WO2022201463A1 - リチウムイオン二次電池、分離膜及びこれらの製造方法 - Google Patents

リチウムイオン二次電池、分離膜及びこれらの製造方法 Download PDF

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WO2022201463A1
WO2022201463A1 PCT/JP2021/012675 JP2021012675W WO2022201463A1 WO 2022201463 A1 WO2022201463 A1 WO 2022201463A1 JP 2021012675 W JP2021012675 W JP 2021012675W WO 2022201463 A1 WO2022201463 A1 WO 2022201463A1
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Prior art keywords
monomer
solvent
separation membrane
mass
negative electrode
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English (en)
French (fr)
Japanese (ja)
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直人 黒田
紘揮 三國
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Resonac Corp
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Showa Denko Materials Co Ltd
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Priority to EP21933068.5A priority Critical patent/EP4293779A4/en
Priority to PCT/JP2021/012675 priority patent/WO2022201463A1/ja
Priority to KR1020237020240A priority patent/KR102861603B1/ko
Priority to US18/278,603 priority patent/US20240162562A1/en
Priority to CN202180094600.7A priority patent/CN116888797A/zh
Priority to JP2023508345A priority patent/JPWO2022201463A1/ja
Priority to TW111110519A priority patent/TWI867279B/zh
Publication of WO2022201463A1 publication Critical patent/WO2022201463A1/ja
Anticipated expiration legal-status Critical
Priority to JP2025113903A priority patent/JP2025129370A/ja
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—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
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • H01M50/42—Acrylic resins
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to lithium ion secondary batteries, separation membranes, and manufacturing methods thereof.
  • the present inventors considered disposing a separation membrane between the positive electrode and the negative electrode. When using the separation membrane, it is desirable that the resistance value is low even though it is a thin film.
  • One aspect of the present invention is a separation membrane having a thin film thickness and a low resistance value, which is used in a lithium ion secondary battery in which the positive electrode mixture layer and the negative electrode mixture layer contain different solvents, and the separation membrane.
  • An object of the present invention is to provide a lithium-ion secondary battery equipped with the above, and a method for manufacturing the same.
  • One aspect of the present invention is a lithium ion secondary battery comprising a positive electrode mixture layer, a separation membrane, and a negative electrode mixture layer in this order, wherein the positive electrode mixture layer comprises a positive electrode active material, a first lithium salt, and A first solvent is contained, the negative electrode mixture layer contains a negative electrode active material, a second lithium salt, and a second solvent different from the first solvent, and the separation membrane has lithium ion conductivity A polymer, a third lithium salt, and a third solvent, wherein the polymer is a first monomer having two (meth)acryloyl groups and a second monomer having three or more (meth)acryloyl groups and as monomer units, a lithium ion secondary battery is provided.
  • Another aspect of the present invention provides a positive electrode mixture layer containing a positive electrode active material, a first lithium salt, and a first solvent, and a negative electrode active material, a second lithium salt, and a first solvent. and a negative electrode mixture layer containing a different second solvent, a separation membrane to be disposed between the positive electrode mixture layer and the negative electrode mixture layer, the separator having lithium ion conductivity , a third lithium salt, and a third solvent, wherein the polymer comprises a first monomer having two (meth)acryloyl groups and a second monomer having three or more (meth)acryloyl groups
  • a separation membrane is provided, which is a copolymer containing as a monomer unit a monomer of
  • Another aspect of the present invention provides a step of obtaining a positive electrode comprising a positive electrode mixture layer containing a positive electrode active material, a first lithium salt, and a first solvent; a step of obtaining a negative electrode comprising a negative electrode mixture layer containing a second solvent different from the first solvent; a first monomer having two (meth)acryloyl groups; a step of forming a slurry containing a second monomer, a third lithium salt, and a third solvent into a film, and then polymerizing the first monomer and the second monomer to obtain a separation membrane; and providing a separation membrane between the positive electrode and the negative electrode.
  • the second monomer may be a monomer having four (meth)acryloyl groups.
  • a separation membrane having a thin film thickness and a low resistance value is used in a lithium-ion secondary battery in which the positive electrode mixture layer and the negative electrode mixture layer contain different solvents, and the separation membrane is provided. It is possible to provide a lithium ion secondary battery and a manufacturing method thereof.
  • FIG. 1 is a perspective view showing a lithium ion secondary battery according to one embodiment
  • FIG. FIG. 2 is an exploded perspective view showing an embodiment of an electrode group in the lithium ion secondary battery shown in FIG. 1;
  • the term "process” includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .
  • the numerical range indicated using “to” indicates the range including the numerical values before and after “to” as the minimum and maximum values, respectively.
  • FIG. 1 is a perspective view showing a lithium ion secondary battery according to one embodiment.
  • a lithium ion secondary battery 1 according to one embodiment is a so-called laminated secondary battery that includes an electrode group 2 and a bag-shaped battery outer body 3 that houses the electrode group 2. be.
  • the electrode group 2 is provided with a positive current collecting tab 4 and a negative current collecting tab 5 .
