Membrane Electrolyzers for Hydrogen Production: From Catalyst Fundamentals to Devices

Water electrolysis powered by renewable sources such as wind or solar produces clean hydrogen gas, which is used for many industrial processes and will be essential in a future clean energy economy. Commercialized membrane electrolyzers use acidic proton exchange membranes (PEMs), which offer high performance but require the use of expensive precious-metal catalysts such as IrO2 and Pt that are nominally stable under the locally acidic conditions. Anion exchange membrane (AEM) electrolyzers in principle offer the performance of PEM electrolyzers with the ability to use earth-abundant catalysts and inexpensive bipolar plate materials. I will present our fundamental work in understanding the chemical and electrochemical processes in earth-abundant water-oxidation catalysts, including the use of integrated reference-electrode device architectures and cross-sectional materials analysis, as well as progress in building high-performance AEM electrolyzers. Baseline systems operate at 1 A·cm-2 in pure water feed at < 2 V at a moderate temperature of ~70 °C using either IrO2 or Co3O4 anode catalyst layers, Versogen TP-85 alkaline ionomers, and stainless-steel porous transport layers. These devices, however, degrade rapidly compared to PEM electrolyzers. The voltage profile corresponding to degradation has initial fast (~10 mV/h) and steady-state slow components (~1 mV/h), which we link to chemical and structural changes in the ionomer catalyst reactive zone. We further discover that dynamic Fe-based OER catalysts – that have world record performance in traditional liquid alkaline electrolyzer systems – perform poorly with enhanced degradation rates in alkaline membrane electrolysis, illustrating fundamentally different chemical design principles for OER catalysts. Lastly, I will discuss these processes in electrolyzer devices and in model systems, as well as present promising new chemical strategies we have developed to mitigate degradation and enhance performance using novel ionomers and electrode catalyst compositions and architectures.