WO2011065391A1 - Matériau actif d'électrode positive destiné à une batterie secondaire au lithium, procédé de production associé, et batterie secondaire au lithium - Google Patents

Matériau actif d'électrode positive destiné à une batterie secondaire au lithium, procédé de production associé, et batterie secondaire au lithium Download PDF

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WO2011065391A1
WO2011065391A1 PCT/JP2010/070962 JP2010070962W WO2011065391A1 WO 2011065391 A1 WO2011065391 A1 WO 2011065391A1 JP 2010070962 W JP2010070962 W JP 2010070962W WO 2011065391 A1 WO2011065391 A1 WO 2011065391A1
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lithium
secondary battery
positive electrode
lithium secondary
active material
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Japanese (ja)
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政博 菊池
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日本化学工業株式会社
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • H01M4/50—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • 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 and a lithium secondary battery using the positive electrode active material for a lithium secondary battery, particularly excellent in cycle characteristics, load characteristics, and safety.
  • lithium cobaltate has been used as a positive electrode active material for lithium secondary batteries.
  • cobalt is a rare metal
  • lithium nickel manganese cobalt-based composite oxides having a low cobalt content see, for example, Patent Documents 1 to 3 have been developed.
  • Lithium secondary batteries that use this lithium nickel manganese cobalt based composite oxide as the positive electrode active material can be manufactured at low cost by adjusting the atomic ratio of nickel, manganese, and cobalt contained in the composite oxide.
  • Patent Documents 4 and 5 it is proposed to use a carbonated Li-excess layered lithium nickel composite oxide having a defined carbonate ion concentration as a positive electrode active material. There is no description or suggestion about using a lithium nickel manganese cobalt composite oxide having a composition.
  • the present inventors have obtained a lithium composite oxide containing a specific metal atom in a specific range in a lithium nickel manganese cobalt composite oxide having a specific composition as a positive electrode active material.
  • the lithium secondary battery shall be excellent in safety. Furthermore, it has been found that by adjusting the amount of Li 2 CO 3 present on the particle surface of the lithium composite oxide within a specific range, the capacity retention rate of lithium secondary batteries, particularly at high temperatures, can be dramatically improved. Completed the invention.
  • an object of the present invention is to provide a positive electrode active for a lithium secondary battery using a lithium nickel manganese cobalt based composite oxide capable of imparting particularly excellent cycle characteristics, load characteristics, and safety to a lithium secondary battery.
  • An object of the present invention is to provide a lithium secondary battery excellent in cycle characteristics, load characteristics, and safety, using a positive electrode active material, and a material, a method for producing the positive electrode active material in an industrially advantageous manner.
  • the first invention to be provided by the present invention is the following general formula (1): Li x Ni y Mn z Co 1-yz O 1 + x (1) (Wherein x represents 1.02 ⁇ x ⁇ 1.25, y represents 0.30 ⁇ y ⁇ 0.40, and z represents 0.30 ⁇ z ⁇ 0.40).
  • a positive electrode active material for a lithium secondary battery characterized in that the amount of Li 2 CO 3 present on the particle surface is 0.05 to 0.20% by weight.
  • the second invention to be provided by the present invention is: (A) a lithium compound and (b) a general formula; Ni y Mn z Co 1-yz (OH) 2 (Wherein y represents 0.30 ⁇ y ⁇ 0.40, z represents 0.30 ⁇ z ⁇ 0.40), and (c) Mg, Al, Ti,
  • One or more metal atom (Me) -containing compounds selected from Cu and Zr have an atomic ratio of Li / (Ni + Mn + Co + Me) of 1.02 to 1.25 and an atomic ratio of Me / (Ni + Mn + Co)
  • a lithium secondary battery comprising: a first step of mixing at 0.001 to less than 0.05; and then a second step of firing the obtained mixture at 800 to 1000 ° C. to obtain a lithium composite oxide It is a manufacturing method of the positive electrode active material.
  • the third invention to be provided by the present invention is a lithium secondary battery using the positive electrode active material for lithium secondary battery according to the first invention.
  • security can be provided using the positive electrode active material which consists of lithium nickel manganese cobalt type complex oxide.
