WO2023120503A1 - 二次電池用正極およびその製造方法、ならびに二次電池 - Google Patents

二次電池用正極およびその製造方法、ならびに二次電池 Download PDF

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WO2023120503A1
WO2023120503A1 PCT/JP2022/046790 JP2022046790W WO2023120503A1 WO 2023120503 A1 WO2023120503 A1 WO 2023120503A1 JP 2022046790 W JP2022046790 W JP 2022046790W WO 2023120503 A1 WO2023120503 A1 WO 2023120503A1
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positive electrode
active material
secondary battery
material layer
electrode active
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English (en)
French (fr)
Japanese (ja)
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真帆 原田
貴仁 中山
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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 CN202280084584.8A priority Critical patent/CN118435390A/zh
Priority to EP22911205.7A priority patent/EP4456200B1/en
Priority to JP2023569451A priority patent/JPWO2023120503A1/ja
Priority to US18/720,824 priority patent/US20250054982A1/en
Publication of WO2023120503A1 publication Critical patent/WO2023120503A1/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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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

  • the present disclosure mainly relates to positive electrodes for secondary batteries.
  • the separator melts due to Joule heat due to the short-circuit current, forming a larger short-circuited portion.
  • the short-circuit portion expands and the short-circuit current increases, the battery temperature rises at an accelerated rate. As the energy density of the secondary battery increases, Joule heat due to short-circuit current increases.
  • Patent Document 1 describes a composite oxide containing lithium and nickel as main components having a layered crystal structure, and having the general formula: Li a Ni 1-bc M1 b M2 c O 2 , 0.95 ⁇ a ⁇ 1.05, 0 .01 ⁇ b ⁇ 0.10, 0.10 ⁇ c ⁇ 0.20 (where M1 is one or more selected from Al, B, Y, Ce, Ti, Sn, V, Ta, Nb, W, Mo and M2 is one or more elements selected from Co, Mn, and Fe).
  • Patent Document 1 According to Patent Document 1, according to the positive electrode active material, the thermal stability in the charged state is improved, and Joule heat generation due to short-circuit current is suppressed even under the condition that the battery has an internal short circuit, and safety can be easily ensured. It is said that it will be
  • Patent Document 1 when controlling the conductivity of the powder compact as in Patent Document 1, the battery as a whole becomes highly resistant, leading to a decrease in battery performance. Furthermore, Patent Document 1 is a countermeasure specialized for composite oxides containing lithium and nickel as main components, and lacks versatility.
  • One aspect of the present disclosure includes a positive electrode current collector and a positive electrode active material layer supported by the positive electrode current collector, wherein the positive electrode active material layer includes active material particles, a binder, and thermal decomposition. and a thermally decomposable additive, wherein the thermally decomposable additive comprises acetamidobenzoic acid.
  • Another aspect of the present disclosure relates to a secondary battery comprising the positive electrode for a secondary battery, a negative electrode, a non-aqueous electrolyte, and a separator interposed between the positive electrode and the negative electrode.
  • Yet another aspect of the present disclosure is preparing a positive electrode slurry including active material particles, a binder, a thermally decomposable additive, and a dispersion medium; preparing a positive electrode current collector; A step of applying the positive electrode slurry to the surface of the positive electrode current collector to form a coating film, a step of drying the coating film to form an unrolled layer, and a step of rolling the unrolled layer to form a positive electrode and forming an active material layer, wherein the thermally decomposable additive contains acetamidobenzoic acid, and the dispersion medium contains an organic solvent.
  • FIG. 1 is a vertical cross-sectional view schematically showing the internal structure of a 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.
  • the present disclosure encompasses any combination of the subject matter recited in any two or more claims selected from the multiple claims recited in the accompanying claims. In other words, as long as there is no technical contradiction, the items described in two or more claims arbitrarily selected from the multiple claims described in the attached claims can be combined.
  • a positive electrode for a secondary battery includes a positive electrode current collector and a positive electrode active material layer supported by the positive electrode current collector.
  • the positive electrode active material layer is formed on the surface of the positive electrode current collector.
  • the positive electrode current collector is composed of a sheet-like conductive material.
  • non-porous conductive substrates metal foil, etc.
  • porous conductive substrates mesh, net, punching sheet, etc.
  • the positive electrode active material layer is carried on one or both surfaces of the positive electrode current collector.
  • the positive electrode active material layer is usually a positive electrode material mixture layer made of a positive electrode material mixture, and has a membranous or film shape.
