WO2023068221A1 - Matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux - Google Patents

Matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux Download PDF

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WO2023068221A1
WO2023068221A1 PCT/JP2022/038573 JP2022038573W WO2023068221A1 WO 2023068221 A1 WO2023068221 A1 WO 2023068221A1 JP 2022038573 W JP2022038573 W JP 2022038573W WO 2023068221 A1 WO2023068221 A1 WO 2023068221A1
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positive electrode
active material
electrode active
electrolyte secondary
ratio
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PCT/JP2022/038573
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English (en)
Japanese (ja)
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敏信 金井
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三洋電機株式会社
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to positive electrode active materials for non-aqueous electrolyte secondary batteries and non-aqueous electrolyte secondary batteries.
  • a non-aqueous electrolyte secondary battery has a positive electrode, a negative electrode, and a non-aqueous electrolyte, and charges and discharges by moving lithium ions etc. between the positive electrode and the negative electrode. Batteries are widely used.
  • Patent Document 1 at least one selected from a first positive electrode active material and a second positive electrode active material is included, and the first positive electrode active material has a general composition formula Li (1+a) Mn x Ni y Co (1-xyz) M z O 2 (where M is at least one element selected from the group consisting of Ti, Zr, Nb, Mo, W, Al, Si, Ga, Ge and Sn is represented by ⁇ 0.15 ⁇ a ⁇ 0.15, 0.1 ⁇ x ⁇ 0.5, 0.6 ⁇ x+y+z ⁇ 1.0, 0 ⁇ z ⁇ 0.1), and the second The positive electrode active material has a general composition formula Li (1-sb) Mg s Co (1-tu) Al t M' u O 2 (where M' is selected from the group consisting of Ti, Zr and Ge). is at least one element that is A non-aqueous electrolyte secondary battery using the active material obtained by the method is disclosed.
  • the composition of the secondary particles serving as the core is Li x1 Ni 1-y1-z1-w1 Co y1 Mn z1 M1 w1 O 2-v K v (1 ⁇ x1 ⁇ 1.3, 0 ⁇ y1 ⁇ 0.33, 0.2 ⁇ z1 ⁇ 0.33, 0 ⁇ w1 ⁇ 0.1, 0 ⁇ v ⁇ 0.05, and M1 is at least one metal selected from Al, Mg and K is at least one anion selected from F ⁇ , PO 4 3- ), the Li—Ni—Mn composite oxide having the composition Li x2 Ni 1-y2 on or near the surface of the secondary particles.
  • M2 is at least selected from Al, Mg, Zr, Ti
  • a non-aqueous electrolyte secondary battery using Li--Ni composite oxide particles for non-aqueous electrolyte secondary batteries coated with or having Li--Ni composite oxide (a type of metal) present therein is disclosed.
  • the present disclosure provides a direct current resistance of a non-aqueous electrolyte secondary battery even when a Ni-containing lithium composite oxide having a high ratio of the number of moles of Ni to the total number of moles of metal elements excluding lithium is used as a positive electrode active material. and suppress deterioration of charge-discharge cycle characteristics.
  • a positive electrode active material for a nonaqueous electrolyte secondary battery which is one aspect of the present disclosure, includes a first positive electrode active material and a second positive electrode active material, and the first positive electrode active material is a Ni-containing lithium composite oxide, , the ratio (B 1 /A 1 ) of the number of moles of Ni (B 1 ) to the total number of moles (A 1 ) of the metal elements excluding Li is 0.85 or more and 0.94 or less, and the metal elements excluding Li
  • the ratio (C 1 /A 1 ) of the number of moles of Li (C 1 ) to the total number of moles (A 1 ) of Li is 0.950 or more and 0.983 or less
  • the second positive electrode active material is a Ni-containing lithium composite an oxide, wherein the ratio of the number of moles of Ni (B 2 ) to the total number of moles of metal elements excluding Li (A 2 ) is 0.85 or more and 0.94 or less, and the total number of metal elements excluding Li is The ratio (
  • a non-aqueous electrolyte secondary battery includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, and the positive electrode contains the positive electrode active material for a non-aqueous electrolyte secondary battery.
