WO2014103211A1 - Matière active d'électrode positive destinée à des batteries rechargeables à électrolyte non aqueux, et batterie rechargeable à électrolyte non aqueux utilisant cette matière - Google Patents

Matière active d'électrode positive destinée à des batteries rechargeables à électrolyte non aqueux, et batterie rechargeable à électrolyte non aqueux utilisant cette matière Download PDF

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WO2014103211A1
WO2014103211A1 PCT/JP2013/007270 JP2013007270W WO2014103211A1 WO 2014103211 A1 WO2014103211 A1 WO 2014103211A1 JP 2013007270 W JP2013007270 W JP 2013007270W WO 2014103211 A1 WO2014103211 A1 WO 2014103211A1
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positive electrode
active material
electrode active
electrolyte secondary
particle
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PCT/JP2013/007270
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English (en)
Japanese (ja)
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昌洋 木下
竜一 夏井
名倉　健祐
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三洋電機株式会社
パナソニック株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
    • C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
    • 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
    • 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
    • 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
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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 positive electrode active material for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery using the same.
  • Patent Document 1 Li a Mn x Ni y Co z O 2 (0 ⁇ a ⁇ 1.2, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ ) for the purpose of increasing the capacity and reducing the resistance of a lithium secondary battery.
  • the secondary particles in which the primary particles of the layered composite oxide represented by 1,0 ⁇ z ⁇ 1, x + y + z 1) are aggregated, and the Co content in the outer peripheral portion of the secondary particles is defined as the internal Co content.
  • a higher positive electrode active material is disclosed.
  • Patent Documents 2 and 3 disclose a positive electrode active material that is provided on at least a part of the composite oxide particles and includes a coating layer made of an oxide containing at least Li and Ni, and a surface layer containing a specific metal element. Has been.
  • Li 2 MnO 3 —LiMO 2 solid solution is used as the positive electrode active material
  • an improvement in energy density is expected.
  • the positive electrode is exposed to a high potential during charging, oxidation of the electrolyte on the active material surface and Reduction of metal ions (especially Mn ions) is likely to occur.
  • the valence of Mn ions in the Li 2 MnO 3 domain is lowered, and disorder occurs due to the movement of Mn ions to the Li ion site, which causes deterioration of battery performance.
  • the positive electrode active material for a non-aqueous electrolyte secondary battery according to the present invention is a Li 2 MnO 3 —LiMO 2 solid solution (M is Ni, Co, Fe, Al, Mg, Ti, Cr, Zr, W, B, Nb, Sr). , La, Ce, Sm, Mo) and a Ni-containing oxide, and the ratio of Ni to Mn (Ni / Mn) on the particle surface is higher than Ni / Mn inside the particle It is characterized by that.
  • a non-aqueous electrolyte secondary battery includes a positive electrode including the positive electrode active material for a non-aqueous electrolyte secondary battery, a negative electrode, and a non-aqueous electrolyte.
  • the positive electrode active material according to the present invention can provide a non-aqueous electrolyte secondary battery having a high capacity and excellent charge / discharge cycle characteristics.
  • a nonaqueous electrolyte secondary battery which is an example of an embodiment of the present invention includes a positive electrode including a particulate positive electrode active material (hereinafter referred to as “positive electrode active material particles”), a negative electrode, and a nonaqueous electrolyte including a nonaqueous solvent. With. A separator is preferably provided between the positive electrode and the negative electrode.
  • the nonaqueous electrolyte secondary battery has, for example, a structure in which an electrode body in which a positive electrode and a negative electrode are wound via a separator and a nonaqueous electrolyte are accommodated in an exterior body.
  • the positive electrode includes, for example, a positive electrode current collector such as a metal foil and a positive electrode active material layer formed on the positive electrode current collector.
  • a positive electrode current collector such as a metal foil and a positive electrode active material layer formed on the positive electrode current collector.
  • the positive electrode current collector it is preferable to use a conductive thin film, particularly a metal foil or alloy foil that is stable in the potential range of the positive electrode such as aluminum, a film having a metal surface layer such as aluminum, and the like.
