WO2024070156A1 - 非水電解質二次電池用正極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および非水電解質二次電池 Download PDF

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WO2024070156A1
WO2024070156A1 PCT/JP2023/026791 JP2023026791W WO2024070156A1 WO 2024070156 A1 WO2024070156 A1 WO 2024070156A1 JP 2023026791 W JP2023026791 W JP 2023026791W WO 2024070156 A1 WO2024070156 A1 WO 2024070156A1
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positive electrode
polymer
secondary battery
electrolyte secondary
binder
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French (fr)
Japanese (ja)
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朋宏 原田
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Panasonic Energy Co Ltd
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Panasonic Energy Co Ltd
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Priority to EP23871399.4A priority patent/EP4597633A4/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • 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
    • H01M4/48—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F114/18—Monomers containing fluorine
    • C08F114/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery.
  • Non-aqueous electrolyte secondary batteries such as lithium-ion secondary batteries, are used as power sources for electronic devices such as mobile terminals, and as power sources for vehicles such as electric cars.
  • the positive electrode comprises a positive electrode mixture that contains a positive electrode active material and a binder.
  • Patent Document 1 proposes a positive electrode for a non-aqueous electrolyte secondary battery, comprising a positive electrode current collector sheet and a positive electrode mixture layer supported on the positive electrode current collector sheet, the positive electrode mixture layer including a positive electrode active material, a binder, and a conductive agent, the positive electrode active material having a layered rock salt type crystal structure and including a composite oxide including lithium and an element A other than the lithium, the element A including at least nickel, the atomic ratio of the nickel to the element A: Ni/A being 0.8 or more and 1.0 or less, the binder including a polymer binder having a three-dimensional mesh structure, and the mass of the positive electrode mixture layer supported per m2 of the positive electrode current collector sheet being 280 g or more.
  • Patent Document 2 proposes a lithium-ion secondary battery comprising "an electrode composite layer containing an electrode active material and an organic ferroelectric having a relative dielectric constant of 25 or more, and an electrolyte containing lithium-bis(fluorosulfonyl)imide and a non-aqueous solvent, the content of the organic ferroelectric being 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the electrode active material, and the proportion of a highly polar solvent having a relative dielectric constant of 10 or more in the non-aqueous solvent being 10 volume % or less.”
  • Patent Document 3 proposes a lithium-ion secondary battery comprising a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and a non-aqueous electrolyte, wherein at least one of the positive electrode active material and the negative electrode active material contains a ferroelectric ceramic having a Curie temperature equal to or lower than the ambient temperature of use.
  • Patent Documents 2 and 3 propose incorporating a ferroelectric material into a battery to improve input/output characteristics. For example, it is said that sintering an inorganic ferroelectric material onto the surface of a positive electrode active material promotes ionization of Li salt at the interface between the positive electrode active material and the electrolyte, improving the output characteristics of the battery.
  • incorporating a ferroelectric material into the positive electrode can reduce the electronic conductivity in the positive electrode mixture. In that case, the capacity retention rate decreases.
  • incorporating a ferroelectric material into a battery reduces the battery capacity accordingly.
  • a positive electrode for a non-aqueous electrolyte secondary battery comprising a positive electrode mixture including a positive electrode active material and a binder having a polymerization structure derived from vinylidene fluoride, wherein an ATR-IR spectrum of the positive electrode mixture has an ⁇ peak in a wavelength region of 760 to 764 cm ⁇ 1 attributable to ⁇ -type crystals of the polymerization structure and a ⁇ peak in a wavelength region of 838 to 842 cm ⁇ 1 attributable to ⁇ -type crystals of the polymerization structure, and the maximum absorption intensity H( ⁇ ) of the ⁇ peak and the maximum absorption intensity H( ⁇ ) of the ⁇ peak satisfy 0.2 ⁇ H( ⁇ )/H( ⁇ ) ⁇ 5.
  • Another aspect of the present invention relates to a nonaqueous electrolyte secondary battery comprising the above-mentioned positive electrode for a nonaqueous electrolyte secondary battery, a negative electrode, and a nonaqueous electrolyte.
  • FIG. 1 is a vertical cross-sectional view of a nonaqueous electrolyte secondary battery according to one embodiment of the present invention.
  • any of the exemplified lower limits and any of the exemplified upper limits can be arbitrarily combined as long as the lower limit is not equal to or greater than the upper limit.
  • one of them may be selected and used alone, or two or more may be used in combination.
  • the present disclosure encompasses a combination of the features described in two or more claims arbitrarily selected from the multiple claims described in the appended claims.
  • the features described in two or more claims arbitrarily selected from the multiple claims described in the appended claims may be combined, provided that no technical contradiction arises.
  • Non-aqueous electrolyte secondary batteries include lithium ion secondary batteries that use a material that reversibly absorbs and releases at least lithium ions as the negative electrode active material, lithium secondary batteries in which lithium metal is precipitated at the negative electrode during charging and dissolves during discharging, and all-solid-state batteries.
  • the nonaqueous electrolyte secondary battery according to the present disclosure comprises a positive electrode, a negative electrode, and a nonaqueous electrolyte.
