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WO2012121220A1 - Matériau actif d'électrode positive pour batterie secondaire au lithium-ion et son procédé de production - Google Patents

Matériau actif d'électrode positive pour batterie secondaire au lithium-ion et son procédé de production Download PDF

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Publication number
WO2012121220A1
WO2012121220A1 PCT/JP2012/055588 JP2012055588W WO2012121220A1 WO 2012121220 A1 WO2012121220 A1 WO 2012121220A1 JP 2012055588 W JP2012055588 W JP 2012055588W WO 2012121220 A1 WO2012121220 A1 WO 2012121220A1
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Prior art keywords
lithium
positive electrode
active material
electrode active
oxide
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Ceased
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PCT/JP2012/055588
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English (en)
Japanese (ja)
Inventor
角崎　健太郎
海生 曽
河里　健
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AGC Inc
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Asahi Glass Co Ltd
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Priority to JP2013503541A priority Critical patent/JP5928445B2/ja
Publication of WO2012121220A1 publication Critical patent/WO2012121220A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C01G45/1228—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO2)-, e.g. LiMnO2 or Li(MxMn1-x)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Complex oxides containing cobalt and at least one other metal element
    • C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
    • C01G51/44—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/50—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode active material for a lithium ion secondary battery and a method for producing the same.
  • the present invention also relates to a positive electrode and a lithium ion secondary battery using the positive electrode active material of the present invention.
  • Lithium ion secondary batteries are widely used in portable electronic devices such as mobile phones and notebook computers.
  • a positive electrode active material for a lithium ion secondary battery a composite oxide of lithium and a transition metal or the like such as LiCoO 2 , LiNiO 2 , LiNi 0.8 Co 0.2 O 2 , LiMn 2 O 4 is used.
  • cycle the discharge capacity per unit mass or the characteristic that the discharge capacity does not decrease after repeated charge / discharge cycles
  • Further improvement is also desired.
  • rate characteristics in which the discharge capacity does not decrease when discharged at a high discharge rate is desired.
  • Patent Document 1 discloses that the surface of a lithium nickel composite oxide represented by LiNi 0.82 Co 0.15 Al 0.03 O 2 is coated with niobium oxide or titanium oxide, and then the lithium nickel composite oxide. A method for producing a surface-modified lithium-nickel composite oxide is shown.
  • Li (1 + x) Co ( 1-y) M y O ( 2 ⁇ 2) has a molar amount of Li element that is 0.9-1.1 times the molar amount of the total molar amount of transition metal elements.
  • z) The surface of the lithium-containing composite oxide represented by ( ⁇ 0.10 ⁇ x ⁇ 0.10, 0 ⁇ y ⁇ 0.50, ⁇ 0.10 ⁇ z ⁇ 0.20) has a crystal phase.
  • a positive electrode active material having a coating layer made of a metal oxide containing no Mo is shown.
  • a particle of a positive electrode active material represented by 0.99 Nb 0.01 O 2 is described. It is also described that the particles have a small amount of Nb in the center of the particle and a large amount of niobium on the outside of the particle.
  • the present invention provides a positive electrode active material for a lithium ion secondary battery having a high ratio of transition metal to Li, which is excellent in cycle characteristics and rate characteristics even when charged at a high voltage, and a method for producing the same. .
  • the present invention also provides a positive electrode using the positive electrode active material and a lithium ion secondary battery.
  • the gist of the present invention is as follows. [1] Including Li element and at least one transition metal element selected from the group consisting of Ni, Co, and Mn (provided that the molar amount of Li element is 1. with respect to the total molar amount of the transition metal element.
  • a positive electrode active material for a lithium ion secondary battery characterized by comprising particles (X) in which the surface of a lithium-containing composite oxide is coated with the following oxide (I).
  • Oxide (I) An oxide containing at least one metal element selected from the group consisting of Nb and Mo. [2] The above [1], wherein the total molar amount of Nb and Mo in the oxide (I) is 0.0005 to 0.06 times the molar amount of the transition metal element of the lithium-containing composite oxide. ] The positive electrode active material for lithium ion secondary batteries of description. [3] The above-mentioned [1] or [2], wherein the particles (X) are particles in which part or all of the surface of the lithium-containing composite oxide is coated with an amorphous layer of oxide (I). Positive electrode active material for lithium ion secondary battery.
  • Me is at least one element selected from the group consisting of Co, Ni, Cr, Fe, Al, Ti, Zr, Mo, Nb, V, and Mg.
  • composition (1) A composition comprising a compound containing at least one metal element selected from the group consisting of Nb and Mo dissolved or dispersed in a solvent.
  • the positive electrode active material of the present invention is excellent in cycle characteristics and rate characteristics even when charged at a high voltage.
  • the positive electrode and the lithium ion secondary battery of the present invention are excellent in cycle characteristics and rate characteristics even when charged at a high voltage. Furthermore, according to the production method of the present invention, it is possible to produce a positive electrode active material that is excellent in cycle characteristics and rate characteristics even when charged at a high voltage.
  • the positive electrode active material of the present invention contains Li element and at least one transition metal element selected from the group consisting of Ni, Co, and Mn (provided that the molar amount of Li element is the total molar amount of the transition metal element) From the particles (X) coated with the oxide (I) containing at least one metal element selected from the group consisting of Nb and Mo on the surface of the lithium-containing composite oxide. It is characterized by becoming.
