Electrochimica Acta 353 (2020) 136491

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Investigation of dry ionomer volume fraction in cathode catalyst layer

under different relative humilities and nonuniform ionomer-gradient
distributions for PEM fuel cells
Yulin Wang a, *, Tao Liu a, Huan Sun a, Wei He a, **, Yuanzhi Fan a, Shixue Wang b
a
Tianjin Key Lab of Refrigeration Technology, Tianjin University of Commerce, Tianjin, 300134, China
b
Key Laboratory of Efficient Utilization of Low and Medium Grade Energy, MOE, Tianjin University, Tianjin, 300350, China

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

Article history: The dry ionomer volume fraction in cathode catalyst layer (CCL) of polymer electrolyte membrane (PEM)
Received 7 November 2019 fuel cells is of great important for determining cell performance. The interaction between the dry ion-
Received in revised form omer volume fraction in CCL and reactant relative humidity (RH), as well as a CCL with through-plane
16 April 2020
(TP) and in-plane (IP) nonuniform ionomer-gradient distributions, is numerically investigated by using
Accepted 10 May 2020
Available online 22 May 2020
a three-dimensional multiphase fuel cell model. Results show that cell performance is highly sensitive to
the variations in dry ionomer volume fraction in CCL under high current densities with lower RHs, and is
less sensitive under low current densities with higher RHs. A higher dry ionomer volume fraction in CCL
Keywords:
PEM fuel Cell
benefits proton conductivity, but causes a lower porosity and higher mass diffusion resistance under the
Cathode catalyst layer same content of Pt/C for CCL. Overall, the dry ionomer volume fraction of 0.25 with a moderate RH of 60%
Dry ionomer volume fraction for a conventional CCL shows the best cell performance. Therefore, the results of our model support the
TP/IP ionomer-Gradient distribution finds of previous studies showing that an optimal ionomer volume fraction is 0.25 by volume and 0.33 by
Relative humidity mass. This study further ascertains that a TP gradient preferable with dry ionomer volume fraction
concentrated near the polymer membrane (PM)-CCL interface contributes to an improvement in cell
performance. Finally, the underlying mechanism is revealed through the observation of the influence of
TP and IP ionomer-gradient distributions under an RH of 60% on the mass diffusion, the proton con-
ductivity and the oxygen reduction reaction (ORR).
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction
Polymer electrolyte membrane (PEM) fuel cells are clean and
promising energy devices with high energy conversion efficiency
and low pollutant emissions [1e4]. A typical PEM fuel cell consists
of bipolar plates (BPs), gas diffusion layers (GDLs), and catalyst
layers (CLs) at both the anode and cathode electrodes, with a
polymer membrane (PM) in between them. The CLs are fabricated
with 15e45 nm carbon-supported platinum particles (Pt/C) and
5e20 nm thick electronic insulation ionomers (i.e., Nafion) [5]. Pt
and the ionomer are very expensive materials, accounting for half
the overall cost of fuel cell. Pt and ionomers are usually inefficiently
utilized, hence the cost of fuel cells is generally high [5,6].
* Corresponding author.
** Corresponding author.
E-mail addresses: wangylok@yeah.net (Y. Wang), weihe@tjcu.edu.cn (W. He).
Therefore, the design of CLs, especially the cathode CL (CCL) with
low Pt and dry ionomer volume fraction for high cell performance
is urgently needed to realize the commercialization of PEM fuel
cells [5,7].
Many approaches and technologies have been proposed to
reduce Pt content in CCL without decreasing overall cell perfor-
mance. Designs of through-plane (TP) and in-plane (IP) gradient Pt
distributions are considered to be promising methods for reducing
Pt content in CCL. For TP gradient Pt distribution, the majority of
experimental studies suggest that a higher Pt ontent near PM could
improve cell performance [8e11]. In contrast, some numerical
studies have found that a higher Pt content in CCL near GDL im-
proves cell performance [12e15]. For IP gradient Pt distribution, it
has been observed that a lower Pt content near the inlet and a
higher content near the cathode outlet enhance cell performance
[12,16e18]. Generally, a higher Pt content should be fabricated near
the active electrode sites with higher reactant concentrations to
facilitate the electrochemical reaction within CLs; additionally, to

https://doi.org/10.1016/j.electacta.2020.136491
0013-4686/© 2020 Elsevier Ltd. All rights reserved.
2 Y. Wang et al. / Electrochimica Acta 353 (2020) 136491

