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