WO2025242519A1 - Lithium-metal composite oxide, method for producing activated lithium-metal composite oxide, activated lithium-metal composite oxide powder, positive electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery - Google Patents

Lithium-metal composite oxide, method for producing activated lithium-metal composite oxide, activated lithium-metal composite oxide powder, positive electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery

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Publication number
WO2025242519A1
WO2025242519A1 PCT/EP2025/063329 EP2025063329W WO2025242519A1 WO 2025242519 A1 WO2025242519 A1 WO 2025242519A1 EP 2025063329 W EP2025063329 W EP 2025063329W WO 2025242519 A1 WO2025242519 A1 WO 2025242519A1
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lithium
composite oxide
metal composite
secondary battery
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PCT/EP2025/063329
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French (fr)
Inventor
Masataka Oyama
Ryo Sakamoto
Junji KASHIWAGI
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BASF SE
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BASF SE
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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
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • C01G53/502—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing lithium and cobalt
    • C01G53/504—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5
    • C01G53/506—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5 with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.8, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.8
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 disclosure relates to a lithium-metal composite oxide, a method for producing an activated lithium-metal composite oxide, an activated lithium-metal composite oxide powder, a positive electrode active material for a non-aqueous electrolyte secondary battery, and a nonaqueous electrolyte secondary battery.
  • lithium ion secondary batteries which contain materials such as lithium nickel oxide in positive electrodes and have advantages such as high charge/discharge capacity are often used.
  • Layered rock salt oxide type positive electrode active materials for lithium ion secondary batteries (basic composition: Li(NiM)02), which are solid solutions of nickel (Ni) and other transition metals M and which are extremely versatile, have been extensively researched as positive electrode active materials in such lithium ion secondary batteries.
  • tungsten in addition to cobalt (Co), manganese (Mn), magnesium (Mg), aluminum (Al), and the like, which have been widely used in the past, as transition metals, and attempts have been made to produce higher performance lithium ion secondary batteries by using such positive electrode active materials because electron conductivity is improved by causing tungsten to be present at particle surfaces and particle interfaces in a positive electrode active material.
  • JP 2014-197556 A discloses a method for producing a layered rock salt oxide type positive electrode active material by adding a tungsten compound either when mixing a lithium compound with a composite oxide or composite hydroxide comprising another transition metal compound or when mixing another transition metal compound with a lithium compound before a firing step for obtaining a positive electrode active material.
  • the purpose of the present disclosure is to provide: a method for producing an activated lithium-metal composite oxide that exhibits superior cycle characteristics and lower resistance when used as a positive electrode active material of a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery; and a lithium-metal composite oxide used in this production method.
  • an activated lithium- metal composite oxide obtained using a method for producing an activated lithium-metal composite oxide, the method including: a mixing step for obtaining a raw material mixture containing a lithium-metal composite oxide which is represented by the general formula LixNii-y.z-wCoyMn z M 1 wO2+a (in the formula, M 1 is one or more elements other than Li, Ni, Co, Mn and O, 0 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.4, 0 ⁇ z ⁇ 0.4, 0 ⁇ w ⁇ 0.1 , and -1.0 ⁇ a ⁇ 0.5) and which has a cumulative pore volume of 25 pL/g or more within a pore diameter range of 25 nm to 334 nm, as measured using mercury intrusion porosimetry and a compound that contains, independently of M 1 , one or more elements M 2 other than Li, Ni, Co, Mn and O
  • the present disclosure provides the followings.
  • a lithium-metal composite oxide which is represented by the general formula LixNii-y.z-wCoyMn z M 1 wO2+a (in the formula, M 1 is one or more elements other than Li, Ni, Co, Mn and O, 0 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.4, 0 ⁇ z ⁇ 0.4, 0 ⁇ w ⁇ 0.1 and -1.0 ⁇ a ⁇ 0.5) and which has a cumulative pore volume of 25 pL/g or more within a pore diameter range of 25 nm to 334 nm, as measured using mercury intrusion porosimetry.
  • a method for producing an activated lithium-metal composite oxide powder including: a mixing step for mixing at least the lithium-metal composite oxide according to (1) above and a compound that contains, independently of M 1 , one or more elements M 2 other than Li, Ni, Co, Mn and O to obtain a raw material mixture; and a firing step for firing the raw material mixture in an oxidizing atmosphere.
  • An activated lithium-metal composite oxide powder which is represented by the general formula Li x Nii.y. z .w-vCoyMn z M 1 wM 2 vO2+ a (in the formula, M 1 and M 2 are each independently one or more elements other than Li, Ni, Co, Mn and O, 0.9 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.4, 0 ⁇ z ⁇ 0.4, 0 ⁇ w ⁇ 0.1 , 0 ⁇ v ⁇ 0.1 and -1 ,0 ⁇ a ⁇ 0.5), and the ratio of the proportion of the total amount of M 2 relative to the total amount of Ni, Co and Mn in terms of mass in the center of a particle is 0.90 or more relative to the proportion of the total amount of M 2 relative to the total amount of Ni, Co and Mn in terms of mass at a position 1 pm from the surface.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery which contains the activated lithium-metal composite oxide powder according to (4) or (5) above.
  • a non-aqueous electrolyte secondary battery which comprises the positive electrode active material for a non-aqueous electrolyte secondary battery according to (7) above.
  • the present disclosure is capable of providing: a method for producing an activated lithium-metal composite oxide that exhibits superior cycle characteristics and lower resistance when used as a positive electrode active material of a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery; and a lithium-metal composite oxide as a precursor, which is used in this production method.
  • the present embodiment Embodiments of the present disclosure (hereinafter referred to as “the present embodiment”) will now be explained, but the present disclosure is in no way limited by statements in these embodiments, and the present disclosure can be carried out by adding appropriate modifications.
  • a lithium-metal composite oxide according to an embodiment of the present disclosure is represented by the general formula LixNii-y-z-wCoy n z 1 wO2+c.
  • M 1 is one or more elements other than Li, Ni, Co, Mn and O, 0 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.4, 0 ⁇ z ⁇ 0.4, 0 ⁇ w ⁇ 0.1 and -1.0 ⁇ a ⁇ 0.5
  • M 1 has a cumulative pore volume of 25 pL/g or more within a pore diameter range of 25 nm to 334 nm, as measured using mercury intrusion porosimetry.
  • An activated lithium-metal composite oxide obtained by firing this type of lithium-metal composite oxide using the method described below exhibits superior cycle characteristics and lower resistance when used as a positive electrode active material of a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery.
  • the chemical composition of the lithium-metal composite oxide is not particularly limited as long as this composition is represented by the general formula Li x Nii-y.z-wCoyMn z M 1 w O2+a (in the formula, M 1 is one or more elements other than Li, Ni, Co, Mn and O, 0 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.4, 0 ⁇ z ⁇ 0.4, 0 ⁇ w ⁇ 0.1 and -1.0 ⁇ a ⁇ 0.5).
  • the value of x is not particularly limited as long as this falls within the range 0 ⁇ x ⁇ 1.2, but may be, for example, 0.01 or more, 0.02 or more, 0.03 or more, 0.04 or more, 0.05 or more, 0.06 or more, 0.07 or more, 0.08 or more, 0.09 or more, 0.1 or more, 0.11 or more, 0.12 or more, 0.13 or more, 0.14 or more, 0.15 or more, 0.16 or more, 0.17 or more, 0.18 or more, 0.19 or more, 0.2 or more, 0.21 or more, 0.22 or more, 0.23 or more, 0.24 or more, 0.25 or more, 0.26 or more, 0.27 or more, 0.28 or more, 0.29 or more, 0.3 or more, 0.31 or more, 0.32 or more, 0.33 or more, 0.34 or more, 0.35 or more, 0.36 or more, 0.37 or more, 0.38 or more, 0.39 or more, 0.4 or more, 0.41 or more, 0.42 or more, 0.43 or more, 0.44 or more, 0.41 or
  • the value of x may be 1.2 or less, 1.195 or less, 1.19 or less, 1.185 or less, 1.18 or less, 1.175 or less, 1.17 or less, 1.165 or less, 1.16 or less, 1.155 or less, 1.15 or less, 1.145 or less, 1.14 or less, 1.135 or less, 1.13 or less, 1.125 or less, 1.12 or less, 1.115 or less, 1.11 or less, 1.105 or less, 1.10 or less, 1.095 or less, 1.09 or less, 1.085 or less, 1.08 or less, 1.075 or less, 1.07 or less, 1.065 or less, 1.06 or less, 1.055 or less, or 1.05 or less.
  • the value of y is not particularly limited as long as this falls within the range 0 ⁇ y ⁇ 0.4, but is, for example, preferably more than 0, 0.001 or more, 0.0015 or more, 0.002 or more, 0.0025 or more, 0.003 or more, 0.0035 or more, 0.004 or more, 0.0045 or more, 0.005 or more, 0.0055 or more, 0.006 or more, 0.0065 or more, 0.007 or more, 0.0075 or more, 0.008 or more, 0.0085 or more, 0.009 or more, 0.0095 or more, 0.01 or more, 0.015 or more, 0.02 or more, 0.025 or more, 0.03 or more, 0.035 or more, 0.04 or more, 0.045 or more, 0.05 or more, 0.055 or more, 0.06 or more, 0.065 or more, 0.07 or more, 0.075 or more, 0.08 or more, 0.085 or more, 0.09 or more, 0.095 or more, 0.1 or more, 0.102 or
  • 0.372 or less 0.367 or less, 0.365 or less, 0.362 or less, 0.36 or less, 0.357 or less, 0.355 or less, 0.352 or less, 0.35 or less, 0.347 or less, 0.345 or less, 0.342 or less, 0.34 or less, 0.337 or less,
  • 0.317 or less 0.315 or less, 0.312 or less, 0.31 or less, 0.307 or less, 0.305 or less, 0.302 or less, 0.3 or less, 0.297 or less, 0.295 or less, 0.292 or less, 0.29 or less, 0.287 or less, 0.285 or less, 0.282 or less, 0.28 or less, 0.277 or less, 0.275 or less, 0.272 or less, 0.27 or less, 0.267 or less,
  • 0.227 or less 0.225 or less, 0.222 or less, 0.22 or less, 0.217 or less, 0.215 or less, 0.212 or less, 0.21 or less, 0.207 or less, 0.205 or less, 0.202 or less, 0.2 or less, 0.197 or less, 0.195 or less,
  • the value of z is not particularly limited as long as this falls within the range 0 ⁇ z ⁇ 0.4, but is, for example, preferably more than 0, 0.001 or more, 0.0015 or more, 0.002 or more, 0.0025 or more, 0.003 or more, 0.0035 or more, 0.004 or more, 0.0045 or more,
  • the value of z is preferably 0.397 or less, 0.395 or less, 0.392 or less, 0.39 or less, 0.387 or less, 0.385 or less, 0.382 or less, 0.38 or less, 0.377 or less, 0.375 or less, 0.372 or less, 0.367 or less, 0.365 or less, 0.362 or less, 0.36 or less, 0.357 or less, 0.355 or less, 0.352 or less, 0.35 or less, 0.347 or less, 0.345 or less, 0.342 or less, 0.34 or less, 0.337 or less, 0.335 or less, 0.332 or less, 0.33 or less, 0.327 or less, 0.325 or less, 0.322 or less, 0.32 or less, 0.317 or less, 0.315 or less, 0.312 or less, 0.31 or less, 0.307 or less, 0.305 or less, 0.302 or less, 0.3 or less, 0.297 or less, 0.295 or less, 0.292 or less, 0.29 or less,
  • 0.0065 or less 0.006 or less, 0.0055 or less, 0.005 or less, 0.0045 or less, 0.004 or less, 0.0035 or less, 0.003 or less, 0.0025 or less, 0.002 or less, 0.0015 or less, or 0.001 or less.
  • the value of w is not particularly limited as long as this falls within the range 0 ⁇ w ⁇ 0.1, but is, for example, preferably 0.001 or more, 0.0012 or more, 0.0015 or more, 0.0017 or more, 0.002 or more, 0.0022 or more, 0.0025 or more, 0.0027 or more, 0.003 or more, 0.0032 or more, 0.0035 or more, 0.0037 or more, 0.004 or more, 0.0042 or more, 0.0045 or more, 0.0047 or more, 0.005 or more, 0.0052 or more, 0.0055 or more, 0.0057 or more, 0.006 or more, 0.0062 or more, 0.0065 or more, 0.0067 or more, 0.007 or more, 0.0072 or more, 0.0075 or more, 0.0077 or more, 0.008 or more, 0.0082 or more, 0.0085 or more, 0.0087 or more, 0.009 or more, 0.0092 or more, 0.0095 or more, 0.0097 or more, 0.01
  • the value of w is preferably 0.097 or less, 0.095 or less, 0.092 or less, 0.09 or less, 0.087 or less, 0.085 or less, 0.082 or less, 0.08 or less, 0.077 or less, 0.075 or less, 0.072 or less, 0.07 or less, 0.067 or less, 0.065 or less, 0.062 or less, 0.06 or less, 0.057 or less, 0.055 or less, 0.052 or less, 0.05 or less, 0.047 or less, 0.045 or less, 0.042 or less, 0.04 or less, 0.037 or less, 0.035 or less, 0.032 or less, 0.03 or less, 0.027 or less, 0.025 or less, 0.022 or less, 0.02 or less, 0.017 or less, 0.015 or less, 0.012 or less, 0.01 or less, 0.0097 or less, 0.0095 or less, 0.0092 or less, 0.009 or less, 0.0087 or less, 0.0085 or less, 0.00
  • the value of v is not particularly limited as long as this falls within the range 0 ⁇ v ⁇ 0.1 , but is, for example, preferably 0.001 or more, 0.0012 or more, 0.0015 or more, 0.0017 or more, 0.002 or more, 0.0022 or more, 0.0025 or more, 0.0027 or more, 0.003 or more, 0.0032 or more, 0.0035 or more, 0.0037 or more, 0.004 or more, 0.0042 or more, 0.0045 or more, 0.0047 or more, 0.005 or more, 0.0052 or more, 0.0055 or more, 0.0057 or more, 0.006 or more, 0.0062 or more, 0.0065 or more, 0.0067 or more, 0.007 or more, 0.0072 or more, 0.0075 or more, 0.0077 or more, 0.008 or more, 0.0082 or more, 0.0085 or more, 0.0087 or more, 0.009 or more, 0.0092 or more, 0.0095 or more, 0.0097 or more, 0.
  • the value of v is preferably 0.097 or less, 0.095 or less, 0.092 or less, 0.09 or less, 0.087 or less, 0.085 or less, 0.082 or less, 0.08 or less, 0.077 or less, 0.075 or less, 0.072 or less, 0.07 or less, 0.067 or less, 0.065 or less, 0.062 or less, 0.06 or less, 0.057 or less, 0.055 or less, 0.052 or less, 0.05 or less, 0.047 or less, 0.045 or less, 0.042 or less, 0.04 or less, 0.037 or less, 0.035 or less, 0.032 or less, 0.03 or less, 0.027 or less, 0.025 or less, 0.022 or less, 0.02 or less, 0.017 or less, 0.015 or less, 0.012 or less, 0.01 or less, 0.0097 or less, 0.0095 or less, 0.0092 or less, 0.009 or less, 0.0087 or less, 0.0085 or less, 0.00
  • the element M 1 is not particularly limited as long as this is one or more elements other than Li, Ni, Co, Mn and O, but can be, for example, Al, Mg, Zn, Nb, W, Mo, Sb, V, Cr, Ca, Fe, Ga, Sr, Y, Ru, In, Sn, Ta, Bi, Zr, B, or the like.
  • the value of a is not particularly limited as long as this falls within the range -1.0 ⁇ a ⁇ 0.5, but is, for example, preferably more than -1, -0.95 or more, -0.9 or more, - 0.85 or more, -0.8 or more, -0.75 or more, -0.7 or more, -0.65 or more, -0.6 or more, -0.5 or more, -0.45 or more, -0.4 or more, -0.35 or more, -0.30 or more, -0.25 or more, -0.2 or more, - 0.15 or more, -0.1 or more, -0.075 or more, -0.05 or more, -0.025 or more, -0.02 or more, -0.015 or more, -0.01 or more, -0.05 or more, 0 or more, 0.001 or more, 0.0015 or more, 0.002 or more, 0.0025 or more, 0.003 or more, 0.0035 or more, 0.004 or more, 0.0045 or more,
  • the value of a is preferably 0.497 or less, 0.495 or less, 0.492 or less, 0.49 or less, 0.487 or less, 0.485 or less, 0.482 or less, 0.48 or less, 0.477 or less, 0.475 or less, 0.472 or less, 0.467 or less, 0.465 or less, 0.462 or less, 0.46 or less, 0.457 or less, 0.455 or less, 0.452 or less,
  • 0.45 or less 0.45 or less, 0.447 or less, 0.445 or less, 0.442 or less, 0.44 or less, 0.437 or less, 0.435 or less, 0.432 or less, 0.43 or less, 0.427 or less, 0.425 or less, 0.422 or less, 0.42 or less, 0.417 or less, 0.415 or less, 0.412 or less, 0.41 or less, 0.407 or less, 0.405 or less, 0.402 or less, 0.4 or less, 0.397 or less, 0.395 or less, 0.392 or less, 0.39 or less, 0.387 or less, 0.385 or less,
  • 0.26 or less 0.26 or less, 0.257 or less, 0.255 or less, 0.252 or less, 0.25 or less, 0.247 or less, 0.245 or less, 0.242 or less, 0.24 or less, 0.237 or less, 0.235 or less, 0.232 or less, 0.23 or less, 0.227 or less, 0.225 or less, 0.222 or less, 0.22 or less, 0.217 or less, 0.215 or less, 0.212 or less,
  • 0.0065 or less 0.006 or less, 0.0055 or less, 0.005 or less, 0.0045 or less, 0.004 or less, 0.0035 or less, 0.003 or less, 0.0025 or less, 0.002 or less, 0.0015 or less, or 0.001 or less.