improve the homogeneous nature of the current density within 2. Model description
CLs, a higher Pt content is also necessary downstream of the flow
direction [10,12,19e21]. Although many studies have been per- 2.1. Computational domain and model assumptions
formed to optimize CCL with gradient Pt distribution, only limited
published studies have focused on designs of gradient ionomer in The computational domain and mesh of a single fuel cell with
CCL to reduce the cost and improve the performance of PEM fuel straight parallel channels is employed in this simulation, covering
cells. bipolar plates (BPs), channels (CHs), gas diffusion layers (GDLs), and
A sufficient dry ionomer volume fraction in CCL is beneficial for catalyst layers (CLs) and a polymer membrane (PM), as shown in
proton transport, however, a higher dry ionomer volume fraction Fig. 1(a). A half CH and BP are taken into account due to the sym-
could decrease the porosity of CCL and lead to a high mass diffusion metrical structure of the parallel fuel cell. The CHs, BPs, GDLs, CLs
resistance, and thus deteriorates cell performance [5,6,22e27]. and PM are divided into 8, 8, 8, 10 and 10 layers of mesh along the x
Moreover, a higher dry ionomer volume fraction increases the cost direction, and 500 and 10 layers along the y and z directions,
of PEM fuel cells as mentioned before. Previous studies found that respectively. A grid independent test of the present fuel cell model
an optimal ionomer content in CCL is 0.25 by volume and 0.33 by
mass [28e31]. To further improve the effective utilization of ion-
omer, recently, dry ionomer gradient designs in CCLs are proposed
with high proton conductivity and mass diffusivity of CCLs
[5,32e38]. Xie et al. [34] investigated a CCL with three sublayers of
different dry ionomer volume fractions and found that at inter-
mediate and high current densities, a higher dry ionomer volume
fraction near PM and a lower content near GDL increase cell per-
formance. In contrast, cell performance significantly declines when
the gradient of dry ionomer volume fraction is reversed. Kim et al.
[37] prepared membrane electrolyte assemblies (MEAs) that had
two different sublayers where the inner layer (close to PM) had a
higher dry ionomer volume fraction and the outer layer (near GDL)
had a lower dry ionomer volume fraction, the experimental results
indicated that the new gradient design of dry ionomer volume
fraction increased cell performance. Recently, Shahgaldi et al. [5]
manufactured well-engineered two sub-layers of ionomer-gradient
CCL and also found that more ionomer near PM and more Pt near
CCL benefited cell performance. For IP ionomer-gradient distribu-
tion, studies by Cetinbas et al. [35] and Herden et al. [38] indicated
that fuel cells with a higher content of ionomers under the channel
and near the outlet in CCL showed better performance than those
with a homogeneous ionomer distribution. However, only a few
such investigations can be found in literature. Moreover, the
mechanisms of influence of IP ionomer distribution in CCL on cell
performance and the underlying causes have remained elusive.
The interaction between dry ionomer volume fraction and
relative humidity (RH) is another significant issue that should be
considered in the optimization of fuel cells [6,22,39e41]. For
instance, an experimental study by Kim et al. [20] indicated that a
higher dry ionomer volume fraction with a higher RH could cause a
serious water flooding problem and thus decreased cell perfor-
mance; however, a lower or moderate dry ionomer volume fraction
with a higher RH could enhance proton conductivity and cell per-
formance. Xing et al. [6] observed that the optimum cathode RH
decreased at first and then increased as dry ionomer volume frac-
tion increased under higher current densities by using a two
dimensional and two-phase PEM fuel cell model. Nevertheless,
thus far, influence of ionomer gradient designs in CCL with different
RH on cell performance has not been well investigated.
This study employs a three-dimensional, multiphase PEM fuel
cell model to investigate the impact of various dry ionomer volume
fractions and TP/IP ionomer gradient distributions in CCL on cell
performance under different RHs. The ionomer swelling in CLs and
the solid fibers from GDLs penetrating into CLs are examined in the
simulation. The objective of this paper is to reveal the mechanism
of how the interaction between dry ionomer volume fraction and
RH affects cell performance, and furthermore, to develop an opti-
mum combination of TP/IP ionomer-gradient distributions in CCL
and RH for the enhancement of proton conductivity and mass Fig. 1. (a) Computational domain and mesh, (b) comparison of predicted polarization
diffusion in PEM fuel cells, thereby improving the utilization of curves by the present fuel cell model with experimental data at operating back
ionomers and ultimately cell performance. pressures of 0.0 and 0.6 bar [42].
 Y. Wang et al. / Electrochimica Acta 353 (2020) 136491 3

is performed successfully through decreasing or increasing the water, thus causing the increase of its volume. However, CLs are
number of grids by 30%. More detailed information about the very thin with a thickness of approximately 10 mm, therefore, the
model structural and physical parameters is provided in Table 1. total volume of CLs can be assumed to be invariable with ionomer
Here are some assumptions about the fuel cell model devel- swelling and the increased ionomer volume only take up the vol-
oped: (1) the fuel cell operates steadily. (2) The effect of gravity on ume of the void space in CLs [5]. Based on the assumption above,
the flow processes is ignored. (3) The flow is incompressible and the key structural parameters of CLs in the present fuel cell model
laminar in the CHs. (4) Fick’s law is applied to describe the gas can be determined as follows.
diffusion in porous electrodes. (5) The supplied gas mixtures from The porosity of CLsεCL , is defined as [6].
both the anode and cathode inlets are supposed to be ideal gases.
(6) The GDLs, CLs and PM are assumed to be of homogeneous εCL ¼ 1  εsI  εPt=C  εPenetrate
GDL (1)
porous structures. (7) The thermal, ionic and electronic transfer
contact resistances are neglected. (8) The water produced in CCL where εsI is the volume fraction of ionomer with swelling and can be
exists in the form of vapor phase. (9) The water in the ionomer/PM calculated by Ref. [6].
is in the dissolved phase, and the phase change among the dis-

