Abstract
Based on the first-principles plane wave pseudo-potential method, the electronic structure and electrochemical performance of Li x Sn4Sb4 (x=2, 4, 6, and 8) and Li x Sn1−x Sb4 (x=9, 10, 11, and 12) phases were calculated. A Sn-Sb thin film on a Cu foil was also prepared by radio frequency magnetron sputtering. The surface morphology, composition, and lithium intercalation/extraction behavior of the fabricated film were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV). Lithium atoms can easily insert into and extract out of the β-SnSb cell due to the low lithium intercalation formation energy. It is found that lithium atoms first occupy the interstitial sites, and then Sn atoms at the lattice positions are replaced by excessive lithium. The dissociative Sn atoms continue to produce different Li-Sn phases, which will affect the electrode stability and lead to the undesirable effect due to their large volume expansion ratio. The calculated lithium intercalation potential is stable at about 0.7 V, which is consistent with the experimental result.
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K. Nishikawa, Y. Fukunaka, T. Sakka, et al., In situ measurement lithium mass transfer during charging and discharging of alloy electrode, J. Power Sources, 174(2007), No.12, p.668.
J.M. Tarascon and M. Armand, Issues and challenges facing rechargeable lithium batteries, Nature, 414(2001), No.6861, p.359.
M. Mladenov, P. Zlatilova, I. Dragieva, and K. Klabunde, Low temperature synthesis and characterization of nanoscale Cu6Sn5 particles as lithium anode material, J. Power Sources, 162(2006), No.2, p.803.
H. Guo, H.L. Zhao, X.D. Jia, X. Li, and W.H. Qiu, A novel micro-spherical CoSn2/Sn alloy composite as high capacity anode materials for Li-ion rechargeable batteries, Electrochim. Acta, 52(2007), No.14, p.4853.
H. Mukaibo, T. Momma, and T. Osaka, Changes of electro-deposited Sn-Ni alloy thin film for lithium ion battery anodes during charge discharge cycling, J. Power Sources, 146(2005), No.1–2, p.457.
C.H. Mi, Y.X. Cao, X.G. Zhang, and H.L. Li, In situ synthesis of a CoSb3/nano-carbon-web anode for Li-ion batteries, Solid State Commun., 149(2009), No.19–20, p.781.
J. Yang, M. Winter, and J.O. Besenhard, Small particle size multiphase Li-alloy anodes for lithium-ion batteries, Solid State Ionics, 90(1996), No.1–4, p.281.
I.A. Coutney, W.R. McKinnon, and J.R. Dahn, On the aggregation of tin in SnO composite glasses caused by the reversible reaction with lithium, J. Electrochem. Soc., 146(1999), p.59.
C.M. Li, Q.M. Huang, R.Y. Zhang, W.S. Li, L.Z. Zhao, and S.J. Hu, A comparison of the performances of two kinds of Sn films as lithium-ion insertion electrodes prepared by electrodeposition, Acta Metall. Sin., 43(2007), p.515.
L.Z. Zhao, S.J. Hu, W.S. Li, et al., Preparation of Sn nano-film by direct current magnetron sputtering and its performance as anode of lithium ion battery, Trans. Nonferrous Met. Soc. China., 17(2007), p.907.
I.A. Courtney and J.R. Dahn, Electrochemical and in-situ X-ray diffraction studies of the reaction of lithium with tin oxide composite, J. Electrochem. Soc., 144(1997), p.2045.
M. Wachtler, J.O. Besenhard, and M. Winter, Tin and tin-based intermetallics as new anode materials for lithium-ion cells, J. Power Sources, 94(2001), p.189.
M.K. Aydinol, A.F. Kohan, G. Ceder, et al., Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides, Phys. Rev. B, 56(1997), No.3, p.1354.
J.W. Lee, Y.K. Anguchamy, and B.N. Popov, Simulation of charge-discharge cycling of lithium-ion batteries under low-earth-orbit conditions, J. Power Scources, 162(2006), No.2, p.1395.
I.A. Courtney, J.S. Tse, O. Mao, J. Hafner, and J.R. Dahn, Ab initio calculation of the lithium-tin voltage profile, Phys. Rev. B, 58(1998), No.23, p.15583.
L. Simonin, U. Lafont, and E.M. Kelder, SnSb micron-sized particles for Li-ion batteries, J. Power Sources, 180(2008), p.859.
X.H Hou, S.J. Hu, W.S. Li, et al., Investigation of lithiation/ delithiation mechanism in lithium-tin alloys for anode materials, Acta Phys. Sin., 57(2008), No.4, p.2374.
X.J. Huang, H. Li, Q. Wang, et al., Nano-scaled materials for lithium storage and lithium ion batteries, Physics., 31(2002), No.7, p.444.
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This work was financially supported by the National Nature Science Foundation of China (No.50771046) and the Educational Commission of Guangdong Province, China (No.C10179).]
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Ru, Q., Tian, Q., Hu, Sj. et al. Lithium intercalation mechanism for β-SnSb in Sn-Sb thin films. Int J Miner Metall Mater 18, 216–222 (2011). https://doi.org/10.1007/s12613-011-0425-x
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DOI: https://doi.org/10.1007/s12613-011-0425-x