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WO2020059471A1 - Matériau actif d'électrode positive pour accumulateur et procédé destiné à le produire - Google Patents

Matériau actif d'électrode positive pour accumulateur et procédé destiné à le produire Download PDF

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Publication number
WO2020059471A1
WO2020059471A1 PCT/JP2019/034407 JP2019034407W WO2020059471A1 WO 2020059471 A1 WO2020059471 A1 WO 2020059471A1 JP 2019034407 W JP2019034407 W JP 2019034407W WO 2020059471 A1 WO2020059471 A1 WO 2020059471A1
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Prior art keywords
secondary battery
positive electrode
active material
electrode active
particles
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English (en)
Japanese (ja)
Inventor
朱里 細野
恭崇 飯田
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Tanaka Chemical Corp
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Tanaka Chemical Corp
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Priority claimed from JP2019097568A external-priority patent/JP6669920B1/ja
Application filed by Tanaka Chemical Corp filed Critical Tanaka Chemical Corp
Priority to EP19861675.7A priority Critical patent/EP3855541A4/fr
Priority to CN201980061771.2A priority patent/CN112740442A/zh
Priority to KR1020217011795A priority patent/KR102648286B1/ko
Publication of WO2020059471A1 publication Critical patent/WO2020059471A1/fr
Priority to US17/202,407 priority patent/US20210210757A1/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • 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
    • 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 secondary battery and a method for producing the same, and more particularly, to a positive electrode active material for a secondary battery capable of exhibiting excellent cycle characteristics under any environment of ordinary temperature and high temperature, and a method for producing the same. .
  • secondary batteries have been used in a wide variety of fields, such as mobile devices and vehicles that use or use electricity as a power source.
  • a lithium metal composite oxide powder containing nickel, cobalt, and manganese is used as the positive electrode active material of the secondary battery.
  • secondary batteries are required to be able to exhibit a high output stably in response to environmental changes such as ambient temperature. Therefore, the positive electrode active material for a secondary battery is required to have a stable and excellent cycle characteristic even when the environment such as the ambient temperature fluctuates.
  • the lithium nickel cobalt manganese composite oxide cathode material of Patent Document 1 contains primary single crystal particles and a small amount of secondary aggregated particles, and the primary single crystal particles have a particle size of 0.5 to 10 ⁇ m and a particle size of 5 ⁇ m or less. The particle size is controlled so that the cumulative% of the particles exceeds 60%.
  • Patent Document 1 Although excellent cycle characteristics can be obtained under a slightly high temperature condition, there is room for improvement in obtaining excellent cycle characteristics over a temperature range from room temperature to high temperature.
  • the conventional positive electrode active material for a secondary battery discloses improvement in cycle characteristics under a predetermined temperature condition.
  • the usage environment of the secondary battery may fluctuate depending on the usage conditions and installation environment of the equipment to be mounted, such as the ambient temperature. Therefore, there is a need for a positive electrode active material for a secondary battery that can stably exhibit excellent cycle characteristics even when the use environment such as the ambient temperature fluctuates.
  • an object of the present invention is to provide a positive electrode active material for a secondary battery that can exhibit excellent cycle characteristics under both normal temperature and high temperature environments, and a method for producing the same.
  • An embodiment of the present invention provides a positive electrode active material for a secondary battery having a layered structure including at least one of nickel, cobalt, and manganese, which is a secondary particle that is an aggregate of single crystal particles and / or a plurality of primary particles.
  • the average particle strength of the particles having a cumulative volume percentage of 50% by volume and having a particle diameter (D50) ⁇ 1.0 ⁇ m is 200 MPa or more;
  • D50 particle diameter
  • the average particle strength of the positive electrode active material for a secondary battery refers to the positive electrode active material particles for a secondary battery arbitrarily selected from a particle diameter (D50) ⁇ 1.0 ⁇ m having a cumulative volume percentage of 50% by volume.
  • the particle strength (MPa) 2.8 ⁇ the weight at the time of crushing (N) / ( ⁇ , based on the value of the weight at the time of crushing (N) measured by Shimadzu Micro Compression Testing Machine MCT-510.
  • X particle diameter (mm) x particle diameter (mm)) this operation is performed for 10 particles, and the average particle intensity is calculated from each particle intensity of 10 particles.
  • An embodiment of the present invention provides a positive electrode active material for a secondary battery having a layered structure including at least one of nickel, cobalt, and manganese, which is a secondary particle that is an aggregate of single crystal particles and / or a plurality of primary particles.
  • the average particle strength of the particles having a cumulative volume percentage of 50% by volume and having a particle diameter (D50) ⁇ 1.0 ⁇ m is 200 MPa or more;
  • the rate of change of the lattice constant before and after the cycle test was calculated as (a axis before the cycle test / a axis after the cycle test)
  • ⁇ 100 A
  • ⁇ 100 C
  • a positive electrode active material for a secondary battery in which at least one of A and C in a cycle test at 25 ° C. and 60 ° C. is 99.30% or more and 100.90% or less.
  • the “cycle test” means that a laminate cell is prepared using a positive electrode active material for a secondary battery, charged at 4.2 V / CC, 2 C, discharged at 3.0 V / CC, 2 C at 25 ° C., 1000 cycles, 60 cycles.
  • a charge / discharge test at 500 ° C. cycles.
  • An embodiment of the present invention is an active material for a secondary battery in which the cumulative volume percentage is 50% by volume and the particle diameter D50 is 2.0 ⁇ m or more and 20.0 ⁇ m or less.
  • An embodiment of the present invention is an active material for a secondary battery having a BET specific surface area of 0.1 m 2 / g or more and 5.0 m 2 / g or less.
  • An embodiment of the present invention is a secondary battery including the above-described positive electrode active material for a secondary battery.
  • An aspect of the present invention is to provide a composite hydroxide particle containing at least one of nickel (Ni), cobalt (Co) and manganese (Mn) with a lithium (Li) compound and at least one of Ni, Co and Mn.
  • a step of adding a mixture of lithium compound and composite hydroxide particles by adding at least an atomic ratio of 1.00 ⁇ Li / M1 ⁇ 1.30 to a metal element (M1) composed of at least one kind of metal element (M1);
  • the mixture is represented by the following formula p ⁇ ⁇ 600q + 1603 (where q is an atomic ratio of Li to the total of at least one metal element (M1) of Ni, Co and Mn (Li / M1); 1.00 ⁇ q ⁇ 1.30, p is a main firing temperature, and means a firing temperature represented by 940 ° C.
  • a calcination step performed before the main sintering step, wherein the sintering temperature is 300 ° C. or more and 800 ° C. or less; (2) a tempering step performed after the main firing step, wherein the firing temperature is 600 ° C. or more and 900 ° C.
  • M2 is Fe, Cu, Ti, Mg, Al, W, Zn, Sn, Zr, Ga, V, B, Mo, As, Ge , P, Pb, Si, Sb, Nb, Ta, Re, and Bi, which means at least one metal element selected from the group consisting of: A method for producing a positive electrode active material for a secondary battery, the method including at least one step of the above.
  • the particle size distribution width of the composite hydroxide particles is set to 0.40 ⁇ (D90 ⁇ D10) /D50 ⁇ 1.00.
  • a ratio of a surface area (S) of the mixture including a contact surface with the sheath to a volume (V) of the mixture when the mixture is filled in a sheath is as follows: This is a method for producing a positive electrode active material for a secondary battery in which 0.08 ⁇ S / V ⁇ 2.00.
  • the particles having a cumulative volume percentage of 50% by volume and having a particle diameter (D50) ⁇ 1.0 ⁇ m have an average particle strength of 200 MPa or more, and the powder X-ray diffraction pattern using CuK ⁇ rays
  • D50 particle diameter
  • the full width at half maximum of the diffraction peak on the high angle side is ⁇
  • ⁇ / ⁇ is By satisfying 0.97 ⁇ ⁇ / ⁇ 1.25, it is possible to obtain a positive electrode active material for a secondary battery that can exhibit excellent cycle characteristics under both normal temperature and high temperature environments.
  • the average particle strength of particles having a particle diameter (D50) of ⁇ 1.0 ⁇ m having a cumulative volume percentage of 50% by volume is 200 MPa or more, and X in a cycle test of a positive electrode using CuK ⁇ radiation.
  • a positive electrode active material for a secondary battery that can exhibit excellent cycle characteristics can be obtained.
