Steering the Orbital Hybridization to Boost the Redox Kinetics for Efficient Li–CO2 Batteries

• Published in: Journal of the American Chemical Society Vol. 146; no. 30; pp. 20814 - 20822
• Main Authors: Lu, Bingyi, Wu, Xinru, Zhang, Mengtian, Xiao, Xiao, Chen, Biao, Liu, Yingqi, Mao, Rui, Song, Yanze, Zeng, Xian-Xiang, Yang, Jinlong, Zhou, Guangmin
• Format: Journal Article
• Language: English
• Published: American Chemical Society 20-07-2024
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.4c04641

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.