High‐Entropy Sulfides Catalyze Rate‐Determining Redox in Fast‐Charging Aqueous Zinc‐Sulfur Batteries

The sluggish kinetics of the solid‐solid Zn‐S redox process significantly hinders the practical energy density and lifespan of fast‐charging aqueous Zn‐S batteries (AZSBs). Conventional catalysts often fail to address these challenges, exhibiting limited sulfur utilization and cycling stability under fast‐charging conditions. To overcome this limitation, we present a three‐step synthesis of high‐entropy sulfide (HES) nanorod catalysts to accelerate the rate‐determining step (RDS) in the Zn‐S redox process. Operando synchrotron powder diffraction, operando synchrotron infrared reflectance microscopy, and operando Raman spectroscopy characterizations reveal that the HES catalysts improve sulfur utilization by accelerating the RDS conversion of ZnS2 to wurtzite ZnS. In contrast, utilizing low‐ and medium‐entropy catalysts results in the formation of by‐products, including S52−, S32−, and SO32− species. Furthermore, near‐edge X‐ray absorption fine structure (NEXAFS) and inductively coupled plasma mass spectrometry (ICP‐MS) analyses demonstrate that the HES catalysts effectively suppress the leaching effect of transition metals and water splitting of the aqueous electrolyte, improving cycling stability. Consequently, the AZSBs with the HES catalysts deliver over 4,000 cycles at a high current density of 20 A g−1 with a capacity decay of 0.086% per cycle. This entropy‐driven catalytic strategy provides an effective approach for developing stable and fast‐charging aqueous metal‐sulfur batteries.