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WO2024176955A1 - Liant d'électrode, couche de mélange d'électrode, matériau pour former une couche de mélange d'électrode, procédé de fabrication de couche de mélange d'électrode, électrode et batterie secondaire au lithium-ion - Google Patents

Liant d'électrode, couche de mélange d'électrode, matériau pour former une couche de mélange d'électrode, procédé de fabrication de couche de mélange d'électrode, électrode et batterie secondaire au lithium-ion Download PDF

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Publication number
WO2024176955A1
WO2024176955A1 PCT/JP2024/005427 JP2024005427W WO2024176955A1 WO 2024176955 A1 WO2024176955 A1 WO 2024176955A1 JP 2024005427 W JP2024005427 W JP 2024005427W WO 2024176955 A1 WO2024176955 A1 WO 2024176955A1
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WIPO (PCT)
Prior art keywords
electrode
polymer
mixture layer
fibrils
electrode mixture
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Ceased
Application number
PCT/JP2024/005427
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English (en)
Japanese (ja)
Inventor
龍宜 河相
邦臣 清澤
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Publication of WO2024176955A1 publication Critical patent/WO2024176955A1/fr
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • 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

  • One embodiment of the present invention relates to an electrode binder, an electrode composite layer, an electrode composite layer forming material, a method for manufacturing an electrode composite layer, an electrode, or a lithium ion secondary battery.
  • Lithium-ion secondary batteries are small, lightweight, have a high energy density, and can be repeatedly charged and discharged, making them popular in fields such as mobile phones and laptop computers.
  • lithium-ion secondary batteries have been a demand for improved performance, such as greater stability, lower resistance, and larger capacity, as well as environmental considerations and cost improvements in the manufacture of lithium-ion secondary batteries.
  • a widely known method for manufacturing electrodes for batteries such as lithium-ion secondary batteries is to dissolve or disperse a binder resin in a solvent, disperse active material and conductive additives in the resin to form a slurry, apply the slurry to a current collector, and then volatilize the solvent (wet method).
  • One embodiment of the present invention provides an electrode binder having fibrils and an electrode mixture layer-forming material that can produce an electrode mixture layer that has excellent windability and adhesion to a current collector by a dry method, and can produce a battery that has excellent battery capacity.
  • An example configuration of the present invention is as follows:
  • the average diameter of the fibrils is 20 to 500 nm and the average length is 100 to 10,000 nm; Binder for electrodes.
  • the intrinsic viscosity [ ⁇ ] measured in decalin solvent at 135° C. is 1 to 50 dl/g.
  • An electrode mixture layer comprising an electrode binder according to any one of [1] to [3] and an active material.
  • (I) Contains 0.1 to 30% by mass of an ultra-high molecular weight olefin polymer (A) and 70 to 99.9% by mass of an active material (wherein the total amount of the ultra-high molecular weight olefin polymer (A) and the active material is 100% by mass).
  • the ultra-high molecular weight olefin polymer (A) has an intrinsic viscosity [ ⁇ ] of 1 to 50 dl/g as measured in decalin solvent at 135°C.
  • (III) Contains fibrils, the average diameter of the fibrils being 20 to 500 nm and the average length being 100 to 10,000 nm.
  • the ultra-high molecular weight olefin polymer (a) has an average particle diameter d50 of 0.10 to 1000 ⁇ m.
  • the ultra-high molecular weight olefin polymer (a) has an intrinsic viscosity [ ⁇ ] measured in decalin solvent at 135° C. of 1 to 50 dl/g.
  • the average diameter of the fibrils is 20 to 500 nm, and the average length is 100 to 10,000 nm.
  • An electrode comprising the electrode mixture layer according to any one of [4] to [6] and a current collector. [9] The electrode according to [8], obtained by a dry method.
  • a lithium ion secondary battery comprising the electrode and electrolyte described in [8] or [9].
  • an electrode binder having fibrils and an electrode mixture layer-forming material that can produce an electrode mixture layer that has excellent windability and adhesion to a current collector by a dry method and can produce a battery that has excellent battery capacity.
  • a self-supporting electrode mixture layer even if thin, can be produced by a dry method.
  • the term “to” indicating a numerical range, for example “M to N”, means “greater than or equal to M and less than or equal to N” unless otherwise specified.
  • the term “(co)polymer” is used as a concept that encompasses both homopolymers and copolymers.
  • the expression “structural unit derived from M” may be used. This refers to a "structural unit corresponding to M", for example, a structural unit having a pair of bonds formed by opening a ⁇ bond constituting a double bond of M.
  • the electrode binder according to one embodiment of the present invention contains an ultra-high molecular weight olefin-based polymer (A) (hereinafter also referred to as “polymer (A)”) that satisfies the following requirement (i), and fibrils of the polymer (A), The fibrils have an average diameter of 20 to 500 nm and an average length of 100 to 10,000 nm.
  • An electrode mixture layer-forming material according to one embodiment of the present invention may be a positive electrode mixture layer-forming material or a negative electrode mixture layer-forming material. However, it is preferable that it is a negative electrode mixture layer-forming material in terms of, for example, better exerting the effects of the present invention.
  • the material comprises an active material, fibrils, and an ultra-high molecular weight olefin polymer (A) that satisfies the following requirement (i): a ratio R D of the average particle size of the active material to the average diameter of the fibrils (average particle size of the active material/average diameter of the fibrils) is 25 to 400; The ratio R L of the average particle size of the active material to the average length of the fibrils (average particle size of the active material/average length of the fibrils) is 1-150. (i) The intrinsic viscosity [ ⁇ ] measured in decalin solvent at 135° C. is 1 to 50 dl/g.
  • the present binder has fibrils with an average diameter and an average length in a specific range, and the specific surface area of the present binder is increased, and the present material has the ratios R D and R L in a specific range, so that the active material can be held with a smaller amount of binder. This is believed to improve the battery capacity.
  • the active material surface is covered with the binder, the conductivity of electrons and lithium ions tends to decrease (coating inhibition), but the present binder has fibrils with an average diameter and an average length in a specific range, and the present material has the ratios R D and R L in a specific range.
  • the active material is less likely to be covered with the binder, and the contact between the binder and the active material is only a point contact, so that it is believed that the decrease in the conductivity of electrons and lithium ions can be suppressed.
  • the material forming the electrode mixture layer electrowetting material, electrode composite material
  • the material forming the electrode mixture layer may be pressed to prepare the electrode mixture layer. Since the intrinsic viscosity [ ⁇ ] of the binder and the polymer (A) contained in the material is within the above range, the polymer (A) is unlikely to flow out of the electrode mixture layer even in a molten state during the pressing.
  • the particle shape can be maintained in the electrode mixture layer. Therefore, the binding property with components other than the binder contained in the electrode mixture layer (e.g., active material and conductive assistant) can be improved, and these can be prevented from falling off from the electrode mixture layer.
  • components other than the binder contained in the electrode mixture layer e.g., active material and conductive assistant
  • the average diameter of the fibrils contained in the binder is 20 to 500 nm, preferably 20 to 450 nm, more preferably 20 to 350 nm, even more preferably 20 to 300 nm, even more preferably 20 to 200 nm, and particularly preferably 50 to 150 nm.
  • the average diameter of the fibrils contained in the material is preferably 20 to 500 nm, more preferably 20 to 450 nm, even more preferably 20 to 350 nm, even more preferably 20 to 300 nm, even more preferably 20 to 200 nm, and particularly preferably 50 to 150 nm.
  • the average diameter of the fibrils is within the above range, the fibrils are less likely to break, and the active material can be supported with a smaller amount of binder.
  • the inhibition of the coating of the active material by the fibrils can be suppressed, and the deterioration of the battery performance can be suppressed.
  • the average diameter of the fibrils is specifically determined by the measurement method described in the Examples below.
  • the average length of the fibrils contained in the binder is 100 to 10,000 nm, preferably 200 to 6,000 nm, more preferably 400 to 6,000 nm, and even more preferably 1,000 to 6,000 nm.
  • the average length of the fibrils contained in the material is preferably 100 to 10,000 nm, more preferably 200 to 6,000 nm, more preferably 400 to 6,000 nm, and especially preferably 1,000 to 6,000 nm.
  • the fibrils can be formed, for example, by the fibrillation process described below. Specifically, the fibrils can be formed by kneading an ultra-high molecular weight olefin polymer with other components as necessary, and in particular, the fibrils can be formed by kneading an ultra-high molecular weight olefin polymer with inorganic particles such as the active material described below.