solved, vapor and liquid water is dependent on the dissolved water εsI ¼ 1 þ ksI l εI (2)
content in the ionomer/PM. (10) The total content of Pt/C (Pt to Pt/C
mass ratio of 40%, %Pt ¼ 40%) in this study is assumed to be where ksI is the swelling coefficient; εI is the volume fraction of dry
invariable with the variation in dry ionomer volume fractions. ionomer (dry ionomer volume fraction); and lis the dissolved/
membrane water content in PM and CLs as discussed in the
following subsections.
2.2. Numerical solution and model validation
Here εPt=C in Eq. (1) is the volume fraction of Pt/C, defined as
[43]:
Fluent 16.0 is employed to solve the fuel cell model established
in this paper with a double-precision strategy. The standard  
1 mPt mC
equations of continuity, momentum, species transport and energy εPt=C ¼ þ (3)
dCL rPt rC
in the Fluent are modified by user-defined functions (UDFs) ac-
cording to the transport properties of fuel cells. The liquid water here dCL is the thickness of CLs; mPt and mC are Pt content and carbon
transport equation in GDLs, CLs and CHs, the dissolved water and content (mg cm2) in CLs, respectively; the Pt content, mPt , in CLs
proton transport equations in CLs and PM, and the electron trans- can be found in Table 2; and the carbon content, mC , in CLs can be
port equation in GDLs, CLs and BPs are described and addressed by calculated according to the Pt/C with Pt to Pt/C mass ratio, where %
four user-defined scalars (UDSs). The SIMPLE algorithm is applied Pt is given as follows [44]:
to settle the coupling of the velocity and pressure. When the rela-
tive differences of each dependent variable between two consec- mPt
%Pt ¼ (4)
utive iterations are less than 105, the solution is deemed to be mPt þ mC
convergent. Numerical result illustrates that the IV curves predicted
Therefore, the volume fraction of Pt/C can finally be determined
by the present fuel cell model fit well with the experimental and
as:
numerical ones [42,48] at ionomer volume fractions of 0.22 and
0.27 in CLs as shown in Fig. 1(b), indicating the reliability of the fuel  
mPt 1 1  %Pt
cell model developed here. εPt=C ¼ þ (5)
dCL rPt %PtrC

2.3. Catalyst layer properties where εPenetrate

GDL in Eq. (1) is the volume fraction of the solid portion
of GDL penetrating into CLs and can be written as [43]:
Catalyst layers (CLs) are porous mediums composed of carbon
skeletons supporting dispersed Pt particles (Pt/C) and ionomer. The εPenetrate
GDL ¼ kpenetrate
GDL ð1  εGDL Þ (6)
total volumes of CLs include the volume of void space, Pt/C and
ionomer. The ionomer tends to swell after absorbing the dissolved here kpenetrate
GDL is the volume fraction of the penetrated GDL

Table 1
Structural parameters and material properties.

Parameters Value Reference

Gas channel length, width, height (m) 0.1, 1.0  103, 1.0  103
Land width (m) 1.0  103
Thickness of GDL, CL, MEM (m) 3.0  104, 105, 2.5  105
Porosity of GDL, εGDL 0.7 [48]
Contact angle of GDL, CL ( ), qGDL, qCL 110, 95 [48,59]
Liquid water density (kg m3), rl 1.0  103
Density of PM (kg m3), rmem 1.98  103 [57]
Platinum density (kg m3), rPt 2.145  104 [44]
Carbon density (kg m3), rC 1.8  103 [44]
Ionomer swelling coefficient, ksI 1.26  102 [58]
Liquid water surface tension (N m1), s 6.25  102 [58]
Volume fraction of penetrated GDL, kpenetrate
GDL
10% [46]
Pt to Pt/C mass ratio, %Pt 40% [20]

Operation temperature ( C), T 80
Pt content (mg cm2), maPt = mcPt 0.4/0.4 [55]
Equivalent weight of ionomer (kg mol1), EW 1.1 [48]
4 Y. Wang et al. / Electrochimica Acta 353 (2020) 136491

Table 2
Transport parameters in the model.

Parameters Value Reference

Permeability of GDL, CL, MEM (m2), KGDL, KCL, Kmem 1012, 1013, 1020 [48]
Bulk diffusivity of hydrogen (m2 s1), Dbulk
H2 9.73  105 [53]
Bulk diffusivity of oxygen (m2 s1), Dbulk
O2 2.73  105 [51]
2 1
Bulk diffusivity of vapor water (m s ), Dbulk v 2.33  105 [51]
Electronic conductivity of GDL, CL, BP (S m1), kGDL, kCL, kBP 5.0  103, 2.0  103, 2.0  104 [48]
Thermal conductivity of CL, MEM, BP (W m1 K1), kCL, kmem, kBP 1.0, 0.95, 20.0 [48]
Anisotropic thermal conductivity of GDL (W m1 K1), kGDL,in, kGDL, through 21.0, 1.7 [54]
Universal gas constant (J mol1 K1), Ru 8.314
Faraday’s constant (C mol1), F 96487.0
Reference concentration (mol m3), Cref ref
H2, CO2 56.4, 3.39 [54]
Vapor water constant condensation rate (s1), gcond 5.0  103 [56]
Liquid water constant evaporation rate (s1 pa1), gevap 1.0  104 [56]
Anode exchange current density multiply specific area (εCL¼ 0.3, dCL ¼ 1.0  105 m), (A m3), Aeff ref
Pt j0;a 1.0  108 [48]
Cathode exchange current density multiply specific area (εCL¼ 0.3, dCL ¼ 1.0  105 m), (A m3), Aeff ref
Pt j0;c 120.0 [48]
Anode/cathode charge transfer coefficient, aa/ac 0.5/0.5 [54]
Anode/cathode entropy change (J mol1 K1), DSa/DSc 130.68/32.55 [48]
Latent heat coefficient (J mol1), h 4.49  104 [48]
Inlet gas stoichiometric ratio xa/xc 2.0/3.0

andεGDL is the porosity of GDLs. pg and pl are the pressures of the gas mixture and liquid water,
1
As for the specific areas of CLs, Aeff
Pt (m ) is employed for both respectively; mg and ml denote the gas mixture and liquid water
the anode and cathode CLs, with a higher content of Pt in CCL due to viscosities, respectively; Cp;g and Cp;l are the specific heats of gas
the slow oxygen reaction rate (ORR) at the cathode electrodes, and mixture and liquid water, respectively; T is the temperature; Di eff is
can be defined as [45]: the gas effective diffusivity of ith (O2, H2O(g), N2 and H2) and can be
determined by Deff
i
¼
mPt As D bulk 1:5 1:5 1:5
ε ð1  sÞ ðT=333:15Þ ð101325:0=PÞ, where D bulk is the
Aeff
Pt ¼ (7)
dCL ð1  εCL Þ bulk diffusion coefficient of the gas species; keff is the effective
thermal conductivity; andSm , Su , Si and ST are the source terms of
here As is the total catalyst surface area per unit mass of the catalyst the conservation equations of continuity, momentum, species
and relates to the Pt to Pt/C mass ratio (%Pt) as follows [46]: transport and energy, respectively.
  Based on Ohm’s law, the potential conservation equations for
As ¼ 103  227:79ð%PtÞ3  158:57ð%PtÞ2  201:53ð%PtÞ (8) the solid phase (solved in GDLs, CLs and BPs) and electrolyte phases
(solved in CLs and PM) are as follows:

