Platinum group metal (PGM)-free catalysts for oxygen reduction reaction are essential for affordable fuel cells.

Low cost and high-performing platinum group metal-free (PGM-free) cathodes have the potential to transform the economics of polymer electrolyte fuel cell (PEFC) commercialization. Significant advancements have been made recently in terms of PGM-free catalyst activity and stability. However, before PGM-free catalysts become viable in PEFCs, several technical challenges must be addressed including cathode's fabrication, ionomer integration, and transport losses. Here, we present an integrated optimization of cathode performance that was achieved by simultaneously optimizing the catalyst morphology and electrode structure for high power density. The chemically doped metal−organic framework derived Fe−N−C catalyst we used allows precise tuning of the particle size over a wide range, enabling this unique study. Our results demonstrate the careful interplay between the catalyst primary particle size and the polymer electrolyte ionomer integration. The primary particles must be sufficiently large to permit uniform ionomer thin films throughout the surrounding pores, but not so large as to impact intraparticle transport to the active sites. The content of ionomer must be carefully balanced between sufficient loading for the complete catalyst coverage and adequate proton conductivity, while not being excessive and inducing large oxygen transport losses and liquid water flooding. With the optimal 100 nm size catalyst and ionomer loading, we achieved a high power density of 410 mW/cm 2 at a rated voltage and a peak power density of 610 mW/ cm 2 in an automotive-relevant operating condition.

Cationic contamination is known to cause performance degradation and reduced lifetime in polymer electrolyte based electrochemical systems. Calcium is an important cationic impurity due to its prevalence in roadside particulates and as an airborne contaminant. The role of calcium ion (Ca 2+ ) is investigated in-situ by injecting a solution of calcium sulfate (CaSO 4 ) in deionized (DI) water into the cathode of a polymer electrolyte membrane (PEM) fuel cell through a nebulizer. Stability tests are conducted to determine the effects at various current densities with various Ca 2+ concentrations. It is found that 5 parts per million (ppm, molar ratio) eq. Ca 2+ in air is sufficient to lead to high cell performance loss at 1 A/cm 2 as well as severe membrane degradation. Precipitation of CaSO 4 is found at the contact regions between the gas diffusion layers (GDL) and bipolar plates of the cathode at all test conditions. The amount of precipitation becomes sufficient to cause mass transport issues.