Uncovering Competitive Surface Adsorption between Ionomers and Supporting Electrolytes in AEM Water Electrolysis

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Anion exchange membrane water electrolyzers (AEMWEs) have emerged as a promising platform for green hydrogen production, offering notable advantages over other electrolysis technologies. While high performance and durability have been achieved in AEMWEs with the use of supporting electrolytes, previous studies attribute this improvement to enhanced local pH and increased electrochemical surface area. 1,2 In this study, we investigate an additional aspect, the role of competitive adsorption between ionomers and supporting electrolytes. Specifically, we systematically vary the supporting electrolyte from alkali metal cations to organic cations to examine how this affects the competitive adsorption behavior of PiperION ionomers on iridium oxide surface under oxygen evolution reaction conditions. Density functional theory calculations are employed to assess adsorption energies and surface morphologies, providing mechanistic insight into the observed behaviors. Our findings help to elucidate the electrochemical surface interactions between ionomers and supporting electrolytes, offering insights into the design of more durable and efficient AEMWE components. References Liu, J. et al. Elucidating the role of hydroxide electrolyte on anion-exchange-membrane water elecrolyzer performance, J. Electrochem. Soc. 168, 054522 (2021). Lim, J. et al. Addressing the challenge of electrochemical ionomer oxidation in future anion exchange membrane water electrolyzers, ACS Energy Letts. 9, 3704-3083 (2024). Acknowledgement This work is supported by US DOE EERE HFTO through H2NEW consortium

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