  • the average diameter of the fibrils can be adjusted, for example, by the temperature in the fibrillation step (kneading step) described below. When the temperature in the fibrillation step is set to be lower than the melting point of the ultra-high molecular weight olefin polymer, the lower the temperature, the larger the average diameter of the fibrils tends to be.
  • the average fibril length can be adjusted by the temperature and the shearing method in the fibrillation step described below. For example, applying shearing in one direction tends to increase the average fibril length.
  • the binder is not particularly limited as long as it contains fibrils of the polymer (A), and may contain fibrils other than the fibrils of the polymer (A). Furthermore, the fibrils contained in the present material may be fibrils of polymer (A) or fibrils of a material other than polymer (A), but preferably contain fibrils of polymer (A). Examples of fibrils other than those of polymer (A) include fibrils of other resins described in the section of other components below.
  • the content of the fibrils of the polymer (A) relative to the total amount of the fibrils in the binder and the material (100% by mass) is preferably 50 to 100% by mass in order to better exhibit the effects of the present invention.
  • the polymer (A) is not particularly limited as long as it is an ultra-high molecular weight olefin polymer that satisfies the above requirement (i).
  • the polymer (A) contained in the present binder and the present material may be one type or two or more types.
  • polymer (A) examples include homopolymers such as polyethylene, polypropylene, poly-1-butene, and poly-4-methyl-1-pentene; and copolymers made from at least two ⁇ -olefins selected from ethylene, propylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene.
  • Ethylene-based polymers have a lower melting point than resins that have been used as binders for conventional electrodes, such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), and therefore can maintain their binding strength with active materials, conductive assistants, etc., without high temperatures during the preparation of the electrode composite layer.
  • ethylene-based polymers can be fibrillated, and have a higher surface free energy than PTFE, etc., and therefore have a high affinity with active materials and conductive assistants, and can increase their binding strength with active materials and conductive assistants.
  • ethylene-based polymers have better electrochemical stability than PTFE, PVDF, etc., and therefore are less likely to cause reduction reactions even at the reduction potential of the negative electrode. For this reason, ethylene-based polymers function as binders for the long term even at the negative electrode, and the use of ethylene-based polymers makes it easier to maintain battery performance. From these and other points of view, ethylene-based polymers (e.g., homopolymers of ethylene, copolymers of ethylene and one or more ⁇ -olefins) are preferable as polymer (A), and homopolymers of ethylene are more preferable.
  • the content of structural units derived from ethylene in the copolymer of ethylene and one or more ⁇ -olefins is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more, relative to 100 mol% of the total of all structural units constituting the copolymer.
  • the intrinsic viscosity [ ⁇ ] of the polymer (A) measured in a decalin solvent at 135° C. is 1 to 50 dl/g, preferably 1.5 to 40 dl/g, more preferably 2 to 40 dl/g, still more preferably 2 to 35 dl/g, still more preferably 3 to 25 dl/g, still more preferably 5 to 25 dl/g, and particularly preferably 8 to 25 dl/g.
  • the electrode mixture layer is produced by a dry method, it may be produced by pressing the material forming the electrode mixture layer (electrode mixture layer forming material, electrode composite material).
  • the polymer (A) is unlikely to flow out of the electrode mixture layer even in a molten state during the pressing, and when the polymer (A) contained in the material forming the electrode mixture layer is in a particle shape, the particle shape can be maintained in the electrode mixture layer, and the binding with components other than the binder contained in the electrode mixture layer (e.g., active material and conductive assistant) can be improved, and these can be suppressed from falling off from the electrode mixture layer. Therefore, it is considered that an electrode mixture layer that can stand on its own even if it is thin can be produced by a dry method, and a battery with excellent battery capacity can be produced.
  • the binder contained in the electrode mixture layer e.g., active material and conductive assistant
  • the melting point of the polymer (A) is preferably from 120 to 150°C, more preferably from 125 to 145°C.
  • fibrillation can be performed at a temperature equal to or lower than the temperature at which the active material, conductive assistant, etc. do not decompose.
  • desired fibrils can be easily formed without increasing the temperature in the fibrillation step.
  • the melting point can be determined by the measurement method described in the Examples below.
  • the method for producing polymer (A) is not particularly limited, but it can be produced by the methods disclosed in documents such as WO 2006/054696, WO 2008/013144, WO 2009/011231, WO 2010/074073, and JP 2012-131959.
  • the polymer (A) may use only biomass-derived raw materials, only fossil fuel-derived raw materials, or both biomass-derived raw materials and fossil fuel-derived raw materials as its raw materials (e.g., monomers such as ethylene and ⁇ -olefin).
  • the biomass-derived raw materials are raw materials made from any (renewable) natural raw materials or their residues, such as those derived from plants or animals, including fungi, yeasts, algae, and bacteria, and examples thereof include raw materials containing about 1 ⁇ 10 ⁇ 12 of 14 C isotope as carbon and having a biomass carbon concentration (unit: pMC) of about 100 pMC as measured in accordance with ASTM D6866.
  • Biomass-derived raw materials e.g., monomers such as ethylene and ⁇ -olefins
  • the polymer (A) can contain a structural unit derived from a raw material derived from biomass from the viewpoint of reducing the environmental load (mainly reducing greenhouse gas emissions).
  • polymer (A) if the production conditions of polymer (A), such as the polymerization catalyst, polymerization process, and polymerization temperature, are equivalent, even if the (co)polymer contains a biomass-derived raw material, the molecular structure other than the content of 14C isotopes at a ratio of about 1 ⁇ 10 -12 to 10 -14 is equivalent to that of a (co)polymer made from a fossil fuel-derived raw material. Therefore, it is considered that the performance of a (co)polymer containing a biomass-derived raw material is the same as that of a (co)polymer made from a fossil fuel-derived raw material.
  • the total content of polymer (A) and fibrils of polymer (A) in this binder is preferably 70 to 100 mass%, more preferably 80 to 100 mass%, even more preferably 90 to 100 mass%, and particularly preferably 100 mass%, from the viewpoint that the electrode mixture layer can be easily produced by a dry method, etc.
  • the total content of the polymer (A) and fibrils in this material is preferably 0.1 to 30 mass%, more preferably 0.5 to 20 mass%, even more preferably 1 to 15 mass%, more preferably 1 to 10 mass%, and particularly preferably 1 to 5 mass%, from the viewpoint of achieving both the physical properties of the electrode mixture layer (e.g., electrolyte permeability, tensile strength) and the battery performance.
  • Examples of the active material used in this material include the same active materials as those described in the section on electrode mixture layer below.
  • the content of the active material in this material is preferably 70 to 99.9% by mass, more preferably 80 to 99.5% by mass, even more preferably 85 to 99% by mass, more preferably 90 to 99% by mass, and particularly preferably 95 to 99% by mass, from the viewpoint of achieving both the physical properties of the electrode mixture layer (e.g., electrolyte permeability, tensile strength) and the battery performance.
  • the ratio R D of the average particle diameter of the active material used in the present material to the average diameter of the fibrils used in the present material is 25 to 400, preferably 30 to 350, more preferably 40 to 300, and even more preferably 50 to 250.
  • the ratio R D is within the above range, the active material can be supported with smaller amounts of polymer (A) and fibrils, and the inhibition of coating of the active material by fibrils can be suppressed, thereby suppressing the deterioration of battery performance.
  • the ratio R L of the average particle diameter of the active material used in this material to the average length of the fibrils used in this material is 1 to 150, preferably 2 to 130, more preferably 3 to 100, and even more preferably 4 to 70.
  • the active material can be supported with a smaller amount of polymer (A) and fibrils, and the electrode mixture layer can be maintained while providing gaps between the active materials through which the electrolyte can penetrate.
  • the present binder may contain components other than the polymer (A) and fibrils of the polymer (A).
  • the other components are not particularly limited, and examples thereof include conventionally known components such as resins other than the polymer (A) and modifiers.
  • the material may contain any optional components other than the polymer (A), fibrils, and active material.
  • the optional components are not particularly limited, and include conventionally known components such as the other components described above and the additives described in the section on electrode mixture layer below.
  • the other components may each be used alone or in combination of two or more.
  • the optional components may each be used alone or in combination of two or more.
  • Examples of the other resins include olefin polymers other than the polymer (A), polyvinyl acetate, polymethyl methacrylate, carboxymethyl cellulose (CMC), nitrocellulose, fluororesins, and rubber.
  • Examples of the fluororesin include PTFE, PVDF, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), vinylidene fluoride-hexafluoropropylene copolymer, and the like.
  • Examples of the rubber include styrene-butadiene rubber (SBR) and acrylonitrile rubber.
  • the other resins may be used alone or in combination of two or more.
