WO2024203399A1 - 樹脂組成物、バインダー樹脂、高分子薄膜及び電池 - Google Patents

樹脂組成物、バインダー樹脂、高分子薄膜及び電池 Download PDF

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WO2024203399A1
WO2024203399A1 PCT/JP2024/010058 JP2024010058W WO2024203399A1 WO 2024203399 A1 WO2024203399 A1 WO 2024203399A1 JP 2024010058 W JP2024010058 W JP 2024010058W WO 2024203399 A1 WO2024203399 A1 WO 2024203399A1
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Prior art keywords
general formula
copolymer
resin composition
thin film
mol
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PCT/JP2024/010058
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English (en)
French (fr)
Japanese (ja)
Inventor
孝至 森岡
康貴 渡邉
紗英 橋本
英生 合田
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Lintec Corp
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Lintec Corp
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Priority to US19/110,480 priority Critical patent/US20260001985A1/en
Priority to EP24779528.9A priority patent/EP4692164A1/en
Priority to KR1020257008741A priority patent/KR102864227B1/ko
Priority to JP2024559708A priority patent/JP7644875B2/ja
Priority to CN202480005681.2A priority patent/CN120322481A/zh
Publication of WO2024203399A1 publication Critical patent/WO2024203399A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0291—Aliphatic polycarbonates unsaturated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M4/62—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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 invention relates to a resin composition, a binder resin, a polymer thin film, and a battery.
  • Polycarbonate is used in various applications, for example, as a material in the battery field.
  • Binder resins containing polycarbonate are used, for example, as binding agents for forming electrodes.
  • Polymer thin films containing polycarbonate are used, for example, as battery separators.
  • Patent Document 1 discloses a polymer binder containing a three-dimensionally crosslinked aliphatic polycarbonate.
  • the polymer binder described in Patent Document 1 is a binder for solid electrolytes, and is not intended for use in batteries that use electrolytic solutions. Therefore, when an electrode made using this polymer binder is used in a battery that uses electrolytic solutions, there is a risk of problems occurring, such as the polymer binder dissolving into the electrolytic solution.
  • the object of the present invention is to provide a crosslinkable resin composition, as well as a binder resin, a polymer thin film, and a battery.
  • R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • L 1 and L 2 are each independently a single bond or an alkylene group having 1 to 3 carbon atoms
  • X 1 is any reactive group among the groups represented by the following structural formula (2-1) and the following structural formula (2-2).
  • the copolymer further contains at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (3) and a structural unit represented by the following general formula (4), in an amount of 0.1 mol % to 30.0 mol %: Resin composition.
  • R2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • L3 and L4 are each independently a single bond or an alkylene group having 1 to 3 carbon atoms
  • X2 is any reactive group selected from the groups represented by the following structural formula (4-1) and the following structural formula (4-2).
  • the crosslinked product of the resin composition is the amount of the copolymer eluted in ethyl acetate is 10% or less;
  • the swelling ratio of the copolymer in a mixed solvent of ethylene carbonate and dimethyl carbonate in a volume ratio of 1:1 is 100% or more.
  • a crosslinkable resin composition as well as a binder resin, a polymer thin film, and a battery.
  • FIG. 1 is a cross-sectional view illustrating an example of a main part of a battery according to an embodiment of the present invention.
  • FIG. 2 is a diagram for explaining the action and effect when the polymer thin film according to the present embodiment is used as a battery separator.
  • 1 is a chart showing the results of 1 H-NMR measurement of the copolymer produced in Example 1.
  • 1 is a chart showing the results of 1 H-NMR measurement of the copolymer produced in Example 3.
  • the resin composition according to this embodiment contains a copolymer that includes a structural unit represented by general formula (1) and 0.3 mol % or more and 20.0 mol % or less of a structural unit represented by general formula (2).
  • the resin composition has the above-mentioned structure, and thus has crosslinking properties.
  • a binder resin having excellent adhesion to metal foil and excellent binding properties to inorganic materials can be obtained.
  • a polymer thin film having high swelling properties in an electrolyte solution or the like can be obtained.
  • the copolymer used in the resin composition according to the present embodiment has a carbonate skeleton as the main polymer skeleton, which improves compatibility with the electrolyte.
