Complementary anion chemistry enabling coordination pre-organization towards a robust disordered interphase for...

Modulating the electrolyte-Zn interface is crucial for high-performance aqueous zinc metal batteries; however, the correlation between bulk electrolyte intrinsic properties and interface chemistry remains vague in novel electrolytes. Herein, a coordination pre-organization strategy was developed via complementary anion chemistry to construct a robust electrolyte-Zn interphase through a dual-anion hybrid aqueous electrolyte with rationally tuned anion molecular structures. Cooperative coordination is achieved in the hybrid electrolyte with the characteristics of anion enrichment, water deficiency, chelation and ion conduction. The pre-organized coordination is further revealed to promote the cation transport kinetics. Consequently, this strategy transfers the microstructural coordination information from the bulk electrolyte to the interface, leading to an anion-dominated homogeneous disordered interphase, as revealed by molecular dynamics calculations, which boosts the interfacial kinetics with the favored activation energies of charge transfer and desolvation, achieving long-term stability of Zn plating/stripping at 5 mA cm^-2 and 5 mAh cm^-2. Furthermore, the hybrid electrolyte endows the V₂O₅/Zn cell with ultrastable long-term cycling, e.g., 10 000 cycles at 10 A g^-1 with a high retention rate of 96.6%. Our work introduces complementary anion chemistry and establishes the coordination pre-organization strategy to bridge electrolyte coordination and interface regulation for rechargeable batteries.