  • the non-aqueous electrolyte secondary battery even when a Ni-containing lithium composite oxide having a high ratio of the number of moles of Ni to the total number of moles of metal elements excluding lithium is used as the positive electrode active material, the non-aqueous electrolyte secondary battery It is possible to reduce the direct current resistance of the battery and suppress the deterioration of the charge-discharge cycle characteristics.
  • FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery that is an example of an embodiment
  • FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery that is an example of an embodiment.
  • the non-aqueous electrolyte secondary battery 10 shown in FIG. A battery case having insulating plates 18 and 19 arranged, and a case main body 16 and a sealing member 17 for accommodating the above members is provided.
  • the wound electrode body 14 another form of electrode body such as a stacked electrode body in which positive and negative electrodes are alternately stacked via a separator may be applied.
  • the battery case include cylindrical, square, coin-shaped, button-shaped metal cases, and resin cases formed by laminating resin sheets (so-called laminated type).
  • the case body 16 is, for example, a bottomed cylindrical metal container.
  • a gasket 28 is provided between the case body 16 and the sealing member 17 to ensure hermeticity inside the battery.
  • the case main body 16 has an overhanging portion 22 that supports the sealing member 17, for example, a portion of the side surface overhanging inward.
  • the projecting portion 22 is preferably annularly formed along the circumferential direction of the case body 16 and supports the sealing member 17 on the upper surface thereof.
  • the sealing body 17 has a structure in which a filter 23, a lower valve body 24, an insulating member 25, an upper valve body 26, and a cap 27 are layered in order from the electrode body 14 side.
  • Each member constituting the sealing member 17 has, for example, a disk shape or a ring shape, and each member other than the insulating member 25 is electrically connected to each other.
  • the lower valve body 24 and the upper valve body 26 are connected to each other at their central portions, and an insulating member 25 is interposed between their peripheral edge portions.
  • the lower valve body 24 deforms and breaks so as to push the upper valve body 26 upward toward the cap 27, thereby breaking the lower valve body 24 and the upper valve.
  • the current path between bodies 26 is interrupted.
  • the upper valve body 26 is broken and the gas is discharged from the opening of the cap 27 .
  • the positive electrode lead 20 attached to the positive electrode 11 extends through the through hole of the insulating plate 18 toward the sealing member 17, and the negative electrode lead 21 attached to the negative electrode 12 is insulated. It extends to the bottom side of the case body 16 through the outside of the plate 19 .
  • the positive electrode lead 20 is connected to the lower surface of the filter 23, which is the bottom plate of the sealing member 17, by welding or the like, and the cap 27, which is the top plate of the sealing member 17 electrically connected to the filter 23, serves as a positive electrode terminal.
  • the negative lead 21 is connected to the inner surface of the bottom of the case body 16 by welding or the like, and the case body 16 serves as a negative terminal.
  • the positive electrode 11 includes a positive electrode current collector and a positive electrode mixture layer arranged on the positive electrode current collector. In addition, it is desirable that the positive electrode mixture layers are arranged on both sides of the positive electrode current collector.
  • the positive electrode current collector a foil of a metal such as aluminum or an aluminum alloy that is stable in the potential range of the positive electrode, or a film in which the metal is placed on the surface can be used.
  • the positive electrode current collector has a thickness of, for example, about 10 ⁇ m to 100 ⁇ m.
  • the positive electrode mixture layer includes a first positive electrode active material and a second positive electrode active material.
  • the positive electrode mixture layer preferably contains a binder in order to bind the positive electrode active materials together and ensure the mechanical strength of the positive electrode mixture layer.
  • the positive electrode mixture layer preferably contains a conductive material in that the conductivity of the layer can be improved.
