WO2024224977A1 - 非水電解質二次電池用正極活物質、非水電解質二次電池用正極、非水電解質二次電池、および非水電解質二次電池用正極活物質の製造方法 - Google Patents

非水電解質二次電池用正極活物質、非水電解質二次電池用正極、非水電解質二次電池、および非水電解質二次電池用正極活物質の製造方法 Download PDF

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WO2024224977A1
WO2024224977A1 PCT/JP2024/013926 JP2024013926W WO2024224977A1 WO 2024224977 A1 WO2024224977 A1 WO 2024224977A1 JP 2024013926 W JP2024013926 W JP 2024013926W WO 2024224977 A1 WO2024224977 A1 WO 2024224977A1
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positive electrode
lithium
secondary battery
electrolyte secondary
active material
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English (en)
French (fr)
Japanese (ja)
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佐々　裕成
晃宏 河北
勝哉 井之上
毅 小笠原
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to JP2025516655A priority Critical patent/JPWO2024224977A1/ja
Priority to CN202480026421.3A priority patent/CN120981936A/zh
Priority to EP24796735.9A priority patent/EP4704186A1/en
Publication of WO2024224977A1 publication Critical patent/WO2024224977A1/ja
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a positive electrode active material for a non-aqueous electrolyte secondary battery, a positive electrode for a non-aqueous electrolyte secondary battery, a non-aqueous electrolyte secondary battery, and a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery.
  • Patent Document 1 discloses a non-aqueous electrolyte secondary battery that uses a lithium-containing transition metal composite oxide with added niobium, tungsten, or molybdenum as the positive electrode active material in order to improve the charge/discharge capacity, charge/discharge efficiency, and cycle characteristics.
  • Patent Document 2 discloses a non-aqueous electrolyte secondary battery that uses a lithium-containing transition metal composite oxide with low-solubility Li salts scattered on the surface as the positive electrode active material in order to reduce reaction resistance when stored at high temperatures.
  • the manufacturing method of a positive electrode active material for a non-aqueous electrolyte secondary battery includes a synthesis step of obtaining a lithium-containing transition metal composite oxide, a washing step of washing the lithium-containing transition metal composite oxide with water and dehydrating it to obtain a cake-like composition, an adding step of adding at least one of a sulfonic acid compound and a sulfonic acid solution to the cake-like composition, and a drying step of drying the cake-like composition to obtain a powder-like composition, and is characterized in that in the washing step or the adding step, a compound containing at least one element selected from the group consisting of P, Ca, Sr, B, Zr, Er, and Al is added to the cake-like composition before adding at least one of the sulfonic acid compound and the sulfonic acid solution.
  • the positive electrode for a non-aqueous electrolyte secondary battery is characterized by including the above positive electrode active material.
  • the nonaqueous electrolyte secondary battery according to one aspect of the present disclosure is characterized by having a positive electrode containing the above-mentioned positive electrode active material, a negative electrode, and a nonaqueous electrolyte.
  • the positive electrode active material for a nonaqueous electrolyte secondary battery can provide a nonaqueous electrolyte secondary battery that has improved output characteristics and cycle characteristics during high-rate charging while maintaining a high capacity.
  • FIG. 1 is a longitudinal sectional view of a nonaqueous electrolyte secondary battery according to an embodiment of the present invention
  • the layered rock salt structure of lithium-containing transition metal complex oxides has a transition metal layer such as Ni, a Li layer, and an oxygen layer, and the charge/discharge reaction of the battery progresses as Li ions in the Li layer reversibly enter and leave the layer.
  • a transition metal layer such as Ni
  • Li layer a Li layer
  • an oxygen layer a transition metal layer
  • Li ions Li ions
  • Li nickel oxide-based lithium-containing transition metal complex oxides that contain Ni as the main component are known as high-capacity positive electrode active materials.
  • the Ni content in the lithium-containing transition metal complex oxide is 75 mol % or more relative to the total number of moles of metal elements excluding Li.
  • hydrogen fluoride may be generated due to decomposition of the non-aqueous electrolyte. If a lithium-containing transition metal complex oxide with a Ni content of 75% or more is used as the positive electrode active material, the generated hydrogen fluoride may react with the positive electrode, resulting in a decrease in the cycle characteristics of the non-aqueous electrolyte secondary battery. This is thought to occur because hydrogen fluoride reacts with the lithium-containing transition metal complex oxide, causing reaction products to accumulate on the surface of the lithium-containing transition metal complex oxide or the transition metal to dissolve from the lithium-containing transition metal complex oxide.
  • compound X a compound containing at least one element selected from the group consisting of P, Ca, Sr, B, Zr, Er and Al, in addition to a sulfonic acid compound, present on the surface of the secondary particles of a lithium-containing transition metal composite oxide, and by having the sulfonic acid compound present on the surface of the lithium-containing transition metal composite oxide via compound X, the output characteristics and cycle characteristics during high-rate charging are improved. This is presumably because the sulfonic acid compound reduces the reaction resistance at the positive electrode, while the generated hydrogen fluoride is preferentially reacted with compound X, thereby protecting the lithium-containing transition metal composite oxide from hydrogen fluoride.
  • compound X containing at least one element selected from the group consisting of P, Ca, Sr, B, Zr, Er and Al
  • a cylindrical battery in which a wound electrode body 14 is housed in a cylindrical exterior body 16 with a bottom is exemplified as a nonaqueous electrolyte secondary battery, but the exterior body of the battery is not limited to a cylindrical exterior body.
  • the nonaqueous electrolyte secondary battery according to the present disclosure may be, for example, a prismatic battery with a prismatic exterior body, a coin-type battery with a coin-shaped exterior body, or a pouch-type battery with an exterior body composed of a laminate sheet including a metal layer and a resin layer.
  • the electrode body is not limited to a wound type, and may be a laminated type electrode body in which multiple positive electrodes and multiple negative electrodes are alternately stacked with separators interposed therebetween.
  • the design of the nonaqueous electrolyte secondary battery according to the present disclosure is not limited to the design of the exemplified nonaqueous electrolyte secondary battery, and a known nonaqueous electrolyte secondary battery design may be applied.
  • the nonaqueous electrolyte secondary battery 10 includes a wound electrode body 14, a nonaqueous electrolyte, and an exterior body 16 that contains the electrode body 14 and the nonaqueous electrolyte.
