Catalyst layer exchange current density

Figure 15.3 Simulated effectiveness factor for porous carbon electrode as a function of the exchange current density jo and DCo for Ip] = 0.4 V for a 10wt% Pt/C catalyst layer with 7= 10, A = 140m g p = 2gcm, Nafion volume fraction 0.6, thickness p,m, and ionic conductivity 0.05 Scm See the text for details. (Reproduced from Gloaguen et al. [1994], with kind permission from Springer Science and Business Media.)...

The most important electrokinetic data pertinent to fuel cell models are the specific interfacial area in the catalyst layer, a, the exchange current density of the oxygen reduction reaction (ORR), io, and Tafel slope of ORR. The specific interfacial area is proportional to the catalyst loading and inversely proportional to the catalyst layer thickness. It is also a strong function of the catalyst layer fabrication methods and procedures. The exchange current density and Tafel slope of ORR have been well documented in refs 28—31. 

Fig. 15 Dependence of basic catalyst layer parameters on composition, according to Eqs. (87-89). The percolation-type dependencies on electrolyte content Xe are depicted for the normalized parameters of (a) proton conductivity, a, and oxygen diffusivity, /, as well as (b) for the exchange current density at the indicated values of Xec (residual reactivity), the percolation threshold Xc = 0.1, and the residual diffusivity parameter Xd = 0.01.

Here, c02 and cm are oxygen and methanol concentrations in the respective catalyst layer, CQ2ref and cAfref are reference concentrations, r]c = cpe — (pc, rja = q>a — anode electrode potentials respectively, ia, ic are exchange current densities per unit volume (A cm-3), aa, ac are transfer coefficients, and ya, yc orders of reaction. 

Physically, the reason for the dramatic difference between performances of cathode and anode active layers is the exchange current density ia at the anode the latter is 10 orders of magnitude higher than at the cathode [6]. Due to the large ia, the electrode potential r]a is small. The anode of PEFC, hence, operates in the linear regime, when both exponential terms in the Butler-Volmer equation can be expanded [178]. This leads to exponential variation of rja across the catalyst layer with the characteristic length (in the exponent)... 

The exchange current density is the key property of catalyst layers. It determines the value of the overpotential needed to attain the targeted fuel cell current density. This property, thus, links fundamental electrode theory with practical aspects of fuel cell performance. The following parameterization distinguishes explicitly the effects of different structural characteristics,... 

So far, we have focused on the formal description of current generation in the catalyst layer and discussed major effects of structure and composition on exchange current density and catalyst utilization. In the remainder of this chapter, we will explore in detail, how electrocatalytic activity interferes with other processes at the catalyst surface (e.g. surface diffusion) and transport in the bulk phases. The key measure of catalyst layer performance is the current density that could be extracted from a cell for a given cell potential. This links the spatially varying concentrations and reaction rates with the global performance, rated in terms of power density and fuel cell efficiency. 

The length scale i a 50 — 100 nm determines the effectiveness of catalyst utilization for spherical agglomerates. Analogous relations apply for ultrathin planar catalyst layers with similar thickness, L 100 — 200 nm. We consider layers that consist of Pt, water-filled pores and potentially an electronically conducting substrate. With these assumptions, we can put/(dfptc, XfXptc = 1 and g Sr) = 1. The volumetric exchange current density is, thus. 

Here, L the is exchange current density (per unit volume), c, and Cref are available in the catalyst layer and reference oxygen molar concentration, respectively, b is the Tafel slope. Introducing the dimensionless variables... 

Electrode Kinetic and Mass Transfer for Fuel Cell Reactions For the reaction occurring inside a porous three-dimensional catalyst layer, a thin-film flooded agglomerate model has been developed [149, 150] to describe the potential-current behavior as a function of reaction kinetics and reactant diffusion. For simplicity, if the kinetic parameters, such as flie exchange current density and diffusion limiting current density, can be defined as apparent parameters, the corresponding Butler-Volmer and mass diffusion relationships can be obtained [134]. For an H2/air (O2) fuel cell, considering bofli the electrode kinetic and the mass transfer, the i-rj relationships of the fuel cell electrode reactions within flie catalyst layer can be expressed as Equations 1.130 and 1.131, respectively, based on Equation 1.122. The i-rj relationship of the catalyzed cathode reaction wifliin the catalyst layer is... 

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