WO2022070898A1 - 非水電解質二次電池用正極活物質および非水電解質二次電池 - Google Patents

非水電解質二次電池用正極活物質および非水電解質二次電池 Download PDF

Info

Publication number
WO2022070898A1
WO2022070898A1 PCT/JP2021/033793 JP2021033793W WO2022070898A1 WO 2022070898 A1 WO2022070898 A1 WO 2022070898A1 JP 2021033793 W JP2021033793 W JP 2021033793W WO 2022070898 A1 WO2022070898 A1 WO 2022070898A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
active material
electrolyte secondary
electrode active
composite oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/033793
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
竜一 夏井
純子 松下
光宏 日比野
健祐 名倉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Intellectual Property Management Co Ltd
Original Assignee
Panasonic Intellectual Property Management Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Panasonic Intellectual Property Management Co Ltd filed Critical Panasonic Intellectual Property Management Co Ltd
Priority to US18/028,364 priority Critical patent/US12512459B2/en
Priority to CN202180065208.XA priority patent/CN116323492B/zh
Priority to JP2022553790A priority patent/JP7702630B2/ja
Priority to EP21875200.4A priority patent/EP4223700B1/en
Publication of WO2022070898A1 publication Critical patent/WO2022070898A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/1315—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 and a non-aqueous electrolyte secondary battery using the positive electrode active material.
  • the positive electrode active material greatly affects the battery performance such as input / output characteristics, capacity, and cycle characteristics.
  • a lithium transition metal composite oxide containing a metal element such as Ni, Co, Mn, and Al is generally used as the positive electrode active material. Since the properties of lithium transition metal composite oxides differ greatly depending on their composition, many studies have been conducted on the types and amounts of additive elements.
  • Patent Document 1 the general formula Li a Co x N y m n z O 2 X b (where X is one or more of the group consisting of F, Cl, P and S, a / (x + y + z) ) Is 1.25 to 1.40, x / (x + y + z) is 0.02 to 0.23, z / (x + y + z) is 0.63 to 0.72, b / a is 0.01 to 0.1,
  • Lithium-rich composite oxides in which the molar ratio of Li to the transition metal exceeds 1 are expected as a high-capacity next-generation positive electrode active material, but there are problems such as the transition metal being easily eluted. It is known that adding F to a lithium-rich composite oxide suppresses the elution of transition metals and improves durability, but in this case, the problem is that the resistance increases and the capacity decreases. There is.
  • the positive electrode active material for a non-aqueous electrolyte secondary battery which is one aspect of the present disclosure, is a composition formula Li x Mn y Ni z P a M b O 2-c F c (in the formula, M is Ti, Co, Si, Sr). , Nb, W, Mo, Ca, Mg, Sb, Na, B, V, Cr, Fe, Cu, Zn, Ge, Zr, Ru, K, Bi, and is at least one element selected from 1.
  • the non-aqueous electrolyte secondary battery includes a positive electrode containing the positive electrode active material, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte.
  • the positive electrode active material which is one aspect of the present disclosure, has high durability and high capacity.
  • FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery which is an example of an embodiment.
  • the present inventors have added at least one kind of P and a specific element M to a lithium excess type F-containing composite oxide containing at least Mn as a transition metal. , Found that it is possible to increase the capacity. In the presence of P and the particular element M, the capacitance is specifically improved as compared to the absence of one or both of them.
  • a cylindrical battery in which the wound electrode body 14 is housed in a bottomed cylindrical outer can 16 is illustrated, but the outer body is not limited to the cylindrical outer can, and for example, a square outer can (for example). It may be a square battery), a coin-shaped outer can (coin-shaped battery), or an outer body (laminated battery) composed of a laminated sheet including a metal layer and a resin layer. Further, the electrode body is not limited to the winding type, and may be a laminated type electrode body in which a plurality of positive electrodes and a plurality of negative electrodes are alternately laminated via a separator.
  • FIG. 1 is a cross-sectional view of a non-aqueous electrolyte secondary battery 10 which is an example of an embodiment.
  • the non-aqueous electrolyte secondary battery 10 includes a winding type electrode body 14, a non-aqueous electrolyte, and an outer can 16 for accommodating the electrode body 14 and the non-aqueous electrolyte.