  • the electrode body 14 includes a positive electrode 11, a negative electrode 12, and a separator 13, and has a wound structure in which the positive electrode 11 and the negative electrode 12 are wound in a spiral shape with the separator 13 interposed therebetween.
  • the exterior body 16 is a cylindrical metal container with a bottom that is open on one axial side, and the opening of the exterior body 16 is closed by a sealing body 17.
  • the sealing body 17 side of the battery is referred to as the top
  • the bottom side of the exterior body 16 is referred to as the bottom.
  • the positive electrode 11, negative electrode 12, and separator 13 that constitute the electrode body 14 are all rectangular, elongated bodies that are spirally wound in the longitudinal direction and stacked alternately in the radial direction of the electrode body 14.
  • the separator 13 isolates the positive electrode 11 and the negative electrode 12 from each other.
  • the two separators 13 are arranged, for example, to sandwich the positive electrode 11.
  • the electrode body 14 includes a positive electrode lead 20 connected to the positive electrode 11 by welding or the like, and a negative electrode lead 21 connected to the negative electrode 12 by welding or the like.
  • the longitudinal direction of the positive electrode 11 and the negative electrode 12 is the winding direction
  • the transverse direction of the positive electrode 11 and the negative electrode 12 is the axial direction. That is, the transverse end faces of the positive electrode 11 and the negative electrode 12 form the axial end faces of the electrode body 14.
  • Insulating plates 18, 19 are arranged above and below the electrode body 14.
  • the positive electrode lead 20 passes through a through hole in the insulating plate 18 and extends toward the sealing body 17, and the negative electrode lead 21 passes outside the insulating plate 19 and extends toward the bottom side of the exterior body 16.
  • the positive electrode lead 20 is connected to the underside of the internal terminal plate 23 of the sealing body 17 by welding or the like, and the cap 27, which is the top plate of the sealing body 17 and is electrically connected to the internal terminal plate 23, serves as the positive electrode terminal.
  • the negative electrode lead 21 is connected to the inner bottom inner surface of the exterior body 16 by welding or the like, and the exterior body 16 serves as the negative electrode terminal.
  • a gasket 28 is provided between the exterior body 16 and the sealing body 17 to ensure airtightness inside the battery.
  • the exterior body 16 has a grooved portion 22 that supports the sealing body 17, with part of the side surface protruding inward.
  • the grooved portion 22 is preferably formed in an annular shape along the circumferential direction of the exterior body 16, and supports the sealing body 17 on its upper surface.
  • the sealing body 17 is fixed to the top of the exterior body 16 by the grooved portion 22 and the open end of the exterior body 16 that is crimped to the sealing body 17.
  • the sealing body 17 has a structure in which, in order from the electrode body 14 side, an internal terminal plate 23, a lower valve body 24, an insulating member 25, an upper valve body 26, and a cap 27 are stacked.
  • Each member constituting the sealing body 17 has, for example, a disk or ring shape, and each member except for the insulating member 25 is electrically connected to each other.
  • the lower valve body 24 and the upper valve body 26 are connected at their respective centers, and the insulating member 25 is interposed between their respective peripheral edges.
  • the positive electrode 11, negative electrode 12, separator 13, and nonaqueous electrolyte that constitute the nonaqueous electrolyte secondary battery 10 will be described in detail, in particular the positive electrode active material that constitutes the positive electrode 11.
  • the positive electrode 11 has, for example, a positive electrode core and a positive electrode mixture layer formed on the surface of the positive electrode core.
  • the positive electrode mixture layer is preferably formed on both sides of the positive electrode core.
  • a foil of a metal such as aluminum or an aluminum alloy that is stable in the potential range of the positive electrode 11, or a film having such a metal disposed on the surface layer can be used.
  • the thickness of the positive electrode core is, for example, 10 ⁇ m to 30 ⁇ m.
  • the positive electrode mixture layer contains, for example, a positive electrode active material, a conductive agent, and a binder.
  • the thickness of the positive electrode mixture layer is, for example, 10 ⁇ m to 150 ⁇ m on one side of the positive electrode core.
  • the positive electrode 11 can be produced, for example, by applying a positive electrode mixture slurry containing a positive electrode active material, a conductive agent, etc., to the surface of the positive electrode core, drying the coating, and then rolling to form a positive electrode mixture layer on both sides of the positive electrode core.
  • Examples of the conductive agent contained in the positive electrode mixture layer include acetylene black (AB), carbon black (CB) such as ketjen black, carbon nanotubes (CNT), graphene, graphite, and other carbon-based particles. These may be used alone or in combination of two or more types.
  • Binders contained in the positive electrode mixture layer include, for example, fluorine-based resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyimide-based resins, acrylic-based resins, polyolefin-based resins, polyacrylonitrile (PAN), etc. These may be used alone or in combination of two or more types.
  • fluorine-based resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF)
  • PVDF polyvinylidene fluoride
  • PAN polyacrylonitrile
  • the positive electrode active material contained in the positive electrode mixture layer includes a lithium-containing transition metal composite oxide.
  • the lithium-containing transition metal composite oxide includes secondary particles formed by agglomeration of primary particles.
  • the particle size of the primary particles constituting the secondary particles of the lithium-containing transition metal composite oxide is, for example, 0.02 ⁇ m to 2 ⁇ m.
  • the particle size of the primary particles is measured as the diameter of a circumscribed circle in a particle image observed by a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the average particle size of the secondary particles of the lithium-containing transition metal composite oxide is, for example, 2 ⁇ m to 30 ⁇ m.
  • the average particle size means the volume-based median diameter (D50).
  • D50 means the particle size at which the cumulative frequency in the volume-based particle size distribution is 50% from the smallest particle size, and is also called the median diameter.
  • the particle size distribution of the secondary particles of the lithium-containing transition metal composite oxide can be measured using a laser diffraction type particle size distribution measuring device (for example, MT3000II manufactured by Microtrack Bell Co., Ltd.) and water as a dispersion medium.
  • the lithium-containing transition metal composite oxide has a layered structure.
  • the layered structure of the lithium-containing transition metal composite oxide include a layered structure belonging to the space group R-3m and a layered structure belonging to the space group C2/m. From the viewpoint of increasing capacity and stabilizing the crystal structure, it is preferable that the lithium-containing transition metal composite oxide has a layered structure belonging to the space group R-3m.
  • the layered structure of the lithium-containing transition metal composite oxide may include a transition metal layer and a Li layer.