  • the lithium-containing composite oxide in the present invention contains Li element and at least one transition metal element selected from the group consisting of Ni, Co, and Mn.
  • the molar amount of Li element is more than 1.2 times the total molar amount of the transition metal element ⁇ (Molar amount of Li element / total molar amount of transition metal element)> 1.2 ⁇ .
  • the ratio (molar ratio) of the Li element to the total molar amount of the transition metal element is preferably 1.25 to 1.75, and more preferably 1.25 to 1.65. By setting the ratio, the discharge capacity per unit mass of the lithium ion secondary battery can be further increased.
  • the transition metal element contained in the lithium-containing composite oxide is at least one selected from the group consisting of Ni, Co, and Mn, more preferably Mn is essential, and all elements of Ni, Co, and Mn It is especially preferable that it contains.
  • metal elements other than Ni, Co, Mn, and Li may be included.
  • other metal elements include at least one selected from the group consisting of Cr, Fe, Al, Ti, Zr, Mo, Nb, V, and Mg.
  • the ratio of the other metal element is preferably 0.001 to 0.50 mol, and more preferably 0.005 to 0.05 mol in the total amount (1 mol) of the transition metal element.
  • the lithium-containing composite oxide in the present invention is preferably represented by the following formula (1).
  • the lithium-containing composite oxide represented by the formula (1) has a composition before undergoing charge / discharge and activation steps.
  • activation means removing lithium oxide (Li 2 O) or lithium and lithium oxide from the lithium-containing composite oxide.
  • As a preferable activation method there is an electrochemical activation method in which a voltage higher than 4.4 V or 4.6 V (expressed as a potential difference from the oxidation / reduction potential of Li + / Li) is applied.
  • the chemical activation method by performing chemical reaction using acids, such as a sulfuric acid, hydrochloric acid, or nitric acid, is mentioned.
  • Me is at least one element selected from the group consisting of Co, Ni, Cr, Fe, Al, Ti, Zr, Mo, Nb, V, and Mg.
  • 0.09 ⁇ x ⁇ 0.3, y> 0, z> 0, 1.9 ⁇ p ⁇ 2.1, 0 ⁇ q ⁇ 0.1, and 0.4 ⁇ y / (y + z) ⁇ 0.8, x + y + z 1, 1.2 ⁇ (1 + x) / (y + z). That is, the ratio of Li exceeds 1.2 times mol with respect to the sum of Mn and Me.
  • the formula (1) is also characterized in that it contains a specific amount of Mn, and the ratio of Mn to the total amount of Mn and Me is preferably 0.4 to 0.8, more preferably 0.55 to 0.75.
  • Mn is in the above range, the discharge capacity becomes high.
  • q represents the proportion of F, but q is 0 when F is not present.
  • p is a value determined according to x, y, z, and q, and is 1.9 to 2.1.
  • At least one element selected from the group consisting of Co, Ni, and Cr is preferable, and Co and Ni are particularly preferable.
  • 0.1 ⁇ x ⁇ 0.25 is preferable, 0.11 ⁇ x ⁇ 0.22 is more preferable, 0.5 ⁇ y / (y + z) ⁇ 0.8 is preferable, and 55 ⁇ y / (y + z) ⁇ 0.75 is more preferable.
  • the Co / Ni molar ratio is preferably 0 to 1, and more preferably 0 to 0.5.
  • lithium-containing composite oxide examples include Li (Li 0.13 Ni 0.26 Co 0.09 Mn 0.52 ) O 2 and Li (Li 0.13 Ni 0.22 Co 0.09 Mn 0.56 ) O. 2 , Li (Li 0.13 Ni 0.17 Co 0.17 Mn 0.53 ) O 2 , Li (Li 0.15 Ni 0.17 Co 0.13 Mn 0.55 ) O 2 , Li (Li 0 .16 Ni 0.17 Co 0.08 Mn 0.59 ) O 2 , Li (Li 0.17 Ni 0.17 Co 0.17 Mn 0.49 ) O 2 , Li (Li 0.17 Ni 0.21 Co 0.08 Mn 0.54 ) O 2 , Li (Li 0.17 Ni 0.14 Co 0.14 Mn 0.55 ) O 2 , Li (Li 0.18 Ni 0.12 Co 0.12 Mn 0 .58 ) O 2 , Li (Li 0.1 8 Ni 0.16 Co 0.12 Mn 0.54 ) O 2 , Li (Li 0.20 Ni 0.12 Co 0.08 Mn 0.60 ) O.
  • Still lithium-containing complex oxide Li (Li 0.16 Ni 0.17 Co 0.08 Mn 0.59) O 2, Li (Li 0.17 Ni 0.17 Co 0.17 Mn 0.49) O 2 , Li (Li 0.17 Ni 0.21 Co 0.08 Mn 0.54 ) O 2 , Li (Li 0.17 Ni 0.14 Co 0.14 Mn 0.55 ) O 2 , Li (Li 0.18 Ni 0.12 Co 0.12 Mn 0.58 ) O 2 , Li (Li 0.18 Ni 0.16 Co 0.12 Mn 0.54 ) O 2 , Li (Li 0.20 Ni 0. 12 Co 0.08 Mn 0.60 ) O 2 , Li (Li 0.20 Ni 0.16 Co 0.08 Mn 0.56 ) O 2 , or Li (Li 0.20 Ni 0.13 Co 0.13 Mn 0.54) O 2 is particularly Masui.
