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WO2025047947A1 - Caoutchouc nitrile hydrogéné - Google Patents

Caoutchouc nitrile hydrogéné Download PDF

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Publication number
WO2025047947A1
WO2025047947A1 PCT/JP2024/031273 JP2024031273W WO2025047947A1 WO 2025047947 A1 WO2025047947 A1 WO 2025047947A1 JP 2024031273 W JP2024031273 W JP 2024031273W WO 2025047947 A1 WO2025047947 A1 WO 2025047947A1
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Prior art keywords
nitrile rubber
hydrogenated nitrile
positive electrode
ppm
mass
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English (en)
Japanese (ja)
Inventor
直樹 高橋
章人 中井
孝司 木内
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Zeon Corp
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Zeon Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to hydrogenated nitrile rubber and a method for producing the same, a veil made of hydrogenated nitrile rubber, a binder for positive electrodes made by dispersing or dissolving hydrogenated nitrile rubber in a solvent, a positive electrode containing hydrogenated nitrile rubber, and a method for producing the same.
  • Electrochemical elements such as lithium-ion secondary batteries, lithium-ion capacitors, and electric double-layer capacitors are small, lightweight, have high energy density, and can be repeatedly charged and discharged, making them used in a wide range of applications. For this reason, in recent years, efforts have been made to improve battery components such as electrodes in order to further improve the performance of electrochemical elements.
  • the electrodes used in electrochemical elements typically include a current collector and an electrode mixture layer formed on the current collector.
  • This electrode mixture layer is formed, for example, by applying a slurry containing an electrode active material, a conductive material, a binder, etc., onto the current collector and then drying the applied slurry.
  • Patent Document 1 discloses a binder composition for a positive electrode of a nonaqueous secondary battery that contains a binder, the binder composition containing at least one of iron, ruthenium, and rhodium, in which the total amount of iron, ruthenium, and rhodium is 5 ⁇ 10 -3 parts by mass or less per 100 parts by mass of the binder, and that forms an SEI coating well even when aging treatment is performed under low temperature and low depth of charge conditions, and has excellent life characteristics.
  • a latex obtained by emulsion polymerization of acrylonitrile and 1,3-butadiene is added to a 12% by mass aqueous magnesium sulfate solution, coagulated, washed with water and filtered, and then subjected to a metathetical reaction using a Grubbs catalyst (ruthenium catalyst) and ethylene as a coolefin, followed by a hydrogenation reaction using a Wilkinson catalyst (rhodium catalyst) with an iodine value of 1.3 mg/100 mg as the end point, followed by adding 0.2 parts of activated carbon having an average diameter of 15 ⁇ m and performing activated carbon treatment for 30 minutes.
  • ruthenium catalyst ruthenium catalyst
  • ethylene as a coolefin
  • a hydrogenated nitrile rubber having a total content of ruthenium and rhodium of 0.2 ⁇ 10 ⁇ 3 parts by mass and iron of 1.2 ⁇ 10 ⁇ 3 parts by mass per 100 parts by mass of binder is used.
  • a hydrogenated nitrile rubber obtained here that further increases the peel strength of the electrode produced and does not cause cracking of the electrode active material after cycle testing.
  • Patent Document 2 JP 2018-160421 A discloses a binder composition that contains a polymer including a conjugated diene monomer unit and/or an alkylene structural unit and a nitrile group-containing monomer unit, and an organic solvent, and has a solution turbidity of 1 to 80 at a solids concentration of 10% by mass, and has an excellent balance between peel strength and secondary battery output characteristics.
  • nitrile rubber latex obtained by emulsion polymerization of acrylonitrile and 1,3-butadiene is added to a 1% by mass calcium chloride aqueous solution to coagulate, washed with water, filtered, and then vacuum dried to obtain nitrile rubber, and the obtained nitrile rubber is subjected to a metathesis reaction with a ruthenium-based Grubbs catalyst and ethylene as a coolefin, and then a hydrogenation reaction is performed with a rhodium-based Wilkinson catalyst with an iodine value of 5 mg/100 mg as the end point, and then 0.2 parts of activated carbon with an average diameter of 15 ⁇ m is added and stirred for 30 minutes to obtain a hydrogenated polymer with a calcium ion concentration of 1000 ppm and an iodine value of 5 mg/100 mg.
  • NMP N-methylpyrrolidone
  • water is evaporated under reduced pressure to obtain an NMP solution of the hydrogenated polymer with a solution turbidity of 20
  • an electrode is produced using a binder composition consisting of 1.6 parts of polyvinylidene fluoride and 0.4 parts of the hydrogenated polymer as a binder composition.
  • a binder composition with even higher adhesive strength peel strength
  • Patent Document 3 discloses an electrochemical element having excellent rate characteristics and high-temperature storage stability, which contains a polymer containing ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units and specific alkylene structural units, and which has a volume average particle diameter D of 50 to 800 nm when dynamic light scattering measurement is performed, and at least one peak detected in the range of 5 ⁇ m to 30 ⁇ m, and a conductive carbon material; specifically, acrylonitrile and 1,3-butadiene are copolymerized, dibutylhydroxytoluene (BHT) is added as an anti-aging agent, and then a 25% by mass aqueous solution of calcium chloride in an amount of 3 parts per 100 parts of polymer is added to coagulate, and 50 times the amount of ion-exchanged water is passed through to wash the polymer, after which a hydrogenation reaction is performed using a palladium catalyst, and the palladium catalyst is filtered off to obtain
  • BHT dibutylhydroxyto
  • Patent Document 4 discloses a non-aqueous secondary battery with excellent electrolyte mobility, which includes a positive electrode, a negative electrode, an electrolyte, and a separator, and in which the positive electrode has a positive electrode composite layer formed on a current collector, the positive electrode composite layer including a positive electrode active material, a conductive material, and polymer A including at least one of a nitrile group-containing monomer unit, a conjugated diene unit, and an alkylene structural unit.
  • polymer A is a polymer obtained by adding dibutylhydroxytoluene (BHT) to an emulsion polymerization liquid obtained by emulsion polymerization of acrylonitrile and 1,3-butadiene, adding a 25% by mass aqueous calcium chloride solution to coagulate the solution, and then hydrogenating the solution using a palladium catalyst. The palladium catalyst is then filtered off to obtain a hydrogenated polymer with an iodine value of 20 mg/100 mg.
  • BHT dibutylhydroxytoluene
  • Patent Document 5 JP Patent Publication 2016-196668 A discloses a nitrile group-containing highly saturated copolymer rubber having ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units and conjugated diene monomer units, and having excellent oil resistance and cold resistance with an iodine value of 10 to 120 mg/100 mg.
  • an emulsion polymerization liquid obtained by emulsion polymerization of acrylonitrile and 1,3-butadiene is coagulated with an aqueous calcium chloride solution, and then a hydrogenation reaction is carried out using a palladium catalyst to obtain a hydrogenated acrylonitrile-butadiene copolymer with an iodine value of 10 to 29.5 mg/100 mg.
  • a hydrogenation reaction is carried out using a palladium catalyst to obtain a hydrogenated acrylonitrile-butadiene copolymer with an iodine value of 10 to 29.5 mg/100 mg.
  • the hydrogenated acrylonitrile-butadiene copolymer obtained here is used as a binder for electrode production, the peel strength and cycle characteristics are poor, and the electrode active material also cracks after cycle testing, making it unsuitable as a binder for electrodes.
  • Patent Document 6 JP Patent Publication 2018-145434 A discloses a hydrogenated nitrile rubber containing a substituted phenol, which is also useful for sealing materials, hose materials, transmission hoses, etc. in the automotive field. Specifically, acrylonitrile and 1,3-butadiene are emulsion polymerized, 4-methyl-2,6-tert-butylphenol (BHT) is added, and the resulting mixture is coagulated with an aqueous sodium chloride solution or an aqueous magnesium chloride solution prepared with tap water containing calcium ions, and washed with tap water containing calcium ions to reduce the calcium content to 2.
  • BHT 4-methyl-2,6-tert-butylphenol
  • NBR with 85 to 595 ppm is obtained, then hydrogenated to a hydrogenation level of 99.4 ⁇ 0.2% with a rhodium-based catalyst, the polymer liquid is diluted until the solid content concentration is 5%, the rhodium is removed, and a carboxyl group-containing water-soluble polymer, a 2% aqueous calcium chloride solution, and a dilute aqueous sodium hydroxide solution are continuously metered and added, and the metering rate of calcium chloride is adjusted so that 0.15 parts of calcium chloride are present at any time based on 100 parts by mass of hydrogenated nitrile rubber, and the hydrogenated nitrile rubber is solidified to obtain the hydrogenated nitrile rubber.
  • the hydrogenated nitrile rubber obtained here is used to manufacture electrodes, it has poor peel strength with the aluminum foil of the positive electrode, poor cycle characteristics, and there is a problem that the electrode active material cracks after cycle testing.
  • the present invention has been made in consideration of the above-mentioned circumstances, and aims to provide hydrogenated nitrile rubber and its manufacturing method, which are useful as a positive electrode material and have excellent conductive material dispersion and peel strength in the electrode when manufacturing electrodes for electrochemical elements, as well as excellent cycle characteristics and output characteristics of electrochemical elements, and excellent suppression of electrode active material cracking after cycle tests; hydrogenated nitrile rubber veil made of hydrogenated nitrile rubber; a positive electrode binder formed by dispersing or dissolving hydrogenated nitrile rubber or hydrogenated nitrile rubber veil in a solvent; and a positive electrode containing hydrogenated nitrile rubber and its manufacturing method.
  • hydrogenated nitrile rubber which contains nitrile group-containing monomer units and conjugated diene monomer units and/or alkylene structural units, has a specific iodine value and weight-average molecular weight (Mw), and limits the content of specific metal elements such as Rh, Ru, Ca, and Fe, is excellent in dispersibility of conductive materials and peel strength of the electrodes produced when used in the manufacture of electrochemical elements, suppresses cracking of the active material in cycle tests of the electrochemical elements, and also has excellent cycle characteristics and output characteristics.
  • Mw weight-average molecular weight
  • the inventors have also found that the above properties can be further improved by limiting the content of Pd, Mg and Na in the hydrogenated nitrile rubber.
  • the inventors have also found that the above properties can be significantly improved by increasing the bulk density of the hydrogenated nitrile rubber. This is believed to be because hydrogenated nitrile rubber with a high bulk density contains almost no oxygen, preventing the generation of oxygen radicals and improving various properties.
  • hydrogenated nitrile rubber obtained by using calcium chloride as a coagulant improves the dispersibility of conductive material dispersions and the electrode peel strength of electrochemical devices such as lithium ion secondary batteries, and also suppresses cracking of the active material layer after cycle testing, improving cycle characteristics.
  • hydrogenated nitrile rubber which is prepared by emulsion polymerizing a nitrile group-containing monomer and a conjugated diene monomer and coagulating the polymer with calcium chloride, can increase the viscosity characteristics of a conductive material dispersion when it is prepared, and can suppress cracking of the electrode active material in the resulting electrode after cycle testing, thereby significantly improving the cycle characteristics of an electrochemical element.
  • hydrogenated nitrile rubber which is excellent for creating electrodes for such electrochemical elements, can be easily obtained by coagulating an emulsion polymerization liquid obtained by emulsion polymerizing monomer components including a nitrile group-containing monomer and a conjugated diene monomer with an aqueous calcium chloride solution, thoroughly washing and drying the resulting hydrous crumbs, subjecting them to metathesis with a Grubbs catalyst and a coolefin, and then hydrogenating them with a Wilkinson catalyst.
  • the Ca content in the hydrogenated nitrile rubber can be easily controlled by treating it with an adsorbent such as activated carbon after hydrogenation.
  • the inventors have also discovered that the effects of the present invention can be maintained by baling and retaining the hydrogenated nitrile rubber of the present invention, and that dispersing or dissolving the hydrogenated nitrile rubber of the present invention in N-methylpyrrolidone makes it a binder suitable for producing positive electrodes for electrochemical elements.
