Drastically Promoting Rate Capability via Dual‐Cations Intercalation of V2O5 Enabling Rapid Zinc‐Ion Storage

Layered vanadium pentoxide (V₂O₅) has drawn enormous attention as cathode material for aqueous zinc-ion batteries (AZIBs). However, the fragile open-framework and the sluggish Zn²⁺ migration due to the strong electrostatic interaction between Zn²⁺ and cathode electrode hinder the development of AZIBs. Here, an effective dual-cations intercalation strategy is employed based on synergistic effect of Mn²⁺ and Zn²⁺, which introduces guest species with robust layered construction and weak electrostatic interaction in the V₂O₅ bulk. Consequently, the (Mn_0.13Zn_0.03)V₂O₅ (abbreviated to MZVO) electrode exhibits a high reversible capacity of 463 mA h g^-1 at 0.1 A g^-1, a high cycling stability (94% of capacity retention after 1000 cycles at 10 A g^-1) and superior rate performance of 256 mAh g^-1 at 20 A g^-1. The outstanding performance of MZVO cathode is attributed to the Mn²⁺-induced fast migration of Zn²⁺ transfer and Zn²⁺-induced high structural stability conducted by density functional theory (DFT) calculations. The two-phase reaction mechanism of MZVO during Zn²⁺ (de)interaction is systematically expounded via operando XRD. This study will provide reference for the design of modified layered metal oxides in the future.