  • the content of the elements constituting the lithium-containing transition metal composite oxide can be measured by an inductively coupled plasma atomic emission spectrometer (ICP-AES), an electron beam microanalyzer (EPMA), an energy dispersive X-ray analyzer (EDX), or the like.
  • ICP-AES inductively coupled plasma atomic emission spectrometer
  • EPMA electron beam microanalyzer
  • EDX energy dispersive X-ray analyzer
  • Ni content in the lithium-containing transition metal composite oxide By setting the Ni content in the lithium-containing transition metal composite oxide to 75 mol% to 95 mol%, a high-capacity battery can be obtained.
  • the Co content in the lithium-containing transition metal composite oxide is 0 mol% to 15 mol%, and Co is an optional component. In other words, the lithium-containing transition metal composite oxide does not have to contain Co. By including Co in the lithium-containing transition metal composite oxide, the heat resistance of the battery can be improved.
  • the Mn content in the lithium-containing transition metal composite oxide is 0 mol% to 25 mol%, and Mn is an optional component. In other words, the lithium-containing transition metal composite oxide does not have to contain Mn. By containing Mn, the lithium-containing transition metal composite oxide can stabilize the crystal structure.
  • the content of M (wherein M is at least one element selected from the group consisting of W, Mg, Mo, Nb, Ti, Si, Al, and Zr) in the lithium-containing transition metal composite oxide is 0 mol% to 10 mol%, and M is an optional component. In other words, the lithium-containing transition metal composite oxide does not have to contain M.
  • a compound (compound X) containing at least one element selected from the group consisting of P, Ca, Sr, B, Zr, Er and Al is present on the surface of the secondary particles of the lithium-containing transition metal composite oxide.
  • Compound X is present in the form of particles or layers on the surface of the secondary particles.
  • Compound X is highly reactive with hydrogen fluoride, and therefore reacts preferentially with hydrogen fluoride produced by decomposition of the non-aqueous electrolyte, thereby protecting the lithium-containing transition metal composite oxide from hydrogen fluoride.
  • the compound X is, for example, a compound containing at least one of phosphate, sulfate, oxide, hydroxide, and chloride containing at least one element selected from the group consisting of P, Ca , Sr, B, Zr, Er, and Al.
  • Examples of the compound X include Li3PO4 , CaO, CaCl2 , Ca(OH) 2 , SrO, SrCl2 , Sr(OH) 2 , B2O3 , B(OH) 3 , ZrSO4 , ZrO2 , Er2 ( SO4 ) 3 , Al2O3 , Al(OH) 3 , NaAl(OH) 4 , and AlPO4 .
  • the compound X may be used alone or in combination of two or more.
  • the amount of P, Ca, Sr, B, Zr, Er and Al contained in compound X in the positive electrode active material is preferably 0.001% by mass to 1% by mass, and more preferably 0.01% by mass to 1% by mass, relative to the mass of the lithium-containing transition metal composite oxide. In this case, the effects of the present disclosure are more pronounced. When multiple types of compound X are used, it is preferable that the total amount of P, Ca, Sr, B, Zr, Er and Al contained in all compounds X is within the above range.
  • compound X can be confirmed by synchrotron radiation XRD measurement, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), etc.
  • Compound X may be present so as to cover at least a part of the surface of the secondary particle, or may be present so as to cover the entire surface of the secondary particle.
  • Compound X is preferably directly attached to the surface of the secondary particle.
  • Compound X may also be present on the surface of the primary particle of the lithium-containing transition metal composite oxide.
  • the sulfonic acid compound represented by formula (I) is present on the surface of the secondary particles of the lithium-containing transition metal composite oxide.
  • the sulfonic acid compound is present in the form of particles or layers on the surface of the secondary particles.
  • compound X is present on the surface of the secondary particles of the lithium-containing transition metal composite oxide, the sulfonic acid compound is present on the surface of the secondary particles via compound X.
  • A is a Group 1 or Group 2 element
  • R is a hydrocarbon group
  • n is 1 or 2.
  • A is preferably a Group 1 element.
  • Li or Na is more preferable, and Li is particularly preferable.
  • R is preferably an alkyl group.
  • the number of carbon atoms in the alkyl group is preferably 5 or less, and more preferably 3 or less. From the viewpoint of reducing reaction resistance, a suitable example of R is an alkyl group having 3 or less carbon atoms, and among these, a methyl group is preferable. Note that in R, some of the hydrogens bonded to the carbons may be substituted with fluorine. Also, n in formula (I) is preferably 1.
  • sulfonic acid compounds include lithium methanesulfonate, lithium ethanesulfonate, lithium propanesulfonate, sodium methanesulfonate, sodium ethanesulfonate, magnesium methanesulfonate, and lithium fluoromethanesulfonate.
  • at least one selected from the group consisting of lithium methanesulfonate, lithium ethanesulfonate, and sodium methanesulfonate is preferred, with lithium methanesulfonate being particularly preferred.
  • the sulfonic acid compound reduces the reaction resistance in the positive electrode 11. This can improve the initial output characteristics of the battery. Although the sulfonic acid compound exerts this effect even in a very small amount, it is preferable that the sulfonic acid compound be present on the secondary particle surface of the complex oxide in an amount of 0.05 mass% or more relative to the mass of the lithium-containing transition metal complex oxide.
  • the upper limit of the sulfonic acid compound content is not particularly limited, but from the viewpoint of cycle characteristics, 1.5 mass% relative to the mass of the lithium-containing transition metal complex oxide is preferable. Therefore, an example of a suitable range of the amount of the sulfonic acid compound is 0.05 mass% to 1.5 mass% relative to the mass of the lithium-containing transition metal complex oxide.
  • the presence of the sulfonic acid compound on the secondary particle surface of the lithium-containing transition metal composite oxide can be confirmed by Fourier transform infrared spectroscopy (FT-IR).
  • FT-IR Fourier transform infrared spectroscopy
  • the positive electrode active material containing lithium methanesulfonate has absorption peaks, for example, near 1238 cm -1 , 1175 cm -1 , 1065 cm -1 , and 785 cm -1 .
  • the peaks near 1238 cm -1 , 1175 cm -1 , and 1065 cm -1 are peaks due to SO stretching vibration derived from lithium methanesulfonate.
  • the peak near 785 cm -1 is a peak due to CS stretching vibration derived from lithium methanesulfonate.
