Flexible Black-Phosphorus Nanoflake/Carbon Nanotube Composite Paper for High-Performance All-Solid-State Supercapacitors

We proposed a simple route for fabrication of the flexible BP nanoflake/carbon nanotube (CNT) composite paper as flexible electrodes in all-solid-state supercapacitors. The highly conductive CNTs not only play a role as active materials but also increase conductivity of the hybrid electrode, enhance electrolyte shuttling and prevent the restacking between BP nanoflakes. The fabricated flexible all-solid-state supercapacitor (ASSP) device at the mass proportion of BP/CNTs 1:4 was found to deliver the highest volumetric capacitance of up to 41.1 F/cm³ at 0.005 V/s, superior to the ASSP based on the bare graphene or BP. The BP/CNTs (1:4) device delivers a rapid charging/discharging up to 500 V/s, which exhibits the characteristic of a high power density of 821.62 W/cm³, while having outstanding mechanical flexibility and high cycling stability over 10 000 cycles (91.5% capacitance retained). Moreover the BP/CNTs (1:4) ASSP device still retains large volumetric capacitance (35.7 F/cm³ at the scan rate of 0.005 V/s) even after 11 months. In addition, the ASSP of BP/CNTs (1:4) exhibits high energy density of 5.71 mWh/cm³ and high power density of 821.62 W/cm³. As indicated in our work, the strategy of assembling stacked-layer composites films will open up novel possibility for realizing BP and CNTs in new-concept thin-film energy storage devices.