  • the positive electrode active material layer preferably contains a conductive material and a binder in addition to the positive electrode active material particles.
  • the positive electrode active material particles are Li 2 MnO 3 —LiMO 2 solid solution (M is Ni, Co, Fe, Al, Mg, Ti, Cr, Zr, W, B, Nb, Sr, La, Ce, Sm, and Mo. At least one selected) and a Ni-containing oxide.
  • M preferably contains at least one of Ni and Co, and particularly preferably Ni and Co, or only Ni.
  • the Ni-containing oxide preferably contains Li in addition to Ni, and more preferably contains at least one of Co and Mn in addition to Ni and Li.
  • the Li 2 MnO 3 —LiMO 2 solid solution has the composition formula Li ⁇ Mn x Ni y M * (1-xy) O ⁇ (1.1 ⁇ ⁇ 1.5, 0.4 ⁇ x ⁇ 1.0 , 0 ⁇ y ⁇ 0.6, 1.9 ⁇ ⁇ ⁇ 2.0, M * is Co, Fe, Al, Mg, Ti, Cr, Zr, W, B, Nb, Sr, La, Ce, Sm, Those represented by at least one selected from Mo) are preferred.
  • the crystal structure (main structure) of the Li 2 MnO 3 —LiMO 2 solid solution is a hexagonal system (space group R-3m).
  • space group R-3m space group R-3m
  • the positive electrode active material may contain other metal oxides in addition to the Li 2 MnO 3 —LiMO 2 solid solution in the form of a mixture or solid solution as long as the object of the present invention is not impaired.
  • the Li 2 MnO 3 —LiMO 2 solid solution in the positive electrode active material preferably exceeds 50% by volume, more preferably 70% by volume or more, and 90% by volume with respect to the total volume of the compounds constituting the positive electrode active material. The above is particularly preferable.
  • the volume average particle diameter of the positive electrode active material particles is, for example, 1 to 30 ⁇ m, preferably 2 to 15 ⁇ m, more preferably 3 to 10 ⁇ m.
  • the volume average particle diameter (hereinafter referred to as “Dv50”) means a particle diameter at which the volume integrated value is 50% in the particle diameter distribution.
  • the Dv50 of the positive electrode active material particles can be measured using a laser diffraction scattering measurement apparatus (for example, “LA-750” manufactured by HORIBA) using water as a dispersion medium.
  • the positive electrode active material particles are characterized in that the ratio of Ni to Mn (Ni / Mn) on the particle surface is higher than Ni / Mn inside the particles. Thereby, even when the positive electrode is exposed to a high potential during charging, it is possible to suppress oxidation of the electrolytic solution and reduction of metal ions, particularly Mn ions, on the active material surface.
  • Ni / Mn on the particle surface is preferably 2 times or more of Ni / Mn inside the particle, more preferably 3 times or more, particularly preferably 5 times or more, and most preferably 9 times or more.
  • the positive electrode active material particles may have no Mn on the particle surface or Ni inside the particles, and the upper limit of the magnification is not particularly limited in terms of improving cycle characteristics.
  • FIG. 1 shows a cross section of positive electrode active material particles as an example of the embodiment.
  • a specific form of the positive electrode active material particles is not illustrated, and is extremely simplified.
  • the positive electrode active material particles include a base material particle 1 composed of the Li 2 MnO 3 —LiMO 2 solid solution and a coating layer 2 composed of the Ni-containing oxide formed on the surface of the base material particle 1. It is suitable to have. That is, the base material particle 1 constitutes the inside of the positive electrode active material particle, and the coating layer 2 constitutes the particle surface of the positive electrode active material particle. And Ni / Mn of the coating layer 2 is higher than Ni / Mn of the base material particle 1. Specifically, Ni / Mn of the coating layer 2 is preferably 2 times or more of Ni / Mn of the base material particle 1, more preferably 3 times or more, particularly preferably 5 times or more, and more than 9 times. Most preferred.
  • the maximum thickness of the coating layer 2 is preferably 10 to 500 nm, more preferably 50 to 400 nm, and particularly preferably 80 to 300 nm.
