Optimizing Electron Modulation Induced by the Interfacial Coupling in Cu₃P‐Cu₂O Heterostructures to Enhance Polysulfide Conversion

Abstract Electrocatalysts can inhibit the shuttling of lithium polysulfides (LiPSs) in Li–S batteries by enabling catalytic conversion of LiPSs. In this research, heterogeneous Cu₃P‐Cu₂O nanoparticles anchored on the porous carbon network (Cu₃P‐Cu₂O/PC) are investigated to stimulate the reaction kinetics of LiPSs conversion. At the heterojunction interface, the high electron density measured by density functional theory energizes electron transfer, anchoring of LiPSs. The strong interfacial coupling effect generated by Cu₃P‐Cu₂O heterostructure endows active sites with promoted LiPSs adsorption capability. The improved sulfur reduction reaction and Li₂S activation suppress LiPSs shuttling. Remarkably, the cells equipped with Cu₃P‐Cu₂O/PC@S cathode marked high capacity of 1254.3 mAh g⁻¹ at 0.2C and ultrahigh cycling stability (0.021% decay rate per cycle after 1200 cycles at 4C). Considering practical applications, Cu₃P‐Cu₂O/PC@S cathode‐based pouch cell exhibited an initial specific capacity of 1069.5 mAh g⁻¹ and a high energy density of 378.8 Wh kg⁻¹. This work established a pathway for regulating LiPSs through the interfacial coupling of copper‐based heterogeneous catalysts, exhorting the design of highly efficient catalysts for Li–S batteries.