Investigating the Applicability of the Tafel Equation in Polymer Electrolyte Membrane Electrolyzers via Statistical Analysis

Analyzing PEM electrolyzer polarization curves via voltage breakdown analysis involves decomposing contributions from underlying processes, typically based on the assumption of reaction kinetics that may be expressed by means of the Tafel equation. When extrapolating the corresponding straight line to high current densities, there is a discrepancy between the measurement and model, which is often attributed to mass transport resistance. In addition to the qualitative description of this mass transport resistance, a consistent quantification is difficult to obtain from the measurement results. Accordingly, the approach to the breakdown analysis of the polarization curves is strongly based on assumptions that evade experimental verification. In this study, an alternative statistical method is introduced that permits the falsifiability of the standard approach. By means of experiments at different hydrogen partial pressures and a subsequent data fit, it is possible to extract the kinetic behavior without prior specification. The results indicate that behavior corresponding to the Tafel equation cannot be proven wrong. In addition, transport coefficients can be evaluated that fall between those of membranes and porous transport layers, indicating that the catalyst layer predominantly contributes to the mass transport resistance.