  • the present invention can provide a lithium secondary battery having excellent cycle characteristics even at high temperatures.
  • this positive electrode active material can be manufactured by an industrially advantageous method.
  • the X-ray diffraction pattern of the composite hydroxide sample A X-ray diffraction diagram of composite hydroxide sample B.
  • FIG. FIG. 4 is an X-ray diffraction pattern of the lithium composite oxide obtained in Example 3.
  • the DSC chart of this lithium composite oxide sample when the lithium composite oxide sample of Example 3 is used as a positive electrode active material and safety is evaluated.
  • the DSC chart of this lithium composite oxide sample when the lithium composite oxide sample of the comparative example 1 is used as a positive electrode active material and safety is evaluated.
  • the DSC chart of this lithium composite oxide sample when the lithium composite oxide sample of the comparative example 3 is used as a positive electrode active material, and safety is evaluated.
  • 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 y Mn z Co 1-yz O 1 + x (1) (Wherein x represents 1.02 ⁇ x ⁇ 1.25, y represents 0.30 ⁇ y ⁇ 0.40, and z represents 0.30 ⁇ z ⁇ 0.40).
  • Lithium in which a specific metal atom (Me) is contained in an amount of 0.1 mol% to less than 5 mol% in a cobalt-based composite oxide (hereinafter sometimes simply referred to as “lithium nickel manganese cobalt-based composite oxide”) It is a composite oxide (hereinafter sometimes simply referred to as “lithium composite oxide”).
  • X in the formula of the lithium composite oxide represented by the general formula (1) is 1.02 or more and 1.25 or less, and particularly x in the formula is in the range of 1.05 or more and 1.20 or less. This is preferable from the viewpoint of improving the capacity retention rate of the lithium secondary battery.
  • Y and Z in the formula are 0.30 or more and 0.40 or less, and when y and z in the formula are in the range of 0.33 or more and 0.34 or less, the target product can be produced at low cost. Moreover, it is preferable from the viewpoint of improving the safety of the lithium secondary battery.
  • the metal atom (Me) contained in the lithium nickel manganese cobalt composite oxide represented by the general formula (1) is one or more metal atoms selected from Mg, Al, Ti, Cu and Zr ( Me) (hereinafter sometimes simply referred to as “metal atom (Me)”), among which Mg, Ti, and Cu are particularly preferable from the viewpoint of further improving the safety of the lithium secondary battery. Further, the amount of metal atom (Me) contained in the lithium nickel manganese cobalt based composite oxide is 0.1 mol% or more and less than 5 mol%.
  • the content of the metal atom (Me) is preferably 0.2 mol% or more and 1 mol% or less from the viewpoint of obtaining a lithium secondary battery having high discharge capacity and further improved safety.
  • the reason why the content of the metal atom (Me) is within the above range is that when the content of the metal atom (Me) is smaller than 0.1 mol%, the safety improvement effect of the lithium secondary battery is improved.
  • the content of the metal atom (Me) is 5 mol% or more, the discharge capacity of the lithium secondary battery is lowered.
  • the metal atom (Me) may be contained as a solid solution in the lithium nickel manganese cobalt-based composite oxide. It may exist on the particle surface of the composite oxide.
  • the amount of Li 2 CO 3 present on the particle surface of the lithium composite oxide is 0.05 to 0.20% by weight, preferably 0.07 to 0. 20% by weight.
  • the reason for this is that when the amount of Li 2 CO 3 present on the particle surface of the lithium composite oxide is less than 0.05% by weight, the formation of a film by the decomposition of the electrolyte solution on the electrode surface is promoted, and the capacity retention rate is increased.
  • it exceeds 0.20% by weight the amount of CO 2 gas generated during high-temperature storage increases and the safety of the lithium secondary battery decreases.
  • the amount of Li 2 CO 3 present on the particle surface of the lithium composite oxide is 1.5 to 10 mg / m 2 , preferably the amount of Li 2 CO 3 present on the particle surface per unit area determined from the BET specific surface area. Is preferably from 2.5 to 7.0 mg / m 2 from the viewpoint of further improving the capacity retention rate at high temperatures of a lithium secondary battery using the positive electrode active material.
