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由戊二酸酐添加剂实现的超长循环钠离子电池。

Ultra-long cycle sodium ion batteries enabled by the glutaric anhydride additive.

作者信息

Zhou Qin, Xia Cong, Kuang Zhifan, Guo Mengran, Zhang Hao, Wan Haojie, Wang Shiquan, Li Lin, Liu Jianwen

机构信息

College of Chemistry and Chemical Engineering, College of New Energy and Electrical Engineering, Ministry of Education Key Laboratory for Green Preparation and Application of Functional Materials, Hubei University Wuhan 430062 P. R. China

School of Chemical Engineering, Guizhou University of Engineering Science Bijie 551700 P. R. China

出版信息

Chem Sci. 2024 Nov 18;15(48):20205-20214. doi: 10.1039/d4sc06492e. eCollection 2024 Dec 11.

Abstract

For sodium-ion batteries, solving the issue of short cycle life is key to their large-scale adoption in the industry, and the electrolyte plays an important role on this. Herein, this work aims to design a practical sodium ion battery electrolyte with industrial application value and introduces anhydride compounds as additives for the first time. Meanwhile, by adjusting the solvent composition and using a combination of ether and ester solvents, the optimal electrolyte formulation of 1 M NaPF (sodium hexafluorophosphate) + DME (glycol dimethyl ether)/VC (vinylidene carbonate) (1 : 1, v/v) + 2 wt% GA (glutaric anhydride) is designed. Na-VC, which has the highest occupied molecular orbital in this electrolyte, is preferentially oxidized to form a cathode electrolyte interface on the cathode. And synchronously, Na-GA with the lowest unoccupied molecular orbital is preferentially reduced to form a surface electrolyte interface on the anode. This electrolyte can achieve simultaneous film formation on both sides of the electrode, thus greatly increasing the cycle life of the sodium-ion battery. For example, the Na‖NVP (sodium vanadium phosphate) battery still maintains a specific capacity of 91.16 mA h g with a capacity retention rate of 85.06% after 2500 cycles. And the NVP‖HC (hard carbon) full battery also maintains a capacity retention rate of 66.50% after 800 cycles. This work will provide important ideas and strong evidence for the industrial application of sodium ion battery electrolytes with long cycle life.

摘要

对于钠离子电池而言,解决循环寿命短的问题是其在行业中大规模应用的关键,而电解质在这方面起着重要作用。在此,本工作旨在设计一种具有工业应用价值的实用钠离子电池电解质,并首次引入酸酐化合物作为添加剂。同时,通过调整溶剂组成并使用醚类和酯类溶剂的组合,设计出了最优的电解质配方:1 M NaPF₆(六氟磷酸钠)+ DME(乙二醇二甲醚)/VC(碳酸亚乙烯酯)(1∶1,v/v)+ 2 wt% GA(戊二酸酐)。在这种电解质中,具有最高占据分子轨道的Na-VC优先被氧化,在阴极上形成阴极电解质界面。同时,具有最低未占据分子轨道的Na-GA优先被还原,在阳极上形成表面电解质界面。这种电解质能够在电极两侧同时成膜,从而大大提高了钠离子电池的循环寿命。例如,Na‖NVP(磷酸钠钒)电池在2500次循环后仍保持91.16 mA h g的比容量,容量保持率为85.06%。而NVP‖HC(硬碳)全电池在800次循环后也保持了66.50%的容量保持率。本工作将为长循环寿命钠离子电池电解质的工业应用提供重要思路和有力依据。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f6bb/11632752/469ebef93481/d4sc06492e-f1.jpg

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