{"title":"具有亚磺酰官能化亚胺阴离子的离子液体及其锂电解质:(I)物理和电化学特性","authors":"","doi":"10.1016/j.powera.2024.100154","DOIUrl":null,"url":null,"abstract":"<div><p>Imide-based ionic liquids (ILs) are intriguing candidates for constructing safer electrolytes and better rechargeable batteries. In this work, a sulfinyl-functionalized imide anion, (trifluoromethanesulfinyl) (trifluoromethanesulfonyl)imide anion ([(CF<sub>3</sub>SO) (CF<sub>3</sub>SO<sub>2</sub>)N]<sup>−</sup>, [qTFSI]<sup>−</sup>), is proposed as negative charge for building low-melting ILs and high-performing electrolytes. The physicochemical properties of [qTFSI]-based ILs and their electrolytes are extensively characterized, and the reference systems with the classic sulfonimide anion, bis(trifluoromethanesulfonyl)imide anion ([(CF<sub>3</sub>SO<sub>2</sub>)<sub>2</sub>N]<sup>−</sup>, [TFSI]<sup>−</sup>) are also comparatively investigated. It has been revealed that the [qTFSI]<sup>−</sup> anion shows lesser extent of negative charge delocalization as compared to the reference [TFSI]<sup>−</sup> anion, which is responsible for slightly stronger interactions between IL cations and the sulfinyl-functionalized anion. The asymmetric feature of the [qTFSI]<sup>−</sup> anion contributes to lower glass and melting transitions of the corresponding ILs vs. [TFSI]-based ones, which effectively expands the operational temperature of the rechargeable batteries. Furthermore, the co-utilization of [qTFSI]<sup>−</sup> with [TFSI]<sup>−</sup> is found to improve the electrochemical compatibility of Li metal anode with the IL-based electrolytes, sustaining better cycling stability of the Li symmetric cells. The current work offers an elegant approach for the design of new anions for interface-favorable ILs and their electrolytes.</p></div>","PeriodicalId":34318,"journal":{"name":"Journal of Power Sources Advances","volume":null,"pages":null},"PeriodicalIF":5.4000,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666248524000209/pdfft?md5=7c9b6e2215ce8193cb108128d1d0697a&pid=1-s2.0-S2666248524000209-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Ionic liquids with sulfinyl-functionalized imide anion and their lithium electrolytes: (I) Physical and electrochemical properties\",\"authors\":\"\",\"doi\":\"10.1016/j.powera.2024.100154\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Imide-based ionic liquids (ILs) are intriguing candidates for constructing safer electrolytes and better rechargeable batteries. In this work, a sulfinyl-functionalized imide anion, (trifluoromethanesulfinyl) (trifluoromethanesulfonyl)imide anion ([(CF<sub>3</sub>SO) (CF<sub>3</sub>SO<sub>2</sub>)N]<sup>−</sup>, [qTFSI]<sup>−</sup>), is proposed as negative charge for building low-melting ILs and high-performing electrolytes. The physicochemical properties of [qTFSI]-based ILs and their electrolytes are extensively characterized, and the reference systems with the classic sulfonimide anion, bis(trifluoromethanesulfonyl)imide anion ([(CF<sub>3</sub>SO<sub>2</sub>)<sub>2</sub>N]<sup>−</sup>, [TFSI]<sup>−</sup>) are also comparatively investigated. It has been revealed that the [qTFSI]<sup>−</sup> anion shows lesser extent of negative charge delocalization as compared to the reference [TFSI]<sup>−</sup> anion, which is responsible for slightly stronger interactions between IL cations and the sulfinyl-functionalized anion. The asymmetric feature of the [qTFSI]<sup>−</sup> anion contributes to lower glass and melting transitions of the corresponding ILs vs. [TFSI]-based ones, which effectively expands the operational temperature of the rechargeable batteries. Furthermore, the co-utilization of [qTFSI]<sup>−</sup> with [TFSI]<sup>−</sup> is found to improve the electrochemical compatibility of Li metal anode with the IL-based electrolytes, sustaining better cycling stability of the Li symmetric cells. The current work offers an elegant approach for the design of new anions for interface-favorable ILs and their electrolytes.</p></div>\",\"PeriodicalId\":34318,\"journal\":{\"name\":\"Journal of Power Sources Advances\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.4000,\"publicationDate\":\"2024-07-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S2666248524000209/pdfft?md5=7c9b6e2215ce8193cb108128d1d0697a&pid=1-s2.0-S2666248524000209-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Power Sources Advances\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2666248524000209\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Power Sources Advances","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2666248524000209","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
酰亚胺基离子液体(ILs)是构建更安全的电解质和更好的可充电电池的理想候选物质。本研究提出了一种亚磺酰官能化的亚胺阴离子--(三氟甲烷亚磺酰基)(三氟甲烷磺酰基)亚胺阴离子([(CF3SO) (CF3SO2)N]-,[qTFSI]-),作为构建低熔点离子液体和高性能电解质的负电荷。研究人员对基于[qTFSI]的离子交换树脂及其电解质的物理化学性质进行了广泛表征,并与经典的磺酰亚胺阴离子、双(三氟甲烷磺酰)亚胺阴离子([(CF3SO2)2N]-,[TFSI]-)参考体系进行了比较研究。研究发现,与参考的[TFSI]-阴离子相比,[qTFSI]-阴离子的负电荷分散程度较低,这也是 IL 阳离子与亚磺酰官能化阴离子之间相互作用略强的原因。与基于[TFSI]的离子相比,[qTFSI]-阴离子的不对称特征有助于降低相应离子醇的玻璃态和熔化态,从而有效地提高了充电电池的工作温度。此外,[qTFSI]- 与 [TFSI]- 的共同使用还能改善锂金属阳极与基于 IL 的电解质之间的电化学相容性,从而使锂离子对称电池保持更好的循环稳定性。目前的工作为设计界面友好型 IL 及其电解质的新阴离子提供了一种优雅的方法。
Ionic liquids with sulfinyl-functionalized imide anion and their lithium electrolytes: (I) Physical and electrochemical properties
Imide-based ionic liquids (ILs) are intriguing candidates for constructing safer electrolytes and better rechargeable batteries. In this work, a sulfinyl-functionalized imide anion, (trifluoromethanesulfinyl) (trifluoromethanesulfonyl)imide anion ([(CF3SO) (CF3SO2)N]−, [qTFSI]−), is proposed as negative charge for building low-melting ILs and high-performing electrolytes. The physicochemical properties of [qTFSI]-based ILs and their electrolytes are extensively characterized, and the reference systems with the classic sulfonimide anion, bis(trifluoromethanesulfonyl)imide anion ([(CF3SO2)2N]−, [TFSI]−) are also comparatively investigated. It has been revealed that the [qTFSI]− anion shows lesser extent of negative charge delocalization as compared to the reference [TFSI]− anion, which is responsible for slightly stronger interactions between IL cations and the sulfinyl-functionalized anion. The asymmetric feature of the [qTFSI]− anion contributes to lower glass and melting transitions of the corresponding ILs vs. [TFSI]-based ones, which effectively expands the operational temperature of the rechargeable batteries. Furthermore, the co-utilization of [qTFSI]− with [TFSI]− is found to improve the electrochemical compatibility of Li metal anode with the IL-based electrolytes, sustaining better cycling stability of the Li symmetric cells. The current work offers an elegant approach for the design of new anions for interface-favorable ILs and their electrolytes.