WO2014007360A1 - Oxyde métallique composite de lithium ainsi que procédé de fabrication de celui-ci, matériau actif d'électrode positive, électrode positive et batterie secondaire à électrolyte non-aqueux - Google Patents

Oxyde métallique composite de lithium ainsi que procédé de fabrication de celui-ci, matériau actif d'électrode positive, électrode positive et batterie secondaire à électrolyte non-aqueux Download PDF

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WO2014007360A1
WO2014007360A1 PCT/JP2013/068454 JP2013068454W WO2014007360A1 WO 2014007360 A1 WO2014007360 A1 WO 2014007360A1 JP 2013068454 W JP2013068454 W JP 2013068454W WO 2014007360 A1 WO2014007360 A1 WO 2014007360A1
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metal oxide
composite metal
lithium composite
positive electrode
lithium
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Japanese (ja)
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健二 高森
剛志 宮本
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住友化学株式会社
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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—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • 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
    • C01P2006/12—Surface area
    • 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
    • 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 lithium composite metal oxide, a method for producing a lithium composite metal oxide, a positive electrode active material, a positive electrode, and a nonaqueous electrolyte secondary battery.
  • Lithium composite metal oxide is used as a positive electrode active material in nonaqueous electrolyte secondary batteries such as lithium secondary batteries.
  • Lithium secondary batteries have already been put into practical use as small power sources for mobile phones and notebook computers, and are also being applied to medium and large power sources for automobiles and power storage.
  • LiCoO 2 is most widely used as a positive electrode active material in commercially available lithium secondary batteries.
  • Co is expensive, lithium composite metal oxidation in which the content of Co is lower than that of LiCoO 2 is used. Things are being researched.
  • lithium composite metal oxides containing Ni and Mn are considered promising.
  • a lithium composite metal oxide having a composition formula of LiNi 1/3 Co 1/3 Mn 1/3 O 2 is known.
  • Patent Document 2 For example, in a layered lithium composite metal oxide containing Mn, Ni and Li, by controlling the oxidation state of Mn and Ni, a lithium composite metal oxide suitable as a positive electrode active material for a non-aqueous electrolyte secondary battery and It has been proposed (Patent Document 2).
  • the lithium composite metal oxide by specifying the intensity ratio of the diffraction peaks of the (003) plane and the (104) plane by X-ray diffraction measurement, the generation of the disorder phase present in this oxide is suppressed.
  • a method for controlling the structure of a lithium composite metal oxide has been proposed, and thus a lithium metal composite oxide suitable for a high-capacity nonaqueous electrolyte secondary battery has been obtained (Patent Document 3).
  • a high-capacity non-aqueous electrolyte can be obtained by a method for controlling an oxidation state or a method for controlling an average crystal structure obtained by X-ray diffraction measurement.
  • Studies have been made to obtain lithium metal composite oxides suitable for secondary batteries.
  • a method for obtaining a lithium metal composite oxide suitable for a high-capacity nonaqueous electrolyte secondary battery by controlling the local structure at the atomic level has not yet been sufficiently studied.
  • the present invention has been made in view of such circumstances, and lithium composites useful for non-aqueous electrolyte secondary batteries exhibiting a high capacity by controlling the local structure at the atomic level without containing Co.
  • An object is to provide a metal oxide.
  • Another object of the present invention is to provide a method for producing such a lithium composite metal oxide, a positive electrode active material using the lithium composite metal oxide, a positive electrode, and a nonaqueous electrolyte secondary battery.
  • one embodiment of the present invention is a lithium composite metal oxide that satisfies the following (a) and (b), which contains Mn, Ni, and Li and does not contain Co.
  • (A) In a radial distribution function obtained by Fourier transform of a wide-range X-ray absorption fine structure (EXAFS) spectrum at the K absorption edge of Mn in the lithium composite metal oxide, 1.5% by oxygen atoms bonded to Mn atoms is obtained.
  • EXAFS X-ray absorption fine structure
  • the intensity I ANi when the next on the intensity of the second closest peak around 2.5 ⁇ by metal atoms near the Ni atom bonded oxygen atom to Ni atom was I BNi, the I BNi / I ANi, 1. It is 0 or more and 1.7 or less.
  • a Li / A when the amount (mol) of Li is A Li and the amount (mol) of a metal other than Li is A, A Li / A is 0.7 or more and 1.4 or less. It is desirable.
  • it is desirable that a product of the I BMn / I AMn and the I BNi / I ANi is 0.7 or more and 2.0 or less.
  • the lithium composite metal oxide has a layered structure and is represented by Formula (1).
  • M Is one or more elements selected from the group consisting of Al, Mg, Ti, Ca, Cu, Zn, Fe, Cr, Mo, Si, Sn, Nb and V.
  • the M is preferably Fe.
  • ⁇ 0 is desirable.
  • a mixture including a salt containing Ni and Mn and a lithium compound is heated at a temperature of 200 ° C. to 500 ° C. in an atmosphere having an oxygen concentration of 5% or more. And calcining the calcined product at a temperature of 600 ° C. or higher and 950 ° C. or lower in an atmosphere having an oxygen concentration of less than 5%.
  • it is desirable to have a step of obtaining the salt by bringing an aqueous solution containing Ni ions and Mn ions into contact with an alkali before the step of obtaining the calcined product.
  • the slurry produced by bringing the aqueous solution into contact with the alkali is subjected to solid-liquid separation, and the separated solid is washed and dried to obtain the salt.
  • the mixture further includes an inert flux.
  • the inert flux is a sulfate, and the content of the sulfate in the mixture is 0.01 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the lithium compound.
  • Another embodiment of the present invention is a lithium composite metal oxide manufactured by the above-described method for manufacturing a lithium composite metal oxide.
  • Another embodiment of the present invention is a positive electrode active material including the above lithium composite metal oxide.
  • Another embodiment of the present invention is a positive electrode including the above positive electrode active material.
  • Another embodiment of the present invention is a nonaqueous electrolyte secondary battery including a negative electrode and the positive electrode described above.
  • the separator is preferably made of a laminated film in which a heat-resistant porous layer and a porous film are laminated.
  • the lithium composite metal oxide of this embodiment contains Mn, Ni, and Li, does not contain Co, and satisfies the following (a) and (b).
  • (A) In a radial distribution function obtained by Fourier transform of a wide-range X-ray absorption fine structure (EXAFS) spectrum at the K absorption edge of Mn in the lithium composite metal oxide, 1.5% by oxygen atoms bonded to Mn atoms Near first adjacent peak A Mn Strength of I AMn , The second adjacent peak B around 2.5 ⁇ due to the metal atom next to the Mn atom next to the oxygen atom bonded to the Mn atom Mn Strength of I BMn When I BMn / I AMn Is 0.5 or more and 1.2 or less.
  • EXAFS X-ray absorption fine structure
  • the EXAFS spectrum used in the present embodiment is handled in the same manner as a general EXAFS spectrum.
  • the measurement and principle of the EXAFS spectrum are described in, for example, “X-ray absorption spectroscopy—XAFS and its applications” (Toshiaki Ohta (2002)).
  • the principle is as follows. First, when an X-ray having a specific wavelength is transmitted through a substance to be measured, the intensity of the X-ray irradiated to the substance (incident X-ray intensity: I 0 ) And the intensity of X-rays transmitted through the substance (transmitted X-ray intensity: I t ), The X-ray absorbance per unit thickness is obtained for the substance to be measured at a specific wavelength.
  • the wavelength of X-rays irradiating the substance is changed (that is, the energy (eV) of incident X-rays is changed), the X-ray absorbance of each wavelength (each energy) with respect to the X-rays is measured,
  • the absorption edge corresponds to the energy level of the atomic shell of the atoms constituting the material and is unique to each atom. For example, an absorption edge corresponding to the K shell of an atom is called a K absorption edge.
  • EXAFS broad X-ray absorption fine structure
  • the intensity of the peak of the radial distribution function is affected by the number of X-ray scattering atoms, but it also affects the isotropy of the interatomic distance between X-ray absorbing atoms and X-ray scattering atoms. Is done.