  • the positive electrode current collector tab 4 and the negative electrode current collector tab 5 are provided in a battery outer body so that the positive electrode current collector and the negative electrode current collector (details will be described later) can be electrically connected to the outside of the lithium ion secondary battery 1. It protrudes from the inside of 3 to the outside.
  • the lithium ion secondary battery 1 may have a shape other than the laminate type (coin type, cylindrical type, etc.).
  • the battery outer package 3 may be a container formed of a laminated film, for example.
  • the laminated film may be, for example, a laminated film in which a polymer film such as a polyethylene terephthalate (PET) film, a metal foil such as aluminum, copper, or stainless steel, and a sealant layer such as polypropylene are laminated in this order.
  • PET polyethylene terephthalate
  • metal foil such as aluminum, copper, or stainless steel
  • sealant layer such as polypropylene
  • FIG. 2 is an exploded perspective view showing one embodiment of the electrode group 2 in the lithium ion secondary battery 1 shown in FIG.
  • the electrode group 2 includes a positive electrode 6, a separation membrane 7, and a negative electrode 8 in this order.
  • the positive electrode 6 includes a positive electrode current collector 9 and a positive electrode mixture layer 10 provided on the positive electrode current collector 9 .
  • a positive current collector tab 4 is provided on the positive current collector 9 .
  • the negative electrode 8 includes a negative electrode current collector 11 and a negative electrode mixture layer 12 provided on the negative electrode current collector 11 .
  • a negative electrode collector tab 5 is provided on the negative electrode collector 11 .
  • the positive electrode current collector 9 is made of, for example, aluminum, titanium, stainless steel, nickel, calcined carbon, conductive polymer, conductive glass, or the like.
  • the thickness of the positive electrode current collector 9 may be, for example, 1 ⁇ m or more and may be 50 ⁇ m or less.
  • the negative electrode current collector 11 is made of, for example, copper, stainless steel, nickel, aluminum, titanium, calcined carbon, conductive polymer, conductive glass, aluminum-cadmium alloy, or the like.
  • the thickness of the negative electrode current collector 11 may be, for example, 1 ⁇ m or more and 50 ⁇ m or less.
  • the positive electrode mixture layer 10 contains a positive electrode active material, a lithium salt (first lithium salt), and a solvent (first solvent).
  • the positive electrode active material may be, for example, lithium oxide.
  • the positive electrode active material may be lithium phosphate.
  • lithium phosphates include lithium manganese phosphate ( LiMnPO4 ), lithium iron phosphate ( LiFePO4 ), lithium cobalt phosphate ( LiCoPO4 ) and lithium vanadium phosphate ( Li3V2 ( PO4). 3 ).
  • the content of the positive electrode active material may be 70% by mass or more, 80% by mass or more, or 85% by mass or more based on the total amount of the positive electrode mixture layer.
  • the content of the positive electrode active material may be 95% by mass or less, 92% by mass or less, or 90% by mass or less based on the total amount of the positive electrode mixture layer.
  • the first lithium salt is, for example, LiPF6 , LiBF4, LiClO4, LiB( C6H5 ) 4 , LiCH3SO3 , CF3SO2OLi , LiN ( SO2F ) 2 ( LiFSI, lithium bis fluorosulfonylimide), LiN(SO 2 CF 3 ) 2 (LiTFSI, lithium bistrifluoromethanesulfonylimide), and LiN(SO 2 CF 2 CF 3 ) 2 .
  • LiPF6 LiBF4, LiClO4, LiB( C6H5 ) 4
  • LiCH3SO3 , CF3SO2OLi LiN ( SO2F ) 2 ( LiFSI, lithium bis fluorosulfonylimide), LiN(SO 2 CF 3 ) 2 (LiTFSI, lithium bistrifluoromethanesulfonylimide), and LiN(SO 2 CF 2 CF 3 ) 2 .
  • the content of the first lithium salt may be 0.5 mol/L or more, 0.7 mol/L or more, or 0.8 mol/L or more, and is 1.5 mol/L. 1.3 mol/L or less, or 1.2 mol/L or less.
  • the first solvent is a solvent for dissolving the first lithium salt.
  • the first solvent include cyclic carbonates such as ethylene carbonate, propylene carbonate, vinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate and difluoroethylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate; Cyclic esters such as butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -hexanolactone, tetrahydrofuran, 1,3-dioxane, dimethoxyethane, diethoxyethane, methoxyethoxyethane, glyme, diglyme, triglyme Ethers such as tetraglyme, phosphate esters such as phosphoric acid triester, nitriles such as acetonitrile, benzonitrile, adiponitrile, glut
  • Solvents preferably used as the first solvent are solvents with excellent oxidation resistance, such as acetonitrile and ethylene carbonate. Thereby, the oxidation resistance of the positive electrode mixture layer 10 can be improved.
  • the content of the first solvent contained in the positive electrode mixture layer 10 can be appropriately set within a range in which the first lithium salt can be dissolved. and may be 80% by mass or less.
  • the positive electrode mixture layer 10 may further contain a binder and a conductive material as other components.
