Scanty graphene-driven phase control and heteroatom functionalization of ZIF-67-derived CoP-draped N-doped carbon/graphene as a hybrid electrode for high-performance asymmetric supercapacitor.

Zeolitic imidazolate framework (ZIF)-derived materials have been explored as promising electrode for energy storage, owing to their tunable composition, high porous structure, and heteroatom-based active sites. Herein, we report cobalt phosphide-draped N-doped carbon/graphene hybrid (CoP-NPC/GS) synthesized from ZIF-67 precursor via a single-step in-situ carbonization and phosphidation. The CoP-NPC/GS hybrid performed as a promising positive electrode with superior electrochemical performance - high capacitance (165 F g at 7 A g compared to 97 F g for CoP-NPC), enhanced rate capability, and promoted cycling stability (88% after 10,000 cycles). Excellent performance of the CoP-NPC/GS was derived from scanty graphene (2 wt%)-driven compositional variation, which promotes the redox-active CoP phase and higher nitrogen content offering enhanced electronic conductivity. Besides, CoP-NPC/GS performed well as a negative electrode, derived from double-layer capacitance of porous carbon, realizing a capacitance of ~71 F g at 1 A g but inferior to CoP-NPC, which was regulated by pyridinic nitrogen-induced pseudocapacitance. A fabricated CoP-NPC/GS||CoP-NPC asymmetric device displayed an energy density of 10 Wh Kg at 700 W kg, with excellent cyclability (100%) till 11,000 cycles. This study clarifies the role of scanty graphene on the phase control and heteroatom functionalization of phosphide-based electrode, beneficial for enhanced supercapacitive performance.