Lithium-ion storage capacitors were assembled using graphene/tantalum carbide/tantalum wire electrodes and carbon hollow spheres as electrolyte. The graphene/tantalum carbide layers were prepared by electron-assisted hot filament chemical vapor deposition; the carbon hollow spheres were synthesized by hydrothermal reaction and pyrolysis treatment. The specific capacitance of the capacitor was 593Fg−1 at a current density of 10Ag−1. The capacitor showed excellent cycling stability, retaining 91.2% of its initial capacitance after 8000 cycles. Moreover, the capacitor provided a high specific energy density of 132Whkg−1 at a high power density of 3.17kWkg−1. The high energy density is attributed to the widened operation window ranging from 0 to 3.0V. The graphene layer of the electrode and carbon hollow spheres in electrolyte synergistic affect influence on the electrochemical performance of the capacitor are discussed. In addition, the use of a low-cost lithium salt, lithium chloride, is also featured in this paper.