 
2.4. Governing equations V , keff
e V4e þ Se ¼ 0 (13)

From the assumptions and discussions above, the three-

dimensional multiphase governing equations for a PEM fuel cell  
can be described as follows. V , keff
ion V4ion þ Sion ¼ 0 (14)
Continuity and momentum conservation equations solved in
GDLs, CLs and CHs:
where 4e and 4ion are potentials of solid and electrolyte phases,
 r !  respectively; keff eff
e and kion are the electron and proton conductivities,
g ug respectively, as calculated by Ref. [47]:
V, ¼ Sm (9)
εð1  sÞ

 
rg ! !
ug ug  m V !
g ug

keff 1:5
V, ¼  Vpg þ V , þ Su (10) e ¼ εPt=C ke (15)
ε2 ð1  sÞ2 εð1  sÞ

Species transport conservation equation solved in GDLs, CLs and

CHs: 8  
> 1 1
>
< ð0:5139 l  0:326Þexp 1268  ; PM
 r !    303:15 T
g ug keff ¼  
V, Xi ¼ V , rg Deff VXi þ Si (11) ion >
> 1 1
ð1  sÞε i : ε 1:5 ð0:5139l  0:326Þexp 1268  ; CLs
I
303:15 T
Energy conservation equation solved in all zones: (16)
   
rg Cp;g ug T The source terms, Se and Sion in Eqs. (13) and (14) are obtained
V , εsrl Cp;l ul T þ ¼ V , keff VT þ ST (12)
εð1  sÞ from the electrochemical reactions within the anode and cathode
CLs (ACL and CCL). For the ACL: Se ¼ ja , Sion ¼ ja ; for the CCL: Se ¼
where εis the porosity of porous mediums of the PEM fuel cell, such jc and Sion ¼ jc . ja and jc are the net current densities at the ACL and
as the GDLs, CLs and PM; rg denotes the density of the gas mixture; CCL, which can be determined by the Butler-Volmer equation as
!
ug represents the vector of velocity; s is the liquid water saturation; [48]:
 Y. Wang et al. / Electrochimica Acta 353 (2020) 136491 5

0 10:5  !   
   2:5l i ion r
@ cH2 A 1 1 V, ¼ mem V , Deff Vl þ Smw (22)
ja ¼ Aeff
Pt ð1  sÞ1:5 jref
0;a exp  1400   22 F EW l
cref
H2
T 353:15
     where rmem and EWare density and the equivalent weight of ion-
2F aa 2F ac omer; Smw is the source term of Eq. (22);Deff
exp ha  exp  ha l represents the dis-
Ru T Ru T solved water diffusivity and which is determined by Ref. [44]:
(17)  
8 7
< 3:1  10 l e
0:28l
 1 e½2346=T ; 0 < l  3
0 11:0 Deff
   l ¼ 8
: 4:17  10 lð1 þ 161e Þe
l ½2346=T
; 3 < l < 17
1:5 ref @ cO2 A 1 1
jc ¼ Aeff
Pt ð1  sÞ j0;c exp  7900   4:1  1010
ðl=25:0Þ0:15
ð1 þ tanhðl  2:5Þ=1:4Þ; l > 17
cref
O2
T 353:15
(23)
    
4F aa 4F ac The phase change between the dissolved water and liquid water
 exp hc þ exp  hc
Ru T Ru T saturation, Sdv , is dependent on the equilibrium membrane water
(18) content, leq , in the PM and CLs, and the expressions of Sdv and
leq are defined as [48]:
In Eqs. (17) and (18), Aeff
Pt is
the specific area of catalyst layer;
jref ref

0;a and j0;c are the anode and cathode reference current densities, Sdv ¼ 1:3EW=rmem leq  l (24)
respectively; aa and ac are the electric transfer coefficients in the
ACL and CCL, respectively; F is Faraday’s constant, and R is the gas 8
constant; ha ¼ 4e;a  4ion;a and hc ¼ 4e;c  4ion;c  Voc are the anode >
> 2 3
< 0:043 þ 17:81aw  39:85aw þ 36:0aw ; 0 < aw  1
and cathode over-potentials, respectively;  the open circuitvoltage
leq ¼ 14:0 þ 1:4ðaw  1Þ ; 1 < aw  3
isVoc ¼ 1:23  0:9  103 ðT  298Þ þ RT in 1 in >
2F ln pH2 þ 2 ln po2 . >
: 16:8 ; a > 3
A two-phase model is employed to describe the water transport w

in the fuel cell and the liquid water transport conservation equation (25)
in GDLs and CLs is:
where aw ¼ pv =psat þ 2s[51,52] is the water activity, which is a
r k kp function of liquid water saturation, vapor water partial pressure
V , l kl Vpg ¼ SL þ V,½rl Dc Vs (19)
ml pv ¼ xH2 O rg Ru T=MH2 O and vapor water saturation pressure, psat ,
which is calculated as follows [53,54].
where Dc ¼ (Kkkl/ml) (vpc/vs) is the liquid water capillary diffu-

5
ðT273:15Þ2 þ1:4454107 ðT273:15Þ3
psat ¼ 101325:0  102:1794þ0:02953ðT273:15Þ9:183710 (26)

sivity; and SL is the source term of Eq. (19); Based on the Leverett-J
function and Wyllie’s model (power law), the capillary pressurepc , Detailed information regarding the transport parameters and
and the liquid water relative permeability, krl , can be expressed as the source terms of the conservation equations are above listed in
[49]. Table 2 and Table 3.

