Graphene scrolls have been widely investigated for applications in electronics, sensors, energy storage, etc. However, graphene scrolls with tens of micrometers in length and with other materials in their cavities have not been obtained. Here nanowire templated semihollow bicontinuous graphene scroll architecture is designed and constructed through "oriented assembly" and "self-scroll" strategy. These obtained nanowire templated graphene scrolls can achieve over 30 μm in length with interior cavities between the nanowire and scroll. It is demonstrated through experiments and molecular dynamic simulations that the semihollow bicontinuous structure construction processes depend on the systemic energy, the curvature of nanowires, and the reaction time. Lithium batteries based on V3O7 nanowire templated graphene scrolls (VGSs) exhibit an optimal performance with specific capacity of 321 mAh/g at 100 mA/g and 87.3% capacity retention after 400 cycles at 2000 mA/g. The VGS also shows a high conductivity of 1056 S/m and high capacity of 162 mAh/g at a large density of 3000 mA/g with only 5 wt % graphene added which are 27 and 4.5 times as high as those of V3O7 nanowires, respectively. A supercapacitor made of MnO2 nanowire templated graphene scrolls (MGSs) also shows a high capacity of 317 F/g at 1A/g, which is over 1.5 times than that of MnO2 nanowires without graphene scrolls. These excellent energy storage capacities and cycling performance are attributed to the unique structure of the nanowire templated graphene scroll, which provides continuous electron and ion transfer channels and space for free volume expansion of nanowires during cycling. This strategy and understanding can be used to synthesize other nanowire templated graphene scroll architectures, which can be extended to other fabrication processes and fields.

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On-chip micro-supercapacitors (MSCs) have attracted great attention recently. However, the performance of MSCs is usually unsatisfactory because of the unreasonable pore structure. The construction of a three-dimensional (3D) interconnected porous carbon-based MSC by controllable activation is proposed. The porous monolithic carbon microelectrode activated by ZnO nanowires provides electron/ion bicontinuous conduction path. The fabricated MSC with this microelectrode rendered a high areal specific capacitance of 10.01 mF cm–2, 6 times higher than that of pure pyrolyzed carbon-based MSC, 1.6–5 times higher than that of the MSC with porous carbon activated by ZnO nanoparticles because of its cross-linking macropore–mesopore–micropore structure and considerable areal atomic ratio. The optimization mechanism of the hierarchical channel pore for the electrochemical performance of MSCs is investigated in detail. Four kinds of electrolytes, including H2SO4, redox additive KI/H2SO4, LiCl, and LiTFSi, are employed for constructing MSCs. The voltage window of water in a salt electrolyte assembled LiTFSi-MSC is expanded to 2.5 V. The energy density of LiTFSi-MSC is 6 times higher than that of H2SO4-MSC, which can drive light-emitting diodes without serial or parallel connection. This high-performance 3D interconnected porous carbon-based MSC shows a great potential in applications for large-scale integration of micro-/nanodevices.