  • the ratio of the Li element to the total molar amount of the transition metal element is 1.2 ⁇ (1 + x) / (y + z). .25 ⁇ (1 + x) / (y + z) ⁇ 1.75 is preferable, and 1.25 ⁇ (1 + x) / (y + z) ⁇ 1.65 is more preferable.
  • the ratio is in the above range, a positive electrode material having a high discharge capacity per unit mass can be obtained.
  • the shape of the lithium-containing composite oxide is preferably particulate.
  • the average particle size (D50) of the lithium-containing composite oxide is preferably 3 to 30 ⁇ m, more preferably 4 to 25 ⁇ m, and particularly preferably 5 to 20 ⁇ m.
  • the average particle size (D50) is a particle size distribution at a point where the cumulative curve is 50% in a cumulative curve obtained by obtaining a particle size distribution on a volume basis and setting the total volume to 100%. It means% diameter.
  • the particle size distribution is obtained from a frequency distribution and a cumulative volume distribution curve measured with a laser scattering particle size distribution measuring apparatus.
  • the particle size is measured by sufficiently dispersing the powder in an aqueous medium by ultrasonic treatment or the like (for example, using a laser diffraction / scattering particle size distribution measuring device Partica LA-950VII manufactured by HORIBA). Is required.
  • the specific surface area of the lithium-containing composite oxide is preferably 0.3 ⁇ 10m 2 / g, particularly preferably 0.5 ⁇ 5m 2 / g.
  • the specific surface area is 0.3 to 10 m 2 / g, the capacity is high and a dense positive electrode layer can be formed.
  • the lithium-containing composite oxide in the present invention preferably has a layered rock salt type crystal structure (space group R-3m).
  • XRD X-ray diffraction
  • the oxide (I) is an oxide containing at least one metal element selected from the group consisting of Nb and Mo.
  • the oxide (I) include Nb oxides such as NbO, Nb 2 O 3 and Nb 2 O 5 ; Nb composite oxides such as LiNbO 3 and Li 3 NbO 4 ; Mo oxides such as MoO 2 and MoO 3 A complex oxide of Mo such as Li 2 MoO 3 , Li 2 MoO 4 , and Li 6 Mo 7 O 24 ;
  • the positive electrode active material of the present invention can reduce the contact between the lithium-containing composite oxide and the electrolyte by coating the oxide (I), Mn from the surface of the lithium-containing composite oxide to the electrolyte It is considered that elution of transition metal elements such as can be suppressed and cycle characteristics are improved.
  • the oxide (I) has conductivity or Li ion diffusibility, it is considered that the conductivity and Li ion diffusibility of the lithium-containing composite oxide surface are improved and rate characteristics are improved.
  • the oxide (I) may be crystalline, amorphous, or amorphous.
  • amorphous means that a peak attributed to the oxide (I) is not observed in X-ray diffraction measurement (hereinafter also referred to as XRD).
  • XRD X-ray diffraction measurement
  • the shape of the oxide (I) coated on the surface of the lithium-containing composite oxide may be a particle shape, a film shape, a fiber shape, a lump shape, or the like.
  • the average particle size of the oxide (I) is preferably from 0.1 to 100 nm, more preferably from 0.1 to 50 nm, and particularly preferably from 0.1 to 30 nm.
  • the shape and average particle diameter of the oxide (I) can be evaluated with an electron microscope such as SEM (scanning electron microscope) or TEM (transmission electron microscope). The average particle diameter is expressed as an average particle diameter of particles covering the surface of the lithium-containing composite oxide.
  • the particles (X) in the present invention are particles in which the surface of the lithium-containing composite oxide is coated with the oxide (I).
  • the coating means a state in which the oxide (I) is chemically adsorbed or physically adsorbed on part or all of the surface of the lithium-containing composite oxide.
  • the shape of the particles (X) may be particulate, fibrous, massive, or the like.
  • the average particle diameter of the particles (X) is preferably 3 to 30 ⁇ m, more preferably 4 to 25 ⁇ m, and particularly preferably 5 to 20 ⁇ m.
  • the oxide (I) may be at least partially coated on the surface of the lithium-containing composite oxide.
  • the particles (X) are preferably particles in which an amorphous layer of the oxide (I) covers a part or all of the surface of the lithium-containing composite oxide.
  • the oxide (I) is coated on the surface of the lithium-containing composite oxide.
  • the cross section is polished, and the X-ray microanalyzer analysis method ( It can be evaluated by elemental mapping with EPMA).
  • the oxide (I) is the center of the lithium-containing composite oxide (here, the center is a portion not in contact with the surface of the lithium-containing composite oxide, and the average distance from the surface is the longest). It can be confirmed that it is present more in the range of 30 nm from the surface.
