Transition-metal sulfides as late-model electrocatalysts usually remain inactive in lithium-sulfur (Li-S) batteries in spite of their advantages to accelerate the rapid conversion of lithium polysulfides (LiPSs). Herein, a series of cobalt-doped vanadium tetrasulfide/reduced graphene oxide (x%Co-VS4/rGO) composites with an ultrathin layered structure as an active sulfur-host material are prepared by a one-pot hydrothermal method. The well-designed two-dimensional ultrathin 3%Co-VS4/rGO with heteroatom architecture defects (defect of Co-doping and defect of S-vacancies) can significantly improve the adsorption ability on LiPSs, the electrocatalytic activity in the Li2S potentiostatic deposition, and the active sulfur reduction/oxidation conversion reactions and greatly boost the electrochemical performances of Li-S batteries. On the one hand, the ultrathin 3%Co-VS4/rGO possesses good conductivity inheriting from rGO which contributes to the capacity of internal redox reactions on lithiation from VS4. On the other hand, the hybrid architectures provide strong adsorption and excellent electrocatalytic ability on LiPSs, which benefit from the surface defects caused by heteroatom doping. The S@3%Co-VS4/rGO cathode displays a high specific capacity of 1332.6 mA h g-1 at 0.2 C and a low-capacity decay of only 0.05% per cycle over 1000 cycles at 3 C with a primary capacity of 633.1 mA h g-1. Furthermore, when the sulfur loading (single-side coating) reaches 4.48 mg cm-2, it still can deliver 756.2 mA h g-1 after the 100th cycle at 0.2 C with 89.5% capacity retention. In addition, the in situ X-ray diffraction test reveals that the sulfur conversion mechanism is the processes of α-S8 → Li2S → β-S8 (first cycle) and then β-S8 ↔ Li2S during the subsequent cycles. The designing strategy with heteroatom doping and self-intercalation capacity adopted in this work would provide novel inspiration for fabricating advanced sulfur-host materials to achieve excellent electrochemical capability in Li-S batteries.
Keywords: defect engineering; electrocatalysis; lithium−sulfur batteries; self-intercalation; vanadium tetrasulfide.