Insights into the electric double-layer capacitance of two-dimensional electrically conductive metal-organic frameworks

Jamie W. Gittins, Chloe J. Balhatchet, Yuan Chen, Cheng Liu, David G. Madden, Sylvia Britto, Matthias J. Golomb, Aron Walsh, David Fairen-Jimenez, Siân E. Dutton, Alexander C. Forse

Research output: Contribution to journalArticlepeer-review

11 Citations (Scopus)

Abstract

Two-dimensional electrically conductive metal-organic frameworks (MOFs) have emerged as promising model electrodes for use in electric double-layer capacitors (EDLCs). However, a number of fundamental questions about the behaviour of this class of materials in EDLCs remain unanswered, including the effect of the identity of the metal node and organic linker molecule on capacitive performance, and the limitations of current conductive MOFs in these devices relative to traditional activated carbon electrode materials. Herein, we address both these questionsviaa detailed study of the capacitive performance of the framework Cu3(HHTP)2(HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) with an acetonitrile-based electrolyte, finding a specific capacitance of 110-114 F g−1at current densities of 0.04-0.05 A g−1and a modest rate capability. By directly comparing its performance with the previously reported analogue, Ni3(HITP)2(HITP = 2,3,6,7,10,11-hexaiminotriphenylene), we illustrate that capacitive performance is largely independent of the identity of the metal node and organic linker molecule in these nearly isostructural MOFs. Importantly, this result suggests that EDLC performance in general is uniquely defined by the 3D structure of the electrodes and the electrolyte, a significant finding not demonstrated using traditional electrode materials. Finally, we probe the limitations of Cu3(HHTP)2in EDLCs, finding a limited stable double-layer voltage window of 1 V and only a modest capacitance retention of 81% over 30 000 cycles, both significantly lower than state-of-the-art porous carbons. These important insights will aid the design of future conductive MOFs with greater EDLC performances.

Original languageEnglish
Pages (from-to)16006-16015
Number of pages10
JournalJournal of Materials Chemistry A
Volume9
Issue number29
DOIs
Publication statusPublished - 2021 Aug 7

Bibliographical note

Funding Information:
J. W. G. acknowledges the School of the Physical Sciences (Cambridge) for the award of an Oppenheimer Studentship. This work was supported by the Faraday Institution (FIRG017),viaa Faraday Undergraduate Summer Experience (FUSE) internship to Y. C. The work at Imperial (A. W.) was supported by a Royal Society University Research Fellowship (UF100278) and benefited from the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). M. J. G. thanks the Royal Society for PhD funding. D. F.-J. thanks the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (NanoMOFdeli), ERC-2016-COG 726380, and Innovate UK (104384). S. E. D. acknowledges funding from the Winton Programme for the Physics of Sustainability (Cambridge). A. C. F. thanks the Isaac Newton Trust of Trinity College (Cambridge) for a Research Grant (G101121), and the Yusuf Hamied Department of Chemistry (Cambridge) for the award of a BP Next Generation Fellowship. This work was also supported by a UKRI Future Leaders Fellowship to A. C. F. (MR/T043024/1). We thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. We thank Dr Phillip Milner and Dr Lewis Owen for collaboration and stimulating discussion over the course of the project. We thank Dr Chris Truscott and Dr Nigel Howard for collaboration and technical expertise.

Funding Information:
J. W. G. acknowledges the School of the Physical Sciences (Cambridge) for the award of an Oppenheimer Studentship. This work was supported by the Faraday Institution (FIRG017), via a Faraday Undergraduate Summer Experience (FUSE) internship to Y. C. The work at Imperial (A. W.) was supported by a Royal Society University Research Fellowship (UF100278) and beneted from the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). M. J. G. thanks the Royal Society for PhD funding. D. F.-J. thanks the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (NanoMOFdeli), ERC-2016-COG 726380, and Innovate UK (104384). S. E. D. acknowledges funding from the Winton Programme for the Physics of Sustainability (Cambridge). A. C. F. thanks the Isaac Newton Trust of Trinity College (Cambridge) for a Research Grant (G101121), and the Yusuf Hamied Department of Chemistry (Cambridge) for the award of a BP Next Generation Fellowship. This work was also supported by a UKRI Future Leaders Fellowship to A. C. F. (MR/T043024/1). We thank the Diamond Light Source for the award of beam time as part of the Energy Materials Block Allocation Group SP14239. We thank Dr Phillip Milner and Dr Lewis Owen for collaboration and stimulating discussion over the course of the project. We thank Dr Chris Truscott and Dr Nigel Howard for collaboration and technical expertise.

Publisher Copyright:
© The Royal Society of Chemistry 2021.

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)

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