过充保护添加剂1,2-二甲氧基-4-硝基苯和1,4-二甲氧基-2-硝基苯在锂离子电池中的应用

引用本文: 任春燕, 卢海, 贾明, 张治安, 赖延清, 李劼. 过充保护添加剂1,2-二甲氧基-4-硝基苯和1,4-二甲氧基-2-硝基苯在锂离子电池中的应用[J]. 物理化学学报, doi: 10.3866/PKU.WHXB201206142 shu

Citation: REN Chun-Yan, LU Hai, JIA Ming, ZHANG Zhi-An, LAI Yan-Qing, LI Jie. Application of 1,2-Dimethoxy-4-nitro-benzene and 1,4-Dimethoxy- 2-nitro-benzene as Overcharge Protection Additives in Lithium-Ion Batteries[J]. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB201206142 shu

过充保护添加剂1,2-二甲氧基-4-硝基苯和1,4-二甲氧基-2-硝基苯在锂离子电池中的应用

任春燕 ^1, ,
卢海 ^2, ,
贾明 ^1,2, ,
张治安 ^1, ,
赖延清 ^1,2, ,
李劼 ^1,2,

基金项目:
国家科技支撑计划(2007BAE12B01) (2007BAE12B01)

国家自然科学基金(20803095)资助项目 (20803095)

摘要:

在锂离子电池电解液1 mol·L^-1 LiPF₆/(碳酸乙烯酯(EC)+碳酸二乙酯(DEC)+碳酸甲乙酯(EMC) (1:1:1,体积比))中分别添加1,2-二甲氧基-4-硝基苯(DMNB1)和1,4-二甲氧基-2-硝基苯(DMNB2)作为防过充添加剂.采用循环伏安(CV)、恒流充放电、过充测试、电化学阻抗谱(EIS)、扫描电子显微镜(SEM)等手段研究了DMNB1和DMNB2 的防过充效果, 以及添加剂与LiNi_1/3Co_1/3Mn_1/3O₂材料的相容性. 结果表明: DMNB1 和DMNB2 的氧化电位都在4.3 V (vs Li/Li⁺)以上, 且均能显著提高电池的过充保护性能. 100%过充和5 V截止电压过充测试表明, DMNB1 的防过充性能优于DMNB2. 采用基础电解液、添加0.1 mol·L^-1 DMNB1 和添加0.1 mol·L^-1DMNB2 电解液的LiNi_1/3Co_1/3Mn_1/3O₂/Li 电池, 0.2C 倍率下循环100 次, 容量保持率分别为98.4%、95.9%和68.1%. 证明硝基在添加剂苯环上的取代位置和其电化学性能之间有着密切联系.

关键词:

English

Application of 1,2-Dimethoxy-4-nitro-benzene and 1,4-Dimethoxy- 2-nitro-benzene as Overcharge Protection Additives in Lithium-Ion Batteries

1.
1. School of Metallurgical Science and Engineering, Central South University, Changsha 410083, P. R. China;
2. Engineering Research Center of Advanced Battery Materials, the Ministry of Education, Changsha 410083, P. R. China
Received Date: 10 April 2012
Available Online: 02 August 2012
Fund Project:
国家科技支撑计划(2007BAE12B01)

国家自然科学基金(20803095)资助项目

Abstract:

1,2-Dimethoxy-4-nitro-benzene (DMNB1) and 1,4-dimethoxy-2-nitro-benzene (DMNB2) were selected as new redox shuttle additives for overcharge protection in lithium-ion batteries. The base electrolyte is 1 mol·L^-1 LiPF₆/(ethylene carbonate (EC)+diethyl carbonate (DEC)+ethyl-methyl carbonate (EMC) (1:1:1, by volume)). Cyclic voltammetry (CV), charge-discharge cycle performance, overcharge tests, electrochemical impedance spectra (EIS), and scanning electron microscopy (SEM) were used to investigate the electrochemical performances of DMNB1 and DMNB2. The overcharge protection of DMNB1 and DMNB2 on lithium-ion batteries and the compatibility of both additives with the LiNi_1/3CoMn_1/3O₂ electrode have been studied. The results show that the working potentials of the both additives are above 4.3 V (vs Li/Li⁺), and thus are suitable for overcharge protection in lithium-ion batteries. Lithium-ion batteries with DMNB1 and DMNB2 have an improved overcharging tolerance. DMNB1 shows better overcharge protective performance, in the 100% overcharge and 5 V cutoff voltage tests, than DMNB2. After 100 cycles at 0.2C rate, the capacity retention rates of the LiNi_1/3Co_1/3Mn_1/3O₂/Li cells with the base electrolyte and the electrolyte with DMNB1 and DMNB2 are 98.4%, 95.9%, and 68.1%, respectively. The electrochemical properties and the location of the nitro-group on the benzene of the overcharge protection additives are closely linked.