  • a separator is usually disposed between the positive electrode and the negative electrode.
  • the nonaqueous electrolyte usually has lithium ion conductivity.
  • a positive electrode for a non-aqueous electrolyte secondary battery includes, for example, a positive electrode current collector sheet and a positive electrode mixture layer supported on the positive electrode current collector sheet.
  • the positive electrode mixture layer is composed of a positive electrode mixture containing a positive electrode active material and a binder having a polymerization structure derived from vinylidene fluoride (VDF) (hereinafter also referred to as a "PVDF structure").
  • VDF vinylidene fluoride
  • the positive electrode mixture may further contain a conductive agent.
  • the polymerization structure refers to a repeating structure of one or more types of monomer units, but here it refers to a repeating structure of vinylidene fluoride units.
  • the ATR-IR spectrum (a spectrum obtained by infrared spectroscopy (IR) using the attenuated-total-reflection method) of the positive electrode mixture contains a spectrum specific to the binder.
  • the ATR-IR spectrum refers to a spectrum obtained by infrared spectroscopy (IR) using the attenuated-total-reflection method.
  • IR infrared spectroscopy
  • As an ATR-IR spectrum specific to the binder an ⁇ peak attributable to ⁇ -type crystals of the PVDF structure in the wavelength region of 760 to 764 cm ⁇ 1 and a ⁇ peak attributable to ⁇ -type crystals of the PVDF structure in the wavelength region of 838 to 842 cm ⁇ 1 are observed.
  • the ⁇ -type crystals act as ferroelectrics.
  • the binder contains ⁇ -type crystals
  • ionization of the salt in the non-aqueous electrolyte is promoted in the vicinity of the positive electrode active material, and the activation energy of the Faraday reaction is reduced.
  • the internal resistance of the positive electrode is reduced and the reaction efficiency is improved.
  • Measurement equipment Fourier transform infrared spectrometer (FT-IR), ALPHA (manufactured by Bruker Corporation) Measurement method: ATR method (Di) Measurement wave number range: 4000 cm -1 to 400 cm -1 Resolution: 4 cm
  • the measurement sample can be a powder of the positive electrode mixture obtained by peeling off the positive electrode mixture layer from the positive electrode. In such a powder, the binder adheres to the surface of the positive electrode active material particles.
  • the measurement sample can be prepared by placing the powder on a crystal and pressing it with a jig.
  • the ratio of the maximum absorption intensity H( ⁇ ) of the ⁇ peak to the maximum absorption intensity H( ⁇ ) of the ⁇ peak, H( ⁇ )/H( ⁇ ), must satisfy 0.2 ⁇ H( ⁇ )/H( ⁇ ) ⁇ 5. If the H( ⁇ )/H( ⁇ ) ratio exceeds 5, the ⁇ -type crystals of the ferroelectric are not sufficiently formed, and the above-mentioned effects cannot be obtained. On the other hand, if the H( ⁇ )/H( ⁇ ) ratio is less than 0.2, the binding strength of the binder decreases, the electron conduction path in the positive electrode mixture is easily deteriorated, and the capacity retention rate decreases due to the decrease in electron conductivity. H( ⁇ )/H( ⁇ ) may satisfy 0.2 ⁇ H( ⁇ )/H( ⁇ ) ⁇ 3 or 0.2 ⁇ H( ⁇ )/H( ⁇ ) ⁇ 2.
  • the binder having a PVDF structure may be a mixture of multiple polymers.
  • the binder having a PVDF structure may include a first polymer having a copolymer structure of vinylidene fluoride (VDF) units and trifluoroethylene (TrFE) units (hereinafter also referred to as "VDF-TrFE copolymer structure"), and a second polymer different from the first polymer.
  • the first polymer is likely to form ⁇ -type crystals, which are ferroelectric.
  • the first polymer may include a VDF-TrFE copolymer structure as a main component.
  • the VDF-TrFE copolymer structure may be a block copolymer structure or a random copolymer structure. In particular, in a random copolymer structure, the polarity of TrFE has a stronger effect on the orientation of VDF, so that the dielectric constant of the copolymer structure is likely to be increased.
  • a vinylidene fluoride unit refers to the minimum structure derived from a monomer before polymerization.
  • a vinylidene fluoride unit is the minimum structure derived from vinylidene fluoride (CF 2 ⁇ H 2 ) and refers to a divalent group represented by -(CF 2 CH 2 )-.
  • the main component refers to a component that accounts for 50 mol% or more of all monomer units that make up the polymer.
  • the main component may account for 70 mol% or more, or may account for 80 mol% or more of all monomer units.
  • the first polymer may be composed of only vinylidene fluoride units and trifluoroethylene units, but may also contain monomer units other than vinylidene fluoride and trifluoroethylene (hereinafter also referred to as "third monomer units").
  • the first polymer may contain a VDF-TrFE copolymer structure as the main component, but it is desirable that 90 mol% or more of all monomer units contained in the first polymer are composed of vinylidene fluoride units and trifluoroethylene units.
