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Conductive MOF electrodes for stable supercapacitors with high areal capacitance

Nature Materials volume 16, pages 220–224 (2017)Cite this article

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Abstract

Owing to their high power density and superior cyclability relative to batteries, electrochemical double layer capacitors (EDLCs) have emerged as an important electrical energy storage technology that will play a critical role in the large-scale deployment of intermittent renewable energy sources, smart power grids, and electrical vehicles1,2,3. Because the capacitance and charge–discharge rates of EDLCs scale with surface area and electrical conductivity, respectively, porous carbons such as activated carbon, carbon nanotubes and crosslinked or holey graphenes are used exclusively as the active electrode materials in EDLCs4,5,6,7,8,9. One class of materials whose surface area far exceeds that of activated carbons, potentially allowing them to challenge the dominance of carbon electrodes in EDLCs, is metal–organic frameworks (MOFs)10. The high porosity of MOFs, however, is conventionally coupled to very poor electrical conductivity, which has thus far prevented the use of these materials as active electrodes in EDLCs. Here, we show that Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2 (Ni3(HITP)2), a MOF with high electrical conductivity11, can serve as the sole electrode material in an EDLC. This is the first example of a supercapacitor made entirely from neat MOFs as active materials, without conductive additives or other binders. The MOF-based device shows an areal capacitance that exceeds those of most carbon-based materials and capacity retention greater than 90% over 10,000 cycles, in line with commercial devices. Given the established structural and compositional tunability of MOFs, these results herald the advent of a new generation of supercapacitors whose active electrode materials can be tuned rationally, at the molecular level.

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Figure 1: Structural schematics of Ni3(HITP)2.
Figure 2: Cyclic voltammetry of Ni3(HITP)2 powder in a three-electrode cell.
Figure 3: Performance of Ni3(HITP)2 electrodes in a symmetrical supercapacitor cell up to 1 V.
Figure 4: Comparison of areal capacitances among various EDLC materials.
Figure 5: Capacitance loss in a symmetric Ni3(HITP)2 supercapacitor cell before and after deep cycling at 1.5 V.

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Acknowledgements

This work was supported as part of the Center for Excitonics, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under award no. DE-SC0001088 (MIT). M.D. gratefully acknowledges early career support from the Sloan Foundation, the Research Corporation for Science Advancement (Cottrell Scholar), and 3M. J.C.B., Y.S.-H. and J.S.E. were supported by BMW and the Skoltech Center for Electrochemical Energy Storage. Part of the characterization was performed at the Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Infrastructure Network (NNIN), which is supported by the National Science Foundation under NSF award no. ECS-0335765. CNS is part of Harvard University. Sector 20 facilities at the Advanced Photon Source, and research at these facilities is supported by the US Department of Energy—Basic Energy Sciences, the Canadian Light Source and its funding partners, and the Advanced Photon Source. Use of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the US DOE under Contract No. DE-AC02-06CH11357.

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Authors and Affiliations

  1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    Dennis Sheberla, Joseph S. Elias & Mircea Dincă

  2. Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    John C. Bachman & Yang Shao-Horn

  3. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 South Cass Avenue, Lemont, Illinois 60439, USA

    Cheng-Jun Sun

Authors
  1. Dennis Sheberla
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  2. John C. Bachman
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  4. Cheng-Jun Sun
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  5. Yang Shao-Horn
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  6. Mircea Dincă
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Contributions

All authors devised experiments; D.S. performed all electrochemical experiments; J.C.B. and J.S.E. assembled full cells; D.S., M.D. and Y.S.-H. interpreted electrochemical data; C.-J.S. and J.S.E. collected and interpreted XAS data; D.S. and M.D. wrote the paper.

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Correspondence to Mircea Dincă.

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Sheberla, D., Bachman, J., Elias, J. et al. Conductive MOF electrodes for stable supercapacitors with high areal capacitance. Nature Mater 16, 220–224 (2017). https://doi.org/10.1038/nmat4766

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