WO2011007751A1 - Matière active d’électrode positive pour pile rechargeable au lithium, procédé de production de celle-ci et pile rechargeable au lithium - Google Patents

Matière active d’électrode positive pour pile rechargeable au lithium, procédé de production de celle-ci et pile rechargeable au lithium Download PDF

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WO2011007751A1
WO2011007751A1 PCT/JP2010/061755 JP2010061755W WO2011007751A1 WO 2011007751 A1 WO2011007751 A1 WO 2011007751A1 JP 2010061755 W JP2010061755 W JP 2010061755W WO 2011007751 A1 WO2011007751 A1 WO 2011007751A1
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positive electrode
active material
electrode active
atom
lithium
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PCT/JP2010/061755
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English (en)
Japanese (ja)
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稔 福知
龍也 荒瀬
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日本化学工業株式会社
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Priority to CN2010800407253A priority Critical patent/CN102498597A/zh
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    • 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
    • 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
    • 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
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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

Definitions

  • the present invention relates to a positive electrode active material for a lithium secondary battery, a manufacturing method thereof, and particularly a lithium secondary battery excellent in cycle characteristics.
  • lithium cobaltate has been used as a positive electrode active material for lithium secondary batteries.
  • cobalt is a rare metal
  • lithium nickel cobalt manganese based composite oxides having a low cobalt content see, for example, Patent Documents 1 to 3 have been developed.
  • This lithium nickel cobalt manganese complex oxide as a positive electrode active material can be manufactured at low cost by adjusting the atomic ratio of nickel, manganese and cobalt contained in the complex oxide. Although it is known that it will also be excellent with respect to the requirement of the property, the thing excellent in cycling characteristics is also requested
  • Patent Document 4 mainly describes a composite oxide such as Li 1.04 Ni 0.86 Co 0.15 O 2 and LiAlO placed as a particle or a layer on the surface of the composite oxide. It has been proposed to use a positive electrode active material composed of an Al-containing compound such as 2 and having a NaFeO 2 type crystal structure having specific physical properties. However, according to Patent Document 4, LiAlO 2 is merely an example of an Al-containing compound, and there is no specific description regarding the positive electrode active material according to the present invention.
  • the present inventors have obtained a lithium secondary battery using a lithium nickel cobalt manganese based composite oxide having a specific composition and a positive electrode active material containing ⁇ -LiAlO 2.
  • the present inventors have found that the cycle characteristics are excellent and have completed the present invention.
  • an object of the present invention is to provide a positive electrode active material for a lithium secondary battery using a lithium nickel cobalt manganese based composite oxide capable of imparting particularly excellent cycle characteristics to the lithium secondary battery, and the positive electrode active material.
  • An object of the present invention is to provide a lithium secondary battery using a method that is industrially advantageous and a particularly excellent cycle characteristic using the positive electrode active material.
  • a first invention to be provided by the present invention is a positive electrode active material containing an Al atom, the following general formula (1) Li x Ni 1-yz Co y Mn z O 2 (1) (Wherein x represents 0.98 ⁇ x ⁇ 1.20, y represents 0 ⁇ y ⁇ 0.5, and z represents 0 ⁇ z ⁇ 0.5, where y + z ⁇ 1).
  • a positive electrode active material for a lithium secondary battery characterized by containing lithium composite oxide and ⁇ -LiAlO 2 .
  • the second invention to be provided by the present invention provides (a) a lithium compound, (b) a nickel atom, a cobalt atom and a manganese atom in an atomic ratio of 0.1 to 1 cobalt atom per 1 mol of nickel atom. 0.0, a compound containing manganese atoms of 0.1 to 1.0 and (c) aluminum phosphate in an atomic ratio of lithium atom to nickel atom, cobalt atom, manganese atom and aluminum atom (Li / ⁇ Ni + Co + Mn + Al ⁇ ).
  • a positive electrode active material for a lithium secondary battery comprising a second step of obtaining a positive electrode active material containing lithium composite oxide and ⁇ -LiAlO 2 .
  • the third invention to be provided by the present invention is a lithium secondary battery using the positive electrode active material for a lithium secondary battery according to the first invention.
  • a lithium secondary battery having particularly excellent cycle characteristics can be provided using a positive electrode active material made of a lithium nickel cobalt manganese based composite oxide. Moreover, according to the manufacturing method of this positive electrode active material for lithium secondary batteries, this positive electrode active material can be manufactured by an industrially advantageous method.
  • FIG. 4 is an X-ray diffraction pattern of a positive electrode active material sample obtained in Reference Experiment 1.
  • FIG. 4 is an SEM photograph of a positive electrode active material sample obtained in Reference Experiment 1.
  • 4 is an X-ray diffraction pattern of a positive electrode active material sample obtained in Reference Experiment 2.
  • FIG. 4 is an SEM photograph of a positive electrode active material sample obtained in Reference Experiment 2.
  • 3 is an SEM photograph of the positive electrode active material sample obtained in Example 1.
