探索氯化溶剂作为锂金属电池的电解质:DFT 和 MD 研究

IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL
Zhe Li, Jingwei Zhang, Weiwei Xie, Qing Zhao
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引用次数: 0

摘要

含氟溶剂电解质一直被认为是稳定锂金属电池(LMB)中高压阴极和锂阳极相间的一种有前途的策略。然而,严格的合成方法和高昂的成本导致人们需要开发具有适合锂金属电池特性的高性价比溶剂。在此,我们利用密度泛函理论(DFT)和经典分子动力学(MD)模拟探索了使用氯化物溶剂作为电解质的可能性。以醚(1,2-二甲氧基乙烷 [DME]、1,3-二氧戊环 [DOL])、碳酸酯(碳酸二甲酯 [DMC] 和碳酸乙烯酯 [EC])为例,我们首先比较了 Cl 和 F 取代后最高占位分子轨道(HOMO)和最低未占位分子轨道(LUMO)的能量变化。我们特别发现,1,2-双(氯甲氧基)乙烷(DME-2Cl-2)在与 Li+ 配位后,在氯化二甲醚中具有最低的 HOMO 和最高的 LUMO 水平,因而具有潜在的宽电压稳定性。进一步的 MD 模拟显示,与二甲醚和 1,2-双(氟甲氧基)乙烷(DME-2F-2)相比,DME-2Cl-2 中的锂离子与溶剂的溶解配位较弱,但与阴离子的相互作用较强,这更有利于形成稳定的阴离子衍生固态电解质相(SEI)。我们的研究结果表明,氯化溶剂可用作 LMB 的理想电解质。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Exploring Chlorinated Solvents as Electrolytes for Lithium Metal Batteries: A DFT and MD Study

Exploring Chlorinated Solvents as Electrolytes for Lithium Metal Batteries: A DFT and MD Study

Electrolytes with fluorinated solvents have been regarded as a promising strategy to stabilize high-voltage cathodes and the interphase of lithium anode in lithium metal batteries (LMBs). However, the rigorous synthesis approach and high cost have led to a demand for developing cost-effective solvents with suitable properties for LMBs. Herein, we explored the possibility of using chlorinate solvents as electrolytes using density functional theory (DFT) and classical molecular dynamics (MD) simulation. Taking ether (1,2-dimethoxyethane [DME], 1,3-dioxolane [DOL]), carbonate (dimethyl carbonate [DMC], and ethylene carbonate [EC]) as examples, we first compared the energy variation of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) upon Cl and F substitution. In particular, we found that 1,2-bis(chloromethoxy)ethane (DME-2Cl-2) has the lowest HOMO and the highest LUMO level among the chlorinated DME after coordinating with Li+, enabling a potentially wide voltage stability. Further MD simulation reveals that lithium ions in DME-2Cl-2 has a weaker solvation coordination with solvents but stronger interaction with anions than DME and 1,2-bis(Fluoromethoxy)ethane (DME-2F-2), which is more beneficial for forming stable anion-derived solid electrolyte interphase (SEI). Our findings suggest that chlorinated solvents can be used as promising electrolytes for LMBs.

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来源期刊
International Journal of Quantum Chemistry
International Journal of Quantum Chemistry 化学-数学跨学科应用
CiteScore
4.70
自引率
4.50%
发文量
185
审稿时长
2 months
期刊介绍: Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.
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