Magnetism in Lithium–Oxygen Discharge Product

Authors

  • Dr. Jun Lu,

    1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL (USA)
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    • These authors contributed equally to this work.

  • Dr. Hun-Ji Jung,

    1. Department of WCU Energy Engineering, Hanyang University, Seoul 133-791 (South Korea)
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    • These authors contributed equally to this work.

  • Dr. Kah Chun Lau,

    1. Materials Science Division, Argonne National Laboratory, Argonne, IL (USA)
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    • These authors contributed equally to this work.

  • Dr. Zhengcheng Zhang,

    1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL (USA)
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    • These authors contributed equally to this work.

  • Dr. John A. Schlueter,

    1. Materials Science Division, Argonne National Laboratory, Argonne, IL (USA)
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  • Dr. Peng Du,

    1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL (USA)
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  • Dr. Rajeev S. Assary,

    1. Materials Science Division, Argonne National Laboratory, Argonne, IL (USA)
    2. Chemical Engineering Department, Northwestern University, Evanston, IL (USA)
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  • Prof. Jeffrey Greeley,

    1. Center for Nanoscale Materials, Argonne National Laboratory, Argonne, IL (USA)
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  • Dr. Glen A. Ferguson,

    1. Materials Science Division, Argonne National Laboratory, Argonne, IL (USA)
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  • Dr. Hsien-Hau Wang,

    1. Materials Science Division, Argonne National Laboratory, Argonne, IL (USA)
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  • Dr. Jusef Hassoun,

    1. Department of Chemistry, University of Rome, Sapienza, 00185, Rome (Italy)
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  • Dr. Hakim Iddir,

    1. Materials Science Division, Argonne National Laboratory, Argonne, IL (USA)
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  • Dr. Jigang Zhou,

    1. Canadian Light Source, Saskatoon, SK, S7N 0X4 (Canada)
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  • Dr. Lucia Zuin,

    1. Canadian Light Source, Saskatoon, SK, S7N 0X4 (Canada)
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  • Dr. Yongfeng Hu,

    1. Canadian Light Source, Saskatoon, SK, S7N 0X4 (Canada)
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  • Prof. Yang-Kook Sun,

    Corresponding author
    1. Department of WCU Energy Engineering, Hanyang University, Seoul 133-791 (South Korea)
    2. Department of Chemical Engineering, Hanyang University, Seoul 133-791 (South Korea)
    • Yang-Kook Sun, Department of WCU Energy Engineering, Hanyang University, Seoul 133-791 (South Korea)

      Larry A. Curtiss, Materials Science Division, Argonne National Laboratory, Argonne, IL (USA)

      Kahlil Amine, Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL (USA)

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  • Prof. Bruno Scrosati,

    1. Department of WCU Energy Engineering, Hanyang University, Seoul 133-791 (South Korea)
    2. Department of Chemistry, University of Rome, Sapienza, 00185, Rome (Italy)
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  • Dr. Larry A. Curtiss,

    Corresponding author
    1. Materials Science Division, Argonne National Laboratory, Argonne, IL (USA)
    2. Department of Chemistry, University of Rome, Sapienza, 00185, Rome (Italy)
    • Yang-Kook Sun, Department of WCU Energy Engineering, Hanyang University, Seoul 133-791 (South Korea)

      Larry A. Curtiss, Materials Science Division, Argonne National Laboratory, Argonne, IL (USA)

      Kahlil Amine, Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL (USA)

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  • Dr. Kahlil Amine

    Corresponding author
    1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL (USA)
    • Yang-Kook Sun, Department of WCU Energy Engineering, Hanyang University, Seoul 133-791 (South Korea)

      Larry A. Curtiss, Materials Science Division, Argonne National Laboratory, Argonne, IL (USA)

      Kahlil Amine, Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL (USA)

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Abstract

Nonaqueous lithium–oxygen batteries have a much superior theoretical gravimetric energy density compared to conventional lithium-ion batteries, and thus could render long-range electric vehicles a reality. A molecular-level understanding of the reversible formation of lithium peroxide in these batteries, the properties of major/minor discharge products, and the stability of the nonaqueous electrolytes is required to achieve successful lithium–oxygen batteries. We demonstrate that the major discharge product formed in the lithium–oxygen cell, lithium peroxide, exhibits a magnetic moment. These results are based on dc-magnetization measurements and a lithium–oxygen cell containing an ether-based electrolyte. The results are unexpected because bulk lithium peroxide has a significant band gap. Density functional calculations predict that superoxide-type surface oxygen groups with unpaired electrons exist on stoichiometric lithium peroxide crystalline surfaces and on nanoparticle surfaces; these computational results are consistent with the magnetic measurement of the discharged lithium peroxide product as well as EPR measurements on commercial lithium peroxide. The presence of superoxide-type surface oxygen groups with spin can play a role in the reversible formation and decomposition of lithium peroxide as well as the reversible formation and decomposition of electrolyte molecules.

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