  • the presence of the positive electrode active material containing a sulfonic acid compound other than lithium methanesulfonate can also be confirmed from the absorption peak derived from the sulfonic acid compound in the in
  • sulfonic acid compounds can also be confirmed by X-ray photoelectron spectroscopy (XPS). In the spectrum obtained by XPS, a peak with a binding energy of approximately 165 to 170 eV and an intensity (c/s) of 200 to 1000 is observed for the positive electrode active material containing lithium methanesulfonate.
  • XPS X-ray photoelectron spectroscopy
  • the sulfonic acid compound may be present so as to cover at least a portion of the surface of the secondary particle of the lithium-containing transition metal composite oxide, or may be present so as to cover the entire surface of the secondary particle.
  • compound X is present in a layer form so as to cover the entire surface of the secondary particle, substantially all of the sulfonic acid compound is fixed to the surface of compound X and is present on the secondary particle surface via compound X.
  • a first layer made of compound X and a second layer made of the sulfonic acid compound covering the first layer may be formed on the surface of the secondary particle.
  • the sulfonic acid compound is preferably attached to the surface of compound X, but may be attached directly to the surface of the secondary particle without going through compound X.
  • the mass of the sulfonic acid compound present on the surface of the secondary particle via compound X is preferably greater than the mass of the sulfonic acid compound directly attached to the surface of the secondary particle.
  • the sulfonic acid compound may be present between compound X and the secondary particle, provided that the object of the present disclosure is not impaired.
  • one particle of the sulfonic acid compound may be present in a state of contact with both the particle surface of compound X and the secondary particle surface.
  • the sulfonic acid compound may be present on the surface of the primary particle of the lithium-containing transition metal composite oxide.
  • the positive electrode active material which is an example of an embodiment, can be manufactured by the following method. Note that the manufacturing method described here is only one example, and the manufacturing method of the positive electrode active material is not limited to this method.
  • the manufacturing process of the positive electrode active material includes a synthesis step of obtaining a lithium-containing transition metal composite oxide, a washing step of washing the lithium-containing transition metal composite oxide obtained by the synthesis step with water and dehydrating it to obtain a cake-like composition, an adding step of adding at least one of a sulfonic acid compound and a sulfonic acid solution to the cake-like composition, and a drying step of drying the cake-like composition to obtain a powder-like composition.
  • a metal oxide containing 75 mol% to 95 mol% Ni, 0 mol% to 15 mol% Co, 0 mol% to 25 mol% Mn, and 0 mol% to 10 mol% M (M is at least one element selected from W, Mg, Mo, Nb, Ti, Si, Al, and Zr) is mixed with a Li compound to obtain a mixture.
  • the metal oxide can be obtained, for example, by dropping an alkaline solution such as sodium hydroxide into a stirred solution of a metal salt containing Ni and an arbitrary metal element (Co, Mn, M, etc.) and adjusting the pH to the alkaline side (e.g., 8.5 to 12.5) to precipitate (co-precipitate) a composite hydroxide containing Ni and the arbitrary metal element, and then heat-treating the composite hydroxide.
  • the heat treatment temperature is not particularly limited, but is, for example, in the range of 250°C to 600°C.
  • Li compounds include Li2CO3 , LiOH, Li2O2 , Li2O , LiNO3 , LiNO2 , Li2SO4 , LiOH.H2O , LiH, LiF, etc.
  • the mixing ratio of the metal oxide and the Li compound is preferably such that the molar ratio of the total amount of metal elements in the metal oxide to Li is in the range of 1:0.8 to 1:1.2, and more preferably in the range of 1:1.0 to 1:1.01.
  • the synthesis process includes a firing process in which the obtained mixture is fired.
  • the firing process is a multi-stage firing process that includes at least a first firing process in which firing is performed at 300°C to 680°C under an oxygen stream, and a second firing process in which the fired product obtained by the first firing process is fired at a temperature exceeding 680°C under an oxygen stream.
  • the temperature is raised to a first set temperature of 680°C or less at a first heating rate of 0.2°C/min to 4.5°C/min.
  • the second firing process the temperature is raised to a second set temperature of 900°C or less at a first heating rate of 0.5°C/min to 3.5°C/min.
  • the first and second heating rates may be set multiple times for each temperature range as long as they are within the ranges specified above.
  • the holding time of the first set temperature in the first firing step is preferably 5 hours or less, more preferably 3 hours or less.
  • the holding time of the first set temperature is the time during which the first set temperature is maintained after the first set temperature is reached, and the holding time may be zero.
  • the holding time of the second set temperature in the second firing step is preferably 1 hour to 10 hours, more preferably 1 hour to 5 hours.
  • the holding time of the second set temperature is the time during which the second set temperature is maintained after the second set temperature is reached.
  • the firing of the mixture is, for example, performed in an oxygen stream with an oxygen concentration of 60% or more, and the flow rate of the oxygen stream is 0.2 mL/min to 4 mL/min per 10 cm3 of the firing furnace, or 0.3 L/min or more per 1 kg of the mixture.
  • the synthesis process is not limited to the above process, and may include, for example, a known synthesis method in which a precursor obtained by co-precipitating or mixing a compound such as a hydroxide, oxide, or carbonate containing at least one of Ni, Co, Mn, or M (M is at least one element selected from W, Mg, Mo, Nb, Ti, Si, Al, and Zr) is mixed with a Li source and fired to obtain a lithium-containing transition metal composite oxide. If the precursor does not contain a compound such as M, these compounds such as M may be mixed and fired when the precursor is mixed with the Li source and fired. In addition, these compounds may be pulverized to appropriately change the particle shape or particle size, or may be used after adjusting the moisture content by including a hydrate.
  • a precursor obtained by co-precipitating or mixing a compound such as a hydroxide, oxide, or carbonate containing at least one of Ni, Co, Mn, or M M is at least one element selected from W, Mg, Mo
  • the lithium-containing transition metal composite oxide is washed with water and dehydrated to obtain a cake-like composition.
  • the particulate lithium-containing transition metal composite oxide obtained in the synthesis step can be used.
  • washing with water it is possible to remove unreacted lithium compounds added in the synthesis step and impurities other than lithium compounds.
  • washing with water for example, 300 g to 5000 g of lithium-containing transition metal composite oxide is added per liter of water. Note that washing with water may be repeated multiple times. Dehydration after washing with water can be performed, for example, using a filter press.
