WO2024247854A1 - 非水電解液二次電池の正極用組成物、正極シート、及び非水電解液二次電池 - Google Patents

非水電解液二次電池の正極用組成物、正極シート、及び非水電解液二次電池 Download PDF

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WO2024247854A1
WO2024247854A1 PCT/JP2024/018890 JP2024018890W WO2024247854A1 WO 2024247854 A1 WO2024247854 A1 WO 2024247854A1 JP 2024018890 W JP2024018890 W JP 2024018890W WO 2024247854 A1 WO2024247854 A1 WO 2024247854A1
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positive electrode
active material
electrode active
particle group
electrolyte secondary
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French (fr)
Japanese (ja)
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広 磯島
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Fujifilm Corp
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Fujifilm Corp
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Priority to EP24815338.9A priority Critical patent/EP4723208A1/en
Priority to CN202480031164.2A priority patent/CN121079789A/zh
Priority to JP2025524027A priority patent/JPWO2024247854A1/ja
Publication of WO2024247854A1 publication Critical patent/WO2024247854A1/ja
Priority to US19/378,255 priority patent/US20260066291A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M2004/028—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

  • Non-aqueous electrolyte secondary batteries such as lithium-ion secondary batteries
  • larger batteries are being used in automobiles and other transportation equipment, and their use as storage devices for nighttime electricity and electricity generated by natural energy sources is also progressing.
  • the electrodes (positive and negative electrodes) of a non-aqueous electrolyte secondary battery generally have an electrode active material layer (positive electrode active material layer or negative electrode active material layer), and this electrode active material layer contains electrode active material particles capable of absorbing or releasing lithium ions during charging and discharging.
  • the electrode active material layer is usually formed by preparing a slurry (composition) containing constituent components of the electrode active material layer such as the electrode active material, applying the slurry, and drying the slurry. In order to improve the performance of non-aqueous electrolyte secondary batteries, studies have been conducted focusing on the positive electrode active material layer.
  • Patent Document 1 states: A method for manufacturing an electrode for a lithium ion secondary battery is disclosed, which includes: preparing a first composite particle containing a first active material and a first binder; and a second composite particle having a higher fluidity than the first composite particle and containing a second active material and a second binder; setting a strip-shaped current collector at at least one end along the longitudinal direction of a long current collector, and supplying the first composite particle to a first portion which is a strip-shaped region adjacent to the current collector; supplying the second composite particle to a second portion which is a region on the width direction center side perpendicular to the longitudinal direction of the current collector than the first portion; and rolling the first and second composite particles supplied onto the current collector to form an active material layer; and in the examples, evaluation is performed on a positive electrode sheet having a positive electrode active material layer formed by the manufacturing method. According to the technology of Patent Document 1, it is said that an electrode can be manufactured while suppressing peeling and sliding of the active material layer.
  • Patent Document 2 states: The battery includes a positive electrode having a conductive substrate and a positive electrode mixture layer laminated on the substrate, the substrate is made of an aluminum alloy having a content ratio of elements other than aluminum of 1 mass % or more, The positive electrode mixture layer contains particles A and particles B having different particle diameters as a positive electrode active material, a particle size ratio (A/B) of the particle size of the particle A to the particle size of the particle B is 3 or more;
  • the nonaqueous electrolyte storage element has a substrate having a tensile breaking strength of 250 MPa or more.
  • the technology of Patent Document 2 is said to be capable of suppressing an increase in resistance caused by repeated charging and discharging.
  • non-aqueous electrolyte secondary batteries with high energy density (high capacity).
  • non-aqueous electrolyte secondary batteries are used as power sources for EVs (Electric Vehicles) and drones, and in order to improve the driving range of EVs and the flight time of drones, it is important to increase the capacity of non-aqueous electrolyte secondary batteries.
  • EVs Electric Vehicles
  • the capacity (energy density) of non-aqueous electrolyte secondary batteries there are attempts to increase the content of the positive electrode active material that stores ions in the positive electrode active material layer and conversely reduce the content of the binder.
  • the amount of the positive electrode active material is increased by reducing the amount of the binder added in the positive electrode composition or the positive electrode active material layer used to form the positive electrode active material layer, or by thickly applying the positive electrode composition to form a thick positive electrode active material layer, there is a problem that the end of the formed positive electrode active material layer partially collapses during the manufacturing process of the non-aqueous electrolyte secondary battery, making it difficult to form a positive electrode active material layer having a desired shape (for example, a rectangular cross section).
  • the present invention aims to provide a positive electrode composition that has excellent formability (shape stability) of the positive electrode active material layer and can produce a nonaqueous electrolyte secondary battery that exhibits excellent battery performance.
  • Another objective of the present invention is to provide a positive electrode sheet having a positive electrode active material layer formed using this positive electrode composition, and a nonaqueous electrolyte secondary battery in which this positive electrode sheet is incorporated into the positive electrode.
  • the inventors have conducted extensive research in light of the above problems and have found that when a positive electrode active material with a specific particle size distribution is used as the positive electrode active material contained in the positive electrode composition for forming the positive electrode active material layer, and the surface tension of a specific small particle positive electrode active material is increased to a specific range, the collapse of the resulting positive electrode active material layer is suppressed, even if the amount of binder in the positive electrode composition or positive electrode active material layer is reduced or the positive electrode active material layer is formed thick, and a positive electrode active material layer with a desired shape can be efficiently formed, and further, a higher capacity can be achieved for the resulting nonaqueous electrolyte secondary battery.
