锂离子电池电极中锂枝晶的实时原位观测

doi:10.3969/j.issn.2095-4239.2015.01.007

储能科学与技术 ›› 2015, Vol. 4 ›› Issue (1): 66-71.doi: 10.3969/j.issn.2095-4239.2015.01.007

锂离子电池电极中锂枝晶的实时原位观测

朱建宇¹, 冯捷敏^{2, 3}, 郭战胜^{1, 2}

1 上海市应用数学和力学研究所,上海 200072;
2 上海市力学在能源工程中的应用重点实验室,上海 200072;
3 上海大学理学院力学系,上海 200444

收稿日期:2014-09-09 出版日期:2015-02-19 发布日期:2015-02-19
通讯作者: 郭战胜,副研究员,主要从事锂电池系统和电极材料的电化学-力学耦合研究,E-mail：davidzsguo@shu.edu.cn。
作者简介:朱建宇（1991—）,男,硕士研究生,主要从事锂电池电极材料的力学性能研究,E-mail：646131522@qq.com
基金资助:
国家自然科学基金（11472165,11332005）; 上海市自然科学基金（12ZR1410200）项目

In situ observation of lithium dendrite on the electrode in a lithium-ion battery

ZHU Jianyu¹, FENG Jiemin^{2, 3}, GUO Zhansheng^{1, 2}

1Shanghai Institute of Applied Mathematics and Mechanics,Shanghai 200072,China; 2Shanghai Key Laboratory of Mechanics in Energy Engineering,Shanghai 200072,China; 3Department of Mechanics,College of Science,Shanghai University,Shanghai 200444,China

Received:2014-09-09 Online:2015-02-19 Published:2015-02-19

摘要/Abstract

摘要： 锂离子电池尽管已成为便携式电子设备的主流电源,也是电动汽车、混合动力汽车等电源的主要选择之一,但依然存在使用过程中因形成锂枝晶而发生内短路的安全隐患。本文设计了一个宏微观实验研究商业用锂离子电池电极材料的充放电循环性能。在常温小电流充放电条件下,实时原位地观测锂枝晶的产生、生长、消融以及死锂残留等过程。实验结果揭示了锂枝晶不仅仅只是大电流过充或低温充电状态下的产物,常温常态小电流充电条件下依然能够生成锂枝晶。实验发现：锂枝晶出现在充电后期,随后直线伸长,尖端区域形貌保持不变;放电时,锂枝晶逐渐消融,尖端区域形貌依然不变,放电结束后电极上有死锂残留。

关键词: 锂离子电池, 原位实时观测, 锂枝晶, 死锂

Abstract: Lithium-ion batteries (LIBs) are the state-of-the-art power sources for portable electronic devices. Furthermore, LIBs have now emerged as the most promising power source for electric vehicles, hybrid vehicles and plug-in hybrid vehicles. LIBs have some safety problems, such as the formation of lithium dendrite which can cause internal short-circuiting. In this paper, the cyclic performance of electrode in commercial lithium-ion battery is studied with a macro-micro experiment. Electrochemical experiment is carried at room temperature with small current G and the generation, growth, dissolution and residue of lithium dendrite are observed. It reveals that lithium dendrite can be formed not only under large-current overcharge or low-temperature charge but also under small current and at room temperature. It has been found that lithium dendrite appears in the late charge, stretching straightly, and its tip topography remains unchanged. Lithium dendrite begins dissolving when discharge, whose tip morphology still unchanged, and dead lithium residues on the electrode after fully discharge.

Key words: lithium-ion battery, in situ observation, lithium dendrite, dead lithium

中图分类号:

TM911

朱建宇, 冯捷敏, 郭战胜. 锂离子电池电极中锂枝晶的实时原位观测[J]. 储能科学与技术, 2015, 4(1): 66-71.

ZHU Jianyu, FENG Jiemin, GUO Zhansheng. In situ observation of lithium dendrite on the electrode in a lithium-ion battery[J]. Energy Storage Science and Technology, 2015, 4(1): 66-71.

