Anode materials with relatively low capacitance remain a great challenge for asymmetric supercapacitors (ASCs) to pursue high energy density. Hematite (α-Fe2O3) has attracted intensive attention as anode material for ASCs, because of its suitable reversible redox reactions in a negative potential window (from 0 V to -1 V vs Ag/AgCl), high theoretical capacitance, rich abundance, and nontoxic features. Nevertheless, the Fe2O3 electrode cannot deliver large volumetric capacitance at a high rate, because of its poor electrical conductivity (∼10(-14) S/cm), resulting in low power density and low energy density. In this work, a hierarchical heterostructure comprising Fe3O4@Fe2O3 core-shell nanorod arrays (NRAs) is presented and investigated as the negative electrode for ASCs. Consequently, the Fe3O4@Fe2O3 electrode exhibits superior supercapacitive performance, compared to the bare Fe2O3 and Fe3O4 NRAs electrodes, demonstrating large volumetric capacitance (up to 1206 F/cm(3) with a mass loading of 1.25 mg/cm(2)), as well as good rate capability and cycling stability. The hybrid electrode design is also adopted to prepare Fe3O4@MnO2 core-shell NRAs as the positive electrode for ASCs. Significantly, the as-assembled 2 V ASC device delivered a high energy density of 0.83 mWh/cm(3) at a power density of 15.6 mW/cm(3). This work constitutes the first demonstration of Fe3O4 as the conductive supports for Fe2O3 to address the concerns about its poor electronic and ionic transport.

Pseudocapacitors hold great promise as charge storage systems that combine battery‐level energy density and capacitor‐level power density. The utilization of pseudocapacitive material, however, is usually restricted to the surface due to poor electrode kinetics, leading to less accessible charge storage sites and limited capacitance. Here, tin oxide is successfully endowed with outstanding pseudocapacitance and fast electrode kinetics in a negative potential window by engineering oxygen‐deficient homo‐interfaces. The as‐prepared SnO2−x@SnO2−x electrode yields a specific capacitance of 376.6 F g−1 at the current density of 2.5 A g−1 and retains 327 F g−1 at a high current density of 80 A g−1. The theoretical calculation reveals that the oxygen defects are more favorable at homo‐interfaces than at the surface due to the lower defect formation energy. Meanwhile, as compared with the surface, the homo‐interface possesses more stable Li+ storage sites that are readily accessed by Li+ due to the occurrence of oxygen vacancies, enabling outstanding pseudocapacitance as well as high rate capability. This oxygen‐deficient homo‐interface design opens up new opportunities to develop high‐energy and power pseudocapacitors.

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