Operando cathode activation with alkali metal cations for high current density operation of water-fed zero-gap carbon dioxide electrolysers

Continuous-flow electrolysers 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 electrolyser cell is periodically infused with alkali cation-containing solutions. This enables deionized water-fed electrolysers to operate at a CO2 reduction rate matching 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 multicell electrolyser stack, with an active area of 100 cm(2) per cell. Precipitates that form in the cathode of continuous-flow CO2 electrolysers hamper their long-term operation, but the alkali metals they are formed from actually boost activity. Endrodi et al. mitigate this dichotomy by using pure water in the electrolyser and periodically infusing the cathode with alkaline cations.