  • the lithium composite oxide according to the positive electrode active material of the present invention is such that the remaining LiOH is 0.15% by weight or less, preferably 0.11% by weight or less and substantially free of LiOH. Is preferable from the viewpoint of facilitating electrode preparation because the coating property is stable and coating properties are improved.
  • the lithium composite oxide has an average particle size of 1 to 30 ⁇ m, preferably 3 to 20 ⁇ m, determined by a laser particle size distribution measurement method.
  • the reason for this is that when the average particle size of the lithium composite oxide is smaller than 1 ⁇ m, the number of highly active fine particles tends to increase, and the effect of improving the safety of the lithium secondary battery tends to be difficult to obtain. This is because applicability to the electrodes tends to be a problem when the size is increased.
  • the lithium composite oxide has a BET specific surface area of 0.1 to 1 m 2 / g, preferably 0.2 to 0.8 m 2 / g.
  • the reason for this is that when the BET specific surface area of the lithium composite oxide is smaller than 0.1 m 2 / g, the load characteristics of the lithium secondary battery tend to deteriorate, whereas when the lithium composite oxide is larger than 1 m 2 / g, the lithium secondary battery This is because the discharge capacity tends to decrease.
  • the lithium composite oxide has a tap density of 1.5 g / ml or more. This is because when the tap density of the lithium composite oxide is less than 1.5 g / ml, the electrode density tends to decrease and the discharge capacity of the lithium secondary battery tends to decrease. In particular, when the tap density of the lithium composite oxide is in the range of 1.7 to 2.8 g / ml, it is particularly preferable from the viewpoint of increasing the discharge capacity of the lithium secondary battery.
  • the positive electrode active material of the present invention includes, for example, (a) a lithium compound, (b) a general formula; Ni y Mn z Co 1-yz (OH) 2 (wherein y is 0.30 ⁇ y ⁇ 0. 40, z represents 0.30 ⁇ z ⁇ 0.40), and (c) the metal atom (Me) -containing compound has an atomic ratio of Li / (Ni + Mn + Co + Me) of 1.
  • Examples of the (a) lithium compound according to the first step include lithium oxide, hydroxide, carbonate, nitrate, and organic acid salt.
  • lithium carbonate is easy to handle as a powder, It is particularly preferably used from the viewpoint of being inexpensive.
  • this lithium compound has an average particle size determined by a laser light scattering method of 1 to 100 ⁇ m, and preferably 5 to 80 ⁇ m, because of good reactivity.
  • composite hydroxide represented by the general formula (b) Ni y Mn z Co 1-yz (OH) 2 according to the first step.
  • y and z correspond to y and z in the formula of the general formula (1), respectively, and y and Z are 0.30 or more and 0.40 or less, and particularly y and z in the formula are 0.
  • the target lithium composite oxide can be produced at low cost, and the obtained lithium composite oxide further improves the safety of the lithium secondary battery. From the viewpoint of being able to do so.
  • the composite hydroxide has an average particle size determined by a laser particle size distribution measurement method of 1 to 30 ⁇ m, preferably 3 to 20 ⁇ m.
  • the reason for this is that when the average particle size of the composite hydroxide is smaller than 1 ⁇ m, in the lithium secondary battery using the obtained lithium composite oxide as a positive electrode active material, the safety improvement effect tends to be small.
  • the average particle size is larger than 30 ⁇ m, the reactivity is deteriorated, and in the lithium secondary battery using the obtained lithium composite oxide as a positive electrode active material, the discharge capacity tends to decrease.
  • the composite hydroxide has a BET specific surface area of 2 to 10 m 2 / g, preferably 2 to 8 m 2 / g.
  • the reason for this is that when the BET specific surface area of the composite hydroxide is smaller than 2 m 2 / g, the reactivity becomes worse, and in the lithium secondary battery using the obtained lithium composite oxide as a positive electrode active material, On the other hand, when the BET specific surface area is larger than 10 m 2 / g, in the lithium secondary battery using the obtained lithium composite oxide as the positive electrode active material, the safety improvement effect tends to be small. Because there is.