  • a mixture of a lithium compound and composite hydroxide particles having an atomic ratio of 1.00 ⁇ Li / M1 ⁇ 1.30 is subjected to main firing to obtain p ⁇ ⁇ 600q + 1603 (where q is , At least the atomic ratio (Li / M1) of Li to the total of the metal elements (M1) composed of at least one of Ni, Co and Mn, where 1.00 ⁇ q ⁇ 1.30, and p is the firing temperature. 940 ° C. ⁇ p ⁇ 1100 ° C.) to produce a positive electrode active material for a secondary battery capable of exhibiting excellent cycle characteristics under both normal temperature and high temperature environments by firing at a firing temperature of 940 ° C. ⁇ p ⁇ 1100 ° C. Can be.
  • FIGS. 1A and 1B are schematic diagrams schematically illustrating an example of a lithium secondary battery.
  • the positive electrode active material for a secondary battery of the present invention is a secondary particle formed by agglomeration of single crystal particles and / or a plurality of primary particles, and has a layered structure containing at least one of nickel, cobalt, and manganese. Having.
  • the shape of the positive electrode active material for a secondary battery of the present invention is not particularly limited, and has various shapes. Examples thereof include a substantially spherical shape, a substantially cubic shape, and a substantially rectangular parallelepiped shape.
  • the positive electrode active material for a secondary battery of the present invention includes one of single crystal particles and secondary particles formed by aggregating a plurality of primary particles, or both single crystal particles and secondary particles.
  • FIG. 1 which is a scanning electron microscope (SEM) image of the positive electrode active material for a secondary battery of the present invention, contains both single crystal particles and secondary particles. As shown in FIG. 1, single crystal particles are in the form of primary particles, and secondary particles are particles formed by aggregating a plurality of primary particles.
  • the crystal structure of the positive electrode active material for a secondary battery of the present invention is a layered structure, and more preferably a hexagonal crystal structure or a monoclinic crystal structure.
  • the hexagonal crystal structure is P3, P31, P32, R3, P-3, R-3, P312, P321, P3112, P3121, P3212, P3221, R32, P3m1, P31m, P3c1, P31c, R3m, R3c, P-31m, P-31c, P-3m1, P-3c1, R-3m, R-3c, P6, P61, P65, P62, P64, P63, P-6, P6 / m, P63 / m, P622, From P6122, P6522, P6222, P6422, P6322, P6mm, P6cc, P63cm, P63mc, P-6m2, P-6c2, P-62m, P-62c, P6 / mmm, P6 / mcc, P63 / mcm, P63 / mmc It belongs to any one space group selected from the group consisting of:
  • the monoclinic crystal structure is composed of P2, P21, C2, Pm, Pc, Cm, Cc, P2 / m, P21 / m, C2 / m, P2 / c, P21 / c, and C2 / c. It belongs to any one space group selected from the group.
  • the crystal structure is a hexagonal crystal structure belonging to the space group R-3m or a monoclinic crystal structure belonging to C2 / m. Particularly preferred is a structure.
  • the cumulative volume percentage of the positive electrode active material for a secondary battery of the present invention is in the range of a particle diameter (D50) of 50% by volume (hereinafter sometimes simply referred to as “D50”) ⁇ 1.0 ⁇ m, that is, (D50) ⁇
  • D50 particle diameter
  • the average particle strength of the particles in the range of 1.0 ⁇ m to (D50) +1.0 ⁇ m is 200 MPa or more. This excellent average particle strength is considered to be due to the fact that the positive electrode active material for a secondary battery of the present invention contains single crystal particles.
  • the average particle strength of ⁇ 1.0 ⁇ m is not particularly limited as long as it is 200 MPa or more, but the lower limit is 230 MPa from the viewpoint of exhibiting more excellent cycle characteristics under both normal temperature and high temperature environments.
  • the upper limit of the average particle strength of (D50) ⁇ 1.0 ⁇ m is not particularly limited, but, for example, is preferably 3000 MPa, more preferably 2200 MPa, and still more preferably 1000 MPa from the viewpoint of efficient production. 700 MPa is particularly preferred.
  • the above lower limit and upper limit can be arbitrarily combined.
  • the lower limit of D50 of the positive electrode active material for a secondary battery of the present invention is not particularly limited, but is preferably 2.0 ⁇ m, more preferably 2.5 ⁇ m, and particularly preferably 3.0 ⁇ m from the viewpoint of improving the handling properties.
  • the upper limit of D50 of the positive electrode active material for a secondary battery is preferably 20.0 ⁇ m, particularly preferably 15.0 ⁇ m, from the viewpoint of improving the density and ensuring a contact surface with the electrolytic solution.
  • the above lower limit and upper limit can be arbitrarily combined.
  • the full width at half maximum of the diffraction peak on the low angle side of two diffraction peaks appearing in the range of 2 ⁇ 64.5 ⁇ 1 °.
  • Is ⁇ and ⁇ is the full width at half maximum of the diffraction peak on the high angle side
  • ⁇ / ⁇ is the configuration of the full width at half maximum of the diffraction peak in which 0.97 ⁇ ⁇ / ⁇ ⁇ 1.25, or CuK ⁇ ray was used.
  • ⁇ / ⁇ is not particularly limited as long as it is 0.97 or more and 1.25 or less, but from the viewpoint of obtaining more excellent cycle characteristics stably at both normal temperature and high temperature, from 1.00 to 1.25.
  • the following is more preferable, and the range of 1.03 to 1.13 is particularly preferable.
  • the rate of change of the lattice constant In the range of the average particle strength in the range of (D50) ⁇ 1.0 ⁇ m and the cycle test at 25 ° C. and 60 ° C., at least one of A and C is 99.30% or more.
  • a lattice constant change rate of 100.90% or less it is possible to obtain a positive electrode active material for a secondary battery that can exhibit excellent cycle characteristics under both normal temperature and high temperature environments. That is, in the 25 ° C. cycle test (normal temperature cycle test) and the 60 ° C. cycle test (high temperature cycle test), the rate of change of at least one of the a-axis and c-axis lattice constants is 99.30% or more and 100.
  • the inventors of the present invention have found that the control at 90% or less contributes to imparting excellent cycle characteristics under both normal temperature and high temperature environments. This is considered to be due to the fact that the change in the crystal structure of the positive electrode active material for the secondary battery before and after the cycle test was reduced in the normal temperature and high temperature cycle tests.
  • both A and C are preferably from 99.30% to 100.90%, and both A and C are particularly preferably from 99.32% to 100.90%.
  • the composition of the positive electrode active material for a secondary battery of the present invention is not particularly limited as long as the composition contains at least one metal element of nickel, cobalt, and manganese.
  • the following general formula (1) Li [Li a (M1 x M2 y ) 1-a ] O 2 + b (1)
  • a is preferably 0 ⁇ a ⁇ 0.30, more preferably 0 ⁇ a ⁇ 0.20, and particularly preferably 0 ⁇ a ⁇ 0.10.
  • B is not particularly limited.
  • M1 is 1 of Ni, Co and Mn.
  • the composition of Ni, Co and Mn is not particularly limited, but the Ni composition range is preferably from 10 mol% to 90 mol%, more preferably from 30 mol% to 80 mol%, and more preferably 50 mol% or more.
  • the content of Co is particularly preferably 60 mol% or less. Is preferably from 10 mol% to 50 mol%, more preferably from 10 mol% to 30 mol%, and the Mn composition range is preferably from 0 mol% to 50 mol%, more preferably from 0 mol% to 40 mol%, and M2 is Fe. , Cu, Ti, Mg, Al, W, Zn, Sn, Zr, Ga, V, B, Mo, As, Ge, P, Pb, Si, Sb, Nb, Ta, Re and Bi. And at least one type of metal element). Among them, by including M2 which is an arbitrary metal element, more excellent cycle characteristics can be obtained stably at both normal temperature and high temperature environments. Among these arbitrary metal elements, Zr and Al are preferable.
  • the positive electrode active material for a secondary battery of the present invention can be used, for example, as a positive electrode active material for a lithium ion secondary battery.
  • the BET specific surface area of the positive electrode active material for a secondary battery of the present invention is not particularly limited, for example, the lower limit is 0.10 m 2 from the viewpoint of improving density and ensuring a contact surface with an electrolyte. / G is preferred, and 0.30 m 2 / g is particularly preferred.