  • the inventors have completed the present invention based on these findings.
  • a hydrogenated nitrile rubber that contains nitrile group-containing monomer units and conjugated diene monomer units and/or alkylene structural units, has an iodine value of 10 to 40 mg/100 mg, a weight average molecular weight (Mw) in the range of 1,000 to 600,000, a rhodium (Rh) and/or ruthenium (Ru) content of 0.5 to 50 ppm, a calcium (Ca) content of 1 to 1500 ppm, and an iron (Fe) content of 100 ppm or less.
  • Mw weight average molecular weight
  • Rh rhodium
  • Ru ruthenium
  • the calcium (Ca) content is preferably in the range of 50 to 500 ppm.
  • the magnesium (Mg) content is 50 ppm or less
  • the sodium (Na) content is 300 ppm or less
  • the palladium (Pd) content is 200 ppm or less.
  • the ratio of the nitrile group-containing monomer units of the hydrogenated nitrile rubber and other repeating units other than the conjugated diene monomer units and/or alkylene structural units is 0% by mass or more and 5% by mass or less.
  • the bulk density is preferably 0.8 g/cm 3 or more.
  • the chlorine (Cl) content is in the range of 10 ppm or more and 2500 ppm or less, and the mass ratio (Ca/Cl) to the calcium (Ca) content is in the range of 0.1 to 4.
  • the total ratio of the nitrile group-containing monomer units and the conjugated diene monomer units and/or alkylene structural units in the hydrogenated nitrile rubber is preferably 97 mass% or more.
  • the polymer (nitrile rubber) obtained by emulsion polymerizing a nitrile group-containing monomer and a conjugated diene monomer and coagulating the polymer with calcium chloride is hydrogenated.
  • the present invention also provides a method for producing the hydrogenated nitrile rubber, which includes a hydrogenation step in which the nitrile rubber is hydrogenated using a rhodium-based catalyst and/or a ruthenium-based catalyst.
  • the nitrile rubber is one that has been subjected to calcium chloride coagulation.
  • the nitrile rubber is produced by an emulsion polymerization process in which a monomer component containing a nitrile group-containing monomer and a conjugated diene monomer is emulsion-polymerized to obtain an emulsion polymerization liquid; a coagulation step of contacting the emulsion polymerization liquid with an aqueous calcium chloride solution to produce a water-containing crumb; A washing and drying step of washing and drying the water-containing crumb to obtain a polymer (nitrile rubber); It is preferred that the composition is produced by a process comprising:
  • an emulsion polymerization process for obtaining an emulsion polymerization liquid by emulsion polymerizing a monomer component including a nitrile group-containing monomer and a conjugated diene monomer; a coagulation step of contacting the emulsion polymerization liquid with an aqueous calcium chloride solution to produce a water-containing crumb; A washing and drying step of washing and drying the water-containing crumb to obtain a polymer (nitrile rubber); a hydrogenation step of hydrogenating the obtained nitrile rubber using a rhodium-based catalyst and/or a ruthenium-based catalyst;
  • a method for producing the hydrogenated nitrile rubber comprising:
  • the hydrogenation step is a step of subjecting the polymer to metathesis using the ruthenium-based catalyst and further a coolefin, and then hydrogenating the polymer using the rhodium-based catalyst.
  • the method for producing hydrogenated nitrile rubber of the present invention it is preferable to further provide a purification step in which the hydrogenated nitrile rubber is subjected to an adsorbent treatment after the hydrogenation step.
  • the screw-type extruder is equipped with a reduced pressure drying barrel.
  • the present invention also provides a hydrogenated nitrile rubber bale obtained by baling the above hydrogenated nitrile rubber.
  • the bulk density is preferably 0.8 g/cm 3 or more.
  • the hydrogenated nitrile rubber veil of the present invention it is preferable that the hydrogenated nitrile rubber veil is a laminate of sheet-shaped hydrogenated nitrile rubber.
  • the present invention also provides a binder for positive electrodes, which is prepared by dispersing or dissolving the hydrogenated nitrile rubber in N-methylpyrrolidone (NMP).
  • NMP N-methylpyrrolidone
  • the present invention also provides a binder for positive electrodes, which is prepared by dispersing or dissolving the hydrogenated nitrile rubber veil in N-methylpyrrolidone (NMP).
  • NMP N-methylpyrrolidone
  • the present invention also provides a positive electrode comprising a positive electrode mixture layer containing a conductive material, a positive electrode active material, and a binder containing the hydrogenated nitrile rubber, and a current collector.
  • the present invention further provides a method for producing a positive electrode, which includes a step of applying a positive electrode composite layer slurry obtained by mixing the positive electrode binder and conductive material and then mixing the positive electrode active material onto a current collector and drying the resulting mixture.
  • the present invention provides hydrogenated nitrile rubber, which is useful as a positive electrode material and has excellent conductive material dispersibility and peel strength of the produced electrodes, suppresses cracking of the electrode active material after cycle testing of electrochemical devices, and has excellent cycle characteristics and output characteristics, as well as a manufacturing method thereof; hydrogenated nitrile rubber veil made of hydrogenated nitrile rubber; a positive electrode binder made by dispersing or dissolving hydrogenated nitrile rubber or hydrogenated nitrile rubber veil in a solvent; and a positive electrode containing hydrogenated nitrile rubber and a manufacturing method thereof.
  • the hydrogenated nitrile rubber of the present invention is characterized by containing nitrile group-containing monomer units and conjugated diene monomer units and/or alkylene structural units, having a weight average molecular weight (Mw) in the range of 1,000 to 600,000, an iodine value in the range of 10 to 40 mg/100 mg, an Rh and/or Ru content of 0.5 to 50 ppm, and a Ca content of 1 to 1500 ppm.
  • Mw weight average molecular weight
  • the hydrogenated nitrile rubber of the present invention contains a nitrile group-containing monomer unit and a conjugated diene monomer unit and/or an alkylene structural unit.
  • the hydrogenated nitrile rubber is a component that can function as a binder that holds an electrode active material and the like from a current collector without causing the electrode active material to be detached from the current collector in an electrode mixture layer formed using a composition for electrochemical devices.
  • the hydrogenated nitrile rubber can also function as a dispersant that can disperse a conductive material in a conductive material dispersion liquid that contains a conductive material.
  • hydrogenated nitrile rubber can be a hydrogenated polymer obtained by hydrogenating a polymer containing conjugated diene monomer units and nitrile group-containing monomer units.
  • the polymer containing conjugated diene monomer units and nitrile group-containing monomer units is completely hydrogenated, the polymer contains alkylene structural units and nitrile group-containing monomer units, and when the hydrogenation is partially performed, the polymer contains conjugated diene monomer units, alkylene structural units, and nitrile group-containing monomer units.
  • nitrile group-containing monomers capable of forming nitrile group-containing monomer units include ⁇ , ⁇ -ethylenically unsaturated nitrile monomers.
  • the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an ⁇ , ⁇ -ethylenically unsaturated compound having a nitrile group, and examples thereof include acrylonitrile; ⁇ -halogenoacrylonitriles such as ⁇ -chloroacrylonitrile and ⁇ -bromoacrylonitrile; ⁇ -alkylacrylonitriles such as methacrylonitrile and ⁇ -ethylacrylonitrile; and the like, with acrylonitrile being preferred.
  • the nitrile group-containing monomer may be used alone or in combination of two or more kinds in any ratio.
  • the content of the nitrile group-containing monomer units in the hydrogenated nitrile rubber is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less, assuming that the total repeating units in the hydrogenated nitrile rubber is 100% by mass. If the content of the nitrile group-containing monomer units is within the above-mentioned range, the dispersion stability of the conductive material dispersion can be increased, and the peel strength of the obtained electrode can be further improved.
  • conjugated diene monomer units examples include conjugated diene compounds having 4 or more carbon atoms, such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, and 1,3-pentadiene. Among these, isoprene and 1,3-butadiene are preferred, and 1,3-butadiene is particularly preferred.
  • the alkylene structural unit is a repeating unit composed only of an alkylene structure represented by the general formula: -C n H 2n - [wherein n is an integer of 2 or more].
  • the alkylene structural unit may be linear or branched, but from the viewpoint of reducing the resistance of the electrode while improving the rate characteristics of the electrochemical device, the alkylene structural unit is preferably linear, i.e., a linear alkylene structural unit.
  • the alkylene structural unit preferably has 4 or more carbon atoms (i.e., n in the above general formula is an integer of 4 or more).
  • the alkylene structural unit may be linear or branched, but it is preferable that the alkylene structural unit is linear, i.e., a linear alkylene structural unit. It is also preferable that the alkylene structural unit has 4 or more carbon atoms (i.e., n in the above general formula is an integer of 4 or more).
  • the method for introducing an alkylene structural unit into a polymer is not particularly limited, but may be, for example, the following method (1) or (2): (1) A method of preparing a polymer from a monomer composition containing a conjugated diene monomer and converting the conjugated diene monomer unit into an alkylene structural unit by hydrogenating the polymer. (2) A method of preparing a polymer from a monomer composition containing a 1-olefin monomer. Among these, the method (1) is preferred because it is easy to produce the polymer.
  • conjugated diene monomers and 1-olefin monomers can be used alone or in combination of two or more.
  • the total content of the conjugated diene monomer units and the alkylene structural units in the hydrogenated nitrile rubber is preferably 50% by mass or more, more preferably 55% by mass or more, particularly preferably 60% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, particularly preferably 80% by mass or less, when the total repeating units (the sum of the structural units and the monomer units) in the hydrogenated nitrile rubber is taken as 100% by mass. If the total content of the conjugated diene monomer units and the alkylene structural units in the polymer is within the above range, the dispersion stability of the conductive material dispersion and the cycle characteristics of the electrochemical element can be improved.
  • the hydrogenated nitrile rubber has only one of the content ratio of alkylene structural units and conjugated diene monomer units, it is preferable that the ratio satisfies the above range.
  • the total ratio of the nitrile group-containing monomer units and the conjugated diene monomer units and/or alkylene structural units in the hydrogenated nitrile rubber of the present invention is not particularly limited, but when it is usually 80 mass % or more, preferably 90 mass % or more, more preferably 95 mass % or more, further preferably 97 mass % or more, and most preferably 99 mass % or more, the dispersion stability of the conductive material dispersion and the cycle characteristics of the electrochemical element can be improved.
  • the other repeating units are not particularly limited, but may include aromatic vinyl monomer units, acidic group-containing monomer units, and (meth)acrylic acid ester monomer units.
  • the hydrogenated nitrile rubber may contain one type of other repeating unit, or may contain two or more types of other repeating units.
  • "(meth)acrylic” means acrylic and/or methacrylic.
  • Aromatic vinyl monomers that can form aromatic vinyl monomer units include, for example, styrene, ⁇ -methylstyrene, p-t-butylstyrene, butoxystyrene, vinyltoluene, chlorostyrene, and vinylnaphthalene.
  • the aromatic vinyl monomers may be used alone or in combination of two or more at any ratio. Among these, styrene is preferred.
  • acidic group-containing monomers capable of forming acidic group-containing monomer units include carboxylic acid group-containing monomers, sulfonic acid group-containing monomers, and phosphoric acid group-containing monomers. Note that the acidic group-containing monomers may be used alone or in combination of two or more types in any ratio.
  • Carboxylic acid group-containing monomers include monocarboxylic acids and their derivatives, dicarboxylic acids and their acid anhydrides, and their derivatives.
  • Monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid.
  • Monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, ⁇ -acetoxyacrylic acid, ⁇ -trans-aryloxyacrylic acid, ⁇ -chloro- ⁇ -E-methoxyacrylic acid, etc.
  • Dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid.
