CA2265372C - Lithium secondary battery - Google Patents

Lithium secondary battery Download PDF

Info

Publication number
CA2265372C
CA2265372C CA002265372A CA2265372A CA2265372C CA 2265372 C CA2265372 C CA 2265372C CA 002265372 A CA002265372 A CA 002265372A CA 2265372 A CA2265372 A CA 2265372A CA 2265372 C CA2265372 C CA 2265372C
Authority
CA
Canada
Prior art keywords
composite oxide
lithium secondary
less
secondary battery
oxide powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA002265372A
Other languages
French (fr)
Other versions
CA2265372A1 (en
Inventor
Takuya Sunagawa
Hiroshi Watanabe
Toshiyuki Nohma
Koji Nishio
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanyo Electric Co Ltd
Original Assignee
Sanyo Electric Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sanyo Electric Co Ltd filed Critical Sanyo Electric Co Ltd
Publication of CA2265372A1 publication Critical patent/CA2265372A1/en
Application granted granted Critical
Publication of CA2265372C publication Critical patent/CA2265372C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/006—Compounds containing copper, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C01G45/1228—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing iron, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Complex oxides containing cobalt and at least one other metal element
    • C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
    • C01G51/44—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/50—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • C01G53/502—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing lithium and cobalt
    • C01G53/504—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • C01G53/502—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing lithium and cobalt
    • C01G53/504—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5
    • C01G53/506—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5 with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.8, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.8
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/006—Compounds containing zinc, with or without oxygen or hydrogen, and containing two or more other elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention provides a positive electrode active material for a lithium secondary battery including a composite oxide powder having a median diameter of 3.0 through 20.0 µm and a content of particles with a grain size of 1 µm or less of 10% by volume or less and being represented by a composition formula, Li a Co b M c Ni 1-b-c O2, in which M is at least one element selected from the group consisting of B, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Y, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In and Sn; 0 <= a <= 1.2; 0.01 <= b <= 0.4; 0.01 <=c <= 0.4; and 0.02 <= b+c <= 0.5. Thus, the lithium secondary battery can be improved in its charge- discharge cycle characteristic.

Description

TITLE OF THE INVENTION
LITHIUM SECONDARY BATTERY
BACKGROUND OF THE INVENTION
The present invention relates to a lithium secondary battery, and more particularly, it relates to improvement of a positive electrode active material used therein for the purpose of providing a lithium secondary battery with an excellent charge-discharge cycle characteristic.
A lithium secondary battery can be improved in its voltage and capacity by appropriately selecting a positive electrode material because there is no need to consider a water decomposition voltage. Therefore, in accordance with recent development of portable and/or cordless electronic equipment, lithium secondary batteries have been regarded as a promising driving power supply for such electronic equipment.
Lithium cobaltite (LiCoO~ has already been practically used as a positive electrode active material in a lithium secondary battery, and the use results in a battery with a high energy density and a high discharge voltage of the 4-V
class.
Cobalt, that is, a raw material of lithium cobaltite, is, however, a scarce resource and expensive, and hence, use of lithium nickelate (LiNiO~ in place of lithium cobaltite is now under examination.
Lithium nickelate has, however, a disadvantage that the capacity of a battery including this material is largely degraded through charge-discharge cycles because its crystal structure is less stable than that of lithium cobaltite.

