Radiation Chemistry Reveals the Reaction Mechanisms Involved in the Reduction of Vinylene Carbonate in the Solid Electrolyte Interphase of Lithium-Ion Batteries.

IF 7.5 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
ChemSusChem Pub Date : 2024-11-26 DOI:10.1002/cssc.202402091
Yanis Souid, Marin Puget, Daniel Ortiz, Laura Piveteau, Sergey Denisov, Nathalie Herlin-Boime, Mehran Mostafavi, Jean-Pierre Dognon, Sophie Le Caër
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Abstract

A safe and efficient lithium-ion battery requires including an additive in the electrolyte. Among the additives used, vinylene carbonate (VC) is particularly interesting, because it leads to the formation of a stable and protective solid electrolyte interphase (SEI) on the negative electrode. However, the reduction behavior of VC, resulting in polymer formation, is complex, and many questions remain as to the corresponding reaction mechanisms. In particular, in conventional battery studies, it is not possible to observe the transient species formed during reduction. Using picosecond pulsed radiolysis coupled with theoretical chemistry calculations, we showed that, once formed, the anion radical VC⋅- can undergo ring opening in a few nanoseconds or generate VC2-. Within 100 ns, each of these anions then leads to the formation of VCC3H2O3-. This latter species starts oligomerizing. Eventually, a polymer is formed. Although it mainly consists of poly(VC) units, other chemical functions, such as alkyl groups, are also present, which highlights the role played by water, even in trace amounts. Lastly, we propose a scheme of the reaction mechanisms involved in VC reduction, leading to its polymerization. Clearly, the polymer formed from VC at the SEI of lithium-ion batteries has a complex structure.

辐射化学揭示了锂离子电池固态电解质间相中碳酸亚乙烯还原所涉及的反应机制。
安全高效的锂离子电池需要在电解液中加入添加剂。在已使用的添加剂中,碳酸乙烯酯(VC)尤其引人关注,因为它能在负极上形成稳定的保护性固体电解质间相(SEI)。然而,VC 的还原行为导致聚合物的形成,这种还原行为非常复杂,相应的反应机制仍存在许多问题。特别是在传统的电池研究中,无法观察到还原过程中形成的瞬态物种。利用皮秒脉冲辐射分析和理论化学计算,我们发现阴离子自由基 VC--一旦形成,可在几纳秒内开环或形成 (VC)2--。在 100 毫微秒内,每个阴离子都会形成 (VC)(C3H2O3--)。后一种物质开始低聚。最终形成聚合物。虽然它主要由聚(VC)单元组成,但也存在其他化学功能,如烷基,这突出了水的作用,即使是微量的水。最后,我们提出了 VC 还原导致其聚合的反应机制方案。显然,锂离子电池 SEI 中的 VC 形成的聚合物具有复杂的结构。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
ChemSusChem
ChemSusChem 化学-化学综合
CiteScore
15.80
自引率
4.80%
发文量
555
审稿时长
1.8 months
期刊介绍: ChemSusChem Impact Factor (2016): 7.226 Scope: Interdisciplinary journal Focuses on research at the interface of chemistry and sustainability Features the best research on sustainability and energy Areas Covered: Chemistry Materials Science Chemical Engineering Biotechnology
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