  • the positive electrode mixture contains active material particles (positive electrode active material particles), a binder, and a thermally decomposable additive as essential components.
  • the active material particles may contain a lithium-containing transition metal oxide.
  • the binder contains at least one selected from the group consisting of fluororesin and hydrogenated nitrile-butadiene rubber.
  • Thermally degradable additives include acetamidobenzoic acid.
  • Acetamidobenzoic acid has almost no effect on battery performance even if it exists in the positive electrode active material layer.
  • Acetamidobenzoic acid may be an acid form in which the COOH group is bonded to a proton, a zwitterionic form, or a salt form in which the proton of the COOH group is substituted with a cation.
  • the cations may be ammonium cations, metal cations (Na, K, Li, etc.), and the like.
  • Acetamidobenzoic acid may be 3-acetamidobenzoic acid or 4-acetamidobenzoic acid, but 3-acetamidobenzoic acid is more preferable.
  • the content of 3-acetamidobenzoic acid in the total amount of acetamidobenzoic acid is desirably 98% by mass or more, and may be 100%.
  • the thermally decomposable additive thermally decomposes and cuts off the conductive path when an internal short circuit occurs in the battery, the short circuit current increases, and the battery temperature rises.
  • the thermally decomposable additive hardly increases the resistance at room temperature and selectively increases the internal resistance of the battery at high temperatures. Since acetamidobenzoic acid is thermally decomposed at a temperature of about 250° C. or higher, the internal resistance of the battery significantly increases before the battery temperature rises excessively. Although the mechanism by which the conductive path is blocked is not clear, thermal decomposition of the thermally decomposable additive generates gas in the positive electrode active material layer, causing local structural changes in the positive electrode active material layer, resulting in an increase in resistance. It is assumed that
  • Acetamidobenzoic acid is thought to have good compatibility with binders containing at least one selected from the group consisting of fluororesins and hydrogenated nitrile-butadiene rubbers (H-NBR).
  • the fluororesin and H-NBR are dissolved in an organic solvent (for example, N-methyl-2-pyrrolidone) used as a dispersion medium when forming the positive electrode active material layer.
  • Acetamidobenzoic acid is also moderately soluble in the organic solvent used as the dispersion medium.
  • acetamidobenzoic acid which is appropriately dissolved in the organic solvent and dispersed in the organic solvent as fine particles or aggregates, can be uniformly dispersed in the positive electrode active material layer together with the binder. Furthermore, acetamidobenzoic acid is considered to be stable in the presence of an organic solvent, with little side reaction. Note that when water is used as a dispersion medium for the positive electrode slurry, the water may deteriorate the positive electrode active material and cause a decrease in capacity.
  • At least part of the thermally decomposable additive is preferably present as particles having a particle diameter of 10 ⁇ m or more in the positive electrode active material layer.
  • particle is a concept including primary particles, secondary particles, and agglomerates of these, and in addition to general particles or particles, aggregation, agglomeration ( Also includes concepts such as agglomeration.
  • the particle diameter (or aggregate diameter) can be regarded as the diameter of an equivalent circle having the same area as the area surrounded by the outline of the particle (or aggregate) in observation of a cross-sectional sample as described later.
  • thermal decomposable additive When the thermally decomposable additive is contained in the positive electrode active material layer in such a size, thermal decomposition of the thermally decomposable additive causes a local structural change in the positive electrode active material layer to increase, resulting in a more pronounced resistance.
  • the particle size of the thermally decomposable additive may be 20 ⁇ m or more, or may be 30 ⁇ m or more.
  • the maximum particle size of the thermally decomposable additive is desirably 100 ⁇ m or less, may be 60 ⁇ m or less, or may be 50 ⁇ m or less. If the maximum value is within the above range, the influence on battery performance can be sufficiently reduced.
  • the particle size can be measured in the following manner.
  • (1) Preparation of positive electrode cross-sectional sample First, a positive electrode to be measured is prepared. Next, the positive electrode active material layer and the positive electrode current collector are simultaneously cut along the thickness direction of the positive electrode to form a cross section. At that time, the positive electrode active material layer may be filled with a thermosetting resin and cured.
  • a cross-sectional sample of the positive electrode is obtained by a CP (cross-section polisher) method, an FIB (focused ion beam) method, or the like.
  • the positive electrode to be measured is taken out from a secondary battery with a depth of discharge (DOD) of 90% or more.
  • the depth of discharge (DOD) is the ratio of the amount of electricity discharged to the amount of electricity a battery has in a fully charged state.
