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/Bi 2 O 3 , 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/Bi 2 O 3 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/Bi 2 O 3 ||MnO 2 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/Bi 2 O 3 ||MnO 2 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.