<i>d</i> ‐ <i>p</i> Orbital Hybridization Tailoring for Boosted Redox Kinetics in Li‐CO ₂ Batteries

Abstract Lithium‐carbon dioxide (Li‐CO 2 ) batteries hold great promise for carbon neutrality but suffer from sluggish CO 2 reduction (CO 2 RR) and evolution (CO 2 ER) 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 CO 2 and Li 2 CO 3 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 CO 2 and Li 2 CO 3 , thereby leading to strengthened adsorption and reducing reaction energy barriers. As a result, Li‐CO 2 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‐CO 2 battery catalysts.