Molecularly Engineered Self‐Healing Polymer Interphase With Synergistic Dipoles for Ultra‐Stable Zinc Metal Anodes

ABSTRACT Artificial interphase engineering is crucial for suppressing parasitic reactions and dendrite growth in Zn metal anodes, yet current designs suffer from sluggish/non‐selective Zn 2+ transport and inferior dynamic adaptability during cycling, leading to interfacial failure. Herein, we construct a molecularly engineered self‐healing polymer interphase (MSP) featuring synergistic functional dipoles, including cyano (─C≡N), hydroxyl (─OH), and boron moieties (─B(OR) 2 ). These dipoles synergistically regulate interfacial Zn 2+ behavior via multivalent dipole interactions: (1) ─OH groups facilitate hydrated Zn 2+ desolvation via hydrogen bonding; (2) zincophilic ─C≡N accelerates Zn 2+ migration via ion‐dipole interactions to balance the reduction kinetics; and (3) electron‐deficient boron sites effectively capture counter anions to enhance Zn 2+ selectivity through Lewis acid–base interactions. Moreover, dynamic borate ester bonds endow the interphase with autonomous crack repair and volume‐change accommodation. This molecular design enables rapid and selective Zn 2+ conduction, significantly inhibiting side reactions and dendrite growth while maintaining dynamic interfacial integrity. As a result, Zn/Zn symmetric cells achieve an impressive cycle life of over 780 h under harsh conditions of 8 mA cm −2 and 8 mAh cm −2 , and the feasibility of this MSP‐modified Zn anode was demonstrated in full cells. This work establishes molecular engineering of multi‐dipole interphases as a promising platform for advanced Zn anodes.