  • the polymer thin film as a separator can be swollen after the electrolyte is injected.
  • the crosslinking reaction proceeds moderately, so that it is possible to achieve both a high degree of swelling and a low amount of elution.
  • the resin composition according to this embodiment may contain other components as long as it contains the specific copolymer having the above structure, as long as the purpose of the present invention is not impaired.
  • the copolymer contained in the resin composition according to this embodiment includes a copolymer containing a constitutional unit represented by the following general formula (1) and 0.3 mol % or more and 20.0 mol % or less of a constitutional unit represented by the following general formula (2).
  • R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.
  • L 1 and L 2 each independently represent a single bond or an alkylene group having 1 to 3 carbon atoms, preferably a methylene group or an ethylene group, and particularly preferably a methylene group.
  • X1 is any one of reactive groups represented by the following structural formula (2-1) and the following structural formula (2-2): The wavy line in the structural formula represents a bond position.
  • Such a copolymer may be a random copolymer or a block copolymer. From the viewpoint of ease of synthesis, it is preferable that the copolymer is a random copolymer.
  • the copolymer contained in the resin composition according to this embodiment for example, when it is a copolymer composed of a constitutional unit represented by general formula (1) and a constitutional unit represented by general formula (2), has the following constitutional ratio.
  • the ratio of the structural unit represented by the general formula (2) must be 0.3 mol% or more and 20 mol% or less with respect to all structural units. If this ratio is less than 0.3 mol%, the amount of elution will be high. On the other hand, if this ratio exceeds 20.0 mol%, the crosslinking density of the copolymer will be high, and the swelling property will be reduced.
  • the ratio of the constitutional unit represented by the general formula (2) is preferably 1.0 mol% or more, more preferably 1.5 mol% or more, and even more preferably 1.8 mol% or more.
  • the ratio of the constitutional unit represented by the general formula (2) is preferably 19.0 mol% or less, more preferably 18.0 mol% or less, even more preferably 12.0 mol% or less, and particularly preferably 6.0 mol% or less.
  • the ratio of the structural units represented by general formula (1) must be 80.0 mol% or more and 99.7 mol% or less with respect to all structural units.
  • the ratio of the structural units represented by general formula (1) is preferably 81.0 mol% or more, more preferably 82.0 mol% or more, even more preferably 88.0 mol% or more, and particularly preferably 94.0 mol% or more.
  • the ratio of the structural units represented by general formula (1) is preferably 99.0 mol% or less, more preferably 98.5 mol% or less, and even more preferably 98.2 mol% or less.
  • the copolymer contained in the resin composition according to this embodiment preferably further contains at least one structural unit selected from the group consisting of structural units represented by the following general formula (3) and structural units represented by the following general formula (4), in an amount of 0.1 mol % or more and 30.0 mol % or less:
  • R2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.
  • L3 and L4 each independently represent a single bond or an alkylene group having 1 to 3 carbon atoms, preferably a methylene group or an ethylene group, and particularly preferably a methylene group.
  • X2 is any one of reactive groups represented by the following structural formula (4-1) and the following structural formula (4-2): The wavy line in the structural formula represents a bond position.
  • the copolymer contained in the resin composition according to the present embodiment has, for example, the following composition ratio in the case of a copolymer composed of a constitutional unit represented by general formula (1), a constitutional unit represented by general formula (2), a constitutional unit represented by general formula (3), and a constitutional unit represented by general formula (4).
  • the ratio of the constitutional units represented by the general formula (2) is as described above.
  • the total ratio of the structural unit represented by general formula (3) and the structural unit represented by general formula (4) is preferably 0.1 mol% or more and 30.0 mol% or less with respect to all structural units. If the total ratio of these is less than 0.1 mol%, the effect of the ether skeleton tends not to be fully exerted.On the other hand, if the total ratio of these is more than 30.0 mol%, the compatibility with the electrolyte solution tends to be poor, the swelling degree tends to decrease, and the ion conductivity tends to decrease.
  • the total ratio of these is preferably 1.0 mol% or more, and more preferably 2.0 mol% or more, while the total ratio of these is preferably 25.0 mol% or less, more preferably 20.0 mol% or less, and particularly preferably 10.0 mol% or less.
  • the ratio of the structural units represented by general formula (1) is preferably 50.0 mol% or more and 99.6 mol% or less with respect to all structural units.
