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Toward Improved Anodic Stability of Ether-Based Electrolytes for Rechargeable Magnesium Batteries

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Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. C 2023, 127, 22, 10419-10433
    C: Energy Conversion and Storage

    Toward Improved Anodic Stability of Ether-Based Electrolytes for Rechargeable Magnesium Batteries
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    • Toshihiko Mandai*
      Toshihiko Mandai
      Center for Green Research on Energy and Environmental Materials, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
      Center for Advanced Battery Collaboration, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
      *Email: [email protected]. Tel: +81-29-860-4464.
      More by Toshihiko Mandai
      Orcidhttps://orcid.org/0000-0002-2403-7794
    • Masaru Yao
      Masaru Yao
      Research Institute of Electrochemical Energy, Department of Energy and Environment, National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, Japan
      More by Masaru Yao
      Orcidhttps://orcid.org/0000-0002-5940-833X
    • Keitaro Sodeyama
      Keitaro Sodeyama
      Center for Advanced Battery Collaboration, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
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      Orcidhttps://orcid.org/0000-0002-9228-0729
    • Akiko Kagatsume
      Akiko Kagatsume
      Center for Green Research on Energy and Environmental Materials, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
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    • Yoshitaka Tateyama
      Yoshitaka Tateyama
      Center for Green Research on Energy and Environmental Materials, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
      Center for Advanced Battery Collaboration, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
      More by Yoshitaka Tateyama
      Orcidhttps://orcid.org/0000-0002-5532-6134
    • Hiroaki Imai
      Hiroaki Imai
      Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku, Yokohama 223-8522, Japan
      More by Hiroaki Imai
      Orcidhttps://orcid.org/0000-0001-6332-9514
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2023, 127, 22, 10419–10433
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    https://doi.org/10.1021/acs.jpcc.3c01452
    Published May 29, 2023
    Copyright © 2023 American Chemical Society
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    Abstract

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    Rechargeable magnesium batteries (RMBs) are one of the promising energy-storage technologies for sustainable energy storage due to the abundant resources and intrinsically remarkable energy-storage properties of magnesium metal. However, to compete with alternative technologies, such as present lithium-ion batteries, there is a need to improve their energy density. One of the approaches to accomplish the above demand is to use high-voltage cathodes. The poor anodic stability of the current ether-based electrolytes compatible with magnesium metal anodes limits their working voltage and the choice of electrode materials. In this study, we explored different organic solvent-based electrolytes to design anodically stable ether-based electrolyte solutions for RMB applications. Through comprehensive experimental and computational surveys, we found that the intrinsic electrochemical/chemical stabilities against magnesium metal and the well-balanced solvating ability were necessary to achieve the desired functionality. Based on this knowledge, we designed and synthesized glyme analogues bearing trifluoroalkyl groups. Consequently, we developed anodically stable electrolytes that support electrochemical magnesium deposition/dissolution by combining suitable fluorinated glyme-based solvents with appropriate conducting salts. These electrolytes showed a remarkable anodic limit of 4.4 V vs Mg2+/Mg (the highest ever reported to the best of our knowledge) and effectively suppressed the undesired corrosion of Al current collectors. However, these electrolytes could not be applied to RMBs with high-voltage oxide-based cathodes. Fragility against oxide-based cathodes caused undesired catalytic decomposition of the fluorinated solvents during charging.

    Copyright © 2023 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/acs.jpcc.3c01452.

    • Oxidation and reduction energies of the fluorinated glyme analogues and anions (Table S1); NMR spectra of the synthesized GnTFE and GnTFP (Figures S1–S4); CV profiles of a series of electrolyte solutions incorporating Mg[B(HFIP)4]2 (Figures S5–S8); ionic conductivities of the selected electrolyte solutions (Figure S9); CV profiles of Mg[Al(HFIP)4]2/EiPS (Figure S10) and Mg[B(HFIP)4]2/ethyl methyl sulfone-G2 (Figure S11); molecular structures of fluorinated and sulfonated glyme analogues (Figure S12); CV profiles of Mg[B(HFIP)4]2 dissolved in G5-S2 (Figure S13) and G2TFP (Figure S14); digital images of Mg[B(HFIP)4]2 salt and its G2TFE solution (Figure S15); CV profiles of Mg[Al(HFIP)4]2/GnTFE (Figure S16); ionic conductivities of Mg[Al(HFIP)4]2/Gn and Mg[Al(HFIP)4]2/GnTFE (Figure S17); discharge–charge profiles of [Mg | Mg[Al(HFIP)4]2/GnTFE | MgMn2O4] cells using three-electrode setup (Figure S18); and chronoamperograms of MgMn2O4 in Mg[Al(HFIP)4]2/GnTFE (Figure S19) (PDF)

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    This article is cited by 7 publications.

    1. Kohei Uosaki, Masayoshi Watanabe, Kiyoshi Kanamura, Shuji Nakanishi, Masahiro Tatsumisago, Kazunori Takada, Shen Ye. Research and Development of Novel Secondary Batteries in Japan. The Journal of Physical Chemistry C 2023, 127 (47) , 22865-22867. https://doi.org/10.1021/acs.jpcc.3c07076
    2. Yasuhiro Domi, Hiroyuki Usui, Hiroki Sakaguchi. Analysis of the interfacial reaction between Si-based anodes and electrolytes in Li-ion batteries. Chemical Communications 2024, 60 (89) , 12986-12999. https://doi.org/10.1039/D4CC04134H
    3. Toshihiko MANDAI. Solvation Structure Analysis by a Combination of Crystallography and Raman Spectroscopy, and Its Application to the Development of Functional Electrolytes for Next Generation Rechargeable Batteries. Denki Kagaku 2024, 92 (2) , 136-143. https://doi.org/10.5796/denkikagaku.24-TE0004
    4. Toshihiko Mandai, Umi Tanaka, Mariko Watanabe. Mg–Zn–Cl-integrated functional interface for enhancing the cycle life of Mg electrodes. Energy Storage Materials 2024, 67 , 103302. https://doi.org/10.1016/j.ensm.2024.103302
    5. Chaoxin Wu, Linlin Xue, Runjing Xu, Jinchen Fan, Tianjun Chen, Wei Tang, Lifeng Cui, Aoxuan Wang, Shi Xue Dou, Chengxin Peng. Toward high-energy magnesium battery anode: recent progress and future perspectives. Materials Today Energy 2024, 40 , 101485. https://doi.org/10.1016/j.mtener.2023.101485
    6. Gunther Brunklaus, Peter Lennartz, Martin Winter. Metal electrodes for next-generation rechargeable batteries. Nature Reviews Electrical Engineering 2024, 1 (2) , 79-92. https://doi.org/10.1038/s44287-023-00006-5
    7. Svetlozar Ivanov. Corrosion of Current Collectors in Metal-Ion Batteries. 2024, 251-288. https://doi.org/10.1007/978-3-031-57012-4_11
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2023, 127, 22, 10419–10433
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpcc.3c01452
    Published May 29, 2023
    Copyright © 2023 American Chemical Society
    Request reuse permissions

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