  • the total molar amount of Nb and Mo in the oxide (I) in the particle (X) is 0.0005 to 0.06 times the molar amount of the transition metal element in the particle (X) of the lithium-containing composite oxide. Is preferable, 0.001 to 0.04 times is more preferable, and 0.0025 to 0.03 times is particularly preferable. If it is the said range, discharge capacity is large and it is excellent in a rate characteristic and cycling characteristics.
  • the proportion of the metal element present in the oxide (I) in the particles (X) can be measured by dissolving the positive electrode active material in an acid and performing ICP (high frequency inductively coupled plasma) measurement.
  • ICP high frequency inductively coupled plasma
  • the production method of the present invention includes Li element and at least one transition metal element selected from the group consisting of Ni, Co, and Mn (provided that the molar amount of Li element is the total molar amount of the transition metal element).
  • the lithium-containing composite oxide is brought into contact with the above composition (1) and heated at 250 to 850 ° C. to thereby form an oxide on the surface of the lithium-containing composite oxide. It is a method for obtaining a positive electrode active material for a lithium ion secondary battery, characterized in that it comprises particles (X) coated with (I).
  • Composition (1) A composition comprising a compound containing at least one metal element selected from the group consisting of Nb and Mo dissolved or dispersed in a solvent.
  • the lithium-containing composite oxide can be used, and the preferred embodiment is also the same.
  • a method for producing a lithium-containing composite oxide a method of mixing and baking a precursor of a lithium-containing composite oxide obtained by a coprecipitation method and a lithium compound, a hydrothermal synthesis method, a sol-gel method, a dry mixing method, an ion The exchange method etc. are mentioned. Since the discharge capacity is excellent because the transition metal elements contained are uniformly mixed, there is a method in which a precursor (coprecipitation composition) of a lithium-containing composite oxide obtained by a coprecipitation method and a lithium compound are mixed and fired. preferable.
  • the composition (1) is a composition obtained by dissolving or dispersing a compound containing at least one metal element selected from the group consisting of Nb and Mo in a solvent, particularly a composition obtained by dissolving a compound containing a metal element in a solvent. Things are preferred.
  • Nb Compounds containing Nb include niobium nitrate, niobium sulfate, niobium chloride, niobium acetate, niobium citrate, niobium maleate, niobium formate, niobium lactate, niobium lactate, niobium oxalate, niobium oxalate, sodium niobate, Organic salts or organic complexes such as potassium niobate, lithium niobate and ammonium niobate, niobium oxide, and niobium hydroxide are preferred.
  • the organic salt or the organic complex is preferable, and niobium oxalate is particularly preferable because it is easily decomposed by heat to generate an oxide and has high solubility in a solvent.
  • sodium molybdate, potassium molybdate, lithium molybdate, ammonium molybdate, molybdenum oxide, or molybdenum hydroxide is preferable. It is easily decomposed by heat to form an oxide, and is soluble in a solvent. Is high, ammonium molybdate represented by (NH 4 ) 6 Mo 7 O 24 is particularly preferable.
  • the compound containing at least one metal element selected from the group consisting of Nb and Mo is preferably fine particles.
  • the average particle diameter of the fine particles is preferably 1 to 100 nm, more preferably 2 to 50 nm, and particularly preferably 3 to 30 nm.
  • the average particle diameter can be determined by a dynamic light scattering method.
  • the solvent for the composition (1) is preferably a solvent containing water in terms of stability and reactivity of the compound containing a metal element, more preferably a mixed solvent of water and a water-soluble alcohol and / or polyol, and only water.
  • the water-soluble alcohol include methanol, ethanol, 1-propanol, and 2-propanol.
  • the polyol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, butanediol, and glycerin.
  • the total content of the water-soluble alcohol and the polyol contained in the solvent is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, based on the amount of the solvent.
  • the solvent is only water, it is particularly preferable because it is excellent in terms of safety, environment, handling, and cost.
  • the composition (1) may contain a pH adjuster.
  • a pH adjuster those that volatilize or decompose upon heating are preferable. Specifically, organic acids such as acetic acid, citric acid, lactic acid, formic acid, maleic acid, and oxalic acid, and ammonia are preferable.
  • organic acids such as acetic acid, citric acid, lactic acid, formic acid, maleic acid, and oxalic acid, and ammonia are preferable.
  • a pH adjuster that volatilizes or decomposes is used, it is difficult for impurities to remain, so that good battery characteristics are easily obtained.
  • the concentration of the compound containing a metal element contained in the composition (1) is preferably higher from the viewpoint that the solvent needs to be removed by heating in a later step. However, if the concentration is too high, the viscosity increases and the uniform mixing property of the composition (1) with another element source that forms the positive electrode active material decreases. ) In terms of conversion, 0.5 to 30% by mass is preferable, and 4 to 20% by mass is particularly preferable.
  • a spray coating method, a dipping method or the like can be applied, and a method of spraying the composition (1) on the lithium-containing composite oxide by the spray coating method is particularly preferable.
  • the immersion method it is necessary to remove the solvent by filtration or evaporation after the contact, so that the process may be complicated.
  • the spray coating method the process is simple, and the oxide (I) can be uniformly coated on the surface of the lithium-containing composite oxide.