  • the ratio of the number of moles of vinylidene fluoride units (mVDF) contained in the first polymer to the number of moles of trifluoroethylene units (mTrFE) is, for example, 50/50 to 90/10, and may be 60/40 to 80/20. In this case, it is easy to control the H( ⁇ )/H( ⁇ ) ratio to satisfy 0.2 ⁇ H( ⁇ )/H( ⁇ ) ⁇ 5, and it is also easy to control it to satisfy 0.2 ⁇ H( ⁇ )/H( ⁇ ) ⁇ 3 or 0.2 ⁇ H( ⁇ )/H( ⁇ ) ⁇ 2.
  • the mVDF/mTrFE ratio can be estimated from the ATR-IR spectrum described above.
  • the second polymer may be at least one selected from the group consisting of polyvinylidene fluoride (PVDF), modified polyvinylidene fluoride (modified PVDF), vinylidene fluoride copolymers, and modified vinylidene fluoride copolymers.
  • PVDF polyvinylidene fluoride
  • modified PVDF modified polyvinylidene fluoride
  • vinylidene fluoride copolymers vinylidene fluoride copolymers
  • modified vinylidene fluoride copolymers modified vinylidene fluoride copolymers.
  • Polyvinylidene fluoride may be composed only of vinylidene fluoride units. It is desirable that 50 mol% or more, and even 90 mol% or more, or 98 mol% or more of all monomer units contained in polyvinylidene fluoride are composed of vinylidene fluoride units.
  • Modified polyvinylidene fluoride refers to a polymer in which the fluorine or hydrogen atoms of the vinylidene fluoride units constituting polyvinylidene fluoride are replaced with other substituents.
  • the modified vinylidene fluoride units may be, for example, 10 mol% or less of the total monomer units. In other words, it is desirable that 50 mol% or more, and even 90 mol% or more of the total monomer units contained in the modified polyvinylidene fluoride are composed of normal vinylidene fluoride units.
  • Other substituents include methacrylic acid, maleic acid, acrylic acid, fumaric acid, itaconic acid, etc.
  • the modified polyvinylidene fluoride may be composed only of modified vinylidene fluoride units, or modified vinylidene fluoride units may constitute 50 mol% or more.
  • vinylidene fluoride copolymer refers to a copolymer that contains vinylidene fluoride units as the main component and also contains monomer units other than vinylidene fluoride and trifluoroethylene (hereinafter also referred to as "fourth monomer units").
  • the vinylidene fluoride copolymer may be modified by replacing 10 mol % or less of the monomer units with other substituents such as fluorine atoms and hydrogen atoms, such as modified polyvinylidene fluoride. It is desirable that 50 mol % or more of all the monomer units contained in the vinylidene fluoride copolymer are composed of vinylidene fluoride units.
  • the modified vinylidene fluoride copolymer refers to a copolymer that contains modified vinylidene fluoride units as the main component and also contains a fourth monomer unit. It is desirable that 50 mol% or more of the total monomer units contained in the modified vinylidene fluoride copolymer are composed of modified vinylidene fluoride units.
  • the third monomer unit and the fourth monomer unit may each be a vinyl monomer such as hexafluoropropylene (HFP), tetrafluoroethylene (TFE), trifluorochloroethylene, ethylene, or propylene. These may be used alone or in combination of two or more. Among these, hexafluoropropylene (HFP), tetrafluoroethylene (TFE), trifluorochloroethylene, etc. are preferred.
  • the second polymer can be generally said to be a polymer whose main components are vinylidene fluoride and monomer units derived from vinylidene fluoride, to the extent that it does not overlap with the first polymer.
  • the ratio (M1/M2 ratio) of the mass M1 of the first polymer contained in the binder to the mass M2 of the second polymer is, for example, 20/80 to 60/40, and may be 40/60 to 60/40.
  • the M1/M2 ratio can be estimated by peeling the positive electrode mixture from the positive electrode, roughly separating the binder from the positive electrode active material, then performing 19F-MAS-NMR analysis of the binder and calculating the ratio of VDF and TrFE from the spectrum.
  • multiple compatible resins of PVDF and PVDF-TrFE copolymers with varying ratios of VDF and TrFE can be prepared, a film can be made from the compatible resin, a calibration curve for viscoelastic behavior can be created, and the mixture ratio can be estimated.
  • the binder can be separated from the positive electrode active material by diluting and dissolving the binder while heating the positive electrode mixture in a solvent such as NMP, and then centrifuging.
  • the number average molecular weight of the first polymer may be, for example, 100,000 to 500,000.
  • the number average molecular weight of the second polymer may be, for example, 300,000 to 2,000,000.
  • the number average molecular weight is a polystyrene equivalent value determined by gel permeation chromatography (GPC).
  • the positive electrode mixture may contain a binder other than the binder having a PVDF structure, as long as the above-mentioned effects are not significantly impaired.
  • the proportion of the binder having a PVDF structure in the entire binder is preferably 80 mass% or more, and all of the binder may be a binder having a PVDF structure.
