Electronic Structure Engineering Enables Dynamic Interfacial Adaptation of Zinc Anodes

In aqueous zinc‐ion batteries, Zn plating/stripping is accompanied by continuous evolution of the local electric field, solvation structure, and interfacial chemical environment. Therefore, conventional electrolyte additives that rely on fixed adsorption or static interfacial layer construction are insufficient for sustained interfacial regulation. Herein, we propose an electronic structure regulation strategy that endows electrolyte additives with dynamic interfacial adaptability through molecular engineering. Using pyrrolidone derivatives as model molecules, we demonstrate that vinyl functionalization strengthens π‐electron delocalization and enhances the polarization response of N ‐vinyl‐2‐pyrrolidone (NVP). Such electronically adaptive behavior allows NVP to respond to the evolving local interfacial environment via electronic redistribution, thereby adaptively modulating the Zn/electrolyte interface while simultaneously optimizing interfacial Zn 2+ solvation, water distribution, and Zn deposition behavior. Consequently, the ZSO+NVP electrolyte enables a Zn//Zn symmetric cell to operate stably for over 4000 h at 10 mA cm −2 , while the Zn//NH 4 V 4 O 10 full cell delivers 92.6% capacity retention after 1500 cycles at 2 A g −1 . This work reveals the critical role of additive electronic responsiveness in stabilizing dynamic Zn/electrolyte interfaces.