  • the voltage of the fully charged battery corresponds to the end-of-charge voltage.
  • the voltage of a fully discharged battery corresponds to the end-of-discharge voltage.
  • Elemental analysis by Electron Probe Microanalyzer is performed using the SEM image of the cross-sectional sample.
  • a map of the thermally decomposable additive is obtained by extracting the component (for example, nitrogen element) derived from the thermally decomposable additive from the EPMA analysis data of the cross-sectional sample.
  • the measurement conditions for nitrogen mapping were an acceleration voltage of 8.0 kV, an irradiation current of 1.0 ⁇ 10 ⁇ 7 A, a threshold of 1 ⁇ 3 of the maximum count number in the positive electrode active material layer, and pixels whose detection level was equal to or higher than the threshold. It is considered as a place where thermally decomposable additives are present. Particles or agglomerates of the thermally decomposable additive are identified from the resulting map. The diameter of an equivalent circle having the same area as the specified particle or aggregate is defined as the particle size of the thermally decomposable additive.
  • Particles (or aggregates) of the thermally decomposable additive having a particle diameter of 10 ⁇ m or more are 300 ⁇ m in length in the surface direction of the positive electrode active material layer ⁇ the positive electrode active material layer (positive electrode active material layers are provided on both sides of the positive electrode current collector). If so, one or more observations may be observed in the rectangular observation field defined by the thickness T of the positive electrode active material layer (the same shall apply hereinafter) on one side, but five or more observations are desirable. As the number of particles of the thermally decomposable additive having a particle diameter of 10 ⁇ m or more observed in the observation field increases, the effect of selectively increasing the internal resistance of the battery at high temperatures increases.
  • the upper limit of the number of particles of the thermally decomposable additive having a particle diameter of 10 ⁇ m or more observed in the observation field is, for example, 40 or less.
  • Each of the above numbers may be an average value of the number of particles of the thermally decomposable additive having a particle diameter of 10 ⁇ m or more counted in a plurality (for example, 3 or more) of observation fields (300 ⁇ m ⁇ T).
  • a small amount of thermally decomposable additive may be included in the positive electrode active material layer.
  • the content of acetamidobenzoic acid contained in the positive electrode active material layer may be, for example, 0.1% by mass or more and 5% by mass or less, 0.3% by mass or more and 3% by mass or less, or 0.5% by mass or more and 2 % by mass or less.
  • the area where acetamidobenzoic acid is present is the length of the positive electrode active material layer in the plane direction.
  • acetamidobenzoic acid contained in the above content does not greatly affect the battery capacity.
  • the acetamidobenzoic acid contained in the above content can be uniformly dispersed in the positive electrode active material layer as particles or aggregates having the appropriate particle size as described above.
  • the thermally decomposable additive may contain an acetic acid component.
  • the acetic acid component has the effect of suppressing sedimentation of the positive electrode mixture in the positive electrode slurry prepared when forming the positive electrode active material layer.
  • the acetic acid component may be acetic acid having an OH group (acid form), or may be a salt form in which protons of the OH group are substituted with cations.
  • the cations may be ammonium cations, metal cations (Na, K, Li, etc.), and the like.
  • the acetic acid component is desirably contained at a ratio of 500 ⁇ g or more and 5000 ⁇ g or less per 1 g of the thermally decomposable additive or acetamidobenzoic acid.
  • the amount of the acetic acid component contained in the thermally decomposable additive or acetamidobenzoic acid can be obtained, for example, by stripping the positive electrode active material layer from the positive electrode, extracting acetamidobenzoic acid from the positive electrode active material layer with a solvent, extracting the acetamidobenzoic acid from the solvent containing acetamidobenzoic acid, can be measured by analyzing by ion chromatography. N-methyl-2-pyrrolidone (NMP) may be used as the solvent.
  • NMP N-methyl-2-pyrrolidone
  • the thermally decomposable additive desirably covers part of the surface of the active material particles. It is thought that the thermally decomposable additive present on the surface of the active material particles effectively blocks the conductive paths between the active material particles, between the active material particles and the conductive material, or between the active material particles and the positive electrode current collector at high temperatures. be done. For example, a thermally decomposable additive existing on the surface of active material particles and interposed between active material particles reduces contact between active material particles due to a change in state such as gasification. On the other hand, when the thermally decomposable additive covers only a portion of the surface of the active material particles and does not cover the entire surface, the resistance to battery reaction hardly increases.
  • thermally decomposable additive covers only a part of the surface of the active material particles.
