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Role of solvent-anion charge transfer in oxidative degradation of battery electrolytes

Author

Listed:
  • Eric R. Fadel

    (Harvard University
    Research and Technology Center
    Massachusetts Institute of Technology)

  • Francesco Faglioni

    (University of Modena and Reggio Emilia)

  • Georgy Samsonidze

    (Research and Technology Center)

  • Nicola Molinari

    (Harvard University
    Research and Technology Center)

  • Boris V. Merinov

    (California Institute of Technology)

  • William A. Goddard III

    (California Institute of Technology)

  • Jeffrey C. Grossman

    (Massachusetts Institute of Technology)

  • Jonathan P. Mailoa

    (Research and Technology Center)

  • Boris Kozinsky

    (Harvard University
    Research and Technology Center)

Abstract

Electrochemical stability windows of electrolytes largely determine the limitations of operating regimes of lithium-ion batteries, but the degradation mechanisms are difficult to characterize and poorly understood. Using computational quantum chemistry to investigate the oxidative decomposition that govern voltage stability of multi-component organic electrolytes, we find that electrolyte decomposition is a process involving the solvent and the salt anion and requires explicit treatment of their coupling. We find that the ionization potential of the solvent-anion system is often lower than that of the isolated solvent or the anion. This mutual weakening effect is explained by the formation of the anion-solvent charge-transfer complex, which we study for 16 anion-solvent combinations. This understanding of the oxidation mechanism allows the formulation of a simple predictive model that explains experimentally observed trends in the onset voltages of degradation of electrolytes near the cathode. This model opens opportunities for rapid rational design of stable electrolytes for high-energy batteries.

Suggested Citation

  • Eric R. Fadel & Francesco Faglioni & Georgy Samsonidze & Nicola Molinari & Boris V. Merinov & William A. Goddard III & Jeffrey C. Grossman & Jonathan P. Mailoa & Boris Kozinsky, 2019. "Role of solvent-anion charge transfer in oxidative degradation of battery electrolytes," Nature Communications, Nature, vol. 10(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:10:y:2019:i:1:d:10.1038_s41467-019-11317-3
    DOI: 10.1038/s41467-019-11317-3
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    Cited by:

    1. Bandara, T.G. Thusitha Asela & Viera, J.C. & González, M., 2022. "The next generation of fast charging methods for Lithium-ion batteries: The natural current-absorption methods," Renewable and Sustainable Energy Reviews, Elsevier, vol. 162(C).

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