  • the present invention was completed after further research based on this knowledge.
  • a composition for a positive electrode of a non-aqueous electrolyte secondary battery comprising: A positive electrode active material including a large particle group A having a particle size of 5.0 ⁇ m or more and a small particle group B having a particle size of less than 5.0 ⁇ m,
  • a positive electrode active material including a large particle group A having a particle size of 5.0 ⁇ m or more and a small particle group B having a particle size of less than 5.0 ⁇ m
  • Formula B1 15.0 ⁇ B ⁇ 40.0 [2]
  • a numerical range expressed using “to” means a range including the numerical values before and after “to” as the lower and upper limits.
  • the term “non-aqueous electrolyte” refers to an electrolyte that does not substantially contain water. That is, the “non-aqueous electrolyte” may contain a small amount of water within a range that does not impede the effects of the present invention.
  • the "non-aqueous electrolyte” has a water concentration of 200 ppm (by mass) or less, preferably 100 ppm or less, and more preferably 20 ppm or less.
  • the "non-aqueous solvent” also means a solvent that does not substantially contain water. That is, the “non-aqueous solvent” may contain a small amount of water within a range that does not impede the effects of the present invention.
  • the "non-aqueous solvent” has a water concentration of 200 ppm (by mass) or less, preferably 100 ppm or less, and more preferably 20 ppm or less. Note that it is practically difficult to make a non-aqueous solvent completely anhydrous, and it usually contains 1 ppm or more of water.
  • the positive electrode composition of the nonaqueous electrolyte secondary battery of the present invention can be used to form a positive electrode active material layer that is less likely to collapse.
  • the positive electrode sheet of the present invention has excellent shape stability of the positive electrode active material layer, and by incorporating this as the positive electrode of a nonaqueous electrolyte secondary battery, a nonaqueous electrolyte secondary battery that exhibits excellent battery performance can be obtained.
  • the nonaqueous electrolyte secondary battery of the present invention has excellent shape stability of the positive electrode active material layer and also has excellent battery performance.
  • FIG. 1 is a vertical cross-sectional view showing a schematic diagram of a basic layered structure of an embodiment of a secondary battery according to the present invention.
  • the positive electrode composition of the nonaqueous electrolyte secondary battery of the present invention contains a positive electrode active material consisting of a large particle group A having a particle size of 5.0 ⁇ m or more and a small particle group B having a particle size of less than 5.0 ⁇ m.
  • a positive electrode active material consisting of a large particle group A having a particle size of 5.0 ⁇ m or more and a small particle group B having a particle size of less than 5.0 ⁇ m.
  • the positive electrode composition of the present invention can be suitably used as a material for forming a positive electrode active material layer constituting a nonaqueous electrolyte secondary battery.
  • the positive electrode composition of the present invention is usually a slurry in which solid particles such as a positive electrode active material and a conductive assistant are dispersed in a liquid medium.
  • the positive electrode composition of the present invention is composed of a positive electrode active material consisting of a large particle group A and a small particle group B, and the surface tension of the small particle group B is controlled within the above range, thereby increasing the surface activity of the small particle group B and effectively increasing the interaction (adhesion) between the solid particles or with the binder.
  • the thickness of the positive electrode active material layer formed is about 250 ⁇ m or the amount of binder used is reduced, the formed positive electrode active material layer has excellent shape stability, and the battery capacity of the obtained nonaqueous electrolyte secondary battery can be sufficiently increased.
  • the positive electrode active material constituting the positive electrode composition of the present invention is composed of a large particle group A having a particle size of 5.0 ⁇ m or more and a small particle group B having a particle size of less than 5.0 ⁇ m. That is, the positive electrode active material used in the present invention is roughly divided into a large particle group having a particle size including the threshold particle size of 5.0 ⁇ m and a particle group having a particle size smaller than this threshold particle size.
  • the particle size can be measured using a particle size measuring device in accordance with the method for measuring particle size distribution based on number, which will be described later.
  • the frequency of the large particle group A (the number of particles of the positive electrode active material classified into the large particle group A) is preferably 60 to 90%, more preferably 60 to 80%, and further preferably 65 to 75%.
  • the frequency of small particle group B (the number of positive electrode active material particles classified into small particle group B) is preferably 10 to 40%, more preferably 20 to 40%, and even more preferably 25 to 35%.
  • the frequency can be controlled by mixing and using positive electrode active materials having different median diameters.
  • the number-based particle size distribution of the positive electrode active material can be obtained by the method described in the Examples.
  • the surface tension of the small particle group B with respect to N-methylpyrrolidone (NMP) is controlled to satisfy the formula B1: 15.0 ⁇ B ⁇ 40.0. If the surface tension ⁇ B is too low, the interaction between the small particle group B particles and the binder cannot be increased to a desired level, and the formed positive electrode active material layer is prone to collapse. On the other hand, if the surface tension ⁇ B is too high, the formed positive electrode active material layer becomes powdery and is also prone to collapse.
  • the surface tension ⁇ B of the small particle group B with respect to N-methylpyrrolidone preferably satisfies the following formula B2, and more preferably satisfies formula B3.
