{"title":"探索氯化溶剂作为锂金属电池的电解质:DFT 和 MD 研究","authors":"Zhe Li, Jingwei Zhang, Weiwei Xie, Qing Zhao","doi":"10.1002/qua.27515","DOIUrl":null,"url":null,"abstract":"<div>\n \n <p>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<sup>+</sup>, 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.</p>\n </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3000,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Exploring Chlorinated Solvents as Electrolytes for Lithium Metal Batteries: A DFT and MD Study\",\"authors\":\"Zhe Li, Jingwei Zhang, Weiwei Xie, Qing Zhao\",\"doi\":\"10.1002/qua.27515\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div>\\n \\n <p>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<sup>+</sup>, 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.</p>\\n </div>\",\"PeriodicalId\":182,\"journal\":{\"name\":\"International Journal of Quantum Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.3000,\"publicationDate\":\"2024-11-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"International Journal of Quantum Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/qua.27515\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"International Journal of Quantum Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/qua.27515","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
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.
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.