LiCoO2电池正极微结构模拟退火重构及传输物性预测

吴伟; 蒋方明; 曾建邦

doi:10.7498/aps.63.048202

摘要

采用实验或数值方法对多孔复合电极微结构进行重构和特征化不仅是锂离子电池介观尺度数值模型的重要组成部分，也是通过数值技术由底向上进行电极微结构虚拟设计与优化的基础. 本文以某商用LiCoO2电池正极的孔隙率、电极组成材料的组分体积分数、活性材料颗粒粒径分布、相关函数等重要结构与统计信息作为输入参数，采用模拟退火法对其微结构进行了数值重建，得到了明确区分活性材料、固体添加物以及孔相（电解液）的微结构，其重要特性参数与实际电极一致. 对重构电极的特征化分析，得到了电极内部各组分的连通性、孔径分布等特征信息. 同时，采用D3Q15 格子Boltzmann 模型计算了重构电极的有效热导率以及电解液（或固相）的有效传输系数. 与随机行走模拟或Bruggemann等经验公式相比，基于实际电极微结构细节信息的介观数值方法对多孔电极有效传输系数的预测更为准确可靠.

关键词:

Abstract

Reconstruction and characterization of the porous composite electrode via experimental and numerical approaches is one of the most important ingredients of mesoscopic modeling. It is also the basis and prerequisite for bottom-to-up design and optimization of electrode microstructure. In the present work, a simulated annealing approach is employed to reconstruct the LiCoO2 cathode of a commercial Li-ion battery. Important statistical characteristic parameters of the real LiCoO2 cathode, such as porosity or component volume fraction, the real size distribution curve of LiCoO2 particles, which are taken from experimental data or extracted from the source materials used to fabricate the cathode, are used to regulate the reconstruction process. The reconstructed electrode evidently distinguishes the three individual phases: LiCoO2 as active material, pores or electrolyte, and additives. An extensive characterization is subsequently performed, which calculates some important structural and transport properties, including the geometrical connectivity of an individual phase, the specific surface area, etc. Particularly, a self-developed D3Q15 LB (lattice Boltzmann) model is utilized to calculate the effective thermal (or electric) conductivity and the effective species diffusivity in electrolyte (or solid) phase, and the tortuosity of an individual phase. The LB model predictions indicate that the effective transport coefficients are closely related to the micro-morphology in electrodes and the tortuosity values assessed by LBM are more reliable than those predicted by random walk simulation or the Bruggeman equation.

Keywords:

effective physical parameters /
mesoscopic modeling to lithium-ion battery /
simulated annealing approach /
lattice Boltzmann method

作者及机构信息

1.
中国科学院广州能源研究所, 先进能源系统实验室, 中国科学院可再生能源重点实验室, 广州 510640;

2.
中国科学院大学, 北京 100049

基金项目: 国家自然科学基金青年科学基金（批准号：51206171）和中国科学院百人计划（批准号：FJ）资助的课题.

Authors and contacts

1.
Key Laboratory of Renewable Energy of Chinese Academy of Sciences, Laboratory of Advanced Energy Systems, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China;

2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds: Project supported by the Young Scientists Fund of the National Natural Science Foundation of China (Grant No. 51206171) and the "100 Talents" Plan of Chinese Academy of Sciences (Grant No. FJ).

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[43]	Hoshen J, Kopelman R 1976 Phys. Rev. B 14 3438
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[46]	Promentilla M A B, Sugiyama T, Hitomi T, Takeda N 2009 Cement Concrete Res. 39 548

