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WO2010090193A1 - Film capable d'oxyder du monoxyde de carbone et son utilisation - Google Patents

Film capable d'oxyder du monoxyde de carbone et son utilisation Download PDF

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Publication number
WO2010090193A1
WO2010090193A1 PCT/JP2010/051452 JP2010051452W WO2010090193A1 WO 2010090193 A1 WO2010090193 A1 WO 2010090193A1 JP 2010051452 W JP2010051452 W JP 2010051452W WO 2010090193 A1 WO2010090193 A1 WO 2010090193A1
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WO
WIPO (PCT)
Prior art keywords
mass
film
carbon dioxide
carbon monoxide
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2010/051452
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English (en)
Japanese (ja)
Inventor
瀬田　寧
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Riken Technos Corp
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Riken Technos Corp
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Filing date
Publication date
Application filed by Riken Technos Corp filed Critical Riken Technos Corp
Priority to JP2010549479A priority Critical patent/JP6042595B2/ja
Publication of WO2010090193A1 publication Critical patent/WO2010090193A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
    • H01G11/20—Reformation or processes for removal of impurities, e.g. scavenging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/117—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/121—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/122—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/141—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against humidity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
    • H01M10/523—Removing gases inside the secondary cell, e.g. by absorption by recombination on a catalytic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a film excellent in heat resistance having a function of oxidizing carbon monoxide to carbon dioxide and adsorbing it even in the absence of gaseous oxygen, and in particular, non-aqueous electrolyte secondary batteries and electric batteries.
  • the present invention relates to a film useful in a multilayer capacitor.
  • non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries and electric storage devices such as electric double layer capacitors are used. Since non-aqueous electrolyte secondary batteries and electric double layer capacitors have a significant decrease in performance in the presence of moisture, thus leading to a reduction in life, their power generation elements are enclosed in containers such as metal cans and aluminum laminate films. ing.
  • the present applicant relates to a film excellent in water absorption and heat resistance, which can remove moisture that deteriorates these performances by disposing inside a non-aqueous electrolyte secondary battery or electric double layer capacitor.
  • This film consists of a composition containing a specific polyethylene-based resin composition and a water-absorbing filler.
  • non-aqueous electrolyte secondary batteries and electric double layer capacitors are oxidized in a container in which a storage element is enclosed because a carbonate-based organic solvent is used as an electrolytic solution or carbon is used as an electrode.
  • Another major problem is that carbon gas is easily generated, and as a result, the life of the container is shortened due to deformation and rupture of the container.
  • the film in the above application is insufficient for suppressing such deformation and destruction.
  • a catalyst for removing carbon monoxide in a gas a catalyst containing a gold nanoparticle catalyst as a carbon monoxide oxidation catalyst and an alkaline porous material as a carbon dioxide removing agent (for example, Patent Document 1).
  • a catalyst for example, Patent Document 2 containing a gold nanoparticle catalyst as a carbon monoxide oxidation catalyst and a zeolite as a carbon dioxide and water removing agent is known. These methods oxidize carbon monoxide gas to carbon dioxide gas and remove the resulting carbon dioxide gas with a carbon dioxide adsorbent, which is less expensive than removing carbon monoxide gas directly.
  • the oxidation of carbon monoxide gas requires the presence of gaseous oxygen. There is no suggestion that the catalyst be compounded with a resin or formed into a film.
  • the nonaqueous electrolyte secondary battery and the electric double layer capacitor do not have a supply source of gaseous oxygen to the inside of the container in which the electricity storage element is enclosed. This is because, for the purpose of enclosing more power storage elements in the container, there is no space in the production stage where gaseous air occupies, and since the container is sealed, it is sealed from the outside. This is because there is virtually no supply of gaseous oxygen.
  • the member If there is a member that can oxidize carbon monoxide to carbon dioxide in the absence of such gaseous oxygen and can adsorb carbon dioxide generated by the oxidation, carbon monoxide generated in the container The deformation and destruction of the container due to gas can be prevented, and therefore, it is advantageous for extending the life of the electric storage device. Further, if the member is in the form of a film, it can be disposed in a narrow space in a container in which a power generation element of a nonaqueous electrolyte secondary battery or an electric double layer capacitor is enclosed, and the nonaqueous electrolyte secondary This is advantageous in terms of downsizing and increasing the capacity of batteries and electric double layer capacitors.
  • An object of the present invention is to provide a film that can oxidize and adsorb carbon monoxide to carbon dioxide even in the absence of gaseous oxygen and has excellent heat resistance.
  • the present inventor has found that a specific ethylene-based resin composition and a resin composition containing a carbon monoxide oxidation catalyst and a carbon dioxide adsorbent having a specific particle size are excellent in film-forming properties and can achieve the above-described object. Reached.
  • the present invention (A) 100 parts by mass of an ethylene-based resin composition
  • a film comprising a resin composition comprising (B) 1 to 150 parts by mass of a carbon monoxide oxidation catalyst and (C) 1 to 200 parts by mass of a carbon dioxide adsorbent
  • the component (A) comprises (A-1) ) To (iv) 99 to 60% by mass of an ethylene polymer having the characteristics
  • Tm peak top melting point
  • the heat of fusion ( ⁇ H) in the DSC melting curve is 90 to 180 J / g.
  • (Xc110) is 10-60%, and (iv) the MFR (190 ° C., 21.18 N) is 0.1-10 g / 10 min.
