Distinct CO2-run-out regime from steric effect of electric double layer in electrochemical CO2 reduction

The field of electrochemical CO2 reduction reaction (eCO2RR) is pursuing high operating current densities, eventually controlled by CO2 transport. Here, we develop a new multiscale modeling approach that is able to more generally describe the effects of the electric double layer (EDL) on CO2 transport over a wide potential window extending to utmost potentials. By leveraging it, we identify a distinct CO2-run-out regime where the supply of CO2 runs out due to the EDL steric effect from a dense layer of solvated cations with the maximum layer thickness equal to the solvated cation size. Consequently, CO2RR current density drops at a relatively negative transition potential generating a bell-shaped polarization curve, which is in contrast to the CO2-transport-limited regime where the current density reaches a plateau. Furthermore, we develop a graphical method, verified by experimental data, to generally predict the transition to the CO2-run-out regime. This work sheds new light on the EDL effects for catalyst design and electrolyzer engineering.