Self-assembled from monometallic-organic framework to bimetallic-organic framework materials with promoted supercapacitor performance

Abstract

Designing new metal–organic frameworks (MOFs) materials with definite structure and introducing heterometallic atom is an effective strategy to develop new electrocatalytic and energy storage materials. Herein, one new 3D close-packed type manganese metal–organic frameworks, namely [Mn2(BPTC)(DMSO)2.5] (Mn-MOF) have been constructed from a rigid biphenylic acid with a rigid biphenyl-3,3′,5,5′-tetracarboxylic acid (H4BPTC) ligand under a solvothermal condition. Besides, adopting the metal doping strategy, a series of bimetallic MnM’-MOF (M’=Co, Ni and Cu) crystalline materials has been successfully grown on nickel foam (NF) and were used for supercapacitor electrode material. By contrast, the MnNi-MOF/NF shows a specific capacitance of 3391.7 mF cm−2 at 1 mA‧cm−2 in 1.0 M KOH, which is 1.6 times that of Mn-MOF/NF electrode. It also displays excellent cycle stability to keep 92.6 % of the initial capacity after GCD 20000 cycles. Finally, a hybrid supercapacitor (HSC) made from on the MnNi-MOF electrode and activated carbon (AC) could deliver an energy density of 0.224 mWh cm−2 at a power density of 1.04 mW cm−2, and a high cycle-to-cycle stability with 90.1 % of the primary capacitance over 20,000 cycles. This work not only confirms the potential supercapacitor properties of as-synthesized new Mn-MOF, but also effectively improves the specific capacity and device stability of pure Mn-MOF by introducing different transition metal ions.