d-p Orbital Hybridization Tailoring for Boosted Redox Kinetics in Li-CO₂ Batteries

Lithium-carbon dioxide (Li-CO₂) batteries hold great promise for carbon neutrality but suffer from sluggish CO₂ reduction (CO₂RR) and evolution (CO₂ER) kinetics, leading to high overpotentials and limited cycling stability. Transition metal chalcogenides are potential cathode materials, but their catalytic activity is hindered by electronic misalignment with CO₂ and Li₂CO₃ intermediates. Here, tailoring the anionic composition in MnX (X = O, S, Se) reveals modulation d-p orbital hybridization, enhancing catalytic activity. Among these, MnS exhibits the strongest hybridization, optimizing orbital coupling with CO₂ and Li₂CO₃, thereby leading to strengthened adsorption and reducing reaction energy barriers. As a result, Li-CO₂ batteries with MnS cathodes achieve an impressive discharge capacity of 19 782 mAh g⁻¹ at 100 mA g⁻¹ and excellent cycling stability over 430 cycles at 500 mA g⁻¹. This findings highlight anion modulation as a powerful approach to turn electronic structures and accelerate redox kinetics for advanced metal-CO₂ battery catalysts.