  • the peak of the radial distribution function For those with high intensity, the interatomic distance between the X-ray absorbing atom and the X-ray scattering atom is isotropic with no difference in direction, and the distance distribution between the X-ray absorbing atom and the X-ray scattering atom is small. Means. Therefore, in the present embodiment, attention is paid to the peak intensity ratio of the radial distribution function obtained at the K absorption edge of Mn and Ni.
  • the intensity ratio of the peak of the radial distribution function within a certain range, the atomic level local structure in the lithium composite metal oxide can be controlled to a specific condition even for samples with different composition ratios.
  • a lithium composite metal oxide useful for a non-aqueous electrolyte secondary battery exhibiting a higher capacity than before can be obtained.
  • the peak due to O (oxygen atom) bonded to the Mn atom in the radial distribution function of the K absorption edge of Mn is the first proximity peak A.
  • Mn And First proximity peak A Mn Preferably appears in the vicinity of 1.5 to 1.9 to 1.9, more preferably 1.5 to 1.6.
  • an atom X next to Mn atom next to O bonded to Mn atom (where X is Li, Mn , And a peak due to a metal atom such as Ni).
  • Mn And Second adjacent peak B Mn Preferably appears in the vicinity of 2.5 mm from 2.44 mm to 2.55 mm, more preferably from 2.46 mm to 2.55 mm.
  • the atom X is bonded to O bonded to the Mn atom.
  • the peak due to O bonded to Ni atoms is the first proximity peak A.
  • Ni And First proximity peak A Ni Preferably appears in the vicinity of 1.5 to 1.9 to 1.9, more preferably 1.5 to 1.6.
  • an atom X that is closest to the Ni atom next to O bonded to the Ni atom (where X is Li, Mn , And a peak due to a metal atom such as Ni).
  • Ni And Second adjacent peak B Ni Preferably appears in the vicinity of 2.5 mm from 2.44 mm to 2.55 mm, more preferably from 2.46 mm to 2.55 mm.
  • atom X is bonded to O bonded to Ni atom.
  • the lithium composite metal oxide of this embodiment has a peak intensity ratio of the radial distribution function, that is, I AMn And I BMn To the ratio (I BMn / I AMn ) And I ANi And I BNi To the ratio (I BNi / I ANi ) Within a specific range, the local structure at the atomic level is controlled.
  • Such a lithium composite metal oxide of this embodiment is useful for a non-aqueous electrolyte secondary battery that exhibits a higher capacity than before.
  • the lithium composite metal oxide of the present embodiment has a high isotropy of the interatomic distance between O and X around the Mn atom, and falls within a specific range, and thus has high characteristics as a positive electrode active material.
  • the lithium composite metal oxide of the present embodiment has a high degree of isotropy in the interatomic distance between O and X around the Ni atom, and falls within a specific range, and thus has high characteristics as a positive electrode active material. .
  • I like this BNi / I ANi The value of is 1.0 or more and 1.7 or less, preferably 1.1 or more and 1.7 or less, more preferably 1.2 or more and 1.7 or less.
  • I BMn / I AMn Range of values and I BNi / I ANi The range of values can be arbitrarily combined. Furthermore, I BMn / I AMn And I BNi / I ANi Product with (I BMn / I AMn ⁇ I BNi / I ANi )) Has both the isotropicity of the interatomic distance between the O and the atom X around the appropriate Mn atom and the isotropicity of the interatomic distance between the O and the atom X around the proper Ni atom. 7 or more and 2.0 or less, preferably 0.9 or more and 2.0 or less, more preferably 1.1 or more and 2.0 or less.
  • the crystal structure of the lithium composite metal oxide of the present embodiment is preferably a layered structure, more preferably a hexagonal crystal structure or a monoclinic crystal structure.
  • the hexagonal crystal structure is P3, P3 1 , P3 2 , R3, P-3, R-3, P312, P321, P3 1 12, P3 1 21, P3 2 12, P3 2 21, R32, P3m1, P31m, P3c1, P31c, R3m, R3c, P-31m, P-31c, P-3m1, P-3c1, R-3m, R-3c, P6, P6 1 , P6 5 , P6 2 , P6 4 , P6 3 , P-6, P6 / m, P6 3 / M, P622, P6 1 22, P6 5 22, P6 2 22, P6 4 22, P6 3 22, P6mm, P6cc, P6 3 cm, P6 3 mc, P-6m2, P-6c2, P-62m, P-62c, P6 /
  • the monoclinic crystal structure is P2, P2. 1 , C2, Pm, Pc, Cm, Cc, P2 / m, P2 1 / M, C2 / m, P2 / c, P2 1 / C, C2 / c is classified into any one space group selected from the group consisting of C2 / c.
  • the crystal structure of the lithium composite metal oxide is a hexagonal crystal structure classified into the space group R-3m, or C2 / m.
  • a monoclinic crystal structure classified as follows is particularly preferable.
  • the space group of the lithium composite metal oxide of the present embodiment can be confirmed by the following method.
  • X-ray powder diffraction measurement was performed on a lithium composite metal oxide using CuK ⁇ as a radiation source and a diffraction angle 2 ⁇ measurement range of 10 ° to 90 °, and then Rietveld analysis was performed based on the results. And determining a crystal structure of the lithium composite metal oxide and a space group in the crystal structure.
  • Rietveld analysis is a technique for analyzing the crystal structure of a material using diffraction peak data (diffraction peak intensity, diffraction angle 2 ⁇ ) in powder X-ray diffraction measurement of the material, and is a conventionally used technique.
  • the composition of the lithium composite metal oxide in this embodiment is such that the amount (mol) of Li is A Li , When the amount (mole) of metal other than Li is A, A Li / A may be 0.7 or more and 1.4 or less.
  • the lithium composite metal oxide in the present embodiment preferably has a layered structure and the composition is represented by the following formula (1). Li 1 + x (Ni 1-x-y- ⁇ Mn y M ⁇ ) O 2 ...
  • ⁇ 0.3 ⁇ x ⁇ 0.4, 0.35 ⁇ y ⁇ 0.7, 0 ⁇ ⁇ ⁇ 0.1, ⁇ 0.05 ⁇ x + y + ⁇ ⁇ 1, and M Is one or more elements selected from the group consisting of Al, Mg, Ti, Ca, Cu, Zn, Fe, Cr, Mo, Si, Sn, Nb and V.
  • the value of x in the formula (1) is ⁇ 0.3 ⁇ x ⁇ 0.4, preferably ⁇ 0.2 ⁇ x ⁇ 0.35, more preferably ⁇ 0.1 ⁇ x ⁇ 0. .3. Since the lithium composite metal oxide of the present embodiment has a high discharge capacity at 60 ° C., M is preferably Fe.
  • the lithium composite metal oxide particles of the present embodiment are used as a core material, and B, Al, Ga, In, Si, Ge, Sn, Mg, and the surface of the core material (lithium composite metal oxide particles)
  • a compound containing one or more atoms selected from the group consisting of transition metals may be attached.
  • at least one selected from the group consisting of B, Al, Mg, Co, Cr, and Mn is preferable, and Al is more preferable because a uniform coating layer can be easily formed.
  • Examples of such a compound include oxides, fluorides, sulfides, hydroxides, oxyhydroxides, carbonates, nitrates, organic acid salts and mixtures thereof of the above atoms.
  • the method for producing a lithium composite metal oxide according to this embodiment includes the following steps (1) to (5).
  • step (4) Separating the coprecipitate from the slurry obtained in (1) (3) A step of mixing the coprecipitate obtained in (2) with a lithium compound. (4) A step of heating the mixture obtained in (3) at a temperature of 200 ° C. or higher and 500 ° C. or lower in an atmosphere having an oxygen concentration of 5% by volume or higher. (5) A step of firing the product obtained in (4) (hereinafter sometimes referred to as “calcined product”) at a temperature of 600 ° C. or higher and 950 ° C. or lower in an atmosphere having an oxygen concentration of less than 5% by volume.
  • the “oxygen concentration” in the step (4) refers to an average oxygen concentration in the heat treatment space when the space (heat treatment space) for heating the mixture is in the range of 200 ° C.
  • the “oxygen concentration” in step (5) refers to the average oxygen concentration in the heat treatment space when the space (heat treatment space) for calcining the calcined product is in the range of 600 ° C. or higher and 950 ° C. or lower.
  • the aqueous raw material solution can be adjusted by dissolving a compound containing Ni and Mn in water.
