Hydrogen‐Bond Acceptor and Anion Receptor‐Mediated Regulation of Interfacial Proton Mobility for Long‐Lifespan Aqueous Zinc Batteries

Abstract Continuous interfacial hydrogen bonds network facilitates efficient proton transfer from the bulk electrolyte to the electrode surface, which exacerbates hydrogen evolution reactions (HER) and accelerates zinc corrosion in aqueous zinc‐ion batteries. Here, a dual‐modulation aqueous electrolyte is designed by incorporating a hydrogen bond acceptor, dimethylacetamide (DMA), and an anion receptor, benzyl alcohol (BA), to simultaneously improve zinc anode reversibility and stabilize the manganese ferrocyanide cathode. DMA disrupts interfacial H‐bond networks via its carbonyl group, hindering proton transport through the Grotthuss mechanism. Meanwhile, BA anchors OTf⁻ anions through hydroxyl‐mediated hydrogen bonding, promoting their selective decomposition into species that form a uniform, electron‐blocking solid electrolyte interphase (SEI) on the zinc surface. This SEI suppresses HER by preventing electron transfer to free water, enabling efficient zinc plating. The Zn||Zn symmetric cell achieves a lifespan of 4000 h (2 mA cm⁻ 2 , 1 mAh cm⁻ 2 ) and 2300 h under harsh conditions (10 mA cm⁻ 2 , 5 mAh cm⁻ 2 ), far outperforming traditional electrolytes. Moreover, controlled proton availability also mitigates Mn/Fe dissolution, enhancing Zn||MnFe(CN) 6 cell cycling to 5000 cycles with 82.0% capacity retention and over 99.4% coulombic efficiency. This synergistic approach offers a promising pathway to stabilize both zinc anodes and cathodes in aqueous systems.