Interfacial Thiophilicity Enrichment for Efficient Li–CO ₂ Batteries

Abstract Despite the promising application potential of Li–CO 2 batteries for carbon capture and energy storage, their commercialization is seriously hindered by sluggish reaction kinetics and poor reversibility accompanied with the accumulation of electrochemically inert discharge products. Herein, efficient tailoring of both electronic structure and geometric configuration in a Co‐based catalyst by leveraging the strong thiophilicity of cobalt is achieved. This is realized through in situ construction of a carbon‐coated outer layer and a Co–S enrichment interfacial layer on the Co surface, using sulfur‐doped carbon dots as dual‐functional sulfur sources and structural modulators, thereby significantly accelerating the CO 2 evolution reaction. The calculation results confirm that CO 2 adsorption is greatly enhanced and Li 2 CO 3 decomposition energy barrier is largely reduced by interfacial Co–S enrichment, collectively promoting the thermodynamic and kinetic efficiency of Li–CO 2 batteries. Co/NSCDs@CNTs cathode delivers an ultrahigh specific capacity of 33,767 mAh g −1 , a small potential gap of 0.49 V, particularly with a low charge potential of 3.07 V at 50 mA g −1 , and maintains exceptional cycling stability with a charge potential consistently below 3.42 V. This work provides a structure‐activity framework that can guide future developments in transition‐metal‐based Li–CO 2 batteries cathode systems.