  • the raw material aqueous solution is preferably an aqueous solution obtained by dissolving Ni sulfate and Mn sulfate in water.
  • the alkali used in step (1) includes LiOH (lithium hydroxide), NaOH (sodium hydroxide), KOH (potassium hydroxide), Li 2 CO 3 (Lithium carbonate), Na 2 CO 3 (Sodium carbonate), K 2 CO 3 (Potassium carbonate) and (NH 4 ) 2 CO 3
  • LiOH lithium hydroxide
  • NaOH sodium hydroxide
  • KOH potassium hydroxide
  • Li 2 CO 3 Lithium carbonate
  • Na 2 CO 3 sodium carbonate
  • K 2 CO 3 (Potassium carbonate) Li 2 CO 3
  • NH 4 NH 4
  • the alkali used may be an anhydride or a hydrate.
  • anhydride and a hydrate may be used in combination.
  • the above aqueous solution of alkali alkaline aqueous solution.
  • Aqueous ammonia can also be used as the alkaline aqueous solution.
  • the alkali concentration in the alkaline aqueous solution is preferably about 0.5 to 10 M (mol / L), more preferably about 1 to 8 M.
  • NaOH or KOH is preferable as the alkali to be used. NaOH and KOH may be used in combination.
  • a contact method in the step (1) As a contact method in the step (1), (i) a method in which an aqueous alkaline solution is added and mixed, (ii) a method in which an aqueous raw material solution is added and mixed, (iii) an aqueous raw material solution in water And a method of adding and mixing an alkaline aqueous solution. In mixing, it is preferable to involve stirring.
  • a method in which a raw material aqueous solution is added to and mixed with an alkaline aqueous solution is preferable because the change in pH is easily controlled.
  • the pH of the alkaline aqueous solution tends to decrease as the raw material aqueous solution is added to and mixed with the alkaline aqueous solution, but the pH is adjusted to 9 or higher, preferably 10 or higher. It is preferable to add a raw material aqueous solution. In addition, it is preferable that one or both of the raw material aqueous solution and the alkaline aqueous solution are brought into contact with each other while being kept at a temperature of 40 ° C. or higher and 80 ° C. or lower, whereby a coprecipitate having a more uniform composition can be obtained.
  • step (1) by bringing the raw material aqueous solution and the alkali into contact with each other as described above, a salt containing Ni ions and Mn ions is coprecipitated, and a slurry in which the salt that is the coprecipitate is dispersed is formed.
  • a coprecipitate is obtained from the slurry obtained in step (1).
  • various methods can be adopted as the method for obtaining the coprecipitate in step (2). However, since the operation is simple, a separation operation for obtaining a solid component such as filtration is performed. Is preferred.
  • the coprecipitate can also be obtained by a method of volatilizing the liquid by heating, such as spray drying of the slurry.
  • the step (2) when a coprecipitate is obtained, it is preferable that the separated coprecipitate is washed and dried in the step (2).
  • the alkali remaining in the obtained coprecipitate SO released from the raw material aqueous solution when Ni sulfate or Mn sulfate is used as the raw material 4 2-
  • the amount of ions can be reduced. It is preferable to reduce these by washing because the amount of the inert flux (described later) can be easily controlled.
  • a water-soluble organic solvent such as alcohol or acetone may be added to the cleaning liquid.
  • the drying of the washed coprecipitate can be performed by heat treatment, but may be performed by air drying, vacuum drying, or a combination thereof.
  • the heating temperature is preferably 50 to 300 ° C, more preferably about 100 to 200 ° C.
  • the coprecipitate obtained in step (2) and the lithium compound are mixed to obtain a mixture.
  • the resulting mixture is a “mixture having a salt containing Ni and Mn and a lithium compound”.
  • the lithium compound examples include one or more salts selected from the group consisting of lithium hydroxide, lithium chloride, lithium nitrate, and lithium carbonate.
  • the lithium compound used may be an anhydride or a hydrate. Moreover, you may use an anhydride and a hydrate together. Mixing may be either dry mixing or wet mixing, but dry mixing is preferred because of the ease of operation.
  • Examples of the mixing apparatus include stirring and mixing, a V-type mixer, a W-type mixer, a ribbon mixer, a drum mixer, and a ball mill. (Process (4))
  • step (4) the mixture obtained in step (3) is heated at a temperature of 200 ° C. or higher and 500 ° C. or lower, preferably 250 ° C. or higher and 450 ° C.
  • the heating atmosphere includes a method using air and oxygen or a mixed gas thereof, a method of mixing an inert gas such as nitrogen and argon into the air and oxygen or a mixed gas thereof, and the oxygen concentration is 5 volumes. % Of the atmosphere.
  • a high-capacity lithium composite metal oxide having an intended local structure can be easily obtained, and when the obtained lithium composite metal oxide is used as a positive electrode active material, a high-capacity secondary battery can be obtained. Therefore, the oxygen concentration is preferably 7% by volume to 20% by volume, and more preferably 10% by volume to 20% by volume.
  • the firing atmosphere may be an atmosphere in which air, oxygen, nitrogen, argon, or the like is mixed and the oxygen concentration is less than 5% by volume.
  • a high-capacity lithium composite metal oxide having an intended local structure can be easily obtained, and when the obtained lithium composite metal oxide is used as a positive electrode active material, a high-capacity secondary battery can be obtained. Therefore, the oxygen concentration is preferably 0.5% by volume or more and less than 5% by volume, and more preferably 1% by volume or more and 3% by volume or less.
  • the step (4) and the step (5) are continuously performed without lowering the temperature from the heating temperature at the end of the step (4) ( 5) is preferably performed.
  • the oxygen concentration is adjusted to the step (4) while maintaining the temperature at the end of the step (4) or raising the temperature to the firing temperature of the step (5).
  • the oxygen concentration in 4) is changed to the oxygen concentration in step (5).
  • a method for changing the oxygen concentration a method of changing the oxygen concentration of the introduced gas is preferably used.
  • the lithium composite metal oxide of the present embodiment can be produced by such steps (1) to (5).
  • the manufacturing method of this embodiment although demonstrated as having a process (1)-a process (5), it is not restricted to this.
  • a mixture obtained by mixing a salt containing Ni ions and Mn ions and a lithium compound by another method in place of the steps (1) to (3) is prepared, and the resulting mixture is used to adjust the oxygen concentration.
  • the above-mentioned “salt containing Ni ions and Mn ions” may be a mixture of a salt containing Ni ions and a salt containing Mn ions.
  • step (3) a method of mixing the above-mentioned metal salts in a solid phase and a slurry by dispersing the above-mentioned metal salts in a liquid phase And a method of spray-drying and mixing the obtained slurry.
  • Ni and Mn need to be contained in the mixture of the step (4), but another metal is added to the mixture heated in the step (4).
  • An atom may be included. Examples of other metal atoms include one or more atoms selected from the group consisting of Al, Mg, Ti, Ca, Cu, Zn, Fe, Cr, Mo, Si, Sn, Nb, and V.
  • the lithium composite metal oxide containing Co when the mixture of step (4) contains Co atoms, the lithium composite metal oxide containing Co is obtained.
  • Various methods can be adopted as a method of including other metal atoms in the mixture to be heated in step (4).
  • Inert flux In the step (4) and step (5), the mixture and calcined product may contain an inert flux.
  • the inert flux is also called a flux or a flux, and is a salt that does not react with the target composite metal oxide and can be easily separated from the target.
  • the inert flux melts at the heating temperature in step (4) and the firing temperature in step (5) to form a reaction field and promotes a uniform reaction. Therefore, when an inert flux is used, a product having a uniform composition is easily obtained.
  • an inert flux K 2 SO 4 , Na 2 SO 4 Sulfate such as K; 2 CO 3 , Na 2 CO 3 Carbonates such as: NaCl, KCl, NH 4 Chlorides such as Cl; LiF, NaF, KF, NH 4 Fluorides such as F; boric acid;
  • sulfate is preferable because the production process becomes simple. More preferably K 2 SO 4 It is.
  • Two or more inert fluxes can be used in combination.
  • the mixture contains an inert flux
  • the reactivity at the time of heating the mixture and calcining the calcined product is improved, and thereby it may be possible to adjust the BET specific surface area of the obtained lithium composite metal oxide. is there.
