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

Electrochemical reaction of lithium with the CoSb3 skutterudite

(Note: The full text of this document is currently only available in the PDF Version )

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.
Click here to see how this site uses Cookies. View our privacy policy here.