Electric Field‐Guided Ion Orchestration for Multi‐Chemistry Zinc Metal Batteries

While nonaqueous cosolvents alleviate hydrogen evolution reaction and dendritic growth in aqueous zinc (Zn) metal batteries (ZMBs), persistent H₂O activity at Zn|electrolyte interfaces originating from unregulated ion distribution leads to premature failure. Here, an electric field-guided ion orchestration (EF-IO) strategy is proposed, leveraging cation interfacial modifiers to reconfigure electric double layers (EDLs) and solvation configurations. Interfacial simulations combined with experimental investigations verify that the ion-orchestrated-EDL synergistically diversifies Zn²⁺/Na⁺ solvation configurations and homogenizes localized electric fields, thereby forming an organic-inorganic gradient solid electrolyte interphase (SEI) that suppresses parasitic reactions. This enables dendrite-free Zn plating with 3400 h cyclability in Zn||Zn symmetric cells, while Zn||V₁₀O₂₄·12H₂O full cells exhibit exceptional durability along with wide temperature adaptability (-45 to 55 °C). Crucially, this EF-IO strategy unlocks ClO₄ ^--based reversible anion storage in high-voltage organic cathodes. By bridging interfacial dynamics and multi-chemistry compatibility, this work establishes a promising paradigm for robust and versatile ZMBs.