  • the covering layer 2 is preferably formed so as to cover substantially the entire surface of the base material particle 1, and the thickness thereof is preferably substantially equal over the entire region of the layer. That is, the average thickness of the coating layer 2 is preferably 10 to 500 nm, more preferably 50 to 400 nm, and particularly preferably 80 to 300 nm.
  • the thickness of the coating layer 2 can be measured by cross-sectional observation using a transmission electron microscope (TEM) or a scanning electron microscope (SEM). The average thickness is an average value of thicknesses measured at arbitrary 10 points.
  • TEM transmission electron microscope
  • SEM scanning electron microscope
  • the Dv50 of the base material particle 1 is, for example, 1 to 30 ⁇ m, preferably 2 to 15 ⁇ m, more preferably 3 to 10 ⁇ m.
  • it can be obtained by measuring the Dv50 of the positive electrode active material particles and subtracting the average thickness of the coating layer 2 from the Dv50.
  • FIG. 2 shows a state of the particle surface and the inside of the particle by excising a part of the surface of the positive electrode active material particle as an example of the embodiment.
  • a large number of primary particles 3 are aggregated to form base material particles 1.
  • the primary particles 3 are preferably composed of the Li 2 MnO 3 —LiMO 2 solid solution.
  • the base material particle 1 is formed by, for example, primary particles 3 obtained by mixing and firing the raw materials of the Li 2 MnO 3 —LiMO 2 solid solution fixed to each other.
  • the coating layer 2 is formed by the coating particles 4 which are particles smaller than the base material particles 1.
  • the coated particles 4 are preferably smaller than the primary particles 3 constituting the base material particles 1 and have a Dv50 of 10 to 200 nm, preferably 10 to 150 nm, more preferably before being fixed to the base material particles 1. 10 to 100 nm.
  • the coated particle 4 is composed of a lithium-containing metal oxide containing Ni.
  • the composition of the oxide is not particularly limited as long as the Ni / Mn is higher than the Ni / Mn of the base material particle 1, but contains at least one of Co and Mn in addition to Li and Ni. Is preferred.
  • the coated particle 4 is made of, for example, LiNi x M2 1-x O 2 (M2 contains at least one of Co and Mn) or the above Li 2 MnO 3 —LiMO 2 solid solution having a higher Ni content than the base material particle 1. Composed.
  • the positive electrode active material particles shown in FIG. 2 can be produced, for example, by fixing the coated particles 4 to the surfaces of the base material particles 1.
  • the covering particles 4 cover substantially the entire surface of the base material particle 1, and a plurality of the covering particles 4 are laminated to form the covering layer 2 having a thickness of about 80 to 300 nm.
  • a method of dry mixing the base material particles 1 and the covering particles 4 is suitable. Such dry mixing can be performed using a commercially available dry mixing apparatus.
  • the temperature at the time of mixing is not specifically limited, For example, it sets to room temperature (25 degreeC).
  • suitable dry mixing devices include “Planet Ball Mill” manufactured by Retsch, “Hybridization System” manufactured by Nara Machinery Co., Ltd., “Nanocula”, “Nobilta”, “Mechanofusion” manufactured by Hosokawa Micron. It is done.
  • the coated particles 4 can be fixed to the surface of the base material particles 1 by wet mixing using water, ethanol or the like as a solvent.
  • the shape of the coating particles 4 is not substantially left, and the dense coating layer 2 can be formed on the surface of the base material particles 1.
  • the base material particle 1 and the coated particle 4 and the coated particles 4 are firmly bonded to each other, and the particle interface of the coated particle 4 remains.
  • a dense coating layer 2 can be formed.
  • FIG. 3 shows a part of positive electrode active material particles as an example of the embodiment as a cross-sectional view.
  • the cross section is marked with dot hatching, and the higher the dot density, the higher the Ni content.
  • the positive electrode active material particles shown in FIG. 3 are particles in which Ni / Mn increases stepwise as the particle surface approaches the particle surface.
  • Ni / Mn is the lowest layer L 3 is formed in the center of the particle
  • the layer L 2 is greater Ni / Mn than layer L 3 in the outer layer L 3
  • the outermost surface of the particles A layer L 1 having the highest Ni / Mn is formed.
