Electrochimica Acta 50 (2004) 731737

Numerical study of PEM fuel cell cathode with non-uniform catalyst layer
Datong Songa , Qianpu Wanga , Zhongsheng Liua, , Titichai Navessina,b , Steven Holdcrofta,b
a

Institute for Fuel Cell Innovation (IFCI), National Research Council (NRC) 3250 East Mall, Vancouver, BC, Canada V6T 1W5 b Department of Chemistry, Simon Fraser University, Burnaby, BC, Canada V5A 1S6

Received 5 June 2003; received in revised form 9 December 2003; accepted 10 January 2004 Available online 5 August 2004

Abstract A one-dimensional, steady-state multi-layer agglomerate model is presented for the performance analysis of the non-uniform catalyst layer in proton exchange membrane (PEM) fuel cell. The catalyst layer is assumed to be composed of several sub-layers. The effects of different material property combinations for these sub-layers on the whole catalyst layer performance are studied numerically. The results show that the performance of the catalyst layer is highly dependent on the properties of the sub-layer close to the membrane when the catalyst layer is operated in the regime of proton conductivity limiting. The performance of the catalyst layer can be improved by adjusting the material properties of each sub-layer, especially these of the sub-layer close to the membrane. Crown Copyright 2004 Published by Elsevier Ltd. All rights reserved.
Keywords: PEM fuel cell; Non-uniform catalyst layer; Agglomerate; Porosity

1. Introduction As one of the most promising candidates of power resource for the next generation applications, proton exchange membrane (PEM) fuel cell has received an increasing attention in recent years. Despite the dramatic improvements achieved both in cell design and material utilization in PEM fuel cell, there are still many theoretical and engineering obstacles that prevent the PEM fuel cell from commercialization. Among these obstacles, perhaps the most important one is the slender understanding of the kinetics of the oxygen reduction reaction (ORR) and the nature of the mass transport limitations in the porous cathode of PEM fuel cell. Hence, an appropriate cathode model of the PEM fuel cell is crucial in order to improve the cell performance because it is in the cathode side where the largest energy loss takes place.

Corresponding author. Tel.: +1 604 221 3068. E-mail address: simon.liu@nrc.gc.ca (Z. Liu).

In the past decade, three types of models have been established for the cathode of the PEM fuel cell. They are the homogeneous model, the lm model and the agglomerate model. In homogeneous model [13], the cathode catalyst layer is assumed to be a uniform, gas pore-free blend of proton conducting polymer and be supported by catalyst. The reactants rst dissolve into the polymer phase and then diffuse through the non-porous catalyst layer to reach the chemical reaction. Experimental study and microscopic analysis [46] showed that the catalyst layer is porous and the reactants can transport through the catalyst layer in gas phase. In order to account for this phenomenon, the so-called lm model [7] and agglomerate model [46,810] have been proposed. In the lm model, the catalyst particles are assumed to be covered by a thin lm of polymer electrolyte and the reactants diffuse through the gas pores in the electrode to the thin lm of the polymer electrolyte and then to the catalyst particles where the chemical reaction takes place. But in the agglomerate model, the catalyst layer is regarded as a region consisting of small homogeneous

0013-4686/$ see front matter. Crown Copyright 2004 Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2004.01.114

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agglomerates and each agglomerate is surrendered by gas pores. Experimental investigation [4] showed that the agglomerate model might be better suited to modeling the cathode behavior, especially at high current density. The cathode catalyst layer is the core part of the PEM fuel cell and its performance is heavily related to its structure or morphology. All of the available works, either numerical or experimental, took the catalyst layer as a one-layer material in which all properties are constants. In this paper, we assume that the catalyst layer is composed of several sublayers and different sub-layer has different material properties, such as porosity, agglomerate size and agglomerate porosity. The effects of different material property combinations for these sub-layers on the performance of the whole catalyst layer are investigated. The performances of multi- and single-layer of the catalyst structure are also compared. 2. Mathematical model The schematic diagram of the catalyst layer in our model is shown in Fig. 1. The porous catalyst layer is assumed to be constituted of a large number of ooded spherical agglomerates. The conguration of the catalyst layer in our model is assumed to have several sub-layers that are constituted of different size of agglomerates due to different manufacturing processes and different ink preparations. Each sub-layer is considered to be homogeneous. But different sub-layer has different material properties, such as agglomerate size, agglomerate porosity, or sub-layer porosity, etc. We assume that the diameter of the spherical agglomerate is small compared to the thickness of each sub-layer in which the agglomerate located. The electrolyte composition is also assumed to be uniform in the agglom-