  • the binder is a polymer containing at least one selected from the group consisting of ethylene tetrafluoride, vinylidene fluoride, hexafluoropropylene, acrylic acid, maleic acid, ethyl methacrylate, methyl methacrylate, and acrylonitrile as a monomer unit, styrene-butadiene It may be rubber such as rubber, isoprene rubber, acrylic rubber, or the like.
  • the binder is preferably polyvinylidene fluoride or a copolymer containing hexafluoropropylene and vinylidene fluoride as monomer units.
  • the content of the binder may be 0.3% by mass or more, 0.5% by mass or more, 1% by mass or more, or 1.5% by mass or more based on the total amount of the positive electrode mixture layer, or 10% by mass. % or less, 8 mass % or less, 6 mass % or less, or 4 mass % or less.
  • the conductive material may be a carbon material such as carbon black, acetylene black, graphite, carbon fiber, or carbon nanotube. These conductive materials are used singly or in combination of two or more.
  • the content of the conductive material may be 0.1% by mass or more, 1% by mass or more, or 3% by mass or more based on the total amount of the positive electrode mixture layer. From the viewpoint of suppressing the increase in the volume of the positive electrode 6 and the accompanying decrease in the energy density of the lithium ion secondary battery 1, the content of the conductive material is preferably 15% by mass or less, based on the total amount of the positive electrode mixture layer, and more. It is preferably 10% by mass or less, more preferably 8% by mass or less.
  • the thickness of the positive electrode mixture layer 10 may be 5 ⁇ m or more, 10 ⁇ m or more, 15 ⁇ m or more, or 20 ⁇ m or more, and may be 100 ⁇ m or less, 80 ⁇ m or less, 70 ⁇ m or less, or 50 ⁇ m or less.
  • the negative electrode mixture layer 12 contains a negative electrode active material, a lithium salt (second lithium salt), and a solvent (second solvent).
  • negative electrode active material those commonly used in the field of energy devices can be used.
  • specific examples of negative electrode active materials include metal lithium, lithium titanate (Li 4 Ti 5 O 12 ), lithium alloys or other metal compounds, carbon materials, metal complexes, organic polymer compounds, and the like. . These negative electrode active materials are used singly or in combination of two or more.
  • Carbon materials include natural graphite (flaky graphite, etc.), graphite such as artificial graphite, amorphous carbon, carbon fiber, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black.
  • the negative electrode active material may be a negative electrode active material containing silicon as a constituent element, a negative electrode active material containing tin as a constituent element, or the like.
  • the negative electrode active material may be a negative electrode active material containing silicon as a constituent element.
  • the negative electrode active material containing silicon as a constituent element may be an alloy containing silicon as a constituent element, for example, silicon and nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, It may be an alloy containing at least one selected from the group consisting of antimony and chromium as constituent elements.
  • the negative electrode active material containing silicon as a constituent element may be an oxide , a nitride, or a carbide. It may be a silicon nitride such as 2N2O , a silicon carbide such as SiC, or the like.
  • the content of the negative electrode active material may be 60% by mass or more, 65% by mass or more, or 70% by mass or more based on the total amount of the negative electrode mixture layer.
  • the content of the negative electrode active material may be 99% by mass or less, 95% by mass or less, or 90% by mass or less based on the total amount of the negative electrode mixture layer.
  • the type and content of the second lithium salt may be the same as those of the first lithium salt contained in the positive electrode mixture layer 10 described above.
  • the second lithium salt may be the same as or different from the first lithium salt.
  • the second solvent is a solvent for dissolving the second lithium salt.
  • the same solvent as that used as the first solvent can be used, but a solvent different from the first solvent is used.
  • suitable solvents can be used for the positive electrode 6 and the negative electrode 8, respectively, and various performances of the lithium ion secondary battery 1, such as improved energy density and improved life, can be improved.
  • Solvents that are preferably used as the second solvent are solvents with excellent resistance to reduction, such as ⁇ -butyrolactone and tetrahydrofuran. Thereby, reductive decomposition of the second solvent contained in the negative electrode mixture layer 12 can be suppressed.
  • the content of the second solvent contained in the negative electrode mixture layer 12 can be appropriately set within a range in which the second lithium salt can be dissolved. and may be 80% by mass or less.
  • the negative electrode mixture layer 12 may further contain a binder and a conductive material as other components.
  • the types and contents of the binder and the conductive material may be the same as the types and the contents of the binder and the conductive material in the positive electrode mixture layer 10 described above.
  • the thickness of the negative electrode mixture layer 12 may be 10 ⁇ m or more, 15 ⁇ m or more, or 20 ⁇ m or more, and may be 100 ⁇ m or less, 80 ⁇ m or less, 70 ⁇ m or less, 50 ⁇ m or less, 40 ⁇ m or less, or 30 ⁇ m or less.
  • the separation membrane 7 is a separation membrane to be arranged between the positive electrode mixture layer 10 and the negative electrode mixture layer 12 in the lithium ion secondary battery 1 .
  • This separation film has a role of separating the first solvent and the second solvent contained in the positive electrode mixture layer 10 and the negative electrode mixture layer 12 from each other and preventing them from being mixed with each other. It is possible to exchange lithium ions through the separation membrane 7 .
