SIOC English
化学学报
高级检索

化学学报 >

2013 , Vol. 71 >Issue 04: 508 - 518

DOI: https://doi.org/10.6023/A12121024

综述

Li-S电池硫正极性能衰减机理分析及研究现状概述

  • 刁岩 ,
  • 谢凯 ,
  • 洪晓斌 ,
  • 熊仕昭
展开
  • 国防科学技术大学 航天科学与工程学院 长沙 410073

收稿日期: 2012-12-10

  网络出版日期: 2013-02-01

收起

Analysis of the Sulfur Cathode Capacity Fading Mechanism and Review of the Latest Development for Li-S Battery

  • Diao Yan ,
  • Xie Kai ,
  • Hong Xiaobin ,
  • Xiong Shizhao
Expand
  • National University of Defense Technology, College of Aerospace Science and Engineering, Changsha 410073

Received date: 2012-12-10

  Online published: 2013-02-01

Fold

摘要

由于汽车工业的持续发展, 对高能量密度二次电池的需求逐步增加, 锂硫电池开始走进人们的视野. 锂硫电池的理论比能量高达2600 Wh/kg, 而单质硫的理论比容量达1680 mAh/g. 同时, 硫的储量丰富, 廉价, 并且环境友好. 虽然可充电锂硫电池相比于传统锂离子电池有诸多优势, 但目前其可实现的实际比容量远低于理论比容量, 循环寿命也较短等弊端限制了其大规模应用. 作者从Li-S电池正极的工作原理出发, 对硫正极容量损失及衰减机理做了深刻的解析, 并结合本实验室的工作归纳总结了导致硫正极容量衰减的主要因素. 针对硫正极容量衰减因素, 从碳导电结构、聚合物包覆以及纳米金属氧化物添加剂等方面, 对近年来提高硫正极性能的主要研究方向及最新研究进展进行了综述, 并对其中存在的问题进行分析, 最后对提高Li-S电池的整体性能提出展望.

关键词： Li-S电池; 硫正极; 容量衰减; 碳导电结构; 聚合物包覆; 纳米金属氧化物添加剂

本文引用格式

刁岩 , 谢凯 , 洪晓斌 , 熊仕昭 . Li-S电池硫正极性能衰减机理分析及研究现状概述[J]. 化学学报, 2013 , 71(04) : 508 -518 . DOI: 10.6023/A12121024

Abstract

Because of automotive industry sustainable development, the demand for higher energy density rechargeable batteries make the lithium-sulfur (Li-S) batteries become one of the most attractive candidates. The Li-S systems have a theoretical specific energy of 2600 Wh/kg while the theoretical capacity of sulfur is 1680 mAh/g. Sulfur is abundant, low cost and environment friendly. Although the rechargeable Li-S batteries possess more advantages over the conventional lithium ion batteries, the practical use faces with a variety of problems such as low specific capacity and short cycle life. Based on the fundamental electrochemical process of the sulfur cathode, the capacity fading mechanism of the sulfur cathode is analyzed in details. Combining with the works of our research team, the factors leading to the cathode property fading mechanism are summarized. Firstly, the main issue is that sulfur is both ionically and electrically insulating. And the insoluble low-order lithium polysulfide discharge products are also expected to be electronic insulators. So the cathode structure must contain electronic conductors (carbon or metal powder) which will decrease the energy density. Secondly, researchers impute the capacity fading into the residual Li2S2 and Li2S in sulfur cathode even at 100% depth of charge. The formation of Li2S2 and Li2S increasing with cycling results in active material loss. And the deposition of irreversible Li2S or Li2S2 at cracked surfaces of carbon particles causes cathode structural failure. Thirdly, high ordered lithium polysulfide (Li2Sn, 3≤n≤8) is soluble in electrolyte, but low ordered lithium polysulfide (Li2S2 and Li2S) is insoluble. Thus chemical precipitation/dissolution reactions occur during the electrochemical process resulting in active material transition between liquid phase and solid phase. But it is difficult for the high ordered lithium polysulfide to transfer completely from liquid phase to solid phase at the end of cycles, so that will lead to the active material loss. Fourthly, another serious problem is the irreversible oxidation of cathode active material. The formation of LixSOy species increasing with cycling indicates an important capacity fading mechanism of Li-S battery. In this paper, the main research directions and the latest development to enhance the performance of sulfur cathode are reviewed from the aspects of carbon conductive structure, polymer coatings and metal oxides additives, and also the problems in each research directions are analyzed. Finally, the further development of Li-S battery is discussed.

