密度泛函理论在高电压电解液设计中的应用

doi:10.16085/j.issn.1000-6613.2018-1808

摘要/Abstract

摘要：

基于密度泛函理论的量子化学计算为高电压电解液的配方设计提供了理论基础。运用Gaussian软件可以有效模拟电解液中某一成分的分子构型和溶剂化状态，计算出化合物的分解路径与分解产物，进而大幅缩短电解液研发周期。本文回顾了近年来该计算方法在锂离子电池电解液研究中的相关进展，并以高电压电解液为例，介绍了该理论在溶剂氧化电位计算方面的应用，结合分子模型的优化，实现了计算值与实验值的基本统一。此外，详细阐述了砜类、氟类、离子液体等几种新型高电压溶剂和磷酸酯类、硼类、腈类等几种成膜添加剂的应用。相信今后随着动力学理论的完善和计算机技术的优化，该方法在高浓度电解液、固液界面作用机理等当前难以实现的理论模拟问题方面的应用指日可待。

关键词: 动力学理论, 计算机模拟, 电化学, 电解液, 氧化

Abstract:

Based on the density function theory (DFT), quantum chemistry calculation provides a platform to design high voltage electrolytes. Gaussian software, developed for DFT application, has been successfully used in simulating the molecular structure of electrolytes, optimizing their solvation state and predicting the decomposition pathway and compositions of the products. By using the software, the time cost in research and development (R&D) can be greatly reduced. In this review, the recent progress of DFT in simulation of lithium-ion battery electrolyte was summarized. Furthermore, taking the R&D of high-voltage electrolyte as an example, we introduced the application of DFT in calculating the oxidation potential of the electrolytes, from which good agreement between theoretical calculation and experimental result was confirmed. Moreover, the application of DFT method was further introduced in the research for different solvents (e.g. sulfones, fluorinated carbonates and ionic liquids) and functional additives (e.g. phosphates, borates and nitriles) for high potential electrolytes. It is expected that with the improvement in kinetic theory and the optimization technique, many problems in simulation of concentrated electrolyte, solid-liquid interface mechanism, and etc. , would be solved imminently.

Key words: kinetic theory, computer simulation, electrochemistry, electrolyte, oxidation

中图分类号:

TM912

李南, 马国强, 车海英, 蒋志敏, 沈旻, 董经博, 陈慧闯, 马紫峰. 密度泛函理论在高电压电解液设计中的应用[J]. 化工进展, 2019, 38(07): 3253-3264.

Nan LI, Guoqiang MA, Haiying CHE, Zhimin JIANG, Min SHEN, Jingbo DONG, Huichuang CHEN, Zifeng MA. Application of density functional theory in the design of high potential electrolyte[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3253-3264.

图/表 12

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分子名称	HOMO/eV	LUMO/eV
EC	-8.468	-0.604
DMC	-8.179	-0.370
EMC	-8.133	-0.256
DEC	-8.055	-0.268

分子名称	HOMO/eV	LUMO/eV
EC	-8.468	-0.604
DMC	-8.179	-0.370
EMC	-8.133	-0.256
DEC	-8.055	-0.268

体系	ε=1	ε=4.2	ε=20.5	ε=78.4
DMC/BF₄ ^-	4.14	5.79	6.21	6.29
EC/BF₄ ^-	4.55	5.95	6.28	6.34
PC/BF₄ ^-	4.57	—	6.25	—
TMS/BF₄ ^-	5.23	6.33	6.49	6.52
DMC/PF₆ ^-	4.56	6.12	6.51	6.58
EC/PF₆ ^-	4.94	6.27	6.57	6.63
TMS/PF₆ ^-	5.44	6.36	6.54	6.57
EMS/PF₆ ^-	5.46	6.47	6.66	6.69
PMS/PF₆ ^-	4.29	5.55	5.84	5.89

体系	ε=1	ε=4.2	ε=20.5	ε=78.4
DMC/BF₄ ^-	4.14	5.79	6.21	6.29
EC/BF₄ ^-	4.55	5.95	6.28	6.34
PC/BF₄ ^-	4.57	—	6.25	—
TMS/BF₄ ^-	5.23	6.33	6.49	6.52
DMC/PF₆ ^-	4.56	6.12	6.51	6.58
EC/PF₆ ^-	4.94	6.27	6.57	6.63
TMS/PF₆ ^-	5.44	6.36	6.54	6.57
EMS/PF₆ ^-	5.46	6.47	6.66	6.69
PMS/PF₆ ^-	4.29	5.55	5.84	5.89

分子构型	结合能/kJ·mol^-1	分子构型	结合能/kJ·mol^-1	分子构型	结合能/kJ·mol^-1
PC-Li-AsF₆	-120.5	2PC-Li-AsF₆	-108.9	3PC-Li-AsF₆	-83.4
3PC-Li-AsF₆-PC	-66.7	3PC-Li-AsF₆-2PC	-75.6	3PC-Li-AsF₆-3PC	-94.6
3PC-Li-AsF₆-4PC	-86.1	4PC-Li-AsF₆-4PC	-117.0	PC-Li-PF₆	-118.8
2PC-Li-PF₆	-110.3	3PC-Li-PF₆	-83.7	3PC-Li-PF₆-PC	-59.3
3PC-Li-PF₆-2PC	-82.7	3PC-Li-PF₆-3PC	-92.3	3PC-Li-PF₆-4PC	-90.7
4PC-Li-PF₆-4PC	-116.5	PC-Li-BF₄	-115.0	2PC-Li-BF₄	-103.0
3PC-Li-BF₄	-72.5	3PC-Li-BF₄-PC	-64.6	3PC-Li-BF₄-2PC	-175.9
3PC-Li-BF₄-3PC	-108.5	3PC-Li-BF₄-4PC	-89.5	4PC-Li-BF₄-4PC	-82.4
PC-Li-ClO₄	-116.8	2PC-Li-ClO₄	-103.5	3PC-Li-ClO₄	-86.5
3PC-Li-ClO₄-PC	-57.9	3PC-Li-ClO₄-2PC	-75.2	3PC-Li-ClO₄-3PC	-100.0
3PC-Li-ClO₄-4PC	-100.6	4PC-Li-ClO₄-4PC	-97.8