Tailoring the Whole Deposition Process from Hydrated Zn2+ to Zn0 for Stable and Reversible Zn Anode

Abstract The practical application of aqueous zinc‐ion batteries (ZIBs) indeed faces challenges primarily attributed to the inherent side reactions and dendrite growth associated with the Zn anode. In the present work, N‐Methylmethanesulfonamide (NMS) is introduced to optimize the transfer, desolvation, and reduction of Zn 2+ , achieving highly stable and reversible Zn plating/stripping. The NMS molecule can substitute one H 2 O molecule in the solvation structure of hydrated Zn 2+ and be preferentially chemisorbed on the Zn surface to protect Zn anode against corrosion and hydrogen evolution reaction (HER), thereby suppressing byproducts formation. Additionally, a robust N‐rich organic and inorganic (ZnS and ZnCO 3 ) hybrid solid electrolyte interphase is in situ generated on Zn anode due to the decomposition of NMS, resulting in enhanced Zn 2+ transport kinetics and uniform Zn 2+ deposition. Consequently, aqueous cells with the NMS achieve a long lifespan of 2300 h at 1 mA cm −2 and 1 mAh cm −2 , high cumulative plated capacity of 3.25 Ah cm −2 , and excellent reversibility with an average coulombic efficiency (CE) of 99.7 % over 800 cycles.