2.5. Boundary conditions

8  ε 0:5  
>
< s cos q 1:417ð1  sÞ  2:120ð1  sÞ2 þ 1:262ð1  sÞ3 q < 90+
K
pc ¼  ε 0:5   (20)
>
:
s cos q 1:417s  2:120s2 þ 1:262s3 q > 90+
K

The mass flow rate boundary condition is employed for defining

krl ¼ s4:0 (21) the anode and cathode inlet boundaries as follows.

here s is the surface tension of the porous electrodes, K and ө are

the intrinsic permeability and contact angle of GDLs and CLs,
respectively and krg ¼ ð1  sÞ4:0 is the relative permeability of the
gaseous mixture [50]. ra xa iref Ar RT
The dissolved water transport conservation equation in PM and ma ¼ (27)
2F pa RHa psat
CLs is given as follows:
6 Y. Wang et al. / Electrochimica Acta 353 (2020) 136491

Table 3
Source terms of the conservation equations.

Source terms Unit

ja M H2 kg m3 s1
ACL: Sm ¼   Svl
2F
jc MH2 O jc MO2
CCL: Sm ¼   Svl
2F 4F
CHs ; GDLs: Sm ¼ Svl
 
mg 1 ! kg m2 s2
GDLs; CLs: Su ¼  ug ,CHs:Su ¼ 0
Kkrg εð1  sÞ
ja kg m3 s1
ACL: SH2 ¼  MH2 ; Sv ¼ Sdv MH2 O  Svl ;
2F
jc jc
CCL: SO2 ¼  MO2 ; Sv ¼ MH2 O þ Sdv MH2 O  Svl
4F 2F
GDLs; CHs: Sv ¼ Svl ; SH2 ¼ 0; SO2 ¼ 0
CHs; GDLs; CLs: SL ¼ Svl ¼ gcond εð1  sÞxH2 O ðpv  psat ÞMH2 O =Ru T; pv > psat kg m3 s1
SL ¼ Svl ¼ gevap εsrðpv  psat Þ; pv < psat
rl Kmem PlACL  PlCCL mol m3 s1
ACL: Smw ¼ Sdv 
MH2 O ml dmem dCL

rl Kmem PlACL  PlCCL

CCL: Smw ¼ Sdv þ
MH2 O ml dmem dCL

PM: Smw ¼ 0
i2e i2ion ja T DSa W m3
ACL: ST ¼ þ þ hSvl þ hSdv þ ja jha j þ
keff
e keff
ion
2F

i2e i2ion jc T DSc

CCL: ST ¼ þ þ hSvl þ hSdv þ jc jhc j þ
keff
e keff
ion
2F

i2e i2e
GDLs: ST ¼ þ hSvl ; BPs: ST ¼ ; CHs: ST ¼ 0
keff
e keff
e

i2ion
PM: ST ¼
keff
ion

Fig. 2. Polarization curves for various dry ionomer volume fractions under different anode and cathode inlet RHs: (a) RHs ¼ 100%, (b) RHs ¼ 80%, (c) RHs ¼ 60%, (d) RHs ¼ 40% (Cell
temperature: 353 K, anode and cathode pressure: 1 atm; anode stoichiometry: 2.0, cathode stoichiometry: 3.0).
 Y. Wang et al. / Electrochimica Acta 353 (2020) 136491 7

rc xc iref Ar RT
mc ¼
4F 0:21ðpc RHc psat Þ
where ra and rc are the gas mixture densities of the anode and
cathode sides, respectively; xa and xc denote the gas stoichiometric
ratio at anode and cathode inlet, respectively; iref is the reference
current density; Ar represents the active reaction area; pa and pc are
the anode and cathode inlet pressures, respectively; and RHa and
RHc are the RHs of the anode and cathode inlet gas, respectively.
The PEM fuel cell operates at 80  C and 1.0 atm. All the sur-
rounding walls are supposed to be the same temperature as the
operating temperature, and the anode and cathode outlet pressures
are set as the same as the operating pressure. At the interface
among the CHs, GDLs, CLs and PM, the mass flux, momentum flux,
species flux, charge flux and water flux are assumed to be contin-
uous. At the interface between the GDLs, BPs, CLs and PM, the mass
flux, momentum flux, species flux and water flux are set as
vXk =vx ¼ 0. The electronic phase potential on the terminal walls of
the anode and cathode BPs are defined as 4e ¼ 0and 4e ¼ Vcell ,
respectively, while the proton phase potential is defined as
v4ion =vx ¼ 0.
3. Results and discussions
The influence of dry ionomer volume fraction on cell perfor-
mance with different RHs is investigated by the fuel cell model
established here. Dry ionomer volume fractions (εI ) of 0.1, 0.15, 0.20,
0.25, 0.30 and 0.40 are chosen in the simulation, and the RH of both
the anode and cathode inlet gas varies among 100%, 80%, 60% and
40%. Additionally, the impact of TP/IP ionomer-gradient distribu-
(28)
tions in the CCL under a reasonable RH on cell performance is also
numerically evaluated and the simulated results are discussed as
follows.
3.1. Effect of dry ionomer volume fraction under different RHs
The polarization curves for various dry ionomer volume frac-
tions under different RHs are shown in Fig. 2. Generally, an increase
of dry ionomer volume fraction (εI ) in the CCL can improve cell
performance under lower current densities with higher RH. While
under higher current densities with higher RHs, it can lead to an
improvement of cell performance at first and then a decline. This is
because under lower current densities, only a small amount of
oxygen can satisfy the rate of the oxygen reduction reaction (ORR)
and a little water is generated. In this case, the mass diffusion in the
CCL is not the determining factor for cell performance, therefore, a
higher dry ionomer volume fraction with a higher RH could
enhance the proton conductivity and cell performance. Further-
more, under higher current densities, sufficient water can be pro-
duced to humidify the ionomer and a reasonable increase of dry
ionomer volume fraction benefits proton conductivity, and mean-
while maintains mass diffusion in the CCL. Nevertheless, when too
much water is generated and extremely high dry ionomer volume
fraction is employed, the reduction of CCL porosity can be signifi-
cantly large, the increase of proton conductivity cannot counter-
weigh the increase of mass diffusion resistance, and thus causing
serious concentration loss. For instance, when dry ionomer volume