  • the amount of the composition (1) to be brought into contact with the lithium-containing composite oxide is preferably 1 to 50% by weight, more preferably 2 to 40% by weight, and particularly preferably 3 to 30% by weight with respect to the lithium-containing composite oxide. . Within the above range, it is easy to uniformly coat the oxide (I) on the surface of the lithium-containing composite oxide, and the lithium-containing composite oxide is formed when the composition (1) is spray-coated on the lithium-containing composite oxide. Easy to stir without clumping.
  • the composition (1) is added to the lithium-containing composite oxide under stirring, and the lithium-containing composite oxide and the composition (1) are mixed together, whereby the composition ( It is preferable to contact 1) with the lithium-containing composite oxide.
  • a drum mixer or a solid-air low shear stirring device can be used as the stirring device.
  • the lithium-containing composite oxide is brought into contact with the composition (1) and heated at 250 to 850 ° C. Heating is preferably performed in an oxygen-containing atmosphere because the oxide (I) is easily formed from a compound containing at least one metal element selected from the group consisting of Nb and Mo.
  • the heating temperature is 250 to 850 ° C, more preferably 350 to 700 ° C.
  • the heating temperature is 250 ° C. or higher, it is easy to form oxide (I) from a compound containing at least one metal element selected from the group consisting of Nb and Mo, and volatile impurities such as residual moisture are reduced. Therefore, the deterioration of cycle characteristics can be suppressed.
  • the heating temperature is 850 ° C. or lower, it is possible to prevent Nb from diffusing inside the particles (X) and reducing the capacity.
  • the heating temperature is preferably 250 ° C. to 550 ° C., more preferably 300 to 500 ° C., and particularly preferably 350 to 480 ° C. . If the heating temperature is less than 550 ° C., the oxide (I) is difficult to crystallize.
  • the heating time is preferably 0.1 to 24 hours, more preferably 0.5 to 18 hours, and particularly preferably 1 to 12 hours.
  • the positive electrode for a lithium ion secondary battery of the present invention is formed by forming a positive electrode active material layer containing the positive electrode active material of the present invention, a conductive material, and a binder on a positive electrode current collector.
  • Examples of the method for producing a positive electrode for a lithium ion secondary battery include a method in which the positive electrode active material, the conductive material and the binder of the present invention are supported on a positive electrode current collector.
  • the conductive material and binder are dispersed in a solvent and / or dispersion medium to prepare a slurry, or a kneaded material kneaded with the solvent and / or dispersion medium is prepared, and then a positive electrode current collector is collected by a method such as a coating method. It can be carried on the body.
  • Examples of the conductive material include carbon black such as acetylene black, graphite, and ketjen black.
  • fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene, polyolefins such as polyethylene and polypropylene, polymers having unsaturated bonds such as styrene / butadiene rubber, isoprene rubber and butadiene rubber, and copolymers thereof,
  • acrylic acid-based polymers such as acrylic acid copolymers and methacrylic acid copolymers, and copolymers thereof.
  • the positive electrode current collector may be aluminum or an aluminum alloy.
  • the lithium ion secondary battery of this invention contains the said positive electrode for lithium ion secondary batteries, a negative electrode, and a nonaqueous electrolyte.
  • the negative electrode is formed by forming a negative electrode active material layer containing a negative electrode active material on a negative electrode current collector.
  • a negative electrode active material layer containing a negative electrode active material on a negative electrode current collector.
  • it can be produced by preparing a slurry by kneading a negative electrode active material with an organic solvent, and applying, drying, and pressing the prepared slurry to a negative electrode current collector.
  • the negative electrode current collector for example, a metal foil such as a nickel foil or a copper foil can be used.
  • the negative electrode active material may be any material that can occlude and release lithium ions at a relatively low potential, such as lithium metal, lithium alloy, lithium compound, carbon material, periodic table 14 and group 15 metal. Oxides, carbon compounds, silicon carbide compounds, silicon oxide compounds, titanium sulfide, boron carbide compounds, and the like can be used.
  • lithium alloys and lithium compounds composed of lithium and a metal capable of forming an alloy or compound with lithium can be used.
  • Examples of the carbon material for the negative electrode active material include non-graphitizable carbon, artificial graphite, natural graphite, pyrolytic carbon, coke such as pitch coke, needle coke, petroleum coke, graphite, glassy carbon, phenol Organic polymer compound fired bodies, carbon fibers, activated carbon, carbon blacks, etc., obtained by firing and carbonizing a resin, furan resin or the like at an appropriate temperature can be used.
  • the group 14 metal of the periodic table is silicon or tin, with silicon being preferred.
  • Other materials that can be used as the negative electrode active material include oxides such as iron oxide, ruthenium oxide, molybdenum oxide, tungsten oxide, titanium oxide, and tin oxide, and nitrides such as Li 2.6 Co 0.4 N. It is done.
  • nonaqueous electrolyte it is preferable to use a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent.
  • a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent.
  • the non-aqueous electrolyte one prepared by appropriately combining an organic solvent and an electrolyte can be used.
  • organic solvent those known as organic solvents for electrolytic solutions can be used, such as propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, diglyme, triglyme, ⁇ -Butyrolactone, diethyl ether, sulfolane, methyl sulfolane, acetonitrile, acetate ester, butyrate ester, propionate ester, and the like can be used.
