Molecular dynamics study of thermodynamic stability and dynamics of [Li(glyme)] + complex in lithium-glyme solvate ionic liquids

• Published in: The Journal of chemical physics Vol. 148; no. 19; p. 193809
• Main Authors: Shinoda, Wataru, Hatanaka, Yuta, Hirakawa, Masashi, Okazaki, Susumu, Tsuzuki, Seiji, Ueno, Kazuhide, Watanabe, Masayoshi
• Format: Journal Article
• Language: English
• Published: United States 21.05.2018
• ISSN: 1089-7690
• DOI: 10.1063/1.5009814

Equimolar mixtures of glymes and organic lithium salts are known to produce solvate ionic liquids, in which the stability of the [Li(glyme)] complex plays an important role in determining the ionic dynamics. Since these mixtures have attractive physicochemical properties for application as electrolytes, it is important to understand the dependence of the stability of the [Li(glyme)] complex on the ion dynamics. A series of microsecond molecular dynamics simulations has been conducted to investigate the dynamic properties of these solvate ionic liquids. Successful solvate ionic liquids with high stability of the [Li(glyme)] complex have been shown to have enhanced ion dynamics. Li-glyme pair exchange rarely occurs: its characteristic time is longer than that of ion diffusion by one or two orders of magnitude. Li-glyme pair exchange most likely occurs through cluster formation involving multiple [Li(glyme)] pairs. In this process, multiple exchanges likely take place in a concerted manner without the production of energetically unfavorable free glyme or free Li ions.