Key words： Li-S battery; sulfur cathode; capacity fading; carbon conductive structure; polymer coatings; nano-metal oxides additives

参考文献

[1] Bruce, P. G.; Freunberger, S. A.; Hardwick, L. J.; Tarascon, J. M. Nat. Mater. 2012, 11, 19.

[2] Ellis, B. L.; Lee, K. T.; Naza, L. F. Chem. Mater. 2010, 22, 691.

[3] Ji, X.; Nazar, L. F. J. Mater. Chem. 2010, 20, 9821.

[4] Evers, S.; Nazar, L. F. Acc. Chem. Res. 2012, DOI: 10.1021/ ar3001348.

[5] Diao, Y.; Xie, K.; Xiong, S.; Hong, X. J. Electrochem. Soc. 2012, 159, A421.

[6] Kumaresan, K.; Mikhaylik, Y.; White, R. E. J. Electrochem. Soc. 2008, 155, A576.

[7] Mikhaylik, Y. V.; Akridge, J. R. J. Electrochem. Soc. 2004, 151, A1969.

[8] Kolosnitsyn, V. S.; Karaseva, E. V. Russ. J. Electrochem. 2008, 44, 506.

[9] Cheon, S. E.; Ko, K. S.; Cho, J. H.; Kim, S. W.; Chin, E. Y. J. Electrochem. Soc. 2003, 150, A796.

[10] Akridge, J. R.; Mikhaylik, Y. V.; White, N. Solid State Ionics 2004, 175, 243.

[11] Hamann, C. H.; Hamnett, A.; Vielstich, W. Electrochemistry, 2nd ed., Chemical Industry Press, Beijing, 2009. (卡尔·哈曼, 活尔夫·菲尔施蒂希, 安德鲁·哈姆内特, 电化学, 第二版, 化学工业出版社, 北京, 2009.)

[12] He, X.; Ren, J.; Wang, L.; Pu, W.; Jiang, C.; Wan, C. J. Power Sources 2009, 190, 154.

[13] Cheon, S. E.; Ko, K. S.; Cho, J. H.; Kim, S. W.; Chin, E. Y. J. Electrochem. Soc. 2003, 150, A800.

[14] Cheon, S. E.; Choi, S. S.; Han, J. S.; Choi, Y. S.; Jung, B. H.; Lima, H. S. J. Electrochem. Soc. 2004, 151, A2067.

[15] Elazari, R.; Salitra, G.; Talyosef, Y.; Grinblat, J.; Kelley, C. S.; Xiao, A.; Affinito, J.; Aurbach, D. J. Electrochem. Soc. 2010, 157, A1131.

[16] Diao, Y.; Xie, K.; Xiong, S.; Hong, X. J. Electrochem. Soc. 2012, 159, A1816.

[17] Barchasz, C.; Leprêtre, J. C.; Alloin, F.; Patoux, S. J. Power Sources 2011.

[18] Barchasz, C.; Molton, F.; Duboc, C.; Leprêtre, J. C.; Patoux, S.; Alloin, F. Anal. Chem. 2011, 84, 3973.

[19] Han, S. C.; Song, M. S.; Lee, H.; Kim, H. S.; Ahn, H. J.; Lee, J. Y. J. Electrochem. Soc. 2003, 150, A889.

[20] Yuan, L.; Yuan, H.; Qiu, X.; Chen, L.; Zhu, W. J. Power Sources 2009, 189, 1141.

[21] Guo, J.; Xu, Y.; Wang, C. Nano Lett. 2011, 11, 4288.

[22] Wei, W.; Wang, J.; Zhou, L.; Yang, J.; Schumann, B.; NuLi, Y. Electrochem. Commun. 2011, 13, 399.

[23] Ahn, W.; Kim, K. B.; Jung, K. N.; Shin, K. H.; Jin, C. S. J. Power Sources 2012, 202, 394.

