新型锂离子电池电解液添加剂的合成与应用

doi:10.7503/cjcu20160920

摘要/Abstract

摘要：

设计并合成了一系列基于苯环和环状碳酸酯的有机分子—双(2,3-环碳酸甘油酯)对苯二甲酸酯、三(2,3-环碳酸甘油酯)均苯三甲酸酯和四(2,3-环碳酸甘油酯)均苯四甲酸酯, 采用倍率测试、恒流充放电测试、交流阻抗测试和扫描电子显微镜测试等手段研究了这些添加剂对锂离子电池性能的影响. 通过对循环20周前后球化石墨电极形貌的对比, 发现含均苯四甲酸酯和均苯三甲酸酯的电解液球化石墨电极表面相对于空白电解液可形成一层致密而稳定的固体电解质中间相膜(SEI), 从而优化电极-电解液的界面性能, 且电池电阻增加较小; 在测试电池的倍率性能时发现, 均苯四甲酸酯的加入可以改善电池的倍率性能, 而对苯二甲酸酯的加入则未能改善电池的循环性能.

关键词: 电解液添加剂, 环碳酸甘油酯衍生物, 锂离子电池, 固体电解质中间相膜

Abstract:

A series of organic molecules combined with benzene ring and cyclic carbonate as electrolyte additives, including terephthalicacidbis-(2-oxo-[1,3]dioxolan-4-ylmethyl)ester(TABE), benzene-1,3,5-tricarboxylic acid tris-(2-oxo-[1,3]dioxolan-4-ylmethyl) ester(BATE1) and benzene-1,2,4,5-tetracarb-oxylic acid tetrakis-(2-oxo-[1,3]dioxolan-4-ylmethyl) ester(BATE2), was designed and synthesized. The effects of these additives on the electrochemical performance of lithium ion batteries were studied by rate capability, constant current charge-discharge test, electrochemical impedance spectroscopy(EIS) and scanning electron microscopy(SEM). The results showed that the amount of substituents on benzene ring greatly influenced the interface between electrolyte and graphite. Compared with the blank electrolyte, a dense and stable Solid electrolyte interface(SEI) film could be observed on the surface of the graphite electrode with BATE1 or BATE2 after 20 charge-discharge cycles, which could optimize the interface between the electrode and the electrolyte and led to the less increase of battery resistance. The test of the rate capability of the battery showed that the addition of BATE2 could improve the rate performance of the battery; meanwhile TABE could make the battery’s performance worse.

Key words: Electrolyte additive, Derivatives of glycerol carbonate, Lithim ion battery, Solid electrolyte interface(SEI) film

中图分类号:

O646

TrendMD:

郭梦雅, 宗成星, 艾淑娟, 付凤至, 王琪, 刘靖, 孙冬兰, 郭艳玲, 郭也平. 新型锂离子电池电解液添加剂的合成与应用. 高等学校化学学报, 2017, 38(10): 1857.

GUO Mengya, ZONG Chengxing, AI Shujuan, FU Fengzhi, WANG Qi, LIU Jing, SUN Donglan, GUO Yanling, GUO Yeping. Synthesis and Application of New Types of Electrolyte Additives for Lithium Ion Battery^†. Chem. J. Chinese Universities, 2017, 38(10): 1857.

图/表 7

Fig.1 Molecular structures of three kinds of compounds

Fig.2 Rate capability of lithium ion batteries with different concentrations of electrolyte additive

Fig.3 Cycling performance of lithium ion batteries with different electrolyte additives

Fig.4 Cycling efficiency of lithium ion battery with different electrolyte additives

Fig.5 Rate capability of lithium ion batteries with different electrolyte additives

Fig.6 AC impedance curves of lithium ion batteries with different electrolyte additives(A) After 2 cycles; (B) after 20 cycles.

Fig.7 SEM images of graphite electrode with different electrolyte additives for lithium ion battery(A) Electrode before cycling; (B) electrode with blank electrolyte after 20 cycles; (C) electrode with 0.7% TABE after 20 cycles;(D) electrode with 0.7% BATE1 after 20 cycles; (E) electrode with 0.7% BATE2 after 20 cycles.

