Journal of Energy Chemistry 81 (2023) 642–655

Contents lists available at ScienceDirect

Journal of Energy Chemistry

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

Fast design of catalyst layer with optimal electrical-thermal-water

performance for proton exchange membrane fuel cells
Jing Yao a, Yuchen Yang a, Xiongpo Hou a, Yikun Yang a, Fusheng Yang a, Zhen Wu a,⇑, Zaoxiao Zhang a,b
a
School of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an 710049, Shaanxi, China
b
State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, Shaanxi, China

a r t i c l e i n f o a b s t r a c t

Article history: The catalyst layer (CL) is the core component in determining the electrical-thermal-water performance
Received 30 December 2022 and cost of proton exchange membrane fuel cell (PEMFC). Systemic analysis and rapid prediction tools
Revised 12 February 2023 are required to improve the design efficiency of CL. In this study, a 3D multi-phase model integrated with
Accepted 22 February 2023
the multi-level agglomerate model for CL is developed to describe the heat and mass transfer processes
Available online 27 March 2023
inside PEMFC. Moreover, a research framework combining the response surface method (RSM) and arti-
ficial neural network (ANN) model is proposed to conduct a quantitative analysis, and further a rapid and
Keywords:
accurate prediction. With the help of this research framework, the effects of CL composition on the
Catalyst layer
Agglomerate model
electrical-thermal-water performance of PEMFC are investigated. The results show that the mass of plat-
Sensitivity analysis inum, the mass of carbon, and the volume fraction of dry ionomer has a significant impact on the
Response surface electrical-thermal-water performance. At the selected points, the sensitivity of the decision variables is
Artificial neural network ranked: volume fraction of dry ionomer > mass of platinum > mass of carbon > agglomerate radius. In
particular, the sensitivity of the volume fraction of dry ionomer is over 50% at these points. Besides,
the comparison results show that the ANN model could implement a more rapid and accurate prediction
than the RSM model based on the same sample set. This in-depth study is beneficial to provide feasible
guidance for high-performance CL design.
Ó 2023 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published
by ELSEVIER B.V. and Science Press. All rights reserved.

1. Introduction involves experiments and numerical simulations [9]. Owejan et al.

[10] investigated the impact of platinum loading and CL structure
Hydrogen energy is regarded as one of the most promising sec- on the PEMFC performance to reveal the transport limitation at the
ondary energy sources in the future due to its high heating value platinum surface by 12 experimental samples. Conde et al. [11]
and zero-emission [1]. As the preferred conversion device of studied experimentally the mass transport properties inside CL
hydrogen energy, fuel cells enable to convert the chemical energy through different characterization techniques. Admittedly, experi-
directly into electrical energy with the advantages of high energy mental studies present the objective facts, which are the founda-
conversion efficiency and low noise [2,3]. Among various kinds of tion of theory. Nevertheless, these studies also show that the
fuel cells, proton exchange membrane fuel cell (PEMFC) has been fabrication and test processes in experiments are complex and
paid much attention due to the mild operating conditions, fast expensive, thereby resulting in the limitation on the number of
start-up, high stability, and simple structure [4,5]. In recent years, experiments. By comparison, numerical simulation is the theoret-
the commercialization of PEMFC has made significant progress, ical summary based on the experimental results [12]. It helps to
especially in the automotive industry [6]. conduct trials at a low cost outside the scope of experiments.
In a PEMFC, membrane electrode assembly (MEA) is the core For numerical simulation, the selected model represents the
component, determining its performance and cost [7]. In particu- mathematical description of the practical physical problem. To
lar, catalyst layer (CL) with the precious platinum dispersed is of describe the CL in PEMFC, about three macro models, including
vital importance. Substantial investigations about CL have been the interface model, pseudo-homogeneous film model, and
conducted over the past 20 years [8]. The research method mainly agglomerate model, have been developed for different purposes
[13,14]. The interface model treats CL as an infinitely thin layer
⇑ Corresponding author. between membrane and gas diffusion layer (GDL). The structure
E-mail address: [email protected] (Z. Wu). of CL is ignored, and the reaction related source terms are set at

https://doi.org/10.1016/j.jechem.2023.02.049
2095-4956/Ó 2023 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.
J. Yao, Y. Yang, X. Hou et al. Journal of Energy Chemistry 81 (2023) 642–655

