Dual-vacancy-engineered V2O3 with VOC covalent coupling enables ultrastable aqueous zinc-ion batteries at 10 A g-1.

Achieving ultrafast kinetics and long-term durability in aqueous zinc-ion batteries (AZIBs) remains challenging because the interplay between interfacial electronic structure and structural stability of vanadium oxide cathodes is poorly understood. Here, we design a locally graphitized carbon-encapsulated V2O3 cathode (V2O3@G-aC) featuring V/O dual vacancies and d-p-π conjugated vanadium‑oxygen‑carbon (VOC) interfaces, fabricated via flash Joule carbothermal reduction followed by terephthalic acid (TPA) mediated interfacial reconstruction and carbonization. Lewis acid-base interactions at the linker-metal node interface, coupled with pellet-confined carbonization, simultaneously introduce dual vacancies and covalent VOC bonding within a mesoporous graphitic shell. Density functional theory (DFT) calculations reveal that these engineered interfaces enable V → O → C charge delocalization by narrowing the V 3d-O 2p-C 2p band gaps, thereby accelerating Zn2+/H+ co-intercalation kinetics and suppressing vanadium dissolution. V2O3@G-aC delivers 346 mAh g-1 at 10 A g-1, which ranks among the highest for vanadium-based AZIBs cathodes, and retains 106 mAh g-1 after 20,000 cycles at 10 A g-1 with suppressed by-product accumulation. A flexible pouch cell retains 202 mAh g-1 after 200 cycles at 1 A g-1 and remains operational during a separate 180° bending demonstration. This work establishes d-p-π conjugated metal‑oxygen‑carbon interfaces as a design principle for stabilizing multivalent-ion cathodes under extreme cycling conditions.