  • the fact that the thermally decomposable additive covers only a part of the surface of the active material particles can be confirmed by observing the SEM image of the cross-sectional sample of the positive electrode obtained by the above-described method by EPMA elemental mapping. can be done.
  • the thermally decomposable additive (in particular, particulate thermally decomposable additive (among them, particles with a particle size of 10 ⁇ m or more)) is not on the positive electrode current collector side of the positive electrode active material layer, but on the outermost surface side (that is, the separator side). It is desirable to be unevenly distributed in This is because the internal short circuit of the battery often begins to expand on the separator side of the positive electrode active material layer. An internal short circuit occurs, for example, when a conductive foreign substance penetrates the separator.
  • the presence probability Pb of the thermally decomposable additive existing in the region from the surface of the positive electrode current collector of the positive electrode active material layer to 0.5 T is , for example, 1.35 ⁇ Pt/Pb may be satisfied, and 1.5 ⁇ Pt/Pb ⁇ 40 may be satisfied.
  • Pt/Pb ⁇ 1.35 it cannot be said that the thermally decomposable additive is substantially unevenly distributed on the outermost surface side of the positive electrode active material layer rather than on the positive electrode current collector side.
  • the region of the positive electrode active material layer from the surface of the positive electrode current collector to 0.5 T is referred to as the “lower layer region”, and from the position of 0.5 T from the surface of the positive electrode current collector of the positive electrode active material layer to the outermost surface. is also referred to as an "upper layer region”.
  • Pb and Pt can be measured by analyzing a cross-sectional sample of the positive electrode obtained by the method described above with SEM and EPMA. Specifically, in the elemental map of the thermally decomposable additive obtained from the EPMA analysis data of the cross-sectional sample, the area occupied by the thermally decomposable additive in the lower layer region and the upper layer region is measured. At this time, all thermally decomposable additives are counted regardless of the particle size of the thermally decomposable additive. Then, the ratio of the area of the thermally decomposable additive to the area of the lower layer region and the upper layer region is regarded as Pb and Pt, respectively.
  • Pb and Pt are measured in a rectangular observation field defined by the length 300 ⁇ m in the plane direction of the positive electrode active material layer ⁇ thickness T of the positive electrode active material layer.
  • Pb and Pt may be average values of Pb and Pt obtained in a plurality of (for example, 3 or more) observation fields, respectively.
  • Existence probability Pt (q ) may satisfy 1.5 ⁇ Pt(q)/Pb(q) ⁇ 50.
  • the production method includes a step (I) of preparing a positive electrode slurry containing active material particles, a binder, a thermally decomposable additive, and a dispersion medium, and a step (II) of preparing a positive electrode current collector.
  • the positive electrode slurry is prepared by mixing a positive electrode material mixture containing active material particles, a binder and a thermally decomposable additive with a liquid dispersion medium and dispersing the mixture in the dispersion medium.
  • the positive electrode mixture may further contain another component (eg, a conductive material).
  • As the liquid dispersion medium an organic solvent having excellent affinity with both the binder and the thermally decomposable additive is used.
  • NMP N-methyl-2-pyrrolidone
  • alcohols such as ethanol, ethers such as tetrahydrofuran, amides such as dimethylformamide, and ketones such as cyclohexanone may also be used.
  • At least acetamidobenzoic acid is used as the thermally decomposable additive.
  • Acetamidobenzoic acid may be partially dissolved in advance by mixing with a dispersion medium.
  • a dispersion liquid of particulate acetamidobenzoic acid having an average particle diameter d1 (d1 ⁇ D1) may be prepared by mixing particulate acetamidobenzoic acid having an average particle diameter D1 with a dispersion medium.
  • the average particle diameter is the median diameter (D 50 ) at which the cumulative volume is 50% in the volume-based particle size distribution obtained by a laser diffraction particle size distribution analyzer.
  • the average particle diameter D1 is desirably 100 ⁇ m or less, and it is more desirably to use acetamidobenzoic acid that passes through a mesh of 100 ⁇ m.
  • the average particle diameter d1 is desirably 50 ⁇ m or less.
  • Fluorine resins include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), vinylidene fluoride-hexafluoropropylene copolymer, and the like. These are readily soluble in organic solvents and suitable for combined use with sulfamic acid. Among them, PVDF is preferable.
  • a sheet-like conductive material (metal foil, mesh, net, punching sheet, etc.) is used. Among them, metal foil is preferred. Examples of materials for the positive electrode current collector include stainless steel, aluminum, aluminum alloys, and titanium. The thickness of the positive electrode current collector is not particularly limited, but is, for example, 1 to 50 ⁇ m, and may be 5 to 30 ⁇ m.
