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DOI: 10.1039/A902060H (Paper) Reference Section for: J. Mater. Chem., 1999, 9, 2517-2521

Electrochemical reaction of lithium with the CoSb3 skutterudite

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Ricardo Alcántara, Francisco J. Fernández-Madrigal, Pedro Lavela, José L. Tirado, Jean Claude Jumas and Josette Olivier-Fourcade

Abstract

The crystalline solid CoSb3 with the skutterudite structure was used as the starting cathodic material in Li|LiClO4(propylene carbonate–ethylene carbonate)|CoSb3 cells. The galvanostatic discharge takes place in two successive plateaux around 0.5 V, leading to a maximum capacity of ca. 800 mA h g–1. Further cycling leads to higher voltages and a reversible capacity in the range 350–200 mA h g–1 during the first 10 cycles. The mechanism of the reaction with lithium was studied by X-ray diffraction and FTIR spectroscopy. The first discharge involves the irreversible decomposition of the solid to non-crystalline cobalt and Li3Sb alloy. On cycling, the reversible extraction–insertion of lithium in the antimony alloy takes place. Part of the irreversible capacity is ascribable to the formation of a passivating film on the surface of the electrode material, which contains ROCO2– and CO32– groups. This material shows superior properties relative to a pure antimony electrode and can be considered as an interesting candidate for the negative electrode of lithium-ion cells.

References

  1. B. G. Hyde and S. Andersson, Inorganic Crystal Structures, J. Wiley & Sons, New York, 1989, p. 299 Search PubMed .
  2. I. Oftedal, Z. Kristallogr., 1928, 66, 517 CAS .
  3. E. H. Roseboom, Am. Mineral., 1962, 47, 310 CAS .
  4. N. Mandel and J. Donuohe, Acta Crystallogr., Sect. B, 1971, 27, 2288 CrossRef CAS .
  5. A. Kjekshus, D. G. Nicholson and T. Rakke, Acta Chem. Scand., 1973, 27, 1307 CAS .
  6. B. C. Sales, D. Mandrus and R. K. Williams, Science, 1996, 272, 1325 CAS .
  7. K. Sawai, Y. Iwakoshi and T. Ohzuku, Solid State Ionics, 1994, 69, 273 CrossRef CAS .
  8. I. A. Courtney and J. R. Dahn, J. Electrochem. Soc., 1997, 144, 2045 CAS .
  9. W. Weppner and R. A. Huggins, J. Electrochem. Soc., 1978, 125, 7 CAS .
  10. J. Wang, I. D. Raistrick and R. A. Huggins, J. Electrochem. Soc., 1986, 133, 457 CAS .
  11. J. O. Besenhard, J. Yang and M. Winter, J. Power Sources, 1997, 68, 87 CrossRef CAS .
  12. J. Yang, M. Wachtler, M. Winter and J. O. Besenhard, Electrochem. Soc. Lett., 1999, 2, 161 Search PubMed .
  13. J. T. Vaughey, K. D. Kepler and M. M. Thackeray, Ext. Abstr., No. 82, 9th Int. Symp. Lithium Batteries, Edinburgh, Scotland, July 1998 Search PubMed .
  14. O. Mao, R. A. Dunlap, I. A. Courtney and J. R. Dahn, J. Electrochem. Soc., 1998, 145, 4195 CAS .
  15. O. Mao, R. A. Dunlap and J. R. Dahn, J. Electrochem. Soc., 1999, 146, 405 CrossRef CAS .
  16. J. Rodríguez Carvajal, AFFMA, Program for the refinement of unit cell parameters, ILL, Grenoble, France, 1987 .
  17. K. Yvon, W. Jeitschko and E. Parthé, LAZY-PULVERIX, Program for the simulation of XRD patterns, University of Geneva, Switzerland, 1987 .
  18. G. Herren and N. E. Walsöe de Reca, Solid State Ionics, 1991, 47, 57 CrossRef CAS .
  19. M. Bonnemay, E. Levart, G. Bronoel, B. Peslerbe and M. Savy, Mém. Sci. Rev. Métall., 1965, 62, 285 Search PubMed .
  20. U. Hashimoto, Nippon Kinzoku Gakkai-Shi, 1937, 1, 177 Search PubMed .
  21. R. Gerardin and J. Aubry, C. R. Acad. Sci., Ser. C., 1974, 278, 1097 Search PubMed .
  22. G. Brauer and E. Zintl, Z. Phys. Chem., Abt. B, 1937, 37, 323 Search PubMed .
  23. R. A. Huggins, in, Batteries for portable applications and electric vehicles, ed. C. F. Holmes and A. R. Landgrebe, Electrochemical Society, Pennington, NJ, 1997, pp. 109–115 Search PubMed .
  24. D. D. Wagman, W. H. Evans, V. B. Parker, I. Halow, S. M. Bailey and R. H. Schumm, Natl. Bur. Stand. (U.S.), Tech. Note 270-4, 1969, p. 68 Search PubMed .
  25. A. Mabuchi, K. Tokumitsu, H. Fujimoto and T. Kasuh, J. Electrochem. Soc., 1995, 142, 3049 CAS .
  26. T. Zheng, J. S. Xue and J. R. Dahn, Chem. Mater., 1996, 8, 389 CrossRef CAS .
  27. A. N. Dey, Thin Solid Films, 1977, 43, 131 CrossRef CAS .
  28. D. Aurbach and Y. Ein-Eli, J. Electrochem. Soc., 1995, 142, 1746 CAS .
  29. K. Kanamura, S. Shiraishi, H. Takezawa and Z. Takehara, Chem. Mater., 1997, 9, 1797 CrossRef CAS .
  30. R. Alcántara, F. J. Fernández Madrigal, P. Lavela, J. L. Tirado, J. M. Jiménez Mateos, R. Stoyanova and E. Zhecheva, Chem. Mater., 1999, 11, 52 CrossRef CAS .
  31. C. J. Pouchert, The Aldrich Library of IR Spectra, Aldrich Chemical Company, Milwaukee, WI, 1975, P5265-2 and E2625-8 Search PubMed .
  32. D. Aurbach, Y. Ein-Eli, O. Chusid, Y. Carmeli, M. Babai and H. Yamin, J. Electrochem. Soc., 1994, 141, 603 CAS .
  33. I. A. Courtney, W. R. McKinnon and J. R. Dahn, J. Electrochem. Soc., 1999, 146, 59 CrossRef CAS .
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