erates and Ohmic losses are negligible within these agglomerates. By making a mass balance for oxygen on a spherical shell within the agglomerate, the governing equation for dissolved oxygen concentration, denoted by cO2 is given as [11]
eff Dagg

1 d r 2 dr

r2

dcO2 dr

=A

iref 0 nF

cO2 ref cO2

exp

r F , RT (1)

0 r Ragg with the following two boundary conditions: dcO2 dr = 0; cO2

r=Ragg s = cO2

(2)

r=0

eff where Dagg is the effective diffusion coefcient of oxygen in the agglomerate, r the radial coordinate in agglomerate, cO2 the dissolved oxygen concentration, A the specic area of the catalyst per unit volume of an agglomerate, n the number of electrons transferred in cathode reaction, F the Faradays ref constant, iref reference exchange current density, cO2 refer0 ence oxygen concentration, r cathodic transfer coefcient of the ORR, R gas constant, T electrode temperature, and the local overpotential in an agglomerate, Ragg the agglomers ate radius and cO2 the dissolved oxygen concentration at the surface of the agglomerate. The effective diffusion coefcient of oxygen in the ageff glomerate, namelyDagg , can be calculated according to the Burggeman relation [12]: eff Dagg = DO2 ,p 3/2 agg

(3)

where agg is the porosity of the polymer electrolyte in an agglomerate, DO2 ,p the bulk oxygen diffusion coefcient in the polymer. The reference exchange current density for oxygen reduction in Naon depends on the temperature T based on

Fig. 1. The schematic diagram of the catalyst layer.

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Parthasarathys experimental results and the relationship [13] is iref = 10(3.5074001/T ) 0 (4)

The analytic solution of Eq. (1), for the rst-order reaction and with the given boundary conditions Eq. (2), is derived by Bird et al. [11]
s cO2 = cO2

where j is the porosity of the jth sub-layer, Ragg,j the radius of the agglomerate in this sub-layer. The current produced in each agglomerate in jth subs eff layer,Iagg,j , can be obtained by substituting Ragg , Dagg , cO2 , eff ,cs and in Eq. (7) by their counterparts Ragg,j ,Dagg,j O2 ,j , and j in the jth sub-layer
eff s Iagg,j = 4nFRagg,j Dagg,j cO2 ,j

Ragg sinh(r) r sinh(Ragg )

(5)

(j Ragg,j coth(j Ragg,j ) 1)

(13)

where = Airef 0 exp eff ref nFDagg cO2 r F 2RT (6)

where the effective diffusion coefcient of oxygen in the agglomerate of the jth sub-layer is estimated from Eq. (3) as:
eff Dagg,j = DO2 ,p agg,j 3/2

(14)

The current generated in each agglomerate is proportional to the molar ux of oxygen into the agglomerate through its surface and is calculated by Faradays law as [11]:
eff s Iagg = 4nFRagg Dagg cO2 (Ragg coth(Ragg ) 1)

and agg,j is the porosity of polymer electrolyte in the agglomerate of jth sub-layer. Applying Ohms law to jth sub-layer gives d 1 = eff i dx j (15)

(7)

The oxygen concentration at the inner side of the aggloms erate surface,cO2 , is related to the oxygen concentration at the outer side of the agglomerate surface by Henrys law:
s cO2 =

eff for lj1 x lj , j = 1, 2, . . ., m. Here, j is the effective proton conductivity in the jth sub-layer and is given by Jaouen et al. [10] eff j = (1 j )agg,j

(16)