  • Dicarboxylic acid derivatives include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, and maleic acid monoesters such as nonyl maleate, decyl maleate, dodecyl maleate, octadecyl maleate, and fluoroalkyl maleates.
  • dicarboxylic acid anhydrides examples include maleic anhydride, acrylic anhydride, methyl maleic anhydride, and dimethyl maleic anhydride.
  • carboxylic acid group-containing monomer an acid anhydride that generates a carboxylic acid group by hydrolysis can be used.
  • acrylic acid and methacrylic acid are preferred as the carboxylic acid group-containing monomer.
  • sulfonic acid group-containing monomer examples include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, (meth)acrylic acid-2-ethyl sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, and 3-allyloxy-2-hydroxypropanesulfonic acid.
  • (meth)allyl means allyl and/or methallyl.
  • Examples of the phosphate group-containing monomer include 2-(meth)acryloyloxyethyl phosphate, methyl-2-(meth)acryloyloxyethyl phosphate, and ethyl-(meth)acryloyloxyethyl phosphate.
  • (meth)acryloyl means acryloyl and/or methacryloyl.
  • Examples of (meth)acrylic acid ester monomers that can form (meth)acrylic acid ester monomer units include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate, etc.
  • Acrylic acid alkyl esters methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl methacrylate, n-tetradecyl methacrylate, and stearyl methacrylate.
  • the (meth)acrylic acid ester monomers may be used alone or in combination of two or more kinds in any ratio.
  • the content of other repeating units in the hydrogenated nitrile rubber is preferably 0% by mass or more and 30% by mass or less, more preferably 0% by mass or more and 20% by mass or less, even more preferably 0% by mass or more and 10% by mass or less, particularly preferably 0% by mass or more and 5% by mass or less, and most preferably 0% by mass or more and 3% by mass or less, with the total repeating units in the hydrogenated nitrile rubber being 100% by mass.
  • the hydrogenated nitrile rubber of the present invention contains the above repeating unit and is characterized by having a specific iodine value and weight average molecular weight (Mw), and by having specific contents of Rh, Ru, Ca and Fe.
  • the iodine value of the hydrogenated nitrile rubber of the present invention is in the range of 10 to 40 mg/100 mg, preferably 10 to 35 mg/100 mg, more preferably 11 to 30 mg/100 mg, even more preferably 12 to 20 mg/100 mg, and most preferably 12 to 25 mg/100 mg.
  • the conductive material dispersibility, the peel strength at the positive electrode, and the output characteristics of the electrochemical element are highly balanced, which is preferable.
  • the weight average molecular weight (Mw) of the hydrogenated nitrile rubber of the present invention is in the range of 1,000 to 600,000, preferably 5,000 to 500,000, more preferably 10,000 to 250,000, and most preferably 20,000 to 200,000. If the weight average molecular weight (Mw) of the hydrogenated nitrile rubber is in this range, it is preferable because it can increase the dispersion stability of the conductive material dispersion and also increase the peel strength of the resulting electrode.
  • the hydrogenated nitrile rubber of the present invention has an Rh and/or Ru content (total amount of Rh and Ru) in the range of 0.5 to 50 ppm, preferably 1 to 25 ppm, and more preferably 1 to 15 ppm, which is suitable for suppressing cracking of the active material in the produced electrode.
  • the Ca content of the hydrogenated nitrile rubber of the present invention is in the range of 1 to 1500 ppm, preferably 15 to 1500 ppm, more preferably 20 to 800 ppm, and most preferably 50 to 500 ppm.
  • the Ca content in the hydrogenated nitrile rubber is in this range, cracking of the electrode active material in the obtained electrode can be effectively suppressed and the peel strength of the electrode can be increased.
  • the Ca content in the hydrogenated nitrile rubber is in this range, the cycle characteristics of the obtained electrochemical element can be improved, which is preferable.
  • the Ca content in the hydrogenated nitrile rubber when highly improving the peel strength of the electrode and the cycle characteristics of the electrochemical element is not particularly limited, but is usually 10 ppm or more, preferably 20 ppm or more, more preferably 30 ppm or more, even more preferably 40 ppm or more, and most preferably 50 ppm or more, and the upper limit is not particularly limited, but is usually 1500 ppm or less, preferably 1000 ppm or less, more preferably 800 ppm or less, even more preferably 600 ppm or less, and most preferably 500 ppm or less.
  • the Cl content in the hydrogenated nitrile rubber of the present invention is not particularly limited, but is usually 2500 ppm or less, preferably 2000 ppm or less, more preferably 1500 ppm or less, even more preferably 1300 ppm or less, and most preferably 1000 ppm or less.
  • the lower limit of the Cl content in the hydrogenated nitrile rubber is not particularly limited, but is usually 0.5 ppm or more, preferably 1 ppm or more, preferably 2.5 ppm or more, or 5 ppm or more, 10 ppm or more, 20 ppm or more, 30 ppm or more, 40 ppm or more, 50 ppm or more, 70 ppm or more, and 100 ppm or more are preferred in this order.
  • the Cl content in the hydrogenated nitrile rubber is in this range, when a conductive material dispersion of the hydrogenated nitrile rubber veil is prepared, the viscosity characteristics of the conductive material dispersion can be increased, and the cycle characteristics of the resulting electrochemical element and cracking of the electrode active material after cycle testing can be suppressed, which is preferable.
  • the mass ratio (Ca/Cl) of the Ca content to the Cl content in the hydrogenated nitrile rubber of the present invention is not particularly limited, but is usually in the range of 0.01 to 10, preferably 0.1 to 5, more preferably 0.1 to 4, even more preferably 0.2 to 4, particularly preferably 0.5 to 3, and most preferably 0.6 to 2.5.
  • the mass ratio of the Ca content to the Cl content in the hydrogenated nitrile rubber is in this range, the viscosity characteristics of the conductive material dispersion can be increased when the conductive material dispersion is prepared, and the cycle characteristics of the resulting electrochemical element and cracking of the electrode active material after cycle testing can be suppressed, which is preferable.
  • the Fe content in the hydrogenated nitrile rubber of the present invention is 100 ppm or less, preferably 80 ppm or less, more preferably 50 ppm or less, even more preferably 30 ppm or less, and most preferably 20 ppm or less.
  • the Fe content in the hydrogenated nitrile rubber is in this range, cracking of the active material in the electrode is suppressed and the cycle characteristics of the electrochemical element are improved, which is preferable.
  • the Pd content in the hydrogenated nitrile rubber of the present invention is not particularly limited, but is usually 200 ppm or less, preferably 100 ppm or less, more preferably 75 ppm or less, preferably 50 ppm or less, and most preferably 10 ppm or less.
  • the Pd content in the hydrogenated nitrile rubber is in this range, cracking of the active material in the electrode is suppressed, and the cycle characteristics of the electrochemical element are improved, which is preferable.
  • the Mg content in the hydrogenated nitrile rubber of the present invention is not particularly limited, but is usually 50 ppm or less, preferably 40 ppm or less, more preferably 30 ppm or less, even more preferably 25 ppm or less, and most preferably 20 ppm or less.
  • the Mg content in the hydrogenated nitrile rubber is in this range, cracking of the active material in the electrode is suppressed, and the cycle characteristics of the electrochemical element are improved, which is preferable.
  • the Na content in the hydrogenated nitrile rubber of the present invention is not particularly limited, but is usually 300 ppm or less, preferably 150 ppm or less, more preferably 100 ppm or less, even more preferably 75 ppm or less, and most preferably 50 ppm or less.
  • the Na content in the hydrogenated nitrile rubber is in this range, cracking of the active material in the electrode is suppressed, and the cycle characteristics of the electrochemical element are improved, which is preferable.
  • the bulk density of the hydrogenated nitrile rubber of the present invention is not particularly limited, but is usually 0.6 g/cm 3 or more, preferably 0.7 g/cm 3 or more, more preferably 0.8 g/cm 3 or more, even more preferably 0.85 g/cm 3 or more, and most preferably 0.9 g/cm 3 or more.
  • the upper limit of the bulk density of the hydrogenated nitrile rubber is not particularly limited, but is usually 1.2 g/cm 3 or less, preferably 1.15 g/cm 3 or less, more preferably 1.1 g/cm 3 or less, even more preferably 1.05 g/cm 3 or less, and most preferably 1 g/cm 3 or less.
  • the bulk density of the hydrogenated nitrile rubber is in this range, the stability of the conductive material dispersion is excellent, and it is suitable for preventing the cycle characteristics of the electrochemical element and cracking of the active material after cycle testing.
  • the bulk density of the hydrogenated nitrile rubber can be easily adjusted, for example, by drying with a screw-type extruder described below or by baling the hydrogenated nitrile rubber.
  • the water content of the hydrogenated nitrile rubber of the present invention is not particularly limited, but is usually excellent in storage stability and is suitable when it is less than 1% by mass, preferably 0.8% by mass or less, and more preferably 0.6% by mass or less.
  • the Mooney viscosity (ML1+4, 100°C) of the hydrogenated nitrile rubber of the present invention is not particularly limited, but is usually in the range of 10 to 150, preferably 15 to 100, and more preferably 20 to 80, which provides a high level of balance between the conductive material dispersibility and the peel strength at the electrode and is suitable.
  • the hydrogenated nitrile rubber of the present invention is not particularly limited, but is preferably one obtained by hydrogenating a polymer (nitrile rubber) obtained by emulsion polymerization of a nitrile group-containing monomer and a conjugated diene monomer and coagulating them with calcium chloride.
  • a polymer nitrile rubber
  • emulsion polymerization liquid the size, shape, and properties of the water-containing crumbs produced will be completely different depending on the type of coagulant used, and the residues of various secondary materials in the polymerization and coagulation processes that can be removed in the subsequent washing and dehydration processes will differ.
  • the hydrogenated nitrile rubber of the present invention may contain a phenolic antioxidant.
  • the phenol-based antioxidant contained is not particularly limited, but examples include 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl- ⁇ -dimethylamino-p-cresol, and 2,2'-methylene-bis(4-methyl-6-t-butylphenol).
  • the content of the phenolic antioxidant in the hydrogenated nitrile rubber of the present invention is not particularly limited, but is usually in the range of 0.001 to 2 mass%, preferably 0.01 to 1 mass%, and more preferably 0.1 to 0.5 mass%.
  • the hydrogenated nitrile rubber of the present invention is preferably produced by emulsion polymerizing a nitrile group-containing monomer and a conjugated diene monomer, adding a phenolic antioxidant, and then coagulating the polymer with calcium chloride, and hydrogenating the polymer.
  • the effect of this phenolic antioxidant is much higher and more preferable when it is added to the emulsion polymerization liquid obtained by emulsion polymerizing a nitrile group-containing monomer and a conjugated diene monomer, rather than mixing it with the hydrogenated nitrile rubber after production.
  • the method for producing the hydrogenated nitrile rubber of the present invention is not particularly limited, but for example, the hydrogenated nitrile rubber can be easily produced by a method including a hydrogenation step in which a polymer (nitrile rubber) coagulated with calcium chloride is hydrogenated using a rhodium-based catalyst and/or a ruthenium-based catalyst.
  • the nitrile rubber is produced by an emulsion polymerization process in which a monomer component containing a nitrile group-containing monomer and a conjugated diene monomer is emulsion-polymerized to obtain an emulsion polymerization liquid; a coagulation step of contacting the emulsion polymerization liquid with an aqueous calcium chloride solution to produce a water-containing crumb; a washing and drying step of washing and drying the water-containing crumbs to obtain a polymer; It is preferred that the composition is produced by a process comprising:
  • the process further includes an emulsion polymerization step of emulsion-polymerizing a monomer component including a nitrile group-containing monomer and a conjugated diene monomer to obtain an emulsion polymerization liquid; a coagulation step of contacting the emulsion polymerization liquid with an aqueous calcium chloride solution to produce a water-containing crumb; a washing and drying step of washing and drying the solidified crumb to obtain a polymer; and a hydrogenation step of hydrogenating the obtained polymer using a rhodium-based catalyst and/or a ruthenium-based catalyst.