  • the separation membrane 7 contains a polymer having lithium ion conductivity, a lithium salt (third lithium salt), and a solvent (third solvent).
  • a polymer having lithium ion conductivity means a polymer having the property of being able to conduct lithium ions derived from the lithium salt in the presence of the lithium salt. Whether or not a polymer can conduct lithium ions can be confirmed by measuring the ionic conductivity of the polymer, and the ionic conductivity measured when 1 to 40% by mass of a lithium salt is added to the polymer If the peak of is 1 ⁇ 10 ⁇ 6 S/cm or more, it can be said that the polymer has lithium ion conductivity.
  • the polymer is a copolymer containing, as monomer units, a first monomer having two (meth)acryloyl groups and a second monomer having three or more (meth)acryloyl groups. It is thought that a separation membrane that is thin and has a low resistance value can be formed because the polymer containing the combination of the first monomer and the second monomer has an appropriate crosslink density. It is not limited to this.
  • the first monomer is a compound having two (meth)acryloyl groups and a linking group that links the two (meth)acryloyl groups.
  • the linking group may contain hydrocarbon groups and/or heteroatom-containing groups.
  • the linking group may include an oxygen atom-containing group as a heteroatom-containing group, such as an ether group (--O--).
  • a linking group may be a divalent group consisting of a hydrocarbon group (eg, an alkylene group) and a heteroatom-containing group (eg, an ether group), such as a polyoxyalkylene group or an oxyalkylene group.
  • the first monomer may be a monomer represented by formula (1-1) below.
  • R 11 and R 12 each independently represent a hydrogen atom or a methyl group (--CH 3 ).
  • n represents an integer of 1 or more. n may be, for example, 5 or more, 10 or more, 15 or more, 20 or more, 40 or less, 35 or less, 30 or less, or 25 or less.
  • Z 11 represents an alkylene group.
  • Z 11 may be, for example, an alkylene group having 1 to 6 or 1 to 3 carbon atoms.
  • Z 11 can be, for example, -CH 2 -CH 2 -, -CH(CH 3 )-CH 2 -.
  • the ionic conductivity of the first monomer at 25° C. may be, for example, 0.01 mS/cm or more, 0.05 mS/cm or more, or 0.10 mS/cm or more, 1.0 mS/cm or less, 0.1 mS/cm or more. It may be 50 mS/cm or less, or 0.30 mS/cm or less.
  • the ionic conductivity of the first monomer at 25° C. can be measured by the following method.
  • a slurry is prepared by mixing the first monomer, lithium salt, solvent, and photoinitiator.
  • a silicon rubber frame (4 ⁇ 4 cm, 1 mm thick) is placed on a PET sheet (8 ⁇ 8 cm, 0.035 mm thick), and the prepared slurry is placed in the frame. Thereafter, ultraviolet light (wavelength: 365 nm) is irradiated to polymerize the first monomer, thereby obtaining a separation membrane.
  • the separation membrane is removed from the frame and subjected to the tests described below.
  • the lithium salt may be LiN( SO2CF3 ) 2 ( LiTFSI, lithium bistrifluoromethanesulfonylimide).
  • the solvent may be 1-ethyl-3-methylimidazolium-bis(trifluoromethanesulfonyl)imide (EMI-TFSI).
  • the photoinitiator may be 2-hydroxy-2-methyl-1-phenylpropanone.
  • the irradiation time of ultraviolet light (wavelength 365 nm) may be 15 minutes.
  • polyethylene glycol #1000 diacrylate for example, trade name: NK Ester A-1000, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • polyethylene glycol #800 diacrylate for example, trade name: NK Ester A-800 , manufactured by Shin-Nakamura Chemical Co., Ltd.
  • the first monomer may be used singly or in combination of two or more.
  • the content of the first polymer contained as a monomer unit in the polymer may be 5% by mass or more, 10% by mass or more, or 15% by mass or more, and may be 70% by mass or less, 60% by mass or less, based on the total weight of the separation membrane. % by mass or less, or 50% by mass or less.
  • a second monomer is a monomer having three or more (meth)acryloyl groups.
  • the number of (meth)acryloyl groups in the second monomer may be, for example, 3-6, 3-4, or 4.
  • the second monomer may be a compound having three or more (meth)acryloyl groups and a linking group linking these (meth)acryloyl groups.
  • the linking group may contain hydrocarbon groups and/or heteroatom-containing groups.
  • the linking group may include an oxygen atom-containing group as a heteroatom-containing group, such as an ether group (--O--).
  • a linking group may be a divalent group consisting of a hydrocarbon group (eg, an alkylene group) and a heteroatom-containing group (eg, an ether group), such as a polyoxyalkylene group or an oxyalkylene group.
  • the second monomer having three (meth)acryloyl groups may be a monomer represented by the following formula (1-2).
  • R 13 , R 14 and R 15 each independently represent a hydrogen atom or a methyl group.
  • Z 2 , Z 3 and Z 4 each independently represent an alkylene group.
  • the alkylene group represented by Z 2 , Z 3 and Z 4 may be an alkylene group having 1 to 6 or 1 to 3 carbon atoms, and may be a methylene group (--CH 2 --).
