Interface Engineering Toward Surface‐Activated Catalysts for Advanced Li–CO2 Batteries

ABSTRACT Lithium–carbon dioxide (Li–CO 2 ) batteries with high theoretical energy density are regarded as promising energy storage system toward carbon neutrality. However, bidirectional catalysts design for improving the sluggish CO 2 reduction reaction (CO 2 RR)/CO 2 evolution reaction (CO 2 ER) kinetics remains a huge challenge. In this work, an advanced catalyst with fast‐interfacial charge transfer was subtly synthesized through element segregation, which significantly improves the electrocatalytic activity for both CO 2 RR and CO 2 ER. Theoretical calculations and characterization analysis demonstrate local charge redistribution at the constructed interface, which leads to optimized binding affinity towards reactants and preferred Li 2 CO 3 decomposition behavior, enabling excellent catalytic activity during CO 2 redox. Benefiting from the enhanced charge transfer ability, the designed highly efficient catalyst with dual active centers and large exposed catalytic area can maintain an ultra‐small voltage gap of 0.33 V and high energy efficiency of 90.2%. This work provides an attractive strategy to construct robust catalysts by interface engineering, which could inspire further design of superior bidirectional catalysts for Li–CO 2 batteries.