1 cO ,g K O2 2

(8)

where cO2 ,g is the oxygen concentration in gas phase in the catalyst layer, KO2 the Henrys law coefcient (dimensionless) for oxygen gas dissolved in liquid water at the surface of the agglomerate and can be calculated from the empirical correlation [14] as: KO2 = 1 666 exp + 14.1 RT T (9)

where is the bulk proton conductivity of the polymer. The variation of the oxygen concentration in gas phase in jth sub-layer follows the Ficks law, which yields dcO2 ,g i itot = eff dx nFDO2 ,j (17)

where itot is the total current density produced in the catalyst eff layer, DO2 ,j is the effective diffusion coefcient of oxygen in the jth sub-layer and is given as:
eff DO2 ,j = DO2 ,g j 3/2

Assuming that the whole catalyst layer is composed of m sub-layers, let us now establish the governing differential equations for current density, overpotiential and oxygen concentration for each sub-layer. The local proton current density in the jth sub-layer (j = 1, 2, . . ., m) can be calculated from the proton mass balance, which gives di = agg,j Iagg,j dx for and lj1 x lj , j = 1, 2, . . ., m, and l0 = 0; l1 = L1 ; l2 = L1 + L2 ; (11) lm = L1 + L2 + + Lm = L (10)

(18)

The boundary conditions for the differential Eqs. (10), (15) and (17) are given as follows: At x = l0 : i|x=l0 = 0; cO2 ,g
x=l0

|x=l0 = tot ; (19) |x=l = |x=l+ ;

j j

= c i|x=l = i|x=l+ ;
j j

At x = lj : cO2 ,g
+ x=lj

= cO2 ,g

x=lj

(20) |x=lm = 0 ;

At x = lm :

i|x=lm = itot ;

where Lj is the thickness of the jth sub-layer, i the local proton current density, agg,j the density of agglomerates in the jth sub-layer and given by: agg,j = 1 j 4/3R3 agg,j (12)

dcO2 ,g =0 (21) dx x=lm where tot is the overpotiential at the interface between the gas diffusion layer and the catalyst layer, 0 a reference overpotiential at the interface of the catalyst layer and the membrane, c the oxygen concentration at the interface of the gas

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Table 1 Operating parameters and physical properties for the baseline n=4 F = 96485 DO2 ,g = 2.837 101 (cm2 s1 ) L = 1.5 103 (cm) PO2 = 0.21 (atm) GDL = 0.2 ref A/cO2 = 3.2 1012 (cm2 mol1 ) L1 = L2 =L3 = 1/3L = 5 104 (cm) agg,1 = agg,2 = agg,3 = 0.2 (C mol1 ) m=3 R = 8.315 (J K1 mol1 ) DO2 ,p = 6 106 (cm2 s1 ) LGDL =4.0 102 (cm) T = 343 (K) = 0.07 (S cm1 ) r = 0.58 Ragg,1 = Ragg,2 = Ragg,3 = 0.9 104 (cm) 1 = 2 = 3 = 0.2

diffusion layer and the catalyst layer and can be obtained by applying Ficks law to the gas diffusion layer as: itot P O2 LGDL + c = eff RT nFDO2 ,GDL

3. Numerical results and discussions For each sub-layer of the catalyst layer, j, the governing differential equations (Eqs. (10), (15) and (17)), combining with their corresponding boundary conditions (Eqs. (19)(21)), consist of a group of boundary value problem (BVP). For the sake of computation, these m VPs are rewritten into one BVP on the whole catalyst layer. The functions involved in the right side of the each governing differential equation in the resulting BVP are piecewise functions on the interval [0, L]. The continuity of these piecewise functions at the inner interfaces of the catalyst layer is guaranteed by the continuity conditions (Eq. (20)). The nal BVP is solved by MATLAB software. The operating parameters and physical properties used in the computation for the baseline are listed in Table 1. Fig. 2 shows the comparison of the polarization curve calculated from the baseline data in Table 1 (in this

(22)

where LGDL is the thickness of the gas diffusion layer, PO2 eff the oxygen pressure in the cathode, DO2 ,GDL the effective diffusion coefcient for oxygen in the gas diffusion layer and related to the oxygen diffusion coefcient by Burggeman relation:
eff DO2 ,GDL = DO2 ,g GDL 3/2

(23)

where DO2 ,g is the oxygen diffusion coefcient in gas phase, GDL the porosity of the gas diffusion layer.

