锂离子动力电池高倍率充放电过程中弛豫行为的仿真

汤依伟; 艾亮; 程昀; 王安安; 李书国; 贾明

doi:10.7498/aps.65.058201

摘要

基于电化学热耦合模型研究了动力锂离子电池高倍率充放电过程中的弛豫行为, 分析对比了不同充放电机制对电池弛豫行为的影响. 研究发现: 充放电过程中, 欧姆极化是造成电压骤变的主要原因; 而恒流-恒压的充电模式能够缓慢消除欧姆极化, 避免电池电压的骤变; 利用恒流恒压对电池进行充电能够充进更多的电量, 有利于电池性能的完全发挥; 固相锂离子浓度的弛豫时间比液相锂离子浓度的弛豫时间长, 并且在放电后期, 固相扩散的特征时间与液相扩散特征时间的比值不断增大, 固相扩散造成的极化在整个放电过程不可忽略.

关键词:

弛豫 /
耦合 /
固相扩散 /
液相扩散

Abstract

The relaxation behaviors of a power lithium-ion battery significantly affect its performance, and these properties are greatly affected by temperature. This study presents a validated electrochemical-thermal model battery model covering the conservations of charge, mass, and energy and the electrochemical reaction kinetics, and considering the effect of heat on electrochemical performance of a battery. Using this battery model, the relaxation behavior of power lithium-ion battery in high-rate charging-discharging process and the effect of difference among charge-discharge systems are investigated. It is found that ohmic polarization is the main reason for voltage change in charging-discharging process. Constant-current-constant-voltage charging mode can effectively remit ohmic polarization and then avoid changing the voltage rapidly. In the shelving process after constant-current-constant-voltage charging, voltage change is smaller and the time for it to take to reach open circuit potential is shorter than in the shelving process after constant-current charging. In charging-discharging process, the values of polarization at positive and negative electrode are almost the same. Power lithium-ion battery can be charged into more energy by constant-current-constant-voltage charging modes, meaning that it is beneficial to battery performance. Because active material particles in electrodes have certain sizes, in discharging process, there is some gradient between the surface and center of solid particle, and the electrodes each have a certain thickness, different place of electrode has a different lithium-ion concentration. In the shelving process after discharging, there is no outer current, so the gradient of lithium-ion concentration disappears due to the effect of diffusion process. The relaxation time of lithium-ion concentration in solid phase is longer than in liquid phase. The ratio between characteristic time of solid diffusion and that of liquid diffusion increases constantly near the end of the discharge, thus the polarization due to solid diffusion cannot be neglected in the whole discharging process.

Keywords:

作者及机构信息

1.
中南大学冶金与环境学院, 长沙 410083;

2.
湖南艾华集团股份有限公司, 益阳 413002

通信作者: 贾明, csulightmetals11@163.com

基金项目: 国家自然科学基金(批准号: 51204211, 51222403)、中南大学基础研究基金(批准号: 2014zzts029)和工信部工业转型升级强基工程专项(批准号: 0714-EMTC02-5271/6)资助的课题.

Authors and contacts

1.
School of Metallurgy and Environment, Central South University, Changsha 410083, China;

2.
Hunan Aihua Group Co., LTD, Yiyang 413002, China

Corresponding author: Jia Ming, csulightmetals11@163.com

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 51204211, 51222403), the Fundamental Research Funds for Central Universities of Central South University, China (Grant No. 2014zzts029), and the Special Foundation for Industrial Upgrading Transformation and Strengthen the Foundation of Ministry of Industry and Information Technology, China (Grant No. 0714-EMTC02-5271/6).

