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Anion Coordination Characteristics of Ion-pair Complexes in Highly Concentrated Aqueous Lithium Bis(trifluoromethane- sulfonyl)amide Electrolytes

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Abstract

We report on the structures of Li-ion complexes in salt-concentrated aqueous electrolytes based on lithium bis(trifluoromethanesulfonyl)amide (LiTFSA), particularly focusing on the anion coordination behavior of the ion-pair complexes in the high concentration region cLi> 3.0 mol dm-3. Quantitative data analysis of the Raman spectra revealed the following. (1) Li ions do not coordinate with TFSA anions at lower cLi (<3.0 mol dm-3) to exist as ion pair-free ions. (2) In the concentrated region (cli= 3.0 - 4.0 mol dm-3), the TFSA anions coordinate as monodentate ligands (mono- TFSA) with Li ions to form ion-pair complexes and coexist with free TFSA in the bulk. (3) Further increasing the cLi(4.0 -5.2 mol dm-3) results in both monodentate and bidentate coordination (bi-TFSA) modes of TFSA anions to Li ions, yielding complicated ion-pair complexes in the first coordination sphere. The Walden plots, based on ionic conductivity and viscosity data, implied that the ion-conducting mechanism in the highly salt-concentrated region was considerably different from that in the dilute region (i.e., vehicle mechanism).

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Acknowledgments

This work was supported by the Japan Society for the Promotion of Science (JSPS), KAKENHI (No. 15K17877 for K. F.).

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Authors and Affiliations

  1. Graduate School of Sciences and Technology for Innovation, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi, 755-8611, Japan

    Tatsuya Tsurumura, Yasushi Hashimoto, Masayuki Morita & Kenta Fujii

  2. TAYCA CORPORATION, Okayama Research Laboratory, 1072 Nishikozai, Higashi, Okayama, 704-8136, Japan

    Tatsuya Tsurumura

  3. Graduate School of Science and Engineering, Niigata University, 8050 Ikarashi, 2-no-cho, Nishi, Niigata, 950-2181, Japan

    Yasuhiro Umebayashi

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  1. Tatsuya Tsurumura
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  2. Yasushi Hashimoto
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  3. Masayuki Morita
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  4. Yasuhiro Umebayashi
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  5. Kenta Fujii
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Correspondence to Kenta Fujii.

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Tsurumura, T., Hashimoto, Y., Morita, M. et al. Anion Coordination Characteristics of Ion-pair Complexes in Highly Concentrated Aqueous Lithium Bis(trifluoromethane- sulfonyl)amide Electrolytes. ANAL. SCI. 35, 289–294 (2019). https://doi.org/10.2116/analsci.18P407

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