Electrochimica Acta 50 (2004) 725730

A mathematical model and optimization of the cathode catalyst layer structure in PEM fuel cells
Qianpu Wanga , Datong Songa , Titichai Navessina,b , Steven Holdcrofta,b , Zhongsheng Liua,
a

National Research Council (NRC), Institute for Fuel Cell Innovation (IFCI), 3250 East Mall, Vancouver, BC, Canada V6T 1W5 b Department of Chemistry, Simon Fraser University (SFU), Burnaby, BC, Canada V5A 1S6 Received 5 June 2003; received in revised form 9 December 2003; accepted 10 January 2004 Available online 6 August 2004

Abstract A spherical ooded-agglomerate model for the cathode catalyst layer of a proton exchange membrane fuel cell, which includes the kinetics of oxygen reduction, at the catalyst|electrolyte interface, proton transport through the polymer electrolyte network, the oxygen diffusion through gas pore, and the dissolved oxygen diffusion through electrolyte, is considered. Analytical and numerical solutions are obtained in various control regimes. These are the limits of (i) oxygen diffusion control, (ii) proton conductivity control, and (iii) mixture control. The structure and material parameters, such as porosity, agglomerate size, catalyst layer thickness and proton conductivity, on the performance are investigated under these limits. The model could help to characterize the system properties and operation modes, and to optimize catalyst layer design. Crown Copyright 2004 Published by Elsevier Ltd. All rights reserved.
Keywords: PEM fuel cell; Catalyst layer; Mathematical modeling; Mass transport

1. Introduction Proton exchange membrane (PEM) fuel cells operate at a low temperature to convert chemical energy directly into electrical energy. Low emission of pollutants and high electricity conversion efciency make this technology attractive, and it is currently being considered as one of the most promising candidates for automotive and stationary applications. Despite the improvements in cathode performance and platinum utilization during the last decade, a major contribution to the potential drop and losses of efciency in PEM fuel cell is still due to the poor kinetics of O2 reduction and transport limitations of reactants in the cathode catalyst layer. In order to improve the catalyst utilization and fuel cell performance, it is important to understand the relation between structural characteristics and performance, particularly, the mass-transport limitations and performance. The

Corresponding author. Tel.: +1 604 221 3068; fax: +1 604 221 3001. E-mail address: simon.liu@nrc.ca (Z. Liu).

determination of mass-transport limitations in a porous cathode is a complex problem, requiring advanced models be confronted with experimental data. Over the past 10 years, numerous works have been published describing modeling of membrane electrode assemblies (MEAs). Notable models are those proposed by Lindbergh et al. [1], Bernardi and Verbrugge [2,3], Springer et al. [4,5], and Perry et al. [6]. There is no standard method for characterizing microscopic features of MEAs. One mathematical approach is the porouselectrode theory, which employs a macroscopic model to account for essential features of a porous electrode without delving into exact geometric details. The macroscopic models treat the catalyst layer as a continuum. The governing equations are derived to address the transfer processes between different phases in the porous media and lumped parameters are needed for the calculation. Three main approaches: the homogeneous [2,3,6,8,9]; lm [7]; and agglomerate models [1,6] have been proposed to describe MEA behaviour. In the homogeneous model, it is assumed that the electrode active layer consists of a uniform, gas pore-free

0013-4686/$ see front matter. Crown Copyright 2004 Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2004.01.113

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blend of proton conducting polymer and supported catalyst. In the lm model, gas pores are assumed to exist within the electrode, and the catalyst particles covered by a thin lm of polymer. In the agglomerate model, the active layer is regarded as a region where small homogeneous domains are surrounded by gas pores. In this paper, a spherical ooded-agglomerate model for the cathode catalyst layer of a proton exchange membrane fuel cell, which includes the kinetics of oxygen reduction, at the catalyst|electrolyte interface, proton transport through the polymer electrolyte network, the oxygen diffusion through gas pore, and the dissolved oxygen diffusion through electrolyte, is considered. Analytical or numerical solutions are obtained under different limit conditions. Depending on the operate conditions and catalyst layer structure, fuel cells could run on the several control regimes. These are the limits of (1) oxygen diffusion control, (2) proton conductivity control, (3) mixture control. Compared with previous study [9], the effects of structure parameters like agglomerate radius and agglomerate density on the performance in the different control regimes have been systematically studied.

the membrane with its origin located at the interface between the cathode electrode and catalyst layer. All uxes are taken as positive in the positive x-direction, while the electric current density is opposite to the x-direction, as shown. The void space is large, about 40300 nm so that the Knudsen diffusion is unimportant compared to the bulk diffusion. It is further assumed that the catalyst layer has a uniform distribution of its agglomerates. Therefore, if we neglect any ohmic losses within these carbon particles, the potential within the agglomerate is constant, and we need only consider the diffusion and reaction of oxygen within the spherical agglomerates:
eff Da

1 d r 2 dr

r2

dcO2 dr

= RORR

(1)

eff where Da is the effective diffusivity of oxygen in the porous agglomerate, which may be dened by Bruggemann relation as: eff Da = DO2 3/2 a

