Zinc Tellurium with Anionic Vacancies Anchored on Ordered Macroporous Carbon Skeleton Enabling Accelerated Polysulfide Conversion for Lithium–Sulfur Batteries

Abstract Lithium–sulfur batteries (LSBs) showcase great promise for large‐scale energy storage systems, however, their practical commercialization is seriously hindered by the sluggish redox reaction kinetics and detrimental shuttle effect of soluble polysulfides. Herein, small ZnTe _{1‐ x} nanoparticles with anionic vacancies firmly anchored on 3D ordered macroporous N‐doped carbon skeleton (3DOM‐ZnTe _{1‐ x} @NC) are elaborately constructed as a high‐efficiency electrocatalyst for LSBs. The ordered macroporous carbon skeleton not only greatly increases the external surface area to expose sufficient active sites but also facilitates the electrolyte penetration. Additionally, the experimental studies combined with theoretical calculations confirm the presence of Te vacancies optimizes the electronic structure to enhance the intrinsic catalytic activity and chemical absorption. Consequently, LSBs assembled with the 3DOM‐ZnTe _{1‐ x} @NC modified separators exhibit high specific discharge capacity, as well as superior rate performance and good long‐term cycling stability. Even under a high sulfur loading of 6.5 mg cm ⁻² and lean electrolyte, an impressive areal capacity of 5.28 mAh cm ⁻² is achieved at 0.1 C after 100 cycles. More significantly, the 3DOM‐ZnTe _{1‐ x} @NC based pouch cells are also fabricated to demonstrate its potential for practical applications. This work highlights that the rational combination of 3DOM architecture and vacancy engineering is important for designing advanced Li–S electrocatalysts.