Measurement of Ionomer Coverage on Carbon and Pt in Catalyst Layer of Polymer Electrolyte Fuel Cells by Electrochemical Impedance Spectroscopy

Surface coverages of ionomer on Pt and carbon support are key properties to clarify the ionomer distribution in cathode catalyst layer of polymer electrolyte fuel cells. However, their measurement is highly challenging especially for carbon, where Faradaic charge is not visible in voltammograms. Conventionally, the capacitance measured by voltammetry or electrochemical impedance spectroscopy is used to determine the ionomer coverage. In these methods, surface coverages are obtained by comparing the double layer capacitance at wet condition with that at dry condition; Pt and carbon surfaces covered by ionomer and water contributes to the capacitance at wet condition, while surfaces covered only by the ionomer contributes at the dry condition because of the absence of water. However, when measured capacitance is converted to surface area, the methods assume that the specific capacitance (capacitance per surface area) is independent of the humidity although it significantly changes in reality, because the double layer structure of ionomer changes. Here, we propose an alternative method that significantly suppresses the change in specific capacitance. The method was applied to porous and nonporous carbon supports with Pt nanoparticle catalyst. The measurement also indicates that the surface coverages on both Pt and carbon are reduced in the case of the porous carbon. Graphical Abstract