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

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 ZrO₂-COF (ZrCOF) organic-inorganic hybrid. In this configuration, the ZrO₂ component homogenizes the interfacial electric field via the Maxwell-Wagner polarization effect, while the COF skeleton facilitates rapid Zn²⁺ 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 I₂ 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.