Hostname: page-component-cd9895bd7-dk4vv Total loading time: 0 Render date: 2024-12-27T02:09:18.676Z Has data issue: false hasContentIssue false
  • English
  • Français

In situ Synchrotron X-ray Studies on Novel Mn Oxide Spinel Cathodes for Li-ion Batteries: Influence of Other Transition Elements

Published online by Cambridge University Press:  10 February 2011

S. Mukerjee ,
X. Q. Yang ,
X. Sun ,
S. J. Lee ,
J. Mcbreen  and
Y. Ein-Eli
S. Mukerjee
Affiliation:
Chemistry Dept., Northeastern University, Boston, MA 02115, [email protected]
X. Q. Yang
Affiliation:
Dept. of Applied Science, Brookhaven National Laboratory, Upton, NY 11973
X. Sun
Affiliation:
Dept. of Applied Science, Brookhaven National Laboratory, Upton, NY 11973
S. J. Lee
Affiliation:
Dept. of Applied Science, Brookhaven National Laboratory, Upton, NY 11973
J. Mcbreen
Affiliation:
Dept. of Applied Science, Brookhaven National Laboratory, Upton, NY 11973
Y. Ein-Eli
Affiliation:
Covalent Associates, 10 State Street, Woburn, MA 01801
Get access

Abstract

Partial substitution of Mn in lithium manganese oxide spinel materials by Cu and Ni greatly affects the electrochemistry and the cycle life characteristics of the cathode. Substitution with either metal or a combination of both shortens the 4.2 V plateau associated with the conversion of Mn3+ to Mn4+. A higher voltage plateau associated with oxidation of the substituted transition element is also observed. These substituent also significantly alter the onset of Jahn Teller distortions in the 3 V plateau. Synchrotron based in situ x-ray absorption (XAS) is used to determine the exact nature of the oxidation state changes in order to explain the overall capacities at the different voltage plateaus. Synchrotron based in situ x-ray diffraction (XRD) studies on LiCu0.5Mn1.504 shows single phase behavior in the 4-5 V region and a good cycle life. Lower cycle life characteristics for LiNi0.5Mn1.504 and LiNi0.25Cu0.25Mn1.504 are accounted for on the basis of several phase coexistence in this potential region. In the 3 V plateau however, the LiCu0.5Mn1.504 shows onset of the Jahn Teller distortions, in contrast to the LiNi0.5Mn1.504 and LNi0.25Cu0.25WMn1.504.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 548: Symposia EE – Solid State Ionics V , 1998 , 149
Copyright
Copyright © Materials Research Society 1999

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

(1) Tarascon, J. M., U. S. Pat., 5,424,205 (1995).Google Scholar
(2) Gummow, R. J., Kock, A. de, and Thackeray, M. M., Solid State Ionics, 69, 59 (1994).Google Scholar
(3) Xia, Y., and Yoshio, M., J. Electrochem. Soc., 144, 4186 (1997).Google Scholar
(4) Tarascon, J. M., Wang, E., Shokoohi, F. K, McKinnon, W. R. and Colson, S., J. Electrochem. Soc., 138, 2859 (1991)Google Scholar
(5) Bittihm, R., Herr, R., and Hoge, D., J. Power Sources, 43–44, 223, (1993).Google Scholar
(6) Li, G., Ikuta, H., Uchida, T., and Wakihara, M., J. Electrochem. Soc., 143, 178 (1996).Google Scholar
(7) Ein-Eli, Y., and Howard, W. F., Electrochem. Soc., 144, L205 (1997).Google Scholar
(8) Ein-Eli, Y., Howard, W. F., Lu, S. H., Mukerjee, S., McBreen, J., Vaughey, J. T., and Thackeray, M. M., J. Electrochem. Soc., 145, 1238 (1998).Google Scholar
(9) Zhong, Q., Bonakdarpour, A., Zhang, M., Gao, Y., and Dahn, J. R., J. Electrochem. Soc., 144, 205 (1997).Google Scholar
(10) Sigala, C., Guyormard, D., Verbaere, A., Piffard, Y., and Tomoux, M., Solid State Ionics, 81, 167 (1995).Google Scholar
(11) Ein-Eli, Y., Mukerjee, S., Yang, X. Q., McBreen, J., Vaughey, J. T. and Thackerey, M. M., J.Electrochem. Soc., (In Press).Google Scholar
(12) McBreen, J., Mukerjee, S., Yang, X. Q., Thurston, T. R., and Jisrawi, N. M., in Proc. 2nd lnt. Symp. On Materials for Fuel Cells and Modern Battery Systems, Montreal, Canada, July 6-10, 1997, O'Savadogo, and Roberge, P. R., Editors, p 348, École Polytechnique, Montreal (1997).Google Scholar
(13) Mukerjee, S., Thurston, T. R., Jisrawi, N. M., Yang, X. Q., McBreen, J., Daroux, M. L., and Xing, X. K., J. Electrocehm. Soc., 145, 466 (1998).Google Scholar
(14) Amine, K., Tukamoto, H., Yasuda, H., and Fujita, Y., J. Electrochem. Soc., 143, 1607 (1996).Google Scholar
(15) Gao, Y., Myrtle, K., Zhang, M., Reimers, J. N. and Dahn, J. R., Phys. Rev., B54, 3878 (1996).Google Scholar
(16) Zheng, Q., Bonakdarpour, A., Zhang, M., Gao, Y., and Dahn, J. R., J Electrochem. Soc., 144, 205 (1997).Google Scholar