Key words:

1. [1]
  
  (1) Chen, Y. S.; Hu, C. C.; Li, Y. Y. J. Power Sources 2008, 181, 69.doi: 10.1016/j.jpowsour.2008.03.015
  (1) Chen, Y. S.; Hu, C. C.; Li, Y. Y. J. Power Sources 2008, 181, 69.doi: 10.1016/j.jpowsour.2008.03.015
2. [2]
  (2) Chen, L.; Buhrmester, C.; Dahn, J. R. Electrochem. Solid-State Lett. 2005, 8, A59.(2) Chen, L.; Buhrmester, C.; Dahn, J. R. Electrochem. Solid-State Lett. 2005, 8, A59.
3. [3]
  (3) Balakrishnan, P. G.; Ramesh, R. T.; Kumar, P. J. Power Sources2006, 155, 401. doi: 10.1016/j.jpowsour.2005.12.002(3) Balakrishnan, P. G.; Ramesh, R. T.; Kumar, P. J. Power Sources2006, 155, 401. doi: 10.1016/j.jpowsour.2005.12.002
4. [4]
  (4) Lan, X.; Li, S. L.; Ai, X. P.; Yang, H. X.; Cao, Y. L. Energy Environ. Sci. 2011, 4, 2845. doi: 10.1039/c0ee00590h(4) Lan, X.; Li, S. L.; Ai, X. P.; Yang, H. X.; Cao, Y. L. Energy Environ. Sci. 2011, 4, 2845. doi: 10.1039/c0ee00590h
5. [5]
  (5) Kise, M.; Yoshioka, S.; Hamano, K.; Kuriki, H.; Nishimura, T.;Urushibata, H.; Yoshiyasu, H. J. Electrochem. Soc. 2005, 152,A1516.(5) Kise, M.; Yoshioka, S.; Hamano, K.; Kuriki, H.; Nishimura, T.;Urushibata, H.; Yoshiyasu, H. J. Electrochem. Soc. 2005, 152,A1516.
6. [6]
  (6) Chen, Z.; Amine, K. Electrochem Commun. 2007, 9, 703. doi: 10.1016/j.elecom.2006.11.002(6) Chen, Z.; Amine, K. Electrochem Commun. 2007, 9, 703. doi: 10.1016/j.elecom.2006.11.002
7. [7]
  (7) Watanabe, Y.; Yamazaki, Y.; Yasuda, K.; Morimoto, H.;Tobishima, S. I. J. Power Sources 2006, 160, 1375. doi: 10.1016/j.jpowsour.2006.03.007(7) Watanabe, Y.; Yamazaki, Y.; Yasuda, K.; Morimoto, H.;Tobishima, S. I. J. Power Sources 2006, 160, 1375. doi: 10.1016/j.jpowsour.2006.03.007
8. [8]
  (8) Zhang, S. S. J. Power Sources 2006, 162, 1379. doi: 10.1016/j.jpowsour.2006.07.074(8) Zhang, S. S. J. Power Sources 2006, 162, 1379. doi: 10.1016/j.jpowsour.2006.07.074
9. [9]
  (9) Guo, Y. J.; Chen, H.; Qi, L. Acta Phys. -Chim. Sin. 2007, 23 (supp.), 80. [郭营军, 晨辉, 其鲁. 物理化学学报, 2007,23 (supp.), 80.] doi: 10.3866/PKU.WHXB2007Supp17(9) Guo, Y. J.; Chen, H.; Qi, L. Acta Phys. -Chim. Sin. 2007, 23 (supp.), 80. [郭营军, 晨辉, 其鲁. 物理化学学报, 2007,23 (supp.), 80.] doi: 10.3866/PKU.WHXB2007Supp17
10. [10]
  (10) Wang, B.; Xia, Q.; Zhang, P.; Li, G. C.;Wu, Y. P.; Luo, H. J.;Zhao, S. Y.; Ree, T. Electrochem. Commun. 2008, 10, 727.doi: 10.1016/j.elecom.2008.02.011(10) Wang, B.; Xia, Q.; Zhang, P.; Li, G. C.;Wu, Y. P.; Luo, H. J.;Zhao, S. Y.; Ree, T. Electrochem. Commun. 2008, 10, 727.doi: 10.1016/j.elecom.2008.02.011
11. [11]
