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Solution Properties and Practical Limits of Concentrated Electrolytes for Nonaqueous Redox Flow Batteries

  • Jingjing Zhang
    Jingjing Zhang
    Joint Center for Energy Storage Research, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
    Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
  • R. E. Corman
    R. E. Corman
    Joint Center for Energy Storage Research, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
    Department of Mechanical Science and Engineering, University of Illinois at Urbana—Champaign, 405 North Mathews Avenue, Urbana, Illinois 61801, United States
    More by R. E. Corman
  • Jonathon K. Schuh
    Jonathon K. Schuh
    Joint Center for Energy Storage Research, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
    Department of Mechanical Science and Engineering, University of Illinois at Urbana—Champaign, 405 North Mathews Avenue, Urbana, Illinois 61801, United States
  • Randy H. Ewoldt
    Randy H. Ewoldt
    Joint Center for Energy Storage Research, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
    Department of Mechanical Science and Engineering, University of Illinois at Urbana—Champaign, 405 North Mathews Avenue, Urbana, Illinois 61801, United States
  • Ilya A. Shkrob*
    Ilya A. Shkrob
    Joint Center for Energy Storage Research, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
    Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
    *E-mail: [email protected]. Phone: (630)2529516.
  • , and 
  • Lu Zhang
    Lu Zhang
    Joint Center for Energy Storage Research, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
    Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
    More by Lu Zhang
Cite this: J. Phys. Chem. C 2018, 122, 15, 8159–8172
Publication Date (Web):April 5, 2018
https://doi.org/10.1021/acs.jpcc.8b02009
Copyright © 2018 American Chemical Society
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Supporting Info (2)»

Abstract

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Nonaqueous redox flow batteries (NRFBs) use energized organic fluids that contain redox active organic molecules (ROMs) and supporting electrolyte. Such all-organic electrolytes have wider electrochemical stability windows than the more familiar aqueous electrolytes, potentially allowing a higher energy density in the solutions of charged ROMs. As this energy density increases linearly with the concentration of the charge carriers, physicochemical properties of concentrated ROM solutions in both states of charge present considerable practical interest. For NRFBs to become competitive with other types of flow cells, the current techno-economic analyses favor highly concentrated solutions (>1 M) with high ionic conductivity (>5 mS/cm). It is not presently clear that such solutions can have the required dynamic properties. In this study, we show that ion diffusivities and conductivities of ROM-containing electrolytes reach maxima around 0.5 M and decrease significantly at higher concentrations; realistic limits are established for variations of these parameters. Furthermore, using closed-shell analogues for open-shell charged ROMs, we show that reconstitution of highly concentrated fluids during electrochemical charging will have strong adverse effects on their properties, including an increase in viscosity and decrease in conductivity and ion diffusivity. Given our results, it appears that the target concentrations of NRFB fluids need to be reconsidered in terms of concentration-dependent conductivity and viscosity.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.8b02009.

  • Lists of abbreviations, additional schemes, figures, and tables and the synthetic and experimental sections, including the details of NMR, viscosity measurements, and QSPR analyses (PDF)

  • An Excel worksheet containing QSPR analyses (XLSX)

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