  • the electrode body 14 has 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 spirally wound via the separator 13.
  • the outer can 16 is a bottomed cylindrical metal container having an opening on one side in the axial direction, and the opening of the outer can 16 is closed by a sealing body 17.
  • the battery sealing body 17 side is on the top and the bottom side of the outer can 16 is on the bottom.
  • the non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • the non-aqueous solvent for example, esters, ethers, nitriles, amides, and a mixed solvent of two or more of these are used.
  • the non-aqueous solvent may contain a halogen-substituted product in which at least a part of hydrogen in these solvents is substituted with a halogen atom such as fluorine.
  • the electrolyte salt for example, a lithium salt such as LiPF 6 is used.
  • the non-aqueous electrolyte is not limited to the liquid electrolyte, and may be a solid electrolyte.
  • the positive electrode 11, the negative electrode 12, and the separator 13 constituting the electrode body 14 are all strip-shaped long bodies, and are alternately laminated in the radial direction of the electrode body 14 by being wound in a spiral shape.
  • the negative electrode 12 is formed to have a size one size larger than that of the positive electrode 11 in order to prevent the precipitation of lithium. That is, the negative electrode 12 is formed longer than the positive electrode 11 in the longitudinal direction and the width direction (short direction).
  • the separator 13 is formed to have a size at least one size larger than that of the positive electrode 11, and for example, two separators 13 are arranged so as to sandwich the positive electrode 11.
  • the electrode body 14 has 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.
  • Insulating plates 18 and 19 are arranged above and below the electrode body 14, respectively.
  • the positive electrode lead 20 extends to the sealing body 17 side through the through hole of the insulating plate 18, and the negative electrode lead 21 extends to the bottom side of the outer can 16 through the outside of the insulating plate 19.
  • the positive electrode lead 20 is connected to the lower surface 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 electrically connected to the internal terminal plate 23, serves as the positive electrode terminal.
  • the negative electrode lead 21 is connected to the inner surface of the bottom of the outer can 16 by welding or the like, and the outer can 16 serves as a negative electrode terminal.
  • a gasket 28 is provided between the outer can 16 and the sealing body 17 to ensure the airtightness inside the battery.
  • the outer can 16 is formed with a grooved portion 22 that supports the sealing body 17, with a part of the side surface portion protruding inward.
  • the grooved portion 22 is preferably formed in an annular shape along the circumferential direction of the outer can 16, and the sealing body 17 is supported on the upper surface thereof.
  • the sealing body 17 is fixed to the upper part of the outer can 16 by the grooved portion 22 and the opening end portion of the outer can 16 crimped to the sealing body 17.
  • the sealing body 17 has a structure in which an internal terminal plate 23, a lower valve body 24, an insulating member 25, an upper valve body 26, and a cap 27 are laminated in this order from the electrode body 14 side.
  • Each member constituting the sealing body 17 has, for example, a disk shape or a ring shape, and each member except the insulating member 25 is electrically connected to each other.
  • the lower valve body 24 and the upper valve body 26 are connected at the central portion of each, and an insulating member 25 is interposed between the peripheral portions of each.
  • the positive electrode 11, the negative electrode 12, and the separator 13 constituting the electrode body 14 will be described in detail, and in particular, the positive electrode active material constituting the positive electrode 11 will be described in detail.
  • the positive electrode 11 has a positive electrode core and a positive electrode mixture layer provided on the surface of the positive electrode core.
  • a foil of a metal stable in the potential range of the positive electrode 11 such as aluminum or an aluminum alloy, a film in which the metal is arranged on the surface layer, or the like can be used.
  • the positive electrode mixture layer contains a positive electrode active material, a conductive material, and a binder, and is preferably provided on both sides of the positive electrode core body.
  • a positive electrode mixture slurry containing a positive electrode active material, a conductive material, a binder, and the like is applied onto a positive electrode core, the coating film is dried, and then compressed to form a positive electrode mixture layer. It can be produced by forming it on both sides of the body.