参考文献

[1] Ding F,Xu W,Graff G L, et al . Dendrite-free lithium deposition via self-healing electrostatic shield mechanism[J]. J. Am. Chem. Soc. ,2013,135：4450-4456.
[2] Chen Ling（陈玲）,Li Xueli（李雪莉）,Zhao Qiang（赵强）, et al . Bipolar pulse current charge method for inhibiting the formation of lithium dendrite[J]. Acta Phys. ： Chim. Sin. （物理化学学报）,2006,22（9）：1155-1158.
[3] Mayers M Z,Kaminski J W,Miller T F. Suppression of dendrite formation via pulse charging in rechargeable lithium metal batteries[J]. J. Phys. Chem. C ,2012,116：26214-26221.
[4] Aryanfar A,Brooks D,Merinov B V, et al . Dynamics of lithium dendrite growth and inhibition：Pulse charging experiments and monte carlo calculations[J]. J. Phys. Chem. Lett. ,2014,5：1721-1726.
[5] Chandrashekar S,Trease N M,Chang H J, et al . 7 Li MRI of Li batteries reveals location of microstructural lithium[J]. Nature Materials ,2012,11：311-315.
[6] Schweikert N,Hofmann A,Schulz M, et al . Suppressed lithium dendrite growth in lithium batteries using ionic liquid electrolytes：Investigation by electrochemical impedance spectroscopy, scanning electron microscopy, and in situ 7 Li nuclear magnetic resonance spectroscopy[J]. J. Power Sources ,2013,228：237-243.
[7] Honbo H,Takei K,Ishii Y, et al . Electrochemical properties and Li deposition morphologies of surface modified graphite after grinding[J]. J. Power Sources ,2009,189：337-343.
[8] Langenhuizen N P W. The effect of mass transport on Li deposition and dissolution[J]. J. Electrochem. Soc. ,1998,145（9）：3094-3099.
[9] Steiger J,Kramer D,Mönig R. Microscopic observations of the formation, growth and shrinkage of lithium moss during electrodeposition and dissolution[J]. Electrochim. Acta ,2014,136：529-536.
[10] Liu X H,Zhong L,Zhang L Q, et al . Lithium fiber growth on the anode in a nanowire lithium ion battery during charging[J]. Appl. Phys. Lett .,2011,98：183107.
[11] Ghassemi H,Au M,Chen N, et al . Real-time observation of lithium fibers growth inside a nanoscale lithiumion battery[J]. Appl. Phys. Lett. ,2011,99：123113.
[12] Nishikawa K,Mori T,Nishida T, et al . In situ observation of dendrite growth of electrodeposited Li metal[J]. J. Electrochem. Soc. ,2010,157（11）：A1212-A1217.
[13] Osaka T,Homma T,Momma T, et al . In situ observation of lithium deposition processes in solid polymer and gel electrolytes[J]. J. Electroanal. Chem. ,1997,421：153-156.
[14] Brissot C,Rosso M,Chazalviel J N, et al . In situ study of dendritic growth in lithium/PEO-salt/lithium cells[J]. Electrochim. Acta ,1998,43（10-11）：1569-1574.
[15] Akolkar R. Mathematical model of the dendritic growth during lithium electrodeposition[J]. J. Power Sources ,2013,232：23-28.
[16] Akolkar R. Modeling dendrite growth during lithium electrodeposition at sub-ambient temperature[J]. J. Power Sources ,2014,246：84-89.
[17] Seong I W,Hong C H,Kim B K, et al . The effects of current density and amount of discharge on dendrite formation in the lithium powder anode electrode[J]. J. Power Sources ,2008,178：769-773.
[18] Park H E,Hong C H,Yoon W Y. The effect of internal resistance on dendritic growth on lithium metal electrodes in the lithium secondary batteries[J]. J. Power Sources ,2008,178：765-768.
[19] Monroe C,Newman J. Dendrite growth in lithium/polymer systems-A propagation model for liquid electrolytes under galvanostatic conditions[J]. J. Electrochem. Soc. ,2003,150：A1377-A1384.
[20] Li Z,Huang J,Zhang J B, et al . A review of lithium deposition in lithium-ion and lithium metal secondary batteries[J]. J. Power Sources ,2014,254：168-182.
[21] Owejana J P,Gagliardoa J J,Harrisa S J, et al . Direct measurement of lithium transport in graphite electrodes using neutrons[J]. Electrochim. Acta ,2012,66：94-99.
[22] Dedryvère R,Martinez H,Leroy S, et al . Surface film formation on electrodes in a LiCoO 2 /graphite cell：A step by step XPS study[J]. J. Power Sources ,2007,174：462-468.
[23] Aurbach D,Mashkovich M. A study of lithium deposition-dissolution processes in a few selected electrolyte solutions by electrochemical quartz crystal microbalance[J]. J. Electrochem. Soc. ,1998,145（8）：A2629.
[24] Harris S J,Timmons A,Baker D R, et al . Direct in situ measurements of Li transport in Li-ion battery negative electrodes[J]. Chem. Phys. Lett. ,2010,485：265-274.