  • the upper limit is preferably 5.0 m 2 / g, more preferably 4.0 m 2 / g, particularly preferably 2.0 m 2 / g. The above lower limit and upper limit can be arbitrarily combined.
  • composite hydroxide particles having at least one of nickel, cobalt, and manganese are prepared.
  • the composite hydroxide particles are a precursor of a positive electrode active material for a secondary battery.
  • the precursor used in the present invention may be a composite oxide having at least one of nickel, cobalt and manganese.
  • the method for preparing the composite hydroxide particles is as follows.
  • a nickel salt solution for example, a sulfate solution
  • a cobalt salt solution for example, a sulfate solution
  • a manganese salt solution for example, a sulfate solution
  • a complexing agent for example, a complexing agent and a pH adjusting agent are appropriately added to react in a reaction vessel to prepare composite hydroxide particles
  • a slurry suspension containing the particles is obtained.
  • a solvent for the suspension for example, water is used.
  • the complexing agent to be added to the metal salt solution is not particularly limited as long as it can form a complex with nickel, cobalt, and manganese ions in an aqueous solution.
  • an ammonium ion donor (ammonium sulfate, chloride, etc.) Ammonium, ammonium carbonate, ammonium fluoride, etc.), hydrazine, ethylenediaminetetraacetic acid, nitrilotriacetic acid, uracil diacetate, and glycine.
  • an alkali metal hydroxide for example, sodium hydroxide or potassium hydroxide
  • the pH adjusting agent and the complexing agent are appropriately and continuously supplied to the reaction tank in addition to the metal salt solution, the metals (one or more of nickel, cobalt, and manganese) of the metal salt solution undergo a coprecipitation reaction, Composite hydroxide particles are prepared.
  • the temperature of the reaction vessel is controlled, for example, in the range of 10 ° C. to 80 ° C., preferably 20 to 70 ° C., and the pH value in the reaction vessel is adjusted to a pH of 9 ° C.
  • the substance in the reaction vessel is appropriately stirred while controlling the pH within a range of from pH 13 to preferably pH 11 to 13.
  • the reaction tank include a continuous type in which the formed composite hydroxide particles overflow to separate them, and a batch type in which the composite hydroxide particles are not discharged out of the system until the end of the reaction.
  • the composite oxide particles obtained as described above are filtered from the suspension, washed with water, and heat-treated to obtain powdery composite hydroxide particles. If necessary, a step of narrowing (D90-D10) / D50 of the particle size distribution width of the obtained composite hydroxide particles may be added by, for example, a dry classifier.
  • the lower limit of D50 of the composite hydroxide particles that are the precursor of the positive electrode active material for a secondary battery of the present invention is not particularly limited, but is preferably 2.0 ⁇ m, more preferably 2.5 ⁇ m, from the viewpoint of improving handling properties. And 3.0 ⁇ m are particularly preferred.
  • the upper limit of D50 of the composite hydroxide particles is preferably 25.0 ⁇ m, particularly preferably 20.0 ⁇ m, from the viewpoint of enhancing the reaction with the lithium compound during firing. The above lower limit and upper limit can be arbitrarily combined.
  • the particle size distribution of the composite hydroxide particles is not particularly limited, but the lower limit of the value of (D90 ⁇ D10) / D50 is preferably 0.40, and more preferably 0.50, from the viewpoint of an efficient production range. Is more preferable, and 0.70 is particularly preferable.
  • the upper limit of the value of (D90 ⁇ D10) / D50 of the composite hydroxide particles is set at 1 because the superior cycle characteristics can be obtained under a normal temperature environment and the superior cycle characteristics can be obtained under a high temperature environment. 0.000 is more preferable, 0.96 is more preferable, and 0.80 is particularly preferable from the viewpoint of obtaining further excellent cycle characteristics under a normal temperature environment.
  • the above lower limit and upper limit can be arbitrarily combined.
  • a lithium compound is added to the obtained powdery composite hydroxide particles to prepare a mixture of the composite hydroxide particles and the lithium compound.
  • the lithium compound is added so that the atomic ratio satisfies 1.00 ⁇ Li / M1 ⁇ 1.30.
  • the lithium compound is not particularly limited as long as it is a compound having lithium, and examples thereof include lithium carbonate and lithium hydroxide.
  • the obtained mixture is fired (hereinafter, sometimes referred to as main firing) at a firing temperature represented by the following formula.
  • main firing the formula p ⁇ ⁇ 600q + 1603 (where q is the atomic ratio of Li to the total of at least one metal element (M1) of Ni, Co and Mn) (Li / M1). 00 ⁇ q ⁇ 1.30, p is a main firing temperature, and means firing at a firing temperature represented by 940 ° C. ⁇ p ⁇ 1100 ° C.).
  • the firing time in the firing step at the above firing temperature is not particularly limited, but is, for example, preferably 5 to 20 hours, and particularly preferably 8 to 15 hours.
  • the rate of temperature rise in the main firing is preferably 50 to 550 ° C./h, more preferably 100 to 400 ° C./h, and 140 ° C. to 380 ° C./h from the viewpoint of keeping the material temperature and the temperature of the firing furnace equal. Is particularly preferred.
  • the atmosphere for the main firing is not particularly limited, and examples thereof include air and oxygen.
  • the firing furnace used for the main firing is not particularly limited, and examples thereof include a stationary box furnace and a roller hearth continuous furnace.
  • the surface area (S) including the contact surface of the filler with the sheath and the filler is not particularly limited, but is preferably 0.08 mm 2 / mm 3 from the viewpoint of making the temperature of the filling uniform.
  • the upper limit is not particularly limited, but is preferably 2.00 mm 2 / mm 3 from the viewpoint of productivity, more preferably 0.68 mm 2 / mm 3, and particularly preferably 0.36mm 2 / mm 3.
  • the above lower limit and upper limit can be arbitrarily combined.
  • a sheath having an inner size of 130 mm ⁇ 130 mm ⁇ 88 mm or 280 mm ⁇ 280 mm ⁇ 88 mm is exemplified.
  • the calcining step is a step for releasing the gas contained in the raw material and oxidizing the same to make the crystallinity of the positive electrode active material for a secondary battery more preferable.
  • the calcination is, for example, preferably at least 300 ° C and at most 800 ° C, particularly preferably at least 650 ° C and at most 760 ° C.
  • the calcination time of the calcination is not particularly limited, but is, for example, preferably 1 to 20 hours, and particularly preferably 3 to 10 hours.
  • the rate of temperature rise in the preliminary firing is preferably 50 to 550 ° C / h, more preferably 100 to 400 ° C / h, and 140 ° C to 380 ° C / h from the viewpoint of keeping the material temperature and the temperature of the firing furnace equal. Is particularly preferred.
  • the atmosphere for the preliminary firing is not particularly limited, and examples thereof include air and oxygen.
  • the firing furnace used for the preliminary firing is not particularly limited, and examples thereof include a stationary box furnace and a roller hearth continuous furnace.
  • the tempering step is a step for making the crystallinity of the positive electrode active material for a secondary battery more preferable.
  • the tempering step is, for example, preferably at least 600 ° C and no more than 900 ° C, particularly preferably at least 650 ° C and no more than 860 ° C.
  • the firing time for tempering is not particularly limited, but is, for example, preferably 1 to 20 hours, and particularly preferably 3 to 10 hours.
  • the temperature rising rate in the tempering is preferably 50 to 550 ° C./h, more preferably 100 to 400 ° C./h, and 140 to 380 ° C./h from the viewpoint of keeping the material temperature and the temperature of the firing furnace equal. Particularly preferred.
  • the tempering atmosphere is not particularly limited, but includes, for example, air and oxygen.
  • the firing furnace used for tempering is not particularly limited, and examples thereof include a stationary box furnace and a roller hearth continuous furnace.
  • the step of adding at least one metal component selected from the above is a step for making the crystallinity of the positive electrode active material for a secondary battery more preferable.
  • One example of a lithium secondary battery using the positive electrode active material for a secondary battery of the present invention as a positive electrode active material is a positive electrode and a negative electrode, a separator sandwiched between the positive electrode and the negative electrode, and disposed between the positive electrode and the negative electrode. Electrolyte solution.
  • FIG. 2 is a schematic diagram showing an example of a lithium secondary battery.