  • the hydrogenated nitrile rubber of the present invention can be produced by a process comprising the steps of:
  • the hydrogenation step involves subjecting nitrile rubber to metathesis using a ruthenium catalyst and a coolefin, followed by hydrogenation using a rhodium catalyst, and by further providing a purification step following the hydrogenation step in which the hydrogenated nitrile rubber is treated with an adsorbent, thereby making it easy to manufacture the product.
  • the emulsion polymerization step in the method for producing hydrogenated nitrile rubber of the present invention is a step of emulsion-polymerizing a monomer component containing a nitrile group-containing monomer and a conjugated diene monomer to obtain an emulsion polymerization liquid.
  • the monomer components used are the same as those described above, and the amounts used may be appropriately selected to obtain the monomer composition of the hydrogenated nitrile rubber.
  • the emulsifier used in emulsion polymerization is not particularly limited, but examples include anionic emulsifiers, cationic emulsifiers, and nonionic emulsifiers, and preferably contains an anionic emulsifier.
  • the anionic emulsifier is not particularly limited, and examples thereof include salts of fatty acids such as myristic acid, palmitic acid, oleic acid, and linolenic acid; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; sulfate salts such as sodium lauryl sulfate, and phosphate salts such as polyoxyalkylene alkyl ether phosphate salts; and alkyl sulfosuccinates.
  • fatty acid salts and sulfate salts are preferred, and fatty acid salts are particularly preferred.
  • Suitable sulfate salts include, for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium myristyl sulfate, sodium laureth sulfate, sodium polyoxyethylene alkyl sulfate, and sodium polyoxyethylene alkylaryl sulfate.
  • Suitable fatty acid salts include, for example, potassium oleate, sodium oleate, and potassium palmitate, with potassium oleate being particularly preferred.
  • emulsifiers can be used alone or in combination of two or more.
  • the amount used is usually 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 1 to 3 parts by mass, per 100 parts by mass of the monomer component.
  • the monomer component, emulsifier, and water can be mixed in the usual manner, such as by stirring the monomer, emulsifier, and water using a stirrer such as a homogenizer or a disk turbine.
  • the amount of water used is usually 10 to 750 parts by mass, preferably 50 to 500 parts by mass, and more preferably 100 to 400 parts by mass, per 100 parts by mass of the monomer component.
  • polymerization catalyst used in emulsion polymerization there are no particular limitations on the polymerization catalyst used in emulsion polymerization, so long as it is one that is commonly used in emulsion polymerization.
  • a redox catalyst consisting of a radical generator and a reducing agent can be used.
  • the radical generator may be, for example, a peroxide or an azo compound, with peroxide being preferred.
  • peroxide inorganic peroxides or organic peroxides may be used.
  • inorganic peroxides examples include sodium persulfate, potassium persulfate, hydrogen peroxide, and ammonium persulfate.
  • potassium persulfate, hydrogen peroxide, and ammonium persulfate are preferred, with potassium persulfate being particularly preferred.
  • the organic peroxide is not particularly limited as long as it is a known peroxide used in emulsion polymerization, and examples thereof include 2,2-di(4,4-di-(t-butylperoxy)cyclohexyl)propane, 1-di-(t-hexylperoxy)cyclohexane, 1,1-di-(t-butylperoxy)cyclohexane, 4,4-di-(t-butylperoxy)n-butyl valerate, 2,2-di-(t-butylperoxy)butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropyl benzene, and the like.
  • benzene hydroperoxide paramenthane hydroperoxide, benzoyl peroxide, 1,1,3,3-tetraethylbutyl hydroperoxide, t-butylcumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, diisobutyryl peroxide, di(3,5,5-trimethylhexanoyl)peroxide, and dilauroyl peroxide.
  • radical generators can be used alone or in combination of two or more types, and the amount used is usually in the range of 0.0001 to 5 parts by mass, preferably 0.0005 to 1 part by mass, and more preferably 0.001 to 0.5 parts by mass, per 100 parts by mass of the monomer component.
  • the amount of water used in the emulsion polymerization reaction may be only that used during the emulsification of the monomer components, but is usually adjusted to be in the range of 10 to 1,000 parts by mass, preferably 50 to 500 parts by mass, more preferably 80 to 400 parts by mass, and most preferably 100 to 300 parts by mass, per 100 parts by mass of the monomer components used in the polymerization.
  • the emulsion polymerization reaction may be carried out in the usual manner, and may be batch, semi-batch, or continuous.
  • the polymerization temperature and polymerization time are not particularly limited and may be appropriately selected depending on the type of polymerization initiator used.
  • the polymerization temperature is usually in the range of 0 to 100°C, preferably 5 to 80°C, and more preferably 10 to 50°C, and the polymerization time is usually 0.5 to 100 hours, and preferably 1 to 10 hours.
  • the polymerization conversion rate of the emulsion polymerization reaction is not particularly limited, but when it is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more, the hydrogenated nitrile rubber produced has excellent strength characteristics and is free of monomer odor, which is suitable.
  • a polymerization terminator may be used to stop the polymerization.
  • a phenol-based antiaging agent can be added to the emulsion polymerization liquid after the above emulsion polymerization, if necessary.
  • the phenol-based antiaging agent to be added is the same as that exemplified for the hydrogenated nitrile rubber of the present invention.
  • the method of addition is not particularly limited and may be in accordance with a conventional method.
  • the phenol-based antiaging agent may be added as it is, or may be emulsified with an emulsifier and then added.
  • the amount of the phenol-based anti-aging agent used may be appropriately selected so as to be the content of the anti-aging agent in the hydrogenated nitrile rubber of the present invention, but is usually in the range of 0.001 to 15 parts by mass, preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, particularly preferably 0.3 to 3 parts by mass, and most preferably 0.5 to 2 parts by mass, per 100 parts by mass of the monomer component.
  • the coagulation step in the method for producing hydrogenated nitrile rubber of the present invention is characterized in that the emulsion polymerization liquid obtained above is brought into contact with calcium chloride to produce water-containing crumbs.
  • calcium chloride as a coagulant and setting the Ca content in the hydrogenated nitrile rubber produced within a specific range, it is preferable because it contributes to the dispersibility of the conductive material dispersion liquid, extremely increases the peel strength of the produced electrode, and is also excellent in the cycle characteristics of the electrochemical element and in the effect of suppressing cracking of the electrode active material after cycle testing.
  • the solids concentration of the emulsion polymerization liquid used in the coagulation step is not particularly limited, but is usually adjusted to the range of 5 to 50% by mass, preferably 10 to 45% by mass, and more preferably 20 to 40% by mass.
  • the calcium chloride used is usually used as an aqueous calcium chloride solution, and the coagulant concentration is usually in the range of 0.1 to 70% by mass, preferably 1 to 60% by mass, more preferably 5 to 50% by mass, and particularly preferably 10 to 30% by mass, which is suitable for concentrating the particle size of the generated hydrous crumbs uniformly in a specific area.
  • the temperature of the coagulation liquid there are no particular limitations on the temperature of the coagulation liquid, but a temperature of 40°C or higher, preferably 40 to 90°C, and more preferably 50 to 80°C, is generally preferred to produce uniform, water-containing crumbs.
  • coagulation liquid there are no particular limitations on the contact between the emulsion polymerization liquid and the calcium chloride aqueous solution (coagulation liquid), but for example, either a method of adding the emulsion polymerization liquid to the coagulation liquid being stirred, or a method of adding the coagulation liquid to the emulsion polymerization liquid being stirred, is acceptable, but the method of adding the coagulation liquid to the emulsion polymerization liquid being stirred is preferable because it makes the shape and diameter of the water-containing crumbs that are generated uniform and concentrated, and significantly improves the washing efficiency of the emulsifier and coagulation agent.
  • the water washing and drying step in the process for producing hydrogenated nitrile rubber of the present invention is a step of washing and drying the water-containing crumbs produced as described above to obtain a polymer.
  • the washing method is not particularly limited and may be any ordinary method, but it is effective to wash the hydrous crumbs coagulated with the high concentration calcium chloride aqueous solution with a large amount of water.
  • the amount of water used is usually 10 to 500 times, preferably 25 to 250 times, and more preferably 50 to 100 times, per 100 parts by mass of the polymer.
  • the temperature of the water used for washing is not particularly limited, but it is preferable to use warm water, which is usually 40°C or higher, preferably 40 to 100°C, more preferably 50 to 90°C, and most preferably 60 to 80°C, as this significantly improves the washing efficiency.
  • warm water which is usually 40°C or higher, preferably 40 to 100°C, more preferably 50 to 90°C, and most preferably 60 to 80°C, as this significantly improves the washing efficiency.
  • the cleaning time is usually in the range of 1 to 120 minutes, preferably 2 to 60 minutes, and more preferably 3 to 30 minutes.
  • the washed hydrous crumbs can be dried in the usual manner, for example, using a dryer such as a hot air dryer, a vacuum dryer, an expander dryer, a kneader type dryer, or a screw type extruder.
  • a dryer such as a hot air dryer, a vacuum dryer, an expander dryer, a kneader type dryer, or a screw type extruder.
  • the shape of the dried rubber is not particularly limited, and examples include crumbs, powder, rods, and sheets.
  • the moisture content of the dried rubber is less than 1% by mass, preferably 0.8% by mass or less, and more preferably 0.6% by mass or less.
  • the hydrogenation step in the production method for hydrogenated nitrile rubber of the present invention is a step of hydrogenating the above-obtained polymer using a rhodium-based catalyst and/or a ruthenium-based catalyst, and can be easily carried out by subjecting the polymer to metathesis using a ruthenium-based catalyst and a coolefin, and then hydrogenating the polymer using a rhodium-based catalyst.
  • Metathesis Reaction The metathesis reaction can be carried out, for example, by using the method described in Japanese Patent No. 4,509,792.
  • ruthenium catalyst can be used as a catalyst for the metathesis reaction.
  • a Grubbs catalyst such as bis(tricyclohexylphosphine)benzylidene ruthenium dichloride or 1,3-bis(2,4,6-trimethylphenyl)-2-(imidazolidinylidene)(dichlorophenylmethylene)(tricyclohexylphosphine)ruthenium as a catalyst for the metathesis reaction.
  • the metathesis reaction is carried out in the presence of a coolefin.
  • coolefins examples include olefins having 2 to 16 carbon atoms, such as ethylene, isobutane, styrene, and 1-hexane, and functional group-containing unsaturated compounds, such as cis-2-butene-1,4-diol, 3-butene-1-amine, vinyltrimethoxysilane, methoxypolyalkylene glycol methacrylate, and 2-(methacryloyloxy)ethanesulfonic acid, with functional group-containing unsaturated compounds being preferred.
  • olefins having 2 to 16 carbon atoms such as ethylene, isobutane, styrene, and 1-hexane
  • functional group-containing unsaturated compounds such as cis-2-butene-1,4-diol, 3-butene-1-amine, vinyltrimethoxysilane, methoxypolyalkylene glycol methacrylate, and 2-(methacryloyloxy)ethan
  • the amount of coolefin used is usually in the range of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the polymer.
  • the polymer concentration in the metathesis reaction is not critical, but is usually in the range of 1 to 20% by weight, preferably 6 to 15% by weight.
  • the reaction solution in the metathesis reaction is usually stirred vigorously, for example, at 200 to 1000 rpm, preferably 300 to 900 rpm, and more preferably 500 to 800 rpm.
  • the hydrogenation reaction can be carried out by dissolving the polymer in a solvent and then adding a hydrogenation catalyst.
  • the hydrogenation reaction after the above-mentioned metathesis is preferably carried out in the same reaction vessel as that for the metathesis reaction, by adding a hydrogenation catalyst to the vessel without isolating the metathesis product, and then carrying out hydrogenation treatment to produce hydrogenated nitrile rubber.