the interface [15]. This model is often used for current density dis- to conduct a rapid prediction for complex non-linear systems
tribution or water balance. In the pseudo-homogeneous film [27]. Herein, the combination of RSM and ANN model is considered
model, CL is assumed to be a homogeneous porous media. The to carry out a systemic analysis of CL composition and a rapid pre-
electrochemical reaction occurs on the surface of porous media. diction of cell performance based on the same sample set. Based on
The corresponding parameters, such as the specific area and poros- this research framework, the effects of CL composition on the
ity, are always considered as constants. Based on this model, the electrical-thermal-water performance are investigated. This
reaction distribution and species transport in CL could be research framework provides a novel idea for the high-efficiency
described. However, the pseudo-homogeneous film model is rela- utilization of the generated data and a fast design of CL. To the
tively rough, especially for the description of mass transport resis- authors’ knowledge, this research framework has not been
tance under high current density [16]. In order to determine the reported to analyze CL composition in the previous literature.
parameters and characterize the species transport inside CL better, The novelty of this work could be summarized as follows: (1) A
the agglomerate model is further developed. This model concen- multi-level agglomerate model is integrated into 3D non-
trates on the oxygen transport between the pores and the agglom- isothermal model of PEMFC to analyze CL; (2) A research frame-
erates, thus providing a more detailed description of CL [17]. work combining RSM and ANN model is proposed to conduct a
Meanwhile, the parameters inside CL could be calculated according quantitative analysis, and further a rapid and accurate prediction;
to their empirical relationship with the actual composition. Previ- (3) Quantitative relationship between CL composition and
ous studies have shown that the agglomerate model is able to pro- electrical-thermal-water performance is established through the
vide a better fit to experimental data [18,19]. Therefore, in this research framework.
study, a 3D multi-phase CFD model integrated with a multi-level
agglomerate model for CL is developed to describe the species
2. Electrical-thermal-water performance of PEMFC
transport behaviors and electrochemical reaction process inside
PEMFC.
A typical PEMFC is composed of the bipolar plane, gas diffusion
Based on the accurate agglomerate model, detailed analysis
layer (GDL), catalyst layer (CL), and membrane, as shown in Fig. 1.
should be performed to test model coverage and to put forward
The fluid channel is engraved in the bipolar plane, which is used for
guidelines for CL design. Moein-Jahromi et al. [20] conducted a
gas delivery. The solid part of the bipolar plane is served as a cur-
comparison of the predicted current density from both the
rent collector. In addition, the GDL, CL, and membrane form the
homogenous model and the agglomerate model. It was found that
MEA [28].
when agglomerate size is reduced to zero, the homogenous model
The gas phase in the fluid channel is first diffused to CL through
is retrieved. Besides, a simple sensitivity analysis of the structural
GDL. Then, at the anode, hydrogen gas is oxidized to protons in CL,
parameters in CL was performed through parametric analysis. The
as shown in Eq. (1). The generated protons are transferred from the
agglomerate sizes (including agglomerate radius and agglomerate
anode to the cathode under electric force, passing through the
thickness) are the most influential parameters on the cell perfor-
membrane [29]. At the cathode, oxygen gas is reduced and then
mance. These conclusions are also obtained by Xing et al. [21]. Sub-
combined with protons to generate water, as seen in Eq. (2). The
sequently, Hu et al. [22] developed a 1D steady-state model to
reaction process at the cathode CL could become the rate-
comprehensively study the effects of the structural and operating
determining step of the electrochemical reaction. On the one hand,
parameters on the cell performance. The trend of performance
the sluggish kinetics of oxygen reduction has been proven to be the
variation with various parameters could be obtained. Recently,
dominant factor of the reaction rate [30]. On the other hand, the
Carcadea et al. [23] performed a parametric study of CL composi-
generated liquid water and heat at the cathode CL have significant
tion and properties with a 3D model of 5 cm2 PEMFC. An optimal
impacts on the cell performance [31].
range of 45%
55% for ionomer volume fraction was concluded.
- þ
Similarly, He et al. [24] conducted a parametric analysis of CL H2 - 2e ! 2H ð1Þ
design parameters with improved electrochemical reaction kinet-
- þ
ics. The best platinum loading of around 0.2 mg Pt/cm2 was found O2 þ 4e þ 4H ! 2H2 O ð2Þ
for CL in the cathode. According to these studies, the analysis pro-
Liquid water in PEMFC has significant impacts on the species
cess of CL parameters based on the agglomerate model is not
transport, thus affecting the output performance. In addition, the
exhaustive. First, most of these studies concentrate on the electri-
electrochemical reaction is exothermic, and temperature is related
cal performance only, thus other performance indexes may be just
to electrochemical activity and structural stability. Therefore, the
presented qualitatively. Secondly, parametric analysis is the main
electrical-thermal-water performance of PEMFC is investigated in
research method, which could not present the quantitative rela-
this work.
tionship between parameters. Thirdly, this method could not be
used for a rapid prediction, which could become an issue, espe-
cially when a long computing time is necessary for a 3D model. 3. Model development
Fourthly, it is difficult to provide interfaces for future research
work, such as multi-objective optimization. This is because these In this study, a 3D non-isothermal multi-phase model of PEMFC
calculated cases are not included in a complete research frame- is developed to describe the heat and mass transfer processes and
work, which results in the generated data being unable to be con- obtain the electrical-thermal-water performance.
solidated to play a more important role. Therefore, more systemic To simplify the calculation, the following assumptions are
analysis and rapid prediction are required to improve the design made:
efficiency of CL.
In this study, a research framework combining the response (1) The PEMFC is operated in a steady state;
surface method (RSM) and artificial neural network (ANN) model (2) The effects of gravity on the fluid flow are negligible;
is proposed to conduct a quantitative analysis, and further a rapid (3) The gas phase is in the laminar flow state due to the low
and accurate prediction. RSM is a statistical method commonly velocity [32];
used to obtain regression equations for multivariate problems, (4) The gases at the anode and cathode are treated as ideal gas
which has been introduced to analyze the operating parameters due to the relatively low pressure and temperature;
of PEMFC [25,26]. Besides, ANN model has also been developed (5) The liquid water is assumed to be in the mist state;
643
J. Yao, Y. Yang, X. Hou et al. Journal of Energy Chemistry 81 (2023) 642–655

Fig. 1. The species transport and electrochemical reaction process in PEMFC.

