WO2011007750A1 - Matière active d’électrode positive pour pile rechargeable au lithium, procédé de fabrication de celle-ci et pile rechargeable au lithium - Google Patents

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

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WO2011007750A1
WO2011007750A1 PCT/JP2010/061754 JP2010061754W WO2011007750A1 WO 2011007750 A1 WO2011007750 A1 WO 2011007750A1 JP 2010061754 W JP2010061754 W JP 2010061754W WO 2011007750 A1 WO2011007750 A1 WO 2011007750A1
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positive electrode
active material
electrode active
atom
lithium
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PCT/JP2010/061754
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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 CN2010800407272A priority Critical patent/CN102498598A/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
    • 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 property requirement, it is further desired to have excellent cycle characteristics.
  • lithium secondary batteries using a positive electrode active material containing lithium nickel cobalt manganese based composite oxide having a specific composition and LiBiO 2 are particularly cycled.
  • the inventors have found that the 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.
  • the first invention to be provided by the present invention is 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 LiBiO 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 0.1 to 1.0 manganese atoms, and (c) a bismuth compound at an atomic ratio of lithium atom to nickel atom, cobalt atom, manganese atom and bismuth atom (Li / ⁇ Ni + Co + Mn + Bi ⁇ ).
  • a method for producing 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 LiBiO 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.
  • the 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 represented by 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”
  • LiBiO 2 LiBiO 2
  • the positive electrode active material having such a structure includes the positive electrode active material.
  • Particularly excellent cycle characteristics can be imparted to a lithium secondary battery using a substance.
  • 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, and particularly in the formula, x is in the range of 1.00 or more and 1.10 or less. This is particularly preferable because the initial discharge capacity of the lithium secondary battery tends to be high.
  • y is greater than 0 and 0.5 or less, and it is particularly preferable that y in the formula is in the range of greater than 0 and 0.4 or less from the viewpoint of the safety of the lithium secondary battery.
  • Z in the formula is greater than 0 and less than or equal to 0.5, and particularly when z in the formula is greater than 0 and less than or equal to 0.4, the initial discharge capacity of the lithium secondary battery tends to increase. Is particularly preferred.
  • 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 properties and the coating film properties 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 improved.
  • the physical property of LiBiO 2 as one component is not particularly limited, but a finer one than the lithium composite oxide represented by the general formula (1) is preferable because it 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 LiBiO 2 content is 0.2 to 7.0% by weight, preferably 1.0 to 4.0% by weight as Bi atoms in the positive electrode active material. preferable.
  • the reason for this is less than 0.2 wt% content of LiBiO 2 as a Bi atom, a lithium secondary battery using the positive electrode active material tends to be not sufficient cycle characteristics can not be obtained, whereas, the LiBiO 2 This is because if the content exceeds 7.0% by weight as Bi atoms, there is a tendency that sufficient initial discharge capacity cannot be obtained in a lithium secondary battery using the positive electrode active material.
  • the presence state of LiBiO 2 may be present as fine particles on the surface of the lithium composite oxide particles, and in the case of the aggregate lithium composite oxide, the aggregate lithium It may exist in the state taken in the particle
  • FIG. 1 illustrates a cross section inside the aggregated lithium composite oxide particle in a state where LiBiO 2 is taken into the aggregated lithium composite oxide particle.
  • fine lithium composite oxide primary particles (2) and LiBiO 2 particles (3) are aggregated to form aggregated lithium composite oxide particles.
  • At least LiBiO 2 is present in a state of being incorporated in the particles of the aggregated lithium composite oxide represented by the general formula (1).
  • the secondary battery is particularly preferable from the viewpoint of excellent 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) a bismuth compound, a lithium atom with respect to the nickel atom, cobalt atom, manganese atom and bismuth atom.
  • the atomic ratio (Li / ⁇ Ni + Co + Mn + Bi ⁇ ) is 0.95 or more, preferably 1.00 to 1.10, and the resulting mixture is preferably 950 ° C. or less, particularly preferably 850 to 940 ° C.
  • the positive electrode active material obtained by such a manufacturing method exists in a state where LiBiO 2 is incorporated inside the particles of the aggregated lithium composite oxide, and the lithium secondary battery using the positive electrode active material is particularly Excellent cycle characteristics.
