Engineering e g ‐Orbital of Octahedral Cobalt Cations via High‐Entropy Design for Superior Li–S Batteries in Spinel Co ₃ O ₄

Both excessive and insufficient electron filling in e g orbitals of the octahedral cations in spinel transition‐metal oxides, weaken interactions with lithium polysulfide (LiPS) intermediates, thereby impairing their catalytic performance. Herein, we propose a high‐entropy‐driven e g ‐orbital engineering strategy to precisely tune the spin state of octahedral Co cations (Co Oh 3+ ) within the spinel‑type Co 3 O 4 framework. Specifically, partial substitution of Co with multiple metals yields high‑entropy (FeNiMnZn) x Co 3 − x O 4 (HS‑HEOs) catalysts with optimized e g ‐orbital occupancy, thereby promoting strong LiPS adsorption and high catalytic activity. The high‑spin state of Co Oh 3+ and the optimized e g ‐orbital occupancy in HS‑HEOs are jointly regulated through two synergistic mechanisms: intra‐atomic transition from low‐energy t 2g to high‐energy e g orbitals, and interatomic electron transfer mediated by strong Co Oh 3+ ─O─TM quantum spin‑exchange interactions. Concurrently, the high‑spin configuration (t 2g 5 e g 1.65 ) shifts the d ‑band center of Co Oh 3+ upward, which weakens Co Oh 3+ ─O covalency, enhances the polarity of the Co Oh 3+ ─O bonds, and strengthens the chemical affinity for LiPSs, thereby accelerating their conversion kinetics. Consequently, the HS‑HEO‑based cell delivers 963.9 mAh g −1 at 9 C and retains a capacity decay rate of only 0.045% per cycle over 700 cycles at 1 C. This approach opens new pathways for rational design of high‐performance catalysts and holds promise for advancing renewable energy technologies.