  • Z5 represents an alkyl group.
  • Z 5 may be, for example, an alkyl group having 1 to 10, 1 to 6 or 1 to 3 carbon atoms, or may be an ethyl group (--CH 2 --CH 3 ).
  • a monovalent hydrocarbon group represented by X may be, for example, an alkyl group.
  • Examples of the second monomer having three (meth)acryloyl groups include trimethylolpropane triacrylate (eg, trade name: NK Ester A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • the second monomer having four (meth)acryloyl groups may be a monomer represented by the following formula (1-3).
  • R 16 , R 17 , R 18 and R 19 each independently represent a hydrogen atom or a methyl group.
  • Z 6 , Z 7 , Z 8 and Z 9 each independently represent an alkylene group.
  • the alkylene group represented by Z 2 , Z 3 and Z 4 may be an alkylene group having 1 to 6 or 1 to 3 carbon atoms, and may be an ethylene group (--CH 2 --CH 2 --).
  • a, b, c and d each independently represent an integer of 1 or more.
  • a+b+c+d may be 4 or more, 10 or more, 20 or more, or 30 or more, and may be 50 or less, or 40 or less.
  • Examples of the second monomer having three (meth)acryloyl groups include ethoxylated pentaerythritol tetraacrylate (eg, trade name: NK Ester A-TM35E, manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • the ionic conductivity of the second monomer at 25° C. may be, for example, 0.001 mS/cm or more, or 0.01 mS/cm or more, and 0.5 mS/cm or less, or 0.05 mS/cm or less. you can The ionic conductivity of the second monomer at 25°C can be measured using the second monomer by the same method as the method for measuring the ionic conductivity of the first monomer at 25°C. In the measurement of the ionic conductivity of the second monomer at 25° C., the ultraviolet light (wavelength: 365 nm) irradiation time may be 2 minutes.
  • the second monomer may be used singly or in combination of two or more.
  • the content of the second polymer contained as a monomer unit in the polymer may be 5% by mass or more, 10% by mass or more, or 15% by mass or more, 70% by mass or less, 60% by mass or less, based on the total weight of the separation membrane. % by mass or less, or 50% by mass or less.
  • the ratio (C2/C1) of the mass (C2) of the second monomer to the mass (C1) of the first monomer, contained as a monomer unit in the polymer, further lowers the resistance value of the separation membrane. can be 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 1/2 or less.
  • the ratio (C2/C1) of the mass (C2) of the second monomer to the mass (C1) of the first monomer, which is contained as a monomer unit in the polymer, is such that the separation ability of the separation membrane is even more excellent. 1/5 or more, 1/4 or more, 1/3 or more, 1/2 or more, 1 or more, or 2 or more.
  • the polymer content may be 60% by mass or more, 70% by mass or more, or 80% by mass or more, and may be 90% by mass or less, 80% by mass or less, or 70% by mass or less, based on the total amount of the separation membrane. .
  • the type of the third lithium salt may be the same as the first lithium salt contained in the positive electrode mixture layer 10 described above.
  • the third lithium salt may be the same as the first lithium salt and/or the second lithium salt, or different from the first lithium salt and/or the second lithium salt.
  • the content of the third lithium salt is preferably 5% by mass or more, more preferably 13% by mass, based on the total amount of the third lithium salt and the third solvent. % or more, more preferably 15 mass % or more.
  • the content of the third lithium salt is preferably 35% by mass or less, more preferably 23% by mass or less, based on the total amount of the third lithium salt and the third solvent, from the viewpoint of the viscosity of the solvent. Preferably, it is 20% by mass or less.
  • the content of the third lithium salt is preferably 2% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass, based on the total amount of the separation membrane. That's it.
  • the content of the third lithium salt is preferably 12% by mass or less, more preferably 9% by mass or less, and even more preferably 6% by mass, based on the total amount of the separation membrane. It is below.
  • the third solvent is a solvent for dissolving the third lithium salt.
  • the third solvent is preferably an ionic liquid or glyme represented by the following formula (2), more preferably an ionic liquid.
  • R 21 and R 22 each independently represent an alkyl group having 1 to 4 carbon atoms, and k represents an integer of 3 to 6.
  • the ionic liquid contains the following anionic and cationic components.
  • the ionic liquid in this specification is a substance that is liquid at -20°C or higher.
  • the anion component of the ionic liquid is not particularly limited, but includes halogen anions such as Cl ⁇ , Br ⁇ and I ⁇ , inorganic anions such as BF 4 ⁇ and N(SO 2 F) 2 ⁇ ([FSI] ⁇ ), B (C 6 H 5 ) 4 ⁇ , CH 3 SO 2 O ⁇ , CF 3 SO 2 O ⁇ , N(SO 2 C 4 F 9 ) 2 ⁇ , N(SO 2 CF 3 ) 2 ⁇ ([TFSI] ⁇ ) , N(SO 2 C 2 F 5 ) 2 — and other organic anions.
  • the anion component of the ionic liquid preferably contains at least one anion component represented by the following formula (3).