  • the composite hydroxide has a tap density of 1 g / ml or more, preferably 1.5 to 2.5 g / ml.
  • the reason for this is that if the tap density of the composite hydroxide is less than 1 g / ml, the tap density and electrode density of the obtained lithium composite oxide are reduced, and thus the obtained lithium composite oxide is used as a positive electrode active material. This is because the discharge capacity tends to decrease in the lithium secondary battery.
  • the composite hydroxide having such various physical properties can be prepared, for example, by a coprecipitation method.
  • the composite hydroxide can be coprecipitated by mixing an aqueous solution containing a predetermined amount of nickel atom, cobalt atom and manganese atom, an aqueous solution of a complexing agent, and an alkaline aqueous solution ( (See JP-A-10-81521, JP-A-10-81520, JP-A-10-29820, 2002-201028, etc.).
  • the composite hydroxide may be a commercial product.
  • metal atom (Me) containing compound chosen from Mg, Al, Ti, Cu, and Zr which concerns on 1st process is an oxide containing these metal atoms (Me), water Oxides, halides, carbonates, nitrates, organic acid salts and the like can be used.
  • this metal atom (Me) -containing compound has an average particle size determined by a laser particle size distribution measuring method of 0.1 to 20 ⁇ m, preferably 0.1 to 10 ⁇ m, since it has good reactivity and is particularly preferable.
  • the raw material (a) lithium compound, (b) composite hydroxide, and (c) metal atom (Me) -containing compound contain as much impurities as possible in order to produce a high-purity positive electrode active material. Those with less are preferred.
  • the compounding ratio of (a) lithium compound, (b) composite hydroxide and (c) metal atom (Me) -containing compound is the atomic ratio of lithium atom to nickel atom, cobalt atom, manganese atom and metal atom (Me) ( Li / (Ni + Co + Mn + Me)) is 1.02 to 1.25, preferably 1.05 to 1.20, in order to obtain a positive electrode active material having excellent cycle characteristics, load characteristics and safety. An important requirement.
  • the reason for this is that when the atomic ratio of lithium atoms to nickel atoms, cobalt atoms, manganese atoms, and metal atoms (Me) is smaller than 1.02, the amount of Li 2 CO 3 present on the particle surface of the resulting lithium composite oxide This is because it is difficult to enter the range of 0.05 to 0.20% by weight. On the other hand, when the atomic ratio of lithium atoms to nickel atoms, cobalt atoms, manganese atoms, and metal atoms (Me) is greater than 1.25, the discharge capacity of the lithium secondary battery is greatly reduced.
  • the compounding ratio of (b) the composite hydroxide and (c) the metal atom (Me) -containing compound is the atomic ratio of the metal atom (Me) to the nickel atom, cobalt atom and manganese atom (Me / ⁇ Ni + Mn + Co ⁇ ). Viewpoint of obtaining a lithium secondary battery that has a high capacity retention rate and is excellent in safety, particularly when the capacity is 0.001 or more and less than 0.05, and particularly 0.002 or more and 0.01 or less. To preferred.
  • the reason why the atomic ratio of the metal atom (Me) to the nickel atom, cobalt atom, and manganese atom is within the above range is that when the atomic ratio of Me / (Ni + Mn + Co) is smaller than 0.01, the safety of the lithium secondary battery is reduced. This is because the improvement effect is not observed, and on the other hand, when the atomic ratio of Me / (Ni + Mn + Co) is 0.05 or more, the discharge capacity of the lithium secondary battery decreases.
  • 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 made of a lithium composite oxide.
  • the second step according to the present invention is a step of obtaining a positive electrode active material made of a lithium composite oxide by firing the mixture obtained by uniformly mixing the raw materials obtained in the first step in a specific temperature range.
  • the firing temperature in the second step is 800 to 1000 ° C., preferably 850 to 950 ° C. This is because when the firing temperature is lower than 800 ° C., the solid solution reaction between (a) the lithium compound, (b) the composite hydroxide, and (c) the metal atom (Me) -containing compound is not completed.