锂离子电池电极中锂枝晶的实时原位观测

In situ observation of lithium dendrite on the electrode in a lithium-ion battery

PDF

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	李海涛, 孔令丽, 张欣, 余传军, 王纪威, 徐琳. N/P设计对高镍NCM/Gr电芯性能的影响[J]. 储能科学与技术, 2022, 11(7): 2040-2045.
[2]	陈龙, 夏权, 任羿, 曹高萍, 邱景义, 张浩. 多物理场耦合下锂离子电池组可靠性研究现状与展望[J]. 储能科学与技术, 2022, 11(7): 2316-2323.
[3]	易顺民, 谢林柏, 彭力. 基于VF-DW-DFN的锂离子电池剩余寿命预测[J]. 储能科学与技术, 2022, 11(7): 2305-2315.
[4]	祝庆伟, 俞小莉, 吴启超, 徐一丹, 陈芬放, 黄瑞. 高能量密度锂离子电池老化半经验模型[J]. 储能科学与技术, 2022, 11(7): 2324-2331.
[5]	王宇作, 王瑨, 卢颖莉, 阮殿波. 孔结构对软碳负极储锂性能的影响[J]. 储能科学与技术, 2022, 11(7): 2023-2029.
[6]	孔为, 金劲涛, 陆西坡, 孙洋. 对称蛇形流道锂离子电池冷却性能[J]. 储能科学与技术, 2022, 11(7): 2258-2265.
[7]	霍思达, 薛文东, 李新丽, 李勇. 基于CiteSpace知识图谱的锂电池复合电解质可视化分析[J]. 储能科学与技术, 2022, 11(7): 2103-2113.
[8]	邓健想, 赵金良, 黄成德. 高能量锂离子电池硅基负极黏结剂研究进展[J]. 储能科学与技术, 2022, 11(7): 2092-2102.
[9]	刘显茜, 孙安梁, 田川. 基于仿生翅脉流道冷板的锂离子电池组液冷散热[J]. 储能科学与技术, 2022, 11(7): 2266-2273.
[10]	于春辉, 何姿颖, 张晨曦, 林贤清, 肖哲熙, 魏飞. 硅基负极与电解液化学反应的分析与抑制策略[J]. 储能科学与技术, 2022, 11(6): 1749-1759.
[11]	丁奕, 杨艳, 陈锴, 曾涛, 黄云辉. 锂离子电池智能消防及其研究方法[J]. 储能科学与技术, 2022, 11(6): 1822-1833.
[12]	张言, 王海, 刘朝孟, 张德柳, 王佳东, 李建中, 高宣雯, 骆文彬. 锂离子电池富镍三元正极材料NCM的研究进展[J]. 储能科学与技术, 2022, 11(6): 1693-1705.
[13]	欧宇, 侯文会, 刘凯. 锂离子电池中的智能安全电解液研究进展[J]. 储能科学与技术, 2022, 11(6): 1772-1787.
[14]	韩俊伟, 肖菁, 陶莹, 孔德斌, 吕伟, 杨全红. 致密储能：基于石墨烯的方法学和应用实例[J]. 储能科学与技术, 2022, 11(6): 1865-1873.
[15]	辛耀达, 李娜, 杨乐, 宋维力, 孙磊, 陈浩森, 方岱宁. 锂离子电池植入传感技术[J]. 储能科学与技术, 2022, 11(6): 1834-1846.