锂硫电池中的三硫自由基陷阱

IF 5.4 Q2 CHEMISTRY, PHYSICAL
Roza Bouchal , Clément Pechberty , Athmane Boulaoued , Niklas Lindahl , Patrik Johansson
{"title":"锂硫电池中的三硫自由基陷阱","authors":"Roza Bouchal ,&nbsp;Clément Pechberty ,&nbsp;Athmane Boulaoued ,&nbsp;Niklas Lindahl ,&nbsp;Patrik Johansson","doi":"10.1016/j.powera.2024.100153","DOIUrl":null,"url":null,"abstract":"<div><p>Lithium-sulfur (Li–S) batteries have emerged as a next-generation battery technology owing to their prospects of high capacity and energy density. They, however, suffer from rapid capacity decay due to the shuttling of reaction intermediate species: Li polysulfides (LiPSs). One of the more important and intriguing PSs is the tri-sulfur radical (<span><math><mrow><msubsup><mi>S</mi><mn>3</mn><mrow><mo>•</mo><mo>−</mo></mrow></msubsup></mrow></math></span>), observed mainly in high-donor number (DN) solvent-based electrolytes. Although this radical has been proposed to be crucial to full active material (AM) utilization, there is currently no direct evidence of the impact of <span><math><mrow><msubsup><mi>S</mi><mn>3</mn><mrow><mo>•</mo><mo>−</mo></mrow></msubsup></mrow></math></span> on cycling stability. To gain more insight into the role of the <span><math><mrow><msubsup><mi>S</mi><mn>3</mn><mrow><mo>•</mo><mo>−</mo></mrow></msubsup></mrow></math></span>, we studied the use of radical traps in low and high DN solvent-based electrolytes by <em>operando</em> Raman spectroscopy. The traps were based on nitrone and iminium cation, and <span><math><mrow><msubsup><mi>S</mi><mn>3</mn><mrow><mo>•</mo><mo>−</mo></mrow></msubsup></mrow></math></span> was indeed successfully trapped in <em>ex situ</em> analysis. However, it was the ionic liquid-based trap, specifically pyridinium, that effectively suppressed <span><math><mrow><msubsup><mi>S</mi><mn>3</mn><mrow><mo>•</mo><mo>−</mo></mrow></msubsup></mrow></math></span> during battery operation. Overall, the PS formation was altered in the presence of the traps and we confirmed the impact of <span><math><mrow><msubsup><mi>S</mi><mn>3</mn><mrow><mo>•</mo><mo>−</mo></mrow></msubsup></mrow></math></span> formation on the Li–S battery redox reactions and show how the trapping correlates with Li–S battery performance. Therefore, stabilization of the <span><math><mrow><msubsup><mi>S</mi><mn>3</mn><mrow><mo>•</mo><mo>−</mo></mrow></msubsup></mrow></math></span> might be a path to improved Li–S batteries.</p></div>","PeriodicalId":34318,"journal":{"name":"Journal of Power Sources Advances","volume":null,"pages":null},"PeriodicalIF":5.4000,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666248524000192/pdfft?md5=d3bf5ed5febce78519798da3441e763a&pid=1-s2.0-S2666248524000192-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Tri-sulfur radical trapping in lithium–sulfur batteries\",\"authors\":\"Roza Bouchal ,&nbsp;Clément Pechberty ,&nbsp;Athmane Boulaoued ,&nbsp;Niklas Lindahl ,&nbsp;Patrik Johansson\",\"doi\":\"10.1016/j.powera.2024.100153\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Lithium-sulfur (Li–S) batteries have emerged as a next-generation battery technology owing to their prospects of high capacity and energy density. They, however, suffer from rapid capacity decay due to the shuttling of reaction intermediate species: Li polysulfides (LiPSs). One of the more important and intriguing PSs is the tri-sulfur radical (<span><math><mrow><msubsup><mi>S</mi><mn>3</mn><mrow><mo>•</mo><mo>−</mo></mrow></msubsup></mrow></math></span>), observed mainly in high-donor number (DN) solvent-based electrolytes. Although this radical has been proposed to be crucial to full active material (AM) utilization, there is currently no direct evidence of the impact of <span><math><mrow><msubsup><mi>S</mi><mn>3</mn><mrow><mo>•</mo><mo>−</mo></mrow></msubsup></mrow></math></span> on cycling stability. To gain more insight into the role of the <span><math><mrow><msubsup><mi>S</mi><mn>3</mn><mrow><mo>•</mo><mo>−</mo></mrow></msubsup></mrow></math></span>, we studied the use of radical traps in low and high DN solvent-based electrolytes by <em>operando</em> Raman spectroscopy. The traps were based on nitrone and iminium cation, and <span><math><mrow><msubsup><mi>S</mi><mn>3</mn><mrow><mo>•</mo><mo>−</mo></mrow></msubsup></mrow></math></span> was indeed successfully trapped in <em>ex situ</em> analysis. However, it was the ionic liquid-based trap, specifically pyridinium, that effectively suppressed <span><math><mrow><msubsup><mi>S</mi><mn>3</mn><mrow><mo>•</mo><mo>−</mo></mrow></msubsup></mrow></math></span> during battery operation. Overall, the PS formation was altered in the presence of the traps and we confirmed the impact of <span><math><mrow><msubsup><mi>S</mi><mn>3</mn><mrow><mo>•</mo><mo>−</mo></mrow></msubsup></mrow></math></span> formation on the Li–S battery redox reactions and show how the trapping correlates with Li–S battery performance. Therefore, stabilization of the <span><math><mrow><msubsup><mi>S</mi><mn>3</mn><mrow><mo>•</mo><mo>−</mo></mrow></msubsup></mrow></math></span> might be a path to improved Li–S batteries.</p></div>\",\"PeriodicalId\":34318,\"journal\":{\"name\":\"Journal of Power Sources Advances\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.4000,\"publicationDate\":\"2024-06-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S2666248524000192/pdfft?md5=d3bf5ed5febce78519798da3441e763a&pid=1-s2.0-S2666248524000192-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/S2666248524000192\",\"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/S2666248524000192","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

