Interfacial Kinetic Gating Mechanism via Controllable SEI Regulation toward Robust Zinc Anodes

Interphase chemistry is conventionally ascribed to electrolyte composition, while electrochemical operating conditions are treated merely as kinetic parameters. Here, we demonstrate applied current programs at the solid electrolyte interphase (SEI) on Zn via an electrochemical kinetic-gating mechanism. N-Hydroxyethyliminodiacetic acid reorganizes Zn2+ solvation and supplies interfacial precursors, whereas current density selects their reaction pathways. High current establishes a kinetically constrained window that promotes coupled conversion of sulfate and NHA species into a compact organic–inorganic SEI enriched in ZnS and Zn–N; low-current formation produces a loose and nonprotective interphase. High-current activation enables stable Zn deposition even after switching to low current, evidencing that interphase properties are determined by formation history. The programmed anode delivers 5300 h at 5 mA cm–2, and Zn||NH4V4O10 pouch cells sustain 700 cycles. These findings establish current as an active control variable for interfacial reaction selection, offering a route toward programmable interphase chemistry beyond composition-only design.