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

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.