Engineering of a Hierarchical Arrayed Architecture with Abundant Heterointerfaces and Anion Vacancies for Kinetically Boosted Lithium‐Sulfur Batteries

Abstract Delicate design high‐efficiency sulfur electrocatalysts is crucial for suppressing the shuttle effect of soluble lithium polysulfides (LiPSs) and improving the electrochemical performance in lithium‐sulfur (Li‐S) electrochemistry. Herein, a self‐supported hierarchical NiCo2Se4@Ni0.85Se/MoSe2 electrocatalyst with abundant heterointerfaces and anion vacancies that directly grows on carbon cloth is elaborately designed to accelerate the sulfur redox reaction kinetics effectively. Noteworthy, the abundant heterointerfaces coupling with anion vacancies greatly facilitate the electron transfer, strengthen the chemical adsorption, provide sufficient active sites, and enhance the catalytic activity. Additionally, the hierarchical hollow arrayed architecture can guide the Li 2 S deposition, relieve the volume expansion, and maintain the structural stability. Consequently, the Li‐S batteries with CC@NiCo 2 Se 4 @Ni 0.85 Se/MoSe 2 exhibit exceptional electrochemical performance and high sulfur utilization even under high sulfur loading. More importantly, the pouch cells are fabricated to demonstrate the potential for practical applications. Furthermore, the integration of experimental and computational studies confirms that the Ni 0.85 Se/MoSe 2 heterostructure possesses stronger chemical adsorption and reduced energy barrier for LiPSs conversion than MoSe 2 . Interestingly, it is also discovered that the incorporation of Ni 0.85 Se promotes the in situ lithium ions intercalation in MoSe 2 , which is conductive to further performance enhancement. This study provides new inspiration for the hierarchical engineering of electrocatalysts toward high‐performance Li‐S batteries