  • a sulfonic acid compound and a sulfonic acid solution is added to the cake-like composition obtained in the washing step.
  • the sulfonic acid compound may be in the form of a powder or a solution.
  • the sulfonic acid solution is, for example, a methanesulfonic acid solution obtained by dissolving methanesulfonic acid in water. Li compounds remain in the cake-like composition, and these remaining Li compounds are dissolved in the water contained in the cake-like composition, so even if a sulfonic acid solution is added, a sulfonic acid compound containing Li is formed.
  • a Li compound or a Li compound solution may be added to the cake-like composition together with the sulfonic acid solution, or a mixed solution in which a sulfonic acid solution and a Li compound or a Li compound solution are mixed in advance may be added to the cake-like composition.
  • the Li compound is, for example, LiOH
  • the Li compound solution is, for example, a LiOH solution obtained by dissolving LiOH in water.
  • the amount of the Li compound and sulfonic acid solution added to the cake-like composition preferably satisfies the relationship of 0 ⁇ Li compound/sulfonic acid ⁇ 1.3 in molar ratio.
  • the amount of the sulfonic acid compound or sulfonic acid added is preferably 0.05% by mass to 1.5% by mass, and more preferably 0.1% by mass to 1.0% by mass, relative to the mass of the lithium-containing transition metal composite oxide.
  • the concentration of each of the sulfonic acid solution and the sulfonic acid compound solution is, for example, 0.5% by mass to 40% by mass.
  • a compound containing at least one element selected from the group consisting of P, Ca, Sr, B, Zr, Er, and Al is added to the cake-like composition before the addition of the sulfonic acid compound.
  • the compound when the compound is added in the adding step, at least one of the sulfonic acid compound and the sulfonic acid solution is added after the compound is added.
  • This allows compound X to be fixed directly to the surface of the secondary particles.
  • compound X may be present on the surface of the secondary particles in a form different from that of the compound added in the adding step.
  • a heat treatment may be performed after the compound is added in the adding step.
  • the heating temperature is, for example, 100°C to 450°C.
  • the heat treatment may be performed after the drying step described below.
  • the cake-like composition obtained in the washing step is dried to obtain a powder-like composition.
  • the drying step may be performed in a vacuum atmosphere.
  • the drying conditions are, for example, 150°C to 400°C and 0.5 hours to 15 hours.
  • the negative electrode 12 may have, for example, a negative electrode core and a negative electrode mixture layer formed on the surface of the negative electrode core, or a metal Li foil may be used as the negative electrode 12.
  • the negative electrode 12 may have a negative electrode core, and lithium metal may be deposited on the surface of the negative electrode core by charging.
  • the negative electrode mixture layer is preferably formed on both sides of the negative electrode core.
  • a foil of a metal that is stable in the potential range of the negative electrode 12, such as copper or a copper alloy, or a film in which the metal is disposed on the surface layer may be used.
  • the thickness of the negative electrode core is, for example, 5 ⁇ m to 30 ⁇ m.
  • the negative electrode mixture layer includes, for example, a negative electrode active material and a binder.
  • the thickness of the negative electrode mixture layer is, for example, 10 ⁇ m to 150 ⁇ m on one side of the negative electrode core.
  • the negative electrode 12 can be produced, for example, by applying a negative electrode mixture slurry containing a negative electrode active material, a binder, etc. to the surface of a negative electrode core body, drying the coating, and then rolling it to form a negative electrode mixture layer on both sides of the negative electrode core body.
  • the negative electrode active material contained in the negative electrode mixture layer is not particularly limited as long as it can reversibly absorb and release lithium ions, and generally carbon materials such as graphite are used.
  • Graphite may be any of natural graphite such as scaly graphite, lump graphite, and earthy graphite, lump artificial graphite, and artificial graphite such as graphitized mesophase carbon microbeads.
  • metals that are alloyed with Li such as Si and Sn, metal compounds containing Si and Sn, and lithium titanium composite oxides may be used as the negative electrode active material.
  • those provided with a carbon coating may be used.
  • Si-containing compound represented by SiO x (0.5 ⁇ x ⁇ 1.6) or a Si-containing compound in which fine particles of Si are dispersed in a lithium silicate phase represented by Li 2y SiO (2+y) (0 ⁇ y ⁇ 2) may be used in combination with graphite.
  • Binders contained in the negative electrode mixture layer include, for example, styrene butadiene rubber (SBR), nitrile butadiene rubber (NBR), carboxymethyl cellulose (CMC) or its salts, polyacrylic acid (PAA) or its salts (PAA-Na, PAA-K, etc., or it may be a partially neutralized salt), polyvinyl alcohol (PVA), etc. These may be used alone or in combination of two or more types.
  • SBR styrene butadiene rubber
  • NBR nitrile butadiene rubber
  • CMC carboxymethyl cellulose
  • PAA polyacrylic acid
  • PAA-Na polyacrylic acid
  • PAA-K polyvinyl alcohol
  • PVA polyvinyl alcohol
  • a porous sheet having ion permeability and insulating properties is used for the separator 13.
  • the porous sheet include a microporous thin film, a woven fabric, and a nonwoven fabric.
  • the material of the separator 13 is preferably a polyolefin such as polyethylene or polypropylene, or cellulose.
  • the separator 13 may have a single layer structure or a multi-layer structure.
  • a highly heat-resistant resin layer such as an aramid resin may be formed on the surface of the separator 13.
  • a filler layer containing an inorganic filler may be formed at the interface between the separator 13 and at least one of the positive electrode 11 and the negative electrode 12.
  • inorganic fillers include oxides and phosphate compounds containing metal elements such as Ti, Al, Si, and Mg.
  • the filler layer can be formed by applying a slurry containing the filler to the surface of the positive electrode 11, the negative electrode 12, or the separator 13.
  • Non-aqueous electrolyte has ion conductivity (for example, lithium ion conductivity).
  • the non-aqueous electrolyte may be a liquid electrolyte (electrolytic solution) or a solid electrolyte.
  • the liquid electrolyte contains, for example, a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • the non-aqueous solvent examples include esters, ethers, nitriles such as acetonitrile, amides such as dimethylformamide, and mixed solvents of two or more of these.
  • the non-aqueous solvent may contain a halogen-substituted product in which at least a portion of the hydrogen of these solvents is replaced with a halogen atom such as fluorine.
