(Invited) Fundamental Structure-Function Relationships for Iridium Oxide Catalysts in PEM Water Electrolyzers

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The intermittency of renewable energy poses significant challenges to developing a grid system that utilizes primarily renewable-based sources. Proton exchange membrane water electrolyzers (PEMWEs) can convert surplus energy from the grid into chemical energy in the form of green hydrogen, which can then be used to generate electricity when the renewable supply is low. Despite much technological advancement over the last two decades, PEMWEs still face many barriers to widespread commercialization. Around a quarter of the cost of the PEMWE system is attributed to iridium, a highly scarce material used as the oxygen evolution reaction (OER) catalyst on the anode side. To enable lower loadings/higher utilization of these catalysts, fundamental studies on iridium activity and degradation are necessary. As it stands in the literature, studies on how physical properties of the catalyst (i.e. crystallinities, valance states, etc.) affect PEMWE performance are scarce. This work aims to elucidate the relationship between structural properties and efficiency/performance for iridium oxide (IrOx ) catalysts in PEMWEs. Five commercially available iridium oxide catalysts were characterized (47491 Alfa Aesar, TEC77100, TEC77110, FIO-01, FIO-11) using transmission electron microscopy (TEM), scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), Brunauer–Emmett–Teller (BET) analysis, and x-ray diffraction (XRD) to obtain crystallinities, particle size distributions, specific surface areas, thermal stabilities, elemental compositions, and valance states. Afterwards, kinetic performance was baselined by taking cyclic voltammograms (CVs) via rotating disk electrode (RDE) experiments and electrochemical surface areas (ECSA) were approximated by using a novel analysis developed in this work that can relate the hysteresis in OER potentials to a double layer capacity. Results show that greater amorphous character of IrOx was correlated with increased kinetic performance at the expense of electrochemical stability across redox potentials between 0-1.6V. From the cyclic voltammograms, the catalyst with the most amorphous character underwent multiple (two, possible three) redox transitions, while the one with the most crystalline character showed no evidence of any redox transitions. It was also found that increased ECSA was correlated with greater physical surface areas obtained from BET analysis and that greater amorphous character resulted in a higher Ir III :Ir IV ratio. For future work, we aim to incorporate these fundamental structure-function insights to create standardized accelerated stress tests for PEMWEs, as standards for durability testing have yet to be established.