  • the surface tension (surface free energy) of the small particle group B with respect to NMP means the surface tension of the small particle group B as a whole with respect to NMP, and can be measured by a penetration rate method.
  • the surface tension of the small particle group B with respect to NMP is specified, but the dispersion medium used in the positive electrode composition of the present invention is not limited to NMP, and various dispersion media described later can be used. The method for measuring the surface tension of the positive electrode active material will be described in detail below.
  • the penetration weight W L (g) is measured in the same manner as above, except that NMP solvent is used instead of hexadecane.
  • W L 2 /t calculated from the actual weight and penetration time and ⁇ 2 r obtained above are substituted into the Washburn equation along with ⁇ L , ⁇ L , and ⁇ L of NMP below to derive the contact angle cos ⁇ of the positive electrode active material with NMP.
  • the obtained contact angle cos ⁇ can be substituted into the following formula to obtain the surface tension ⁇ B.
  • ⁇ B ⁇ NMP ⁇ cos ⁇
  • ⁇ NMP is the surface tension of N-methylpyrrolidone (40.3 mN/m), and this surface tension is a constant.
  • the surface tension of the small particle group B against the NMP can be controlled by subjecting at least the positive electrode active material classified into the small particle group B to a surface smoothing treatment in advance and blending this in the positive electrode composition.
  • this surface smoothing treatment include mixing.
  • the atmosphere during the surface smoothing treatment is not particularly limited, and it is preferable to perform the surface smoothing treatment under an inert gas atmosphere in order to prevent oxidation of the active material particle surface during treatment. For example, mixing under an argon atmosphere, a nitrogen atmosphere, a nitrogen-hydrogen mixed atmosphere, etc. can be mentioned.
  • the treatment device in the surface smoothing treatment is not particularly limited, and examples thereof include a planetary ball mill (trade name: P-5, manufactured by Fritsch), a jet mill crusher (trade name: JETMILL100, manufactured by Powrex Corporation), a powder treatment device Nobilta (trade name: NOB MINI, manufactured by Hosokawa Micron Corporation), and a powder treatment device Composite (trade name: CP15, manufactured by Nippon Coke and Engineering Co., Ltd.).
  • the treatment conditions for the above surface smoothing treatment are not particularly limited.
  • mixing can be performed using a powder processing device Nobilta (product name: NOB MINI, manufactured by Hosokawa Micron Corporation) in a nitrogen atmosphere at a rotation speed of 5,000 to 9,000 rpm for a treatment time of 5 to 20 minutes.
  • NOB MINI powder processing device Nobilta
  • the surface tension ⁇ A (mN/m) of the large particle group A with respect to N-methylpyrrolidone (NMP) preferably satisfies the following formula A0, preferably satisfies formula A1, and more preferably satisfies formula A2.
  • the surface tension ⁇ B of the small particle group B has a larger effect on the interparticle interaction than the surface tension ⁇ A of the large particle group A because the surface area of the small particle group B is larger.
  • the surface tension of the large particle group A against NMP can be controlled within the above range by subjecting the large particle group A to a surface smoothing treatment, similar to that of the small particle group B.
  • the surface smoothing treatment is the same as that described for the small particle group B.
  • the surface tension ⁇ A of the large particle group A in N-methylpyrrolidone (NMP) means the surface tension of the large particle group A as a whole in NMP, and can be measured in the same manner as the surface tension ⁇ B of the small particle group B in NMP.
  • the closest packing rate of the positive electrode active material calculated from the cumulative particle size distribution based on volume of the positive electrode active material is preferably 75% or more, more preferably 80% or more.
  • the packing rate of the positive electrode active material in the obtained positive electrode active material layer can be increased.
  • This close packing ratio is an estimated value calculated based on data on the volume-based cumulative particle size distribution of the positive electrode active material contained in the positive electrode composition of the present invention. Specifically, the closest packing ratio can be calculated by the method described in the examples of the present invention.
  • the specific surface area of the small particle group B is preferably 8.0 to 13.0 m 2 /g, and more preferably 9.0 to 12.5 m 2 /g.
  • the specific surface area of the large particle group A is preferably 5.0 to 8.5 m 2 /g, and more preferably 5.2 to 8.3 m 2 /g.
  • the specific surface area of each of the large particle group A and the small particle group B can be measured by the BET method as described below. -BET specific surface area measurement method- 0.2 g of a sample is dried at 120° C. for 6 hours, and then measured using a BELSORP mini (product name) manufactured by Microtrac under the following measurement conditions.
  • Adsorption gas N2 Equilibration time: 100 seconds
  • a positive electrode active material having a large median diameter (D50) and a positive electrode active material having a small median diameter (D50) can be mixed and used as the positive electrode active material.
  • the median diameter (D50) of the positive electrode active material (positive electrode active material a, large particle group a) having a large median diameter (D50) can be 6.0 to 20.0 ⁇ m, preferably 7.0 to 15.0 ⁇ m, more preferably 8.0 to 14.0 ⁇ m, and even more preferably 8.3 to 13.0 ⁇ m.
  • the median diameter (D50) of the positive electrode active material (positive electrode active material b, small particle group b) having a small median diameter (D50) can be 0.1 to 4.0 ⁇ m, preferably 0.2 to 3.0 ⁇ m, more preferably 0.5 to 2.0 ⁇ m, and even more preferably 0.8 to 1.2 ⁇ m.