  • the ratio of the structural units represented by general formula (1) is preferably 55.0 mol% or more, and more preferably 60.0 mol% or more.
  • the ratio of the structural units represented by general formula (1) is preferably 98.0 mol% or less, and more preferably 94.0 mol% or less.
  • the molecular weight of the copolymer according to this embodiment, measured by the method shown in the measurement example, is preferably 5,000 or more and 5,000,000 or less, and more preferably 10,000 or more and 1,000,000 or less, when expressed as a weight average molecular weight (Mw). Furthermore, the molecular weight of the copolymer according to this embodiment, measured by the method shown in the measurement example, is preferably 3,000 or more and 3,000,000 or less, and more preferably 5,000 or more and 500,000 or less, when expressed as a number average molecular weight (Mn). In addition, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 1 to 10, more preferably 1.1 to 5.
  • the molecular weight and molecular weight distribution of the copolymer are in the above range, sufficient handling properties can be obtained when the copolymer is formed into a film. Furthermore, when the copolymer is used as a binder, when the molecular weight and molecular weight distribution of the copolymer are in the above range, the viscosity of the slurry becomes appropriate when preparing an electrode slurry, the sedimentation of the active material and the conductive assistant is suppressed, and sufficient dispersibility of the active material and the conductive assistant can be obtained.
  • the method for producing the copolymer contained in the resin composition according to the present embodiment is not particularly limited, and the copolymer can be obtained by a known method.
  • the copolymer can be produced by the following method. As described in the Examples below, it can be produced by copolymerizing an epoxide monomer such as propylene oxide with carbon dioxide in the presence of a polymerization catalyst. Specifically, propylene oxide undergoes ring-opening to become a constitutional unit represented by general formula (3), and a part of propylene oxide undergoes ring-opening polymerization with carbon dioxide to become a constitutional unit represented by general formula (1).
  • the polymerization catalyst used in producing the copolymer is not particularly limited, and examples include metal salen complex catalysts such as cobalt salen catalysts and organozinc catalysts.
  • the amount of the polymerization catalyst used in the copolymerization reaction of the epoxide monomer with carbon dioxide is preferably 0.05 mol or less, more preferably 0.01 mol or less, and particularly preferably 0.001 mol or less, per 1 mol of the epoxide monomer.
  • a metal-salen complex catalyst is used, a co-catalyst can be used.
  • the co-catalyst for example, an onium salt compound is preferable.
  • onium salt compound examples are not particularly limited, but from the viewpoint of having high reaction activity, bis(triphenylphosphoranylidene)ammonium chloride, piperidine, bis(triphenylphosphoranylidene)ammonium fluoride, ammonium pentafluorobenzoate, tetra-n-butylammonium chloride, and the like are preferable.
  • the optimum polymerization conditions vary depending on the type of catalyst, but for example, the pressure of carbon dioxide in the reaction vessel is 0.1 MPa or more and 10 MPa or less, preferably 0.5 MPa or more and 5 MPa or less.
  • the polymerization temperature is preferably about room temperature (25° C.) from the viewpoint of good catalytic action and accelerated reaction rate.
  • examples of the epoxide monomer used as a starting material include ethylene oxide, propylene oxide, 1,2-butylene oxide, allyl glycidyl ether, and 4-hydroxybutyl acrylate glycidyl ether.
  • the molar ratio of the structural unit represented by general formula (1) and the structural unit represented by general formula (2) in the copolymer may not match the molar mixture ratio of the epoxide monomer that is the starting material for the structural unit represented by general formula (1) and the epoxide monomer that is the starting material for the structural unit represented by general formula (2) due to differences in reactivity.
  • the amount of copolymer eluted in ethyl acetate is preferably 40% or less, more preferably 30% or less, even more preferably 20% or less, particularly preferably 10% or less, and very preferably 7% or less.
  • the amount of eluted copolymer is preferably as low as possible because the eluted low molecular weight component becomes an irreversible capacity.
  • the lower limit of the amount of eluted copolymer is not particularly limited, and may be, for example, 1% or more, 0.1% or more, or 0%.
  • the amount of the copolymer eluted in ethyl acetate is within the above range, and that the degree of swelling of the copolymer in a mixed solvent of ethylene carbonate and dimethyl carbonate in a volume ratio of 1:1 is 100% or more.
