Coupled Electronic‐Catalytic Regulation in All‐in‐One VN/B 2 O 3 Ceramic Enables Fast Polysulfides Conversion in Li‐S Batteries

ABSTRACT Lithium‐sulfur (Li‐S) batteries hold great promise for next‐generation high‐energy storage but are challenged by sluggish lithium polysulfides (LiPSs) conversion, low sulfur utilization, and limited practical loading. Herein, we report an all‐in‐one ant‐nest‐like porous VN/B 2 O 3 (VNBO) ceramic, constructed through a bottom‐up sintering‐diffusion process of VN nanoparticles coupled with the phase transition of B 2 O 3 . This integrated porous ceramic provides a continuous conductive framework with minimized interfacial resistance. The VN nano‐units serve as highly active catalytic centers to accelerate LiPSs redox kinetics, while B 2 O 3 component promotes the formation of the hierarchical ant‐nest‐like network and modulates the electronic structure of the VN/B 2 O 3 heterointerface. This coupled electronic‐catalytic regulation effectively suppresses LiPSs shuttling and enables fast, reversible LiPSs conversion. Benefiting from this synergistic architecture, the 2‐VNBO@S cathode delivers outstanding electrochemical performances, achieving 1187.2 mAh g −1 at 0.5 C after 200 cycles and retaining 944.3 mAh g −1 over 300 cycles at 3 C with a capacity decay of only 0.054% per cycle. Even under a high sulfur loading of 4 mg cm −2 , it maintains 557.9 mAh g −1 after 150 cycles. This work establishes a robust design strategy for high‐energy and catalytically active sulfur cathodes.