  • cyclic carbonates such as propylene carbonate and chain carbonates such as dimethyl carbonate and diethyl carbonate.
  • An organic solvent may be used individually by 1 type, and may mix and use 2 or more types.
  • non-aqueous electrolyte a solid electrolyte containing an electrolyte salt, a polymer electrolyte, a solid electrolyte obtained by mixing or dissolving an electrolyte in a polymer compound, or the like can be used.
  • the solid electrolyte may be any material having lithium ion conductivity, and an inorganic solid electrolyte and a polymer solid electrolyte can be used.
  • an inorganic solid electrolyte lithium nitride, lithium iodide, or the like can be used.
  • an electrolyte salt and a polymer compound that dissolves the electrolyte salt can be used.
  • electrolyte salt and the polymer compound that dissolves the electrolyte salt examples include polyethylene oxide, polypropylene oxide, polyphosphazene, polyaziridine, polyethylene sulfide, polyvinyl alcohol, polyvinylidene fluoride, and polyhexafluoropropylene, or derivatives, mixtures thereof, And composites can be used.
  • the gel electrolyte or the like various polymer compounds that absorb the nonaqueous electrolyte and gelate can be used.
  • the polymer compound used for the gel electrolyte fluorine-based polymers such as poly (vinylidene fluoride) and poly (vinylidene fluoride-hexafluoropropylene) copolymers can be used.
  • an ether polymer such as polyacrylonitrile, a polyacrylonitrile copolymer, polyethylene oxide, a polyethylene oxide copolymer, and a crosslinked product thereof can be used.
  • Examples of the monomer used in the copolymer include polypropylene oxide, methyl methacrylate, butyl methacrylate, methyl acrylate, and butyl acrylate.
  • a fluorine-based polymer is particularly preferable from the viewpoint of stability against redox reaction.
  • LiClO 4 LiPF 6 , LiBF 4 , CH 3 SO 3 Li, or the like
  • the shape of the lithium ion secondary battery of the present invention can be appropriately selected from coin shapes, sheet shapes (film shapes), folded shapes, wound bottomed cylindrical shapes, button shapes, and the like according to applications. .
  • Distilled water (1920.8 g) was added to ammonium sulfate (79.2 g) and dissolved uniformly to obtain a mother liquor.
  • Distilled water 600 g was added to sodium hydroxide (400 g) and dissolved uniformly to obtain a pH adjusting solution.
  • the mother liquor was placed in a 2 L baffled glass reaction vessel, heated to 50 ° C. with a mantle heater, and a pH adjusting solution was added so that the pH was 11.0.
  • the raw material solution was added at a rate of 5.0 g / min, and the ammonia source solution was added at a rate of 1.0 g / min, and a composite hydroxide of nickel, cobalt, and manganese was added. Precipitated.
  • a pH adjusting solution was added so as to keep the pH in the reaction vessel at 11.0.
  • nitrogen gas was flowed at a flow rate of 0.5 L / min in the reaction tank so that the precipitated hydroxide was not oxidized. Further, the liquid was continuously extracted so that the amount of the liquid in the reaction tank did not exceed 2 L.
  • the precursor (20 g) and lithium carbonate (12.6 g) having a lithium content of 26.9 mol / kg were mixed and calcined at 900 ° C. for 12 hours in an oxygen-containing atmosphere to obtain a lithium-containing composite oxide.
  • the composition of the obtained lithium-containing composite oxide (hereinafter referred to as the lithium-containing composite oxide in the synthesis example) is Li (Li 0.2 Ni 0.137 Co 0.125 Mn 0.538 ) O 2 .
  • the average particle diameter D50 of the lithium-containing composite oxide was 5.9 ⁇ m, and the specific surface area measured using the BET (Brunauer, Emmett, Teller) method was 2.6 m 2 / g.
  • Example 1 Preparation niobium oxalate solution of lithium-containing composite oxide coated with Nb (Nb concentration Nb 2 O 3 in terms of 8.0% by mass, an oxalic acid concentration of 22.8%, specific gravity 1.16 g / cc ) 7.7 g of distilled water was added to 7.3 g to prepare an Nb aqueous solution (composition (1)). Next, 3 g of the prepared Nb aqueous solution was sprayed and added to 15 g of the lithium-containing composite oxide of the synthesis example under stirring, and the lithium-containing composite oxide of the synthesis example and the Nb aqueous solution were contacted while being mixed. . Next, the obtained mixture was dried at 90 ° C.
  • the positive electrode active material of Example 1 consisting of The molar ratio of the amount of niobium coated on the surface of the obtained positive electrode active material and the total amount of nickel, cobalt and manganese contained in the lithium-containing composite oxide before coating, ⁇ (mol of coated Nb Number) / (total number of moles of Ni, Co, and Mn of the lithium-containing composite oxide before coating) ⁇ is 0.0063.
  • the obtained positive electrode active material was subjected to XRD measurement using CuK ⁇ rays as an X-ray source.
  • RRD measurement the product name RINT-TTR-III manufactured by Rigaku Corporation was used.
  • Example 3 Production example of lithium-containing composite oxide coated with Nb
  • a positive electrode active material of Example 3 was obtained in the same manner as in Example 1 except that the heating temperature was 800 ° C.