  • the crosslinked product of the resin composition according to this embodiment preferably has high swelling properties in the electrolyte and in carbonate-based solvents used as the solvent for the electrolyte.
  • the degree of swelling of the copolymer in the above-mentioned mixed solvent of ethylene carbonate and dimethyl carbonate in a volume ratio of 1:1 is preferably 100% or more, more preferably 200% or more, even more preferably 300% or more, particularly preferably 500% or more, very preferably 700% or more, and most preferably 900% or more.
  • the upper limit of this degree of swelling is not particularly limited, and may be, for example, 2000% or less.
  • a photopolymerization initiator is preferably used from the viewpoint of easily obtaining a polymer thin film in which the copolymer is crosslinked.
  • the thin film containing the copolymer is crosslinked by reaction of reactive groups (allyl group and (meth)acryloyl group) in the side chain of the copolymer in the thin film.
  • the photopolymerization initiator is not particularly limited, and examples thereof include known compounds.
  • the photopolymerization initiator is preferably a photopolymerization initiator that is sensitive to ultraviolet light.
  • the photopolymerization initiator may be used alone or in combination of two or more types.
  • photopolymerization initiators include ⁇ -ketol compounds such as 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, ⁇ -hydroxy- ⁇ , ⁇ '-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, and 1-hydroxycyclohexylphenylketone; acetophenone compounds such as methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, and 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinopropane-1; benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether, and anisoin methyl ether; Ketal compounds such as benzyl dimethyl ketal; aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; photoactive oxime compounds such as 1-phenone-1,1-propyl
  • the content of the photopolymerization initiator is, for example, preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 7.5 parts by mass or less, and even more preferably 1 part by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the copolymer.
  • the resin composition according to this embodiment is molded into a predetermined shape, and the molded product is irradiated with energy rays, whereby the copolymer is crosslinked, and a thin film that is a crosslinked product of the copolymer is obtained.
  • the type of energy rays is not particularly limited, but ultraviolet rays are preferred in terms of reactivity and workability.
  • the device for irradiating the molded product with ultraviolet rays is not particularly limited, and may be, for example, a device equipped with an ultraviolet LED lamp, a device equipped with a high-pressure mercury lamp, or a device equipped with a metal halide lamp.
  • the conditions for irradiating the molded product with ultraviolet light are not particularly limited.
  • Examples of the maximum illuminance and the cumulative light amount when irradiating the molded product with ultraviolet light include the following conditions.
  • the maximum illuminance is preferably 5 mW/cm2 or more and 1000 mW/ cm2 or less.
  • the cumulative light amount is preferably 50 mJ/ cm2 or more and 5000 mJ/ cm2 or less.
  • the binder resin according to the present embodiment contains the resin composition according to the present embodiment.
  • the binder resin according to the present embodiment When used as a material for a composite layer in an electrode of a secondary battery, the binder resin according to the present embodiment has excellent swelling properties with respect to an electrolyte, and has excellent adhesion to a metal foil and binding properties for inorganic materials. The reason for this is unclear, but is considered to be as follows.
  • binder resins when used in the composite layer of secondary batteries such as lithium ion batteries, have been designed to have low swelling properties in response to an electrolyte, so that even if the binder resin swells with the electrolyte, it is possible to obtain adhesion between the composite layer and the current collector and binding between the active materials in the composite layer. It is considered that the composite layer in contact with the electrolyte has a contact area between the binder resin and the active material, and a contact area between the active material and the electrolyte, due to the electrolyte permeating into the composite layer.
  • binder resins have low swelling properties with respect to the electrolyte, so that ionic conductivity is difficult to be expressed, and the ionic conductivity of lithium ions and the like contained in the electrolyte is low in the contact area between the binder resin and the active material. On the other hand, the ionic conductivity of lithium ions and the like contained in the electrolyte is improved in the contact area between the active material and the electrolyte.
  • conventional binder resins have low swelling properties with respect to the electrolyte, so the area of the contact area between the binder resin and the active material does not expand much, and while the contact area is small, the area of the contact area between the active material and the electrolyte is large.
