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 c > 3.0 mol dm. Quantitative data analysis of the Raman spectra revealed the following. (1) Li ions do not coordinate with TFSA anions at lower c (<3.0 mol dm) to exist as ion pair-free ions. (2) In the concentrated region (c = 3.0 - 4.0 mol dm), 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 c (4.0 - 5.2 mol dm) 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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http://dx.doi.org/10.2116/analsci.18P407DOI Listing

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