  • a coating film is formed by applying the positive electrode slurry to the surface of the positive electrode current collector.
  • a bar coater, a gravure coater, a blade coater, a roll coater, a comma coater, a die coater, a lip coater, and the like are used as the positive electrode slurry coating apparatus, for example.
  • the thermally decomposable additive exists in the form of particles having a particle size of 10 ⁇ m or more.
  • a positive electrode active material layer containing a thermally decomposable additive having a particle size of 10 ⁇ m or more can be easily obtained.
  • the thermally decomposable additive makes it easier to coat only a part of the surface of the active material particles.
  • the coating film is dried to volatilize the dispersion medium to form an unrolled coating film.
  • the thermally decomposable additive can migrate from the lower layer region to the upper layer region (that is, from the positive electrode current collector side to the separator side) together with the dispersion medium.
  • the thermally decomposable additive is unevenly distributed on the separator side of the positive electrode active material layer rather than on the positive electrode current collector side.
  • the thermally decomposable additive tends to be unevenly distributed on the separator side of the positive electrode active material layer rather than on the positive electrode current collector side.
  • the presence probability P2b of the thermally decomposable additive existing in the region from the surface of the positive electrode current collector of the unrolled layer to 0.5T2, and the positive electrode collector of the unrolled layer may satisfy 1.35 ⁇ P2t/P2b.
  • the rolling conditions are not particularly limited . It may be 3 or more and 4.0 g/cm 3 or less.
  • a positive electrode active material layer composed of two or more layers with different contents of the thermally decomposable additive may be formed by laminating and applying two or more kinds of positive electrode slurries.
  • a secondary battery includes the positive electrode for a secondary battery, a negative electrode, a lithium ion conductive electrolyte, and a separator interposed between the positive electrode and the negative electrode.
  • the secondary battery may be a flooded secondary battery containing an electrolytic solution as a lithium ion conductive electrolyte, and the electrolytic solution may be a non-aqueous electrolytic solution or an aqueous electrolytic solution.
  • a gel electrolyte or a solid electrolyte in which an electrolytic solution is retained in a matrix material may be used.
  • An all-solid secondary battery containing a solid electrolyte as a lithium ion conductive electrolyte may also be used.
  • Secondary batteries include a lithium ion secondary battery that uses a material that reversibly absorbs and releases lithium ions as a negative electrode active material, and a lithium secondary battery that deposits lithium metal on the negative electrode during charging and dissolves lithium metal during discharging. , solid state batteries containing gel or solid electrolytes, and the like.
  • the configuration of the secondary battery will be specifically described below, taking a lithium-ion secondary battery as an example.
  • the positive electrode As the positive electrode, a positive electrode for a secondary battery having the characteristics described above is used.
  • the positive electrode active material layer is composed of a positive electrode mixture.
  • the positive electrode mixture contains active material particles (particles of positive electrode active material), a binder, and a thermally decomposable additive (at least acetamidobenzoic acid) as essential components, and may contain optional components.
  • Optional components may include conductive materials, thickeners, and the like.
  • the thickness of the positive electrode active material layer is not particularly limited.
  • a plurality of layers having different shapes may form one positive electrode active material layer.
  • two or more layers containing active material particles having different average particle sizes may be laminated, or two or more layers having different types or compositions of positive electrode active materials may be laminated.
  • the average particle size of the active material particles is, for example, 3 ⁇ m or more and 30 ⁇ m or less, and may be 5 ⁇ m or more and 25 ⁇ m or less.
  • the average particle diameter is the median diameter (D 50 ) at which the cumulative volume is 50% in the volume-based particle size distribution obtained by a laser diffraction particle size distribution analyzer.
  • the active material particles may be separated and recovered from the positive electrode.
  • "LA-750" manufactured by HORIBA, Ltd. can be used as the measuring device.
  • the average particle size of the active material particles may be measured from the above-mentioned cross-sectional sample of the positive electrode. A cross-sectional SEM image is taken so that 10 or more active material particles are observed, and the diameters of equivalent circles having the same area as the cross section of 10 or more active material particles are obtained by image processing. The value may be the average particle size.
  • the positive electrode active material that constitutes the active material particles may contain a lithium-containing transition metal oxide. From the viewpoint of increasing the capacity, it is desirable that the lithium-containing transition metal oxide contains lithium and Ni and contains a lithium nickel oxide (composite oxide N) having a layered rock salt crystal structure.
