Nanoarchitectured Graphene/CNT@Porous Carbon with Extraordinary Electrical Conductivity and Interconnected Micro/Mesopores for Lithium‐Sulfur Batteries

Abstract

The sp 2‐hybridized nanocarbon (e.g., carbon nanotubes (CNTs) and graphene) exhibits extraordinary mechanical strength and electrical conductivity but limited external accessible surface area and a small amount of pores, while nanostructured porous carbon affords a huge surface area and abundant pore structures but very poor electrical conductance. Herein the rational hybridization of the sp 2 nanocarbon and nanostructured porous carbon into hierarchical all‐carbon nanoarchitectures is demonstrated, with full inherited advantages of the component materials. The sp 2 graphene/CNT interlinked networks give the composites good electrical conductivity and a robust framework, while the meso‐/microporous carbon and the interlamellar compartment between the opposite graphene accommodate sulfur and polysulfides. The strong confinement induced by micro‐/mesopores of all‐carbon nanoarchitectures renders the transformation of S 8 crystal into amorphous cyclo‐S 8 molecular clusters, restraining the shuttle phenomenon for high capacity retention of a lithium‐sulfur cell. Therefore, the composite cathode with an ultrahigh specific capacity of 1121 mAh g−1 at 0.5 C, a favorable high‐rate capability of 809 mAh g−1 at 10 C, a very low capacity decay of 0.12% per cycle, and an impressive cycling stability of 877 mAh g−1 after 150 cycles at 1 C. As sulfur loading increases from 50 wt% to 77 wt%, high capacities of 970, 914, and 613 mAh g−1 are still available at current densities of 0.5, 1, and 5 C, respectively. Based on the total mass of packaged devices, gravimetric energy density of GSH@APC‐S//Li cell is expected to be 400 Wh kg−1 at a power density of 10 000 W kg−1, matching the level of engine driven systems.