  • a positive electrode active material for a lithium secondary battery according to the present invention (hereinafter simply referred to as “positive electrode active material” unless otherwise specified) is a positive electrode active material containing Al atoms, and has the following general formula (1): Li x Ni 1-yz Co y Mn z O 2 (1) (Wherein x represents 0.98 ⁇ x ⁇ 1.20, y represents 0 ⁇ y ⁇ 0.5, and z represents 0 ⁇ z ⁇ 0.5, where y + z ⁇ 1).
  • Lithium composite oxide (hereinafter also referred to simply as “lithium composite oxide”) and ⁇ -LiAlO 2 , and the positive electrode active material having such a structure includes Particularly excellent cycle characteristics can be imparted to a lithium secondary battery using a positive electrode active material.
  • X in the formula of the lithium composite oxide represented by the general formula (1) is 0.98 or more and 1.20 or less, preferably x is in the range of 1.00 or more and 1.10 or less. Since the initial discharge capacity of the lithium secondary battery tends to be high, it is preferable.
  • Y in the formula is greater than 0 and 0.5 or less, and preferably y in the formula is greater than 0 and in a range of 0.4 or less from the viewpoint of safety of the lithium secondary battery.
  • Z in the formula is greater than 0 and 0.5 or less, and preferably in the range where z in the formula is greater than 0 and 0.4 or less, the initial discharge capacity of the lithium secondary battery tends to increase. This is preferable.
  • x in the formula is 1.00 or more and 1.05 or less
  • y is 0.1 or more and 0.3 or less
  • z is 0.1 or more. 0.3 or less.
  • the lithium composite oxide represented by the general formula (1) has good dispersibility in the paint when the aggregated lithium composite oxide is formed by aggregating primary particles to form secondary particles.
  • the average particle size of primary particles obtained by observation with a scanning electron microscope is 0.2 to 4 ⁇ m, preferably 0.5 to 2 ⁇ m. It is preferable in that the cycle characteristics of the secondary battery are good.
  • the coating property and the coating film characteristics are good, and further, lithium using the positive electrode active material This is preferable in that the cycle characteristics of the secondary battery are also good.
  • ⁇ -LiAlO 2 as one component are not particularly limited, but those finer than the lithium composite oxide represented by the general formula (1) are preferable in that they can be uniformly dispersed with the lithium composite oxide. .
  • “finer than the lithium composite oxide represented by the general formula (1)” means that the average particle diameter is smaller than the secondary particles of the lithium composite oxide represented by the general formula (1).
  • the positive electrode active material of the present invention contains Al atoms, and the Al atoms are present in a state of at least ⁇ -LiAlO 2 . That is, the positive electrode active material of the present invention may be present as all Al atoms alpha-LiAlO 2 contained in the positive electrode active material, Al atom in addition to alpha-LiAlO 2 is a partially lithium composite oxide It may be dissolved.
  • the content of Al atoms is preferably 0.025 to 0.90 wt%, preferably 0.05 to 0.70 wt% as Al atoms. This is because if the content of Al atoms is less than 0.025 wt% as Al atoms, there is a tendency that sufficient cycle characteristics cannot be obtained in a lithium secondary battery using the positive electrode active material. This is because when the content exceeds 0.9% by weight as Al atoms, there is a tendency that a sufficient initial discharge capacity cannot be obtained in a lithium secondary battery using the positive electrode active material.
  • lithium nickel cobalt manganese based composite oxide containing Al atoms when aluminum hydroxide is usually used as the aluminum source, aluminum atoms are preferentially dissolved in lithium nickel cobalt manganese based composite oxide.
  • the present inventor uses aluminum phosphate as the aluminum source, and more than a specific amount of lithium atoms relative to nickel atoms, cobalt atoms, manganese atoms, and aluminum atoms in the raw material mixture.
  • ⁇ -LiAlO 2 is generated and the reaction is performed with lithium using a positive electrode active material. It has been found that the secondary battery is particularly improved in cycle characteristics.
  • the positive electrode active material of the present invention comprises (a) a lithium compound, (b) a compound containing a nickel atom, a cobalt atom and a manganese atom, and (c) an aluminum phosphate.
  • a lithium compound a compound containing a nickel atom, a cobalt atom and a manganese atom
  • an aluminum phosphate an atomic ratio of lithium atoms to aluminum atoms (Li / ⁇ Ni + Co + Mn + Al ⁇ ) of 0.95 or more, preferably 1.00 to 1.10, and the resulting mixture is 950 ° C. or less, preferably 870 to 940 It is particularly preferable that the product is produced by firing at 0 ° C.
  • the positive electrode active material obtained by such a manufacturing method can obtain a uniform mixture of the lithium composite oxide represented by the general formula (1) and ⁇ -LiAlO 2, and a lithium secondary battery using the positive electrode active material Is particularly preferable from the viewpoint of excellent cycle characteristics.
  • the remaining LiOH is 0.1% by weight or less, preferably 0.05% by weight or less, and the remaining Li 2 CO 3 is 0.5% by weight or less, preferably 0.8%.