  • Examples of the conductive material contained in the positive electrode mixture layer include carbon materials such as carbon black, acetylene black, ketjen black, and graphite.
  • Examples of the binder contained in the positive electrode mixture layer include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, and polyolefin resins. .. These resins may be used in combination with cellulose derivatives such as carboxymethyl cellulose (CMC) or salts thereof, polyethylene oxide (PEO) and the like.
  • the positive electrode active material is composed of Li x Mn y Ni z P a M b O 2-c F c (in the formula, M is Ti, Co, Si, Sr, Nb, W, Mo, Ca, Mg, Sb, Na. , B, V, Cr, Fe, Cu, Zn, Ge, Zr, Ru, K, Bi, Al, at least one element, 1.0 ⁇ x ⁇ 1.2, 0.4 ⁇ Lithium transition metal composite represented by y ⁇ 0.8, 0 ⁇ z ⁇ 0.4, 0 ⁇ a ⁇ 0.01, 0 ⁇ b ⁇ 0.05, 0 ⁇ c ⁇ 0.1, x + y + z + a + b ⁇ 2) Contains oxides.
  • the composite oxide is a Li excess material in which the molar ratio of Li to the transition metal exceeds 1, and a predetermined amount of fluoride ions are introduced and a part of O is replaced with F.
  • the positive electrode active material contains a composite oxide represented by the above composition formula as a main component.
  • the principal component means the component having the highest mass ratio among the constituent components of the composite oxide.
  • a composite oxide other than the composite oxide represented by the above composition formula (for example, a composite oxide that is not an excess Li system or a composite compound that does not contain fluoride ions) is used in combination with the positive electrode 11 as a positive electrode active material.
  • the content of the composite oxide is preferably 50% by mass or more, and may be substantially 100% by mass.
  • the composition of the composite oxide can be measured using an ICP emission spectrophotometer (iCAP6300 manufactured by Thermo Fisher Scientific).
  • the lithium transition metal composite oxide represented by the above composition formula preferably contains Ni in addition to Li, Mn, and P.
  • Ni contributes to high capacity. Further, it is selected from Ti, Co, Si, Sr, Nb, W, Mo, Ca, Mg, Sb, Na, B, V, Cr, Fe, Cu, Zn, Ge, Zr, Ru, K, Bi and Al.
  • P is contained in the composite oxide and the element M is not contained, the capacity is rather lowered by the addition of P. In addition, the capacity improvement effect cannot be obtained with the element M alone. Only when P and element M are used in combination, the capacity is specifically improved.
  • the lithium transition metal composite oxide represented by the above composition formula contains two or more kinds of elements M.
  • it is two or more kinds of elements selected from Ti, Co, Si, Sr, Nb, Mg, Sb, Ge and Al.
  • at least one of two or more kinds of elements M is selected from Ti, Co, Nb, Sb, and Al.
  • the two or more kinds of elements M may be selected from Ti, Co, Nb, Sb, and Al.
  • the lithium transition metal composite oxide contains two or more kinds of elements M
  • suitable combinations of the elements M include (1) Ti and Co, (2) Ti and Nb, and (3) Ti and Sb. Examples thereof include (4) Co and Nb, (5) Co and Sb, (6) Nb and Sb, and (7) Sb and Al.
  • the lithium transition metal composite oxide may contain another element M in addition to these two types of elements M. Examples of suitable combinations of the three types of elements M include Co and Al and Ti, Co and Sb and Ti, Co and Sb and Ge, and the like.
  • the type of the element M contained in the lithium transition metal composite oxide is, for example, 5 or less or 4 or less.
  • the lithium transition metal composite oxide does not have to contain Co substantially. Even if another element M is used instead of Co, the same or higher capacity improvement effect can be obtained.
  • the molar ratio (x) of Li is 1.0 ⁇ x ⁇ 1.2, preferably 1.1 ⁇ x ⁇ 1.2.
  • the molar ratio (y) of Mn is 0.4 ⁇ y ⁇ 0.8, preferably 0.45 ⁇ y ⁇ 0.6.
  • Ni is an optional component, but is preferably contained in a smaller amount than Mn, for example.
  • the suitable content (molar ratio) of Ni is 0.05 ⁇ z ⁇ 0.3.
  • the total molar amount (x + y + z + a + b) of Li, Mn, Ni, P, and element M is 2 or less, preferably 2. That is, it is preferable that the composite oxide is a Li-rich composite oxide and not a cation-rich composite oxide.
  • the molar ratio (c) of F is 0 ⁇ c ⁇ 0.1, preferably 0.05 ⁇ x ⁇ 0.085.
  • the molar ratio (a) of P is 0 ⁇ a ⁇ 0.01, preferably 0.002 ⁇ a ⁇ 0.01 or 0.002 ⁇ a ⁇ 0.005.
  • P is effective even in a small amount, but when it is present in an amount of 0.2 mol% or more with respect to the total number of moles of the elements excluding Li, O, and F, the capacity improving effect becomes more remarkable.