  • a normal grinder or classifier may be used in order to make the positive electrode active material a (large particle group a) and the positive electrode active material b (small particle group b) have a predetermined median diameter (D50).
  • the positive electrode active material obtained by the firing method may be used after washing with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the median diameter (D50) of the positive electrode active material a (large particle group a) and the positive electrode active material b (small particle group b) can be measured by the following method. -Method of measuring median diameter (D50)-
  • the positive electrode active material is dispersed in water, and the particle size (volume-based median diameter D50 in water) obtained by measuring the particle size distribution using a laser diffraction/scattering particle size distribution measuring device (e.g., Particle LA-960V2 manufactured by HORIBA) is used. This also applies to the median diameter (D50) of solid particles other than the positive electrode active material.
  • the positive electrode composition of the present invention may contain the same components as a typical positive electrode composition, except that it contains a positive electrode active material consisting of the large particle group A and the small particle group B.
  • a positive electrode active material consisting of the large particle group A and the small particle group B.
  • it may contain a conductive assistant, a binder, a dispersion medium, etc.
  • the positive electrode active material is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited, and examples thereof include transition metal oxides, organic substances, and substances that can be composited with Li, such as sulfur, and also include composites of sulfur and metals.
  • the positive electrode active material it is preferable to use a lithium-containing transition metal oxide, and a lithium-containing transition metal oxide having a transition metal element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu and V) is more preferable.
  • this lithium-containing transition metal oxide may be mixed with an element M b (an element of the first (Ia) group of the periodic table other than lithium, an element of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P or B, etc.).
  • the amount of the mixture is preferably 0 to 30 mol% with respect to the amount of the transition metal element M a (100 mol%). It is more preferable to mix and synthesize the Li/M a so that the molar ratio is 0.3 to 2.2.
  • lithium-containing transition metal oxide examples include (MA) a lithium-containing transition metal oxide having a layered rock salt structure, (MB) a lithium-containing transition metal oxide having a spinel structure, (MC) a lithium-containing transition metal phosphate compound, (MD) a lithium-containing transition metal halide phosphate compound, and (ME) a lithium-containing transition metal silicate compound.
  • MA a lithium-containing transition metal oxide having a layered rock salt structure
  • MB lithium-containing transition metal oxide having a spinel structure
  • MC lithium-containing transition metal phosphate compound
  • MD lithium-containing transition metal halide phosphate compound
  • ME lithium-containing transition metal silicate compound
  • lithium - containing transition metal oxides having a layered rock salt structure include LiCoO2 (lithium cobalt oxide [LCO]), LiNi2O2 (lithium nickel oxide ) , LiNi0.85Co0.10Al0.05O2 (lithium nickel cobalt aluminum oxide [NCA]), LiNi1 /3Co1 / 3Mn1 / 3O2 (lithium nickel manganese cobalt oxide [NMC]), and LiNi0.5Mn0.5O2 (lithium manganese nickel oxide ) .
  • LiCoO2 lithium cobalt oxide [LCO]
  • LiNi2O2 lithium nickel oxide
  • LiNi0.85Co0.10Al0.05O2 lithium nickel cobalt aluminum oxide [NCA]
  • LiNi1 /3Co1 / 3Mn1 / 3O2 lithium nickel manganese cobalt oxide [NMC]
  • LiNi0.5Mn0.5O2 lithium manganese nickel oxide
  • lithium - containing transition metal oxides having a spinel structure examples include LiMn2O4 ( LMO ) , LiCoMnO4 , Li2FeMn3O8 , Li2CuMn3O8 , Li2CrMn3O8 , and Li2NiMn3O8 .
  • lithium-containing transition metal phosphate compounds include olivine-type iron phosphates such as LiFePO4 and Li3Fe2 ( PO4 ) 3 , iron pyrophosphates such as LiFeP2O7 , cobalt phosphates such as LiCoPO4 , and monoclinic Nasicon-type vanadium phosphates such as Li3V2 ( PO4 ) 3 (lithium vanadium phosphate).
  • the lithium-containing transition metal halophosphate compound include iron fluorophosphates such as Li 2 FePO 4 F, manganese fluorophosphates such as Li 2 MnPO 4 F, and cobalt fluorophosphates such as Li 2 CoPO 4 F.
  • the positive electrode active material is preferably a lithium-containing transition metal oxide having a layered rock salt structure (MA) and a lithium-containing transition metal phosphate compound (MC), more preferably LiNi1 / 3Co1/ 3Mn1 / 3O2 and LiFePO4 , and even more preferably LiFePO4 .
  • MA layered rock salt structure
  • MC lithium-containing transition metal phosphate compound
  • the chemical formula of the compound obtained by the above calcination method can be measured using inductively coupled plasma (ICP) emission spectroscopy, or, as a simplified method, calculated from the mass difference of the powder before and after calcination.
  • ICP inductively coupled plasma
  • the surface of the positive electrode active material may be coated with an oxide such as another metal oxide, a carbon-based material, etc. These surface coating layers can function as an interface resistance stabilizing layer.
  • Surface coating materials include metal oxides containing Ti, Nb, Ta, W, Zr, Al, Si, or Li.
