Coordinated Immobilization and Rapid Conversion of Polysulfide Enabled by a Hollow Metal Oxide/Sulfide/Nitrogen‐Doped Carbon Heterostructure for Long‐Cycle‐Life Lithium‐Sulfur Batteries

Abstract Lithium‐sulfur batteries (LSBs) are recognized as the prospective candidate in next‐generation energy storage devices due to their gratifying theoretical energy density. Nonetheless, they still face the challenges of the practical application including low utilization of sulfur and poor cycling life derived from shuttle effect of lithium polysulfides (LiPSs). Herein, a hollow polyhedron with heterogeneous CoO/Co 9 S 8 /nitrogen‐doped carbon (CoO/Co 9 S 8 /NC) is obtained through employing zeolitic imidazolate framework as precursor. The heterogeneous CoO/Co 9 S 8 /NC balances the redox kinetics of Co 9 S 8 with chemical adsorption of CoO toward LiPSs, effectively inhibiting the shuttle of LiPSs. The mechanisms are verified by both experiment and density functional theory calculation. Meanwhile, the hollow structure acts as a sulfur storage chamber, which mitigates the volumetric expansion of sulfur and maximizes the utilization of sulfur. Benefiting from the above advantages, lithium‐sulfur battery with S‐CoO/Co 9 S 8 /NC achieves a high initial discharge capacity (1470 mAh g −1 ) at 0.1 C and long cycle life (ultralow capacity attenuation of 0.033% per cycle after 1000 cycles at 1 C). Even under high sulfur loading of 3.0 mg cm −2 , lithium‐sulfur battery still shows the satisfactory electrochemical performance. This work may provide an idea to elevate the electrochemical performance of LSBs by constructing a hollow metal oxide/sulfide/nitrogen‐doped carbon heterogeneous structure.