▎ 摘　　要

We demonstrate hierarchically structured, phosphorous (P)-incorporated reduced graphene oxide (HPG) films prepared by a vacuum-filtrated and ice-frozen assembly, freeze-drying and thermal treatment for all solid-state flexible pseudocapacitors. The porous morphology is originated from the interconnected networks of graphene layers and the surface roughness is reduced by the P doping, which results in improving the electrochemical performances. The P = 0 sites of C-P = 0 bonding acting as electro-active sites of HPG film are identified by XPS spectra and their charge storage behavior is monitored by in-situ and ex-situ spectrochemical analyses. The HPG film achieves the specific capacitance of 149 F g(-1), the capacitance retention of 90.8% from 1 to 30 A g-1, and the cyclic stability of 94.2% over 1000 charging/discharging cycles. Moreover, the pseudocapacitive performances of the HPG films are preserved at the bending state of 120 degrees angle. These excellent electrochemical behaviors are attributed to the unique hierarchical structure and the formation of electro-active of P = 0 sites by heteroatom doping.