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Title: 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. In this paper, 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. In conclusion, these promising results demonstrate the potential of using redox-active conductive MOFs in energy-storage applications.

Authors:
 [1]; ORCiD logo [1];  [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [1];  [1];  [3];  [4];  [4];  [4];  [1];  [2];  [5];  [1]
  1. Stanford Univ., CA (United States). Department of Chemical Engineering
  2. Stockholm Univ. (Sweden). Berzelii Centre EXSELENT on Porous Materials, Department of Materials and Environmental Chemistry
  3. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division, Advanced Photon Source
  4. Stanford Univ., CA (United States). Department of Chemical Engineering, SUNCAT Center for Interface Science and Catalysis
  5. Stanford Univ., CA (United States). Department of Materials Science and Engineering
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Knut and Alice Wallenberg Foundation; Swedish Research Council (SRC)
OSTI Identifier:
1426494
Alternate Identifier(s):
OSTI ID: 1461332
Grant/Contract Number:  
AC02-76SF00515; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Energy
Additional Journal Information:
Journal Volume: 3; Journal Issue: 1; Journal ID: ISSN 2058-7546
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Batteries; Metal-organic frameworks

Citation Formats

Feng, Dawei, Lei, Ting, Lukatskaya, Maria R., Park, Jihye, Huang, Zhehao, Lee, Minah, Shaw, Leo, Chen, Shucheng, Yakovenko, Andrey A., Kulkarni, Ambarish, Xiao, Jianping, Fredrickson, Kurt, Tok, Jeffrey B., Zou, Xiaodong, Cui, Yi, and Bao, Zhenan. Robust and conductive two-dimensional metal-organic frameworks with exceptionally high volumetric and areal capacitance. United States: N. p., 2018. Web. doi:10.1038/s41560-017-0044-5.
Feng, Dawei, Lei, Ting, Lukatskaya, Maria R., Park, Jihye, Huang, Zhehao, Lee, Minah, Shaw, Leo, Chen, Shucheng, Yakovenko, Andrey A., Kulkarni, Ambarish, Xiao, Jianping, Fredrickson, Kurt, Tok, Jeffrey B., Zou, Xiaodong, Cui, Yi, & Bao, Zhenan. Robust and conductive two-dimensional metal-organic frameworks with exceptionally high volumetric and areal capacitance. United States. doi:10.1038/s41560-017-0044-5.
Feng, Dawei, Lei, Ting, Lukatskaya, Maria R., Park, Jihye, Huang, Zhehao, Lee, Minah, Shaw, Leo, Chen, Shucheng, Yakovenko, Andrey A., Kulkarni, Ambarish, Xiao, Jianping, Fredrickson, Kurt, Tok, Jeffrey B., Zou, Xiaodong, Cui, Yi, and Bao, Zhenan. Mon . "Robust and conductive two-dimensional metal-organic frameworks with exceptionally high volumetric and areal capacitance". United States. doi:10.1038/s41560-017-0044-5. https://www.osti.gov/servlets/purl/1426494.
@article{osti_1426494,
title = {Robust and conductive two-dimensional metal-organic frameworks with exceptionally high volumetric and areal capacitance},
author = {Feng, Dawei and Lei, Ting and Lukatskaya, Maria R. and Park, Jihye and Huang, Zhehao and Lee, Minah and Shaw, Leo and Chen, Shucheng and Yakovenko, Andrey A. and Kulkarni, Ambarish and Xiao, Jianping and Fredrickson, Kurt and Tok, Jeffrey B. and Zou, Xiaodong and Cui, Yi and Bao, Zhenan},
abstractNote = {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. In this paper, 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. In conclusion, these promising results demonstrate the potential of using redox-active conductive MOFs in energy-storage applications.},
doi = {10.1038/s41560-017-0044-5},
journal = {Nature Energy},
issn = {2058-7546},
number = 1,
volume = 3,
place = {United States},
year = {2018},
month = {1}
}

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Figures / Tables:

Fig. 1 Fig. 1: | Synthesis and structural characterization of HAB MOFs. a, Synthesis scheme of Cu- /Ni-HAB MOFs. b, Experimental and Powley fitted PXRD patterns of Cu-HAB. c, 2D GIXD pattern of a Cu-HAB thin film on a Si substrate. d, HR-TEM image of Cu-HAB along [001] that shows a hexagonalmore » pore packing with d100=1.15 nm (a=1.33 nm). Scale bar, 10 nm, Inset: Fourier transform of the image. e, HR-TEM image of the region within the blue square in d, f, Symmetry-imposed and lattice-averaged image calculated from the HR-TEM image. Embedded is the eclipsed structure model of Cu-HAB. Scale bar, 2 nm. g,h, Experimental (g) and simulated (h) electron-diffraction pattern (eclipsed model) of Cu-HAB viewed along [-110]. Scale bar 5 nm-1. Insel (g): the crystal from which the electron-diffraction pattern was taken. Scale bar, 50 nm. i, A space-filling model of the Cu-HAB model. Blue, grey, green and white spheres represent N, C, Ni and H atoms, respectively; a.u.: arbitrary units.« less

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