Abstract

For miniaturized capacitive energy storage, volumetric and areal capacitances are more important metrics than gravimetric ones because of the constraints imposed by device volume and chip area. Typically used in commercial supercapacitors, porous carbons, although they provide a stable and reliable performance, lack volumetric performance because of their inherently low density and moderate capacitances. Here we report a high-performing electrode based on conductive hexaaminobenzene (HAB)-derived two-dimensional metal−organic frameworks (MOFs). In addition to possessing a high packing density and hierarchical porous structure, these MOFs also exhibit excellent chemical stability in both acidic and basic aqueous solutions, which is in sharp contrast to conventional MOFs. Submillimetre-thick pellets of HAB MOFs showed high volumetric capacitances up to 760 F cm−3 and high areal capacitances over 20 F cm−2. Furthermore, the HAB MOF electrodes exhibited highly reversible redox behaviours and good cycling stability with a capacitance retention of 90% after 12,000 cycles. These promising results demonstrate the potential of using redox-active conductive MOFs in energy-storage applications.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from $8.99

All prices are NET prices.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

References

  1. 1.

    Huang, P. et al. On-chip and freestanding elastic carbon films for micro-supercapacitors. Science 351, 691–695 (2016).

  2. 2.

    Beidaghi, M. & Gogotsi, Y. Capacitive energy storage in micro-scale devices: recent advances in design and fabrication of micro-supercapacitors. Energy Environ. Sci. 7, 867–884 (2014).

  3. 3.

    Simon, P. & Gogotsi, Y. Materials for electrochemical capacitors. Nat. Mater. 7, 845–854 (2008).

  4. 4.

    Xu, Y. et al. Holey graphene frameworks for highly efficient capacitive energy storage. Nat. Commun. 5, 4554 (2014).

  5. 5.

    Zhu, Y. et al. Carbon-based supercapacitors produced by activation of graphene. Science 332, 1537–1541 (2011).

  6. 6.

    Zhao, X. et al. Incorporation of manganese dioxide within ultraporous activated graphene for high-performance electrochemical capacitors. ACS Nano 6, 5404–5412 (2012).

  7. 7.

    Snook, G. A., Kao, P. & Best, A. S. Conducting-polymer-based supercapacitor devices and electrodes. J. Power Sources 196, 1–12 (2011).

  8. 8.

    Kyeremateng, N. A., Brousse, T. & Pech, D. Microsupercapacitors as miniaturized energy-storage components for on-chip electronics. Nat. Nanotech. 12, 7–15 (2016).

  9. 9.

    Gogotsi, Y. & Simon, P. True performance metrics in electrochemical energy storage. Science 334, 917–918 (2011).

  10. 10.

    Zhou, H.-C., Long, J. R. & Yaghi, O. M. Introduction to metal–organic frameworks. Chem. Rev. 112, 673–674 (2012).

  11. 11.

    Wang, L. et al. Metal–organic frameworks for energy storage: batteries and supercapacitors. Coord. Chem. Rev. 307, 361–381 (2016).

  12. 12.

    Mulzer, C. R. et al. Superior charge storage and power density of a conducting polymer-modified covalent organic framework. ACS Cent. Sci. 2, 667–673 (2016).

  13. 13.

    Sheberla, D. et al. Conductive MOF electrodes for stable supercapacitors with high areal capacitance. Nat. Mater. 16, 220–224 (2017).

  14. 14.

    Zhang, Z. & Awaga, K. Redox-active metal–organic frameworks as electrode materials for batteries. MRS Bull. 41, 883–889 (2016).

  15. 15.

    Dincă, M. & Léonard, F. Metal–organic frameworks for electronics and photonics. MRS Bull. 41, 854–857 (2016).

  16. 16.

    Wang, Q., Yan, J. & Fan, Z. Carbon materials for high volumetric performance supercapacitors: design, progress, challenges and opportunities. Energy Environ. Sci. 9, 729–762 (2016).

  17. 17.

    Sun, L., Campbell, M. G. & Dincă, M. Electrically conductive porous metal–organic frameworks. Angew. Chem. Int. Ed. 55, 3566–3579 (2016).

  18. 18.

    Sheberla, D. et al. High electrical conductivity in Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2, a semiconducting metal–organic graphene analogue. J. Am. Chem. Soc. 136, 8859–8862 (2014).

