Synthesis of Li2Mn4O9 using lithium permanganate precursor

Details Synthesis of Li2Mn4O9 using lithium permanganate precursor Synthesis of Li2Mn4O9 using lithium permanganate precursor

2002-07-01

2004-08-10

Silverman, Stanley S. (Department: 1754)

Chemistry: electrical current producing apparatus, product, and

Current producing cell, elements, subcombinations and...

Electrode

C423S594130, C423S599000, C429S231950

Reexamination Certificate

active

06773851

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the synthesis of Li
2
Mn
4
O
8+z
, with z greater than zero and less than one, prepared from LiMnO
4
and an appropriate complimentary compound, such as MnOOH, MnO
2
or MnCO
3
precursors, and its use in highly oxidized lithium manganospinels.
2. Brief Description of the Related Art
Lithium manganospinels have been investigated as lithium insertion cathodes for lithium-ion batteries (see e.g., A. de Kock, M. H. Rossouw, L. A. de Picciotto, M. M. Thackeray, W. I. F. David and I. M. Ibberson.
Mater. Res. Bull.
25 (1990); M. M. Thackeray, A. de Kock, M. H. Rossouw, D. Liles, R. Bittihn and D. Hoge.
J. Electrochem. Soc.
139 (1992); M. M. Thackeray and M. H. Rossouw.
J. Solid State Chem.
113 (1994); M. M. Thackeray, A. de Kock and W. I. David.
Mat. Res. Bull.
28 (1993); M. M. Thackeray and M. H. Rossouw.
J. Solid State Chem.
113 (1994); and R. J. Gummow, A. de Kock and M. M. Thackeray.
Solid State Ionics
69 (1994)). The difficulty in preparing the fully oxidized material Li
2
Mn
4
O
9
, in a reproducible manner, is well known (see e.g., C. Masquelier, M. Tabuchi, K. Ado, R. Kanno, Y. Kobayashi, Y. Maki, O. Nakamura and J. B. Goodenough.
J. Solid State Chem.
123 (1996)). Strict control of experimental conditions such as temperature, time, particle size of the precursor materials, and oxygen partial pressure has been essential for producing fully oxidized, single-phase material. Studies to date, however, show clearly that the fully oxidized Li
2
Mn
4
O
9
phase has never been prepared successfully.
Many compounds and synthesis methods have been tried in attempting to produce suitable cathode active materials for rechargeable lithium batteries. Compounds, which function as lithium insertion electrodes, include LiCoO
2
and LiTiS
2
. However, lower cost and higher energy density materials are desirable. In particular, lithium-manganese-oxides contain multiple attractive properties of high cell voltage, long shelf life, wide operating temperature and relatively non-toxicity (see e.g., M. M. Thackeray et al., J. Electrochem. Soc. Vol. 139, No. 2, February 1992). Ordinary manganese dioxide, MnO
2
, cathodes, used in primary lithium/manganese dioxide 3 volt cell, show limited rechargeability in lithium cells. A significant improvement in capacity stability with cycling is obtained with cathodes prepared by reacting gamma MnO
2
with lithium hydroxide at moderate temperature (see e.g., N. Furukawa et al. in “Primary and Secondary Ambient Temperature Lithium Batteries”, J. Gavitno, Z. Takeharn and P Bro, Editors, PV 8-6, p. 557, The Electrochemical Soc. Softbound Proc. Series, Pennington, N.J. (1988)). This reaction results primarily in the formation of a lithium-manganese oxide spinel component with a cubic close-packed oxygen array, which has been shown to be advantageous over one having a hexagonal close-packing arrangement (see e.g., M. M. Thackeray in “Proceeding of MRS Symposium,” boston, November/December 1988, Vol. 135, p. 585 (1989)).
SUMMARY OF THE INVENTION
The present invention includes a process for making Li
2
Mn
4
O
8+z
, wherein z is greater than zero and less than 1, comprising the steps of mixing lithium permanganate with a precursor selected from the group consisting of MnOOH, MnO
2
and MnCO
3,
and heating the mixture effective to form Li
2
Mn
4
O
8+z
, wherein z is greater than zero and less than 1.
The present invention also includes Li
2
Mn
4
O
8+z
, wherein z is greater than zero and less than 1, produced by the process of the present invention.
Furthermore, the present invention includes Li
2
Mn
4
O
8+z
, wherein z is greater than 0.65, and Li
2
Mn
4
O
8+z
, wherein z is less than 0.88.
Additionally, the present invention includes a cathode comprising the Li
2
Mn
4
O
8+z
made by the present process.


REFERENCES:
patent: 5316877 (1994-05-01), Thackeray et al.
patent: 5658693 (1997-08-01), Thackeray et al.
patent: 6183910 (2001-02-01), Praas et al.
Dallek, Steven “Characterization of Li2Mn4O9Cathode Material by Thermogravimetry”, Proceedings of the 38thPower Sources Conference, Jun. 8-11, 1998, pp. 378-381.
Kilroy, W.P., Ferrando, W.A., Dallek, S. “Synthesis and Characterization of Li2Mn4O9Cathode Material”, IMLB Conference, Como, Italy, Abstract No. 141, May 28-Jun. 2, 2000. Abstract became available to the public on the Internet Mar. 1, 2000 prior to IMLB conference.
Kilroy, W.P., Ferrando, W.A., Dallek, S. “Synthesis and Characterization of Li2Mn4O9Cathode Material”, Journal of Power Sources 97-98 Jul. 10, 2001 pp. 366-343.
Dallek, S., Kilroy, W.P., Ferrando, W.A., “Thermogravimetry and Solid State Synthesis of Li2Mn4O9Cathode Material”, 7thWorkshop for Battery Development, Phil., PA, Jun. 25-28, 2001.
Kock, A de, Rossouw, M.H., Picciotto, L. A. de, Thackeray, M.M. “Defect Spinels in the System Li20.yMn02(y>2.5): A Neutron-Diffraction Study and Electrochemical Characterization of Li2Mn409”, Mat. Res. Bull., vol. 25, pp. 657-664 1990.
Thackeray, M.M., Kock, A. de, Rossouw, M.H. and Liles, D., “Spinel Electrodes from the Li-Mn-O System for Rechargeable Lithium Battery Applications”, J. Electrochem. Soc., vol. 139, No. 2, Feb. 1992.
Thackeray, M.M. and Kock, A. de, David, W.I.F., “Synthesis and Structural Characterization of Defect Spinels in the Lithium-Manganese-Oxide System”, Mat. Res. Bull., vol. 28, pp. 1041-1049, 1993.
Tarascon, J.M., McKinnon, W.R., Coowar, F., Bowmer, T.N., Amatucci, G. and Guyomard, D., “Synthesis Conditions and Oxygen Stoichiometry Effects on Li Insertion into the Spinel LiMn2O4”, J. Electrochem. Soc., vol. 141, No. 6, Jun. 1994.
Gummow, R.J., Kock, A. de, Thackeray, M.M. “Improved Capacity Retention in Rechargeable 4 V Lithium/lithium-manganese Oxide (Spinel) Cells”, Solid State Ionics 69, pgs 59-67, 1994.
Thackeray, M.M. and Rossouw, M.H., “Synthesis of Lithium-Manganese-Oxide Spinels: A Study by Thermal Analysis”, Journal of Solid State Chemistry 113, pp. 441-443, 1994.
Masquelier, Christian, Tabuchi, Mitsuharu, Ado, Kazuaki, Kanno, Ryoji, Kobayashi, Yo, Maki, Yuzuru, Nakamura, Osamu and Goodenough, John B., “Chemical and Magnetic Characterization of Spinel Materials in the LiMn2O4-Li2Mn4o9-LI4Mn5O12System”, Journal of Solid State Chemistry 123, pp. 255-266, 1996.
Xia, Yongyao and Yoshio, Masaki, “Optimization of Spinel Li1+xMn2-yO4as a 4 V Li-Cell Cathode in Terms of a Li-Mn-O Phase Diagram”, J. Electrochem. Soc., vol. 144, No. 12, Dec. 1997.
Gabano, J.P. , Takehara Z., and Bro, P., editors, “Primary and Secondary Ambient Temperature Lithium Batteries”, The Electrochemical Soc., Proceedings vol. 88-6, pp. 557-564 (1988).
Thackeray, M.M., “Developments in Rechargeable Mn02Electrodes For Lithium Batteries”, Proceedings of MRS Symposium, Boston, Nov./Dec. 1988, vol. 135, pp. 585-596 (1989).

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