  • the content of 3% by weight or less is particularly preferable from the viewpoints of suppressing gelation of the paint and suppressing battery swelling.
  • the positive electrode active material according to the present invention further, on the production process, irreversibly LiPO 4 to be mixed may be contained within a range not to impair the effects of the present invention.
  • the positive electrode active material for a lithium secondary battery of the present invention comprises (a) a lithium compound, (b) a nickel atom, a cobalt atom, and a manganese atom in an atomic ratio of 0.1 to 1.0 cobalt atoms per 1 mol of nickel atoms. 0.95 or more in terms of atomic ratio of lithium atom to nickel atom, cobalt atom, manganese atom and aluminum atom (Li / ⁇ Ni + Co + Mn + Al ⁇ ) And a second step of obtaining a positive electrode active material containing the lithium composite oxide represented by the general formula (1) and ⁇ -LiAlO 2 by firing the resulting mixture.
  • a lithium compound represented by the general formula (1) and ⁇ -LiAlO 2
  • lithium compound (a) lithium compound according to the first step examples include lithium oxide, hydroxide, carbonate, nitrate, and organic acid salt. Among these, lithium carbonate is inexpensive and has excellent productivity. Are particularly preferably used.
  • the lithium compound has an average particle size determined from a laser particle size distribution measurement method of 1 to 100 ⁇ m, and preferably 5 to 80 ⁇ m, because of good reactivity.
  • a composite hydroxide, a composite oxyhydroxide, a composite carbonate or a composite oxide is preferably used as the compound (b) containing a nickel atom, a cobalt atom and a manganese atom according to the first step.
  • the composite hydroxide can be prepared, for example, by a coprecipitation method. Specifically, a composite hydroxide can be coprecipitated by mixing an aqueous solution containing the nickel atom, cobalt atom and manganese atom, an aqueous solution of a complexing agent, and an aqueous solution of an alkali (Japanese Patent Application Laid-Open No. Hei. No.
  • the composite oxide can be obtained by obtaining a composite hydroxide precipitate in accordance with the coprecipitation operation, followed by heat treatment at 200 to 500 ° C., for example.
  • an aqueous solution containing the nickel atom, cobalt atom and manganese atom and an aqueous solution of a complexing agent are prepared in the same manner as in the coprecipitation operation described above, and the alkaline aqueous solution is converted to an alkali carbonate or carbonate carbonate.
  • a composite carbonate can be obtained by mixing this as an aqueous solution of hydrogen alkali.
  • the compound containing a nickel atom, a cobalt atom and a manganese atom is preferably a composite hydroxide containing each of these atoms from the viewpoint of (a) high reactivity with the lithium compound.
  • this (b) compound containing nickel atom, cobalt atom and manganese atom is an aggregated lithium composite that retains the shape of the aggregate when an aggregate in which primary particles are aggregated to form secondary particles is used.
  • An oxide is obtained, and the use of a positive electrode active material containing this aggregated lithium composite oxide and ⁇ -LiAlO 2 is preferable in that a lithium secondary battery with improved cycle characteristics can be obtained.
  • the aggregated nickel atom, cobalt atom and manganese atom-containing compound has an average primary particle size of 0.2 to 4 ⁇ m, preferably 0.5 to 2 ⁇ m, which is obtained by observation with a scanning electron microscope.
  • the resulting positive electrode active material has good coatability and coating film properties, and further the positive electrode active material It is preferable in that the cycle characteristics of a lithium secondary battery using the lithium ion battery are also good.
  • the composition of the compound containing nickel atom, cobalt atom and manganese atom is within the range of molar ratio of nickel atom, cobalt atom and manganese atom in the formula of the lithium composite oxide represented by the general formula (1). It is. That is, the cobalt atom is 0.1 to 1.0, preferably 0.2 to 0.7, and the manganese atom is 0.1 to 1.0, preferably 0.2 to 0.7, per 1 mol of nickel atom. .
  • the (c) aluminum phosphate according to the first step is not particularly limited as long as it is industrially available, but the average particle size determined from the laser particle size distribution measurement method is not limited.
  • a thickness of 1 to 30 ⁇ m, preferably 5 to 20 ⁇ m is particularly preferable from the viewpoint of (a) good reactivity with the lithium compound.
  • the raw material (a) lithium compound, (b) compound containing nickel atom, cobalt atom and manganese atom and (c) aluminum phosphate are as impurities as possible in order to produce a high purity positive electrode active material. Those having a low content are preferred.
  • the compounding ratio of (a) lithium compound, (b) compound containing nickel atom, cobalt atom and manganese atom and (c) aluminum phosphate is the atomic ratio of lithium atom to nickel atom, cobalt atom, manganese atom and aluminum atom (Li / (Ni + Co + Mn + Al)) is 0.95 or more, preferably 1.00 to 1.10, which is one important requirement for obtaining a positive electrode active material having excellent cycle characteristics. This is because, when the atomic ratio of lithium atoms to nickel atoms, cobalt atoms, manganese atoms, and aluminum atoms is smaller than 0.95, the cycle characteristics are good in the lithium secondary battery using the positive electrode active material obtained by the method. Furthermore, it is because a product having a sufficient initial discharge capacity cannot be obtained.