Fig. 2. Comparison of the baseline with the experimental data from Ref. [4].

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Fig. 3. The effect of agglomerate size combination on the performance of catalyst layer.

case, the catalyst layer is considered as a one-layer material) with the experimental data from Ref. [4]. As an illustration example, we assume that the catalyst layer is constituted by three sub-layers (m = 3). The effects of different combinations or patterns of agglomerate radii, agglomerate porosities or sub-layer porosities on the whole catalyst layer performance are discussed. Fig. 3 shows that if the agglomerate radii in the three sub-layers decrease from the left side (the side close to the gas diffusion layer) to the right

side (the side close to the membrane), i.e. the agglomerate radii in the three sub-layers take the pattern of (big, medium, small), the whole catalyst layer performance will be improved comparing to the baseline in which all the agglomerate radii are assumed to be same for different sub-layers. This is because when the agglomerate radius decrease, the agglomerate density in the catalyst layer increase, which results in the increase of the current produced in the agglomerate and nally improves the catalyst layer performance. If the agglomerate

Fig. 4. The effect of agglomerate porosity combination on the performance of catalyst layer.

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D. Song et al. / Electrochimica Acta 50 (2004) 731737

Fig. 5. The effect of sub-layer porosity combination on the performance of catalyst layer.

radii take the pattern of (small, medium, big), the performance of the whole catalyst layer will be also improved. Further investigation shows that the agglomerate size of the sub-layer of the right side (i.e. the sub-layer next to the membrane) has a bigger effect on the whole catalyst layer performance than the agglomerate sizes of other two sub-layers. The catalyst layer which operates in the baseline is in the proton conductivity limiting regime. In this regime, the active reaction region is close to the membrane and this region is more sensitive than the area close to the gas diffusion layer. Fig. 4 gives the effects of different patterns of agglomerate porosities for these three sub-layers on the whole catalyst layer performance. From Fig. 4, we can see that the pattern of (small, medium, big) for the agglomerate porosities in three sub-layers will increase the catalyst layer performance while the pattern (big, medium, small) will decrease the performance comparing to the baseline because increasing the agglomerate porosity can increase the oxygen diffusion in the agglomerate, thus improve the catalyst layer performance. Again, the performance of the catalyst layer is mainly inuenced by the agglomerate porosity of the sub-layer close to the membrane regarding changing of the agglomerate porosities in sub-layers because of the limitation of the proton conductivity. Fig. 5 shows the effects of the different patterns of the porosities for the three sub-layers on the whole catalyst layer performance. From Fig. 5, it can be seen that the pattern of (small, medium, big) of the porosities for the three sublayers will degrade the performance. On the contrary, the pattern (big, medium, small) will improve the performance. The explanation for this phenomenon is given as follows: small sub-layer porosity will increase the agglomerate den-

sity, which causes the specic reaction area increasing and results in the improvement of the performance.

4. Conclusions A multi-layer agglomerate model is presented to account for the cathode catalyst layer in a PEM fuel cell and the performance of the cathode catalyst layer has been studied by dividing the whole catalyst layer into several sub-layers with different agglomerate sizes, different agglomerate porosities and different sub-layer porosities. The properties of the sublayer next to membrane have major effect on the whole catalyst layer performance comparing to the properties of the other sub-layers when the catalyst layer is working in the proton conductivity limiting regime. The more the sub-layer is close to the membrane, the more the effects of the agglomerate size, agglomerate porosity, and sub-layer porosity on the whole catalyst layer performance are. Furthermore, decreasing the agglomerate sizes, increasing the agglomerate porosities or decreasing the sub-layer porosities for sublayers from the side of the gas diffusion layer to the side of the membrane layer will also improve the performance of the whole catalyst layer.

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