  • the modifier examples include weather resistance stabilizers, heat resistance stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, nucleating agents, lubricants, pigments, dyes, antioxidants, hydrochloric acid absorbers, inorganic or organic fillers, foaming agents, crosslinking agents, crosslinking assistants, adhesives, plasticizers, flame retardants, secondary antioxidants, natural oils, synthetic oils, and waxes.
  • the plasticizer is preferably a component capable of increasing the flexibility of the ultra-high molecular weight olefin polymer, and an example of the plasticizer is decane.
  • the modifiers may each be used alone or in combination of two or more kinds.
  • the content of the other components in the present binder and the present material is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and even more preferably 0 to 10% by mass, and it is particularly preferable that the present binder and the present material do not contain the other components (the content of the other components in the present binder and the present material is particularly preferably 0% by mass).
  • the content of the olefin-based polymer other than the polymer (A) in the present binder and the present material is preferably 0 to 30 mass%, more preferably 0 to 20 mass%, and even more preferably 0 to 10 mass%, and it is particularly preferable that the present binder and the present material do not contain any olefin-based polymer other than the polymer (A) (the content of the olefin-based polymer other than the polymer (A) in the present binder and the present material is particularly preferably 0 mass%).
  • the raw materials for the other components may be only raw materials derived from biomass, only raw materials derived from fossil fuels, or both raw materials derived from biomass and raw materials derived from fossil fuels. It is preferable that the other components contain structural units derived from raw materials derived from biomass from the viewpoint of reducing the environmental load (mainly reducing greenhouse gas emissions).
  • Electrode mixture layer 1 An electrode mixture layer according to one embodiment of the present invention (hereinafter also referred to as “electrode mixture layer 1”) contains the present binder and an active material.
  • the electrode mixture layer 1 is preferably an electrode mixture layer capable of absorbing and releasing lithium ions.
  • the electrode mixture layer 1 may be a positive electrode mixture layer used in a positive electrode, or a negative electrode mixture layer used in a negative electrode.
  • Electrode mixture layer 2 An electrode mixture layer according to another embodiment of the present invention (hereinafter also referred to as "electrode mixture layer 2”) satisfies the following requirements (I) to (III).
  • the electrode mixture layer 2 is preferably an electrode mixture layer capable of absorbing and releasing lithium ions.
  • the electrode mixture layer 2 may be a positive electrode mixture layer used in a positive electrode, or a negative electrode mixture layer used in a negative electrode.
  • Requirement (II) The ultra-high molecular weight olefin polymer (A) has an intrinsic viscosity [ ⁇ ] of 1 to 50 dl/g as measured in decalin solvent at 135° C.
  • An embodiment of the present invention is preferably an electrode mixture layer (hereinafter also referred to as "electrode mixture layer 3") formed from this material.
  • the electrode mixture layer 3 is preferably an electrode mixture layer capable of absorbing and releasing lithium ions.
  • the electrode mixture layer 3 may be a positive electrode mixture layer used in a positive electrode, or a negative electrode mixture layer used in a negative electrode.
  • electrode mixture layer 1, electrode mixture layer 2, and electrode mixture layer 3 will also be collectively referred to as the present electrode mixture layer.
  • the ultra-high molecular weight olefin polymer (A) in the electrode mixture layer 2 may be the same as the polymer (A) in the electrode binder column, the requirement (II) is the same as the requirement (i), and the average diameter and average length of the fibrils in the requirement (III) are the same as the average diameter and average length of the fibrils in the electrode binder column.
  • the fibrils contained in the electrode mixture layer 2 may be fibrils of the polymer (A) or fibrils other than the polymer (A), but preferably contain fibrils of the polymer (A).
  • fibrils other than those of polymer (A) include fibrils of other resins described in the section of other components.
  • the content of the fibrils of polymer (A) relative to the total amount of fibrils in electrode mixture layer 2 (100% by mass) is preferably 50 to 100% by mass in order to better exhibit the effects of the present invention.
  • the thickness of the electrode mixture layer is not particularly limited and may be the same as that of a conventionally known electrode mixture layer, but is preferably 30 to 500 ⁇ m, more preferably 30 to 300 ⁇ m, and even more preferably 30 to 150 ⁇ m. According to one embodiment of the present invention, even when the electrode mixture layer has such a thickness, it is possible to obtain an electrode mixture layer that can stand on its own without a support.
  • the content of the present binder in the electrode mixture layer 1 is preferably 0.1 to 30 mass%, more preferably 0.5 to 20 mass%, even more preferably 1 to 15 mass%, still more preferably 1 to 10 mass%, and particularly preferably 1 to 5 mass%, from the viewpoint of achieving both the physical properties of the electrode mixture layer (e.g., electrolyte permeability, tensile strength) and the battery performance.
  • the content of the polymer (A) in the electrode mixture layer 2 is, from the viewpoint of achieving both the physical properties (e.g., electrolyte permeability, tensile strength) of the electrode mixture layer and the battery performance, 0.1 to 30 mass%, preferably 1 to 20 mass%, more preferably 1 to 15 mass%, even more preferably 1 to 10 mass%, and particularly preferably 1 to 5 mass%, relative to 100 mass% of the total amount of the polymer (A) and the active material.
  • the physical properties e.g., electrolyte permeability, tensile strength
  • the contents of the polymer (A) and fibrils in the electrode mixture layers 2 and 3 are, from the viewpoint of achieving both the physical properties (e.g., electrolyte permeability, tensile strength) of the electrode mixture layer and the battery performance, preferably 0.1 to 30 mass%, more preferably 1 to 20 mass%, even more preferably 1 to 15 mass%, still more preferably 1 to 10 mass%, and particularly preferably 1 to 5 mass%, relative to 100 mass% of the total amount of the polymer (A), fibrils, and active material.
  • the physical properties e.g., electrolyte permeability, tensile strength
  • the content of the present binder in the electrode mixture layer 1 the content of the polymer (A) in the electrode mixture layer 2, and the content of the polymer (A) and fibrils in the electrode mixture layer 2 and the electrode mixture layer 3 are within the above-mentioned ranges, an electrode mixture layer having excellent windability, adhesion to a current collector, and binding between active materials can be easily produced by a dry method.
  • the amount of active material in the electrode mixture layer can be increased, a battery with a large capacity can be easily obtained by using the electrode mixture layer.
  • a positive electrode active material is usually used as the active material
  • a negative electrode active material is usually used as the active material
  • the content of the active material in the electrode mixture layer 1 is preferably 70 to 99.9% by mass, more preferably 80 to 99.5% by mass, even more preferably 85 to 99% by mass, still more preferably 90 to 99% by mass, and particularly preferably 95 to 99% by mass.
  • the content of the active material in the electrode mixture layer 2 is 70 to 99.9% by mass, preferably 80 to 99% by mass, more preferably 85 to 99% by mass, even more preferably 90 to 99% by mass, and particularly preferably 95 to 99% by mass, relative to 100% by mass of the total amount of the polymer (A) and the active material.
  • the content of the active material in the electrode mixture layer 2 and the electrode mixture layer 3 is preferably 70 to 99.9% by mass, more preferably 80 to 99% by mass, even more preferably 85 to 99% by mass, still more preferably 90 to 99% by mass, and particularly preferably 95 to 99% by mass, relative to 100% by mass of the total amount of the polymer (A), the fibrils, and the active material.
  • the average particle size of the active material is preferably 5 to 50 ⁇ m, and more preferably 10 to 30 ⁇ m.
  • the average particle size can be measured by a Coulter counter method, a laser diffraction particle size distribution analyzer, or the like.
  • the positive electrode active material can be a conventionally known positive electrode active material, and is not particularly limited.
  • the positive electrode active material is preferably a material capable of absorbing and releasing lithium ions, and examples of the positive electrode active material include positive electrode active materials that are commonly used in lithium ion secondary batteries.
  • the positive electrode active material may be used alone or in combination of two or more.
  • Examples of the positive electrode active material include An oxide having lithium (Li) and nickel (Ni) as constituent metal elements; An oxide containing, as constituent metal elements, Li, Ni, and at least one metal element other than Li and Ni (e.g., transition metal element, typical metal element); Examples include:
  • the metal element is preferably contained in an amount equivalent to or less than that of Ni in terms of the number of atoms.
  • the metal elements other than Li and Ni include at least one selected from the group consisting of Co, Mn, Al, Cr, Fe, V, Mg, Ca, Na, Ti, Zr, Nb, Mo, W, Cu, Zn, Ga, In, Sn, La, and Ce.
  • the positive electrode active material preferably contains a lithium-containing composite oxide (hereinafter also referred to as "NCM") represented by the following formula (C1).
