A Covalent Black Phosphorus/Metal–Organic Framework Hetero‐nanostructure for High‐Performance Flexible Supercapacitors

Abstract We develop hetero‐nanostructured black phosphorus/metal‐organic framework hybrids formed by P‐O‐Co covalent bonding based on a designed droplet microfluidic strategy consisting of confined and ultrafast microdroplet reactions. The resulting hybrid exhibits large capacitance (1347 F g −1 ) in KOH electrolytes due to its large specific‐surface‐area (632.47 m 2 g −1 ), well‐developed micro‐porosity (0.38 cm 3 g −1 ), and engineered electroactivity. Furthermore, the proposed 3D printing method allows to construct all‐integrated solid‐state supercapacitor, which maintains interconnected porous network, good interfacial adhesion, and robust flexibility for short‐path diffusion and excessive accommodation of ions. Consequently, the fabricated flexible supercapacitor delivers ultrahigh volumetric energy density of 109.8 mWh cm −3 , large capacitance of 506 F cm −3 , and good long‐term stability of 12000 cycles.