  • Lithium secondary batteries having a lithium composite oxide as a positive electrode active material have a low discharge capacity, and it is difficult to obtain a battery with excellent load characteristics and safety.
  • the firing temperature is higher than 1000 ° C., the obtained lithium This is because it is difficult to obtain a lithium secondary battery using a composite oxide as a positive electrode active material with good load characteristics.
  • the firing atmosphere may be an air atmosphere or an oxygen atmosphere, and the firing time is 5 hours or longer, preferably 7 to 15 hours. Moreover, in this invention, you may perform baking as many times as desired. Alternatively, for the purpose of making the powder characteristics uniform, the fired material may be pulverized and then refired. After firing, the lithium composite oxide of the present invention is obtained by appropriately cooling and pulverizing as necessary.
  • the pulverization is appropriately performed when the obtained lithium composite oxide is brittle and in a block shape, and the lithium composite oxide has specific powder characteristics. That is, the average particle size determined by the laser particle size distribution measurement method is 1 to 30 ⁇ m, preferably 3 to 20 ⁇ m, and the BET specific surface area is 0.1 to 1 m 2 / g, preferably 0.2 to 0.8 m 2 /. g, the tap density is 1.5 g / ml or more, preferably 1.7 to 2.8 g / ml.
  • Li 2 CO 3 is present in an amount of 0.05 to 0.15 wt%
  • LiOH is also present in an amount of 0.02 to 0.15 wt%.
  • the lithium secondary battery using the positive electrode active material obtained by applying the third step further improves battery performance such as cycle characteristics, load characteristics and safety.
  • the lithium composite oxide obtained in the second step is brought into contact with carbon dioxide.
  • the contact between the lithium composite oxide and carbon dioxide is performed in an atmosphere containing a carbon dioxide concentration of 50% by volume or more, preferably 90 to 100% by volume. This is because if the carbon dioxide concentration is smaller than 50% by volume, the conversion to Li 2 CO 3 tends to be insufficient.
  • the contact between the lithium nickel manganese cobalt composite oxide and carbon dioxide can be efficiently converted to Li 2 CO 3 by performing stirring or moderate vibration.
  • the contact temperature is 5 to 90 ° C., preferably 10 to 80 ° C., for 5 minutes or more, preferably 0.1 to 10 hours.
  • the product After completion of the third step, the product is dried, crushed or crushed as necessary, and then classified to obtain a product.
  • the drying treatment temperature is preferably from 100 to 300 ° C., preferably from 150 to 250 ° C., from the viewpoint that moisture can be quickly removed.
  • the drying time is 30 minutes or longer, preferably 1 to 2 hours.
  • a lithium secondary battery according to the present invention uses the above-described 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 made of the lithium composite oxide of the present invention is uniformly applied to the positive electrode. For this reason, the lithium secondary battery according to the present invention is particularly excellent in load characteristics, capacity retention at high temperatures, and safety.
  • 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.
  • Tap density is based on the method of apparent density or apparent specific volume described in JIS-K-5101, 50 g of sample is put into a 50 ml measuring cylinder, made by Yuasa Ionics, DUAL It set to the AUTOTAP apparatus, tapped 500 times, the capacity was read, the apparent density was calculated, and it was set as the tap density.
  • the average particle size was determined by a laser particle size distribution measurement method.
  • Examples 1 to 5, Comparative Examples 1 to 3 The composite hydroxide sample A (Ni 0.334 Mn 0.333 Co 0.333 (OH) 2 ), lithium carbonate (average particle size 4.5 ⁇ m) and magnesium fluoride (average particle size 5.9 ⁇ m), Nickel atoms, manganese atoms, cobalt atoms, and magnesium atoms were weighed so as to have the blending ratios shown in Table 1, and sufficiently mixed with a mixer. This mixture was fired at 900 ° C. for 10 hours in the air, and the fired product obtained by cooling after firing was pulverized and classified to obtain a lithium composite oxide sample comprising a magnesium-containing lithium nickel manganese cobalt composite oxide. It was.