  • the oxides include titanate spinel, tantalum-based oxides, niobium -based oxides, and lithium niobate -based compounds, such as Li4Ti5O12 , Li2Ti2O5 , LiTaO3 , LiNbO3 , LiAlO2 , Li2ZrO3, Li2WO4 , Li2TiO3 , Li2B4O7, Li3PO4 , Li2MoO4 , Li3BO3 , LiBO2 , Li2CO3 , Li2SiO3 , SiO2 , TiO2 , ZrO2 , Al2O3 , B2O3 , and Li3 AlF6 .
  • Carbon-based materials such as C, SiC, and SiOC (carbon-doped silicon oxide) can also be used as the surface coating material.
  • the positive electrode active material is preferably surface-coated with a carbon-based material in order to increase the electronic conductivity to a desired level.
  • the positive electrode active material is preferably surface-coated with carbon (C).
  • the carbon surface coating can be formed by baking the positive electrode active material in the presence of an additive (organic substance) that serves as a carbon source. Examples of additives that can be used include styrene-maleic anhydride copolymer, polystyrene, polycarbonate, etc.
  • the surface of the positive electrode active material may be treated with sulfur or phosphorus. Furthermore, the particle surfaces of the positive electrode active material may be subjected to a surface treatment with active rays or active gas (plasma, etc.) before or after the above-mentioned surface coating.
  • the positive electrode active materials may be used alone or in combination of two or more.
  • the content of the positive electrode active material in the positive electrode composition is preferably 96.00 to 99.50 mass%, more preferably 96.00 to 99.40 mass%, still more preferably 97.00 to 99.40 mass%, still more preferably 98.00 to 99.30 mass%, still more preferably 98.50 to 99.20 mass%, and particularly preferably 99.00 to 99.15 mass%, based on the solid content of the composition.
  • the positive electrode composition of the present invention may contain a conductive assistant.
  • the conductive assistant may be any of those known as general conductive assistants.
  • it may be an electron conductive material such as graphites, such as natural graphite and artificial graphite, carbon blacks, such as acetylene black, ketjen black, and furnace black, amorphous carbon, such as needle coke, carbon fibers, such as vapor-grown carbon fibers and carbon nanotubes, carbonaceous materials, such as graphene and fullerene, metal powders, metal fibers, such as copper and nickel, or conductive polymers, such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyphenylene derivatives.
  • the conductive assistant is preferably a carbonaceous material, more preferably carbon blacks, and more preferably ketjen black.
  • the positive electrode active material and the conductive assistant among the above conductive assistants, those that do not insert or release Li when the battery is charged and discharged and do not function as an active material are considered to be conductive assistants. Therefore, among the conductive assistants, those that can function as an active material in the active material layer when the battery is charged and discharged are classified as active materials rather than conductive assistants. Whether or not they function as an active material when the battery is charged and discharged is not unique, but is determined by the combination with the active material.
  • the shape of the conductive assistant is not particularly limited, but a particulate shape is preferred.
  • the median diameter (D50) of the conductive assistant is not particularly limited and is, for example, preferably 0.01 to 50 ⁇ m, more preferably 0.1 to 10 ⁇ m, and further preferably 0.2 to 2.0 ⁇ m.
  • the conductive assistant may be surface-treated.
  • the method of surface treatment is not particularly limited, and surface treatment using a chemical treating agent and atomic layer deposition (ALD) treatment are preferred.
  • ALD atomic layer deposition
  • an organic silicon compound more preferably, a silane coupling agent
  • an organic phosphonic acid compound and the like are preferable, and examples thereof include methyltrimethoxysilane (MTMS), octadecyltrimethoxysilane, hexamethyldisilazane, tetraethoxysilane, trifluoropropyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3-aminopropyltriethoxysilane, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, trimethoxy(octyl)silane, 1H,1H,2H,2H-perfluor
  • the content (mass %) of the conductive assistant is preferably 0.03 to 4.00 mass % of the solid content of the positive electrode composition, more preferably 0.03 to 2.00 mass %, even more preferably 0.05 to 1.00 mass %, and particularly preferably 0.10 to 0.80 mass %.
  • the positive electrode composition of the present invention may contain a dispersion medium.
  • the dispersion medium is not particularly limited and may be, for example, water or a non-aqueous solvent.
  • an aprotic organic solvent is preferable, and among them, an aprotic organic solvent having 2 to 10 carbon atoms is more preferable.
  • non-aqueous solvents include linear or cyclic carbonate compounds, lactone compounds, linear or cyclic ether compounds, ester compounds, nitrile compounds, amide compounds, oxazolidinone compounds, nitro compounds, linear or cyclic sulfone or sulfoxide compounds, and phosphate ester compounds.
  • compounds having an ether bond, a carbonyl bond, an ester bond or a carbonate bond are preferred. These compounds may have a substituent.
  • non-aqueous solvents examples include ethylene carbonate, fluorinated ethylene carbonate, vinylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, 1,4-dioxane, and methyl acetate.
  • the dispersion medium is preferably N-methylpyrrolidone (NMP).
  • the positive electrode composition of the present invention preferably has a solids content (components other than the dispersion medium (solvent)) of 70 mass% or more, more preferably 72 mass% or more, even more preferably 74 mass% or more, and even more preferably 78 mass% or more.
  • the solids content is preferably 70 to 95 mass%, more preferably 70 to 90 mass%, even more preferably 72 to 87 mass%, even more preferably 74 to 85 mass%, and particularly preferably 78 to 83 mass%.