  • the upper limit of the content is preferably 1 mol%.
  • the molar ratio (b) of the element M is 0 ⁇ b ⁇ 0.05, preferably 0 ⁇ b ⁇ 0.035 or 0.002 ⁇ b ⁇ 0.01.
  • the total of them needs to be 5 mol% or less with respect to the total number of moles of the elements excluding Li, O and F.
  • the ratio of the content of P and the element M is not particularly limited, but the suitable ratio range is slightly different depending on the type of the element M and the like.
  • the element M contains one selected from Sb, Sr, Ti, Mg, Nb, and Si
  • the content of P is set to be equal to or higher than the content of the element M
  • the element M is Co or Al
  • the content of P is set to be equal to or less than the content of element M.
  • the lithium transition metal composite oxide may contain elements other than Li, Mn, Ni, P, elements M, O, and F as long as the object of the present disclosure is not impaired.
  • the lithium transition metal composite oxide is, for example, a secondary particle formed by aggregating a plurality of primary particles.
  • An example of a volume-based median diameter (D50) of a lithium transition metal composite oxide is 1 to 20 ⁇ m, or 2 to 15 ⁇ m.
  • D50 is a particle size having a volume integrated value of 50% in the particle size distribution measured by the laser diffraction / scattering method.
  • the BET specific surface area of the lithium transition metal composite oxide is, for example, 1.0 to 4.0 mm 2 / g. When the BET specific surface area is within the range, it becomes easy to achieve both high durability and high capacity.
  • the BET specific surface area is measured according to the BET method (nitrogen adsorption method) described in JIS R1626.
  • the lithium transition metal composite oxide represented by the above composition formula is a mixture of, for example, a carbonate containing Mn and Ni, a compound containing P, a compound containing element M, and lithium fluoride (LiF).
  • the mixture can be synthesized by firing.
  • An example of firing conditions is 700 to 900 ° C. ⁇ 10 to 30 hours.
  • the compound containing P may be added to the fired product after the other components are mixed and fired. In this case, P tends to be unevenly distributed on the particle surface of the lithium transition metal composite oxide.
  • Examples of the compound containing P include lithium phosphate, diphosphorus pentoxide and the like.
  • Examples of the compound containing the element M include cobalt sulfate, diantimonate trioxide, aluminum oxide, titanium oxide, magnesium oxide, niobium oxide, silicon oxide, germanium oxide and the like.
  • the positive electrode active material contains a lithium transition metal composite oxide represented by the composition formula Li x Mn y Ni z P a M b O 2-c F c as a main component.
  • the element M is derived from Ti, Co, Si, Sr, Nb, W, Mo, Ca, Mg, Sb, Na, B, V, Cr, Fe, Cu, Zn, Ge, Zr, Ru, K, Bi and Al. At least one selected, preferably two or more.
  • An example of a suitable range of P content is 0.2 to 1 mol%, and an example of a suitable range of element M content is 2 mol% or less with respect to the total number of moles of elements excluding Li, O, and F. be.
  • the negative electrode 12 has a negative electrode core and a negative electrode mixture layer provided on the surface of the negative electrode core.
  • a metal foil stable in the potential range of the negative electrode 12 such as copper, a film on which the metal is arranged on the surface layer, or the like can be used.
  • the negative electrode mixture layer contains a negative electrode active material and a binder, and is preferably provided on both sides of the negative electrode core.
  • a negative electrode mixture slurry containing a negative electrode active material, a conductive material, a binder, and the like is applied to the surface of the negative electrode core, the coating film is dried, and then compressed to form a negative electrode mixture layer. It can be manufactured by forming it on both sides of the core body.
  • the negative electrode mixture layer contains, for example, a carbon-based active material that reversibly occludes and releases lithium ions as a negative electrode active material.
  • Suitable carbon-based active materials are natural graphite such as scaly graphite, massive graphite and earthy graphite, and graphite such as artificial graphite such as massive artificial graphite (MAG) and graphitized mesophase carbon microbeads (MCMB).
  • a Si-based active material composed of at least one of Si and a Si-containing compound may be used, or a carbon-based active material and a Si-based active material may be used in combination.
  • the conductive material contained in the negative electrode mixture layer carbon materials such as carbon black, acetylene black, ketjen black, and graphite can be used as in the case of the positive electrode 11.
