Interlayer Modification of Pseudocapacitive Vanadium Oxide and Zn(H2O)n2+ Migration Regulation for Ultrahigh Rate and Durable Aqueous Zinc‐Ion Batteries

The interlayer modification and the intercalation pseudocapacitance have been combined in vanadium oxide electrode for aqueous zinc‐ion batteries. Intercalation pseudocapacitive hydrated vanadium oxide Mn1.4V10O24·12H2O with defective crystal structure, interlayer water, and large interlayer distance has been prepared by a spontaneous chemical synthesis method. The inserted Mn2+ forms coordination bonds with the oxygen of the host material and strengthens the interaction between the layers, preventing damage to the structure. Combined with the experimental data and DFT calculation, it is found that Mn2+ refines the structure stability, adjusts the electronic structure, and improves the conductivity of hydrated vanadium oxide. Also, Mn2+ changes the migration path of Zn2+, reduces the migration barrier, and improves the rate performance. Therefore, Mn2+‐inserted hydrated vanadium oxide electrode delivers a high specific capacity of 456 mAh g−1 at 0.2 A g–1, 173 mAh g–1 at 40 A g–1, and a capacity retention of 80% over 5000 cycles at 10 A g–1. Furthermore, based on the calculated zinc ion mobility coefficient and Zn(H2O)n2+ diffusion energy barrier, the possible migration behavior of Zn(H2O)n2+ in vanadium oxide electrode has also been speculated, which will provide a new reference for understanding the migration behavior of hydrated zinc‐ion. The strategy of interlayer modification of Mn2+ is applied to regulate the interlayer atomic coordination structure, electronic structure, and affect Zn2+ migration behavior in the vanadium oxide (V10O24·nH2O). Zinc ion intercalation pseudocapacitance, ultra‐high rate performance, and cycling stability are achieved and the Zn(H2O)n2+ migration behavior is analyzed and speculated. ​