Electron-Donating or -Withdrawing Groups of Carbonate Solvent on Lithium-Ion (De)intercalation Chemistry,ACS Energy Letters

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Electron-Donating or -Withdrawing Groups of Carbonate Solvent on Lithium-Ion (De)intercalation Chemistry
ACS Energy Letters ( IF 19.3 ) Pub Date : 2024-08-15 , DOI: 10.1021/acsenergylett.4c01920
Jia Wang _{1,

2} , Pushpendra Kumar ₃ , Zheng Ma ₁ , Honghong Liang _{1,

2} , Fei Zhao _{1,

2} , Hongliang Xie ₁ , Yuqi Wang _{1,

2} , Tao Cai _{1,

2} , Zhen Cao ₄ , Luigi Cavallo ₄ , Qian Li ₁ , Jun Ming _{1,

2}

Affiliation

Cyclic carbonate solvents have been extensively utilized as cosolvents and/or additives in formulating electrolytes for lithium-ion batteries. However, their application often relies on empirical knowledge, lacking a universally applicable perspective to elucidate how different functional groups in cyclic carbonates affect battery performance. Herein, by focusing on the substituted functional group at the α-H in the ethylene carbonate (EC) solvent, it is discovered that solvents containing electron-withdrawing groups (e.g., −F) enable reversible Li⁺ (de)intercalation in graphite electrodes, while those with electron-donating groups (e.g., −CH₃, −CH₂CH₃) may lead to Li⁺-solvent cointercalation. Furthermore, solvents with electron-withdrawing groups can help the electron-donating groups achieve Li⁺ (de)intercalation, whereas the reverse is not feasible. These phenomena are elucidated through intermolecular interactions, characterized by 2D ¹H–¹⁹F heteronuclear Overhauser enhancement spectroscopy, revealing interactions between electron-withdrawing and -donating groups in the electrolyte solvation structure. This study offers insights into the roles of electron-donating or -withdrawing groups in electrolyte formulations.

中文翻译：

碳酸酯溶剂的给电子或吸电子基团对锂离子（脱）插层化学的影响

环状碳酸酯溶剂已广泛用作配制锂离子电池电解质的助溶剂和/或添加剂。然而，它们的应用通常依赖于经验知识，缺乏普遍适用的视角来阐明环状碳酸酯中的不同官能团如何影响电池性能。本文通过关注碳酸亚乙酯（EC）溶剂中α-H处的取代官能团，发现含有吸电子基团（例如-F）的溶剂能够在石墨电极中实现可逆的Li ⁺ （脱）嵌入，而具有给电子基团（例如-CH ₃ 、-CH ₂ CH ₃ ）的那些可能导致Li ⁺ -溶剂共插层。此外，具有吸电子基团的溶剂可以帮助给电子基团实现Li ⁺ (脱)嵌入，而反之则不可行。这些现象通过分子间相互作用得到阐明，其特征为 2D ¹ H– ¹⁹ F 异核欧沃豪瑟增强光谱，揭示了电解质溶剂化结构中吸电子基团和供电子基团之间的相互作用。这项研究深入了解了电解质配方中给电子或吸电子基团的作用。

更新日期：2024-08-15

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