Synergistic Integration of a Zirconia Field‐Homogenizer and a COF Ion‐Regulator for Ultrastable Zinc Metal Anodes

ABSTRACT The practical deployment of aqueous zinc‐ion batteries is impeded by rampant zinc dendrite growth and parasitic water‐induced side reactions. To address these challenges, we propose a new interfacial design paradigm through an artificial protective layer comprising a spherical ZrO 2 ‐COF (ZrCOF) organic‐inorganic hybrid. In this configuration, the ZrO 2 component homogenizes the interfacial electric field via the Maxwell‐Wagner polarization effect, while the COF skeleton facilitates rapid Zn 2+ flux through its ordered nanochannels and zinc‐affinity sites. This synergistic interplay ensures regulated desolvation and uniform deposition of zinc, thereby effectively suppressing dendrite formation and corrosive reactions. As a result, the ZrCOF@Zn symmetric cell achieves exceptional cycling stability over 2000 h at 1 mA cm −2 and 1 mAh cm −2 . When paired with an I 2 cathode, the full cell delivers a high specific capacity, outstanding rate performance, and a prolonged lifespan of 10 000 cycles at 5 A g −1 . The excellent performance of the assembled pouch cell further confirms its practical potential. This work not only elucidates the synergistic stabilization mechanism of organic–inorganic hybrid interphases, but also establishes a versatile design paradigm for developing advanced zinc‐metal batteries capable of meeting real‐world application requirements.