  • Specific examples of binders other than binders having a PVDF structure include polytetrafluoroethylene (PTFE), polyethylene, polypropylene, polyacrylic acid, polymethyl acrylate, ethylene-acrylic acid copolymer, etc. These may be used alone or in combination of two or more.
  • the content of the binder having a PVDF structure in the positive electrode mixture is, for example, 0.5 parts by mass or more and 2 parts by mass or less, or may be 0.5 parts by mass or more and 1.5 parts by mass or less, per 100 parts by mass of the positive electrode active material.
  • the binding strength of the positive electrode mixture and the adhesion strength between the positive electrode mixture layer and the positive electrode current collector sheet are also likely to be improved while increasing the positive electrode capacity.
  • the positive electrode active material includes, for example, a composite oxide having a layered rock salt type crystal structure and containing lithium and an element A other than lithium.
  • the element A contains at least nickel.
  • the atomic ratio of nickel to element A: Ni/A may be, for example, 0.8 or more and 1.0 or less.
  • a composite oxide containing Ni at such a high concentration is prone to forming high resistance components on the surface.
  • the binder contains ⁇ -type crystals and 0.2 ⁇ H( ⁇ )/H( ⁇ ) ⁇ 5 is satisfied, ionization of salt in the non-aqueous electrolyte is promoted near the positive electrode active material, and the activation energy of the Faraday reaction is reduced, so that the increase in the internal resistance of the positive electrode is suppressed. In other words, the effect of the high resistance components can be reduced.
  • a composite oxide having a layered rock salt type crystal structure, containing lithium and element A, and having an atomic ratio of nickel to element A, Ni/A, of 0.8 to 1.0 is also referred to as a "composite oxide HN".
  • the proportion of the composite oxide HN in the entire positive electrode active material is, for example, 80 mass% or more, and the entire positive electrode active material may be the composite oxide HN.
  • the positive electrode active material may contain a small amount of a composite oxide other than the composite oxide HN (e.g., LiCoO 2 , Li 2 NiO 2 , Li 5 FeO 4 , etc.).
  • Element A contains at least Ni, and may further contain at least one element selected from the group consisting of cobalt (Co), manganese (Mn), aluminum (Al), magnesium (Mg), calcium (Ca), iron (Fe), copper (Cu), zinc (Zn), chromium (Cr), titanium (Ti), niobium (Nb), zirconium (Zr), vanadium (V), tantalum (Ta), molybdenum (Mo), tungsten (W), strontium (Sr), silicon (Si), and boron (B).
  • element A preferably contains Ni and at least one selected from the group consisting of Co, Mn and Al, and more preferably contains Ni, Co, Mn and/or Al.
  • element A contains Co, the phase transition of the composite oxide containing Li and Ni during charging and discharging is suppressed, the stability of the crystal structure is improved, and the capacity retention rate is likely to be improved.
  • element A contains at least one of Mn and Al, the thermal stability is improved.
  • the composite oxide HN is preferably an oxide represented by the general formula: Li a Ni x Co y M 1-x-y O 2. In the formula, 0.97 ⁇ a ⁇ 1.2, 0.8 ⁇ x ⁇ 1.0, and 0 ⁇ y ⁇ 0.2, and M is preferably at least one selected from the group consisting of Mn, Al, B, W, Sr, Mg, Mo, Nb, Ti, Si, and Zr.
  • a which indicates the Li composition ratio
  • cation mixing in which Ni ions enter the Li site, is less likely to occur, and output characteristics are likely to improve.
  • x which indicates the Ni composition ratio
  • y may be greater than 0 and less than 0.2.
  • the element M may be Al, and 0 ⁇ y ⁇ 0.2, 0 ⁇ (1-x-y) ⁇ 0.05.
  • the complex oxide HN contains Al, the thermal stability of the complex oxide is likely to be improved. The value of a changes during charging and discharging.
  • the density of the positive electrode mixture layer may be 3.45 g/cm 3 or more and 3.75 g/cm 3 or less, or 3.5 g/cm 3 or more and 3.75 g/cm 3 or less.
  • the density of the positive electrode mixture layer is 3.45 g/cm 3 or more, the number of contact points between the composite oxide and the conductive agent and the binder increases. In addition, the contact points between the composite oxide particles are easily formed. As a result, the electron conduction path is sufficiently formed, and it is easy to obtain a high capacity and improve the capacity maintenance rate. In addition, the adhesion between the positive electrode mixture layer and the positive electrode current collector sheet is also improved.
  • Complex oxide particles usually contain secondary particles that are an agglomeration of multiple primary particles.
  • the average particle size (D50) of the secondary particles is, for example, 5 ⁇ m or more and 20 ⁇ m or less.
  • the average particle size (D50) here refers to the median diameter at which the volumetric cumulative value is 50% in the volume-based particle size distribution.
  • the average particle size (D50) of the secondary particles is determined by measuring the particle size distribution using a laser diffraction method.
  • the positive electrode mixture may contain a conductive agent.
  • the conductive agent forms sufficient conductive paths between the positive electrode active materials and between the positive electrode active material and the positive electrode current collector sheet.
