双(氟磺酰)亚胺锂在 273.15 K 至 313.15 K 有机溶剂中的溶解行为、热力学分析和分子模拟

IF 2.2 3区 工程技术 Q3 CHEMISTRY, PHYSICAL
Xin Fang, Bolun Mei, Xingchuan Yang, Yi Yu, Chunmei Cao, Li Xu, Guoji Liu
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引用次数: 0

摘要

在 273.15 K 至 313.15 K 的温度下,测定了 LiFSI 在乙醇、正丙醇、异丙醇、正丁醇、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、碳酸二甲酯、碳酸甲乙酯和碳酸二乙酯中的溶解度。温度升高可促使 LIFSI 在上述 11 种液体中继续混合。相比之下,在结构相似的溶剂分子的碳链上添加一个烷基会导致锂辉石油的溶解度降低。总体而言,LiFSI 在酯类中的摩尔溶解度明显高于其他四种醇类。此外,还通过经典方程拟合得到了相应的理论结果。拟合值与测量值的偏差表明,Apelblat 方程和 Yaws 模型能更有效地拟合 LiFSI 的溶解度。然后,用 Van't Hoff 方程讨论了电解质溶液的 ΔsolHo、ΔsolGo 和 ΔsolSo。结果表明,LiFSI 的溶解过程伴随着吸热和增熵过程。最后,通过分子可视化分析和分子动力学模拟计算了溶剂分子极性指数和溶解自由能,并进行了溶解度顺序的相关分析,解释了分子特征对 LiFSI 溶解度的作用。静电相互作用和分子极性是决定其溶解极限的主要因素。这些结果将为提纯 LiFSI 和开发新的电解质溶液提供有价值的参考。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Dissolution behavior, thermodynamic analysis and molecular simulation of lithium bis(fluorosulfonyl)imide in organic solvent at 273.15 K to 313.15 K

Dissolution behavior, thermodynamic analysis and molecular simulation of lithium bis(fluorosulfonyl)imide in organic solvent at 273.15 K to 313.15 K

Dissolution behavior, thermodynamic analysis and molecular simulation of lithium bis(fluorosulfonyl)imide in organic solvent at 273.15 K to 313.15 K

The solubility of LiFSI in ethanol, n-propanol, isopropanol, n-butanol, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate at 273.15 K to 313.15 K were determined. Elevated temperatures can actuate the continued mixing of LIFSI in the 11 fluids outlined above. In comparison, the addition of an alkyl group to the carbon chain of a structurally similar solvent molecule will result in a smaller solubility of LiFSI. Overall the molar solubility of LiFSI in esters are significantly higher than the other four alcohols. Besides, the corresponding theoretical results were mounted by fitting the classical equation. The deviation of the fitted values from the measured values showed that the Apelblat equation and Yaws model was more effectively in fitting the solubility of LiFSI. Then, The ΔsolHo, ΔsolGo, ΔsolSo of electrolyte solution were discussed by Van’t Hoff equation. Their fruits implied that the dissolution of LiFSI is found to be accompanied by heat absorption and entropy gain processes. Finally, the solvent molecular polarity index and solvation free energy were calculated by molecular visualization analysis and molecular dynamics simulation, and the correlation analysis with solubility order was carried out to illustrate the role of molecular features on the LiFSI solubility was explained. Electrostatic interactions and molecular polarity are the leading players in determining its solubility limit. These results will provide valuable reference for the purification of LiFSI and the development of new electrolyte solutions.

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来源期刊
Journal of Chemical Thermodynamics
Journal of Chemical Thermodynamics 工程技术-热力学
CiteScore
5.60
自引率
15.40%
发文量
199
审稿时长
79 days
期刊介绍: The Journal of Chemical Thermodynamics exists primarily for dissemination of significant new knowledge in experimental equilibrium thermodynamics and transport properties of chemical systems. The defining attributes of The Journal are the quality and relevance of the papers published. The Journal publishes work relating to gases, liquids, solids, polymers, mixtures, solutions and interfaces. Studies on systems with variability, such as biological or bio-based materials, gas hydrates, among others, will also be considered provided these are well characterized and reproducible where possible. Experimental methods should be described in sufficient detail to allow critical assessment of the accuracy claimed. Authors are encouraged to provide physical or chemical interpretations of the results. Articles can contain modelling sections providing representations of data or molecular insights into the properties or transformations studied. Theoretical papers on chemical thermodynamics using molecular theory or modelling are also considered. The Journal welcomes review articles in the field of chemical thermodynamics but prospective authors should first consult one of the Editors concerning the suitability of the proposed review. Contributions of a routine nature or reporting on uncharacterised materials are not accepted.
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