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•MIL-125 derived micro-mesoporous Co/NC-TiO2 sulfur host was developed.•Multistate porous structure offers sulfur loading space and adapts volume variation.•Polar TiO2 and Co sites realize strengthened trapping and conversion of LiPSs.•The S@Co/NC-TiO2 cathode shows excellent performance in Li-S batteries.
Lithium-sulfur (Li-S) battery is a promising high-energy density device. However, the shuttling of lithium polysulfide (LiPS) and severe volume variation of sulfur has hindered its practical application. Herein, a nitrogen-doped micro-mesoporous Co/NC-TiO2 composite derived from cobalt-doped MIL-125 is prepared as efficient multifunctional sulfur host. In the design of this composite, abundant micro-mesoporous structure is introduced by cobalt ion etching and ammonia treatment, which affords sufficient space for sulfur loading and adapts to large volume variation. Meanwhile, the polar TiO2 endows the composite with high sulfur affinity, and the introduction of cobalt offers strong LiPS adsorption and fast redox reaction kinetics. Accordingly, the Co/NC-TiO2 electrode achieves a specific capacity of 941 mAh g−1 at 1 C and a low capacity decay rate of 0.062% per cycle after 500 cycles. It is also capable of delivering a high capacity of 730 mAh g−1 at 3 C. At sulfur loading of 5.5 mg cm−2, the Co/NC-TiO2 electrode provides a high areal initial capacity of 5.6 mAh cm−2, showing promising application in Li-S batteries.