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Recent advancements in metal organic framework based electrodes for supercapacitors

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  • ReceivedSep 21, 2017
  • AcceptedOct 27, 2017
  • PublishedJan 12, 2018

Abstract

Metal organic frameworks (MOFs) are considered as very promising candidates to build electrodes for electrochemical energy storage devices such as lithium ion batteries, fuel cells and supercapacitors, due to their diverse structure, adjustable aperture, large specific surface area and abundant active sites. Supercapacitor has been widely investigated in the past decades. Of critical importance in these devices is the electrode active materials, and this application has been intensively studied with the development of novel nanomaterials. In this review we summarize recent reports on MOFs as electrode materials for supercapacitors. Specifically, the synthesis of MOF materials for supercapacitor electrodes and their performance in electrochemical energy storage are discussed. We aim to include supercapacitor electrode materials related to MOFs, such as carbon, metal and composite materials. It is proposed that MOFs play an important role in the development of a new generation of supercapacitor electrode materials. Finally, we discuss the current challenges in the field of supercapacitors, with a view towards how to address these challenges with the future development of MOFs and their derivatives.


Funded by

the Fundamental Research Funds for Central Universities’ through Beihang University and the Queensland Government through the Q-CAS Collaborative Science Fund 2016 “Graphene-Based Thin Film Supercapacitors”.


Acknowledgment

This work was supported by the Fundamental Research Funds for Central Universities’ through Beihang University and the Queensland Government through the Q-CAS Collaborative Science Fund 2016 “Graphene-Based Thin Film Supercapacitors”.


Interest statement

The authors declare that they have no conflict interest.


Contributions statement

Zhao Y wrote the manuscript. Liu J organized the manuscript structure and contributed to the general discussion; Horn M and Motta N revised the manuscript. Hu M and Li Y contributed to the general contribution.


Author information

Yujie Zhao received her Master’s degree from Chongqing University, China, in 2017. Currently, she is a PhD student at Beihang University, China. Her research interest is focused on functional nanomaterials and related energy applications.


Jinzhang Liu received his PhD degree in Condensed Matter Physics from Lanzhou University in 2006. He then continued his academic career in South Korea (2006–2011) and Australia (2011–2015). Currently, he is an associated professor at the School of Materials Science and Engineering of Beihang University. His research interests include the synthesis of carbon materials and their applications in supercapacitors and solar-powered desalination.


Yan Li is a professor of the School of Materials Science and Engineering of Beihang University. He received his PhD degree form Dalian University of Technology in 2001. His current research interests include shape memory materials, biomedical materials, supercapacitors and battery materials.


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  • Figure 1

    (a) Scanning electron microscopy (SEM) top and cross-sectional view (inset) of Co-MOF films; (b) X-ray diffraction (XRD) patterns of Co-MOF films after 1000 cycles in different electrolytes; (c) CV curves of Co-MOF film in different electrolytes. Reproduced with permission from Ref. [45], Copyright 2012, Elsevier.

  • Figure 2

    SEM images of (a) Co-BDC, (b) Co-NDC and (c) Co-BPDC MOF films on an ITO-glass substrate. (d) Specific capacitance of different Co-MOFs at various scan rates; (e) cycllic stability of different Co-MOFs at 100 mV s−1; (f) XRD patterns of different Co-MOFs after 1000 cycles at 100 mV s−1. Reproduced with permission from Ref. [48], Copyright 2013, Elsevier.

  • Figure 3

    Schematic of a “conformal transformation” with formation of a porous product. Reproduced with permission from Ref. [49], Copyright 2013, Elsevier.

  • Figure 4

    (a) The crystal structure of the Ni-MOF; (b) schematic representation of the proposed charge/discharge process; (c, d) SEM images of Ni-MOF; (e, f) transmission electron microscopy (TEM) images of Ni-MOF. Reproduced with permission from ref. [51], Copyright 2016, the Royal Society of Chemistry.

  • Figure 5

    (a) The specific capacitance of the supercapacitor device at different current densities. The inset image is a photograph of the device. (b) Cycling performance of the device at 5.0 mA cm−2 after 5,000 cycles. The inset image is a photograph of the flexible ASC based Ni-MOF. Reproduced with permission from Ref. [51], Copyright 2016, the Royal Society of Chemistry.

  • Figure 6

    (a) An illustration of the experimental setup to fabricate the ZIF coatings; (b) powder XRD confirms the identity of the coating as ZIF-67 with the reflections in the experimental pattern (red) matching the predicted positions (black); (c) N2 adsorption and desorption curves of ZIF-67; (d) the coherency of the coating of ZIF-67 on the anode and (e) the lack of a clear morphology in the constituent crystals. Reproduced with permission from Ref. [55], Copyright 2016, Elsevier.

