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Anion Association Strength as a Unifying Descriptor for the Reversibility of Divalent Metal Deposition in Nonaqueous Electrolytes

  • Justin G. Connell*
    Justin G. Connell
    Joint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United States
    Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
    *Email: [email protected]
  • Milena Zorko
    Milena Zorko
    Joint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United States
    Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
    Department of Materials Chemistry, National Institute of Chemistry, Hajdrihova 19, Ljubljana SI-1000, Slovenia
    More by Milena Zorko
  • Garvit Agarwal
    Garvit Agarwal
    Joint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United States
    Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
  • Mengxi Yang
    Mengxi Yang
    Joint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United States
    Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
    More by Mengxi Yang
  • Chen Liao
    Chen Liao
    Joint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United States
    Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
    More by Chen Liao
  • Rajeev S. Assary
    Rajeev S. Assary
    Joint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United States
    Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
  • Dusan Strmcnik
    Dusan Strmcnik
    Joint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United States
    Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
  • , and 
  • Nenad M. Markovic
    Nenad M. Markovic
    Joint Center for Energy Storage Research, Argonne National Laboratory, Lemont, Illinois 60439, United States
    Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
Cite this: ACS Appl. Mater. Interfaces 2020, 12, 32, 36137–36147
Publication Date (Web):July 15, 2020
https://doi.org/10.1021/acsami.0c09404
Copyright © 2020 American Chemical Society

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    Abstract

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    Developing next-generation battery chemistries that move beyond traditional Li-ion systems is critical to enabling transformative advances in electrified transportation and grid-level energy storage. In this work, we provide the first evidence for common descriptors for improved reversibility of metal plating/stripping in nonaqueous electrolytes for multivalent ion batteries. Focusing first on the specific role of chloride (Cl) in promoting electrochemical reversibility in multivalent systems, rotating disk (RDE) and ring-disk electrode (RRDE) investigations were performed utilizing a variety of divalent cations (Mg2+, Zn2+, and Cu2+) and the bis-(trifluoromethane sulfonyl) imide (TFSI) anion. By introducing varying concentrations of Cl, a cooperative effect is observed between TFSI and Cl that yields the more reversible behavior of mixed electrolytes relative to electrolytes containing only TFSI. This effect is shown to be general for Mg, Zn, and Cu electrodeposition, and mechanistic understanding of the role of Cl in improving reversibility of TFSI-based electrolytes is obtained through the combination of R(R)DE experimental results and density functional theory (DFT) evaluation of the redox activity and thermodynamic stability of various TFSI- and Cl-based solution complexes of metal ions. The cooperative anion effect is further generalized to other mixed-anion systems, where systematic variations in anion association strength predicted from DFT (i.e., Cl > OTf ≈ TFSI > BF4 > PF6) yield corresponding trends in redox potentials and improvements of ≥200 mV in the reversibility of metal deposition/dissolution. These results identify anion association strength as a common descriptor for the reversibility of divalent metal anodes and suggest a set of general design principles for developing new electrolytes with improved activity and stability.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.0c09404.

    • Additional electrochemical measurements and results of DFT calculations summarizing reduction potentials and binding energies of multiple Zn2+ and Mg2+ complexes with diglyme, Cl, TFSI, OTf, BF4, and PF6 (PDF)

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    Cited By

    This article is cited by 22 publications.

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    18. Zhenzhen Yang, Mengxi Yang, Nathan T. Hahn, Justin Connell, Ira Bloom, Chen Liao, Brian J. Ingram, Lynn Trahey. Toward practical issues: Identification and mitigation of the impurity effect in glyme solvents on the reversibility of Mg plating/stripping in Mg batteries. Frontiers in Chemistry 2022, 10 https://doi.org/10.3389/fchem.2022.966332
    19. Juan D. Forero‐Saboya, Deyana S. Tchitchekova, Patrik Johansson, M. Rosa Palacín, Alexandre Ponrouch. Interfaces and Interphases in Ca and Mg Batteries. Advanced Materials Interfaces 2022, 9 (8) https://doi.org/10.1002/admi.202101578
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