The design and development of nanomaterials has become central to the advancement of pseudocapacitive performance. Many one-dimensional nanostructures (1D NSs), two-dimensional nanostructures (2D NSs), and three-dimensional hierarchical structures (3D HSs) composed of these building blocks have been synthesized as pseudocapacitive materials via different methods. However, due to the unclear assembly mechanism of these NSs, reports of HSs simultaneously assembled from two or more types of NSs are rare. In this article, NiCo2O4 multiple hierarchical structures (MHSs) composed of 1D nanowires and 2D nanosheets are simply grown on Ni foam using an ordered two-step hydrothermal synthesis followed by annealing processing. The low-dimensional nanowire is found to hold priority in the growth order, rather than the high-dimensional nanosheet, thus effectively promoting the integration of these different NSs in the assembly of the NiCo2O4 MHSs. With vast electroactive surface area and favorable mesoporous architecture, the NiCo2O4 MHSs exhibit a high specific capacitance of up to 2623.3 F g(-1), scaled to the active mass of the NiCo2O4 sample at a current density of 1 A g(-1). A nearly constant rate performance of 68% is achieved at a current density ranging from 1 to 40 A g(-1), and the sample retains approximately 94% of its maximum capacitance even after 3000 continuous charge-discharge cycles at a consistently high current density of 10 A g(-1).

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