  (11) Xiong, L. Q.; Zhang, Y. J.; Dong, P.; Yang, R. M.; Xia, S. B.Chem. Ind. Eng. Prog. 2011, 30, 1198. [熊琳强, 张英杰, 董鹏, 杨瑞明, 夏书标. 化工进展, 2011, 30, 1198.](11) Xiong, L. Q.; Zhang, Y. J.; Dong, P.; Yang, R. M.; Xia, S. B.Chem. Ind. Eng. Prog. 2011, 30, 1198. [熊琳强, 张英杰, 董鹏, 杨瑞明, 夏书标. 化工进展, 2011, 30, 1198.]
12. [12]
  (12) Xu, M. Q.; Xing, L. D.; Li,W. S.; Zuo, X. X.; Shu, D.; Li, G. L.J. Power Sources 2008, 184, 427. doi: 10.1016/j.jpowsour.2008.03.036(12) Xu, M. Q.; Xing, L. D.; Li,W. S.; Zuo, X. X.; Shu, D.; Li, G. L.J. Power Sources 2008, 184, 427. doi: 10.1016/j.jpowsour.2008.03.036
13. [13]
  (13) Guo, Y. X.; Yin, Z. G.; Tao, Z. Y.; Li, X. H. Trans. Nonferrous Met. Soc. China 2008, 18, 2025. [郭永兴, 殷振国, 陶芝勇, 李新海. 中国有色金属学报, 2008, 18, 2025.](13) Guo, Y. X.; Yin, Z. G.; Tao, Z. Y.; Li, X. H. Trans. Nonferrous Met. Soc. China 2008, 18, 2025. [郭永兴, 殷振国, 陶芝勇, 李新海. 中国有色金属学报, 2008, 18, 2025.]
14. [14]
  (14) Zhang, Q. Y.; Qiu, C. C.; Fu, Y. B.; Ma, X. H. Chin. J. Power Sources 2009, 33, 774. [张千玉, 秋沉沉, 付延鲍, 马晓华. 电源技术, 2009, 33, 774.](14) Zhang, Q. Y.; Qiu, C. C.; Fu, Y. B.; Ma, X. H. Chin. J. Power Sources 2009, 33, 774. [张千玉, 秋沉沉, 付延鲍, 马晓华. 电源技术, 2009, 33, 774.]
15. [15]
  (15) Xiao, L.; Ai, X.; Cao, Y.; Yang, H. Electrochim. Acta 2004, 49,4189. doi: 10.1016/j.electacta.2004.04.013(15) Xiao, L.; Ai, X.; Cao, Y.; Yang, H. Electrochim. Acta 2004, 49,4189. doi: 10.1016/j.electacta.2004.04.013
16. [16]
  (16) Buhrmester, C.; Moshurchak, L.;Wang, R. L.; Dahn, J. R.J. Electrochem. Soc. 2006, 153, A288.(16) Buhrmester, C.; Moshurchak, L.;Wang, R. L.; Dahn, J. R.J. Electrochem. Soc. 2006, 153, A288.
17. [17]
  (17) Wang, R. L.; Buhrmester, C.; Dahn, J. R. J. Electrochem. Soc.2006, 153, A445.(17) Wang, R. L.; Buhrmester, C.; Dahn, J. R. J. Electrochem. Soc.2006, 153, A445.
18. [18]
  (18) Luo, H. J.; Zhang, X. G.; Chen, L. Chin. J. Power Sources 2012,36, 172. [骆宏钧, 张校刚, 陈黎. 电源技术, 2012, 36, 172](18) Luo, H. J.; Zhang, X. G.; Chen, L. Chin. J. Power Sources 2012,36, 172. [骆宏钧, 张校刚, 陈黎. 电源技术, 2012, 36, 172]
19. [19]
  (19) Feng, J. K.; Ai, X. P.; Cao, Y. L.; Yang, H. X. Electrochem. Commun. 2007, 9, 25. doi: 10.1016/j.elecom.2006.08.033(19) Feng, J. K.; Ai, X. P.; Cao, Y. L.; Yang, H. X. Electrochem. Commun. 2007, 9, 25. doi: 10.1016/j.elecom.2006.08.033
20. [20]
  (20) Moshuchak, L. M.; Bulinski, M.; Lamanna,W. M.;Wang, R. L.;Dahn, J. R. Electrochem. Commun. 2007, 9, 1497. doi: 10.1016/j.elecom.2007.01.059(20) Moshuchak, L. M.; Bulinski, M.; Lamanna,W. M.;Wang, R. L.;Dahn, J. R. Electrochem. Commun. 2007, 9, 1497. doi: 10.1016/j.elecom.2007.01.059
