 0.30
E2 Pt(Z) ¼ 0.0028 þ 0.014Z εCL ¼ 0.62 to 0.44 εm ¼ 0.1882, 0.2013, 0.1977 2.951 0.20% 0.9254, 1.1773, 1.1101 1.051 0.34%
(0.8 LPT - 1.2 LPT) 0.22 to 0.32
E3 Pt(Z) ¼ 0.00245 þ 0.021Z εCL ¼ 0.67 to 0.39 εm ¼ 0.1753, 0.2064, 0.1972 2.958 0.45% 0.9486, 1.1696, 1.1064 1.054 0.67%
(0.7 LPT - 1.3 LPT) 0.19 to 0.35
E4 Pt(Z) ¼ 0.0021 þ 0.028Z εCL ¼ 0.72 to 0.34 εm ¼ 0.1558, 0.2151, 0.1965 2.969 0.81% 0.9704, 1.183, 1.1012 1.059 1.14%
(0.6 LPT - 1.4 LPT) 0.16 to 0.38
E5 Pt(Z) ¼ 0.00175 þ 0.035Z εCL ¼ 0.75 to 0.30 εm ¼ 0.1351, 0.2247, 0.1956 2.982 1.26% 0.9121, 1.2033, 1.0945 1.066 1.74%
(0.5 LPT - 1.5 LPT) 0.14 to 0.40
F - decreasing catalyst gradient from cathode inlet to outlet
F1 Pt(Z) ¼ 0.00385e0.007Z εCL ¼ 0.48 to 0.58 εm ¼ 0.1536, 0.2451, 0.1981 2.945 0.00% 0.8439, 1.3553, 1.114 1.047 0.01%
(1.1 LPT - 0.9 LPT) 0.30 to 0.24
F2 Pt(Z) ¼ 0.0042e0.014Z εCL ¼ 0.44 to 0.62 εm ¼ 0.1409, 0.2605, 0.1978 2.949 0.15% 0.8109, 1.4058, 1.1129 1.048 0.09%
(1.2 LPT - 0.8 LPT) 0.32 to 0.22
F3 Pt(Z) ¼ 0.00455e0.021Z εCL ¼ 0.39 to 0.67 εm ¼ 0.1277, 0.2752, 0.1973 2.957 0.40% 0.7733, 1.4529, 1.1105 1.051 0.31%
(1.3 LPT - 0.7 LPT) 0.35 to 0.19
F4 Pt(Z) ¼ 0.0049e0.028Z εCL ¼ 0.34 to 0.72 εm ¼ 0.1136, 0.2894, 0.1966 2.967 0.76% 0.7298, 1.4968, 1.1067 1.054 0.65%
(1.4 LPT - 0.6 LPT) 0.38 to 0.16
F5 Pt(Z) ¼ 0.00525e0.035Z εCL ¼ 0.30 to 0.75 εm ¼ 0.0986, 0.3029, 0.1957 2.981 1.21% 0.6781, 1.5377, 1.1013 1.059 1.13%
(1.5 LPT - 0.5 LPT) 0.40 to 0.14

4025
4026 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 7 ( 2 0 2 2 ) 4 0 1 8 e4 0 3 2