Fig. 3. (a) Porosity (b) oxygen mass fraction (c) dissolved water content and (d) proton conductivity distribution maps in the y-z plane in the middle of the CCL for various dry
ionomer volume fractions (Cell temperature: 353 K; anode and cathode inlet RHs: 60%; anode and cathode pressure:1 atm; anode stoichiometry: 2.0, cathode stoichiometry: 3.0;
Vcell ¼ 0.4 V).
8 Y. Wang et al. / Electrochimica Acta 353 (2020) 136491
Fig. 4. (a) Dry ionomer volume fraction (b) polarization curves and (c) maximum
power densities for various TP ionomer-gradient and the conventional ionomer dis-
tributions in CCL along the x direction (cathode total dry ionomer volume fraction:
0.25; Cell temperature: 353 K; anode and cathode inlet RHs: 60%; anode and cathode
pressure:1 atm; anode stoichiometry: 2.0, cathode stoichiometry: 3.0).
fraction in the CCL reaches 0.4, it can lead to a plummet of cell
voltage under higher current densities with higher RHs. Finally, we
find that the fuel cell operating under RHs of 60% with a dry ion-
omer volume fraction of 0.25 in the CCL shows the best overall cell
performance as plotted in Fig. 2.
Fig. 5. (a) Porosity (b) oxygen mass fraction (c)dissolved water content (d) proton
conductivity (e)water saturation and (f) cathode current density distribution maps in
the x-z plane in the middle of the MEA along the x direction (cathode total dry ionomer
volume fraction: 0.25; Cell temperature: 353 K; anode and cathode inlet RHs: 60%;
anode and cathode pressure:1 atm; anode stoichiometry: 2.0, cathode stoichiometry:
3.0; Vcell ¼ 0.4 V).
To understand the influence mechanism of dry ionomer volume
fraction on the mass diffusion and proton conductivity, Fig. 3 pre-
sents detailed distributions of the porosity, oxygen mass fraction,
dissolved water content and proton conductivity on the middle y-z
plane of the CCL along the y direction forεI ¼
0:1; 0:25 and 0:4under RH ¼ 60%. It can be observed that the
 Y. Wang et al. / Electrochimica Acta 353 (2020) 136491
porosity of the CCL drops with increased dry ionomer volume
fraction, forεI ¼ 0:1; 0:25 and 0:4, the CCL porosities (εCL ) are 0.5,
0.36 and 0.14, respectively. The corresponding oxygen mass fraction
also decreases with increased dry ionomer volume fraction as
shown in Fig. 3(b). Very little oxygen is transported into the CCL
when the dry ionomer volume fraction is 0.4. Furthermore,
although much more oxygen has been found in the CCL underεI ¼
0:1, the extremely low dry ionomer volume fraction can cause very
low dissolved water content and proton conductivity, as indicated
in Fig. 3(c) and (d). The average proton conductivity on the middle
y-z plane of the CCL along the y direction for εI ¼
0:1; 0:25 and 0:4under Vcell ¼ 0.4 V approximate 0.20, 2.29 and
3.71, respectively. The analyses above clearly indicate that PEM fuel
cell performance is closely related to the trade-off between mass
diffusion and proton conductivity resulting from the variation of
dry ionomer volume fraction in CCL.
3.2. Effect of TP ionomer-gradient distribution
This subsection investigates the PEM fuel cell with different TP
ionomer-gradient distributions in the CCL based on the given dry
ionomer volume fractionεI ¼ 0:25, and RH ¼ 60% due to its highest
overall cell performance as shown in Fig. 2. Linear profiles are
proposed to describe the TP ionomer-gradient as plotted in
Fig. 6. Distributions of various IP ionomer-gradient and the conventional ionomer in
the CCL (a) along the y direction and (b) along the z direction.
9
Fig. 4(a), and this gradient is a function of spatial distance along the
thickness of the CCL from the PM to the CGDL according to the
following expression:
 