As a positive electrode active material usable for overcoming this problem, a composite oxide obtained by substituting part of nickel atoms included in lithium nickelate with cobalt atoms and manganese atoms is reported (see Japanese Laid-Open Patent Publication No. 8-37007/1996). However, the stability, during charge-discharge cycles, of the crystal structure of this composite oxide is still not sufficient to be used in place of lithium cobaltite.
SUMMARY OF THE INVENTION
In consideration of the aforementioned conventional disadvantages, an object of the invention is providing a lithium secondary battery having an excellent charge-discharge characteristic. This object can be achieved by utilizing a specific positive electrode active material as follows:
The lithium secondary battery of this invention comprises, as a positive electrode active material, a composite oxide powder having a median diameter of 3.0 through 20.0 a m and a content of particles with a grain size of 1 ,u m or less of 10% by volume or less and being represented by a composition formula, LiBCobM~Nil.b.~Oz, in which M is at least one element selected from the group consisting of B, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Y, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In and Sn; 0 <_ a <_ 1.2; 0.01 < b < 0.4; 0.01 < c < 0.4; and 0.02 < b+c <
0.5.
Alternatively, the lithium secondary battery of this invention comprises, as a positive electrode active material, a composite oxide powder having a median diameter of 6.0 through 15.0 a m and a content of particles with a grain size of 1 ~c m or less of 10% by volume or less and being represented by a composition formula, LiaCobM~Nil.b-~02, in which M is at least one element selected from the group consisting of B, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Y, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In and Sn; 0 < a < 1.2; 0.01 < b < 0.4; 0.01 < c <
0.4; and 0.02<_b+c<_0.5.
Alternatively, the lithium secondary battery of this invention comprises, as a positive electrode active material, a composite oxide powder having a median diameter of 3.0 through 20.0 a m and a content of particles with a grain size of 1 a m or less of 10% by volume or less and being represented by a composition formula, LiaCobM~Nil.b.~02, in which M is at least one element selected from the group consisting of B, Mg, Al, Ca, Ti, V, Mn, Fe, Cu, Zn and Ga; 0 < a < 1.2;
0.01 < b <_0.4;0.01<_c<_0.4;and0.02<b+c<0.5.
Alternatively, the lithium secondary battery of this invention comprises, as a positive electrode active material, a composite oxide powder having a median diameter of 6.0 through 15.0 ~c m and a content of particles with a grain size of 1 a m or less of 10% by volume or less and being represented by a composition formula, LiaCobM~Nil_b.~02, in which M is at least one element selected from the group consisting of B, Mg, Al, Ca, Ti, V, Mn, Fe, Cu, Zn and Ga; 0 < a < 1.2;
0.01 <b <_0.4;0.01<_c<_0.4;and0.02_<b+c<0.5.
Owing to these features of the composite oxide powder according to the invention, a lithium secondary battery having an excellent charge-discharge cycle characteristic can be obtained.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same become better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
Figure 1 is a sectional view of a lithium secondary battery manufactured in an experiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
A lithium secondary battery according to the invention comprises, as a positive electrode active material, a composite oxide powder having a median diameter of 3.0 through 20.0 a m and a content of particles with a grain size of 1 ~c m or less of 10 % by volume or less and represented by a composition formula, LiaCobM~Nil_b.~02, in which M indicates at least one element selected from the group consisting of B, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Y, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In and Sn; 0 < a < 1.2; 0.01 < b < 0.4; 0.01 < c <
0.4; and 0.02 <_ b+c < 0.5. A median diameter is a grain size attained at frequency of 50%
on a frequency curve, and is used as a kind of average grain sizes.
The composite oxide powder having the aforementioned composition is used in this invention because this composite oxide powder is less degraded in its crystal structure through repeated occlusion and discharge of lithium ions during charge-discharge cycles. A composite oxide powder represented by a composition formula, LiaCobM~Nil.b-~Oz, in which M indicates at least one element selected from the group consisting of B, Mg, Al, Ca, Ti, V, Mn, Fe, Cu, Zn and Ga; 0 < a <
1.2;
0.01 <_ b <_ 0.4; 0.01 < c < 0.4; and 0.02 < b+c < 0.5, is more preferred because its crystal structure is further less degraded during charge-discharge cycles.
The median diameter of the composite oxide powder is specified to 3.0 through 20.0 ~c m for the following reasons: When the median diameter is smaller than 3.0 a m, the total surface area of the powder is too large to easily react with an electrolyte solution. As a result, a decomposition product of the electrolyte solution is deposited on the particle surfaces of the positive electrode active material, thereby abruptly decreasing the discharge capacity during charge-discharge cycles. On the other hand, when the median diameter exceeds 20.0 ~c m, the total surface area of the powder is so small that the lithium ions are occluded and discharged in merely a small area during charge-discharge cycles.
As a result, the positive electrode active material is abruptly degraded during charge-discharge cycles. More preferably, the composite oxide powder has a median diameter of 6.0 through 15.0 a m.
The content of the particles with a grain size of 1 ~c m or less in the composite oxide powder is specified to 10% by volume or less for the following reason: When the content of the fine particles with a grain size of 1 ,u m or less exceeds 10% by volume, the total surface area of the powder is too large to easily react with the electrolyte solution. As a result, the decomposition product of the electrolyte solution is deposited on the particle surfaces of the composite oxide, thereby abruptly decreasing the discharge capacity during charge-discharge cycles.
The composite oxide powder preferably has a specific surface area measured by a BET method of 0.15 through 2.00 m2/g because a lithium secondary battery with an excellent charge-discharge cycle characteristic can be obtained by using such a powder.
The present invention relates to improvement of a positive electrode active material for the purpose of providing a lithium secondary battery with a good charge-discharge cycle characteristic. Accordingly, materials for other members such as a negative electrode and an electrolyte solution can be any of various materials practically used or proposed as materials for conventional lithium secondary batteries.
Examples of the negative electrode material include a material capable of electrochemically occluding and discharging lithium ions and metallic lithium.
Examples of the material capable of electrochemically occluding and discharging lithium ions include carbon materials such as graphite (including natural graphite and artificial graphite), coke and an organic baked substance;
lithium alloys such as lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, lithium-tin alloy, lithium-thallium alloy, lithium-lead alloy and lithium-bismuth alloy; and metal oxides and metal sulfides including one of or two or more of tin, titanium, iron, molybdenum, niobium, vanadium and zinc.
An example of the electrolyte solution includes a solution obtained by dissolving an electrolytic salt such as LiPFs, LiC104, LiCF3S03 and LiN(CF3S02)z in an organic solvent, such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, y -butyrolactone, sulfolane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-ethoxymethoxyethane, tetrahydrofuran, 2-methyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, dimethyl ether and diethyl ether, in a concentration of 0.7 through 1.5 moles per liter.
Other features of the invention will become more apparent in the course of the following descriptions of exemplary embodiments which are given for illustration of the invention and not intended to be limiting thereof.
Experiment 1:
The relationship between the composition of a positive electrode active material and the charge-discharge cycle characteristic was examined as follows:
Lithium hydroxide (LiOH), nickel hydroxide (Ni(OH)2), cobalt hydroxide (Co(OH)2) and manganese dioxide (Mn02) were mixed in various ratios in mortars, and the resultant mixtures were baked in an atmosphere of oxygen at a temperature of 750°C for 20 hours. In this manner, sixteen kinds of composite oxides each in the form of a mass were obtained.
Each of the composite oxides was crushed by using a jet mill, thereby preparing a composite oxide powder to be used as a positive electrode active material. Table 1 lists the following features of each composite oxide: An atomic ratio among respective elements (i.e., Li:Ni:Co:Mn), a median diameter ( in ~c m), a content of particles with a grain size of 1 ~c m or less (in % by volume), and a specific surface area measured by the BET method (in m2/g). The median diameter was obtained through laser diffraction. Also, helium was used as an absorbed substance in the BET method.
Table 1:
Content of Specific Charge-Atomic ratio of elements Median particles with surface discharge in composite oxide diameter size of 1 ~ m or less area cycles Battery Li Ni Co Mn ( ~, m) (% by volume) (m2/g) A1 1.00 0.98 0.010.01 10.3 9.5 1.32 325 (invention) A2 1.00 0.79 0.010.20 10.5 9.2 1.51 332 (invention) A3 1.00 0.59 0.010.40 9.7 9.2 1.15 340 (invention) A4 1.00 0.50 0.100.40 10.0 9.3 1.12 329 (invention) A5 1.00 0.79 0.200.01 10.9 8.9 1.26 330 (invention) A6 1.00 0.60 0.200.20 10.3 9.0 0.98 329 (invention) A7 1.00 0.50 0.200.30 9.6 9.6 1.01 327 (invention) A8 1.00 0.59 0.400.01 10.2 8.9 1.22 325 (invention) A9 1.00 0.50 0.400.10 11.0 8.8 1.18 331 (invention) B1 1.00 0.50 0.450.05 9.2 9.2 1.54 159 (comparison) B2 1.00 0.50 0.050.45 9.5 9.7 1.25 157 (comparison) B3 1.00 0.45 0.150.40 10.1 9.6 0.86 160 (comparison) B4 1.00 0.45 0.400.15 10.7 9.5 1.23 162 (comparison) B5 1.00 0.90 0.000.10 9.9 9.4 0.94 103 (comparison) B6 1.00 0.90 0.100.00 10.6 9.0 1.16 110 (comparison) B7 1.00 1.00 0.000.00 9.8 8.9 1.04 57 (comparison) Each of the composite oxide powders, acetylene black serving as a conducting agent and poly(vinylidene fluoride) serving as a binder were mixed in a ratio by weight of 90:6:4 and kneaded to give a positive electrode mixed material.
The positive electrode mixed material was pressed at a pressure of 2 ton/cm2, so as to be formed into a disk with a diameter of 20 mm. The resultant disk was heat-treated under vacuum at a temperature of 250°C for 2 hours. Thus, the positive electrode of each battery was prepared.
A negative electrode was prepared by punching a rolled plate of lithium-aluminum alloy into a disk with a diameter of 20 mm.
An electrolyte solution was prepared by dissolving LiPFs in a mixed solvent including ethylene carbonate and dimethyl carbonate in a ratio by volume of 1:1.
Manufacture of batteries:
Flat type lithium secondary batteries (i.e., batteries A1 through A9 according to the invention and comparative batteries B1 through B7) were manufactured by using the aforementioned positive and negative electrodes and electrolyte solution. Figure 1 is a sectional view of the lithium secondary battery The lithium secondary battery BA of Figure 1 comprises a positive electrode 1, a negative electrode 2, a separator 3 for separating the positive and negative electrodes, a positive electrode can 4, a negative electrode can 5, a positive electrode collector 6, a negative electrode collector 7 and an insulating packing 8.
The positive electrode 1 and the negative electrode 2, opposing each other with the separator 3 impregnated with the electrolyte solution sandwiched therebetween, are housed in a battery can formed by the positive and negative electrode cans and 5. The positive electrode 1 is connected with the positive electrode can 4 through the positive electrode collector 6 and the negative electrode 2 is connected with the negative electrode can 5 through the negative electrode collector 7, so that a chemical energy generated within the battery can be taken out as an electric energy.
Each battery was subjected to a charge-discharge cycle test, in which the battery was charged at a current density of 0.5 mA/cm2 to 4.25 V and discharged at a current density of 0.5 mA/cm2 to 2.75V in each cycle. In this manner, the number of charge-discharge cycles repeated until the discharge capacity became smaller than 90% of that in the first cycle was obtained with regard to each battery The thus obtained numbers of charge-discharge cycles are also shown in Table 1 above.
It is understood from Table 1 that the present batteries A1 through A9 have remarkably better charge-discharge cycle characteristics than the comparative batteries B1 through B7. This is because the composite oxides used in the present batteries A1 through A9 are more stable in their crystal structures during charge-discharge cycles than the composite oxides used in the comparative batteries B1 through B7.
Lithium hydroxide, nickel hydroxide, cobalt hydroxide and an M material shown in Table 2 (namely, selected from the group consisting of B, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Fe, Cu, Zn, Ga, Ge, Y, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In and Sn) were mixed in a mortar in an atomic ratio of Li:Ni:Co:M of 1.0:0.6:0.3:0.1, and the resultant mixture was baked in an atmosphere of oxygen at a temperature of 750°C for 20 hours. Thus, twenty four kinds of composite oxides each in the form of a mass were obtained.
Each of the composite oxides was crushed by using a jet mill, thereby preparing a composite oxide powder. Table 2 also lists a median diameter (in ~c m), a content of particles with a grain size of 1 a m or less (in % by volume) and a specific surface area (in m2/g) measured by the BET method of each composite oxide powder.

