Synthesis and electrochemical characteristics of spinel phase LiMn₂O₄-based cathode materials for lithium polymer batteries

Abstract

Spinel LiMn₂O₄ and LiMn_1.95Ni_0.05O₄ powders have been synthesized by a sol-gel method using an aqueous solution of metal acetates containing glycine. The dependence of the physicochemical properties of the spinel LiMn₂O₄ powders on the calcination temperature and glycine quantity have been extensively investigated. The porous LiMn₂O₄ and LiMn_1.95N_0.05O₄ electrodes were electrochemically characterized by using charge/discharge experiments along with ac impedance spectroscopy. The LiMn_1.95Ni_0.05O₄ electrode exhibited improved cycling performance in comparison with the stoichiometric LiMn₂O₄ one in spite of a small reduction in the initial capacity. The good capacity retention of the LiMn_1.95Ni_0.05O₄ electrode is attributed to stabilization of the spinel structure by Ni doping for Mn ion sites and higher chemical diffusivity of lithium ions with cycling.

References

1. T. Ohuzuka, M. Kitagawa and T. Hirai, J. Electrochem. Soc., 1990, 137, 760.
2. D. Guyomard and J. M. Tarascon, Solid State Ionics, 1994, 69, 222.
3. R. J. Gummow, A. de Kock and M. M. Thackeray, Solid State Ionics, 1994, 69, 59.
4. D. H. Jang, Y. J. Shin and S. M. Oh, J. Electrochem. Soc., 1996, 143, 2204.
5. Y. Xia, Y. Zhou and M. Yoshio, J. Electrochem. Soc., 1997, 144, 2593.
6. D. Guyomard and J. M. Tarascon, Solid State Ionics, 1994, 69, 222.
7. X. Qiu, X. Sun, W. Shen and N. Chen, Solid State Ionics, 1997, 93, 335.
8. Y.-K. Sun, Solid State Ionics, 1997, 100, 115.
9. Li Guohua, H. Ikuta, T. Uchida and M. Wakihara, J. Electrochem. Soc., 1996, 143, 178.
10. R. Bittihn, R. Herr and D. Hoge, J. Power Sources, 1993, 43–44, 223.
11. G. Pistoia and G. Wang, Solid State Ionics, 1993, 66, 135.
12. W. Liu, K. Kowal and G. C. Farrington, J. Electrochem. Soc., 1997, 143, 3590.
13. A. D. Robertson, S. H. Lu, W. F. Averill and W. F. Howard, Jr., J. Electrochem. Soc., 1997, 144, 3500.
14. T. Tsumura, A. Shimizu and M. Inagaki, J. Mater. Chem., 1993, 3, 995.
15. W. Liu, G. C. Farrington, F. Chaput and B. Dunn, J. Electrochem. Soc., 1996, 143, 87.
16. Y.-K. Sun, I.-H. Oh and K. W. Kim, Ind. Eng. Chem. Res., 1997, 36, 4839.
17. A. Hooper and B. C. Tofield, J. Power Sources, 1984, 11, 33.
18. B. C. H. Steele, G. E. Lagos, P. C. Spurdens, C. Forsyth and A. D. Foord, Solid State Ionics, 1983, 9 and 10, 391.
19. P. G. Bruce and F. Krok, Solid State Ionics, 1989, 36, 171.
20. B. V. Ratnakumar, S. DiStefano and C. P. Bankston, J. Appl. Electrochem., 1989, 19, 813.
21. R. Koksbang, I. I. Olsen, P. E. Tonder, N. Knudsen and D. Fauteux, J. Appl. Electrochem., 1991, 21, 301.
22. C. Masquelier, M. Tabuchi, K. Ado, R. Kanno, Y. Kobayashi, Y. Maki, O. Nakamura and J. B. Goodenough, J. Solid State Chem., 1996, 123, 255.
23. M. M. Thackery, W. I. F. David, P. G. Bruce and J. B. Goodenough, Mater. Res. Bull., 1983, 18, 461.
24. Y.-M. Choi and S.-I. Pyun, Solid State Ionics, 1997, 99, 173.
25. B. E. Conway, J. Electrochem. Soc., 1991, 138, 1569.