Assembly of Metal–Organic Chemical Conversion Layers as Ion Sieves along with Exposing Zn(002) Planes for Stable Zn Metal Anode

Abstract The development of aqueous rechargeable Zn metal batteries, as one of the most promising large‐scale energy storage technology, is hindered largely by dendrite growth and surface passivation of Zn metal anode, which are deleterious to the battery life and Coulombic efficiency (CE). This report demonstrates that ethylenediamine tetramethylenephosphonic acid can in situ coordinate with Zn (EDTMP‐Zn) along with exposing (002) planes for highly reversible and stable Zn plating/stripping. The zincophilic EDTMP‐Zn layer may serve as ion sieves that homogenize Zn ion flux at the Zn anode surface and consequently induce uniform deposition of Zn. The hydrophobic groups in such functional layer is thought to circumvent the Zn anode surface from corrosion and hydrogen evolution reaction. EDTMP15‐Zn modified Zn anode (EDTMP15‐Zn@Zn) delivers a lifespan exceeding 1400 h at 5 mA cm⁻², and 1 mAh cm⁻² for Zn||Zn symmetric cell and improved CE of 99.7% over 1000 cycles in a Zn||Cu cell. The full cell coupled with NH₄V₄O₁₀ cathode demonstrates improved rate performance and cycle stability.