Table 2:
Content of Specific Charge-Median particles with surface discharge Material diameter size of 1 ~ area cycles of m or less Battery M ( ~c m) (% by volume) (m2/g) A10 H3B03 10.2 9.7 1.55 330 (invention) A11 Mg(OH)2 11.0 9.4 0.93 328 (invention) A12 Al(OH)3 9.8 8.9 1.26 342 (invention) A13 Si0 9.7 9.6 1.07 312 (invention) A14 Ca(OH)2 10.9 10.2 1.32 325 (invention) A15 Scz03 10.5 10.7 1.23 308 (invention) A16 ~(OH)4 9.5 9.7 0.84 330 (invention) A17 V205 10.1 10.1 1.01 331 (invention) A18 Cr203 9.9 10.0 0.93 310 (invention) A19 Fe00H 10.7 9.7 1.15 339 (invention) A20 Cu(OH)2 10.4 11.2 0.96 328 (invention) A21 Zn0 11.0 10.7 1.24 330 (invention) A22 Ca203 9.5 10.4 1.27 329 (invention) A23 Ge02 10.4 9.7 1.38 305 (invention) A24 Y203 10.3 8.8 0.75 301 (invention) A25 Nb2O5 9.7 10.2 1.54 309 (invention) A26 Mo02 10.0 10.3 1.33 302 (invention) Table 2 (continued):
Content of Specific Charge-Median particles with surface discharge Material of diameter size of 1 ~ m or less area cycles Battery M ( ~ m) (% by volume) (m2/g) A27 Ru02 10.1 10.9 0.84 304 (invention) A28 Rh~03 9.9 10.7 1.45 305 (invention) A29 Pd0 9.7 9.7 1.22 310 (invention) A30 Ag20 11.0 10.4 0.74 301 (invention) A31 Cd(OI~2 10.7 9.9 1.63 302 (invention) A32 In203 10.4 10.0 1.31 301 (invention) A33 Sn0 9.7 9.6 1.77 304 (invention) Lithium secondary batteries (i.e., present batteries A10 through A33) were manufactured in the same manner as in Experiment 1 except that the aforementioned composite oxide powders were used as the positive electrode active materials for the respective batteries. These batteries were subjected to the charge-discharge cycle test under the same conditions as in Experiment 1, and the obtained numbers of charge-discharge cycles are also shown in Table 2 above.
It is understood from Table 2 that the element M partially substituted in Ni for improving the stability of the composite oxide in charge-discharge cycles can be not only Mn but also B, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Fe, Cu, Zn, Ga, Ge, Y, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In and Sn. Also, it is understood from Tables 1 and 2 that B, Mg, Al, Ca, Ti, V, Mn, Fe, Cu, Zn and Ga are more preferably used as the element M partially substituted in Ni.
Lithium hydroxide, nickel hydroxide, cobalt hydroxide and manganese dioxide were mixed in a mortar in an atomic ratio of Li:Ni:Co:Mn of 1.0:0.6:0.3:0.1, and the resultant mixture was baked in an atmosphere of oxygen at a temperature of 750°C for 20 hours. Thus, a composite oxide in the form of a mass represented by a composition formula of LiNi°.sCo°.3Mn°.102 was obtained.
This composite oxide was crushed by using a jet mill under various conditions, thereby preparing nine kinds of composite oxide powders. The median diameter, the content of particles with a grain size of 1 ,u m or less (in by volume) and the specific surface area (in m2/g) of each of the composite oxide powders are shown in Table 3.

