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Continuous-flow electrolyzers allow CO2 reduction at industrially relevant rates, but long-term operation is still challenging. One reason for this is the formation of precipitates in the porous cathode from the alkaline electrolyte and the CO2 feed. Here we show that while precipitate formation is detrimental for the long-term stability, the presence of alkali metal cations at the cathode improves performance. To overcome this contradiction, we develop an operando activation and regeneration process, where the cathode of a zero-gap electrolyzer cell is periodically infused with alkali cation-containing solutions. This enables deionized water-fed electrolyzers to operate at a CO2 reduction rate matching that of those using alkaline electrolytes (CO partial current density of 420 ± 50 mA cm-2 for over 200 hours). We deconvolute the complex effects of activation and validate the concept with five different electrolytes and three different commercial membranes. Finally, we demonstrate the scalability of this approach on a multi-cell electrolyzer stack, with a 100 cm2 / cell active area.

A poly(aryl piperidinium)-based anion exchange membrane (PiperION) with high carbonate conductance is employed for CO2 electrolysis to CO in conjunction with a tailored electrolyzer cell structure. This combination results in unprecedentedly high partial current densities in zero-gap cells (jCO > 1.0 A cm−2), while maintaining high conversion (20–45%), selectivity (up to 90%) and low cell voltage (2.6–3.4 V).