  • the cumulative pore volume within a pore diameter range of 25 nm to 334 nm is not particularly limited as long as this is 25 pL/g or more, but may be, for example, 25.5 pL/g or more, 26 or more, 30 pL/g or more, 35 pL/g or more, 40 pL/g or more, 45 pL/g or more, 50 pL/g or more, or 55 pL/g or more.
  • the cumulative pore volume within a pore diameter range of 25 nm to 334 nm may be 150 pL/g or less, 120 pL/g or less, 100 pL/g or less, 90 pL/g or less, 80 pL/g or less, or 70 pL/g or less.
  • a method for measuring the cumulative pore volume of within a pore diameter range of 25 nm to 334 nm is in line with a method shown in the Examples section below.
  • An activated lithium-metal composite oxide powder according to the present embodiment is represented by the general formula LixNii-y-z- w - C0yMn z M 1 w M 2 vO2+a (in the formula, M 1 and M 2 are each independently one or more elements other than Li, Ni, Co, Mn and O, 0.9 ⁇ x ⁇ 1.2, 0 ⁇ y ⁇ 0.4, 0 ⁇ z ⁇ 0.4, 0 ⁇ w ⁇ 0.1 , 0 ⁇ v ⁇ 0.1 and -1.0 ⁇ a ⁇ 0.5), and the ratio of the proportion of the total amount of M 2 relative to the total amount of Ni, Co and Mn in terms of mass in the center of a particle is 0.90 or more relative to the proportion of the total amount of M 2 relative to the total amount of Ni, Co and Mn in terms of mass at a position 1 pm from the surface.
  • the proportion of the total amount of M 2 relative to the total amount of Ni, Co and Mn in terms of mass is expressed as total amount of M 2 /(total amount of Ni+total amount of Co+total amount of Mn).
  • this is also abbreviated to “proportion of M 2 ”.
  • the ratio of the proportion of M 2 in the center of a particle relative to the proportion of M 2 at a position 1 pm from the surface is not particularly limited as long as this is 0.90 or more, but is, for example, preferably 0.91 or more, 0.92 or more, 0.93 or more, 0.94 or more, or 0.95 or more.
  • the ratio of the proportion of M 2 in the center of a particle relative to the proportion of M 2 at a position 1 pm from the surface may be 5 or less, 3 or less, 2.5 or less, 2 or less, 1 .7 or less, 1 .5 or less, 1 .2 or less, or 1 . 1 or less. Note that the method for calculating the proportion of M 2 in the center of a particle relative to the proportion of M 2 at a position 1 pm from the surface is in line with a method shown in the Examples section below.
  • the element M 2 is not particularly limited as long as this is one or more elements other than Li, Ni, Co, Mn and O, but can be, for example, Al, Mg, Zn, Nb, W, Mo, Sb, V, Cr, Ca, Fe, Ga, Sr, Y, Ru, In, Sn, Ta, Bi, Zr, B, or the like. In one embodiment, it is preferable to use W as the element M 2 .
  • the activated lithium-metal composite oxide powder preferably includes a secondary particle for which the distance from the surface to the center of the particle is 10 pm or more.
  • the distance from the surface to the center of the particle means the shortest distance from each point on the surface (the outline of the particle) to the center (geometric center) of the particle when the activated lithium-metal composite oxide powder is observed using a scanning electron microscope.
  • a method for producing activated lithium-metal composite oxide includes: a mixing step for obtaining a raw material mixture of the lithium- metal composite oxide described above and a compound that contains, independently of M 1 , one or more elements M 2 other than Li, Ni, Co, Mn and O; and a firing step for firing the raw material mixture in an oxidizing atmosphere.
  • An activated lithium-metal composite oxide obtained in the manner described above exhibits superior cycle characteristics and lower resistance when used as a positive electrode active material of a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery.
  • the reason for this is currently unclear and is not necessarily limited to a specific theory, but the inventors of the present invention think that the reason is as follows.
  • the lithium-metal composite oxide described above is used in the method for producing an activated lithium-metal composite oxide according to the present embodiment, but this lithium-metal composite oxide has a cumulative pore volume of 25 pL/g or more within a pore diameter range of 25 nm to 334 nm.
  • An activated lithium-metal composite oxide having a large cumulative pore volume such as this takes in compounds containing the element M 2 from pores in the composite oxide, and these compounds easily reach the inner part of the particle. It is expected that the element M 2 achieves effects such as suppressing elution of transition metals at the surface of an active material during cycles, improving electron conductivity, lowering charge transfer resistance during lithium removal/insertion, and suppressing sintering of primary particles during firing, but because added elements penetrate sufficiently into the inner part of a secondary particle, these effects are exhibited as far as the inner part of a secondary particle, which is thought to lead to an improvement in cycle characteristics and a reduction in resistance.
  • the method for producing an activated lithium-metal composite oxide can include the following steps:
  • Precursor preparation step a precursor composite compound containing at least nickel is prepared.
  • Precursor mixing step a precursor mixture is prepared by mixing the precursor composite compound prepared in the precursor preparation step with a lithium compound.
  • Primary firing step if necessary, the precursor mixture prepared in the precursor mixing step is fired.
  • Mixing step at least the lithium-metal composite oxide obtained as a primary fired product in the primary firing step, a compound containing the element M 2 and, if necessary, a lithium compound are mixed.
  • Secondary firing step (this refers to the “firing step” mentioned above, this is referred to as a “secondary firing step” here for the sake of convenience in order to differentiate from the primary firing step): the raw material mixture prepared in the mixing step is fired.
  • the interior of the reaction tank is preferably purged with an inert gas or preferably nitrogen gas for industrial purposes, to create a nitrogen atmosphere in order to lower the oxygen concentration within the reaction tank system or in the solution. If the oxygen concentration is excessively high, there is a risk that the coprecipitated hydroxide will be overoxidized by any oxygen remaining over a predetermined amount, and a risk that the formation of agglomerates due to crystallization will be compromised.
  • nickel compounds that can be used include, but are not particularly limited to, one or more compounds selected from among nickel sulfate, nickel oxide, nickel hydroxide, nickel nitrate, nickel carbonate, nickel chloride, nickel iodide, metallic nickel, and the like.
  • cobalt compounds that can be used include, but are not particularly limited to, one or more compounds selected from among cobalt sulfate, cobalt oxide, cobalt hydroxide, cobalt nitrate, cobalt carbonate, cobalt chloride, cobalt iodide, metallic cobalt, and the like.
  • manganese compounds examples include, but are not particularly limited to, one or more compounds selected from among manganese sulfate, manganese oxide, manganese hydroxide, manganese nitrate, manganese carbonate, manganese chloride, manganese iodide, metallic manganese, and the like.
  • the element M 1 is not particularly limited as long as this is one or more elements other than Li, Ni, Co, Mn and O, but can be, for example, Al, Mg, Zn, Nb, W, Mo, Sb, V, Cr, Ca, Fe, Ga, Sr, Y, Ru, In, Sn, Ta, Bi, Zr, B, or the like. Specific examples of compounds containing the element M 1 will now be described.
  • titanium compounds examples include, but are not particularly limited to, one or more compounds selected from among titanyl sulfate, titanium oxide, titanium hydroxide, titanium nitrate, titanium carbonate, titanium chloride, titanium iodide, metallic titanium, and the like.
  • aluminum compounds examples include, but are not particularly limited to, aluminum sulfate, aluminum oxide, aluminum hydroxide, aluminum nitrate, aluminum carbonate, aluminum chloride, aluminum iodide, sodium aluminate, metallic aluminum, and the like.
  • iron compounds examples include, but are not particularly limited to, one or more compounds selected from among iron sulfate, iron oxide, iron hydroxide, iron nitrate, iron carbonate, iron chloride, iron iodide, metallic iron, and the like.
  • niobium compounds that can be used include, but are not particularly limited to, one or more compounds selected from among niobium oxide, niobium chloride, lithium niobate, niobium iodide, and the like.
  • tungsten compounds examples include, but are not particularly limited to, one or more compounds selected from among tungsten oxide, sodium tungstate, ammonium para-tungstate, hexacarbonyl tungsten, tungsten sulfide, and the like.
  • magnesium compounds examples include, but are not particularly limited to, one or more compounds selected from among magnesium sulfate, magnesium oxide, magnesium hydroxide, magnesium nitrate, magnesium carbonate, magnesium chloride, magnesium iodide, metallic magnesium, and the like.
  • zirconium compounds examples include, but are not particularly limited to, one or more compounds selected from among zirconium sulfate, zirconium oxide, zirconium nitrate, ammonium zirconium carbonate, zirconium chloride, zirconium iodide, metallic zirconium, and the like.
  • other elements examples include one or more selected from among sulfates, oxides, hydroxides, nitrates, carbonates, chlorides, iodides, metals, and the like.
  • the mixing proportions of these compounds should be adjusted so that the amounts of these elements are prescribed proportions.
  • An appropriate pH range for when the precursor composite compound is synthesized is not particularly limited, and can be determined so as to achieve a desired secondary particle size and coarseness/fineness, but the pH is generally within the range of approximately 10 to 13.
  • the precursor composite compound obtained by means of a wet reaction is preferably washed and then dried after being de-watered.
  • Washing the precursor composite compound makes it possible to wash out impurities such as sulfate radicals or carbonate radicals and sodium components that have been incorporated into aggregated particles or that have become stuck on the surface layer during the reaction.
  • Washing treatments that can be used for small amounts of impurities include a procedure in which Nutsche washing using a Buchner funnel is carried out, or a procedure in which a reacted suspension is pumped through a press filter, washed with water, and de-watered.
  • the washing treatment can be carried out using, for example, pure water, an aqueous solution of sodium hydroxide, an aqueous solution of sodium carbonate, or the like, but use of pure water is industrially preferable.
  • a sodium hydroxide aqueous solution in which the pH is controlled according to the amount that remains may be used.
  • a precursor mixture is prepared by mixing the thus obtained precursor composite compound and a lithium compound at prescribed proportions.
  • the mixing may be solvent-based mixing in which the precursor composite compound and the lithium compound are in the form of solutions such as aqueous solutions and these solutions are mixed at prescribed proportions, or non-solvent-based mixing in which a powder of the precursor composite compound and a powder of the lithium compound are weighed out at prescribed proportions and dry mixed.
  • the lithium compound is not particularly limited, and a variety of lithium salts can be used.
  • Specific examples of lithium compounds that can be used include one or more compounds selected from among anhydrous lithium hydroxide, lithium hydroxide hydrate, lithium nitrate, lithium carbonate, lithium acetate, lithium bromide, lithium chloride, lithium citrate, lithium fluoride, lithium iodide, lithium lactate, lithium oxalate, lithium phosphate, lithium pyruvate, lithium sulfate, lithium oxide, and the like. Of these, it is preferable to use one or more compounds selected from among anhydrous lithium hydroxide and lithium hydroxide hydrate.
  • the blending proportions of the lithium compound and the precursor composite compound are not particularly limited, but in view of the composition of the target lithium-metal composite oxide, the amount of lithium and the total amount of the other elements should be adjusted, as appropriate, to achieve a prescribed ratio.
  • a lithium-metal composite oxide having a cumulative pore volume of 25 L/g or more within a pore diameter range of 25 nm to 334 nm is used, but this cumulative pore volume can be adjusted by altering the primary firing temperature. Therefore, it is preferable to carry out primary firing in order to obtain a lithium-metal composite oxide having a cumulative pore volume of 25 L/g or more within a pore diameter range of 25 nm to 334 nm.
  • the primary firing step is not an essential step.
  • the secondary firing step described later is generally carried out by weighing out the lithium compound, the precursor compound and, if necessary, compounds of other elements, mixing with a mixer to obtain a mixed powder, and loading the mixed powder in a container such as a crucible or a sagger, but as the bottom of the container loaded with the mixed powder is approached in a lithiation reaction in particular, discharge of produced gas to the outside and diffusion of the required oxygen concentration become more difficult. As a result, it is difficult to control reaction homogeneity and primary particle size. It is preferable to carry out primary firing from these perspectives also.
  • a firing means for promoting a lithiation reaction in particular.
  • a specific example thereof is a method comprising enabling heat to be applied to the precursor mixture more easily, enabling gas generated by the lithium compound to be easily discharged, and allowing gas having a high oxygen partial pressure to diffuse into the precursor mixture (into particles). For example, by firing a smaller amount of the precursor mixture, it is possible to achieve desired characteristics.
  • the primary firing step it is possible to load the precursor mixture in a sagger or a crucible and fire the precursor mixture in a static furnace, a roller hearth kiln or a pusher furnace in order to subject the precursor mixture to primary firing, but it is preferable to carry out the firing while the precursor mixture is flowing, and in such a case, it is possible to use a rotary kiln as a firing device.
  • the primary firing temperature is not particularly limited, but is, for example, preferably 350°C or higher, 360°C or higher, 370°C or higher, 380°C or higher, or 390°C or higher. Meanwhile, the primary firing temperature is preferably 650°C or lower, 640°C or lower, 630°C or lower, 620°C or lower, or 610°C or lower. Note that in a case where the cumulative pore volume is to be controlled in particular, the cumulative pore volume can be controlled by altering the chemical compositions and surface states of the precursor composite compound and the lithium compound, the pore condition, the particle size, and so on, and the primary firing temperature can be lower than 350°C or higher than 650°C.
  • the duration of the primary firing is not particularly limited as long as a lithiation reaction can progress reliably and uniformly, but is, for example, preferably 1-10 hours or 2-8 hours.
  • the firing temperature in the present disclosure is the maximum temperature when an object-to-be-heated is heated.
  • the maximum temperature means the temperature of a part having the highest temperature in the object-to-be-heated.
  • the firing duration is the duration for which the firing temperature is maintained after the temperature reaches a prescribed range.
  • the primary firing atmosphere is not particularly limited, and may be an oxidizing atmosphere in which a lithiation reaction can progress reliably and uniformly.
  • a decarburized oxidizing gas atmosphere having a carbon dioxide gas concentration of 30 ppm or less, or an oxygen atmosphere having an oxygen concentration of 80 vol% or more, 85 vol% or more, 90 vol% or more, or 95 vol% or more.
  • Secondary firing is carried out in a subsequent step in order to effect crystal growth or particle growth at a higher temperature in a fired product obtained by carrying out primary firing in this way and for the element M 2 to penetrate throughout the lithium-metal composite oxide.
  • a powder may be formed by using a grinder, a mortar, or the like.
  • At least a lithium-metal composite oxide, a compound containing the element M 2 and, if necessary, a lithium compound are added and mixed.
  • the added quantities of the compounds and the addition method may be similar to those described in the precursor preparation step.
  • the compound containing the element M 2 may be similar to the compound containing the element M 1 described in the precursor preparation step.
  • the element M 1 and the element M 2 may be the same as, or different from, each other.
  • the element M 2 is not particularly limited as long as this is one or more elements other than Li, Ni, Co, Mn and O, but can be, for example, Al, Mg, Zn, Nb, W, Mo, Sb, V, Cr, Ca, Fe, Ga, Sr, Y, Ru, In, Sn, Ta, Bi, Zr, B, or the like.
  • compounds containing the element M 2 can be one or more types of compound selected from among sulfates, oxides, hydroxides, nitrates, carbonates, chlorides, iodides, metals, and the like.
  • a lithium compound may, if necessary, be added in the mixing step, in a case where, for example, lithium is used in the raw material mixing step at a quantity that is less than in the target lithium-metal composite oxide.
  • the lithium compound is not particularly limited, and it is possible to use a lithium salt that is similar to the lithium salts able to be used in the raw material mixing step.
  • Specific examples of lithium compounds that can be used include one or more compounds selected from among anhydrous lithium hydroxide, lithium hydroxide hydrate, lithium nitrate, lithium carbonate, lithium acetate, lithium bromide, lithium chloride, lithium citrate, lithium fluoride, lithium iodide, lithium lactate, lithium oxalate, lithium phosphate, lithium pyruvate, lithium sulfate, lithium oxide, and the like. Of these, it is preferable to use one or more compounds selected from among anhydrous lithium hydroxide and lithium hydroxide hydrate. Note that it is not necessary to use the same lithium compound as that used in the raw material mixing step.
