Pre-Regulated Inner Helmholtz Plane via Coupling Crystallographic Orientation with Anion-Rich Dual-Functional Surface...

The stable operation of Zn metal anodes under high current densities remains a critical challenge due to the aggravated interfacial parasitic reactions at the inner Helmholtz plane (IHP). Herein, we report an electrode-side preconstruction strategy to preregulate the IHP by constructing a dual-functional Zn surface featuring preferential Zn(002) orientation and SO32--rich interfacial chemistry before cell assembly. After contact with the aqueous ZnSO4 electrolyte, this surface induces resting-induced interfacial reconstruction and promotes the formation of a uniform ZHS-derived solid-electrolyte interphase, enabling homogeneous Zn2+ flux, suppressed hydrogen evolution, and dendrite-free Zn deposition. Operando optical microscopy and theoretical simulations reveal the synergistic roles of crystallographic orientation and anion-rich IHP regulation in stabilizing Zn nucleation and growth kinetics. Consequently, Zn//Zn symmetric cells achieve ultralong cycling stability for 1300 h at 10 mA cm-2 and sustain stable operation for 380 h at an ultrahigh current density of 50 mA cm-2. Moreover, Zn//MnO2 full cells deliver 80% capacity retention after 3000 cycles at 1 A g-1, demonstrating the feasibility of this strategy for high-rate Zn-ion batteries.