  • Such positive electrode active material particles can be prepared, for example, by preparing a plurality of compound particles having different Ni contents and sequentially dry-mixing them.
  • the surface of the positive electrode active material particles is covered with fine particles of an oxide such as aluminum oxide (Al 2 O 3 ), an inorganic compound such as a phosphoric acid compound, and a boric acid compound as long as the object of the present invention is not impaired. Also good.
  • an oxide such as aluminum oxide (Al 2 O 3 )
  • an inorganic compound such as a phosphoric acid compound, and a boric acid compound
  • the conductive material is used to increase the electrical conductivity of the positive electrode active material layer.
  • the conductive material include carbon materials such as carbon black, acetylene black, ketjen black, and graphite. These may be used alone or in combination of two or more.
  • the content of the conductive material is preferably 0% by mass to 30% by mass with respect to the total mass of the positive electrode active material layer, more preferably 0% by mass to 20% by mass, and particularly preferably 0% by mass to 10% by mass. preferable.
  • the binder is used to maintain a good contact state between the positive electrode active material particles and the conductive material and to increase the binding property of the positive electrode active material particles and the like to the surface of the positive electrode current collector.
  • the binder for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyvinyl acetate, polymethacrylate, polyacrylate, polyacrylonitrile, polyvinyl alcohol, or a mixture of two or more thereof are used.
  • the binder may be used in combination with a thickener such as carboxymethyl cellulose (CMC) or polyethylene oxide.
  • the content of the binder is preferably 0% by mass to 30% by mass, more preferably 0% by mass to 20% by mass, and more preferably 0% by mass to 10% by mass with respect to the total mass of the positive electrode active material layer. Particularly preferred.
  • the positive electrode potential in a fully charged state of the positive electrode having the above structure can be set to a high potential of 4.0 V (vs. Li / Li + ) or higher.
  • the charge termination potential of the positive electrode is preferably 4.5 V (vs. Li / Li + ) or more, more preferably 4.6 V (vs. Li / Li + ) or more, from the viewpoint of increasing the capacity.
  • the upper limit of the charge termination potential of the positive electrode is not particularly limited, but is preferably 5.0 V (vs. Li / Li + ) or less from the viewpoint of suppressing decomposition of the nonaqueous electrolyte.
  • the negative electrode includes, for example, a negative electrode current collector such as a metal foil, and a negative electrode active material layer formed on the negative electrode current collector.
  • a negative electrode current collector such as a metal foil
  • a negative electrode active material layer formed on the negative electrode current collector.
  • the negative electrode current collector it is preferable to use a conductive thin film, particularly a metal foil or alloy foil that is stable in the potential range of the negative electrode such as copper, a film having a metal surface layer such as copper, or the like.
  • the negative electrode active material layer preferably contains a binder in addition to the negative electrode active material capable of inserting and extracting lithium ions.
  • PTFE or the like can be used as in the case of the positive electrode, but it is preferable to use a styrene-butadiene copolymer or a modified product thereof.
  • the binder may be used in combination with a thickener such as CMC.
  • Examples of the negative electrode active material include natural graphite, artificial graphite, lithium, silicon, carbon, tin, germanium, aluminum, lead, indium, gallium, lithium alloy, carbon and silicon in which lithium is previously occluded, and alloys and mixtures thereof. Etc. can be used.
  • the non-aqueous electrolyte includes a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • the nonaqueous electrolyte is not limited to a liquid electrolyte (nonaqueous electrolyte solution), and may be a solid electrolyte using a gel polymer or the like.
  • the non-aqueous solvent for example, esters, ethers, nitriles, amides, a mixed solvent of two or more thereof, and the like can be used.
  • halogen-substituted products obtained by substituting hydrogen in various solvents with halogen atoms such as fluorine may be used.
  • a fluorinated cyclic carbonate, a fluorinated chain carbonate, or a mixed solvent thereof can be used.
  • esters examples include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, chain carbonates such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl isopropyl carbonate, Examples thereof include carboxylic acid esters such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, and ⁇ -butyrolactone.