  • the conductive agent preferably contains carbon nanotubes (CNTs). CNTs easily become entangled with the binder, and the binder firmly maintains the contact points between the CNTs and the positive electrode active material during charging and discharging.
  • the average length of the CNTs is preferably 0.5 ⁇ m or more, more preferably 0.5 ⁇ m or more and 10.0 ⁇ m or less, and even more preferably 0.5 ⁇ m or more and 5.0 ⁇ m or less.
  • the CNTs are likely to be interposed between the particles of the positive electrode active material, and the CNTs are likely to sufficiently form an electronic conduction path between the particles of the positive electrode active material.
  • the average diameter of the CNTs may be 0.5 nm or more and 30 nm or less, or 0.5 nm or more and 20 nm or less.
  • the average diameter of the CNTs is 0.5 nm or more, the strength of the CNTs is sufficiently ensured, and the CNTs tend to maintain an electronic conduction path during charging and discharging.
  • the CNTs tend to be interposed between the particles of the positive electrode active material.
  • the average length and average diameter of the CNTs are determined by taking an image of the cross section of the positive electrode mixture layer or the CNTs using a scanning electron microscope (SEM) or a transmission electron microscope (TEM), randomly selecting a number of CNTs (e.g., about 50 to 200) using the image to measure their lengths and diameters, and then averaging the lengths and diameters. Note that the length of the CNTs refers to the length when they are linear.
  • the conductive agent may contain a conductive material other than CNT.
  • conductive materials other than CNT include graphite, such as natural graphite and artificial graphite; carbon black, such as acetylene black; graphene sheets; metal fibers; and metal powders, such as aluminum.
  • the conductive agent may be used alone or in combination of two or more types.
  • the content of the conductive agent in the positive electrode mixture layer is preferably, for example, 0.01 part by mass or more and 1.0 part by mass or less per 100 parts by mass of the positive electrode active material.
  • all of the conductive agent may be CNT.
  • the positive electrode current collector sheet may be, for example, a non-porous conductive substrate (metal foil, etc.) or a porous conductive substrate (mesh, net, punched sheet, etc.).
  • Examples of the material for the positive electrode current collector sheet include stainless steel, aluminum, aluminum alloy, titanium, etc.
  • the thickness of the positive electrode current collector sheet is, for example, 3 to 50 ⁇ m.
  • the method for manufacturing the positive electrode includes, for example, a step of preparing a positive electrode slurry by dispersing a positive electrode mixture containing a positive electrode active material and a binder having a PVDF structure as essential components and a conductive agent as an optional component in a dispersion medium, and a step of applying the positive electrode slurry to the surface of a positive electrode current collector sheet, drying it, and forming a positive electrode mixture layer.
  • the coating film after drying may be rolled as necessary.
  • the positive electrode mixture layer may be formed on one surface or both surfaces of the positive electrode current collector sheet.
  • water, alcohol such as ethanol, N-methyl-2-pyrrolidone (NMP), etc. are used as the dispersion medium.
  • the negative electrode may, for example, include a negative electrode current collector sheet and a negative electrode mixture layer supported on the negative electrode current collector sheet.
  • the negative electrode may, for example, be obtained by applying a negative electrode slurry in which the negative electrode mixture is dispersed in a dispersion medium to the surface of the negative electrode current collector sheet, drying the slurry, and forming a negative electrode mixture layer. The coating film after drying may be rolled as necessary.
  • the negative electrode mixture layer may be formed on one surface or both surfaces of the negative electrode current collector sheet.
  • the negative electrode mixture contains a negative electrode active material as an essential component, and may contain a binder, a conductive agent, a thickener, etc. as optional components.
  • the binder include fluororesin, acrylic resin, and rubber material.
  • fluororesin include tetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), modified PVDF, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP).
  • PTFE tetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • acrylic resin include polyacrylic acid and acrylic acid-methacrylic acid copolymer.
  • Examples of the rubber material include styrene butadiene rubber. It is preferable to use water as the dispersion medium.
  • Examples of the conductive agent include those exemplified for the positive electrode, except for graphite.
  • Examples of the thickener include carboxymethylcellulose (CMC), CMC salt, etc.
  • a carbon material can be used as the negative electrode active material.
  • carbon materials include graphite, easily graphitized carbon (soft carbon), and difficult-to-graphitize carbon (hard carbon). Among them, graphite is preferred because of its excellent charge/discharge stability and low irreversible capacity.
  • Graphite refers to a material having a graphite-type crystal structure, and includes, for example, natural graphite, artificial graphite, and graphitized mesophase carbon particles. One type of carbon material may be used alone, or two or more types may be used in combination.
  • the negative electrode active material contains a silicon-containing material.
  • the silicon-containing material include a material containing a lithium ion conductive phase and a silicon phase dispersed in the lithium ion conductive phase.
  • the lithium ion conductive phase include a silicate phase (e.g., Li 2u SiO u+2 (0 ⁇ u ⁇ 2)) containing at least one of an alkali metal element and a group 2 element, a SiO 2 phase, and an amorphous carbon phase.
