Preferential Lewis-basic ion pathways for accelerated Zn2+ diffusion and uniform deposition at zinc metal anodes

With advantages of high safety, low cost, and environmental friendliness, aqueous zinc metal batteries (ZMBs) are widely recognized as potential next-generation systems for grid-scale energy storage. However, their widespread application suffers from unstable Zn/electrolyte interfaces induced by uncontrolled Zn 2+ desolvation, migration, and deposition. Herein, we propose a molecularly engineered interfacial layer, created through a hydrolysis-condensation molecular assembly, that couples hydrophobic exclusion, preferential Zn 2+ transport pathways, and Lewis-basic coordination centers within a single framework. The strong electronegativity and hydrophobic properties of the macromolecular layer effectively repel anions and exclude free water molecules from the Zn surface, thereby suppressing hydrogen evolution and byproduct accumulation. Meanwhile, the preferential ion channels enriched with Lewis-base sites provide favorable Zn 2+ coordination environments, accelerate desolvation kinetics, and promote preferential ion migration, ultimately lowering nucleation barriers and homogenizing Zn 2+ flux. Benefiting from this regulation of interfacial chemistry and transport kinetics, the modified Zn anode achieves dendrite-free and highly reversible Zn plating/stripping, delivering a long cycling lifespan (3600 h at 1 mA cm −2 and 1 mAh cm −2 ), high Coulombic efficiency (99.7% after 1200 cycles), and excellent full-cell capacity retention (95% after 2000 cycles).