  • a positive electrode mixture slurry containing a first positive electrode active material, a second positive electrode active material, a binder, a conductive material, and the like is prepared, and this positive electrode mixture slurry is applied on a positive electrode current collector and coated. After drying the film, it can be prepared by rolling the coating film.
  • the ratio (B 1 /A 1 ) of the number of moles of Ni (B 1 ) to the total number of moles (A 1 ) of metal elements excluding Li is 0.85 or more and 0.94 or less.
  • a Ni-containing lithium composite oxide in which the ratio (C 1 /A 1 ) of the number of moles (C 1 ) of Li to the total number of moles (A 1 ) of metal elements excluding Li is 0.950 or more and 0.983 or less be.
  • the ratio (B 2 /A 2 ) of the number of moles (B 2 ) of Ni to the total number of moles (A 2 ) of metal elements excluding Li is 0.85 or more and 0.94 or less.
  • Ni-containing lithium composite oxide having a ratio (C 2 /A 2 ) of the number of moles (C 2 ) of Li to the total number of moles (A 2 ) of metal elements excluding Li of 0.984 or more and 1.004 or less is.
  • the Ni-containing lithium composite oxide of the first positive electrode active material has the following general formula (1) in terms of reducing the direct current resistance of the non-aqueous electrolyte secondary battery or suppressing deterioration in charge-discharge cycle characteristics. It is preferably a Ni-containing lithium composite oxide represented by. LizNi1 -xyMxAlyO2 ( 1 ) where x, y and z are 0 ⁇ x ⁇ 0.15, 0 ⁇ y ⁇ 0.10, 0.85 ⁇ 1-xy ⁇ 0.94, 0.950 ⁇ z ⁇ 0.983 0.02 ⁇ x ⁇ 0.10, 0.03 ⁇ y ⁇ 0.07, 0.85 ⁇ 1-xy ⁇ 0.94, 0.970 ⁇ z ⁇ 0.983 is more preferable.
  • M is preferably at least one element selected from the group consisting of Co, W, Nb, Mg, Ti, Mn and Mo, and at least one element selected from Co, Mn and W is more preferably an element of
  • the Ni-containing lithium composite oxide of the second positive electrode active material has the following general formula (2) in terms of reducing the direct current resistance of the non-aqueous electrolyte secondary battery or suppressing deterioration in charge-discharge cycle characteristics. It is preferably a Ni-containing lithium composite oxide represented by. LizNi1 -xyMxAlyO2 ( 2 ) where x, y and z are 0 ⁇ x ⁇ 0.15, 0 ⁇ y ⁇ 0.10, 0.85 ⁇ 1-xy ⁇ 0.94, 0.984 ⁇ z ⁇ 1.004 0.02 ⁇ x ⁇ 0.10, 0.03 ⁇ y ⁇ 0.07, 0.85 ⁇ 1-xy ⁇ 0.94, 0.984 ⁇ z ⁇ 1.000 is more preferable.
  • M is preferably at least one element selected from the group consisting of Co, W, Nb, Mg, Ti, Mn and Mo, and at least one element selected from Co, Mn and W is more preferably an element of
  • the composition of the Ni-containing lithium composite oxide is measured by inductively coupled plasma (ICP) emission spectrometry.
  • ICP inductively coupled plasma
  • the mixing ratio of the first positive electrode active material and the second positive electrode active material is 95: 5 to 75 in mass ratio in terms of reducing the direct current resistance of the non-aqueous electrolyte secondary battery and suppressing deterioration of charge-discharge cycle characteristics. :25, preferably 90:10 to 80:20.
  • the total amount of the first positive electrode active material and the second positive electrode active material contained in the positive electrode mixture layer is preferably 80% by mass or more, preferably 90% by mass, with respect to the total mass of the positive electrode mixture layer. It is more preferable to be above.