  • the anion component represented by formula (3) is, for example, N(SO 2 C 4 F 9 ) 2 ⁇ , N(SO 2 F) 2 ⁇ ([FSI] ⁇ ), N(SO 2 CF 3 ) 2 ⁇ ([TFSI] ⁇ ) and N(SO 2 C 2 F 5 ) 2 ⁇ .
  • the anion component of the ionic liquid is more preferably N(SO 2 C 4 F 9 ) 2 ⁇ , CF 3 SO 2 O ⁇ , [FSI] ⁇ . , [TFSI] ⁇ , and N(SO 2 C 2 F 5 ) 2 ⁇ , more preferably [FSI] ⁇ .
  • the cationic component of the ionic liquid is not particularly limited, it is preferably at least one selected from the group consisting of chain quaternary onium cations, piperidinium cations, pyrrolidinium cations, pyridinium cations, and imidazolium cations.
  • a chain quaternary onium cation is, for example, a compound represented by the following formula (4).
  • R 31 to R 34 are each independently a chain alkyl group having 1 to 20 carbon atoms or a chain alkoxyalkyl group represented by RO-(CH 2 ) n - (R represents a methyl group or an ethyl group, n represents an integer of 1 to 4), and X represents a nitrogen atom or a phosphorus atom.
  • the number of carbon atoms in the alkyl group represented by R 31 to R 34 is preferably 1-20, more preferably 1-10, still more preferably 1-5.
  • the piperidinium cation is, for example, a nitrogen-containing six-membered cyclic compound represented by the following formula (5).
  • R 35 and R 36 are each independently an alkyl group having 1 to 20 carbon atoms, or an alkoxyalkyl group represented by R—O—(CH 2 ) n — (R is methyl group or an ethyl group, and n represents an integer of 1 to 4).
  • the number of carbon atoms in the alkyl group represented by R 35 and R 36 is preferably 1-20, more preferably 1-10, still more preferably 1-5. ]
  • a pyrrolidinium cation is, for example, a five-membered cyclic compound represented by the following formula (6).
  • R 37 and R 38 are each independently an alkyl group having 1 to 20 carbon atoms, or an alkoxyalkyl group represented by R—O—(CH 2 ) n — (R is methyl group or an ethyl group, and n represents an integer of 1 to 4).
  • the number of carbon atoms in the alkyl group represented by R 37 and R 38 is preferably 1-20, more preferably 1-10, still more preferably 1-5.
  • a pyridinium cation is, for example, a compound represented by the following formula (7).
  • R 39 to R 43 are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group represented by RO-(CH 2 ) n - (R is a methyl group, or an ethyl group, and n represents an integer of 1 to 4), or a hydrogen atom.
  • the number of carbon atoms in the alkyl group represented by R 39 to R 43 is preferably 1-20, more preferably 1-10, still more preferably 1-5.
  • the imidazolium cation is, for example, a compound represented by the following formula (8).
  • R 44 to R 48 are each independently an alkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group represented by R—O—(CH 2 ) n — (R is a methyl group, or an ethyl group, and n represents an integer of 1 to 4), or a hydrogen atom.
  • the number of carbon atoms in the alkyl group represented by R 44 to R 48 is preferably 1-20, more preferably 1-10, still more preferably 1-5.
  • the ionic liquid is more specifically N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium-bis(trifluoromethanesulfonyl)imide (DEME-TFSI), N,N-diethyl-N -methyl-N-(2-methoxyethyl)ammonium-bis(fluorosulfonyl)imide (DEME-FSI), 1-ethyl-3-methylimidazolium-bis(trifluoromethanesulfonyl)imide (EMI-TFSI), 1- Ethyl-3-methylimidazolium-bis(fluorosulfonyl)imide (EMI-FSI), N-methyl-N-propylpyrrolidinium-bis(trifluoromethanesulfonyl)imide (Py13-TFSI), N-methyl-N- Propylpyrrolidinium-bis(fluorosulfonyl)imide (P
  • R 21 and R 22 each independently represent an alkyl group having 4 or less carbon atoms or a fluoroalkyl group having 4 or less carbon atoms, and k represents an integer from 1 to 6.
  • R 21 and R 22 are each independently preferably a methyl group or an ethyl group.
  • the separation membrane 7 contains glyme as a solvent, part or all of the glyme may form a complex with the lithium salt (third lithium salt).
  • the content of the third solvent is 40% by mass or less, 38% by mass or less based on the total amount of the separation membrane, from the viewpoint of obtaining a separation membrane 7 excellent in the separation ability of the solvents (first solvent and second solvent). 35% by mass or less, 33% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, 13% by mass or less, or 10% by mass or less . From the viewpoint of further increasing the ionic conductivity of the separation membrane 7, the content of the third solvent is 5% by mass or more, 8% by mass or more, 18% by mass or more, or 27% by mass or more based on the total amount of the separation membrane. may
  • the content of the third solvent can be measured by the method shown below. First, after diluting the separation membrane about 10 times with methanol, extraction is performed for 15 minutes by ultrasonic irradiation to obtain an extract. 1.0 ⁇ L of this extract is injected into the gas chromatograph to perform gas chromatograph mass spectrometry. Specific conditions for gas chromatography mass spectrometry are as follows.