  • the cylindrical lithium secondary battery 10 shown in FIG. 2 is manufactured as follows.
  • a pair of separators 1 having a band shape, a band-shaped positive electrode 2 having a positive electrode lead 21 at one end, and a band-shaped negative electrode 3 having a negative electrode lead 31 at one end are separated from each other by a separator 1.
  • the positive electrode 2, the separator 1, and the negative electrode 3 are laminated in this order and wound to form an electrode group 4.
  • the bottom of the battery can 5 is sealed, and the electrode group 4 is impregnated with the electrolytic solution 6. Then, an electrolyte is disposed between the positive electrode 2 and the negative electrode 3. Further, by sealing the upper portion of the battery can 5 with the top insulator 7 and the sealing body 8, the lithium secondary battery 10 can be manufactured.
  • the shape of the electrode group 4 is not particularly limited.
  • the cross-sectional shape when the electrode group 4 is cut in a direction perpendicular to the axis of winding is a circle, an ellipse, a rectangle, and a rounded rectangle.
  • Columnar shapes can be mentioned.
  • a shape defined by IEC60086 which is a standard for batteries defined by the International Electrotechnical Commission (IEC), or a shape defined by JIS C # 8500 can be adopted.
  • Examples of the shape defined by the standard include a cylindrical shape and a square shape.
  • the lithium secondary battery is not limited to the above-described wound configuration, and may be a stacked configuration in which a stacked structure of a positive electrode, a separator, a negative electrode, and a separator is repeatedly stacked.
  • the stacked lithium secondary battery include a so-called coin battery, a button battery, and a paper (or sheet) battery.
  • a positive electrode mixture containing a positive electrode active material (a positive electrode active material for a secondary battery of the present invention), a conductive material and a binder is prepared, and the positive electrode mixture is supported on a positive electrode current collector. It can be manufactured by
  • a carbon material As the conductive material of the positive electrode of the lithium secondary battery, a carbon material can be used. Examples of the carbon material include graphite powder, carbon black (for example, acetylene black), and a fibrous carbon material. Carbon black is a fine particle and has a large surface area.By adding a small amount to the positive electrode mixture, the conductivity inside the positive electrode can be increased, and the charge / discharge efficiency and output characteristics can be improved. Both the binding force between the positive electrode mixture and the positive electrode current collector and the binding force inside the positive electrode mixture decrease, which causes an increase in internal resistance.
  • the proportion of the conductive material in the positive electrode mixture can be appropriately selected depending on the use conditions and the like, but is preferably 5 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the positive electrode active material.
  • a fibrous carbon material such as graphitized carbon fiber or carbon nanotube is used as the conductive material, the ratio can be reduced.
  • thermoplastic resin As a binder included in the positive electrode of the lithium secondary battery, a thermoplastic resin can be used.
  • the thermoplastic resin include polyvinylidene fluoride (hereinafter sometimes referred to as PVdF), polytetrafluoroethylene (hereinafter sometimes referred to as PTFE), and ethylene tetrafluoride / propylene hexafluoride / vinylidene fluoride.
  • Fluororesins such as polymers, propylene hexafluoride / vinylidene fluoride copolymers, and tetrafluoroethylene / perfluorovinyl ether copolymers; polyolefin resins such as polyethylene and polypropylene; These thermoplastic resins may be used alone or in combination of two or more.
  • thermoplastic resins a fluororesin and a polyolefin resin are used as a binder, and the ratio of the fluororesin to the whole positive electrode mixture is 1% by mass to 10% by mass, and the ratio of the polyolefin resin is 0.1% by mass to 2% by mass. % Or less, it is possible to obtain a positive electrode mixture in which both the adhesion to the positive electrode current collector and the bonding force inside the positive electrode mixture are high.
  • a belt-shaped member formed using a metal material such as Al, Ni, or stainless steel can be used as the positive electrode current collector included in the positive electrode of the lithium secondary battery.
  • a material formed into a thin film using Al as a forming material is preferable because it is easy to process and inexpensive.
  • the method for supporting the positive electrode mixture on the positive electrode current collector is not particularly limited.
  • a method in which the positive electrode mixture is pressure-formed on the positive electrode current collector may be mentioned.
  • the positive electrode mixture is paste-formed using an organic solvent, the obtained positive electrode mixture paste is applied to at least one surface of the positive electrode current collector, dried, pressed and fixed, so that the positive electrode A mixture may be carried.
  • organic solvent examples include, for example, amine solvents such as N, N-dimethylaminopropylamine and diethylenetriamine; ether solvents such as tetrahydrofuran; ketone solvents such as methyl ethyl ketone; Ester solvents such as methyl acetate; amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone (hereinafter sometimes referred to as NMP). These may be used alone or in combination of two or more.
  • amine solvents such as N, N-dimethylaminopropylamine and diethylenetriamine
  • ether solvents such as tetrahydrofuran
  • ketone solvents such as methyl ethyl ketone
  • Ester solvents such as methyl acetate
  • amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone (hereinafter sometimes referred to as NMP).
  • Examples of the method of applying the paste of the positive electrode mixture to the positive electrode current collector include a slit die coating method, a screen coating method, a curtain coating method, a knife coating method, a gravure coating method, and an electrostatic spray method.
  • the positive electrode can be manufactured by the method described above.
  • the negative electrode of the lithium secondary battery may be capable of doping and undoping lithium ions at a potential lower than that of the positive electrode, and an electrode in which a negative electrode mixture containing a negative electrode active material is supported on a negative electrode current collector, a negative electrode An electrode made of the active material alone can be used.
  • the negative electrode active material of the negative electrode of the lithium secondary battery is a carbon material, a chalcogen compound (oxide, sulfide, etc.), a nitride, a metal, or an alloy. Doping and undoping of lithium ions at a lower potential than the positive electrode is performed. Possible materials are listed.
  • Examples of the carbon material that can be used as the negative electrode active material of the lithium secondary battery include natural graphite, graphite such as artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fibers, and fired organic polymer compounds. be able to.
  • Examples of the sulfide that can be used as the negative electrode active material of the lithium secondary battery include titanium sulfide represented by the formula TiS x (where x is a positive real number) such as Ti 2 S 3 , TiS 2 , and TiS.
  • nitride usable as a negative electrode active material of a lithium secondary battery for example, Li 3 N, Li 3-x A x N (where A is one or both of Ni and Co, and 0 ⁇ x ⁇ 3).
  • These carbon materials, oxides, sulfides and nitrides may be used alone or in combination of two or more.
  • these carbon materials, oxides, sulfides, and nitrides may be either crystalline or amorphous.
  • examples of the metal that can be used as the negative electrode active material of the lithium secondary battery include lithium metal, silicon metal, tin metal, and the like.
  • alloys usable as the negative electrode active material of the lithium secondary battery include lithium alloys such as Li-Al, Li-Ni, Li-Si, Li-Sn, and Li-Sn-Ni; silicon such as Si-Zn alloy; it may also be mentioned; Sn-Mn, Sn-Co , Sn-Ni, Sn-Cu, tin alloys such as Sn-La; Cu 2 Sb, alloys such as La 3 Ni 2 Sn 7.
  • These metals and alloys are mainly used alone as a negative electrode after being processed into a foil shape, for example.
  • the potential of the negative electrode hardly changes from an uncharged state to a fully charged state during charging (good potential flatness), the average discharge potential is low, and the capacity retention rate when repeatedly charged and discharged is low.
  • a carbon material containing graphite as a main component such as natural graphite or artificial graphite, is preferred because of its high property (good cycle characteristics).
  • the shape of the carbon material is not particularly limited, and may be, for example, any of a flaky shape such as natural graphite, a spherical shape such as mesocarbon microbeads, a fibrous shape such as graphitized carbon fiber, and an aggregate of fine powder. May be.
  • the negative electrode mixture of the lithium secondary battery may contain a binder, if necessary.
  • the binder include thermoplastic resins, and examples thereof include PVdF, thermoplastic polyimide, carboxymethyl cellulose, and polyolefin resins such as polyethylene and polypropylene. These may be used alone or in combination of two or more.
  • Examples of the negative electrode current collector included in the negative electrode of the lithium secondary battery include a band-shaped member formed of a metal material such as Cu, Ni, and stainless steel. Among them, it is preferable to use Cu as a forming material and process it into a thin film, since it is difficult to form an alloy with lithium and easy to process.