  • the electrolyte is unlikely to decompose in the contact area between the binder resin and the active material, but a decomposition layer of the electrolyte, called a solid electrolyte interface (SEI) layer, is likely to be formed in the contact area between the active material and the electrolyte.
  • SEI solid electrolyte interface
  • the binder resin according to the present embodiment when used in a composite layer of a secondary battery such as a lithium ion battery, the binder resin according to the present embodiment has high swelling properties with respect to the electrolyte, since it contains a copolymer having a carbonate skeleton as the main polymer skeleton, and thus has improved compatibility with the electrolyte.
  • the binder resin according to the present embodiment swells significantly upon contact with the electrolyte, thereby exhibiting ionic conductivity.
  • the binder resin according to the present embodiment since the binder resin according to the present embodiment has high swelling properties with respect to the electrolyte, the area of the contact region between the binder resin and the active material is large, while the area of the contact region between the active material and the electrolyte is small. For this reason, when the binder resin according to the present embodiment is used, ionic conductivity is exhibited in the contact region between the binder resin and the active material, and the electrolyte is unlikely to decompose, and the area in which the SEI layer is formed in the contact region between the active material and the electrolyte is thought to be suppressed.
  • the binder resin according to the present embodiment when used in a composite layer of a secondary battery such as a lithium ion battery, it is thought to contribute to improving the life of the electrolyte, which is thought to result in improved battery performance.
  • the swelling in the electrolyte is too high, the adhesion to the metal foil and the binding of the inorganic material are likely to decrease.
  • the binder resin according to this embodiment has excellent adhesion to metal foil and binding properties for inorganic materials, and can be used in applications where such properties are required.
  • the binder resin according to this embodiment is preferably used in battery applications, for example.
  • the binder resin according to this embodiment is preferably a binder resin for battery electrodes, for example, and is also preferably a binder resin for electrodes of secondary batteries such as lithium ion batteries.
  • the binder resin according to this embodiment may be used as a binder resin used in a composite layer in a positive electrode, or may be used as a binder resin used in a composite layer in a negative electrode.
  • the polymer thin film according to the present embodiment contains the resin composition according to the present embodiment. According to the polymer thin film according to the present embodiment, a polymer thin film having high swelling properties in an electrolyte solution or the like can be obtained. The reason is unclear, but is thought to be as follows.
  • the copolymer used in the polymer thin film according to the present embodiment has a carbonate skeleton as the main polymer skeleton, which improves compatibility with the electrolyte solution. Therefore, when assembling a battery, the polymer thin film as a separator can be swollen after the electrolyte solution is injected. And, by containing a predetermined amount of a constitutional unit represented by the general formula (2) having a reactive group, the crosslinking reaction proceeds appropriately, so that it is possible to achieve both a high degree of swelling and a low amount of elution.
  • the polymer thin film according to this embodiment has high swelling properties in electrolytes and the like, and can therefore be used in applications where such properties are required.
  • the polymer thin film according to this embodiment is preferably used, for example, in batteries.
  • the polymer thin film according to this embodiment is preferably, for example, a battery separator, and is also preferably a battery separator for a lithium ion or other secondary battery.
  • the polymer thin film according to this embodiment is also preferably, for example, an anode protective film that covers at least a portion of the anode of a battery, and is also preferably an anode protective film for a lithium ion or other secondary battery.
  • the battery according to this embodiment is a battery to which the resin composition according to this embodiment is applied.
  • the battery according to this embodiment includes the binder resin according to this embodiment as a material constituting the electrodes of the battery.
  • the battery according to this embodiment also includes the polymer thin film according to this embodiment as, for example, a battery separator.
  • the battery is composed of a positive electrode, a negative electrode, and an electrolyte layer disposed between the positive electrode and the negative electrode. With this configuration, a battery with excellent characteristics can be obtained.
  • the battery is preferably a secondary battery, and more preferably a lithium ion secondary battery or the like.
  • the structure of the battery according to this embodiment is not particularly limited, and may be a stacked structure or a wound structure.
  • FIG. 1 shows an example of a battery using the polymer thin film according to the present embodiment.
  • the battery 100 shown in FIG. 1 is a lithium ion secondary battery.
  • the battery 100 includes a positive electrode 10, a negative electrode 20, and an electrolyte layer 30 between the positive electrode 10 and the negative electrode 20.
