Phytochemical Molecular Engineering Reconfiguring Solvation Chemistry and Interfacial Energy for Highly Reversible and Long‐Lifespan Zn‐Ion Batteries

ABSTRACT Severe hydrogen evolution, sluggish desolvation kinetics, and chaotic dendritic growth severely impede the commercialization of aqueous zinc‐ion batteries. Herein, a sustainable phytochemical molecular engineering strategy is proposed by introducing a natural chenpi extract (CPi) additive featuring multi‐component synergy. Benefiting from abundant multi‐functional bio‐molecules, CPi serves as a dual hydrogen‐bond donor/acceptor to disrupt the aggressive proton‐conduction network, fundamentally suppressing side reactions and parasitic hydrogen evolution. Concurrently, strong Zn 2+_ CPi coordination reconfigures the Zn 2+ solvation sheath, lowering the desolvation energy barrier and accelerating transmission kinetics. Furthermore, the preferential adsorption of aromatic moieties precisely modulates the interfacial energy, guiding rapid lateral ion flux and promoting the exclusive growth of the thermodynamically stable (100) texture. Consequently, this modified electrolyte empowers Zn 2+ symmetric cells with an ultra‐long lifespan exceeding 3600 h, and ensures an exceptional average Coulombic efficiency of 99.53% over 1000 cycles in Zn||Cu cells. Crucially, the practical Zn||MnO 2 full cells exhibit a remarkable capacity retention of 84.7% after 2000 cycles. This work opens a green, bio‐inspired avenue for implementing highly reversible, long‐life zinc metal anodes.