and 0.3 V. The corresponding multi-dimensional contours for
current and overpotential distributions are presented and
discussed in the subsequent sections.
Effect of Pt distribution across the cathode thickness
High catalyst density close to the membrane resulting in the
shortening of the proton conduction path for accessing the
catalyst. Lower catalyst density and hence high porosity close
to the GDL enhances the oxygen transport. Fig. 4 compares the
current density distributions in the membrane of the cell
having a graded Pt loading with that of uniform Pt loading (A)
across the cathode thickness at cell operating voltage 0.3 V
(high current density region). In the two-layers (B) and three-
layers (C) catalyst structures, the highest catalyst loading is
maintained in the layer close to the membrane, and low
catalyst loading is kept in the layer near the GDL. The total
catalyst loading in the cathode is maintained at 0.35 mg/cm2.
Considering two layers at the cathode (B), the authors
observed that the graded catalyst cases present higher non-
uniformity than the uniform catalyst loading. The non-
uniformity significantly increases with the loading (B1 to B4)
at the CL/membrane interface. From Table 2, it can be seen
that the increase in the catalyst loading near the membrane
increases the ionomer fraction, whereas the void porosity
decreases. As presented in the table, the increasing catalyst
loading in the layer near the membrane yield improved
catalyst utilization and average current density in the mem-
brane. The catalyst utilization is calculated as the ratio of
catalyst loading to the cell output power. For instance, from B1
to B4, the catalyst utilization improved from 1.021 g/kW to
0.983 g/kW, and cell performance increased from 2.55% to
6.60% with respect to the uniform catalyst loading case. A
tradeoff between the decreasing proton and increasing oxy-
gen transport resistances is visible from the change in per-
formance from B1 to B4. A similar trend, i.e., increase in the
non-uniformity with the higher Pt loading near the mem-
brane, is observed with three-step layers in the cathode (C).
Interesting conclusions can be drawn by comparing the re-
sults of two and three-layer cathodes. Comparing B1 and C4,
where B1 has 60% (near the membrane) and 40% loadings for
each 1/2nd of CL thickness and C4 has 60% loading for 1/3rd of

Fig. 4 e Current density distribution (A/cm2) in the membrane for uniform Pt loading (A) and graded Pt loading across the
cathode CL thickness using two-step (B1eB4), three-step (C1eC5), and smooth gradient (D1-D5) layers at operating voltage of
0.3 V with a total Pt loading of 0.35 mg/cm.2.
 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 7 ( 2 0 2 2 ) 4 0 1 8 e4 0 3 2 4027

CL thickness (near the membrane) and a total of 40% loading
in the remaining 2/3rd of CL thickness, the change in perfor-
mance and catalyst utilization for B1 and C4 are 2.55% and
1.021 g/kW, and 6.05% and 0.988 g/kW, respectively. The re-
sults indicate that the maximum electrochemical reaction
occurs near the membrane only due to the reduced proton
transport resistance. However, further increasing the catalyst
loading near the membrane, i.e., 70% in the 1/3rd of CL
thickness (C5), significantly reduced the change in perfor-
mance and catalyst utilization, primarily due to the consid-
erable decrease in the void porosity, i.e., to 0.013, whereas the
uniformity in the current density is slightly improved.
In a multiple-step gradient or smooth gradient (D), the
catalyst density gradually decreases in the CL from near the
membrane region to the CL/GDL interface. The catalyst
loading may have a varying slope across the thickness of the
CL. The zero slope represents the uniform catalyst loading,
and loading will have a positive slope from the middle of CL
thickness to the CL/membrane interface and a negative slope
on the other side. Several patents discuss the preparation
method of graded catalyst structures in one-dimensional,
two-dimensional, and three-dimensional directions [46]. As
shown in the figure, the non-uniformity in the current
distribution gradually increases with an increase in the
gradient (D1 to D5), and cell performance and catalyst utili-
zation steadily improve with respect to the uniform catalyst
loading. The contours similar to Fig. 4 at cell voltage 0.6 V are
presented in Fig. 5. Similar observations are made for current
density distributions. However, the degree of non-uniformity
is comparatively less due to the reduced reactant consump-
tion at higher cell operating voltage and hence no scarcity of
reactant downstream.
The results illustrate the interplay between the catalyst
loading across the CL thickness and its consequences on
proton and oxygen transports. The higher catalyst loading
near the membrane consumes most of the oxygen upstream,
resulting in reduced concentration downstream. In the in-
plane direction (Y), the oxygen transportation limitations are
apparent under the rib region. As the applied potential on the
current collector is the same in every plane along the flow
direction, the electrode polarization shall gradually increase
along the flow direction resulting in reduced local current and
therefore uneven distribution of current density. Thus,
reducing reactant transportation limitation while retaining
optimal ionomer conductivity allows maximum utilization of
the catalyst sites for the electrochemical reactions.