  • ethers examples include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,4 -Cyclic ethers such as dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineol, crown ether, 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether , Dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, benzyl ethyl ether, diphenyl ether, diphen
  • nitriles examples include acetonitrile, and examples of the amides include dimethylformamide.
  • the electrolyte salt is preferably a lithium salt.
  • lithium salts include LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , LiN (FSO 2 ) 2 , LiN (C 1 F 2l + 1 SO 2 ) (C m F 2m + 1 SO 2) (l, m is an integer of 1 or more), LiC (C P F 2p + 1 SO 2) (C q F 2q + 1 SO 2) (C r F 2r + 1 SO 2) (p, q, r Is an integer of 1 or more), Li [B (C 2 O 4 ) 2 ] (bis (oxalate) lithium borate (LiBOB)), Li [B (C 2 O 4 ) F 2 ], Li [P (C 2 O 4 ) F 4 ], Li [P (C 2 O 4 ) 2 F 2 ], and a mixture of two or more thereof.
  • separator a porous sheet having ion permeability and insulating properties is used.
  • the porous sheet include a microporous thin film, a woven fabric, and a nonwoven fabric.
  • material of the separator polyolefin such as polyethylene and polypropylene is suitable.
  • Nickel sulfate (NiSO 4 ) and manganese sulfate (MnSO 4 ) are mixed in an aqueous solution so as to have a molar weight ratio of 1: 3, and coprecipitated to obtain (Ni, Mn) (OH) 2 as a precursor substance. Obtained. Thereafter, the precursor material and lithium hydroxide monohydrate (LiOH.H 2 O) were mixed at a molar weight ratio of 1: 1.5, and the mixture was calcined at 850 ° C. for 12 hours. Base material particles A1 of the positive electrode active material were obtained.
  • the crystal structure of the lithium-containing transition metal oxide constituting the base material particle A1 was analyzed by a powder X-ray diffraction method (manufactured by Rigaku Corporation, using a powder XRD measuring device RINT2200 (radiation source Cu-K ⁇ ), and so on). .
  • the crystal structure (main structure) of the lithium-containing transition metal oxide composing the base material particle A1 was a hexagonal crystal (space group R-3m).
  • the composition of the lithium-containing transition metal oxide constituting the base material particle A1 was analyzed by ICP emission analysis (Thermo Fisher Scientific, ICP emission spectroscopic analyzer iCAP6300 was used. The same applies hereinafter). As a result, the composition of the lithium-containing transition metal oxide constituting the base material particle A1 was Li 1.2 Mn 0.6 Ni 0.2 O 2 .
  • Base material particle A1 is a spherical secondary particle formed by adhering a large number of primary particles to each other, and Dv50 was about 7 ⁇ m. Dv50 was measured using a laser diffraction / scattering type measurement apparatus (manufactured by HORIBA, LA-750).
  • NiSO 4 and MnSO 4 were mixed in an aqueous solution so as to have a molar weight ratio of 1: 1 and coprecipitated, and (Ni, Mn) (OH) 2 and LiOH ⁇ H 2 O had a molar weight ratio of 1 : 1 to mix.
  • the mixture was fired at 850 ° C. for 12 hours, and then crushed using a planetary ball mill (manufactured by Retsch, PM400) until Dv50 was 100 nm or less, whereby the coated particles B1 constituting the coating layer of the positive electrode active material were obtained. Obtained.
  • the composition of the lithium-containing transition metal oxide constituting the coated particle B1 was analyzed by ICP emission analysis. As a result, the composition of the lithium-containing transition metal oxide constituting the coated particle B1 was LiMn 0.5 Ni 0.5 O 2 .
  • the base material particle A1 and the covering particle B1 were dry mixed to produce the positive electrode active material particle C1. Details of the dry mixing step are as follows. Apparatus: Rolling ball mill (manufactured by Retsch) Temperature condition: 25 ° C Mixing time: 12 hours
  • the test cell D1 shown in FIG. 3 was produced by the following procedure. First, using the positive electrode active material particles C1 as the positive electrode active material, acetylene black as the conductive material, and polyvinylidene fluoride as the binder, the mass ratio of the positive electrode active material, the conductive material, and the binder is 80:10:10. And slurried with N-methyl-2-pyrrolidone. Next, this slurry was applied on an aluminum foil current collector as a positive electrode current collector, and vacuum dried at 110 ° C. to produce a working electrode (positive electrode).
