Boundaries of High-Temperature Co-Electrolysis Towards Direct CO2-Electrolysis

In this work, the transition boundary of high-temperature co-electrolysis towards pure CO2-electrolysis was investigated. AC and DC measurements with H2O concentrations from 0.0%eq to 39.7%eq led to the identification of the underlying electrochemical processes. Comparison of CO2 conversion in the (R)WGS reaction with electrochemical CO2 reduction by means of area specific resistance (ASR) showed that gas composition determines the dominant reduction reaction (H2O or CO2 reduction). The cell performance of CO2-electrolysis was found to be comparable to co-electrolysis in the boundary region up to around 4.7 %eq H2O. The threshold for the perception of CO2-electrolysis during co-electrolysis has been established to be around 31.7 %eq H2O. The hypothesis that pre-domination of CO2-electrolysis increases with decreasing H2O concentrations below this boundary limit was underlined by measurement results.