  • the compounding ratio of (b) a compound containing nickel atom, manganese atom and cobalt atom and (c) aluminum phosphate is 0 in terms of atomic ratio of aluminum atom to nickel atom, cobalt atom and manganese atom (Al / ⁇ Ni + Co + Mn ⁇ ).
  • a lithium secondary battery using a positive electrode active material obtained by the above method having both excellent initial discharge capacity and cycle characteristics is 0.001 to 0.03, preferably 0.005 to 0.02. It is particularly preferable from the viewpoint of.
  • the cycle characteristics of the lithium secondary battery using the positive electrode active material obtained by the method are deteriorated.
  • the atomic ratio of aluminum atoms to nickel atoms, cobalt atoms, and manganese atoms is greater than 0.03, the initial discharge capacity of the lithium secondary battery using the positive electrode active material obtained by the method tends to decrease. Is not preferable.
  • the mixing may be either a dry method or a wet method, but a dry method is preferable because of easy production. In the case of dry mixing, it is preferable to use a blender or the like that uniformly mixes the raw materials.
  • the mixture obtained by uniformly mixing the raw materials obtained in the first step is then subjected to the second step, and the positive electrode active material containing the lithium composite oxide represented by the general formula (1) and ⁇ -LiAlO 2 Get.
  • the second step according to the present invention is a step of obtaining a positive electrode active material containing a lithium composite oxide and ⁇ -LiAlO 2 by firing the mixture in which the raw materials obtained in the first step are uniformly mixed.
  • the firing temperature in the second step is 950 ° C. or lower, preferably 870 to 940 ° C. This is because when the firing temperature is higher than 950 ° C., the initial discharge capacity and cycle characteristics of the lithium secondary battery using the positive electrode active material obtained by the method tend to be lowered.
  • the firing is preferably performed while appropriately adjusting the temperature rising rate until the predetermined firing temperature is reached. That is, the temperature is raised from room temperature (25 ° C.) to 600 ° C. at 400 to 800 ° C./hr, preferably 500 to 700 ° C./hr, and then to a predetermined firing temperature of 50 to 150 ° C./hr, preferably 75 to 125 ° C. It is preferable to raise the temperature at / hr from the viewpoint of good production efficiency and, in particular, a lithium secondary battery using a positive electrode active material obtained by the method, which has excellent cycle characteristics.
  • the firing is preferably performed in the air or in an oxygen atmosphere for 1 to 30 hours.
  • the fired material may be pulverized and then refired. After firing, the cathode active material of the present invention can be obtained by appropriately cooling and grinding if necessary.
  • the remaining LiOH and / or LiCO is further performed by performing a third step of washing the obtained positive electrode active material with a solvent, and then performing a fourth step of annealing the positive electrode active material after the washing treatment.
  • 3 can be reduced, and the coating properties and coating film characteristics can be further improved, and a positive electrode active material in which the battery swelling of the lithium secondary battery is further suppressed can be obtained.
  • the obtained positive electrode active material contains residual LiOH in an amount greater than 0.1% by weight and Li 2 CO 3 in an amount greater than 0.5% by weight.
  • the remaining LiOH is 0.1 wt% or less, preferably 0.05 wt% or less, and Li 2 CO 3 is 0.5 wt% or less, preferably 0.4 wt% or less.
  • a positive electrode active material that is reduced and substantially free of LiOH and Li 2 CO 3 is obtained.
  • the positive electrode active material which does not substantially contain LiOH and Li 2 CO 3 can suppress gelation during kneading with a binder resin when producing the positive electrode material, and can improve the coating property.
  • the solvent according to the third step for example, water, warm water, ethanol, methanol, acetone or the like can be used as one or two or more mixed solvents.
  • water is preferable from the viewpoint of low cost and high cleaning efficiency.
  • cleaning method in a 3rd process The method of making a solvent and a positive electrode active material contact under stirring, or usual methods, such as a repulp, can be used.
  • the positive electrode active material subjected to the cleaning process is annealed in the fourth step.
  • the lithium secondary battery using the positive electrode active material subjected to the annealing treatment has improved initial discharge capacity and cycle characteristics compared to the lithium secondary battery using the positive electrode active material subjected only to the cleaning treatment.
  • the positive electrode active material subjected to the annealing treatment can further suppress the battery swelling of the lithium secondary battery.
  • the annealing conditions are 400 to 800 ° C, preferably 500 to 700 ° C.
  • the reason for this is that if the heat treatment temperature is less than 400 ° C., sufficient cycle characteristics tend not to be obtained in the lithium secondary battery using the positive electrode active material obtained by the method, while if it exceeds 800 ° C., In a lithium secondary battery using a positive electrode active material obtained by the method, the initial discharge capacity tends to decrease, which is not preferable.
  • the atmosphere in which the annealing treatment is performed is not particularly limited, and may be either in the air or in an oxygen atmosphere.