[24] Chen, J. J.; Zhang, Q.; Shi, Y. N.; Qin, L. L.; Cao, Y.; Zheng, M. S.; Dong, Q. F. Phys. Chem. Chem. Phys. 2012, 14, 5376.

[25] Dörfler, S.; Hagen, M.; Althues, H.; Tübke, J.; Kaskel, S.; Hoffmann, M. J. Chem. Commun. 2012, 48, 4097.

[26] Su, Y. S.; Fu, Y.; Manthiram, A. Phys. Chem. Chem. Phys. 2012, 14, 14495.

[27] Zhou, G. M.; Wang, D. W.; Li, F.; Hou, P. X.; Yin, L. C.; Liu, C.; Lu, G. Q.; Gentle, I. R.; Cheng, H. M. Energy Environ. Sci. 2012, 5, 8901.

[28] Zheng, W.; Liu, Y. W.; Hu, X. G.; Zhang, C. F. Electrochim. Acta 2006, 51, 1330.

[29] Choi, Y. J.; Kim, K. W.; Ahn, H. J.; Ahn, J. H. J. Alloys Compd. 2008, 449, 313.

[30] Ji, L.; Rao, M.; Aloni, S.; Wang, L.; Cairns, E. J.; Zhang, Y. Energy Environ. Sci. 2011, 4, 5053.

[31] Zheng, G.; Yang, Y.; Cha, J. J.; Hong, S. S.; Cui, Y. Nano Lett. 2011, 11, 4462.

[32] Ji, X.; Lee, K. T.; Nazar, L. F. Nat. Mater. 2009, 8, 500.

[33] Wang, J.; Chew, S. Y.; Zhao, Z. W.; Ashraf, S.; Wexler, D.; Chen, J.; Ng, S. H.; Chou, S. L.; Liu, H. K. Carbon 2008, 46, 229.

[34] Lai, C.; Gao, X. P.; Zhang, B.; Yan, T. Y.; Zhou, Z. J. Phys. Chem. C 2009, 113, 4712.

[35] Chen, S. R.; Zhai, Y. P.; Xu, G. L.; Jiang, Y. X.; Zhao, D. Y.; Li, J. T.; Huang, L.; Sun, S. G. Electrochim. Acta 2011, 56, 9549.

[36] Li, X.; Cao, Y.; Qi, W.; Saraf, L. V.; Xiao, J.; Nie, Z.; Mietek, J.; Zhang, J. G.; Schwenzer, B.; Liu, J. J. Mater. Chem. 2011, 21, 16603.

[37] Liang, X.; Wen, Z.; Liu, Y.; Zhang, H.; Huang, L.; Jin, J. J. Power Sources 2011, 196, 3655.

[38] Schuster, J.; He, G.; Mandlmeier, B.; Yim, T.; Lee, K. T.; Bein, T.; Nazar, L. F. Angew. Chem. 2012, 124, 3651.

[39] Kim, J.; Lee, D. J.; Jung, H. G.; Sun, Y.-K.; Hassoun, J.; Scrosati, B. Adv. Funct. Mater. 2012, DOI: 10.1002/adfm.201200689.

[40] He, G.; Ji, X.; Nazar, L. Energy Environ. Sci. 2011, 4, 2878.

[41] Jayaprakash, N.; Shen, J.; Moganty, S. S.; Corona, A.; Archer, L. A. Angew. Chem. 2011, 123, 6026.

[42] Zhang, C.; Wu, H. B.; Yuan, C.; Guo, Z.; Lou, X. W. Angew. Chem. 2012, 124, 9730.

[43] Liang, C.; Dudney, N. J.; Howe, J. Y. Chem. Mater. 2009, 21, 4724.

[44] Zhang, B.; Qin, X.; Li, G. R.; Gao, X. P. Energy Environ. Sci. 2010, 3, 1531.

[45] Cao, Y.; Li, X.; Aksay, I. A.; Lemmon, J.; Nie, Z.; Yang, Z.; Liu, J. Phys. Chem. Chem. Phys. 2011, 13, 7660.

[46] Ji, L.; Rao, M.; Zheng, H.; Zhang, L.; Li, Y.; Duan, W.; Guo, J.; Cairns, E. J.; Zhang, Y. J. Am. Chem. Soc. 2011, 133, 18522.

