The sluggish CO₂ reduction and evolution reaction kinetics are thorny problems for developing high-performance Li–CO₂ batteries. For the complicated multiphase reactions and multielectron transfer processes in Li–CO₂ batteries, exploring efficient cathode catalysts and understanding the interplay between structure and activity are crucial to couple with these pendent challenges. In this work, we applied the CoS as a model catalyst and adjusted its electronic structure by introducing sulfur vacancies to optimize the d-band and p-band centers, which steer the orbital hybridization and boost the redox kinetics between Li and CO₂, thus improving the discharge platform of Li–CO₂ batteries and altering the deposition behavior of discharge products. As a result, a highly efficient bidirectional catalyst exhibits an ultrasmall overpotential of 0.62 V and a high energy efficiency of 82.8% and circulates stably for nearly 600 h. Meanwhile, density functional theory calculations and multiphysics simulations further elucidate the mechanism of bidirectional activity. This work not only provides a proof of concept to design a remarkably efficient catalyst but also sheds light on promoting the reversible Li–CO₂ reaction by tailoring the electronic structure.

中文翻译：

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引导轨道杂交以增强高效锂二氧化碳电池的氧化还原动力学


缓慢的CO ₂ 还原和析出反应动力学是开发高性能Li-CO ₂ 电池的棘手问题。对于Li-CO ₂ 电池中复杂的多相反应和多电子转移过程，探索高效的阴极催化剂并了解结构和活性之间的相互作用对于应对这些悬而未决的挑战至关重要。在这项工作中，我们应用 CoS 作为模型催化剂，并通过引入硫空位来调整其电子结构，以优化 d 带和 p 带中心，从而引导轨道杂化并增强 Li 和 CO 之间的氧化还原动力学 ₂ ，从而改善Li-CO ₂ 电池的放电平台并改变放电产物的沉积行为。结果，高效双向催化剂表现出0.62 V的超小过电势和82.8%的高能量效率，并稳定循环近600 h。同时，密度泛函理论计算和多物理场模拟进一步阐明了双向活动的机制。这项工作不仅提供了设计高效催化剂的概念证明，而且还为通过调整电子结构促进可逆 Li-CO ₂ 反应提供了线索。