Bubble Formation in the Electrolyte Triggers Voltage Instability in CO₂ Electrolyzers

The electrochemical reduction of CO₂ is promising for mitigating anthropogenic greenhouse gas emissions; however, voltage instabilities currently inhibit reaching high current densities that are prerequisite for commercialization. Here, for the first time, we elucidate that product gaseous bubble accumulation on the electrode/electrolyte interface is the direct cause of the voltage instability in CO₂ electrolyzers. Although bubble formation in water electrolyzers has been extensively studied, we identified that voltage instability caused by bubble formation is unique to CO₂ electrolyzers. The appearance of syngas bubbles within the electrolyte at the gas diffusion electrode (GDE)-electrolyte chamber interface (i.e. ∼10% bubble coverage of the GDE surface) was accompanied by voltage oscillations of 60 mV. The presence of syngas in the electrolyte chamber physically inhibited two-phase reaction interfaces, thereby resulting in unstable cell performance. The strategic incorporation of our insights on bubble growth behavior and voltage instability is vital for designing commercially relevant CO₂ electrolyzers.