(6) The porous media including GDL and CL are considered to be alyst (always precious platinum), carbon particles (as a conductive
homogenous [33]; substrate), ionomer for proton conduction, and pores. In the
(7) The membrane is impermeable to gas phase and electrons, agglomerate model, each agglomerate could be viewed as a cluster
while it is permeable to dissolved water and protons [34]; of carbon particles with catalyst dispersed on the surface. These
(8) The water generated by the electrochemical reaction at the agglomerates are coated with a thin ionomer film and connected
cathode is assumed to be in the form of dissolved water [35]. by ionomer network.
With regard to the design of CL, the mass of the main composi-
3.1. Governing equations tion is usually known, written as mPt , mC , and mIonomer , respectively.
In addition, the thickness of CL is assumed to be constant in this
This model of PEMFC mainly includes 12 equations, as summa- paper.
rized in Table 1. All these equations could be written as the general At the macro level, the sum of the volume fraction of each part
form of the equation shown in Eq. (3). The corresponding terms for is equal to 1.0, expressed as Eq. (4).
these equations have been presented in our previous paper [36].
LIonomer þ LPt=C þ LGDL þ eCL ¼ 1 ð4Þ
@ !
ðquÞ þ r  ðq u uÞ ¼ r  ðCruÞ þ Su ð3Þ The volume fraction of the dry ionomer is expressed as Eq. (5).
@t
Moreover, the volume expansion of the ionomer due to water
uptake is also taken into account in this model, written as Eq. (6).
3.2. Multi-level agglomerate model
mIonomer
LIonomer;dry ¼ ð5Þ
In this paper, spherical agglomerate structure is employed to qIonomer dCL
describe the microscopic structure and species transport process
inside CL, as shown in Fig. 2. The CL mainly includes four parts: cat- LIonomer ¼ ð1 þ kswe kÞLIonomer;dry ð6Þ

Table 1
Governing equations for the PEMFC model.

Equation Expression
Mass conservation equation @ðeqg Þ !
@t þ r  ðqg u g Þ ¼ Sm
Momentum conservation equation ! !!
@ qg u g qg u g u g l ! !T !
@t ð e Þ þ r  ð e2 Þ ¼ rP g þ r  ð eg ððr u g þ r u g Þ  23 r  u g ÞÞ þ Su
Species transport equation (for H2, O2, and H2O) @ðeqg wi Þ !
@t þ r  ðqg u g wi Þ ¼ r  ðqg Di rwi Þ þ Si
eff

!
Energy conservation equation @
eqg C p;g þ ð1  eÞqs C p;s ÞTÞ þ r  ðu g qg C p;g TÞ ¼ r  ðkeff
@t ðð T rTÞ þ ST
Electronic charge conservation equation 0 ¼ r  ðrele r/ele Þ þ Sele
Ionic charge conservation equation 0 ¼ r  ðrion r/ion Þ þ Sion
Dissolved water transport equation qmem @ðxkÞ qmem
@t þ r  ðnd Jion
F Þ ¼ EW r  ðDd rkÞ þ Sd;w
eff
EW


Liquid water transport equation @
@t ðeql sÞ þ r  f ðsÞql !
u ¼ r  ðql Dl rsÞ þ Sl;w

644
J. Yao, Y. Yang, X. Hou et al. Journal of Energy Chemistry 81 (2023) 642–655

Fig. 2. The schematic diagram of spherical agglomerate structure.


The volume fraction of platinum dispersed carbon is expressed as 3 2
Area ¼ 227:79f  158:57f  201:53f þ 159:5  103 ð14Þ
Eq. (7). Generally, platinum mass ratio, f , is defined as Eq. (8).
Therefore, by substituting Eq. (8) into Eq. (7), the volume fraction Substituting Eq. (12) into Eq. (13), the specific area of CL could
of platinum dispersed carbon could be also written as Eq. (9). be written as Eq. (15).
 
1 mPt mC mPt Area ð1  eCL Þ
LPt=C ¼ þ ð7Þ aagg ¼ ð15Þ
dCL qPt qC dCL LPt=C

mPt Besides, the volume fraction of the primary pores occupied by

f ¼ ð8Þ the ionomer is defined as BM. The thickness of ionomer film cover-
mPt þ mC
ing the agglomerate is given as Eq. (16).
 
mPt 1 1f 1 sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi !
LPt=C ¼ þ ð9Þ 3 ð1  eCL Þð1  eCL  LGDL Þ þ LPt=C eCL ð1  BM Þ
dCL qPt f qC dIonomer ¼ r agg 1
LPt=C
According to Eqs. (4–9), the porosity of CL could be obtained, as
seen in Eq. (10). ð16Þ

eCL ¼ 1  LIonomer  LPt=C  LGDL ð10Þ Furthermore, all the generated liquid water is assumed to cover
the surface of agglomerates considering the hydrophobicity of
At the micro level, the pores inside CL could be further divided into ionomer [40]. The thickness of liquid water coating is given as
primary pores (in the agglomerates) and secondary pores (between Eq. (17).
the agglomerates), expressed as Eq. (11) [37]. sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
3  3 seCL ð1  eCL Þr3agg  
eCL ¼ epri þ esec ð11Þ dw ¼ r agg þ dIonomer þ  r agg þ dIonomer ð17Þ
LPt=C
For simplicity, the porosity of agglomerate (before filled with
ionomer) is assumed to be approximately equal to the porosity The detailed derivation process in this part could be referred to in
of CL [38]. Based on this assumption, the agglomerate density Ref. [38].
(i.e., number of agglomerates per unit volume of CL) is expressed
as Eq. (12). 3.3. Electrochemical reaction kinetics
3LPt=C
Nagg ¼ ð12Þ
4ð1  eCL Þpr3agg At the anode, the electrochemical reaction kinetics is given as
Butler-Volmer equation, expressed in Eq. (18).
The specific area of these agglomerates without liquid water
coating could be written as Eq. (13). !0:5     
ref P H2 ð1  aa ÞF ga aa F ga
3mPt Area ia ¼ aagg ia exp  exp
aagg ¼ ð13Þ cref
H2 H H2
RT RT
4pdCL Nagg r 3agg
ð18Þ
where Area denotes reaction area per unit platinum mass, as
ref
expressed in Eq. (14) [39]. where ia denotes reference exchange current density.
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J. Yao, Y. Yang, X. Hou et al. Journal of Energy Chemistry 81 (2023) 642–655