  • the silicon-containing material in which the silicon phase is dispersed in the SiO 2 phase may have a composition of, for example, SiO x (0.5 ⁇ x ⁇ 1.5) as a whole.
  • the proportion of the silicon-containing material in the total of the carbon material and the silicon-containing material is, for example, 0.5 mass% or more, more preferably 1 mass% or more, and even more preferably 2 mass% or more. From the viewpoint of improving cycle characteristics, the proportion of the silicon-containing material in the total of the silicon-containing material and the carbon material is, for example, 30 mass% or less, more preferably 20 mass% or less, and even more preferably 15 mass% or less.
  • negative electrode current collector sheets include sheets in the same form as the positive electrode current collector sheets (e.g., metal foil) made of materials such as stainless steel, nickel, nickel alloys, copper, and copper alloys.
  • the thickness of the negative electrode current collector sheet is, for example, 1 to 50 ⁇ m.
  • the non-aqueous electrolyte may be a liquid electrolyte (electrolytic solution), a gel electrolyte, or a solid electrolyte.
  • the gel electrolyte includes a lithium salt and a matrix polymer, or includes a lithium salt, a non-aqueous solvent, and a matrix polymer.
  • a polymer material that absorbs a non-aqueous solvent and gels is used as the matrix polymer. Examples of the polymer material include fluororesin, acrylic resin, polyether resin, and polyethylene oxide.
  • the solid electrolyte may be an inorganic solid electrolyte.
  • the inorganic solid electrolyte for example, a material known in all-solid-state lithium ion secondary batteries (for example, an oxide-based solid electrolyte, a sulfide-based solid electrolyte, a halide-based solid electrolyte, etc.) is used as the inorganic solid electrolyte.
  • the liquid electrolyte electrolytic solution
  • the liquid electrolyte includes a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
  • cyclic carbonate esters for example, cyclic carbonate esters, chain carbonate esters, cyclic carboxylate esters, chain carboxylate esters, etc. are used as non-aqueous solvents.
  • cyclic carbonate esters include propylene carbonate (PC) and ethylene carbonate (EC).
  • Cyclic carbonate esters having unsaturated bonds such as vinylene carbonate (VC) may be used.
  • Cyclic carbonate esters having fluorine atoms such as fluoroethylene carbonate (FEC) may be used.
  • chain carbonate esters include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), etc.
  • cyclic carboxylate esters examples include ⁇ -butyrolactone (GBL), ⁇ -valerolactone (GVL), etc.
  • chain carboxylate esters examples include methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, etc.
  • the non-aqueous solvents may be used alone or in combination of two or more.
  • lithium salts include LiClO4 , LiBF4 , LiPF6 , LiAlCl4, LiSbF6 , LiSCN , LiCF3SO3 , LiCF3CO2 , LiAsF6 , LiB10Cl10 , lower aliphatic lithium carboxylates, LiCl, LiBr , LiI, borates, imide salts, etc.
  • borates include lithium bis( oxalate )borate, lithium difluorooxalateborate, etc.
  • imide salts include 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 )), and lithium bispentafluoroethanesulfonate imide (LiN(C 2 F 5 SO 2 ) 2 ).
  • the lithium salt may be used alone or in combination of two or more.
  • the concentration of the lithium salt in the nonaqueous electrolyte is, for example, 0.5 mol/L or more and 2 mol/L or less.
  • Separator usually, it is desirable to interpose a separator between the positive electrode and the negative electrode.
  • the separator has high ion permeability and has appropriate mechanical strength and insulation properties.
  • a microporous thin film, a woven fabric, a nonwoven fabric, etc. can be used.
  • polyolefin such as polypropylene and polyethylene is preferable.
  • Non-aqueous electrolyte secondary battery An example of the structure of a non-aqueous electrolyte secondary battery is a structure in which an electrode group formed by winding a positive electrode and a negative electrode with a separator interposed therebetween is housed in an exterior body together with a non-aqueous electrolyte.
  • the present invention is not limited to this, and other types of electrode groups may be applied.
  • a laminated type electrode group in which a positive electrode and a negative electrode are laminated with a separator interposed therebetween may be used.
  • the shape of the secondary battery is also not limited, and may be, for example, a cylindrical type, a square type, a coin type, a button type, a laminate type, or the like.
  • FIG. 1 is a vertical cross-sectional view of a cylindrical secondary battery that is an example of this embodiment.
  • the present disclosure is not limited to the following configuration.
  • the non-aqueous electrolyte secondary battery (hereinafter, battery 10) comprises an electrode group 18, a non-aqueous electrolyte (not shown), and a cylindrical battery can 22 with a bottom that accommodates these.
  • a sealing body 11 is crimped and fixed to the opening of the battery can 22 via a gasket 21. This seals the inside of the battery.
  • the sealing body 11 comprises a valve body 12, a metal plate 13, and an annular insulating member 14 interposed between the valve body 12 and the metal plate 13.
  • the valve body 12 and the metal plate 13 are connected to each other at their respective centers.
  • a positive electrode lead 15a derived from the positive electrode 15 is connected to the metal plate 13.
