Rechargeable Li-CO₂ batteries (LCBs) are considered as a promising candidate for the next generation energy storage system, but still be impeded by the lack of high-performance cathode catalyst and poor understanding for the complicated reaction mechanism. In the present work, we demonstrate that the catalytic capability of cathode catalyst of LCBs can be remarkably enhanced from the accelerated reaction kinetics using a p-type substrate as adsorption/desorption promoter for refined reaction route. A carbon-free atomic Ir-Te cathode catalyst with Ir atomic cluster is uniformly super-assembled on the surface of Te nanowires forming an amorphous surface layer (ca. 3 nm) to maximize the catalytic capability of active Ir sites and provide a refined reaction pathway due to synergistic effect of Ir active sites and Te substrate. The adsorption ability of Li₂C₂O₄ during discharging and the desorption ability of CO₂ species during charging of the p-type Te substrate could both promote the catalytic reaction kinetics and optimize the reaction pathways on Ir active sites. Finally, a large specific capacity of 13,247.1 mAh g⁻¹ and an excellent high rate cyclability with stably over 350 and 200 cycles at the current density of 1000 and 2000 mA g⁻¹ are achieved. This contribution provides a rational design strategy for high performance cathode catalyst, and intrinsic insight towards the understanding the reaction mechanisms of LCBs.

可充电 Li-CO ₂电池（LCBs）被认为是下一代储能系统的有希望的候选者，但仍然受到缺乏高性能阴极催化剂和对复杂反应机理的了解不足的阻碍。在目前的工作中，我们证明了通过使用 p 型底物作为精细反应路线的吸附/解吸促进剂的加速反应动力学，可以显着提高 LCB 阴极催化剂的催化能力。具有 Ir 原子簇的无碳原子 Ir-Te 阴极催化剂均匀地超组装在 Te 纳米线的表面，形成无定形表面层（约 3 nm），以最大限度地提高活性 Ir 位点的催化能力并提供精细的反应由于 Ir 活性位点和 Te 底物的协同作用。Li的吸附能力放电过程中的₂ C ₂ O ₄和p 型 Te 衬底充电过程中 CO ₂物种的解吸能力都可以促进催化反应动力学并优化 Ir 活性位点上的反应途径。最后，实现了 13,247.1 mAh g ^-1的大比容量和优异的高倍率循环性能，在 1000 和 2000 mA g ^-1的电流密度下可稳定超过 350 和 200 次循环。这一贡献为高性能阴极催化剂提供了合理的设计策略，以及对理解 LCB 反应机制的内在见解。