Utilizing ink composition to tune bulk-electrode gas transport, performance, and operational robustness for a Fe–N–C catalyst in polymer electrolyte fuel cell

With lower site density and turnover frequency, platinum group metal (PGM)-free catalysts based electrodes are often greater than 50 μm thick in order to increase performance across the fuel cell operating range. Consequently, PGM-free electrodes have an additional bulk electrode transport resistance beyond the local or aggregate level transport in thin platinum-based electrodes. In parallel to the development of more active and durable PGM-free catalysts, advancements in understanding the interplay between PGM-free electrode fabrication, bulk-electrode transport, proton conductivity and performance are needed. Here, the relationship between ionic and gas phase transport through the electrode thickness is modified by adjusting electrocatalyst and ionomer flocculation/interaction at the ink level. The influence of the ink composition (water/n-propanol content) is examined via various in-situ electrochemical and ex-situ characterization techniques and the resulting electrode structure/performance relationship contrasted with electrode performance robustness across a range of relative humidity (RH). For the electrocatalyst examined here, a water-rich (82 wt% H2O) ink formulation was favorable for operation at high RH due to improved molecular diffusion through larger electrode pores. In contrast, the improved interactions between ionomer and electrocatalyst enabled a more robust electrode and higher performance during low RH operation for the 50 wt% H2O content ink. [Display omitted] •Ink formulation was varied to elucidate changes in PGM-free electrode structure.•PEFC performance strongly depends on the water-to-alcohol ratio in the ink.•Ink composition affects ionomer distribution and bulk electrode transport properties.•Ink composition influences ionomer-catalyst interaction.