锂硫(Li-S)电池因其高容量和高能量密度的前景而成为下一代电池技术。然而,由于反应中间产物的穿梭,它们的容量衰减很快:多硫化锂(LiPSs)。三硫自由基(S3--)是其中一种较为重要且引人关注的多硫化物,主要出现在高放电数(DN)溶剂型电解质中。虽然这种自由基被认为对活性材料(AM)的充分利用至关重要,但目前还没有直接证据表明 S3--对循环稳定性的影响。为了更深入地了解 S3--的作用,我们通过操作拉曼光谱研究了低 DN 和高 DN 溶剂型电解质中自由基陷阱的使用情况。捕获器基于腈和亚胺阳离子,在原位分析中确实成功捕获了 S3--。然而,在电池运行过程中,基于离子液体的捕集器(特别是吡啶鎓)有效地抑制了 S3--。总之,PS 的形成在捕集剂的存在下发生了改变,我们证实了 S3--的形成对锂-S 电池氧化还原反应的影响,并展示了捕集剂与锂-S 电池性能之间的关联。因此,稳定 S3--可能是改进锂-S 电池的一条途径。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Tri-sulfur radical trapping in lithium–sulfur batteries

Tri-sulfur radical trapping in lithium–sulfur batteries

Lithium-sulfur (Li–S) batteries have emerged as a next-generation battery technology owing to their prospects of high capacity and energy density. They, however, suffer from rapid capacity decay due to the shuttling of reaction intermediate species: Li polysulfides (LiPSs). One of the more important and intriguing PSs is the tri-sulfur radical (S3), observed mainly in high-donor number (DN) solvent-based electrolytes. Although this radical has been proposed to be crucial to full active material (AM) utilization, there is currently no direct evidence of the impact of S3 on cycling stability. To gain more insight into the role of the S3, we studied the use of radical traps in low and high DN solvent-based electrolytes by operando Raman spectroscopy. The traps were based on nitrone and iminium cation, and S3 was indeed successfully trapped in ex situ analysis. However, it was the ionic liquid-based trap, specifically pyridinium, that effectively suppressed S3 during battery operation. Overall, the PS formation was altered in the presence of the traps and we confirmed the impact of S3 formation on the Li–S battery redox reactions and show how the trapping correlates with Li–S battery performance. Therefore, stabilization of the S3 might be a path to improved Li–S batteries.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
CiteScore
9.10
自引率
0.00%
发文量
18
审稿时长
64 days
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信