  • the separation membrane 7 may further contain, for example, an inorganic filler as another component, or may not contain an inorganic filler in order to further improve the ionic conductivity of the separation membrane.
  • the thickness of the separation membrane 7 may be 85 ⁇ m or more, or 90 ⁇ m or more, and may be 400 ⁇ m or less, 300 ⁇ m or less, 200 ⁇ m or less, or 100 ⁇ m or less.
  • the resistance value of the separation membrane may be, for example, less than 180 ⁇ , 160 ⁇ or less, 140 ⁇ or less, 120 ⁇ or less, or 100 ⁇ or less.
  • the resistance value of the separation membrane may be, for example, 30 ⁇ or more or 50 ⁇ or more.
  • the resistance value of the separation membrane is measured by the following method. First, an upper lid (CR2032 cap, manufactured by Hosensha), a 1.6 mm thick plate spring, a 1.0 mm thick SUS spacer (2 pieces), a separation membrane, a gasket, a lower lid (CR2032 case, manufactured by Hosensha ) are laminated in order, and the upper and lower lids are crimped to prepare a test cell, and the resistance value (bulk resistance) of the separation membrane is measured.
  • the measurement equipment and measurement conditions are as follows. Measurement device: VSP electrochemical measurement system (manufactured by BioLogic) Measurement temperature: 25°C AC amplitude: 10mV Frequency range: 10mHz to 1MHz
  • the ionic conductivity of the separation membrane may be, for example, 0.04 mS/cm or more, or 0.05 mS/cm or more, and may be, for example, 0.15 mS/cm or less.
  • a method for manufacturing a lithium ion secondary battery 1 includes steps of obtaining a positive electrode 6 including a positive electrode mixture layer 10 containing a positive electrode active material, a first lithium salt, and a first solvent; obtaining a negative electrode 8 comprising a negative electrode mixture layer 12 containing a substance, a second lithium salt, and a second solvent different from the first solvent; a step of forming a slurry containing a lithium salt and a third solvent into a film and then polymerizing a first monomer and a second monomer to obtain a separation membrane 7; and a step of providing a separation membrane 7 therebetween.
  • the order of each step is arbitrary.
  • the positive electrode active material, the first lithium salt, the first solvent, the negative electrode active material, the second lithium salt, the second solvent, the third lithium salt, and the third solvent are specifically Aspects are as described above.
  • the positive electrode 6 and the negative electrode 8 can be obtained using a known method.
  • a material used for the positive electrode mixture layer 10 or the negative electrode mixture layer 12 is dispersed in an appropriate amount of dispersion medium using a kneader, a disperser, or the like to obtain a slurry of the positive electrode mixture or the negative electrode mixture.
  • the positive electrode mixture or the negative electrode mixture is applied onto the positive electrode current collector 9 or the negative electrode current collector 11 by a doctor blade method, a dipping method, a spray method, or the like, and the dispersion medium is volatilized to obtain the positive electrode 6 and the negative electrode mixture.
  • a negative electrode 8 is obtained.
  • the dispersion medium may be water, N-methyl-2-pyrrolidone (NMP), or the like.
  • a slurry containing a first monomer, a second monomer, a third lithium salt, and a third solvent is prepared. Specific aspects of the first monomer and the second monomer are as described above.
  • the content of the first monomer in the slurry may be 5% by mass or more, 10% by mass or more, or 15% by mass or more, and may be 70% by mass or less, 60% by mass or less, or 50% by mass, based on the total amount of the slurry. may be:
  • the content of the second monomer in the slurry may be 5% by mass or more, 10% by mass or more, or 15% by mass or more, and may be 70% by mass or less, 60% by mass or less, or 50% by mass, based on the total amount of the slurry. may be:
  • the mass of the second monomer to the mass of the first monomer in the slurry is the same as the amount stated as the ratio of the mass of the second monomer to the mass of the first monomer contained as monomeric units in the polymer.
  • the content of the third solvent in the slurry is 40% by mass or less, 38% by mass or less, 35% by mass or less, 33% by mass or less, 30% by mass or less, 25% by mass or less, and 20% by mass, based on the total amount of the slurry. 18% by mass or less, 15% by mass or less, 13% by mass or less, or 10% by mass or less. From the viewpoint of further increasing the ionic conductivity of the separation membrane 7, the content of the third solvent is 5% by mass or more, 8% by mass or more, 18% by mass or more, or 27% by mass or more based on the total amount of the slurry. good too.
  • a polymerization initiator may be added to the slurry. Thereby, the first monomer and the second monomer can be suitably polymerized, and the separation membrane can be suitably produced from the slurry.
  • the polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, and can be appropriately selected depending on the purpose.
  • Thermal polymerization initiators include azobisisobutyronitrile and azobis(2-methylbutyronitrile).
  • photopolymerization initiators examples include 2-hydroxy-2-methyl-1-phenylpropanone and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.
  • the content of the polymerization initiator may be 0.5% by mass or more, 1% by mass or more, 10% by mass or more, or 20% by mass or more, 50% by mass or less, 40% by mass or less, It may be 30% by mass or less, 10% by mass or less, 5% by mass or less, or 3% by mass or less.
