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Mesopores inside electrode particles can change the Li-ion transport mechanism and diffusion-induced stress

Published online by Cambridge University Press:  31 January 2011

Stephen J. Harris ,
Rutooj D. Deshpande ,
Yue Qi ,
Indrajit Dutta  and
Yang-Tse Cheng
Stephen J. Harris*
Affiliation:
General Motors R&D Center—Electrochemistry and Battery Systems, Warren, Michigan 48090
Rutooj D. Deshpande
Affiliation:
University of Kentucky, Department of Chemical and Materials Engineering, Lexington, Kentucky 40506-0046
Yue Qi
Affiliation:
General Motors R&D Center—Materials and Processes Laboratory Warren, Michigan 48090
Indrajit Dutta
Affiliation:
Trison Business Solutions, Inc.
Yang-Tse Cheng*
Affiliation:
University of Kentucky, Department of Chemical and Materials Engineering, Lexington, Kentucky 40506-0046
*
a)Address all correspondence to this author.e-mail:Stephen.j.harris@gm.com
b)This author was an editor of this journal during the review and decision stage. For the JMR policy on review and publication of manuscripts authored by editors, please refer to http://www.mrs.org/jmr_policy
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Abstract

Following earlier work of Huggins and Nix [Ionics6, 57 (2000)], several recent theoretical studies have used the shrinking core model to predict intraparticle Li concentration profiles and associated stress fields. A goal of such efforts is to understand and predict particle fracture, which is sometimes observed in degraded electrodes. In this paper we present experimental data on LiCoO2 and graphite active particles, consistent with previously published data, showing the presence of numerous internal pores or cracks in both positive and negative active electrode particles. New calculations presented here show that the presence of free surfaces, from even small internal cracks or pores, both quantitatively and qualitatively alters the internal stress distributions such that particles are prone to internal cracking rather than to the surface cracking that had been predicted previously. Thus, the fracture strength of particles depends largely on the internal microstructure of particles, about which little is known, rather than on the intrinsic mechanical properties of the particle materials. The validity of the shrinking core model for explaining either stress maps or transport is questioned for particles with internal structure, which includes most, if not all, secondary electrode particles.

Keywords

LiMicrostructureStress/strain relationship
Type
Articles
Information
Journal of Materials Research , Volume 25 , Issue 8: Materials for Electrical Energy Storage , August 2010 , pp. 1433 - 1440
Copyright
Copyright © Materials Research Society 2010

