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用于高性能锂金属电池的基于丁二烯砜的二元深共晶电解质

Butadiene Sulfone Based Binary Deep Eutectic Electrolyte for High Performance Lithium Metal Batteries.

作者信息

Zhou Tiankun, Lei Chengjun, Li Jinye, Wang Huijian, Liu Tingting, He Xin, Liang Xiao

机构信息

State Key Laboratory of Chem/Biosensing and Chemometrics, Joint International Research Laboratory of Energy Electrochemistry, Joint International Research Laboratory of Energy Electrochemistry, College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, China.

出版信息

Angew Chem Int Ed Engl. 2024 Oct 7;63(41):e202408728. doi: 10.1002/anie.202408728. Epub 2024 Sep 5.

Abstract

Deep eutectic electrolytes (DEEs) have attracted significant interest due to the unique physiochemical properties, yet challenges persist in achieving satisfactory Li anode compatibility through a binary DEE formula. In this study, we introduce a nonflammable binary DEE electrolyte comprising of lithium bis(trifluoro-methane-sulfonyl)imide (LiTFSI) and solid butadiene sulfone (BdS), which demonstrates enhanced Li metal compatibility while exhibiting high Li ion migration number (0.52), ionic conductivity (1.48 mS ⋅ cm), wide electrochemical window (~4.5 V vs. Li/Li) at room temperature. Experimental and theoretical results indicate that the Li compatibility derives from the formation of a LiF-rich SEI, attributed to the undesirable adsorption and deformation of BdS on Li surface that facilitates the preferential reactions between LiTFSI and Li metal. This stable SEI effectively suppresses dendrites growth and gas evolution reactions, ensuring a long lifespan and high coulombic efficiency in both the Li||Li symmetric cells, Li||LiCoO and Li||LiNiCoMnO full cells. Moreover, the BdS eutectic strategy exhibit universal applicability to other metal such as Na and Zn by pairing with the corresponding TFSI-based salts.

摘要

深共晶电解质(DEEs)因其独特的物理化学性质而备受关注,但通过二元DEE配方实现令人满意的锂负极兼容性仍存在挑战。在本研究中,我们引入了一种由双(三氟甲烷磺酰)亚胺锂(LiTFSI)和固体丁二烯砜(BdS)组成的不可燃二元DEE电解质,该电解质在室温下表现出增强的锂金属兼容性,同时具有高锂离子迁移数(0.52)、离子电导率(1.48 mS·cm)和宽电化学窗口(相对于Li/Li约4.5 V)。实验和理论结果表明,锂兼容性源于富含LiF的固体电解质界面(SEI)的形成,这归因于BdS在锂表面的不良吸附和变形,促进了LiTFSI与锂金属之间的优先反应。这种稳定的SEI有效地抑制了枝晶生长和析气反应,确保了Li||Li对称电池、Li||LiCoO和Li||LiNiCoMnO全电池的长寿命和高库仑效率。此外,通过与相应的基于TFSI的盐配对,BdS共晶策略对其他金属如Na和Zn具有普遍适用性。

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