  • the lithium-metal composite oxide contained in the raw material mixture undergoes a lithiation reaction and crystal growth, but of these, the lithiation reaction requires a certain oxygen partial pressure.
  • An activated lithium-metal composite oxide containing lithium is obtained from the lithiation reaction.
  • crystal growth is promoted by increasing the temperature to a prescribed temperature.
  • the secondary firing temperature is not particularly limited as long as this is higher than the primary firing temperature, and can be adjusted according to the composition of the activated lithium-metal composite oxide to be obtained, and so on.
  • the firing temperature is preferably 700°C or higher, 710°C or higher, 720°C or higher, 730°C or higher, 740°C or higher, or 750°C or higher.
  • the secondary firing temperature is preferably 1100°C or lower, 1070°C or lower, 1050°C or lower, 1020°C or lower, 1000°C or lower, 970°C or lower, 950°C or lower, 920°C or lower, 900°C or lower, 870°C or lower, 850°C or lower, 820°C or lower, or 800°C or lower.
  • the secondary firing temperature falls within the prescribed range, it is possible to obtain an activated lithium-metal composite oxide having a desired crystal structure.
  • the secondary firing duration is not particularly limited, and should be a duration sufficient for an activated lithium-metal composite oxide having a desired crystal structure to be formed. This duration is, for example, preferably 1-15 hours, 2-12 hours, or 2-10 hours.
  • the secondary firing atmosphere is not particularly limited, but should be an atmosphere having an oxygen partial pressure whereby crystal growth occurs reliably and uniformly and a transition metal contained in the raw material mixture to be fired is not reduced, and is preferably an atmosphere having a low moisture content and carbon dioxide gas concentration.
  • a decarburized oxidizing gas atmosphere having a carbon dioxide gas concentration of 30 ppm or less, or an oxygen atmosphere having an oxygen concentration of preferably 80 vol% or more, or 90 vol% or more.
  • the activated lithium-metal composite oxide obtained in the secondary firing step can contain, as impurities, unreacted lithium compounds and lithium compounds that appear in a particle surface layer from the crystal structure during the primary and secondary firing steps.
  • Water washing and heat treatment can therefore be performed, for example, in order to remove or minimize such impurities. Note that the water washing step is not an essential feature.
  • the elemental compound added for the surface treatment noted above may be selected, for example, from among aluminum compounds, boron compounds, tungsten compounds, manganese compounds, cobalt compounds, phosphorus compounds, niobium compounds, strontium compounds, antimony compounds, zirconium compounds, titanium compounds, and the like, and one or more of these compounds may be used.
  • the heat treatment temperature is not particularly limited, but is, for example, preferably 200°C or higher, 210°C or higher, 220°C or higher, 230°C or higher, 240°C or higher, or 250°C or higher. Meanwhile, the heat treatment temperature is preferably 500°C or lower, 490°C or lower, 480°C or lower, 470°C or lower, 460°C or lower, 450°C or lower, 440°C or lower, 430°C or lower, 420°C or lower, 410°C or lower, or 400°C or lower.
  • the heat treatment duration is not particularly limited, but is, for example, preferably 1-15 hours, 2-12 hours, or 2-10 hours.
  • a non-aqueous electrolyte secondary battery is provided with a positive electrode that contains the activated lithium-metal composite oxide powder described above as a positive electrode active material for a nonaqueous electrolyte secondary battery, and the non-aqueous electrolyte secondary battery is constituted from the positive electrode, a negative electrode and an electrolyte solution containing an electrolyte.
  • an electrically conductive agent and a binder are added to, and mixed with, the activated lithium-metal composite oxide powder according to an embodiment of the present disclosure.
  • the electrically conductive agent is, for example, preferably acetylene black, carbon black, graphite, or the like.
  • the binder is, for example, preferably polytetrafluoroethylene, poly(vinylidene fluoride), or the like.
  • the negative electrode is not particularly limited, but can be, for example, not only a negative electrode active material such as lithium metal, graphite or a low crystallinity carbon material, but also one or more non-metallic or metallic elements selected from among Si, Al, Sn, Pb, Zn, Bi and Cd, alloys containing these, and chalcogen compounds containing these.
  • a negative electrode active material such as lithium metal, graphite or a low crystallinity carbon material
  • non-metallic or metallic elements selected from among Si, Al, Sn, Pb, Zn, Bi and Cd, alloys containing these, and chalcogen compounds containing these.
  • the solvent in the electrolyte solution is not particularly limited, but can be, for example, an organic solvent including one or more types selected from among carbonates, such as ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate, and ethers such as dimethoxyethane.
  • organic solvent including one or more types selected from among carbonates, such as ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate, and ethers such as dimethoxyethane.
  • the electrolyte can be one or more types selected from among lithium salts such as lithium perchlorate and lithium tetrafluoroborate, in addition to lithium hexafluorophosphate (LiPF s ) in particular, dissolved in a solvent.
  • lithium salts such as lithium perchlorate and lithium tetrafluoroborate
  • LiPF s lithium hexafluorophosphate
  • a mixed aqueous solution was obtained by mixing an aqueous solution of nickel sulfate and an aqueous solution of manganese sulfate at an Ni:Mn ratio (molar ratio) of 90:10.
  • 300 g of an aqueous solution of sodium hydroxide and 500 g of aqueous ammonia added to 10 L of pure water was prepared in advance as a base liquid in a reaction tank, a nitrogen atmosphere was created in the reaction tank using nitrogen gas at a flow rate of 0.7 L/min, and a reaction was carried out in the nitrogen atmosphere.
  • a coaxial nozzle having a double-pipe structure comprising an internal pipe was installed inside the reaction tank, and the raw material introduction nozzle (internal pipe) for introducing the solution obtained by mixing nickel sulfate and manganese sulfate was lengthened so that a distance (nozzle introduction port distance) between the introduction port of the raw material introduction nozzle and the introduction port of the alkali introduction nozzle for introducing the sodium hydroxide aqueous solution and ammonia water was 1 mm, and the raw material was continuously added into the reaction base liquid.
  • a reaction slurry was sampled as appropriate from an overflow pipe disposed in the upper part of the reaction tank, and when it was confirmed that the pH of the reaction had stabilized at 10.8, the slurry was recovered.
  • the slurry was subjected to solid-liquid separation and then washed with pure water to reduce the amount of residual impurities, after which the cake-like coprecipitate was dried for 10 hours at 100°C in an air environment to obtain a precursor composite compound 1 represented by the compositional formula Nio.9oMno.io(OH) 2 .
  • the precursor composite compound 1 and lithium hydroxide were weighed out and mixed at an Li/(Ni+M n) ratio of 1.040.
  • a lithium-metal composite oxide was obtained by carrying out primary firing for 6 hours at 400°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • lithium-metal composite oxide and tungsten (VI) oxide were weighed out and mixed at a W/(Ni+Mn) ratio of 0.5 mol%, and the obtained mixture was subjected to secondary firing for 6 hours at 800°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • a sample of an activated lithium-metal composite oxide powder of Example 1 was obtained by pulverizing the obtained fired product.
  • Example 2 A sample of an activated lithium-metal composite oxide powder of Example 2 was obtained in the same way as Example 1 , except that the primary firing was carried out at 500°C.
  • Example 3 A sample of an activated lithium-metal composite oxide powder of Example 3 was obtained in the same way as Example 1 , except that the primary firing was carried out at 600°C.
  • Example 1 A sample of an activated lithium-metal composite oxide powder of Comparative Example 1 was obtained in the same way as Example 1 , except that the primary firing was carried out at 700°C.
  • a sample of an activated lithium-metal composite oxide powder of Comparative Example 2 was obtained in the same way as Example 1 , except that the primary firing was carried out at 800°C.
  • the precursor composite compound, lithium hydroxide and tungsten (VI) oxide were weighed out and mixed at an Li/(Ni+Mn) ratio of 1.040 and a W/(Ni+Mn) ratio of 0.5 mol%.
  • a lithium-metal composite oxide was obtained by carrying out primary firing for 6 hours at 570°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • lithium-metal composite oxide was subjected to secondary firing for 6 hours at 800°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • a sample of an activated lithium-metal composite oxide powder of Comparative Example 3 was obtained by pulverizing the obtained fired product.
  • a mixed aqueous solution was obtained by mixing an aqueous solution of nickel sulfate, an aqueous solution of cobalt sulfate and an aqueous solution of manganese sulfate at an Ni:Co:Mn ratio (molar ratio) of 90:5:5.
  • 300 g of an aqueous solution of sodium hydroxide and 500 g of aqueous ammonia added to 10 L of pure water was prepared in advance as a base liquid in a reaction tank, a nitrogen atmosphere was created in the reaction tank using nitrogen gas at a flow rate of 0.7 L/min, and a reaction was carried out in the nitrogen atmosphere.
  • a coaxial nozzle having a double-pipe structure comprising an internal pipe was installed inside the reaction tank, and the raw material introduction nozzle (internal pipe) for introducing the solution obtained by mixing nickel sulfate and manganese sulfate was lengthened so that a distance (nozzle introduction port distance) between the introduction port of the raw material introduction nozzle and the introduction port of the alkali introduction nozzle for introducing the sodium hydroxide aqueous solution and ammonia water was 15 mm, and the raw material was continuously added into the reaction base liquid.
  • a reaction slurry was sampled as appropriate from an overflow pipe disposed in the upper part of the reaction tank, and when it was confirmed that the pH of the reaction had stabilized at 11.4, the slurry was recovered.
  • the slurry was subjected to solid-liquid separation and then washed with pure water to reduce the amount of residual impurities, after which the cake-like coprecipitate was dried for 10 hours at 100°C in an air environment to obtain a precursor composite compound 2 represented by the compositional formula Nio.9oCoooslVlnoo5(OH)2.
  • the precursor composite compound 2 and lithium hydroxide were weighed out and mixed at an Li/(Ni+Co+Mn) ratio of 1 .040.
  • a lithium-metal composite oxide was obtained by carrying out primary firing for 6 hours at 400°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • the obtained lithium-metal composite oxide after the primary firing and tungsten (VI) oxide were weighed out and mixed at a W/(Ni+Mn) ratio of 0.5 mol%, and the obtained mixture was subjected to secondary firing for 6 hours at 800°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • a sample of an activated lithium-metal composite oxide of Example 4 was obtained by pulverizing the obtained fired product.
  • a sample of an activated lithium-metal composite oxide powder of Example 5 was obtained in the same way as Example 4, except that the primary firing was carried out at 500°C.
  • a sample of an activated lithium-metal composite oxide powder of Comparative Example 4 was obtained in the same way as Example 4, except that the primary firing was carried out at 600°C.
  • a sample of an activated lithium-metal composite oxide powder of Comparative Example 5 was obtained in the same way as Example 4, except that the primary firing was carried out at 700°C.
  • a sample of an activated lithium-metal composite oxide powder of Comparative Example 6 was obtained in the same way as Example 4, except that the primary firing was carried out at 800°C.
  • the precursor composite compound 2, lithium hydroxide and tungsten (VI) oxide were weighed out and mixed at an Li/(Ni+Co+Mn) ratio of 1.040 and a W/(Ni+Co+Mn) ratio of 0.5 mol%.
  • a lithium-metal composite oxide was obtained by carrying out primary firing for 6 hours at 570°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • lithium-metal composite oxide was subjected to secondary firing for 6 hours at 800°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • a sample of an activated lithium-metal composite oxide powder of Comparative Example 7 was obtained by pulverizing the obtained fired product.
  • a lithium-metal composite oxide was obtained in the same way as Example 3. This lithium-metal composite oxide and aluminum hydroxide were weighed out and mixed at an AI/(Ni+Mn) ratio of 1.0 mol%, and the obtained mixture was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide powder of Example 6 was obtained by pulverizing the obtained fired product.
  • the precursor composite compound 1 , lithium hydroxide and aluminum hydroxide were weighed out and mixed at an Li/(Ni+Mn) ratio of 1.040 and an AI/(Ni+Mn) ratio of 1.0 mol%.
  • a lithium-metal composite oxide of Comparative Example 8 was obtained by carrying out primary firing for 6 hours at 600°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • the obtained lithium-metal composite oxide after the primary firing was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • a sample of an activated lithium-metal composite oxide powder of Comparative Example 8 was obtained by pulverizing the obtained fired product.
  • a lithium-metal composite oxide was obtained in the same way as Example 3. This lithium-metal composite oxide after the primary firing and titanium oxide were weighed out and mixed at a Ti/(Ni+M n) ratio of 1.0 mol%, and the obtained mixture was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide powder of Example 7 was obtained by pulverizing the obtained fired product.
  • the precursor composite compound 1 , lithium hydroxide and titanium oxide were weighed out and mixed at an Li/(Ni+Mn) ratio of 1.040 and a Ti/(Ni+Mn) ratio of 1.0 mol%.
  • a lithium- metal composite oxide of Comparative Example 9 was obtained by carrying out primary firing for 6 hours at 600°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • the obtained lithium-metal composite oxide was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • a sample of an activated lithium-metal composite oxide powder of Comparative Example 9 was obtained by pulverizing the obtained fired product.
  • a sample of a lithium-metal composite oxide was obtained in the same way as Example 3. Next, the obtained lithium-metal composite oxide and niobium (V) oxide were weighed out and mixed at an Nb/(Ni+Mn) ratio of 0.2 mol%, and the obtained mixture was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • a sample of an activated lithium-metal composite oxide powder of Example 8 was obtained by pulverizing the obtained fired product.
  • the precursor composite compound 1 , lithium hydroxide and niobium (V) oxide were weighed out and mixed at an Li/(N i+M n) ratio of 1.040 and an Nb/(Ni+Mn) ratio of 0.2 mol%.
  • a lithium-metal composite oxide of Comparative Example 10 was obtained by carrying out primary firing for 6 hours at 600°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • lithium-metal composite oxide was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • a sample of an activated lithium-metal composite oxide powder of Comparative Example 10 was obtained by pulverizing the obtained fired product.
  • a lithium-metal composite oxide was obtained in the same way as Example 3. Next, the obtained lithium-metal composite oxide and zirconium oxide were weighed out and mixed at a Zr/(Ni+Mn) ratio of 1.0 mol%, and the obtained mixture was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide powder of Example 9 was obtained by pulverizing the obtained fired product.
  • the precursor composite compound 1 , lithium hydroxide and zirconium oxide were weighed out and mixed at an Li/(Ni+Mn) ratio of 1.040 and a Zr/(Ni+Mn) ratio of 1.0 mol%.
  • a lithium- metal composite oxide of Comparative Example 11 was obtained by carrying out primary firing for 6 hours at 600°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • lithium-metal composite oxide was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
  • a sample of an activated lithium-metal composite oxide powder of Comparative Example 11 was obtained by pulverizing the obtained fired product.
  • composition of the precursor composite compound was determined using the following method. 0.2 g of a sample was heated and dissolved in 25 m Lof a 20% hydrochloric acid solution, cooled, and transferred to a 100 mL volumetric flask, and pure water was added to produce a preparation liquid. The obtained preparation liquid was subjected to elemental quantification using ICP-AES (Optima 8300 produced by PerkinElmer Japan).
  • the cumulative pore volume of pores having diameters of 25-336 nm was determined for the precursor composite compound and the lithium-metal composite oxide following primary firing.
  • the pore diameter was calculated using the Washburn equation.
  • Measurement device AutoPore V9620 (produced by Micromeritics)
  • a 2032 type coin cell obtained using positive electrode active material particles was produced using a positive electrode, a negative electrode and an electrolyte solution which were produced using the following methods.
  • Positive electrode Using acetylene black and graphite at a weight ratio of 1:1 as an electrically conductive agent and poly(vinylidene fluoride) as a binder, a positive electrode active material, the electrically conductive agent and the binder were blended at a weight ratio of 90:6:4, and these were mixed with N-methylpyrrolidone and coated on an aluminum foil. A sheet was produced by drying the coated aluminum foil at 110°C, and the sheet was punched out at a diameter of 15mm ⁇ P, and rolled at a pressure of 3 t/cm 2 to obtain a positive electrode.
  • Negative electrode A lithium foil having a thickness of 500 pm was punched out at a diameter of 16 mmcp and used as a negative electrode.
  • Electrolyte solution A mixed solvent of EC and DMC was prepared at an EC:DMC volume ratio of 1:2, and a solution obtained by mixing an electrolyte with 1 mol/L of LiPFs was used as an electrolyte solution.
  • the coin cell produced using the method described above was subjected to constant current charging up to a voltage of 4.3 V at a current density of 0.1 C in an environment at a temperature of 25°C, and when the voltage reached 4.3 V, the coin cell was subjected to constant voltage charging until a rate of 0.01 C was reached. The coin cell was allowed to rest for 5 minutes, and then subjected to constant current discharging in the same environment at a current density of 0.1 C to a voltage of 3.0 V.
