Disrupting Interfacial Hydrogen-Bond Networks to Build a Local H2O-Poor Microenvironment for Durable Aqueous Zn Anodes

Aqueous zinc metal anodes (ZMAs) suffer from H 2 O-driven parasitic reactions and dendritic plating, both rooted at the electrode-electrolyte interface. Herein, we report a molecular microenvironment engineering strategy that disrupts the interfacial hydrogen-bond (HB) network dynamically to deplete interfacial H 2 O at the ZMA surface. The low-molecular-weight additive N-methylsuccinimide (NMS) exhibits stronger HB interactions with H 2 O and high affinity for Zn than H 2 O itself, thereby displacing interfacial H 2 O and enriching the Helmholtz double layer with NMS. Together with its fast self-diffusion and robust Zn 2+ coordination capability, NMS accelerates Zn 2+ transport, effectively compensating for the interfacial Zn 2+ consumption and alleviating local concentration polarization. Consequently, ZMAs achieve dense, highly ordered Zn deposits with a preferential (101) orientation, while parasitic reactions are markedly suppressed. As a result, Zn||Zn symmetric cells cycle for >1730 h at 10 mA cm -2 and 1 mAh cm -2 without short circuiting, and Zn||V 2 O 5 full cells sustain reliable operation for >2500 cycles at 10 A g -1 . Combined MD/DFT calculations and in situ/operando characterizations support a dynamic solvation-displacement mechanism that reconstructs the interfacial HB network. Beyond enhanced performance, this interfacial HB-network regulation provides a generalizable paradigm for controlling solvation–reaction coupling in aqueous metal batteries.