  • preferred physical properties of the positive electrode active material existing in a state where LiBiO 2 is incorporated inside the particles of the aggregated lithium composite oxide represented by the general formula (1) are the above-described general formula (1).
  • the cycle characteristics are excellent. That is, the average primary particle size determined from observation with a scanning electron microscope is 0.2 to 4 ⁇ m, preferably 0.5 to 2 ⁇ m, and the average secondary particle size determined by the laser particle size distribution measurement method is 4. It is ⁇ 25 ⁇ m, preferably 5 to 20 ⁇ m.
  • the BET specific surface area of the positive electrode active material is 0.2 to 0.8 m 2 / g, preferably 0.3 to 0.7 m 2 / g.
  • 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 viewpoint of suppressing gelation of the paint and suppressing battery swelling.
  • the positive electrode active material according to the present invention is an oxide such as nickel, cobalt, manganese, etc. that is irreversibly mixed in the manufacturing method as a component other than the lithium composite oxide represented by the general formula (1) and LiBiO 2 .
  • 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.
  • 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 these atoms from the viewpoint of (a) high reactivity with the lithium compound.
  • the compound containing nickel atoms, cobalt atoms, and manganese atoms when an aggregate in which primary particles aggregate to form secondary particles is used, the target LiBiO 2 retains the shape of the aggregate. Is preferable in that a lithium secondary battery in which cycle characteristics are improved can be obtained by using the aggregated lithium composite oxide.
  • the compound containing agglomerated nickel atom, cobalt atom and manganese atom has an average primary particle size of 0.2 to 4 ⁇ m, preferably 0.5 to 2 ⁇ m, as determined by scanning electron microscope observation.
  • the resulting positive electrode active material has good coating properties 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. .
  • oxides, sulfates, nitrates, chlorides and the like can be used as the (c) bismuth compound according to the first step.
  • bismuth oxide is particularly preferably used from the viewpoint that (a) the reactivity with the lithium compound is high and that a positive electrode active material in which LiBiO 2 is incorporated into the particles of the aggregated lithium composite oxide is easily obtained.
  • the bismuth compound has an average particle size determined by a laser light scattering method of 5 to 50 ⁇ m, preferably 10 to 40 ⁇ m, and (a) it is particularly preferable from the viewpoint that it easily reacts uniformly with the lithium compound.
  • the raw material (a) lithium compound, (b) compound containing nickel atom, cobalt atom and manganese atom and (c) bismuth compound are as impurities as possible 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) bismuth compound is the atomic ratio of lithium atom to nickel atom, cobalt atom, manganese atom and bismuth atom (Li / ⁇ Ni + Co + Mn + Bi ⁇ ) 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 bismuth 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) bismuth compound is 0 in terms of atomic ratio of bismuth atom to nickel atom, cobalt atom and manganese atom (Bi / ⁇ 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 (Bi / ⁇ Ni + Co + Mn ⁇ ) of bismuth atoms to nickel atoms, cobalt atoms, and manganese atoms is greater than 0.03, the lithium secondary battery using the positive electrode active material obtained by the method The initial discharge capacity tends to decrease, which 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 a second step to obtain a positive electrode active material containing the lithium composite oxide represented by the general formula (1) and LiBiO 2 .
  • a positive electrode active material containing a lithium composite oxide represented by the general formula (1) and LiBiO 2 is obtained by firing the mixture in which the raw materials obtained in the first step are uniformly mixed. It is a process to obtain.
  • the firing temperature in the second step is 950 ° C. or lower, preferably 850 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 LiBiO 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.
  • the positive electrode active material in which LiBiO 2 which is a preferable positive electrode active material is incorporated into the particles of the aggregated lithium composite oxide is, for example, a compound containing a nickel atom, a cobalt atom and a manganese atom. It is obtained when the reaction is carried out using an aggregate having a particle shape and using bismuth oxide as the bismuth compound. This is because bismuth oxide and lithium compounds have a lower melting point than compounds containing agglomerated nickel, cobalt and manganese atoms, and contain agglomerated nickel, cobalt and manganese atoms above a certain temperature.