  • XRD measurement was performed on the obtained positive electrode active material. From the XRD spectrum, it was confirmed that the positive electrode active material had a layered rock salt type crystal structure (space group R-3m).
  • Example 4 Production example of lithium-containing composite oxide coated with Nb
  • composition (1) 14.6 g of niobium oxalate aqueous solution and 0.4 g of distilled water were used. Obtained the positive electrode active material of Example 4 like Example 1.
  • the molar ratio of the amount of niobium coated on the surface of the obtained positive electrode active material and the total amount of nickel, cobalt and manganese contained in the lithium-containing composite oxide before coating, ⁇ (mol of coated Nb Number) / (total number of moles of Ni, Co, and Mn of the lithium-containing composite oxide before coating) ⁇ is 0.0125.
  • Example 5 Production example of lithium-containing composite oxide coated with Nb When preparing an Nb aqueous solution (Composition (1)), spraying was performed using 14.6 g of niobium oxalate aqueous solution and 0.4 g of distilled water. A positive electrode active material of Example 5 was obtained in the same manner as Example 1 except that the amount of Nb aqueous solution to be changed was 6 g.
  • Example 8 Production example of lithium-containing composite oxide coated with Nb
  • composition (1) 1.46 g of niobium oxalate aqueous solution and 13.54 g of distilled water were used. Obtained a positive electrode active material of Example 8 in the same manner as Example 1.
  • the molar ratio of the amount of niobium coated on the surface of the obtained positive electrode active material and the total amount of nickel, cobalt and manganese contained in the lithium-containing composite oxide before coating, ⁇ (mol of coated Nb Number) / (total number of moles of Ni, Co, and Mn of the lithium-containing composite oxide before coating) ⁇ is 0.0013.
  • Example 9 Production example of lithium-containing composite oxide coated with Nb
  • composition (1) 14.6 g of niobium oxalate aqueous solution and 0.4 g of distilled water were used for spraying.
  • a positive electrode active material of Example 9 was obtained in the same manner as Example 1 except that the amount of Nb aqueous solution to be changed was 12 g.
  • the molar ratio of the amount of niobium coated on the surface of the obtained positive electrode active material and the total amount of nickel, cobalt and manganese contained in the lithium-containing composite oxide before coating, ⁇ (mol of coated Nb Number) / (total number of moles of Ni, Co, and Mn of the lithium-containing composite oxide before coating) ⁇ is 0.050.
  • ⁇ (mol of coated Nb Number) / (total number of moles of Ni, Co, and Mn of the lithium-containing composite oxide before coating) ⁇ is 0.050.
  • Example 10 Preparation of ammonium molybdate of the lithium-containing composite oxide coated with Mo (composition formula (NH 4) 6Mo 7 O 24 ⁇ 4H 2 O) 0.78g in distilled water 14.22 g Mo A solution (composition (1)) was prepared. Next, 3 g of the prepared aqueous Mo solution was sprayed and added to 15 g of the lithium-containing composite oxide of the synthesis example under stirring, and the lithium-containing composite oxide of the synthesis example and the aqueous Mo solution were mixed and contacted. . Next, the obtained mixture was dried at 90 ° C. for 2 hours, and then heated at 500 ° C. for 8 hours in an oxygen-containing atmosphere, so that particles (X) containing Mo element on the surface of the lithium-containing composite oxide were coated (X).
  • the positive electrode active material of Example 10 consisting of
  • the molar ratio of the amount of niobium coated on the surface of the obtained positive electrode active material and the total amount of nickel, cobalt and manganese contained in the lithium-containing composite oxide before coating, ⁇ (mol of coated Nb Number) / (total number of moles of Ni, Co, and Mn of the lithium-containing composite oxide before coating) ⁇ is 0.0063.
  • the result of Mo mapping the particle cross section of the positive electrode active material with EPMA (X-ray microanalyzer) Also, more Mo could be detected on the outer surface of the particles. XRD measurement was performed on the obtained positive electrode active material.
  • the positive electrode active material had a layered rock salt type crystal structure (space group R-3m).
  • the positive electrode active material of Comparative Example 3 is obtained. Molar ratio of the amount of niobium coated on the surface of the obtained positive electrode active material and the total amount of nickel and manganese contained in LiMn 1.5 Ni 0.5 O 4 before coating, ⁇ (coated The number of moles of Nb / (total number of moles of Ni and Mn of the lithium-containing composite oxide before coating) ⁇ is 0.0063.
  • Example of positive electrode production A polyvinylidene fluoride solution containing 12.1% by mass of positive electrode active materials of Examples 1 to 10 and Comparative Examples 1 to 3, acetylene black (conductive material), and polyvinylidene fluoride (binder) as positive electrode active materials, respectively. (Solvent N-methylpyrrolidone) was mixed, and N-methylpyrrolidone was further added to prepare a slurry.
  • the positive electrode active material, acetylene black, and polyvinylidene fluoride were in a mass ratio of 82/10/8.
  • One side of the slurry was applied to a 20 ⁇ m thick aluminum foil (positive electrode current collector) using a doctor blade.