  • the binder contained in the negative electrode mixture layer fluororesin, PAN, polyimide, acrylic resin, polyolefin or the like can be used as in the case of the positive electrode 11, but styrene-butadiene rubber (SBR) should be used. Is preferable.
  • the negative electrode mixture layer preferably further contains CMC or a salt thereof, polyacrylic acid (PAA) or a salt thereof, polyvinyl alcohol (PVA) and the like. Above all, it is preferable to use SBR in combination with CMC or a salt thereof, PAA or a salt thereof.
  • a porous sheet having ion permeability and insulating property is used as the separator 13.
  • the porous sheet include a microporous thin film, a woven fabric, and a non-woven fabric.
  • the material of the separator 13 polyethylene, polypropylene, polyolefin such as a copolymer of ethylene and ⁇ -olefin, cellulose and the like are suitable.
  • the separator 13 may have either a single-layer structure or a laminated structure.
  • a heat-resistant layer containing inorganic particles, a heat-resistant layer made of a highly heat-resistant resin such as an aramid resin, polyimide, or polyamide-imide may be formed on the surface of the separator 13.
  • the above lithium transition metal composite oxide was used as the positive electrode active material.
  • Positive electrode active material, acetylene black, and polyvinylidene fluoride are mixed at a solid content mass ratio of 7: 2: 1, and N-methyl-2-pyrrolidone (NMP) is used as a dispersion medium to prepare a positive electrode mixture slurry.
  • NMP N-methyl-2-pyrrolidone
  • a positive electrode mixture slurry was applied onto a positive electrode core made of aluminum foil, the coating film was dried and compressed, and then cut to a predetermined electrode size to obtain a positive electrode.
  • Ethylene carbonate (EC), ethylmethyl carbonate (EMC), and dimethyl carbonate (DMC) were mixed in a predetermined volume ratio. LiPF 6 was added to the mixed solvent to obtain a non-aqueous electrolytic solution.
  • the positive electrode and the negative electrode made of lithium metal leaf were arranged to face each other via a separator to form an electrode body, and the electrode body was housed in a coin-shaped outer can. After injecting the non-aqueous electrolyte solution into the outer can, the outer can was sealed to obtain a coin-shaped test cell (non-aqueous electrolyte secondary battery).
  • the initial capacity of the test cell was evaluated by the following method, and the evaluation results are shown in Table 1 together with the contents of P and element M in the positive electrode active material.
  • test cell is CC-charged to a battery voltage of 5.2 V with a constant current of 0.05 C under a normal temperature environment, then paused for 20 minutes, and CC-discharged to a battery voltage of 2.5 V with a constant current of 0.05 C to discharge. The capacity was measured.
  • test cells of the examples are significantly improved as compared with the test cells of the comparative examples.
  • test cells of the examples and the comparative examples differ only in the composition of the positive electrode active material, and have the same other configurations.
  • the positive electrode active material of the example has a composition formula Li x Mn y Ni z P a M b O 2-c F c (in the formula, 1.0 ⁇ x ⁇ 1.2, 0.4 ⁇ y ⁇ 0.8, It is a lithium excess type composite oxide represented by 0 ⁇ z ⁇ 0.4, 0 ⁇ a ⁇ 0.01, 0 ⁇ b ⁇ 0.05, 0 ⁇ c ⁇ 0.1, x + y + z + a + b ⁇ 2).
  • the positive electrode active material used in the test cell of the comparative example is not represented by this composition formula. Therefore, it is understood that the capacity is specifically improved by using the composite oxide represented by this composition formula.
  • the initial capacity of the test cell was 4070 Wh / L (Comparative Example 1).
  • the initial capacity of the test cell was lower than when a positive electrode active material containing both P and element M was used (the initial capacity of the test cell was lower). Comparative Examples 2 and 3). That is, if only P is added to the composite oxide, the capacity will rather decrease. Further, even when the positive electrode active material to which only the element M is added is used, the capacity improving effect is not seen as compared with the case where the positive electrode active material containing neither P nor the element M is used (Comparative Examples 4 to 4 to). 6).
  • Non-aqueous electrolyte secondary battery 11 Positive electrode 12 Negative electrode 13 Separator 14 Electrode body 16 Exterior can 17 Sealing body 18, 19 Insulation plate 20 Positive electrode lead 21 Negative electrode lead 22 Grooving part 23 Internal terminal plate 24 Lower valve body 25 Insulation member 26 Upper valve Body 27 Cap 28 Gasket