  • Bismuth atoms diffuse into the particles of the compound containing aggregated nickel, cobalt, and manganese atoms from the gaps between the primary particles of the compound to be produced, and LiBiO 2 formation reaction takes place first in the particles of the aggregate. Then, it is considered that the compound containing nickel atom, cobalt atom and manganese atom and the unreacted lithium atom are dissolved and reacted while maintaining the shape of the aggregate.
  • Ni: Co: Mn molar ratio in composite hydroxide 0.60: 0.20: 0.20
  • Table 1 shows lithium carbonate (average particle: 7 ⁇ m), aggregated composite hydroxide containing nickel atom, cobalt atom and manganese atom and bismuth oxide (average particle size: 28.2 ⁇ m, manufactured by Wako Pure Chemical Industries, Ltd.). The indicated amount was added and mixed thoroughly to obtain a uniform mixture of these raw materials. Next, the temperature was raised to 600 ° C. over 1 hour, further raised to 900 ° C. over 3 hours, then held at 900 ° C. for 10 hours and fired in the air. After the firing, the fired product obtained by cooling was pulverized to obtain a positive electrode active material sample.
  • the particle shape of the positive electrode active material sample was an aggregate.
  • the average primary particle size determined by scanning electron microscope observation is 0.5 ⁇ m
  • the secondary particle average particle size determined by the laser particle size distribution measurement method is 13.7 ⁇ m
  • the BET specific surface area. was 0.64 m 2 / g.
  • the average particle diameter of primary particles was calculated
  • An SEM photograph of the positive electrode active material sample is shown in FIG.
  • the positive electrode active material sample obtained in the reference experiment was subjected to X-ray diffraction analysis using CuK ⁇ rays.
  • X-ray diffraction analysis using CuK ⁇ rays.
  • LiBiO 2 diffraction peaks were confirmed at 40.13 °, 41.48 °, 46.29 °, 47.65 ° and 57.31 ° (see FIG. 3).
  • the obtained positive electrode active material sample was cut as aggregated particles, and the particle cross section was measured using EPMA (device name; field emission electron probe microanalyzer (manufactured by JEOL JEOL Datum Co., Ltd., measurement conditions; acceleration voltage 15 kV, magnification 3000).
  • Bi was subjected to mapping analysis with an irradiation current of 4.861e-08A), (a) in Fig. 4 shows an SEM image, and a lump in the SEM image of (a) in Fig. 4 represents one aggregated particle. Accordingly, several aggregated particles are included in (a) in Fig. 4. Also, (b) in Fig. 4 is a Bi mapping image, white in (b) in Fig. 4.
  • Table 2 shows lithium carbonate (average particle: 7 ⁇ m), aggregated composite hydroxide containing nickel atom, cobalt atom and manganese atom and bismuth oxide (average particle diameter: 28.2 ⁇ m, manufactured by Wako Pure Chemical Industries, Ltd.). The indicated amount was added and mixed thoroughly to obtain a uniform mixture of these raw materials. Next, the temperature was raised to 600 ° C. over 1 hour, further raised to 900 ° C. over 3 hours, then held at 900 ° C. for 10 hours and fired in the air. After the firing, the fired product obtained by cooling was pulverized to obtain a positive electrode active material sample (A) present in a state where LiBiO 2 was taken into the particles of the aggregated lithium composite oxide.
  • A positive electrode active material sample
  • Example 2 ⁇ ⁇ 3rd process and 4th process 18 parts by weight of the positive electrode active material sample (A) obtained in Example 1 and 45 parts by weight of pure water were charged into a beaker, and the mixture was stirred at room temperature (25 ° C.) for 15 minutes for washing treatment. After the washing, solid-liquid separation was performed by a conventional method, and the positive electrode active material sample (B) was collected in a wet state. Next, the positive electrode active material sample (B) in the wet state is heat-treated at 600 ° C.
  • a positive electrode active material sample (C2) was obtained in a state in which LiBiO 2 was incorporated into.
  • An SEM photograph of the positive electrode active material sample is shown in FIG.
  • Example 3 In the second step, Example 1 and Example 2 except that 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 air.
  • the first to fourth steps were carried out in the same manner as described above to obtain a positive electrode active material sample (C3) present in a state where LiBiO 2 was taken into the particles of the aggregated lithium composite oxide.