  • the solvent for the hydrogenation reaction can be either an aqueous solvent or an organic solvent, but an organic solvent is preferred.
  • Suitable organic solvents include, for example, acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, 1,3-dioxane, benzene, toluene, methylene chloride, chloroform, monochlorobenzene (MCB), and dichlorobenzene.
  • MCB is particularly suitable as it is a good solvent for both the nitrile group-containing polymer before hydrogenation and the hydrogenated nitrile rubber after hydrogenation.
  • the hydrogenation catalyst can be any method known in the art without any particular limitations.
  • the method described in Japanese Patent No. 6309634 can be used, and it is particularly preferable to use a known homogeneous hydrogenation catalyst such as Wilkinson's catalyst ((PPh 3 ) 3 RhCl).
  • Wilkinson's catalyst (PPh 3 ) 3 RhCl)
  • the Grubbs catalyst is converted into a dihydride complex (PR 3 ) 2 RuCl 2 H 2 , which is itself an olefin hydrogenation catalyst, in the presence of hydrogen.
  • the hydrogenation reaction can be carried out without adding the Wilkinson catalyst, but the hydrogenation rate tends to be slow.
  • the amount of hydrogenation catalyst used may be appropriately selected depending on the purpose of use and the iodine value, but is usually in the range of 0.001 to 0.5 parts by mass, preferably 0.005 to 0.1 parts by mass, or 0.01 to 0.05 parts by mass, based on 100 parts by mass of the polymer before hydrogenation.
  • cocatalyst in the hydrogenation reaction, can be used as necessary.
  • cocatalysts for the Wilkinson catalyst include phosphine, diphosphine, and triphenylphosphine, with triphenylphosphine being preferred.
  • These cocatalysts can be used alone or in combination of two or more types, and the amount used is usually in the range of 0.01 to 15 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the polymer to be hydrogenated.
  • the polymer concentration in the hydrogenation reaction is not particularly limited as long as the polymer is soluble, but is usually in the range of 1 to 30 mass%, preferably 5 to 25 mass%, and more preferably 7 to 20 mass%.
  • the pressure of the hydrogenation reaction is not particularly limited, but is usually in the range of 0.1 to 30 MPa, preferably 1 to 20 MPa, and more preferably 5 to 15 MPa.
  • the hydrogenation reaction temperature is usually in the range of 30 to 200°C, preferably 50 to 170°C, and more preferably 100 to 150°C.
  • the reaction time is usually 1 to 50 hours, and preferably 2 to 25 hours.
  • the hydrogenation reaction can be stopped once the desired hydrogenation level has been reached by depressurizing or cooling the reactor. Residual hydrogen is usually removed with a nitrogen purge.
  • the hydrogenation catalyst can also be removed prior to removal of the solvent and isolation of the hydrogenated nitrile rubber from the organic layer.
  • the purification step in the method for producing hydrogenated nitrile rubber of the present invention is preferably carried out after the hydrogenation reaction, and can be subjected to an adsorbent treatment so that the Ca content in the hydrogenated nitrile rubber becomes a value of 1 to 1500 ppm.
  • Adsorbents are not particularly limited, but examples include activated carbon, ion exchange resins, and synthetic zeolites, with activated carbon being preferred.
  • the adsorbent treatment can be carried out by adding an adsorbent to the reaction liquid containing the hydrogenated nitrile rubber after hydrogenation and mixing.
  • an adsorbent there are no particular limitations on the amount of adsorbent added, but it is usually in the range of 0.001 to 1 part by mass, preferably 0.05 to 0.5 parts by mass, and more preferably 0.01 to 0.4 parts by mass per 100 parts by mass of hydrogenated nitrile rubber.
  • the mixing temperature is usually in the range of room temperature to 80°C, preferably room temperature to 60°C, and the mixing time is usually 1 minute to 1 hour, preferably 20 to 40 minutes.
  • the adsorbent is removed by filtration or decantation, and the filtrate is dried to obtain hydrogenated nitrile rubber.
  • Refining methods by filtration and decantation include, for example, (i) a method of filtering using a bag filter, cartridge filter, filter paper, membrane filter, etc., after adding an adsorbent as necessary; (ii) a method of using a filter such as a leaf filter, filter press, candle filter, drum filter, etc., forming a cake layer of a filter aid such as diatomaceous earth or perlite, and then draining the filtrate; (iii) a method of removing the metal salts by sedimenting the metal salts formed by the residues and metal ions during polymerization using centrifugation and then removing them from the bottom; etc.
  • a filter such as a leaf filter, filter press, candle filter, drum filter, etc.
  • the solvent is removed and the resulting rubber is dried.
  • drying with a screw-type extruder is preferable because it can remove the air contained therein and increase the bulk density.
  • the hydrogenated nitrile rubber-containing solution after the hydrogenation reaction or after the purification step after the hydrogenation reaction is solidified, and the resulting water-containing crumbs can be dried using a screw-type extruder.
  • the coagulation step of the filtrate containing hydrogenated nitrile rubber from which impurities have been removed and obtained in the above purification step is not particularly limited, and may be performed according to a conventional method.
  • Specific coagulation methods include a method of contacting with a coagulant and a method of contacting with a large amount of poor solvent, and preferably a method of contacting with a large amount of poor solvent.
  • the poor solvent methanol, water, steam, etc. are preferably used.
  • the coagulation reaction may be appropriately selected, and for example, the coagulation reaction temperature is usually selected within the range of room temperature to 100°C, and the coagulation reaction time is appropriately selected within the range of several minutes to several hours.
  • the hydrous crumbs of hydrogenated nitrile rubber produced by the coagulation reaction can be washed as necessary.
  • the washing method is not particularly limited and may be any conventional method, but washing with a large amount of water is efficient.
  • the amount of water used is usually 10 to 500 times, preferably 25 to 250 times, and more preferably 50 to 100 times, per 100 parts by mass of the polymer.
  • the temperature of the water used for washing is not particularly limited, but it is preferable to use warm water, and it is usually preferable to use warm water at a temperature of 40°C or higher, preferably 40 to 100°C, more preferably 50 to 90°C, and most preferably 60 to 80°C, since this significantly increases the washing efficiency.
  • the temperature of the washing water at or above the lower limit, the emulsifier and coagulant are released from the hydrous crumbs, and the washing efficiency is further improved.
  • the hydrous crumbs can be isolated by filtration.
  • the hydrous crumb of the hydrogenated nitrile rubber isolated above can be dried using a screw extruder.
  • a screw extruder By melting and kneading the hydrogenated nitrile rubber under reduced pressure in the screw extruder and drying it, the air present inside is removed to obtain a dry rubber (hydrogenated nitrile rubber) having a high bulk density.
  • a dry rubber hydrogenated nitrile rubber
  • it is suitable because it has excellent dispersion stability with the conductive material, and prevents the peel strength of the electrochemical element electrode and cracking of the active material layer after cycle testing.
  • the dehydration of the dehydrated hydrous crumbs in the dehydration barrel is carried out in a dehydration barrel having a dehydration slit.
  • the opening of the dehydration slit may be appropriately selected depending on the conditions of use, but when it is in the range of usually 0.1 to 1 mm, preferably 0.2 to 0.6 mm, the loss of the hydrous crumbs is small and the hydrous crumbs can be efficiently dehydrated.
  • the number of dehydration barrels in a screw-type extruder is not particularly limited, but typically multiple barrels, preferably 2 to 10 barrels, and more preferably 3 to 6 barrels, are suitable for efficiently dehydrating the sticky hydrogenated nitrile rubber.
  • the set temperature of the dehydration barrel is selected appropriately depending on the type of hydrogenated nitrile rubber, the ash content, the water content, the operating conditions, etc., but is usually in the range of 60 to 150°C, preferably 70 to 140°C, and more preferably 80 to 130°C.
  • the set temperature of the dehydration barrel for dehydration in a drainage state is usually in the range of 60 to 120°C, preferably 70 to 110°C, and more preferably 80 to 100°C.
  • the set temperature of the dehydration barrel for drying in an exhaust steam state is usually in the range of 100 to 150°C, preferably 105 to 140°C, and more preferably 110 to 130°C.
  • the moisture content after dehydration in which the moisture is squeezed out of the hydrous crumb, but it is usually 1 to 45% by mass, preferably 1 to 40% by mass, more preferably 5 to 35% by mass, and particularly preferably 10 to 35% by mass.
  • the water-containing crumbs dehydrated in the above-mentioned dehydration barrel section are further dried in the drying barrel section under reduced pressure.
  • the degree of reduced pressure in the drying barrel may be appropriately selected, but is usually 1 to 50 kPa, preferably 2 to 30 kPa, and more preferably 3 to 20 kPa, which is suitable for efficiently drying the water-containing crumbs.
  • the air present therein is also removed, and a sheet-like hydrogenated nitrile rubber having a high bulk density can be produced, which is suitable.
  • the set temperature of the drying barrel may be selected as appropriate, but typically, when it is in the range of 100 to 250°C, preferably 110 to 200°C, and more preferably 120 to 180°C, the hydrogenated nitrile rubber can be dried efficiently without discoloration or deterioration.
  • the number of drying barrels in a screw-type extruder is not particularly limited, but is usually multiple, preferably 2 to 10, and more preferably 3 to 8.
  • the degree of vacuum may be similar for all drying barrels or may be different.
  • the set temperature may be similar for all drying barrels or may be different, but it is preferable to make the temperature of the discharge part (closer to the die) higher than the temperature of the introduction part (closer to the dehydration barrel) in order to increase the drying efficiency.
  • the moisture content of the dried rubber after drying is usually less than 1% by mass, preferably 0.8% by mass or less, and more preferably 0.6% by mass or less.
  • Hydrogenated nitrile rubber extrusion (die section) The hydrogenated nitrile rubber dehydrated and dried in the screw section of the dehydrating barrel and the drying barrel is sent to a screw-free straightening die section.
  • a breaker plate or a wire mesh may or may not be provided between the screw section and the die section.
  • the hydrogenated nitrile rubber extruded can be produced in a variety of shapes, including granules, columns, rods, and sheets, depending on the shape of the die nozzle.
  • using a roughly rectangular die shape to produce a sheet-like rubber is ideal, as it produces dried rubber with less air entrapment, a high bulk density, and excellent storage stability.
  • the resin pressure in the die section is not particularly limited, but a pressure in the range of 0.1 to 10 MPa, preferably 0.5 to 5 MPa, and more preferably 1 to 3 MPa is usually suitable as it reduces air entrapment and provides excellent productivity.
  • Screw-type extruder and operating conditions The screw length (L) of the screw-type extruder used may be appropriately selected depending on the purpose of use, but is usually in the range of 2000 to 15000 mm, preferably 2500 to 10000 mm, and more preferably 3000 to 7000 mm.
  • the screw diameter (D) of the screw-type extruder used may be selected appropriately depending on the intended use, but is usually in the range of 50 to 250 mm, preferably 70 to 200 mm, and more preferably 80 to 160 mm.
  • the ratio (L/D) of the screw length (L) to the screw diameter (D) of the screw-type extruder used is not particularly limited, but is usually in the range of 10 to 150, preferably 15 to 100, more preferably 20 to 80, and particularly preferably 30 to 60, which is suitable for reducing the moisture content to less than 1% by mass without causing a decrease in the molecular weight of the dried rubber or burning.
  • the rotation speed (N) of the screw-type extruder used may be selected appropriately depending on the various conditions, but is usually 10 to 1000 rpm, preferably 30 to 800 rpm, more preferably 50 to 600 rpm, and most preferably 100 to 400 rpm.
  • the throughput (Q) of the screw extruder used is not particularly limited, but is usually in the range of 100 to 1500 kg/hr, preferably 120 to 1200 kg/hr, more preferably 150 to 1000 kg/hr, and most preferably 200 to 800 kg/hr.