  • the ratio of the composite oxide N in the positive electrode active material is, for example, 70% by mass or more, may be 90% by mass or more, or may be 95% by mass or more.
  • the ratio of Ni to the metal elements other than Li contained in the composite oxide N may be 50 atomic % or more.
  • the composite oxide N is represented, for example, by formula (1): Li ⁇ Ni x1 M1 x2 M2 (1 ⁇ x1 ⁇ x2) O 2+ ⁇ .
  • the element M1 is at least one selected from the group consisting of V, Co and Mn.
  • Element M2 is at least one selected from the group consisting of Mg, Al, Ca, Ti, Cu, Zn and Nb.
  • formula (1) is 0.95 ⁇ ⁇ ⁇ 1.05, -0.05 ⁇ ⁇ ⁇ 0.05, 0.5 ⁇ x1 ⁇ 1, 0 ⁇ x2 ⁇ 0.5, 0 ⁇ 1-x1- satisfies x2 ⁇ 0.5. ⁇ increases and decreases due to charging and discharging.
  • the composite oxide N contains Ni and may contain at least one selected from the group consisting of Co, Mn and Al as the element M1 and the element M2. Co, Mn and Al contribute to stabilization of the crystal structure of the composite oxide N.
  • the ratio of Co in the metal elements other than Li contained in the composite oxide N is preferably 0 atomic % or more and 20 atomic % or less, and 0 atomic % or more and 15 atoms. % or less is more desirable.
  • the proportion of Mn in metal elements other than Li may be 10 atomic % or less, or may be 5 atomic % or less.
  • the ratio of Mn to the metal elements other than Li may be 1 atomic % or more, 3 atomic % or more, or 5 atomic % or more.
  • the ratio of Al to the metal elements other than Li may be 10 atomic % or less, or 5 atomic % or less.
  • the ratio of Al to the metal elements other than Li may be 1 atomic % or more, 3 atomic % or more, or 5 atomic % or more.
  • the composite oxide N can be represented, for example, by formula (2): Li ⁇ Ni (1-y1-y2-y3-z) Co y1 Mn y2 Al y3 M z O 2+ ⁇ .
  • Element M is an element other than Li, Ni, Co, Mn, Al and oxygen, and consists of Ti, Zr, Nb, Mo, W, Fe, Zn, B, Si, Mg, Ca, Sr, Sc and Y. At least one selected from the group may be used.
  • formula (2) is 0.95 ⁇ 1.05, ⁇ 0.05 ⁇ 0.05, 0 ⁇ y1 ⁇ 0.1, 0 ⁇ y2 ⁇ 0.1, 0 ⁇ y3 ⁇ 0. 1, satisfies 0 ⁇ z ⁇ 0.10.
  • v which indicates the atomic ratio of Ni
  • 0.8 or more may be 0.85 or more, or may be 0.90 or more or 0.95 or more.
  • v which indicates the atomic ratio of Ni, may be 0.98 or less, or may be 0.95 or less.
  • Examples of conductive materials that can be included as optional components in the positive electrode active material layer include carbon nanotubes (CNT), carbon fibers other than CNT, and conductive particles (eg, carbon black and graphite).
  • CNT carbon nanotubes
  • carbon fibers other than CNT carbon fibers other than CNT
  • conductive particles eg, carbon black and graphite
  • the negative electrode includes at least a negative electrode current collector.
  • the negative electrode includes, for example, a negative electrode current collector and a negative electrode active material layer.
  • the negative electrode active material layer is supported on one or both surfaces of the negative electrode current collector.
  • the negative electrode active material layer may be a negative electrode mixture layer composed of a negative electrode mixture.
  • the negative electrode mixture layer is membranous or film-like.
  • the negative electrode mixture contains particles of a negative electrode active material as an essential component, and may contain a binder, a conductive agent, a thickener, and the like as optional components. Also, a lithium metal foil or a lithium alloy foil may be attached to the negative electrode current collector as the negative electrode active material layer.
  • the negative electrode mixture layer can be formed, for example, by applying a negative electrode slurry in which a negative electrode mixture containing particles of a negative electrode active material, a binder, etc. is dispersed in a dispersion medium on the surface of the negative electrode current collector and drying the slurry. .
  • the dried coating film may be rolled if necessary.
