Metal–organic frameworks (MOFs) have obtained increasing attention as a kind of novel electrode material for energy storage devices. Yet low capacity in most MOFs largely thwarts their application. In this study, an effective strategy was developed to improve the conductivity of MOFs by partially substituting Ni²⁺ in the Ni-MOF with Co²⁺ or Zn²⁺. The mixed-metal organic frameworks (M-MOFs) showed excellent electrochemical performance, which is attributed not only to the favorable paths for charge transport due to the presence of free pores, but also to the raised electrochemical double-layer capacitance (EDLC) at the enlarged specific surface area of the material. Meanwhile, the cycling stability of the assembled hybrid supercapacitors (M-MOFs//CNTs–COOH) is enhanced due to the alleviation of phase transformation during electrochemical cycling tests. More interestingly, the Co/Ni-MOF//CNTs–COOH also exhibited an excellent energy density (49.5 W h kg⁻¹) and power density (1450 W kg⁻¹) simultaneously. These values demonstrated the better performance of all the MOF materials in supercapacitors at present. In addition to broadening the application of MOFs, our study may open a new avenue for bridging the performance gap between batteries and supercapacitors.

The synergistic effect between “Ni-MOF and Fe(CN) ₆ ⁴⁻ /Fe(CN) ₆ ³⁻ ” can deliver high energy density and power density simultaneously.