  • the coin cell was allowed to rest for a further 5 minutes and then subjected to constant current charging in the same environment up to a voltage of 4.3 V at a current density of 0.1 C, and when the voltage reached 4.3 V, the coin cell was subjected to constant voltage charging until a rate of 0.01 C was reached, and then allowed to rest for 5 minutes.
  • impedance measurements were carried out under the following conditions, and reactive resistance was calculated.
  • Impedance measurement devices Solartron 1400 & FRA 1470, produced by Solartron
  • a coin cell produced using the method described above was subjected to a cycle test.
  • the coin cell was subjected to constant current charging up to a voltage of 4.3 V at a current density of 0.2 C in an environment at a temperature of 60°C, and when the voltage reached 4.3 V, the coin cell was subjected to constant voltage charging until a rate of 0.01 C was reached. The coin cell was then allowed to rest for 5 minutes, and then subjected to constant current discharging in the same environment at a current density of 0.2 C from a voltage of 4.3 V to a voltage of 3.0 V.
  • the coin cell was allowed to rest for 5 minutes and then subjected to constant current charging in the same environment up to a voltage of 4.3 V at a current density of 0.1 C, and when the voltage reached 4.3 V, the coin cell was subjected to constant voltage charging until a rate of 0.01 C was reached, and then allowed to rest for 5 minutes.
  • the coin cell was subjected to constant current charging up to a voltage of 4.3 V at a current density of 0.5 C in an environment at a temperature of 60°C, and when the voltage reached 4.3 V, the coin cell was subjected to constant voltage charging until a rate of 0.01 C was reached, allowed to rest for 5 minutes, then subjected to constant current discharging in the same environment at a current density of 1 .0 C until a voltage of 3.0 V was reached, and then allowed to rest for 5 minutes, and this procedure was repeated 100 times.
  • cycle characteristics were calculated on the basis of the following formula.
  • Cycle characteristics (%) [(discharge capacity for 100 th cycle)/(discharge capacity for first cycle)] x 1OO(%)
  • the uniformity of an added element M 2 in secondary particles in a positive electrode active material sample was evaluated in the following way.
  • a cross-section of a secondary particle was produced using a cross-section polisher (SM-09010) produced by JEOL Ltd. at an accelerating voltage of 6 kV.
  • the SEM-EDX measurements described above were carried out on 100 secondary particles having lengths of 20 pm or more, the average of 100 values for added element M 2 /(Ni+Co+Mn) at a distance of 1 pm from the top surface of the secondary particle was calculated as A for the value of added element M 2 /(Ni+Co+Mn) at the secondary particle surface, and the average of 100 values for added element M 2 /(Ni+Co+Mn) at the furthest point from the top surface of the secondary particle was calculated as B for the value of added element M 2 /(Ni+Co+Mn) at the secondary particle center.
  • Examples 4-9 and Comparative Examples 4-11 were evaluated in the manner described above. The results are shown in Table 2. Note that B/A values are not shown in the tables, but the activated lithium-metal composite oxides of Examples 4-9 satisfied a B/A value of 0.9 or more, and Comparative Examples 4-11 had B/A values of less than 0.90.

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Abstract

This invention provides a method for producing an activated lithium-metal composite oxide that exhibits superior cycle characteristics and lower resistance when used as a positive electrode active material of a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery; and a lithium-metal composite oxide used in this production method, represented by the general formula LixNi1-y-z-wCoyMnzM1 wO2+α (in the formula, M1 is one or more elements other than Li, Ni, Co, Mn and O, 0<x≤1.2, 0≤y≤0.4, 0≤z≤0.4, 0≤w≤0.1 and -1.0≤α≤0.5), and has a cumulative pore volume of 25 μL/g or more within a pore diameter range of 25 nm to 334 nm, as measured using mercury intrusion porosimetry.

Description

LITHIUM-METAL COMPOSITE OXIDE, METHOD FOR PRODUCING ACTIVATED LITHIUM- METAL COMPOSITE OXIDE, ACTIVATED LITHIUM-METAL COMPOSITE OXIDE POWDER, POSITIVE ELECTRODE ACTIVE MATERIAL FOR NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY, AND NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY
TECHNICAL FIELD
The present disclosure relates to a lithium-metal composite oxide, a method for producing an activated lithium-metal composite oxide, an activated lithium-metal composite oxide powder, a positive electrode active material for a non-aqueous electrolyte secondary battery, and a nonaqueous electrolyte secondary battery.
BACKGROUND
In recent years, the use of portable, cordless electronic devices such as cellphones and laptops has rapidly increased, and power sources for operating these devices include non-aqueous secondary batteries that are small and lightweight and have high energy density. Of these, lithium ion secondary batteries which contain materials such as lithium nickel oxide in positive electrodes and have advantages such as high charge/discharge capacity are often used.
Layered rock salt oxide type positive electrode active materials for lithium ion secondary batteries (basic composition: Li(NiM)02), which are solid solutions of nickel (Ni) and other transition metals M and which are extremely versatile, have been extensively researched as positive electrode active materials in such lithium ion secondary batteries.
Among these layered rock salt oxide type positive electrode active materials, attention has been focused on materials that contain, for example, tungsten (W) in addition to cobalt (Co), manganese (Mn), magnesium (Mg), aluminum (Al), and the like, which have been widely used in the past, as transition metals, and attempts have been made to produce higher performance lithium ion secondary batteries by using such positive electrode active materials because electron conductivity is improved by causing tungsten to be present at particle surfaces and particle interfaces in a positive electrode active material.
For example, JP 2014-197556 A discloses a method for producing a layered rock salt oxide type positive electrode active material by adding a tungsten compound either when mixing a lithium compound with a composite oxide or composite hydroxide comprising another transition metal compound or when mixing another transition metal compound with a lithium compound before a firing step for obtaining a positive electrode active material.
SUMMARY OF THE INVENTION
In recent years, electric vehicles and hybrid vehicles have been developed and put into practical use out of concern for the global environment, and demand is increasing for lithium ion secondary batteries, which exhibit superior cycle characteristics and low resistance, for large scale applications. In view of the circumstances mentioned above, the purpose of the present disclosure is to provide: a method for producing an activated lithium-metal composite oxide that exhibits superior cycle characteristics and lower resistance when used as a positive electrode active material of a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery; and a lithium-metal composite oxide used in this production method.
The inventors of the present invention engaged in extensive research to solve the problems noted above. As a result, the inventors of the present invention discovered an activated lithium- metal composite oxide obtained using a method for producing an activated lithium-metal composite oxide, the method including: a mixing step for obtaining a raw material mixture containing a lithium-metal composite oxide which is represented by the general formula LixNii-y.z-wCoyMnzM1wO2+a (in the formula, M1 is one or more elements other than Li, Ni, Co, Mn and O, 0<x<1.2, 0<y<0.4, 0<z<0.4, 0<w<0.1 , and -1.0<a<0.5) and which has a cumulative pore volume of 25 pL/g or more within a pore diameter range of 25 nm to 334 nm, as measured using mercury intrusion porosimetry and a compound that contains, independently of M1, one or more elements M2 other than Li, Ni, Co, Mn and O; and a firing step for firing the raw material mixture in an oxidizing atmosphere, and found that a non-aqueous electrolyte secondary battery obtained using said activated lithium-metal composite oxide exhibits superior cycle characteristics and lower resistance.
Specifically, the present disclosure provides the followings.
(1) A lithium-metal composite oxide which is represented by the general formula LixNii-y.z-wCoyMnzM1wO2+a (in the formula, M1 is one or more elements other than Li, Ni, Co, Mn and O, 0<x<1.2, 0<y<0.4, 0<z<0.4, 0<w<0.1 and -1.0<a<0.5) and which has a cumulative pore volume of 25 pL/g or more within a pore diameter range of 25 nm to 334 nm, as measured using mercury intrusion porosimetry.
(2) A method for producing an activated lithium-metal composite oxide powder, the method including: a mixing step for mixing at least the lithium-metal composite oxide according to (1) above and a compound that contains, independently of M1, one or more elements M2 other than Li, Ni, Co, Mn and O to obtain a raw material mixture; and a firing step for firing the raw material mixture in an oxidizing atmosphere.
(3) The method for producing an activated lithium-metal composite oxide powder according to (2) above, wherein a lithium compound is also mixed in the mixing step.
(4) An activated lithium-metal composite oxide powder which is represented by the general formula LixNii.y.z.w-vCoyMnzM1wM2vO2+a (in the formula, M1 and M2 are each independently one or more elements other than Li, Ni, Co, Mn and O, 0.9<x<1.2, 0<y<0.4, 0<z<0.4, 0<w<0.1 , 0<v<0.1 and -1 ,0<a<0.5), and the ratio of the proportion of the total amount of M2 relative to the total amount of Ni, Co and Mn in terms of mass in the center of a particle is 0.90 or more relative to the proportion of the total amount of M2 relative to the total amount of Ni, Co and Mn in terms of mass at a position 1 pm from the surface.
(5) The activated lithium-metal composite oxide powder according to (4), wherein M2 is W. (6) The activated lithium-metal composite oxide powder according to (4) or (5) above, which includes a secondary particle for which the distance from the surface to the center of the particle is 10 pm or more.
(7) A positive electrode active material for a non-aqueous electrolyte secondary battery, which contains the activated lithium-metal composite oxide powder according to (4) or (5) above.
(8) A non-aqueous electrolyte secondary battery which comprises the positive electrode active material for a non-aqueous electrolyte secondary battery according to (7) above.
The present disclosure is capable of providing: a method for producing an activated lithium-metal composite oxide that exhibits superior cycle characteristics and lower resistance when used as a positive electrode active material of a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery; and a lithium-metal composite oxide as a precursor, which is used in this production method.
Embodiments of the present disclosure (hereinafter referred to as “the present embodiment”) will now be explained, but the present disclosure is in no way limited by statements in these embodiments, and the present disclosure can be carried out by adding appropriate modifications.
A lithium-metal composite oxide according to an embodiment of the present disclosure is represented by the general formula LixNii-y-z-wCoy nz 1wO2+c. (in the formula, M1 is one or more elements other than Li, Ni, Co, Mn and O, 0<x<1.2, 0<y<0.4, 0<z<0.4, 0<w<0.1 and -1.0<a<0.5) and has a cumulative pore volume of 25 pL/g or more within a pore diameter range of 25 nm to 334 nm, as measured using mercury intrusion porosimetry.
An activated lithium-metal composite oxide obtained by firing this type of lithium-metal composite oxide using the method described below exhibits superior cycle characteristics and lower resistance when used as a positive electrode active material of a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery.
The chemical composition of the lithium-metal composite oxide is not particularly limited as long as this composition is represented by the general formula LixNii-y.z-wCoyMnzM1 wO2+a (in the formula, M1 is one or more elements other than Li, Ni, Co, Mn and O, 0<x<1.2, 0<y<0.4, 0<z<0.4, 0<w<0.1 and -1.0<a<0.5).
In the general formula, the value of x is not particularly limited as long as this falls within the range 0<x<1.2, but may be, for example, 0.01 or more, 0.02 or more, 0.03 or more, 0.04 or more, 0.05 or more, 0.06 or more, 0.07 or more, 0.08 or more, 0.09 or more, 0.1 or more, 0.11 or more, 0.12 or more, 0.13 or more, 0.14 or more, 0.15 or more, 0.16 or more, 0.17 or more, 0.18 or more, 0.19 or more, 0.2 or more, 0.21 or more, 0.22 or more, 0.23 or more, 0.24 or more, 0.25 or more, 0.26 or more, 0.27 or more, 0.28 or more, 0.29 or more, 0.3 or more, 0.31 or more, 0.32 or more, 0.33 or more, 0.34 or more, 0.35 or more, 0.36 or more, 0.37 or more, 0.38 or more, 0.39 or more, 0.4 or more, 0.41 or more, 0.42 or more, 0.43 or more, 0.44 or more, 0.45 or more, 0.46 or more, 0.47 or more, 0.48 or more, 0.49 or more, 0.5 or more, 0.51 or more, 0.52 or more, 0.53 or more, 0.54 or more, 0.55 or more, 0.56 or more, 0.57 or more, 0.58 or more, 0.59 or more, 0.6 or more, 0.61 or more, 0.62 or more, 0.63 or more, 0.64 or more, 0.65 or more, 0.66 or more, 0.67 or more, 0.68 or more, 0.69 or more, 0.7 or more, 0.71 or more, 0.72 or more, 0.73 or more, 0.74 or more, 0.75 or more, 0.76 or more, 0.77 or more, 0.78 or more, 0.79 or more, 0.8 or more, 0.81 or more, 0.82 or more, 0.83 or more, 0.84 or more, 0.85 or more, 0.86 or more, 0.87 or more, 0.88 or more, 0.89 or more, 0.9 or more, 0.91 or more, 0.92 or more, 0.93 or more, 0.94 or more, 0.95 or more, or 0.96 or more. Meanwhile, the value of x may be 1.2 or less, 1.195 or less, 1.19 or less, 1.185 or less, 1.18 or less, 1.175 or less, 1.17 or less, 1.165 or less, 1.16 or less, 1.155 or less, 1.15 or less, 1.145 or less, 1.14 or less, 1.135 or less, 1.13 or less, 1.125 or less, 1.12 or less, 1.115 or less, 1.11 or less, 1.105 or less, 1.10 or less, 1.095 or less, 1.09 or less, 1.085 or less, 1.08 or less, 1.075 or less, 1.07 or less, 1.065 or less, 1.06 or less, 1.055 or less, or 1.05 or less.
In the general formula, the value of y is not particularly limited as long as this falls within the range 0<y<0.4, but is, for example, preferably more than 0, 0.001 or more, 0.0015 or more, 0.002 or more, 0.0025 or more, 0.003 or more, 0.0035 or more, 0.004 or more, 0.0045 or more, 0.005 or more, 0.0055 or more, 0.006 or more, 0.0065 or more, 0.007 or more, 0.0075 or more, 0.008 or more, 0.0085 or more, 0.009 or more, 0.0095 or more, 0.01 or more, 0.015 or more, 0.02 or more, 0.025 or more, 0.03 or more, 0.035 or more, 0.04 or more, 0.045 or more, 0.05 or more, 0.055 or more, 0.06 or more, 0.065 or more, 0.07 or more, 0.075 or more, 0.08 or more, 0.085 or more, 0.09 or more, 0.095 or more, 0.1 or more, 0.102 or more, 0.105 or more, 0.107 or more, 0.11 or more, 0.112 or more, 0.115 or more, 0.117 or more, 0.12 or more, 0.122 or more, 0.125 or more, 0.127 or more, 0.13 or more, 0.132 or more, 0.135 or more, 0.137 or more, 0.14 or more, 0.142 or more, 0.145 or more, 0.147 or more, 0.15 or more, 0.152 or more, 0.155 or more, 0.157 or more, 0.16 or more, 0.162 or more, 0.165 or more, 0.167 or more, 0.17 or more, 0.172 or more, 0.175 or more, 0.177 or more, 0.18 or more, 0.182 or more, 0.185 or more, 0.187 or more, 0.19 or more, 0.192 or more, 0.195 or more, 0.197 or more, 0.2 or more, 0.202 or more, 0.205 or more, 0.207 or more, 0.21 or more, 0.212 or more, 0.215 or more, 0.217 or more, 0.22 or more, 0.222 or more, 0.225 or more, 0.227 or more, 0.23 or more, 0.232 or more, 0.235 or more, 0.237 or more, 0.24 or more, 0.242 or more, 0.245 or more, 0.247 or more, 0.25 or more, 0.252 or more, 0.255 or more, 0.257 or more, 0.26 or more, 0.262 or more, 0.265 or more, 0.267 or more, 0.27 or more, 0.272 or more, 0.275 or more, 0.277 or more, 0.28 or more, 0.282 or more, 0.285 or more, 0.287 or more, 0.29 or more, 0.292 or more, 0.295 or more, 0.297 or more, 0.3 or more, 0.302 or more, 0.305 or more, 0.307 or more, 0.31 or more, 0.312 or more, 0.315 or more, 0.317 or more, 0.32 or more, 0.322 or more, 0.325 or more, 0.327 or more, 0.33 or more, 0.332 or more, 0.335 or more, 0.337 or more, 0.34 or more, 0.342 or more, 0.345 or more, 0.347 or more, 0.35 or more, 0.352 or more, 0.355 or more, 0.357 or more, 0.36 or more, 0.362 or more, 0.365 or more, 0.367 or more, 0.37 or more, 0.372 or more, 0.375 or more, 0.377 or more, 0.38 or more, 0.382 or more, 0.385 or more, 0.387 or more, 0.39 or more, 0.392 or more, 0.395 or more, or 0.397 or more. Meanwhile, the value of y is preferably 0.397 or less, 0.395 or less, 0.392 or less,
0.39 or less, 0.387 or less, 0.385 or less, 0.382 or less, 0.38 or less, 0.377 or less, 0.375 or less,
0.372 or less, 0.367 or less, 0.365 or less, 0.362 or less, 0.36 or less, 0.357 or less, 0.355 or less, 0.352 or less, 0.35 or less, 0.347 or less, 0.345 or less, 0.342 or less, 0.34 or less, 0.337 or less,
0.335 or less, 0.332 or less, 0.33 or less, 0.327 or less, 0.325 or less, 0.322 or less, 0.32 or less,
0.317 or less, 0.315 or less, 0.312 or less, 0.31 or less, 0.307 or less, 0.305 or less, 0.302 or less, 0.3 or less, 0.297 or less, 0.295 or less, 0.292 or less, 0.29 or less, 0.287 or less, 0.285 or less, 0.282 or less, 0.28 or less, 0.277 or less, 0.275 or less, 0.272 or less, 0.27 or less, 0.267 or less,
0.265 or less, 0.26 or less, 0.257 or less, 0.255 or less, 0.252 or less, 0.25 or less, 0.247 or less,
0.245 or less, 0.242 or less, 0.24 or less, 0.237 or less, 0.235 or less, 0.232 or less, 0.23 or less,
0.227 or less, 0.225 or less, 0.222 or less, 0.22 or less, 0.217 or less, 0.215 or less, 0.212 or less, 0.21 or less, 0.207 or less, 0.205 or less, 0.202 or less, 0.2 or less, 0.197 or less, 0.195 or less,
0.192 or less, 0.19 or less, 0.187 or less, 0.185 or less, 0.182 or less, 0.18 or less, 0.177 or less,
0.175 or less, 0.172 or less, 0.17 or less, 0.167 or less, 0.165 or less, 0.162 or less, 0.16 or less,
0.155 or less, 0.152 or less, 0.15 or less, 0.147 or less, 0.145 or less, 0.142 or less, 0.14 or less,
0.137 or less, 0.135 or less, 0.132 or less, 0.13 or less, 0.127 or less, 0.125 or less, 0.122 or less, 0.12 or less, 0.117 or less, 0.115 or less, 0.112 or less, 0.11 or less, 0.107 or less, 0.105 or less, 0.102 or less, 0.1 or less, 0.095 or less, 0.09 or less, 0.085 or less, 0.08 or less, 0.075 or less, 0.07 or less, 0.065 or less, 0.06 or less, 0.055 or less, 0.05 or less, 0.045 or less, 0.04 or less, 0.035 or less, 0.03 or less, 0.025 or less, 0.02 or less, 0.015 or less, 0.01 or less, 0.0095 or less, 0.009 or less, 0.0085 or less, 0.008 or less, 0.0075 or less, 0.007 or less, 0.0065 or less, 0.006 or less, 0.0055 or less, 0.005 or less, 0.0045 or less, 0.004 or less, 0.0035 or less, 0.003 or less, 0.0025 or less, 0.002 or less, 0.0015 or less, or 0.001 or less.
