Unveiling the Mechanism of Interfacial Water Reconfiguration via Zincophilic Additives for Highly Reversible Aqueous Zinc‐Ion Batteries

The stability of aqueous zinc‐ion batteries (AZIBs) is compromised by uncontrolled dendrite growth and parasitic side reactions, largely attributed to the high reactivity of interfacial water within the electric double layer (EDL). Regulating the composition of interfacial water emerges as a key strategy for stabilizing AZIBs, this task is fraught with substantial complexities owing to the dynamic and intricate nature of the EDL microenvironment. Here, we introduce a zincophilic structure additive to reconstruct the Zn 2+ solvation shell and enforce interfacial water regulation, which effectively suppresses parasitic side reactions and mitigates cathode dissolution. In situ Raman spectroscopy revealed the dynamic evolution of interfacial water, demonstrating that 4‐hydroxy‐L‐proline reconstructs the interfacial hydrogen‐bond network to create a Zn 2+ ‐enriched interface with stable Zn 2+ flux, promoting the stabilization of the interface. In the optimized electrolyte, Zn//Zn cells achieve exceptional cycling stability exceeding 8000 h; Zn//Cu asymmetric cells achieve an average Coulombic efficiency of 99.71% over 4000 cycles; and Zn//MnO 2 full cells exhibit stable cycling for 4000 cycles. This work provides a fundamental insight for interfacial water management in high‐performance AZIBs.