  • Negative electrode active materials include materials that electrochemically absorb and release lithium ions, lithium metal, and lithium alloys. Carbon materials, alloy materials, and the like are used as materials that electrochemically occlude and release lithium ions. Examples of carbon materials include graphite, graphitizable carbon (soft carbon), and non-graphitizable carbon (hard carbon). Among them, graphite is preferable because it has excellent charging/discharging stability and low irreversible capacity.
  • alloy-based materials include those containing at least one metal capable of forming an alloy with lithium, and specific examples include silicon, tin, silicon alloys, tin alloys, and silicon compounds. Silicon oxide, tin oxide, etc. may be used, and other silicon-containing materials may also be used.
  • a nonporous conductive substrate metal foil, etc.
  • a porous conductive substrate mesh, net, punching sheet, etc.
  • materials for the negative electrode current collector include stainless steel, nickel, nickel alloys, copper, and copper alloys.
  • binder for example, styrene-butadiene rubber can be used, but it is not particularly limited.
  • Examples of conductive materials include carbon nanotubes (CNT), carbon fibers other than CNT, and conductive particles (eg, carbon black, graphite).
  • CNT carbon nanotubes
  • carbon fibers other than CNT carbon fibers other than CNT
  • conductive particles eg, carbon black, graphite
  • thickeners examples include carboxymethyl cellulose (CMC) and modified products thereof (including salts such as Na salts), cellulose derivatives such as methyl cellulose (cellulose ethers, etc.); polymer cellulose having a vinyl acetate unit such as polyvinyl alcohol; compound; polyether (polyalkylene oxide such as polyethylene oxide, etc.), and the like.
  • CMC carboxymethyl cellulose
  • modified products thereof including salts such as Na salts
  • cellulose derivatives such as methyl cellulose (cellulose ethers, etc.)
  • polymer cellulose having a vinyl acetate unit such as polyvinyl alcohol
  • compound compound
  • polyether polyalkylene oxide such as polyethylene oxide, etc.
  • a separator is interposed between a positive electrode and a negative electrode.
  • the separator has high ion permeability and moderate mechanical strength and insulation. Examples of separators include microporous thin films, woven fabrics, non-woven fabrics, and the like.
  • Polyolefin such as polypropylene or polyethylene is used as the material of the separator.
  • the separator may have a heat-resistant insulating layer on at least one surface layer.
  • the heat-resistant insulating layer may contain an inorganic oxide filler as a main component (for example, 80% by mass or more), or may contain a heat-resistant resin as a main component (for example, 40% by mass or more).
  • a polyamide resin such as an aromatic polyamide (aramid), a polyimide resin, a polyamideimide resin, or the like may be used as the heat-resistant resin.
  • the electrolyte may be a liquid electrolyte (electrolytic solution), a gel electrolyte, or a solid electrolyte.
  • the gel electrolyte contains a lithium salt and a matrix polymer, or contains a lithium salt, a non-aqueous solvent and a matrix polymer.
  • the matrix polymer for example, a polymer material that gels by absorbing a non-aqueous solvent is used. Examples of polymer materials include fluorine resins, acrylic resins, polyether resins, polyethylene oxide, and the like.
  • the solid electrolyte may be an inorganic solid electrolyte.
  • the inorganic solid electrolyte for example, a known material (for example, an oxide-based solid electrolyte, a sulfide-based solid electrolyte, a halide-based solid electrolyte, etc.) is used for all-solid-state lithium ion secondary batteries and the like.
  • the electrolyte may be, for example, a non-aqueous electrolyte containing a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
  • the concentration of the lithium salt in the non-aqueous electrolyte is, for example, 0.5 mol/L or more and 2 mol/L or less.
  • the non-aqueous electrolyte may contain known additives.
  • non-aqueous solvent for example, cyclic carbonate, chain carbonate, cyclic carboxylate, and the like are used.
  • Cyclic carbonates include propylene carbonate (PC) and ethylene carbonate (EC).
  • 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).
  • the non-aqueous solvent may be used singly or in combination of two or more.
  • Lithium salts include, for example, lithium salts of chlorine-containing acids ( LiClO4 , LiAlCl4 , LiB10Cl10 , etc.), lithium salts of fluorine-containing acids ( LiPF6 , LiBF4 , LiSbF6 , LiAsF6 , LiCF3SO3 ) . , LiCF3CO2 , etc.
  • LiN( SO2F ) 2 lithium salts of fluorine - containing acid imides (LiN( SO2F ) 2 , LiN ( CF3SO2 ) 2 , LiN( CF3SO2 ) ( C4F9SO2 ) , LiN ( C2F5SO2 ) 2 , etc.), lithium halides (LiCl, LiBr, LiI, etc.).
