In Situ Conversion of Metal-Organic Frameworks into VO₂ -V₃ S₄ Heterocatalyst Embedded Layered Porous Carbon as an "All-in-One" Host for Lithium-Sulfur Batteries

Although lithium-sulfur batteries exhibit a fivefold higher energy density than commercial lithium-ion batteries, their volume expansion and insulating nature, and intrinsic polysulfide shuttle have hindered their practical application. An alternative sulfur host is necessary to realize porous, conductive, and polar functions; however, there is a tradeoff among these three critical factors in material design. Here, the authors report a layered porous carbon (LPC) with VO₂ /V₃ S₄ heterostructures using one-step carbonization-sulfidation of metal-organic framework templates as a sulfur host that meets all the criteria. In situ conversion of V-O ions into V₃ S₄ nuclei in the confined 2D space generated by dynamic formation of the LPC matrix creates {200}-facet-exposed V₃ S₄ nanosheets decorated with tiny VO₂ nanoparticles. The VO₂ /V₃ S₄ @ LPC composite facilitates high sulfur loading (70 wt%), superior energy density (1022 mA h g^-1 at 0.2 C, 100 cycles), and long-term cyclability (665 mA h g^-1 at 1 C, 1000 cycles). The enhanced Li-S chemistry is attributed to the synergistic heterocatalytic behavior of polar VO₂ and conductive V₃ S₄ in the soft porous LPC scaffold, which accelerates polysulfide adsorption, conversion, and charge-transfer ability simultaneously.