  • the temperature is the same, the BET specific surface area of the oxide tends to increase as the content of the inert flux increases.
  • an inert fluxing agent is contained during heating or firing, a uniform reaction can be performed, so that the local structure can be controlled at the atomic level of the lithium composite metal oxide by adjusting the heating atmosphere.
  • the inert flux may be mixed with the coprecipitate obtained by allowing the coprecipitate obtained by the separation operation in step (2) to contain the above inert flux solution and then drying.
  • step (1) when Ni sulfate or Mn sulfate is used as a raw material, SO in the raw material aqueous solution 4 2- Ions are liberated. This SO 4 2-
  • the ions and metal ions contained in the alkali used for the coprecipitation for example, K ions when KOH is used as the alkali
  • the inert flux K in the above example 2 SO 4
  • the raw material aqueous solution after the coprecipitation in the step (1) is used as the “inert flux solution”, and the coprecipitate obtained in the step (2) is dried while the raw aqueous solution after the coprecipitation is included.
  • an inert flux may be mixed with the coprecipitate obtained.
  • the inert flux can be added and mixed at the time of mixing the coprecipitate and the lithium compound in the step (3). Since it is easy to control the amount of the inert flux, the method of adding the inert flux in the step (3) is preferable to the method of adding the inert flux in the step (2).
  • the coprecipitate obtained in step (2) is washed and an anion derived from an alkali remaining in the coprecipitate, a Ni salt or a Mn salt
  • the amount of the inert flux can be easily controlled by reducing the amount of.
  • the inert flux may remain in the lithium composite metal oxide or may be removed by washing.
  • the inert flux is a sulfate, and when the mixture or calcined product and the sulfate are mixed, the content of the sulfate in the resulting mixture is the lithium used. It is preferable that it is 0.01 to 400 mass parts with respect to 100 mass parts of compounds.
  • the lithium composite metal oxide obtained by the method for producing a lithium composite metal oxide of the present embodiment may be pulverized using a ball mill or a jet mill. It may be possible to adjust the BET specific surface area of the lithium composite metal oxide by grinding. Further, the lithium composite metal oxide obtained by carrying out the steps (1) to (5) may be pulverized, and the steps (4) and (5) may be performed again to perform baking after the pulverization. . Furthermore, you may repeat a grinding
  • the lithium composite metal oxide of the present embodiment is preferably a mixture of primary particles having a particle size of 0.05 ⁇ m or more and 1 ⁇ m or less and secondary particles having a particle size of 2 ⁇ m or more and 100 ⁇ m or less formed by aggregation of the primary particles. Consists of.
  • the particle diameters of the primary particles and secondary particles can be measured by observing with SEM.
  • the size of the secondary particles of the lithium composite metal oxide is preferably in the range of 2 ⁇ m to 50 ⁇ m, more preferably in the range of 2 ⁇ m to 10 ⁇ m, and even more preferably in the range of 3 ⁇ m to 8 ⁇ m. Especially preferably, it is the range of 3.5 micrometers or more and 7 micrometers or less.
  • the primary particle size of the lithium composite metal oxide is preferably in the range of 0.08 ⁇ m to 0.8 ⁇ m, more preferably in the range of 0.10 ⁇ m to 0.7 ⁇ m, and still more preferably in the range of 0.8. It is in the range of 15 ⁇ m or more and 0.7 ⁇ m or less, and particularly preferably in the range of 0.2 ⁇ m or more and 0.5 ⁇ m or less. These increase the discharge capacity at a high current rate of the obtained nonaqueous electrolyte secondary battery.
  • the average particle diameter of lithium composite metal oxide (D 50 ) Is preferably in the range of 1 ⁇ m to 50 ⁇ m, more preferably in the range of 1.5 ⁇ m to 30 ⁇ m, even more preferably in the range of 2 ⁇ m to 20 ⁇ m, and particularly preferably in the range of 3 ⁇ m to 10 ⁇ m. It is. As a result, the density of the electrode using the lithium composite metal oxide is increased, and a non-aqueous electrolyte secondary battery having a higher capacity can be obtained.
  • Average particle size of lithium composite metal oxide (D 50 ) Can be measured by the following method.
  • the BET specific surface area of the lithium composite metal oxide is preferably 0.1 m 2 / G or more 20m 2 / G or less, more preferably 0.5 m 2 / G or more 15m 2 / G or less, even more preferably 1 m 2 / G or more 10m 2 / G or less, particularly preferably 2 m 2 / G or more 8m 2 / G or less. These increase the discharge capacity at a high current rate of the obtained nonaqueous electrolyte secondary battery.
  • the BET specific surface area of the lithium composite metal oxide can be measured by the following method. ⁇ Measurement of BET specific surface area of lithium composite metal oxide> After 1 g of the lithium composite metal oxide powder to be measured is dried at 150 ° C.
  • Nonaqueous electrolyte secondary battery Next, while explaining the configuration of the nonaqueous electrolyte secondary battery, the positive electrode using the lithium composite metal oxide of the present embodiment as the positive electrode active material of the nonaqueous electrolyte secondary battery, and the nonaqueous electrolyte secondary having the positive electrode The battery will be described.
  • FIG. 1 is a schematic view showing an example of the nonaqueous electrolyte secondary battery of the present embodiment.
  • the cylindrical nonaqueous electrolyte secondary battery 10 of this embodiment is manufactured as follows. First, as shown in FIG. 1A, two separators 1 each having a strip shape, a strip-like positive electrode 2 having a positive electrode lead 21 at one end, and a strip-like negative electrode 3 having a negative electrode lead 31 at one end, 2, separator 1, and negative electrode 3 are laminated in this order and wound to form electrode group 4. Next, as shown in FIG.
  • the nonaqueous electrolyte secondary battery 10 can be manufactured by sealing the upper part of the battery can 5 with the top insulator 7 and the sealing body 8.
  • a columnar shape in which the cross-sectional shape when the electrode group 4 is cut in a direction perpendicular to the winding axis is a circle, an ellipse, a rectangle, or a rectangle with rounded corners. Can be mentioned.
  • the nonaqueous electrolyte secondary battery having such an electrode group 4 a shape defined by IEC 60086 or JIS C 8500, which is a standard for batteries determined by the International Electrotechnical Commission (IEC), should be adopted. Can do. For example, cylindrical shape, square shape, etc. can be mentioned.
  • the non-aqueous electrolyte secondary battery is not limited to the above-described wound type configuration, and may have a stacked type configuration in which a stacked structure of a positive electrode, a separator, a negative electrode, and a separator is repeatedly stacked.
  • Examples of the laminated nonaqueous electrolyte secondary battery include so-called coin-type batteries, button-type batteries, and paper-type (or sheet-type) batteries.
  • the positive electrode of the present embodiment can be manufactured by first adjusting a positive electrode mixture containing a positive electrode active material, a conductive material and a binder, and supporting the positive electrode mixture on a positive electrode current collector.
  • the positive electrode active material of the present embodiment has the above-described lithium composite metal oxide.
  • a carbon material can be used as a conductive material included in the positive electrode of the present embodiment.
  • the carbon material examples include graphite powder, carbon black (for example, acetylene black), and a fibrous carbon material. Since carbon black is fine and has a large surface area, adding a small amount to the positive electrode mixture can improve the conductivity inside the positive electrode and improve the charge / discharge efficiency and output characteristics. Both the binding force between the positive electrode mixture and the positive electrode current collector and the binding force inside the positive electrode mixture are reduced, which causes an increase in internal resistance.
  • the proportion of the conductive material in the positive electrode mixture is preferably 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the positive electrode active material. When a fibrous carbon material such as graphitized carbon fiber or carbon nanotube is used as the conductive material, this ratio can be lowered.
  • thermoplastic resin can be used as the binder of the positive electrode of the present embodiment.
  • thermoplastic resin include polyvinylidene fluoride (hereinafter sometimes referred to as PVdF), polytetrafluoroethylene (hereinafter sometimes referred to as PTFE), tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride.
  • fluororesins such as copolymers, propylene hexafluoride / vinylidene fluoride copolymers, tetrafluoroethylene / perfluorovinyl ether copolymers; polyolefin resins such as polyethylene and polypropylene.