  • the positive electrode sheets obtained from the positive electrode active materials of Examples 1 to 10 were respectively positive electrode sheets 1 to 10 and the positive electrode sheets obtained from the positive electrode active materials of Comparative Examples 1 to 3 were respectively positive electrode sheets 11. ⁇ 13.
  • Example of battery production Using the positive electrode sheets 1 to 13 produced above as the positive electrode, a stainless steel simple sealed cell type lithium battery was assembled in an argon glove box. A metal lithium foil having a thickness of 500 ⁇ m is used for the negative electrode, a stainless steel plate having a thickness of 1 mm is used for the negative electrode current collector, porous polypropylene having a thickness of 25 ⁇ m is used for the separator, and a concentration of 1 (mol) is used for the electrolyte.
  • LiPF 6 / EC ethylene carbonate
  • DEC diethyl carbonate
  • the lithium batteries using the positive electrode sheets 1 to 10 are referred to as lithium batteries 1 to 10
  • the batteries using the comparative positive electrode sheets 1 to 3 are referred to as lithium batteries 11 to 13.
  • the lithium batteries of Examples 1 to 10 and Comparative Examples 1 to 3 which were charged and discharged in this manner were continuously charged to 4.6 V at a load current of 200 mA per 1 g of the charge / discharge positive electrode active material, and 100 mA per 1 g of the positive electrode active material.
  • the battery was discharged to 2.5V at a load current of.
  • the discharge capacity of the positive electrode active material at 4.6 to 2.5 V is set to 4.6 V initial capacity.
  • the lithium batteries 1 to 10 using the positive electrode active material coated with the oxide (I) exhibit excellent cycle maintenance rate and rate maintenance rate.
  • the cycle maintenance ratio in the lithium batteries 1, 4, and 5 is remarkably good.
  • a positive electrode active material for a lithium ion secondary battery having a high discharge capacity per unit mass and excellent rate characteristics and cycle characteristics can be obtained.
  • the positive electrode active material can be used for lithium-ion secondary batteries for electronic devices such as small and light mobile phones, in-vehicle batteries, and the like.

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Abstract

La présente invention concerne un matériau actif d'électrode positive pour une batterie secondaire au lithium-ion pouvant présenter d'excellentes propriétés de cycle et d'excellentes propriétés de vitesse, y compris lorsqu'elle est chargée avec une tension élevée. L'invention concerne en outre un procédé de production du matériau actif d'électrode positive. Un matériau actif d'électrode positive pour une batterie secondaire au lithium-ion est caractérisé en ce qu'il comprend des particules (X) produites chacune en revêtant la surface d'un oxyde composite contenant du lithium avec un oxyde (I) tel que mentionné ci-dessous, l'oxyde composite contenant du lithium comprenant un élément Li et au moins un élément de type métal de transition choisi dans le groupe constitué par Ni, Co et Mn (la quantité molaire de l'élément Li étant supérieure à 1,2 fois la quantité molaire totale de l'élément de type métal de transition). Oxyde (I) : un oxyde contenant au moins un élément métallique choisi dans le groupe constitué par Nb et Mo.
PCT/JP2012/055588 2011-03-07 2012-03-05 Matériau actif d'électrode positive pour batterie secondaire au lithium-ion et son procédé de production Ceased WO2012121220A1 (fr)

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EP2908365A4 (fr) * 2012-10-12 2015-12-16 Nissan Motor Substance active d'électrode positive pour pile secondaire à électrolyte non aqueux, procédé de production de substance active d'électrode positive pour pile secondaire à électrolyte non aqueux, et pile secondaire à électrolyte non aqueux
JP2016071969A (ja) * 2014-09-26 2016-05-09 旭化成株式会社 酸化物複合体及び非水系リチウムイオン二次電池
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JP2018524769A (ja) * 2015-06-15 2018-08-30 ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングＲｏｂｅｒｔ Ｂｏｓｃｈ Ｇｍｂｈ Ｎａドープされた、およびＮｂドープされた、Ｗドープされたおよび／またはＭｏドープされたＨＥ−ＮＣＭ
KR20190095302A (ko) * 2016-12-26 2019-08-14 스미토모 긴조쿠 고잔 가부시키가이샤 비수계 전해질 이차 전지용 정극 활물질과 그의 제조 방법 및 비수계 전해질 이차 전지
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JP2014096351A (ja) * 2012-11-07 2014-05-22 Ngk Insulators Ltd セラミック正極−固体電解質複合体
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JP2016071969A (ja) * 2014-09-26 2016-05-09 旭化成株式会社 酸化物複合体及び非水系リチウムイオン二次電池
JP2016091626A (ja) * 2014-10-30 2016-05-23 旭硝子株式会社 正極活物質、その製造方法、リチウムイオン二次電池用正極およびリチウムイオン二次電池
JP2016219278A (ja) * 2015-05-21 2016-12-22 株式会社Ｇｓユアサ 非水電解質二次電池用正極活物質及び非水電解質二次電池
JP2018524769A (ja) * 2015-06-15 2018-08-30 ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングＲｏｂｅｒｔ Ｂｏｓｃｈ Ｇｍｂｈ Ｎａドープされた、およびＮｂドープされた、Ｗドープされたおよび／またはＭｏドープされたＨＥ−ＮＣＭ
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