At the cathode, the electrochemical reaction kinetics is obtained Table 2

by the agglomerate model, which considers the oxygen transport The involved parameters in the developed model.

inside agglomerates [41]. First of all, the oxygen concentration at Parameter Value
the interface between gas phase and liquid water film is defined Boundary temperature 343.15 K
as cO2 ;gjw , and that in the agglomerates is defined as cO2 ;agg . The dis- Relative humidity at the inlet 100%
solved oxygen concentration, cO2 ;gjw could be obtained by Eq. (19). Operating pressure 1 atm
Stoichiometry ratio at anode and cathode 3.5/2.6
cO2 ;agg is viewed as the oxygen concentration actually participating
Conductivity of CL/GDL 450/1250 S/m
in the electrochemical reaction. Density of ionomer 2000 kg/m3
Equivalent weight of ionomer 1.1 kg/mol
P O2
cO2 ;gjw ¼ ð19Þ Membrane swelling coefficient 0.0126
HO2 Volume fraction of GDL penetration 0.06
Reference exchange current density at anode 10 A/m2
Then, from the perspective of oxygen diffusion, the oxygen trans- Reference hydrogen concentration and oxygen 56.4/3.39 mol/m3
port process at a certain section in the ionomer/liquid water film concentration
is expressed as Eq. (20). As a consequence, the oxygen flux through Henry’s constant of hydrogen 4.56  103 Pa
the spherical ionomer/liquid water film could be written as Eq. (21). m3/mol
Charge transfer coefficient at anode and cathode 0.5/0.95
Also, Eq. (21) could be reduced to Eq. (22). Herein, the liquid water Density of platinum 2.14  104 kg/m3
and ionomer film are considered to cover the agglomerates evenly. Density of carbon 1800 kg/m3

@cO2
RO2 ¼ DO2 ð20Þ
@r
3.4. Model implementation and validation
 
cO2 ;gjw  cO2 ;agg
RO2 ¼ aagg
  2 ð21Þ This computational fluid dynamics (CFD) model is solved by
1
4pDO
1
r agg
 dþr1agg 4p d þ r agg
2 software Fluent (ANASY Inc., USA). The basic equations have been
  built in the software, while other equations are defined by UDF
r agg cO2 ;gjw  cO2 ;agg (user defined function). Velocity boundaries are applied at the inlet
RO2 ¼ aagg DO2  
r agg þ d d of anode and cathode, while pressure boundaries are set at the out-
cragg   let. At the end of current collectors, constant temperature and
¼  cO2 ;gjw  cO2 ;agg ð22Þ potential are applied. A structured grid is used for the spatial dis-
ragg þ d
cretization of the computational domain. The verification of grid
where c is the oxygen diffusion rate through the ionomer/liquid independence has been conducted in the previous paper [36].
water film. The element number is 182000, and the computing time of each
Next, this process could be also illustrated from the perspective case achieves about 2 h with 6 compute cores.
of reaction. The electrochemical reaction rate at the cathode has Moreover, a comprehensive model validation is performed
been observed to follow first-order kinetics with respect to the under various operating conditions, as seen in Fig. 3(a and b). In
oxygen concentration [42]. Therefore, the oxygen consumption Fig. 3(a), the simulation is conducted under different temperatures
rate is written as Eq. (23). and different stoichiometry ratios with a cell length of 10 cm. In
Fig. 3(b), different pressures are applied for PEMFC with a cell
R0O2 ¼ Eagg kagg cO2 ;agg ð23Þ
length of 5 cm. The geometry parameters and operating conditions
where Eagg denotes the effectiveness factor of the agglomerate; kagg are consistent with those in the experiments. The humidification
denotes the reaction rate coefficient, written as Eq. (24). temperature at the inlet is the same as the operating temperature.
Besides, the relative humidity is set to 100%. The results show that
ref     
aagg ic ac F gc ð1  ac ÞF gc the simulation results have good agreement with the experiment
kagg ¼ ref
exp  exp ð24Þ
4F cO2 RT RT data, indicating the reliability and accuracy of the developed CFD
model. Besides, a base case is selected for the following study
Finally, according to the mass conservation of oxygen, the oxy- based on the experiment data from Ref. [43], as shown in Fig. 3(c
gen flux induced by diffusion effect is equal to the oxygen con- and d). It is found that both the current density and power density
sumption rate, as expressed in Eq. (25). obtained from the model agree well with the experiment data.
RO2 ¼ R0O2 ð25Þ
4. Analysis process
Thus, the oxygen concentration cO2 ;agg in the agglomerates could be
obtained, as written in Eq. (26). Correspondingly, the oxygen con-
To conduct quantitative analysis and accurate prediction, a
sumption rate is presented in Eq. (27).
research framework combining the response surface method
cragg
cO2 ;agg ¼  c ð26Þ (RSM) and artificial neural network (ANN) model is proposed in
cragg þ Eagg kagg ragg þ d O2 ;gjw this work, as shown in Fig. 4. This framework is able to take the
 1 advantage of each part to achieve the high-efficiency utilization
1 r agg þ d
RO2 ¼ þ cO2 ;gjw ð27Þ of the generated data.
Eagg kagg cragg In Fig. 4, first, the decision variables should be selected. After
In summary, the electrochemical reaction kinetics at the cathode is that, the central composite design (CCD) method is employed to
written as Eq. (28). determine the parameter combinations. The corresponding results
 1 of these parameter combinations could be obtained by CFD simu-
P O2 1 r agg þ d
ic ¼ 4FRO2 ¼ 4F þ ð28Þ lation or experiment, thereby generating a sample set. Then, fol-
H O2 Eagg kagg cragg lowing the steps of RSM, a quadric surface is derived and could
The relevant derivation process in this part could be found in Ref. be used to perform a quantitative analysis and a relatively rough
[42] for more details. The involved parameters in the model are prediction. Afterward, the sample set also enables to train an
listed in Table 2. ANN model to achieve a rapid and accurate prediction. Finally, a
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J. Yao, Y. Yang, X. Hou et al. Journal of Energy Chemistry 81 (2023) 642–655

Fig. 3. Model validation under different operating conditions: (a) at a temperature of 335.15 K, stoichiometry ratio of 1 and a temperature of 343.15 K, stoichiometry ratio of
2 [44,45]; (b) at the pressure of 1 and 3 atm [46–48]. The selected base case for the following study: (c) voltage-current density curve; (d) power density–current density
curve [43].

