Anomalous Zn²⁺ Storage Behavior in Dual‐Ion‐In‐Sequence Reconstructed Vanadium Oxides

Abstract Vanadium oxides with fast and stable Zn²⁺ storage are of great significance to the development of high‐performance aqueous zinc ion batteries (ZIBs), and yet they commonly suffer from structural instability and sluggish diffusion kinetics. Herein, a new “dual‐ion‐in‐sequence” intercalation strategy based on quenching is proposed to address these issues. Interestingly, it is found that the Zn²⁺ storage mechanism evolves from the common solid‐state ion diffusion kinetic into an intercalation pseudocapacitance as a result of the enlarged interlayer spacing of V₂O₅. Together with the expanded interlayer spacing arising from the “dual‐ion‐in‐sequence” intercalation, oxygen defects are simultaneously generated at the sub‐surface of the reconstructed Li@MnVO materials. Benefitting from the improved ionic diffusivity, intercalation pseudocapacitance, and fast charge transferability, full cell based on Li@MnVO cathode shows impressive rate capability and excellent cycling stability of 5000 cycles with a high energy density of 253 Wh kg^‐1 at 10 A g^‐1. More importantly, the capacity can maintain at 125 mAh g^‐1 at 4 A g^‐1 even under a raised mass loading of 10 mg cm^‐2. The proposed “dual‐ion‐in‐sequence” intercalation strategy of manipulating V₂O₅ structure at atomic scales is a viable pathway for the high‐performance layered metal oxides, not only for ZIBs but also for other energy storage systems.