The combination of operando small- and wide-angle X-ray scattering (SAXS, WAXS) is here presented to provide insights into the changes in mean particle sizes and phase fractions in fuel cell catalyst layers during accelerated stress tests (ASTs). As fuel cell catalyst, a bimodal Pt/C catalyst was chosen that consists of two distinguishable particle size populations. The presence of the two different sizes should favor and uncover electrochemical Ostwald ripening as degradation mechanism, i.e., the growth of larger particles in the Pt/C catalyst at the expense of the smaller particles via the formation of ionic metal species. However, instead of electrochemical Ostwald ripening, the results point toward classical Ostwald ripening via the local diffusion of metal atoms on the support. Furthermore, the grazing incidence mode provides insights into the catalyst layer depth-dependent degradation. While the larger particles show the same particle size changes close to the electrolyte-catalyst interface and within the catalyst layer, the smaller Pt nanoparticles exhibit a slightly decreased size at the electrolyte-catalyst interface. During the AST, both size populations increase in size, independent of the depth. Their phase fraction, i.e., the ratio of smaller to larger size population, however, exhibits a depth-dependent behavior. While at the electrolyte-catalyst interface the phase fraction of the smaller size population decreases, it increases in the inner catalyst layer. The results of a depth-dependent degradation suggest that employing a depth-dependent catalyst design can be used for future improvement of catalyst stability.
Theoretical analysis of particle size re-distribution due to Ostwald ripening in the fuel cell catalyst layer