Electrocatalytic Interlayer with Fast Lithium–Polysulfides Diffusion for Lithium–Sulfur Batteries to Enhance Electrochemical Kinetics under Lean Electrolyte Conditions

Abstract Lithium–sulfur batteries are promising energy‐storage devices because of their high theoretical energy densities. For practical Li–S batteries, reducing the amount of electrolyte used is essential for achieving the high energy densities. However, reducing the electrolyte amount leads to severe performance degradation, mainly because of sluggish deposition of discharge products (Li 2 S) and the accompanying passivation issue that arise from the insulating nature of Li 2 S. In this study, a lightweight, robust interlayer, with a 3D open structure and a low surface area is designed and fabricated. The structure facilitates electrolyte infiltration without trapping too much electrolyte. Moreover, the electrocatalytic Co nanoparticles embedded in the skeleton surface within the interlayer effectively promote Li ion diffusion, polysulfides conversion, and Li 2 S deposition, and therefore enhance the electrochemical kinetics under lean electrolyte conditions. The mechanisms involved in the interlayer effects are investigated by microstructural characterizations, electrochemical performance tests, density functional theory calculations, and in situ X‐ray diffraction characterization. These results show the feasibility of using an interlayer strategy to improve the electrochemical performances of Li–S batteries under lean electrolyte conditions to potentially increase the practical energy densities of Li–S batteries.