  • the positive electrode composition of the present invention may contain, as desired, a binder, an ionic liquid, a thickener, an antifoaming agent, a leveling agent, a dehydrating agent, an antioxidant, etc. These may be those commonly used in non-aqueous electrolyte secondary batteries.
  • a binder polyvinylene difluoride (PVDF) and styrene-butadiene copolymer (SBR) are preferred.
  • the content of the binder in the positive electrode composition of the present invention is preferably 0.10 to 3.00 mass%, more preferably 0.20 to 2.00 mass%, still more preferably 0.20 to 1.00 mass%, and particularly preferably 0.25 to 0.40 mass%, based on the solid content of the positive electrode composition.
  • the positive electrode composition of the present invention can be prepared as a mixture, preferably as a slurry, by mixing the positive electrode active material consisting of the large particle group A and the small particle group B with any other components, for example, using any of various commonly used mixers.
  • the positive electrode sheet of the present invention is a positive electrode sheet having a positive electrode active material layer formed using the positive electrode composition of the present invention, and is a positive electrode sheet suitable as a positive electrode sheet for a non-aqueous electrolyte secondary battery.
  • the positive electrode active material contained in the positive electrode active material layer is composed of a large particle group A having a particle size of 5.0 ⁇ m or more and a small particle group B having a particle size of less than 5.0 ⁇ m, and when the total frequency in the number-based particle size distribution of the positive electrode active material is taken as 100%, the frequency of the large particle group A is 60% or more and the frequency of the small particle group B is 40% or less, and the surface tension ⁇ B (mN/m) of the small particle group B with respect to N-methylpyrrolidone satisfies the above formula B1.
  • the term "positive electrode sheet” includes both an embodiment in which the sheet is incorporated as a component of a nonaqueous electrolyte secondary battery (in a state in which the sheet is incorporated in a secondary battery) and an embodiment in which the sheet is a positive electrode material before being incorporated in a nonaqueous electrolyte secondary battery.
  • the structure (area, thickness, etc.) of the positive electrode sheet may be a structure used as a positive electrode or a structure that can be processed into a structure used as a positive electrode.
  • the positive electrode sheet of the present invention may have a positive electrode active material layer formed using the positive electrode composition of the present invention, and may be in a form in which the positive electrode active material layer and the positive electrode current collector are laminated.
  • the positive electrode active material layer may be laminated on both sides of the positive electrode current collector, or the positive electrode active material layer may be laminated on one side of the positive electrode current collector.
  • the positive electrode sheet is usually a sheet having a configuration in which the positive electrode active material layer is laminated on the positive electrode current collector.
  • the positive electrode active material layer may be composed of a single layer or multiple layers.
  • the positive electrode sheet may further have other layers as necessary. Examples of the other layers include a protective layer (release sheet), a coating layer, etc.
  • the positive electrode active material layer is preferably laminated in a state of being in direct contact with the positive electrode current collector.
  • the thickness of the positive electrode active material layer is preferably 120 ⁇ m or more, and can be 120 to 500 ⁇ m, preferably 150 to 450 ⁇ m, more preferably 180 to 400 ⁇ m, and even more preferably 200 to 350 ⁇ m.
  • the positive electrode current collector constituting the positive electrode sheet of the present invention is not particularly limited, and a positive electrode current collector used in a normal secondary battery can be appropriately applied.
  • a positive electrode current collector used in a normal secondary battery for example, JP 2016-201308 A, JP 2005-108835 A, JP 2012-185938 A, WO 2018/135395, etc. can be appropriately referred to.
  • the positive electrode current collector is preferably made of aluminum, an aluminum alloy, or the like.
  • the positive electrode sheet of the present invention is less susceptible to collapse (peeling) of the positive electrode active material layer. Usually, this collapse is most noticeable at the ends of the positive electrode active material layer.
  • the binder is preferably unevenly distributed in contact with the small particle group B.
  • the binder uneven distribution rate is preferably 58% or more, more preferably 60% or more, even more preferably 70% or more, still more preferably 80% or more, and particularly preferably 85% or more.
  • the upper limit of the binder uneven distribution rate is practically 99%. Therefore, the binder uneven distribution rate is preferably 58 to 99%, more preferably 60 to 98%, even more preferably 70 to 97%, still more preferably 80 to 96%, and particularly preferably 85 to 95%.
  • the binder uneven distribution rate can be determined by measuring the amount of element ⁇ derived from the binder in contact with the small particle group B in an element mapping image of the cross section of the positive electrode active material layer, quantifying the amount of ⁇ in contact with the small particle group B relative to the amount of element ⁇ in the entire element mapping image, and calculating the ratio ([amount of ⁇ in contact with the small particle group B]/[total amount of ⁇ ] ⁇ 100(%)).
  • the uneven distribution of the binder is believed to occur due to the binder moving to the periphery of the small particle group B during the drying step in the formation of the positive electrode active material layer.
  • the uneven distribution rate can be controlled by adjusting the surface tension, ratio, etc. of the large particle group A and the small particle group B.
  • the positive electrode sheet of the present invention can be obtained by forming a positive electrode active material layer using the positive electrode composition of the present invention.
  • the positive electrode sheet of the present invention can be manufactured by forming a film using the positive electrode composition of the present invention. More specifically, the positive electrode sheet can be prepared by forming the positive electrode active material layer on the positive electrode current collector or the like as a substrate.
