Synergy of Dendrites‐Impeded Atomic Clusters Dissociation and Side Reactions Suppressed Inert Interface Protection for Ultrastable Zn Anode

Abstract The sluggish ions‐transfer and inhomogeneous ions‐nucleation induce the formation of randomly oriented dendrites on Zn anode, while the chemical instability at anode–electrolyte interface triggers detrimental side reactions. Herein, this report in situ designs a multifunctional hybrid interphase of Bi/Bi₂O₃, for the first time resulting in a novel synergistic regulation mechanism involving: (i) chemically inert interface protection mechanism suppresses side reactions; and more fantastically, (ii) innovative thermodynamically favorable Zn atomic clusters dissociation mechanism impedes dendrites formation. Assisted by collaborative modulation behavior, the Zn@Bi/Bi₂O₃ symmetry cell delivers an ultrahigh cumulative plating capacity of 1.88 Ah cm⁻² at 5 mA cm⁻² and ultralong lifetimes of 300 h even at high current density and depth of discharge (10 mA cm⁻², DOD_Zn: 60%). Furthermore, under a low electrolyte‐to‐capacity ratio (E/C: 45 µL mAh⁻¹) and negative‐to‐positive capacity ratio (N/P: 6.3), Zn@Bi/Bi₂O₃||MnO₂ full‐cell exhibits a superior capacity retention of 86.7% after 500 cycles at 1 A g⁻¹, which outperforms most existing interphases. The scaled‐up Zn@Bi/Bi₂O₃||MnO₂ battery module (6 V, 1 Ah), combined with the photovoltaic panel, presents excellent renewable‐energy storage ability and long output lifetime (12 h). This work provides a fantastic synergistic mechanism to achieve the ultrastable Zn anode and can be greatly promised to apply it into other metal‐based batteries.