参考文献

[1]	Chen Y, Li J, Jia M, Tang Y W, Du S L, Ai L H, Yin B H, Ai L 2015 Acta Phys. Sin. 64 210202 (in Chinese) [程昀, 李劼, 贾明, 汤依伟, 杜双龙, 艾立华, 殷宝华, 艾亮 2015 64 210202]
[2]	Scrosati B, Garche J 2010 J. Power Sources 195 2419
[3]	Hannan M A, Azidin F A, Mohamed A 2014 Renew. Sust. Energ. Rev. 29 135
[4]	Newman J, Tiedemann W 1975 AICHE J 21 25
[5]	Doyle M, Newman J 1995 Electrochim. Acta 40 2191
[6]	Li J, Cheng Y, Jia M, Tang Y W, Lin Y, Zhang Z A, Liu Y X 2014 J. Power Sources 255 130
[7]	Huang L, Li J Y 2015 Acta Phys. Sin. 64 108202 (in Chinese) [黄亮, 李建远 2015 64 108202]
[8]	Tang Y W, Jia M, Li J, Lai Y Q, Cheng Y, Liu Y X 2014 J. Electrochem. Soc. 161 E3021
[9]	Tang Y W, Jia M, Chen Y, Zhang K, Zhang H L, Li J 2013 Acta Phys. Sin. 62 158201 (in Chinese) [汤依伟, 贾明, 程昀, 张凯, 张红亮, 李劼 2013 62 158201]
[10]	Du S L, Jia M, Cheng Y, Tang Y W, Zhang H L, Ai L H, Zhang K, Lai Y Q 2015 Int. J. Them. Sci. 89 327
[11]	Dai Y, Cai L, White R E 2014 J. Power Sources 247 365
[12]	Zheng H, Liu X, Wei M 2015 Chin. Phys. B24 098801
[13]	Dai Y, Cai L, White R E 2013 J. Electorchem. Soc. 160 A182
[14]	Kang J Q, Conlisk A T, Rizzoni G 2014 J. Solid State Electrochem 18 2425
[15]	Nyman A, Zavalis T G, Elger R, Behm, M, Lindbergh, G 2010 J. Electrochem. Soc. 157 A1236
[16]	Safari M, Delacourt C 2011 J. Electrochem. Soc. 158 A562
[17]	Fuller T F, Doyle M, Newman J 1994 J. Electrochem. Soc. 141 982
[18]	Bernardi D M, Go J Y 2011 J. Power Sources 196 412
[19]	Reichert M, Andre D, Rösmann A, Janssen P, Bremes H G, Sauer D U, Passerini S, Winter M 2013 J. Power Sources 239 45
[20]	Smith K, Wang C Y 2006 J. Power Sources 160 662
[21]	Jin W R, Lu S G, Pang J 2011 Chin. J. Inorg. Chem. 27 1675
[22]	Gerver R E, Meyers J P 2011 J. Electrochem. Soc. 158 A835
[23]	Tang Y W, Jia M, Li J, Lai Y Q, Cheng Y, Liu Y X 2014 J. Electrochem. Soc. 161 E3021
[24]	Ramadass P, Haran B, Gomadam P M, White R E, Popov B N 2004 J. Electrochem. Soc. 151 A196
[25]	Srinivasan V, Wang C Y 2003 J. Electrochem. Soc. 150 A98
[26]	Bernardi D, Pawlikowski E, Newman J 1985 J. Electrochem. Soc. 132 5
[27]	Valoen L O, Reimers J N 2005 J. Electorchem. Soc. 152 A882

施引文献

[1]	Chen Y, Li J, Jia M, Tang Y W, Du S L, Ai L H, Yin B H, Ai L 2015 Acta Phys. Sin. 64 210202 (in Chinese) [程昀, 李劼, 贾明, 汤依伟, 杜双龙, 艾立华, 殷宝华, 艾亮 2015 64 210202]
[2]	Scrosati B, Garche J 2010 J. Power Sources 195 2419
[3]	Hannan M A, Azidin F A, Mohamed A 2014 Renew. Sust. Energ. Rev. 29 135
[4]	Newman J, Tiedemann W 1975 AICHE J 21 25
[5]	Doyle M, Newman J 1995 Electrochim. Acta 40 2191
[6]	Li J, Cheng Y, Jia M, Tang Y W, Lin Y, Zhang Z A, Liu Y X 2014 J. Power Sources 255 130
[7]	Huang L, Li J Y 2015 Acta Phys. Sin. 64 108202 (in Chinese) [黄亮, 李建远 2015 64 108202]
[8]	Tang Y W, Jia M, Li J, Lai Y Q, Cheng Y, Liu Y X 2014 J. Electrochem. Soc. 161 E3021
[9]	Tang Y W, Jia M, Chen Y, Zhang K, Zhang H L, Li J 2013 Acta Phys. Sin. 62 158201 (in Chinese) [汤依伟, 贾明, 程昀, 张凯, 张红亮, 李劼 2013 62 158201]
[10]	Du S L, Jia M, Cheng Y, Tang Y W, Zhang H L, Ai L H, Zhang K, Lai Y Q 2015 Int. J. Them. Sci. 89 327
[11]	Dai Y, Cai L, White R E 2014 J. Power Sources 247 365
[12]	Zheng H, Liu X, Wei M 2015 Chin. Phys. B24 098801
[13]	Dai Y, Cai L, White R E 2013 J. Electorchem. Soc. 160 A182
[14]	Kang J Q, Conlisk A T, Rizzoni G 2014 J. Solid State Electrochem 18 2425
[15]	Nyman A, Zavalis T G, Elger R, Behm, M, Lindbergh, G 2010 J. Electrochem. Soc. 157 A1236
[16]	Safari M, Delacourt C 2011 J. Electrochem. Soc. 158 A562
[17]	Fuller T F, Doyle M, Newman J 1994 J. Electrochem. Soc. 141 982
[18]	Bernardi D M, Go J Y 2011 J. Power Sources 196 412
[19]	Reichert M, Andre D, Rösmann A, Janssen P, Bremes H G, Sauer D U, Passerini S, Winter M 2013 J. Power Sources 239 45
[20]	Smith K, Wang C Y 2006 J. Power Sources 160 662
[21]	Jin W R, Lu S G, Pang J 2011 Chin. J. Inorg. Chem. 27 1675
[22]	Gerver R E, Meyers J P 2011 J. Electrochem. Soc. 158 A835
[23]	Tang Y W, Jia M, Li J, Lai Y Q, Cheng Y, Liu Y X 2014 J. Electrochem. Soc. 161 E3021
[24]	Ramadass P, Haran B, Gomadam P M, White R E, Popov B N 2004 J. Electrochem. Soc. 151 A196
[25]	Srinivasan V, Wang C Y 2003 J. Electrochem. Soc. 150 A98
[26]	Bernardi D, Pawlikowski E, Newman J 1985 J. Electrochem. Soc. 132 5
[27]	Valoen L O, Reimers J N 2005 J. Electorchem. Soc. 152 A882

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