Understanding the mechanism of high capacitance in nickel hexaaminobenzene-based conductive metal-organic frameworks in aqueous electrolytes

Maria R. Lukatskaya; Dawei Feng; Seong Min Bak; John W.F. To; Xiao Qing Yang; Yi Cui; Jeremy I. Feldblyum; Zhenan Bao

doi:10.1021/acsnano.0c07292

Understanding the mechanism of high capacitance in nickel hexaaminobenzene-based conductive metal-organic frameworks in aqueous electrolytes

Maria R. Lukatskaya, Dawei Feng, Seong Min Bak, John W.F. To, Xiao Qing Yang, Yi Cui, Jeremy I. Feldblyum, Zhenan Bao

Department of Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

Abstract

Recently, intrinsically conductive metal-organic frameworks (MOFs) have demonstrated promising performance in fast-charging energy storage applications and may outperform some current electrode materials (e.g., porous carbons) for supercapacitors in terms of both gravimetric and volumetric capacitance. In this report, we examine the mechanism of high capacitance in a nickel hexaaminobenzene-based MOF (NiHAB). Using a combination of in situ Raman and X-ray absorption spectroscopies, as well as detailed electrochemical studies in a series of aqueous electrolytes, we demonstrate that the charge storage mechanism is, in fact, a pH-dependent surface pseudocapacitance, and unlike typical inorganic systems, where transition metals change oxidation state during charge/discharge cycles, NiHAB redox activity is ligand-centered.

Original language	English
Pages (from-to)	15919-15925
Number of pages	7
Journal	ACS Nano
Volume	14
Issue number	11
DOIs	https://doi.org/10.1021/acsnano.0c07292
Publication status	Published - 2020 Nov 24

Bibliographical note

Funding Information:
Z.B. and Y.C. at Stanford University and S.-M.B. and X.-Q.Y. at Brookhaven National Laboratory were supported by the Department of Energy, Battery 500 program (for Z.B. and Y.C., Grant No. 32023 at SLAC National Accelerator Laboratory, under Contract DE-AC02-76SF00515; and for A.B. and X.-Q.Y. at BNL under contract number DE-SC0012704). We would like to thank Dr. D. Mackanic for his help with DLS measurements. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-1542152. J.I.F. acknowledges support from the Donors of the American Chemical Society Petroleum Research Fund (#59835-DNI10) in support of this work. The XAS research used beamline 8-ID (ISS) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704.

Publisher Copyright:
© 2020 American Chemical Society.

All Science Journal Classification (ASJC) codes

Materials Science(all)
Engineering(all)
Physics and Astronomy(all)

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10.1021/acsnano.0c07292

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title = "Understanding the mechanism of high capacitance in nickel hexaaminobenzene-based conductive metal-organic frameworks in aqueous electrolytes",

abstract = "Recently, intrinsically conductive metal-organic frameworks (MOFs) have demonstrated promising performance in fast-charging energy storage applications and may outperform some current electrode materials (e.g., porous carbons) for supercapacitors in terms of both gravimetric and volumetric capacitance. In this report, we examine the mechanism of high capacitance in a nickel hexaaminobenzene-based MOF (NiHAB). Using a combination of in situ Raman and X-ray absorption spectroscopies, as well as detailed electrochemical studies in a series of aqueous electrolytes, we demonstrate that the charge storage mechanism is, in fact, a pH-dependent surface pseudocapacitance, and unlike typical inorganic systems, where transition metals change oxidation state during charge/discharge cycles, NiHAB redox activity is ligand-centered.",

author = "Lukatskaya, {Maria R.} and Dawei Feng and Bak, {Seong Min} and To, {John W.F.} and Yang, {Xiao Qing} and Yi Cui and Feldblyum, {Jeremy I.} and Zhenan Bao",

note = "Funding Information: Z.B. and Y.C. at Stanford University and S.-M.B. and X.-Q.Y. at Brookhaven National Laboratory were supported by the Department of Energy, Battery 500 program (for Z.B. and Y.C., Grant No. 32023 at SLAC National Accelerator Laboratory, under Contract DE-AC02-76SF00515; and for A.B. and X.-Q.Y. at BNL under contract number DE-SC0012704). We would like to thank Dr. D. Mackanic for his help with DLS measurements. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-1542152. J.I.F. acknowledges support from the Donors of the American Chemical Society Petroleum Research Fund (#59835-DNI10) in support of this work. The XAS research used beamline 8-ID (ISS) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. Publisher Copyright: {\textcopyright} 2020 American Chemical Society.",

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AU - Lukatskaya, Maria R.

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AU - To, John W.F.

AU - Yang, Xiao Qing

AU - Cui, Yi

AU - Feldblyum, Jeremy I.

AU - Bao, Zhenan

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PY - 2020/11/24

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AB - Recently, intrinsically conductive metal-organic frameworks (MOFs) have demonstrated promising performance in fast-charging energy storage applications and may outperform some current electrode materials (e.g., porous carbons) for supercapacitors in terms of both gravimetric and volumetric capacitance. In this report, we examine the mechanism of high capacitance in a nickel hexaaminobenzene-based MOF (NiHAB). Using a combination of in situ Raman and X-ray absorption spectroscopies, as well as detailed electrochemical studies in a series of aqueous electrolytes, we demonstrate that the charge storage mechanism is, in fact, a pH-dependent surface pseudocapacitance, and unlike typical inorganic systems, where transition metals change oxidation state during charge/discharge cycles, NiHAB redox activity is ligand-centered.

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Understanding the mechanism of high capacitance in nickel hexaaminobenzene-based conductive metal-organic frameworks in aqueous electrolytes

Abstract

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