Molecular dynamics study of thermodynamic stability and dynamics of [Li(glyme)]+ complex in lithium-glyme solvate ionic liquids.
Molecular dynamics study of thermodynamic stability and dynamics of [Li(glyme)]+ complex in lithium-glyme solvate ionic liquids.
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锂-甘醇二甲醚溶剂化离子液体中[Li(甘醇二甲醚)]配合物的热力学稳定性和动力学的分子动力学研究。
DOI：
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发表时间：
2018
影响因子：
4.4
通讯作者：
M. Watanabe
中科院分区：
文献类型：
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作者：
W. Shinoda;Yuta Hatanaka;M. Hirakawa;S. Okazaki;S. Tsuzuki;K. Ueno;M. Watanabe
已知glyme和有机锂盐的等摩尔混合物可产生溶剂化离子液体，其中[Li(glyme)]+配合物的稳定性在决定离子动力学方面起着重要作用。由于这些混合物具有吸引人的物理化学性质，可以用作电解质，因此了解[Li(glyme)]+配合物的稳定性对离子动力学的依赖是很重要的。通过一系列的微秒分子动力学模拟研究了这些溶剂化物离子液体的动力学性质。具有高稳定性的[Li(glyme)]+配合物的溶剂化物离子液体已被证明具有增强的离子动力学。Li-glyme对交换很少发生，其特征时间比离子扩散的特征时间长一到两个数量级。Li-glyme对交换最可能发生在包含多个[Li(glyme)]+对的团簇形成过程中。在这个过程中，多种交换可能以协调一致的方式进行，而不会产生能量上不利的自由甘氨酸或自由Li+离子。
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.