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
PCT/JP2021/033793 2020-09-30 2021-09-14 非水電解質二次電池用正極活物質および非水電解質二次電池 Ceased WO2022070898A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US18/028,364 US12512459B2 (en) 2020-09-30 2021-09-14 Positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery
CN202180065208.XA CN116323492B (zh) 2020-09-30 2021-09-14 非水电解质二次电池用正极活性物质及非水电解质二次电池
JP2022553790A JP7702630B2 (ja) 2020-09-30 2021-09-14 非水電解質二次電池用正極活物質および非水電解質二次電池
EP21875200.4A EP4223700B1 (en) 2020-09-30 2021-09-14 Positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-166027 2020-09-30
JP2020166027 2020-09-30

Publications (1)

Publication Number Publication Date
WO2022070898A1 true WO2022070898A1 (ja) 2022-04-07

Family

ID=80951461

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/033793 Ceased WO2022070898A1 (ja) 2020-09-30 2021-09-14 非水電解質二次電池用正極活物質および非水電解質二次電池

Country Status (5)

Country Link
US (1) US12512459B2 (https=)
EP (1) EP4223700B1 (https=)
JP (1) JP7702630B2 (https=)
CN (1) CN116323492B (https=)
WO (1) WO2022070898A1 (https=)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024062364A (ja) * 2022-10-24 2024-05-09 エコプロ ビーエム カンパニー リミテッド 正極活物質、正極およびリチウム二次電池
JP2025073996A (ja) * 2023-10-27 2025-05-13 エコプロ ビーエム カンパニー リミテッド 正極活物質およびこれを含むリチウム二次電池

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022138848A1 (ja) * 2020-12-24 2022-06-30 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および非水電解質二次電池
EP4280301A4 (en) 2022-03-04 2024-06-26 Contemporary Amperex Technology Co., Limited Positive electrode sheet, secondary battery, battery module, battery pack, and electric apparatus

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007145695A (ja) * 2005-10-31 2007-06-14 Agc Seimi Chemical Co Ltd リチウム含有複合酸化物の製造方法
JP5946011B2 (ja) 2011-09-16 2016-07-05 株式会社Ｇｓユアサ 非水電解質二次電池用活物質、非水電解質二次電池用電極及び非水電解質二次電池
WO2018100792A1 (ja) * 2016-12-02 2018-06-07 パナソニックＩｐマネジメント株式会社 正極活物質、および、正極活物質を用いた電池
WO2018198410A1 (ja) * 2017-04-24 2018-11-01 パナソニックＩｐマネジメント株式会社 正極活物質、および、電池
WO2020003848A1 (ja) * 2018-06-29 2020-01-02 株式会社豊田自動織機 層状岩塩構造のリチウムニッケルコバルトタングステン酸化物
WO2021172010A1 (ja) * 2020-02-28 2021-09-02 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および非水電解質二次電池