In the general formula, the value of z is not particularly limited as long as this falls within the range 0<z<0.4, but is, for example, preferably more than 0, 0.001 or more, 0.0015 or more, 0.002 or more, 0.0025 or more, 0.003 or more, 0.0035 or more, 0.004 or more, 0.0045 or more,
0.005 or more, 0.0055 or more, 0.006 or more, 0.0065 or more, 0.007 or more, 0.0075 or more,
0.008 or more, 0.0085 or more, 0.009 or more, 0.0095 or more, 0.01 or more, 0.015 or more,
0.02 or more, 0.025 or more, 0.03 or more, 0.035 or more, 0.04 or more, 0.045 or more, 0.05 or more, 0.055 or more, 0.06 or more, 0.065 or more, 0.07 or more, 0.075 or more, 0.08 or more, 0.085 or more, 0.09 or more, 0.095 or more, 0.1 or more, 0.102 or more, 0.105 or more, 0.107 or more, 0.11 or more, 0.112 or more, 0.115 or more, 0.117 or more, 0.12 or more, 0.122 or more, 0.125 or more, 0.127 or more, 0.13 or more, 0.132 or more, 0.135 or more, 0.137 or more, 0.14 or more, 0.142 or more, 0.145 or more, 0.147 or more, 0.15 or more, 0.152 or more, 0.155 or more, 0.157 or more, 0.16 or more, 0.162 or more, 0.165 or more, 0.167 or more, 0.17 or more, 0.172 or more, 0.175 or more, 0.177 or more, 0.18 or more, 0.182 or more, 0.185 or more, 0.187 or more, 0.19 or more, 0.192 or more, 0.195 or more, 0.197 or more, 0.2 or more, 0.202 or more, 0.205 or more, 0.207 or more, 0.21 or more, 0.212 or more, 0.215 or more, 0.217 or more, 0.22 or more, 0.222 or more, 0.225 or more, 0.227 or more, 0.23 or more, 0.232 or more, 0.235 or more, 0.237 or more, 0.24 or more, 0.242 or more, 0.245 or more, 0.247 or more, 0.25 or more, 0.252 or more, 0.255 or more, 0.257 or more, 0.26 or more, 0.262 or more, 0.265 or more, 0.267 or more, 0.27 or more, 0.272 or more, 0.275 or more, 0.277 or more, 0.28 or more, 0.282 or more, 0.285 or more, 0.287 or more, 0.29 or more, 0.292 or more, 0.295 or more, 0.297 or more, 0.3 or more, 0.302 or more, 0.305 or more, 0.307 or more, 0.31 or more, 0.312 or more, 0.315 or more, 0.317 or more, 0.32 or more, 0.322 or more, 0.325 or more, 0.327 or more, 0.33 or more, 0.332 or more, 0.335 or more, 0.337 or more, 0.34 or more, 0.342 or more, 0.345 or more, 0.347 or more, 0.35 or more, 0.352 or more, 0.355 or more, 0.357 or more, 0.36 or more, 0.362 or more, 0.365 or more, 0.367 or more, 0.37 or more, 0.372 or more, 0.375 or more, 0.377 or more, 0.38 or more, 0.382 or more, 0.385 or more, 0.387 or more, 0.39 or more, 0.392 or more, 0.395 or more, or 0.397 or more. Meanwhile, the value of z is preferably 0.397 or less, 0.395 or less, 0.392 or less, 0.39 or less, 0.387 or less, 0.385 or less, 0.382 or less, 0.38 or less, 0.377 or less, 0.375 or less, 0.372 or less, 0.367 or less, 0.365 or less, 0.362 or less, 0.36 or less, 0.357 or less, 0.355 or less, 0.352 or less, 0.35 or less, 0.347 or less, 0.345 or less, 0.342 or less, 0.34 or less, 0.337 or less, 0.335 or less, 0.332 or less, 0.33 or less, 0.327 or less, 0.325 or less, 0.322 or less, 0.32 or less, 0.317 or less, 0.315 or less, 0.312 or less, 0.31 or less, 0.307 or less, 0.305 or less, 0.302 or less, 0.3 or less, 0.297 or less, 0.295 or less, 0.292 or less, 0.29 or less, 0.287 or less, 0.285 or less, 0.282 or less, 0.28 or less, 0.277 or less, 0.275 or less, 0.272 or less, 0.27 or less, 0.267 or less, 0.265 or less, 0.26 or less, 0.257 or less, 0.255 or less, 0.252 or less, 0.25 or less, 0.247 or less, 0.245 or less, 0.242 or less, 0.24 or less, 0.237 or less, 0.235 or less, 0.232 or less, 0.23 or less, 0.227 or less, 0.225 or less, 0.222 or less, 0.22 or less, 0.217 or less, 0.215 or less, 0.212 or less, 0.21 or less, 0.207 or less, 0.205 or less, 0.202 or less, 0.2 or less, 0.197 or less, 0.195 or less, 0.192 or less, 0.19 or less, 0.187 or less, 0.185 or less, 0.182 or less, 0.18 or less, 0.177 or less, 0.175 or less, 0.172 or less, 0.17 or less, 0.167 or less, 0.165 or less, 0.162 or less, 0.16 or less, 0.155 or less, 0.152 or less, 0.15 or less, 0.147 or less, 0.145 or less, 0.142 or less, 0.14 or less, 0.137 or less, 0.135 or less, 0.132 or less, 0.13 or less, 0.127 or less, 0.125 or less, 0.122 or less, 0.12 or less, 0.117 or less, 0.115 or less, 0.112 or less, 0.11 or less, 0.107 or less, 0.105 or less, 0.102 or less, 0.1 or less, 0.095 or less, 0.09 or less, 0.085 or less, 0.08 or less, 0.075 or less, 0.07 or less, 0.065 or less, 0.06 or less, 0.055 or less, 0.05 or less, 0.045 or less, 0.04 or less, 0.035 or less, 0.03 or less, 0.025 or less, 0.02 or less, 0.015 or less, 0.01 or less, 0.0095 or less, 0.009 or less, 0.0085 or less, 0.008 or less, 0.0075 or less, 0.007 or less,
0.0065 or less, 0.006 or less, 0.0055 or less, 0.005 or less, 0.0045 or less, 0.004 or less, 0.0035 or less, 0.003 or less, 0.0025 or less, 0.002 or less, 0.0015 or less, or 0.001 or less.
In the general formula, the value of w is not particularly limited as long as this falls within the range 0<w<0.1, but is, for example, preferably 0.001 or more, 0.0012 or more, 0.0015 or more, 0.0017 or more, 0.002 or more, 0.0022 or more, 0.0025 or more, 0.0027 or more, 0.003 or more, 0.0032 or more, 0.0035 or more, 0.0037 or more, 0.004 or more, 0.0042 or more, 0.0045 or more, 0.0047 or more, 0.005 or more, 0.0052 or more, 0.0055 or more, 0.0057 or more, 0.006 or more, 0.0062 or more, 0.0065 or more, 0.0067 or more, 0.007 or more, 0.0072 or more, 0.0075 or more, 0.0077 or more, 0.008 or more, 0.0082 or more, 0.0085 or more, 0.0087 or more, 0.009 or more, 0.0092 or more, 0.0095 or more, 0.0097 or more, 0.01 or more, 0.012 or more, 0.015 or more, 0.017 or more, 0.02 or more, 0.022 or more, 0.025 or more, 0.027 or more, 0.03 or more, 0.032 or more, 0.035 or more, 0.037 or more, 0.04 or more, 0.042 or more, 0.045 or more, 0.047 or more, 0.05 or more, 0.052 or more, 0.055 or more, 0.057 or more, 0.06 or more, 0.062 or more, 0.065 or more, 0.067 or more, 0.07 or more, 0.072 or more, 0.075 or more, 0.077 or more, 0.08 or more, 0.082 or more, 0.085 or more, 0.087 or more, 0.09 or more, 0.092 or more, 0.095 or more, or 0.097 or more. Meanwhile, the value of w is preferably 0.097 or less, 0.095 or less, 0.092 or less, 0.09 or less, 0.087 or less, 0.085 or less, 0.082 or less, 0.08 or less, 0.077 or less, 0.075 or less, 0.072 or less, 0.07 or less, 0.067 or less, 0.065 or less, 0.062 or less, 0.06 or less, 0.057 or less, 0.055 or less, 0.052 or less, 0.05 or less, 0.047 or less, 0.045 or less, 0.042 or less, 0.04 or less, 0.037 or less, 0.035 or less, 0.032 or less, 0.03 or less, 0.027 or less, 0.025 or less, 0.022 or less, 0.02 or less, 0.017 or less, 0.015 or less, 0.012 or less, 0.01 or less, 0.0097 or less, 0.0095 or less, 0.0092 or less, 0.009 or less, 0.0087 or less, 0.0085 or less, 0.0082 or less, 0.008 or less, 0.0077 or less, 0.0075 or less,
0.0072 or less, 0.007 or less, 0.0067 or less, 0.0065 or less, 0.0062 or less, 0.006 or less,
0.0057 or less, 0.0055 or less, 0.0052 or less, 0.005 or less, 0.0047 or less, 0.0045 or less,
0.0042 or less, 0.004 or less, 0.0037 or less, 0.0035 or less, 0.0032 or less, 0.003 or less,
0.0027 or less, 0.0025 or less, 0.0022 or less, 0.002 or less, 0.0017 or less, 0.0015 or less,
0.0012 or less, or 0.001 or less.
In the general formula, the value of v is not particularly limited as long as this falls within the range 0<v<0.1 , but is, for example, preferably 0.001 or more, 0.0012 or more, 0.0015 or more, 0.0017 or more, 0.002 or more, 0.0022 or more, 0.0025 or more, 0.0027 or more, 0.003 or more, 0.0032 or more, 0.0035 or more, 0.0037 or more, 0.004 or more, 0.0042 or more, 0.0045 or more, 0.0047 or more, 0.005 or more, 0.0052 or more, 0.0055 or more, 0.0057 or more, 0.006 or more, 0.0062 or more, 0.0065 or more, 0.0067 or more, 0.007 or more, 0.0072 or more, 0.0075 or more, 0.0077 or more, 0.008 or more, 0.0082 or more, 0.0085 or more, 0.0087 or more, 0.009 or more, 0.0092 or more, 0.0095 or more, 0.0097 or more, 0.01 or more, 0.012 or more, 0.015 or more, 0.017 or more, 0.02 or more, 0.022 or more, 0.025 or more, 0.027 or more, 0.03 or more, 0.032 or more, 0.035 or more, 0.037 or more, 0.04 or more, 0.042 or more, 0.045 or more, 0.047 or more, 0.05 or more, 0.052 or more, 0.055 or more, 0.057 or more, 0.06 or more, 0.062 or more, 0.065 or more, 0.067 or more, 0.07 or more, 0.072 or more, 0.075 or more, 0.077 or more, 0.08 or more, 0.082 or more, 0.085 or more, 0.087 or more, 0.09 or more, 0.092 or more, 0.095 or more, or 0.097 or more. Meanwhile, the value of v is preferably 0.097 or less, 0.095 or less, 0.092 or less, 0.09 or less, 0.087 or less, 0.085 or less, 0.082 or less, 0.08 or less, 0.077 or less, 0.075 or less, 0.072 or less, 0.07 or less, 0.067 or less, 0.065 or less, 0.062 or less, 0.06 or less, 0.057 or less, 0.055 or less, 0.052 or less, 0.05 or less, 0.047 or less, 0.045 or less, 0.042 or less, 0.04 or less, 0.037 or less, 0.035 or less, 0.032 or less, 0.03 or less, 0.027 or less, 0.025 or less, 0.022 or less, 0.02 or less, 0.017 or less, 0.015 or less, 0.012 or less, 0.01 or less, 0.0097 or less, 0.0095 or less, 0.0092 or less, 0.009 or less, 0.0087 or less, 0.0085 or less, 0.0082 or less, 0.008 or less, 0.0077 or less, 0.0075 or less, 0.0072 or less, 0.007 or less, 0.0067 or less, 0.0065 or less, 0.0062 or less, 0.006 or less, 0.0057 or less, 0.0055 or less, 0.0052 or less, 0.005 or less, 0.0047 or less, 0.0045 or less, 0.0042 or less, 0.004 or less, 0.0037 or less, 0.0035 or less, 0.0032 or less, 0.003 or less, 0.0027 or less, 0.0025 or less, 0.0022 or less, 0.002 or less, 0.0017 or less, 0.0015 or less, 0.0012 or less, or 0.001 or less.
In the formula, the element M1 is not particularly limited as long as this is one or more elements other than Li, Ni, Co, Mn and O, but can be, for example, Al, Mg, Zn, Nb, W, Mo, Sb, V, Cr, Ca, Fe, Ga, Sr, Y, Ru, In, Sn, Ta, Bi, Zr, B, or the like.
