Mechanistic understanding of CO2 reduction and evolution reactions in Li-CO2 batteries.

Abstract

Rechargeable Li-CO2 batteries have attracted extensive attention owing to their high theoretical energy density (1876 W h Kg-1). However, their practical application is hindered by large polarization, low coulombic efficiency, and cathode degradation. The electrochemical performance of Li-CO2 batteries is significantly affected by the thermodynamic stability and reaction kinetics of discharge products. Although advances have been achieved in cathode design and electrolyte optimization over the past decade, the reaction mechanism of the CO2 cathode has not yet been clear. In this review, various reaction mechanisms of CO2 reduction and evolution at the cathode interface are discussed, including different reaction routes under mixed O2/CO2 and pure CO2 environments. Furthermore, the regulating strategies of different discharge products, including Li2CO3, Li2C2O6, and Li2C2O4, are summarized to decrease the polarization and improve the cycling performance of Li-CO2 batteries. Finally, the challenges and perspectives are discussed from three aspects: reaction mechanisms, cathode catalysts, and electrolyte engineering, offering insights for the development of Li-CO2 batteries in the future.