  • the first positive electrode active material and the second positive electrode active material are composed of secondary particles that are aggregated primary particles.
  • the average particle size of the secondary particles of the first positive electrode active material and the average particle size of the secondary particles of the second positive electrode active material are, for example, 5 ⁇ m or more and 15 ⁇ m or less in terms of increasing the capacity of the non-aqueous electrolyte secondary battery. and more preferably 8 ⁇ m or more and 12 ⁇ m or less.
  • the average particle size of the secondary particles is the volume average particle size measured by the laser diffraction method, and means the median size at which the volume integrated value is 50% in the particle size distribution.
  • the average particle size of the secondary particles of the first positive electrode active material and the second positive electrode active material can be measured using, for example, a laser diffraction scattering particle size distribution analyzer (manufactured by HORIBA, Ltd.).
  • the average particle size of the primary particles of the first positive electrode active material and the average particle size of the primary particles of the second positive electrode active material should be 0.1 ⁇ m or more from the viewpoint of increasing the capacity of the non-aqueous electrolyte secondary battery. It is preferably 0 ⁇ m or less, more preferably 0.2 ⁇ m or more and 0.8 ⁇ m or less.
  • the average particle size of the primary particles of the first positive electrode active material and the second positive electrode active material is obtained by randomly selecting 100 primary particles in the SEM image of the first positive electrode active material and the second positive electrode active material, It is obtained by measuring the diameter of the circumscribed circle of and averaging the measured values.
  • the positive electrode mixture layer may contain a positive electrode active material other than the first positive electrode active material and the second positive electrode active material.
  • the positive electrode active material other than the first positive electrode active material and the second positive electrode active material is not particularly limited as long as it is a compound capable of reversibly intercalating and deintercalating lithium .
  • Ni-free Li composite oxides, Ni-containing lithium composite oxides having a smaller Ni content than the first positive electrode active material and the second positive electrode active material, and the like can be mentioned.
  • Carbon materials such as carbon black, acetylene black, ketjen black, and graphite can be exemplified as the conductive material contained in the positive electrode mixture layer. These may be used alone or in combination of two or more.
  • the content of the conductive material in the positive electrode mixture layer is, for example, preferably 0.5% by mass or more and 4% by mass or less, and more preferably 0.5% by mass or more and 1.5% by mass or less.
  • the binder contained in the positive electrode mixture layer includes fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, polyolefin resins, styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC) or salts thereof, polyacrylic acid (PAA) or salts thereof (PAA-Na, PAA-K, etc., may also be partially neutralized salts), polyethylene oxide (PEO), polyvinyl alcohol (PVA) and the like. These may be used alone or in combination of two or more.
  • the content of the binder in the positive electrode mixture layer is, for example, preferably 0.5% by mass or more and 4% by mass or less, and more preferably 0.5% by mass or more and 1.5% by mass or less. .
  • the negative electrode 12 is composed of, for example, a negative electrode current collector and a negative electrode mixture layer formed on the current collector.
  • a negative electrode current collector a foil of a metal such as copper that is stable in the potential range of the negative electrode, a film having the metal on the surface layer, or the like can be used.
  • the negative electrode mixture layer includes, for example, a negative electrode active material, a binder, and the like.
  • a negative electrode mixture slurry containing a negative electrode active material, a binder, etc. is prepared, the negative electrode mixture slurry is applied on a negative electrode current collector, the coating film is dried, and then the coating film is applied. It can be produced by rolling.
  • the negative electrode active material is not particularly limited as long as it is a material capable of intercalating and deintercalating lithium ions.
  • Lithium alloys such as tin alloys, graphite, coke, carbon materials such as organic sintered bodies, metal oxides such as SnO 2 , SnO, TiO 2 and the like. These may be used singly or in combination of two or more.
  • the binder contained in the negative electrode mixture layer as in the case of the positive electrode, fluorine resin, PAN, polyimide resin, acrylic resin, polyolefin resin, SBR, CMC or its salt, PAA or its salt, Examples include PEO and PVA.