  • NCM lithium-containing composite oxide
  • NCM include LiNi0.33Co0.33Mn0.33O2 , LiNi0.5Co0.3Mn0.2O2 , LiNi0.5Co0.2Mn0.3O2 , LiNi0.6Co0.2Mn0.2O2 , and LiNi0.8Co0.1Mn0.1O2 .
  • the positive electrode active material may contain a lithium-containing composite oxide (hereinafter also referred to as "NCA”) represented by the following formula (C2):
  • NCA LiNi 0.8 Co 0.15 Al 0.05 O 2 .
  • the negative electrode active material can be a conventionally known negative electrode active material, and is not particularly limited.
  • the negative electrode active material is preferably a material capable of absorbing and releasing lithium ions, and examples of the negative electrode active material include negative electrode active materials that are commonly used in lithium ion secondary batteries.
  • the negative electrode active material may be used alone or in combination of two or more.
  • the negative electrode active material examples include at least one selected from the group consisting of metallic lithium, lithium-containing alloys, metals or alloys capable of being alloyed with lithium, oxides capable of being doped and dedoped with lithium ions, transition metal nitrides capable of being doped and dedoped with lithium ions, and carbon materials capable of being doped and dedoped with lithium ions.
  • metallic lithium lithium-containing alloys, metals or alloys capable of being alloyed with lithium
  • oxides capable of being doped and dedoped with lithium ions oxides capable of being doped and dedoped with lithium ions, transition metal nitrides capable of being doped and dedoped with lithium ions, and carbon materials capable of being doped and dedoped with lithium ions.
  • carbon materials capable of being doped and dedoped with lithium ions are preferred.
  • the carbon material examples include carbon black, activated carbon, amorphous carbon materials, and graphite materials.
  • the carbon material may be in any shape, such as fiber, sphere, potato, or flake, and is preferably in a spherical shape.
  • the average particle size of the carbon material is preferably 5 to 50 ⁇ m, and more preferably 10 to 30 ⁇ m.
  • amorphous carbon material examples include hard carbon, coke, mesocarbon microbeads (MCMB), and mesophase pitch carbon fiber (MCF).
  • Examples of the graphite material include artificial graphite and natural graphite.
  • the graphite material may contain boron.
  • the graphite material may be coated with a metal such as gold, platinum, silver, copper, or tin, or with amorphous carbon, or may be a mixture of amorphous carbon and graphite.
  • Examples of the artificial graphite include graphitized MCMB and graphitized MCF.
  • the electrode mixture layer 1 may further contain additives other than the binder and the active material.
  • the electrode mixture layers 2 and 3 may further contain additives other than the polymer (A), fibrils, and the active material.
  • the additives include a conductive assistant, a thickener, a surfactant, a dispersant, a wetting agent, and an antifoaming agent.
  • the additives may be used alone or in combination of two or more.
  • the conductive assistant is not particularly limited as long as it is a material other than the active material, and a known conductive assistant can be used. However, it is preferable that the conductive assistant be a material that improves the electrical conductivity between active materials and the electrical conductivity between the active material and a current collector. It is preferable to use a conductive assistant in the positive electrode composite layer, and it is also preferable to use a conductive assistant when a negative electrode active material other than the carbon material is used as the negative electrode active material in the negative electrode composite layer, and when the carbon material is used as the negative electrode active material in the negative electrode composite layer, a conductive assistant may or may not be used. The conductive assistant may be used alone or in combination of two or more kinds.
  • the conductive assistant used in the positive electrode composite layer, and in the negative electrode composite layer, when a negative electrode active material other than the carbon material is used as the negative electrode active material are not particularly limited, but are preferably carbon materials having electrical conductivity, such as graphite, carbon black, conductive carbon fibers (e.g., carbon nanotubes, carbon nanofibers, carbon fibers), fullerenes, etc.
  • carbon black commercially available products may be used.
  • Examples of commercially available carbon black include Toka Black #4300, #4400, #4500, and #5500 (furnace black, manufactured by Tokai Carbon Co., Ltd.), Printex L (furnace black, manufactured by Degussa Corporation), Raven 7000, 5750, 5250, 5000 ULTRA III, 5000 ULTRA, Conductex SC ULTRA, Conductex 975 ULTRA, and PUER.
  • BLACK 100, 115, 205 (Columbian, furnace black), #2350, #2400B, #2600B, #30050B, #3030B, #3230B, #3350B, #3400B, #5400B (Mitsubishi Chemical, furnace black), MONARCH 1400, 1300, 900, Vulcan XC-72R, Black Pearls 2000, LI Examples of such blacks include TX-50, LITX-200 (manufactured by Cabot Corporation, furnace black), Ensaco 250G, Ensaco 260G, Ensaco 350G, and Super-P (manufactured by Timcal Corporation), Ketjen Black EC-300J and EC-600JD (manufactured by Akzo Nobel), Denka Black, Denka Black HS-100, and FX-35 (manufactured by Denka Co., Ltd., acetylene black).
  • graphite examples include artificial graphite and natural graphite (e.g., flake graphite, lump graphite, and earthy graphite).
  • the electrode mixture layer according to one embodiment of the present invention can be produced by forming the material into a layer having the above-mentioned thickness by a conventionally known method.
  • a method for producing an electrode mixture layer according to one embodiment of the present invention includes a mixing step of mixing 0.1 to 30 mass% of an ultrahigh molecular weight olefin polymer (a) (hereinafter also referred to as "polymer (a)") satisfying the following requirements (1) and (2) with 70 to 99.9 mass% of an active material (wherein the total amount of polymer (a) and active material is 100 mass%), and a fibrillation step of forming fibrils of the polymer (a) that satisfy the following requirement (3).
  • polymer (a) ultrahigh molecular weight olefin polymer
  • Requirement (1) The average particle diameter d50 of the polymer (a) is 0.10 to 1000 ⁇ m.
  • Requirement (2) The intrinsic viscosity [ ⁇ ] of the polymer (a) measured in decalin solvent at 135° C. is 1 to 50 dl/g.
  • Requirement (3) The average diameter of the fibrils is 20 to 500 nm, and the average length is 100 to 10000 nm.
  • the requirement (2) is the same as the requirement (i), and the average diameter and average length of the fibrils in the requirement (3) are the same as the average diameter and average length of the fibrils in the electrode binder column.
  • the polymer (a) is the polymer (A) before fibrillation, and its type, physical properties (e.g. melting point), manufacturing method, etc. are the same as those in the section on polymer (A).
  • the average particle size d50 of the polymer (a) is 0.10 to 1000 ⁇ m, preferably 1 to 1000 ⁇ m, more preferably 1 to 200 ⁇ m, even more preferably 1 to 100 ⁇ m, more preferably 1 to 50 ⁇ m, and particularly preferably 3 to 12 ⁇ m.
  • the average particle diameter d50 of the polymer (a) and the average particle diameter d50 of the active material are made approximately the same, an electrode mixture layer from which the active material is less likely to fall off tends to be easily produced by a dry method.
  • the average particle size d50 of the polymer (a) means the average primary particle size.
  • the average particle diameter d50 is specifically determined by the measurement method described in the following Examples.
  • the mixing step is not particularly limited as long as it is a step of mixing 0.1 to 30 mass % of the polymer (a) with 70 to 99.9 mass % of an active material (wherein the total amount of the polymer (a) and the active material is 100 mass %), but it is preferable to dry mix a specific amount of the polymer (a) and the active material.
  • the polymer (a) and the active material are preferably dry-mixed in amounts such that the contents of the polymer (a) and the active material in the resulting mixture are in the same range as the contents of the polymer (A) and the active material in the electrode mixture layer.
  • the above-mentioned additives may be further used.
  • the mixing step it is preferable to mix the raw material components, such as the polymer (a), uniformly, and it is preferable to mix them without applying shear force so as not to change the form or properties of the raw material components.
  • the method of mixing is not particularly limited, and includes various known methods, such as mixing using a degassing mixer, a blade planetary motion mixer, a container rotation type planetary motion mixer, a low-frequency resonant vibration acoustic mixer, a Henschel mixer, a tumbler blender, a V-blender, etc.
  • the fibrillation step is not particularly limited as long as it is a step of forming fibrils of the polymer (a) that satisfy the requirement (3), and any conventionally known fibrillation step can be used.
  • the mixing and fibrillation may be performed as different steps or simultaneously. That is, the mixing step and the fibrillation step may be different steps, or may be a single step in which mixing and fibrillation are performed simultaneously.