  • Example 6 The composite hydroxide sample A (Ni 0.334 Mn 0.333 Co 0.333 (OH) 2 ), lithium carbonate (average particle size 4.5 ⁇ m) and magnesium oxide (average particle size 2.9 ⁇ m) were mixed with nickel. Atoms, manganese atoms, cobalt atoms, and magnesium atoms were weighed so as to have the blending ratios shown in Table 1, and sufficiently mixed with a mixer. This mixture was fired at 900 ° C. for 10 hours in the air, and the fired product obtained by cooling after firing was pulverized and classified to obtain a lithium composite oxide sample comprising a magnesium-containing lithium nickel manganese cobalt composite oxide. It was.
  • Example 7 A lithium composite oxide sample comprising a magnesium-containing lithium nickel manganese cobalt based composite oxide was obtained under the same conditions and operating method as in Example 3 except that the composite hydroxide sample B was used instead of the composite hydroxide sample A. It was.
  • Example 8 The composite hydroxide sample A (Ni 0.334 Mn 0.333 Co 0.333 (OH) 2 ), lithium carbonate (average particle size 4.5 ⁇ m) and copper oxide (average particle size 5.3 ⁇ m) were mixed with nickel. Atoms, manganese atoms, cobalt atoms, and copper atoms were weighed so as to have a blending ratio shown in Table 1, and sufficiently mixed with a mixer. The mixture was fired at 900 ° C. for 10 hours in the air, and the fired product obtained by cooling after firing was pulverized and classified to obtain a lithium composite oxide sample comprising a copper-containing lithium nickel manganese cobalt composite oxide. It was.
  • Example 9 The composite hydroxide sample A (Ni 0.334 Mn 0.333 Co 0.333 (OH) 2 ), lithium carbonate (average particle size 4.5 ⁇ m) and titanium dioxide (average particle size 0.4 ⁇ m) were mixed with nickel. Atoms, manganese atoms, cobalt atoms, and titanium atoms were weighed so as to have the blending ratio shown in Table 1, and sufficiently mixed with a mixer. The mixture was fired at 900 ° C. for 10 hours in the air, and the fired product obtained by cooling after firing was pulverized and classified to obtain a lithium composite oxide sample comprising a titanium-containing lithium nickel manganese cobalt composite oxide. It was.
  • Example 4 A lithium composite oxide sample made of a magnesium-containing lithium nickel manganese cobalt composite oxide was obtained under the same conditions and operating method as in Example 3 except that the firing temperature was 750 ° C. for 10 hours.
  • Example 5 A lithium composite oxide sample made of a magnesium-containing lithium nickel manganese cobalt composite oxide was obtained under the same conditions and operating method as in Example 3 except that the firing temperature was 1050 ° C. for 10 hours.
  • the molar ratio A is the molar ratio of ⁇ Li / (Ni + Mn + Co + Me) ⁇
  • the molar B is the molar ratio of ⁇ Me / (Ni + Mn + Co) ⁇ .
  • Example 10 100 g of each of the lithium composite oxide samples obtained in Example 3 were put into a 500 ml container that can be sealed, and CO 2 gas was sealed and sealed as an atmosphere having a carbon dioxide concentration of 95% by volume.
  • the container was attached to a vibration device (paint shaker), and was vibrated at room temperature (25 ° C.) for the treatment times shown in Table 2.
  • the lithium composite oxide treated with CO 2 gas was dried at 200 ° C. for 2 hours to obtain a lithium composite oxide sample with an increased Li 2 CO 3 content.
  • the amount of Li 2 CO 3 per unit area was obtained from the following calculation formula (2).
  • a coin-type lithium secondary battery was manufactured using each member such as a negative electrode, a separator, a current collector plate, an electrolyte, a case for CR2032, a mounting bracket, an external terminal, and the like.
  • a lithium metal foil was used for the negative electrode, and 1 mol of LiPF 6 was dissolved in 1 liter of a mixed solvent of 25:60:15 (v / v / v) of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate in the electrolyte. We used what we did.
