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Water dissociation efficiencies control the viability of reverse-bias bipolar membranes for CO2 electrolysis

Gerard Prats Vergel, Huan Sheng Mu, Nikita Kolobov, Jasper Biemolt, David A. Vermaas, Thomas Burdyny

2025Nature Chemical Engineering8 citationsDOIOpen Access PDF

Abstract

Abstract Bipolar membranes operated under reverse-bias (r-BPM) provide the only potential route to use anodes free of platinum group metals in CO 2 electrolyzers when paired with the oxygen evolution reaction. Under 100% water dissociation efficiency (WDE) conditions, the OH − generated by a r-BPM fully replenishes the OH − consumed by the oxygen evolution reaction, maintaining an alkaline anolyte. However, unwanted co-ion crossover leads to <100% WDEs, gradually causing anolyte acidification and nickel-based anodes to corrode over time. Here we experimentally measured the WDE of r-BPMs in a membrane–electrode assembly configuration as a function of the current density, anolyte concentration and cation identity, finding that the highest measured WDE of 98% is insufficient to maintain an alkaline environment over extended operation. We further highlight through modeling that WDEs >99.8% are required to operate for >10,000 h with reasonable anolyte volumes. Our results show that r-BPMs CO 2 electrolyzers require additional strategies, such as reverting to platinum group metal anodes or regenerating the anolyte, to operate stably at an industrial scale.

Topics & Concepts

ElectrolysisAnodeOxygen evolutionDissociation (chemistry)MembranePlatinumChemistryInorganic chemistryElectrolysis of waterOxygenChemical engineeringMetalAlkali metalMaterials scienceTransition metalPotable waterWater treatmentPlatinum groupClark electrodeElectrochemistryElectrodeAlkaline water electrolysisCO2 Reduction Techniques and CatalystsElectrocatalysts for Energy ConversionAdvancements in Solid Oxide Fuel Cells
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