  • thermoplastic resins may be used as a mixture of two or more.
  • a fluororesin and a polyolefin resin as a binder, the ratio of the fluororesin to the whole positive electrode mixture is 1% by mass or more and 10% by mass or less, and the ratio of the polyolefin resin is 0.1% by mass or more and 2% by mass or less.
  • a positive electrode mixture having both high adhesion to the current collector and high bonding strength inside the positive electrode mixture can be obtained.
  • a band-shaped member made of a metal material such as Al, Ni, stainless steel or the like can be used.
  • Examples of the method of supporting the positive electrode mixture on the positive electrode current collector include a method of pressure-molding the positive electrode mixture on the positive electrode current collector. Further, the positive electrode mixture is made into a paste using an organic solvent, and the obtained positive electrode mixture paste is applied to at least one surface of the positive electrode current collector, dried, pressed and fixed, whereby the positive electrode current collector is bonded to the positive electrode current collector. A mixture may be supported.
  • organic solvents that can be used include amine solvents such as N, N-dimethylaminopropylamine and diethylenetriamine; ether solvents such as tetrahydrofuran; ketone solvents such as methyl ethyl ketone; methyl acetate And amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone (hereinafter sometimes referred to as NMP).
  • amine solvents such as N, N-dimethylaminopropylamine and diethylenetriamine
  • ether solvents such as tetrahydrofuran
  • ketone solvents such as methyl ethyl ketone
  • amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone
  • the negative electrode included in the nonaqueous electrolyte secondary battery of this embodiment is only required to be able to dope and dedope lithium ions at a lower potential than the positive electrode, and the negative electrode mixture containing the negative electrode active material is supported on the negative electrode current collector. And an electrode composed of the negative electrode active material alone.
  • Examples of the negative electrode active material possessed by the negative electrode include carbon materials, chalcogen compounds (oxides, sulfides, etc.), nitrides, metals, and alloys that can be doped and dedoped with lithium ions at a lower potential than the positive electrode. It is done.
  • Examples of carbon materials that can be used as the negative electrode active material include graphites such as natural graphite and artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fibers, and organic polymer compound fired bodies.
  • As an oxide that can be used as a negative electrode active material SiO 2 , SiO etc. formula SiO x (Wherein x is a positive real number) silicon oxide represented by: TiO 2 TiO, formula TiO x (Where x is a positive real number) titanium oxide; V 2 O 5 , VO 2 Etc.
  • VO x (Where x is a positive real number) oxide of vanadium; Fe 3 O 4 , Fe 2 O 3 FeO and other formulas FeO x (Where x is a positive real number) iron oxide; SnO 2 , SnO etc. formula SnO x (Where x is a positive real number) tin oxide represented by WO 3 , WO 2 General formula WO x (Where x is a positive real number) 4 Ti 5 O 12 , LiVO 2 And a composite metal oxide containing lithium and titanium or vanadium.
  • Ti 2 S 3 TiS 2 TiS and other formula TiS x (Where x is a positive real number) titanium sulfide; V 3 S 4 , VS 2, VS formula VS x (Where x is a positive real number) Vanadium sulfide; Fe 3 S 4 , FeS 2 FeS and other formulas x (Where x is a positive real number) iron sulfide; Mo 2 S 3 , MoS 2 Etc. MoS x (Where x is a positive real number) molybdenum sulfide represented by SnS 2, SnS etc.
  • carbon materials, oxides, sulfides and nitrides may be used alone or in combination of two or more. These carbon materials, oxides, sulfides and nitrides may be crystalline or amorphous.
  • the metal that can be used as the negative electrode active material include lithium metal, silicon metal, and tin metal.
  • alloys that can be used as the negative electrode active material include lithium alloys such as Li—Al, Li—Ni, Li—Si, Li—Sn, and Li—Sn—Ni; silicon alloys such as Si—Zn; Sn—Mn and Sn.
  • -Tin alloys such as Co, Sn-Ni, Sn-Cu, Sn-La; Cu 2 Sb, La 3 Ni 2 Sn 7 And alloys such as: These metals and alloys are mainly used alone as electrodes after being processed into a foil shape, for example.
  • the potential of the negative electrode hardly changes from the uncharged state to the fully charged state during charging (potential flatness is good), the average discharge potential is low, and the capacity retention rate when repeatedly charged and discharged is high.
  • a carbon material mainly composed of graphite such as natural graphite or artificial graphite is preferably used.
  • the shape of the carbon material may be any of a flake shape such as natural graphite, a spherical shape such as mesocarbon microbeads, a fibrous shape such as graphitized carbon fiber, or an aggregate of fine powder.
  • the negative electrode mixture may contain a binder as necessary.
  • the binder include thermoplastic resins, and specific examples include PVdF, thermoplastic polyimide, carboxymethyl cellulose, polyethylene, and polypropylene.
  • Negative electrode current collector examples include a band-shaped member made of a metal material such as Cu, Ni, and stainless steel.
  • Cu As a forming material and process it into a thin film from the viewpoint that it is difficult to make an alloy with lithium and it is easy to process.
  • a method of supporting the negative electrode mixture on such a negative electrode current collector as in the case of the positive electrode, a method using pressure molding, pasting with a solvent, etc., applying to the negative electrode current collector, drying and pressing. The method of crimping is mentioned.
  • Examples of the separator included in the nonaqueous electrolyte secondary battery of the present embodiment include a porous film, a nonwoven fabric, a woven fabric, and the like made of a material such as a polyolefin resin such as polyethylene and polypropylene, a fluororesin, and a nitrogen-containing aromatic polymer. A material having the following form can be used. Moreover, a separator may be formed by using two or more of these materials, or a separator may be formed by laminating these materials. Examples of the separator include separators described in JP 2000-30686 A, JP 10-324758 A, and the like.
  • the thickness of the separator should be as thin as possible as long as the mechanical strength is maintained because the volume energy density of the battery is increased and the internal resistance is reduced, preferably about 5 to 200 ⁇ m, more preferably about 5 to 40 ⁇ m. is there.
  • the separator preferably has a porous film containing a thermoplastic resin. In a nonaqueous electrolyte secondary battery, when an abnormal current flows in the battery due to a short circuit between the positive electrode and the negative electrode, the current at the short circuit point is interrupted to prevent an excessive current from flowing (shut down). It preferably has a function.
  • the shutdown is performed by overheating the separator at the short-circuit location due to a short circuit, and when the temperature exceeds a presumed operating temperature, the porous film in the separator is softened or melted to close the micropores. And even if the temperature in a battery rises to a certain high temperature after a separator shuts down, it is preferable to maintain the shut-down state, without breaking at the temperature.
  • a separator include a laminated film in which a heat resistant porous layer and a porous film are laminated. By using such a laminated film as a separator, the heat resistance of the secondary battery in this embodiment can be further increased. In the laminated film, the heat resistant porous layer may be laminated on both surfaces of the porous film.
  • the heat resistant porous layer is a layer having higher heat resistance than the porous film.
  • the heat resistant porous layer may be formed from an inorganic powder (first heat resistant porous layer), may be formed from a heat resistant resin (second heat resistant porous layer), and includes a heat resistant resin and a filler. (A third heat-resistant porous layer).
  • first heat resistant porous layer may be formed from a heat resistant resin
  • second heat resistant porous layer may be formed from a heat resistant resin
  • a third heat-resistant porous layer may be formed by an easy technique such as coating.
  • the heat resistant porous layer is formed of an inorganic powder
  • examples of the inorganic powder used for the heat resistant porous layer include inorganic substances such as metal oxides, metal nitrides, metal carbides, metal hydroxides, carbonates, and sulfates.
  • a powder made of an inorganic substance having low conductivity (insulator) is preferably used.
  • Specific examples include powders made of alumina, silica, titanium dioxide, calcium carbonate, or the like.
  • Such inorganic powders may be used alone or in combination of two or more.
  • alumina powder is preferable because of its high chemical stability.
  • all of the particles constituting the inorganic powder are alumina particles, all of the particles constituting the inorganic powder are alumina particles, and part or all of them are substantially spherical alumina particles.
