Unveiling the Curvature‐Dependent Electrocatalytic Kinetics for Sulfur Redox Reaction in Li‐S Chemistry

Abstract Lithium‐sulfur (Li‐S) batteries have suffered from serious “shuttle effect” and sluggish kinetic of sulfur redox reaction (SRR). Herein, we focus on the circumferential strain engineering on tailoring the single‐atom catalysts (SACs) for fast SRR in Li‐S batteries. A distinguish coaxial V‐doped MoS₂@CNTs (V‐MoS₂@CNTs) heterostructure with uniform biaxial strain is developed as the platform to unveil the curvature‐dependent electrocatalytic kinetics in SRR. Both experimental results and theoretical calculations show that this circumferential strain not only benefits the interaction between cathodes and LiPSs, but also dynamically strengthens the SRR by a modified d‐band structure of dual‐metal active sites, i.e., V and Mo. Consequently, the V‐MoS₂@CNTs catalysts with strong circumferential strain exhibit a discharge capacity of 1202 mAh cm⁻² at 0.5 C and a capacity fading of 0.052% at 1 C, while an outstanding rate performance of 796 mAh g⁻¹ at 5 C. In addition, a high area capacity of 3.2 mAh cm⁻² is maintained after 65 cycles at 0.1 C with a high sulfur loading of 3.7 mg cm⁻². The strategy developed in this work deepens understanding the impact of curving strain engineering in SRR, and provides a feasible way to the scale‐up synthesis of high‐performance SACs with tunable electrocatalytic activities.