  • the positive electrode current collector is used as a substrate, and the positive electrode composition of the present invention is applied thereon (may be via another layer) to form a coating film, which is then dried to obtain a positive electrode sheet having a positive electrode active material layer (coated and dried layer) on the substrate.
  • the coating film may be subjected to a press treatment as necessary.
  • the method for applying the positive electrode composition of the present invention to the positive electrode current collector is not particularly limited, and a conventional method can be used.
  • the nonaqueous electrolyte secondary battery of the present invention (hereinafter also referred to as the "secondary battery of the present invention") has the positive electrode sheet of the present invention as a positive electrode.
  • the battery may have the same structure as a normal non-aqueous electrolyte secondary battery. That is, the secondary battery of the present invention can be obtained by incorporating the positive electrode sheet of the present invention into the positive electrode of a normal nonaqueous electrolyte secondary battery.
  • FIG. 1 is a cross-sectional view showing a typical laminated structure of a nonaqueous electrolyte secondary battery 10, including the operating portion when the battery is operated.
  • the nonaqueous electrolyte secondary battery 10 has a laminated structure (hereinafter also referred to as an electrode laminate) having a negative electrode current collector 1, a negative electrode active material layer 2, a separator 3, a positive electrode active material layer 4, and a positive electrode current collector 5 in this order, as viewed from the negative electrode side.
  • the negative electrode active material layer 2 and the positive electrode active material layer 4 are filled with a nonaqueous electrolyte (not shown) and are separated by the separator 3.
  • the secondary battery of the present invention has the positive electrode sheet of the present invention instead of the positive electrode active material layer 4 and the positive electrode current collector 5 of the above-mentioned general non-aqueous electrolyte secondary battery.
  • the secondary battery of the present invention has the positive electrode sheet of the present invention as the positive electrode of the secondary battery, the negative electrode active material layer, the negative electrode current collector, the electrolyte such as an electrolyte (aqueous electrolyte, nonaqueous electrolyte) or a solid electrolyte material, the separator, and other components are not particularly limited. These materials and components can be appropriately applied to those used in normal secondary batteries. In addition, with regard to the method of manufacturing the secondary battery of the present invention, a normal method can be appropriately adopted, except that the positive electrode sheet of the present invention is used as the positive electrode. For the components and manufacturing methods normally used in these secondary batteries, for example, JP 2016-201308 A, JP 2005-108835 A, JP 2012-185938 A, and WO 2020/067106 A can be appropriately referred to.
  • the secondary battery of the present invention can be installed in electronic devices such as notebook computers, pen-input computers, mobile computers, electronic book players, mobile phones, cordless phone handsets, pagers, handheld terminals, mobile fax machines, mobile copiers, mobile printers, headphone stereos, video movie machines, liquid crystal televisions, handheld cleaners, portable CDs, mini-discs, electric shavers, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, and memory cards. It can also be installed in consumer devices such as automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, and medical equipment (pacemakers, hearing aids, shoulder massagers, etc.). It can also be used for various military and space applications. It can also be combined with solar cells.
  • electronic devices such as notebook computers, pen-input computers, mobile computers, electronic book players, mobile phones, cordless phone handsets, pagers, handheld terminals, mobile fax machines, mobile copiers, mobile
  • the positive electrode active material was prepared as follows.
  • LFP1-1 to LFP1-3 (large particle group a)>
  • LFP1-1 An LFP (LiFePO 4 ) powder raw material (manufactured by LOPAL, P198-S13 (product name)) was used.
  • LFP1-2 and LFP1-3 20 g of LFP1-1 was put into a powder processing device Nobilta (product name: NOB MINI, manufactured by Hosokawa Micron Corporation), and surface smoothing treatment was performed in a nitrogen atmosphere at the rotation speed and treatment time shown in Table 1. As a result, positive electrode active materials LFP1-2 and LFP1-3 in the form of powder were obtained, respectively.
  • LFP2-1 to LFP2-6 small particle group b>
  • An LFP (LiFePO 4 ) powder raw material P198-T5 (product name) manufactured by LOPAL) was used.
  • LFP2-2 to LFP2-6) 20 g of LFP2-1 was put into a powder processing device Nobilta (product name: NOB MINI, manufactured by Hosokawa Micron Corporation), and surface smoothing treatment was performed in a nitrogen atmosphere at the rotation speed and treatment time shown in Table 1. As a result, positive electrode active materials LFP2-2 to LFP2-6 having the shape of a powder were obtained, respectively.
  • NMC1-1 to NMC1-3 (large particle group a)>
  • NMC1-1 An NMC (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) powder raw material (manufactured by Toshima Manufacturing Co., Ltd., NCM111 (particle size 12 ⁇ m) (product name)) was used.
  • NMC1-2 and NMC1-3 20 g of NMC1-1 was put into a powder processing device Nobilta (product name: NOB MINI, manufactured by Hosokawa Micron Corporation), and surface smoothing treatment was performed in a nitrogen atmosphere at the rotation speed and treatment time shown in Table 1. As a result, positive electrode active materials NMC1-2 and NMC1-3 in the shape of a powder were obtained, respectively.
  • NMC2-1 to NMC2-6 small particle group b>
  • NMC2-1 An NMC (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) powder raw material (manufactured by Toshima Manufacturing Co., Ltd., NCM111 (particle size 2 ⁇ m) (product name)) was used.