Table 3:
Content of Specific Charge-Median particles with surface discharge diameter size of 1 ~c m or less area cycles Battery ( ~c m) (% by volume) (m2/g) A34 3.0 10.0 1.99 301 (invention) A35 6.0 10.0 1.72 329 (invention) A36 12.5 8.2 1.55 332 (invention) A37 15.0 5.5 1.34 335 (invention) A38 20.0 2.1 1.27 302 (invention) B8 2.2 10.0 1.97 195 (comparison) B9 21.4 0.5 0.74 182 (comparison) B10 12.6 10.5 1.18 173 (comparison) B11 10.5 12.0 1.24 165 (comparison) Lithium secondary batteries (i.e., present batteries A34 through A38 and comparative batteries B8 through B11) were manufactured in the same manner as in Experiment 1 except that the aforementioned composite oxide powders were used as the positive electrode active materials for the respective batteries.
These batteries were subjected to the charge-discharge cycle test under the same conditions as in Experiment 1. The thus obtained numbers of charge-discharge cycles are also shown in Table 3 above.
It is understood from Table 3 that the present batteries A34 through A38, each of which has a median diameter of 3.0 through 20.0 ~c m and a content of particles with a grain size of 1 ,u m or less of 10 % by volume or less, have better charge-discharge cycle characteristics than the comparative batteries B8 through B11, in which the median diameter or the content of particles with a grain size of 1 ~c m or less does not fall within the range herein specified. Also, as is shown in Table 3, among the present batteries A34 through A38, the batteries A35 through A37 have particularly good charge-discharge cycle characteristics. Therefore, it is understood that a composite oxide with a median diameter of 6.0 through 15.0 ,u m is more preferred.
Experiment 4:
Lithium hydroxide, nickel hydroxide, cobalt hydroxide and manganese dioxide were mixed in a mortar in an atomic ratio of Li:Ni:Co:Mn of 1.0:0.6:0.3:0.1, and the resultant mixture was baked in an atmosphere of oxygen at a temperature of 750°C for 20 hours. Thus, a composite oxide in the form of a mass represented by a composition formula of LiNio.6Co°.3Mn°,102 was obtained. At this point, the grain sizes of the materials to be used were variously changed so as to adjust the shapes of the resultant composite oxides and pores included therein.

Thus, eighteen kinds of composite oxides, each in the form of a mass, different from one another in the median diameter or the specific surface area were obtained.
Each of the thus obtained composite oxides was crushed by using a jet mill, thereby preparing a composite oxide powder. Table 4 lists the median diameter, the content of particles with a grain size of 1 ,u m or less (in % by volume) and the specific surface area measured by the BET method of each composite oxide powder.

Table 4:
Content of Specific Charge-Median particles with surface discharge diameter size of 1 a m or less area cycles Battery ( ~c m) (% by volume) (m2~g) A39 3.0 9.9 2.00 301 (invention) A40 3.0 10.0 2.12 275 (invention) A41 6.0 3.2 0.12 304 (invention) A42 6.0 9.8 0.15 325 (invention) A35 6.0 10.0 1.72 329 (invention) A43 6.0 9.7 2.00 325 (invention) A44 6.0 9.9 2.05 300 (invention) A45 12.5 3.9 0.13 297 (invention) A46 12.5 4.2 0.15 330 (invention) A36 12.5 8.2 1.55 332 (invention) A47 12.5 8.9 2.00 323 (invention) A48 12.5 9.2 2.09 302 (invention) A49 15.0 3.1 0.13 296 (invention) A50 15.0 4.5 0.15 342 (invention) A37 15.0 5.5 1.34 335 (invention) A51 15.0 9.5 2.00 325 (invention) A52 15.0 9.7 2.05 299 (invention) Table 4 (continued):
Content of Specific Charge-Median ~ particles with surface discharge diameter size of 1 a m or less area cycles Battery ( ~c m) (% by volume) (m2/g) A53 20.0 0.5 0.13 270 (invention) A54 20.0 0.8 0.15 298 (invention) A38 20.0 2.1 1.27 302 (invention) A55 20.0 3.2 2.00 305 (invention) A56 20.0 4.3 2.09 267 (invention) Lithium secondary batteries (i.e., present batteries A39 through A56) were manufactured in the same manner as in Experiment 1 except that the aforementioned composite oxide powders were used as the positive electrode active materials for the respective batteries. The respective batteries were subjected to the charge-discharge cycle test under the same conditions as in Experiment 1, and the results are also shown in Table 4 above. It is noted that Table 4 also lists the results obtained in the present batteries A35 through shown in Table 3 for comparison.
On the basis of comparison in Table 4 between the present battery A39 and the present battery A40, between the present batteries A35, A42 and A43 and the present batteries A41 and A44, between the present batteries A36, A46 and A47 and the present batteries A45 and A48, between the present batteries A37, A50 and A51 and the present batteries A49 and A52, and between the present batteries A38, A54 and A55 and the present batteries A53 and A56, it is understood that a lithium secondary battery having an excellent charge-discharge cycle characteristic can be obtained when the composite oxide powder has a specific surface area measured by the BET method of 0.15 through 2.00 m2/g.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described herein.

