Zirun Wang, Jie Ren, Yuehua Zhao, Ying Lin, Ruobing Lang, Xiumei Pan
{"title":"含酯硫醚基团的固体聚合物电解质结构信息和改性设计的密度泛函理论研究","authors":"Zirun Wang, Jie Ren, Yuehua Zhao, Ying Lin, Ruobing Lang, Xiumei Pan","doi":"10.1007/s10008-024-06025-y","DOIUrl":null,"url":null,"abstract":"<div><p>Poly (ethylene glycol dimethacrylate-1,2-ethanedithiol) (P(EDGMA-EDT)) and poly (ethylene glycol dimethacrylate-3,6-dioxy-1,8-octanedithiol) (P(EDGMA-DODT)) are excellent solid polymer electrolytes synthesized experimentally. The coordination structure, redox properties, and modification design of P(EDGMA-EDT)-LiTFSI and P(EDGMA-DODT)-LiTFSI are investigated by density functional theory. The theoretical simulation of infrared spectra and the coordination structure information show that the ester carbonyl group in P(EDGMA-EDT) and the ester carbonyl group and ether oxygen in P(EDGMA-DODT) interact with Li<sup>+</sup> ions. Li<sup>+</sup> ion coordination numbers in these two electrolytes are 4 and 5; thioether and ester groups in polymers are their redox active sites, respectively. Modified sulfone oxide P(EDGMA-EDT)2-SO<sub>2</sub> and P(EDGMA-DODT)2-SO<sub>2</sub> cannot only maintain the reduction stability but also greatly improve the oxidation potential. LiPF<sub>6</sub>, LiDFBOP, and LiBF<sub>3</sub>Cl are good candidates for sulfone-based polymers. The electron-withdrawing groups (− 4Br, − 4Cl, − 4F, − NO<sub>2</sub>, and − CN) substitution can improve the oxidation potential of P(EDGMA-EDT) but have little effect on the oxidation potential of P(EDGMA-DODT) and reduce the reduction stability of both polymers. These findings provide theoretical guidance for the coordination structure as well as the molecular design of solid electrolytes containing ester groups and thioether.</p></div>","PeriodicalId":665,"journal":{"name":"Journal of Solid State Electrochemistry","volume":null,"pages":null},"PeriodicalIF":2.6000,"publicationDate":"2024-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Density functional theory study on structure information and modification design of solid polymer electrolytes containing ester-thioether groups\",\"authors\":\"Zirun Wang, Jie Ren, Yuehua Zhao, Ying Lin, Ruobing Lang, Xiumei Pan\",\"doi\":\"10.1007/s10008-024-06025-y\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Poly (ethylene glycol dimethacrylate-1,2-ethanedithiol) (P(EDGMA-EDT)) and poly (ethylene glycol dimethacrylate-3,6-dioxy-1,8-octanedithiol) (P(EDGMA-DODT)) are excellent solid polymer electrolytes synthesized experimentally. The coordination structure, redox properties, and modification design of P(EDGMA-EDT)-LiTFSI and P(EDGMA-DODT)-LiTFSI are investigated by density functional theory. The theoretical simulation of infrared spectra and the coordination structure information show that the ester carbonyl group in P(EDGMA-EDT) and the ester carbonyl group and ether oxygen in P(EDGMA-DODT) interact with Li<sup>+</sup> ions. Li<sup>+</sup> ion coordination numbers in these two electrolytes are 4 and 5; thioether and ester groups in polymers are their redox active sites, respectively. Modified sulfone oxide P(EDGMA-EDT)2-SO<sub>2</sub> and P(EDGMA-DODT)2-SO<sub>2</sub> cannot only maintain the reduction stability but also greatly improve the oxidation potential. LiPF<sub>6</sub>, LiDFBOP, and LiBF<sub>3</sub>Cl are good candidates for sulfone-based polymers. The electron-withdrawing groups (− 4Br, − 4Cl, − 4F, − NO<sub>2</sub>, and − CN) substitution can improve the oxidation potential of P(EDGMA-EDT) but have little effect on the oxidation potential of P(EDGMA-DODT) and reduce the reduction stability of both polymers. These findings provide theoretical guidance for the coordination structure as well as the molecular design of solid electrolytes containing ester groups and thioether.</p></div>\",\"PeriodicalId\":665,\"journal\":{\"name\":\"Journal of Solid State Electrochemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.6000,\"publicationDate\":\"2024-07-31\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Solid State Electrochemistry\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s10008-024-06025-y\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"ELECTROCHEMISTRY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Solid State Electrochemistry","FirstCategoryId":"5","ListUrlMain":"https://link.springer.com/article/10.1007/s10008-024-06025-y","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"ELECTROCHEMISTRY","Score":null,"Total":0}
Density functional theory study on structure information and modification design of solid polymer electrolytes containing ester-thioether groups
Poly (ethylene glycol dimethacrylate-1,2-ethanedithiol) (P(EDGMA-EDT)) and poly (ethylene glycol dimethacrylate-3,6-dioxy-1,8-octanedithiol) (P(EDGMA-DODT)) are excellent solid polymer electrolytes synthesized experimentally. The coordination structure, redox properties, and modification design of P(EDGMA-EDT)-LiTFSI and P(EDGMA-DODT)-LiTFSI are investigated by density functional theory. The theoretical simulation of infrared spectra and the coordination structure information show that the ester carbonyl group in P(EDGMA-EDT) and the ester carbonyl group and ether oxygen in P(EDGMA-DODT) interact with Li+ ions. Li+ ion coordination numbers in these two electrolytes are 4 and 5; thioether and ester groups in polymers are their redox active sites, respectively. Modified sulfone oxide P(EDGMA-EDT)2-SO2 and P(EDGMA-DODT)2-SO2 cannot only maintain the reduction stability but also greatly improve the oxidation potential. LiPF6, LiDFBOP, and LiBF3Cl are good candidates for sulfone-based polymers. The electron-withdrawing groups (− 4Br, − 4Cl, − 4F, − NO2, and − CN) substitution can improve the oxidation potential of P(EDGMA-EDT) but have little effect on the oxidation potential of P(EDGMA-DODT) and reduce the reduction stability of both polymers. These findings provide theoretical guidance for the coordination structure as well as the molecular design of solid electrolytes containing ester groups and thioether.
期刊介绍:
The Journal of Solid State Electrochemistry is devoted to all aspects of solid-state chemistry and solid-state physics in electrochemistry.
The Journal of Solid State Electrochemistry publishes papers on all aspects of electrochemistry of solid compounds, including experimental and theoretical, basic and applied work. It equally publishes papers on the thermodynamics and kinetics of electrochemical reactions if at least one actively participating phase is solid. Also of interest are articles on the transport of ions and electrons in solids whenever these processes are relevant to electrochemical reactions and on the use of solid-state electrochemical reactions in the analysis of solids and their surfaces.
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