▎ 摘　　要

Boosting the utilization rate of graphene sheets in compact graphene film is essential to realize high-density energy storage for graphene film based supercapacitors. Here, a p-phenylenediamine (PPDA) molecules supporting holey graphene sheets framework is built in graphene film (PPDA-HGF). In PPDA-HGF, the nanopores across the basal plane of graphene sheets promote ion access to graphene sheet surface, the PPDA molecular "supports" between graphene layers create uniformly expanding interlayer spacing (similar to 1.2 nm), which is beneficial for ion transport between layers. So, the open framework contributes to synergistic effect for ion access and transport in PPDA-HGF. With abundant ion-accessible transport channels, good wettability (42 degrees) and high conductivity (3927 S m(-1)), PPDA-HGF exhibits significant improvement of electrochemical performance comparing to counterparts and delivers a gravimetric capacitance of 300 F g(-1) and a volumetric capacitance of 516 F cm(-3), excellent rate capability (78.3% capacitance retention from 0.5 to 100 A g(-1)), and superior cycling stability. Furthermore, the flexible solid-state supercapacitor based on PPDA-HGFs delivers comparable volumetric energy density of 2.7 Wh L-1 to 4 V/500 Ah Li thin-film batteries and practicably mechanical flexibility. This work opens up a structural cooperation strategy to achieve synergistic effect for ion access and transport in compact graphene film.