Claims (16)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A lithium secondary battery comprising, as a positive electrode active material, a composite oxide powder having a median diameter of 3.0 through 20.0 µ m and a content of particles with a grain size of 1 µ m or less of 10%
by volume or less and being represented by a composition formula, Li a Co b M c N i1-b-c O2, in which M is at least one element selected from the group consisting of Si, Sc, Ti, V, Cu, Zn, Ga; Ge, Y, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In and Sn; 0 <= a <= 1.2; 0.01 <=
b <= 0.4; 0.01 <= c <= 0.4; and 0.02 <= b + c <=
0.5.
2. The lithium secondary battery according to Claim 1, wherein the composite oxide powder has a specific surface area measured by a BET method of 0.15 through 2.00 m2/g.
3. A lithium secondary battery comprising, as a positive electrode active material, a composite oxide powder having a median diameter of 6.0 through 15.0 µ m and a content of particles with a grain size of 1 µ m or less of 10%
by volume or less and being represented by a composition formula, Li a Co b M c Ni1-b-c O2, in which M is at least one element selected from the group consisting of Si, Sc, Ti, V, Cu, Zn, Ga, Ge, Y, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In and Sn; 0 <= a <= 1.2; 0.01 <=
b <= 0.4; 0.01 <= c <= 0.4; and 0.02 <= b + c <=
0.5.
4. The lithium secondary battery according to Claim 3, wherein the composite oxide powder has a specific surface area measured by a BET method of 0.15 through 2.00 m2/g.
5. A lithium secondary battery comprising, as a positive electrode active material, a composite oxide powder having a median diameter of 3.0 through 20.0 µ m and a content of particles with a grain size of 1 µ m or less of 10%
by volume or less and being represented by a composition formula, Li a Co b M c Ni1-b-c O2, in which M is at least one element selected from the group consisting of Ti, V, Cu, Zn and Ga; 0 <= a <= 1.2;0.01 <= b <= 0.4;01 <=
c <= 0.4; and 0.02 <= b + c <= 0.5.
6. The lithium secondary battery according to Claim 5, wherein the composite oxide powder has a specific surface area measured by a BET method of 0.15 through 2.00 m2/g.
7. A lithium secondary battery comprising, as a positive electrode active material, a composite oxide powder having a median diameter of 6.0 through 15.0 µ m and a content of particles with a grain size of 1 µ m or less of 10%
by volume or less and being represented by a composition formula, Li a Co b M c Ni1-b-c O3, in which M is at least one element selected from the group consisting of Ti, V, Cu, Zn and Ga;0 <= a <= 1.2; 0.01 <= b <= 0.4; 0.01 <= c <= 0.4; and 0.02 <= b + c <= 0.5.
8. The lithium secondary battery according to Claim 7, wherein the composite oxide powder has a specific surface area measured by a BET method of 0.15 through 2.00 m2/g.
9. A positive electrode active material for a lithium secondary battery comprising a composite oxide powder having a median diameter of 3.0 through 20.0 µ m and a content of particles with a grain size of 1 µ m or less of 10% by volume or less and being represented by a composition formula, Li a C o b M c Ni1-b-c O2, in which M is at least one element selected from the group consisting of Si, Sc, Ti, V, Cu, Zn, Ga, Ge, Y, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In and Sn; 0 <= a <= 1.2; 0.01 <=
b <= 0.4; 0.01 <= c <= 0.4; and 0.02 <= b + c <=
0.5.
10. The positive electrode active material for a lithium secondary battery according to Claim 9, wherein the composite oxide powder has a specific surface area measured by a BET method of 0.15 through 2.00 m2/g.
11. A positive electrode active material for a lithium secondary battery comprising a composite oxide powder having a median diameter of 6.0 through 15.0 µ m and a content of particles with a grain size of 1 µ m or less of 10% by volume or less and being represented by a composition formula, Li a Co b M c Ni1-b-c O2, in which M is at least one element selected from the group consisting of Si, Sc, Ti, V, Cu, Zn, Ga, Ge, Y, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In and Sn; 0 <= a <= 1.2; 0.01 <=
b <= 0.4; 0.01 <= c <= 0.4; and 0.02 <= b + c <=
0.5.
12. The positive electrode active material for a lithium secondary battery according to Claim 11, wherein the composite oxide powder has a specific surface area measured by a BET method of 0.15 through 2.00 m2/g.
13. A positive electrode active material for a lithium secondary battery comprising a composite oxide powder having a median diameter of 3.0 through 20.0 µ m and a content of particles with a grain size of 1 µ m or less of 10% by volume or less and being represented by a composition formula, Li a Co b M c Ni1-b-c O2, in which M is at least one element selected from the group consisting of Ti, V, Cu, Zn and Ga; 0 <= a <= 1.2; 0.01 <= b <= 0.4; 0.01 <= c <= 0.4; and 0.02 <= b + c <= 0.5.
14. The positive electrode active material for a lithium secondary battery according to Claim 13, wherein the composite oxide powder has a specific surface area measured by a BET method of 0.15 through 2.00 m2/g.
15. A positive electrode active material for a lithium secondary battery comprising a composite oxide powder having a median diameter of 6.0 through 15.0 µ m and a content of particles with a grain size of 1 µ m or less of 10% by volume or less and being represented by a composition formula, Li a Co b M c Ni1-b-c O2, in which M is at least one element selected from the group consisting of Ti, V, Cu, Zn and Ga; 0 <= a <= 1.2; 0.1 <= b <= 0.4; 0.01 <= c <= 0.4; and 0.02 <=b + c <= 0.5.
16. The positive electrode active material for a lithium secondary battery according to Claim 15, wherein the composite oxide powder has a specific surface area measured by a BET method of 0.15 through 2.00 m2/g.
CA002265372A 1998-03-19 1999-03-16 Lithium secondary battery Expired - Fee Related CA2265372C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10-92734/1998 1998-03-19
JP09273498A JP3524762B2 (en) 1998-03-19 1998-03-19 Lithium secondary battery

Publications (2)

Publication Number Publication Date
CA2265372A1 CA2265372A1 (en) 1999-09-19
CA2265372C true CA2265372C (en) 2004-11-02