  • the fibrillation method is not particularly limited, and various known methods can be used, such as kneading using a (degassing) kneader, dry ball mill, dry bead mill, crusher, mortar, homogenizer, roll mill, etc.
  • the fibrillation step it is preferable to apply a shear force to the polymer (a) in order to form fibrils of the polymer (a).
  • the average fibril length can be adjusted by temperature and the way in which shear is applied. For example, the average fibril length can be made longer by applying shear in one direction.
  • a heat treatment may be performed to soften the polymer (a).
  • the heat treatment is preferably performed at a temperature not higher than the temperature at which the active material, the conductive assistant, etc. are not decomposed.
  • the temperature of the heat treatment is preferably in the range of from 5° C. lower than the melting point of polymer (a) to 5° C. higher than the melting point of polymer (a), and more preferably in the range of from 3° C. lower than the melting point of polymer (a) to the melting point of polymer (a).
  • the polymer (a) may be softened by wetting it with a plasticizer or a solvent before fibrillation. Wetting it with a plasticizer or a solvent is preferable because it makes it easier for the polymer (a) to be sheared and easier to form fibrils.
  • Electrodes An electrode according to an embodiment of the present invention includes the present electrode mixture layer (electrode mixture layers 1 to 3) and a current collector, and when the electrode is used in, for example, a lithium ion secondary battery, it is preferable that the electrode is an electrode capable of absorbing and releasing lithium ions.
  • the electrode may be either a positive electrode or a negative electrode.
  • the electrode is preferably an electrode having the present electrode mixture layer on at least the surface of a current collector, in which case the present electrode mixture layer may be present on the entire surface of the current collector, or the present electrode mixture layer may be present on a part of the current collector.
  • the electrode may further include a layer (film) other than the present electrode mixture layer and the current collector.
  • a positive electrode current collector is usually used as the current collector
  • a negative electrode current collector is usually used as the current collector
  • the positive electrode current collector is not particularly limited, and any known positive electrode current collector can be used.
  • the material for the positive electrode current collector include metal materials such as aluminum (including aluminum alloys), stainless steel, nickel, titanium, and tantalum; and carbon materials such as carbon cloth and carbon paper.
  • aluminum is preferable as the material for the positive electrode current collector in terms of the balance between high conductivity and cost, etc.
  • "aluminum” means pure aluminum or an aluminum alloy.
  • the positive electrode current collector is preferably made of aluminum foil.
  • the material of the aluminum foil is not particularly limited, and examples thereof include A1085 material and A3003 material.
  • the negative electrode current collector is not particularly limited, and any known negative electrode current collector can be used.
  • the material for the negative electrode current collector include metal materials such as copper, nickel, stainless steel, and nickel-plated steel. Among these, the material of the negative electrode current collector is preferably copper from the viewpoint of workability, and the negative electrode current collector is preferably copper foil.
  • the electrode is preferably an electrode obtained by a dry method from the viewpoints of simplification of electrode production, economy, safety, environmental load, and the like.
  • Specific examples of electrodes obtained by the dry method include: A step 1 of dry-mixing the polymer (a) and the active material to obtain an electrode composite material; A step 2 of fibrillating at least a portion of the polymer (a); An electrode obtained by an electrode manufacturing method including: a step 3 of forming an electrode mixture layer from an electrode composite material containing the fibrillated polymer (a); and a step 4 of manufacturing an electrode including the electrode mixture layer and a current collector is preferred.
  • an electrode can be produced by a dry method including step 3 of forming an electrode mixture layer from the present material and step 4 of producing an electrode including the electrode mixture layer and a current collector.
  • Step 1 is a step of dry-mixing the polymer (a) and the active material to obtain an electrode composite material, in which the polymer (a) and the active material are dry-mixed without using a solvent or a dispersion medium.
  • step 1 it is preferable to mix the raw material components such as the polymer (a) uniformly, and it is preferable to mix them without applying shear force so as not to change the morphology or properties of the raw material components.
  • the above-mentioned additives may further be used.
  • the raw material components are preferably dry-mixed in amounts such that the content of each component in the resulting electrode composite material is in the same range as the content of each component in the electrode mixture layer.
  • the method for dry mixing is not particularly limited, and various known methods, such as mixing using a degassing mixer, a blade planetary motion mixer, a container rotation type planetary motion mixer, a low-frequency resonant vibration acoustic mixer, a Henschel mixer, a tumbler blender, a V-blender, etc., can be used.
  • Step 2 is a step of fibrillating at least a part of the polymer (a), and a conventionally known fibrillation step can be adopted.
  • Step 2 may be the same as the fibrillation step in the method for producing the electrode mixture layer.
  • step 1 and step 2 may be performed as different steps or simultaneously. In other words, step 1 and step 2 may be different steps, or may be a single step in which dry mixing and fibrillation are performed simultaneously.
  • Step 3 is a step of forming an electrode mixture layer from an electrode composite material containing the fibrillated polymer (a) or a step of forming an electrode mixture layer from this material, and is preferably a step of forming the electrode composite material containing the fibrillated polymer (a) or this material into a layer (membrane, film).
  • Step 3 is preferably a step of forming an electrode mixture layer so that the thickness of the resulting electrode mixture layer is within the above-mentioned range, and preferably includes a step of applying pressure to the electrode composite material containing the fibrillated polymer (a) or this material to form it.
  • the pressure When the pressure is applied for molding, it is preferable to apply pressure so that the press density of the resulting electrode mixture layer is 1.0 to 4.0 g/cm 3 .
  • the press density of the resulting negative electrode mixture layer is preferably 1.0 to 2.0 g/cm 3 , and more preferably 1.3 to 1.8 g/cm 3 .
  • the press density of the resulting positive electrode mixture layer is 2.5 to 4.0 g/cm 3 .
  • the pressure is preferably 0.1 tons to 100 tons.
  • the temperature during molding under pressure is preferably 20 to 300°C, more preferably 80 to 200°C, and even more preferably 100 to 200°C.
  • step 3 after the electrode composite material containing the fibrillated polymer (a) or this material is molded by applying pressure, a step of heat drying may be carried out, if necessary.
  • the heat drying method includes drying with warm air, hot air, or low humidity air; vacuum drying; drying by irradiation with infrared rays (for example, far infrared rays); and the like.
  • the drying time and drying temperature in the heat drying are not particularly limited, but the drying time is, for example, 1 minute to 24 hours, and the drying temperature is, for example, 80 to 180°C.
  • Step 4 is a step of producing an electrode including the electrode mixture layer and a current collector, and is preferably a step of producing an electrode by laminating the electrode mixture layer and a current collector.
  • the lamination method is preferably a method in which the electrode mixture layer is placed on a current collector and pressed.
  • pressing method various known pressing methods such as roll pressing and plate pressing can be appropriately adopted.
  • the pressing is preferably performed so that the electrode mixture layer in the resulting electrode has a press density of 1.0 to 4.0 g/cm 3 .
  • the press density of the negative electrode mixture layer in the resulting negative electrode is preferably 1.0 to 2.0 g/cm 3 , and more preferably 1.3 to 1.8 g/cm 3 .
  • the pressing is preferably performed so that the press density of the electrode mixture layer in the resulting electrode falls within the above-mentioned range, and the pressing pressure is preferably 0.1 tons to 100 tons.
  • the pressing temperature is preferably 20 to 300°C, more preferably 80 to 200°C, and further preferably 100 to 200°C.
  • the current collector used in step 4 may be subjected to surface treatment such as roughening or the formation of a conductive adhesive layer in order to improve adhesion with the electrode mixture layer.
  • step 4 after pressing the electrode mixture layer onto the current collector, a step of heating and drying may be carried out as necessary.
  • the heat drying method include drying with warm air, hot air, or low-humidity air; vacuum drying; and drying by irradiation with infrared rays (for example, far-infrared rays).
  • the drying time and drying temperature in the heat drying are not particularly limited, but the drying time is, for example, 1 minute to 24 hours, and the drying temperature is, for example, 80 to 180°C.
  • the step 4 may be carried out simultaneously with the step 3, or after the step 3.
  • the electrode composite material containing the fibrillated polymer (a) obtained in the step 2 or this material may be directly placed (e.g., coated) on a current collector and pressed to form an electrode mixture layer, thereby producing an electrode in which the electrode mixture layer and the current collector are laminated.
  • the lithium ion secondary battery according to one embodiment of the present invention is not particularly limited as long as it includes the electrodes and the electrolyte.
  • the lithium ion secondary battery may have a separator between the negative electrode and the positive electrode, and may have a case that contains the electrodes, the electrolyte, and the like.
