Structural Effects of Solvents on Li-Ion-Hopping Conduction in Highly Concentrated LiBF4/Sulfone Solutions
- Yosuke UgataYosuke UgataDepartment of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, JapanMore by Yosuke Ugata
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- Shohei SasagawaShohei SasagawaDepartment of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, JapanMore by Shohei Sasagawa
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- Ryoichi TataraRyoichi TataraDepartment of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, JapanMore by Ryoichi Tatara
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- Kazuhide UenoKazuhide UenoDepartment of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, JapanAdvanced Chemical Energy Research Center, Institute of Advanced Sciences, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, JapanMore by Kazuhide Ueno
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- Masayoshi WatanabeMasayoshi WatanabeAdvanced Chemical Energy Research Center, Institute of Advanced Sciences, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, JapanMore by Masayoshi Watanabe
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- Kaoru Dokko*Kaoru Dokko*Email: [email protected]Department of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, JapanAdvanced Chemical Energy Research Center, Institute of Advanced Sciences, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, JapanUnit of Elements Strategy Initiative for Catalysts & Batteries (ESICB), Kyoto University, Kyoto 615-8510, JapanMore by Kaoru Dokko
Abstract
Li-ion-hopping conduction is known to occur in certain highly concentrated electrolytes, and this conduction mode is effective for achieving lithium batteries with high rate capabilities. Herein, we investigated the effects of the solvent structure on the hopping conduction of Li ions in highly concentrated LiBF4/sulfone electrolytes. Raman spectroscopy revealed that a Li+ ion forms complexes with sulfone and anions, and contact ion pairs and ionic aggregates are formed in the highly concentrated electrolytes. Li+ exchanges ligands (sulfone and BF4–) rapidly to produce unusual hopping conduction in highly concentrated electrolytes. The structure of the solvent significantly influences the hopping conduction process. We measured the self-diffusion coefficients of Li+ (DLi), anions (Danion), and sulfone solvents (Dsol) in electrolytes. The ratio of the self-diffusion coefficients (DLi/Dsol) tended to be higher for cyclic sulfones (sulfolane and 3-methylsulfolane) than for acyclic sulfones, which suggests that cyclic sulfone molecules facilitate Li-ion hopping. The hopping conduction increases the Li+-transference number (
) under anion-blocking conditions, and 
of [LiBF4]/[cyclic sulfone] = 1/2 is as high as 0.8.
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