  • the annealing treatment time is usually 3 hours or more, preferably 5 to 10 hours. Further, the annealing treatment may be performed as many times as desired. Alternatively, for the purpose of making the powder characteristics uniform, the one that has been annealed may be pulverized and then reannealed. After the annealing treatment is completed, crushing or pulverization is performed as necessary, followed by classification to obtain a product.
  • a lithium secondary battery according to the present invention uses the positive electrode active material for a lithium secondary battery, and includes a positive electrode, a negative electrode, a separator, and a nonaqueous electrolyte containing a lithium salt.
  • the positive electrode is formed, for example, by applying and drying a positive electrode mixture on a positive electrode current collector, and the positive electrode mixture includes a positive electrode active material, a conductive agent, a binder, and a filler added as necessary. Consists of.
  • the positive electrode active material containing the lithium composite oxide represented by the general formula (1) of the present invention and ⁇ -LiAlO 2 is uniformly applied to the positive electrode. For this reason, the lithium secondary battery according to the present invention is particularly excellent in cycle characteristics.
  • the content of the positive electrode active material contained in the positive electrode mixture is 70 to 100% by weight, preferably 90 to 98% by weight.
  • the positive electrode current collector is not particularly limited as long as it is an electronic conductor that does not cause a chemical change in the constituted battery.
  • the surface include carbon, nickel, titanium, and silver surface-treated. The surface of these materials may be oxidized and used, or the current collector surface may be provided with irregularities by surface treatment.
  • the current collector include foils, films, sheets, nets, punched ones, lath bodies, porous bodies, foam bodies, fiber groups, nonwoven fabric molded bodies, and the like.
  • the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m.
  • the conductive agent is not particularly limited as long as it is an electron conductive material that does not cause a chemical change in a configured battery.
  • graphite such as natural graphite and artificial graphite, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, carbon black such as thermal black
  • conductive fibers such as carbon fiber and metal fiber
  • Examples include metal powders such as carbon fluoride, aluminum and nickel powder, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and conductive materials such as polyphenylene derivatives.
  • graphite include scaly graphite, scaly graphite, and earthy graphite. These can be used alone or in combination of two or more.
  • the blending ratio of the conductive agent is 1 to 50% by weight, preferably 2 to 30% by weight in the positive electrode mixture.
  • binder examples include starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, regenerated cellulose, diacetylcellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer ( EPDM), sulfonated EPDM, styrene butadiene rubber, fluoro rubber, tetrafluoroethylene-hexafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, fluorinated Vinylidene-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetraf Oroethylene copolymer, polychlorotrifluoroethylene
  • the compound containing a functional group which reacts with lithium like a polysaccharide it is preferable to add the compound like an isocyanate group and to deactivate the functional group, for example.
  • the blending ratio of the binder is 1 to 50% by weight, preferably 5 to 15% by weight in the positive electrode mixture.
  • the filler suppresses the volume expansion of the positive electrode in the positive electrode mixture, and is added if necessary.
  • any fibrous material can be used as long as it does not cause a chemical change in the constructed battery.
  • olefinic polymers such as polypropylene and polyethylene, and fibers such as glass and carbon are used.
  • the addition amount of the filler is not particularly limited, but is preferably 0 to 30% by weight in the positive electrode mixture.
  • the negative electrode is formed by applying and drying a negative electrode material on the negative electrode current collector.
  • the negative electrode current collector is not particularly limited as long as it is an electronic conductor that does not cause a chemical change in a configured battery.
  • stainless steel, nickel, copper, titanium, aluminum, calcined carbon, copper or stainless steel examples include carbon, nickel, titanium, silver surface-treated, and an aluminum-cadmium alloy. Further, the surface of these materials may be used after being oxidized, or the surface of the current collector may be provided with irregularities by surface treatment.
  • Examples of the current collector include foils, films, sheets, nets, punched ones, lath bodies, porous bodies, foam bodies, fiber groups, nonwoven fabric molded bodies, and the like.
  • the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m.
  • the negative electrode material is not particularly limited, and examples thereof include carbonaceous materials, metal composite oxides, lithium metals, lithium alloys, silicon-based alloys, tin-based alloys, metal oxides, conductive polymers, and chalcogen compounds. And Li—Co—Ni-based materials.
  • Examples of the carbonaceous material include non-graphitizable carbon materials and graphite-based carbon materials.
  • Examples of the metal composite oxide include Sn P (M 1 ) 1-p (M 2 ) q Or (wherein M 1 represents one or more elements selected from Mn, Fe, Pb and Ge, M 2 represents one or more elements selected from Al, B, P, Si, Group 1, Group 2, Group 3 and a halogen element in the periodic table, and 0 ⁇ p ⁇ 1, 1 ⁇ q ⁇ 3 ,. showing a 1 ⁇ r ⁇ 8), Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), include compounds of lithium titanate.
  • the metal oxide GeO, GeO 2, SnO, SnO 2, PbO, PbO 2, Pb 2 O 3, Pb 3 O 4, Sb 2 O 3, Sb 2 O 4, Sb 2 O 5, Bi 2 O 3 Bi 2 O 4 , Bi 2 O 5 and the like.