  • the ratio (Q/N) of the extrusion rate (Q) to the rotation speed (N) of the screw extruder used is not particularly limited, but is usually in the range of 1 to 10, preferably 1 to 5, and more preferably 1 to 3.
  • the shape of the dried rubber extruded from the dried rubber screw-type extruder is not particularly limited, and examples thereof include crumb, powder, rod, and sheet shapes, with the sheet shape being particularly preferred.
  • the hydrogenated nitrile rubber bale of the present invention can be produced by baling the above-mentioned hydrogenated nitrile rubber.
  • the hydrogenated nitrile rubber bale of the present invention is made of the hydrogenated nitrile rubber, and by baling it, the effects of the hydrogenated nitrile rubber of the present invention can be maintained even during storage, which is preferable.
  • by increasing the bulk density of the hydrogenated nitrile rubber bale and reducing the amount of air contained therein it is possible to improve the dispersibility and stability of the conductive material dispersion when used as a positive electrode binder, the cycle characteristics of electrochemical elements, and cracking of the active material after cycle testing.
  • the shape of the hydrogenated nitrile rubber veil of the present invention is not particularly limited, but is usually a rectangular parallelepiped.
  • the size is not particularly limited, but the width is usually in the range of 100 to 800 mm, preferably 200 to 500 mm, and more preferably 250 to 450 mm, the length is usually in the range of 300 to 1200 mm, preferably 400 to 1000 mm, and more preferably 500 to 800 mm, and the height is usually in the range of 50 to 500 mm, preferably 100 to 300 mm, and more preferably 150 to 250 mm.
  • the iodine value, rhodium (Rh) content, ruthenium (Ru) content, calcium (Ca) content, iron (Fe) content, palladium (Pd) content, magnesium (Mg) content and sodium (Na) content of the hydrogenated nitrile rubber veil of the present invention are the same as those of the hydrogenated nitrile rubber.
  • the moisture content of the hydrogenated nitrile rubber veil of the present invention is not particularly limited, but is generally excellent in storage stability and is suitable when it is less than 1% by mass, preferably 0.8% by mass or less, and more preferably 0.6% by mass or less.
  • the Mooney viscosity (ML1+4, 100°C) of the hydrogenated nitrile rubber veil of the present invention is not particularly limited, but is usually in the range of 10 to 150, preferably 15 to 100, and more preferably 20 to 80, which provides a high level of balance between the conductive material dispersibility and the peel strength at the electrode and is suitable.
  • the bulk density of the hydrogenated nitrile rubber bale of the present invention is not particularly limited, but is usually 0.6 g/cm 3 or more, preferably 0.7 g/cm 3 or more, more preferably 0.8 g/cm 3 or more, even more preferably 0.85 g/cm 3 or more, and most preferably 0.9 g/cm 3 or more.
  • the upper limit of the bulk density of the hydrogenated nitrile rubber bale is not particularly limited, but is usually 1.2 g/cm 3 or less, preferably 1.15 g/cm 3 or less, more preferably 1.1 g/cm 3 or less, even more preferably 1.05 g/cm 3 or less, and most preferably 1 g/cm 3 or less.
  • the hydrogenated nitrile rubber can be baled in the usual manner, for example by putting the dried hydrogenated nitrile rubber into a baler and compressing it.
  • the compression pressure is selected appropriately depending on the purpose of use, but is usually in the range of 0.1 to 15 MPa, preferably 0.5 to 10 MPa, and more preferably 1 to 5 MPa.
  • the compression time is not particularly limited, but is usually in the range of 1 to 60 seconds, preferably 5 to 50 seconds, and more preferably 10 to 40 seconds.
  • dried rubber in sheet form can be made and layered to make bales. Baling by layering sheets is easy to manufacture, produces bales with few air bubbles (high specific gravity), and is suitable for excellent storage stability.
  • the positive electrode binder of the present invention is prepared by dissolving or dispersing the hydrogenated nitrile rubber or the hydrogenated nitrile rubber veil in N-methylpyrrolidone (NMP), and is suitable as a material for producing a positive electrode of an electrochemical element.
  • NMP N-methylpyrrolidone
  • the positive electrode binder of the present invention can be combined with other components as necessary in addition to hydrogenated nitrile rubber and NMP.
  • the other components are not particularly limited, but examples include binders other than hydrogenated nitrile rubber (polyvinylidene fluoride, polyacrylate, etc.), reinforcing materials, leveling agents, viscosity adjusters, and electrolyte additives. These are not particularly limited as long as they do not affect the battery reaction, and known substances can be used.
  • the positive electrode binder of the present invention may also contain a solvent other than NMP to the extent that the characteristics of the present invention are not impaired. Note that these other components may be used alone, or two or more types may be combined in any ratio.
  • the solid content of the binder for a positive electrode of the present invention is not particularly limited, but is usually in the range of 0.1 to 40% by mass, preferably 0.5 to 20% by mass, and more preferably 1 to 10% by mass.
  • the hydrogenated nitrile rubber, NMP and other components used as necessary may be mixed in a conventional manner.
  • the positive electrode of the present invention is characterized by comprising a positive electrode mixture layer containing a binder containing the hydrogenated nitrile rubber, a conductive material, and a positive electrode active material, and can be produced by coating the positive electrode mixture layer slurry on a current collector and drying it.
  • the positive electrode binder and the conductive material are mixed, optionally with a solvent, and then mixed with the positive electrode active material.
  • the conductive material is a component that functions to ensure electrical contact between electrode active materials.
  • a carbonaceous material can be suitably used.
  • carbonaceous materials include carbon black (e.g., acetylene black, Ketjen Black (registered trademark), furnace black, etc.), single-layer or multi-layer carbon nanotubes (multi-layer carbon nanotubes include cup-stack type), carbon nanohorns, vapor-grown carbon fibers, milled carbon fibers obtained by crushing polymer fibers after baking, single-layer or multi-layer graphene, and carbon nonwoven fabric sheets obtained by baking nonwoven fabric made of polymer fibers. Note that these may be used alone or in combination of two or more types in any ratio. Among these, carbon nanotubes (CNTs) are preferable from the viewpoint of forming a good conductive path.
  • the ratio of the conductive material to the positive electrode binder is not particularly limited.
  • the conductive material and the positive electrode binder may be mixed, for example, in such a way that the resulting conductive material dispersion contains typically 1 to 100 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass of hydrogenated nitrile rubber per 100 parts by mass of conductive material.
  • NMP can be added as necessary to adjust the viscosity.
  • the solids concentration when the positive electrode binder of the present invention is mixed with the conductive material is usually 0.01 mass% or more, preferably 1.0 mass% or more, and more preferably 3.0 mass% or more, and the upper limit is usually 10.0 mass% or less, preferably 9.0 mass% or less, and more preferably 8.0 mass% or less. If the solids concentration is equal to or greater than the lower limit, the coatability of the conductive material dispersion can be improved. Also, if the solids concentration is equal to or less than the upper limit, the rate characteristics of the resulting electrochemical element can be improved.
  • the method for mixing the positive electrode binder of the present invention and the conductive material is not particularly limited, and for example, they can be mixed using a known mixing device.
  • the positive electrode active material is not particularly limited, but when the electrochemical element is a lithium ion secondary battery, a metal oxide containing lithium (Li) can be used.
  • the positive electrode active material is preferably a positive electrode active material containing at least one selected from the group consisting of cobalt (Co), nickel (Ni), manganese (Mn) and iron (Fe) in addition to lithium (Li).
  • positive electrode active materials examples include lithium-containing cobalt oxide (LiCoO 2 ), lithium manganate (LiMn 2 O 4 ), lithium-containing nickel oxide (LiNiO 2 ), lithium-containing composite oxides of Co—Ni—Mn, lithium-containing composite oxides of Ni—Mn—Al, lithium-containing composite oxides of Ni—Co—Al, olivine-type lithium manganese phosphate (LiMnPO 4 ), olivine-type lithium iron phosphate (LiFePO 4 ), lithium-excess spinel compounds represented by Li 1+x Mn 2-x O 4 (0 ⁇ x ⁇ 2), Li[Ni 0.17 Li 0.2 Co 0.07 Mn 0.56 ]O 2 , LiNi 0.5 Mn 1.5 O 4 , Li[Ni 0.5 Co 0.2 Mn 0.3 ]O 2.
  • the particle size of the positive electrode active material is not particularly limited and can be the same as that of a conventionally used electrode active material.
  • the positive electrode active material may be used alone or
  • the positive electrode active material can be mixed with the mixture of the positive electrode binder and conductive material to form a positive electrode composite layer slurry.
  • the mixing method is not particularly limited, and can be performed using a known mixing device.
  • the amount of the positive electrode active material is not particularly limited, and can be within the range that has been conventionally used.
  • the positive electrode of the present invention can be obtained by applying the positive electrode mixture layer slurry onto a current collector and drying it. Since the positive electrode mixture layer of the positive electrode of the present invention is formed from the positive electrode binder containing the hydrogenated nitrile rubber of the present invention, the positive electrode of the present invention has excellent flexibility and is less susceptible to cracking of the electrode active material.
  • the current collector is made of a material that is electrically conductive and electrochemically durable.
  • the current collector is not particularly limited and any known current collector can be used.
  • a current collector made of aluminum or an aluminum alloy can be used as a current collector provided in the positive electrode of a lithium ion secondary battery.
  • aluminum and an aluminum alloy may be used in combination, or different types of aluminum alloys may be used in combination.
  • Aluminum and aluminum alloys are excellent current collector materials because they are heat resistant and electrochemically stable.
  • the method for manufacturing the positive electrode of the present invention is not particularly limited.
  • the positive electrode of the present invention can be manufactured by applying the above-mentioned positive electrode composite layer slurry of the present invention to at least one surface of a current collector and drying to form a positive electrode composite layer.
  • the manufacturing method includes a step of applying the positive electrode composite layer slurry to at least one surface of a current collector (application step), and a step of drying the positive electrode composite layer slurry applied to at least one surface of the current collector to form a positive electrode composite layer on the current collector (drying step).
  • the method of applying the positive electrode composite layer slurry onto the current collector is not particularly limited and any known method can be used.
  • the application method can be a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, a brush coating method, or the like.
  • the electrode slurry may be applied to only one side of the current collector, or may be applied to both sides.
  • the thickness of the slurry film on the current collector after application and before drying can be appropriately set according to the thickness of the positive electrode composite layer obtained by drying.
  • the method for drying the positive electrode mixture layer slurry on the current collector is not particularly limited and may be a known method, for example, drying with warm air, hot air, or low humidity air, vacuum drying, or drying by irradiation with infrared rays or electron beams, etc.
  • a positive electrode mixture layer can be formed on the current collector, and a positive electrode including the current collector and the positive electrode mixture layer can be obtained.
  • the electrode mixture layer may be subjected to a pressure treatment using a die press or roll press. This pressure treatment allows the positive electrode mixture layer to adhere well to the current collector.
  • the polymer may be cured after the positive electrode composite layer is formed.
  • An electrochemical device comprising the above-mentioned positive electrode of the present invention has excellent cycle characteristics, and is preferably a lithium ion secondary battery in particular.
  • This lithium ion secondary battery includes a positive electrode, a negative electrode, an electrolyte, and a separator, and the positive electrode is the electrode of the present invention.
  • the negative electrode is not particularly limited, and any known electrode can be used.
  • an organic electrolyte in which a supporting electrolyte is dissolved in an organic solvent is usually used.
  • a lithium salt is used.
  • the lithium salt for example, LiPF6 , LiAsF6, LiBF4 , LiSbF6 , LiAlCl4 , LiClO4, CF3SO3Li , C4F9SO3Li , CF3COOLi , ( CF3CO ) 2NLi , ( CF3SO2 ) 2NLi , ( C2F5SO2 )NLi , etc. are listed.
  • LiPF6 LiClO4 , and CF3SO3Li are preferred, and LiPF6 is particularly preferred, because they are easily dissolved in the solvent and show a high degree of dissociation.