  • halogen-substituted product examples 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
  • esters examples include cyclic carbonate esters such as ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate; chain carbonate esters such as dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl propyl carbonate, ethyl propyl carbonate, and methyl isopropyl carbonate; cyclic carboxylate esters such as gamma-butyrolactone (GBL) and gamma-valerolactone (GVL); and chain carboxylate esters such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate (MP), and ethyl propionate (EP).
  • cyclic carbonate esters such as ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate
  • chain carbonate esters such as dimethyl carbonate (DMC), ethyl methyl carbonate (EMC
  • 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-cineole, cyclic ethers such as crown ethers, 1,2-dimethoxyethane, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether, methylphenyl ether, Examples of such chain ethers include ethyl phenyl ether, ethyl phenyl ether, butyl phenyl ether, pentyl phenyl ether, methoxytoluene,
  • the electrolyte salt is preferably a lithium salt.
  • the lithium salt include LiClO4 , LiBF4, LiPF6 , LiAlCl4 , LiSbF6 , LiSCN , LiCF3SO3 , LiCF3CO2 , LiAsF6 , LiB10Cl10 , lower aliphatic lithium carboxylate, LiCl, LiBr, LiI, phosphates, borates, and imide salts.
  • the phosphates include lithium difluorophosphate ( LiPO2F2 ) , lithium difluorobis(oxalato ) phosphate (LiDFBOP), and lithium tetrafluoro(oxalato)phosphate.
  • borates examples include lithium bis(oxalato)borate (LiBOB), and lithium difluoro(oxalato)borate (LiDFOB).
  • imide salt lithium bisfluorosulfonylimide (LiN(FSO 2 ) 2 ), lithium bistrifluoromethanesulfonate imide (LiN(CF 3 SO 2 ) 2 ), lithium trifluoromethanesulfonate nonafluorobutanesulfonate imide (LiN(CF 3 SO 2 )(C 4 F 9 SO 2 )), lithium bispentafluoroethanesulfonate imide (LiN(C 2 F 5 SO 2 ) 2 ), etc. are used.
  • the concentration of the lithium salt may be, for example, 4 mol or less per 1 L of nonaqueous solvent, may be 3 mol or less, preferably 1.8 mol or less, and more preferably 0.8 to 1.8 mol.
  • the non-aqueous electrolyte may contain an additive.
  • the additive include unsaturated carbonate esters, acid anhydrides, phenol compounds, benzene compounds, nitrile compounds, isocyanate compounds, sultone compounds, sulfate compounds, borate ester compounds, phosphate ester compounds, and phosphite ester compounds.
  • unsaturated cyclic carbonates examples include vinylene carbonate, 4-methylvinylene carbonate, 4,5-dimethylvinylene carbonate, 4-ethylvinylene carbonate, 4,5-diethylvinylene carbonate, 4-propylvinylene carbonate, 4,5-dipropylvinylene carbonate, 4-phenylvinylene carbonate, 4,5-diphenylvinylene carbonate, vinylethylene carbonate, and divinylethylene carbonate.
  • One type of unsaturated cyclic carbonate may be used alone, or two or more types may be used in combination. In the unsaturated cyclic carbonate, some of the hydrogen atoms may be substituted with fluorine atoms.
  • the acid anhydride may be an anhydride in which multiple carboxylic acid molecules are condensed intermolecularly, but is preferably an acid anhydride of a polycarboxylic acid.
  • acid anhydrides of polycarboxylic acids include succinic anhydride, maleic anhydride, and phthalic anhydride.
  • Phenol compounds include, for example, phenol and hydroxytoluene.
  • Benzene compounds include, for example, fluorobenzene, hexafluorobenzene, and cyclohexylbenzene (CHB).
  • Nitrile compounds include adiponitrile, pimelonitrile, propionitrile, succinonitrile, etc.
  • Isocyanate compounds include methyl isocyanate (MIC), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), bisisocyanatomethylcyclohexane (BIMCH), etc.
  • Sultone compounds include propane sultone, propene sultone, etc.
  • Sulfate compounds include ethylene sulfate, ethylene sulfite, dimethyl sulfate, lithium fluorosulfate, etc.
  • Boron ester compounds include trimethyl borate, tris(trimethylsilyl)borate, etc.
  • Phosphate ester compounds include trimethyl phosphate, tris(trimethylsilyl)phosphate, etc.
  • Phosphite ester compounds include trimethyl phosphite, tris(trimethylsilyl)phosphite, etc.
  • the solid electrolyte for example, a solid or gel-like polymer electrolyte, an inorganic solid electrolyte, etc. can be used.
  • the inorganic solid electrolyte a material known in all-solid-state lithium ion secondary batteries, etc. (for example, an oxide-based solid electrolyte, a sulfide-based solid electrolyte, a halogen-based solid electrolyte, etc.) can be used.
  • the polymer electrolyte includes, for example, a lithium salt and a matrix polymer, or a non-aqueous solvent, a lithium salt, and a matrix polymer.
  • the matrix polymer for example, a polymer material that absorbs a non-aqueous solvent and gels is used.
  • the polymer material for example, a fluororesin, an acrylic resin, a polyether resin, etc. can be used.
  • Example 1 [Preparation of Positive Electrode Active Material]
  • the composite hydroxide represented by [Ni 0.90 Mn 0.10 ] (OH) 2 obtained by the coprecipitation method was calcined at 500 ° C. for 8 hours to obtain a metal oxide containing Ni and Mn.
  • lithium hydroxide monohydrate LiOH.H 2 O
  • this mixture was heated from room temperature to 650 ° C. at a heating rate of 2.0 ° C.
  • Example 1 Example 1
  • the produced positive electrode active material was measured by Fourier transform infrared spectroscopy (FT-IR), and it was confirmed that lithium methanesulfonate was present on the secondary particle surface of the lithium-containing transition metal composite oxide. Furthermore, it was confirmed by TOF-SIMS that a P-containing compound was present on the secondary particle surface as compound X, and that lithium methanesulfonate was present on the surface of the P-containing compound.
  • FT-IR Fourier transform infrared spectroscopy
  • the positive electrode active material, acetylene black (AB), and polyvinylidene fluoride were mixed in a mass ratio of 86:10:4, and N-methyl-2-pyrrolidone (NMP) was used as a dispersion medium to prepare a positive electrode mixture slurry.