[47] Li, S.; Xie, M.; Liu, J.; Wang, H.; Yan, H. Electrochem. Solid-State Lett. 2011, 14, A105.

[48] Wang, H.; Yang, Y.; Liang, Y.; Robinson, J. T.; Li, Y.; Jackson, A.; Cui, Y.; Dai, H. Nano Lett. 2011, 11, 2644.

[49] Wang, J. Z.; Lu, L.; Choucair, M.; Stride, J. A.; Xu, X.; Liu, H. K. J. Power Sources 2011, 196, 7030.

[50] Evers, S.; Nazar, L. F. Chem. Commun. 2012, 48, 1233.

[51] Li, N.; Zheng, M.; Lu, H.; Hu, Z.; Shen, C.; Chang, X.; Ji, G.; Cao, J.; Shi, Y. Chem. Commun. 2012, 48, 4016.

[52] Park, M. S.; Yu, J. S.; Kim, K. J.; Jeong, G.; Kim, J. H.; Jo, Y. N.; Hwang, U.; Kang, S.; Woo, T.; Kim, Y. J. Phys. Chem. Chem. Phys. 2012, 14, 6796.

[53] Sun, H.; Xu, G. L.; Xu, Y. F.; Sun, S. G.; Zhang, X.; Qiu, Y.; Yang, S. Nano Res. 2012, 10, 726.

[54] Wang, D. W.; Zhou, G.; Li, F.; Wu, K. H.; Lu, G. Q.; Cheng, H. M.; Gentle, I. R. Phys. Chem. Chem. Phys. 2012, 14, 8703.

[55] Wang, Y. X.; Huang, L.; Sun, L. C.; Xie, S. Y.; Xu, G. L.; Chen, S. R.; Xu, Y. F.; Li, J. T.; Chou, S. L.; Dou, S. X.; Sun, S. G. J. Mater. Chem. 2012, 22, 4744.

[56] Wei, Z. K.; Chen, J. J.; Qin, L. L.; Nemage, A. W.; Zheng, M. S.; Dong, Q. F. J. Electrochem. Soc. 2012, 159, A1236.

[57] Yan, Y.; Yin, Y. X.; Xin, S.; Guo, Y. G.; Wan, L. J. Chem. Commun. 2012, 48, 10663.

[58] Zhang, F. F.; Zhang, X. B.; Dong, Y. H.; Wang, L. M. J. Mater. Chem. 2012, 22, 11452.

[59] Zhang, L.; Ji, L.; Glans, P. A.; Zhang, Y.; Zhu, J.; Guo, J. Phys. Chem. Chem. Phys. 2012, 14, 13670.

[60] Huang, J. Q.; Liu, X. F.; Zhang, Q.; Chen, C. M.; Zhao, M. Q.; Zhang, S. M.; Zhu, W.; Qian, W. Z.; Wei, F. Nano Energy 2012, DOI: 10.1016/j.nanoen.2012.10.003.

[61] Elazari, R.; Salitra, G.; Garsuch, A.; Panchenko, A.; Aurbach, D. Adv. Mater. 2011, 23, 5641.

[62] Wang, J.; Yang, J.; Xie, J.; Xu, N. Adv. Mater. 2002, 14, 962.

[63] Wang, J.; Yang, J.; Wan, C.; Du, K.; Xie, J.; Xu, N. Adv. Funct. Mater. 2003, 13, 487.

[64] Yu, X.; Xie, J.; Li, Y.; Huang, H.; Lai, C.; Wang, K. J. Power Sources 2005, 146, 335.

[65] Yin, L.; Wang, J.; Yang, J.; Nuli, Y. J. Mater. Chem. 2011, 21, 6807.

[66] Yin, L.; Wang, J.; Lin, F.; Yang, J.; Nuli, Y. Energy Environ. Sci. 2012, 5, 6966.

[67] Yin, L.; Wang, J.; Yu, X.; Monroe, C. W.; NuLi, Y.; Yang, J. Chem. Commun. 2012, 48, 7868.

