Massively Reconstructing Hydrogen Bonding Network and Coordination Structure Enabled by a Natural Multifunctional Co‐Solvent for Practical Aqueous Zn‐Ion Batteries

Abstract The practical application of aqueous Zn‐ion batteries (AZIBs) is hindered by the crazy Zn dendrites growth and the H 2 O‐induced side reactions, which rapidly consume the Zn anode and H 2 O molecules, especially under the lean electrolyte and Zn anode. Herein, a natural disaccharide, d ‐trehalose (DT), is exploited as a novel multifunctional co‐solvent to address the above issues. Molecular dynamics simulations and spectral characterizations demonstrate that DT with abundant polar −OH groups can form strong interactions with Zn 2+ ions and H 2 O molecules, and thus massively reconstruct the coordination structure of Zn 2+ ions and the hydrogen bonding network of the electrolyte. Especially, the strong H‐bonds between DT and H 2 O molecules can not only effectively suppress the H 2 O activity but also prevent the rearrangement of H 2 O molecules at low temperature. Consequently, the AZIBs using DT30 electrolyte can show high cycling stability even under lean electrolyte (E/C ratio = 2.95 µL mAh −1 ), low N/P ratio (3.4), and low temperature (−12 °C). As a proof‐of‐concept, a Zn||LiFePO 4 pack with LiFePO 4 loading as high as 506.49 mg can be achieved. Therefore, DT as an eco‐friendly multifunctional co‐solvent provides a sustainable and effective strategy for the practical application of AZIBs.