Heteroatoms Synergistic Anchoring Vacancies in Phosphorus-Doped CoSe2 Enable Ultrahigh Activity and Stability in Li–S Batteries

Abstract Electrocatalyst activity and stability demonstrate a “seesaw” relationship. Introducing vacancies (Vo) enhances the activity by improving reactant affinity and increasing accessible active sites. However, deficient or excessive Vo reduces polysulfide adsorption and lowers catalytic stability. Herein, a novel “heteroatoms synergistic anchoring vacancies” strategy is proposed to address the trade-off between high activity and stability. Phosphorus-doped CoSe 2 with remained rich selenium vacancies (P-CS-Vo-0.5) was synthesized by producing abundant selenium Vo followed by controlled P atom doping. Atomic-scale microstructure analysis elucidated a dynamic process of surface vacancy generation and the subsequent partial occupation of these vacancies by P atoms. Density functional theory simulations and in situ Raman tests revealed that the Se vacancies provide highly active catalytic sites, accelerating polysulfide conversion, while P incorporation effectively reduces the surface energy of Se vacancies and suppresses their inward migration, enhancing structural robustness. The battery with the optimal P-CS-Vo-0.5 separator delivers an initial discharge capacity of 1306.7 mAh g −1 at 0.2C, and maintain 5.04 mAh cm −2 at a high sulfur loading (5.7 mg cm −2 , 5.0 μL mg −1 ), achieving 95.1% capacity retention after 80 cycles. This strategy of modifying local atomic environments offers a new route to designing highly active and stable catalysts.