  • the lithium ion secondary battery includes the electrode, and therefore has excellent battery characteristics (e.g., charge/discharge capacity, battery resistance, etc.).
  • the lithium ion secondary battery can be suitably used in portable devices, vehicle-mounted devices, and the like.
  • At least one of the positive electrode and the negative electrode is an electrode obtained by a dry method, particularly an electrode manufactured by the electrode manufacturing method.
  • one of the positive electrode and the negative electrode of the lithium ion secondary battery may be an electrode manufactured by a wet method or the like.
  • the electrode obtained by the dry method is preferably the negative electrode, from the viewpoint of being less likely to cause a reduction reaction at the reduction potential of the negative electrode than PTFE or PVDF, and being able to function as a binder for a long period of time.
  • the electrolyte is not particularly limited as long as it can be a conductor of alkali metal cations such as lithium ions.
  • the nature of the electrolyte is not particularly limited, and may be, for example, a liquid dissolved in a non-aqueous solvent described below, a gel, or a solid.
  • the electrolyte may be used alone or in combination of two or more.
  • the electrolyte preferably contains at least one type of lithium salt containing fluorine (hereinafter also referred to as "fluorine-containing lithium salt").
  • fluorine-containing lithium salts include inorganic acid anion salts such as lithium hexafluorophosphate ( LiPF6 ), lithium tetrafluoroborate ( LiBF4 ), lithium hexafluoroarsenate ( LiAsF6 ), and lithium hexafluorotantalate ( LiTaF6 ); and organic acid anion salts such as lithium trifluoromethanesulfonate ( LiCF3SO3 ), lithium bis(trifluoromethanesulfonyl)imide (Li( CF3SO2 ) 2N ), and lithium bis( pentafluoroethanesulfonyl)imide (Li(C2F5SO2 ) 2N ) .
  • LiPF6 is particularly preferred as the fluorine-containing lithium salt.
  • the lithium ion secondary battery may contain an electrolyte that is a fluorine-free lithium salt, such as lithium perchlorate ( LiClO4 ), lithium tetrachloroaluminate ( LiAlCl4 ), or lithium decachlorodecaborate ( Li2B10Cl10 ).
  • an electrolyte that is a fluorine-free lithium salt, such as lithium perchlorate ( LiClO4 ), lithium tetrachloroaluminate ( LiAlCl4 ), or lithium decachlorodecaborate ( Li2B10Cl10 ).
  • the lithium ion secondary battery may contain an electrolytic solution in which one or more of the above electrolytes are dissolved in one or more solvents.
  • the electrolytic solution is more preferably a non-aqueous electrolytic solution containing one or more of the above electrolytes and one or more non-aqueous solvents.
  • the electrolytic solution may contain, in addition to the electrolyte and the electrolytic solution, a conventionally known additive used for improving battery performance or the like.
  • the proportion of the fluorine-containing lithium salt relative to 100% by mass of the electrolyte in the electrolytic solution is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and further preferably 80 to 100% by mass.
  • the proportion of LiPF 6 relative to 100% by mass of the electrolyte in the electrolytic solution is also preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and further preferably 80 to 100% by mass.
  • the concentration of the electrolyte in the electrolytic solution is preferably 0.1 to 3 mol/L, and more preferably 0.5 to 2 mol/L.
  • the concentration of LiPF 6 in the electrolyte is also preferably 0.1 to 3 mol/L, more preferably 0.5 to 2 mol/L.
  • non-aqueous solvent examples include cyclic carbonates, fluorine-containing cyclic carbonates, chain carbonates, fluorine-containing chain carbonates, aliphatic carboxylic acid esters, fluorine-containing aliphatic carboxylic acid esters, ⁇ -lactones, fluorine-containing ⁇ -lactones, cyclic ethers, fluorine-containing cyclic ethers, chain ethers, fluorine-containing chain ethers, nitriles, amides, lactams, nitromethane, nitroethane, sulfolane, trimethyl phosphate, dimethyl sulfoxide, and dimethyl sulfoxide phosphate.
  • cyclic carbonates examples include ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC).
  • FEC fluoroethylene carbonate
  • chain carbonates examples include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), and dipropyl carbonate (DPC).
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • MPC methyl propyl carbonate
  • EPC ethyl propyl carbonate
  • DPC dipropyl carbonate
  • fluorine-containing chain carbonate is methyl 2,2,2-trifluoroethyl carbonate.
  • aliphatic carboxylate esters examples include methyl formate, methyl acetate, methyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethylbutyrate, ethyl formate, ethyl acetate, ethyl propionate, ethyl butyrate, ethyl isobutyrate, and ethyl trimethylbutyrate.
  • gamma-lactones examples include gamma-butyrolactone and gamma-valerolactone.
  • Cyclic ethers include, for example, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, and 1,4-dioxane.
  • chain ethers examples include 1,2-ethoxyethane (DEE), ethoxymethoxyethane (EME), diethyl ether, 1,2-dimethoxyethane, and 1,2-dibutoxyethane.
  • nitriles examples include acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, and 3-methoxypropionitrile.
  • An example of an amide is N,N-dimethylformamide.
  • lactams examples include N-methylpyrrolidinone, N-methyloxazolidinone, and N,N'-dimethylimidazolidinone.
  • the non-aqueous solvent preferably contains at least one selected from the group consisting of cyclic carbonates, fluorine-containing cyclic carbonates, chain carbonates, and fluorine-containing chain carbonates.
  • the total proportion of the cyclic carbonates, fluorine-containing cyclic carbonates, chain carbonates and fluorine-containing chain carbonates in the nonaqueous solvent is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, and even more preferably 80 to 100 mass%.
  • the non-aqueous solvent more preferably contains at least one selected from the group consisting of cyclic carbonates and chain carbonates.
  • the total proportion of the cyclic carbonates and chain carbonates in the non-aqueous solvent is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 80 to 100% by mass.
  • the intrinsic viscosity of the non-aqueous solvent is preferably 10.0 mPa ⁇ s or less at 25°C, as this can further improve the dissociation properties of the electrolyte and the mobility of ions.
  • the proportion of the nonaqueous solvent in the nonaqueous electrolyte is preferably 60% by mass or more, and more preferably 70% by mass or more.
  • the upper limit of the proportion of the nonaqueous solvent in the nonaqueous electrolyte solution depends on the contents of other components (e.g., electrolyte), but is, for example, 99 mass %, preferably 97 mass %, and more preferably 90 mass %.
  • the separator is not particularly limited as long as it can electrically insulate the positive electrode from the negative electrode and can allow lithium ions to pass therethrough.
  • the material for the separator include resins such as polyethylene (PE), polypropylene (PP), polyester, cellulose, polyamide, etc.
  • the separator include a porous flat plate containing the resin, a nonwoven fabric containing the resin, etc.
  • the separator is preferably a porous resin film having a single layer or multilayer structure mainly composed of one or more kinds of polyolefin resins.
  • the thickness of the separator is, for example, 5 to 30 ⁇ m.
  • the case is not particularly limited, and may be any known case for a lithium ion secondary battery. Specific examples include a case including a laminate film, and a case including a battery can and a battery can lid.
  • Examples of the method for producing a lithium ion secondary battery include known methods for producing lithium ion secondary batteries, such as a production method including a precursor production step of producing a lithium ion secondary battery precursor by housing a positive electrode, a negative electrode, an electrolyte (or an electrolytic solution), and, if necessary, a separator in a case, and an aging step of subjecting the lithium ion secondary battery precursor to an aging treatment to obtain a lithium ion secondary battery.
  • a production method including a precursor production step of producing a lithium ion secondary battery precursor by housing a positive electrode, a negative electrode, an electrolyte (or an electrolytic solution), and, if necessary, a separator in a case, and an aging step of subjecting the lithium ion secondary battery precursor to an aging treatment to obtain a lithium ion secondary battery.
  • the precursor preparation process preferably includes a step of housing a positive electrode and a negative electrode (with a separator interposed therebetween, if necessary) in a case, and a step of injecting an electrolyte (or an electrolyte solution) into the case housing the positive electrode and the negative electrode (with a separator, if necessary).
  • the aging step preferably comprises subjecting the lithium ion secondary battery precursor to a combination of charging and discharging at least once in an environment of 25 to 70°C.
  • the internal resistance (particularly the positive electrode resistance) of the lithium ion secondary battery tends to be reduced.
  • ⁇ Intrinsic viscosity [ ⁇ ]> The intrinsic viscosity [ ⁇ ] of the ultra-high molecular weight olefin polymer was measured at 135° C. by dissolving the polymer in decalin.
