Molecular Geometry‐ Mediated Interfacial Desolvation Kinetics of Disaccharide Isomers for Dendrite‐Free Zinc Anodes

Abstract Electrolyte additive engineering is pivotal for stabilizing zinc anodes, yet the role of molecular geometry remains unexplored. Here, three disaccharide isomers (sucrose, maltose, lactose) with identical molecular formulas but distinct configurations are investigated as additives in ZnSO 4 electrolytes. It is found that maltose exhibits superior electrochemical performance due to its linear α‐1,4‐glycosidic backbone. This specific geometry promotes hydroxyl‐mediated ordered adsorption on the zinc surface, facilitating the formation of a water‐repellent interface and the reconstruction of the electric double layer, thereby enhancing interfacial stability. Additionally, the reduced steric hindrance lowers the desolvation energy barrier and enhances the Zn 2 ⁺ transport selectivity. This synergistic regulation achieves dense and uniform zinc deposition, effectively suppressing dendrites, minimizing hydrogen evolution and side reactions. Zn||Zn symmetric cells with maltose electrolyte achieve a cycling lifetime of 400 h (10mA·cm −2 , 10mAh·cm −2 ), while Zn||NVO full cell retain 83.2% capacity after 600 cycles. This work highlights molecular geometry as a design criterion for biomolecule‐based electrolyte additives, advancing sustainable strategies for zinc‐metal anodes.