  • NMP N-methyl-2-pyrrolidone
  • the positive electrode mixture slurry was applied onto a positive electrode core made of aluminum foil, the coating was dried and compressed, and then the positive electrode core was cut into a predetermined electrode size to obtain a positive electrode in which a positive electrode mixture layer was disposed on both sides of the positive electrode core. An exposed portion in which the surface of the positive electrode core was exposed was provided in a part of the positive electrode.
  • Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) were mixed in a volume ratio of 3: 3: 4.
  • Lithium hexafluorophosphate (LiPF 6 ) was dissolved in the mixed solvent to a concentration of 1.2 mol/L to prepare a non-aqueous electrolyte.
  • a positive electrode lead was attached to the exposed portion of the positive electrode, and a negative electrode lead was attached to the lithium metal foil as the negative electrode, and the positive electrode and the negative electrode were spirally wound with a polyolefin separator interposed therebetween to produce a wound electrode body.
  • This electrode body was housed in an exterior body made of an aluminum laminate sheet, and the nonaqueous electrolyte was injected, and then the opening of the exterior body was sealed to obtain a test cell.
  • Example 2 A test cell was prepared and evaluated in the same manner as in Example 1, except that ZrSO4 was added instead of H3PO4 in the preparation of the positive electrode active material. ZrSO4 was added so that the mass of Zr in the positive electrode active material was 0.06 mass% with respect to the total mass of the lithium-containing transition metal composite oxide. In addition, it was confirmed by TOF-SIMS that a Zr-containing compound was present as compound X on the surface of the secondary particles of the lithium-containing transition metal composite oxide.
  • Example 3 A test cell was prepared and evaluated in the same manner as in Example 1, except that CaCl 2 was added instead of H 3 PO 4 in the preparation of the positive electrode active material. CaCl 2 was added so that the mass of Ca in the positive electrode active material was 0.01 mass% with respect to the total mass of the lithium-containing transition metal composite oxide. In addition, it was confirmed by TOF-SIMS that a Ca-containing compound was present on the secondary particle surface of the lithium-containing transition metal composite oxide as compound X.
  • Example 4 A test cell was prepared and evaluated in the same manner as in Example 1, except that Er 2 (SO 4 ) 3 was added instead of H 3 PO 4 in the preparation of the positive electrode active material. Er 2 (SO 4 ) 3 was added so that the mass of Er in the positive electrode active material was 0.2 mass% with respect to the total mass of the lithium-containing transition metal composite oxide. In addition, it was confirmed by TOF-SIMS that an Er-containing compound was present as compound X on the surface of the secondary particles of the lithium-containing transition metal composite oxide.
  • Example 5 A test cell was prepared and evaluated in the same manner as in Example 1, except that NaAl(OH) 4 was added instead of H 3 PO 4 in the preparation of the positive electrode active material. NaAl(OH) 4 was added so that the mass of Al in the positive electrode active material was 0.02 mass% with respect to the total mass of the lithium-containing transition metal composite oxide. In addition, it was confirmed by TOF-SIMS that an Al-containing compound was present as compound X on the surface of the secondary particles of the lithium-containing transition metal composite oxide.
  • Example 6 A test cell was prepared and evaluated in the same manner as in Example 1, except that B(OH) 3 was added instead of H 3 PO 4 in the preparation of the positive electrode active material. B(OH) 3 was added so that the mass of B in the positive electrode active material was 0.1 mass% with respect to the total mass of the lithium-containing transition metal composite oxide. In addition, it was confirmed by TOF-SIMS that a B-containing compound was present as compound X on the surface of the secondary particles of the lithium-containing transition metal composite oxide.
  • Example 7 A test cell was prepared and evaluated in the same manner as in Example 1, except that in the preparation of the positive electrode active material, the composition of the composite hydroxide was changed to [ Ni0.90Mn0.10 ](OH) 2 and ZrSO4 was added as compound X. ZrSO4 was added so that the mass of Zr in the positive electrode active material was 0.06 mass% with respect to the total mass of the lithium-containing transition metal composite oxide.
  • Example 1 A test cell was prepared and evaluated in the same manner as in Example 1, except that lithium methanesulfonate and compound X were not added in the preparation of the positive electrode active material.
  • Example 2 A test cell was prepared and evaluated in the same manner as in Example 1, except that compound X was not added in the preparation of the positive electrode active material.
  • Example 3 A test cell was prepared and evaluated in the same manner as in Example 1, except that in the preparation of the positive electrode active material, lithium methanesulfonate was not added, and ZrSO4 was added as compound X. ZrSO4 was added so that the mass of Zr in the positive electrode active material was 0.06 mass% with respect to the total mass of the lithium-containing transition metal composite oxide.
  • ⁇ Comparative Example 4> In the preparation of the positive electrode active material, a test cell was prepared and evaluated in the same manner as in Example 1, except that lithium methanesulfonate was added to the obtained cake-like composition and then ZrSO 4 was added. More specifically, in the preparation of the positive electrode active material, powdered lithium methanesulfonate was added to the obtained cake-like composition (addition step). The amount of lithium methanesulfonate added was 0.3 mass% with respect to the total mass of the lithium-containing transition metal composite oxide. Then, ZrSO 4 was added to the cake-like composition to which lithium methanesulfonate had been added.
  • ZrSO 4 was added so that the mass of Zr in the positive electrode active material was 0.06 mass% with respect to the total mass of the lithium-containing transition metal composite oxide.
  • TOF-SIMS it was confirmed by TOF-SIMS that a Zr-containing compound was present on the secondary particle surface of the lithium-containing transition metal composite oxide via lithium methanesulfonate.
  • Example 5 A test cell was prepared and evaluated in the same manner as in Example 7, except that lithium methanesulfonate and compound X were not added in the preparation of the positive electrode active material.
  • Example 6 A test cell was prepared and evaluated in the same manner as in Example 7, except that compound X was not added in the addition step of preparing the positive electrode active material.
  • Example 7 A test cell was prepared and evaluated in the same manner as in Example 7, except that in the preparation of the positive electrode active material, lithium methanesulfonate was not added, and ZrSO4 was added as compound X. ZrSO4 was added so that the mass of Zr in the positive electrode active material was 0.06 mass% with respect to the total mass of the lithium-containing transition metal composite oxide.
  • the initial output and capacity retention of the test cells of the examples and comparative examples are shown in Tables 1 and 2.
