Optimal Molecular Configuration of Electrolyte Additives Enabling Stabilization of Zinc Anodes

Abstract For the development of electrolyte additives as an effective strategy to improve the performance of zinc‐ion batteries (ZIBs), most researchers focus on the functional groups but overlook the crucial molecular configuration. Herein, six stereoisomers of 2,3,4,5‐tetrahydroxyvaleraldehyde with identical groups but various spatial arrangements are studied as the electrolyte additive in ZIBs. Based on the experimental analysis and theoretical calculations, the adsorption with Zn (002) plane is found to be an important dominant for the stereoisomer to enhance the Zn anode performance. Among these stereoisomers, D‐Arabinose with preferential and strongest chemisorption effect modifies the anode/electrolyte interface most effectively, leading to the highest stability and reversibility of the Zn anode. The adsorbed D‐Arabinose shows multifunctional effects at the interface, which not only regulates the Zn 2+ solvation structure and reconfigures the hydrogen bond framework, but also facilitates uniform Zn 2+ deposition by promoting 3D Zn 2+ diffusion and homogenizing the electric field. Therefore, with the D‐Arabinose additive in ZnSO 4 electrolyte, the undesired Zn dendrite growth and side reactions including hydrogen evolution reaction, corrosion, and passivation are significantly limited during the Zn plating/stripping processes. This work proposes a new insight toward the optimal molecular configuration of additive designing for electrolyte engineering in stable ZIBs.