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Bis(diisopropylamino)cyclopropenium-arene Cations as High Oxidation Potential and High Stability Catholytes for Non-aqueous Redox Flow Batteries

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    Bis(diisopropylamino)cyclopropenium-arene Cations as High Oxidation Potential and High Stability Catholytes for Non-aqueous Redox Flow Batteries
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    • Yichao Yan
      Yichao Yan
      Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United States
      Joint Center for Energy Storage Research (JCESR), 9700 South Cass Avenue, Argonne, Illinois 60439, United States
      More by Yichao Yan
    • Thomas P. Vaid
      Thomas P. Vaid
      Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United States
      Joint Center for Energy Storage Research (JCESR), 9700 South Cass Avenue, Argonne, Illinois 60439, United States
      More by Thomas P. Vaid
      Orcidhttp://orcid.org/0000-0003-4597-0847
    • Melanie S. Sanford*
      Melanie S. Sanford
      Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United States
      Joint Center for Energy Storage Research (JCESR), 9700 South Cass Avenue, Argonne, Illinois 60439, United States
      [email protected]
      More by Melanie S. Sanford
      Orcidhttp://orcid.org/0000-0001-9342-9436
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2020, 142, 41, 17564–17571
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    https://doi.org/10.1021/jacs.0c07464
    Published October 2, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    This Article describes the development of 1,2-bis(diisopropylamino)-3-cyclopropenylium-functionalized (DAC-functionalized) benzene derivatives as high-potential catholytes for non-aqueous redox flow batteries. Density functional theory (DFT) calculations predict that the oxidation potentials (in CH3CN) of various DAC-benzene derivatives will range from +0.96 to +1.64 V vs Fc+/0, depending upon the substituents on the benzene ring. To test these predictions, a set of eight DAC-arene derivatives were synthesized and evaluated electrochemically. The molecule 1-DAC-4-tert-butyl-2-methoxy-5-pentafluoropropoxybenzene was found to offer the optimal balance of high redox potential (E1/2 = +1.19 V vs Fc+/0) and charge–discharge cycling stability (with 92% capacity retention over 116 h of cycling at 0.3 M concentration in a symmetrical flow cell). This optimal derivative was successfully deployed as a catholyte in a non-aqueous redox flow cell with butyl viologen as the anolyte to yield a 2.0 V battery.

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2020, 142, 41, 17564–17571
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.0c07464
    Published October 2, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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