Encasing Few‐Layer MoS₂ within 2D Ordered Cubic Graphitic Cages to Smooth Trapping‐Conversion of Lithium Polysulfides for Dendrite‐Free Lithium–Sulfur Batteries

Abstract The industrialization of lithium–sulfur (Li–S) batteries faces challenges due to the shuttling effect of lithium polysulfides (LiPSs) and the growth of lithium dendrites. To address these issues, a simple and scalable method is proposed to synthesize 2D membranes comprising a single layer of cubic graphitic cages encased with few‐layer, curved MoS₂. The distinctive 2D architecture is achieved by confining the epitaxial growth of MoS₂ within the open cages of a 2D‐ordered mesoporous graphitic framework (MGF), resulting in MoS₂@MGF heterostructures with abundant sulfur vacancies. The experimental and theoretical studies establish that these MoS₂@MGF membranes can act as a multifunctional interlayer in Li–S batteries to boost their comprehensive performance. The inclusion of the MoS₂@MGF interlayer facilitates the trapping and conversion kinetics of LiPSs, preventing their shuttling effect, while simultaneously promoting uniform lithium deposition to inhibit dendrite growth. As a result, Li–S batteries with the MoS₂@MGF interlayer exhibit high electrochemical performance even under high sulfur loading and lean electrolyte conditions. This work highlights the potential of designing advanced MoS₂‐encased heterostructures as interlayers, offering a viable solution to the current limitations plaguing Li–S batteries.