  • the heat resistant porous layer is formed from a heat resistant resin
  • the heat resistant resin used for the heat resistant porous layer is polyamide, polyimide, polyamideimide, polycarbonate, polyacetal, polysulfone, polyphenylene sulfide, polyether ketone, aromatic polyester, polyether. Mention may be made of sulfone and polyetherimide.
  • the heat-resistant resin used for the heat-resistant porous layer is a nitrogen-containing aromatic polymer such as aromatic polyamide (para-oriented aromatic polyamide, meta-oriented aromatic polyamide), aromatic polyimide, aromatic polyamideimide, Aromatic polyamides are preferred, and para-oriented aromatic polyamides (hereinafter sometimes referred to as para-aramids) are particularly preferred because they are easy to produce.
  • the heat resistant resin include poly-4-methylpentene-1 and a cyclic olefin polymer.
  • the heat resistance of the laminated film used as the separator of the nonaqueous electrolyte secondary battery that is, the thermal film breaking temperature of the laminated film can be further increased.
  • the compatibility with the electrolytic solution that is, the liquid retention in the heat-resistant porous layer may be improved depending on the polarity in the molecule.
  • the rate of impregnation with the electrolytic solution during the production of the electrolyte secondary battery is also high, and the charge / discharge capacity of the nonaqueous electrolyte secondary battery is further increased.
  • the thermal film breaking temperature of such a laminated film depends on the type of heat-resistant resin, and is selected and used according to the use scene and purpose of use. More specifically, as the heat-resistant resin, when the nitrogen-containing aromatic polymer is used, the cyclic olefin polymer is about 400 ° C. When using, the thermal film breaking temperature can be controlled to about 300 ° C., respectively. In addition, when the heat resistant porous layer is made of an inorganic powder, the thermal film breaking temperature can be controlled to, for example, 500 ° C. or higher.
  • the para-aramid is obtained by polycondensation of a para-oriented aromatic diamine and a para-oriented aromatic dicarboxylic acid halide, and the amide bond is in the para position of the aromatic ring or an oriented position equivalent thereto (for example, 4,4′-biphenylene, It consists essentially of repeating units that are bound together in the opposite orientation, such as 1,5-naphthalene, 2,6-naphthalene, etc., in an orientation that extends coaxially or parallelly.
  • para-aramid having a structure according to the type.
  • the aromatic polyimide is preferably a wholly aromatic polyimide produced by polycondensation of an aromatic dianhydride and a diamine.
  • aromatic dianhydride used for the polycondensation include pyromellitic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4. 4,4′-benzophenone tetracarboxylic dianhydride, 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. It is done.
  • diamines used for polycondensation include oxydianiline, paraphenylenediamine, benzophenonediamine, 3,3′-methylenedianiline, 3,3′-diaminobenzophenone, 3,3′-diaminodiphenylsulfone. And 1,5-naphthalenediamine.
  • aromatic polyimide a polyimide soluble in a solvent can be suitably used. Examples of such a polyimide include a polycondensate polyimide of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and an aromatic diamine.
  • aromatic polyamideimide examples include those obtained from polycondensation of aromatic dicarboxylic acid and aromatic diisocyanate, and those obtained from polycondensation of aromatic diacid anhydride and aromatic diisocyanate.
  • aromatic dicarboxylic acid examples include isophthalic acid and terephthalic acid.
  • aromatic dianhydride is trimellitic anhydride.
  • aromatic diisocyanate examples include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, orthotolylene diisocyanate, and m-xylene diisocyanate.
  • the thickness of the heat resistant porous layer of the laminated film is preferably 1 ⁇ m or more and 10 ⁇ m or less, more preferably 1 ⁇ m or more and 5 ⁇ m or less, and particularly preferably 1 ⁇ m or more and 4 ⁇ m or less.
  • the heat-resistant porous layer has fine pores, and the size (diameter) of the pores is preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less. (Third heat-resistant porous layer) Further, when the heat resistant porous layer is formed including a heat resistant resin and a filler, the same heat resistant resin as that used for the second heat resistant porous layer can be used.
  • the filler one or more selected from the group consisting of organic powder, inorganic powder, or a mixture thereof can be used.
  • the particles constituting the filler preferably have an average particle size of 0.01 ⁇ m or more and 1 ⁇ m or less.
  • the organic powder that can be used as the filler include, for example, styrene, vinyl ketone, acrylonitrile, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, methyl acrylate, and the like, or two or more types of copolymers; Fluorine resin such as tetrafluoroethylene-6-propylene copolymer, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride; melamine resin; urea resin; polyolefin resin; polymethacrylate; A powder is mentioned.
  • Such organic powders may be used alone or in combination of two or more.
  • PTFE powder is preferred because of its high chemical stability.
  • examples of the inorganic powder that can be used as the filler include the same inorganic powder used in the heat-resistant porous layer.
  • the filler content depends on the specific gravity of the filler material, for example, when all of the particles constituting the filler are alumina particles
  • the mass of the filler is preferably 5 parts by mass or more and 95 parts by mass or less, more preferably 20 parts by mass or more and 95 parts by mass or less, Preferably they are 30 to 90 mass parts. These ranges can be appropriately set depending on the specific gravity of the filler material.
  • the shape of the filler include substantially spherical, plate-like, columnar, needle-like, and fiber-like shapes, and any particle can be used.
  • the substantially spherical particles include particles having a particle aspect ratio (long particle diameter / short particle diameter) of 1 or more and 1.5 or less.
  • the aspect ratio of the particles can be measured by an electron micrograph.
  • the porous film preferably has fine pores and has a shutdown function.
  • the porous film contains a thermoplastic resin.
  • the size of the micropores in the porous film is preferably 3 ⁇ m or less, more preferably 1 ⁇ m or less.
  • the porosity of the porous film is preferably 30% to 80% by volume, more preferably 40% to 70% by volume.
  • the porous film containing the thermoplastic resin has micropores due to softening or melting of the thermoplastic resin constituting the porous film. Can be occluded. What is necessary is just to select the thermoplastic resin used for a porous film what does not melt
  • the polyethylene examples include polyethylene such as low density polyethylene, high density polyethylene, and linear polyethylene, and ultra high molecular weight polyethylene having a molecular weight of 1,000,000 or more.
  • the thermoplastic resin constituting the porous film contains at least ultra high molecular weight polyethylene.
  • the thermoplastic resin may preferably contain a wax made of polyolefin having a low molecular weight (weight average molecular weight of 10,000 or less).
  • the thickness of the porous film in the laminated film is preferably 3 ⁇ m or more and 30 ⁇ m or less, more preferably 3 ⁇ m or more and 25 ⁇ m or less.
  • the thickness of a laminated film becomes like this. Preferably it is 40 micrometers or less, More preferably, it is 30 micrometers or less. Moreover, when the thickness of the heat resistant porous layer is A ( ⁇ m) and the thickness of the porous film is B ( ⁇ m), the value of A / B is preferably 0.1 or more and 1 or less.
  • the separator allows the electrolyte to permeate well when the battery is used (during charging / discharging). Or less, more preferably 50 seconds / 100 cc or more and 200 seconds / 100 cc or less.
  • the porosity of the separator is preferably 30% by volume to 80% by volume, more preferably 40% by volume to 70% by volume.
  • the separator may be a laminate of separators having different porosity.
  • the electrolyte solution included in the nonaqueous electrolyte secondary battery of this embodiment contains an electrolyte and an organic solvent.
  • As the electrolyte contained in the electrolyte LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiN (SO 2 CF 3 ) (COCF 3 ), Li (C 4 F 9 SO 3 ), LiC (SO 2 CF 3 ) 3 , Li 2 B 10 Cl 10 , LiBOB (where BOB is bis (oxalato) borate), lower aliphatic carboxylic acid lithium salt, LiAlCl 4 And a mixture of two or more of these may be used.
  • LiPF containing fluorine 6 LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 And LiC (SO 2 CF 3 ) 3
  • organic solvent contained in the electrolyte include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one, and 1,2-di- Carbonates such as (methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran, 2- Ethers such as methyltetrahydr
  • a mixed solvent containing carbonates is preferable, and a mixed solvent of cyclic carbonate and acyclic carbonate and a mixed solvent of cyclic carbonate and ether are more preferable.
  • a mixed solvent of cyclic carbonate and acyclic carbonate a mixed solvent containing ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate is preferable.