  19. 19.

    Kambe, T. et al. Redox control and high conductivity of nickel bis(dithiolene) complex π-nanosheet: a potential organic two-dimensional topological insulator. J. Am. Chem. Soc. 136, 14357–14360 (2014).

  20. 20.

    Huang, X. et al. A two-dimensional πd conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour. Nat. Commun. 6, 7408 (2015).

  21. 21.

    Givaja, G., Amo-Ochoa, P., Gomez-Garcia, C. J. & Zamora, F. Electrical conductive coordination polymers. Chem. Soc. Rev. 41, 115–147 (2012).

  22. 22.

    Mahmood, J., Kim, D., Jeon, I.-Y., Lah, M. S. & Baek, J.-B. Scalable synthesis of pure and stable hexaaminobenzene trihydrochloride. Synlett 24, 246–248 (2013).

  23. 23.

    Mahmood, J. et al. Nitrogenated holey two-dimensional structures. Nat. Commun. 6, 6486 (2015).

  24. 24.

    Nandasiri, M. I., Jambovane, S. R., McGrail, B. P., Schaef, H. T. & Nune, S. K. Adsorption, separation, and catalytic properties of densified metal–organic frameworks. Coord. Chem. Rev. 311, 38–52 (2016).

  25. 25.

    Kobayashi, Y., Jacobs, B., Allendorf, M. D. & Long, J. R. Conductivity, doping, and redox chemistry of a microporous dithiolene-based metal−organic framework. Chem. Mater. 22, 4120–4122 (2010).

  26. 26.

    Hmadeh, M. et al. New porous crystals of extended metal-catecholates. Chem. Mater. 24, 3511–3513 (2012).

  27. 27.

    Campbell, M. G., Sheberla, D., Liu, S. F., Swager, T. M. & Dincă, M. Cu3(hexaiminotriphenylene)2: an electrically conductive 2D metal–organic framework for chemiresistive sensing. Angew. Chem. Int. Ed. 54, 4349–4352 (2015).

  28. 28.

    Wang, K. et al. Pyrazolate-based porphyrinic metal–organic framework with extraordinary base-resistance. J. Am. Chem. Soc. 138, 914–919 (2016).

  29. 29.

    Conway, B. Electrochemical Supercapacitors: Scientific Fundamentals and Technological Applications (Kluwer Academic/Plenum, New York, 1999).

  30. 30.

    Augustyn, V. et al. High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. Nat. Mater. 12, 518–522 (2013).

  31. 31.

    Ghidiu, M., Lukatskaya, M. R., Zhao, M.-Q., Gogotsi, Y. & Barsoum, M. W. Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance. Nature 516, 78–81 (2014).

  32. 32.

    Wolff, J. J. et al. Hexaaminobenzene derivatives:  synthesis and unusual oxidation behavior. J. Org. Chem. 66, 2769–2777 (2001).

  33. 33.

    Herebian, D., Bothe, E., Neese, F., Weyhermüller, T. & Wieghardt, K. Molecular and electronic structures of bis-(o-diiminobenzosemiquinonato)metal(ii) complexes (Ni, Pd, Pt), their monocations and -anions, and of dimeric dications containing weak metal−metal bonds. J. Am. Chem. Soc. 125, 9116–9128 (2003).

  34. 34.

    Yu, Z., Tetard, L., Zhai, L. & Thomas, J. Supercapacitor electrode materials: nanostructures from 0 to 3 dimensions. Energy Environ. Sci. 8, 702–730 (2015).

  35. 35.

    Lukatskaya, M. R., Dunn, B. & Gogotsi, Y. Multidimensional materials and device architectures for future hybrid energy storage. Nat. Commun. 7, 12647 (2016).

  36. 36.

    Lin, T. et al. Nitrogen-doped mesoporous carbon of extraordinary capacitance for electrochemical energy storage. Science 350, 1508–1513 (2015).

  37. 37.

    Xu, Y. et al. A metal-free supercapacitor electrode material with a record high volumetric capacitance over 800 F cm−3. Adv. Mater. 27, 8082–8087 (2015).

  38. 38.

    Acerce, M., Voiry, D. & Chhowalla, M. Metallic 1T phase MoS2 nanosheets as supercapacitor electrode materials. Nat. Nanotech. 10, 313–318 (2015).

