Transition metal phosphides (TMPs) have recently emerged as an important type of electrode material for use in supercapacitors thanks to their intrinsically outstanding specific capacity and high electrical conductivity. Herein, we report the synthesis of bimetallic CoxNi1–xP ultrafine nanocrystals supported on carbon nanofibers (CoxNi1–xP/CNF) and explore their use as positive electrode materials of asymmetric supercapacitors. We find that the Co:Ni ratio has a significant impact on the specific capacitance/capacity of CoxNi1–xP/CNF, and CoxNi1–xP/CNF with an optimal Co:Ni ratio exhibits an extraordinary specific capacitance/capacity of 3514 F g–1/1405.6 C g–1 at a charge/discharge current density of 5 A g–1, which is the highest value for TMP-based electrode materials reported by far. Our density functional theory calculations demonstrate that the significant capacitance/capacity enhancement in CoxNi1–xP/CNF, compared to the monometallic NiP/CNF and CoP/CNF, originates from the enriched density of states near the Fermi level. We further fabricate a flexible solid-state asymmetric supercapacitor using CoxNi1–xP/CNF as positive electrode material, activated carbon as negative electrode material, and a polymer gel as the electrolyte. The supercapacitor shows a specific capacitance/capacity of 118.7 F g–1/166.2 C g–1 at 20 mV s–1, delivers an energy density of 32.2 Wh kg–1 at 3.5 kW kg–1, and demonstrates good capacity retention after 10000 charge/discharge cycles, holding substantial promise for applications in flexible electronic devices.

High-Performance Flexible Solid-State Asymmetric Supercapacitors Based on Bimetallic Transition Metal Phosphide Nanocrystals