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Fast charge transfer and lithium-ion transport in the electrodes are necessary for high performance Li–S batteries. Herein, a N-doped carbon-coated intercalated-bentonite (Bent@C) with interlamellar ion path and 3D conductive network architecture is designed to improve the performance of Li–S batteries by expediting ion/electron transport in the cathode. The interlamellar ion pathways are constructed through inorganic/organic intercalation of bentonite. The 3D conductive networks consist of N-doped carbon, both in the interlayer and on the surface of the modified bentonite. Benefiting from the unique structure of the Bent@C, the S/Bent@C cathode exhibits a high initial capacity of 1,361 mA h g −1  at 0.2C and achieves a high reversible capacity of 618.1 m Ah g −1  at 2C after 500 cycles with a sulfur loading of 2 mg cm −2 . Moreover, with a higher sulfur loading of 3.0 mg cm −2 , the cathode still delivers a reversible capacity of 560.2 mA h g −1  at 0.1C after 100 cycles.

Effective ion pathways and 3D conductive carbon networks in bentonite host enable stable and high-rate lithium–sulfur batteries