  • Lithium salts may be used singly or in combination of two or more.
  • a secondary battery there is a structure in which an electrode group, in which a positive electrode and a negative electrode are wound with a separator interposed therebetween, is housed in an outer package together with an electrolytic solution.
  • an electrode group in which a positive electrode and a negative electrode are wound with a separator interposed therebetween
  • an electrolytic solution e.g., aqueous solution
  • a laminated electrode group in which a positive electrode and a negative electrode are laminated with a separator interposed therebetween may be used.
  • the form of the secondary battery is also not limited, and may be, for example, cylindrical, square, coin, button, laminate, or the like.
  • FIG. 1 is a vertical cross-sectional view of a cylindrical non-aqueous secondary battery 10 that is an example of the present embodiment.
  • the present disclosure is not limited to the following configurations.
  • the secondary battery 10 includes an electrode group 18, an electrolytic solution (not shown), and a bottomed cylindrical battery can 22 that accommodates 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.
  • PVDF polyvinylidene fluoride
  • the positive electrode slurry was applied to the surface of the aluminum foil, which was the positive electrode current collector, and the coating was dried to form unrolled layers on both sides of the aluminum foil. At this time, the drying temperature was controlled at 200° C. so that the distribution of 3-acetamidobenzoic acid in the later-described positive electrode active material layer was Pt/Pb ⁇ 1.5.
  • the unrolled layer was rolled to form a positive electrode active material layer having a positive electrode active material density of 3.6 g/cm 3 .
  • the thickness of the whole positive electrode after rolling was 160 ⁇ m.
  • a non-aqueous electrolyte was prepared by dissolving LiPF 6 at a concentration of 1.0 mol/L in a mixed solvent containing ethylene carbonate (EC) and diethyl carbonate (DEC) at a volume ratio of 3:7.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • a tab was attached to each electrode, and an electrode group was produced by spirally winding the positive electrode and the negative electrode with the separator interposed therebetween so that the tab was located at the outermost periphery. After inserting the electrode group into an outer package made of an aluminum laminate film and vacuum-drying at 105° C. for 2 hours, an electrolytic solution was injected and the opening of the outer package was sealed to obtain a secondary battery A1.
  • Example 2>> A secondary battery A2 was produced in the same manner as in Example 1, except that the drying temperature was controlled to room temperature so that the distribution of 3-acetamidobenzoic acid in the positive electrode active material layer satisfied Pt/Pb ⁇ 1.
  • Example 3>> A secondary battery A3 was produced in the same manner as in Example 1, except that 3-acetamidobenzoic acid was completely dissolved in NMP in advance when preparing the positive electrode slurry. Specifically, 3-acetamidobenzoic acid in an amount corresponding to 1.3% by mass of the positive electrode mixture is added to NMP at 50 ° C. and dissolved over 3 hours, and then the active material particles and acetylene black. , and polyvinylidene fluoride (PVDF) were added in a mass ratio of 95:2.5:2.5 to an NMP solution of 3-acetamidobenzoic acid and stirred to prepare a positive electrode slurry. The drying temperature was controlled at 200° C. so that the distribution of 3-acetamidobenzoic acid in the positive electrode active material layer was Pt/Pb ⁇ 1.5.
  • PVDF polyvinylidene fluoride
  • Example 4>> A secondary battery A4 was produced in the same manner as in Example 3, except that the drying temperature was controlled to room temperature so that the distribution of 3-acetamidobenzoic acid in the positive electrode active material layer satisfied Pt/Pb ⁇ 1.
  • a secondary battery B1 was produced in the same manner as in Example 1, except that the positive electrode mixture did not contain 3-acetamidobenzoic acid (the content of 3-acetamidobenzoic acid was 0%).
  • a secondary battery A4 was produced in the same manner as in Example 1, except that the drying temperature was controlled to 2.
  • a secondary battery A7 was fabricated in the same manner as in Example 3 except for the above.
  • Example 8>> A secondary battery A8 was produced in the same manner as in Example 4, except that the thermally decomposable additive was changed from 3-acetamidobenzoic acid to 4-acetamidobenzoic acid. [Evaluation 2] The secondary batteries obtained in Examples 5 to 8 were evaluated in the same manner as in Evaluation 1. Table 2 shows the surface temperatures of the batteries A5 to A8.
  • a positive electrode for a secondary battery according to the present disclosure and a secondary battery including the same are useful as main power sources for mobile communication devices, portable electronic devices, electric vehicles, and the like.

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