εI ðXÞ ¼ 0:5  2ε0I X þ ε0I (29)
where ε0I (0  ε0I  0:5) is the initial dry ionomer volume fraction at
the terminal surface near the PM; and X is the normalized distance
from the CCL surface near the PM to that near the CGDL. Six initial
dry ionomer volume fraction values, ε0I ¼ 0:0; 0:1; 0:2 ; 0:3; 0:4;
0:5, for different TP ionomer-gradient distributions are compara-
tively studied with the conventional ionomer distribution, as
shown in Fig. 4(a), which are represented by I-X-1, I-X-2, I-X-3, I-X-
4, I-X-5, I-X-6 and the base case, respectively. It is worth noting that
all the six TP ionomer-gradient distributions have the same total
dry ionomer volume fraction in the CCL as the conventional ion-
omer distribution.
Fig. 4(b) and (c) shows the polarization curves and maximum
power densities for various TP ionomer-gradient and conventional
ionomer distributions in the CCL along the x direction. The pre-
dicted current densities among various ionomer distributions in
the CCL exhibit no striking differences at high operational voltages,
especially when initial dry ionomer volume fraction is higher than
0.25. This is because the mass diffusion shows a weak influence on
cell performance under low current densities as discussed in
Fig. 7. Polarization curves for various IP ionomer-gradient and the conventional ion-
omer distributions in the CCL (a) along the y direction and (b) along the z direction
(cathode total dry ionomer volume fraction: 0.25; cell temperature: 353 K; anode and
cathode inlet RHs: 60%; anode and cathode pressure: 1 atm; anode stoichiometry: 2.0,
cathode stoichiometry: 3.0).
10 Y. Wang et al. / Electrochimica Acta 353 (2020) 136491

section 3.1. With the increase of current density at low operational
voltages, a higher initial dry ionomer volume fraction of the TP
ionomer-gradient distributions (a lower slope of Eq. (29)) demon-
strates a better cell performance under higher current densities, but
a higher slope of Eq. (29) can worsen cell performance. When
compared with the conventional ionomer distribution, the TP
ionomer-gradient distribution of I-X-1 increases the maximum
power density by 6.3%; however, the TP ionomer-gradient distri-
bution of I-X-6 drastically reduces the maximum power density by
32.5%. The reasons for the differences in predicted cell perfor-
mances among various TP ionomer-gradient distributions will be
discussed in details as follows.
As is known protons are transported from ACL to CCL through
PM, so a higher dry ionomer volume fraction in CCL near PM is
beneficial for proton transport. Meanwhile, oxygen must be
transported through CGDL into CCL for ORR, which need a higher
porosity of CCL near CGDL. For ionomer-gradient distribution of I-
X-1, much more ionomer is placed near PM, which makes a higher
porosity of CCL near CGDL and proton conductivity in CCL near PM
as plotted in Fig. 5, so, there is no doubt that I-X-1 shows higher
current density and liquid water saturation value in the cathode
electrode than the base case under the same operation conditions
as indicated in Fig. 5 (e) and (f). However, a larger amount of oxygen
remains in the CCL for I-X-6 due to the lower oxygen diffusion
ability and slower ORR resulting from the lower porosity of the CCL
near the CGDL and lower proton conductivity near the PM.
Therefore, in comparison with the base case, much lower current
density in the CCL and even no liquid water in the cathode elec-
trode can be found as shown in Fig. 5(e) and (f), indicating that I-X-
6 exhibits a negative effect on cell performance.
3.3. Effect of IP-ionomer-gradient distribution
The effect of different IP ionomer-gradient distributions on the
cell performance at the given dry ionomer volume fraction εI ¼
0:25and RH ¼ 60% is evaluated in this subsection. Fig. 6(a) and (b)
show linear profiles of IP ionomer-gradient in the CCL along the y
and z directions, respectively. They are functions of spatial distance
along the channel from the inlet to the outlet and from the BP to the
channel as expressed by the following equations:
 
εI ðYÞ ¼ 0:5  2ε0I Y þ ε0I (30)
 
εI ðZÞ ¼ 0:5  2ε0I Z þ ε0I (31)
Similar to the TP ionomer-gradient distribution study, six initial
dry ionomer volume fraction values, ε0I ¼ 0:0; 0:1; 0:2 ; 0:3; 0:4;
0:5, for different IP ionomer-gradient distributions are compara-
tively examined with the conventional ionomer distribution as
shown in Fig. 6(a) and (b), which are represented by IeY-1, IeY-2,
IeY-3, IeY-4, IeY-5, IeY-6 and I-Z-1, I-Z-2, I-Z-3, I-Z-4, I-Z-5, I-Z-6
and the base case, respectively. The total dry ionomer volume
fraction of each case is equivalent to that of the conventional ion-
omer distribution in the CCL.
Fig. 7 shows the polarization curves for various IP ionomer-
gradient and the conventional ionomer distributions in the CCL
along the y and z directions, respectively. Different from the TP
ionomer-gradient distributions, a higher or lower initial dry ion-
omer volume fraction (a higher absolute slope of Eqs. (30) and (31))
in the CCL leads to a drastic decrease in cell performance at both the
low and high operational voltages for IP ionomer-gradient distri-
butions. For example, for the IP ionomer-gradient distributions of

Fig. 8. Distribution maps in the y-z plane in the middle of the CCL for (a) oxygen mass fraction (b) proton conductivity of IP ionomer-gradient along the y direction; and (c) oxygen
mass fraction (d) proton conductivity of IP ionomer-gradient along the z direction (cathode total dry ionomer volume fraction: 0.25; cell temperature: 353 K; anode and cathode
inlet RHs: 60%; anode and cathode pressure:1 atm; anode stoichiometry: 2.0, cathode stoichiometry: 3.0; Vcell ¼ 0.4 V).
 Y. Wang et al. / Electrochimica Acta 353 (2020) 136491 11

Fig. 9. Distribution maps at the interface between CCL and CGDL for (a) current density (b) water saturation of IP ionomer-gradient along the y direction; and (c) current density (d)
water saturation of IP ionomer-gradient along the z direction (cathode total dry ionomer volume fraction: 0.25; Cell temperature: 353 K; anode and cathode inlet RHs: 60%; anode
and cathode pressure: 1 atm; anode stoichiometry: 2.0, cathode stoichiometry: 3.0; Vcell ¼ 0.4 V).