  • the electrolyte using such a mixed solvent has a wide operating temperature range, hardly deteriorates even when charged and discharged at a high current rate, hardly deteriorates even when used for a long time, and natural graphite as an active material of the negative electrode.
  • LiPF 6 it is preferable to use an electrolytic solution containing a lithium salt containing fluorine and an organic solvent having a fluorine substituent.
  • a mixed solvent containing dimethyl carbonate and ethers having fluorine substituents such as pentafluoropropyl methyl ether and 2,2,3,3-tetrafluoropropyl difluoromethyl ether is capable of capacity even when charging / discharging at a high current rate. Since the maintenance rate is high, it is more preferable.
  • a solid electrolyte may be used instead of the above electrolyte.
  • the solid electrolyte for example, an organic polymer electrolyte such as a polyethylene oxide polymer compound, a polymer compound containing at least one of a polyorganosiloxane chain or a polyoxyalkylene chain can be used.
  • maintained the non-aqueous electrolyte in the high molecular compound can also be used.
  • An inorganic solid electrolyte containing a sulfide such as may be used.
  • the safety of the nonaqueous electrolyte secondary battery may be further improved.
  • the solid electrolyte secondary battery of this embodiment when a solid electrolyte is used, the solid electrolyte may serve as a separator, and in that case, the separator may not be required.
  • the nonaqueous electrolyte secondary battery using the positive electrode active material can exhibit a higher capacity than before. Further, since the positive electrode has a positive electrode active material using the above-described lithium composite metal oxide of the present embodiment, the non-aqueous electrolyte secondary battery can exhibit a higher capacity than before. Furthermore, since the nonaqueous electrolyte secondary battery has the positive electrode described above, it exhibits a higher capacity than before.
  • evaluation of the lithium composite metal oxide (positive electrode active material) and production evaluation of the positive electrode and the lithium secondary battery were performed as follows.
  • (1) Evaluation of lithium composite metal oxide Composition analysis of lithium composite metal oxide The composition analysis of lithium composite metal oxide was conducted by dissolving the obtained lithium composite metal oxide powder in hydrochloric acid and then using an inductively coupled plasma emission spectrometer (SII Nanotechnology Inc.) Manufactured by SPS3000). 2.
  • the incident X-ray intensity (I 0 ) is measured at room temperature using a 17 cm ion chamber using N 2 as a filling gas
  • the transmitted X-ray intensity (I t ) is measured as a filling gas. It was measured at room temperature using a 31cm ion chamber of using N 2 as.
  • the measured energy range and the number of measurement points were 4932 at an equal energy interval from 6040 eV to 7640.5 eV for the K absorption edge of Mn.
  • the K absorption edge of Ni was 5333 points at equal energy intervals from 7834 eV to 9434.5 eV.
  • the energy calibration is performed using a pre-edge peak (about about X-ray Absorption Near-Edge Structure) spectrum of the obtained K absorption edge when measured using copper alone as a standard sample.
  • the angle of the spectral crystal at 8980 eV) was set to 12.7185 °.
  • each incident X-ray energy, measured I 0, I t the following equation was determined X-ray absorbance.
  • X-ray absorbance ⁇ t ⁇ ln (I 0 / I t )
  • discrete X-ray absorbance is obtained corresponding to the wavelength of X-rays used for measurement (corresponding to the energy of X-rays used for measurement).
  • the obtained X-ray absorbance was averaged and data interpolated as follows. First, the X-ray absorbance in the range corresponding to the K absorption edge of Mn was averaged by the following method.
  • the Mn K absorption edge E 0 was set to an energy value at which the first-order differential coefficient was maximum in the vicinity of the Mn K absorption edge in the X-ray absorption spectrum.
  • the K absorption edge E 0 of Ni is set to an energy value at which the first-order differential coefficient becomes maximum in the spectrum near the K absorption edge of Ni.
  • the spectrum background is a spectrum in a lower energy region than the K absorption edge of Mn and the K absorption edge of Ni, and Victory's formula (A ⁇ 3 ⁇ B ⁇ 4 + C; ⁇ is the wavelength of incident X-rays, A, B and C are arbitrary constants) and determined by applying the least square method.
  • the EXAFS spectrum was obtained by subtracting the background value corresponding to this Victreeen equation from the X-ray absorption spectrum. (Calculation of radial distribution function) A radial distribution function was obtained from the obtained EXAFS spectrum.
  • the absorbance ( ⁇ 0 ) of isolated atoms was estimated by the Spline Smoothing method (smoothing spline method), and the EXAFS function ⁇ (k) was extracted. Note that k is the wave number of photoelectrons defined by 0.5123 ⁇ (E ⁇ E 0 ) 1/2 , and the unit of k is ⁇ 1 .
  • N-methyl-2-pyrrolidone was used as the organic solvent.
  • the obtained positive electrode mixture was applied to a 40 ⁇ m thick Al foil serving as a current collector and vacuum dried at 150 ° C. for 8 hours to obtain a positive electrode.
  • (3) Production of nonaqueous electrolyte secondary battery (coin cell) The following operation was performed in a glove box in an argon atmosphere.
  • the positive electrode created in “(2) Preparation of positive electrode” is placed on the lower lid of a coin cell (manufactured by Hosen Co., Ltd.) for coin-type battery R2032 with the aluminum foil surface facing downward, and a laminated film separator (polyethylene) is placed thereon.
  • a separator (thickness 16 ⁇ m) having a heat-resistant porous layer laminated thereon was placed on the porous film. 300 ⁇ l of electrolyte was injected here.
  • the electrolyte used was prepared by dissolving LiPF 6 in a 30:35:35 (volume ratio) mixture of ethylene carbonate, dimethyl carbonate, and ethyl methyl carbonate to a concentration of 1 mol / l.
  • the lithium metal is placed on the upper side of the laminated film separator, covered with a gasket, and caulked with a non-aqueous electrolyte secondary battery (coin type battery R2032, hereinafter, (Sometimes referred to as a “coin-type battery”).
  • the amount (mol) of Li is 1.3 with respect to the obtained coprecipitate Q 1 and the total amount (mol) 1 of transition metals contained in the coprecipitate Q 1.
  • the lithium carbonate weighed in this manner and potassium sulfate as an inert flux were mixed in a mortar to obtain a mixture.
  • the obtained mixture was placed in an alumina firing container, and the alumina firing container was placed in an electric furnace (manufacturer name, model number).
  • the oxygen concentration was adjusted to 8.5% by volume and heated at 400 ° C. to obtain a calcined product. Further, the oxygen concentration was adjusted to 1% by volume, the mixture was held at 850 ° C.
  • a coin type battery was produced by using a charge-discharge test A 1 of the non-aqueous electrolyte secondary battery was subjected to a discharge test, the discharge capacity at 0.2C (mAh / g), respectively, was 144. When a discharge test at 60 ° C. was conducted, the discharge capacity (mAh / g) at 0.2 C was 161.
  • Example 2 Production of lithium composite metal oxide precursor (coprecipitate) Nickel sulfate hexahydrate and manganese sulfate monohydrate were weighed so that the molar ratio of Ni: Mn was 0.50: 0.50. Then, an aqueous transition metal solution containing Ni and Mn was obtained by dissolving in pure water.
  • the intensity ratio I BMn / I AMn of the peak A Mn of 1.53 ⁇ and the peak B Mn of 2.49 ⁇ was 0.94.
  • the intensity ratio I BNi / I ANi between the peak A Ni of 1.56 ⁇ and the peak B Ni of 2.49 ⁇ ⁇ ⁇ was 2.05. 3.
  • a coin type battery was produced by using a charge-discharge test R 1 of the non-aqueous electrolyte secondary battery was subjected to a discharge test at 25 ° C., the discharge capacity at 0.2C (mAh / g) was 142. When a discharge test at 60 ° C.
  • the crystal structure of R 2 was hexagonal and classified into the space group R-3m.
  • a radial distribution function was obtained by Fourier transform.
  • the intensity ratio I BMn / I AMn of the peak A Mn of 1.53 ⁇ and the intensity B Mn of the peak of 2.49 ⁇ was 1.27.
  • the intensity ratio I BNi / I ANi between the peak A Ni of 1.56 ⁇ and the peak intensity B Ni of 2.52 ⁇ was 1.55. 3.
