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Submicro-sized Si–Ge solid solutions with high capacity and long cyclability for lithium-ion batteries

Published online by Cambridge University Press:  25 May 2018

Kuber Mishra*
Affiliation:
Department of Chemical Engineering, University of South Carolina, Columbia, South Carolina 29208, USA
Xiao-Chen Liu
Affiliation:
College of Chemistry and Molecular Science, Wuhan University, Wuhan 430072, China
Mark Geppert
Affiliation:
Department of Chemical Engineering, University of South Carolina, Columbia, South Carolina 29208, USA
James J. Wu
Affiliation:
Electrochemistry Division, NASA Glenn Research Center, Cleveland, Ohio 44135, USA
Jun-Tao Li
Affiliation:
State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, China
Ling Huang
Affiliation:
State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, China
Shi-Gang Sun
Affiliation:
State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, China
Xiao-Dong Zhou*
Affiliation:
State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, China; and Department of Chemical Engineering, Institute for Materials Research and Innovation, University of Louisiana, Lafayette, Louisiana 70503, USA
Fu-Sheng Ke*
Affiliation:
College of Chemistry and Molecular Science, Wuhan University, Wuhan 430072, China
*
a)Address all correspondence to these authors. e-mail: kmishra@email.sc.edu
c)e-mail: kefs@whu.edu.cn
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Abstract

Mastery of strengthening strategies to achieve high-capacity anodes for lithium-ion batteries can shed light on understanding the nature of diffusion-induced stress and offer an approach to use submicro-sized materials with an ultrahigh capacity for large-scale batteries. Here, we report solute strengthening in a series of silicon (Si)–germanium (Ge) alloys. When the larger solute atom (Ge) is added to the solvent atoms (Si), a compressive stress is generated in the vicinity of Ge atoms. This local stress field interacts with resident dislocations and subsequently impedes their motion to increase the yield stress in the alloys. The addition of Ge into Si substantially improves the capacity retention, particularly in Si0.50Ge0.50, aligning with literature reports that the Si/Ge alloy showed a maximum yield stress in Si0.50Ge0.50. In situ X-ray diffraction studies on the Si0.50Ge0.50 electrode show that the phase change undergoes three subsequent steps during the lithiation process: removal of surface oxide layer, formation of cluster-size Lix(Si,Ge), and formation of crystalline Li15(Si,Ge)4. Furthermore, the lithiation process starts from higher index facets, i.e., (220) and (311), then through the low index facet (111), suggesting the orientation-dependence of the lithiation process in the Si0.50Ge0.50 electrode.

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Article
Copyright
Copyright © Materials Research Society 2018 

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Footnotes

d)

These authors contributed equally to this work.