  • a test cell D1 which is a non-aqueous electrolyte secondary battery is manufactured using the above working electrode, counter electrode (negative electrode), separator, non-aqueous electrolyte, and an exterior body that accommodates them under dry air at a dew point of ⁇ 50 ° C. or lower. did. Details of each component are as follows. Counter electrode; Lithium metal separator; Polyethylene separator Nonaqueous electrolyte; Ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed at a volume ratio of 1: 1 to obtain a nonaqueous solvent.
  • a nonaqueous electrolyte was prepared by dissolving lithium hexafluorophosphate (LiPF 6 ) as an electrolyte salt in the nonaqueous solvent so as to have a concentration of 1.0 mol / l.
  • Example 4 Cathode active material particles C4 and test cells D4 were prepared in the same manner as in Example 1 except that coated particles B4 having a composition of LiNi 0.8 Co 0.2 O 2 (not containing Mn) were used instead of the coated particles B1. Produced.
  • Table 1 shows capacity retention rates after 15 cycles for test cells D1 to D4 of Examples 1 to 4 and test cells Z1 and Z2 of Comparative Examples 1 and 2.
  • test cells D1 to D4 of the example have a higher capacity retention rate after 15 cycles and excellent cycle characteristics than the test cells Z1 and Z2 of the comparative example.
  • the test cells D1 to D4 of the examples were expected to have a high capacity but were inferior in cycle characteristics. This is a significant improvement in cycle characteristics, which was a problem.
  • Ni / Mn on the particle surface is made higher than Ni / Mn inside the particle, specifically, Ni on the surface of the positive electrode active material particle.
  • the magnification is preferably 5 times (Example 2) rather than 3 times (Example 1) and 9 times or more (Examples 3 and 4) than 5 times.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

Selon un mode de réalisation, la présente invention se rapporte à une matière active d'électrode positive qui est une matière active d'électrode positive particulaire utilisée dans une batterie rechargeable à électrolyte non aqueux. Cette matière active d'électrode positive est caractérisée en ce qu'elle comprend une solution solide Li2MnO3-LiMO2 (M représentant au moins un élément sélectionné parmi du Co, du Ni, du Fe, de l'Al, du Mg, du Ti, du Cr, du Zr, du W, du B, du Nb, du Sr, du La, du Ce, du Sm et du Mo) ainsi qu'un oxyde contenant du Ni, et elle est également caractérisée en ce que le rapport entre le Ni et le Mn (Ni/Mn) à la surface de la particule est supérieur au rapport Ni/Mn à l'intérieur de la particule.
PCT/JP2013/007270 2012-12-28 2013-12-10 Matière active d'électrode positive destinée à des batteries rechargeables à électrolyte non aqueux, et batterie rechargeable à électrolyte non aqueux utilisant cette matière WO2014103211A1 (fr)

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WO2018026650A1 (fr) * 2016-08-02 2018-02-08 Apple Inc. Matériaux de cathode à base de nickel revêtus et procédés de préparation associés
CN112820868A (zh) * 2021-03-01 2021-05-18 合肥国轩高科动力能源有限公司 包覆型镍钴锰三元单晶材料及其制备方法

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CN114287073A (zh) * 2019-08-30 2022-04-05 松下电器产业株式会社 非水电解质二次电池用正极活性物质和非水电解质二次电池
WO2021108945A1 (fr) * 2019-12-02 2021-06-10 宁德时代新能源科技股份有限公司 Feuille d'électrode positive destinée à une batterie rechargeable, batterie rechargeable, module de batterie, bloc-batterie et dispositif
JP7275094B2 (ja) * 2020-12-07 2023-05-17 プライムプラネットエナジー＆ソリューションズ株式会社 正極活物質調製用材料とその利用

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CN112820868B (zh) * 2021-03-01 2022-04-12 合肥国轩高科动力能源有限公司 包覆型镍钴锰三元单晶材料及其制备方法

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