Developing multicomponent transition-metal phosphides has become an efficient way to improve the capacitive performance of single-component transition-metal phosphides. However, reports on quaternary phosphides for supercapacitor applications are still scarce. Here, we report high capacity and energy density of Zn−Ni−Co−P quaternary phosphide nanowire arrays on nickel foam (ZNCP-NF) composed of highly conductive metal-rich phosphides as an advanced binder-free electrode in aqueous asymmetric supercapacitors. In a three-electrode system using the new electrode, a high specific capacity of 1111 C g −1 was obtained at a current density of 10 A g −1 . Analysis of this aqueous asymmetric supercapacitor with ZNCP-NF as the positive electrode and commercial activated carbon as the negative electrode reveals a high energy density (37.59 Wh kg −1 at a power density of 856.52 W kg −1 ) and an outstanding cycling performance (capacity retention of 92.68% after 10 000 cycles at 2 A g −1 ). Our results open a path for a new design of advanced electrode material for supercapacitors.

Although Ni–P based metal phosphides have high theoretical specific capacity, the poor rate capability and cycling stability hinder their practical application.