21. [21]
  (21) Han, Y. K.; Jung, J.; Yu, S.; Lee, H. J. Power Sources 2009, 187,581. doi: 10.1016/j.jpowsour.2008.10.137(21) Han, Y. K.; Jung, J.; Yu, S.; Lee, H. J. Power Sources 2009, 187,581. doi: 10.1016/j.jpowsour.2008.10.137
22. [22]
  (22) Chen, Z.; Qin, Y.; Amine, K. Electrochim. Acta 2009, 54, 5605.doi: 10.1016/j.electacta.2009.05.017(22) Chen, Z.; Qin, Y.; Amine, K. Electrochim. Acta 2009, 54, 5605.doi: 10.1016/j.electacta.2009.05.017
23. [23]
  (23) Li, T. T.;Wang, C. Y.; Xing, L. D.; Li,W. S.; Peng, B.; Xu, M.Q.; Gu, F. L.; Hu, S. J. Acta Phys. -Chim. Sin. 2012, 28, 818.[李田田, 王朝阳, 刑丽丹, 李伟善, 彭彬, 许梦清, 顾凤龙,胡社军. 物理化学学报, 2012, 28, 818.] doi: 10.3866/PKU.WHXB201201132(23) Li, T. T.;Wang, C. Y.; Xing, L. D.; Li,W. S.; Peng, B.; Xu, M.Q.; Gu, F. L.; Hu, S. J. Acta Phys. -Chim. Sin. 2012, 28, 818.[李田田, 王朝阳, 刑丽丹, 李伟善, 彭彬, 许梦清, 顾凤龙,胡社军. 物理化学学报, 2012, 28, 818.] doi: 10.3866/PKU.WHXB201201132
24. [24]
  (24) Dahn, J. R.; Jiang, J.; Moshurchak, L. M.; Fleischauer, M. D.;Buhrmester, C.; Krause, L. J. Electrochem. Soc. 2005, 152,A1283.(24) Dahn, J. R.; Jiang, J.; Moshurchak, L. M.; Fleischauer, M. D.;Buhrmester, C.; Krause, L. J. Electrochem. Soc. 2005, 152,A1283.
25. [25]
  (25) Weng,W.; Zhang, Z.; Redfern, P. C.; Curtiss, L. A.; Amine, K.J. Power Sources 2011, 196, 1530. doi: 10.1016/j.jpowsour.2010.08.049(25) Weng,W.; Zhang, Z.; Redfern, P. C.; Curtiss, L. A.; Amine, K.J. Power Sources 2011, 196, 1530. doi: 10.1016/j.jpowsour.2010.08.049
26. [26]
  (26) Zhang, S. S.; Xu, K.; Jow, T. R. Electrochim. Acta 2004, 49,1057. doi: 10.1016/j.electacta.2003.10.016(26) Zhang, S. S.; Xu, K.; Jow, T. R. Electrochim. Acta 2004, 49,1057. doi: 10.1016/j.electacta.2003.10.016
27. [27]
  (27) Zhang, S. S. J. Power Source 2007, 163, 713. doi: 10.1016/j.jpowsour.2006.09.040
  (27) Zhang, S. S. J. Power Source 2007, 163, 713. doi: 10.1016/j.jpowsour.2006.09.040

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

过充保护添加剂1,2-二甲氧基-4-硝基苯和1,4-二甲氧基-2-硝基苯在锂离子电池中的应用

English

Application of 1,2-Dimethoxy-4-nitro-benzene and 1,4-Dimethoxy- 2-nitro-benzene as Overcharge Protection Additives in Lithium-Ion Batteries

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

过充保护添加剂1,2-二甲氧基-4-硝基苯和1,4-二甲氧基-2-硝基苯在锂离子电池中的应用

English

Application of 1,2-Dimethoxy-4-nitro-benzene and 1,4-Dimethoxy- 2-nitro-benzene as Overcharge Protection Additives in Lithium-Ion Batteries

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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