  • the electrolyte may be used alone or in any combination of two or more kinds in any ratio. Usually, the lithium ion conductivity tends to be higher when a supporting electrolyte with a higher degree of dissociation is used, so the lithium ion conductivity can be adjusted by the type of supporting electrolyte.
  • the organic solvent used in the electrolyte is not particularly limited as long as it can dissolve the supporting electrolyte, but examples of suitable organic solvents include carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), and methyl ethyl carbonate (EMC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; and sulfur-containing compounds such as sulfolane and dimethyl sulfoxide.
  • a mixture of these solvents may also be used.
  • it is preferable to use carbonates because they have a high dielectric constant and a wide stable potential range, and it is even more preferable to use a mixture of ethylene carbonate and diethyl carbonate.
  • the concentration of the electrolyte in the electrolyte solution can be adjusted as appropriate, and is preferably 0.5 to 15 mass%, more preferably 2 to 13 mass%, and even more preferably 5 to 10 mass%.
  • known additives such as vinylene carbonate, fluoroethylene carbonate, and ethyl methyl sulfone may be added to the electrolyte solution.
  • the separator is not particularly limited, and for example, those described in JP 2012-204303 A can be used. Among these, a microporous film made of a polyolefin resin (polyethylene, polypropylene, polybutene, polyvinyl chloride) is preferred, since it can reduce the thickness of the entire separator, thereby increasing the ratio of the electrode active material in the lithium ion secondary battery and increasing the capacity per volume.
  • a polyolefin resin polyethylene, polypropylene, polybutene, polyvinyl chloride
  • the lithium ion secondary battery according to the present invention can be produced, for example, by stacking a positive electrode and a negative electrode with a separator therebetween, wrapping or folding the stack according to the battery shape as necessary, placing the stack in a battery container, injecting an electrolyte into the battery container, and sealing the container.
  • a fuse In order to prevent the occurrence of an internal pressure rise in the secondary battery, overcharging and overdischarging, etc., a fuse, an overcurrent prevention element such as a PTC element, an expanded metal, a lead plate, etc. may be provided as necessary.
  • the shape of the secondary battery may be, for example, any of a coin type, a button type, a sheet type, a cylindrical type, a square type, a flat type, etc.
  • the ratio of monomer units formed by polymerizing a certain monomer in the polymer usually coincides with the ratio (feed ratio) of that certain monomer to all monomers used in the polymerization of the polymer, unless otherwise specified.
  • a polymer is a hydrogenated polymer obtained by hydrogenating a polymer containing a conjugated diene monomer unit
  • the total content ratio of unhydrogenated conjugated diene monomer units and alkylene structural units as hydrogenated conjugated diene monomer units in the hydrogenated polymer coincides with the ratio (feed ratio) of the conjugated diene monomer to all monomers used in the polymerization of the polymer.
  • the iodine value of the hydrogenated nitrile rubber was measured in accordance with JIS K 6235.
  • ⁇ Weight average molecular weight> The weight average molecular weight (Mw) of the hydrogenated nitrile rubber was measured by gel permeation chromatography (GPC) using a 10 mM LiBr-dimethylformamide (DMF) solution under the following measurement conditions. Separation column: Shodex KD-806M (manufactured by Showa Denko K.K.) ⁇ Detector: Differential refractometer detector RID-10A (manufactured by Shimadzu Corporation) Eluent flow rate: 0.3 mL/min Column temperature: 40° C. Standard polymer: TSK standard polystyrene (manufactured by Tosoh Corporation)
  • ⁇ Bulk density> A piece measuring approximately 2 cm ⁇ 3 cm ⁇ 0.2 cm was cut out from the hydrogenated nitrile rubber bale, and the bulk density (g/cm 3 ) was measured using an automatic pycnometer (manufactured by Toyo Seiki Seisakusho, product name: "DSG-1").
  • ⁇ Viscosity of conductive material dispersion> The conductive material dispersion obtained in each of the Examples and Comparative Examples was measured for viscosity for 120 seconds at a temperature of 25° C. and a shear rate of 10 (1/s) using a rheometer ("MCR302" manufactured by Anton Paar). The average viscosity measured from 61 seconds to 120 seconds was evaluated according to the following criteria. A: 4 Pa.s or less B: More than 4 Pa.s and less than 6 Pa.s C: More than 6 Pa.s and less than 8 Pa.s D: More than 8 Pa.s
  • ⁇ Viscosity stability of conductive material dispersion liquid The conductive material dispersions obtained in each of the Examples and Comparative Examples were measured for viscosity ( ⁇ 0), and then stored in a sealed container at 25° C. for 10 days. After that, the viscosity of the dispersion was measured again ( ⁇ 1), and the viscosity change rate was calculated.
  • the lithium ion secondary batteries prepared in the examples and comparative examples were left to stand at a temperature of 25°C for 5 hours after injecting the electrolyte.
  • the batteries were charged to a cell voltage of 3.65V at a constant current of 0.2C at a temperature of 25°C, and then aged at a temperature of 60°C for 12 hours.
  • the batteries were discharged to a cell voltage of 3.00V at a constant current of 0.2C at a temperature of 25°C.
  • the batteries were CC-CV charged (upper cell voltage 4.20V) at a constant current of 0.2C, and CC discharged to 3.00V at a constant current of 0.2C. This charge and discharge at 0.2C was repeated three times.
  • the discharge capacity of the first cycle was defined as X1
  • the discharge capacity of the 300th cycle was defined as X2.
  • the capacity retention rate (X2/X1) x 100 (%) was calculated and evaluated according to the following criteria. A larger value of the capacity retention rate indicates that the lithium ion secondary battery has better cycle characteristics.
  • D Capacity retention rate is less than 75%.
  • Example 1 ⁇ Production of hydrogenated nitrile rubber> - Emulsion polymerization process - Washing and drying process -
  • 100 parts of ion-exchanged water, 33 parts of acrylonitrile as an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer, and 67 parts of 1,3-butadiene as a conjugated diene monomer were charged, and 2 parts of potassium oleate as an emulsifier, 0.1 parts of potassium phosphate as a stabilizer, and further, 0.3 parts of tert-dodecyl mercaptan (TDM) as a molecular weight regulator were added, and emulsion polymerization was carried out at a temperature of 5° C. in the presence of 0.35 parts of potassium persulfate as a polymerization initiator, thereby copolymerizing acrylonitrile and 1,3-butadiene.
  • TDM tert-dodecyl mercaptan
  • 920 parts of NMP was weighed out into a 2 L container equipped with a stirring blade and heated to 80° C.
  • 80 parts of hydrogenated nitrile rubber A cut into pieces of about 1 cm square from the hydrogenated nitrile rubber bale A produced above was added and dissolved while continuing to stir for 5 hours, thereby preparing a positive electrode binder A with a solid content concentration of 8%.
  • a ternary active material LiNi0.5Co0.2Mn0.3O2 ) having a layered structure as a positive electrode active material (average particle size: 10 ⁇ m )
  • 1.0 parts of polyvinylidene fluoride as a binder 1.0 parts of the above-mentioned conductive material dispersion (solid content equivalent amount), and NMP were added, and mixed with a planetary mixer (60 rpm, 30 minutes) to prepare a positive electrode slurry.
  • the amount of NMP added was adjusted so that the viscosity of the obtained positive electrode slurry (measured with a single cylindrical rotational viscometer in accordance with JIS Z8803:1991. Temperature: 25 ° C., rotation speed: 60 rpm) was within the range of 4000 to 5000 mPa s.
  • a 20 ⁇ m thick aluminum foil was prepared as a current collector.
  • the above positive electrode slurry was applied to the aluminum foil with a comma coater so that the weight per unit area after drying was 20 mg/cm 2 , and then dried at 120° C. for 5 minutes and 130° C. for 5 minutes, and then heated at 60° C. for 10 hours to obtain a positive electrode raw sheet.
  • This positive electrode raw sheet was rolled with a roll press to produce a sheet-shaped positive electrode consisting of a positive electrode composite layer with a density of 3.5 g/cm 3 and aluminum foil.
  • This sheet-shaped positive electrode was cut to a width of 4.8 cm and a length of 50 cm to obtain a positive electrode for a lithium ion secondary battery.
  • the peel strength of the obtained positive electrode for a lithium ion secondary battery was evaluated. The results are shown in Table 1.
  • the mixture was cooled to stop the polymerization reaction, and a mixture containing a particulate binder (styrene-butadiene copolymer) was obtained.
  • a mixture containing a particulate binder styrene-butadiene copolymer
  • the unreacted monomer was removed by heating and vacuum distillation.
  • the mixture was then cooled to 30 ° C. or less to obtain an aqueous dispersion containing a binder for the negative electrode.
  • ion-exchanged water was added to obtain a viscosity of 3000 ⁇ 500 mPa ⁇ s (measured with a B-type viscometer at 25°C and 60 rpm), to prepare a slurry for the negative electrode composite layer.
  • a copper foil having a thickness of 15 ⁇ m was prepared as a current collector.
  • the above-mentioned negative electrode slurry was applied to both sides of the copper foil so that the coating amount after drying was 10 mg/cm 2 , and then dried at 80 ° C for 5 minutes and at 120 ° C for 5 minutes to obtain a negative electrode raw sheet.
  • This negative electrode raw sheet was rolled with a roll press to produce a sheet-shaped negative electrode consisting of a negative electrode composite layer (both sides) having a density of 1.6 g/cm 3 and copper foil. Then, the sheet-shaped negative electrode was cut to a width of 5.0 cm and a length of 52 cm to obtain a negative electrode for a lithium ion secondary battery.
  • the positive electrode for lithium ion secondary battery and the negative electrode for lithium ion secondary battery thus prepared were arranged so that the electrode mixture layers faced each other, and a separator (a microporous film made of polyethylene) having a thickness of 15 ⁇ m was interposed between them, and the electrodes were wound using a core having a diameter of 20 mm to obtain a wound body.
  • the wound body thus obtained was then compressed in one direction at a speed of 10 mm/sec until the thickness became 4.5 mm.
  • the wound body after compression had an elliptical shape in a plan view, and the ratio of the major axis to the minor axis (major axis/minor axis) was 7.7.
  • additive containing 2 vol% vinylene carbonate (solvent ratio)
  • the compressed wound body was then placed in an aluminum laminate case together with 3.2 g of non-aqueous electrolyte.
  • a nickel lead wire was then connected to a designated location on the negative electrode, and an aluminum lead wire was connected to a designated location on the positive electrode, after which the opening of the case was sealed with heat to obtain a lithium-ion secondary battery.
  • This lithium-ion secondary battery was a pouch-shaped battery of a designated size capable of containing the wound body, and had a nominal capacity of 700 mAh.
  • the resulting lithium-ion secondary batteries were evaluated for output characteristics, cycle characteristics, and cracking of the electrode active material after cycling. The results are shown in Table 1.
  • Example 2 Hydrogenated nitrile rubber B, hydrogenated nitrile rubber veil B and positive electrode binder B were obtained in the same manner as in Example 1, except that the amount of activated carbon used in the purification step was changed to 0.5 parts. The measurement and evaluation results are shown in Table 1.
  • Example 3 Hydrogenated nitrile rubber C, hydrogenated nitrile rubber veil C and positive electrode binder C were obtained in the same manner as in Example 1, except that the amount of activated carbon used in the purification step was changed to 0.08 parts. The measurement and evaluation results are shown in Table 1.
  • Example 4 Hydrogenated nitrile rubber D, hydrogenated nitrile rubber veil D and positive electrode binder D were obtained in the same manner as in Example 1, except that the amount of activated carbon used in the purification step was changed to 0.07 parts. The measurement and evaluation results are shown in Table 1.
  • Example 5 Hydrogenated nitrile rubber E, hydrogenated nitrile rubber veil E and positive electrode binder E were obtained in the same manner as in Example 1, except that the amount of activated carbon used in the purification step was changed to 0.05 parts. The measurement and evaluation results are shown in Table 1.