In the general formula, the value of a is not particularly limited as long as this falls within the range -1.0<a<0.5, but is, for example, preferably more than -1, -0.95 or more, -0.9 or more, - 0.85 or more, -0.8 or more, -0.75 or more, -0.7 or more, -0.65 or more, -0.6 or more, -0.5 or more, -0.45 or more, -0.4 or more, -0.35 or more, -0.30 or more, -0.25 or more, -0.2 or more, - 0.15 or more, -0.1 or more, -0.075 or more, -0.05 or more, -0.025 or more, -0.02 or more, -0.015 or more, -0.01 or more, -0.05 or more, 0 or more, 0.001 or more, 0.0015 or more, 0.002 or more, 0.0025 or more, 0.003 or more, 0.0035 or more, 0.004 or more, 0.0045 or more, 0.005 or more, 0.0055 or more, 0.006 or more, 0.0065 or more, 0.007 or more, 0.0075 or more, 0.008 or more, 0.0085 or more, 0.009 or more, 0.0095 or more, 0.01 or more, 0.015 or more, 0.02 or more, 0.025 or more, 0.03 or more, 0.035 or more, 0.04 or more, 0.045 or more, 0.05 or more, 0.055 or more, 0.06 or more, 0.065 or more, 0.07 or more, 0.075 or more, 0.08 or more, 0.085 or more, 0.09 or more, 0.095 or more, 0.1 or more, 0.102 or more, 0.105 or more, 0.107 or more, 0.11 or more, 0.112 or more, 0.115 or more, 0.117 or more, 0.12 or more, 0.122 or more, 0.125 or more, 0.127 or more, 0.13 or more, 0.132 or more, 0.135 or more, 0.137 or more, 0.14 or more, 0.142 or more, 0.145 or more, 0.147 or more, 0.15 or more, 0.152 or more, 0.155 or more, 0.157 or more, 0.16 or more, 0.162 or more, 0.165 or more, 0.167 or more, 0.17 or more, 0.172 or more, 0.175 or more, 0.177 or more, 0.18 or more, 0.182 or more, 0.185 or more, 0.187 or more, 0.19 or more, 0.192 or more, 0.195 or more, 0.197 or more, 0.2 or more, 0.202 or more, 0.205 or more, 0.207 or more, 0.21 or more, 0.212 or more, 0.215 or more, 0.217 or more, 0.22 or more, 0.222 or more, 0.225 or more, 0.227 or more, 0.23 or more, 0.232 or more, 0.235 or more, 0.237 or more, 0.24 or more, 0.242 or more, 0.245 or more, 0.247 or more, 0.25 or more, 0.252 or more, 0.255 or more, 0.257 or more, 0.26 or more, 0.262 or more, 0.265 or more, 0.267 or more, 0.27 or more, 0.272 or more, 0.275 or more, 0.277 or more, 0.28 or more, 0.282 or more, 0.285 or more, 0.287 or more, 0.29 or more, 0.292 or more, 0.295 or more, 0.297 or more, 0.3 or more, 0.302 or more, 0.305 or more, 0.307 or more, 0.31 or more, 0.312 or more, 0.315 or more, 0.317 or more, 0.32 or more, 0.322 or more, 0.325 or more, 0.327 or more, 0.33 or more, 0.332 or more, 0.335 or more, 0.337 or more, 0.34 or more, 0.342 or more, 0.345 or more, 0.347 or more, 0.35 or more, 0.352 or more, 0.355 or more, 0.357 or more, 0.36 or more, 0.362 or more, 0.365 or more, 0.367 or more, 0.37 or more, 0.372 or more, 0.375 or more, 0.377 or more, 0.38 or more, 0.382 or more, 0.385 or more, 0.387 or more, 0.39 or more, 0.392 or more, 0.395 or more, 0.397 or more, 0.4 or more, 0.402 or more, 0.405 or more, 0.407 or more, 0.41 or more, 0.412 or more, 0.415 or more, 0.417 or more, 0.42 or more, 0.422 or more, 0.425 or more, 0.427 or more, 0.43 or more, 0.432 or more, 0.435 or more, 0.437 or more, 0.44 or more, 0.442 or more, 0.445 or more, 0.447 or more, 0.45 or more, 0.452 or more, 0.455 or more, 0.457 or more, 0.46 or more, 0.462 or more, 0.465 or more, 0.467 or more, 0.47 or more, 0.472 or more, 0.475 or more, 0.477 or more, 0.48 or more, 0.482 or more, 0.485 or more, 0.487 or more, 0.49 or more, 0.492 or more, 0.495 or more, or 0.497 or more. Meanwhile, the value of a is preferably 0.497 or less, 0.495 or less, 0.492 or less, 0.49 or less, 0.487 or less, 0.485 or less, 0.482 or less, 0.48 or less, 0.477 or less, 0.475 or less, 0.472 or less, 0.467 or less, 0.465 or less, 0.462 or less, 0.46 or less, 0.457 or less, 0.455 or less, 0.452 or less,
0.45 or less, 0.447 or less, 0.445 or less, 0.442 or less, 0.44 or less, 0.437 or less, 0.435 or less, 0.432 or less, 0.43 or less, 0.427 or less, 0.425 or less, 0.422 or less, 0.42 or less, 0.417 or less, 0.415 or less, 0.412 or less, 0.41 or less, 0.407 or less, 0.405 or less, 0.402 or less, 0.4 or less, 0.397 or less, 0.395 or less, 0.392 or less, 0.39 or less, 0.387 or less, 0.385 or less,
0.382 or less, 0.38 or less, 0.377 or less, 0.375 or less, 0.372 or less, 0.367 or less, 0.365 or less, 0.362 or less, 0.36 or less, 0.357 or less, 0.355 or less, 0.352 or less, 0.35 or less, 0.347 or less, 0.345 or less, 0.342 or less, 0.34 or less, 0.337 or less, 0.335 or less, 0.332 or less, 0.33 or less, 0.327 or less, 0.325 or less, 0.322 or less, 0.32 or less, 0.317 or less, 0.315 or less, 0.312 or less, 0.31 or less, 0.307 or less, 0.305 or less, 0.302 or less, 0.3 or less, 0.297 or less, 0.295 or less, 0.292 or less, 0.29 or less, 0.287 or less, 0.285 or less, 0.282 or less, 0.28 or less, 0.277 or less, 0.275 or less, 0.272 or less, 0.27 or less, 0.267 or less, 0.265 or less,
0.26 or less, 0.257 or less, 0.255 or less, 0.252 or less, 0.25 or less, 0.247 or less, 0.245 or less, 0.242 or less, 0.24 or less, 0.237 or less, 0.235 or less, 0.232 or less, 0.23 or less, 0.227 or less, 0.225 or less, 0.222 or less, 0.22 or less, 0.217 or less, 0.215 or less, 0.212 or less,
0.21 or less, 0.207 or less, 0.205 or less, 0.202 or less, 0.2 or less, 0.197 or less, 0.195 or less,
0.192 or less, 0.19 or less, 0.187 or less, 0.185 or less, 0.182 or less, 0.18 or less, 0.177 or less, 0.175 or less, 0.172 or less, 0.17 or less, 0.167 or less, 0.165 or less, 0.162 or less, 0.16 or less, 0.155 or less, 0.152 or less, 0.15 or less, 0.147 or less, 0.145 or less, 0.142 or less,
0.14 or less, 0.137 or less, 0.135 or less, 0.132 or less, 0.13 or less, 0.127 or less, 0.125 or less, 0.122 or less, 0.12 or less, 0.117 or less, 0.115 or less, 0.112 or less, 0.11 or less, 0.107 or less, 0.105 or less, 0.102 or less, 0.1 or less, 0.095 or less, 0.09 or less, 0.085 or less, 0.08 or less, 0.075 or less, 0.07 or less, 0.065 or less, 0.06 or less, 0.055 or less, 0.05 or less, 0.045 or less, 0.04 or less, 0.035 or less, 0.03 or less, 0.025 or less, 0.02 or less, 0.015 or less, 0.01 or less, 0.0095 or less, 0.009 or less, 0.0085 or less, 0.008 or less, 0.0075 or less, 0.007 or less,
0.0065 or less, 0.006 or less, 0.0055 or less, 0.005 or less, 0.0045 or less, 0.004 or less, 0.0035 or less, 0.003 or less, 0.0025 or less, 0.002 or less, 0.0015 or less, or 0.001 or less.
The cumulative pore volume within a pore diameter range of 25 nm to 334 nm is not particularly limited as long as this is 25 pL/g or more, but may be, for example, 25.5 pL/g or more, 26 or more, 30 pL/g or more, 35 pL/g or more, 40 pL/g or more, 45 pL/g or more, 50 pL/g or more, or 55 pL/g or more. Meanwhile, the cumulative pore volume within a pore diameter range of 25 nm to 334 nm may be 150 pL/g or less, 120 pL/g or less, 100 pL/g or less, 90 pL/g or less, 80 pL/g or less, or 70 pL/g or less. Note that a method for measuring the cumulative pore volume of within a pore diameter range of 25 nm to 334 nm is in line with a method shown in the Examples section below.
An activated lithium-metal composite oxide powder according to the present embodiment is represented by the general formula LixNii-y-z-w- C0yMnzM1 wM2vO2+a (in the formula, M1 and M2 are each independently one or more elements other than Li, Ni, Co, Mn and O, 0.9<x<1.2, 0<y<0.4, 0<z<0.4, 0<w<0.1 , 0<v<0.1 and -1.0<a<0.5), and the ratio of the proportion of the total amount of M2 relative to the total amount of Ni, Co and Mn in terms of mass in the center of a particle is 0.90 or more relative to the proportion of the total amount of M2 relative to the total amount of Ni, Co and Mn in terms of mass at a position 1 pm from the surface.
Here, “the proportion of the total amount of M2 relative to the total amount of Ni, Co and Mn in terms of mass” is expressed as total amount of M2/(total amount of Ni+total amount of Co+total amount of Mn). Hereinafter, this is also abbreviated to “proportion of M2”.
The ratio of the proportion of M2 in the center of a particle relative to the proportion of M2 at a position 1 pm from the surface is not particularly limited as long as this is 0.90 or more, but is, for example, preferably 0.91 or more, 0.92 or more, 0.93 or more, 0.94 or more, or 0.95 or more. The ratio of the proportion of M2 in the center of a particle relative to the proportion of M2 at a position 1 pm from the surface may be 5 or less, 3 or less, 2.5 or less, 2 or less, 1 .7 or less, 1 .5 or less, 1 .2 or less, or 1 . 1 or less. Note that the method for calculating the proportion of M2 in the center of a particle relative to the proportion of M2 at a position 1 pm from the surface is in line with a method shown in the Examples section below.
The element M2 is not particularly limited as long as this is one or more elements other than Li, Ni, Co, Mn and O, but can be, for example, Al, Mg, Zn, Nb, W, Mo, Sb, V, Cr, Ca, Fe, Ga, Sr, Y, Ru, In, Sn, Ta, Bi, Zr, B, or the like. In one embodiment, it is preferable to use W as the element M2.
The activated lithium-metal composite oxide powder preferably includes a secondary particle for which the distance from the surface to the center of the particle is 10 pm or more. Note that “the distance from the surface to the center of the particle” means the shortest distance from each point on the surface (the outline of the particle) to the center (geometric center) of the particle when the activated lithium-metal composite oxide powder is observed using a scanning electron microscope.
A method for producing activated lithium-metal composite oxide according to an embodiment of the present disclosure includes: a mixing step for obtaining a raw material mixture of the lithium- metal composite oxide described above and a compound that contains, independently of M1, one or more elements M2 other than Li, Ni, Co, Mn and O; and a firing step for firing the raw material mixture in an oxidizing atmosphere.
An activated lithium-metal composite oxide obtained in the manner described above exhibits superior cycle characteristics and lower resistance when used as a positive electrode active material of a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery. The reason for this is currently unclear and is not necessarily limited to a specific theory, but the inventors of the present invention think that the reason is as follows. The lithium-metal composite oxide described above is used in the method for producing an activated lithium-metal composite oxide according to the present embodiment, but this lithium-metal composite oxide has a cumulative pore volume of 25 pL/g or more within a pore diameter range of 25 nm to 334 nm. An activated lithium-metal composite oxide having a large cumulative pore volume such as this takes in compounds containing the element M2 from pores in the composite oxide, and these compounds easily reach the inner part of the particle. It is expected that the element M2 achieves effects such as suppressing elution of transition metals at the surface of an active material during cycles, improving electron conductivity, lowering charge transfer resistance during lithium removal/insertion, and suppressing sintering of primary particles during firing, but because added elements penetrate sufficiently into the inner part of a secondary particle, these effects are exhibited as far as the inner part of a secondary particle, which is thought to lead to an improvement in cycle characteristics and a reduction in resistance.
Specifically, the method for producing an activated lithium-metal composite oxide can include the following steps:
Precursor preparation step: a precursor composite compound containing at least nickel is prepared.
Precursor mixing step: a precursor mixture is prepared by mixing the precursor composite compound prepared in the precursor preparation step with a lithium compound.
Primary firing step: if necessary, the precursor mixture prepared in the precursor mixing step is fired.
Mixing step: at least the lithium-metal composite oxide obtained as a primary fired product in the primary firing step, a compound containing the element M2 and, if necessary, a lithium compound are mixed.
Secondary firing step (this refers to the “firing step” mentioned above, this is referred to as a “secondary firing step” here for the sake of convenience in order to differentiate from the primary firing step): the raw material mixture prepared in the mixing step is fired.
Water washing step: if necessary, the activated lithium-metal composite oxide obtained by firing in the secondary firing step is washed with water.
Surface treatment step: if necessary, the activated lithium-metal composite oxide obtained in the secondary firing step or the water washing step is surface-treated.
First, a precursor composite compound containing at least nickel is synthesized. In one embodiment, an aggregate can be obtained through aggregation of primary particles. The method for synthesizing a precursor composite compound is not particularly limited, and it is possible to use a method comprising, for example, adding an aqueous solution, which includes an aqueous solution containing a transition metal such as nickel and aqueous solutions of compounds containing other elements according to the composition of the target lithium-metal composite oxide, dropwise to a reaction tank in which a base liquid comprising an alkaline aqueous solution such as an aqueous solution of sodium hydroxide or an ammonia solution is being stirred, monitoring and controlling the pH within a suitable range while adding sodium hydroxide or the like dropwise, coprecipitating by means of a wet reaction, and obtaining a precursor composite compound as, for example, a hydroxide, an oxide obtained by calcining a hydroxide, a carbonate, or the like.
Note that in synthesis-related reactions, after the alkaline aqueous solution that serves as the base liquid is prepared, the interior of the reaction tank is preferably purged with an inert gas or preferably nitrogen gas for industrial purposes, to create a nitrogen atmosphere in order to lower the oxygen concentration within the reaction tank system or in the solution. If the oxygen concentration is excessively high, there is a risk that the coprecipitated hydroxide will be overoxidized by any oxygen remaining over a predetermined amount, and a risk that the formation of agglomerates due to crystallization will be compromised.
The transition metal aqueous solution is not particularly limited, but use of an acidic aqueous solution, for example, is preferred, and use of a sulfuric acid aqueous solution such as a nickel sulfate aqueous solution is even more preferred in the case of nickel compounds. In addition, it is possible to use one or more transition metal aqueous solutions.
Examples of nickel compounds that can be used include, but are not particularly limited to, one or more compounds selected from among nickel sulfate, nickel oxide, nickel hydroxide, nickel nitrate, nickel carbonate, nickel chloride, nickel iodide, metallic nickel, and the like. Examples of cobalt compounds that can be used include, but are not particularly limited to, one or more compounds selected from among cobalt sulfate, cobalt oxide, cobalt hydroxide, cobalt nitrate, cobalt carbonate, cobalt chloride, cobalt iodide, metallic cobalt, and the like.
Examples of manganese compounds that can be used include, but are not particularly limited to, one or more compounds selected from among manganese sulfate, manganese oxide, manganese hydroxide, manganese nitrate, manganese carbonate, manganese chloride, manganese iodide, metallic manganese, and the like.
In the formula, the element M1 is not particularly limited as long as this is one or more elements other than Li, Ni, Co, Mn and O, but can be, for example, Al, Mg, Zn, Nb, W, Mo, Sb, V, Cr, Ca, Fe, Ga, Sr, Y, Ru, In, Sn, Ta, Bi, Zr, B, or the like. Specific examples of compounds containing the element M1 will now be described.
Examples of titanium compounds that can be used include, but are not particularly limited to, one or more compounds selected from among titanyl sulfate, titanium oxide, titanium hydroxide, titanium nitrate, titanium carbonate, titanium chloride, titanium iodide, metallic titanium, and the like.
Examples of aluminum compounds that can be used include, but are not particularly limited to, aluminum sulfate, aluminum oxide, aluminum hydroxide, aluminum nitrate, aluminum carbonate, aluminum chloride, aluminum iodide, sodium aluminate, metallic aluminum, and the like.
Examples of iron compounds that can be used include, but are not particularly limited to, one or more compounds selected from among iron sulfate, iron oxide, iron hydroxide, iron nitrate, iron carbonate, iron chloride, iron iodide, metallic iron, and the like.
Examples of niobium compounds that can be used include, but are not particularly limited to, one or more compounds selected from among niobium oxide, niobium chloride, lithium niobate, niobium iodide, and the like.
Examples of tungsten compounds that can be used include, but are not particularly limited to, one or more compounds selected from among tungsten oxide, sodium tungstate, ammonium para-tungstate, hexacarbonyl tungsten, tungsten sulfide, and the like.
Examples of magnesium compounds that can be used include, but are not particularly limited to, one or more compounds selected from among magnesium sulfate, magnesium oxide, magnesium hydroxide, magnesium nitrate, magnesium carbonate, magnesium chloride, magnesium iodide, metallic magnesium, and the like.
Examples of zirconium compounds that can be used include, but are not particularly limited to, one or more compounds selected from among zirconium sulfate, zirconium oxide, zirconium nitrate, ammonium zirconium carbonate, zirconium chloride, zirconium iodide, metallic zirconium, and the like. Examples of other elements that can be used include one or more selected from among sulfates, oxides, hydroxides, nitrates, carbonates, chlorides, iodides, metals, and the like.
In view of the composition of the target lithium-metal composite oxide, the mixing proportions of these compounds should be adjusted so that the amounts of these elements are prescribed proportions.
An appropriate pH range for when the precursor composite compound is synthesized is not particularly limited, and can be determined so as to achieve a desired secondary particle size and coarseness/fineness, but the pH is generally within the range of approximately 10 to 13.