Fig. 4. The research framework combining RSM and ANN model.

comparative analysis between RSM and ANN models could be con- Therefore, through the combination of RSM and ANN model, the
ducted to increase the fault tolerance. It should be noted that the framework could be used to improve the analysis and prediction
ANN model is a black box, resulting in difficulties in the analysis. efficiency.

647
J. Yao, Y. Yang, X. Hou et al. Journal of Energy Chemistry 81 (2023) 642–655

4.1. Sensitivity analysis by RSM prediction could be possible, as shown in Fig. 5(a). Compared with
other strong classifiers, ANN has the advantages of simple opera-
As shown in Fig. 4, RSM mainly includes five steps: (1) selecting tion and good reliability, which is beneficial to the application of
the decision variables for analysis; (2) determining the parameter the proposed research framework. To train an ANN model, five
combinations; (3) generating a sample set; (4) establishing the steps are mainly included: (1) obtaining the input samples; (2)
response surface; (5) sensitivity analysis based on the multivariate determining the network size and training method; (3) training
quadratic regression equation. These steps are performed by soft- an ANN model; (4) validating the model; (5) predicting the results.
ware Design-Expert. As depicted in Fig. 5(b), a back propagation ANN model is devel-
As mentioned above, the catalyst layer in PEMFC mainly oped by software MATLAB in this work. In this model, 60 samples
includes three components: platinum (catalyst), carbon, and iono- generated by RSM are used to train the ANN model. The output
mer. Besides, the agglomerate radius is also involved in the fixed variables include current density, maximum temperature, and
structure of the catalyst layer. These parameters are significant to mass flow rate of liquid water. In the second step, the number of
determine the electrochemical reaction. Therefore, the CL composi- hidden neurons is first estimated by the empirical formula [49],
tion parameters, including the mass of platinum, the mass of car- as seen in Eq. (31). Then, the final size is determined by trials. As
bon, the volume fraction of dry ionomer, and the agglomerate a result, three neurons are set in the hidden layer to avoid the
radius, are selected as the decision variables in this work. The cor- over-fitting problem. Meanwhile, the model is also verified by 5-
responding parameter range is listed in Table 3. fold cross validation. As shown in Fig. S2, the average relative error
The parameter combination design is significant to reduce the during the validation is within the small range of 0.1%-1%. In addi-
number of trials. If the conventional single variable method is used, tion, the tansig function is used as the active function of the hidden
1024 trials are required for 4 variables (each variable has 5 levels). layer, and the purelin function is used as the active function of the
For RSM, Box-Behnken design (BBD) method and central composite output layer in this fully connected ANN model. Bayesian Regular-
design (CCD) method are generally used. The selected parameter ization algorithm is selected as the training method. During the
combinations of both methods are illustrated in Fig. S1. For BBD training, the maximum epochs are set as 10000.
method, each parameter is divided into 3 levels, while that is
divided into 5 levels for CCD method. Herein, CCD method is Nhid 6 N train =½R þ ðNin þ Nout Þ ð31Þ
employed for sample generation, considering that this method
Where N train denotes the sample size; 5R  10.
helps to cover a wide range. Besides, the selected parameter com-
binations are close to the center point for CCD method. The param-
eter combinations generated by CCD method are listed in Table S1. 5. Results and discussion
Each combination is repeated twice to reduce the error and to pro-
vide a little more data for the following ANN model. 5.1. Response surface for current density
The response values of these parameter combinations are calcu-
lated by the CFD model mentioned above. The current density, Based on the sample set, each response variable could generate
maximum temperature, and mass flow rate of liquid water are cal- a quadratic response surface through the analysis of variance
culated to represent the electrical-thermal-water performance, i.e., (ANOVA). For current density, the ANOVA of the quadratic
used as response variables. Based on the generated samples, the response surface is presented in Table S2. In this table, p-value rep-
response surface is able to be established. The corresponding mul- resents the probability of seeing the observed F-value. Generally,
tivariate quadratic regression equation is expressed as Eq. (29). p-values of less than 0.05 indicate that the model terms are signif-
X
n X
n X
n X
n icant, while the values of greater than 0.1 indicate that the model
Y ¼ b0 þ bi X i þ bij X i X j þ bii X 2ii ð29Þ terms are not significant. Therefore, A-A, B-B, C–C, AB, and A2 have
i¼1 i¼1 i–j i¼1 an important impact on the response surface of current density. On
the whole, most of these terms involve mass of platinum and mass
Where b denotes the coefficients obtained by the least square
of carbon, probably because the two variables determine the num-
method; X is the decision variables; Y is the fitted response value.
ber of reactive sites together.
The sensitivity of each decision variable is defined as the ratio of
The variation of externally studentized residuals with run order
the partial derivative of each response value to the sum of the par-
is presented in Fig. 6(a). The data in this graph should be in a ran-
tial derivative of each response value, as shown in Eq. (30).
dom state to exclude the effects of time-related variables. Fig. 6(b)
j@Y=@X i j shows the comparison between actual current density and pre-
I X i ¼ Pn ð30Þ
j¼1 @Y=@X j
dicted current density, indicating the good fitting ability of this
response surface. The correlation coefficient R2, which is usually
used to represent the fit degree, is calculated to be 0.9766.
4.2. Prediction by ANN model The obtained multivariate quadratic regression equation for
current density is shown in Eq. (32). Besides, the cell performance
ANN model is generally developed to establish the mapping near the center point (0.3, 0.6, 0.3, and 0.7) is always concerned
relation between input and output, especially for non-linear sys- because it is the most commonly used. Hence, the equation at
tems. With the help of the mapping relation, the rapid and accurate the center point is plotted in Fig. 7. The maximum current density

Table 3
The selected decision variables and the corresponding range.

