Research Papers

Three-Dimensional Finite Element Study on Lithium Diffusion and Intercalation-Induced Stress in Polycrystalline LiCoO2 Using Anisotropic Material Properties

[+] Author and Article Information
Linmin Wu

Department of Mechanical and
Energy Engineering,
Indiana University-Purdue University
Indianapolis, IN 46202

Jing Zhang

Department of Mechanical and
Energy Engineering,
Indiana University-Purdue University
Indianapolis, IN 46202
e-mail: jz29@iupui.edu

1Corresponding author.

Manuscript received August 24, 2018; final manuscript received November 5, 2018; published online December 12, 2018. Assoc. Editor: Ying Sun.

J. Electrochem. En. Conv. Stor. 16(2), 021008 (Dec 12, 2018) (5 pages) Paper No: JEECS-18-1089; doi: 10.1115/1.4041981 History: Received August 24, 2018; Revised November 05, 2018

In this study, lithium (Li) intercalation-induced stress of LiCoO2 with anisotropic properties using three-dimensional (3D) microstructures has been studied systematically. Phase field method was employed to generate LiCoO2 polycrystals with varying grain sizes. Li diffusion and stresses inside the polycrystalline microstructure with different grain size, grain orientation, and grain boundary diffusivity were investigated using finite element method. The results show that the anisotropic mechanical properties and Li concentration-dependent volume expansion coefficient have a very small influence on the Li chemical diffusion coefficients. The low partial molar volume of LiCoO2 leads to this phenomenon. The anisotropic mechanical properties have a large influence on the magnitude of stress generation. Since the Young's modulus of LiCoO2 along the diffusion pathway (a–b axis) is higher than that along c–axis, the Li concentration gradient is larger along the diffusion pathway. Thus, for the same intercalation-induced strain, the stress generation will be higher (∼40%) than that with isotropic mechanical properties as discussed in our previous study (Wu, L., Zhang, Y., Jung, Y.-G., and Zhang, J., 2015, “Three-Dimensional Phase Field Based Finite Element Study on Li Intercalation-Induced Stress in Polycrystalline LiCoO2,” J. Power Sources, 299, pp. 57–65). This work demonstrates the importance to include anisotropic property in the model.