  • the negative electrode mixture layer may contain a conductive material as in the case of the positive electrode.
  • the separator 13 for example, a porous sheet or the like having ion permeability and insulation is used. Specific examples of porous sheets include microporous thin films, woven fabrics, and non-woven fabrics.
  • the separator 13 is made of, for example, polyolefin such as polyethylene or polypropylene, or cellulose.
  • the separator 13 may be a laminate having a cellulose fiber layer and a thermoplastic resin fiber layer such as polyolefin.
  • the separator 13 may be a multilayer separator including a polyethylene layer and a polypropylene layer, and may have a surface layer composed of an aramid resin or a surface layer containing an inorganic filler.
  • the non-aqueous electrolyte contains 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), and may be a solid electrolyte using a gel polymer or the like.
  • non-aqueous solvents that can be used include esters, ethers, nitriles such as acetonitrile, amides such as dimethylformamide, and mixed solvents of two or more thereof.
  • the non-aqueous solvent may contain a halogen-substituted product obtained by substituting at least part of the hydrogen atoms of these solvents with halogen atoms such as fluorine.
  • esters examples include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl propyl carbonate. , Ethyl propyl carbonate, methyl isopropyl carbonate and other chain carbonates, ⁇ -butyrolactone, ⁇ -valerolactone and other cyclic carboxylic acid esters, methyl acetate, ethyl acetate, propyl acetate, methyl propionate (MP), ethyl propionate, etc. and chain carboxylic acid esters of.
  • cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl propyl carbonate.
  • 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 -dioxane, 1,3,5-trioxane, furan, 2-methylfuran, 1,8-cineol, cyclic ethers such as 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, methoxytoluene, benzyl ethyl ether, diphenyl ether, cycl
  • nitriles examples include acetonitrile, propionitrile, butyronitrile, valeronitrile, n-heptanirile, succinonitrile, glutaronitrile, adibonitrile, pimeronitrile, 1,2,3-propanetricarbonitrile, 1,3 , 5-pentanetricarbonitrile and the like.
  • halogen-substituted compounds include fluorinated cyclic carbonates such as fluoroethylene carbonate (FEC), fluorinated chain carbonates, and fluorinated chain carboxylates such as methyl fluoropropionate (FMP). .
  • FEC fluoroethylene carbonate
  • FMP fluorinated chain carboxylates
  • FEC fluoroethylene carbonate
  • FMP fluorinated chain carboxylates
  • electrolyte salts examples include LiBF4 , LiClO4 , LiPF6 , LiAsF6 , LiSbF6 , LiAlCl4 , LiSCN, LiCF3SO3 , LiCF3CO2 , Li(P( C2O4 ) F4 ) , LiPF 6-x (C n F 2n+1 ) x (1 ⁇ x ⁇ 6, n is 1 or 2), LiB 10 Cl 10 , LiCl, LiBr, LiI, lithium chloroborane, lithium lower aliphatic carboxylate, Li 2 B 4O7 , borates such as Li(B( C2O4 ) F2 ) , LiN( SO2CF3 ) 2 , LiN( ClF2l + 1SO2 )( CmF2m + 1SO2 ) ⁇ l , where m is an integer of 1 or more ⁇ . Electrolyte salts may be used singly or in combination of two or more. The concentration of the electrolyte
  • the composite oxide containing Ni, Co and Al and LiOH were mixed so that the total molar ratio of Li to Ni, Co and Al was 1.02:1.
  • the mixture was fired in an oxygen atmosphere at 740° C. for 3.5 hours to obtain Ni, Co and Al-containing lithium composite oxide A (Li 1.02 Ni 0.90 Co 0.05 Al 0.05 O 2 ).
  • Ni-, Co- and Al-containing lithium composite oxide B Li 1.05 Ni 0.90 Co 0.05 Al 0.05 O 2 .