Family

ID=14062658

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002265372A Expired - Fee Related CA2265372C (en) 1998-03-19 1999-03-16 Lithium secondary battery

Country Status (4)

Country Link
US (1) US6333128B1 (en)
EP (1) EP0944125B1 (en)
JP (1) JP3524762B2 (en)
CA (1) CA2265372C (en)

Families Citing this family (77)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3526223B2 (en) * 1998-09-17 2004-05-10 日本碍子株式会社 Lithium secondary battery
US6660432B2 (en) 2000-09-14 2003-12-09 Ilion Technology Corporation Lithiated oxide materials and methods of manufacture
JP4183374B2 (en) * 2000-09-29 2008-11-19 三洋電機株式会社 Nonaqueous electrolyte secondary battery
JP4813453B2 (en) * 2000-11-16 2011-11-09 日立マクセルエナジー株式会社 Lithium-containing composite oxide and non-aqueous secondary battery
AU2002214289A1 (en) 2000-11-16 2002-05-27 Hitachi Maxell, Ltd. Lithium-containing composite oxide and nonaqueous secondary cell using the same,and method for manufacturing the same
WO2002073718A1 (en) * 2001-03-14 2002-09-19 Yuasa Corporation Positive electrode active material and nonaqueous electrolyte secondary cell comprising the same
DE60237441D1 (en) * 2001-04-20 2010-10-07 Gs Yuasa Corp ÜR, ANODE FOR USE IN A SECONDARY BATTERY WITH A WATER-FREE ELECTROLYTE AND SECONDARY BATTERY WITH A WATER-FREE ELECTROLYTE
US6964828B2 (en) * 2001-04-27 2005-11-15 3M Innovative Properties Company Cathode compositions for lithium-ion batteries
CA2388936C (en) 2001-06-07 2006-07-18 Kawatetsu Mining Co., Ltd. Cathode material for use in lithium secondary battery and manufacturing method thereof
JP2003086249A (en) * 2001-06-07 2003-03-20 Mitsubishi Chemicals Corp Lithium secondary battery
JP4635386B2 (en) * 2001-07-13 2011-02-23 株式会社Ｇｓユアサ Positive electrode active material and non-aqueous electrolyte secondary battery using the same
GB0117235D0 (en) * 2001-07-14 2001-09-05 Univ St Andrews Improvements in or relating to electrochemical cells
JP2003034536A (en) * 2001-07-19 2003-02-07 Mitsubishi Chemicals Corp Method for producing layered lithium nickel manganese composite oxide powder
JP4951824B2 (en) * 2001-07-27 2012-06-13 三菱化学株式会社 Electrode active material-containing composition, and electrode and lithium secondary battery using the same
CN100459242C (en) 2001-08-07 2009-02-04 3M创新有限公司 Improved positive electrode composition for lithium ion batteries
JP2003089526A (en) * 2001-09-12 2003-03-28 Mitsubishi Chemicals Corp Lithium nickel manganese composite oxide, positive electrode material for lithium secondary battery using the same, positive electrode for lithium secondary battery, and lithium secondary battery
JP4774661B2 (en) * 2001-09-25 2011-09-14 三菱化学株式会社 Lithium transition metal composite oxide, positive electrode material for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery, and method for producing lithium transition metal composite oxide
US7393476B2 (en) 2001-11-22 2008-07-01 Gs Yuasa Corporation Positive electrode active material for lithium secondary cell and lithium secondary cell
JP4813450B2 (en) * 2001-11-22 2011-11-09 日立マクセルエナジー株式会社 Lithium-containing composite oxide and non-aqueous secondary battery using the same
US7026068B2 (en) 2001-12-19 2006-04-11 Nichia Corporation Positive electrode active material for lithium ion secondary battery
US20030182172A1 (en) * 2002-03-25 2003-09-25 Claggett Stuart Lee System and method to build project management processes
US7241532B2 (en) 2002-03-28 2007-07-10 Mitsubishi Chemical Corporation Positive-electrode material for lithium secondary battery, secondary battery employing the same, and process for producing positive-electrode material for lithium secondary battery
JP4655453B2 (en) * 2002-03-28 2011-03-23 三菱化学株式会社 Positive electrode material for lithium secondary battery, secondary battery using the same, and method for producing positive electrode material for lithium secondary battery
CN101127400A (en) * 2002-03-28 2008-02-20 三菱化学株式会社 Positive electrode material for lithium secondary battery, lithium secondary battery using the same, and method for preparing positive electrode material for lithium secondary battery
US7788129B2 (en) * 2002-06-25 2010-08-31 American Express Travel Related Services Company, Inc. System and method for redeeming vouchers
US7606730B2 (en) * 2002-06-25 2009-10-20 American Express Travel Relate Services Company, Inc. System and method for a multiple merchant stored value card
JP4707299B2 (en) 2002-11-20 2011-06-22 住友金属鉱山株式会社 Lithium secondary battery positive electrode active material and lithium secondary battery
JP4803486B2 (en) * 2003-05-15 2011-10-26 株式会社Ｇｓユアサ Non-aqueous electrolyte battery
US7211237B2 (en) 2003-11-26 2007-05-01 3M Innovative Properties Company Solid state synthesis of lithium ion battery cathode material
CN100440594C (en) * 2004-04-27 2008-12-03 三菱化学株式会社 Layered lithium nickel manganese cobalt-based composite oxide powder for positive electrode material of lithium secondary battery, method for producing same, positive electrode for lithium secondary battery using same, and lithium secondary battery
JP4997693B2 (en) * 2004-10-01 2012-08-08 住友金属鉱山株式会社 Positive electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery using the same, and method for producing the same
US20080008933A1 (en) * 2005-12-23 2008-01-10 Boston-Power, Inc. Lithium-ion secondary battery
US7811707B2 (en) * 2004-12-28 2010-10-12 Boston-Power, Inc. Lithium-ion secondary battery
JP2008544468A (en) 2005-06-28 2008-12-04 トダ・コウギョウ・ヨーロッパ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング Inorganic compounds
US7656125B2 (en) 2005-07-14 2010-02-02 Boston-Power, Inc. Method and device for controlling a storage voltage of a battery pack
KR20070009447A (en) * 2005-07-14 2007-01-18 마츠시타 덴끼 산교 가부시키가이샤 Positive electrode for lithium secondary battery and lithium secondary battery using same
