Composition engineering of ZIF-derived cobalt phosphide/cobalt monoxide heterostructures for high-performance...

The fabrication of interpenetrated heterostructures from desirable energy materials for the development of efficient supercapacitors is promising yet challenging. Herein, a leaf-shaped cobalt phosphide/cobalt oxide heterostructure, (CoP_x)_1-y/CoO_y (0.44 > y > 0.06), was synthesized from 2D-zeolitic-imidazolate-framework (ZIF-Co-L) molecular precursor via phosphidation of the Co₃O₄ intermediate. The efficient construction of heterostructure through the variation of surface/bulk composition significantly alters the interfacial properties and electronic structure, yielding enhanced supercapacitor performance. Further, gas-phase phosphidation entails a core-shell formation mechanism via gas diffusion, regulated by the Kirkendall effect. The optimized heterostructure (y = 0.10) exhibits remarkable interfacial properties derived from the CoO/Co⁰/CoP interface, thus facilitating a high specific capacitance (467 F g^-1 at 5 A g^-1) and excellent cycling stability (~91% after 10000 cycles) at 30 A g^-1. A further increase in the cyclability (~107%) was achieved by employing a graphene hybrid. Further, an asymmetric supercapacitor device was fabricated, that delivers reasonably high energy density of 12.7 Wh kg^-1 at a power density of 370 W kg^-1 and cycling stability of ~93% after 10000 cycles. This study reports on the modulation of interfacial properties of CoP_x/CoO heterostructure to enhance energy storage performance via bulk/surface compositional variation, thereby providing a strategy to develop heterostructure electrodes for high-performance supercapacitor.