References

REFERENCES

Chan, C.K., Peng, H., Liu, G., McIlwrath, K., Zhang, X.F., Huggins, R.A., and Cui, Y.: High-performance lithium battery anodes using silicon nanowires. Nat. Nanotechnol. 3, 31 (2008).CrossRefGoogle ScholarPubMed
Dębski, A., Zakulski, W., Major, Ł., Góral, A., and Gąsior, W.: Enthalpy of formation of the Li22Si5 intermetallic compound. Thermochim. Acta 551, 53 (2013).Google Scholar
Hatchard, T.D. and Dahn, J.R.: In situ XRD and electrochemical study of the reaction of lithium with amorphous silicon. J. Electrochem. Soc. 151, A838 (2004).Google Scholar
Dismukes, J.P., Ekstrom, L., and Paff, R.J.: Lattice parameter and density in germanium–silicon alloys1. J. Phys. Chem. 68, 3021 (1964).CrossRefGoogle Scholar
Wang, C., Wu, H., Chen, Z., McDowell, M.T., Cui, Y., and Bao, Z.: Self-healing chemistry enables the stable operation of silicon microparticle anodes for high-energy lithium-ion batteries. Nat. Chem. 5, 1042 (2013).Google Scholar
Liang, W., Yang, H., Fan, F., Liu, Y., Liu, X.H., Huang, J.Y., Zhu, T., and Zhang, S.: Tough germanium nanoparticles under electrochemical cycling. ACS Nano 7, 3427 (2013).Google Scholar
Zhao, K., Pharr, M., Vlassak, J.J., and Suo, Z.: Inelastic hosts as electrodes for high-capacity lithium-ion batteries. J. Appl. Phys. 109, 016110 (2011).Google Scholar
Murugesan, S., Harris, J.T., Korgel, B.A., and Stevenson, K.J.: Copper-coated amorphous silicon particles as an anode material for lithium-ion batteries. Chem. Mater. 24, 1306 (2012).Google Scholar
Abel, P.R., Chockla, A.M., Lin, Y-M., Holmberg, V.C., Harris, J.T., Korgel, B.A., Heller, A., and Mullins, C.B.: Nanostructured Si1−xGex for tunable thin film lithium-ion battery anodes. ACS Nano 7, 2249 (2013).Google Scholar
Munao, D., Valvo, M., van Erven, J., Kelder, E.M., Hassoun, J., and Panero, S.: Silicon-based nanocomposite for advanced thin film anodes in lithium-ion batteries. J. Mater. Chem. 22, 1556 (2012).CrossRefGoogle Scholar
Guo, J., Sun, A., Chen, X., Wang, C., and Manivannan, A.: Cyclability study of silicon–carbon composite anodes for lithium-ion batteries using electrochemical impedance spectroscopy. Electrochim. Acta 56, 3981 (2011).Google Scholar
Yang, D., Yu, X., Li, X., Wang, P., and Wang, L.: Germanium-doped crystal silicon for solar cells. In 2010 10th IEEE International Conference on Solid-State and Integrated Circuit Technology (Shanghai, 2010); p. 1994.Google Scholar
Wang, P., Yu, X., Li, Z., and Yang, D.: Improved fracture strength of multicrystalline silicon by germanium doping. J. Cryst. Growth 318, 230 (2011).Google Scholar
Song, T., Cheng, H., Choi, H., Lee, J-H., Han, H., Lee, D.H., Yoo, D.S., Kwon, M-S., Choi, J-M., Doo, S.G., Chang, H., Xiao, J., Huang, Y., Park, W.I., Chung, Y-C., Kim, H., Rogers, J.A., and Paik, U.: Si/Ge double-layered nanotube array as a lithium ion battery anode. ACS Nano 6, 303 (2011).Google Scholar
Duveau, D., Fraisse, B., Cunin, F., and Monconduit, L.: Synergistic effects of Ge and Si on the performances and mechanism of the GexSi1−x electrodes for Li ion batteries. Chem. Mater. 27, 3226 (2015).Google Scholar
Wang, X., Yang, A., and Xia, S.: Fracture toughness characterization of lithiated germanium as an anode material for lithium-ion batteries. J. Electrochem. Soc. 163, A90 (2016).CrossRefGoogle Scholar
Gao, X., Luo, W., Zhong, C., Wexler, D., Chou, S-L., Liu, H-K., Shi, Z., Chen, G., Ozawa, K., and Wang, J-Z.: Novel germanium/polypyrrole composite for high power lithium-ion batteries. Sci. Rep. 4, 6095 (2014).Google Scholar
Graetz, J., Ahn, C.C., Yazami, R., and Fultz, B.: Nanocrystalline and thin film germanium electrodes with high lithium capacity and high rate capabilities. J. Electrochem. Soc. 151, A698 (2004).Google Scholar
Huggins, R.A. and Nix, W.D.: Decrepitation model for capacity loss during cycling of alloys in rechargeable electrochemical systems. Ionics 6, 57 (2000).Google Scholar
