The practical application of Li−S batteries is still limited by the fundamental problems of the insulation properties of sublimed S and the “shuttle effect” of polysulfides. S‐doped porous carbon cage (SPCC) obtained by the catalytic guidance methodology is employed as a highly efficient S host material for Li−S batteries, which presents the cage‐like morphology coupled with abundant pore channels. Compared to the undoped PCC, SPCC exhibits higher electrical conductivity. The composite of sublimed S and SPCC (S@SPCC) employed as cathode for Li−S batteries possesses a higher reversible capacity, superior rate capability and better durability in comparison with that of S@PCC cathode. The synergistic effect of robust matrix associated with good electrical conductivity and abundant pore channels of SPCC is beneficial for the fast electron transport and shorten the Li‐ion diffusion distance. Besides, S doping possesses the positive function to attract Li‐polysulfides, inhibiting the shuttle of Li‐polysulfides and contributing to the superior electrode behavior of the S@SPCC cathode.
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