  • the method for supporting the negative electrode mixture on the negative electrode current collector is not particularly limited.
  • a separator included in the lithium secondary battery for example, polyethylene, a polyolefin resin such as polypropylene, a fluorine resin, a material such as a nitrogen-containing aromatic polymer, a porous film, a nonwoven fabric, a material having a form such as a woven fabric. Can be used. Further, one or more of these materials may be used to form a separator, or these materials may be laminated to form a separator.
  • Examples of the separator of the lithium secondary battery include separators described in JP-A-2000-30686 and JP-A-10-324758.
  • the thickness of the separator can be appropriately selected depending on the use conditions and the like, but it is preferable that the thickness be reduced as long as the mechanical strength is maintained, in that the volume energy density of the lithium secondary battery increases and the internal resistance decreases. And more preferably about 5 to 200 ⁇ m, particularly preferably about 5 to 40 ⁇ m.
  • the separator of the lithium secondary battery preferably has a porous film containing a thermoplastic resin.
  • the function of shutting off the current at the short-circuit point and preventing the excessive current from flowing (shut down) It is preferred to have.
  • the shutdown is performed by overheating of the separator at the short-circuited portion due to the short-circuit, and when the operating temperature exceeds a previously assumed use temperature, the porous film in the separator softens or melts to close the micropores. Then, even if the temperature in the lithium secondary battery rises to a certain high temperature after the separator is shut down, it is preferable that the shut down state be maintained without causing film breakage due to the temperature.
  • the temperature-resistant separator After the separator shuts down, even if the temperature inside the lithium secondary battery rises to a certain high temperature, the temperature-resistant separator does not break down, and as a separator, the heat-resistant porous layer and the porous film are laminated. And the resulting laminated film.
  • the heat-resistant porous layer By using such a laminated film as a separator, the heat resistance of the secondary battery can be further increased.
  • the heat-resistant porous layer may be laminated on both sides of the porous film.
  • the heat-resistant porous layer is a layer having higher heat resistance than the porous film.
  • the heat-resistant porous layer may be formed from an inorganic powder (first heat-resistant porous layer), may be formed from a heat-resistant resin (second heat-resistant porous layer), and includes a heat-resistant resin and a filler. (Third heat-resistant porous layer).
  • first heat-resistant porous layer may be formed from a heat-resistant resin
  • second heat-resistant porous layer may be formed from a heat-resistant resin
  • the heat-resistant porous layer can be formed by an easy method such as coating.
  • the heat-resistant porous layer is formed from an inorganic powder
  • examples of the inorganic powder used for the heat-resistant porous layer include inorganic substances such as metal oxides, metal nitrides, metal carbides, metal hydroxides, carbonates, and sulfates. Of these, and among these, a powder made of an inorganic material having low conductivity (high insulation) is preferably used. Specific examples include alumina powder, silica powder, titanium dioxide powder, calcium carbonate powder and the like. Such inorganic powders may be used alone or in combination of two or more.
  • alumina powder is preferred because of its high chemical stability. Further, it is more preferable that all of the particles constituting the inorganic powder are alumina particles, all of the particles constituting the inorganic powder are alumina particles, and some or all of the particles are substantially spherical alumina particles. Is more preferable.
  • the heat-resistant porous layer is formed from a heat-resistant resin
  • a heat-resistant resin for example, polyamide, polyimide, polyamideimide, polycarbonate, polyacetal, polysulfone, polyphenylene sulfide, polyether ketone, aromatic polyester, Examples thereof include polyethersulfone and polyetherimide.
  • polyamide, polyimide, polyamideimide, polyethersulfone, and polyetherimide are preferred, and polyamide, polyimide, and polyamideimide are more preferred.
  • the heat-resistant resin used for the heat-resistant porous layer is more preferably a nitrogen-containing aromatic polymer such as an aromatic polyamide (para-oriented aromatic polyamide or meta-oriented aromatic polyamide), aromatic polyimide, or aromatic polyamide-imide, Particularly preferred is an aromatic polyamide, and particularly preferred from the viewpoint of productivity is a para-oriented aromatic polyamide (hereinafter sometimes referred to as para-aramid).
  • aromatic polyamide para-oriented aromatic polyamide or meta-oriented aromatic polyamide
  • aromatic polyimide aromatic polyimide
  • aromatic polyamide-imide aromatic polyamide-imide
  • para-aramid para-oriented aromatic polyamide
  • examples of the heat-resistant resin include poly-4-methylpentene-1 and a cyclic olefin polymer.
  • the heat resistance of the laminated film used as the separator of the lithium secondary battery that is, the thermal rupture temperature of the laminated film can be further increased.
  • these heat-resistant resins when using a nitrogen-containing aromatic polymer, it may be due to the polarity in the molecule, compatibility with the electrolytic solution, that is, the liquid retention in the heat-resistant porous layer may be improved, The rate of impregnation of the electrolyte during the production of the lithium secondary battery is also high, and the charge / discharge capacity of the lithium secondary battery is further increased.
  • the thermal rupture temperature of the laminated film depends on the type of heat-resistant resin, and is selected and used according to the use scene and purpose. Specifically, when the above nitrogen-containing aromatic polymer is used as the heat-resistant resin, the cyclic olefin-based polymer is heated to about 400 ° C., and when poly-4-methylpentene-1 is used, to about 250 ° C. When used, the thermal rupture temperature can be controlled to about 300 ° C., respectively. When the heat-resistant porous layer is made of an inorganic powder, the thermal rupture temperature can be controlled to, for example, 500 ° C. or more.
  • the para-aramid is obtained by condensation polymerization of a para-oriented aromatic diamine and a para-oriented aromatic dicarboxylic acid halide, and the amide bond has a para-position of an aromatic ring or an alignment position corresponding thereto (for example, 4,4 ′).
  • aromatic polyimide a wholly aromatic polyimide produced by condensation polymerization of an aromatic diacid anhydride and a diamine is preferable.
  • aromatic dianhydride used for the condensation polymerization examples include pyromellitic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4 , 4'-benzophenonetetracarboxylic dianhydride, 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and the like No.
  • diamine used for the condensation polymerization examples include oxydianiline, paraphenylenediamine, benzophenonediamine, 3,3′-methylenedianiline, 3,3′-diaminobensophenone, and 3,3′-diaminodiphenylsulfone. , 1,5-naphthalenediamine and the like.
  • a polyimide soluble in a solvent can be suitably used.
  • a polyimide which is a polycondensate of 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and an aromatic diamine.
  • aromatic polyamide-imide for example, those obtained from the condensation polymerization thereof using an aromatic dicarboxylic acid and an aromatic diisocyanate, those obtained from the condensation polymerization thereof using an aromatic dianhydride and an aromatic diisocyanate are included.
  • aromatic dicarboxylic acid include isophthalic acid and terephthalic acid.
  • aromatic dianhydride include trimellitic anhydride.
  • aromatic diisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, ortho tolylene diisocyanate, and m-xylene diisocyanate.
  • the thickness of the heat-resistant porous layer of the laminated film is preferably a thin heat-resistant porous layer, more preferably 1 ⁇ m or more and 10 ⁇ m or less, further preferably 1 ⁇ m or more and 5 ⁇ m or less. More preferably, it is 4 ⁇ m or less.
  • the heat-resistant porous layer has fine pores, and the size (diameter) of the pores is preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less.
  • the heat-resistant porous layer is formed to include a heat-resistant resin and a filler
  • the same heat-resistant resin as that used for the second heat-resistant porous layer can be used.
  • the filler at least one selected from the group consisting of organic powders, inorganic powders, and mixtures thereof can be used.
  • the particles constituting the filler preferably have an average particle diameter of 0.01 ⁇ m or more and 1 ⁇ m or less.
  • organic powder examples include, for example, a homopolymer or a copolymer of two or more of styrene, vinyl ketone, acrylonitrile, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, and methyl acrylate; PTFE, tetrafluoroethylene-6-fluoropropylene copolymer, fluorocarbon resin such as tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride; melamine resin; urea resin; polyolefin resin; polymethacrylate; A powder consisting of Such organic powders may be used alone or in combination of two or more. Among these organic powders, PTFE powder is preferred because of its high chemical stability.
  • the same powder as the inorganic powder used for the heat-resistant porous layer can be exemplified.