  • Tables 1 and 2 also show the composition of the lithium-containing transition metal composite oxide, and the composition and amount of the added sulfonic acid compound and compound X.
  • the initial output and capacity retention of the test cells of Examples 1 to 6 and Comparative Examples 1 to 4 shown in Table 1 are expressed relatively to the initial output and capacity retention of the test cell of Comparative Example 1, which is set to 100.
  • the initial output and capacity retention of the test cells of Example 7 and Comparative Examples 5 to 7 shown in the table are expressed relatively to the initial output and capacity retention of the test cell of Comparative Example 5, which is set to 100.
  • a larger initial output value indicates better output characteristics, and a larger capacity retention value indicates better cycle characteristics during high-rate charging.
  • the test cells of the examples have improved output characteristics and cycle characteristics during high-rate charging compared to the test cells of the comparative examples.
  • a positive electrode active material in which a sulfonic acid compound is present on the surface of the secondary particles and the sulfonic acid compound is present on the surface of the secondary particles via compound X, a nonaqueous electrolyte secondary battery with improved output characteristics and cycle characteristics during high-rate charging can be provided.
  • the test cells of comparative examples 2 and 6 in which only a sulfonic acid compound is present on the surface of the secondary particles have improved output characteristics compared to the test cells of comparative examples 1 and 5, but do not have improved cycle characteristics during high-rate charging.
  • test cells of comparative examples 3 and 7 in which only compound X is present on the surface of the secondary particles have worse output characteristics compared to the test cells of comparative examples 1 and 5.
  • test cell of comparative example 4 in which compound X is provided on the surface of the sulfonic acid compound has no improved output characteristics or cycle characteristics during high-rate charging compared to the test cell of comparative example 1.
  • Configuration 2 The positive electrode active material for a non-aqueous electrolyte secondary battery according to configuration 1, wherein A is a Group 1 element.
  • Configuration 3 The positive electrode active material for a non-aqueous electrolyte secondary battery according to configuration 1 or 2, wherein A is Li.
  • Configuration 4 The positive electrode active material for a non-aqueous electrolyte secondary battery according to any one of configurations 1 to 3, wherein R is an alkyl group.
  • Configuration 5 The positive electrode active material for a nonaqueous electrolyte secondary battery according to any one of configurations 1 to 4, wherein R is a methyl group.
  • Configuration 6 The positive electrode active material for a nonaqueous electrolyte secondary battery according to any one of Configurations 1 to 5, wherein the amount of the sulfonic acid compound present on the surface of the lithium-containing transition metal composite oxide is 0.05 mass % or more and 1.5 mass % or less, based on the mass of the lithium-containing transition metal composite oxide.
  • Configuration 7 The positive electrode active material for a nonaqueous electrolyte secondary battery according to any one of Configurations 1 to 6, wherein the amount of P, Ca, Sr, B, Zr, Er, and Al contained in the compound X is 0.001 mass % or more and 1 mass % or less, based on the mass of the lithium-containing transition metal composite oxide.
  • Configuration 8 A method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery, the method including: a synthesis step of obtaining a lithium-containing transition metal composite oxide; a washing step of washing the lithium-containing transition metal composite oxide with water and dehydrating it to obtain a cake-like composition; an addition step of adding at least one of a sulfonic acid compound and a sulfonic acid solution to the cake-like composition; and a drying step of drying the cake-like composition to obtain a powder-like composition, wherein in the washing step or the addition step, a compound containing at least one element selected from the group consisting of P, Ca, Sr, B, Zr, Er, and Al is added to the cake-like composition before adding at least one of the sulfonic acid compound and the sulfonic acid solution.
  • Configuration 9 A positive electrode for a non-aqueous electrolyte secondary battery, comprising the positive electrode active material for a non-aqueous electrolyte secondary battery according to any one of configurations 1 to 7.
  • Aspect 10 A nonaqueous electrolyte secondary battery comprising the positive electrode for a nonaqueous electrolyte secondary battery according to aspect 9, a negative electrode, and a nonaqueous electrolyte.

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009193780A (ja) * 2008-02-13 2009-08-27 Sony Corp 正極活物質、これを用いた正極および非水電解質二次電池
JP2012084420A (ja) * 2010-10-13 2012-04-26 Hitachi Maxell Energy Ltd リチウム二次電池
WO2013021955A1 (ja) * 2011-08-05 2013-02-14 旭硝子株式会社 リチウムイオン二次電池用正極活物質
CN109616657A (zh) * 2018-12-17 2019-04-12 中科廊坊过程工程研究院 一种高镍复合正极材料及其制备方法和应用
JP2019169286A (ja) 2018-03-22 2019-10-03 Tdk株式会社 リチウムイオン二次電池用正極活物質及びリチウムイオン二次電池
WO2023013494A1 (ja) 2021-08-03 2023-02-09 住友化学株式会社 リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
WO2023100535A1 (ja) * 2021-11-30 2023-06-08 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用正極活物質、非水電解質二次電池用正極、非水電解質二次電池、及び非水電解質二次電池用正極活物質の製造方法
WO2023162698A1 (ja) * 2022-02-25 2023-08-31 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用正極活物質、及び非水電解質二次電池

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009193780A (ja) * 2008-02-13 2009-08-27 Sony Corp 正極活物質、これを用いた正極および非水電解質二次電池
JP2012084420A (ja) * 2010-10-13 2012-04-26 Hitachi Maxell Energy Ltd リチウム二次電池
WO2013021955A1 (ja) * 2011-08-05 2013-02-14 旭硝子株式会社 リチウムイオン二次電池用正極活物質
JP2019169286A (ja) 2018-03-22 2019-10-03 Tdk株式会社 リチウムイオン二次電池用正極活物質及びリチウムイオン二次電池
CN109616657A (zh) * 2018-12-17 2019-04-12 中科廊坊过程工程研究院 一种高镍复合正极材料及其制备方法和应用
WO2023013494A1 (ja) 2021-08-03 2023-02-09 住友化学株式会社 リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
WO2023100535A1 (ja) * 2021-11-30 2023-06-08 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用正極活物質、非水電解質二次電池用正極、非水電解質二次電池、及び非水電解質二次電池用正極活物質の製造方法
WO2023162698A1 (ja) * 2022-02-25 2023-08-31 パナソニックＩｐマネジメント株式会社 非水電解質二次電池用正極活物質、及び非水電解質二次電池

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