  • the valve body 12 functions as an external terminal for the positive electrode.
  • a negative electrode lead 16a derived from the negative electrode 16 is connected to the inner bottom surface of the battery can 22.
  • An annular groove portion 22a is formed near the open end of the battery can 22.
  • a first insulating plate 23 is disposed between one end face of the electrode group 18 and the annular groove portion 22a.
  • a second insulating plate 24 is disposed between the other end face of the electrode group 18 and the bottom of the battery can 22.
  • the electrode group 18 is formed by winding a positive electrode 15 and a negative electrode 16 with a separator 17 interposed therebetween.
  • a positive electrode mixture including a positive electrode active material and a binder having a polymerization structure derived from vinylidene fluoride,
  • the ATR-IR spectrum of the positive electrode mixture is an ⁇ peak attributable to the ⁇ -type crystal of the polymer structure in the wavelength region of 760 to 764 cm;
  • the binder includes a first polymer and a second polymer, the first polymer has a copolymer structure of vinylidene fluoride units and ethylene trifluoride units, 2.
  • the positive electrode for a non-aqueous electrolyte secondary battery according to any one of the first to third aspects, wherein the ratio of the number of moles mVDF of vinylidene fluoride units contained in the first polymer to the number of moles mTrFE of trifluoroethylene units contained in the first polymer: mVDF/mTrFE is 50/50 to 90/10.
  • the positive electrode active material includes a composite oxide having a layered rock salt type crystal structure and including lithium and an element A other than lithium, The element A includes at least nickel, 5.
  • the composite oxide is represented by the general formula: Li a Ni x Co y M 1-x-y O 2 ; In the formula, 0.97 ⁇ a ⁇ 1.2, 0.8 ⁇ x ⁇ 1.0, and 0 ⁇ y ⁇ 0.2, and M is at least one selected from the group consisting of Mn, Al, B, W, Sr, Mg, Mo, Nb, Ti, Si, and Zr.
  • a non-aqueous electrolyte secondary battery comprising the positive electrode for a non-aqueous electrolyte secondary battery according to any one of claims 1 to 6, a negative electrode, and a non-aqueous electrolyte.
  • Comparative Example 1 Preparation of composite oxide HN
  • Ni0.8Co0.17Al0.03 (OH) 2 obtained by coprecipitation and Li2CO3 were mixed so that the atomic ratio of Li to the total of Ni, Co and Al: Li / (Ni+Co+Al) was 1.05 /1, and the mixture was fired under an oxygen atmosphere to obtain a composite oxide .
  • the composition of the composite oxide was determined by ICP emission spectrometry.
  • a powder of composite oxide HN with an average particle size of 12 ⁇ m was obtained by crushing and classification using a sieve.
  • a positive electrode slurry was prepared by adding 1 part by mass of a binder having a PVDF polymer structure, 1 part by mass of a conductive agent, and an appropriate amount of N-methyl-2-pyrrolidone (NMP) to 100 parts by mass of a composite oxide HN, which is a positive electrode active material (PAM), and stirring the mixture.
  • NMP N-methyl-2-pyrrolidone
  • a composite oxide HN which is a positive electrode active material
  • PAM positive electrode active material
  • the binder polyvinylidene fluoride
  • CNT average length 1 ⁇ m, average diameter 10 nm
  • the positive electrode slurry was applied to the surface of an aluminum foil (positive electrode current collector sheet), the coating was dried, and then rolled to form a positive electrode mixture layer (density 3.6 g/cm 3 ) on both sides of the aluminum foil. In this way, a positive electrode was obtained. At this time, the amount of the positive electrode slurry applied was adjusted so that the amount of the positive electrode mixture layer carried per 1 m 2 of the positive electrode current collector sheet was 280 g.
  • a mixture of silicon-containing material and graphite (average particle size (D50) 25 ⁇ m) was used as the negative electrode active material.
  • the mass ratio of the silicon-containing material to the graphite was 10:90.
  • the amount of the conductive layer was 5 parts by mass per 100 parts by mass of the total of the SiO x particles and the conductive layer.
  • the negative electrode slurry was applied to the surface of a copper foil (negative electrode current collector sheet), the coating was dried, and then rolled to form a negative electrode mixture layer (thickness 200 ⁇ m, density 1.5 g/cm 3 ) on both sides of the copper foil. In this way, a negative electrode was obtained.
  • a non-aqueous electrolyte was obtained by dissolving LiPF6 at a concentration of 1.0 mol/L in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio 3:7).
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • the opening of the battery case was closed using a metal sealing body that also served as a positive electrode terminal.
  • a resin gasket was interposed between the sealing body and the open end of the battery case. In this way, a 18650-type cylindrical non-aqueous electrolyte secondary battery (battery C1) was prepared.
  • Battery A1 was prepared in the same manner as in Comparative Example 1 except for the above.
  • Battery A2 was prepared in the same manner as in Comparative Example 1 except for the above.
  • Battery A3 was prepared in the same manner as in Comparative Example 1 except for the above.
