Modulating Cation Migration and Deposition with Xylitol Additive and Oriented Reconstruction of Hydrogen Bonds for Stable Zinc Anodes

Abstract Highly reversible plating/stripping in aqueous electrolytes is one of the critical processes determining the performance of Zn‐ion batteries, but it is severely impeded by the parasitic side reaction and dendrite growth. Herein, a novel electrolyte engineering strategy is first proposed based on the usage of 100 mM xylitol additive, which inhibits hydrogen evolution reaction and accelerates cations migration by expelling active H 2 O molecules and weakening electrostatic interaction through oriented reconstruction of hydrogen bonds. Concomitantly, xylitol molecules are preferentially adsorbed by Zn surface, which provides a shielding buffer layer to retard the sedimentation and suppress the planar diffusion of Zn 2+ ions. Zn 2+ transference number and cycling lifespan of Zn ∥ Zn cells have been significantly elevated, overwhelmingly larger than bare ZnSO 4 . The cell coupled with a NaV 3 O 8 cathode still behaves much better than the additive‐free device in terms of capacity retention.