Metal-Organic Framework Materials for Electrochemical Supercapacitors

Abstract

Exploring new materials with high stability and capacity is full of challenges in sustainable energy conversion and storage systems. Metal-organic frameworks (MOFs), as a new type of porous material, show the advantages of large specific surface area, high porosity, low density, and adjustable pore size, exhibiting a broad application prospect in the field of electrocatalytic reactions, batteries, particularly in the field of supercapacitors. This comprehensive review outlines the recent progress in synthetic methods and electrochemical performances of MOF materials, as well as their applications in supercapacitors. Additionally, the superiorities of MOFs-related materials are highlighted, while major challenges or opportunities for future research on them for electrochemical supercapacitors have been discussed and displayed, along with extensive experimental experiences.

Keywords: Electrochemistry; Electrode materials; Metal–organic frameworks (MOFs); Supercapacitors.

Fig. 1

Schematic diagram of a an electric double-layer capacitor, b a pseudocapacitor, c a hybrid-capacitor. Reprinted with permission from Ref. [11]. Copyright 2015 Royal Society of Chemistry

Fig. 2

a Publications of the ratio of MOFs used in three types of supercapacitors. Data from Web of Science using the keywords “metal–organic framework, double-layer capacitors, faraday pseudocapacitors, and hybrid capacitors.” b Publications of MOFs application in supercapacitors. Data from Web of Science using the keywords “metal–organic framework, supercapacitors”

Fig. 3

Timeline of the traditional one-pot synthesis. Reprinted with permission from Ref. [, , –72]. Copyright @1999 Macmillan Magazines Ltd. @2006 Royal Society of Chemistry, @ 2008 Elsevier, @ 2020 American Chemical Society, @ 2015 Nature Publishing Group

Fig. 4

Diagram of emerging preparation methods. Reprinted with permission from Ref. [–76]. Copyright @2013 Nature Publishing Group, @ 2017 American Chemical Society, @ 2016 American Chemical Society, @ 2018 Springer Science Business Media

Fig. 5

a The synthesis diagram of Co-L MOF. Reprinted with permission from Ref. [82]. Copyright 2019 Elsevier B.V. b Influence of temperature on synthesis of two Ni-MOFs. Reprinted with permission from Ref. [86]. Copyright 2019 Elsevier Inc. c Schematic diagram of preparation process of HP-UiO-66. Reprinted with permission from Ref. [92].Copyright 2017 American Chemical Society d Schematic diagram of liquid–liquid interface reaction of Ni-pPDA MOF at room temperature. Reprinted with permission from Ref. [94]. Copyright 2018 Elsevier B.V

Fig. 6

a Schematic diagram of the synthesis process. Reprinted with permission from Ref. [99]. Copyright 2020 Elsevier B.V. b Preparation technology of NiCo-MOF. Reprinted with permission from Ref. [100].Copyright 2019 American Chemical Society. c Schematic diagram of Ni/Co-MOF preparation process. Reprinted with permission from Ref. [102]. Copyright 2018 Royal Society of Chemistry. d Schematic diagram of the preparation of bimetallic Co/Mn-MOF and activated carbon. Reprinted with permission from Ref. [104]. Copyright 2019 Elsevier Ltd

Fig. 7

a Schematic diagram of the synthesis of NiCo-MOF/AB composites. Reprinted with permission from Ref. [112]. Copyright 2019 Elsevier B.V. b Synthesis diagram of CNF@Ni-CAT. Reprinted with permission from Ref. [113]. Copyright 2019 Royal Society of Chemistry. c Preparation process diagram of Ni-Co-MOF/graphene oxide composites. Reprinted with permission from Ref. [114]. Copyright 2019 Elsevier Ltd

Fig. 8

a SEM of PANI/Cu-MOF nanocomposite. b Specific capacitance of Cu-MOF and PANI/Cu-MOF. Reprinted with permission from Ref. [118]. Copyright 2019 Springer Science Business Media. c Schematic diagram of electron conduction in MOF and MOF interweaves. Reprinted with permission from Ref. [119]. Copyright 2015 American Chemical Society. d Schematic diagram of Ni-MOF/PANI/NF synthesis. Reprinted with permission from Ref. [121]. Copyright 2019 Royal Society of Chemistry

Fig. 9

a Possible structural changes of Ni-MOF before and after Zn doping. Reprinted with permission from Ref. [123]. Copyright 2014 Royal Society of Chemistry. b Specific capacitance at different current densities. Reprinted with permission from Ref. [124]. Copyright 2020 Elsevier Ltd. c BET of Ni-MOF. d A Zn-doped Ni-MOF with honeycomb layered spherical structure by the microwave-assisted synthesis method. Reprinted with permission from Ref. [126]. Copyright 2020 Wiley–VCH GmbH

Fig. 10

a Schematic synthesis diagram of IRMOF-1 (top) and carbon-coated ZnO QDs without agglomeration produced by IRMOF-1 after controlled pyrolysis (bottom). Reprinted with permission from Ref. [134]. Copyright 2013 American Chemical Society. b HHCF synthesis process diagram. c SEM images of HHCF. Reprinted with permission from Ref. [136]. Copyright 2019 Elsevier B.V. d Specific capacitance with respect to scan rate. e Specific capacitance as a function of current density. Reprinted with permission from Ref. [138]. Copyright 2018 Elsevier Ltd

Fig. 11

a Synthesis scheme of Co₃O₄ nanostructure. Reprinted with permission from Ref. [143]. Copyright 2012 Royal Society of Chemistry. b Nitrogen-doped Co₃O₄ nanosheets contain oxygen vacancy prepared on CC substrate. Reprinted with permission from Ref. [145]. Copyright 2019 Elsevier Ltd. c Diagram of synthesis of NiO nanospheres. Reprinted with permission from Ref. [147]. Copyright 2017 Elsevier B.V. d Schematic diagram of synthesis for NiO/ZnO hollow spheres with double shells. Reprinted with permission from Ref. [148]. Copyright 2016 Royal Society of Chemistry

Fig. 12

a Diagram of NiS nanoframe formation process. b The specific capacitance was calculated from the discharge curve. Reprinted with permission from Ref. [150]. Copyright 2015 WILEY–VCH Verlag GmbH & Co. KGaA c Scheme of the synthesis of NC/Ni-Ni₃S₄/CNTs composite. d The specific capacitances at different current densities. Reprinted with permission from Ref. [151]. Copyright 2020 American Chemical Society. e Schematic diagram of the formation of amorphous NixSy@CoS double-shelled nanocages. f Corresponding specific capacitance calculated from the discharge curves. Reprinted with permission from Ref. [152]. Copyright 2017 Elsevier Ltd

Fig. 13

a Schematic illustration of the formation process for MOF-derived Co(OH)₂. Reprinted with permission from Ref. [158]. Copyright 2015 Royal Society of Chemistry. b Illustration of the synthetic procedure of sheet-like Ni(OH)₂ and sphere-like Ni(OH)₂. c The eis of sheet-like and sphere-like Ni(OH)₂. Reprinted with permission from Ref. [159]. Copyright 2019 Springer Science Business Media