Research Papers

Coupled Mechanical and Electrochemical Analyses of Three-Dimensional Reconstructed LiFePO4 by Focused Ion Beam/Scanning Electron Microscopy in Lithium-Ion Batteries

[+] Author and Article Information
Sangwook Kim

Mechanical and Aerospace
Engineering Department,
North Carolina State University,
R3311 Engineering Building 3,
Campus Box 7910 911,
911 Oval Drive,
Raleigh, NC 27695
e-mail: skim49@ncsu.edu

Hongjiang Chen

Mechanical and Aerospace
Engineering Department,
North Carolina State University,
R3311 Engineering Building 3,
Campus Box 7910 911,
911 Oval Drive,
Raleigh, NC 27695
e-mail: hchen30@ncsu.edu

Hsiao-Ying Shadow Huang

Mechanical and Aerospace
Engineering Department,
North Carolina State University,
R3158 Engineering Building 3,
Campus Box 7910 911,
911 Oval Drive,
Raleigh, NC 27695
e-mail: hshuang@ncsu.edu

1Corresponding author.

Manuscript received April 9, 2018; final manuscript received June 26, 2018; published online August 6, 2018. Assoc. Editor: Partha P. Mukherjee.

J. Electrochem. En. Conv. Stor. 16(1), 011010 (Aug 06, 2018) (7 pages) Paper No: JEECS-18-1032; doi: 10.1115/1.4040760 History: Received April 09, 2018; Revised June 26, 2018

Limited lifetime and performance degradation in lithium ion batteries in electrical vehicles and power tools is still a challenging obstacle which results from various interrelated processes, especially under specific conditions such as higher discharging rates (C-rates) and longer cycles. To elucidate these problems, it is very important to analyze electrochemical degradation from a mechanical stress point of view. Specifically, the goal of this study is to investigate diffusion-induced stresses and electrochemical degradation in three-dimensional (3D) reconstructed LiFePO4. We generate a reconstructed microstructure by using a stack of focused ion beam-scanning electron microscopy (FIB/SEM) images combined with an electrolyte domain. Our previous two-dimensional (2D) finite element model is further improved to a 3D multiphysics one, which incorporates both electrochemical and mechanical analyses. From our electrochemistry model, we observe 95.6% and 88.3% capacity fade at 1.2 C and 2 C, respectively. To investigate this electrochemical degradation, we present concentration distributions and von Mises stress distributions across the cathode with respect to the depth of discharge (DoD). Moreover, electrochemical degradation factors such as total polarization and over-potential are also investigated under different C-rates. Further, higher total polarization is observed at the end of discharging, as well as at the early stage of discharging. It is also confirmed that lithium intercalation at the electrode-electrolyte interface causes higher over-potential at specific DoDs. At the region near the separator, a higher concentration gradient and over-potential are observed. We note that higher over-potential occurs on the surface of electrode, and the resulting concentration gradient and mechanical stresses are observed in the same regions. Furthermore, mechanical stress variations under different C-rates are quantified during the discharging process. With these coupled mechanical and electrochemical analyses, the results of this study may be helpful for detecting particle crack initiation.

Copyright © 2019 by ASME
Your Session has timed out. Please sign back in to continue.