Fig. 5 e Current density distribution (A/cm2) in the membrane for uniform Pt loading (A) and graded Pt loading across the
cathode CL thickness using two-step (B1eB4), three-step (C1eC5), and smooth gradients (D1-D5) layers at operating voltage
of 0.6 V with a total Pt loading of 0.35 mg/cm.2.
4028 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 7 ( 2 0 2 2 ) 4 0 1 8 e4 0 3 2

Grading along the cathode channel
It is known that providing more active catalyst sites in the
regions of reactant deficiency shall result in better unifor-
mity in the current distribution. When the intrinsic reaction
rate becomes slower than the gas transport rate, the sub-
stantial increase in the Pt gradient will benefit the uniformity
in the current density distribution. The optimal Pt gradient
should be a tradeoff between the gas transport rate and the
intrinsic reaction rate. Therefore, in the present study,
catalyst loading is increased (E) from the cathode inlet to the
outlet to stave off the effect of reactant depletion. Different
gradient (E1-E5) are simulated to optimize the catalyst
loading, and Case A represents the uniform catalyst loading,
i.e., zero slope. In addition, a set of simulations are also
performed with decreasing catalyst loading from the cathode
inlet to the outlet (F1eF5) to investigate its effect on the cell
performance. Fig. 6 presents the current distributions in the
membrane for the cells having uniform and gradient catalyst
loadings along the cathode flow at operating cell voltages
0.3 V (i) and 0.6 V (ii). Table 3 presents the catalyst utilization
and change in performance for the corresponding simula-
tions. With the decreasing catalyst loading towards the
outlet (F1eF5), the non-uniformity in current distribution is

