Understanding the Super-Theoretical Capacity Behavior of VO₂ in Aqueous Zn Batteries

VO₂ material, as a promising intercalation host, is widely investigated not only in aqueous lithium-ion batteries, but also in aqueous zinc-ion batteries (AZIBs) owing to its stable tunnel-like framework and multivalence of vanadium. Different from lithium-ion storage, VO₂ can provide higher capacity when storing zinc ions, even exceeding its theoretical capacity (323 mAh g^-1), but the specific reason for this unconventional performance in AZIBs is still unclear. The present study proposes a catalytic oxygen evolution reaction (OER) coupled with an interface oxidation mechanism of VO₂ during the initial charging to a high voltage. This coupling induces a phase transformation of VO₂ into a high oxidation state of V₅O₁₂∙6H₂O, enabling a nearly two-electron reaction and providing additional zinc storage sites to achieve super-theoretical capacity. Furthermore, it is demonstrated that these vanadium oxide cathodes (V₂O₃, VO₂, and V₂O₅) will all undergo phase change after the first charge or short cycle. Notably, water molecules participate in the final formation of layered vanadium-based hydrate, highlighting their crucial role as "pillars" for stabilizing the structure. This work significantly enhances the understanding of vanadium-based oxide cathodes.