  • the positive electrode 10 is composed of a positive electrode current collector 13 and a positive electrode composite layer 11 laminated on the positive electrode current collector 13, and the negative electrode 20 is composed of a negative electrode current collector 23 and a negative electrode composite layer 21 laminated on the negative electrode current collector 23.
  • the electrolyte layer 30 is composed of an electrolyte solution 33 and a separator 31 impregnated with the electrolyte solution 33, and the separator 31 separates the positive electrode 10 side from the negative electrode 20 side.
  • the battery 100 has a laminated structure in which a positive electrode current collector 13, a positive electrode composite layer 11, an electrolyte layer 30, a negative electrode composite layer 21, and a negative electrode current collector 23 are laminated in this order from the positive electrode current collector 13 toward the negative electrode current collector 23, and the laminated structure is contained inside a container not shown.
  • positive electrode mixture layer 11 and negative electrode mixture layer 21 preferably contain a binder resin (not shown) according to the present embodiment.
  • positive electrode mixture layer 11 and negative electrode mixture layer 21 contain electrolyte solution 33 due to permeation of electrolyte solution 33 of electrolyte layer 30, and the binder resin according to the present embodiment (not shown) is swelled by electrolyte solution 33.
  • the polymer thin film according to this embodiment is preferably used as the separator 31.
  • the polymer thin film according to this embodiment is preferably used as a negative electrode protective film (not shown) that covers at least a portion of negative electrode mixture layer 21 .
  • the battery using the polymer thin film according to this embodiment has the above-mentioned configuration, and thus can suppress the generation of dendrites.
  • the reason for this is unclear, but is thought to be as follows.
  • the polymer thin film according to this embodiment is used as the separator 31, when assembling the battery, after the electrolyte is injected, the separator 31 and the electrolyte 33 are separated as shown in FIG. 2(A). In this state, a gap due to fine irregularities exists between the negative electrode mixture layer 21 and the separator 31. The inventors presume that dendrites precipitate in this portion.
  • the separator 31 using the polymer thin film according to this embodiment has high swelling properties in the electrolyte 33, so that after a certain time has passed after the electrolyte is injected, the separator 31 swells as shown in FIG. 2(B). Then, due to this swelling of the separator 31, the gap between the negative electrode mixture layer 21 and the separator 31 disappears as shown in FIG. 2(C). Therefore, when the polymer thin film according to this embodiment is used as the separator 31, the occurrence of dendrites can be suppressed.
  • the example of the battery according to this embodiment is not limited to this.
  • the battery according to this embodiment can adopt various forms as long as the polymer thin film according to this embodiment is used.
  • Materials used for the positive and negative electrode current collectors include, for example, metal foils or metal plates such as copper, aluminum, nickel, titanium, and stainless steel, as well as carbon sheets and carbon nanotube sheets.
  • the positive electrode composite layer is preferably composed of a positive electrode active material such as a lithium-containing composite oxide, a conductive assistant such as a carbon-based material, and the binder resin according to this embodiment.
  • the negative electrode composite layer is preferably composed of a negative electrode active material such as acetylene black, carbon nanotubes, carbon nanofibers, graphene, etc., and the binder resin according to this embodiment.
  • the electrolyte layer is preferably composed of, for example, an electrolyte solution and a separator that is a polymer thin film according to this embodiment.
  • the electrolyte preferably contains a lithium salt and a carbonate-based solvent.
  • the molar ratio of the lithium salt to the carbonate-based solvent is preferably 1/6 or more and 1/1 or less. This molar ratio is more preferably 1/4 or more and 1/1 or less, and even more preferably 1/3 or more and 1/1 or less.
  • lithium salts include lithium hexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium 2-trifluoromethyl-4,5-dicyanoimidazolate, lithium 4,5-dicyano-1,2,3-triazolate, lithium bis(pentafluoroethylsulfonyl)imide, lithium borofluoride, lithium bis(oxalato)borate, lithium nitrate, lithium chloride, lithium bromide, and lithium fluoride.
  • lithium salts include lithium hexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium 2-trifluoromethyl-4,5-dicyanoimidazolate, lithium 4,5-dicyano-1,2,3-triazolate, lithium bis(pentafluoroethylsulfonyl)imi
  • carbonate-based solvents include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, ethylene carbonate, propylene carbonate, and butylene carbonate.