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References

REFERENCES

1.Huggins, R., Nix, W.Decrepitation model for capacity loss during cycling of alloys in rechargeable electrochemical systems. Ionics 6, 57 (2000)CrossRefGoogle Scholar
2.Cheng, Y., Verbrugge, M.The influence of surface mechanics on diffusion induced stresses within spherical nanoparticles. J. Appl. Phys. 104, 83521 (2008)CrossRefGoogle Scholar
3.Christensen, J., Newman, J.A mathematical model of stress generation and fracture in lithium manganese oxide. J. Electrochem. Soc. 153, A1019 (2006)CrossRefGoogle Scholar
4.Garcia, E., Chiang, Y., Carter, W., Limthongkul, P., Bishop, C.Microstructural modeling and design of rechargeable lithium-ion batteries. J. Electrochem. Soc. 152, A255 (2005)CrossRefGoogle Scholar
5.Zhang, X., Shyy, W., Sastry, A.M.Numerical simulation of intercalation-induced stress in Li-ion battery electrode particles. J. Electrochem. Soc. 154, A910 (2007)CrossRefGoogle Scholar
6.Gabrisch, H., Wilcox, J., Doeff, M.TEM study of fracturing in spherical and plate-like LiFePO4 particles. Electrochem. Solid-State Lett. 11, A25 (2008)CrossRefGoogle Scholar
7.Markervich, E., Salitra, G., Levi, M., Aurbach, D.Capacity fading of lithiated graphite electrodes studied by a combination of electroanalytical methods, Raman spectroscopy and SEM. J. Power Sources 146, 146 (2005)CrossRefGoogle Scholar
8.Itou, Y., Ukyo, Y.Performance of LiNiCoO2 materials for advanced lithium-ion batteries. J. Power Sources 146, 39 (2005)CrossRefGoogle Scholar
9.Ohzuku, T., Tamura, H., Sawai, K.Monitoring of particle fracture by acoustic emission during charge and discharge of Li/MnO2 cells. J. Electrochem. Soc. 144, 3496 (1997)CrossRefGoogle Scholar
10.Srinivasan, V., Newman, J.Discharge model for the lithium iron-phosphate electrode. J. Electrochem. Soc. 151, A1517 (2004)CrossRefGoogle Scholar
11.Srinivasan, V., Newman, J.Existence of path-dependence in the LiFePO4 electrode. Electrochem. Solid-State Lett. 9, A110 (2006)CrossRefGoogle Scholar
12.Andersson, A., Thomas, J.The source of first-cycle capacityloss in LiFePO4. J. Power Sources 97, 498 (2001)CrossRefGoogle Scholar
13.Wang, C., Sastry, A.M.Mesoscale modeling of a Li-ion polymer cell. J. Electrochem. Soc. 154, A1035 (2007)CrossRefGoogle Scholar
14.Singh, G., Ceder, G., Bazant, M.Intercalation dynamics in rechargeable battery materials: General theory and phase-transformation waves in LiFePO4. Electrochim. Acta 53, 7599 (2008)CrossRefGoogle Scholar
15.Delmas, C., Maccario, M., Croguennec, L., Cras, F.L., Weill, F.Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model. Nat. Mater. 7, 665 (2008)CrossRefGoogle Scholar
16.Chen, G., Song, X., Richardson, T.Electron microscopy study of the LiFePO4 to FePO4 phase transition. Electrochem. Solid-State Lett. 9, A295 (2006)CrossRefGoogle Scholar
17.Laffont, L., Delacourt, C., Gibot, P., Wu, M., Kooyman, P., Masquelier, C., Tarascon, J.M.Study of the LiFePO4/FePO4 two-phase system by high-resolution electron energy loss spectroscopy. Chem. Mater. 18, 5520 (2006)CrossRefGoogle Scholar
18.Joho, F., Rykarta, B., Blomea, A., Novák, P., Wilhelm, H., Spahr, M.E.Relation between surface properties, pore structure and first-cycle charge loss of graphite as negative electrode in lithium-ion batteries. J. Power Sources 97–98, 78 (2001)CrossRefGoogle Scholar
19.Zhang, H., Li, F., Liu, C., Tan, J., Cheng, H.New insight into the solid electrolyte interphase with use of a focused ion beam. J. Phys. Chem. B 109, 22205 (2005)CrossRefGoogle ScholarPubMed
20.Gostovic, D., Smith, J., Kundinger, D., Jones, K., Wachsman, E.Three-dimensional reconstruction of porous LSCF cathodes. Electrochem. Solid-State Lett. 10, B214 (2007)CrossRefGoogle Scholar
21.Uchic, M., Holzer, L., Inkson, B., Principe, E., Munroe, P.Three-dimensional microstructural characterization using focused ion beam tomography. MRS Bull. 32, (5)408 (2007)CrossRefGoogle Scholar
22.Wilson, J.R., Kobsiriphat, W., Mendoza, R., Chen, H-Y., Hiller, J.M., Miller, D.J., Thornton, K., Voorhees, P.W., Adler, S.B., Barnett, S.A.Three-dimensional reconstruction of a solid-oxide fuel-cell anode. Nat. Mater. 5, 541 (2006)CrossRefGoogle ScholarPubMed
23.Cheng, Y-T., Verbrugge, M.W.Evolution of stress within aspherical insertion electrode particle under potentiostatic andgalvanostatic operation. J. Power Sources 190, (2)453 (2009)CrossRefGoogle Scholar
24.Pollard, R., Newman, J.Mathematical modeling of the lithium-aluminum, iron sulfide battery. J. Electrochem. Soc. 128, 491 (1981)CrossRefGoogle Scholar
25.Hibbeler, R.C.Mechanics of Materials 3rd ed (Prentice Hall, Upper Saddle River, NJ 1997)Google Scholar