(2)

The ORR kinetics in a proton conducting polymer electrolyte was assumed to follow a Tafel law and to be rst-order in oxygen concentration. RORR = Aa iref ia = Aa 0 nF nF cO2 ref c0 exp r F RT (3)

2. Model description The model proposed in this paper is one-dimensional, isothermal, steady state and includes the elements dening the cathode side of PEM fuel cell. The cathode catalyst layer is assumed to consist of a mixture of spherical agglomerates, void space. The spatial coordinate x is dened in Fig. 1 so that the positive direction points from the cathode electrode to

An analytic solution to the Eq. (1) for a rst-order reaction with the given boundary condition, is provided by Scott [10]:
s cO2 = cO2

Ra sinh(r) r sinh(Ra )

(4)

Fig. 1. Schematic diagram of catalyst layer microstructure and ooded-agglomerate model.

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where Ra is a dimensionless parameter, commonly known as the Thiele modulus. In this case, Ra = Aa iref 0 R exp eff ref a nFDa c0 r F 2RT (5)

3. Modeling results A fully analytical solution exists in the case of fast proton transport. In the case of proton transport control or mixture control, a fourth-order RungeKutta method is used to solve the set of governing differential equations and the program was written using the MATLAB software. A total overpotential at the active-layer/polymer-membrane interface is given and the total current, current density and oxygen concentration distribution are then computed. 3.1. Fast proton transport If we neglect the proton migration resistance in the catalyst layer, an analytical solution to the Eq. (14) with the given boundary condition, is cO2 ,g = c [cosh(x) tanh(L) sinh(x)] The total current density is
eff Itot = DO2 ,cl c tanh(L)

The current produced in an agglomerate, Ia by Faradays law: Ia = nF (4R2 )N0 a

eff s = 4nFRa Da cO2 [Ra coth(Ra ) 1]

(6)

By using Henry law,

s co2 = KO2 cO2 ,g

(7)

The experimental data of Parthasarathy et al. [11] were used to correlate the reference exchange current density for oxygen reduction in Naon with temperature. log10 (iref ) = 7.507 0 4001 T (8)

(15)

(16)

The current density and overpotential distributions in the catalyst layer can be calculated by means of the proton mass balance in the catalyst layer and Ohms law in the polymer phase, which give the two differential equations: dj = a Ia dx j d = eff dx (9) (10)

In which L is a dimensionless parameter or Thiele modulus in the catalyst layer, L = 3(1 )KO2 eff L Da [(Ra coth(Ra ) 1)] eff Ra DO2 ,cl (17)

The oxygen concentration and proton current density proles determined by: cO2 ,g = [cosh(x) tanh(L) sinh(x)] c j = [cosh(x) tanh(L) sinh(x)] Itot (18) (19)

a is the density of agglomerates in the active layer and is dened as: a = 1 c (4/3)R3 a (11)

The oxygen ux through the catalyst layer is assumed due to concentration gradient only, so that from the Ficks law of diffusion, we have dcO2 ,g NO = eff2 dx DO ,c
2

Fig. 2 shows the proles of oxygen concentration and proton current density with different catalyst layer Thiele modulus in the case of fast proton transport. With high proton conductivity but strong transport limitations due to oxygen

(12)

and NO2 (x) = j Itot 4F

3/2

(13)

eff where DO2 ,c = DO2 ,g (eff ) , eff is the effective porosity of c c the catalyst layer and DO2 ,g the oxygen diffusion constant in the gas pore. Itot the total current density of active layer. Combining with Eqs. (12), (15) and (16) we have eff nFDO2 ,c

d2 cO2 ,g = a Ia dx2

(14)

Fig. 2. Dimensionless proles of O2 concentration and proton current density in the case of fast proton transport in the catalyst layer.

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Fig. 3. Polarization curves at various catalyst layer thickness in the case of eff fast proton transport (DO2 ,cl = 5e 6 cm2 s1 ).

Fig. 5. Polarization curves at various catalyst layer thickness in the case of proton transport control.

diffusion, at Thiele modulus L > 1 considerable depletion of oxygen begins. At high Thiele modulus L > 4, only a small layer of thickness Leff close to the gas backing side contributes actively to the reaction. Because of the poor oxygen diffusivity, all the supplied oxygen is consumed in a layer with the thickness Leff . The agglomerate size and porosity, the effective catalyst layer porosity in this narrow region will play a key role on the performance. The analytical solution (Eq. (19)) clearly shows how these parameters affect the performance. Fig. 3 shows that when these transport rates are too low to utilize platinum throughout the catalyst layer, a thicker catalyst layer can generate higher currents only at very low current density. 3.2. Fast oxygen diffusion Fig. 4 shows the active part of the catalyst layer may be conned to a narrow region near the membrane side of the

catalyst layer associated with a lower cell potential when the proton conductivity is the limiting factor. It is because of a sharp increase of the potential drop at lower cell potential due to ohmic contributions of the poorly conducting electrolyte phase. The agglomerate size and porosity, the effective catalyst layer porosity in this narrow region will play a key role on the performance. Any efforts, which include decreasing the catalyst layer porosity, increasing Naon content and water content, to increase the proton transport will improve the cell performance. Fig. 5 shows the inuence of the catalyst layer thickness, in which a thicker catalyst layer can generate higher currents only at very low current density. 3.3. Mix control In the mix control shown in Fig. 6, the proton current density distribution will move up or downwards which de-

Fig. 4. Dimensionless proles of O2 concentration and proton current density in the case of proton transport control ( = 0.001).