Parameter Symbol Variable Level-1 Level-2 Level-3 Level-4 Level-5

(Code: 2) (Code: 1) (Code: 0) (Code: 1) (Code: 2)
Mass of platinum (mg/cm2) mPt A 0.1 0.2 0.3 0.4 0.5
Mass of carbon (mg/cm2) mC B 0.4 0.5 0.6 0.7 0.8
Volume fraction of dry ionomer LIonomer;dry C 0.2 0.25 0.3 0.35 0.4
Agglomerate radius (lm) r agg D 0.3 0.5 0.7 0.9 1.1

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J. Yao, Y. Yang, X. Hou et al. Journal of Energy Chemistry 81 (2023) 642–655

Fig. 5. (a) The schematic diagram of the mapping relation between input and output in the ANN model; (b) the developed back propagation ANN model by MATLAB.

Fig. 6. (a) The variation of externally studentized residuals with run order; (b) the comparison between actual current density and predicted current density.

achieves 0.766 A/cm2, and the minimum current density is 0.489 of carbon (e.g., 0.8 mg C/cm2), the current density is raised with
A/cm2, both of which appear in Fig. 7(b). the increase of mass of platinum. However, it is worth noting that

Current density ¼ 0:224576 þ 0:982823  mPt þ 0:081042  mC þ 1:04744  LIonomer;dry

0:022062  r agg þ 0:808750  mPt  mC  0:066250  mPt  LIonomer;dry þ 0:000312  mPt  r agg
ð32Þ
0:452500  mC  LIonomer;dry þ 0:002500  mC  r agg  0:024375  LIonomer;dry  r agg  1:74521  m2Pt
0:116458  m2C  0:383333  L2Ionomer;dry þ 0:017448  r2agg

From Fig. 7(a), under a low mass of carbon (e.g., 0.4 mg C/cm2), the the rate of increase slows down and even goes backwards under
current density is increased first and then slightly decreased with high mass of platinum. Besides Fig. 7(a), the first increasing and
the increasing mass of platinum. Meanwhile, under a high mass then decreasing tendency of current density with the increasing

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J. Yao, Y. Yang, X. Hou et al. Journal of Energy Chemistry 81 (2023) 642–655

Fig. 7. The response surface at the center point for current density: (a) interaction between the mass of platinum and mass of carbon; (b) interaction between the mass of
platinum and volume fraction of dry ionomer; (c) interaction between the mass of platinum and agglomerate radius; (d) interaction between the mass of carbon and volume
fraction of dry ionomer; (e) interaction between the mass of carbon and agglomerate radius; (f) interaction between the volume fraction of dry ionomer and agglomerate
radius.

mass of platinum is also shown in Fig. 7(b and c), less depending on According to the theoretical calculation, when f is lower than about
other decision variables. Considering the high density of platinum, 0.48, the specific area has an uptrend with the increasing mass of
the mass of platinum mainly has a significant effect on the specific platinum. This is because the increasing mass of platinum raises
area of CL through the auxiliary variable, platinum mass ratio f . the triple-phase boundary inside CL. However, increasing the mass

Fig. 8. The oxygen fraction distribution under different cases.

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J. Yao, Y. Yang, X. Hou et al. Journal of Energy Chemistry 81 (2023) 642–655