  • the slurry may or may not contain an inorganic filler as another component.
  • the slurry described above is formed into a film, and then the first monomer and the second monomer are polymerized.
  • a method of forming the slurry into a film is, for example, a method of setting a frame of arbitrary size on one side of a base material such as a PET sheet and pouring the slurry into the frame.
  • the slurry may be formed into a film by applying the slurry onto one surface of the substrate by a doctor blade method, dipping method, spray method, or the like.
  • a method of polymerizing the first monomer and the second monomer is a method of applying heat under predetermined conditions when the slurry contains a thermal polymerization initiator.
  • the heating temperature may be, for example, 80-90°C.
  • the heating time may be appropriately adjusted depending on the heating temperature, and is, for example, 1 to 10 minutes.
  • a method for polymerizing the first monomer and the second monomer is a method of irradiating light under predetermined conditions when the slurry contains a photopolymerization initiator.
  • the polymerizable compound may be polymerized by irradiation with light containing wavelengths within the range of 200-400 nm (ultraviolet light).
  • the positive electrode 6, the separation film 7 and the negative electrode 8 are laminated by lamination, for example.
  • the electrode group 2 including the positive electrode 6, the negative electrode 8, and the separation film 7 provided between the positive electrode 6 and the negative electrode 8 can be obtained.
  • the lithium ion secondary battery 1 can be obtained by housing the electrode group 2 in the battery exterior body 3 .
  • a silicon rubber frame (4 ⁇ 4 cm, 1 mm thick) was placed on a PET sheet (8 ⁇ 8 cm, 0.035 mm thick), and the prepared slurry was placed in the frame. After that, ultraviolet light (wavelength: 365 nm) was irradiated for 5 minutes to polymerize the above monomer, thereby obtaining a separation membrane. The separation membrane was removed from the frame and subjected to the tests described below.
  • Example 2 A separation membrane was produced in the same manner as in Example 1, except that the composition of the slurry was changed as shown in Table 1 and the irradiation time of ultraviolet light (wavelength: 365 nm) was changed to 4 minutes.
  • Example 3 A separation membrane was produced in the same manner as in Example 1, except that the composition of the slurry was changed as shown in Table 1 and the irradiation time of ultraviolet light (wavelength: 365 nm) was changed to 3.5 minutes. did.
  • Example 1 A separation membrane was produced in the same manner as in Example 1, except that the composition of the slurry was changed as shown in Table 1 and the irradiation time of ultraviolet light (wavelength: 365 nm) was changed to 15 minutes.
  • Example 2 A separation membrane was produced in the same manner as in Example 1, except that the composition of the slurry was changed as shown in Table 1 and the irradiation time of ultraviolet light (wavelength: 365 nm) was changed to 2 minutes.
  • the film thickness of the separation membrane was measured by the following method. Using a micrometer (PMU150-25MX, manufactured by Mitutoyo Co., Ltd.), the film thickness was measured at three arbitrary points, and the average value thereof was taken as the film thickness of the separation membrane.
  • the separation membrane according to the example could be made thinner and had a low resistance value.
  • the solvent separation ability of the separation membranes according to Examples 1 to 3 was evaluated by the method shown below.
  • the separation membrane according to Example 3 and a separator (UP3085, manufactured by Ube Industries, Ltd.) were layered and sandwiched between two silicon rubber (thickness: 0.5 mm) sheets, which were placed between H-shaped cells. did.
  • Dimethyl carbonate (DMC) was put into the cell on the separation membrane side, and the appearance of the separator was visually observed after a predetermined number of days had passed. If the separation membrane has excellent solvent separation ability, DMC does not easily permeate through the separation membrane. Penetrate the separator. Therefore, by observing the appearance of the separator and confirming whether or not DMC has permeated into the separator, it is possible to evaluate the solvent separation ability of the separation membrane (solvents corresponding to the first solvent and the second solvent). can.
  • the separation membrane according to Example 3 was superior to the separation membranes according to Examples 1 and 2 in solvent separation ability. In the separation membrane according to Example 3, DMC did not permeate into the separator even after 7 days from the start of the test.
  • SYMBOLS 1 Lithium ion secondary battery, 2... Electrode group, 3... Battery outer body, 4... Positive electrode collector tab, 5... Negative electrode collector tab, 6... Positive electrode, 7... Separation membrane, 8... Negative electrode, 9... Positive electrode collector 10. Positive electrode mixture layer, 11. Negative electrode current collector, 12. Negative electrode mixture layer.

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KR1020237020240A KR102861603B1 (ko) 2021-03-25 2021-03-25 리튬 이온 2차 전지, 분리막 및 이들의 제조 방법
US18/278,603 US20240162562A1 (en) 2021-03-25 2021-03-25 Lithium ion secondary battery, separation membrane, and manufacturing methods therefor
CN202180094600.7A CN116888797A (zh) 2021-03-25 2021-03-25 锂离子二次电池、隔膜及其制造方法
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TW111110519A TWI867279B (zh) 2021-03-25 2022-03-22 鋰離子二次電池、分離膜及該等之製造方法
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