  • ⁇ Average particle diameter d50> When the average particle diameter d50 of the ultra-high molecular weight olefin polymer is 100 ⁇ m or less, the average particle diameter d50 is measured by mass standard using a particle size distribution measuring device ("Coulter Counter Multisizer 4e type", manufactured by Beckman Co., Ltd.). The particle size distribution was measured, and the particle size at which the cumulative mass was 50% in the mass-based particle size distribution was determined as the average particle size d50. When the average particle diameter d50 of the ultra-high molecular weight olefin polymer exceeds 100 ⁇ m, sieves with different mesh sizes were used, and the mass of the particles remaining on each sieve (non-passed portion) was calculated. The cumulative distribution (cumulative unpassed particles (%)/sieve opening ( ⁇ m)) was plotted, and the sieve opening at which the unpassed particles accounted for 50 mass % was determined as the average particle diameter d50 of the particles.
  • ⁇ Melting Point> Using a differential scanning calorimeter (Discovery DSC2500, manufactured by TA Instruments), an ultra-high molecular weight olefin polymer (about 5 mg) was heated from 30° C. to 200° C. at 10° C./min under a nitrogen atmosphere, held for 10 minutes, then cooled to 30° C. at 10° C./min, held at 30° C. for 1 minute, and then heated to 200° C. at 10° C./min. The temperature at the peak apex of the crystal melting peak during the first heating process was taken as the melting point.
  • Discovery DSC2500 manufactured by TA Instruments
  • ⁇ Fibril> Using a scanning electron microscope, the kneaded material (electrode binder) and the electrode mixture layer (mixture layer) prepared by the method described below were observed and photographed. In the photographed field of view, the case where fibrils (fibrous matter) were observed was evaluated as ⁇ (having fibrils), and the case where fibrils (fibrous matter) were not observed was evaluated as ⁇ (having no fibrils). For samples in which fibrils were observed, five fibrils were randomly selected, and the diameter and length of the fibrils were measured by the following procedure, and the average values were calculated. The results are shown in Table 1. The fibril length was measured at a magnification of 3000 times (observation field of view: 40 ⁇ m ⁇ 30 ⁇ m).
  • the observed fibrils were observed at a magnification of 10,000 times, and the diameter of the fibrils was measured.
  • Table 1 the column for fibrils in the composite layer of Examples 3 to 11 is marked with "-". This is because an electrode composite layer (composite layer) was not prepared in Examples 3 to 11, and does not mean that fibrils are not observed in the resulting electrode composite layer (composite layer) when the kneaded product (electrode binder) obtained in Examples 3 to 11 is used.
  • the positive electrode was prepared by a wet method as follows.
  • NCM523 manufactured by Umicore, composition formula: LiNi0.5Co0.2Mn0.3O2
  • Super-P conductive carbon manufactured by TIMCAL
  • KS-6 lake graphite manufactured by TIMREX
  • PVDF polyvinylidene fluoride
  • the prepared slurry was applied to one side of an aluminum foil having a thickness of 20 ⁇ m using a die coater so that the coating mass after drying was 19.0 mg/cm 2 , and then dried.
  • the prepared slurry was similarly applied to the opposite side (uncoated side) of the aluminum foil using a die coater so that the coating mass was 19.0 mg/cm 2 , and then dried.
  • the resulting double-sided coated aluminum foil (total coating amount on both sides: 38.0 mg/cm 2 ) was dried in a vacuum drying oven at 130° C. for 12 hours.
  • the gap (gap) between the upper and lower rolls was adjusted, and the double-sided coated aluminum foil after drying was pressed to a press density of 2.9 ⁇ 0.05 g/cm 3 .
  • the pressed aluminum foil coated on both sides was slit to obtain the coated area (front side: 56 mm x 334 mm, back side: 56 mm x 408 mm) and a tab welding margin, and an aluminum tab was joined to the tab welding margin (the area other than the coated area of the positive electrode current collector) using an ultrasonic joining machine to obtain a positive electrode.
  • the negative electrode was prepared by a dry method as follows.
  • a copper foil having a thickness of 10 ⁇ m was used as a negative electrode current collector, and an electrode mixture layer prepared by the method described below was laminated on two main surfaces of the negative electrode current collector by roll rolling under a condition of 130° C. so that the press density of each side of the obtained negative electrode was 1.45 ⁇ 0.05 g/cm 3. Thereafter, the obtained laminate of the current collector and the electrode mixture layer was slit so as to obtain an electrode mixture layer portion (front surface: 56 mm ⁇ 334 mm, back surface: 56 mm ⁇ 408 mm) and a tab welding margin, and a nickel tab was bonded to the tab welding margin portion (a portion of the negative electrode current collector where the electrode mixture layer was not laminated) by an ultrasonic bonding machine to prepare a negative electrode.
  • Lamination A negative electrode, a separator, a positive electrode, a separator, and a negative electrode were alternately laminated in this order to obtain a laminate including a total of 5 positive electrode layers and 6 negative electrode layers. Note that the positive and negative electrode tabs were laminated on the same side.
  • the obtained laminate was sandwiched between laminate sheets, and three sides of the laminate sheets were heat-sealed to prepare a case containing electrodes. Note that, at this time, the three sides other than the tab side were heat-sealed so that the tabs of the positive and negative electrodes protruded from the laminate sheets.
  • a single-sided composite layer negative electrode was prepared in the same manner as in the preparation of the negative electrode, except that an electrode composite layer prepared by a method described below was laminated on one main surface of the negative electrode current collector.
  • the prepared single-sided composite layer negative electrodes were wound around stainless steel round bars (diameters: 1 mm ⁇ , 3 mm ⁇ , 5 mm ⁇ , 7 mm ⁇ , 10 mm ⁇ ) with the electrode composite layer side facing outward, and the presence or absence of cracks on the surface of the electrode composite layer was visually confirmed, and the diameter of the largest round bar that did not develop cracks was measured.
  • Table 1 it can be determined that the smaller the diameter of the round bar that is wound, the better the windability.
  • ⁇ Peel strength> A double-sided tape manufactured by Nichiban Co., Ltd. having a width of 20 mm and a length of 82 mm was attached to a stainless steel plate, and the electrode composite layer side of the single-sided composite layer negative electrode prepared in the same manner as the winding property was attached to the double-sided tape. Then, a cellophane tape manufactured by Nichiban Co., Ltd. having a width of 12 mm and a length of 100 mm was attached to the negative electrode current collector of the attached single-sided composite layer negative electrode.
  • the end of the cellophane tape attached to the negative electrode current collector was pulled at an angle of 180° by a tensile tester (manufactured by Intesco Co., Ltd., 201x, tensile speed 50 mm/min), and the peel strength between the electrode composite layer of the single-sided composite layer negative electrode and the current collector was measured.
  • the results are shown in Table 1.
  • reaction product was filtered, washed three times with 500 mL of xylene and twice with 500 mL of decane, filtered, and then 120 mL of decane was added to prepare a decane slurry of the solid catalyst component (b).
  • a part of the obtained decane slurry of the solid catalyst component (b) was collected and the concentration was examined, and the zirconium concentration was 0.000307 mmol/mL and the magnesium concentration was 0.0576 mmol/mL.
  • Adeka Pluronic L-71 manufactured by ADEKA Corporation
  • 3.75 mL of hydrogen were charged as an antistatic agent, and a polymerization reaction was carried out at 50°C for 117 minutes while supplying ethylene gas so that the total pressure was 0.5 MPaG.
  • the obtained polymer was filtered and washed with decane, washed with hexane, and then dried under reduced pressure at 80° C. for 18 hours to obtain 25.5 g of polymer (a-5).
  • Polymer (a-6) was produced in the same manner as in Synthesis Examples 4 and 5, except that the amount of each raw material added was adjusted so as to obtain an ultrahigh molecular weight ethylene polymer (a-6) (hereinafter also referred to as "polymer (a-6)") having the following physical properties.
  • Polymer (a-7) was produced in the same manner as in Synthesis Examples 4 and 5, except that the amount of each raw material added was adjusted so as to obtain an ultrahigh molecular weight ethylene polymer (a-7) (hereinafter also referred to as "polymer (a-7)") having the following physical properties.
  • Polymer (a-8) was produced in the same manner as in Synthesis Examples 1 to 3, except that the amount of each raw material added was adjusted so as to obtain an ultrahigh molecular weight ethylene polymer (a-8) (hereinafter also referred to as "polymer (a-8)") having the following physical properties.
  • Polymer (a-9) was produced in the same manner as in Synthesis Examples 1 to 3, except that the amount of each raw material added was adjusted so as to obtain an ultrahigh molecular weight ethylene polymer (a-9) (hereinafter also referred to as "polymer (a-9)") having the following physical properties.
