In Situ Construction of a Polyacrylate–Zinc Interphase Suppresses Iodide‐Mediated Corrosion for Durable Aqueous Zn–S Batteries

ABSTRACT Aqueous zinc–sulfur batteries (ZSBs) exhibit high capacity and sustainability, but often require ZnI 2 as an electrolyte additive, which introduces corrosive polyiodides (I 3 − and I 5 − ) and leads to severe self‐discharge and anode corrosion. Herein, an in situ formed organic‐metal interphase (PA‐Zn) is constructed on the zinc anode. The PA‐Zn layer not only effectively suppresses the shuttle of iodine species but also guides uniform zinc ion deposition by reducing nucleation overpotential, enabling 3D Zn‐ion diffusion, stabilizing current density, and promoting uniform zinc deposition. As a result, the symmetric cell with a PA‐Zn@Zn anode achieves an ultralong cycling stability of 1000 h at 1 mA cm −2 and 1 mAh cm −2 , together with remarkable high‐current endurance of 150 h even at 5 mA cm −2 . When applied in ZSBs, Coulombic efficiency of the cell with bare Zn drops sharply after more than 50 cycles, while that of the cell with PA‐Zn‐modified anode remains stable. This work offers a feasible interphase engineering strategy to suppress interfacial corrosion in ZSBs, especially in electrolytes containing iodine‐based additives.