参考文献 37

[1]	Armand M., Tarascon J. M., Nature,2008, 451(7), 652—658
[2]	He X. G., Yang G. L., Sun L. Q., Xie H. M., Wang R. S., Chem. J. Chinese Universities,2010, 31(11), 2148—2152
	(和兴广, 杨桂玲, 孙立群, 谢海明, 王荣顺. 高等学校化学学报, 2010, 31(11), 2148—2152)
[3]	Qiu C. G., Liu L. N., Du F., Yang X., Wang C. Z., Chen G., Wei Y. J., Chem. Res. Chinese Universities,2015, 31(2), 270—275
[4]	Chen J., Tao Z.L., Gou X. L., Chemical Power Sources, Chemical Industry Press, Beijing, 2005, 46—50
	(陈军, 陶占良, 苟兴龙. 化学电源, 北京:化学工业出版社, 2005, 46—50)
[5]	Xie M., Wang K. K., Chen R. J., Li L., Wu F., Chem. Res. Chinese Universities,2015, 31(3), 443—446
[6]	Ren Y., Wen Y., Lian F., Qiu W. H., Chemistry,2015, 78(2), 107—112
	(任岩, 文焱, 连芳, 仇卫华. 化学通报, 2015, 78(2), 107—112)
[7]	Yu J. Y., Qian Z. H., Zhao M., Wang Y. J., Niu L., Chem. Res. Chinese Universities,2013, 29(2), 374—378
[8]	Sharabi R., Markevich E., Fridman K., Gershinsky G., Salitra G., Aurbach D., Semrau G., Schmidt M. A., Schall N., Bruenig C., Electrochem. Commun., 2013, 28(1), 20—23
[9]	Luo X.W., The Synthesis and Application of Electrolyte Containing Tetrafluoroborate Ionic Liquid for Lithium Ion Batteries, Shandong University of Technology, Zibo, 2015
	(罗兴武. 四氟硼酸离子液体的制备及作为锂离子电池电解液的应用, 淄博: 山东理工大学, 2015)
[10]	Eom J. Y., Jung I. H., Lee J. H., J. Power Sources,2011, 196(22), 9810—9814
[11]	Yang X. L., Wang Y., Cao H. K., Xu X. M., Chin. J. Power Sources,2012, 36(8), 1235—1238
	(杨续来, 汪洋, 曹贺坤, 徐小明. 电源技术, 2012, 36(8), 1235—1238)
[12]	Aurbach D., Chusid O., Carmeli Y., Babai M., Yamin H., J. Electrochem., 1994, 141(3), 603—611
[13]	Zhang Y., Feng H., Zhang A. Q., Zhang C. F., Zhang P., Ionics,2011, 17(8), 677—682
[14]	Ein-Eli Y., Thomas S. R., Koch V. R., J. Electrochem. Soc., 1997, 144(4), 1159—1165
[15]	Tian L. L., Zhuang Q. C., Wang R., Cui Y. L., Fang L., Qiang Y. H., Chem. J. Chinese Universities,2010, 31(12), 2468—2473
	(田雷雷, 庄全超, 王蓉, 崔永莉, 方亮, 强颖怀. 高等学校化学学报, 2010, 31(12), 2468—2473)
[16]	Zhang S. S., Xu K., Jow T. R., J. Power Sources,2006, 156, 629—633
[17]	Wang D. Y., Sinha N. N., Burns J. C., Petibon R., Dahn J. R., J. Power Sources,2014, 270, 68—78
[18]	Sato K., Zhao L. W., Okada S., Yamaki J., J. Power Sources,2011, 196, 5617—5622
[19]	Huang W. H., Yan Y. S., Wan C. R., Jiang C. Y., Ying J. R., Chin. J. Power Sources,2001, 25(2), 91—93
	(黄文煌, 严玉顺, 万春荣, 姜长印, 应皆荣. 电源技术, 2001, 25(2), 91—93)
[20]	Shu Z. X., McMillan R. S., Murray J. J., Appl. J. Electrochem., 1996, 41, 2753—2759