The precursor composite compound obtained by means of a wet reaction is preferably washed and then dried after being de-watered.
Washing the precursor composite compound makes it possible to wash out impurities such as sulfate radicals or carbonate radicals and sodium components that have been incorporated into aggregated particles or that have become stuck on the surface layer during the reaction. Washing treatments that can be used for small amounts of impurities include a procedure in which Nutsche washing using a Buchner funnel is carried out, or a procedure in which a reacted suspension is pumped through a press filter, washed with water, and de-watered. Note that the washing treatment can be carried out using, for example, pure water, an aqueous solution of sodium hydroxide, an aqueous solution of sodium carbonate, or the like, but use of pure water is industrially preferable. For a sizable amount of residual sulfate radicals, however, a sodium hydroxide aqueous solution in which the pH is controlled according to the amount that remains may be used.
Next, a precursor mixture is prepared by mixing the thus obtained precursor composite compound and a lithium compound at prescribed proportions. The mixing may be solvent-based mixing in which the precursor composite compound and the lithium compound are in the form of solutions such as aqueous solutions and these solutions are mixed at prescribed proportions, or non-solvent-based mixing in which a powder of the precursor composite compound and a powder of the lithium compound are weighed out at prescribed proportions and dry mixed.
The lithium compound is not particularly limited, and a variety of lithium salts can be used. Specific examples of lithium compounds that can be used include one or more compounds selected from among anhydrous lithium hydroxide, lithium hydroxide hydrate, lithium nitrate, lithium carbonate, lithium acetate, lithium bromide, lithium chloride, lithium citrate, lithium fluoride, lithium iodide, lithium lactate, lithium oxalate, lithium phosphate, lithium pyruvate, lithium sulfate, lithium oxide, and the like. Of these, it is preferable to use one or more compounds selected from among anhydrous lithium hydroxide and lithium hydroxide hydrate.
The blending proportions of the lithium compound and the precursor composite compound are not particularly limited, but in view of the composition of the target lithium-metal composite oxide, the amount of lithium and the total amount of the other elements should be adjusted, as appropriate, to achieve a prescribed ratio.
In the mixing step described later, a lithium-metal composite oxide having a cumulative pore volume of 25 L/g or more within a pore diameter range of 25 nm to 334 nm is used, but this cumulative pore volume can be adjusted by altering the primary firing temperature. Therefore, it is preferable to carry out primary firing in order to obtain a lithium-metal composite oxide having a cumulative pore volume of 25 L/g or more within a pore diameter range of 25 nm to 334 nm. However, the primary firing step is not an essential step.
In addition, the secondary firing step described later is generally carried out by weighing out the lithium compound, the precursor compound and, if necessary, compounds of other elements, mixing with a mixer to obtain a mixed powder, and loading the mixed powder in a container such as a crucible or a sagger, but as the bottom of the container loaded with the mixed powder is approached in a lithiation reaction in particular, discharge of produced gas to the outside and diffusion of the required oxygen concentration become more difficult. As a result, it is difficult to control reaction homogeneity and primary particle size. It is preferable to carry out primary firing from these perspectives also.
In the primary firing step, it is preferable to include a firing means for promoting a lithiation reaction in particular. A specific example thereof is a method comprising enabling heat to be applied to the precursor mixture more easily, enabling gas generated by the lithium compound to be easily discharged, and allowing gas having a high oxygen partial pressure to diffuse into the precursor mixture (into particles). For example, by firing a smaller amount of the precursor mixture, it is possible to achieve desired characteristics.
In the primary firing step, it is possible to load the precursor mixture in a sagger or a crucible and fire the precursor mixture in a static furnace, a roller hearth kiln or a pusher furnace in order to subject the precursor mixture to primary firing, but it is preferable to carry out the firing while the precursor mixture is flowing, and in such a case, it is possible to use a rotary kiln as a firing device.
The primary firing temperature is not particularly limited, but is, for example, preferably 350°C or higher, 360°C or higher, 370°C or higher, 380°C or higher, or 390°C or higher. Meanwhile, the primary firing temperature is preferably 650°C or lower, 640°C or lower, 630°C or lower, 620°C or lower, or 610°C or lower. Note that in a case where the cumulative pore volume is to be controlled in particular, the cumulative pore volume can be controlled by altering the chemical compositions and surface states of the precursor composite compound and the lithium compound, the pore condition, the particle size, and so on, and the primary firing temperature can be lower than 350°C or higher than 650°C.
The duration of the primary firing is not particularly limited as long as a lithiation reaction can progress reliably and uniformly, but is, for example, preferably 1-10 hours or 2-8 hours.
Note that the firing temperature in the present disclosure is the maximum temperature when an object-to-be-heated is heated. The maximum temperature means the temperature of a part having the highest temperature in the object-to-be-heated. In addition, the firing duration is the duration for which the firing temperature is maintained after the temperature reaches a prescribed range. These definitions for firing temperature and firing duration are the same hereinafter.
The primary firing atmosphere is not particularly limited, and may be an oxidizing atmosphere in which a lithiation reaction can progress reliably and uniformly. For example, it is preferable to use a decarburized oxidizing gas atmosphere having a carbon dioxide gas concentration of 30 ppm or less, or an oxygen atmosphere having an oxygen concentration of 80 vol% or more, 85 vol% or more, 90 vol% or more, or 95 vol% or more.
Secondary firing is carried out in a subsequent step in order to effect crystal growth or particle growth at a higher temperature in a fired product obtained by carrying out primary firing in this way and for the element M2 to penetrate throughout the lithium-metal composite oxide.
Note that in a case where a lithium-metal composite oxide obtained through the primary firing agglomerates, a powder may be formed by using a grinder, a mortar, or the like.
In the present disclosure, at least a lithium-metal composite oxide, a compound containing the element M2 and, if necessary, a lithium compound are added and mixed. The added quantities of the compounds and the addition method may be similar to those described in the precursor preparation step. In addition, the compound containing the element M2 may be similar to the compound containing the element M1 described in the precursor preparation step. Furthermore, the element M1 and the element M2 may be the same as, or different from, each other.
Specifically, the element M2 is not particularly limited as long as this is one or more elements other than Li, Ni, Co, Mn and O, but can be, for example, Al, Mg, Zn, Nb, W, Mo, Sb, V, Cr, Ca, Fe, Ga, Sr, Y, Ru, In, Sn, Ta, Bi, Zr, B, or the like.
In addition, compounds containing the element M2 can be one or more types of compound selected from among sulfates, oxides, hydroxides, nitrates, carbonates, chlorides, iodides, metals, and the like.
Note that a lithium compound may, if necessary, be added in the mixing step, in a case where, for example, lithium is used in the raw material mixing step at a quantity that is less than in the target lithium-metal composite oxide.
The lithium compound is not particularly limited, and it is possible to use a lithium salt that is similar to the lithium salts able to be used in the raw material mixing step. Specific examples of lithium compounds that can be used include one or more compounds selected from among anhydrous lithium hydroxide, lithium hydroxide hydrate, lithium nitrate, lithium carbonate, lithium acetate, lithium bromide, lithium chloride, lithium citrate, lithium fluoride, lithium iodide, lithium lactate, lithium oxalate, lithium phosphate, lithium pyruvate, lithium sulfate, lithium oxide, and the like. Of these, it is preferable to use one or more compounds selected from among anhydrous lithium hydroxide and lithium hydroxide hydrate. Note that it is not necessary to use the same lithium compound as that used in the raw material mixing step.
In the secondary firing, the lithium-metal composite oxide contained in the raw material mixture undergoes a lithiation reaction and crystal growth, but of these, the lithiation reaction requires a certain oxygen partial pressure. An activated lithium-metal composite oxide containing lithium is obtained from the lithiation reaction. Next, crystal growth is promoted by increasing the temperature to a prescribed temperature.
The secondary firing temperature is not particularly limited as long as this is higher than the primary firing temperature, and can be adjusted according to the composition of the activated lithium-metal composite oxide to be obtained, and so on. For example, the firing temperature is preferably 700°C or higher, 710°C or higher, 720°C or higher, 730°C or higher, 740°C or higher, or 750°C or higher. Meanwhile, the secondary firing temperature is preferably 1100°C or lower, 1070°C or lower, 1050°C or lower, 1020°C or lower, 1000°C or lower, 970°C or lower, 950°C or lower, 920°C or lower, 900°C or lower, 870°C or lower, 850°C or lower, 820°C or lower, or 800°C or lower. By ensuring that the secondary firing temperature falls within the prescribed range, it is possible to obtain an activated lithium-metal composite oxide having a desired crystal structure. In addition, it is possible to reduce the amount of unreacted components and also prevent a decrease in battery characteristics of a non-aqueous electrolyte secondary battery in which the obtained activated lithium-metal composite oxide is used in a positive electrode.
The secondary firing duration is not particularly limited, and should be a duration sufficient for an activated lithium-metal composite oxide having a desired crystal structure to be formed. This duration is, for example, preferably 1-15 hours, 2-12 hours, or 2-10 hours.
The secondary firing atmosphere is not particularly limited, but should be an atmosphere having an oxygen partial pressure whereby crystal growth occurs reliably and uniformly and a transition metal contained in the raw material mixture to be fired is not reduced, and is preferably an atmosphere having a low moisture content and carbon dioxide gas concentration. For example, it is preferable to use a decarburized oxidizing gas atmosphere having a carbon dioxide gas concentration of 30 ppm or less, or an oxygen atmosphere having an oxygen concentration of preferably 80 vol% or more, or 90 vol% or more.
The activated lithium-metal composite oxide obtained in the secondary firing step can contain, as impurities, unreacted lithium compounds and lithium compounds that appear in a particle surface layer from the crystal structure during the primary and secondary firing steps. Water washing and heat treatment can therefore be performed, for example, in order to remove or minimize such impurities. Note that the water washing step is not an essential feature.
It is possible to add and mix compounds of prescribed elements with the activated lithium-metal composite oxide obtained in the secondary firing step or the water washing step, and then carry out a heat treatment so as to subject surfaces of primary particles and/or secondary particles of the activated lithium-metal composite oxide to a surface treatment with compounds of lithium and added elements. As a result, it is possible to achieve effects such as lowering the amount of lithium compounds remaining in a particle surface layer, improving lithium ion conductivity and lowering reactive resistance. Note that the surface treatment step is not an essential feature.
The elemental compound added for the surface treatment noted above may be selected, for example, from among aluminum compounds, boron compounds, tungsten compounds, manganese compounds, cobalt compounds, phosphorus compounds, niobium compounds, strontium compounds, antimony compounds, zirconium compounds, titanium compounds, and the like, and one or more of these compounds may be used.
The heat treatment temperature is not particularly limited, but is, for example, preferably 200°C or higher, 210°C or higher, 220°C or higher, 230°C or higher, 240°C or higher, or 250°C or higher. Meanwhile, the heat treatment temperature is preferably 500°C or lower, 490°C or lower, 480°C or lower, 470°C or lower, 460°C or lower, 450°C or lower, 440°C or lower, 430°C or lower, 420°C or lower, 410°C or lower, or 400°C or lower.
The heat treatment duration is not particularly limited, but is, for example, preferably 1-15 hours, 2-12 hours, or 2-10 hours.
A non-aqueous electrolyte secondary battery according to an embodiment of the present disclosure is provided with a positive electrode that contains the activated lithium-metal composite oxide powder described above as a positive electrode active material for a nonaqueous electrolyte secondary battery, and the non-aqueous electrolyte secondary battery is constituted from the positive electrode, a negative electrode and an electrolyte solution containing an electrolyte.
When producing the positive electrode, an electrically conductive agent and a binder are added to, and mixed with, the activated lithium-metal composite oxide powder according to an embodiment of the present disclosure. The electrically conductive agent is, for example, preferably acetylene black, carbon black, graphite, or the like. The binder is, for example, preferably polytetrafluoroethylene, poly(vinylidene fluoride), or the like.
The negative electrode is not particularly limited, but can be, for example, not only a negative electrode active material such as lithium metal, graphite or a low crystallinity carbon material, but also one or more non-metallic or metallic elements selected from among Si, Al, Sn, Pb, Zn, Bi and Cd, alloys containing these, and chalcogen compounds containing these.
The solvent in the electrolyte solution is not particularly limited, but can be, for example, an organic solvent including one or more types selected from among carbonates, such as ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate, and ethers such as dimethoxyethane.
The electrolyte can be one or more types selected from among lithium salts such as lithium perchlorate and lithium tetrafluoroborate, in addition to lithium hexafluorophosphate (LiPFs) in particular, dissolved in a solvent.
Embodiments of the present disclosure have been explained above using specific examples, but the present disclosure can be carried out by adding appropriate modifications as long as the effect of the present invention is not impaired.
EXAMPLE
The present disclosure will now be explained in greater detail through the use of examples, but is not limited to these examples.
Preparation of sample of activated lithium-metal composite oxide powder>
Samples of activated lithium-metal composite oxide powders of Examples 1-9 and Comparative Examples 1-12 were prepared using the method shown below.
Example 1
A mixed aqueous solution was obtained by mixing an aqueous solution of nickel sulfate and an aqueous solution of manganese sulfate at an Ni:Mn ratio (molar ratio) of 90:10. 300 g of an aqueous solution of sodium hydroxide and 500 g of aqueous ammonia added to 10 L of pure water was prepared in advance as a base liquid in a reaction tank, a nitrogen atmosphere was created in the reaction tank using nitrogen gas at a flow rate of 0.7 L/min, and a reaction was carried out in the nitrogen atmosphere.
Next, while stirring at 600 rpm using a stirring blade, the mixed aqueous solution, the aqueous solution of sodium hydroxide and the aqueous ammonia were added dropwise using a metering pump, the added quantities of the alkaline solutions were adjusted so as to attain a pH of 10.8, and a crystallization reaction was carried out. A coaxial nozzle having a double-pipe structure comprising an internal pipe was installed inside the reaction tank, and the raw material introduction nozzle (internal pipe) for introducing the solution obtained by mixing nickel sulfate and manganese sulfate was lengthened so that a distance (nozzle introduction port distance) between the introduction port of the raw material introduction nozzle and the introduction port of the alkali introduction nozzle for introducing the sodium hydroxide aqueous solution and ammonia water was 1 mm, and the raw material was continuously added into the reaction base liquid. During a crystallization reaction, a reaction slurry was sampled as appropriate from an overflow pipe disposed in the upper part of the reaction tank, and when it was confirmed that the pH of the reaction had stabilized at 10.8, the slurry was recovered.
Next, the slurry was subjected to solid-liquid separation and then washed with pure water to reduce the amount of residual impurities, after which the cake-like coprecipitate was dried for 10 hours at 100°C in an air environment to obtain a precursor composite compound 1 represented by the compositional formula Nio.9oMno.io(OH)2.
The precursor composite compound 1 and lithium hydroxide were weighed out and mixed at an Li/(Ni+M n) ratio of 1.040. Next, a lithium-metal composite oxide was obtained by carrying out primary firing for 6 hours at 400°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
Next, the obtained lithium-metal composite oxide and tungsten (VI) oxide were weighed out and mixed at a W/(Ni+Mn) ratio of 0.5 mol%, and the obtained mixture was subjected to secondary firing for 6 hours at 800°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide powder of Example 1 was obtained by pulverizing the obtained fired product.
Example 2
A sample of an activated lithium-metal composite oxide powder of Example 2 was obtained in the same way as Example 1 , except that the primary firing was carried out at 500°C.
Example 3
A sample of an activated lithium-metal composite oxide powder of Example 3 was obtained in the same way as Example 1 , except that the primary firing was carried out at 600°C.
Comparative Example 1
A sample of an activated lithium-metal composite oxide powder of Comparative Example 1 was obtained in the same way as Example 1 , except that the primary firing was carried out at 700°C.
Comparative Example 2
A sample of an activated lithium-metal composite oxide powder of Comparative Example 2 was obtained in the same way as Example 1 , except that the primary firing was carried out at 800°C.
Comparative Example 3
The precursor composite compound, lithium hydroxide and tungsten (VI) oxide were weighed out and mixed at an Li/(Ni+Mn) ratio of 1.040 and a W/(Ni+Mn) ratio of 0.5 mol%. Next, a lithium-metal composite oxide was obtained by carrying out primary firing for 6 hours at 570°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
Next, the obtained lithium-metal composite oxide was subjected to secondary firing for 6 hours at 800°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide powder of Comparative Example 3 was obtained by pulverizing the obtained fired product.