  • the carbonate-based solvent may be one or more of these lithium salts.
  • the carbonate-based solvent in this embodiment refers to a compound having a carbonate skeleton in its molecular structure.
  • the thin film obtained in each of the examples and comparative examples described below was weighed to about 300 mg.
  • the mass of the thin film at this time was taken as M 0.
  • the thin film was wrapped in a polyester mesh (mesh size 200).
  • the mass of the thin film wrapped in the polyester mesh was weighed, and the mass of the thin film was subtracted to calculate the mass of the polyester mesh alone.
  • the thin film wrapped in the polyester mesh was immersed in ethyl acetate at 23 ° C. for 48 hours. Thereafter, the thin film wrapped in the polyester mesh was taken out of the ethyl acetate, dried in an oven at 120 ° C.
  • the thin film obtained in each of the examples and comparative examples described below was cut to about 3 cm (vertical) x about 3 cm (horizontal), and the obtained thin film piece was weighed to about 1 g. The mass at this time was W 0.
  • the thin film piece was wrapped in a polyester mesh (mesh size 200), and the mass of the thin film piece wrapped in the polyester mesh was weighed, and the mass of the thin film piece was subtracted to calculate the mass of the polyester mesh alone.
  • W0 represents the mass of the thin film piece weighed before being wrapped in the polyester mesh
  • W1 represents the mass of only the thin film piece after swelling.
  • ⁇ A is ionic conductivity (unit: S ⁇ cm ⁇ 1 )
  • RA is resistance (unit: ⁇ )
  • SA is the cross-sectional area of the solid electrolyte membrane at the time of measurement (unit: cm 2 )
  • LA is the distance between the electrodes (unit: cm).
  • the measurement temperature was 25° C.
  • the ionic conductivity ( ⁇ A ) was calculated from the results of the complex impedance measurement.
  • the structure of the obtained copolymer A was confirmed by nuclear magnetic resonance spectroscopy ( 1H -NMR, Biospin Avance 500, manufactured by Bruker) using a solvent ( CDCl3 , containing 0.03 volume% tetramethylsilane).
  • the number average molecular weight Mn of the resulting copolymer A was 24,000, and the molecular weight distribution Mw/Mn was 1.1.
  • a second release film (manufactured by Lintec Corporation, product name "SP-PET382150”) was prepared, and the release-treated surface of this release film was attached to the surface of the thin film layer. Thereafter, the laminate of the thin films sandwiched between the first release film and the second release film was placed on a stainless steel plate and irradiated with ultraviolet light at a temperature of 50°C [illuminance: 200 mW/cm 2 , accumulated light quantity: 1000 mJ/cm 2 , measured using an illuminance actinometer (controller: EYE UV METER UVPF-A2, light receiver: EYE UV METER PD-365A2) manufactured by EYE GRAPHICS CO., LTD.] to obtain a thin film having a thickness of 10 ⁇ m. The obtained thin film was a negative electrode protective film. The amount of elution and the degree of swelling of the obtained thin film were measured by the above-mentioned method.
  • Example 2 Polymerization of Copolymer B Except for using a mixture of propylene oxide and allyl glycidyl ether in a molar ratio of 90:10 as the epoxide monomer, polymerization was carried out in the same manner as in Example 1.
  • the number average molecular weight Mn of the resulting copolymer B was 25,000, and the molecular weight distribution Mw/Mn was 1.2.
  • Example 3 Polymerization of Copolymer C
  • Polymerization was carried out in the same manner as in Example 1, except that a mixture of propylene oxide and 4-hydroxybutyl acrylate glycidyl ether in a molar ratio of 98:2 was used as the epoxide monomer.
  • the copolymer C thus obtained had a number average molecular weight Mn of 38,000 and a molecular weight distribution Mw/Mn of 1.2.
  • Example 4 Polymerization of Copolymer D
  • Polymerization was carried out in the same manner as in Example 1, except that a mixture of propylene oxide and 4-hydroxybutyl acrylate glycidyl ether in a molar ratio of 95:5 was used as the epoxide monomer.
  • the number average molecular weight Mn of the resulting copolymer D was 41,000, and the molecular weight distribution Mw/Mn was 1.1.

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