  • Example 6 Hydrogenated nitrile rubber F, hydrogenated nitrile rubber veil F and positive electrode binder F were obtained in the same manner as in Example 1, except that the amount of Grubbs catalyst for the metathesis reaction was changed to 500 ppm. The measurement and evaluation results are shown in Table 1.
  • Example 7 Hydrogenated nitrile rubber G, hydrogenated nitrile rubber veil G and positive electrode binder G were obtained in the same manner as in Example 1, except that the amount of Grubbs catalyst for the metathesis reaction was changed to 400 ppm. The measurement and evaluation results are shown in Table 1.
  • the hydrogenated nitrile rubbers A to G of the present invention contain nitrile group-containing monomer units and conjugated diene monomer units and/or alkylene structural units, have an iodine value of 10 to 40 mg/100 mg, a weight average molecular weight (Mw) in the range of 1,000 to 600,000, an Rh and/or Ru content of 0.5 to 50 ppm, a Ca content of 1 to 1500 ppm, and an Fe content of 100 ppm or less, have excellent viscosity characteristics (dispersibility) of the conductive material dispersion, have excellent peel strength of the produced electrodes, and excellent output characteristics and cycle characteristics as an electrochemical element, and have no cracking of the electrode active material after cycle testing, and are highly balanced in performance evaluation consisting of only "A" and "B" evaluations (comparison of Examples 1 to 7 and Comparative Examples 1 to 4).
  • Table 1 also shows that the characteristic evaluations of the hydrogenated nitrile rubbers A to G of the present invention were only rated A or B, and even a single C was deemed a failure, and in particular, in the peel characteristic evaluation, the hydrogenated nitrile rubber with an iodine value of 3 was rated D (Comparative Example 1), an iodine value of 5 was rated C (Comparative Example 2), and an iodine value of 13 was rated A (Example 1), with a rating of C for an iodine value of 5 being the comparative example.
  • All of the hydrogenated nitrile rubbers A to G of the present invention are excellent in terms of dispersibility of the conductive material dispersion, but it is particularly evident that the dispersibility of the conductive material dispersion deteriorates as the iodine value of the hydrogenated nitrile rubber increases, as the viscosity of the conductive material dispersion increases (comparison with Examples 1, 6 to 7, and Comparative Examples 1 to 3).
  • the dispersibility of the conductive material dispersion is affected by the Ca content in the hydrogenated nitrile rubber, and that when the Ca content is particularly high, the viscosity of the dispersion increases and tends to deteriorate, even if only slightly (viscosity change from Example 4 to Example 6 and Comparative Example 5). It is therefore evident that in order to improve the dispersibility of the conductive material dispersion, it is necessary to reduce the iodine value of the hydrogenated nitrile rubber and to reduce the Ca content in the hydrogenated nitrile rubber.
  • the peel strength of the electrode correlates with the iodine value of the hydrogenated nitrile rubber, and deteriorates as the iodine value of the hydrogenated nitrile rubber decreases, and it is found that it drops sharply in particular at an iodine value of 5 or less (Comparative Examples 1-2). In other words, it is found that the influence of the iodine value of the hydrogenated nitrile rubber is in a contradictory relationship between the dispersibility of the conductive material dispersion and the peel strength of the electrode.
  • the amount of Ca in the hydrogenated nitrile rubber also has a large effect on the peel strength of the electrode, with the higher the Ca content, the better (particularly when comparing Comparative Examples 4 and 5).
  • the Ca content in the hydrogenated nitrile rubber increases, the dispersibility of the conductive material dispersion tends to deteriorate, but this is not too severe, and the appropriate amount of Ca compensates for the decrease in the iodine value of the hydrogenated nitrile rubber and the resulting drop in peel strength, and it can be seen that the hydrogenated nitrile rubbers A to G of the present invention achieve a high level of balance between these two properties.
  • the output characteristics of the electrochemical element correlate with the iodine value of the hydrogenated nitrile rubber, and it can be seen that a smaller iodine value is preferable (comparison of Examples 1-7 and Comparative Examples 1-5).
  • the cycle characteristics of the electrochemical element are significantly affected by the amount of Ca in the hydrogenated nitrile rubber, and it can be seen that if there is too much, the characteristics deteriorate rapidly (especially in Example 5 and Comparative Example 5).
  • the inhibition of cracking of the electrode active material after cycle testing of the electrochemical element correlates with the amount of Ca in the hydrogenated nitrile rubber, and tends to worsen as the amount decreases (especially in Example 2 and Comparative Example 4).
  • the iodine value and Ca content of hydrogenated nitrile rubber are involved in various characteristics, and the present invention summarizes the optimal relationship between the iodine value and Ca content, and it is believed that an appropriate amount of Ca can compensate for the shortcomings of electrochemical element manufacture, particularly when the iodine value is low.
  • hydrogenated nitrile rubbers C and D of the present invention are rated only as "A" rank, and show the optimal Ca content.
  • the novel hydrogenated nitrile rubbers A to G of the present invention can be manufactured by combining known methods, such as adjusting the [Mw] by the amount of catalyst in the metathesis reaction, adjusting the [iodine value] by the amount of hydrogenation catalyst and monitoring the polymer molecular weight and hydrogenation rate after the metathesis reaction, adjusting the [Mg, Na] content without using auxiliary materials that are causative in the production stages such as the emulsion polymerization process and hydrogenation process, and adjusting the [Ca] used in the coagulant and the [Ru, Rh] used in the hydrogenation catalyst by washing with water and treating with an adsorbent.
  • known methods such as adjusting the [Mw] by the amount of catalyst in the metathesis reaction, adjusting the [iodine value] by the amount of hydrogenation catalyst and monitoring the polymer molecular weight and hydrogenation rate after the metathesis reaction, adjusting the [Mg, Na] content without using auxiliary materials that are causative in the production stages such as the emulsion
  • Example 8 to 14 A large amount of steam was introduced into the hydrogenated nitrile rubber-containing monochlorobenzene solution filtered after the purification process of Examples 1 to 7 to isolate hydrous crumbs.
  • the isolated hydrous crumbs were then dried under conditions that would not affect the properties of the hydrogenated nitrile rubber using a screw-type extruder having a vacuum drying barrel and a roughly rectangular die section, and a sheet-like dried rubber (width 300 mm x thickness 30 mm) was extruded. After the dried rubber sheet reached 50°C or lower, it was cut to a predetermined length of 650 mm, and 10 sheets were stacked to obtain hydrogenated nitrile rubber bales M to S.
  • the hydrogenated nitrile rubber bales M to S from which the internal air had been removed using the screw-type extruder all had a bulk density of 0.85 g/cm 3 or more, which was much larger than the bulk density of 0.7 to 0.75 of the hydrogenated nitrile rubber bales A to G compressed at 3 MPa using the baler of Examples 1 to 7.
  • the positive electrode binders M to S were adjusted in the same manner as in Examples 1 to 7, and performance evaluation was performed. Although the evaluation level was not changed, all performances were significantly higher than the results when the hydrogenated nitrile rubber bales A to G of Examples 1 to 7 were used.
  • the evaluation of the conductive material dispersion stability was originally all rated "A", but when the hydrogenated nitrile rubber bales M to S with a large bulk density (almost no air inside) were used, the viscosity change rate ⁇ was almost unchanged, at a value close to 100%.
  • the evaluation was performed on the average of five times, the results were good with little variation.
  • the screw-type extruder used in Examples 8 to 14 was composed of one feed barrel, three dehydration barrels (first to third dehydration barrels), five drying barrels (first to fifth drying barrels), and a die section, and the operating conditions of the screw-type extruder were as follows:
  • the hydrogenated nitrile rubber bales M to S produced above differ only in bulk density as a bale characteristic compared to the hydrogenated nitrile rubber bales A to G produced in Examples 1 to 7, but the molecular weight, iodine value, antioxidant content, and various metal contents of the constituent hydrogenated nitrile rubber were unchanged.
  • a hydrogenated nitrile rubber and a production method thereof which can increase the viscosity characteristics of a conductive material dispersion liquid, as well as increase the peel strength of an electrode and the effect of suppressing cracking of an active material, and improve the cycle characteristics and output characteristics of an electrochemical element.
  • a hydrogenated nitrile rubber veil and a binder for positive electrodes which can increase the viscosity characteristics of a conductive material dispersion, as well as increase the peel strength of an electrode and the effect of suppressing cracking of an active material, thereby improving the cycle characteristics and output characteristics of an electrochemical element.
  • a positive electrode binder that can increase the viscosity characteristics of a conductive material dispersion, as well as increase the peel strength of an electrode and the effect of suppressing cracking of an active material, thereby improving the cycle characteristics and output characteristics of an electrochemical element. Furthermore, according to the present invention, it is possible to provide a positive electrode for an electrochemical element which has excellent peel strength and which is less susceptible to cracking of the electrode active material, and a method for producing the same.

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Abstract

L'invention fournit un caoutchouc nitrile hydrogéné qui, lorsqu'une électrode pour élément électrochimique est fabriquée, se révèle excellent en termes de dispersibilité de matériau conducteur ainsi que de résistance au pelage au niveau de l'électrode, et également en termes de caractéristiques de cycle, caractéristiques de sortie ainsi que de suppression de fracture de matière active dans l'électrode après essai de cycle d'un élément électrochimique. Le caoutchouc nitrile hydrogéné de l'invention contient une unité monomère à teneur en groupe nitrile, et une unité monomère de diène conjugué et/ou une unité structurale alkylène, et présente un indice d'iode compris entre １０ et ４０ｍｇ／１００ｍｇ et une masse moléculaire moyenne en poids (Mw) comprise dans une plage de １０００ à ６０００００. Enfin, sa teneur en rhodium (Rh) et/ou ruthénium (Ru) est comprise entre ０,５ et ５０ｐｐｍ, sa teneur en calcium (Ca) est comprise entre １ et １５００ｐｐｍ et sa teneur en fer (Fe) est inférieure ou égale à １００ｐｐｍ.
PCT/JP2024/031273 2023-08-30 2024-08-30 Caoutchouc nitrile hydrogéné Pending WO2025047947A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016043528A (ja) * 2014-08-21 2016-04-04 日本ゼオン株式会社 重合体の脱水方法
WO2018173975A1 (fr) * 2017-03-23 2018-09-27 日本ゼオン株式会社 Composition de liant pour électrodes positives de batterie secondaire non aqueuse, composition pour électrodes positives de batterie secondaire non aqueuse, électrode positive pour batteries secondaires non aqueuses, et batterie secondaire non aqueuse
WO2022085458A1 (fr) * 2020-10-23 2022-04-28 日本ゼオン株式会社 Composition de liant pour batteries secondaires tout solide, composition de type suspension épaisse pour batteries secondaires tout solide, couche contenant un électrolyte solide et batterie secondaire tout solide
WO2022163769A1 (fr) * 2021-01-29 2022-08-04 日本ゼオン株式会社 Batterie secondaire non aqueuse

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016043528A (ja) * 2014-08-21 2016-04-04 日本ゼオン株式会社 重合体の脱水方法
WO2018173975A1 (fr) * 2017-03-23 2018-09-27 日本ゼオン株式会社 Composition de liant pour électrodes positives de batterie secondaire non aqueuse, composition pour électrodes positives de batterie secondaire non aqueuse, électrode positive pour batteries secondaires non aqueuses, et batterie secondaire non aqueuse
WO2022085458A1 (fr) * 2020-10-23 2022-04-28 日本ゼオン株式会社 Composition de liant pour batteries secondaires tout solide, composition de type suspension épaisse pour batteries secondaires tout solide, couche contenant un électrolyte solide et batterie secondaire tout solide
WO2022163769A1 (fr) * 2021-01-29 2022-08-04 日本ゼオン株式会社 Batterie secondaire non aqueuse

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