Interfacial Orbital Hybridization in Multiphase Mn‐V Oxide Enabling Long‐Life and High‐Power Aqueous Zinc‐Ion Batteries

ABSTRACT Manganese (Mn)‐based cathode materials show great promise for aqueous zinc‐ion batteries (AZIBs) owing to their inherent safety and low cost. However, they still suffer from substantial disadvantages, such as Mn dissolution and structural degradation. To address these issues, we designed a multiphase Mn‐V oxide/carbon composite (MnVO/C‐2) derived from a bimetallic Mn‐V‐based metal–organic framework (MOF). The incorporation of vanadium results in a well‐defined heterostructure consisting of MnO, MnV 2 O 4 , and V 2 O 3 phases. This multi‐component architecture not only provides abundant active sites for redox reactions but also effectively mitigates volume variation via strain compensation at phase boundaries during cycling, thus significantly enhancing structural integrity. More importantly, interfacial orbital hybridization between different oxide phases facilitates charge transfer and substantially lowers the energy barrier for ion and electron transport. As a result, the MnVO/C‐2 cathode exhibits exceptional cycling stability, delivering a capacity of 268.9 mAh g −1 after 10,000 cycles at a high current density of 4 A g −1 . A combination of ex situ XRD/SEM/XPS and in situ Raman analyses reveals that the charge storage mechanism involves the reversible insertion of Zn 2+ . When assembled into a flexible pouch cell, the electrode exhibits excellent cycling stability at 1.5 A g −1 , retaining a discharge capacity retention of 90% after 100 cycles, underscoring its promising practical potential. This work demonstrates that the rational material design strategy of multiphase engineering would open a new avenue for the development of high‐energy and durable cathode materials for advanced AZIBs.