Sluggish kinetics of the CO₂ reduction/evolution reactions lead to the accumulation of Li₂CO₃ residuals and thus possible catalyst deactivation, which hinders the long-term cycling stability of Li-CO₂ batteries. Apart from catalyst design, constructing a fluorinated solid-electrolyte interphase is a conventional strategy to minimize parasitic reactions and prolong cycle life. However, the catalytic effects of solid-electrolyte interphase components have been overlooked and remain unclear. Herein, we systematically regulate the compositions of solid-electrolyte interphase via tuning electrolyte solvation structures, anion coordination, and binding free energy between Li ion and anion. The cells exhibit distinct improvement in cycling performance with increasing content of C-N species in solid-electrolyte interphase layers. The enhancement originates from a catalytic effect towards accelerating the Li₂CO₃ formation/decomposition kinetics. Theoretical analysis reveals that C-N species provide strong adsorption sites and promote charge transfer from interface to *CO₂²⁻ during discharge, and from Li₂CO₃ to C-N species during charge, thereby building a bidirectional fast-reacting bridge for CO₂ reduction/evolution reactions. This finding enables us to design a C-N rich solid-electrolyte interphase via dual-salt electrolytes, improving cycle life of Li-CO₂ batteries to twice that using traditional electrolytes. Our work provides an insight into interfacial design by tuning of catalytic properties towards CO₂ reduction/evolution reactions.

CO ₂还原/放出反应的缓慢动力学导致Li ₂ CO ₃残留物的积累，从而可能导致催化剂失活，这阻碍了Li-CO ₂电池的长期循环稳定性。除了催化剂设计之外，构建氟化固体电解质界面是最小化寄生反应和延长循环寿命的传统策略。然而，固体电解质界面成分的催化作用被忽视并且仍不清楚。在此，我们通过调节电解质溶剂化结构、阴离子配位以及锂离子与阴离子之间的结合自由能来系统地调节固体电解质界面的组成。随着固体电解质中间层中 CN 物质含量的增加，电池表现出循环性能的显着改善。该增强源于加速Li ₂ CO ₃形成/分解动力学的催化作用。理论分析表明，CN物种提供了强大的吸附位点，并在放电过程中促进电荷从界面转移到*CO ₂ ²⁻ ，以及在充电过程中从Li ₂ CO ₃到CN物种，从而构建了CO ₂还原/的双向快速反应桥。进化反应。这一发现使我们能够通过双盐电解质设计富含 CN 的固体电解质界面，将 Li-CO ₂电池的循环寿命提高到使用传统电解质的两倍。我们的工作通过调整 CO ₂还原/演化反应的催化性能，为界面设计提供了深入的见解。