TWI426678B (en) 2006-06-28 2014-02-11 波士頓電力公司 Electronic device with multiple charging rate, battery pack, method for charging lithium ion charge storage power supply in electronic device and portable computer
KR20090037452A (en) * 2006-07-10 2009-04-15 스미또모 가가꾸 가부시끼가이샤 Lithium composite metal oxide
JP5521266B2 (en) * 2006-11-21 2014-06-11 住友化学株式会社 Positive electrode active material powder and positive electrode active material
US20080280205A1 (en) * 2007-05-07 2008-11-13 3M Innovative Properties Company Lithium mixed metal oxide cathode compositions and lithium-ion electrochemical cells incorporating same
BRPI0813288A2 (en) 2007-06-22 2014-12-30 Boston Power Inc CURRENT INTERRUPT DEVICE, BATTERY, LITHIUM BATTERY, METHODS FOR MANUFACTURING A CURRENT INTERRUPTION DEVICE, A BATTERY, AND A LITHIUM BATTERY.
CN101808939B (en) * 2007-09-28 2012-10-03 3M创新有限公司 Sintered cathode compositions
EP2210298A1 (en) * 2007-09-28 2010-07-28 3M Innovative Properties Company Method of making cathode compositions
US8993051B2 (en) * 2007-12-12 2015-03-31 Technische Universiteit Delft Method for covering particles, especially a battery electrode material particles, and particles obtained with such method and a battery comprising such particle
JP2011515824A (en) * 2008-03-24 2011-05-19 スリーエム イノベイティブ プロパティズ カンパニー High voltage cathode composition
US8153301B2 (en) * 2008-07-21 2012-04-10 3M Innovative Properties Company Cathode compositions for lithium-ion electrochemical cells
JP2010086896A (en) * 2008-10-02 2010-04-15 Sanyo Electric Co Ltd Nonaqueous electrolyte secondary battery and active material for nonaqueous electrolyte secondary battery
KR101147602B1 (en) * 2009-03-03 2012-05-21 주식회사 엘지화학 Lithium Secondary Battery Containing Cathode Materials Having High Energy Density and Organic/Inorganic Composite Porous Membrane
US8483886B2 (en) 2009-09-01 2013-07-09 Boston-Power, Inc. Large scale battery systems and method of assembly
US9023526B2 (en) 2010-06-13 2015-05-05 Samsung Sdi Co., Ltd. Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same
EP2399869B1 (en) 2010-06-25 2015-07-29 Evonik Degussa GmbH Mixed oxide powder containing the elements lithium, manganese, nickel and cobalt and method for producing same
CN103238240B (en) * 2010-12-07 2016-05-18 株式会社半导体能源研究所 Electrical storage device
JP6035013B2 (en) 2011-08-30 2016-11-30 株式会社半導体エネルギー研究所 Electrode fabrication method
JP2013054878A (en) 2011-09-02 2013-03-21 Semiconductor Energy Lab Co Ltd Method of manufacturing electrode and power storage device
JP5826653B2 (en) * 2012-02-01 2015-12-02 株式会社Ｇｓユアサ Positive electrode active material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same
US9384904B2 (en) 2012-04-06 2016-07-05 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device, method for forming the same, and power storage device
JP6216154B2 (en) 2012-06-01 2017-10-18 株式会社半導体エネルギー研究所 Negative electrode for power storage device and power storage device
US9692039B2 (en) 2012-07-24 2017-06-27 Quantumscape Corporation Nanostructured materials for electrochemical conversion reactions
WO2014073461A1 (en) 2012-11-07 2014-05-15 Semiconductor Energy Laboratory Co., Ltd. Electrode for power storage device, power storage device, and manufacturing method of electrode for power storage device
TWI473330B (en) * 2012-12-10 2015-02-11 Ind Tech Res Inst Electrode structure of lithium battery
JP6064615B2 (en) * 2013-01-21 2017-01-25 三洋電機株式会社 Non-aqueous electrolyte secondary battery and manufacturing method thereof
KR102044735B1 (en) * 2013-04-12 2019-11-15 에스케이이노베이션 주식회사 Layered lithium nickel oxide, process for producing the same and lithium secondary cell employing it
CN105612123B (en) 2013-10-24 2018-06-08 陶氏环球技术有限责任公司 Improved lithium metal oxide positive electrode and the method for preparing it
JP6156078B2 (en) 2013-11-12 2017-07-05 日亜化学工業株式会社 Method for producing positive electrode active material for non-aqueous electrolyte secondary battery, positive electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
JP2015118901A (en) * 2013-11-12 2015-06-25 信越化学工業株式会社 Positive electrode active material for lithium ion secondary batteries and method for manufacturing the same, and lithium ion secondary battery
JP6524651B2 (en) 2013-12-13 2019-06-05 日亜化学工業株式会社 Positive electrode active material for non-aqueous electrolyte secondary battery and method for producing the same
WO2015130831A1 (en) 2014-02-25 2015-09-03 Quantumscape Corporation Hybrid electrodes with both intercalation and conversion materials
WO2015183568A1 (en) * 2014-05-27 2015-12-03 Dow Global Technologies Llc Improved lithium metal oxide cathode materials and method to make them
US10326135B2 (en) 2014-08-15 2019-06-18 Quantumscape Corporation Doped conversion materials for secondary battery cathodes
KR101802018B1 (en) * 2014-09-26 2017-11-27 주식회사 엘지화학 Non-aqueous liquid electrolyte and lithium secondary battery comprising the same
US11437646B2 (en) 2014-09-26 2022-09-06 Lg Energy Solution, Ltd. Non-aqueous liquid electrolyte and lithium secondary battery comprising the same
CN107210419B (en) * 2014-12-23 2021-06-08 昆腾斯科普电池公司 Lithium-rich nickel manganese cobalt oxide (LR-NMC)
JP6915964B2 (en) * 2016-02-29 2021-08-11 富山薬品工業株式会社 Non-aqueous electrolyte for lithium-ion secondary batteries
US10483541B2 (en) 2016-05-09 2019-11-19 Nichia Corporation Method of producing nickel-cobalt composite hydroxide and method of producing positive electrode active material for non-aqueous electrolyte secondary battery
JP2022505069A (en) 2018-11-06 2022-01-14 クアンタムスケープ バッテリー，インコーポレイテッド Electrochemical cell with casolite additive and lithium-filled garnet separator
CN118318325A (en) 2021-11-30 2024-07-09 昆腾斯科普电池公司 Catholyte for solid-state batteries
WO2023114436A1 (en) 2021-12-17 2023-06-22 Quantumscape Battery, Inc. Cathode materials having oxide surface species