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Tarascon, J. M. , and Armand, M. , 2001, “ Issues and Challenges Facing Rechargeable Lithium Batteries,” Nature, 414(6861), pp. 359–367. [CrossRef] [PubMed]
Wang, H. , Jang, Y. I. , Huang, B. , Sadoway, D. R. , and Chiang, Y. M. , 1999, “ TEM Study of Electrochemical Cycling—Induced Damage and Disorder in LiCoO2 Cathodes for Rechargeable Lithium Batteries,” J. Electrochem. Soc., 146(2), pp. 473–480. [CrossRef]
Chen, G. , Song, X. , and Richardson, T. J. , 2006, “ Electron Microscopy Study of the LiFePO4 to FePO4 Phase Transition,” Electrochem. Solid-State Lett., 9(6), pp. A295–A298. [CrossRef]
Gabrisch, H. , Wilcox, J. , and Doeff, M. M. , 2008, “ TEM Study of Fracturing in Spherical and Plate-Like LiFePO4 Particles,” Electrochem. Solid-State Lett., 11(3), pp. A25–A29. [CrossRef]
Boulineau, A. , Simonin, L. , Colin, J.-F. , Canévet, E. , Daniel, L. , and Patoux, S. , 2012, “ Evolutions of Li1.2Mn0.61Ni0.18Mg0.01O2 During the Initial Charge/Discharge Cycle Studied by Advanced Electron Microscopy,” Chem. Mater., 24(18), pp. 3558–3566. [CrossRef]
Wu, L. , Xiao, X. , Wen, Y. , and Zhang, J. , 2016, “ Three-Dimensional Finite Element Study on Stress Generation in Synchrotron X-Ray Tomography Reconstructed Nickel–Manganese–Cobalt Based Half Cell,” J. Power Sources, 336, pp. 8–18. [CrossRef]
Wu, L. , Wen, Y. , and Zhang, J. , 2016, “ Three-Dimensional Finite Element Study on Li Diffusion Induced Stress in FIB-SEM Reconstructed LiCoO2 Half Cell,” Electrochim. Acta, 222, pp. 814–820. [CrossRef]
Zhang, J. , Lu, B. , Song, Y. , and Ji, X. , 2012, “ Diffusion Induced Stress in Layered Li-Ion Battery Electrode Plates,” J. Power Sources, 209, pp. 220–227. [CrossRef]
Yamakawa, S. , Nagasako, N. , Yamasaki, H. , Koyama, T. , and Asahi, R. , 2018, “ Phase-Field Modeling of Stress Generation in Polycrystalline LiCoO2,” Solid State Ionics, 319, pp. 209–217. [CrossRef]
Lu, Y. , Zhang, P. , Wang, F. , Zhang, K. , and Zhao, X. , 2018, “ Reaction-Diffusion-Stress Coupling Model for Li-Ion Batteries: The Role of Surface Effects on Electrochemical Performance,” Electrochim. Acta, 274, pp. 359–369. [CrossRef]
Wu, L. , and Zhang, J. , 2015, “ Ab Initio Study of Anisotropic Mechanical Properties of LiCoO2 During Lithium Intercalation and Deintercalation Process,” J. Appl. Phys., 118(22), p. 225101. [CrossRef]
Christensen, J. , and Newman, J. , 2006, “ A Mathematical Model of Stress Generation and Fracture in Lithium Manganese Oxide,” J. Electrochem. Soc., 153(6), pp. A1019–A1030. [CrossRef]
Christensen, J. , and Newman, J. , 2006, “ Stress Generation and Fracture in Lithium Insertion Materials,” J. Solid State Electrochem., 10(5), pp. 293–319. [CrossRef]
Cheng, Y.-T. , and Verbrugge, M. W. , 2010, “ Diffusion-Induced Stress, Interfacial Charge Transfer, and Criteria for Avoiding Crack Initiation of Electrode Particles,” J. Electrochem. Soc., 157(4), pp. A508–A516. [CrossRef]
Woodford, W. H. , Chiang, Y.-M. , and Carter, W. C. , 2010, “‘ Electrochemical Shock’ of Intercalation Electrodes: A Fracture Mechanics Analysis,” J. Electrochem. Soc., 157(10), pp. A1052–A1059. [CrossRef]
Sun, G. , Sui, T. , Song, B. , Zheng, H. , Lu, L. , and Korsunsky, A. M. , 2016, “ On the Fragmentation of Active Material Secondary Particles in Lithium Ion Battery Cathodes Induced by Charge Cycling,” Extreme Mech. Lett., 9, pp. 449–458. [CrossRef]
Song, B. , Sui, T. , Ying, S. , Li, L. , Lu, L. , and Korsunsky, A. M. , 2015, “ Nano-Structural Changes in Li-Ion Battery Cathodes During Cycling Revealed by FIB-SEM Serial Sectioning Tomography,” J. Mater. Chem. A, 3(35), pp. 18171–18179. [CrossRef]
Han, S. , Park, J. , Lu, W. , and Sastry, A. M. , 2013, “ Numerical Study of Grain Boundary Effect on Li+ Effective Diffusivity and Intercalation-Induced Stresses in Li-Ion Battery Active Materials,” J. Power Sources, 240, pp. 155–167. [CrossRef]
Wu, L. , Zhang, Y. , Jung, Y.-G. , and Zhang, J. , 2015, “ Three-Dimensional Phase Field Based Finite Element Study on Li Intercalation-Induced Stress in Polycrystalline LiCoO2,” J. Power Sources, 299, pp. 57–65. [CrossRef]
Pavoni, F. H. , Sita, L. E. , dos Santos, C. S. , da Silva, S. P. , da Silva, P. R. C. , and Scarminio, J. , 2018, “ LiCoO2 Particle Size Distribution as a Function of the State of Health of Discarded Cell Phone Batteries,” Powder Technol., 326, pp. 78–83. [CrossRef]
Deng, Z. , Mo, Y. , and Ong, S. P. , 2016, “ Computational Studies of Solid-State Alkali Conduction in Rechargeable Alkali-Ion Batteries,” NPG Asia Mater., 8(3), p. e254. [CrossRef]
Wu, L. , Lee, W. H. , and Zhang, J. , 2014, “ First Principles Study on the Electrochemical, Thermal and Mechanical Properties of LiCoO2 for Thin Film Rechargeable Battery,” Mater. Today, 1(1), pp. 82–93. [CrossRef]
Zhang, X. , Shyy, W. , and Marie Sastry, A. , 2007, “ Numerical Simulation of Intercalation-Induced Stress in Li-Ion Battery Electrode Particles,” J. Electrochem. Soc., 154(10), pp. A910–A916. [CrossRef]
Reimers, J. N. , and Dahn, J. R. , 1992, “ Electrochemical and In Situ X-Ray Diffraction Studies of Lithium Intercalation in LixCoO2,” J. Electrochem. Soc., 139(8), pp. 2091–2097. [CrossRef]
Wen, C. J. , Boukamp, B. A. , Huggins, R. A. , and Weppner, W. , 1979, “ Thermodynamic and Mass Transport Properties of ‘LiAl’,” J. Electrochem. Soc., 126(12), pp. 2258–2266. [CrossRef]
Van der Ven, A. , Aydinol, M. , Ceder, G. , Kresse, G. , and Hafner, J. , 1998, “ First-Principles Investigation of Phase Stability in LixCoO2,” Phys. Rev. B, 58(6), pp. 2975–2987. [CrossRef]
Yamakawa, S. , Yamasaki, H. , Koyama, T. , and Asahi, R. , 2013, “ Numerical Study of Li Diffusion in Polycrystalline LiCoO2,” J. Power Sources, 223, pp. 199–205. [CrossRef]
Ramadass, P. , Haran, B. , White, R. , and Popov, B. N. , 2003, “ Mathematical Modeling of the Capacity Fade of Li-Ion Cells,” J. Power Sources, 123(2), pp. 230–240. [CrossRef]
Chen, B. , Zhou, J. , Zhu, J. , and Liu, Z. , 2014, “ Diffusion Induced Stress and the Distribution of Dislocations in a Nanostructured Thin Film Electrode During Lithiation,” RSC Adv., 4(109), pp. 64216–64224. [CrossRef]
Jang, Y.-I. , Neudecke, B. J. , and Dudney, N. J. , 2001, “ Lithium Diffusion in LixCoO2 (0.45 < x < 0.7) Intercalation Cathode,” Electrochem. Solid-State Lett., 4(6), pp. A94–A77. [CrossRef]
Hao, F. , and Mukherjee, P. P. , 2018, “ Mesoscale Analysis of the Electrolyte-Electrode Interface in All-Solid-State Li-Ion Batteries,” J. Electrochem. Soc., 165(9), pp. A1857–A1864. [CrossRef]
Zhao, K. , Pharr, M. , Vlassak, J. J. , and Suo, Z. , 2010, “ Fracture of Electrodes in Lithium-Ion Batteries Caused by Fast Charging,” J. Appl. Phys., 108(7), p. 073517.


