Liquid Structures and Transport Properties of Lithium Bis(fluorosulfonyl)amide/Glyme Solvate Ionic Liquids for Lithium Batteries
Shoshi Terada A , Kohei Ikeda A , Kazuhide Ueno A , Kaoru Dokko
A B C and Masayoshi Watanabe A
A Department of Chemistry and Biotechnology, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan.
B Unit of Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, Kyoto 615-8510, Japan.
C Corresponding author. Email: dokko-kaoru-js@ynu.ac.jp
Australian Journal of Chemistry 72(2) 70-80 https://doi.org/10.1071/CH18270
Submitted: 2 June 2018 Accepted: 9 August 2018 Published: 7 September 2018
Journal Compilation © CSIRO 2019 Open Access CC BY-NC-ND
Abstract
The liquid structures and transport properties of electrolytes composed of lithium bis(fluorosulfonyl)amide (Li[FSA]) and glyme (triglyme (G3) or tetraglyme (G4)) were investigated. Raman spectroscopy indicated that the 1 : 1 mixtures of Li[FSA] and glyme (G3 or G4) are solvate ionic liquids (SILs) comprising a cationic [Li(glyme)]+ complex and the [FSA]− anion. In Li[FSA]-excess liquids with Li[FSA]/glyme molar ratios greater than 1, anionic Lix[FSA]y(y – x)– complexes were formed in addition to the cationic [Li(glyme)]+ complex. Pulsed field gradient NMR measurements revealed that the self-diffusion coefficients of Li+ (DLi) and glyme (Dglyme) are identical in the Li[FSA]/glyme = 1 liquid, suggesting that Li+ and glyme diffuse together and that a long-lived cationic [Li(glyme)]+ complex is formed in the SIL. The ratio of the self-diffusion coefficients of [FSA]− and Li+, DFSA/DLi, was essentially constant at ~1.1–1.3 in the Li[FSA]/glyme < 1 liquid. However, DFSA/DLi increased rapidly as the amount of Li[FSA] increased in the Li[FSA]/glyme > 1 liquid, indicating that the ion transport mechanism in the electrolyte changed at the composition of Li[FSA]/glyme = 1. The oxidative stability of the electrolytes was enhanced as the Li[FSA] concentration increased. Furthermore, Al corrosion was suppressed in the electrolytes for which Li[FSA]/glyme > 1. A battery consisting of a Li metal anode, a LiNi1/3Mn1/3Co1/3O2 cathode, and Li[FSA]/G3 = 2 electrolyte exhibited a discharge capacity of 105 mA h g−1 at a current density of 1.3 mA cm−2, regardless of its low ionic conductivity of 0.2 mS cm−1.
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