Skip to main content Accessibility help

Solution-Based Synthesis of Manganese Oxide Cathodes for Lithium Batteries

  • A. Manthiram (a1), J. Kim (a1) and S. Choi (a1)


With an objective to overcome the cyclability problems of manganese oxides, solution-based procedures are pursued to synthesize metastable manganese oxides. Reduction of permanganate with lithium iodide in an acetonitrile medium followed by heating at 250 °C in vacuum gives an amorphous lithium sodium manganese oxyiodide that is intimately mixed with crystalline NaIO3. On the other hand, oxidation of manganese acetate with lithium or hydrogen peroxide in presence of lithium hydroxide followed by firing at T < 500 °C gives the metastable spinel oxides, Li4Mn5O12 and Li2Mn4O9-δ. The amorphous manganese oxide exhibits excellent cyclability with a capacity > 275 mAh/g at 4.3-1.5 V. The presence of NaIO3 and a unique microstructure are found to play a critical role in the electrochemical properties. Although Li4Mn5O12 could be achieved without much oxygen vacancies, Li2Mn4O9-δ has significant amount of oxygen vacancies with δ > 0.35. Both Li4Mn5O12 and Li2Mn4O9-δ exhibit capacities around 150 mAh/g with good cyclability in the 3 V region.



Hide All
1. Scrosati, B., Nature 373, 557(1995).
2. Lave, L. B., Henrickson, C. T. and McMichael, F. C., Science 268, 993(1995).
3. Lithium Battery Energy Storage (LIBES) Publication, Technological Research Association, Tokyo, 1994.
4. Whittingham, M. S. and Jacobson, A. J., Intercalation Chemistry, (Academic Press, New York, 1982).
5. Linden, D., Handbook of Batteries, 2nd Edition, edited by Linden, D. (McGraw-Hill, New York, 1995) p. 14.1.
6. Thackeray, M. M., David, W. I. F., Bruce, P. G. and Goodenough, J. B., Mater. Res. Bull. 18 461(1983).
7. Tarascon, J. -M., McKinnon, W. R., Coowar, F., Bowmer, T. N., Amatucci, G. G., Guyomard, D., J. Electrochem. Soc. 141, 1421(1994).
8. Thackeray, M. M., Shao-Horn, Y., Kahaian, A. J., Kepler, K. D., Skinner, E., Vaughey, J. T. and Hackney, S. A., Electrochem. Solid State Lett. 1, 7 (1998).
9. Gummow, R. J., Liles, D. C. and Thackeray, M. M., Mater. Res. Bull. 28, 1249(1993).
10. Armstrong, A. R. and Bruce, P. G., Nature 381, 499(1996).
11. Vitins, G. and West, K., J. Electrochem. Soc. 142, 2558(1995).
12. Gummow, R. J. and Thackeray, M. M., J. Electrochem. Soc. 141, 1178(1994).
13. Croguennec, L., Deniard, P., Brec, R., Biesan, P., and Broussely, M., Solid State Ionics 89, 127(1996).
14. de Kock, A., Rossouw, M. H.. Picciotto, L. A. de, Thackeray, M. M., David, W. I. F. and Ibberson, M. R., Mater. Res. Bull. 25, 657(1990).
15. Thackeray, M. M., De Kock, A., Rossouw, M. H., Liles, D. C., Hoge, D. and Bittihn, R., J. Electrochem. Soc. 139 363(1992).
16. Thackeray, M. M., Rossouw, M. H., de Kock, A. and de la Harpe, A. P., J. Power Sources 43–44, 289 (1993).
17. Thackeray, M. M. and de Kock, A., Mater. Res. Bull. 28, 1041(1993).
18. Gummow, R. J., De Kock, A. and Thackeray, M. M., Solid State Ionics 69, 59(1994).
19. Thackeray, M. M., Mansuetto, M. F., Dees, D. W. and Vissers, D. R., Mater. Res. Bull. 31, 133(1996).
20. Gao, Y. and Dahn, J. R., J. Electrochem. Soc. 143, 1783(1996).
21. Takada, T., Hayakawa, H. and Akiba, E., J. Solid State Chem. 115, 420(1995).
22. Thackeray, M. M., Mansuetto, M. F. and Johnson, C. S., J. Solid State Chem. 125, 274(1996).
23. Kim, J. and Manthiram, A., Nature 390, 265(1997).
24. Kim, J. and Manthiram, A., Electrochem. Solid State Lett. 2, 55(1999).
25. Kim, J. and Manthiram, A., J. Electrochem. Soc. 145, L53 (1998).
26. Choi, S. and Manthiram, A., Electrochem. Solid State Lett. (submitted).
27. Tsang, C. and Manthiram, A., Solid State Ionics 89, 305(1996).
28. Xu, J. J., Kinser, A. J., Owens, B. B. and Smyrl, W. H., Electrochem. Solid State Lett. 1, 1 (1998).

Solution-Based Synthesis of Manganese Oxide Cathodes for Lithium Batteries

  • A. Manthiram (a1), J. Kim (a1) and S. Choi (a1)


Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed