Chemistry: electrical current producing apparatus – product – and – Current producing cell – elements – subcombinations and... – Electrode
Reexamination Certificate
2001-02-26
2003-09-02
Gulakowski, Randy (Department: 1746)
Chemistry: electrical current producing apparatus, product, and
Current producing cell, elements, subcombinations and...
Electrode
Reexamination Certificate
active
06613479
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to positive electrode active material and lithium secondary batteries. More specifically, the present invention relates to lithium containing manganese layered oxide suitable as positive electrode active material for nonaqueous electrolyte secondary batteries and nonaqueous electrolyte secondary batteries using, as positive electrode active material, the lithium containing manganese layered oxide which is higher in capacity than conventional lithium manganese composite oxide having a spinel structure, and advantageous in cycle durability at high temperatures than conventional lithium manganese composite oxide having a layered structure.
Among various rechargeable secondary batteries, the lithium secondary battery with its high charge-discharge voltage and large charge-discharge capacity has shown much promise as source of electricity for electric vehicles to meet the recent intense demand for zero-emission vehicles in environmental problem.
In consideration of some aspects of LiCoO2 such as the stability in working environment, cost and natural reserves of LiCoO2 used as positive electrode active material for a lithium secondary battery, investigation is currently under way on spinel structure lithium manganese composite oxide (LiMn2O4) as positive electrode active material of a secondary battery for an automotive vehicle. However, LiMn2O4 is deficient in durability at high temperatures and liable to cause deterioration in performance of the negative electrode due to dissolution of the positive electrode material into the electrolyte. In view of this, Japanese Published Patent Applications, Publication (Kokai) Nos. 11(1999)-171550 and 11(1999)-73962 propose technique of substituting transition metal element or typical metal element for part of Mn.
SUMMARY OF THE INVENTION
However, the substitution of various elements for part of Mn to improve the high temperature cycle durability as disclosed in Published Japanese Patent Application, Publication (Kokai) No. 11(1999)-71115 is liable to cause distortion in the crystal structure and hence deteriorate the cycle durability at room temperature. Published Japanese Patent Applications, Publication (Kokai) Nos. 10(1998)-334918 and 11(1999)-45710 propose the substitution of halogen such as fluorine for part of oxygen to improve the cycle durability. However, an increase in the amount of substitution for further improvement of the cycle durability tends to lower the capacity of the active material.
As to the capacity, lithium cobalt oxides (LiCoO2: the active material capacity=140 mAh/g) are higher in capacity than spinel type lithium manganese composite oxides (LiMn2O4: the active material capacity=100 mAh/g). However, lithium cobalt oxides are disadvantageous in the stability etc., as mentioned before. Therefore, a desired positive electrode active material is a high-capacity Mn containing lithium composite oxide which is higher in the Li content in the crystal structure than the spinel lithium manganese composite oxides (LiMn2O4) and which is superior in stability in operating environment to the lithium cobalt oxides (LiCoO2: active material capacity=140 mAh/g).
In such a high-capacity type positive electrode active material for a lithium secondary battery, the lithium content in a chemical formula based on the crystal structure is determinative. Japanese Patent 2870741 seeks for a high-capacity Mn containing lithium composite oxide on the basis of crystal-chemical studies.
A recent report (A. Robert Armstrong & P. G. Bruce “Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries”, Nature, vol.381 (1996) p499) reveals LiMnO2 layered oxide has a positive electrode active material capacity of about 270 mAh/g, more than twice of that of a conventional spinel structure lithium manganese oxide.
With this layered oxide, a sufficient charge-discharge characteristic is obtainable at 55° C., for example. However, the active material capacity decreases to about one third at room temperature. Moreover, the capacity is decreased gradually by repetition of charge and discharge at temperatures over room temperature, so that the cycle durability is insufficient.
It is therefore an object of the present invention to provide a lithium manganese layered composite oxide positive electrode active material which is higher in capacity than the conventional spinel structure lithium manganese composite oxide, and advantageous in high temperature cycle durability to the conventional layered structure lithium manganese composite oxide, and to provide a high-performance lithium secondary battery using this high-capacity lithium manganese layered composite oxide.
According to the present invention, a positive electrode active material for a nonaqueous electrolyte secondary battery comprises: a lithium-containing manganese layered composite oxide represented by the general formula Li1-xMO2-y-&dgr;Fy where x is a lithium deficiency quantity representing a quantity of deficiency in lithium with respect to a composite oxide represented by the general formula LiMO2, y is a fluorine substitution quantity representing a quantity of fluorine substituting for part of oxygen, &dgr; is an oxygen defect quantity, and M is a metallic constituent comprising Mn.
REFERENCES:
patent: 5316877 (1994-05-01), Thackeray et al.
patent: 6168888 (2001-01-01), Iwata et al.
patent: 6432581 (2002-08-01), Amatucci et al.
patent: 0 581 290 (1994-02-01), None
patent: 10-334918 (1998-12-01), None
patent: 2870741 (1999-01-01), None
patent: 11-45710 (1999-02-01), None
patent: 11-71115 (1999-03-01), None
patent: 11-73962 (1999-03-01), None
patent: 11-171550 (1999-06-01), None
A. Robert Armstrong & P.G. Bruce, “Synthesis Of Layered LiMnO2 As An Electrode For Rechargeable Lithium Batteries”,Nature, vol. 381, Issue No. 6582, pp. 499-500, Jun. 6, 1996, published by Macmillan Magazines Ltd.
Patent Abstracts of Japan, vol. 018, No. 263, May 19, 1994; Shoji Yamanaka, “Lithium Secondary Battery and Manufacture Thereof”, 06044973, Feb. 18, 1994.
Dai et al., “Synthesis and Characterization of the Hollandite-type MnO2as a Cathode Material in Lithium Batteries”, Electrochimica Acta, Elsevier Science Publishers, vol. 45, No. 14, pp. 2211-2217, Mar. 2000.
Johnson et al., “Structural and Electrochemical Studeis of &agr;-Manganese Dioxide (&agr;-MnO2)”, Journal of Power Sources, Elsevier, vol. 68, No. 2, pp. 570-577, Oct. 1, 1997.
Fukuzawa Tatsuhiro
Kimura Takashi
Mihara Takuya
Munakata Fumio
Ohsawa Yasuhiko
Foley & Lardner
Nissan Motor Co,. Ltd.
Wills Monique
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