Mass transfer Butler-Volmer model

The analysis of the kinetics of the charge transfer is presented in Sect. 1.7 for the Butler-Volmer and Marcus-Hush formalisms, and in the latter, the extension to the Marcus-Hush-Chidsey model and a discussion on the adiabatic character of the charge transfer process are also included. The presence of mass transport and its influence on the current-potential response are discussed in Sect. 1.8. 

The static - double-layer effect has been accounted for by assuming an equilibrium ionic distribution up to the positions located close to the interface in phases w and o, respectively, presumably at the corresponding outer Helmholtz plane (-> Frumkin correction) [iii], see also -> Verwey-Niessen model. Significance of the Frumkin correction was discussed critically to show that it applies only at equilibrium, that is, in the absence of faradaic current [vi]. Instead, the dynamic Levich correction should be used if the system is not at equilibrium [vi, vii]. Theoretical description of the ion transfer has remained a matter of continuing discussion. It has not been clear whether ion transfer across ITIES is better described as an activated (Butler-Volmer) process [viii], as a mass transport (Nernst-Planck) phenomenon [ix, x], or as a combination of both [xi]. Evidence has been also provided that the Frumkin correction overestimates the effect of electric double layer [xii]. Molecular dynamics (MD) computer simulations highlighted the dynamic role of the water protrusions (fingers) and friction effects [xiii, xiv], which has been further studied theoretically [xv,xvi]. 

Kawamoto (2) developed a two-dimensional model that is based on a double iterative boundary element method. The numerical method calculates the secondary current distribution and the current distribution within anisotropic resistive electrodes. However, the model assumes only the initial current distribution and does not take into account the effect of the growing deposit. Matlosz et al. (3) developed a theoretical model that predicts the current distribution in the presence of Butler-Volmer kinetics, the current distribution within a resistive electrode and the effect of the growing metal. Vallotton et al. (4) compared their numerical simulations with experimental data taken during lead electrodeposition on a Ni-P substrate and found limitations to the applicability of the model that were attributed to mass transfer effects. 

Eor very high exchange current densities (i.e., rapid reactions), a linearized form of Eq. 27 can often be used. For very slow reaction kinetics, either the anodic or cathodic term dominates the kinetics, and so the other term is often ignored, yielded what is known as a Tafel equation for the kinetics. Often, more complicated expressions than that of Eq. 27 are used. For example, if the elementary reaction steps are known, one can write down the individual steps and derive the concentration dependence of the exchange current density and the kinetic equation. Other examples include accounting for surface species adsorption or additional internal or external mass transfer to the reaction site [9]. All of these additional issues are beyond the scope of this chapter, and often an empirically based Butler-Volmer equation is used for modeling the charge transfer in porous electrodes. 

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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