  • the conductive polymer include polyacetylene and poly-p-phenylene.
  • an insulating thin film having a large ion permeability and a predetermined mechanical strength is used.
  • Sheets and non-woven fabrics made of olefin polymers such as polypropylene, glass fibers or polyethylene are used because of their organic solvent resistance and hydrophobicity.
  • the pore diameter of the separator may be in a range generally useful for batteries, for example, 0.01 to 10 ⁇ m.
  • the thickness of the separator may be in a range for a general battery, for example, 5 to 300 ⁇ m.
  • the solid electrolyte such as a polymer is used as the electrolyte described later, the solid electrolyte may also serve as a separator.
  • the non-aqueous electrolyte containing a lithium salt is composed of a non-aqueous electrolyte and a lithium salt.
  • a non-aqueous electrolyte a non-aqueous electrolyte, an organic solid electrolyte, or an inorganic solid electrolyte is used.
  • Non-aqueous electrolytes include, for example, N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ⁇ -butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran, 2-methyl Tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 3-methyl -2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, diethyl ether, 1,3- Ropansaruton, methyl propionate, and a solvent
  • organic solid electrolyte examples include a polyethylene derivative, a polyethylene oxide derivative or a polymer containing the same, a polypropylene oxide derivative or a polymer containing the same, a phosphate ester polymer, polyphosphazene, polyaziridine, polyethylene sulfide, polyvinyl alcohol, polyvinylidene fluoride, Examples thereof include a polymer containing an ionic dissociation group such as polyhexafluoropropylene, and a mixture of a polymer containing an ionic dissociation group and the above non-aqueous electrolyte.
  • Li nitride, halide, oxyacid salt, sulfide and the like can be used, for example, Li 3 N, LiI, Li 5 NI 2 , Li 3 N—LiI—LiOH, LiSiO 4.
  • the inorganic solid electrolyte is amorphous (glass), lithium phosphate (Li 3 PO 4 ), lithium oxide (Li 2 O), lithium sulfate (Li 2 SO 4 ), phosphorus oxide (P 2 O 5) ), Compounds containing oxygen such as lithium borate (Li 3 BO 3 ), Li 3 PO 4-x N 2x / 3 (x is 0 ⁇ x ⁇ 4), Li 4 SiO 4-x N 2x / 3 (x is Nitrogen such as 0 ⁇ x ⁇ 4), Li 4 GeO 4-x N 2x / 3 (x is 0 ⁇ x ⁇ 4), Li 3 BO 3-x N 2x / 3 (x is 0 ⁇ x ⁇ 3)
  • the compound to be contained can be contained in the inorganic solid electrolyte.
  • lithium salt those dissolved in the non-aqueous electrolyte are used.
  • the following compounds can be added to the non-aqueous electrolyte for the purpose of improving discharge, charge characteristics, and flame retardancy.
  • pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, hexaphosphoric triamide, nitrobenzene derivative, sulfur, quinoneimine dye, N-substituted oxazolidinone and N, N-substituted imidazolidine, ethylene glycol dialkyl ether , Ammonium salt, polyethylene glycol, pyrrole, 2-methoxyethanol, aluminum trichloride, conductive polymer electrode active material monomer, triethylenephosphonamide, trialkylphosphine, morpholine, aryl compound with carbonyl group, hexamethylphosphine
  • Examples include hollic triamide and 4-alkylmorpholine, bicyclic tertiary amines, oils, phosphonium salts and
  • a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride can be included in the electrolyte.
  • carbon dioxide gas can be included in the electrolytic solution in order to make it suitable for high-temperature storage.
  • the lithium secondary battery according to the present invention is a lithium secondary battery excellent in battery performance, particularly in cycle characteristics, and the shape of the battery may be any shape such as a button, a sheet, a cylinder, a corner, or a coin type.
  • the use of the lithium secondary battery according to the present invention is not particularly limited.
  • electronic devices such as memory cards and video movies, and consumer electronic devices such as automobiles, electric vehicles, and game machines.
  • Ni: Co: Mn molar ratio in composite hydroxide 0.60: 0.20: 0.20
  • Table 1 shows amounts of lithium carbonate (average particle: 7 ⁇ m), the above-mentioned aggregated composite hydroxide containing nickel, cobalt, and manganese atoms and aluminum phosphate (average particle size: 16.2 ⁇ m, manufactured by Junsei Chemical Co., Ltd.) The mixture was added and sufficiently dried to obtain a uniform mixture of these raw materials. Next, the temperature was raised to 600 ° C. over 1 hour, further raised to 925 ° C. over 3 hours, then held at 925 ° C. for 10 hours and fired in the atmosphere. After the firing, the fired product obtained by cooling was pulverized to obtain a positive electrode active material sample.
  • the positive electrode active material sample is an aggregate in which primary particles are aggregated to form secondary particles. Was confirmed to be uniformly distributed.
  • An SEM photograph of the positive electrode active material sample is shown in FIG.