  • a coin type battery was produced by using a charge-discharge test R 2 of the non-aqueous electrolyte secondary battery was subjected to a discharge test at 25 ° C., the discharge capacity at 0.2C (mAh / g) was 65. A discharge test at 60 ° C. was not performed.
  • Comparative Example 3 1. Except for using the prepared coprecipitate Q 2 of the lithium composite metal oxide, the same operation as in Comparative Example 1 to obtain a powdered lithium composite metal oxide R 3. 2. Evaluation of Lithium Composite Metal Oxide When the composition analysis of the obtained R 3 was performed, the molar ratio of Li: Ni: Mn was 1.17: 0.50: 0.50.
  • Nickel sulfate hexahydrate, manganese sulfate monohydrate, and cobalt sulfate heptahydrate have a Ni: Mn: Co molar ratio of 0.47: 0. .48: 0.05, each was weighed and dissolved in pure water to obtain an aqueous transition metal solution containing Ni ions, Mn ions, Co ions and SO 4 2- ions. To this transition metal aqueous solution, an aqueous potassium hydroxide solution was added to perform coprecipitation to produce a precipitate, thereby obtaining a slurry.
  • the obtained slurry was subjected to solid-liquid separation, washed with distilled water to obtain a coprecipitate Q 3 and dried for 8 hours at 100 ° C.. 2. Except for using the prepared coprecipitate Q 3 of the lithium composite metal oxide, the same operation as in Comparative Example 1, to obtain a lithium mixed metal oxide R 5 in powder form. 3.
  • the crystal structure of R 5 was hexagonal and was classified into the space group R-3m.
  • a radial distribution function was obtained by Fourier transform.
  • the intensity ratio I BMn / I AMn of the peak A Mn of 1.53 ⁇ and the peak B Mn of 2.49 ⁇ is 0.94
  • the Ni radial distribution function 1.60 ⁇
  • the intensity ratio I BNi / I ANi between the peak A Ni and the peak B Ni of 2.49 ° was 2.04. 4).
  • a coin type battery was produced by using a charge-discharge test R 5 of the nonaqueous electrolyte secondary battery was subjected to a discharge test at 25 ° C., the discharge capacity at 0.2C (mAh / g) was 149. When a discharge test at 60 ° C. was performed, the discharge capacity (mAh / g) at 0.2 C was 160.
  • the results of Examples 1 and 2, Comparative Examples 1 to 4, and Reference Example 1 are shown in Table 1 below. As a result of the evaluation, in the nonaqueous electrolyte secondary batteries using the lithium composite metal oxides of Examples 1 and 2 as the positive electrode active material, the lithium composite metal oxides of Comparative Examples 1 to 4 are used as the positive electrode active material.
  • the discharge capacity was inferior under the measurement conditions of 25 ° C. Further, under the measurement conditions of 60 ° C., the non-aqueous electrolyte secondary battery of the example had a larger discharge capacity than the non-aqueous electrolyte secondary battery of the comparative example, and a high-performance secondary battery was obtained. Furthermore, the non-aqueous electrolyte secondary batteries of Examples 1 and 2 are comparable to the non-aqueous electrolyte secondary battery of Reference Example 1 containing Co in the positive electrode active material, or exceed the discharge capacity at 60 ° C. under measurement conditions. showed that.
  • the lithium composite metal oxide of the present invention is useful for a non-aqueous electrolyte secondary battery exhibiting a high capacity without using Co. Further, the positive electrode active material using the lithium composite metal oxide of the present invention, the positive electrode is useful for a low-cost yet high-performance non-aqueous electrolyte secondary battery, the non-aqueous electrolyte secondary battery of the present invention is It was found that the high capacity was exhibited at a lower cost than before.
  • a lithium composite metal oxide useful for a nonaqueous electrolyte secondary battery exhibiting a high capacity without containing Co.
  • a method for producing a lithium composite metal oxide, a positive electrode active material using the lithium composite metal oxide, a positive electrode, and a nonaqueous electrolyte secondary battery can be provided.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Separators (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention concerne un oxyde métallique composite de lithium qui comprend Mn, Ni et Li mais ne comprend pas de Co, et satisfait (a) et (b) tels que : (a) dans une fonction de distribution radiale obtenue à partir d'un spectre EXAFS d'une extrémité d'absorption K de Mn, un rapport IBMn/IAMn entre l'intensité (IAMn) d'un premier pic de rapprochement (AMn) et l'intensité (IBMn) d'un second pic de rapprochement (BMn), est supérieur ou égal à 0,5 et inférieur ou égal à 1,2; et (b) dans une fonction de distribution radiale obtenue à partir d'un spectre EXAFS d'une extrémité d'absorption K de Ni, un rapport IBNi/IANi entre l'intensité (IANi) d'un premier pic de rapprochement (ANi) et l'intensité (IBNi) d'un second pic de rapprochement (BNi), est supérieur ou égal à 1,0 et inférieur ou égal à 1,7.
PCT/JP2013/068454 2012-07-06 2013-06-28 Oxyde métallique composite de lithium ainsi que procédé de fabrication de celui-ci, matériau actif d'électrode positive, électrode positive et batterie secondaire à électrolyte non-aqueux WO2014007360A1 (fr)

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WO2020012739A1 (fr) * 2018-07-12 2020-01-16 パナソニックＩｐマネジメント株式会社 Matériau actif d'électrode positive et cellule le comprenant
CN113677628A (zh) * 2019-04-12 2021-11-19 住友化学株式会社 锂金属复合氧化物粉末、锂二次电池用正极活性物质以及锂金属复合氧化物粉末的制造方法
CN114667616A (zh) * 2019-10-30 2022-06-24 松下知识产权经营株式会社 二次电池用的正极活性物质和二次电池
JP2023500117A (ja) * 2019-12-26 2023-01-04 蜂巣能源科技股▲ふん▼有限公司 リチウムイオン電池のコバルトフリー正極材料、その調製方法およびリチウムイオン電池
JP2023501070A (ja) * 2020-05-18 2023-01-18 蜂巣能源科技股▲ふん▼有限公司 コバルトフリーシステム、正極スラリー、その均質化方法および使用
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WO2016157744A1 (fr) * 2015-03-31 2016-10-06 株式会社デンソー Matériau de cathode, cathode de batterie rechargeable à électrolyte non aqueux, et batterie rechargeable à électrolyte non aqueux
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WO2016157745A1 (fr) * 2015-03-31 2016-10-06 株式会社デンソー Matériau de cathode, cathode de batterie rechargeable à électrolyte non aqueux et batterie rechargeable à électrolyte non aqueux
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WO2020012739A1 (fr) * 2018-07-12 2020-01-16 パナソニックＩｐマネジメント株式会社 Matériau actif d'électrode positive et cellule le comprenant
US11955630B2 (en) 2018-09-05 2024-04-09 Panasonic Intellectual Property Management Co., Ltd. Positive electrode active material and battery including the same
CN113677628A (zh) * 2019-04-12 2021-11-19 住友化学株式会社 锂金属复合氧化物粉末、锂二次电池用正极活性物质以及锂金属复合氧化物粉末的制造方法
CN113677628B (zh) * 2019-04-12 2024-02-20 住友化学株式会社 锂金属复合氧化物粉末、锂二次电池用正极活性物质以及锂金属复合氧化物粉末的制造方法
CN114667616B (zh) * 2019-10-30 2024-02-09 松下知识产权经营株式会社 二次电池用的正极活性物质和二次电池
CN114667616A (zh) * 2019-10-30 2022-06-24 松下知识产权经营株式会社 二次电池用的正极活性物质和二次电池
JP2023500117A (ja) * 2019-12-26 2023-01-04 蜂巣能源科技股▲ふん▼有限公司 リチウムイオン電池のコバルトフリー正極材料、その調製方法およびリチウムイオン電池
JP7385030B2 (ja) 2019-12-26 2023-11-21 蜂巣能源科技股▲ふん▼有限公司 リチウムイオン電池のコバルトフリー正極材料、その調製方法およびリチウムイオン電池
JP2023501070A (ja) * 2020-05-18 2023-01-18 蜂巣能源科技股▲ふん▼有限公司 コバルトフリーシステム、正極スラリー、その均質化方法および使用

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