Lithium-sulfur (Li-S) batteries have attracted considerable attention due to their high theoretical energy density, low cost and low toxicity of active materials. Despite the great progress achieved recently, the practical application of Li-S batteries still faces several critical challenges, i.e, low capacities, low coulombic efficiency and rapid capacity decay during cycling. These problems mainly originate from the reasons of:(i) the poor intrinsic electrical conductivity of sulfur and Li₂S decreasing the utilization of sulfur, (ii) the shuttle effect of soluble polysulfide intermediates losing active components, (iii) the large volumetric change pulverizing electrode during cycling, which become more and more serious when the sulfur loading is increased to the practical level of 3~5 mg·cm^-2. To address these issues, some approaches have been developed, including hybridizing sulfur with highly conductive materials to enhance the conductivity, encapsulating sulfur in porous materials to inhibit the loss of polysulfides and accommodate the volumetric expansion, blending sulfur with polar materials to restrain the diffusion of polysulfides by chemical interaction. Recently, our group reported the mesostructured cathode material of sulfur-filled carbon nanocages (S@hCNC), which demonstrated the large capacity, high-rate capability and long cycle life owing to unique mesostructured feature, physical confinement, good conductivity and coexisting micro-meso-macropores. However, the non-polar sp² carbons only have weak interaction with polar polysulfides. The introduction of chemical adsorption sites for polysulfides through heteroatom doping or surface modification can obviously enhance the interaction between the host and lithium polysulfides, thus further improving the cycling stability. Herein, we report the free-standing monolithic materials of reduced graphene oxide wrapped S@hCNC (S@hCNC@rGO), which can be directly used as the cathode without using binders, conductive materials and current collector. The S@hCNC@rGO battery with the high areal sulfur loading of 3.8 mg·cm^-2 delivers excellent electrochemical performances surpassing the counterpart of S@hCNC, e.g., high reversible specific capacity (1104 mAh·g^-1@0.2 A·g^-1), superior cycle stability (low degradation rate of 0.049% per-cycle@1.0 A·g^-1), high coulombic efficiency (>99.9%) and the top-ranking areal capacity of 3.7 mAh·cm^-2. Such excellent electrochemical performances can be ascribed to the synergism of the physical confinement of hCNC, the chemical adsorption of oxygen functional groups on rGO, the accelerated charge transfer kinetics arising from the hierarchical porous structure and high electrical conductivity, and the free-standing structure with high stability. This study also suggests a simple and efficient method to develop sulfur cathode with high areal capacity, which pave a way for the practical application of Li-S batteries.

Key words: lithium-sulfur batteries, monolithic materials, physical confinement, chemical adsorption, cycling stability, areal capacity, high sulfur loading