Unlocking the Potential of A-Site Ca-Doped LaCo0.2Fe0.8O3−δ: A Redox-Stable Cathode Material Enabling High Current Density in Direct CO2 Electrolysis

Massive carbon dioxide (CO2) emission from recent human industrialization has affected the global ecosystem and raised great concern for environmental sustainability. The solid oxide electrolysis cell (SOEC) is a promising energy conversion device capable of efficiently converting CO2 into valuable chemicals using renewable energy sources. However, Sr-containing cathode materials face the challenge of Sr carbonation during CO2 electrolysis, which greatly affects the energy conversion efficiency and long-term stability. Thus, A-site Ca-doped La1–xCaxCo0.2Fe0.8O3−δ (0.2 ≤ x ≤ 0.6) oxides are developed for direct CO2 conversion to carbon monoxide (CO) in an intermediate-temperature SOEC (IT-SOEC). With a polarization resistance as low as 0.18 Ω cm2 in pure CO2 atmosphere, a remarkable current density of 2.24 A cm–2 was achieved at 1.5 V with La0.6Ca0.4Co0.2Fe0.8O3−δ (LCCF64) as the cathode in La0.8Sr0.2Ga0.83Mg0.17O3−δ (LSGM) electrolyte (300 μm) supported electrolysis cells using La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) as the air electrode at 800 °C. Furthermore, symmetrical cells with LCCF64 as the electrodes also show promising electrolysis performance of 1.78 A cm–2 at 1.5 V at 800 °C. In addition, stable cell performance has been achieved on direct CO2 electrolysis at an applied constant current of 0.5 A cm–2 at 800 °C. The easily removable carbonate intermediate produced during direct CO2 electrolysis makes LCCF64 a promising regenerable cathode. The outstanding electrocatalytic performance of the LCCF64 cathode is ascribed to the highly active and stable metal/perovskite interfaces that resulted from the in situ exsolved Co/CoFe nanoparticles and the additional oxygen vacancies originated from the Ca2Fe2O5 phase synergistically providing active sites for CO2 adsorption and electrolysis. This study offers a novel approach to design catalysts with high performance for direct CO2 electrolysis.