  • Polymer (a-10) was produced in the same manner as in Synthesis Examples 1 to 3, except that the amount of each raw material added was adjusted so as to obtain an ultrahigh molecular weight ethylene polymer (a-10) (hereinafter also referred to as "polymer (a-10)") having the following physical properties.
  • Polymer (a-11) was produced in the same manner as in Synthesis Examples 1 to 3, except that the amount of each raw material added was adjusted so as to obtain an ultrahigh molecular weight ethylene polymer (a-11) (hereinafter also referred to as "polymer (a-11)") having the following physical properties.
  • Example 1 A mixture was prepared by stirring 4 parts by mass of the polymer (a-1) and 96 parts by mass of natural graphite (average particle diameter 20 ⁇ m) as an active material at room temperature for 5 minutes using a planetary centrifugal degassing mixer (ARE-310, manufactured by Thinky Corporation). Next, the prepared mixture was kneaded for 10 minutes in a 500 mL mortar heated to 135° C. and a pestle heated to the same temperature as the mortar, to prepare a kneaded product (electrode binder).
  • ARE-310 planetary centrifugal degassing mixer
  • the prepared kneaded material was rolled using a heated roll press (manufactured by Thank Metal Co., Ltd., roll diameter: 250 mm ⁇ , roll temperature: 130° C., roll speed: 0.3 m/min, gap: 100 ⁇ m) to prepare a film-like electrode mixture layer having a thickness of 100 ⁇ m.
  • a heated roll press manufactured by Thank Metal Co., Ltd., roll diameter: 250 mm ⁇ , roll temperature: 130° C., roll speed: 0.3 m/min, gap: 100 ⁇ m
  • Example 2 A mixture, a kneaded material and an electrode mixture layer were prepared in the same manner as in Example 1, except that the polymer (a-2) was used instead of the polymer (a-1).
  • Example 3 A mixture and a kneaded product were prepared in the same manner as in Example 1, except that the polymer (a-3) was used instead of the polymer (a-1).
  • Example 4 A mixture and a kneaded product were prepared in the same manner as in Example 1, except that the polymer (a-4) was used instead of the polymer (a-1).
  • Example 5 A mixture and a kneaded product were prepared in the same manner as in Example 1, except that the polymer (a-5) was used instead of the polymer (a-1).
  • Example 6 A mixture and a kneaded product were prepared in the same manner as in Example 1, except that the polymer (a-6) was used instead of the polymer (a-1).
  • Example 7 A mixture and a kneaded product were prepared in the same manner as in Example 1, except that the polymer (a-7) was used instead of the polymer (a-1).
  • Example 8 To 80 parts by mass of the polymer (a-2), 20 parts by mass of decane was added, and the mixture was heated in a heat-resistant glass bottle at 80° C. for 48 hours to obtain a polymer (a-2) moistened with decane.
  • the intrinsic viscosity [ ⁇ ] of the obtained polymer (a-2) moistened with decane was 11.5 dl/g, and the average particle diameter d50 was 11.5 ⁇ m.
  • Example 9 A mixture and a kneaded product were prepared in the same manner as in Example 8, except that the polymer (a-5) was used instead of the polymer (a-2).
  • the intrinsic viscosity [ ⁇ ] of the resulting polymer (a-5) wetted with decane was 35.0 dl/g, and the average particle size d50 was 520 ⁇ m.
  • Example 10 A mixture and a kneaded product were prepared in the same manner as in Example 8, except that the polymer (a-6) was used instead of the polymer (a-2).
  • the intrinsic viscosity [ ⁇ ] of the resulting polymer (a-6) wetted with decane was 5.1 dl/g, and the average particle size d50 was 530 ⁇ m.
  • Example 11 A mixture and a kneaded product were prepared in the same manner as in Example 8, except that the polymer (a-7) was used instead of the polymer (a-2).
  • the intrinsic viscosity [ ⁇ ] of the obtained polymer (a-8) wetted with decane was 12.3 dl/g, and the average particle size d50 was 520 ⁇ m.
  • Example 12 A mixture was prepared by stirring 4 parts by mass of the polymer (a-1) and 96 parts by mass of natural graphite (average particle diameter 20 ⁇ m) as an active material at room temperature for 5 minutes using a planetary centrifugal degassing mixer (ARE-310, manufactured by Thinky Corporation). Next, the prepared mixture was kneaded for 10 minutes using a grinder (manufactured by Ishikawa Plant Co., Ltd.) set to 135°C while rotating and revolving a pestle set to 135°C at a rotation speed of 30 rpm to prepare a kneaded product. Further, an electrode mixture layer was produced in the same manner as in Example 1, except that the produced kneaded material was used.
  • ARE-310 planetary centrifugal degassing mixer
  • Example 13 A mixture, a kneaded material and an electrode mixture layer were prepared in the same manner as in Example 12, except that the polymer (a-2) was used instead of the polymer (a-1).
  • Example 14 A mixture, a kneaded material, and an electrode mixture layer were prepared in the same manner as in Example 1, except that the polymer (a-8) was used instead of the polymer (a-1).
  • Example 15 A mixture, a kneaded material, and an electrode mixture layer were prepared in the same manner as in Example 1, except that the polymer (a-9) was used instead of the polymer (a-1).
  • Example 16 A mixture, a kneaded material and an electrode mixture layer were prepared in the same manner as in Example 1, except that the polymer (a-10) was used instead of the polymer (a-1).
  • Example 17 A mixture, a kneaded material, and an electrode mixture layer were prepared in the same manner as in Example 1, except that the polymer (a-11) was used instead of the polymer (a-1).
  • Example 1 A mixture, a kneaded product, and an electrode mixture layer were prepared in the same manner as in Example 1, except that the polymer (a-2) was used instead of the polymer (a-1) and the temperature of the mortar and pestle was heated to 130° C. and kneaded.
  • Example 2 A mixture, a kneaded product, and an electrode mixture layer were prepared in the same manner as in Example 1, except that the polymer (a-2) was used instead of the polymer (a-1) and the temperature of the mortar and pestle was heated to 145° C. and kneaded.
  • Reference Example 2 A mixture and an electrode mixture layer were prepared in the same manner as in Reference Example 1, except that the polymer (a-2) was used instead of the polymer (a-1). Since no kneading was performed before preparing the electrode mixture layer, no fibrils were formed in the electrode mixture layer.

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Abstract

Un premier mode de réalisation de la présente invention concerne un liant d'électrode, une couche de mélange d'électrode, un procédé de fabrication d'une couche de mélange d'électrode, une électrode ou une batterie secondaire au lithium-ion, le liant d'électrode contenant un polymère d'oléfine de poids moléculaire ultra-élevé (A) qui satisfait l'exigence (i), et des fibrilles du polymère d'oléfine de poids moléculaire ultra-élevé (A), les fibrilles ayant un diamètre de 20 à 500 nm et une longueur de 100 à 10000 nm.　Exigence (i) : La viscosité limite [η] mesurée dans un solvant de décaline à 135°C est de 1 à 50 dl/g.
PCT/JP2024/005427 2023-02-21 2024-02-16 Liant d'électrode, couche de mélange d'électrode, matériau pour former une couche de mélange d'électrode, procédé de fabrication de couche de mélange d'électrode, électrode et batterie secondaire au lithium-ion Ceased WO2024176955A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010507264A (ja) * 2006-10-17 2010-03-04 マックスウェル テクノロジーズ， インク エネルギー保存装置用電極
JP2022003694A (ja) * 2016-03-01 2022-01-11 マックスウェル テクノロジーズ インコーポレイテッド エネルギー貯蔵装置用電極フィルム、電極およびエネルギー貯蔵装置
WO2022050252A1 (fr) * 2020-09-01 2022-03-10 ダイキン工業株式会社 Mélange d'accumulateurs entièrement solides, feuille de mélange d'accumulateurs entièrement solides, procédé de fabrication y relatif et accumulateur entièrement solide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010507264A (ja) * 2006-10-17 2010-03-04 マックスウェル テクノロジーズ， インク エネルギー保存装置用電極
JP2022003694A (ja) * 2016-03-01 2022-01-11 マックスウェル テクノロジーズ インコーポレイテッド エネルギー貯蔵装置用電極フィルム、電極およびエネルギー貯蔵装置
WO2022050252A1 (fr) * 2020-09-01 2022-03-10 ダイキン工業株式会社 Mélange d'accumulateurs entièrement solides, feuille de mélange d'accumulateurs entièrement solides, procédé de fabrication y relatif et accumulateur entièrement solide

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