  • ⁇ Comparative Example 4 ⁇ 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 2 and fully 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 sample (a4) composed of an aggregated lithium composite oxide containing Al atoms as a solid solution.
  • the average particle size of primary particles, the average particle size of secondary particles, the BET specific surface area, the content of LiBiO 2 , the amount of remaining LiOH and Li 2 CO 2 were determined.
  • the particle shape of the obtained positive electrode active material was determined by observation with a scanning electron microscope.
  • the average particle diameter of the primary particles was measured by observation with a scanning electron microscope as an average value of 100 aggregated particles arbitrarily extracted.
  • the average particle size of the secondary particles was determined by a laser particle size distribution measurement method.
  • the amount of Bi atoms was determined by ICP emission analysis.
  • the Mg content and Al content were also determined by ICP emission analysis. (Evaluation of LiOH and Li 2 CO 3 content) 5 g of sample and 100 g of pure water are measured in a beaker and dispersed for 5 minutes using a magnetic stirrer. The dispersion was then filtered, and 30 ml of the filtrate was titrated with 0.1 N HCl with an automatic titrator (model COMMITITE-2500) to calculate residual LiOH and Li 2 CO 3 .
  • 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.
  • the lithium secondary battery using the positive electrode active material of the present invention has particularly excellent cycle characteristics, and the initial discharge capacity is the same as that of Comparative Example 1 in which LiBiO 2 was not contained in Example 2.
  • Example 3 it can be seen that the practical range is the same as Comparative Example 2 in which LiBiO 2 was not contained.
  • the third step and a positive electrode active material is substantially free of LiOH and Li 2 CO 3 obtained by performing the fourth step (Example 2 and Example 3), the coating property is improved I understand.
  • 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, caractérisée en ce qu’elle contient LiBiO2 et un oxyde complexe de lithium représenté par l’équation (1): LixNi1-y-zCoyMnzO2 (x satisfaisant la relation 0,98≦x≦1,20, y satisfaisant la relation 0＜y≦0,5, z satisfaisant la relation 0＜z≦0,5, mais ｙ＋ｚ＜1). Cette matière active d’électrode positive pour pile rechargeable au lithium utilise un oxyde complexe à base de lithium nickel cobalt manganèse, qui confère en particulier d’excellentes caractéristiques de cycle à une pile rechargeable au lithium. L’invention concerne aussi un procédé de production industriellement avantageux de cette matière active d’électrode positive, et une pile rechargeable au lithium présentant en particulier d’excellentes caractéristiques de cycle qui utilise ladite matière active d’électrode positive.
PCT/JP2010/061754 2009-07-13 2010-07-12 Matière active d’électrode positive pour pile rechargeable au lithium, procédé de fabrication de celle-ci et pile rechargeable au lithium WO2011007750A1 (fr)

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CN102683671A (zh) * 2012-05-07 2012-09-19 宁德新能源科技有限公司 层状锂镍系复合氧化物正极材料
WO2019057536A1 (fr) * 2017-09-20 2019-03-28 Basf Se Procédé de fabrication de matériau actif d'electrode
EP3641028A4 (fr) * 2017-10-19 2020-06-03 LG Chem, Ltd. Matériau de cathode pour batterie rechargeable au lithium, son procédé de fabrication, cathode comprenant celui-ci destinée à une batterie rechargeable au lithium, et batterie rechargeable au lithium

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JP6549565B2 (ja) * 2014-05-29 2019-07-24 住友化学株式会社 リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
JP6554725B2 (ja) * 2015-08-10 2019-08-07 株式会社東芝 非水電解質電池
JP6733140B2 (ja) * 2015-08-27 2020-07-29 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の製造方法
JP6733139B2 (ja) 2015-08-27 2020-07-29 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の製造方法
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
WO2022097653A1 (fr) 2020-11-05 2022-05-12 日本化学工業株式会社 Procédé de production de particules d'oxyde composite de lithium-nickel-manganèse-cobalt modifiées

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EP3641028A4 (fr) * 2017-10-19 2020-06-03 LG Chem, Ltd. Matériau de cathode pour batterie rechargeable au lithium, son procédé de fabrication, cathode comprenant celui-ci destinée à une batterie rechargeable au lithium, et batterie rechargeable au lithium
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