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4980080A (en) * 1988-06-09 1990-12-25 Societe Anonyme Dite: Saft Process of making a cathode material for a secondary battery including a lithium anode and application of said material
US5180574A (en) * 1990-07-23 1993-01-19 Moli Energy (1990) Limited Hydrides of lithiated nickel dioxide and secondary cells prepared therefrom
US5264201A (en) 1990-07-23 1993-11-23 Her Majesty The Queen In Right Of The Province Of British Columbia Lithiated nickel dioxide and secondary cells prepared therefrom
JP3244314B2 (en) 1991-11-13 2002-01-07 三洋電機株式会社 Non-aqueous battery
US5361105A (en) 1993-03-05 1994-11-01 Matsushita Electric Corporation Of America Noise reduction system using multi-frame motion estimation, outlier rejection and trajectory correction
JP3550783B2 (en) 1994-05-16 2004-08-04 東ソー株式会社 Lithium-containing transition metal composite oxide, method for producing the same, and use thereof
US5631105A (en) * 1995-05-26 1997-05-20 Matsushita Electric Industrial Co., Ltd. Non-aqueous electrolyte lithium secondary battery
CA2209933C (en) * 1995-11-24 2005-04-12 Fuji Chemical Industry Co., Ltd. A lithium nickel complex oxide, a process for preparing the same and a positive electrode active material for a secondary battery
US5718989A (en) 1995-12-29 1998-02-17 Japan Storage Battery Co., Ltd. Positive electrode active material for lithium secondary battery
JPH09293497A (en) 1996-04-25 1997-11-11 Mitsui Mining & Smelting Co Ltd Non-aqueous electrolyte secondary battery
TW363940B (en) * 1996-08-12 1999-07-11 Toda Kogyo Corp A lithium-nickle-cobalt compound oxide, process thereof and anode active substance for storage battery
JP4120014B2 (en) * 1996-08-16 2008-07-16 堺化学工業株式会社 Method for producing particulate composition
US5783333A (en) * 1996-11-27 1998-07-21 Polystor Corporation Lithium nickel cobalt oxides for positive electrodes
JP3301931B2 (en) * 1996-12-27 2002-07-15 三洋電機株式会社 Lithium secondary battery
DE69819395T2 (en) * 1997-04-15 2004-09-09 Sanyo Electric Co., Ltd., Moriguchi Positive electrode material for use of the non-aqueous electrolyte-containing battery and method of manufacturing the same and the non-aqueous electrolyte-containing battery
JP3633223B2 (en) * 1997-04-25 2005-03-30 ソニー株式会社 Positive electrode active material, method for producing the same, and nonaqueous electrolyte secondary battery
JPH1154120A (en) * 1997-07-29 1999-02-26 Japan Storage Battery Co Ltd Lithium ion secondary battery

Also Published As

Publication number Publication date
US6333128B1 (en) 2001-12-25
JPH11273677A (en) 1999-10-08
CA2265372A1 (en) 1999-09-19
EP0944125B1 (en) 2012-05-02
EP0944125A1 (en) 1999-09-22
JP3524762B2 (en) 2004-05-10

Similar Documents

Publication Publication Date Title
US6333128B1 (en) Lithium secondary battery
US6337158B1 (en) Lithium secondary battery
US10790506B2 (en) Spherical or spherical-like cathode material for lithium-ion battery and lithium-ion battery
US6168888B1 (en) Spinel-type lithium-manganese oxide containing heteroelements, preparation process and use thereof
US6346348B1 (en) Rechargeable lithium battery with a lithium molybdenum oxide electrode
US6521379B2 (en) Non-aqueous electrolyte secondary cell with a lithium cobalt oxide positive electrode
EP2715856B1 (en) Positive electrode material having a size dependent composition
KR102724244B1 (en) Surface-coated cathode material and method for producing the same, lithium ion battery
US12633524B2 (en) Positive electrode active material for all-solid-state lithium ion secondary battery, method for producing the same, and all-solid-state lithium ion secondary battery
EP3998234B1 (en) Positive electrode active material for lithium ion secondary battery and lithium ion secondary battery
JP2003142101A (en) Positive electrode for secondary battery and secondary battery using the same
EP4576257A1 (en) Cathode for lithium secondary battery, and lithium secondary battery comprising same
CN100401562C (en) Positive electrode material for lithium secondary battery and manufacturing method thereof
US6551743B1 (en) Nonaqueous secondary battery
EP4589688A1 (en) Positive electrode for lithium secondary battery, and lithium secondary battery comprising same
EP1122802B1 (en) Non-aqueous electrolyte secondary cell
JP4224995B2 (en) Secondary battery and current collector for secondary battery
JPH08264179A (en) Lithium battery
JPH08250119A (en) Lithium secondary battery
US6391496B1 (en) Lithium secondary battery with orthorhombic molybdenum and niobium oxide electrodes
US20050037263A1 (en) Positive electrodes for rechargeable batteries
JP2023093555A (en) Positive electrode active material for lithium ion secondary battery, method for producing positive electrode active material for lithium ion secondary battery, lithium ion secondary battery
CA2298095C (en) Lithium secondary battery
KR100578865B1 (en) Cathode active material for lithium secondary battery and lithium secondary battery comprising same
JP7173275B2 (en) Positive electrode active material for lithium ion secondary battery, method for producing positive electrode active material for lithium ion secondary battery, lithium ion secondary battery

Legal Events

Date Code Title Description
EEER Examination request
MKLA Lapsed

Effective date: 20150316