Grahic Jump Location
Fig. 2

Schematics of local lithium diffusion coordinate system and the global lithium diffusion coordinate system. e1, e2, and e3 are local lithium diffusion coordinate system, while e1′, e2′, and e3′ are global lithium diffusion coordinate system. α and γ are crystallographic orientation angles. The global lithium influx is in e1′.

Grahic Jump Location
Fig. 1

Generated polycrystalline LiCoO2 microstructures. Different colors mean different grain orientations. Average grain size is (a) 1.84 μm, (b) 2.14 μm, (c) 2.56 μm, and (d) 2.7 μm.

Grahic Jump Location
Fig. 3

Chemical diffusion coefficients with different orientation: (a) β = 0.01 and (b) β = 1. Dashed lines are guide to the eyes for literature data. Solid lines are guide to the eyes for this work.

Grahic Jump Location
Fig. 4

The hydrostatic stresses on different grain sizes and orientation angles: (a) β = 0.01 and (b) β = 1. Dashed lines are guide to the eyes for literature data. Solid lines are guide to the eyes for this work.

Grahic Jump Location
Fig. 5

(a) Lithium concentration profiles and (b) Hydrostatic stresses of polycrystalline LiCoO2 with 1.84 μm grain size and different grain boundary diffusivities. The plane shown is a cut plane at z = 6.4 μm, t = 50 s, and orientation angle 30 deg.



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