Activating Inert Metallic Zinc for Bifunctional Sulfur Reaction Catalysis Through Anion‐Controlled Tensile Lattice Strain

Abstract Modulating surface strain is recognized as an effective strategy to enhance the bifunctional activity of the catalyst, yet not been well investigated in rechargeable lithium‐sulfur (Li─S) batteries. Herein, a generalized tensile strained Te‐ZnSe catalyst is developed to create a redistributed surface with enriched electronic states that optimize intermediate binding and activate sulfur reduction reaction (SRR) and sulfur evolution reaction (SER). Theoretically, the generated tensile strain can upshift the d‐band center of Zn atoms and decrease the occupancy of anti‐bonding orbitals, thus increasing adsorption capacity and weakening S─S bonds of polysulfides (LiPSs) for lithium polysulfides. Experimental characterization and theoretical analysis further confirm that tensile strained Te‐ZnSe boosts Li─S bond breaking and lowers lithium migration barriers, which is energetically beneficial for SER. The Li─S battery based on ZnSe with tensile strain retains an excellent reversible capacity of 761 mAh g −1 with an ultralow decay rate of 0.0065% per cycle after 700 cycles under 1 C. This research deeply reveals the effect of tensile strain in improving the bifunctional activity of sulfur reaction, offering feasible guidance for designing high‐performance catalysts in Li─S batteries.