Zn Powder Anodes With Stabilized Interfacial Chemistry via Facet‐Selective ZnTCPP Adsorption for Aqueous Zn‐Ion Batteries

ABSTRACT Zn powder anodes are regarded as promising alternatives to Zn foil for the scalable fabrication of aqueous Zn‐ion batteries, yet their large specific surface area inevitably induces severe interfacial instability, including uncontrolled dendrite growth and aggravated parasitic reactions. Herein, a porphyrin‐based metal‐organic framework ZnTCPP is in situ constructed on Zn powder to engineer both surface crystallography and interfacial chemistry. Benefiting from its facet‐selective adsorption behavior, the ZnTCPP preferentially anchors onto the Zn(101) and Zn(100) facets, thereby thermodynamically suppressing their participation in Zn deposition. Meanwhile, the porphyrin ligands serve as effective Zn ²⁺ affinity centers that homogenize Zn ²⁺ flux and redirect Zn nucleation toward the low‐energy Zn(002) plane, enabling compact and dendrite‐free Zn growth. Moreover, the ZnTCPP layer promotes the desolvation of hydrated Zn ²⁺ at the electrode surface and mitigates interfacial side reactions, leading to a stabilized Zn‐electrolyte interface. Consequently, the ZnTCPP‐modified Zn powder anode exhibits significantly enhanced electrochemical reversibility and durability, delivering an average Coulombic efficiency of 99.7%, maintaining stable plating/stripping behavior for over 500 h, and supporting high critical current densities up to 500 mA g ⁻¹ . Furthermore, full cells assembled with the modified anode demonstrate superior cycling stability and rate capability compared with those using the pristine Zn powder anode.