Abstract Interlayer modification can effectively tailor the local environment of vanadates and enhance ion migration kinetics in aqueous zinc‐ion batteries (ZIBs). However, the regulation of various intercalants on the Zn 2+ insertion mechanism and the resulting precise phase evolution are still unknown. Based on the findings, pre‐intercalated Y 3+ ion generates the transition from stable V 5+ O 5 to the metastable V 4+ O 5 due to the charge balance. Interlayer water induces local structure change from V 4+ O 5 to V 4+ O 6 , resulting in the reconfiguration from monolayer α‐V 2 O 5 to heterogeneous bilayer δ‐V 2 O 5 ·nH 2 O structure. Notably, the Zn 2+ storage behavior of vanadium is governed by the local structural transformation from VO 5 pyramids to VO 6 octahedra. Correspondingly, the Y‐doped monolayer α‐V 2 O 5 transforms into a wavy‐like γ‐V 2 O 5 , whereas water‐doped bilayer δ‐V 2 O 5 ·nH 2 O maintains its original crystal structure with only interlayer spacing variation. In other words, interlayer water promotes the formation of a stable bilayer structure, preventing lattice distortion and phase transitions during Zn 2 ⁺ insertion/extraction, thereby effectively enhancing cycling stability. The co‐doped V 2 O 5 exhibits a capacity of ≈400 mAh g −1 at 0.1 A g −1 , and an outstanding capacity retention of ≈90% over 3000 cycles. This work offers valuable insights into the local environment modification of advanced cathode materials.
Li et al. (2025) studied this question.