A rechargeable hybrid aqueous battery (ReHAB) containing NASICON-type M₃V₂(PO₄)₃ (M = Li, Na) as the cathodes and Zinc metal as the anode, working in Li₂SO₄-ZnSO₄ aqueous electrolyte, has been studied. Both of Li₃V₂(PO₄)₃ and Na₃V₂(PO₄)₃ cathodes can be reversibly charge/discharge with the initial discharge capacity of 128 mAh g⁻¹ and 96 mAh g⁻¹ at 0.2C, respectively, with high up to 84% of capacity retention ratio after 200 cycles. The electrochemical assisted ex-XRD confirm that Li₃V₂(PO₄)₃ and Na₃V₂(PO₄)₃ are relative stable in aqueous electrolyte and Na₃V₂(PO₄)₃ showed more complicated electrochemical mechanism due to the co-insertion of Li⁺ and Na⁺. The effect of pH of aqueous electrolyte and the dendrite of Zn on the cycling performance of as designed MVP/Zn ReHABs were investigated and weak acidic aqueous electrolyte with pH around 4.0–4.5 was optimized. The float current test confirmed that the designed batteries are stable in aqueous electrolytes. The MVP//Zn ReHABs could be a potential candidate for future rechargeable aqueous battery due to their high safety, fast dynamic speed and adaptable electrochemical window. Moreover, this hybrid battery broadens the scope of battery material research from single-ion-involving to double-ions -involving rechargeable batteries.

Aqueous zinc-ion batteries offer sustainable large-scale storage potential with inherent safety and low cost, yet suffer from limited energy density and cycle life due to aqueous electrolyte constraints. Here, we introduce affordable, stable electrolyte (0.33 $·kg⁻¹) incorporating minimal multi-halogen anions (Cl⁻, Br⁻, and I⁻) to create a high-entropy solvation structure enabling high-performance zinc batteries. Despite the small amount, the diversified mono-halogenated contact ion pair and multi-halogenated aggregate solvation structures create the unique high-entropy solvation structure, to form the lean-water halogenated interfacial environment, suppressing the hydrogen evolution reaction, while facilitating cascade desolvation. Multi-halogen additives generate diverse contact ion pairs (Zn-X, X = Cl/Br/I) with compact solvation shells accelerating ion transport. In this way, the high-entropy solvation structure breaks the trade-off between plating overpotential (energy efficiency) and plating/stripping reversibility (Coulombic efficiency). As a result, the high-entropy solvation-based electrolyte enables practical zinc metal battery with 152.2 Wh kg⁻¹_electrode for 120 cycles at lean electrolyte of 2.4 μL mg⁻¹ and an Ah-level pouch cell is validated with high Coulombic efficiency of over 99.90% for over 250 cycles. Our findings emphasize the importance of electrolyte design for the precise control of anion-cation interactions for stable Zn/electrolyte interface and enable practical zinc metal battery with high energy and low cost.