Short‐Range‐Ordered VO6 Oxides with Oxygen Vacancy‐Free Frameworks Boost Zinc‐Ion Battery Performance

Abstract Vanadium‐based cathodes have attracted extensive attention in aqueous zinc‐ion batteries (AZIBs) because of their high theoretical capacity. However, the development of high‐performance vanadium‐based cathodes and the establishment of effective design principles remain major challenges, hindering the progress of AZIBs technology. In this study, the critical role of structural building blocks ([VO 4 ] tetrahedra, [VO 5 ] square pyramids, and [VO 6 ] octahedra) is unveiled in vanadium‐based oxides, demonstrating their distinct contributions to both capacity and stability. Among these, [VO 6 ] octahedra stand out for their superior capacity and stability, making vanadium oxides with [VO 6 ] octahedra promising candidates for AZIBs cathodes. Furthermore, it is shown that the presence of oxygen vacancies undermines the stability of [VO 6 ] building blocks by increasing the exposure of the vanadium sites. Based on these findings, amorphous vanadium oxide (ZVO‐O v ‐free), composed of oxygen vacancy‐free [VO 6 ] octahedra arranged in short‐range‐ordered chains, is synthesized, maximizing the utilization of highly active vanadium sites. The ZVO‐O v ‐free cathode achieves a specific capacity of up to 483 mAh g −1 at 0.3 A g −1 , with a capacity retention of 94% after 150 cycles. These findings provide valuable insights for the rational design of vanadium‐based oxides at the atomic and framework levels, paving the way for the practical development of AZIBs.