Li+ Solvation and Ionic Transport in Lithium Solvate Ionic Liquids ...
Supporting Information for
Li+ Solvation and Ionic Transport in Lithium Solvate Ionic Liquids Diluted by Molecular Solvents Kazuhide Ueno,a Junichi Murai,b Kohei Ikeda, b Seiji Tsuzuki,c Mizuho Tsuchiya, b Ryoichi Tatara,b Toshihiko Mandai, b Yasuhiro Umebayashi,d Kaoru Dokko,b and Masayoshi Watanabeb*
a
Graduate School of Medicine, Yamaguchi University, 2-16-1 Tokiwadai, Ube, 755-8611, Japan
b
Department of Chemistry and Biotechnology, Yokohama National University,79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan
c
Research Center for Computational Design of Advanced Functional Materials (CD-FMat), National
Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, Japan d
Graduate School of Science and Technology, Niigata University, 8050 Ikarashi, 2-no-cho, Nishi-ku, Niigata City, 950-2181, Japan
CORRESPONDING AUTHOR FOOTNOTE: To whom correspondence should be addressed. Telephone/Fax: +81-45-339-3955. E-mail: [email protected]
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Figure S1. Raman spectra (900800 cm−1) at different mixing ratios of solvent to SILs= (cS/cLi) for (a) water / [Li(G4)][TFSA], (b) AN/[Li(G4)][TFSA], and (c) toluene/[Li(G4)][TFSA].
Figure S2. Concentration dependence of the self-diffusion coefficients of the components in (a) [Li(G3)][TFSA] and (b) [Li(G4)][TFSA] diluted by AN at 30 °C.
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Figure S3. Optimized structures for [Li(solvent)n]+ complexes calculated by ab initio calculations at the MP2/6-311G**//HF/6-311G** level. Stabilization energies (kcal mol−1) are also shown for each structure.
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The complete author list for refs 37, 39, 41, and 46.
37. Dokko, K.; Tachikawa, N.; Yamauchi, K.; Tsuchiya, M.; Yamazaki, A.; Takashima, E.; Park, J.-W.; Ueno, K.; Seki, S.; Serizawa, N.; Watanabe, M. Solvate Ionic Liquid Electrolyte for Li–S Batteries. J. Electrochem. Soc. 2013, 160 (8), A1304-A1310. 39. Ueno, K.; Tatara, R.; Tsuzuki, S.; Saito, S.; Doi, H.; Yoshida, K.; Mandai, T.; Matsugami, M.; Umebayashi, Y.; Dokko, K.; Watanabe, M. Li+ Solvation in Glyme-Li Salt Solvate Ionic Liquids. Phys. Chem. Chem. Phys. 2015, 17 (12), 8248-8257. 41. Shimizu, K.; Freitas, A. A.; Atkin, R.; Warr, G. G.; FitzGerald, P. A.; Doi, H.; Saito, S.; Ueno, K.; Umebayashi, Y.; Watanabe, M.; Canongia Lopes, J. N. Structural and Aggregate Analyses of (Li salt + glyme) Mixtures: the Complex Nature of Solvate Ionic Liquids. Phys. Chem. Chem. Phys. 2015, 17 (34), 22321-22335. 46. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Gaussian, Inc.: Wallingford, CT, USA, 2009.
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Li+ Solvation and Ionic Transport in Lithium Solvate Ionic Liquids Diluted by Molecular Solvents Kazuhide Ueno,a Junichi Murai,b Kohei Ikeda, b Seiji Tsuzuki,c Mizuho Tsuchiya, b Ryoichi Tatara,b Toshihiko Mandai, b Yasuhiro Umebayashi,d Kaoru Dokko,b and Masayoshi Watanabeb*
a
Graduate School of Medicine, Yamaguchi University, 2-16-1 Tokiwadai, Ube, 755-8611, Japan
b
Department of Chemistry and Biotechnology, Yokohama National University,79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan
c
Research Center for Computational Design of Advanced Functional Materials (CD-FMat), National
Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, Japan d
Graduate School of Science and Technology, Niigata University, 8050 Ikarashi, 2-no-cho, Nishi-ku, Niigata City, 950-2181, Japan
CORRESPONDING AUTHOR FOOTNOTE: To whom correspondence should be addressed. Telephone/Fax: +81-45-339-3955. E-mail: [email protected]
1
Figure S1. Raman spectra (900800 cm−1) at different mixing ratios of solvent to SILs= (cS/cLi) for (a) water / [Li(G4)][TFSA], (b) AN/[Li(G4)][TFSA], and (c) toluene/[Li(G4)][TFSA].
Figure S2. Concentration dependence of the self-diffusion coefficients of the components in (a) [Li(G3)][TFSA] and (b) [Li(G4)][TFSA] diluted by AN at 30 °C.
2
Figure S3. Optimized structures for [Li(solvent)n]+ complexes calculated by ab initio calculations at the MP2/6-311G**//HF/6-311G** level. Stabilization energies (kcal mol−1) are also shown for each structure.
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The complete author list for refs 37, 39, 41, and 46.
37. Dokko, K.; Tachikawa, N.; Yamauchi, K.; Tsuchiya, M.; Yamazaki, A.; Takashima, E.; Park, J.-W.; Ueno, K.; Seki, S.; Serizawa, N.; Watanabe, M. Solvate Ionic Liquid Electrolyte for Li–S Batteries. J. Electrochem. Soc. 2013, 160 (8), A1304-A1310. 39. Ueno, K.; Tatara, R.; Tsuzuki, S.; Saito, S.; Doi, H.; Yoshida, K.; Mandai, T.; Matsugami, M.; Umebayashi, Y.; Dokko, K.; Watanabe, M. Li+ Solvation in Glyme-Li Salt Solvate Ionic Liquids. Phys. Chem. Chem. Phys. 2015, 17 (12), 8248-8257. 41. Shimizu, K.; Freitas, A. A.; Atkin, R.; Warr, G. G.; FitzGerald, P. A.; Doi, H.; Saito, S.; Ueno, K.; Umebayashi, Y.; Watanabe, M.; Canongia Lopes, J. N. Structural and Aggregate Analyses of (Li salt + glyme) Mixtures: the Complex Nature of Solvate Ionic Liquids. Phys. Chem. Chem. Phys. 2015, 17 (34), 22321-22335. 46. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M. J.; Heyd, J.; Brothers, E. N.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A. P.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Gaussian, Inc.: Wallingford, CT, USA, 2009.
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