  • the Ni-, Co- and Al-containing lithium composite oxide A was washed with water and dried. This was used as the first positive electrode active material.
  • the Ni-, Co- and Al-containing lithium composite oxide B was washed with water and dried to obtain a second positive electrode active material.
  • composition of the second positive electrode active material was analyzed by ICP and found to be Li 0.997 Ni 0.895 Co 0.048 Al 0.057 O 2 .
  • the first positive electrode active material (secondary particle average particle size: 11 ⁇ m) and the second positive electrode active material (secondary particle average particle size: 11 ⁇ m) were mixed at a mass ratio of 80:20.
  • NMP N-methyl-2-pyrrolidone
  • a non-aqueous electrolyte was prepared by dissolving LiPF 6 at a concentration of 1.0 mol/L in a mixed non-aqueous solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 3:7. got
  • a positive electrode lead was attached to the positive electrode prepared above, and a negative electrode lead was attached to the negative electrode prepared above.
  • a separator was placed between these two electrodes and spirally wound to produce a wound electrode assembly. After the electrode assembly and the non-aqueous electrolyte were arranged in an aluminum laminate outer package, the periphery of the outer package was heated and welded to obtain a non-aqueous electrolyte secondary battery.
  • Example 2 A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that the first positive electrode active material and the second positive electrode active material were mixed at a mass ratio of 85:15.
  • Example 1 A nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that only the first positive electrode active material was used as the positive electrode active material.
  • Example 2 A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that only the second positive electrode active material was used as the positive electrode active material.
  • Example 3 A nonaqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that the first positive electrode active material and the second positive electrode active material were mixed at a mass ratio of 70:30.
  • Example 3 A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1, except that the first positive electrode active material and the second positive electrode active material were mixed at a mass ratio of 95:5.
  • a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 using only the first positive electrode active material obtained above as a positive electrode active material.
  • Table 1 summarizes the results of DCR, initial capacity, and capacity retention rate in each example and each comparative example. However, these results represent the results of other examples and comparative examples as relative values, with the result of Comparative Example 1 as a reference (100).
  • the ratio (B 1 /A 1 ) of the number of moles (B 1 ) of Ni to the total number of moles (A 1 ) of the metal elements excluding Li is 0.85 or more and 0.94 or less, and the metal excluding Li
  • the ratio of the number of moles of Ni (B 2 ) to the total number of moles (A 2 ) of is 0.85 or more and 0.94 or less, and the number of moles of Li to the total number of moles (A 2 ) of the metal elements excluding Li

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Abstract

La présente invention concerne un matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux qui comprend un premier matériau actif d'électrode positive et un second matériau actif d'électrode positive. Le premier matériau actif d'électrode positive est un oxyde composite de lithium contenant du Ni. Le rapport (B1/A1) du nombre molaire (B1) de Ni par rapport au nombre molaire total (A1) des éléments métalliques à l'exclusion de Li est de 0,85 à 0,94 inclus. Le rapport (C1/A1) du nombre molaire (C1) de Li par rapport au nombre molaire total (A1) des éléments métalliques à l'exclusion de Li est de 0,950 à 0,983 inclus. Le second matériau actif d'électrode positive est un oxyde composite de lithium contenant du Ni. Le rapport du nombre molaire (B2) de Ni par rapport au nombre molaire total (A2) des éléments métalliques à l'exclusion de Li est de 0,85 à 0,94 inclus. Le rapport (C2/A2) du nombre molaire (C2) de Li par rapport au nombre molaire total (A2) des éléments métalliques à l'exclusion de Li est de 0,984 à 1,004 inclus. Le rapport de mélange du premier matériau actif d'électrode positive au second matériau actif d'électrode positive est de 95 : 5 à 75 : 25 en rapport en masse.
PCT/JP2022/038573 2021-10-20 2022-10-17 Matériau actif d'électrode positive pour batteries secondaires à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux WO2023068221A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
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