Positive active material and nonaqueous electrolyte secondary battery

a technology of active materials and secondary batteries, applied in secondary cells, cell components, service/maintenance of secondary cells, etc., can solve the problems of short circuit, short circuit, and sudden rise of battery temperature, and achieve excellent charging and discharging cyclic performance, excellent electrode performance, and large capacity

Active Publication Date: 2006-05-04
MURATA MFG CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0012] It is an object of the present invention.to.solve the problems of the conventional positive active material: and to provide a positive active material used for cathode and a nonaqueous electrolyte secondary battery which can realize an excellent electrode performance and a nonaqueous electrolyte secondary battery performance without including an addition material which does not contribute to charging and discharging reactions and in which an excellent charging and discharging cyclic performance and a storage performance with a large capacity may be compatible with the suppression of the rise of temperature of the battery upon overcharging. Further, it is another object of the present invention to propose a new positive active material utilizing the mixture obtained by mixing composite oxides of lithium and transition metals and a new battery element structure upon using the positive active material and to provide a nonaqueous electrolyte secondary battery with a large capacity which can maintain a stable structure and is excellent in its cyclic characteristics.

Problems solved by technology

When this overcharged state is continued, an abnormal reaction that the electrolyte or the active materials are rapidly decomposed is generated and the temperature of the battery abruptly rises.
However, in the nonaqueous electrolyte secondary battery, the decomposition of the electrolyte or the active materials may advance to generate heat which leads to the quick rise of temperature so that the current cut-off means may not effectively operate, before the internal pressure of the battery rises to reach the threshold value.
However, when lithium carbonate is included in a cathode in order to obtain an assured suppressing effect for the rise of temperature of the battery, as described above, a battery capacity has been inconveniently deteriorated.
8-45498, there has been a problem that charging and discharging cyclic characteristics cannot be sufficiently improved depending on the particle diameter of the lithium manganese oxide and lithium nickel oxide.
Further, in the nonaqueous electrolyte battery, since battery characteristics such as an initial capacity are deteriorated depending on the selection of an negative active material, especially, a larger deterioration is generated upon storage of the battery, there is left room for improvement of the battery characteristics.
Thus, the volume change of the positive active material is generated, and accordingly, there inconveniently arises a phenomenon that a composite mixture layer including the active materials is peeled off or electrodes are deformed as charging and discharging cycles advance to deteriorate the cyclic characteristics.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

example 1

[0059] Now, Examples of the present invention will be described on the basis of specific experimental results. However, it is to be understood that the present invention is not limited to the Examples.

experiment 1-1

[0060] Initially, the numerical ranges of y and z in LimCoxAlyMgzO2 were examined.

Sample 1

[0061] Firstly, a positive active material was manufactured as described below. Commercialized lithium carbonate, cobalt oxide, aluminum hydroxide and magnesium carbonate were mixed together in the mole ratio of Li, Co, Al and Mg 1.02:0.98:0.01:0.01. The obtained mixture was sintered in dry air current by using a crucible made of alumina. When the produced powder was quantitatively analyzed by an atomic absorption analysis method, the.composition of LiCo0.98Al0.01Mg0.01O2 was recognized. When an X-ray diffraction measurement was carried out for this powder, it was recognized that the pattern of the powder was similar to the pattern of LiCoO2 existing in 36-1004 of the ICDD (International Centre for Diffraction Data) and formed a similar layer structure to that of LiCoO2.

[0062] When the amount of lithium carbonate included in the powder was measured, it was recognized that the lithium carbon...

experiment 1-2

[0083] Subsequently, other elements constituting LimCoxAyBzO2 were examined.

Sample 10

[0084] The powder of LiCo0.98Al0.01Ca0.01O2 was manufactured in the same manner as that of the Sample 1 except that calcium carbonate was used in place of magnesium carbonate. This powder was used as the positive active material to manufacture a nonaqueous electrolyte secondary battery.

Sample 11

[0085] The powder of LiCo0.98Cr0.01Mg0.01O2 was manufactured in the same manner as that of the Sample 1 except that chromium oxide was used in place of aluminum hydroxide. This powder was used as the positive active material to manufacture a nonaqueous electrolyte secondary battery.

Sample 12

[0086] The powder of LiCo0.98V0.01Mg0.01O2 was manufactured in the same manner as that of the Sample 1 except that vanadium oxide was used in place of aluminum hydroxide. This powder was used as the poistive active material to manufacture a nonaqueous electrolyte secondary battery.

Sample 13

[0087] The powder of ...

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Abstract

A positive active material including a compound expressed by a general formula LimMxM′yM″zO2 (here, M designates at least one kind of element selected from Co, Ni and Mn, M′ designates at least one kind of element selected from Al, Cr, V, Fe, Cu, Zn, Sn, Ti, Mg, Sr, B, Ga, In, Si and Ge, and M″ designates at least one kind of element selected from Mg, Ca, B and Ga. Further, x is designated by an expression of 0.9≦x<1, y is indicated by an expression of 0.001≦y≦0.5, z is indicated by an expression of 0≦z≦0.5, and m is indicated by an expression of 0.5≦m) and lithium manganese oxide expressed by a general formula LisMn2-tMatO4 (here, the value of s is expressed by 0.9≦s, the value of t is located within a range expressed by 0.01≦t≦0.5, and Ma indicates one or a plurality of elements between Fe, Co, Ni, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si and Ge) are included, so that both a large capacity and the suppression of the rise of temperature of a battery upon overcharging operation are achieved.

Description

CROSS REFERENCE TO RELATED APPLICATIONS [0001] This is a divisional of co-pending application Ser. No. 10 / 204,952, filed Oct. 25, 2002, which claims priority to PCT Application No. JP01 / 11303, filed Dec. 21, 2001, which claims priority to Japanese Patent Application Nos. P2000-403455, P2000-403460 and P2000-403463, each of which was filed Dec. 28, 2000. Each of the above references is incorporated herein by reference in its entirety.TECHNICAL FIELD [0002] The present invention relates to a positive active material capable of being reversibly doped with and dedoped from lithium and a nonaqueous electrolyte secondary battery using this positive active material. BACKGROUND OF THE INVENTION [0003] In recent years, with the development of various kinds of compact and cordless electronic devices, it has been demanded for secondary batteries as power sources for driving them to have high capacity and decrease weight. As representative secondary batteries, there are well-known lead-acid bat...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): H01M4/48H01M4/52H01M4/38C01G45/00C01G51/00C01G53/00H01M2/34H01M4/02H01M4/36H01M4/485H01M4/50H01M4/505H01M4/525H01M10/0525H01M10/36H01M10/42
CPCC01G45/1242C01G51/54C01G53/54C01P2002/54C01P2006/10C01P2006/12C01P2006/40C01P2006/80H01M2/345H01M4/364H01M4/485H01M4/505H01M4/525H01M10/0525H01M10/4235H01M2004/021Y02E60/122H01M50/578Y02E60/10H01M4/38
Inventor TANAKA, TAKEHIKOHOSOYA, YOSUKEYAMAMOTO, YOSHIKATSUSUZUKI, KIYOHIKOKOGA, KEIZO
Owner MURATA MFG CO LTD
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