Exploring Low Temperature Proton Exchange Membrane Water Electrolysis Anode Catalyst Degradation Under Cathode Backpressure Conditions
Authors: Medina Samantha , Alia Shaun M 
Published: August 2024

Hydrogen is expected to play an important role in the decarbonization of the future energy landscape by integrating renewable, nuclear, and fossil fuels and using excess power from the grid to produce H2 that can then be stored and used for a variety of applications ranging from ammonia and steel production, stationary power, buildings, and transportation.1 In order to achieve low-cost hydrogen production that is competitive with steam methane reformation (SMR), it is necessary to decrease the capital cost and this can be done by leveraging variable renewable energy (VRE) as an electricity feedstock for LTE.2 However, cost, and durability are still current challenges in state-of-the art water electrolysis systems. More research is needed to better understand the effects of dynamic operation on electrolyzer degradation. Understanding the degradation mechanisms governing intermittent electrolysis operation can enable future improvements related to component design and system operation.
In recent years, electrolyzer anode degradation has been investigated during continual intermittent operation at the single cell level. Square-wave potential cycling demonstrated higher anode degradation compared to the triangle-wave cycling over the same 525 hour test (21.9 d).3 Electrolyzers operating at differential pressures and producing electrochemically compressed hydrogen could decrease the hydrogen production cost by eliminating the need for equipment related to mechanical compression.4 This work investigates the dynamics of low-temperature proton exchange membrane (PEM) electrolyzers, with a specific focus on anode catalyst layer degradation from redox transition when subjected to hydrogen crossover from cathode backpressure conditions. While cathode backpressure and operation requirements are well understood from an industry perspective, its impact on degradation mechanisms and loss rates has been relatively underexplored when low-temperature electrolysis is focused on cost reduction and variable load.
In this study, hydrogen cross-over rates were varied by cathode backpressure conditions (ambient to 30 Bar) and were compared to elucidate the impact hydrogen has on anode catalyst layer degradation. The durability test duration varied from 168 – 500+ hrs. Hydrogen cross-over rates were found to correlate to cell potential during operational shutdowns and loss rates during load cycling. Electrochemical impedance spectroscopy further demonstrates higher degrees of kinetic loss and the immergence of additional loss mechanisms. The findings presented in this research contribute to the fundamental understanding of low-temperature PEM electrolysis dynamics under cathode backpressure conditions. The implications of this research offer practical insights for the design and operation of efficient and durable electrolysis systems crucial for the advancement of sustainable hydrogen production technologies.
(1) H2@Scale. Hydrogen and Fuel Cell Technologies Office. https://www.energy.gov/eere/fuelcells/h2scale.
(2) Mark, R.; Jadun, P.; Gilroy, N.; Connelly, E.; Boardman, R.; Simon, A. J.; Elgowainy, A.; Zuboy, J. The Technical and Economic Potential of the H2@Scale Concept within the United States; NREL/TP-6A20-77610; National Renewable Energy Laboratory: Golden, CO, 2020.
(3) Alia, S. M.; Reeves, K. S.; Yu, H.; Park, J.; Kariuki, N.; Kropf, A. J.; Myers, D. J.; Cullen, D. A. Electrolyzer Performance Loss from Accelerated Stress Tests and Corresponding Changes to Catalyst Layers and Interfaces. Journal of The Electrochemical Society
2022, 169 (5), 054517. https://doi.org/10.1149/1945-7111/ac697e.
(4) Ragnhild Hancke, Thomas Holm, and Øystein Ulleberg, “The Case for High-Pressure PEM Water Electrolysis,” Energy Conversion and Management 261 (2022): 115642, https://doi.org/10.1016/j.enconman.2022.115642.

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