  • the content of the filler depends on the specific gravity of the material of the filler, for example, when all of the particles constituting the filler are alumina particles
  • the mass of the filler is preferably 5 parts by mass or more and 95 parts by mass or less, more preferably 20 parts by mass or more and 95 parts by mass or less, Preferably it is 30 parts by mass or more and 90 parts by mass or less. These ranges can be appropriately set depending on the specific gravity of the material of the filler.
  • the shape of the filler is not particularly limited, and examples thereof include shapes such as a substantially spherical shape, a plate shape, a column shape, a needle shape, and a fibrous shape, and any particles can be used, but since it is easy to form uniform pores,
  • the particles are substantially spherical particles.
  • the substantially spherical particles include particles having an aspect ratio of particles (major axis of particles / minor axis of particles) of 1.0 or more and 1.5 or less. The aspect ratio of the particles can be measured by an electron micrograph.
  • the porous film preferably has fine pores and has a shutdown function.
  • the porous film contains a thermoplastic resin.
  • the size of the micropores in the porous film is preferably as small as possible, more preferably 3 ⁇ m or less, and particularly preferably 1 ⁇ m or less.
  • the porosity of the porous film can be appropriately selected depending on the use conditions and the like, but is preferably 30% by volume or more and 80% by volume or less, more preferably 40% by volume or more and 70% by volume or less.
  • the porous film containing a thermoplastic resin closes the micropores by softening or melting of the thermoplastic resin constituting the porous film. be able to.
  • thermoplastic resin used for the porous film can be used without any particular limitation as long as it does not dissolve in the electrolytic solution of the lithium secondary battery.
  • specific examples include polyolefin resins such as polyethylene and polypropylene, and thermoplastic polyurethane resins. A mixture of two or more of these may be used.
  • the porous film preferably contains polyethylene.
  • polyethylene include polyethylene such as low-density polyethylene, high-density polyethylene, and linear polyethylene, and ultrahigh-molecular-weight polyethylene having a molecular weight of 1,000,000 or more.
  • the thermoplastic resin constituting the porous film preferably contains at least ultrahigh molecular weight polyethylene.
  • the thermoplastic resin may preferably contain a wax composed of a polyolefin having a low molecular weight (weight average molecular weight of 10,000 or less).
  • the thickness of the porous film in the laminated film can be appropriately selected according to the conditions of use and the like, it is preferably 3 ⁇ m or more and 30 ⁇ m or less, more preferably 3 ⁇ m or more and 25 ⁇ m or less.
  • the thickness of the laminated film can be appropriately selected depending on the use conditions and the like, but is preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less.
  • the thickness of the heat-resistant porous layer is A ( ⁇ m) and the thickness of the porous film is B ( ⁇ m)
  • the value of A / B is preferably 0.1 or more and 1.0 or less.
  • the separator has a gas permeability resistance of 50 seconds / 100 cc or more and 300 seconds / hour according to the Gurley method defined in JIS P # 8117 in order to allow the electrolyte to pass well when the battery is used (during charge / discharge). It is preferably 100 cc or less, more preferably 50 seconds / 100 cc or more and 200 seconds / 100 cc or less.
  • the porosity of the separator can be appropriately selected depending on the use conditions and the like, but is preferably 30% by volume or more and 80% by volume or less, more preferably 40% by volume or more and 70% by volume or less.
  • the separator used may be a laminate of separators having different porosity.
  • the electrolytic solution of the lithium secondary battery contains an electrolyte and an organic solvent.
  • the electrolyte is selected from the group consisting of LiPF 6 containing fluorine, LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 and LiC (SO 2 CF 3 ) 3. It is preferable to use one containing at least one kind.
  • organic solvent contained in the electrolytic solution examples include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one, and 1,2.
  • Carbonates such as -di (methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropylmethyl ether, 2,2,3,3-tetrafluoropropyldifluoromethyl ether, tetrahydrofuran, Ethers such as 2-methyltetrahydrofuran; esters such as methyl formate, methyl acetate and ⁇ -butyrolactone; nitriles such as acetonitrile and butyronitrile; N, N-dimethylformamide, N, N-dimethyl Amides such as acetamide; carbamates such as 3-methyl-2-oxazolidone; sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, and 1,3-propane sultone; or those obtained by further introducing a fluoro group into these organic solvents ( In which one or more of the hydrogen atoms of the organic
  • a mixed solvent containing carbonates is preferable, and a mixed solvent of cyclic carbonate and acyclic carbonate, and a mixed solvent of cyclic carbonate and ether are more preferable.
  • a mixed solvent of the cyclic carbonate and the non-cyclic carbonate a mixed solvent containing ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate is preferable.
  • the electrolytic solution using such a mixed solvent has a wide operating temperature range, hardly deteriorates even when charged and discharged at a high current rate, hardly deteriorates even when used for a long time, and natural graphite as an active material of a negative electrode. It has many features that it is hardly decomposable even when a graphite material such as artificial graphite is used.
  • an electrolyte containing a lithium salt containing fluorine such as LiPF 6 and an organic solvent having a fluorine substituent it is preferable to use an electrolyte containing a lithium salt containing fluorine such as LiPF 6 and an organic solvent having a fluorine substituent.
  • a mixed solvent containing dimethyl carbonate and ethers having a fluorine substituent such as pentafluoropropyl methyl ether and 2,2,3,3-tetrafluoropropyl difluoromethyl ether performs charge / discharge at a high current rate.
  • the capacity retention ratio is high, it is more preferable.
  • a solid electrolyte may be used instead of the above electrolyte.
  • the solid electrolyte for example, an organic polymer electrolyte such as a polyethylene oxide polymer compound or a polymer compound containing at least one polyorganosiloxane chain or polyoxyalkylene chain can be used. Further, a so-called gel type in which a non-aqueous electrolyte is held in a polymer compound can also be used.
  • the solid electrolyte may serve as a separator, and in such a case, the separator may not be required.
  • the positive electrode active material having the above-described configuration uses the positive electrode active material for a secondary battery of the present invention, a lithium secondary battery using the positive electrode active material can be used in an excellent cycle at room temperature and high temperature. It can be characteristic.
  • a lithium secondary battery may exhibit excellent cycle characteristics at normal temperature and high temperature. it can.
  • the lithium secondary battery having the above-described configuration includes the positive electrode having the positive electrode active material for a secondary battery of the present invention, it exhibits excellent cycle characteristics at ordinary temperatures and high temperatures in both environments. can do.
  • nickel, cobalt, and manganese composite hydroxide particles used in Examples 1, 2, 6, and 7 The nickel, cobalt, and manganese composite hydroxide particles used in Examples 3 and 4 and Comparative Examples 2 and 3 were dry-classified. Thus, nickel, cobalt, and manganese composite hydroxide particles having a D50 of 4.2 to 4.4 ⁇ m and a (D90-D10) / D50 of 0.78 to 0.88 were prepared.
  • the produced hydroxide overflows from the overflow tube of the reaction tank and is continuously taken out, filtered, washed, dehydrated, and dried at 100 ° C. to be a precursor of a positive electrode active material for a secondary battery.
  • Nickel, cobalt and manganese composite hydroxide particles were obtained. D50 of the nickel, cobalt and manganese composite hydroxide particles was 11.6 ⁇ m, and (D90 ⁇ D10) / D50 was 0.90.
  • D50 and (D90-D10) / D50 of the nickel, cobalt and manganese composite hydroxide particles used in Examples 1 to 7 and Comparative Examples 1 to 4 are shown in Table 1 below.
  • the values of D50, D90 and D10 in Table 1 below were measured using a laser diffraction particle size distribution analyzer (LA-950, manufactured by Horiba Seisakusho Co., Ltd.) using 0.1 g of nickel, cobalt and manganese composite hydroxide particles as 0%.
  • the solution was added to 50 ml of a 0.2% by mass aqueous sodium hexametaphosphate solution to obtain a dispersion in which the particles were dispersed.
  • the particle size distribution of the obtained dispersion was measured to obtain a volume-based cumulative particle size distribution curve.
  • the value of the particle diameter (D10) viewed from the fine particle side at the time of 10% accumulation and the value of the particle diameter (D50) viewed from the fine particle side at the time of 50% accumulation are 90%.
  • the value of the particle size (D90) viewed from the fine particle side at the time of% accumulation was defined as the average particle size of the nickel, cobalt, and manganese composite hydroxide particles.