  • the charging and discharging method of the coin-type lithium secondary battery is as follows. First, the battery is charged to 4.3 V at a current amount of 0.5 C (2 hour rate), and then held at 4.3 V for about 3 hours for a total constant current of 5 hours. Charging was performed by voltage (CCCV) charging, and subsequently, constant current (CC) discharging was performed to discharge to 2.7 V at a current amount of 0.2 C (5-hour rate). With these operations as one cycle, the capacity was measured every cycle. This cycle was repeated 20 times, and the capacity retention rate was calculated from the discharge capacity of the first cycle and the 20th cycle according to the following formula. The discharge capacity at the first cycle was defined as the initial discharge capacity. The results are shown in Table 5.
  • the charging and discharging method of the coin-type lithium secondary battery is as follows. First, the battery is charged to 4.3 V at a current amount of 0.5 C (2 hour rate), and then held at 4.3 V for about 3 hours for a total constant current of 5 hours. Charging was performed by voltage (CCCV) charging, and then, constant current (CC) discharging was performed for 2 cycles at a current amount of 0.2 C (5 hour rate) to 2.7 V. In the subsequent cycles, only the current amount at the time of discharge is changed, the third cycle is 2C (1/2 hour rate), the fifth cycle is 1C (one hour rate), and the seventh cycle is 0.5C (two hour rate). Was discharged.
  • CCCV voltage
  • CC constant current
  • Safety evaluation was performed by performing differential scanning calorimetry (DSC) on the lithium composite oxide samples of Example 3, Example 6, Example 8, Example 9, Example 11, Comparative Example 1, and Comparative Example 3. evaluated.
  • the coin battery prepared above was charged to 4.4 V, recovered from the measuring machine in a charged state, disassembled in the glove box, and the positive electrode was taken out.
  • the positive electrode was cut out so that the amount of the active material was 5 mg, and placed in a pressure-resistant pan for DSC together with 10 mg of the electrolyte.
  • the pressure pan was heated to 350 ° C. at a rate of 2 ° C./min to obtain a DSC chart. From this chart, the maximum value of the exothermic peak seen up to around 240 ° C.
  • FIG. 4 is a DSC chart when the lithium composite oxide sample of Example 3 is used as a positive electrode active material
  • FIG. 5 is a DSC chart when the lithium composite oxide sample of Comparative Example 1 is used as a positive electrode active material.
  • FIG. 6 shows a DSC chart when the lithium composite oxide sample of Comparative Example 3 is used as the positive electrode active material.
  • a lithium secondary battery having excellent cycle characteristics, load characteristics, and safety is provided using a positive electrode active material made of a lithium nickel manganese cobalt based composite oxide. can do.
  • the present invention can provide a lithium secondary battery having excellent cycle characteristics even at high temperatures.
  • this positive electrode active material can be manufactured by an industrially advantageous method.

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Abstract

L'invention concerne un matériau actif d'électrode positive destiné à une batterie secondaire au lithium, qui utilise un oxyde complexe de lithium nickel manganèse cobalt qui peut former une batterie secondaire au lithium dont les caractéristiques de cycle, les caractéristiques de charge et la sécurité sont particulièrement excellentes. L'invention concerne en particulier un matériau actif d'électrode positive destiné à une batterie secondaire au lithium, qui est caractérisé en ce qu'il est composé d'un oxyde complexe de lithium qui est obtenu avec un oxyde complexe de lithium nickel manganèse cobalt représenté par la formule générale (1) suivante : LixNiyMnzCo1-y-zO1+x (dans laquelle x satisfait 1,02 ≤ x ≤ 1,25, y satisfait 0,30 ≤ y ≤ 0,40, et z satisfait 0,30 ≤ z ≤ 0,40) contenant un ou plusieurs types d'atomes de métal (Me) choisis parmi Mg, Al, Ti, Cu et Zr dont la quantité est de 0,1 % en mole ou plus mais est inférieure à 5 % en mole. Le matériau actif d'électrode positive destiné à une batterie secondaire au lithium est également caractérisé en ce que la quantité de Li2CO3 présent dans les surfaces de particule est de 0,05 à 0,20 % en poids.
PCT/JP2010/070962 2009-11-26 2010-11-25 Matériau actif d'électrode positive destiné à une batterie secondaire au lithium, procédé de production associé, et batterie secondaire au lithium WO2011065391A1 (fr)

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