  • Figure 7

    (a) SEM image of Co-MOFs; (b) TEM image of Co-MOFs; (c) the inter/deintercalation process of OH in the layered structure of the Co-MOF crystal; (d) the electron transport process in the conductive network of the Co-MOF crystal. Reproduced with permission from Ref. [56], Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA.

  • Figure 8

    (a) Molecular structure of Ni-MOF; (b) relative size of pores, electrolyte Et4N+ and BF4, and acetonitrile solvent molecules shown in a space-filling diagram of idealized Ni-MOF. Ni: green; F: lime; N: blue; C: gray; B: brown; H: white. Reproduced with permission from Ref. [57], Copyright 2017, Nature Publishing Group.

  • Figure 9

    (a) Schematic structure of MOF-5 and IRMOF-3; (b) XRD patterns; (c, d) SEM images of CIRMOF-3-950; (e, f) SEM images of CMOF-5-950. Reproduced with permission from Ref. [59], Copyright 2014, American Chemical Society.

  • Figure 10

    (a) Fabrication schematic of 3D IPCs. TEM images of IPC2-M (b), IPC3-M (c), IPC4-M (d) and IPC5-M (e). (f) XRD patterns of IPCs; (g) XRD patterns of IPC4-M before and after washing; (h) specific capacitance of IPC electrodes at different current densities; (i) cyclic stability of IPC3-M. Reproduced with permission from Ref. [62], Copyright 2016, Elsevier.

  • Figure 11

    (a, b) Schematic of the fabrication of the Al-MOF, metal organic gels drying with supercritical CO2 (MOA) and after further carbonization (denoted as MOA-C), metal organic drying with air (MOX) and after further carbonization (denoted as MOX-C); (c, d) photographs of as-prepared MOX and final carbon products (MOX-C); (e) photographs of as-prepared MOA and MOA-C. Reproduced with permission from Ref. [63], Copyright 2013, Nature Publishing Group. (f) Schematic of the constructed ASC using nanoporous carbon and carbonized metal organic xerogels using Fe(NO3)3 (MOXC-Fe), respectively, as electrode materials. Reproduced with permission from Ref. [64], Copyright 2016, American Chemical Society.

  • Figure 12

    (a) Photographs of MOX-Al (i) and MOX-Fe (ii); (b) XRD patterns of MOX-Al and MOX-Fe; (c) pore size distribution of MOXs; (d) the schematic diagram of ASC; (e) the cyclic stability of ASC. Reproduced with permission from Ref. [64], Copyright 2016, American Chemical Society.

  • Figure 13

    (a) Schematic illustration of the synthesis process of Carbon-ZSR; (b) SEM image of ZIF-67; (c) SEM images of ZIF-67/SiO2/RF and (c') ZIF-67/SiO2/RF-M; (d) SEM image of carbon/SiO2; (e) SEM images of carbon-ZSR. Reproduced with permission from Ref. [68], Copyright 2017, Elsevier.

  • Figure 14

    The coordination environment of the CoII ion (a). (b, c) 2D layer structure and 3D polycatenation array supramolecular architecture of Co-MOF; (d) TEM image of Co3O4; (e) cyclic stability of porous Co3O4 at 1 A g−1. Reproduced with permission from Ref. [76], Copyright 2013, the Royal Society of Chemistry.

  • Figure 15

    SEM images of Ce-MOF (a) and CeO2 (b). (c) Specific capacitance of CeO2 in different electrolytes. (d) Cyclic stability of CeO2 in different electrolytes and coulombic efficiency. Reproduced with permission from Ref. [77], Copyright 2014, the Royal Society of Chemistry.

  • Figure 16

    (a) Schematic of the fabrication process of NiCo oxide materials; (b) specific capacitance of different NiCo oxides at various current densities; (c) cyclic stability of NiCo oxides at the current density of 10 A g−1. Reproduced with permission from Ref. [79], Copyright 2015, the Royal Society of Chemistry.

  • Figure 17

    (a) The synthesis route of nanoporous carbon and Co3O4; (b) the specific capacitance of nanoporous carbon and Co3O4 at various scan rates; (c) schematic illustration of the fabricated ASC. Reproduced with permission from Ref. [80], Copyright 2015, American Chemical Society.

  • Figure 18

    (a) Schematic illustration of Co-MOFs crystals. (b) XRD patterns. (c) SEM image of Co-MOF-bulk. (d) SEM image of Co-MOF-cuboid. Reproduced with permission from Ref. [81], Copyright 2017, the Royal Society of Chemistry.

