Metal-organic framework-mediated construction of confined ultrafine nickel phosphide immobilized in reduced graphene oxide with excellent cycle stability for asymmetric supercapacitors.

Transition metal phosphides (TMPs) with unique metalloid features have been promised great application potential in developing high-efficiency electrode materials for electrochemical energy storage. Nevertheless, sluggish ion transportation and poor cycling stability are the critical hurdles limiting their application prospects. Herein, we presented the metal-organic framework-mediated construction of ultrafine NiP immobilized in reduced graphene oxide (rGO). Nano-porous two-dimensional (2D) Ni-metal-organic framework (Ni-MOF) was grown on holey graphene oxide (Ni(BDC)-HGO), followed by MOF-mediated tandem pyrolysis (carbonization and phosphidation; Ni(BDC)-HGO-X-P, X denoted carbonization temperature and P represented phosphidation). Structural analysis revealed that the open-framework structure in Ni(BDC)-HGO-X-Ps had endowed them with excellent ion conductivity. The NiP wrapped by carbon shells and the PO bonds linking between NiP and rGO ensured the better structural stability of Ni(BDC)-HGO-X-Ps. The resulting Ni(BDC)-HGO-400-P delivered a capacitance of 2333.3 F g at 1 A g in a 6 M KOH aqueous electrolyte. More importantly, Ni(BDC)-HGO-400-P//activated carbon, the assembled asymmetric supercapacitor with an energy density of 64.5 Wh kg and a power density of 31.7 kW kg, almost maintained its initial capacitance after 10,000 cycles. Furthermore, in situ electrochemical-Raman measurements were exploited to demonstrate the electrochemical changes of Ni(BDC)-HGO-400-P throughout the charging and discharging processes. This study has further shed light on the design rationality of TMPs for optimizing supercapacitor performance.