Stereometric Molecular Engineering for Ultra‐Stable Aqueous Zinc‐Ion Batteries

Abstract

ABSTRACT Aqueous zinc‐ion batteries (AZIBs) offer a safe and low‐cost energy storage platform yet are plagued by interfacial instability. Here, we investigate the relationship between molecular stereoisomerism and interfacial adsorption using inositol as a model system. Theoretical calculations reveal that the hydroxyl group orientation, arrangement, and geometric compatibility from different stereoisomers dictate the molecular adsorption at the Zn interface. The resulting tilted adsorption configuration of myo‐inositol establishes a water‐deficient electric double layer that effectively suppresses interfacial side reactions, restricts lateral Zn 2+ diffusion, and induces preferential Zn (101) deposition. Meanwhile, myo‐inositol reorganizes the hydrogen‐bond network and replaces coordinated water, thereby optimizing Zn 2+ desolvation process. Consequently, the assembled Zn//Zn symmetric cell shows markedly improved cycling stability for over 4500 h at 2 mA cm −2 . The Zn//NaV 3 O 8 ·1.5H 2 O full cell achieves excellent long‐term stability over 5000 cycles, with 0.002% capacity degradation per cycle. Pouch cells with different mass loadings operate stably without obvious capacity loss. This work elucidates how stereoisomerism governs interfacial adsorption through hydroxyl‐group arrangement, providing critical design insights for the molecular engineering of stable AZIBs.