  • PVDF vinylidene fluoride
  • TrFE trifluoroethylene
  • P(VDF-TrFE) a copolymer
  • VDF vinylidene fluoride
  • TrFE trifluoroethylene
  • Battery C4 was prepared in the same manner as in Comparative Example 1 except for the above.
  • Comparative Example 5 In the preparation of the positive electrode, 0.8 parts by mass of PVDF, which is a second polymer, was used as a binder having a PVDF polymerization structure, and 0.2 parts by mass of BaTiO 3 powder (average particle size 80 nm) was added to the positive electrode mixture. Battery C5 was prepared in the same manner as in Comparative Example 1 except for the above. The BaTiO 3 powder was mixed with the positive electrode active material and stirred at 2700 rpm for 3 minutes, and then sintered at 500 ° C for 4 hours to be supported on the surface of the positive electrode active material.
  • Comparative Example 6 In the preparation of the positive electrode, 1.2 parts by mass of PVDF, which is a second polymer, was used as a binder having a PVDF polymerization structure, and 0.3 parts by mass of BaTiO 3 powder (average particle size 80 nm) was added to the negative electrode mixture. Battery C6 was prepared in the same manner as in Comparative Example 1 except for the above. The BaTiO 3 powder was supported on the surface of the positive electrode active material in the same manner as in Comparative Example 5.
  • the initial battery was disassembled to remove the positive electrode, the positive electrode was washed with DMC, and the positive electrode mixture layer was peeled off after vacuum drying to obtain a sample of the positive electrode mixture.
  • the maximum absorption intensity H( ⁇ ) and maximum absorption intensity H( ⁇ ) of the ⁇ peak attributable to the ⁇ -type crystal of the PVDF polymerization structure observed in the wavelength region of 760 to 764 cm ⁇ 1 and the ⁇ peak attributable to the ⁇ -type crystal of the PVDF polymerization structure observed in the wavelength region of 838 to 842 cm ⁇ 1 were measured, and the H( ⁇ )/H( ⁇ ) ratio was calculated.
  • Each maximum absorption intensity H is the height of the peak from the baseline.
  • the ratio (percentage) of the discharge capacity at the 100th cycle to the discharge capacity at the 1st cycle was calculated as the capacity retention rate (%).
  • the capacity retention rate was expressed as a relative value when the capacity retention rate of battery C1 of Comparative Example 1 was set to 100.
  • Battery B6 showed an improvement in capacity retention rate, but a significant decrease in initial capacity.
  • the positive electrode for a non-aqueous electrolyte secondary battery according to the present disclosure is suitable for use in, for example, a non-aqueous electrolyte secondary battery that requires high capacity and high capacity retention rate (cycle characteristics).

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PCT/JP2023/026791 2022-09-29 2023-07-21 非水電解質二次電池用正極および非水電解質二次電池 Ceased WO2024070156A1 (ja)

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JPH08250127A (ja) * 1995-03-03 1996-09-27 Elf Atochem North America Inc ポリマー系電極及び電解質製品
JPH11329441A (ja) * 1998-05-13 1999-11-30 Toshiba Corp 非水電解液二次電池
JP2011228073A (ja) * 2010-04-19 2011-11-10 Hitachi Maxell Energy Ltd リチウム二次電池用正極およびリチウム二次電池
JP2013073670A (ja) * 2011-09-26 2013-04-22 Toyota Motor Corp リチウム二次電池とその製造方法
JP2016164832A (ja) 2015-03-06 2016-09-08 トヨタ自動車株式会社 リチウムイオン二次電池
WO2018168241A1 (ja) 2017-03-16 2018-09-20 株式会社村田製作所 リチウムイオン二次電池
US20190051926A1 (en) * 2017-08-11 2019-02-14 Industrial Technology Research Institute Negative electrode and lithium ion battery
WO2022070891A1 (ja) 2020-09-30 2022-04-07 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および非水電解質二次電池
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JPH08250127A (ja) * 1995-03-03 1996-09-27 Elf Atochem North America Inc ポリマー系電極及び電解質製品
JPH11329441A (ja) * 1998-05-13 1999-11-30 Toshiba Corp 非水電解液二次電池
JP2011228073A (ja) * 2010-04-19 2011-11-10 Hitachi Maxell Energy Ltd リチウム二次電池用正極およびリチウム二次電池
JP2013073670A (ja) * 2011-09-26 2013-04-22 Toyota Motor Corp リチウム二次電池とその製造方法
JP2016164832A (ja) 2015-03-06 2016-09-08 トヨタ自動車株式会社 リチウムイオン二次電池
WO2018168241A1 (ja) 2017-03-16 2018-09-20 株式会社村田製作所 リチウムイオン二次電池
US20190051926A1 (en) * 2017-08-11 2019-02-14 Industrial Technology Research Institute Negative electrode and lithium ion battery
US20220263057A1 (en) * 2019-07-11 2022-08-18 Spindeco Technologies Oy A method for reducing internal resistance of a battery and a battery with reduced internal resistance
WO2022070891A1 (ja) 2020-09-30 2022-04-07 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および非水電解質二次電池

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Title
See also references of EP4597633A4

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