WO2024070704A1 - 非水電解質二次電池用の正極、それを用いた非水電解質二次電池、および、非水電解質二次電池の正極用の正極スラリー - Google Patents

非水電解質二次電池用の正極、それを用いた非水電解質二次電池、および、非水電解質二次電池の正極用の正極スラリー Download PDF

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WO2024070704A1
WO2024070704A1 PCT/JP2023/033401 JP2023033401W WO2024070704A1 WO 2024070704 A1 WO2024070704 A1 WO 2024070704A1 JP 2023033401 W JP2023033401 W JP 2023033401W WO 2024070704 A1 WO2024070704 A1 WO 2024070704A1
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positive electrode
active material
electrolyte secondary
mixture layer
secondary battery
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French (fr)
Japanese (ja)
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秀也 峯岸
洋一郎 宇賀
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to EP23871937.1A priority Critical patent/EP4597609A1/en
Priority to CN202380068891.1A priority patent/CN119948638A/zh
Priority to US19/113,634 priority patent/US20260094824A1/en
Priority to JP2024550055A priority patent/JPWO2024070704A1/ja
Publication of WO2024070704A1 publication Critical patent/WO2024070704A1/ja
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • 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
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    • 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
    • C01G53/502—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 containing lithium and cobalt
    • C01G53/504—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 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5
    • C01G53/506—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 containing lithium and cobalt with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.5, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.5 with the molar ratio of nickel with respect to all the metals other than alkali metals higher than or equal to 0.8, e.g. Li(MzNixCoyMn1-x-y-z)O2 with x ≥ 0.8
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    • 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
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H—ELECTRICITY
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    • 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
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • C—CHEMISTRY; METALLURGY
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    • C01—INORGANIC CHEMISTRY
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    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/40—Electric properties
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
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    • 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

  • This disclosure relates to a positive electrode for a non-aqueous electrolyte secondary battery, a non-aqueous electrolyte secondary battery using the same, and a positive electrode slurry for the positive electrode of a non-aqueous electrolyte secondary battery.
  • Non-aqueous electrolyte secondary batteries have high output and high energy density, and are therefore used in a wide range of applications, including consumer and automotive applications. In recent years, there has been a demand for even higher performance non-aqueous electrolyte secondary batteries. Various proposals have been made for non-aqueous electrolyte secondary batteries.
  • Patent Document 1 discloses "a positive electrode mixture for non-aqueous batteries, which is made by adding an organic acid to a mixture consisting of a positive electrode active material made of a composite metal oxide, a conductive additive, a vinylidene fluoride polymer, and an organic solvent.”
  • One of the objectives of this disclosure is to provide a positive electrode for a non-aqueous electrolyte secondary battery that is high capacity and easy to manufacture.
  • a positive electrode for a non-aqueous electrolyte secondary battery including a positive electrode mixture layer, the positive electrode mixture layer including at least one compound selected from the group consisting of carboxylic acids and carboxylic acid anhydrides, a positive electrode active material, a conductive material, a fluorine-containing polymer, and a dispersant, the positive electrode active material including a composite oxide represented by a composition formula Li y Ni x M (1-x) O 2- ⁇ (wherein 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1.2, 0 ⁇ 0.05, and M including at least one element selected from the group consisting of Co, Mn, Al, Fe, Ti, Sr, Ca, and B), the conductive material including a carbon material, and the dispersant including a nitrile group-containing rubber.
  • the positive electrode active material including a composite oxide represented by a composition formula Li y Ni x M (1-x) O 2- ⁇ (wherein 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1.2, 0 ⁇ 0.05, and M including at
  • the non-aqueous electrolyte secondary battery includes a positive electrode according to the present disclosure.
  • a positive electrode slurry for a positive electrode of a non-aqueous electrolyte secondary battery including at least one compound selected from the group consisting of carboxylic acids and carboxylic acid anhydrides, a positive electrode active material, a conductive material, a fluorine-containing polymer, a dispersant, and a liquid medium
  • the positive electrode active material including a composite oxide represented by the composition formula Li y Ni x M (1-x) O 2- ⁇ (wherein 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1.2, 0 ⁇ 0.05, and M including at least one element selected from the group consisting of Co, Mn, Al, Fe, Ti, Sr, Ca, and B)
  • the conductive material including a carbon material
  • the dispersant including a nitrile group-containing rubber.
  • a positive electrode for a non-aqueous electrolyte secondary battery that has a high capacity and is easy to manufacture can be obtained.
  • a high-capacity non-aqueous electrolyte secondary battery can be easily manufactured.
  • FIG. 1 is a schematic perspective view of a nonaqueous electrolyte secondary battery according to an embodiment of the present disclosure, with a portion cut away.
  • the positive electrode according to the present embodiment is a positive electrode for a non-aqueous electrolyte secondary battery.
  • the positive electrode includes a positive electrode mixture layer.
  • the positive electrode mixture layer includes at least one compound selected from the group consisting of carboxylic acids and carboxylic anhydrides, a positive electrode active material, a conductive material, a fluorine-containing polymer, and a dispersant.
  • the positive electrode active material includes a composite oxide (composite metal oxide) represented by the composition formula Li y Ni x M (1-x) O 2- ⁇ (wherein 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1.2, 0 ⁇ 0.05, M includes at least one element selected from the group consisting of Co, Mn, Al, Fe, Ti, Sr, Ca, and B).
  • the conductive material includes a carbon material.
  • the dispersant includes a nitrile group-containing rubber.
  • at least one compound selected from the group consisting of carboxylic acids and carboxylic anhydrides may be referred to as a "carboxylic acid compound".
  • the dispersibility of the components of the positive electrode mixture layer decreases. If the dispersibility of the components of the positive electrode mixture layer decreases, the internal resistance increases and the utilization efficiency of the positive electrode active material decreases, resulting in a decrease in the performance of the battery.
  • the reaction between the fluorine-containing polymer and alkaline impurities can be suppressed, and gelation of the positive electrode slurry can be suppressed.
  • the inventors of the present application found that the added carboxylic acid compound can decompose at high potential and generate gas. If gas is generated in the positive electrode mixture layer, the performance and safety of the battery can decrease depending on the amount. In particular, if the potential varies inside the positive electrode mixture layer, it is easy for localized areas with high potential to occur, and the decomposition of the carboxylic acid compound present in that area is particularly accelerated, increasing gas generation and significantly reducing battery performance.
  • the inventors of the present application have newly discovered that the problems caused by the addition of carboxylic acid compounds can be solved by using a nitrile group-containing rubber (rubber that contains nitrile groups) as a dispersant.
  • the present disclosure is based on this new finding. According to the present disclosure, a high-capacity, easy-to-manufacture positive electrode for a non-aqueous electrolyte secondary battery can be obtained. Furthermore, according to the present disclosure, it is possible to suppress gas generation in the secondary battery.
  • nitrile group-containing rubber can solve the problems caused by the addition of carboxylic acid compounds.
  • the addition of nitrile group-containing rubber improves the dispersibility of the carbon material (conductive material) and reduces the variation in potential inside the positive electrode mixture layer.
  • nitrile group-containing rubber has a particularly high affinity with fluorine-containing polymers, such as vinylidene fluoride polymers. Therefore, these two polymer materials both exert their effect as dispersants, further improving the dispersibility of the carbon material. Therefore, it is believed that a particularly high effect can be obtained by using a combination of nitrile group-containing rubber, fluorine-containing polymer, and carbon material.
  • the positive electrode active material may be a material capable of absorbing and releasing lithium ions.
  • Examples of the positive electrode active material include a composite oxide containing lithium and a transition metal.
  • the composite oxide may have a layered structure (e.g., a rock salt crystal structure).
  • the positive electrode active material may be a composite oxide represented by the above-mentioned composition formula.
  • M may be at least one element selected from the group consisting of Co, Mn, Al, Fe, Ti, Sr, Ca, Si, Nb, Zr, Mo, Zn, W, and B.
  • M may be at least one element selected from the group consisting of Co, Mn, Al, Fe, Ti, Sr, Ca, and B. It is preferable that M contains at least one element selected from the group consisting of Co, Mn, Al, and Fe.
  • the value of y indicating the composition ratio of lithium in the above composition formula increases and decreases by charging and discharging.
  • Specific examples of the composite oxide include lithium-nickel-cobalt-aluminum composite oxide (LiNi 0.9 Co 0.05 Al 0.05 O 2 , etc.).
  • the battery capacity can be increased.
  • 0.8 ⁇ x ⁇ 1 may be satisfied.
  • the battery capacity can be particularly increased.
  • x is 0.8 or more, gelation of the positive electrode slurry occurs more easily, so it is particularly important to combine a carboxylic acid compound, a nitrile group-containing rubber, and a carbon material.
  • the above complex oxides are usually used in the form of particles.
  • the average particle size of the complex oxides may be 1 ⁇ m or more, 2 ⁇ m or more, or 5 ⁇ m or more, and may be 20 ⁇ m or less, or 15 ⁇ m or less, 10 ⁇ m or less, 6 ⁇ m or less, or 5 ⁇ m or less.
  • the average particle size is the median diameter (D50) at which the cumulative volume is 50% in the volume-based particle size distribution.
  • D50 the median diameter
  • the median diameter is determined using a laser diffraction/scattering particle size distribution measuring device.
  • the particle size of the particles contained in the positive electrode mixture can also be evaluated by observing the cross section of the positive electrode mixture.
  • the positive electrode active material may include first particles of the above complex oxide having an average particle size of 1 ⁇ m or more and 6 ⁇ m or less, and second particles of the above complex oxide having an average particle size of 8 ⁇ m or more and 20 ⁇ m or less.
  • a particle size distribution curve (volume basis) of the entire complex oxide particles may show a peak in the range of about 1 to 6 ⁇ m (particle size) and a peak in the range of about 8 to 20 ⁇ m (particle size).
  • the average particle size of the composite oxide particles is large, the particles are likely to break during charging. If the particles break, gas generation from the grain boundaries and metal elution from the grain boundaries are likely to occur, and the durability of the battery is reduced. On the other hand, if the average particle size of the composite oxide particles is small, the particles are likely to aggregate, so it becomes necessary to add a large amount of binder and conductive material, and the battery capacity is reduced. In addition, if a large amount of them is added, the stability of the positive electrode slurry is significantly reduced. The capacity and durability of the battery can be increased by using two types of active material particles with different average particle sizes.
  • the average surface area of the positive electrode active material in the mixture increases, and the positive electrode active material, alkaline impurities, and fluorine-containing polymers are more likely to come into contact with each other in the positive electrode slurry. Therefore, gelation is particularly likely to occur when two types of active material particles with different average particle sizes are prepared using a high Ni active material and used to make a positive electrode slurry. Therefore, it is particularly important to use a nitrile group-containing polymer and a carboxylic acid compound in combination.
  • the proportion R1 of the mass M1 of the first particles in the composite oxide particle may be in the range of 10 to 40 mass% (e.g., 15 to 30 mass%).
  • the proportion R2 of the mass M2 of the second particles in the composite oxide particle may be in the range of 60 to 90 mass% (e.g., 70 to 85 mass%).
  • the content of the elements that make up the complex oxide can be measured using an inductively coupled plasma atomic emission spectroscopy (ICP-AES), an electron probe microanalyzer (EPMA), or an energy dispersive X-ray spectroscopy (EDX).
  • ICP-AES inductively coupled plasma atomic emission spectroscopy
  • EPMA electron probe microanalyzer
  • EDX energy dispersive X-ray spectroscopy
  • Examples of the carbon material (conductive material) include conductive carbon particles such as carbon black, carbon nanotubes, and other conductive carbon materials.
  • the carbon material preferably includes carbon nanotubes.
  • carbon nanotubes By using carbon nanotubes as the conductive material, the variation in potential in the positive electrode can be particularly suppressed, and gas generation can be particularly suppressed. Furthermore, by using carbon nanotubes, the resistance of the positive electrode mixture layer can be reduced by adding a small amount.
  • the proportion of carbon nanotubes in all carbon materials (conductive materials) is, for example, 50% by mass or more, and preferably in the range of 80 to 100% by mass (for example, in the range of 90 to 100% by mass).
  • the amount of carbon nanotubes per 100 parts by mass of the positive electrode active material may be 0.01 parts by mass or more and 1 part by mass or less, or 0.02 parts by mass or more and 0.5 parts by mass or less.
  • the average length of the carbon nanotubes may be 1 ⁇ m or more.
  • the aspect ratio of the carbon nanotubes ratio of length to diameter of the fiber
  • Carbon nanotubes with a large aspect ratio tend to come into linear contact with the positive electrode active material and the current collector.
  • carbon nanotubes have excellent electrical conductivity. Therefore, the use of carbon nanotubes can significantly reduce the direct current resistance (DCR) of the battery.
  • the carbon nanotubes present in the positive electrode may be in the form of a bundle of multiple carbon nanotubes. The length of a single carbon nanotube present in the bundle of carbon nanotubes is used to calculate the above average length.
  • the average length of the carbon nanotubes is preferably 1 ⁇ m or more from the viewpoint of increasing the conductivity in the mixture layer.
  • the upper limit of the length of the carbon nanotubes is not particularly limited, but it is preferable that the length of the carbon nanotubes is not excessively larger than the particle size of the positive electrode active material.
  • the average length of the carbon nanotubes may be 1 ⁇ m or more or 5 ⁇ m or more, and may be 20 ⁇ m or less or 15 ⁇ m or less.
  • the average length of carbon nanotubes can be determined by image analysis using a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the average length of carbon nanotubes is determined by measuring the lengths of 100 randomly selected carbon nanotubes and taking the arithmetic average.
  • the length refers to the length of the carbon nanotubes when stretched in a straight line.
  • the average diameter of the carbon nanotubes may be 20 nm or less, 15 nm or less, or 1 nm or more. By making the average diameter 20 nm or less, a small amount can provide a high effect.
  • the average diameter of carbon nanotubes can be determined by image analysis using a transmission electron microscope (TEM).
  • the average diameter of carbon nanotubes can be measured by the following method. First, 100 carbon nanotubes are randomly selected, and the diameter (outer diameter) of each is measured at one random location. The average diameter is then determined by taking the arithmetic average of the measured diameters.
  • the carbon nanotubes may be either single-walled carbon nanotubes (SWCNT) or multi-walled (MWCNT). Examples of multi-walled carbon nanotubes include double-walled carbon nanotubes, triple-walled carbon nanotubes, and carbon nanotubes with four or more walls.
  • the positive electrode mixture layer preferably contains single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
  • the multi-walled carbon nanotubes contained in the positive electrode mixture layer may be one type of multi-walled carbon nanotube, or may be multiple types of multi-walled carbon nanotubes with different numbers of walls.
  • the BET specific surface area of the carbon nanotubes may be 200 m 2 /g or more, 250 m 2 /g or more, or 300 m 2 /g or more.
  • the upper limit of the BET specific surface area is not particularly limited, but may be 2000 m 2 /g or less.
  • the BET specific surface area of the carbon nanotubes can be measured by the BET method (nitrogen adsorption method) described in JIS (Japanese Industrial Standard) R1626.
  • the carboxylic acid compound may be a monovalent carboxylic acid, a polyvalent carboxylic acid (e.g., a divalent or trivalent carboxylic acid), or a carboxylic acid anhydride.
  • carboxylic acids include formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, and aconitic acid.
  • carboxylic acid anhydrides examples include acetic anhydride, propionic acid anhydride, oxalic acid anhydride, succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, and malonic acid anhydride.
  • Carboxylic acid may react with alkaline impurities.
  • Carboxylic acid anhydrides added to the positive electrode slurry may change to carboxylic acid and/or react with alkaline impurities.
  • the amount of the carboxylic acid compound per 100 parts by mass of the positive electrode active material may be 0.001 parts by mass or more, or 0.01 parts by mass or more, and may be 0.2 parts by mass or less, or 0.1 parts by mass or less.
  • the amount of the carboxylic acid compound per 100 parts by mass of the positive electrode active material may be in the range of 0.001 to 0.2 parts by mass. By setting it in this range, gelation of the positive electrode slurry can be particularly suppressed, and a high-performance positive electrode can be stably obtained.
  • the nitrile group-containing rubber contains a nitrile group.
  • the nitrile group-containing rubber functions as a dispersant.
  • the nitrile group-containing rubber can also function as a binder in the positive electrode mixture layer.
  • Examples of the nitrile group-containing rubber include copolymers of monomers containing acrylonitrile and diene (e.g., butadiene).
  • examples of the nitrile group-containing rubber include nitrile rubber (NBR), hydrogenated nitrile rubber (H-NBR), and modified products thereof.
  • the weight average molecular weight of the nitrile group-containing rubber may be in the range of 5,000 to 500,000.
  • the amount of nitrile group-containing rubber per 100 parts by mass of the positive electrode active material may be 0.01 parts by mass or more, or 0.05 parts by mass or more, and may be 1 part by mass or less, or 0.5 parts by mass or less.
  • the fluorine-containing polymer functions as a binder in the positive electrode mixture layer.
  • the fluorine-containing polymer is a polymer containing fluorine.
  • Examples of the fluorine-containing polymer include vinylidene fluoride polymers.
  • Examples of the vinylidene fluoride polymer include polymers of monomers containing vinylidene fluoride.
  • the fluorine-containing polymer may be a combination of a vinylidene fluoride polymer and another fluorine-containing polymer.
  • the vinylidene fluoride polymer may be a copolymer of vinylidene fluoride and another monomer. Examples of the vinylidene fluoride polymer include polyvinylidene fluoride (PVDF).
  • the amount of fluorine-containing polymer per 100 parts by mass of the positive electrode active material may be 0.1 parts by mass or more, or 0.5 parts by mass or more, and may be 2.0 parts by mass or less, or 1.2 parts by mass or less.
  • the weight average molecular weight of the fluorine-containing polymer may be 800,000 or more, 1,000,000 or more, or 1,200,000 or more, or may be 2,000,000 or less, or 1,800,000 or less. By making the weight average molecular weight 1,000,000 or more, it is possible to obtain a high effect as a binder with a small amount.
  • the positive electrode mixture layer may contain components (e.g., thickeners) and compounds other than those described above.
  • the positive electrode mixture layer may contain polyvinylpyrrolidone, cellulose derivatives (e.g., alkyl cellulose, carboxyalkyl cellulose, and salts thereof), and the like.
  • Polymer materials such as polyvinylpyrrolidone and cellulose derivatives can function as dispersants and binders.
  • the proportion of the positive electrode active material in the positive electrode mixture layer is determined using a mixture sample.
  • the mixture sample is obtained by the following procedure. First, the secondary battery in a discharged state is disassembled and the positive electrode is removed. Next, the positive electrode is washed with an organic solvent and then vacuum dried. After that, only the positive electrode mixture layer is removed and used as the mixture sample. By performing TG-DTA, NMR, pyrolysis GC-MS, etc. on the mixture sample, the proportion of the binder and conductive material other than the positive electrode active material can be calculated. When the conductive material contains multiple types of carbon materials, the proportion of carbon nanotubes in the conductive material can be calculated by performing microscopic Raman spectroscopy on the cross section of the positive electrode mixture layer.
  • the mass per m2 of the positive electrode mixture layer may be 200 g or more, and is preferably 250 g or more. By making the mass 250 g or more, it is possible to increase the capacity of the lithium ion battery. As described above, according to the positive electrode plate according to the present disclosure, the adverse effects caused by increasing the mass can be suppressed.
  • the mass can be increased by thickening the positive electrode mixture layer or increasing the density of the positive electrode mixture layer.
  • the thickness of the positive electrode mixture layer may be in the range of 50 ⁇ m to 250 ⁇ m. According to this embodiment, even if the positive electrode mixture layer is made thick, an increase in internal resistance can be suppressed.
  • the positive electrode may include a positive electrode current collector.
  • the positive electrode mixture layer may be disposed on the positive electrode current collector.
  • the shape and thickness of the positive electrode current collector may be selected according to the application, and may be selected to correspond to the shape and thickness of the negative electrode current collector. Examples of the material of the positive electrode current collector include stainless steel, aluminum, aluminum alloy, and titanium.
  • the positive electrode slurry of this embodiment is a slurry for a positive electrode of a non-aqueous electrolyte secondary battery. This slurry is used for manufacturing the above-mentioned positive electrode.
  • the matters described about the positive electrode can be applied to the positive electrode slurry, so that the overlapping description may be omitted.
  • the positive electrode slurry includes the above-mentioned components of the positive electrode mixture layer and a liquid medium (dispersion medium) in which they are dispersed.
  • the positive electrode slurry includes a carboxylic acid compound, a positive electrode active material, a conductive material, a fluorine-containing polymer, a dispersant, and a liquid medium.
  • the positive electrode active material includes a composite oxide represented by the composition formula Li y Ni x M (1-x) O 2- ⁇ (wherein 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1.2, 0 ⁇ 0.05, M includes at least one element selected from the group consisting of Co, Mn, Al, Fe, Ti, Sr, Ca, and B).
  • the conductive material includes a carbon material.
  • the dispersant includes a nitrile group-containing rubber. Each component has been described above, so duplicated explanations will be omitted.
  • the positive electrode slurry may further include the above-mentioned optional components (polyvinylpyrrolidone, cellulose derivative, etc.).
  • the liquid medium is not particularly limited, and water, organic solvents, and mixtures thereof may be used.
  • organic solvents include alcohols (such as ethanol), ethers (such as tetrahydrofuran), amides (such as dimethylformamide), and N-methyl-2-pyrrolidone (NMP).
  • the ratio of the components in the positive electrode slurry is reflected in the ratio of the components in the positive electrode mixture layer. Therefore, by changing the ratio of the components in the positive electrode slurry, the ratio of the components in the positive electrode mixture layer can be changed.
  • the ratios of the components given as examples for the positive electrode mixture layer can be applied to the ratios of the components in the positive electrode slurry.
  • the positive electrode may be formed by the following method. First, a positive electrode slurry is prepared by dispersing the materials for the positive electrode mixture layer (positive electrode active material, carboxylic acid compound, conductive material, fluorine-containing polymer, dispersant, and other optional components as necessary) in a liquid medium. Next, the positive electrode slurry is applied to the surface of the positive electrode current collector to form a coating film, and the coating film is then dried to form the positive electrode mixture layer. The dried coating film 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.
  • the materials for the positive electrode mixture layer positive electrode active material, carboxylic acid compound, conductive material, fluorine-containing polymer, dispersant, and other optional components as necessary
  • the positive electrode slurry is applied to the surface of the positive electrode current collector to form a coating film, and the coating film is then dried to form the positive electrode mixture layer.
  • the dried coating film may be rolled as necessary.
  • the positive electrode mixture layer may be
  • the present disclosure provides a conductive material dispersion liquid.
  • the conductive material dispersion liquid can be used to prepare a positive electrode slurry.
  • the conductive material dispersion liquid includes a carboxylic acid compound, a conductive material, a fluorine-containing polymer, a dispersant, and a liquid medium.
  • the conductive material includes a carbon material.
  • the dispersant includes a nitrile group-containing rubber.
  • the liquid medium for the conductive material dispersion may be the same as that described for the positive electrode slurry, or a different liquid medium may be used.
  • the conductive material dispersion basically does not contain a positive electrode active material.
  • the positive electrode slurry can be prepared by adding a positive electrode active material to the conductive material dispersion.
  • the conductive material dispersion may contain optional components of the positive electrode mixture layer and a liquid medium in addition to the positive electrode active material.
  • the ratio of components in the positive electrode mixture layer can be changed by changing the ratio of components contained in the conductive material dispersion liquid.
  • the ratio of components exemplified for the positive electrode mixture layer can be applied to the ratio of components in the conductive material dispersion liquid.
  • the ratio of each component to each other can be calculated from the ratio of each component to 100 parts by mass of the positive electrode active material exemplified in the explanation of the positive electrode mixture layer.
  • the nonaqueous electrolyte secondary battery according to the present embodiment includes the positive electrode according to the present embodiment.
  • the secondary battery includes at least a negative electrode and a nonaqueous electrolyte in addition to the positive electrode.
  • the secondary battery may include a positive electrode, a negative electrode, a nonaqueous electrolyte, a separator, and an exterior body. Examples of the secondary battery include a lithium ion secondary battery and a lithium metal secondary battery.
  • the components other than the positive electrode mixture layer are not particularly limited, and known components may be used. Examples of the components of the secondary battery are described below.
  • the positive electrode according to this embodiment is used as the positive electrode.
  • the negative electrode typically includes a negative electrode mixture layer containing a negative electrode active material.
  • the negative electrode may include a negative electrode current collector and a negative electrode mixture layer disposed on the negative electrode current collector.
  • a negative electrode current collector on which lithium metal or a lithium alloy can be deposited is used for the negative electrode.
  • the negative electrode mixture layer contains a negative electrode active material as an essential component.
  • the negative electrode mixture layer may contain optional components such as a binder, a thickener, and a conductive material.
  • the optional components may include the components exemplified as the components of the positive electrode.
  • the negative electrode mixture layer may be formed by applying a negative electrode slurry, in which the components of the negative electrode mixture layer are dispersed in a liquid medium (dispersion medium), to the surface of the negative electrode current collector and drying it.
  • the coating film after drying may be rolled as necessary.
  • the liquid medium may be any of the liquid media exemplified as the liquid medium for the positive electrode slurry.
  • the negative electrode active material is selected according to the type of the secondary battery.
  • An example of the negative electrode active material is a material capable of absorbing and releasing lithium ions. Examples of such materials include carbonaceous materials, Si-containing materials, and the like.
  • the negative electrode active material may include a Si-containing material or may be a Si-containing material. Metallic lithium, lithium alloys, and the like may be used as the negative electrode active material.
  • the negative electrode may include one type of negative electrode active material, or may include a combination of two or more types.
  • carbonaceous materials examples include graphite, easily graphitized carbon (soft carbon), and difficult-to-graphitize carbon (hard carbon).
  • the carbonaceous materials may be used alone or in combination of two or more.
  • Graphite is preferred because it has excellent charge/discharge stability and low irreversible capacity.
  • Examples of graphite include natural graphite, artificial graphite, and graphitized mesophase carbon particles.
  • Si-containing material examples include simple Si, silicon alloys, silicon compounds (such as silicon oxides), and composite materials in which a silicon phase is dispersed in a lithium ion conductive phase (matrix).
  • silicon oxides include SiO x particles. x may be, for example, 0.5 ⁇ x ⁇ 2, or 0.8 ⁇ x ⁇ 1.6.
  • the lithium ion conductive phase at least one selected from the group consisting of a SiO 2 phase, a silicate phase, and a carbon phase may be used.
  • the negative electrode current collector may be a metal foil.
  • the negative electrode current collector may be porous. Examples of materials for the negative electrode current collector include stainless steel, nickel, nickel alloys, copper, and copper alloys.
  • the non-aqueous electrolyte includes a solvent (non-aqueous solvent) and a solute dissolved in the solvent.
  • a solvent non-aqueous solvent
  • a solute include a lithium salt.
  • Various additives may be added to the electrolyte solution.
  • cyclic carbonate esters can be used as the solvent.
  • cyclic carbonate esters include propylene carbonate (PC), ethylene carbonate (EC), fluoroethylene carbonate (FEC), vinylene carbonate (VC), etc.
  • Chain carbonate esters include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), etc.
  • cyclic carboxylate esters include ⁇ -butyrolactone (GBL), ⁇ -valerolactone (GVL), etc.
  • chain carboxylate esters examples include non-aqueous solvents such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate (MP), and ethyl propionate (EP).
  • the non-aqueous solvents may be used alone or in combination of two or more.
  • lithium salts include lithium salts of chlorine-containing acids (LiClO 4 , LiAlCl 4 , LiB 10 Cl 10 , etc.), lithium salts of fluorine-containing acids (LiPF 6 , LiPF 2 O 2 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , etc.), lithium salts of fluorine-containing acid imides (LiN (FSO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiN (C 2 F 5 SO 2 ) 2 , etc.), lithium halides (LiCl, LiBr, LiI, etc.), etc.
  • the lithium salts may be used alone or in combination of two or more.
  • the concentration of the lithium salt in the electrolyte may be 1 mol/L or more and 2 mol/L or less, or 1 mol/L or more and 1.5 mol/L or less.
  • the electrolyte may contain known additives.
  • additives include 1,3-propane sultone, methylbenzenesulfonate, cyclohexylbenzene, biphenyl, diphenyl ether, fluorobenzene, etc.
  • the separator is disposed between the positive electrode and the negative electrode.
  • the separator preferably has high ion permeability and appropriate mechanical strength and insulating properties.
  • a microporous thin film, a woven fabric, a nonwoven fabric, etc. can be used.
  • Examples of the material of the separator include polyolefins (polypropylene, polyethylene, etc.) and other resins.
  • the electrode group and the non-aqueous electrolyte are housed in the exterior body (battery case).
  • the exterior body is not particularly limited, and a known exterior body may be used.
  • the electrode group is composed of a positive electrode, a negative electrode, and a separator.
  • the configuration of the electrode group is not particularly limited, and may be a wound type or a laminated type.
  • the wound type electrode group is formed by winding a positive electrode and a negative electrode with a separator interposed therebetween.
  • the laminated type electrode group is formed by stacking a positive electrode and a negative electrode with a separator interposed therebetween.
  • the shape of the non-aqueous electrolyte secondary battery is not particularly limited, and may be a cylindrical shape, a square shape, a coin shape, a button shape, a laminate shape, or the like.
  • FIG. 1 is a schematic perspective view of a secondary battery 10 according to an embodiment of the present disclosure, with a portion cut away.
  • FIG. 1 shows a rectangular non-aqueous electrolyte battery as an example.
  • the secondary battery 10 shown in FIG. 1 includes a battery case 4 in the shape of a rectangular cylinder with a bottom, and an electrode group 1 and a non-aqueous electrolyte (not shown) housed within the battery case 4.
  • the electrode group 1 includes a long strip-shaped negative electrode, a long strip-shaped positive electrode, and a separator disposed between them.
  • the negative electrode current collector of the negative electrode is electrically connected to a negative electrode terminal 6 provided on a sealing plate 5 via a negative electrode lead 3.
  • the negative electrode terminal 6 is insulated from the sealing plate 5 by a resin gasket 7.
  • the positive electrode current collector of the positive electrode is electrically connected to the back surface of the sealing plate 5 via a positive electrode lead 2.
  • the periphery of the sealing plate 5 is fitted into the open end of the battery case 4, and the fitting portion is laser welded. In other words, the positive electrode is electrically connected to the battery case 4, which also serves as the positive electrode terminal.
  • the sealing plate 5 has an injection hole for a non-aqueous electrolyte. The injection hole is closed by a seal plug 8 after the non-aqueous electrolyte is injected.
  • the positive electrode includes a positive electrode current collector and a positive electrode mixture layer disposed on the positive electrode current collector.
  • the positive electrode mixture layer is the positive electrode mixture layer described above.
  • a positive electrode for a non-aqueous electrolyte secondary battery comprising: A positive electrode mixture layer is included, the positive electrode mixture layer contains at least one compound selected from the group consisting of carboxylic acids and carboxylic acid anhydrides, a positive electrode active material, a conductive material, a fluorine-containing polymer, and a dispersant,
  • the positive electrode active material includes a composite oxide represented by the composition formula Li y Ni x M (1-x) O 2- ⁇ (wherein 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1.2, 0 ⁇ 0.05, and M includes at least one element selected from the group consisting of Co, Mn, Al, Fe, Ti, Sr, Ca, and B), the conductive material includes a carbon material;
  • the positive electrode according to claim 1 wherein 0.8 ⁇ x ⁇ 1 is satisfied in the composition formula of the composite oxide.
  • the positive electrode according to Technology 1 or 2 wherein the positive electrode active material includes first particles of the complex oxide having an average particle size of 1 ⁇ m or more and 6 ⁇ m or less, and second particles of the complex oxide having an average particle size of 8 ⁇ m or more and 20 ⁇ m or less.
  • the positive electrode according to claim 1 or 2 wherein the carbon material comprises carbon nanotubes.
  • a positive electrode slurry for a positive electrode of a non-aqueous electrolyte secondary battery comprising:
  • the present invention includes at least one compound selected from the group consisting of carboxylic acids and carboxylic anhydrides, a positive electrode active material, a conductive material, a fluorine-containing polymer, a dispersant, and a liquid medium
  • the positive electrode active material includes a composite oxide represented by the composition formula Li y Ni x M (1-x) O 2- ⁇ (wherein 0.6 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1.2, 0 ⁇ 0.05, and M includes at least one element selected from the group consisting of Co, Mn, Al, Fe, Ti, Sr, Ca, and B), the conductive material includes a carbon material;
  • the positive electrode slurry, wherein the dispersant comprises a nitrile group-containing rubber.
  • the positive electrode according to any one of claims 8 to 10 wherein the carbon material comprises carbon nanotubes.
  • CMC-Na sodium carboxymethylcellulose
  • SBR styrene-butadiene rubber
  • a positive electrode active material polyvinylidene fluoride (binder), carbon nanotubes (conductive material), nitrile group-containing rubber (dispersant), a carboxylic acid compound, and N-methyl-2-pyrrolidone (dispersion medium) were mixed in a predetermined mass ratio to prepare a positive electrode slurry SA1.
  • a composite oxide represented by the composition formula LiNi 0.80 Co 0.10 Mn 0.10 O 2 was used as the positive electrode active material.
  • the positive electrode active material (composite oxide) was a mixture of particles with an average particle size of 1 ⁇ m and particles with an average particle size of 8 ⁇ m.
  • the average length and average diameter of the carbon nanotubes were 1 ⁇ m and 10 nm, respectively.
  • the amount of carbon nanotubes added was 0.5 parts by mass per 100 parts by mass of the positive electrode active material.
  • the amount of polyvinylidene fluoride added was 1 part by mass per 100 parts by mass of the positive electrode active material.
  • Maleic anhydride was used as the carboxylic acid compound.
  • the amount of the carboxylic acid compound added was 0.05 parts by mass per 100 parts by mass of the positive electrode active material.
  • the amount of the nitrile group-containing rubber added was 0.1 parts by mass per 100 parts by mass of the positive electrode active material.
  • a coating film was formed by applying the positive electrode slurry to the surface of an aluminum foil (positive electrode current collector), and a laminate of the aluminum foil and the coating film was obtained. Next, the coating film was dried, and the laminate was rolled. In this way, a positive electrode PA1 was produced, which includes an aluminum foil and a positive electrode mixture layer formed on both sides of the aluminum foil.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • the positive electrode slurries SA2 to SA6 and the positive electrode slurries SC1 to SC5 were prepared in the same manner and under the same conditions as those for preparing the positive electrode slurry SA1 of the battery A1, except that the types of components (conductive material, carboxylic acid compound, and nitrile group-containing rubber) contained in the positive electrode slurry, the composition of the positive electrode active material, and the particle size distribution of the positive electrode active material were changed as shown in Table 1.
  • the composite oxide constituting the positive electrode active material was the composite oxide constituting the positive electrode active material used in the positive electrode slurry SA1.
  • the active material particles having two particle size distributions were used by mixing particles having an average particle size of 1 ⁇ m and particles having an average particle size of 8 ⁇ m, as in the positive electrode slurry SA1.
  • the active material particles having one particle size distribution were used by mixing active material particles having an average particle size of 12 ⁇ m. Except for using these positive electrode slurries, positive electrodes PA2 to PA6 and positive electrodes PC1 to PC5 were produced by the same method and conditions as those for producing positive electrode PA1 of battery A1. Except for using these positive electrodes, batteries A2 to A6 and batteries C1 to C5 were produced by the same method and conditions as those for producing battery A1.
  • the stability of the prepared positive electrode slurry was evaluated by the following method. The viscosity on the day of preparation of the slurry and the viscosity after leaving the prepared slurry to stand for two days were measured, and the increase rate was taken as the viscosity increase rate of the slurry. The viscosity of the slurry was measured using a B-type viscometer.
  • the amount of gas generated from the prepared battery was evaluated by the following method. First, the prepared battery was stored in a thermostatic chamber set at 80° C. in a charged state. Next, the battery was discharged and then disassembled in a sealed container, and the amount of gas generated was evaluated.
  • Table 1 shows some of the components contained in the positive electrode mixture layer and the evaluation results.
  • the slurry viscosity increase rate indicates a relative value when the viscosity increase rate of the slurry C1 is set to 100%
  • the battery capacity indicates a relative value when the battery capacity of the battery C1 is set to 100%
  • the gas generation amount indicates a relative value when the gas generation amount of the battery C1 is set to 100%.
  • Ni ratio x in the active material composition is the value of x when the positive electrode active material is expressed by the above-mentioned composition formula Li y Ni x M (1-x) O 2- ⁇ .
  • two types of particle size distribution of active material particles means that two types of positive electrode active materials with different average particle sizes are mixed and used, and "one type” means that two types of positive electrode active materials with different average particle sizes are not mixed and used. That is, the particle size distribution curve of active material particles having "two types of particle size distribution” has two peaks, while the particle size distribution curve of active material particles having "one type of particle size distribution” has one peak.
  • Batteries A1 to A6, the positive electrode slurry, and the positive electrodes used in their manufacture are batteries, positive electrode slurries, and positive electrodes according to this embodiment. Batteries C1 to C5, the positive electrode slurries, and positive electrodes used in their manufacture are comparative examples.
  • the slurry viscosity increase rate and the amount of gas generated are low, and it is preferable that the battery capacity is high.
  • the positive electrode slurry according to the present disclosure had a small increase in viscosity, and the positive electrode could be easily manufactured.
  • the battery according to the present disclosure had a high battery capacity and the amount of gas generated could be suppressed.
  • good batteries were obtained when carbon nanotubes were used as the conductive material and hydrogenated nitrile rubber was used as the nitrile group-containing rubber.
  • the present disclosure can be used for a positive electrode for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery.
  • the secondary battery according to the present disclosure can be used for various applications, and is preferably used as a main power source for, for example, mobile communication devices, portable electronic devices, and the like.
  • Electrode group 1: Electrode group, 2: Positive electrode lead, 3: Negative electrode lead, 4: Battery case, 5: Sealing plate, 6: Negative electrode terminal, 7: Gasket, 8: Seal, 10: Secondary battery (non-aqueous electrolyte secondary battery)

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PCT/JP2023/033401 2022-09-29 2023-09-13 非水電解質二次電池用の正極、それを用いた非水電解質二次電池、および、非水電解質二次電池の正極用の正極スラリー Ceased WO2024070704A1 (ja)

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