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Ion Pairing and Redissociaton in Low-Permittivity Electrolytes for Multivalent Battery Applications

  • Julian Self
    Julian Self
    Department of Materials Science and Engineering, University of California, Berkeley, California 94720, United States
    Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
    More by Julian Self
  • Nathan T. Hahn
    Nathan T. Hahn
    Material, Physical, and Chemical Sciences Center, Sandia National Laboratories, Albuquerque, New Mexico 87185, United States
  • Kara D. Fong
    Kara D. Fong
    Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United States
    Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
    More by Kara D. Fong
  • Scott A. McClary
    Scott A. McClary
    Material, Physical, and Chemical Sciences Center, Sandia National Laboratories, Albuquerque, New Mexico 87185, United States
  • Kevin R. Zavadil
    Kevin R. Zavadil
    Material, Physical, and Chemical Sciences Center, Sandia National Laboratories, Albuquerque, New Mexico 87185, United States
  • , and 
  • Kristin A. Persson*
    Kristin A. Persson
    Department of Materials Science and Engineering, University of California, Berkeley, California 94720, United States
    Energy Technologies Area, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
    *E-mail: [email protected]
Cite this: J. Phys. Chem. Lett. 2020, 11, 6, 2046–2052
Publication Date (Web):February 20, 2020
https://doi.org/10.1021/acs.jpclett.0c00334
Copyright © 2020 American Chemical Society

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    Abstract

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    Detailed speciation of electrolytes as a function of chemical system and concentration provides the foundation for understanding bulk transport as well as possible decomposition mechanisms. In particular, multivalent electrolytes have shown a strong coupling between anodic stability and solvation structure. Furthermore, solvents that are found to exhibit reasonable stability against alkaline-earth metals generally exhibit low permittivity, which typically increases the complexity of the electrolyte species. To improve our understanding of ionic population and associated transport in these important classes of electrolytes, the speciation of Mg(TFSI)2 in monoglyme and diglyme systems is studied via a multiscale thermodynamic model using first-principles calculations for ion association and molecular dynamics simulations for dielectric properties. The results are then compared to Raman and dielectric relaxation spectroscopies, which independently confirm the modeling insights. We find that the significant presence of free ions in the low-permittivity glymes in the concentration range from 0.02 to 0.6 M is well-explained by the low-permittivity redissociation hypothesis. Here, salt speciation is largely dictated by long-range electrostatics, which includes permittivity increases due to polar contact ion pairs. The present results suggest that other low-permittivity multivalent electrolytes may also reach high conductivities as a result of redissociation.

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