  • Figure 19

    (a) Illustration of the fabrication of Fe3O4/carbon composite; (b) TEM image of ion based MOF (Fe-MIL-88B-NH2); (c) SEM image and energy dispersive X-ray spectroscopy (EDS) spectrum of Fe3O4/carbon composite; (d) SEM image of Fe3O4/carbon composite; (e) EIS measurements of Fe3O4/carbon composite electrode with different temperatures with insert showing the high frequency region of the Nyquist plot (enlarged profile showing as inset); (f) cyclic stability of Fe3O4/carbon composite with varied temperature at 2 A g−1. Reproduced with permission from Ref. [90], Copyright 2014, Elsevier.

  • Figure 20

    (a) Schematic illustrating the process of porphyrin paddlewheel framework-3 (PPF-3) nanosheets; (b) SEM image of PPF-3; (c) atomic force microscope (AFM) image of PPF-3; (d) TEM image of PPF-3, inset: selected area electron diffraction (SAED) pattern of PPF-3 nanosheets; (e) schematic for the synthesis process of 2D CoSNC nanocomposites. Reproduced with permission from Ref. [92], Copyright 2016, American Chemical Society.

  • Figure 21

    (a) Schematic of the synthesis of Ni/Zn-MOF microspheres and NiO/ZnO hollow spheres. Reproduced with permission from Ref. [93], Copyright 2016, the Royal Society of Chemistry. (b) The structural change of the Ni-MOF before and after Zn-doping. Reproduced with permission from Ref. [94], Copyright 2014, the Royal Society of Chemistry.

  • Figure 22

    (a) Schematic for the fabrication process of MWCNTs/nanoporous carbon-Small/Middle/Large. (b, c, d) TEM images of MWCNTs/nanoporous carbon with different sizes. (e) SEM image of MWCNTs/nanoporous carbon-Large. Reproduced with permission from Ref. [98], Copyright 2017, the Royal Society of Chemistry.

  • Figure 23

    (a) Illustration of Ni-MOFs with graphene oxide (GO) nanosheets; (b) the specific capacitance of Ni-MOF@GO with different GO weight ratio; (c) cyclic stability of Ni-MOF-HCl-180 and Ni-MOF@GO-3. Reproduced with permission from Ref. [104], Copyright 2016, American Chemical Society.

  • Figure 24

    (a) Schematic illustration of the synthesis processes of RGO@Co3O4 and Co3O4-RGO-Co3O4. SEM images of GO@ZIF (b); RGO@Co3O4 (c); ZIF/GO/ZIF (d) and Co3O4-RGO-Co3O4 (e). Reproduced with permission from Ref. [105], Copyright 2016, Elsevier.

  • Figure 25

    Schematic of the two-step fabrication of PANI-ZIF-67-CC and SEM images of (a, b) carbon cloths, ZIF-67-CC (c, d), and PANI-ZIF-67-CC (e, f). (g) Electron and electrolyte can access MOF surfaces and form an EDLC on the surface of PANI-ZIF-67-CC. Reproduced with permission from Ref. [106], Copyright 2015, American Chemical Society.

  • Figure 26

    (a) CV curves of AQ-NPCs, pure NPCs and AQ at 10 mV s−1. (b) CV curves of TN-NPCs, pure NPCs, NQ and TCBQ at 10 mV s−1. (c) The CV curves of ASC at 10 mV s−1. Reproduced with permission from Ref. [109], Copyright 2017, Elsevier.

  • Figure 27

    (a) The formation mechanism of MnO2 hollow spheres; (b) chemical structure representation of the constituent ions in the ionic liquid electrolytes; (c) the specific capacitance of AC//IL//MnO2 ASC in different electrolytes; (d) cyclic stability of AC//IL//MnO2 ASC in different electrolytes. Reproduced with permission from Ref. [110], Copyright 2015, the Royal Society of Chemistry.

  • Figure 28

    SEM images of carbon nanotube film (CNTF) (a) and HKUST-1 (b); (c) SEM image of H-1-15G, and the inset is a high resolution image; (d) SEM image of PEDOT/H-15G-CNTF, and the inset is a high resolution image; (e) the CV curves at 50 mV s−1 for solid-state supercapacitors bent at different angles; (f) the specific capacitance of the device bent at different angels and (g) the accompanying photographs. Reproduced with permission from Ref. [113], Copyright 2016, Elsevier.

  • Figure 29

    Schematic of the fabrication of MOF-5NiRGO applied as a supercapacitor electrode, and also depicted are the coexisting EDLC charge storage RGO, and the reversible redox reactions of Ni metal centers. Reproduced with permission from Ref. [114], Copyright 2016, American Chemical Society.

  • Table 1   Summary of the solution resistances () and charge transfer resistances () calculated from the fitting of electrochemical impedance spectroscopy (EIS) data

    RS (Ω)

    RCT (Ω)

    ZIF-zni

    2.10

    62,600

    ZIF-7

    2.25

    86,100

    ZIF-8

    3.45

    3,740

    ZIF-14

    3.21

    8,320

    ZIF-67

    2.77

    21

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