Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Robust and conductive two-dimensional metal−organic frameworks with exceptionally high volumetric and areal capacitance

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.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Synthesis and structural characterization of HAB MOFs.
Fig. 2: Preparation, absorption spectrum and conductivity of HAB MOFs pellets.
Fig. 3: Electrochemical performance of HAB MOFs in 1 M KOH.
Fig. 4: Comparison of the volumetric and areal capacitance of Ni-HAB additive-free electrodes (green area) with the performance of other materials.

Similar content being viewed by others

References

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Book  Google Scholar 

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

    Article  Google Scholar 

  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).

    Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

Authors and Affiliations

Authors

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.

Corresponding author

Correspondence to Zhenan Bao.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Additional information

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

Supplementary information

Supplementary Figures, Tables and References

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

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Feng, D., Lei, T., Lukatskaya, M.R. et al. Robust and conductive two-dimensional metal−organic frameworks with exceptionally high volumetric and areal capacitance. Nat Energy 3, 30–36 (2018). https://doi.org/10.1038/s41560-017-0044-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

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

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing