WO2023054308A1 - 非水電解質二次電池 - Google Patents

非水電解質二次電池 Download PDF

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WO2023054308A1
WO2023054308A1 PCT/JP2022/035831 JP2022035831W WO2023054308A1 WO 2023054308 A1 WO2023054308 A1 WO 2023054308A1 JP 2022035831 W JP2022035831 W JP 2022035831W WO 2023054308 A1 WO2023054308 A1 WO 2023054308A1
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particles
composite oxide
positive electrode
negative electrode
oxide particles
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French (fr)
Japanese (ja)
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典子 深道
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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 EP22876175.5A priority Critical patent/EP4411916A4/en
Priority to US18/697,353 priority patent/US20240396035A1/en
Priority to CN202280065641.8A priority patent/CN118020183A/zh
Priority to JP2023551501A priority patent/JPWO2023054308A1/ja
Publication of WO2023054308A1 publication Critical patent/WO2023054308A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to non-aqueous electrolyte secondary batteries.
  • Non-aqueous electrolyte secondary batteries especially lithium-ion secondary batteries, have high output and high energy density, so they are expected to be used as power sources for small consumer applications, power storage devices, and electric vehicles.
  • Patent Document 1 discloses a first lithium having a volume particle distribution of 3.0 ⁇ m ⁇ D25 ⁇ 10.0 ⁇ m, 5.0 ⁇ m ⁇ D50 ⁇ 20.0 ⁇ m and 10.0 ⁇ m ⁇ D75 ⁇ 25.0 ⁇ m as measured by a particle size analyzer.
  • a second nickel composite oxide having a volume particle distribution of 0.01 ⁇ m ⁇ D25 ⁇ 5.0 ⁇ m, 1.0 ⁇ m ⁇ D50 ⁇ 10.0 ⁇ m, and 5.0 ⁇ m ⁇ D75 ⁇ 15.0 ⁇ m as measured by a particle size analyzer and a lithium-nickel composite oxide, wherein the first lithium-nickel composite oxide contains more nickel atoms, which is the proportion of nickel atoms in the chemical formula, than the second lithium-nickel composite oxide, and the total content of the positive electrode active material is A positive electrode for a lithium battery, wherein the content of the first lithium-nickel composite oxide is 80 to 97% by weight, and the content of the second lithium-nickel composite oxide is 3 to 20% by weight, based on weight. Proposing active materials.
  • Patent No. 5868604 Japanese Patent Application Laid-Open No. 2011-216485 (Patent No. 5868604)
  • one aspect of the present disclosure includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein the positive electrode is a positive electrode current collector and a positive electrode mixture containing a positive electrode active material provided on the surface of the positive electrode current collector.
  • the positive electrode active material includes first composite oxide particles containing Li and Ni and second composite oxide particles containing Li and Ni, wherein the first composite oxide particles are having a first average particle diameter D1 satisfying 1 ⁇ m ⁇ D1 ⁇ 6 ⁇ m, and the ratio of Ni to the metal elements other than Li contained in the first composite oxide particles is 50 atomic% or more, and the second composite oxide particles The oxide particles have a second average particle diameter D2 that satisfies 8 ⁇ m ⁇ D2 ⁇ 20 ⁇ m, and the ratio of Ni to the metal elements other than Li contained in the second composite oxide particles is 50 atomic % or more.
  • the negative electrode includes a negative electrode current collector and a negative electrode mixture layer containing a negative electrode active material provided on the surface of the negative electrode current collector, and the negative electrode active material includes a graphite material and a Si-containing material.
  • the graphite material includes first graphite particles having a first internal porosity P1 and second graphite particles having a second internal porosity P2 that satisfies P1 ⁇ P2; Divided into a first region and a second region having a thickness, and when the first region is closer to the positive electrode than the second region, the first graphite particles are contained more in the first region than in the second region.
  • the average value Pf of the internal porosity of the graphite material contained in the first region is 14% or less, and the average value Pf is the internal porosity of the graphite material contained in the second region It relates to a non-aqueous electrolyte secondary battery that is smaller than the average value Ps of.
  • the durability of a non-aqueous electrolyte secondary battery having a high-capacity positive electrode is improved.
  • FIG. 1 is a diagram schematically showing a cross section of graphite particles according to an embodiment of the present disclosure
  • FIG. 1 is a diagram schematically showing a cross section of a negative electrode according to an embodiment of the present disclosure
  • FIG. 1 is a vertical cross-sectional view of a non-aqueous electrolyte secondary battery according to an embodiment of the present disclosure
  • any of the illustrated lower limits and any of the illustrated upper limits can be arbitrarily combined as long as the lower limit is not greater than or equal to the upper limit.
  • a plurality of materials are exemplified, 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 matters described in two or more claims arbitrarily selected from the multiple claims described in the attached claims. In other words, as long as there is no technical contradiction, the matters described in two or more claims arbitrarily selected from the multiple claims described in the attached claims can be combined.
  • containing or “including” include expressions that include “containing (or including),” “consisting essentially of,” and “consisting of.” is.
  • Secondary batteries include at least non-aqueous electrolyte secondary batteries such as lithium ion batteries, lithium metal secondary batteries, and all-solid-state batteries.
  • a nonaqueous electrolyte secondary battery includes a positive electrode, a negative electrode, and a nonaqueous electrolyte.
  • a separator is usually interposed between the positive electrode and the negative electrode.
  • the positive electrode, negative electrode and separator constitute an electrode group.
  • the electrode group is accommodated in the exterior body together with the non-aqueous electrolyte.
  • a cylindrical electrode group is formed by winding a positive electrode and a negative electrode with a separator interposed therebetween, or a laminated electrode group is formed by laminating a positive electrode and a negative electrode with a separator interposed therebetween.
  • the form of the electrode group is not particularly limited.
  • the shape of the nonaqueous electrolyte secondary battery is not limited, either, and may be, for example, cylindrical, square, coin, button, laminate, or the like.
  • a non-aqueous electrolyte secondary battery includes, for example, a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator as described below.
  • the positive electrode includes a positive electrode current collector and a positive electrode mixture layer containing a positive electrode active material provided on the surface of the positive electrode current collector.
  • the positive electrode current collector is composed of a sheet-like conductive material.
  • the positive electrode current collector may be in the form of a long sheet.
  • the positive electrode mixture layer is carried on one or both surfaces of the positive electrode current collector.
  • the positive electrode mixture layer is usually a layer (including a membrane or film) composed of a positive electrode mixture.
  • the positive electrode mixture contains a positive electrode active material as an essential component.
  • a positive electrode active material is a material that develops capacity by intercalating and deintercalating lithium ions.
  • the positive electrode active material includes first composite oxide particles containing Li and Ni and second composite oxide particles containing Li and Ni.
  • the second composite oxide particles are a different material from the first composite oxide particles.
  • Different materials refer to materials that differ in physical properties at least other than particle size.
  • the first composite oxide particles and the second composite oxide particles differ, for example, in the composition of the composite oxide, the morphology of the particles, and the like.
  • SEM, TEM This includes cases where the photographed image is clearly different when observed with an optical instrument such as an electron microscope.
  • the first composite oxide particles have a first average particle diameter D1 that satisfies 1 ⁇ m ⁇ D1 ⁇ 6 ⁇ m.
  • the ratio of Ni to the metal elements other than Li contained in the first composite oxide particles (hereinafter also referred to as "first Ni ratio”) is 50 atomic % or more. D1 is smaller than D2, which will be described later.
  • first Ni ratio the ratio of Ni to the metal elements other than Li contained in the first composite oxide particles
  • D1 is smaller than D2, which will be described later.
  • the first composite oxide particles By using the first composite oxide particles, the packing density of the positive electrode active material in the positive electrode mixture layer is improved. Further, by setting the first Ni ratio to 50 atomic % or more, particularly preferably 80 atomic % or more, the capacity density of the first composite oxide particles can be increased. Since D1 is relatively small, there is little need to make the primary particles of the first composite oxide particles that small in order to ensure output characteristics.
  • the first average particle diameter D1 of the first composite oxide particles may be 5 ⁇ m or less, and is particularly preferably 2 ⁇ m or more and 5 ⁇ m or less.
  • the first composite oxide particles may have a layered rock salt crystal structure.
  • the ratio of the first Ni should be 50 atomic % or more, preferably 70 atomic % or more, and particularly preferably 80 atomic % or more.
  • the first composite oxide particles desirably contain Mn.
  • the proportion of Mn in the metal elements other than Li contained in the first composite oxide particles is preferably 1 atomic % or more and 20 atomic % or less, more preferably 2 atomic % or more and 15 atomic % or less. It is believed that Mn contributes to cost reduction and capacity increase of the first composite oxide particles.
  • the first composite oxide particles may contain Co.
  • the proportion of Co in the metal elements other than Li contained in the first composite oxide particles is preferably 0 atomic % or more and 20 atomic % or less, more preferably 2 atomic % or more and 15 atomic % or less. Co is believed to increase the compressive strength and electrical conductivity of the first composite oxide particles.
  • the first composite oxide particles are, for example , LiaNi1 - xyCoxMyO2 (where 0 ⁇ a ⁇ 1.2, 0 ⁇ x ⁇ 0.1 , 0 ⁇ y ⁇ 0.1 , x + y ⁇ 0.2, and M is at least one selected from the group consisting of Mn, W, Mg, Mo, Nb, Ti, Si and Al.). .
  • the value a which indicates the molar ratio of lithium, increases or decreases due to charging and discharging.
  • M includes at least Mn.
  • Specific examples of the first composite oxide particles include lithium-nickel-cobalt-manganese composite oxides (such as LiNi 0.85 Co 0.10 Mn 0.05 O 2 ).
  • the second composite oxide particles have a second average particle size D2 that satisfies 8 ⁇ m ⁇ D2 ⁇ 20 ⁇ m.
  • the ratio of Ni to the metal elements other than Li contained in the second composite oxide particles (hereinafter also referred to as “second Ni ratio”) is 50 atomic % or more. D2 is greater than D1.
  • the second composite oxide particles may have a layered rock salt crystal structure.
  • the filling density of the positive electrode active material in the positive electrode mixture layer may be increased to, for example, 3.5 g/cm 3 or more, or may be increased to 3.55 g/cm 3 or more. From the viewpoint of achieving both high capacity and high density, it is desirable to have a density of 3.55 g/cm 3 or more.
  • the second composite oxide particles desirably contain Al.
  • the proportion of Al in the metal elements other than Li contained in the second composite oxide particles is preferably 0.1 atomic % or more and 10 atomic % or less, more preferably 1 atomic % or more and 7 atomic % or less. It is believed that Al enhances the stability of the crystal structure and output characteristics of the second composite oxide particles.
  • the second composite oxide particles may contain Co.
  • the proportion of Co in the metal elements other than Li contained in the second composite oxide particles is desirably 0 atomic % or more and 20 atomic % or less, and more desirably 1 atomic % or more and 10 atomic % or less. Co is believed to increase the compressive strength and electrical conductivity of the first composite oxide particles.
  • the second composite oxide particles are also Li a Ni 1-xy Co x My O 2 (where 0 ⁇ a ⁇ 1.2, 0 ⁇ x ⁇ 0.1, 0 ⁇ y ⁇ 0.1, x+y ⁇ 0.2, and M is at least one selected from the group consisting of Mn, W, Mg, Mo, Nb, Ti, Si and Al.). Preferably, M contains at least Co and Al.
  • Specific examples of the second composite oxide particles include lithium-nickel-cobalt-aluminum composite oxides (such as LiNi 0.85 Co 0.10 Al 0.05 O 2 ).
  • the first average particle diameter D1 and the second average particle diameter D2 can be measured from a cross section in the thickness direction obtained by simultaneously cutting the positive electrode mixture layer and the positive electrode current collector.
  • the cross section may be formed using a cross section polisher (CP).
  • the positive electrode mixture layer may be filled with a thermosetting resin and cured.
  • a scanning electron micrograph (hereinafter referred to as an SEM image) of the cross section is taken.
  • the SEM image is taken such that ten or more first composite oxide particles and ten or more second composite oxide particles are observed. Since the first composite oxide particles and the second composite oxide particles differ in composition or morphology, they can be visually distinguished.
  • the cross-sectional first circle equivalent diameters of all the first composite oxide particles contained in the image area of at least 54 ⁇ m 2 are obtained, and the average value thereof is obtained as D1.
  • the second circle equivalent diameters of the cross sections of all the second composite oxide particles contained in the image area of at least 54 ⁇ m 2 are obtained, and the average value thereof is obtained as D2.
  • the equivalent circle diameter refers to the diameter of a circle having the same area as the cross-sectional area of the particle (the area of the particle observed in the cross section of the positive electrode mixture layer).
  • the second composite oxide particles may be pulverized to produce small particles when the electrode plate is compressed, such small particles are not used as particles for measuring the second average particle size D2. Particles that are clearly cracked and pulverized by compression are not used for the measurement of D1 and D2.
  • the median in the volume-based particle size distribution of each of the first composite oxide particles and the second composite oxide particles is The diameter (D50: particle size at 50% cumulative volume) may be determined as D1 and D2.
  • the volume-based particle size distribution can be measured by a laser diffraction scattering method. For example, "LA-750" manufactured by HORIBA, Ltd. can be used as the measuring device.
  • the first composite oxide particles may be particles in a non-aggregated state.
  • Particles in a non-aggregated state include particles that exist separately as a single primary particle, as well as particles that are formed by gathering several to ten-odd (for example, 2 to 19) primary particles. .
  • Particles in a non-aggregated state are less likely to be crushed and are excellent in durability because the increase in surface area is suppressed.
  • Such first composite oxide particles are less likely to be crushed when the positive electrode mixture layer is formed by being compressed by rolling. Therefore, it becomes easy to increase the packing density of the positive electrode mixture layer by increasing the pressure during rolling.
  • the average particle size d1 of the primary particles of the non-aggregated particles is, for example, 1 ⁇ m or more, and may be 1.5 ⁇ m or more.
  • the average particle size d1 may be, for example, 3 ⁇ m or less.
  • the second composite oxide particles may be aggregated particles.
  • Particles in an aggregated state refer to particles that exist as secondary particles formed by agglomeration of 10 or more (specifically, 20 or more) primary particles.
  • particles in an aggregated state may consist of 10,000 to 5,000,000 primary particles.
  • the aggregated second composite oxide particles have a small average primary particle diameter d2 and tend to be easily crushed, but have a large reaction area with the non-aqueous electrolyte, and are excellent in output characteristics and high capacity. Cheap.
  • the average particle size d2 of primary particles of aggregated particles is, for example, 500 nm or less, and may be 300 nm or less.
  • the average particle size d2 may be, for example, 100 nm or more.
  • the average particle diameters d1 and d2 of the primary particles of the first and second composite oxide particles are obtained by observing the grain boundaries of the primary particles based on the SEM image of each composite oxide particle.
  • the SEM images for obtaining the average particle diameters d1 and d2 of the primary particles may be the same SEM images as for obtaining the first average particle diameter D1 and the second average particle diameter D2.
  • the outline is specified from the grain boundaries of a plurality of (for example, 20 or more) selected primary particles, the maximum diameter of each primary particle is obtained from the outline, and the average length is obtained.
  • the compressive strength of the first composite oxide particles is, for example, 160 MPa or more.
  • the compressive strength of the second composite oxide particles is, for example, 150 MPa or less.
  • Compressive strength is the compressive strength per primary particle in the case of primary particles, and the compressive strength per secondary particle in the case of secondary particles.
  • d is the particle diameter of the secondary particles or primary particles, and the secondary particle diameter is used to calculate the compressive strength of the secondary particles, and the primary particle diameter is used to calculate the compressive strength of the primary particles.
  • the particle diameter is the diameter of an equivalent circle having an area surrounded by the contours of particle images observed by CCD or the like. Twenty particles are randomly selected, the compressive strength of the selected secondary particles is measured with a microcompression tester, and the average value is taken as the compressive strength.
  • the BET specific surface area of the first composite oxide particles is, for example, 0.7 m 2 /g or less.
  • the BET specific surface area of the second composite oxide particles is, for example, 0.8 m 2 /g or more.
  • the BET specific surface area is measured by a gas adsorption method (BET single-point method). Nitrogen gas is used as the gas.
  • the measuring device for example, an automatic specific surface area/pore size distribution measuring device "Tristar II 3020" manufactured by Shimadzu Corporation is used.
  • the positive electrode mixture layer may have a total pore volume of 0.1 mL/g or less, and a pore mode diameter of 0.7 ⁇ m or less.
  • the liquid circulation of the non-aqueous electrolyte is usually likely to be restricted, but according to the configuration of the present disclosure (especially the configuration of the negative electrode), the liquid circulation can be significantly improved. can be done.
  • the total pore volume of the positive electrode mixture layer is measured by, for example, a mercury porosimeter.
  • "AutoPore IV9520" manufactured by Micromeritics is used as the measuring device.
  • the measurement range (pore size) is 0.003 ⁇ m to 109.4 ⁇ m. Note that, in order to remove impurities, the sample of the positive electrode mixture layer after washing is pretreated by heating and evacuation (for example, at 250° C. and 50 mTorr or less), and then the measurement is performed.
  • the content of the first composite oxide particles contained in the positive electrode active material is, for example, 5% by mass or more and 50% by mass or less, and may be 10% by mass or more and 45% by mass or less.
  • the content of the second composite oxide particles contained in the positive electrode active material is, for example, 50% by mass or more and 95% by mass or less, and may be 55% by mass or more and 90% by mass or less.
  • the content ratios of the first composite oxide particles and the second composite oxide particles contained in the positive electrode active material can be obtained by the following method by image analysis of the SEM photograph of the cross section of the positive electrode.
  • the area surrounded by the contours is obtained.
  • the diameter of an equivalent circle having the same area as the contour area of the first composite oxide particle is obtained and taken as the particle diameter of each particle i, and the volume of a sphere having the same diameter is regarded as the volume Vi of each particle i.
  • the diameter of an equivalent circle having the same area as the contour area of the second composite oxide particle is obtained and taken as the particle size of each particle j, and the volume of a sphere having the same diameter is regarded as the volume Vj of each particle j.
  • the density of the first composite oxide particles is ⁇ 1, and the density of the second composite oxide particles is ⁇ 2.
  • the content C1 of the first composite oxide particles in the predetermined region is obtained by the following formula by deriving Vi or Vj for each particle present in the predetermined region of the cross-sectional SEM image of the positive electrode mixture layer.
  • the content C2 of the second composite oxide particles in a predetermined region is obtained by the following formula by deriving Vi or Vj for each particle present in a predetermined region of the cross-sectional SEM image of the positive electrode mixture layer. .
  • C1 ⁇ i ⁇ 1Vi /( ⁇ i ⁇ 1Vi + ⁇ j ⁇ 2Vj )
  • C2 ⁇ j ⁇ 2Vj /( ⁇ i ⁇ 1Vi + ⁇ j ⁇ 2Vj )
  • the content of the first composite oxide particles is derived by arbitrarily selecting a plurality of small regions (for example, 20 or more) in the positive electrode mixture layer, calculating C1 in each small region, and obtaining the average value. good too.
  • the content of the second composite oxide particles can be determined by arbitrarily selecting a plurality of (for example, 20 or more) small regions in the positive electrode mixture layer, calculating C2 in each small region, and obtaining the average value. can be derived.
  • a compound containing at least one selected from Zr, Ti, B, Sr, Ca, W, Mg, Nb and Al (hereinafter referred to as "metal element M") is present on the particle surface of each composite oxide. It may be fixed.
  • the M compound containing the metal element M may be scattered on the particle surface of the composite oxide, or may be present in a layer so as to cover the entire particle surface.
  • the thickness of the M compound layer is, for example, 0.1 to 5 nm.
  • the M compound is thought to protect the surface of the composite oxide, thereby suppressing the side reaction of the electrolyte on the particle surface of the composite oxide.
  • M compounds are oxides, hydroxides, or carbonates. Specific examples of M compounds include SrO, CaO, Sr(OH) 2 , Ca(OH) 2 , SrCO 3 , CaCO 3 and the like.
  • the amount of the M compound is, for example, 0.05 to 0.5 mol % in terms of the metal element M with respect to the total number of moles of the metal elements excluding Li constituting the composite oxide.
  • the presence of M compounds can be confirmed by energy dispersive X-ray spectroscopy (TEM-EDX). Also, the metal element M can be measured by ICP emission spectroscopic analysis of a solution in which a composite oxide is dissolved in hydrofluoric-nitric acid.
  • the composite oxide is produced by, for example, a first step of obtaining a composite oxide containing Ni, a metal element M, etc., a second step of mixing the composite oxide and the Li raw material to obtain a mixture, and a third step of firing the mixture. It is manufactured through a process.
  • a raw material containing the metal element M hereinafter referred to as "M raw material”
  • M raw material a raw material containing the metal element M
  • the composition, particle size, BET specific surface area, and the like of the composite oxide and M compound can be adjusted by controlling the mixing ratio of raw materials, the firing conditions in the third step, and the like.
  • the first step for example, while stirring a solution of a metal salt containing a metal element such as Ni and metal element M, an alkaline solution such as sodium hydroxide is added dropwise, and the pH is adjusted to the alkaline side (eg, 8.5 to 12.5 ) to precipitate (coprecipitate) a composite hydroxide containing a metal element.
  • an alkaline solution such as sodium hydroxide
  • the pH is adjusted to the alkaline side (eg, 8.5 to 12.5 ) to precipitate (coprecipitate) a composite hydroxide containing a metal element.
  • the firing temperature is not particularly limited, it is 300 to 600° C. as an example.
  • the composite oxide obtained in the first step, the Li raw material, and, if necessary, the M raw material are mixed to obtain a mixture.
  • Li raw materials include Li 2 CO 3 , LiOH, Li 2 O 2 , Li 2 O, LiNO 3 , LiNO 2 , Li 2 SO 4 , LiOH ⁇ H 2 O, LiH, and LiF.
  • M raw materials include M oxides, hydroxides, carbonates, nitrates, sulfates, and the like.
  • the mixing ratio of the composite oxide obtained in the first step and the Li raw material is adjusted, for example, so that the molar ratio of metal elements other than Li to Li is 1:0.98 to 1:1.22. .
  • the mixing ratio of the composite oxide and the M raw material is adjusted, for example, so that the molar ratio of metal elements excluding Li to M is 1:0.0005 to 1:0.005.
  • the mixture obtained in the second step is fired at a predetermined temperature and time to obtain a fired product.
  • Firing of the mixture includes, for example, a first firing step of firing at a first heating rate to a first set temperature of 450 ° C. or higher and 680 ° C. or lower in a firing furnace under an oxygen stream, and after the first firing step, a firing furnace A second firing step of firing at a second heating rate to a second set temperature of over 680° C. and not more than 800° C. in an oxygen stream.
  • the first heating rate is 1.5 to 5.5° C./min
  • the second heating rate is slower than the first heating rate and may be 0.1 to 3.5° C./min.
  • the mixture may be molded into pellets and then fired, or the pellets may be pulverized after firing.
  • the second set temperature of the first composite oxide particles is higher than that of the second composite oxide particles. For example, it is 800°C.
  • the holding time of the first set temperature in the first baking step is, for example, 0 to 5 hours or 0 to 3 hours.
  • the holding time of the set temperature is the time for maintaining the set temperature after reaching the set temperature.
  • the retention time of the second set temperature in the second firing step is, for example, 1 to 10 hours or 1 to 5 hours.
  • Firing of the mixture is performed in an oxygen stream having an oxygen concentration of 60% or more, and the flow rate of the oxygen stream may be 0.2 to 4 mL/min per 10 cm 3 of the firing furnace and 0.3 L/min or more per 1 kg of the mixture. .
  • the baked product may be washed with water, dehydrated and dried to remove impurities. In order to promote crystal growth, it is desirable that the holding time of the first composite oxide particles at the second set temperature be longer than that of the second composite oxide particles. For example, 10 hours.
  • the M raw material is not added in the second step, and the M raw material is added in the third step, when the fired product is washed with water or dried, for example, in a vacuum atmosphere at 150 to 400 ° C. for 0.5 to 15 hours.
  • the M compound may be fixed to the particle surface of the composite oxide by performing the heat treatment of .
  • the positive electrode mixture layer is formed by, for example, applying a positive electrode slurry in which a positive electrode mixture containing a positive electrode active material, a binder, etc. is dispersed in a dispersion medium on the surface of the positive electrode current collector, drying the coating film after drying. Formed by rolling.
  • the positive electrode mixture contains a positive electrode active material as an essential component, and may contain a binder, a conductive material, and the like as optional components.
  • the conductive material forms a good conductive path in the positive electrode mixture layer and contributes to lower resistance of the positive electrode mixture layer.
  • Known materials can be used as the binder, the conductive material, and the like.
  • a particulate conductive agent may be used, or a fibrous conductive agent may be used.
  • the particulate conductive agent include carbon black such as acetylene black and ketjen black, and graphite.
  • fibrous conductive agents include carbon nanotubes (CNT), vapor-grown carbon fibers (VGCF), electrospun carbon fibers, polyacrylonitrile (PAN)-based carbon fibers, pitch-based carbon fibers, and graphene.
  • CNTs are thought to form good conductive paths in the positive electrode mixture layer, connect particles of each composite oxide, and promote the effect of improving durability by the first composite oxide.
  • the content of CNTs may be, for example, 0.01 to 5% by mass, more preferably 0.04 to 2% by mass, or 0.06 to 0.8% by mass, relative to the total mass of the positive electrode mixture layer. be. If the CNT content is within this range, the cycle characteristics can be efficiently improved.
  • the positive electrode mixture layer may contain only CNT as a conductive agent.
  • the content of the conductive material is, for example, 1 part by mass or less with respect to 100 parts by mass of the positive electrode active material (the positive electrode active material in a discharged state).
  • the content of CNTs may be 0.01 parts by mass or more and 1 part by mass or less, or may be 0.02 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass of the positive electrode active material. .
  • Carbon black, carbon nanotubes (CNT), etc. are preferable as the conductive material.
  • the proportion of CNTs in the conductive material is, for example, 50% by mass or more, preferably 66% by mass or more and 100% by mass or less (eg, 80 to 100% by mass or 90 to 100% by mass).
  • the average fiber length of CNT is, for example, 0.5 ⁇ m or longer, preferably 0.7 ⁇ m or longer, more preferably 0.8 ⁇ m or longer, or 1 ⁇ m or longer.
  • the upper limit of the average fiber length of CNT is not particularly limited, but is 20 ⁇ m or less, 10 ⁇ m, or 5 ⁇ m as an example.
  • An example of a suitable range for the average fiber length of CNTs is 1 to 10 ⁇ m, or 1 to 5 ⁇ m. If the average fiber length of CNTs is within the range, the effect of improving cycle characteristics is enhanced compared to the case of using CNTs having an average fiber length outside the range.
  • the average fiber length of CNTs is determined by image analysis using a scanning electron microscope (SEM).
  • the average fiber length of CNTs is determined by, for example, arbitrarily selecting a plurality of (for example, 100) CNTs, measuring their lengths, and averaging them.
  • the fiber length refers to the length of the CNT when it is stretched linearly.
  • the average fiber diameter (outer diameter) of CNTs is, for example, 50 nm or less, preferably 40 nm or less, more preferably 25 nm or less, or 20 nm or less, and may be 15 nm or less.
  • the lower limit of the average fiber diameter of CNT is not particularly limited, it is 1 nm or 5 nm as an example.
  • An example of a suitable range for the average fiber diameter of CNTs is 1 to 20 nm, or 5 to 20 nm. If the average fiber diameter of CNTs is within the range, the effect of improving cycle characteristics is enhanced compared to the case of using CNTs having an average fiber diameter outside the range.
  • the average fiber diameter of CNTs is determined by image analysis using a transmission electron microscope (TEM). The average fiber diameter is obtained, for example, by arbitrarily selecting a plurality of (eg, 100) CNTs, measuring the fiber diameters, and averaging them.
  • the contact between the positive electrode active material and the positive electrode current collector is not a point contact but a linear contact, which improves the output characteristics.
  • CNTs occupy only a small volume in the positive electrode mixture layer, it is easy to increase the proportion of the positive electrode active material in the positive electrode mixture layer.
  • the CNTs may be single-walled CNTs (SWCNTs), double-walled (DWCNTs) and multi-walled (MWCNTs), or at least two or more of them. Among them, MWCNT is preferable.
  • MWCNT for example, a CNT having a tubular structure in which a graphene sheet composed of a six-membered carbon ring is wound parallel to the fiber axis, and a graphene sheet composed of a six-membered carbon ring are arranged perpendicular to the fiber axis.
  • a CNT with a poolet structure, a CNT with a herringbone structure in which a graphene sheet composed of a six-membered ring of carbon is wound at an oblique angle with respect to the fiber axis, or the like can be used. Two or more types of CNTs may be added to the positive electrode mixture layer.
  • a non-porous conductive substrate (metal foil, etc.) or a porous conductive substrate (mesh body, net body, punching sheet, etc.) is used for the positive electrode current collector.
  • the thickness of the positive electrode current collector is, for example, 5 ⁇ m or more and 30 ⁇ m or less, may be 10 ⁇ m or more and 25 ⁇ m or less, or may be 15 ⁇ m or more and 20 ⁇ m or less.
  • Examples of materials for the positive electrode current collector include stainless steel, aluminum, aluminum alloys, and titanium.
  • the negative electrode includes a negative electrode current collector and a negative electrode mixture layer containing a negative electrode active material provided on the surface of the negative electrode current collector.
  • the negative electrode current collector is composed of a sheet-like conductive material.
  • the negative electrode current collector may be in the form of a long sheet.
  • the negative electrode mixture layer is carried on one or both surfaces of the negative electrode current collector.
  • the negative electrode mixture layer is usually a layer (including a film or a film) composed of a negative electrode mixture.
  • the negative electrode mixture contains a negative electrode active material as an essential component.
  • a negative electrode active material is a material that develops capacity by intercalating and deintercalating lithium ions.
  • the negative electrode active material includes a graphite material and a Si-containing material. Further, the graphite material includes graphite particles (first graphite particles) having an internal porosity (first internal porosity P1) and graphite particles (second graphite particles) having an internal porosity (second internal porosity P2). include. However, P1 ⁇ P2, P1 is 5% or less and P2 is greater than 5%.
  • the first graphite particles and the second graphite particles are different materials.
  • the first graphite particles and the second graphite particles differ in particle morphology, for example.
  • the morphology of the particles is different, when the crystallinity of graphite (for example, the interplanar spacing d002 of the (002) plane) is clearly different (for example, one is 1.05 times or more than the other), When the circularity is clearly different (For example, one is 1.05 times or more than the other), and the photographed images are clearly different when observed with an optical instrument such as an electron microscope such as SEM or TEM.
  • Internal voids refer to voids that are closed inside the graphite particles, and are distinguished from external voids that connect to the space outside the graphite particles.
  • the first internal porosity P1 may be 4% or less.
  • the second internal porosity may be 6% or more and 25% or less, and particularly preferably 8% or more and 20% or less.
  • Graphite is a carbonaceous material with a developed graphite-type crystal structure. If the interplanar spacing d002 of the (002) plane measured by the X-ray diffraction method is, for example, 0.340 nm or less, it is classified as graphite, but the interplanar spacing d002 is preferably 0.3354 nm or more. Further, the crystallite size Lc(002) of graphite may be, for example, 5 nm or more, or may be 5 nm or more and 200 nm or less. The crystallite size Lc(002) is measured, for example, by the Scherrer method. When the interplanar spacing d002 of the (002) planes of graphite and the crystallite size Lc(002) are within the above ranges, high capacity is likely to be obtained.
  • FIG. 1 is a diagram schematically showing a cross section of graphite particles used in a non-aqueous electrolyte secondary battery according to an embodiment of the present invention.
  • the graphite particles Gr have internal voids G1 closed inside the graphite particles Gr and external voids G2 connected to spaces outside the graphite particles Gr.
  • the external voids G2 are included in the voids between the negative electrode active material particles.
  • the internal porosity of the graphite particles Gr means the ratio of the area SC2 of the internal voids G1 to the area SC1 of the graphite particles Gr in the cross section of the graphite particles Gr, and is obtained by (SC2/SC1) ⁇ 100.
  • the area SC1 of the graphite particle Gr is the area of the region surrounded by the outer periphery of the graphite particle Gr, and means the total area of the carbon material portion (shaded portion in FIG. 2) and the internal void G1.
  • the area SC2 of the internal voids G1 means the total area of the multiple internal voids G1.
  • the internal porosity of graphite particles can be obtained by the following method.
  • An initial battery an unused battery or a battery that has been charged and discharged several times
  • the negative electrode is taken out, a part of the negative electrode is sampled, and a sample cross section of the negative electrode mixture layer is obtained using an ion milling device or the like.
  • the ion milling device for example, the device name “IM4000PLUS” manufactured by Hitachi High-Tech Co., Ltd. can be used.
  • a plurality of graphite particles may be embedded in an epoxy resin or the like and polished to obtain a cross section of the plurality of graphite particles, which may be used as a sample cross section.
  • a backscattered electron image (magnification: 3,000 to 5,000 times) of the cross section of the sample is taken to obtain a cross section image of the sample.
  • the cross-sectional image of the sample obtained above is taken into a computer and binarized.
  • image analysis software "ImageJ” manufactured by the National Institutes of Health in the United States can be used.
  • graphite particles including internal voids
  • voids between particles are represented in white.
  • Graphite particles with a maximum diameter of 5 ⁇ m or more and 50 ⁇ m or less are arbitrarily selected using the binarized cross-sectional image.
  • the area SC1 of the graphite particles and the area SC2 of the internal voids of the graphite particles are calculated.
  • the internal void ratio (%) of the graphite particles is calculated from the following formula.
  • Internal porosity of graphite particles (SC2/SC1) x 100
  • Graphite particles with an internal porosity of 5% or less are defined as first graphite particles, and graphite particles with an internal porosity of more than 5% are defined as second graphite particles.
  • the average value of the internal porosity of the ten first graphite particles is obtained as the first internal porosity P1.
  • the average value of the internal porosity of the ten second graphite particles is obtained as the second internal porosity P2.
  • the first graphite particles are contained more in the first region than in the second region.
  • the content rate (% by mass) C11 of the first graphite particles contained in the negative electrode active material in the first region is higher than the content rate (% by mass) C21 of the first graphite particles contained in the negative electrode active material in the second region.
  • C21 may be 0% by mass.
  • C11 may be at least twice as large as C21.
  • the first graphite particles having a small internal porosity are less likely to be crushed when they are compressed by rolling to form the negative electrode mixture layer.
  • the non-aqueous electrolyte has a higher liquid circulation property than in the second region, and can function as a reservoir of the non-aqueous electrolyte to be supplied to the positive electrode mixture layer during rapid charging.
  • the negative electrode mixture layer contains the Si-containing material, the expansion and contraction of the negative electrode mixture layer is increased, and the Si-containing material acts as a pump to move the non-aqueous material from the negative electrode mixture layer to the positive electrode mixture layer. Electrolyte supply proceeds smoothly.
  • C11 and C21 correspond to the contents C1 and C2 of the first and second composite oxide particles in the positive electrode mixture layer, and correspond to the outline images of the first and second graphite particles in the SEM photograph.
  • the diameter of the circle may be determined, the volume of each particle may be taken as the volume of a sphere with the same diameter, and the density of each particle may be used.
  • the average internal porosity Pf of the graphite material contained in the first region is set to 14% or less.
  • the average value Pf is set smaller than the average value Ps of the internal porosity of the graphite material contained in the second region.
  • Pf/Ps may be less than 1, but is preferably 0.7 or less.
  • the average value Pf and average value Ps can be obtained by the following method.
  • An initial battery an unused battery or a battery that has been charged and discharged several times
  • the negative electrode is taken out, part of the negative electrode is embedded in epoxy resin or the like, and a cross-sectional sample of the negative electrode mixture layer is obtained by polishing.
  • a scanning electron microscope SEM
  • a backscattered electron image magnification: 3,000 to 5,000 times
  • the cross-sectional image of the sample obtained above is taken into a computer and binarized.
  • the binarized cross-sectional image is divided into 10 equal parts in the thickness direction of the negative electrode mixture layer.
  • the area Sf1 of all graphite particles and the area Sf2 of internal voids of all graphite particles are calculated, and (Sf2/Sf1) i is calculated. do.
  • voids with a maximum diameter of 3 ⁇ m or less are regarded as internal voids.
  • FIG. 2 is a schematic cross-sectional view schematically showing the negative electrode.
  • the negative electrode plate 16 has a sheet-like negative electrode current collector 161 and negative electrode mixture layers 162 having a thickness T formed on both sides of the negative electrode current collector 161 .
  • the negative electrode mixture layer 162 is divided into two layers of a first region 162a and a second region 162b having the same thickness, and the first region 162a is closer to the positive electrode than the second region 162b. That is, the first region and the second region each have a thickness of T/2.
  • the first region 162a is a half region of the negative electrode mixture layer 162 on the negative electrode surface side
  • the second region 162b is a half region of the negative electrode mixture layer 162 on the negative electrode current collector 161 side. More first graphite particles are contained in the first region than in the second region, and more second graphite particles are contained in the second region than in the first region.
  • the ability to retain the non-aqueous electrolyte on the surface side of the negative electrode mixture layer is improved.
  • the transfer of the non-aqueous electrolyte between the positive electrode and the negative electrode becomes smooth, and the rapid charge/discharge cycle characteristics are significantly improved.
  • Such an effect becomes apparent when the filling density of the positive electrode mixture layer is significantly increased.
  • the filling density of the positive electrode active material in the positive electrode mixture layer is increased by using the first composite oxide particles and the second composite oxide particles that differ in physical properties and average particle size from each other.
  • the packing density of the positive electrode active material in the positive electrode mixture layer is, for example, 3.5 g/cm 3 or more, and may be 3.55 g/cm 3 or more.
  • the liquid circulation of the positive electrode mixture layer is significantly improved. This is thought to be because when a small amount of non-aqueous electrolyte is supplied from the first region to a small number of voids, the ratio of increase in the non-aqueous electrolyte in the positive electrode mixture layer increases, and the effect of the supplied non-aqueous electrolyte also increases. be done.
  • Such an effect is particularly remarkable when the negative electrode contains a Si-containing material and expands and contracts significantly during charging and discharging.
  • the effect is remarkable when the positive electrode mixture layer and the negative electrode mixture layer are thick. It is considered that this is because the thicker the mixture layer, the more likely the Li reaction unevenness occurs in the thickness direction, which promotes the deterioration of the durability due to the deterioration of the liquid circulation of the positive electrode.
  • the second graphite particles may be contained more in the second region than in the first region.
  • the content rate (% by mass) C22 of the second graphite particles contained in the negative electrode active material in the second region is higher than the content rate (% by mass) C12 of the second graphite particles contained in the negative electrode active material in the first region.
  • C22 may be at least twice as large as C12.
  • the second graphite particles having a large internal porosity are densely filled in the second region when the negative electrode mixture layer is formed by being compressed by rolling, and thus play a role in increasing the negative electrode capacity.
  • C12 may be 0% by mass
  • the region on the second region side of the first region contains the second graphite particles in terms of increasing the capacity of the negative electrode.
  • the diameter of an equivalent circle is obtained from the contour images of the first and second graphite particles in the cross-sectional SEM photograph, and the volume of each particle is determined as a sphere having the same diameter. , and may be obtained using the density of each particle.
  • the negative electrode mixture layer is divided into a first layer having a different shape from each other and at least one other layer other than the first layer, and when the first layer is closest to the positive electrode, the first graphite particles , is preferably contained in the first layer the most.
  • the content of the first graphite particles contained in the negative electrode active material in the first layer may be 90% by mass or more, or may be 100% by mass.
  • the content of the second graphite particles in the first layer may be 0% by mass.
  • the thickness of the first layer may be, for example, 0.1 T or more, or may be 0.2 T or more.
  • the thickness of the first layer may be, for example, 0.5T or less, 0.4T or less, or 0.3T or less.
  • the thickness T of the negative electrode mixture layer is, for example, 65 ⁇ m or more on one side, preferably 70 to 120 ⁇ m on one side.
  • Each layer other than the first layer may or may not contain the first graphite particles.
  • the content of the first graphite particles contained in the negative electrode active material in each layer other than the first layer may be, for example, 30% by mass or less, 10% by mass or less, or 0% by mass.
  • the BET specific surface area of the first graphite particles may be 2.0 m 2 /g or less, or may be 1.5 m 2 /g or less.
  • the BET specific surface area of the second graphite particles may be 3.0 m 2 /g or more, or 4.0 m 2 /g or more.
  • the first graphite particles are less likely to be crushed during rolling in the first region or the first layer, and the second graphite particles are more likely to be densely packed in the second region.
  • the BET specific surface area is measured by a gas adsorption method (BET single-point method). Nitrogen gas is used as the gas.
  • the measuring device for example, an automatic specific surface area/pore size distribution measuring device "Tristar II 3020" manufactured by Shimadzu Corporation is used.
  • the average particle size of the first graphite particles and the second graphite particles may be, for example, 1 ⁇ m or more and 30 ⁇ m or less, or 12 ⁇ m or more and 25 ⁇ m or less.
  • the average particle diameters of the first graphite particles and the second graphite particles may be obtained as the median diameter (D50: particle diameter at cumulative volume of 50%) in each volume-based particle size distribution.
  • the volume-based particle size distribution can be measured by a laser diffraction scattering method. For example, "LA-750" manufactured by HORIBA, Ltd. can be used as the measuring device.
  • diameters of equivalent circles may be obtained from the contour images of the first and second graphite particles in the cross-sectional SEM photograph, and the average value thereof may be obtained.
  • the first graphite particles can be produced, for example, by the following method.
  • Coke precursor
  • a binder is added to the pulverized material, and the pulverized material is aggregated.
  • the average particle size (D50) of the pulverized coke is, for example, 12 ⁇ m or more and 20 ⁇ m or less.
  • the resulting agglomerates are calcined, graphitized and sieved to obtain primary graphite particles of desired size.
  • the firing temperature is, for example, 2600° C. or higher, and may be 2600° C. or higher and 3000° C. or lower.
  • the internal porosity P1 of the first graphite particles can be controlled by, for example, the particle size of coke pulverized matter or aggregates. For example, when the internal porosity P1 is to be decreased, the particle size of the pulverized coke or aggregates may be increased. Further, when part of the binder contained in the agglomerates volatilizes during firing, the internal porosity P1 may be controlled by the amount of the binder added. Pitch is exemplified as such a binder.
  • the second graphite particles can be produced, for example, by the following method.
  • Coke precursor
  • a binder is added to the pulverized material, and the pulverized material is aggregated.
  • the average particle size (D50) of the pulverized coke is, for example, 12 ⁇ m or more and 20 ⁇ m or less.
  • the obtained agglomerate is pressure-molded to obtain a block-shaped compact, which is then sintered and graphitized.
  • the firing temperature is, for example, 2600° C. or higher, and may be 2600° C. or higher and 3000° C. or lower.
  • the density of the compact is, for example, 1.6 g/cm 3 or more and 1.9 g/cm 3 or less.
  • the resulting blocky graphitized material is pulverized and sieved to obtain secondary graphite particles of desired size.
  • the internal porosity P2 of the second graphite particles may be controlled by the particle size of pulverized coke or aggregates.
  • the internal porosity P2 of the second graphite particles may be controlled by the amount of the volatile component added to the block-shaped compact.
  • the binder may also serve as a volatile component added to the compact.
  • the internal porosity P2 may be controlled by the amount of binder added. Pitch is exemplified as such a binder.
  • the internal voids are larger than the first graphite particles.
  • a second graphite particle with a higher modulus may be produced.
  • a negative electrode slurry in which a negative electrode mixture containing a negative electrode active material, a binder, etc. is dispersed in a dispersion medium is applied to the surface of the negative electrode current collector, dried, and the dried coating film is formed. Formed by rolling.
  • the negative electrode mixture contains a negative electrode active material as an essential component, and may contain a binder, a conductive material, a thickener, and the like as optional components. Known materials can be used as the binder, the conductive material, the thickener, and the like.
  • the negative electrode active material includes graphite such as graphitizable carbon (soft carbon) and non-graphitizable carbon (hard carbon) as materials that electrochemically occlude and release lithium ions.
  • graphite such as graphitizable carbon (soft carbon) and non-graphitizable carbon (hard carbon) as materials that electrochemically occlude and release lithium ions.
  • Other carbon materials, alloy materials, and the like may also be included.
  • the alloy-based material contains at least one metal (Si, Sn, Sb, Ge, etc.) capable of forming an alloy with lithium.
  • the content of the material that electrochemically absorbs and releases lithium ions other than the first and second graphite particles contained in the negative electrode active material is preferably 15% by mass or less, 5% by mass or more and 10% by mass or less. is particularly preferred.
  • Si-containing particles with high capacity and inexpensive raw materials are preferable.
  • composite materials containing a lithium ion conductive phase and a silicon phase dispersed therein are preferable.
  • the lithium ion conductive phase include a Si oxide phase containing silicon dioxide as a main component (eg, 95 to 100% by mass), a silicate phase, and a carbon phase composed of carbon with low crystallinity (eg, amorphous carbon). be done.
  • a composite material containing a Si oxide phase and a silicon phase dispersed therein hereinafter referred to as SiO
  • a composite material containing a silicate phase and a silicon phase dispersed therein hereinafter referred to as LSX
  • a carbon phase and a silicon phase dispersed therein It is preferable to use a composite material (hereinafter referred to as Si—C) containing a silicon phase and the like.
  • SiO is preferable because of its high durability.
  • LSX is preferable in terms of high capacity and low irreversible capacity.
  • the average particle size (D50) of the alloy material is, for example, 1 ⁇ m or more and 15 ⁇ m or less.
  • SiO and LSX are particles whose D50 is smaller than that of graphite, for example.
  • the D50 for SiO and LSX may be between 3 ⁇ m and 10 ⁇ m.
  • a conductive layer made of a highly conductive material may be formed on the surface of the SiO and LSX particles.
  • a suitable conductive layer is a carbon coating composed of a carbon material.
  • the thickness of the conductive layer is preferably 1 to 200 nm or 5 to 100 nm in consideration of ensuring conductivity and diffusibility of lithium ions into the particles.
  • SiO has a grain structure in which fine Si particles are dispersed in a Si oxide phase.
  • Suitable SiO has a sea-island structure in which fine Si particles are substantially uniformly dispersed in an amorphous Si oxide matrix, and has the general formula SiO x (0 ⁇ x ⁇ 2 or 0.8 ⁇ x ⁇ 1 .6).
  • the Si oxide phase is composed of aggregates of particles finer than Si particles.
  • the content of Si particles is preferably 35 to 75% by mass with respect to the total mass of SiO from the viewpoint of compatibility between battery capacity and cycle characteristics.
  • the average particle diameter of Si particles dispersed in Si oxide is, for example, 500 nm or less, preferably 200 nm or less or 50 nm or less, before charging and discharging. After charging and discharging, it is, for example, 400 nm or less or 100 nm or less.
  • the average particle diameter of Si particles is obtained by observing the cross section of SiO particles using a SEM or a transmission electron microscope (TEM) and averaging the longest diameters of 100 Si particles.
  • LSX may have a grain structure in which fine Si particles are dispersed in the silicate phase.
  • a suitable LSX has a sea-island structure in which fine Si particles are substantially uniformly dispersed in a lithium silicate matrix.
  • the lithium silicate phase is composed of aggregates of particles finer than Si particles.
  • the content of Si particles is preferably 35 to 75% by mass with respect to the total mass of LSX.
  • the average particle size of the Si particles is, for example, 500 nm or less before charge/discharge, preferably 200 nm or less or 50 nm or less.
  • the content of the main component is preferably more than 50% by mass, more preferably 80% by mass or more, relative to the total mass of the lithium silicate phase. .
  • Si--C may have a carbon phase and Si particles dispersed within the carbon phase.
  • the content of suitable Si—C Si particles is preferably 30% by mass or more and 80% by mass or less, and preferably 35% by mass or more and 75% by mass or less in terms of increasing capacity. , 55% by mass or more and 70% by mass or less.
  • the carbon phase preferably does not contain crystalline carbon in the Si—C particles in order to improve strength.
  • the average particle size of Si particles is generally 500 nm or less, preferably 200 nm or less, and more preferably 100 nm or less before charging and discharging.
  • the thickness is preferably 400 nm or less, more preferably 100 nm or less.
  • the average particle size of silicon particles is measured by observing the cross section of Si—C particles using SEM or TEM, and specifically, it is obtained as the average value of the longest diameters of 100 silicon particles.
  • the silicate phase may contain, for example, at least one selected from the group consisting of Group 1 elements and Group 2 elements of the long period periodic table.
  • Group 1 elements of the long period periodic table and Group 2 elements of the long period periodic table include lithium (Li), potassium (K), sodium (Na), magnesium (Mg), and calcium (Ca). , strontium (Sr), barium (Ba), and the like.
  • Other elements may include aluminum (Al), boron (B), lanthanum (La), phosphorus (P), zirconium (Zr), titanium (Ti), and the like.
  • a lithium silicate phase having a small irreversible capacity and a high initial charge/discharge efficiency is particularly preferable.
  • the lithium silicate phase may be an oxide phase containing lithium (Li), silicon (Si), and oxygen (O), and may contain other elements.
  • the atomic ratio of O to Si: O/Si in the lithium silicate phase is greater than 2 and less than 4, for example.
  • O/Si is greater than 2 and less than 3.
  • the atomic ratio of Li to Si in the lithium silicate phase: Li/Si is greater than 0 and less than 4, for example.
  • binders include fluorine-based resins, polyacrylonitrile (PAN), polyimide-based resins, acrylic-based resins, polyolefin-based resins, styrene-butadiene rubber (SBR), carboxymethylcellulose (CMC) or salts thereof, and polyacrylic acid.
  • PAN polyacrylonitrile
  • SBR styrene-butadiene rubber
  • CMC carboxymethylcellulose
  • PAA polyacrylic acid
  • PAA polyacrylonitrile
  • PAA polyimide-based resins
  • acrylic-based resins acrylic-based resins
  • polyolefin-based resins polyolefin-based resins
  • CMC carboxymethylcellulose
  • PVA polyvinyl alcohol
  • PVA polyvinyl alcohol
  • Examples of conductive materials include carbon black (CB), acetylene black (AB), ketjen black, carbon nanotubes (CNT), and carbon-based particles such as graphite. These may be used alone or in combination of two or more.
  • a negative electrode mixture slurry for the first region is prepared by mixing a negative electrode active material containing first graphite particles and a Si-containing material, a binder, and the like with a solvent such as water.
  • second graphite particles may be added to the slurry, for example, in order to adjust the average value of the internal porosity of the graphite particles.
  • the negative electrode mixture slurry for the second region is prepared by mixing the negative electrode active material containing the second graphite particles and the Si-containing material, the binder, etc. with a solvent such as water. .
  • the first graphite particles may be added to the slurry, for example, in order to adjust the average value of the internal porosity of the graphite particles.
  • the negative electrode mixture slurry for the second region is applied to both surfaces of the negative electrode current collector and dried.
  • the negative electrode mixture slurry for the first region is applied onto the coating films of the negative electrode mixture slurry for the second region on both surfaces, and dried.
  • a negative electrode mixture layer is formed.
  • the negative electrode mixture slurry for the second region is applied, dried, and then the negative electrode mixture slurry for the first region is applied.
  • the present invention is not limited to this, and the negative electrode mixture slurry for the first region may be applied after applying the negative electrode mixture slurry for the second region and before drying, or the negative electrode mixture slurry for the second region may be applied. and the negative electrode mixture slurry for the first region may be applied at the same time.
  • a non-porous conductive substrate (metal foil, etc.) or a porous conductive substrate (mesh body, net body, punching sheet, etc.) is used for the negative electrode current collector.
  • materials for the negative electrode current collector include stainless steel, nickel, nickel alloys, copper, and copper alloys.
  • the thickness of the negative electrode current collector is, for example, 5 ⁇ m or more and 30 ⁇ m or less, may be 8 ⁇ m or more and 20 ⁇ m or less, or may be 10 ⁇ m or more and 15 ⁇ m or less.
  • a non-aqueous electrolyte includes a non-aqueous solvent and a solute dissolved in the non-aqueous solvent.
  • a solute is an electrolyte salt that ionically dissociates in a non-aqueous solvent. Solutes include, for example, lithium salts.
  • non-aqueous solvents examples include chain nitriles, cyclic ethers, chain ethers, cyclic carbonates, chain carbonates, cyclic carboxylates, and chain carboxylates.
  • Cyclic carbonates include vinyl ethylene carbonate (VEC), propylene carbonate (PC), ethylene carbonate (EC), vinylene carbonate (VC), fluoroethylene carbonate (FEC) and the like.
  • Chain carbonates include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC) and the like.
  • cyclic carboxylic acid esters include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
  • Chain carboxylic acid esters include methyl acetate, ethyl acetate, propyl acetate, methyl propionate (MP), ethyl propionate (EP) and the like.
  • the non-aqueous solvent may be used singly or in combination of two or more.
  • As the chain nitrile, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, pivalonitrile, succinonitrile, adiponitrile, pimeronitrile, etc. can be used, and these may be used alone or in combination of two or more. may be used.
  • 1,3-dioxolane, 1,4-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran and the like can be used, and these may be used alone or in combination of two or more.
  • chain ether 1,2-dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether and the like can be used, and these may be used alone or in combination of two or more. .
  • lithium salts include LiSO3CF3 , lithium difluorooxalateborate , lithium bisoxalateborate, LiPF6 , LiPF2O2 , LiBF4 , LiSbF6 , LiAsF6 , LiCF3SO3 , LiCF3CO2 . , LiClO4 , LiAlCl4 , LiB10Cl10 , LiN ( FSO2 ) 2 , LiN( CF3SO2 ) 2 , LiN( CF3SO2 ) ( C4F9SO2 ) , LiN( C2F5 SO 2 ) 2 , LiCl, LiBr, LiI and the like can be used.
  • Lithium salts may be used singly or in combination of two or more.
  • the concentration of the lithium salt in the non-aqueous electrolyte may be 1 mol/liter or more and 2 mol/liter or less, or may be 1 mol/liter or more and 1.5 mol/liter or less. Thereby, a non-aqueous electrolyte having excellent ionic conductivity and moderate viscosity can be obtained.
  • the lithium salt concentration is not limited to the above.
  • the non-aqueous electrolyte may contain additives in addition to the non-aqueous solvent and electrolyte salt.
  • the additive include sulfonate, sulfate, sulfite, and isocyanate compounds.
  • Sulfonic acid esters include 1,3-propanesultone (PS), 1,4-butanesultone, 1,3-propenesultone (PRES), 1,4-butenesultone and the like.
  • Sulfate esters include ethylene sulfate and the like.
  • Sulfites include ethylene sulfite (ethylene sulfite) and the like.
  • isocyanate compounds include 1,6-diisocyanatohexane (hexamethylene diisocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, and the like.
  • the additive content may be, for example, 0.01% by mass or more and 5% by mass or less.
  • the separator has high ion permeability and moderate mechanical strength and insulation.
  • a microporous thin film, a woven fabric, a nonwoven fabric, or the like can be used as the separator.
  • Polyolefins such as polypropylene and polyethylene are preferable as the material of the separator.
  • a separator whose surface is coated with a material such as aramid resin or ceramic may be used.
  • FIG. 3 is a vertical cross-sectional view of a cylindrical non-aqueous electrolyte secondary battery according to one embodiment of the present disclosure.
  • the non-aqueous electrolyte secondary battery 10 includes an electrode group 18, an electrolytic solution (not shown), and a bottomed cylindrical battery can 22 containing them.
  • a sealing member 11 is crimped and fixed to the opening of the battery can 22 via a gasket 21 . The inside of the battery is thereby sealed.
  • the sealing body 11 includes 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 15 a led out from the positive electrode plate 15 is connected to the metal plate 13 . Therefore, the valve body 12 functions as a positive external terminal.
  • a negative lead 16 a led out from the negative plate 16 is connected to the inner surface of the bottom of the battery can 22 .
  • An annular groove 22 a is formed near the open end of the battery can 22 .
  • a first insulating plate 23 is arranged between one end face of the electrode group 18 and the annular groove portion 22a.
  • a second insulating plate 24 is arranged 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 the positive electrode plate 15 and the negative electrode plate 16 with the separator 17 interposed therebetween.
  • the volume-based particle size distribution of each of the first composite oxide particles and the second composite oxide particles measured by a laser diffraction scattering method using "LA-750" manufactured by HORIBA, Ltd. before the production of the positive electrode All of the median diameters substantially coincided with the first average particle diameter D1 and the second average particle diameter D2.
  • a positive electrode slurry was prepared by mixing parts by mass, 0.6 parts by mass of acetylene black, 0.6 parts by mass of polyvinylidene fluoride, and an appropriate amount of N-methyl-2-pyrrolidone (NMP). Therefore, the content C1 of the first composite oxide particles contained in the positive electrode active material is 40% by mass, and the content C2 of the second composite oxide particles is 60% by mass. These numerical values almost coincided with the contents C1 and C2 obtained by the method described above.
  • the positive electrode slurry is applied to the surface of an aluminum foil, which is a positive electrode current collector, and the coating film is dried and then rolled to obtain a positive electrode having a positive electrode mixture layer (thickness on one side: 87.5 ⁇ m) on both sides of the aluminum foil.
  • the packing density of the positive electrode active material in the positive electrode mixture layer after rolling is 3.55 g/cm 3
  • the pore mode diameter obtained by the above-described method is 0.30 ⁇ m, and the diameter is in the range of 3 nm to 109.4 ⁇ m.
  • Total pore volume was 0.08 mL/g.
  • the internal porosity P1 of the first graphite particles measured by the above-described method from the SEM image of the cross section in the thickness direction of the negative electrode mixture layer produced by the procedure described later was set to 3%.
  • the internal porosity P1 was adjusted by adjusting the amount of pitch added during the production process of the first graphite particles.
  • the BET specific surface area of the first graphite particles measured by the method described above was 1.5 m 2 /g.
  • the internal porosity P2 of the second graphite particles measured by the above-described method from the SEM image of the cross section in the thickness direction of the negative electrode mixture layer produced by the procedure described later was set to 15%.
  • the internal porosity P2 was adjusted by adjusting the amount of pitch added during the production process of the second graphite particles.
  • the BET specific surface area of the second graphite particles measured by the method described above was 4.0 m 2 /g.
  • first negative electrode slurry 100 parts by mass of the first negative electrode active material, which is a mixture of the first graphite particles and the alloy material at a mass ratio of 95:5, 1 part by mass of styrene-butadiene copolymer rubber (SBR), and 1 part of carboxymethyl cellulose (CMC) A mixture with parts by mass was prepared as a first negative electrode mixture. An appropriate amount of water was added to the first negative electrode mixture to prepare a first negative electrode slurry.
  • the coating amount of the conductive carbon was 5 parts by mass per 100 parts by mass of the total of the SiOx particles and the conductive carbon.
  • a second negative electrode slurry was prepared in the same manner as the first negative electrode slurry, except that the second graphite particles were used instead of the first graphite particles.
  • the second negative electrode slurry was applied to both sides of a copper foil (thickness 10 ⁇ m) as a negative electrode current collector, and after drying the coating film, the first negative electrode slurry was applied thereon and the coating film was dried.
  • a doctor blade method was used to apply the first negative electrode slurry and the second negative electrode slurry.
  • the coating amounts of the first negative electrode slurry and the second negative electrode slurry were the same.
  • the application amount of the negative electrode slurry refers to the mass of the negative electrode slurry applied per unit area of the negative electrode current collector.
  • the dried two-layered coating film was rolled to prepare a negative electrode having negative electrode mixture layers (thickness on one side: 91 ⁇ m) on both sides of the negative electrode current collector.
  • the packing density of the negative electrode active material in the negative electrode mixture layer after rolling was 1.5 g/cm 3 .
  • the average value Pf measured by the method described above was 13%, and the average value Ps was 20%.
  • a non-aqueous electrolyte was prepared by adding LiPF6 as a lithium salt to a mixed solvent containing fluoroethylene carbonate (FEC), ethyl methyl carbonate (EMC) and dimethyl ether (DME) at a volume ratio of 4:1:15.
  • the LiPF 6 concentration in the non-aqueous electrolyte was set to 1.0 mol/liter.
  • a lead tab was attached to each electrode, and an electrode group was produced by spirally winding the positive electrode and the negative electrode through a separator so that the lead was located at the outermost periphery. After inserting the electrode group into an outer package made of a laminated film with aluminum foil as a barrier layer and vacuum drying at 105 ° C. for 2 hours, a non-aqueous electrolyte was injected, the opening of the outer package was sealed, and battery A1. got
  • Example 2 In the preparation of the first negative electrode slurry, a mixture of the first graphite particles and the alloy material with a mass ratio of 90:10 is used, and in the preparation of the second negative electrode slurry, the mass ratio of the second graphite particles and the alloy material is 90:10.
  • a negative electrode was prepared in the same manner as in Example 1, except that the mixture was used.
  • Battery A2 was obtained in the same manner as in Example 1, except that this negative electrode was used.
  • the average value Pf measured by the method described above was 5%, and the average value Ps was 20%.
  • Example 3 In the preparation of the positive electrode slurry, the same as in Example 1 except that 0.5 parts by mass of MWCNT (average fiber length 0.9 ⁇ m, average fiber diameter 20 nm) was used with respect to 100 parts by mass of the positive electrode active material, and acetylene black was not used. A positive electrode was produced in Battery A3 was obtained in the same manner as in Example 2, except that this positive electrode was used.
  • the packing density of the positive electrode active material in the positive electrode mixture layer after rolling is 3.55 g/cm 3
  • the pore mode diameter obtained by the above-described method is 0.35 ⁇ m
  • the diameter is in the range of 3 nm to 109.4 ⁇ m.
  • Total pore volume was 0.08 mL/g.
  • Example 4 In the preparation of the positive electrode slurry, the positive electrode was prepared in the same manner as in Example 3, except that 0.1 part by mass of SWCNT (average fiber length 3 ⁇ m, average fiber diameter 10 nm) was used instead of MWCNT with respect to 100 parts by mass of the positive electrode active material. made. Battery A4 was obtained in the same manner as in Example 2, except that this positive electrode was used.
  • the packing density of the positive electrode active material in the positive electrode mixture layer after rolling is 3.55 g/cm 3
  • the pore mode diameter obtained by the above-described method is 0.50 ⁇ m
  • the diameter is in the range of 3 nm to 109.4 ⁇ m.
  • Total pore volume was 0.08 mL/g.
  • Example 1 A negative electrode was produced in the same manner as in Example 2, except that only the second negative electrode slurry was used in producing the negative electrode.
  • the coating amount of the second negative electrode slurry was the same as the total coating amount of the first negative electrode slurry and the second negative electrode slurry in Example 1, and the thickness of the negative electrode mixture layer was the same as in Example 1.
  • Battery B1 was obtained in the same manner as in Example 3, except that this negative electrode was used.
  • Example 3 except that 100 parts by mass of the second composite oxide particles were used instead of the mixture of the first composite oxide particles and the second composite oxide particles in a mass ratio of 4:6 in the preparation of the positive electrode slurry.
  • a positive electrode was prepared in the same manner.
  • the packing density of the positive electrode active material in the positive electrode mixture layer after rolling was 3.55 g/cm 3 as in Example 1.
  • the pore mode diameter determined by the method described above was 0.6, and the total pore volume in the range of 3 nm to 109.4 ⁇ m was 0.08 mL/g.
  • a battery B2 was obtained in the same manner as in Comparative Example 1, except that this positive electrode was used.
  • Example 3 except that 100 parts by mass of the second composite oxide particles were used instead of the mixture of the first composite oxide particles and the second composite oxide particles in a mass ratio of 4:6 in the preparation of the positive electrode slurry.
  • a positive electrode was prepared in the same manner.
  • a battery B3 was obtained in the same manner as in Example 2, except that this positive electrode was used.
  • Example 3 except that 100 parts by mass of the first composite oxide particles were used instead of the mixture of the first composite oxide particles and the second composite oxide particles in a mass ratio of 4:6 in the preparation of the positive electrode slurry.
  • a positive electrode was prepared in the same manner.
  • the packing density of the positive electrode active material in the positive electrode mixture layer after rolling is 3.55 g/cm 3
  • the pore mode diameter obtained by the above-described method is 0.20
  • the diameter is in the range of 3 nm to 109.4 ⁇ m.
  • Total pore volume was 0.08 mL/g.
  • a battery B4 was obtained in the same manner as in Comparative Example 1, except that this positive electrode was used.
  • Example 3 except that 100 parts by mass of the first composite oxide particles were used instead of the mixture of the first composite oxide particles and the second composite oxide particles in a mass ratio of 4:6 in the preparation of the positive electrode slurry.
  • a positive electrode was prepared in the same manner.
  • a battery B4 was obtained in the same manner as in Example 3, except that this positive electrode was used.
  • a negative electrode was produced in the same manner as in Example 3, except that only the first negative electrode slurry was used in the production of the negative electrode.
  • the coating amount of the first negative electrode slurry was the same as the total coating amount of the first negative electrode slurry and the second negative electrode slurry in Example 1, and the thickness of the negative electrode mixture layer was the same as in Example 1.
  • a battery B6 was obtained in the same manner as in Example 3, except that this negative electrode was used.
  • Table 1 shows the evaluation results of the initial capacity C0 and the capacity retention rate R1 of the batteries A1 to A4 and B1 to B6. From Table 1, it can be understood that the batteries A1 to A4 have significantly improved capacity retention rates in rapid charge/discharge cycles. Also, it can be understood that it is difficult to increase the initial capacity when only one of the first composite oxide and the second composite oxide is used.
  • a non-aqueous electrolyte secondary battery according to the present disclosure is useful as a main power source for mobile communication devices, portable electronic devices, hybrid vehicles, electric vehicles, and the like.

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JP2024179925A (ja) * 2023-06-16 2024-12-26 プライムプラネットエナジー＆ソリューションズ株式会社 二次電池の負極、および当該負極を用いた二次電池
EP4492488A2 (en) 2023-07-12 2025-01-15 Prime Planet Energy & Solutions, Inc. Nonaqueous electrolyte secondary battery
KR20250010553A (ko) 2023-07-12 2025-01-21 프라임 플래닛 에너지 앤드 솔루션즈 가부시키가이샤 비수전해질 이차 전지
JP2025011910A (ja) * 2023-07-12 2025-01-24 プライムプラネットエナジー＆ソリューションズ株式会社 非水電解質二次電池
EP4492488A3 (en) * 2023-07-12 2025-02-19 Prime Planet Energy & Solutions, Inc. Nonaqueous electrolyte secondary battery
JP7825599B2 (ja) 2023-07-12 2026-03-06 プライムプラネットエナジー＆ソリューションズ株式会社 非水電解質二次電池
JP2025534908A (ja) * 2023-07-28 2025-10-21 エルジー エナジー ソリューション リミテッド 負極およびリチウム二次電池
WO2025264041A1 (ko) * 2024-06-21 2025-12-26 주식회사 엘지에너지솔루션 양극 활물질층 조성물, 양극 및 이를 포함하는 이차전지

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