Tailoring Electronic Structure and Size of Ultrastable Metalated Metal–Organic Frameworks with Enhanced Electroconductivity for High‐Performance Supercapacitors

Abstract

Utilization of metal-organic frameworks (MOFs) as electrodes for energy storage/conversion is challenging because of the low chemical stability and poor electrical conductivity of MOFs in electrolytes.Ananoscale MOF, Co 0.24 Ni 0.76 -bpa-200, possessing ultrahigh stability with uncommon semiconductor behavior (s = 4.2 10 À3 Sm À1 )w as fabricated. The MOF comprises ar obust hydrophobic paddlewheel and an optimized Co/Ni ratio,with consequent control over MOF size and the degree of conjugation of the coligand. AD FT study revealed that appropriate Ni 2+ doping reduces the activation energy of the system, thus providing ah igher carrier concentration, and the strongly delocalized N-donor ligand notably increases the metal-ligand orbital overlap to achieve efficient charge migration, leading to continuous through-bond (-CoNi-N-CoNi-) 1 conduction paths.These structural features endow the MOF with agood cycling stability of 86.5 %(10 000 cycles) and ahigh specific capacitance of 1927.14 Fg À1 among pristine MOF-based electrodes.

Bimetallic electronic effects of Mn-doped Ni-MOF shuttle-like nanosheets remarkably enhance the supercapacitive performance

“…6e and S13, † the calculated E g value of Ni 0.7 Mn 0.3 -MOFs (1.31 eV) is much narrower than that of the Ni-MOF (1.60 eV), which indicates that the introduction of Mn ions greatly reduces the bandgap of the Ni-MOF and can easily activate more electrons from the VBM to the CBM to increase the carrier concentration. 65…”

Progress and Perspectives of Conducting Metal–Organic Frameworks for Electrochemical Energy Storage and Conversion

“…Compared with lithium and sodium batteries, it effectively reduces the safety risk of leakage and combustion of organic electrolytes. Zinc-based batteries usually use zinc as the negative electrode and use hydrolyses, which makes the rechargeable zinc-based batteries have the advantages of low cost, high safety, and high theoretical capacity [110]. Compared with the lithium battery and sodium battery, the zinc water-based battery has remarkable rate performance and upper power density because of the excellent ionic conductivity of the electrolyte in water.…”

Controlled synthesis of a cobalt-organic framework: hierarchical micro/nanospheres for high-performance supercapacitors

“…11,12 However, the low electrical conductivity in most MOFs significantly limits their application as electrode materials of supercapacitors. 13 To address these issues, one effective approach is to tailor the geometrical scale and morphologies of traditional bulk MOFs, [14][15][16] which will provide further opportunities to integrate novel properties and functions into these materials without perturbing their characteristic features.…”