  • the nickel, cobalt, and manganese composite hydroxide particles which are dry powders, used in Examples 1 to 7 and Comparative Examples 1 to 4 had the Li / M1 atomic ratios shown in Table 1 below, respectively.
  • the fired product was pulverized using a pulverizer (Super Mascolloid MKCA6-2, manufactured by Masuko Sangyo Co., Ltd.), and then sieved with a 325 mesh sieve, and the next step was performed.
  • the filling amount of the mixed powder or the mixed powder after the calcining step in the main firing step into the sheath having an inner size of 130 ⁇ 130 ⁇ 88 mm is such that the S / V shown in Table 1 below is obtained. did.
  • Example 3 ZrO 2 was added at 0.3 mol% to the nickel, cobalt, and manganese composite hydroxide particles before the main firing step, and the main firing was performed. Further, before the tempering step, Al 2 O 3 was added. Was added to nickel, cobalt, and manganese composite hydroxide particles in an amount of 1.0 mol% to perform tempering. In Example 4, before the tempering step, Al 2 O 3 was added to nickel, cobalt, and manganese composite hydroxide particles in an amount of 1.0 mol% to perform tempering. Further, in Example 7, the main firing was performed before the main firing step by adding 0.3 mol% of ZrO 2 to the nickel, cobalt, and manganese composite hydroxide particles.
  • the positive electrode active materials for secondary batteries of Examples 1 to 7 and Comparative Examples 1 to 4 were produced.
  • Table 2 below shows D50 values of the positive electrode active materials for secondary batteries of Examples 1 to 7 and Comparative Examples 1 to 4.
  • the value of D50 in Table 2 below was measured using a laser diffraction particle size distribution analyzer (LA-950, manufactured by Horiba, Ltd.) in the same manner as in the above composite hydroxide.
  • the evaluation items of the positive electrode active materials for secondary batteries of the examples and comparative examples are as follows.
  • Composition Analysis of Secondary Battery Positive Electrode Active Materials The secondary battery positive electrode active materials obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were analyzed for composition. After dissolving the substance powder in hydrochloric acid, the measurement was performed using an inductively coupled plasma emission spectrometer (Perkin Elmer Japan Co., Ltd., Optima 7300DV).
  • An X-ray powder diffraction pattern was obtained by performing the measurement under the conditions of a width of 0.03 ° and a scan speed of 20 ° / min.
  • the integrated powder X-ray analysis software PDXL of the two peaks appearing in the range of 64.5 ⁇ 1 ° from the powder X-ray diffraction pattern, the full width at half maximum of the peak on the low angle side is ⁇ , and the peak on the high angle side is ⁇ .
  • the full width at half maximum was defined as ⁇ , and the half width ratio ⁇ / ⁇ was calculated.
  • An X-ray diffraction pattern was obtained by performing the measurement at a scan speed of 2.6 ° / min. Then, using the XRD analysis software TOPAS, lattice constants of the a-axis and the c-axis were obtained from the X-ray diffraction pattern, and (a-axis before the cycle test / a-axis after the cycle test) ⁇ 100, (c before the cycle test) Axis / c axis after cycle test) ⁇ 100, the rate of change of the lattice constant before and after the cycle test at 25 ° C. and 60 ° C. was calculated.
  • the positive electrode active material for a secondary battery positive electrode active material
  • a conductive material acetylene black
  • a binder PVdF
  • N-methyl-2-pyrrolidone was used as an organic solvent.
  • the obtained positive electrode mixture was applied to a 15 ⁇ m-thick Al foil serving as a current collector so as to have a basis weight of 10 mg / cm 2 , followed by vacuum drying at 120 ° C. for 8 hours to obtain a positive electrode.
  • the electrode area of this positive electrode was 9 cm 2 .
  • Negative Electrode Graphite positive electrode active material
  • a thickener CMC
  • SBR400 binder
  • a paste-like negative electrode mixture was prepared by adding and kneading so as to obtain a composition.
  • water was used as a solvent.
  • the obtained negative electrode mixture was applied to a 10- ⁇ m-thick Cu foil serving as a current collector, and vacuum-dried at 120 ° C. for 8 hours to obtain a negative electrode.
  • the electrode area of this negative electrode was 12 cm 2 .
  • the positive electrode prepared in “Preparation of positive electrode” is placed on a laminate with the aluminum foil surface facing down, and a laminated film separator (a heat-resistant porous layer is laminated on a polyethylene porous film (thickness: 16 ⁇ m)) ), And among the negative electrodes prepared in “Preparation of negative electrode”, a negative electrode having an NP ratio of 1.1 is placed with the aluminum foil surface facing upward, and a laminate is further laminated. The side was fastened and vacuum dried at 60 ° C. for 10 hours. 1.4 g of an electrolytic solution was injected therein, and the other side was sealed with vacuum. The electrolyte was prepared by dissolving LiPF 6 at a concentration of 1 mol / l in a 3: 5: 2 (volume ratio) mixture of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate.
  • Capacity maintenance rate (cycle characteristics)
  • two cycles of charging and discharging at 0.2 C were performed before charging and discharging. Thereafter, a charge / discharge test was performed under the following conditions.
  • Test temperature 25 ° C Charging conditions: maximum charging voltage 4.2V, charging time 0.5 hour, charging current 2C, CC Discharge conditions: minimum discharge voltage 3.0V, discharge time 0.5 hour, discharge current 2C, CC Number of times of charge and discharge: 1000 times
  • Test temperature 60 ° C Charging conditions: maximum charging voltage 4.2V, charging time 0.5 hour, charging current 2C, CC Discharge conditions: minimum discharge voltage 3.0V, discharge time 0.5 hour, discharge current 2C, CC Number of charge / discharge cycles: 500
  • Example 1 in which the average particle strength is 200 MPa or more and ⁇ / ⁇ is 0.97 ⁇ ⁇ / ⁇ ⁇ 1.25 from the peak of the powder X-ray diffraction pattern using CuK ⁇ radiation.
  • the capacity retention rate at 25 ° C. 1000 cycles is 80% or more, and the capacity retention rate at 60 ° C. 500 cycles is 75% or more.
  • a positive electrode active material for a secondary battery capable of exhibiting characteristics was obtained.
  • the average particle strength is 200 MPa or more, and the rate of change of the lattice constant before and after the cycle test is 25.degree. C. and 60.degree.
  • the positive electrode active materials for secondary batteries of Examples 1 to 7 have a capacity retention rate of 80% or more at 25 ° C. and 1000 cycles and a capacity retention rate of 75% or more at 60 ° C. and 500 cycles.
  • a positive electrode active material for a secondary battery capable of exhibiting excellent cycle characteristics under both normal temperature and high temperature environments.
  • good D50 and BET specific surface area could be obtained.
  • Example 6 in which (D90-D10) / D50 of the nickel, cobalt, and manganese composite hydroxide particles was 0.78 was (D90-D10) / D50 of 0.96.
  • the cycle characteristics at room temperature were further improved by controlling (D90-D10) / D50 of the composite hydroxide particles to 0.80 or less.
  • Examples 1 to 7 which can exhibit excellent cycle characteristics under both normal temperature and high temperature environments, a good BET specific surface area of 0.35 m 2 to 6.1 m 2 / g can be obtained.
  • the surface area (S) / volume (V) of the mixed powder at the time of filling was in the range of 0.08 to 0.24 mm 2 / mm 3 .
  • the positive electrode active material for a secondary battery of the present invention can exhibit excellent cycle characteristics under both normal temperature and high temperature environments, it can be used in a wide range of fields, for example, in an environment where the use environment such as ambient temperature fluctuates. High value of use in the field of mounting on equipment used for

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'objet de la présente invention est de mettre en œuvre : un matériau actif d'électrode positive pour un accumulateur qui peut présenter d'excellentes caractéristiques de cycle aussi bien dans des environnements à température ambiante et que dans des environnements à haute température ; et un procédé destiné à produire le matériau actif d'électrode positive. Le matériau actif d'électrode positive pour un accumulateur a une structure stratifiée contenant au moins du nickel, du cobalt, et du manganèse, lesquels sont des particules monocristallines et/ou des particules secondaires qui sont des agrégats d'une pluralité de particules primaires, la résistance de particules moyenne de particules dont la taille est (D50) ± 1,0 µm étant d'au moins 200 MPa, et 0,97 ≤ β/α ≤ 1,25, où (D50) est une taille de particules à un pourcentage volumique cumulatif de 50 % en volume, α est la largeur totale au demi-maximum du pic d'angle inférieur parmi deux pics de diffraction apparaissant dans la plage 2θ = 64,5 ± 1°<sp /> dans le motif de diffraction aux rayons X, et β est la largeur totale au demi-maximum du pic d'angle supérieur parmi les deux pics de diffraction.