IeY-1, IeY-6, I-Z-1 and I-Z-6, the current density decreases by 11.2%,
24.9%, 17.9% and 11.8% at Vcell ¼ 0.4 V, respectively. Moreover, the IP
ionomer-gradient distributions with a moderate initial dry ionomer
volume fraction show almost the same cell performance as the
conventional ionomer distribution in the CCL as also plotted in
Fig. 7, and a slightly better cell performance is observed for IeY-3
than for the base case under high current density, with an increase
in the current density by 0.7% at Vcell ¼ 0.4 V. These results indicate
that the ionomer-gradient distributions in the CCL are more
important along the TP direction than along the IP direction.
The differences in cell performances among various IP ionomer-
gradient distributions mentioned above can be explained by the
oxygen diffusion and proton conductivity on the middle y-z plane
of the CCL along the y and z directions as shown in Fig. 8. The IP
ionomer-gradient distribution of IeY-3 has reasonably higher dry
ionomer volume fraction near the inlet which can maintain rela-
tively high oxygen diffusivity and proton conductivity at the CCL
upstream of the channel as indicated in Fig. 8 (a) and (b). Because
oxygen concentration is higher and ORR is stronger in the upstream
region, thus the distribution of IeY-3 benefits fuel cell. However,
too high dry ionomer volume fraction (IeY-1) near the inlet results
in a sudden drop of porosity and mass diffusivity in the upstream
region, and the increase of proton conductivity cannot counter-
weigh the loss of mass diffusion, and thus deteriorating cell per-
formance. Additionally, the reverse ionomer-gradient distribution,
for instance, IeY-6 has a higher proton conductivity of the CCL in
the upstream region but the proton conductivity in this region is
very low, which can also bring down cell performance. Fig. 9 shows
the distributions of current density and water saturation on the
interface between the CCL and CGDL for various IP-ionomer-
gradient distributions. Generally, a higher current density can be
observed at the higher dry ionomer volume fraction areas due to
the higher proton conductivity there. However, the IP-ionomer-
gradient distributions of IeY-1 and IeY-6 behave more nonuni-
form distributions of current density in the CCL compared with that
in the base case, thereby worsening overall cell performance. The
influence of the IP ionomer-gradient distribution along the z di-
rection on cell performance can also be explained by the counter-
balance between mass diffusion and proton conductivity as
analyzed above, which are also presented in Figs. 8 and 9.
4. Conclusion
The effect of interactions between dry ionomer volume fraction
and RH, as well as a CCL with TP/IP ionomer-gradient distributions,
on the mass diffusion, proton conductivity and cell performance is
numerically investigated by using a three-dimensional multiphase
fuel cell model in this study. The results of our model support the
finds of previous studies showing that an optimal ionomer content
is 0.25 by volume and 0.33 by mass; and that TP gradients prefer-
able with dry ionomer volume fraction concentrated near the PM-
CCL interface, and further results are obtained as following.
A higher dry ionomer volume fraction is beneficial for the pro-
ton conductivity, but it can decrease the porosity of CCL, thereby
increasing the mass diffusion resistance. Under lower current
densities, a higher dry ionomer volume fraction with a higher RH
benefits fuel cell. While under higher current densities, increasing
dry ionomer volume fraction can lead to the improvement of fuel
cell at first and then a decline, especially with a higher RH.
Nevertheless, a lower dry ionomer volume fraction with a higher
12 Y. Wang et al. / Electrochimica Acta 353 (2020) 136491
RH can enhance cell performance. In conclusion, cell performance
is greatly dependent on the counterbalance between the proton
conductivity and the mass diffusion in CCL, and the interaction
between the dry ionomer volume fraction and RH should be taken
into account in PEM fuel cell optimization. Furthermore, the PEM
fuel cell with a dry ionomer volume fraction of 0.25 under an RH of
60% the best performance as investigated in this study.
The CCL with TP/IP ionomer-gradient distributions shows a
great influence on fuel cells. Higher dry ionomer volume fractions
near the PM and CCL interface enhances the proton conduction
from the PM to CCL, and a lower content near CGDL and CCL
interface improves the oxygen diffusion from CGDL into CCL. Re-
sults show that the TP ionomer-gradient distribution I-X-1 under
an RH of 60% increases the maximum power density by 6.3%
compared with that of the conventional ionomer distribution.
However, reverse dry ionomer gradient distributions in CCL decline
the proton conductivity and mass diffusivity. A higher dry ionomer
volume fraction near the cathode inlet and under the channel
benefits fuel cell, however the reverse distributions also lead to a
plummet in cell performance. Overall, the influence of dry
ionomer-gradient distributions on cell performance is greatly
dependent on the counterbalance between the proton conductivity
and the mass diffusion which is closely related with their transport
process.
Author contributions
Yulin Wang: Conceptualization, Methodology, Software, Inves-
tigation, Writing - original draft. Tao Liu: Validation, Formal anal-
ysis, Visualization, Software, Data curation. Yuanzhi Fan:
Validation, Formal analysis, Visualization. Shixue Wang: Resources,
Writing - review & editing, Supervision, Funding acquisition. Wei
He: Writing, Review & Editing, Supervision. Hong Sun: Supervision.
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.
Acknowledgments
The authors are grateful for the financial support from the Na-
tional Natural Science Foundation of China (No.51806153) and the
National Key Research and Development Program of China
(NO.2018YFE0202003).
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Nomenclature Sat: saturation
Pt: platinum
TP: through-plane
aw: water activity v: vapor
Ar: reactive area, m2