Example 4
A mixed aqueous solution was obtained by mixing an aqueous solution of nickel sulfate, an aqueous solution of cobalt sulfate and an aqueous solution of manganese sulfate at an Ni:Co:Mn ratio (molar ratio) of 90:5:5. 300 g of an aqueous solution of sodium hydroxide and 500 g of aqueous ammonia added to 10 L of pure water was prepared in advance as a base liquid in a reaction tank, a nitrogen atmosphere was created in the reaction tank using nitrogen gas at a flow rate of 0.7 L/min, and a reaction was carried out in the nitrogen atmosphere. Next, while stirring at 600 rpm using a stirring blade, the mixed aqueous solution, the aqueous solution of sodium hydroxide and the aqueous ammonia were added dropwise using a metering pump, the added quantities of the alkaline solutions were adjusted so as to attain a pH of 11.4, and a crystallization reaction was carried out. A coaxial nozzle having a double-pipe structure comprising an internal pipe was installed inside the reaction tank, and the raw material introduction nozzle (internal pipe) for introducing the solution obtained by mixing nickel sulfate and manganese sulfate was lengthened so that a distance (nozzle introduction port distance) between the introduction port of the raw material introduction nozzle and the introduction port of the alkali introduction nozzle for introducing the sodium hydroxide aqueous solution and ammonia water was 15 mm, and the raw material was continuously added into the reaction base liquid. During a crystallization reaction, a reaction slurry was sampled as appropriate from an overflow pipe disposed in the upper part of the reaction tank, and when it was confirmed that the pH of the reaction had stabilized at 11.4, the slurry was recovered.
Next, the slurry was subjected to solid-liquid separation and then washed with pure water to reduce the amount of residual impurities, after which the cake-like coprecipitate was dried for 10 hours at 100°C in an air environment to obtain a precursor composite compound 2 represented by the compositional formula Nio.9oCoooslVlnoo5(OH)2.
The precursor composite compound 2 and lithium hydroxide were weighed out and mixed at an Li/(Ni+Co+Mn) ratio of 1 .040. Next, a lithium-metal composite oxide was obtained by carrying out primary firing for 6 hours at 400°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
Next, the obtained lithium-metal composite oxide after the primary firing and tungsten (VI) oxide were weighed out and mixed at a W/(Ni+Mn) ratio of 0.5 mol%, and the obtained mixture was subjected to secondary firing for 6 hours at 800°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide of Example 4 was obtained by pulverizing the obtained fired product.
Example 5
A sample of an activated lithium-metal composite oxide powder of Example 5 was obtained in the same way as Example 4, except that the primary firing was carried out at 500°C.
Comparative Example 4
A sample of an activated lithium-metal composite oxide powder of Comparative Example 4 was obtained in the same way as Example 4, except that the primary firing was carried out at 600°C.
Comparative Example 5
A sample of an activated lithium-metal composite oxide powder of Comparative Example 5 was obtained in the same way as Example 4, except that the primary firing was carried out at 700°C.
Comparative Example 6
A sample of an activated lithium-metal composite oxide powder of Comparative Example 6 was obtained in the same way as Example 4, except that the primary firing was carried out at 800°C.
Comparative Example 7
The precursor composite compound 2, lithium hydroxide and tungsten (VI) oxide were weighed out and mixed at an Li/(Ni+Co+Mn) ratio of 1.040 and a W/(Ni+Co+Mn) ratio of 0.5 mol%. Next, a lithium-metal composite oxide was obtained by carrying out primary firing for 6 hours at 570°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
Next, the obtained lithium-metal composite oxide was subjected to secondary firing for 6 hours at 800°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide powder of Comparative Example 7 was obtained by pulverizing the obtained fired product.
Example 6
A lithium-metal composite oxide was obtained in the same way as Example 3. This lithium-metal composite oxide and aluminum hydroxide were weighed out and mixed at an AI/(Ni+Mn) ratio of 1.0 mol%, and the obtained mixture was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide powder of Example 6 was obtained by pulverizing the obtained fired product.
Comparative Example 8
The precursor composite compound 1 , lithium hydroxide and aluminum hydroxide were weighed out and mixed at an Li/(Ni+Mn) ratio of 1.040 and an AI/(Ni+Mn) ratio of 1.0 mol%. Next, a lithium-metal composite oxide of Comparative Example 8 was obtained by carrying out primary firing for 6 hours at 600°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
Next, the obtained lithium-metal composite oxide after the primary firing was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide powder of Comparative Example 8 was obtained by pulverizing the obtained fired product.
Example 7
A lithium-metal composite oxide was obtained in the same way as Example 3. This lithium-metal composite oxide after the primary firing and titanium oxide were weighed out and mixed at a Ti/(Ni+M n) ratio of 1.0 mol%, and the obtained mixture was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide powder of Example 7 was obtained by pulverizing the obtained fired product.
Comparative Example 9
The precursor composite compound 1 , lithium hydroxide and titanium oxide were weighed out and mixed at an Li/(Ni+Mn) ratio of 1.040 and a Ti/(Ni+Mn) ratio of 1.0 mol%. Next, a lithium- metal composite oxide of Comparative Example 9 was obtained by carrying out primary firing for 6 hours at 600°C in an oxygen atmosphere (oxygen concentration: 97 vol%). Next, the obtained lithium-metal composite oxide was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide powder of Comparative Example 9 was obtained by pulverizing the obtained fired product.
Example 8
A sample of a lithium-metal composite oxide was obtained in the same way as Example 3. Next, the obtained lithium-metal composite oxide and niobium (V) oxide were weighed out and mixed at an Nb/(Ni+Mn) ratio of 0.2 mol%, and the obtained mixture was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide powder of Example 8 was obtained by pulverizing the obtained fired product.
Comparative Example 10
The precursor composite compound 1 , lithium hydroxide and niobium (V) oxide were weighed out and mixed at an Li/(N i+M n) ratio of 1.040 and an Nb/(Ni+Mn) ratio of 0.2 mol%. Next, a lithium-metal composite oxide of Comparative Example 10 was obtained by carrying out primary firing for 6 hours at 600°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
Next, the obtained lithium-metal composite oxide was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide powder of Comparative Example 10 was obtained by pulverizing the obtained fired product.
Example 9
A lithium-metal composite oxide was obtained in the same way as Example 3. Next, the obtained lithium-metal composite oxide and zirconium oxide were weighed out and mixed at a Zr/(Ni+Mn) ratio of 1.0 mol%, and the obtained mixture was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide powder of Example 9 was obtained by pulverizing the obtained fired product.
Comparative Example 11
The precursor composite compound 1 , lithium hydroxide and zirconium oxide were weighed out and mixed at an Li/(Ni+Mn) ratio of 1.040 and a Zr/(Ni+Mn) ratio of 1.0 mol%. Next, a lithium- metal composite oxide of Comparative Example 11 was obtained by carrying out primary firing for 6 hours at 600°C in an oxygen atmosphere (oxygen concentration: 97 vol%).
Next, the obtained lithium-metal composite oxide was subjected to secondary firing for 6 hours at 780°C in an oxygen atmosphere (oxygen concentration: 97 vol%). A sample of an activated lithium-metal composite oxide powder of Comparative Example 11 was obtained by pulverizing the obtained fired product.
<Evaluation methods> Compositional analysis of precursor composite compound
The composition of the precursor composite compound was determined using the following method. 0.2 g of a sample was heated and dissolved in 25 m Lof a 20% hydrochloric acid solution, cooled, and transferred to a 100 mL volumetric flask, and pure water was added to produce a preparation liquid. The obtained preparation liquid was subjected to elemental quantification using ICP-AES (Optima 8300 produced by PerkinElmer Japan).
Measurement of cumulative pore volume in com and lithium-metal
The cumulative pore volume in the lithium-metal composite oxide following primary firing was measured after washing with water and drying. Specifically, a slurry produced by mixing the lithium-metal composite oxide following the primary firing and pure water adjusted to a liquid temperature of 25°C at a ratio of 200 g/Lwas stirred for 10 minutes and then de-watered to obtain a cake-like compound. The cake-like compound was dried for 2 hours at 75°C and 10 hours at 120°C in a vacuum dryer, and then used for various evaluations.
Using mercury intrusion porosimetry, the cumulative pore volume of pores having diameters of 25-336 nm was determined for the precursor composite compound and the lithium-metal composite oxide following primary firing. The pore diameter was calculated using the Washburn equation.
Mercury intrusion porosimetry measurement conditions
Measurement device: AutoPore V9620 (produced by Micromeritics)
Mercury surface tension: 480 dynes/cm
Contact angle between mercury and sample: 140 degrees
Evaluation of battery characteristics using coin cell obtained using positive electrode active material sample
A 2032 type coin cell obtained using positive electrode active material particles was produced using a positive electrode, a negative electrode and an electrolyte solution which were produced using the following methods.
Positive electrode: Using acetylene black and graphite at a weight ratio of 1:1 as an electrically conductive agent and poly(vinylidene fluoride) as a binder, a positive electrode active material, the electrically conductive agent and the binder were blended at a weight ratio of 90:6:4, and these were mixed with N-methylpyrrolidone and coated on an aluminum foil. A sheet was produced by drying the coated aluminum foil at 110°C, and the sheet was punched out at a diameter of 15mm<P, and rolled at a pressure of 3 t/cm2 to obtain a positive electrode.
Negative electrode: A lithium foil having a thickness of 500 pm was punched out at a diameter of 16 mmcp and used as a negative electrode.
Electrolyte solution: A mixed solvent of EC and DMC was prepared at an EC:DMC volume ratio of 1:2, and a solution obtained by mixing an electrolyte with 1 mol/L of LiPFs was used as an electrolyte solution.
Reactive resistance of non-;
The coin cell produced using the method described above was subjected to constant current charging up to a voltage of 4.3 V at a current density of 0.1 C in an environment at a temperature of 25°C, and when the voltage reached 4.3 V, the coin cell was subjected to constant voltage charging until a rate of 0.01 C was reached. The coin cell was allowed to rest for 5 minutes, and then subjected to constant current discharging in the same environment at a current density of 0.1 C to a voltage of 3.0 V. The coin cell was allowed to rest for a further 5 minutes and then subjected to constant current charging in the same environment up to a voltage of 4.3 V at a current density of 0.1 C, and when the voltage reached 4.3 V, the coin cell was subjected to constant voltage charging until a rate of 0.01 C was reached, and then allowed to rest for 5 minutes. Next, impedance measurements were carried out under the following conditions, and reactive resistance was calculated.
Impedance measurement devices: Solartron 1400 & FRA 1470, produced by Solartron
Measurement environment: 25°C
Coin cell: half-cell
Measurement voltage: 4.3 V
Applied voltage: 10 mV
Scanning frequency: 1 M to 0.01 Hz
A coin cell produced using the method described above was subjected to a cycle test.
1). Initial charging and discharging
The coin cell was subjected to constant current charging up to a voltage of 4.3 V at a current density of 0.2 C in an environment at a temperature of 60°C, and when the voltage reached 4.3 V, the coin cell was subjected to constant voltage charging until a rate of 0.01 C was reached. The coin cell was then allowed to rest for 5 minutes, and then subjected to constant current discharging in the same environment at a current density of 0.2 C from a voltage of 4.3 V to a voltage of 3.0 V. Next, the coin cell was allowed to rest for 5 minutes and then subjected to constant current charging in the same environment up to a voltage of 4.3 V at a current density of 0.1 C, and when the voltage reached 4.3 V, the coin cell was subjected to constant voltage charging until a rate of 0.01 C was reached, and then allowed to rest for 5 minutes.
2). Cycle test
The coin cell was subjected to constant current charging up to a voltage of 4.3 V at a current density of 0.5 C in an environment at a temperature of 60°C, and when the voltage reached 4.3 V, the coin cell was subjected to constant voltage charging until a rate of 0.01 C was reached, allowed to rest for 5 minutes, then subjected to constant current discharging in the same environment at a current density of 1 .0 C until a voltage of 3.0 V was reached, and then allowed to rest for 5 minutes, and this procedure was repeated 100 times. Next, cycle characteristics were calculated on the basis of the following formula.
Cycle characteristics (%) = [(discharge capacity for 100th cycle)/(discharge capacity for first cycle)] x 1OO(%)
The uniformity of an added element M2 in secondary particles in a positive electrode active material sample was evaluated in the following way.
SEM-EDX measurements of cross-section of secondary particle
A cross-section of a secondary particle was produced using a cross-section polisher (SM-09010) produced by JEOL Ltd. at an accelerating voltage of 6 kV.
SEM-EDX measurements of the cross-section of the secondary particle were carried out using a field emission type scanning electron microscope (JSM-7100F produced by JEOL Ltd.) at an accelerating voltage of 20 kV. First, quantitative analysis was carried out at a distance of 1 pm from the top surface of the secondary particle towards the center of gravity of the cross-section, and the added element M2/(Ni+Co+Mn) ratio at a distance of 1 pm from the top surface of the secondary particle was calculated from the obtained atomic weight ratios of the added element M2 and Ni, Co and Mn. Next, quantitative analysis was carried out at the center of gravity of the cross-section, and the added element M2/(Ni+Co+Mn) ratio at the furthest point from the top surface of the secondary particle was calculated from the obtained atomic weight ratios of the added element M2 and Ni, Co and Mn.
The SEM-EDX measurements described above were carried out on 100 secondary particles having lengths of 20 pm or more, the average of 100 values for added element M2/(Ni+Co+Mn) at a distance of 1 pm from the top surface of the secondary particle was calculated as A for the value of added element M2/(Ni+Co+Mn) at the secondary particle surface, and the average of 100 values for added element M2/(Ni+Co+Mn) at the furthest point from the top surface of the secondary particle was calculated as B for the value of added element M2/(Ni+Co+Mn) at the secondary particle center.
Next, a value obtained by dividing B by A (B/A) was calculated as an indicator for assessing the uniformity of the added element M2 in secondary particles.
<Evaluation results>
Examples 1-3 and Comparative Examples 1-3 were evaluated in the manner described above. The results are shown in Table 1.
Examples 4-9 and Comparative Examples 4-11 were evaluated in the manner described above. The results are shown in Table 2. Note that B/A values are not shown in the tables, but the activated lithium-metal composite oxides of Examples 4-9 satisfied a B/A value of 0.9 or more, and Comparative Examples 4-11 had B/A values of less than 0.90.

Claims

1. A lithium-metal composite oxide which is represented by the general formula LixNii-y.z-wCOyMnzM1 wO2+a (in the formula, M1 is one or more elements other than Li, Ni, Co, Mn and O, 0<x<1.2, 0<y<0.4, 0<z<0.4, 0<w<0.1 and -1.0<a<0.5) and which has a cumulative pore volume of 25 pL/g or more within a pore diameter range of 25 nm to 334 nm, as measured using mercury intrusion porosimetry.
2. A method for producing an activated lithium-metal composite oxide, the method including: a mixing step for mixing at least the lithium-metal composite oxide according to claim 1 and a compound that contains, independently of M1, one or more elements M2 other than Li, Ni, Co, Mn and O to obtain a raw material mixture; and a firing step for firing the raw material mixture in an oxidizing atmosphere.
3. The method for producing an activated lithium-metal composite oxide according to claim 2, wherein a lithium compound is also mixed in the mixing step.
4. An activated lithium-metal composite oxide powder which is represented by the general formula LixNii.y-z-w-vCOyMnzM1 w 2vO2+a (in the formula, M1 and M2 are each independently one or more elements other than Li, Ni, Co, Mn and O, 0.9<x<1.2, 0<y<0.4, 0<z<0.4, 0<w<0.1 , 0<v<0.1 and -1.0<a<0.5), and the ratio of the proportion of the total amount of M2 relative to the total amount of Ni, Co and Mn in terms of mass in the center of a particle is 0.90 or more relative to the proportion of the total amount of M2 relative to the total amount of Ni, Co and Mn in terms of mass at a position 1 pm from the surface.
5. The activated lithium-metal composite oxide powder according to claim 4, wherein M2 is W.
6. The activated lithium-metal composite oxide powder according to any one of claims 4 to 5, which includes a secondary particle for which the distance from the surface to the center of the particle is 10pm or more.
7. A positive electrode active material for a non-aqueous electrolyte secondary battery, which contains the activated lithium-metal composite oxide powder according to any one of claims 4 to 5.
8. A non-aqueous electrolyte secondary battery which comprises the positive electrode active material for a non-aqueous electrolyte secondary battery according to claim 7.
PCT/EP2025/063329 2024-05-24 2025-05-15 Lithium-metal composite oxide, method for producing activated lithium-metal composite oxide, activated lithium-metal composite oxide powder, positive electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery Pending WO2025242519A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014197556A (en) 2011-05-30 2014-10-16 住友金属鉱山株式会社 Positive electrode active material for nonaqueous secondary battery and nonaqueous electrolyte secondary battery using positive electrode active material
EP3272710A1 (en) * 2016-07-20 2018-01-24 Samsung SDI Co., Ltd. Nickel-based active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including positive electrode including the nickel-based active material
WO2022208047A1 (en) * 2021-03-31 2022-10-06 Ev Metals Uk Limited Process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014197556A (en) 2011-05-30 2014-10-16 住友金属鉱山株式会社 Positive electrode active material for nonaqueous secondary battery and nonaqueous electrolyte secondary battery using positive electrode active material
EP3272710A1 (en) * 2016-07-20 2018-01-24 Samsung SDI Co., Ltd. Nickel-based active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including positive electrode including the nickel-based active material
WO2022208047A1 (en) * 2021-03-31 2022-10-06 Ev Metals Uk Limited Process

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