Decoupling Stability and Kinetics via Interfacial Electronic Structure Engineering for Long‐Life Aqueous Zinc‐Ion Batteries

ABSTRACT Anchoring single‐atom catalysts on conductive hosts is a prevalent strategy to accelerate Zn anode kinetics but inadvertently creates “hotspots” for parasitic hydrogen evolution reaction (HER) due to the host's electroactivity. We resolve this intrinsic kinetics‐stability trade‐off by shifting the paradigm from conductive to insulating hosts. Breaking this bottleneck, we propose an atomic‐site‐driven orbital reconfiguration strategy by anchoring Cu atomic sites into an in situ grown, insulating ZnS protective layer (Cu‐ZnS@Zn), which is constructed via a facile in situ gas‐solid reaction followed by a brief ion‐exchange solution impregnation. Strong Cu‐S interactions induce this orbital reconfiguration, triggering an upward shift of the ZnS d‐band center. This shift strengthens Zn 2+ adsorption and lowers the desolvation energy barrier, facilitating uniform plating. Simultaneously, the intensified H * adsorption firmly locks intermediates onto active sites, blocking HER kinetics; combined with the insulating layer's dense shielding, dendrite growth and hydrogen evolution are effectively suppressed. Consequently, the Cu‐ZnS@Zn electrode exhibits an ultra‐low overpotential of 30 mV at 5 mA cm −2 and a 2000 h lifespan. The full cell retains 92.33% capacity after 2500 cycles at 10 A g −1 . This work decouples interfacial stability from plating kinetics through orbital reconfiguration, providing an efficient pathway toward durable zinc anodes for stable, long‐life ZIBs.