PCT/JP2019/034407 2018-09-21 2019-09-02 Matériau actif d'électrode positive pour accumulateur et procédé destiné à le produire Ceased WO2020059471A1 (fr)

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EP19861675.7A EP3855541A4 (fr) 2018-09-21 2019-09-02 Matériau actif d'électrode positive pour accumulateur et procédé destiné à le produire
CN201980061771.2A CN112740442A (zh) 2018-09-21 2019-09-02 二次电池用正极活性物质及其制造方法
KR1020217011795A KR102648286B1 (ko) 2018-09-21 2019-09-02 이차 전지용 양극 활물질 및 그 제조방법
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JP2019097568A JP6669920B1 (ja) 2018-09-21 2019-05-24 二次電池用正極活物質及びその製造方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112768685A (zh) * 2021-04-09 2021-05-07 湖南长远锂科股份有限公司 一种长循环、高功率的锂离子电池正极材料及其制备方法
CN115362133A (zh) * 2020-04-03 2022-11-18 株式会社田中化学研究所 复合氢氧化物的制备方法以及复合氢氧化物
CN116487525A (zh) * 2023-06-05 2023-07-25 中创新航科技集团股份有限公司 一种正极片、含有其的电池
CN116504922A (zh) * 2023-06-19 2023-07-28 蔚来电池科技(安徽)有限公司 正极极片、电化学装置和用电装置

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000030686A (ja) 1998-04-27 2000-01-28 Sumitomo Chem Co Ltd 非水電解質電池セパレ―タ―とリチウム二次電池
JP2003002661A (ja) * 2001-06-20 2003-01-08 Seimi Chem Co Ltd リチウムコバルト複合酸化物の製造方法
JP2004335152A (ja) * 2003-04-30 2004-11-25 Sumitomo Metal Mining Co Ltd 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
JP2007257985A (ja) * 2006-03-23 2007-10-04 Sumitomo Metal Mining Co Ltd 非水系電解質二次電池用正極活物質およびその製造方法とそれを用いた非水系電解質二次電池
WO2007116971A1 (fr) * 2006-04-07 2007-10-18 Mitsubishi Chemical Corporation Poudre de composé de métal de transition au lithium pour matériau positif d'électrode dans un accumulateur rechargeable au lithium, procédé de fabrication de la poudre, produit de la poudre séché par pulvérisation, précurseur de la poudre, électrod
KR20110063376A (ko) * 2009-12-03 2011-06-10 주식회사 엘앤에프신소재 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 이용한 리튬 이차 전지
WO2013038918A1 (fr) * 2011-09-12 2013-03-21 三洋電機株式会社 Matière active d'électrode positive destinée à une pile rechargeable à électrolyte non aqueux, et pile rechargeable à électrolyte non aqueux
JP2013107791A (ja) * 2011-11-21 2013-06-06 Sumitomo Chemical Co Ltd 複合金属酸化物の製造方法、複合金属酸化物、正極活物質、正極及び非水電解質二次電池
WO2013161619A1 (fr) * 2012-04-27 2013-10-31 三井金属鉱業株式会社 Oxyde de composé de métal de lithium à structure stratifiée
WO2016129361A1 (fr) * 2015-02-12 2016-08-18 Ｊｘ金属株式会社 Matériau actif d'électrode positive pour pile au lithium-ion, électrode positive pour pile au lithium-ion, pile au lithium-ion, et procédé de fabrication de matériau actif d'électrode positive pour pile au lithium-ion
WO2017169184A1 (fr) * 2016-03-30 2017-10-05 パナソニックＩｐマネジメント株式会社 Substance active d'électrode positive pour pile rechargeable à électrolyte non aqueux, et pile rechargeable à électrolyte non aqueux
JP2018045998A (ja) 2016-09-18 2018-03-22 貴州振華新材料有限公司 球形又は類球形リチウムイオン電池の正極材料、製造方法及び応用
WO2018110256A1 (fr) * 2016-12-14 2018-06-21 住友化学株式会社 Poudre d'oxyde composite de métal au lithium, matière active d'électrode positive pour batterie secondaire au lithium, électrode positive pour batterie secondaire au lithium, et batterie secondaire au lithium

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000030686A (ja) 1998-04-27 2000-01-28 Sumitomo Chem Co Ltd 非水電解質電池セパレ―タ―とリチウム二次電池
JP2003002661A (ja) * 2001-06-20 2003-01-08 Seimi Chem Co Ltd リチウムコバルト複合酸化物の製造方法
JP2004335152A (ja) * 2003-04-30 2004-11-25 Sumitomo Metal Mining Co Ltd 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
JP2007257985A (ja) * 2006-03-23 2007-10-04 Sumitomo Metal Mining Co Ltd 非水系電解質二次電池用正極活物質およびその製造方法とそれを用いた非水系電解質二次電池
WO2007116971A1 (fr) * 2006-04-07 2007-10-18 Mitsubishi Chemical Corporation Poudre de composé de métal de transition au lithium pour matériau positif d'électrode dans un accumulateur rechargeable au lithium, procédé de fabrication de la poudre, produit de la poudre séché par pulvérisation, précurseur de la poudre, électrod
KR20110063376A (ko) * 2009-12-03 2011-06-10 주식회사 엘앤에프신소재 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 이용한 리튬 이차 전지
WO2013038918A1 (fr) * 2011-09-12 2013-03-21 三洋電機株式会社 Matière active d'électrode positive destinée à une pile rechargeable à électrolyte non aqueux, et pile rechargeable à électrolyte non aqueux
JP2013107791A (ja) * 2011-11-21 2013-06-06 Sumitomo Chemical Co Ltd 複合金属酸化物の製造方法、複合金属酸化物、正極活物質、正極及び非水電解質二次電池
WO2013161619A1 (fr) * 2012-04-27 2013-10-31 三井金属鉱業株式会社 Oxyde de composé de métal de lithium à structure stratifiée
WO2016129361A1 (fr) * 2015-02-12 2016-08-18 Ｊｘ金属株式会社 Matériau actif d'électrode positive pour pile au lithium-ion, électrode positive pour pile au lithium-ion, pile au lithium-ion, et procédé de fabrication de matériau actif d'électrode positive pour pile au lithium-ion
WO2017169184A1 (fr) * 2016-03-30 2017-10-05 パナソニックＩｐマネジメント株式会社 Substance active d'électrode positive pour pile rechargeable à électrolyte non aqueux, et pile rechargeable à électrolyte non aqueux
JP2018045998A (ja) 2016-09-18 2018-03-22 貴州振華新材料有限公司 球形又は類球形リチウムイオン電池の正極材料、製造方法及び応用
WO2018110256A1 (fr) * 2016-12-14 2018-06-21 住友化学株式会社 Poudre d'oxyde composite de métal au lithium, matière active d'électrode positive pour batterie secondaire au lithium, électrode positive pour batterie secondaire au lithium, et batterie secondaire au lithium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HIRAMATSU, JOURNAL OF THE MINING AND METALLURGICAL INSTITUTE OF JAPAN, vol. 81, 1965

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115362133A (zh) * 2020-04-03 2022-11-18 株式会社田中化学研究所 复合氢氧化物的制备方法以及复合氢氧化物
CN112768685A (zh) * 2021-04-09 2021-05-07 湖南长远锂科股份有限公司 一种长循环、高功率的锂离子电池正极材料及其制备方法
CN116487525A (zh) * 2023-06-05 2023-07-25 中创新航科技集团股份有限公司 一种正极片、含有其的电池
CN116487525B (zh) * 2023-06-05 2024-02-02 中创新航科技集团股份有限公司 一种正极片、含有其的电池
CN116504922A (zh) * 2023-06-19 2023-07-28 蔚来电池科技(安徽)有限公司 正极极片、电化学装置和用电装置
CN116504922B (zh) * 2023-06-19 2023-09-22 蔚来电池科技(安徽)有限公司 正极极片、电化学装置和用电装置

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