Chasiotis, I., Cho, S.W., and Jonnalagadda, K.: Fracture toughness and subcritical crack growth in polycrystalline silicon. J. Appl. Mech. 73, 714 (2005).CrossRefGoogle Scholar
Zhao, K.: Mechanics of Electrodes in Lithium-Ion Batteries (Harvard University, Cambridge, MA, 2012).Google Scholar
Zhu, X-K. and Joyce, J.A.: Review of fracture toughness (G, K, J, CTOD, CTOA) testing and standardization. Eng. Fract. Mech. 85, 1 (2012).Google Scholar
Yonenaga, I.: Hardness, yield strength, and dislocation velocity in elemental and compound semiconductors. Mater. Trans. 46, 1979 (2005).CrossRefGoogle Scholar
Yonenaga, I.: Growth and fundamental properties of SiGe bulk crystals. J. Cryst. Growth 275, 91 (2005).Google Scholar
Yonenaga, I.: Dislocation dynamics in SiGe alloys. J. Phys.: Conf. Ser. 471, 012002 (2013).Google Scholar
Mishra, K., Zheng, J., Patel, R., Estevez, L., Jia, H., Luo, L., El-Khoury, P.Z., Li, X., Zhou, X-D., and Zhang, J-G.: High performance porous Si@C anodes synthesized by low temperature aluminothermic reaction. Electrochim. Acta 269, 509 (2018).CrossRefGoogle Scholar
Ke, F-S., Mishra, K., Jamison, L., Peng, X-X., Ma, S-G., Huang, L., Sun, S-G., and Zhou, X-D.: Tailoring nanostructures in micrometer size germanium particles to improve their performance as an anode for lithium ion batteries. Chem. Commun. 50, 3713 (2014).Google Scholar
Aubry, J.C., Tyliszczak, T., Hitchcock, A.P., Baribeau, J.M., and Jackman, T.E.: First-shell bond lengths in SixGe1−x crystalline alloys. Phys. Rev. B 59, 12872 (1999).Google Scholar
Martins, J.L. and Zunger, A.: Stability of ordered bulk and epitaxial semiconductor alloys. Phys. Rev. Lett. 56, 1400 (1986).CrossRefGoogle ScholarPubMed
Tzoumanekas, C. and Kelires, P.C.: Theory of bond-length variations in relaxed, strained, and amorphous silicon–germanium alloys. Phys. Rev. B 66, 195209 (2002).Google Scholar
Yu, M., Jayanthi, C.S., Drabold, D.A., and Wu, S.Y.: Strain relaxation mechanisms and local structural changes in Si1−xGex alloys. Phys. Rev. B 64, 165205 (2001).Google Scholar
Wortman, J.J. and Evans, R.A.: Young’s modulus, shear modulus, and Poisson’s ratio in silicon and germanium. J. Appl. Phys. 36, 153 (1965).CrossRefGoogle Scholar
Zhao, K., Pharr, M., Vlassak, J.J., and Suo, Z.: Fracture of electrodes in lithium-ion batteries caused by fast charging. J. Appl. Phys. 108, 073517 (2010).Google Scholar
Weker, J.N., Liu, N., Misra, S., Andrews, J.C., Cui, Y., and Toney, M.F.: In situ nanotomography and operando transmission X-ray microscopy of micron-sized Ge particles. Energy Environ. Sci. 7, 2771 (2014).Google Scholar
Silberstein, K.E., Lowe, M.A., Richards, B., Gao, J., Hanrath, T., and Abruña, H.D.: Operando X-ray scattering and spectroscopic analysis of germanium nanowire anodes in lithium ion batteries. Langmuir 31, 2028 (2015).Google Scholar
Misra, S., Liu, N., Nelson, J., Hong, S.S., Cui, Y., and Toney, M.F.: In situ X-ray diffraction studies of (de)lithiation mechanism in silicon nanowire anodes. ACS Nano 6, 5465 (2012).Google Scholar
Liu, X.H., Huang, S., Picraux, S.T., Li, J., Zhu, T., and Huang, J.Y.: Reversible nanopore formation in Ge nanowires during lithiation–delithiation cycling: An in situ transmission electron microscopy study. Nano Lett. 11, 3991 (2011).Google Scholar
Baggetto, L. and Notten, P.H.L.: Lithium-ion (de)insertion reaction of germanium thin-film electrodes: An electrochemical and in situ XRD study. J. Electrochem. Soc. 156, A169 (2009).Google Scholar
Datta, M.K. and Kumta, P.N.: In situ electrochemical synthesis of lithiated silicon–carbon based composites anode materials for lithium ion batteries. J. Power Sources 194, 1043 (2009).Google Scholar
Zhang, J-G., Wang, W., Xiao, J., Xu, W., Graff, G.L., Yang, G., Choi, D., Wang, D., Li, X., and Liu, J.: Silicon-based anodes for Li-ion batteries. In Batteries for Sustainability: Selected Entries from the Encyclopedia of Sustainability Science and Technology, Brodd, R.J., ed. (Springer, New York, 2013); p. 471.Google Scholar
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