[68] Wang, J.; Chen, J.; Konstantinov, K.; Zhao, L.; Ng, S. H.; Wang, G. X.; Guo, Z. P.; Liu, H. K. Electrochim. Acta 2006, 51, 4634.

[69] Sun, M.; Zhang, S.; Jiang, T.; Zhang, L.; Yu, J. Electrochem. Commun. 2008, 10, 1819.

[70] Qiu, L.; Zhang, S.; Zhang, L.; Sun, M.; Wang, W. Electrochim. Acta 2010, 55, 4632.

[71] Liang, X.; Liu, Y.; Wen, Z.; Huang, L.; Wang, X.; Zhang, H. J. Power Sources 2011, 196, 6951.

[72] Liang, X.; Wen, Z.; Liu, Y.; Wang, X.; Zhang, H.; Wu, M.; Huang, L. Solid State Ionics 2011, 192, 347.

[73] Liang, X.; Wen, Z.; Liu, Y.; Zhang, H.; Jin, J.; Wu, M.; Wu, X. J. Power Sources 2012, 206, 409.

[74] Fu, Y.; Manthiram, A. RSC Adv. 2012, 2, 5927.

[75] Fu, Y.; Manthiram, A. Chem. Mater. 2012, 24, 3081.

[76] Fu, Y.; Su, Y. S.; Manthiram, A. J. Electrochem. Soc. 2012, 159, A1420.

[77] Zhang, Y.; Bakenov, Z.; Zhao, Y.; Konarov, A.; Doan, T. N. L.; Malik, M.; Paron, T.; Chen, P. J. Power Sources 2012, 208, 1.

[78] Wu, F.; Wu, S.; Chen, R.; Chen, J.; Chen, S. Electrochem. Solid-State Lett. 2010, 13, A29.

[79] Wu, F.; Chen, J.; Chen, R.; Wu, S.; Li, L.; Chen, S.; Zhao, T. J. Phys. Chem. C 2011, 115, 6057.

[80] Wu, F.; Chen, J.; Li, L.; Zhao, T.; Chen, R. J. Phys. Chem. C 2011, 115, 24411.

[81] Li, G. C.; Li, G. R.; Ye, S. H.; Gao, X. P. Adv. Energy Mater. 2012, 2, 1238.

[82] Xiao, L.; Cao, Y.; Xiao, J.; Schwenzer, B.; Engelhard, M. H.; Liu, J. Adv. Mater. 2012, 24, 1176.

[83] Yang, Y.; Yu, G.; Cha, J. J.; Wu, H.; Vosgueritchian, M.; Yao, Y.; Bao, Z.; Cui, Y. ACS Nano 2011, 5, 9187.

[84] Song, M. S.; Han, S. C.; Kim, H. S.; Kim, J. H.; Kim, K. T.; Kang, Y. M.; Ahn, H. J.; Dou, S. X.; Lee, J. Y. J. Electrochem. Soc. 2004, 151, A791.

[85] Zheng, W.; Hu, X. G.; Zhang, C. F. Electrochem. Solid-State Lett. 2006, 9, A364.

[86] Zhang, Y.; Wu, X.; Feng, H.; Wang, L.; Zhang, A.; Xia, T.; Dong, H. Int. J. Hydrogen Energy 2009, 34, 1556.

[87] Evers, S.; Yim, T.; Nazar, L. F. J. Phys. Chem. C 2012, 116, 19653.

[88] Zhang, Y.; Bakenov, Z.; Zhao, Y.; Konarov, A.; Doan, T. N. L.; Sun, K. E. K.; Yermukhambetova, A.; Chen, P. Powder Technol. 2013, 235, 248.

[89] Zhang, Y.; Zhao, Y.; Yermukhambetova, A.; Bakenov, Z.; Chen, P. J. Mater. Chem. A 2013, 1, 295.

[90] Lee, K. T.; Black, R.; Yim, T.; Ji, X.; Nazar, L. F. Adv. Energy Mater. 2012, 2, 1490.

[91] Cakan, R. D.; Morcrette, M.; Nouar, F.; Davoisne, C.; Devic, T.; Gonbeau, D.; Dominko, R.; Serre, C.; Tarascon, J. M. J. Am. Chem. Soc. 2011, 133, 16154.
Options
文章导航

/

〈 〉