The sp2‐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 sp2 nanocarbon and nanostructured porous carbon into hierarchical all‐carbon nanoarchitectures is demonstrated, with full inherited advantages of the component materials. The sp2 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 S8 crystal into amorphous cyclo‐S8 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.

Peng, H., Huang, J., Zhao, M., Zhang, Q., Cheng, X., Liu, X., Qian, W., & Wei, F. (2014). Nanoarchitectured Graphene/CNT@Porous Carbon with Extraordinary Electrical Conductivity and Interconnected Micro/Mesopores for Lithium‐Sulfur Batteries. Advanced Functional Materials, 24(19), 2772–2781. Portico.