Pseudocapacitance holds great promise for improving energy densities of electrochemical supercapacitors, but state-of-the-art pseudocapacitive materials show capacitances far below their theoretical values and deliver much lower levels of electrical power than carbon-based materials due to poor cation accessibility and/or long-range electron transferability. Here we show that in situ corundum-to-rutile phase transformation in electron-correlated vanadium sesquioxide can yield nonstoichiometric rutile vanadium dioxide layers that are composed of highly sodium ion accessible oxygen-deficiency quasi-hexagonal tunnels sandwiched between conductive rutile slabs. This unique structure serves to boost redox and intercalation kinetics for extraordinary pseudocapacitive energy storage in hierarchical isomeric vanadium oxides, leading to a high specific capacitance of ~1856 F g–1 (almost sixfold that of the pristine vanadium sesquioxide and dioxide) and a bipolar charge/discharge capability at ultrafast rates in aqueous electrolyte. Symmetric wide voltage window pseudocapacitors of vanadium oxides deliver a power density of ~280 W cm–3 together with an exceptionally high volumetric energy density of ~110 mWh cm–3 as well as long-term cycling stability.

Nanostructured transition‐metal oxides can store high‐density energy in fast surface redox reactions, but their poor conductivity causes remarkable reductions in the energy storage of most pseudocapacitors at high power delivery (fast charge/discharge rates). Here it is shown that electron‐correlated oxide hybrid electrodes made of nanocrystalline vanadium sesquioxide and manganese dioxide with 3D and bicontinuous nanoporous architecture (NP V2O3/MnO2) have enhanced conductivity because of metallization of electron‐correlated V2O3 skeleton via insulator‐to‐metal transition. The conductive V2O3 skeleton at ambient temperature enables fast electron and ion transports in the entire electrode and facilitates charge transfer at abundant V2O3/MnO2 interface. These merits significantly improve the pseudocapacitive behavior and rate capability of the constituent MnO2. Symmetric pseudocapacitors assembled with binder‐free NP V2O3/MnO2 electrodes deliver ultrahigh electrical powers (up to ≈422 W cm23) while maintaining the high volumetric energy of thin‐film lithium battery with excellent stability.

No abstract