Steering the Orbital Hybridization to Boost the Redox Kinetics for Efficient Li–CO<sub>2</sub> Batteries
Bingyi Lu, Xinru Wu, Mengtian Zhang, Xiao Xiao, Biao Chen, Yingqi Liu, Rui Mao, Yanze Song, Xian‐Xiang Zeng, Jinlong Yang, Guangmin Zhou
Abstract
The sluggish CO 2 reduction and evolution reaction kinetics are thorny problems for developing high-performance Li–CO 2 batteries. For the complicated multiphase reactions and multielectron transfer processes in Li–CO 2 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 CO 2, thus improving the discharge platform of Li–CO 2 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–CO 2 reaction by tailoring the electronic structure.