Fig. 6. Dimensionless proles of O2 concentration and proton current density in the case of mix control in the catalyst layer. (1) j0 = 1.0 A cm2 and eff = 0.01; (2) j0 = 0.5 A cm2 and eff = 0.01; (3) j0 = 0.1 A cm2 cl cl eff and eff = 0.01; (4) j0 = 0.5 A cm2 and DO2 ,cl = 5e 5 cm2 s1 ; (5) j0 = cl
eff 1.0 A cm2 and DO2 ,cl = 5e 5 cm2 s1 ).

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as possible to minimize the adverse effects of mass transport at high current density. Only part of the electrocatalyst is effectively utilized when either the oxygen or the proton cannot fully penetrate all parts of electrode. 1. The interplay of oxygen diffusion coefcient and proton conductivity limitations is a key property of the catalyst layer that could signicantly affect PEFC performance at medium and high current densities. 2. If the oxygen diffusion is very limited relative to the current density, the active region of the catalyst layer may be conned to a narrow region of the catalyst layer close to the gas diffusion layer. 3. If the proton conductivity is the limiting factor, the active part of the catalyst layer may be conned to a narrow region near the membrane side of the catalyst layer associated with a higher effective overpotential. 4. To achieve high catalyst utilization and cell performance, it is better to design and manufacture nonuniform catalyst layer, which will be studied elsewhere.

Fig. 7. Polarization curves at various catalyst layer thickness in the case of mix control (eff = 0.01). cl

pends on oxygen and proton transport resistance. From the gure, various control regimes such as fast oxygen diffusion, fast proton transport and mix control can be dened. In the left up area, it is the oxygen diffusion control regime. In the right down area, it is the proton transport control regime. In the area close the diagonal line, it is the mix control regime. The thickness of the catalyst layer is investigated in the mix control. Fig. 7 shows that at low current density, a thicker catalyst layer can generate higher current. At high current density, the additional thickness of the catalyst layer serves only as a mass- and/or proton-transport barrier, and lead to diminished currents in spite of the increased catalyst loading. The thickness, or catalyst loading, in the catalyst layer is an important consideration of electrode design. Generally, fuel cells are designed to operate at a given potential to meet an efciency goal. At constant potential, the current density will increase with catalyst loading until some point where mass transfer (oxygen and proton) becomes rate limiting. From the above analysis, the ideal catalyst layer structure may be nonuniform in which both the oxygen diffusion and proton conductivity can be satised. On the side of catalyst layer close the gas diffusion layer, the main issue is to increase the oxygen transport and electron transport. It can be achieved by increasing the catalyst layer porosity, carbon content and increasing the hydrophobicity. On the membrane side of the catalyst layer, the main issue is to improve the proton transport. It can be achieved by decreasing this region porosity, increasing Naon content and hydrophilicity.

Appendix A. Nomenclature

Aa b c
ref c0 cO2

cO2 ,g DO2
eff Da

DO2 ,g eff DO2 ,c F iref 0 Itotal j KO2 L n R Ra T c eff c a

4. Conclusions The results of these models reinforce an important point that has been emphasized in previous modelsboth the thickness and the size of the agglomerate should be kept as small

catalyst specic area per unit volume of agglomerate (m1 ) Tefal slope, b = (RT)/r oxygen concentration on the interface of GDL and catalyst layer (mol m3 ) oxygen reference concentration (mol m3 ) dissolved oxygen concentration inside the agglomerate (mol m3 ) oxygen concentration in the gas phase (mol m3 ) dissolved oxygen diffusion coefcient in polymer (m2 s1 ) dissolved oxygen effective diffusion coefcient in polymer (m2 s1 ) Oxygen diffusion coefcient in gas phase (m2 s1 ) effective oxygen diffusion coefcient in gas phase (m2 s1 ) Faradays constant (C mol1 ) reference exchange current density (A m2 ) total current density (A m2 ) proton current density (A m2 ) oxygen Henrys constant catalyst layer thickness (m) number of electrons transferred in cathode reaction gas constant (J K1 mol1 ) agglomerate radius (m) cell temperature (K) catalyst layer porosity effective porosity of the catalyst layer polymer volume fraction inside agglomerate nucleus proton bulk conductivity (S m1 )

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eff r a

effective proton bulk conductivity (S m1 ) cathode transfer coefcient density of agglomerates in the active layer overpotential (V)

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