Fig. 6 e Current density distribution (A/cm2) in the membrane for uniform Pt loading (A) and Pt loading graded along the
channel length with increasing (E1-E5) and decreasing (F1eF5) smooth gradients towards the outlet at operating voltages of
0.3 V (i) and 0.6 V (ii) with a total cathode Pt loading of 0.35 mg/cm.2.
 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 7 ( 2 0 2 2 ) 4 0 1 8 e4 0 3 2
significantly increased with an increase in the gradient due
to the combined effect of reduced active catalyst sites and
oxygen concentration in the downstream. As presented in
the table, expectedly, the change in performance has nega-
tive values, and catalyst utilization has deteriorated. An
interesting result is obtained by increasing the gradient to-
wards the outlet (E1-E5). The cells having higher catalyst
loading downstream shown a substantial uniformity in the
current distribution. As shown in the figure, the uniformity
improves with an increase in the gradient, which can be
attributed to two factors. First is, the increased availability of
reactants downstream due to reduced consumption in up-
stream, and second is the improved electrochemical activity
downstream. The optimization of the gradient is essential as
a high slope will significantly decrease the electrochemical
activity at the inlet, resulting in reduced local current density
(as presented in E5). By comparing the contours at 0.3 V and
0.6 V, the authors would like to convey that tailoring the
catalyst loading gradient based on the fuel cell application,
i.e., power requirement, will be beneficial in terms of current
distribution, cell performance, and durability.
To analyze the current distributions more accurately, the
corresponding overpotential distributions are presented in
Fig. 7 at an operating voltage of 0.3 V. The increase in the
overpotential towards the outlet in the cell having uniform
catalyst loading is primarily due to the oxygen depletion.
However, the cell having decreasing gradient (F1eF5) is due
to the combined effect of oxygen depletion and reduction in
the effective catalyst sites. With the increasing catalyst
loading towards the outlet (E1-E5), nearly uniform over-
potential distribution is observed due to the counter-effect of
Fig. 7 e Overpotential distribution (Volts) in the cathode CL for uniform Pt loading (A) and Pt loading graded along the
channel length with increasing (E1-E5) and decreasing (F1eF5) smooth gradients towards the outlet at operating voltage
0.3 V with a total cathode Pt loading of 0.35 mg/cm.2.
4029
the increase in the electrochemical activity for oxygen
depletion downstream.
Hybrid cathode CL
In the above studies, it is observed that gradient catalyst
loading along the CL thickness improves the cell performance
and catalyst utilization, however substantial increase in the
non-uniformity in current density distributions. Also, with an
increasing gradient along the reactant flow direction, the
performance and catalyst utilization deteriorated, but the
distribution's uniformity is greatly improved. Therefore, an
attempt is made to combine the benefits of two cathode
structure configurations called hybrid cathode CL. The cath-
ode CLs of two and three layers are used. The layer near the
membrane has an increasing Pt gradient along the reactant
flow direction, and the remaining layer(s) are uniformly
loaded along the path of flow. The contours of current and
overpotential distributions for the cells having uniformly
loaded CL (A), two-layers CL (B3), three-layers CL (C3), CL with
an increasing gradient along with the cathode flow (E3), and
hybrid CL structures (B3þE3 and C3þE3) at operating voltage
of 0.3 V are presented in Fig. 8. The average current density
values for the hybrid CL structures lie between the values for
the cases of gradient only along the CL thickness and flow
direction. It is also interesting to note the substantial
improvement in the current distribution with the hybrid CL
structures compared to the cells with the two and three-layers
CL configurations. There is no significant difference in the
average current density and distributions are observed be-
tween the two-hybrid structures, as shown in the figure. The
4030 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 7 ( 2 0 2 2 ) 4 0 1 8 e4 0 3 2
Fig. 8 e Current density (A/cm2) (i) and cathode overpotential (Volt) (ii) distributions for uniform (A), unidirectional gradient
(B3, C3, and E3), and hybrid CL structures at operating voltage 0.3 V with a total cathode Pt loading of 0.35 mg/cm.2.
corresponding distributions of cathode overpotential are
shown in Fig. 8 (ii).
Conclusion
The optimal catalyst distribution in the electrode has a sig-
nificant effect on the fuel cell performance and durability.
The objective of the present numerical study is to investigate
the impact of gradient cathode CL structures on HT-PEMFC
performance and distributions of current and over-
potential. Several simulation cases with catalyst gradient
across the CL thickness, along the cathode channel, and
simultaneous variation in the above directions are explored.
The simulation results with the graded CL along the thick-
ness show that the higher the catalyst loading near the
membrane better the performance, however uneven distri-
bution of current and overpotential. The results with two and
three CLs pronounce the importance of optimal catalyst
loading at the CL/membrane interface to avoid scarcity of
reactant due to the reduction in the void porosity. The
increasing catalyst gradient along the cathode flow direction
greatly improve the uniformity in the distributions due to the
higher active catalyst sites at the outlet, which in turn
counterbalances the effect of reactant deficiency. An inter-
esting result is obtained when the catalyst loading is graded
along the reactant flow direction in the layer near the
membrane and maintained constant loading in the other
layers. An improvement in both cell performance and uni-
formity in the distributions is observed. This study empha-
sizes the significance of gradient catalyst loading in HT-
PEMFC and its optimal distribution to improve cell perfor-
mance and durability.
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.
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Superscripts
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method for their production. 2010. WO 2010/051637 A1. chan: channel
e: electrolyte
H2: hydrogen
Nomenclature
H2O: water
i: species index
A: area, m2 in: channel inlet
C: molar concentration, mol m3 m: mass equation
D: mass diffusivity of species, m2 s1 mem: membrane
F: Faraday constant, 96,487, C mol1 N2: nitrogen
i: exchange current density, A m2 O2: oxygen
j: transfer current density, A m3 Pt: platinum
K: hydraulic permeability, m2 s: electron/solid phase
L: Loading 0: standard condition
MW: molecular weight, kg mol1