Palacín, M. R. , and De Guibert, A. , 2016, “Why Do Batteries Fail?,” Science, 351(6273), pp. 574–581.
Kim, S. , and Huang, H.-Y. S. , 2016, “Mechanical Stresses at the Cathode–Electrolyte Interface in Lithium-Ion Batteries,” J. Mater. Res., 31(22), pp. 3506–3512. [CrossRef]
Kim, S. , Wee, J. , Peters, K. , and Huang, H.-Y. S. , 2018, “Multiphysics Coupling in Lithium-Ion Batteries With Reconstructed Porous Microstructures,” J. Phys. Chem. C, 122(10), pp. 5280–5290. [CrossRef]
Xu, R. , and Zhao, K. , 2016, “Mechanical Interactions Regulated Kinetics and Morphology of Composite Electrodes in Li-Ion Batteries,” Extrem. Mech. Lett., 8, pp. 13–21. [CrossRef]
Lu, B. , Song, Y. , Zhang, Q. , Pan, J. , Cheng, Y.-T. , and Zhang, J. , 2016, “Voltage Hysteresis of Lithium Ion Batteries Caused by Mechanical Stress,” Phys. Chem. Chem. Phys., 18(6), pp. 4721–4727. [CrossRef] [PubMed]
Mendoza, H. , Roberts, S. A. , Brunini, V. E. , and Grillet, A. M. , 2016, “Mechanical and Electrochemical Response of a LiCoO2 Cathode Using Reconstructed Microstructures,” Electrochim. Acta, 190, pp. 1–15. [CrossRef]
Ghorbani Kashkooli, A. , Foreman, E. , Farhad, S. , Lee, D. U. , Ahn, W. , Feng, K. , De Andrade, V. , and Chen, Z. , 2017, “Synchrotron X-Ray Nano Computed Tomography Based Simulation of Stress Evolution in LiMn2O4electrodes,” Electrochim. Acta, 247, pp. 1103–1116. [CrossRef]
Liu, Z. , Chen-Wiegart, Y. K. , Wang, J. , Barnett, S. A. , and Faber, K. T. , 2016, “Three-Phase 3D Reconstruction of a LiCoO2 Cathode Via FIB-SEM Tomography,” Microsc. Microanal., 22(1), pp. 140–148. [CrossRef] [PubMed]
Biton, M. , Yufit, V. , Tariq, F. , Kishimoto, M. , and Brandon, N. , 2017, “Enhanced Imaging of Lithium Ion Battery Electrode Materials,” J. Electrochem. Soc., 164(1), pp. 6032–6038. [CrossRef]
Ender, M. , Joos, J. , Carraro, T. , and Ivers-Tiffee, E. , 2012, “Quantitative Characterization of LiFePO4 Cathodes Reconstructed by FIB/SEM Tomography,” J. Electrochem. Soc., 159(7), pp. A972–A980. [CrossRef]
Scipioni, R. , Jorgensen, P. S. , Ngo, D.-T. , Simonsen, S. B. , Liu, Z. , Yakal-Kremski, K. J. , Wang, H. , Hjelm, J. , Norby, P. , Barnett, S. A. , and Jensen, S. H. , 2016, “Electron Microscopy Investigations of Changes in Morphology and Conductivity of LiFePO4/C Electrodes,” J. Power Sources, 307, pp. 259–269. [CrossRef]
Kashkooli, A. G. , Farhad, S. , Lee, D. U. , Feng, K. , Litster, S. , Babu, S. K. , Zhu, L. , and Chen, Z. , 2016, “Multiscale Modeling of Lithium-Ion Battery Electrodes Based on Nano-Scale X-Ray Computed Tomography,” J. Power Sources, 307, pp. 496–509. [CrossRef]
Christensen, J. , 2010, “Modeling Diffusion-Induced Stress in Li-Ion Cells With Porous Electrodes,” J. Electrochem. Soc., 157(3), pp. A366–A380. [CrossRef]
Tahmasebi, A. , Sedaghat, A. , Kalbasi, R. , and Zand, M. M. , 2013, “Performance Assessment of a Hybrid Fuel Cell and Micro Gas Turbine Power System,” Energy Equip. Syst., 1, pp. 59–74. http://www.energyequipsys.com/article_2740_6c670cb4ab1e364b64d01c6c27c5efe7.pdf
Kim, S. , 2015, “Stresses at Electrode-Electrolyte Interface in Lithium-Ion Batteries Via Multiphysics Modeling,” M.S. thesis, North Carolina State University, Raleigh, NC. http://www.lib.ncsu.edu/resolver/1840.16/10671
Zhu, M. , Park, J. , and Sastry, A. M. , 2012, “Fracture Analysis of the Cathode in Li-Ion Batteries: A Simulation Study,” J. Electrochem. Soc., 159(4), pp. A492–A498. [CrossRef]
Xu, R. , Scalco De Vasconcelos, L. , and Zhao, K. , 2016, “Computational Analysis of Chemomechanical Behaviors of Composite Electrodes in Li-Ion Batteries,” J. Mater. Res., 31(18), pp. 2715–2727. [CrossRef]
ChiuHuang, C.-K. , and Huang, H.-Y. S. , 2015, “Critical Lithiation for C-Rate Dependent Mechanical Stresses in LiFePO4,” J. Solid State Electrochem., 19(8), pp. 2245–2253. [CrossRef]
ChiuHuang, C.-K. , and Shadow Huang, H.-Y. , 2013, “Stress Evolution on the Phase Boundary in LiFePO4 Particles,” J. Electrochem. Soc., 160(11), pp. A2184–A2188. [CrossRef]
Maxisch, T. , and Ceder, G. , 2006, “Elastic Properties of Olivine LixFePO4 From First Principles,” Phys. Rev. B, 73(17), p. 174112.


Grahic Jump Location
Fig. 1

(a) Experimental setup for FIB-SEM, (b) a stack of 2D images, (c) 3D reconstructed microstructure of LiFePO4, and (d) final microstructure and mesh in comsolmultiphysics

Grahic Jump Location
Fig. 2

Potential change during the discharging process under different C-rates

Grahic Jump Location
Fig. 3

Concentration distribution at 0.6 C at (a) 1200 s, (b) 2400 s, (c) 3600 s, (d) 4800 s, (e) 5400 s (color legend), and (f) cross-sectional contour plot at 5400 s in cyclic legend

Grahic Jump Location
Fig. 4

Concentration variation at three different points, P1, P2, and P3 (marked in Fig. 3) under various C-rates (i.e., 0.6 C, 1.2 C, and 2.0 C)

Grahic Jump Location
Fig. 5

(a) Total polarization and (b) overpotential at the interface between the electrode and the electrolyte at different points under 0.6 C, 1.2 C, and 2.0 C

Grahic Jump Location
Fig. 6

((a)–(c)) Contour plots of overpotential at the interface at different DoDs. ((d)–(f)) Contour plots of normalized concentration gradient at different DoDs. ((g)–(i)) Contour plots of von Mises stress distribution at different DoDs. C-rate = 0.6 C.

Grahic Jump Location
Fig. 7

Maximum normalized von Mises stress variation during discharging at 0.2 C, 0.6 C, 1.2 C, and 2.0 C



Some tools below are only available to our subscribers or users with an online account.

Related Content

Customize your page view by dragging and repositioning the boxes below.

Related Journal Articles
Related eBook Content
Topic Collections

Sorry! You do not have access to this content. For assistance or to subscribe, please contact us:

  • TELEPHONE: 1-800-843-2763 (Toll-free in the USA)
  • EMAIL: asmedigitalcollection@asme.org
Sign In