Coordination‐Unsaturated Cu–OSe Directs (002)/(100) Dual‐Texture Zn Growth via Cu‐Centered Charge Redistribution

ABSTRACT Controlling Zinc (Zn) nucleation and subsequent crystal growth is critical for long‐lifespan aqueous Zn‐metal batteries. However, the concurrent parasitic reactions and dendritic growth impede the continuous Zn‐metal electrodeposition. Here, we demonstrate that coordination unsaturation is exploited to reconstruct the electronic structure of a metal host, thereby regulating the crystallographic pathway of Zn deposition. A partially selenized Cu‐OSe framework with locally unsaturated mixed O/Se coordination stabilizes a mixed‐valence Cu configuration and redistributes Cu‐derived electronic states, establishing continuous local‐current pathways. These pathways homogenize interfacial electron transport and redirect Zn growth toward a stable Zn(002)/(100) dual texture. This coordination regime preserves structural integrity while avoiding framework collapse and morphological deformation associated with complete selenization. Macroscale characterization confirms the spatial continuity of local‐current pathways across the Cu‐OSe substrate, attesting to its scalability toward pouch‐cell applications. Accordingly, the Cu‐OSe@Zn anode sustains stable Zn plating/stripping for over 3100 h at 1 mA cm −2 while Cu‐OSe@Zn||VO 2 full cells deliver 2200 cycles at 1 A g −1 with 71% capacity retention. These findings establish a direct mechanistic link, whereby coordination unsaturation drives Cu‐centered electronic reconstruction to generate local‐current pathways that direct Zn dual‐texture growth, identifying local coordination engineering as a general electronic‐structure design principle for regulating metal‐electrodeposition interfaces.