Analytical Sciences

Abstract − Analytical Sciences, 35(3), 289 (2019).

Anion Coordination Characteristics of Ion-pair Complexes in Highly Concentrated Aqueous Lithium Bis(trifluoromethanesulfonyl)amide Electrolytes
Tatsuya TSURUMURA,*,** Yasushi HASHIMOTO,* Masayuki MORITA,* Yasuhiro UMEBAYASHI,*** and Kenta FUJII*
*Graduate School of Sciences and Technology for Innovation, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi 755-8611, Japan
**TAYCA CORPORATION, Okayama Research Laboratory, 1072 Nishikozai, Higashi, Okayama 704-8136, Japan
***Graduate School of Science and Engineering, Niigata University, 8050 Ikarashi, 2-no-cho, Nishi, Niigata 950-2181, Japan
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).