  • NMC2-2 to NMC2-6) 20 g of NMC2-1 was put into a powder processing device Nobilta (product name: NOB MINI, manufactured by Hosokawa Micron Corporation), and surface smoothing treatment was performed in a nitrogen atmosphere at the rotation speed and treatment time shown in Table 1. As a result, positive electrode active materials NMC2-2 to NMC2-6 having the shape of a powder were obtained, respectively.
  • the number-based particle size distributions of LFP1-1 to LFP1-3 and NMC1-1 to NMC1-3 were obtained as described below, and each of the positive electrode active materials contained substantially no particles with a particle size of less than 5.0 ⁇ m.
  • the number-based particle size distributions of LFP2-1 to LFP2-6 and NMC2-1 to NMC2-6 were obtained as described below, and each of the positive electrode active materials contained substantially no particles with a particle size of 5.0 ⁇ m or more.
  • the positive electrode active material shown in Table 2 acetylene black (Li-100 (trade name), manufactured by Denka) as a conductive assistant, polyvinylene difluoride (PVDF) as a binder, and N-methylpyrrolidone (NMP) as a dispersion medium were mixed to obtain 79.3% by mass of the positive electrode active material, 0.4% by mass of the conductive assistant, 0.3% by mass of the binder, and 20.0% by mass of the dispersion medium, to obtain positive electrode slurries (positive electrode compositions) (Nos. 1 to 24).
  • the positive electrode slurry was applied to one side of a 12 ⁇ m thick positive electrode current collector (aluminum foil) (length: 200 mm, width: 150 mm) and dried at 120° C. until the dispersion medium volatilized. Thereafter, pressing was performed using a roll press machine to obtain a sheet-shaped positive electrode sheet having a positive electrode current collector and a positive electrode active material (Nos. 1 to 24). The thickness of each positive electrode active material layer was 250 ⁇ m.
  • EDX energy dispersive X-ray analyzer
  • EDX Noran System 7 type (product name), manufactured by Thermo Fisher Scientific
  • F fluorine
  • the negative electrode slurry was applied to one side of a 12 ⁇ m thick negative electrode current collector (copper foil) and dried at 150° C. until the solvent evaporated. Then, a pressing process was performed using a roll press machine to obtain a sheet-shaped negative electrode (negative electrode sheet) having a negative electrode current collector and a negative electrode active material layer. The thickness of this negative electrode active material layer was about 180 ⁇ m.
  • the positive electrode sheet used in the preparation of each of the nonaqueous electrolyte secondary batteries was punched out to a diameter of 10 mm, the positive electrode current collector was removed from the punched piece, and the thickness of the positive electrode active material layer was measured.
  • the thickness of the negative electrode active material layer was measured in the same manner.
  • the thickness of the power generating element was calculated by the thickness of the positive electrode current collector + the thickness of the positive electrode active material layer + the thickness of the separator + the thickness of the negative electrode active material layer + the thickness of the negative electrode current collector.
  • the thickness of each constituent layer was measured using a constant pressure thickness measuring device (product name: PG-20J, manufactured by Techlock Corporation).
  • the volume (L) of the power generating element was calculated by multiplying the thickness of the power generating element by the area of the circular surface of the power generating element.
  • the ideal volume of the power generating element was calculated without taking into account the volume reduction due to the collapse of the end due to punching of the positive electrode sheet, etc.
  • the volumetric energy density of the nonaqueous electrolyte secondary battery was calculated by dividing the amount of power (Wh) thus obtained by the volume (L) of the power generating element obtained above.
  • the obtained value was evaluated according to the following evaluation criteria.
  • Charge/discharge conditions> Charge and discharge conditions for Experiments No.
  • Constant current (CC)-constant voltage (CV) charging current value 15mA, upper limit voltage value 3.6V, final current value 0.5mA CC discharge: current value 15mA, final voltage value 2.0V (Charge and discharge conditions for Experiments No. 13 to 24 (Experiments using NMC as the positive electrode active material))
  • CC-CV charging current value 15mA, upper limit voltage value 4.2V, final current value 0.5mA CC discharge: current value 15mA, upper limit voltage value 3.0V
  • the positive electrode composition contains the large particle group A and the small particle group B at the frequency specified in the present invention, and the surface tension ⁇ B of the small particle group B against NMP satisfies the formula B1: 15.0 ⁇ B ⁇ 40.0 (Experiment Nos. 2, 3, 6 to 10, 14, 15, 18 to 22), even if the binder amount is as small as 0.3 mass% and a positive electrode active material layer having a thickness of 250 ⁇ m is formed, the collapse of the edge of the positive electrode active material in the obtained positive electrode sheet is suppressed, resulting in excellent shape stability.
  • the nonaqueous electrolyte secondary battery having this positive electrode sheet as the positive electrode also had an improved battery capacity.
  • Non-aqueous electrolyte secondary battery 1 Negative electrode current collector 2 Negative electrode active material layer 3 Separator 4 Positive electrode active material layer 5 Positive electrode current collector 6 Working part (light bulb)

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PCT/JP2024/018890 2023-05-31 2024-05-22 非水電解液二次電池の正極用組成物、正極シート、及び非水電解液二次電池 Ceased WO2024247854A1 (ja)

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