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Insights into Spontaneous Solid Electrolyte Interphase Formation at Magnesium Metal Anode Surface from Ab Initio Molecular Dynamics Simulations

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    Surfaces, Interfaces, and Applications

    Insights into Spontaneous Solid Electrolyte Interphase Formation at Magnesium Metal Anode Surface from Ab Initio Molecular Dynamics Simulations
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    • Garvit Agarwal*
      Garvit Agarwal
      Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
      Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
      *Email: [email protected]
      More by Garvit Agarwal
      Orcidhttps://orcid.org/0000-0002-7814-6072
    • Jason D. Howard
      Jason D. Howard
      Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
      Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
      More by Jason D. Howard
      Orcidhttps://orcid.org/0000-0002-6786-3076
    • Venkateshkumar Prabhakaran
      Venkateshkumar Prabhakaran
      Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
      Pacific Northwest National Laboratory, Richland, Washington 99352, United States
      More by Venkateshkumar Prabhakaran
      Orcidhttps://orcid.org/0000-0001-6692-6488
    • Grant E. Johnson
      Grant E. Johnson
      Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
      Pacific Northwest National Laboratory, Richland, Washington 99352, United States
      More by Grant E. Johnson
      Orcidhttps://orcid.org/0000-0003-3352-4444
    • Vijayakumar Murugesan
      Vijayakumar Murugesan
      Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
      Pacific Northwest National Laboratory, Richland, Washington 99352, United States
      More by Vijayakumar Murugesan
      Orcidhttps://orcid.org/0000-0001-6149-1702
    • Karl T. Mueller
      Karl T. Mueller
      Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
      Pacific Northwest National Laboratory, Richland, Washington 99352, United States
      More by Karl T. Mueller
      Orcidhttps://orcid.org/0000-0001-9609-9516
    • Larry A. Curtiss
      Larry A. Curtiss
      Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
      Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
      More by Larry A. Curtiss
      Orcidhttps://orcid.org/0000-0001-8855-8006
    • Rajeev S. Assary*
      Rajeev S. Assary
      Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
      Joint Center for Energy Storage Research (JCESR), Argonne National Laboratory, Lemont, Illinois 60439, United States
      *Email: [email protected]. Phone: 630-252-3536.
      More by Rajeev S. Assary
      Orcidhttps://orcid.org/0000-0002-9571-3307
    Other Access OptionsSupporting Information (2)

    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2021, 13, 32, 38816–38825
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    https://doi.org/10.1021/acsami.1c07864
    Published August 6, 2021
    Copyright © 2021 UChicago Argonne LLC, Operator of Argonne National Laboratory. Published by American Chemical Society
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    Abstract

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    Spontaneous chemical reactivity at multivalent (Mg, Ca, Zn, Al) electrode surfaces is critical to solid electrolyte interphase (SEI) formation, and hence, directly affects the longevity of batteries. Here, we report an investigation of the reactivity of 0.5 M Mg(TFSI)2 in 1,2-dimethoxyethane (DME) solvent at a Mg(0001) surface using ab initio molecular dynamics (AIMD) simulations and detailed Bader charge analysis. Based on the simulations, the initial degradation reactions of the electrolyte strongly depend on the structure of the Mg(TFSI)2 species near the anode surface. At the surface, the dissociation of Mg(TFSI)2 species occurs via cleavage of the N–S bond for the solvent separated ion pair (SSIP) and via cleavage of the C–S bond for the contact ion pair (CIP) configuration. In the case of the CIP, both TFSI anions undergo spontaneous bond dissociation reactions to form atomic O, C, S, F, and N species adsorbed on the surface of the Mg anode. These products indicate that the initial SEI layer formed on the surface of the pristine Mg anode consists of a complex mixture of multiple components such as oxides, carbides, sulfides, fluorides, and nitrides. We believe that the atomic-level insights gained from these simulations will lay the groundwork for the rational design of tailored and functional interphases that are critical for the success of multivalent battery technology.

    Copyright © 2021 UChicago Argonne LLC, Operator of Argonne National Laboratory. Published by American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.1c07864.

    • Additional AIMD snapshots for the reduction reaction of 0.5 M Mg(TFSI)2 salt species in DME solvent on the Mg(0001) surface at different temperatures (350, 650, and 750 K). AIMD snapshots and Bader charge analysis of the reduction reaction of the TFSI-2 anion of the Mg(TFSI)2 species in the SSIP, CIP-1, and CIP-2 configurations. Six AIMD simulation movies showing the reduction reaction of the TFSI-1 and TFSI-2 anions of the Mg(TFSI)2 species in the SSIP, CIP-1, and CIP-2 configurations on the Mg(0001) surface (PDF)

    • Entire AIMD simulation of the reductive reaction of the TFSI-1 and TFSI-2 anions of Mg(TFSI)2 in the SSIP configuration (Movies S1a,b); entire AIMD simulation of the reduction reactions of the TFSI-1 and TFSI-2 anions of Mg(TFSI)2 species in the CIP-1 configuration (Movies S2a,b); entire AIMD simulations of the reduction reactions of the TFSI-1 and TFSI-2 anions of Mg(TFSI)2 in the CIP-2 configuration (Movies S3a,b) (ZIP)

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    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2021, 13, 32, 38816–38825
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsami.1c07864
    Published August 6, 2021
    Copyright © 2021 UChicago Argonne LLC, Operator of Argonne National Laboratory. Published by American Chemical Society
    Request reuse permissions

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