  39. 39.

    Yang, X., Cheng, C., Wang, Y., Qiu, L. & Li, D. Liquid-mediated dense integration of graphene materials for compact capacitive energy storage. Science 341, 534–537 (2013).

  40. 40.

    Sarkisov, L. & Harrison, A. Computational structure characterisation tools in application to ordered and disordered porous materials. Mol. Simul. 37, 1248–1257 (2011).

  41. 41.

    Zhu, Y. et al. Unravelling surface and interfacial structures of a metal–organic framework by transmission electron microscopy. Nat. Mater. 16, 532–536 (2017).

Download references

Acknowledgements

This work was supported by Stanford School of Engineering SUNCAT seed funding. Part of this work was funded by the Office of Energy Efficiency and Renewable Energy (EERE), US Department of Energy, under Battery Materials Research Program. We gratefully acknowledge support from the US Department of Energy, Office of Sciences, Office of Basic Energy Sciences to the SUNCAT Center for Interface Science and Catalysis. J.P. acknowledges supported by the Dreyfus Foundation Environmental Postdoc Fellowship. L.S. gratefully acknowledges support from Kodak Graduate Fellowship. The structure characterization by TEM and PXRD was supported by the Knut & Alice Wallenberg Foundation through project grant 3DEM-NATUR and the Swedish Research Council (VR) through the MATsynCELL project of the Röntgen-Ångström Cluster. Use of the SSRL, SLAC National Accelerator Laboratory, is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No. DE-AC02-76SF00515.

Author information

Author notes

  1. Dawei Feng, Ting Lei and Maria R. Lukatskaya contributed equally to this work.

Affiliations

  1. Department of Chemical Engineering, Stanford University, Stanford, CA, USA

    • Dawei Feng
    • , Ting Lei
    • , Maria R. Lukatskaya
    • , Jihye Park
    • , Minah Lee
    • , Leo Shaw
    • , Shucheng Chen
    • , Jeffrey B. Tok
    •  & Zhenan Bao
  2. Berzelii Centre EXSELENT on Porous Materials, Department of Materials and Environmental Chemistry, Stockholm University, Stockholm, Sweden

    • Zhehao Huang
    •  & Xiaodong Zou
  3. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL, USA

    • Andrey A. Yakovenko
  4. Department of Chemical Engineering, SUNCAT Center for Interface Science and Catalysis, Stanford University, Stanford, CA, USA

    • Ambarish Kulkarni
    • , Jianping Xiao
    •  & Kurt Fredrickson
  5. Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA

    • Yi Cui

Authors

  1. Search for Dawei Feng in:

  2. Search for Ting Lei in:

  3. Search for Maria R. Lukatskaya in:

  4. Search for Jihye Park in:

  5. Search for Zhehao Huang in:

  6. Search for Minah Lee in:

  7. Search for Leo Shaw in:

  8. Search for Shucheng Chen in:

  9. Search for Andrey A. Yakovenko in:

  10. Search for Ambarish Kulkarni in:

  11. Search for Jianping Xiao in:

  12. Search for Kurt Fredrickson in:

  13. Search for Jeffrey B. Tok in:

  14. Search for Xiaodong Zou in:

  15. Search for Yi Cui in:

  16. Search for Zhenan Bao in:

Contributions

D.F., T.L., M.R.L and J.P. designed and synthesized the HAB MOFs. M.R.L. performed the electrochemical characterization and analysis. D.F. performed the gas absorption measurements. T.L. measured the photophysical and electrical properties and performed the structure modelling. Z.H. and X.Z. performed the TEM measurements and structure refinement. M.L. performed the SEM imaging. L.S. performed the GIXD experiments and analysis. S.C. performed the XPS characterization. A.A.Y. performed the synchrotron powder X-ray measurements. A.K., J.X. and K.F. performed the DFT calculations. D.F., T.L., M.R.L., J.B.T., Y.C. and Z.B. co-wrote the paper. All the authors discussed the results and commented on the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Zhenan Bao.

Supplementary information

  1. Supplementary Figures, Tables and References

    Supplementary Methods, Supplementary Figure 1–35, Supplementary Tables 1–6, Supplementary Discussion, Supplementary References

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/s41560-017-0044-5