Complementary Anion Chemistry Enabling Coordination Pre-Organization towards A Robust Disordered Interphase for Long-Life Aqueous Zn Battery

Abstract

Modulating electrolyte-Zn interface is crucial for high-performance aqueous zinc metal batteries, the correlation between bulk electrolyte intrinsics and interface chemistry however 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-enriched, water-deficient, chelating and ion conducting. The pre-organized coordination is further revealed to promote the cation transport kinetics. Consequently, this strategy transfer 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 energies, achieving long-term stability of Zn plating/stripping at 5 mA cm -2 and 5 mAh cm -2 . Further, the hybrid electrolyte endows the V 2 O 5 /Zn cell with an ultra-stable long-term cycling, e.g, 10000 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.