施引文献

[1]	Xin X G, Shen J Q, Shi S Q 2012 Chin. Phys. B 21 128202
[2]	Huang Z W, Hu S J, Hou X H, Zhao L Z, Ru Q, Li W S, Zhang Z W 2010 Chin. Phys. B 19 117101
[3]	Chen X C, Song Q, L H 2011 Marine Electr. Electron. Engineer. 31 1 (in Chinese) [陈新传, 宋强, 吕昊 2011 船电技术 31 1]
[4]	Chen Y C, Xie K, Pan Y, Zheng C M, Wang H L 2011 Chin. Phys. B 20 028201
[5]	Wang C W, Sastry A M 2007 J. Electrochem. Soc. 154 A1035
[6]	Du W B, Gupta A, Zhang X C, Sastry A M, Wei S Y 2010 Int. J. Heat Mass Transfer 53 3552
[7]	Gupta A, Seo J H, Zhang X C, Du W B, Sastry A M, Wei S Y 2011 J. Electrochem. Soc. 158 A487
[8]	Spanne P, Thovert J F, Jacquin C J 1994 Phys. Rev. Lett. 73 2001
[9]	Yoshizawa N, Tanaike O, Hatori H 2006 Carbon 44 2558
[10]	Groeber M A, Haley B K, Uchic M D 2006 Mater. Cha ract. 57 259
[11]	Shearing P R, Golbert J, Chater R 2009 J. Chem. Eng. Sci. 64 3928
[12]	Xu B, Wang S L, Li L Q, Li S J 2012 Acta Phys. Sin. 61 090201 (in Chinese) [徐波, 王树林, 李来强, 李生娟 2012 61 090201]
[13]	Li J, Yang C Z, Zhang X G, Zhang J, Xia B J 2009 Acta Phys. Sin. 58 6573 (in Chinese) [李佳, 杨传铮, 张熙贵, 张建, 夏保佳 2009 58 6573]
[14]	Qin P, Lou Y W, Yang C Z, Xia B J 2006 Acta Phys. Sin. 55 1325 (in Chinese) [钦佩, 娄豫皖, 杨传铮, 夏保佳 2006 55 1325]
[15]	Quiblier J 1984 J. Colloid Interface Sci. 98 84
[16]	Yeong C L Y, Torquato S 1998 Phys. Rev. E 57 495
[17]	Kim S H, Pitsch H. 2009 J. Electrochem. Soc. 156 B673
[18]	Čapek P, Hejtmánek V, Brabec L, Zikánová A, Kočiřík M 2008 Transport in Porous Media 76 179
[19]	Wu W, Jiang F M 2013 Mater. Charact. 80 62
[20]	Bakke S, Oren P E 1997 J. SPE 2 136
[21]	Stephenson D E, Walker B C, Skelton C B, Gorzkowski E P, Rowenhorst D J, Wheeler D R 2011 J. Electrochem. Soc. 158 A781
[22]	Wu W, Jiang F M, Chen Z, Wang Y, Zhao F G, Zeng Y Q 2013 J. Inorg. Mater. 28 1243 (in Chinese) [吴伟, 蒋方明, 陈治, 汪颖, 赵丰刚, 曾毓群 2013 无机材料学报 28 1243]
[23]	Zhang T 2009 Ph. D. Dissertation ( Hefei: University of Science and Technology of China) (in Chinese) [张挺 2009 博士学位论文 (合肥: 中国科学技术大学)]
[24]	Carson J K S, Lovatt J, Tanner D J, Cleland A C 2006 J. Food. Eng. 75 297
[25]	Wang J F, Carson J K, North M F, Cleland A C 2006 Int. J. Heat Mass Transfer 49 3075
[26]	Doyle M, Newman J, Fuller T F 1993 J. Electrochem. Soc. 140 1526
[27]	Das P K, Li X G, Liu Z S 2010 Appl. Energy 87 2785
[28]	Doyle M, Newman J, Gozdz A S, Schmutz C N, Tarascon J M 1996 J. Electrochem. Soc. 143 1890
[29]	Fuller T F, Doyle M, Newman J 1994 J. Electrochem. Soc. 141 1
[30]	Fan D, White R E 1991 J. Electrochem. Soc. 138 17
[31]	Patel K K, Paulser K M, Desilvestro J 2003 J. Power Sources 122 144
[32]	Thovert J F, Wary F, Adler P M 1990 J. Appl. Phys. 68 3872
[33]	Jiang F M, Sousa A C M 2006 Heat Mass Transfer 43 479
[34]	Shoshany Y, Prialnik D, Podolak M 2002 Icarus 157 219
[35]	Barta S, Dieska P 2002 Kovove Mater. 40 99
[36]	Wang M, Wang K, Pan N, Chen S 2007 Phys. Rev. E 75 036702
[37]	Xuan Y M, Zhao K, Li Q 2010 Heat Mass Transfer 46 1039
[38]	Joshi A S, Grew K N, Izzo J R, Peracchio A A, Chiu S W K 2010 J. Fuel Cell Sci. Technol. 7 011006
[39]	Torquato S 2002 Random Heterogeneous Materials: Microstructure and Macroscopic Properties (New York: Springer) p23
[40]	Zou Q, He X 1997 Phys. Fluids 9 1591
[41]	Wang J K, Wang M, Li Z X 2007 Int. J. Thermal Sci. 46 228
[42]	Ziegler D 1993 J. Stat. Phys. 71 1171
[43]	Hoshen J, Kopelman R 1976 Phys. Rev. B 14 3438
[44]	Kiyohara K, Sugino T, Asaka K 2010 J. Chem. Phys. 132 144705
[45]	Thorat V, Stephenson D E, Zacharias N A, Zaghib K, Harb J N, Wheeler D R 2009 J. Power Sources 188 592
[46]	Promentilla M A B, Sugiyama T, Hitomi T, Takeda N 2009 Cement Concrete Res. 39 548

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