Molecular Structure Engineering of Isomeric Additives for Long Lifetime Zn Anodes

Abstract Modulating the solvation structure of hydrated zinc ions using organic additives stands as a pragmatic approach to suppress dendrite formation and corrosion on zinc metal anodes (ZMAs), thereby enhancing the rechargeability of aqueous Zn‐ion batteries. However, fundamental screening principles for organic additives with diverse molecular structures remain elusive, especially for isomers with the same molecular formula. This study delves into the impact of three isomeric hexagonal alcohols (mannitol, sorbitol, and galactitol) as additives in adjusting Zn 2+ solvation structural behaviors within ZnSO 4 baseline electrolytes. Electrical measurements and molecular simulations reveal the specific molecular structure of mannitol, which features interweaving electron clouds between adjacent hydroxyl groups, achieving a high local electron cloud density. This phenomenon significantly enhances desolvation abilities, thus establishing a more stable anode/electrolyte interface chemistry. Even at 5 mA cm −2 for 2.5 mAh cm −2 capacity, Zn||Zn symmetric cells with mannitol‐regulated electrolyte display an impressive 1170 h lifespan, far exceeding those with other isomer additives and is nearly tenfold longer than that with a pure ZnSO 4 electrolyte (120 h). Rather than strictly adhering to focusing on chemical composition, this study with emphasis on optimizing molecular structure offers a promising untapped dimension to screen more efficient additives to enhance the reversibility of ZMAs.