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4297709B2 (ja) * 2003-03-25 2009-07-15 三洋電機株式会社 非水電解質二次電池
WO2006085588A1 (ja) * 2005-02-14 2006-08-17 Agc Seimi Chemical Co., Ltd. リチウム二次電池正極用のリチウム含有複合酸化物の製造方法
JP2007273427A (ja) * 2006-03-31 2007-10-18 Sony Corp 正極活物質および非水電解質二次電池
CN103828099B (zh) * 2011-07-25 2018-04-20 A123系统有限责任公司 掺混的阴极材料
KR101375701B1 (ko) * 2011-11-11 2014-03-20 에스케이씨 주식회사 플루오르화 포스페이트 함유 리튬이차전지용 양극활물질 및 이의 제조방법
JP6103313B2 (ja) * 2014-07-22 2017-03-29 トヨタ自動車株式会社 リチウム二次電池用正極活物質およびその利用
CN106058250A (zh) * 2016-07-22 2016-10-26 天津巴莫科技股份有限公司 一种氟化富锂磷酸钒锂正极材料
JP2019023990A (ja) * 2017-07-21 2019-02-14 株式会社豊田自動織機 正極活物質
JP7241287B2 (ja) * 2017-07-27 2023-03-17 パナソニックＩｐマネジメント株式会社 正極活物質、および、電池
KR102498342B1 (ko) * 2017-09-29 2023-02-10 주식회사 엘지에너지솔루션 리튬 과잉의 리튬 망간계 산화물 및 리튬 과잉의 리튬 망간계 산화물상에 리튬 텅스텐 화합물, 또는 추가적으로 텅스텐 화합물을 더 포함하는 양극 활물질 및 이를 포함하는 리튬 이차전지용 양극
EP4113661B1 (en) * 2020-02-27 2024-11-13 Panasonic Intellectual Property Management Co., Ltd. Positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007145695A (ja) * 2005-10-31 2007-06-14 Agc Seimi Chemical Co Ltd リチウム含有複合酸化物の製造方法
JP5946011B2 (ja) 2011-09-16 2016-07-05 株式会社Ｇｓユアサ 非水電解質二次電池用活物質、非水電解質二次電池用電極及び非水電解質二次電池
WO2018100792A1 (ja) * 2016-12-02 2018-06-07 パナソニックＩｐマネジメント株式会社 正極活物質、および、正極活物質を用いた電池
WO2018198410A1 (ja) * 2017-04-24 2018-11-01 パナソニックＩｐマネジメント株式会社 正極活物質、および、電池
WO2020003848A1 (ja) * 2018-06-29 2020-01-02 株式会社豊田自動織機 層状岩塩構造のリチウムニッケルコバルトタングステン酸化物
WO2021172010A1 (ja) * 2020-02-28 2021-09-02 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および非水電解質二次電池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4223700A4

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024062364A (ja) * 2022-10-24 2024-05-09 エコプロ ビーエム カンパニー リミテッド 正極活物質、正極およびリチウム二次電池
JP7728300B2 (ja) 2022-10-24 2025-08-22 エコプロ ビーエム カンパニー リミテッド 正極活物質、正極およびリチウム二次電池
JP2025073996A (ja) * 2023-10-27 2025-05-13 エコプロ ビーエム カンパニー リミテッド 正極活物質およびこれを含むリチウム二次電池

Also Published As

Publication number Publication date
JPWO2022070898A1 (https=) 2022-04-07
CN116323492B (zh) 2025-09-05
EP4223700A4 (en) 2024-04-17
US20230402594A1 (en) 2023-12-14
US12512459B2 (en) 2025-12-30
JP7702630B2 (ja) 2025-07-04
EP4223700A1 (en) 2023-08-09
EP4223700B1 (en) 2024-11-06
CN116323492A (zh) 2023-06-23

Similar Documents

Publication Publication Date Title
JP7702630B2 (ja) 非水電解質二次電池用正極活物質および非水電解質二次電池
JP7804945B2 (ja) 非水電解質二次電池
WO2021153527A1 (ja) 非水電解質二次電池用正極活物質および非水電解質二次電池
JP7692170B2 (ja) 非水電解質二次電池用正極活物質および非水電解質二次電池
JP7689286B2 (ja) 非水電解質二次電池用正極活物質および非水電解質二次電池
JP7664545B2 (ja) 非水電解質二次電池用正極活物質および非水電解質二次電池
JP7752330B2 (ja) 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
JP7672077B2 (ja) 非水電解質二次電池
WO2023054041A1 (ja) 非水電解質二次電池用正極活物質および非水電解質二次電池
JP7685708B2 (ja) 非水電解質二次電池用正極活物質および非水電解質二次電池
JP7792577B2 (ja) 非水電解質二次電池用正極活物質および非水電解質二次電池
JP7685709B2 (ja) 非水電解質二次電池用正極活物質および非水電解質二次電池
WO2021241027A1 (ja) 非水電解質二次電池用正極活物質および非水電解質二次電池
JP7792579B2 (ja) 非水電解質二次電池用正極活物質および非水電解質二次電池
US20250210646A1 (en) Positive electrode active material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
WO2024161962A1 (ja) 非水電解質二次電池用正極および非水電解質二次電池
WO2023068229A1 (ja) 非水電解質二次電池用正極及び非水電解質二次電池
WO2023053582A1 (ja) 二次電池用正極、及びそれを用いた二次電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21875200

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022553790

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2021875200

Country of ref document: EP

Effective date: 20230502

WWG Wipo information: grant in national office

Ref document number: 202180065208.X

Country of ref document: CN

WWG Wipo information: grant in national office

Ref document number: 18028364

Country of ref document: US