  • the positive electrode active material sample has an average primary particle size of 0.5 ⁇ m determined from observation with a scanning electron microscope and an average secondary particle size of 8.3 ⁇ m determined by a laser particle size distribution measurement method.
  • the BET specific surface area was 0.92 m 2 / g.
  • the average particle diameter of the primary particles was obtained by observation with a scanning electron microscope for 100 arbitrarily extracted aggregated particles.
  • a positive electrode active material sample was obtained by performing the reaction under the same conditions as in Reference Experiment 1 except that aluminum phosphate was changed to aluminum hydroxide (average particle size: 1.4 ⁇ m).
  • the positive electrode active material sample obtained in Reference Experiment 2 was subjected to X-ray diffraction analysis using CuK ⁇ rays. As a result, it was confirmed that it was LiNi 0.60 Co 0.20 Mn 0.20 Al 0.10 O 2 (see FIG. 3).
  • the positive electrode active material sample has an average primary particle size of 0.5 ⁇ m determined by observation with a scanning electron microscope, and an average secondary particle size of 9.6 ⁇ m determined by a laser particle size distribution measurement method.
  • the BET specific surface area was 0.40 m 2 / g.
  • the average particle diameter of the primary particles was obtained by observation with a scanning electron microscope for 100 arbitrarily extracted aggregated particles. An SEM photograph of the positive electrode active material sample is shown in FIG.
  • ⁇ Example 1 ⁇ First step and second step> Amounts shown in Table 3 of lithium carbonate (average particle: 7 ⁇ m), aggregated composite hydroxide containing nickel atom, cobalt atom and manganese atom and aluminum phosphate (average particle size: 16.2 ⁇ m, manufactured by Junsei Chemical Co., Ltd.) The mixture was added and sufficiently dried to obtain a uniform mixture of these raw materials. Next, the temperature was raised to 600 ° C. over 1 hour, further raised to 925 ° C. over 3 hours, then held at 925 ° C. for 10 hours and fired in the atmosphere.
  • the fired product obtained by cooling was pulverized to obtain a positive electrode active material sample (A) containing LiNi 0.6 Co 0.2 Mn 0.2 O 2 and ⁇ -LiAlO 2 . Moreover, the SEM photograph of the obtained positive electrode active material sample (A) is shown in FIG.
  • Example 3 Except for changing the addition amount of aluminum phosphate as shown in Table 3, the first to second steps were performed in the same manner as in Example 1, and the third to fourth steps were further performed in the same manner as in Example 2.
  • ⁇ Comparative Example 2 ⁇ First step and second step> Lithium carbonate (average particle: 7 ⁇ m), aggregated complex oxide containing nickel atom, cobalt atom and manganese atom and magnesium oxide (average particle size: 5.3 ⁇ m) were added in the amounts shown in Table 3 and sufficiently dry. By mixing, a uniform mixture of these raw materials was obtained. Next, the temperature was raised to 600 ° C. over 1 hour, further raised to 925 ° C. over 3 hours, then held at 925 ° C. for 10 hours and fired in the atmosphere. After the completion of firing, the fired product obtained by cooling was pulverized to obtain a positive electrode active material (a2).
  • ⁇ Comparative Example 3 ⁇ First step and second step> Lithium carbonate (average particle: 7 ⁇ m), aggregated complex oxide containing nickel atom, cobalt atom and manganese atom, and aluminum hydroxide (average particle size: 1.4 ⁇ m) were added in the amounts shown in Table 3, and sufficiently dry To obtain a uniform mixture of these raw materials. Next, the temperature was raised to 600 ° C. over 1 hour, further raised to 925 ° C. over 3 hours, then held at 925 ° C. for 10 hours and fired in the atmosphere. After the firing, the fired product obtained by cooling was pulverized to obtain a positive electrode active material (a3).
  • a lithium secondary battery was manufactured using each member such as a separator, a negative electrode, a positive electrode, a current collector plate, a mounting bracket, an external terminal, and an electrolytic solution.
  • a metal lithium foil was used for the negative electrode, and 1 mol of LiPF 6 dissolved in 1 liter of a 1: 1 kneaded solution of ethylene carbonate and methyl ethyl carbonate was used for the electrolyte.
  • a lithium secondary battery having particularly excellent cycle characteristics can be provided using a positive electrode active material made of a lithium nickel cobalt manganese based composite oxide. Moreover, according to the manufacturing method of this positive electrode active material for lithium secondary batteries, this positive electrode active material can be manufactured by an industrially advantageous method.

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Abstract

L’invention concerne une matière active d’électrode positive pour pile rechargeable au lithium, qui constitue une matière active d’électrode positive contenant des atomes d’Al et est caractérisée en ce qu’elle contient α-LiAlO2 et un oxyde complexe de lithium représenté par la formule générale (1) LixNi1-y-zCoyMnzO2 (dans laquelle x satisfait la relation 0,98≦x≦1,20, y satisfait la relation 0<y≦0,5 et z satisfait la relation 0<z≦0,5, mais y+z<1). L’invention concerne de plus: cette matière active d’électrode positive pour pile rechargeable au lithium, qui utilise un oxyde complexe de lithium nickel cobalt manganèse et permet de produire une pile rechargeable au lithium présentant des propriétés exceptionnelles de cyclage; un procédé de production de cette matière active d’électrode positive utilisant un processus industriellement avantageux; et une pile rechargeable au lithium qui utilise cette matière active d’électrode positive et présente en particulier d’excellentes propriétés de cyclage.
