Qian He, Weikun Chen, Bin Fan, Qingya Wei, Zhiyun Xu, Yingping Zou
ABSTRACT The energy density and cycle life of lithium‒sulfur (Li‒S) batteries remain severely limited by the shuttle effect of soluble lithium polysulfides (LiPSs), sluggish liquid‒solid conversion kinetics, and structural instability associated with volume changes. To address these coupled degradation processes, this study proposes a multidimensional synergistic regulation strategy. Through temperature‐controlled synthesis, a N/P/S multicomponent doping three‐dimensionally interconnected hollow carbon composite hosting a CoP/CoP 2 heterojunction (CoP/CoP 2 @NPSC) is constructed. The built‐in electric field across the CoP/CoP 2 interface drives directional charge migration, modulating adsorption/desorption balance and reducing kinetic barriers during sulfur species transformation. Meanwhile, the polar site network introduced by N/P/S multicomponent doping provides gradient anchoring toward different sulfur intermediates, while the interconnected hollow carbon framework ensures continuous electron/ion transport and suppresses disordered intermediate diffusion. Through these coupled structural and interfacial effects, the conversion energy barriers of LiPSs are effectively lowered, accelerating overall sulfur redox kinetics. As a result, CoP/CoP 2 @NPSC battery delivers a reversible capacity of 663.8 mAh g ‒1 after 1200 cycles at 2.0 C, with an ultralow decay rate of 0.022% per cycle. This work highlights the effectiveness of built‐in electric fields in regulating complex liquid‒solid transformation reactions and provides a scalable design paradigm for constructing multifunctional sulfur host materials with coupled interfacial regulation.