Molecular-Level Insights into the Reactivity of Siloxane-Based Electrolytes at a Lithium-Metal Anode

Authors

  • Dr. Rajeev S. Assary,

    1. Materials Science Division, Argonne National Laboratory, Argonne, IL, 60439 (USA)
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    • These authors contributed equally to the work.

  • Dr. Jun Lu,

    1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL, 60439 (USA)
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    • These authors contributed equally to the work.

  • Xiangyi Luo,

    1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL, 60439 (USA)
    2. Metallurgical Engineering, Department, The University of Utah, Salt Lake City, UT 84112 (USA)
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    • These authors contributed equally to the work.

  • Dr. Xiaoyi Zhang,

    1. X-ray Science Division, Argonne National Laboratory, Argonne, IL, 60439 (USA)
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  • Dr. Yang Ren,

    1. X-ray Science Division, Argonne National Laboratory, Argonne, IL, 60439 (USA)
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  • Dr. Huiming Wu,

    1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL, 60439 (USA)
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  • Dr. Hassan M. Albishri,

    1. King Abdulaziz University, Faculty of Science, Chemistry Department, 80203 Jeddah (Saudi Arabia)
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  • Dr. D. Abd El-Hady,

    1. King Abdulaziz University, Faculty of Science, Chemistry Department, 80203 Jeddah (Saudi Arabia)
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  • Dr. A. S. Al-Bogami,

    1. King Abdulaziz University, Faculty of Science, Chemistry Department, 80203 Jeddah (Saudi Arabia)
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  • Dr. Larry A. Curtiss,

    Corresponding author
    1. Materials Science Division, Argonne National Laboratory, Argonne, IL, 60439 (USA)
    2. Center for Nanoscale Materials, Argonne National Laboratory, Argonne, IL, 60439 (USA)
    • Larry A. Curtiss, Materials Science Division, Argonne National Laboratory, Argonne, IL, 60439 (USA)===

      Khalil Amine, Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL, 60439 (USA)===

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  • Dr. Khalil Amine

    Corresponding author
    1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL, 60439 (USA)
    2. King Abdulaziz University, Faculty of Science, Chemistry Department, 80203 Jeddah (Saudi Arabia)
    • Larry A. Curtiss, Materials Science Division, Argonne National Laboratory, Argonne, IL, 60439 (USA)===

      Khalil Amine, Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL, 60439 (USA)===

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Abstract

A molecular-level understanding of the reactions that occur at the lithium-metal anode/electrolyte interphase is essential to improve the performance of Li–O2 batteries. Experimental and computational techniques are applied to explore the reactivity of tri(ethylene glycol)-substituted trimethylsilane (1NM3), a siloxane-based ether electrolyte, at the lithium-metal anode. In situ/ex situ X-ray diffraction and Fourier-transform infrared spectroscopy studies provide evidence of the formation of lithium hydroxide and lithium carbonates at the anode upon gradual degradation of the metallic lithium anode and the solvent molecules in the presence of oxygen. Density functional calculations performed to obtain a mechanistic understanding of the reductive decomposition of 1NM3 indicate that the decomposition does not require any apparent barrier to produce lithium hydroxide and lithium carbonates when the reduced 1NM3 solvent molecules interact with the oxygen crossing over from the cathode. This study indicates that degradation may be more significant in the case of the 1NM3 solvent, compared to linear ethers such as tetraglyme or dioxalone, because of its relatively high electron affinity. Also, both protection of the lithium metal and prevention of oxygen crossover to the anode are essential for minimizing electrolyte and anode decomposition.

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