PCT/JP2010/061755 2009-07-13 2010-07-12 Matière active d’électrode positive pour pile rechargeable au lithium, procédé de production de celle-ci et pile rechargeable au lithium WO2011007751A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN103299456A (zh) * 2011-03-31 2013-09-11 Jx日矿日石金属株式会社 锂离子电池用正极活性物质、锂离子电池用正极和锂离子电池
US8993160B2 (en) 2009-12-18 2015-03-31 Jx Nippon Mining & Metals Corporation Positive electrode for lithium ion battery, method for producing said positive electrode, and lithium ion battery
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US10122012B2 (en) 2010-12-03 2018-11-06 Jx Nippon Mining & Metals Corporation Positive electrode active material for lithium-ion battery, a positive electrode for lithium-ion battery, and lithium-ion battery
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EP2673823B1 (fr) * 2011-02-07 2015-12-09 Umicore Matériau de cathode à forte teneur en nickel ayant une faible teneur en base soluble
WO2013062313A1 (fr) 2011-10-24 2013-05-02 주식회사 엘지화학 Procédé de fabrication de matière active de cathode, matière active de cathode et batterie secondaire au lithium comprenant celle-ci
US10593942B2 (en) * 2014-10-30 2020-03-17 Sumitomo Metal Mining Co., Ltd. Nickel-containing composite hydroxide and production process therefor, positive-electrode active material for a nonaqueous-electrolyte secondary battery and production process therefor, and nonaqueous-electrolyte secondary battery
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WO2017164237A1 (fr) * 2016-03-24 2017-09-28 住友金属鉱山株式会社 Matière active d'électrode positive pour pile secondaire à électrolyte non aqueux et son procédé de fabrication, pâte de matière d'électrode positive pour pile secondaire à électrolyte non aqueux, et pile secondaire à électrolyte non aqueux
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JP7262418B2 (ja) * 2020-04-28 2023-04-21 住友金属鉱山株式会社 非水系電解質二次電池用正極活物質、および非水系電解質二次電池
KR20240037680A (ko) 2022-09-15 2024-03-22 주식회사 엘지화학 양극 활물질 전구체의 제조 방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1173958A (ja) * 1997-06-18 1999-03-16 Sony Corp 正極活物質の製造方法
JP2005243301A (ja) * 2004-02-24 2005-09-08 Sanyo Electric Co Ltd 非水電解液二次電池
JP2006202702A (ja) * 2005-01-24 2006-08-03 Hitachi Maxell Ltd 非水電解質二次電池
JP2007103141A (ja) * 2005-10-04 2007-04-19 Sumitomo Chemical Co Ltd 正極活物質および非水電解質二次電池

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1331267C (zh) * 2003-08-15 2007-08-08 比亚迪股份有限公司 一种锂离子二次电池及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1173958A (ja) * 1997-06-18 1999-03-16 Sony Corp 正極活物質の製造方法
JP2005243301A (ja) * 2004-02-24 2005-09-08 Sanyo Electric Co Ltd 非水電解液二次電池
JP2006202702A (ja) * 2005-01-24 2006-08-03 Hitachi Maxell Ltd 非水電解質二次電池
JP2007103141A (ja) * 2005-10-04 2007-04-19 Sumitomo Chemical Co Ltd 正極活物質および非水電解質二次電池

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JP7054065B2 (ja) 2017-08-29 2022-04-13 住友金属鉱山株式会社 非水系電解質二次電池用正極活物質とその製造方法、及び該正極活物質を用いた非水系電解質二次電池
WO2019044338A1 (fr) * 2017-08-29 2019-03-07 住友金属鉱山株式会社 Matière active d'électrode positive pour batterie secondaire à électrolyte non aqueux ainsi que procédé de fabrication associé, et batterie secondaire à électrolyte non aqueux mettant en œuvre cette matière active d'électrode positive
US11637284B2 (en) 2017-08-29 2023-04-25 Sumitomo Metal Mining Co., Ltd. Positive electrode active material for non-aqueous electrolyte secondary batteries, production method therefor, and non-aqueous electrolyte secondary batteries using said positive electrode active material
US11637283B2 (en) 2017-08-29 2023-04-25 Sumitomo Metal Mining Co., Ltd. Positive electrode active material for non-aqueous electrolyte secondary batteries, production method therefor, and non-aqueous electrolyte secondary batteries using said positive electrode active material
JP2019153435A (ja) * 2018-03-01 2019-09-12 住友化学株式会社 リチウム金属複合酸化物、リチウム二次電池用正極活物質、正極及びリチウム二次電池

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