of platinum continuously, the specific area of CL is slightly that at the low volume fraction of dry ionomer due to the worse
decreased instead. This is probably because of the notable aggrega- oxygen transport.
tion of platinum particles. Nevertheless, from Fig. 7(a), the mass of From Fig. 7(c), agglomerate radius within this range has little
platinum corresponding to peak performance is different under var- effect on the current density. This phenomenon could also be seen
ious mass of carbon. It becomes larger with the increase of mass of in Fig. 7(f). The weak effect of agglomerate radius on the current
carbon. As a result, the decreasing tendency is not observed within density is mainly presented in Fig. 7(e) where the current density
the range of 0.1–0.5 mg Pt/cm2 under high mass of carbon. In this has a small variation. It is found that the middle agglomerate
case, the specific area of CL steadily increases with the increasing radius could result in the minimum current density. Under
mass of platinum. As seen in Fig. 8, case 46 and case 7 are per- 0.6 mg C/cm2, the maximum current density achieves 0.700 A/
formed under the different masses of platinum. At a high mass of cm2, while the minimum value is 0.696 A/cm2, decreasing by only
platinum, the oxygen consumption rate is obviously faster than that 0.57%. The agglomerate radius is relevant to the thickness of iono-
at a low mass of platinum. Therefore, the oxygen mole fraction at mer film and liquid water film in the CFD model. That’s to say, the
the outlet of PEMFC for 0.5 mg Pt/cm2 is about 0.115, which is lower variation of agglomerate radius within the range 0.3–1.1 lm
than that (about 0.125) for 0.1 mg Pt/cm2. slightly changes the thickness of ionomer film and liquid water
Under a high mass of platinum (e.g., 0.5 mg Pt/cm2), the current film, thus affecting the oxygen transport with small degree.
density is raised with the increasing mass of carbon, as seen in From the analysis mentioned above, the mass of platinum, mass
Fig. 7(a). By contrast, it is found that under a low mass of platinum of carbon, and volume fraction of dry ionomer, are the significant
(e.g., 0.1 mg Pt/cm2), the current density is decreased as increasing decision variables. The interaction between the mass of platinum
the mass of carbon. For the former, the specific area of CL only has a and mass of carbon is significant and complex, while others are rel-
minor variation within the 0.4–0.8 mg C/cm2. Hence, the specific atively independent. To maintain the high current density, the
area of CL could not be the main reason for the increasing current mass of platinum should be around 0.4 mg/cm2. In this situation,
density. From Fig. 8, the oxygen mole fraction distribution for the increasing mass of carbon and volume fraction of dry ionomer also
different masses of carbon (case 44 and case 5) is also quite similar. helps to reduce the oxygen transport resistance in the agglomer-
Nevertheless, the presented oxygen mole fraction distribution only ates and proton transport resistance, and thus raise the current
shows the oxygen transport in the secondary pores. Therefore, the density. Nevertheless, this conclusion simply illustrates the effects
oxygen transport in the agglomerates should be paid more atten- of a single decision variable. In practical situations, the coupling
tion to. In fact, the high mass of carbon raises the agglomerate den- effects of these variables on the electrical performance should be
sity, resulting in the thin ionomer film and liquid water film on the further considered.
agglomerate surface. For this reason, the oxygen transport resis-
tance in the agglomerate is decreased. The high oxygen concentra- 5.2. Response surface for other variables
tion in the agglomerate contributes to the high current density
under high mass of carbon. For the latter, when the mass of plat- The response surfaces for maximum temperature and mass flow
inum is low, the significant reduction of f , which reduces the speci- rate of liquid water are quite similar to that for current density.
fic area of CL, still dominates the decrease of current density. These three variables are positively correlated. The multivariate
As shown in Fig. 7(b), the current density is increased with the quadratic regression equation for maximum temperature is
volume fraction of dry ionomer raised regardless of the mass of expressed as Eq. (33), plotted in Fig. 9. Through the ANOVA, the
platinum. The uptrend of current density with the increasing vol- correlation coefficient R2, is calculated to be 0.9760 for maximum
ume fraction of dry ionomer is also seen in Fig. 7(d and f). The vol- temperature. The maximum temperature value is 345.88 K in the
ume fraction of dry ionomer mainly affects the porosity of CL, the range of calculation. Compared with boundary conditions, the tem-
transport of oxygen in the agglomerates, and the transport of pro- perature inside PEMFC only has a small increase, about 2.5 K.

Max:temperature ¼ 344:23015 þ 3:17651  mPt þ 0:131302  mC þ 3:02156  LIonomer;dry

0:137161  r agg þ 2:75313  mPt  mC  0:006250  mPt  LIonomer;dry þ 0:001563  mPt  r agg
ð33Þ
1:58125  mC  LIonomer;dry þ 0:020313  mC  r agg  0:040625  LIonomer;dry  r agg
5:81094  m2Pt  0:292187  m2C  0:643750  L2Ionomer;dry þ 0:087891  r 2agg

ton. The high volume fraction of dry ionomer could lead to low The temperature distribution under different cases is presented in
porosity of CL and thick ionomer film on the agglomerate surface. Fig. 10. The temperature in the porous media is significantly higher
In other words, the high volume fraction of dry ionomer has an than that in the channel and current collector owing to the low
adverse effect on the oxygen transport in the secondary pores thermal conductivity of porous media. Moreover, the temperature
and agglomerates. Therefore, the increase of current density with at the cathode is higher than that at the anode, which conforms
the increasing volume fraction of dry ionomer is mainly caused to the thermodynamics of electrochemical reaction. Besides, along
by the reduction of proton transport resistance. The proton trans- the direction of fluid flow, the temperature in PEMFC is increased
port is viewed as the dominant factor for electrical performance gradually and diffused from porous media to channel. Therefore,
because of the low conductivity of the ionomer. The oxygen mole the maximum temperature appears in the porous media close to
fraction distribution for different volume fractions of dry ionomer the outlet of PEMFC. The small temperature increase should be
(case 25 and case 17) is presented in Fig. 8. The oxygen concentra- attributed to the high thermal conductivity of current collector. In
tion in CL at the high volume fraction of dry ionomer is lower than fact, the heat source at the cathode achieves 3.0e8 W/m3, and that

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J. Yao, Y. Yang, X. Hou et al. Journal of Energy Chemistry 81 (2023) 642–655

Fig. 9. The response surface at the center point for maximum temperature: (a) interaction between the mass of platinum and mass of carbon; (b) interaction between the
mass of platinum and volume fraction of dry ionomer; (c) interaction between the mass of platinum and agglomerate radius; (d) interaction between the mass of carbon and
volume fraction of dry ionomer; (e) interaction between the mass of carbon and agglomerate radius; (f) interaction between the volume fraction of dry ionomer and
agglomerate radius.