[21]	Bordes A., Eom K., Fuller T. F., J. Power Sources,2014, 257, 163—169
[22]	Yao Y.Y., The Performance Study of NaODFB and LiBOB as Additives for Lithium Ion Battery Electrolyte, Taiyuan University of Technology, Taiyuan, 2015
	(姚洋洋. 锂离子电池电解液添加剂NaODFB和LiBOB的性能研究, 太原: 太原理工大学, 2015)
[23]	Capiglia C., Saito Y., Kageyama H., Mustarelli P., Iwamoto T., Tabuchi T., Tukamoto H., J. Power Sources,1999, 81/82, 859—892
[24]	Xiao L. F., Ai X. P., Yang H. X., Cao Y. L., Battery Bimonthly,2004, 34(1), 10—12
	(肖利芬, 艾新平, 杨汉西, 曹余良. 电池, 2004, 34(1), 10—12)
[25]	Xiao L. F., Cao Y. L., Ai X. P., Yang H. X., Electrochimica Acta,2004, 49, 4857—4863
[26]	Wang L. S., Study on Performance of the Several Lithium-ion Battery Electrolytes Based on LiPF6, Xinjiang University, Urumqi, 2006
	(王立仕. 基于LiPF6的几种锂离子电池电解液的性能研究, 乌鲁木齐: 新疆大学, 2006)
[27]	Xiao D. G., liu J., Guo Y. P., Li R. J., Sun D. L., Chin. J. Power Sources,2017, 41(5), 681—683
	(肖大刚, 刘靖, 郭也平, 李汝娟, 孙冬兰. 电源技术, 2017, 41(5), 681—683)
[28]	Xiao D. G., Liu J., Li R. J., Guo Y. P., Zong C. X., Sun D. L., Feng W., Int. J. Metall. Mater. Eng., 2016, 2, 1—6
[29]	Sun D. L., Li R. J., Cheng S. L., Xiao D. G., Dong D. X., J. Jilin University(Sci. Ed.), 2015, 53(5), 1049—1053
	(孙冬兰, 李汝娟, 程绍玲, 肖大刚, 董丹霞. 吉林大学学报(理学版), 2015, 53(5), 1049—1053)
[30]	Zhao Q. Y., Effect of Carbonate as Plasticizers on the P(MMA-AN)-based Gel Electrolyte, Tianjin University of Science and Technology, Tianjin, 2014
	(赵庆云. 以碳酸酯为增塑剂的 P(MMA-AN)基凝胶电解质的研究, 天津: 天津科技大学, 2014)
[31]	Li F. Q., Lai Y. Q., Zhang Z. A., Gao H. Q., Yang J., Acta Phys. Chim. Sin., 2008, 24(7), 1302—1306
	(李凡群, 赖延清, 张治安, 高宏权, 杨娟. 物理化学学报, 2008, 24(7), 1302—1306)
[32]	Balakrishnan P. G., Ramesh R., Kumar T. P., J. Power Sources,2006, 155, 401—414
[33]	Li Y., Lian F., Ma L. L., Liu C. L., Yang L., Sun X. M., Chou K. C., Electrochim. Acta,2015, 168, 261—270
[34]	Ryou M. H., Lee D. J., Lee J. N., Lee Y. M., Park J. K., Choi J. W., Adv. Energy Mater., 2012, 2(6), 645—650
[35]	Chen S. B., Wu X. M., Chen S., Ding Q. C., He H. L., Chemistry,2016, 45(1),18—25
	(陈守彬, 吴显明, 陈上, 丁其晨, 何海亮. 化学通报, 2016, 45(1),18—25)
[36]	Yang C. H., Study on AC Impedance Characteristics of LiFePO4 as Cathode Materials for Lithium Ion Batteries, Shandong University of Science and Technology, Shandong, 2015
	(杨传浩. 锂离子电池正极材料LiFePO4交流阻抗的研究, 山东: 山东科技大学, 2015)
[37]	Xu J., Yao W. H., Yao Y. W., Wang Z. C., Yang Y., Acta Phys. Chim. Sin., 2009, 25(2), 201—206
	(许杰, 姚万浩, 姚宜稳, 王周成, 杨勇. 物理化学学报, 2009, 25(2), 201—206)