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Lithium–sulfur batteries (LSBs) suffer from the unavoidable ‘shuttle effects’ of lithium polysulfides (LPSs) and the infinite volume change of the sulfur. Herein, the authors prepared a yolk–shell structured N-doped carbon nanotubes/sulfur/poly(3,4-ethylenedioxythiophene) nanotube (N-CNTs/S@PEDOT) composite as a cathode for LSBs. The yolk–shell structure with void spaces can effectively buffer the volume expansion of sulfur, while the outer ‘shell’ can act as a physical barrier to minimise the ‘shuttle effects’ of LPSs. Moreover, the N-CNTs with high conductivity and superior structural stability are able to improve the electron transfer efficiency and cycling performance. Therefore, the specially designed yolk–shell structured N-CNTs/S@PEDOT composite cathode exhibits an extraordinary rate performance and enhanced cycling stability (602 mAh g−1 after 200 cycles at 0.1 C).

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