Fig. 10. The temperature distribution in PEMFC under different cases.

at the anode is 7e7 W/m3. As a result, the heat source generated For the mass flow rate of liquid water, the multivariate quadra-
by electrochemical reaction is about 2.3e8 W/m3, which is quite tic regression equation is written as Eq. (34). According to the
large. The heat could be removed from both the outlet and the cur- ANOVA, the correlation coefficient R2, is calculated to be 0.9767
rent collector. According to the results, about 80% of the heat is for the mass flow rate of liquid water. The corresponding response
removed from the current collector at both the anode and cathode. surface at the center point is plotted in Fig. S3. It is found that the

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J. Yao, Y. Yang, X. Hou et al. Journal of Energy Chemistry 81 (2023) 642–655

mass flow rate of liquid water for this geometry is within the range 5.3. Sensitivity analysis
of 2.0e-6–3.5e-6 kg/s.
Based on the RSM mentioned above, sensitivity analysis is per-
formed to determine the importance of decision variables quanti-

Liquid water ¼ 9:05386e  7 þ 4:51844e  6  mPt þ 3:67568e  7  mC þ 4:81176e  6  LIonomer;dry

1:01523e  7  ragg þ 3:71406e  6  mPt  mC  3:26875e  7  mPt  LIonomer;dry
þ7:81250e  10  mPt  ragg  2:07187e  6  mC  LIonomer;dry þ 8:90625e  9  mC  r agg ð34Þ
1:10937e  7  LIonomer;dry  r agg  8:00891e  6  m2Pt  5:33906e  7  m2C
1:77562e  6  L2Ionomer;dry þ 8:12109e  8  r 2agg

The liquid water is mainly generated in CL at the cathode. The tatively, as seen in Fig. 11. At the center point, volume fraction of
transport of water inside PEMFC is a complex multi-phase process. dry ionomer has the most prominent effect on the response vari-
For example, the vapor at the anode could be absorbed and then ables. The corresponding sensitivity achieves 52%. Then, the sensi-
moved to cathode by electro-osmotic drag force. Also, the water tivity of mass of platinum is the second highest, about 42%. The
at the cathode could diffuse reversely into anode due to the con- sum of the sensitivities of these two variables reaches over 90%.
centration difference of water. Even so, the generated liquid water In other words, the effects of mass of carbon and agglomerate
under the same operating conditions still changes linearly with the radius on the electrical-thermal-water performance are fairly
current density. weak. As a consequence, the sensitivities of the decision variables
RSM could also be used to conduct a simple performance opti- are ranked: volume fraction of dry ionomer > mass of plat-
mization with the help of a regression equation. The optimal inum > mass of carbon > agglomerate radius. Combined with the
parameters and the obtained electrical-thermal-water perfor- analysis mentioned above, volume fraction of dry ionomer mainly
mance by RSM are listed in Table 4. The optimal decision variables affects the proton transport resistance. That’s to say, this variable
are relatively consistent with the results from the experiment [50]. has a more significant effect on the cell performance than other
For instance, under the medium voltage, the optimal mass of plat- variables when catalyst reaches a relatively high activity. Besides,
inum for high current density is about 0.4 mg Pt/cm2. Besides, the mass of carbon is relevant to specific area of catalyst, oxygen trans-
optimal mass ratio of ionomer to carbon is calculated to be 1.43 in port, and liquid water distribution. Among these properties, rea-
the study. This value is close to 1.11–1.36 (which also leads to high sonable mass of carbon should be first used to achieve high
current density) in the experiment. The good agreement between specific area of catalyst.
the decision variables and experiment data could also demonstrate At the optimal point, it is found that the sensitivity of mass of
the accuracy of the developed CFD model. Compared with the base platinum is decreased to about 18%. At the same time, the sensitiv-
case, the optimized current density is increased by 6.3%. ities of the other three variables are raised. Especially, the sensitiv-

Table 4
The optimal decision variables and the corresponding response variables by RSM.

Decision variables
Mass of platinum (mg/cm2) Mass of carbon (mg/cm2) Volume fraction of dry ionomer Agglomerate radius (lm)
0.4185 0.7505 0.3588 1.0998
Response variables
Current density (A/cm2) Maximum temperature (K) Mass flow rate of liquid water (kg/s)
0.7636 345.87 3.3766e-6

Fig. 11. Sensitivity analysis of the decision variables: (a) at the center point; (b) at the optimal point.

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J. Yao, Y. Yang, X. Hou et al. Journal of Energy Chemistry 81 (2023) 642–655

Fig. 12. Comparison of the predicted performance by RSM and ANN model.

ity of volume fraction of dry ionomer achieves 65%. At this point, target values represent the normalized sample set. The regres-
the catalyst activity is further enhanced, which also leads the smal- sion R values, which present the correlation between output val-
ler sensitivity of catalyst. Therefore, further improvement for cata- ues and target values, reach over 0.999, indicating the high
lyst is quite difficult. Nevertheless, the sensitivity order of the performance of the ANN model. Besides, the error histogram dia-
decision variables has no change. Therefore, it could also be con- gram shows the error between the output values and target val-
cluded that dry ionomer in CL should be paid more attention ues. The mean squared error for training is calculated to be
besides catalyst. 5.84e-6.
With the help of ANN model, the performance of PEMFC could
5.4. ANN prediction be predicted. Herein, 10 samples that are not included in the pre-
vious sample set, are calculated by the developed CFD model, as
Based on the same sample set, an ANN model is trained for seen in Table S3. The comparison between the results obtained
rapid and accurate prediction of the electrical-thermal-water by CFD model and the predicted values by RSM and ANN model
performance. The regression diagram and error histogram dia- is illustrated in Fig. 12. It is found that the ANN model could imple-
gram during the training process is shown in Fig. S4. The output ment a more rapid and accurate prediction than RSM. The maxi-
values denote the predicted data by the ANN model, while the mum relative error for ANN model is about 2%, while that for

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J. Yao, Y. Yang, X. Hou et al. Journal of Energy Chemistry 81 (2023) 642–655

RSM is up to 5%. Besides, for most samples, the relative error for Appendix A. Supplementary material
ANN model is lower than that for RSM.
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jechem.2023.02.049.
6. Conclusions
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