  • (A-2) acid-modified ethylene resin 1 to 40% by mass Where the total amount of component (A-1) and component (A-2) is 100% by weight, and components (B) and (C) each have a particle size (D99) of 30 ⁇ m or less and Having a particle size (D50) of 20 ⁇ m or less, where D99 and D55 refer to the particle size at the point where the particle size distribution becomes 99% by mass and 50% by mass from the smaller particle size, respectively. It is a film.
  • the film of the present invention can oxidize and adsorb carbon monoxide to carbon dioxide in the absence of gaseous oxygen and has excellent heat resistance, and in particular, a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery. And is advantageous for use in electric double layer capacitors.
  • the film of the present invention enables the oxidation of carbon monoxide to carbon dioxide in the absence of gaseous oxygen is not well understood, it is due to the supply of oxygen atoms from component (B).
  • the oxygen atoms are supplied during the production of the resin composition or the film comprising them in a normal environment where gaseous oxygen is present.
  • the film of the present invention comprises a resin composition containing components (A) to (C) described below.
  • Ethylene-based resin composition Component (A) includes an ethylene-based polymer (A-1) and an acid-modified ethylene-based resin (A-2). Since ethylene-based polymers are excellent in filler acceptability, a large amount of carbon monoxide oxidation catalyst (B) and carbon dioxide adsorbent (C) as fillers are filled by using this as the main resin component. However, good film forming properties can be obtained.
  • (A-1) Ethylene-based polymer The ethylene-based polymer in the present invention has sufficient heat resistance and sufficient filler acceptability to give good film-forming properties as follows. It is necessary to satisfy (i) to (iv).
  • the peak top melting point (Tm) on the highest temperature side in the DSC melting curve is 110 ° C. or higher.
  • the heat of fusion ( ⁇ H) in the DSC melting curve is 90 to 180 J / g.
  • the crystallization fraction (Xc110) at 110 ° C. is 10 to 60%, and (iv) MFR (190 ° C., 21.18 N) is 0.1 to 10 g / 10 min.
  • the peak top melting point (Tm) is preferably 120 ° C. or higher, more preferably 125 ° C. or higher.
  • the upper limit of the peak top melting point (Tm) is not particularly limited, but is actually about 135 ° C. because it is an ethylene polymer.
  • the said heat of fusion ((DELTA) H) exceeds 180 J / g, filler acceptability is inadequate and film forming property may be inferior. If it is less than 90 J / g, heat resistance and solvent resistance tend to be insufficient. Lithium secondary batteries and electric double layer capacitors may be exposed to high environmental temperatures, and many organic solvents used as electrolytes in power generation elements have strong permeability and dissolving power. Therefore, it is advantageous that the obtained resin composition has heat resistance and solvent resistance.
  • the heat of fusion ( ⁇ H) is preferably 100 to 170 J / g.
  • the crystallinity (Xc110) exceeds 60%, the filler acceptability may be insufficient and the film forming property may be inferior. If it is less than 10%, the heat resistance and solvent resistance may be insufficient.
  • the crystallinity (Xc110) is preferably 15 to 45%.
  • the crystallinity at 110 ° C. means the ratio of the heat of fusion at 110 ° C. or higher to the total heat of fusion ⁇ H in the DSC melting curve.
  • the melt-kneading property (filler dispersibility) of the polyethylene resin composition (A) with the carbon monoxide oxidation catalyst (B) and the carbon dioxide adsorbent (C) as fillers. May be insufficient, or the dropability during film formation may be reduced. If it is less than 0.1 g / 10 min, it may be difficult to adjust the thickness of the film.
  • the MFR is preferably 0.2 to 7 g / 10 minutes, more preferably 0.5 to 5 g / 10 minutes.
  • DSC melting curves are obtained by using a DSC Q1000 model of TA Instruments (TE Instruments Japan Co., Ltd.) and holding the sample at 190 ° C. for 5 minutes. Obtained by performing DSC measurement with a temperature program of cooling to ⁇ 10 ° C. at a temperature decrease rate of 10 ° C./min, holding at ⁇ 10 ° C. for 5 minutes, and then heating to 190 ° C. at a temperature increase rate of 10 ° C./min. It is a curved line.
  • the ethylene polymer in the present invention is not particularly limited as long as it satisfies the above requirements (i) to (iv).
  • low density polyethylene linear low density polyethylene, ultra low density polyethylene, high density polyethylene, and a copolymer of ethylene and ⁇ -olefin (for example, 1-butene, 1-hexene, 1-octene, etc.) can be mentioned.
  • An ethylene copolymer using vinyl acetate, methyl acrylate, ethyl acrylate, or the like as a comonomer has a large decrease in crystallinity due to the comonomer, and thus it is difficult to satisfy the requirements (i) to (iv).
  • An ethylene-type polymer can be used individually by 1 type or as a mixture which mix
  • ethylene-based polymer (A-1) examples include linear low density polyethylene commercially available from Nippon Polyethylene Co., Ltd. under the trade names KF271 and UF240, and SP2040 and SP2520 from Prime Polymer Co., Ltd. The linear low density polyethylene etc. which are marketed with the brand name of these are mentioned.
  • the acid-modified ethylene-based resin includes a hydrophobic ethylene-based polymer (A-1) and a hydrophilic carbon monoxide oxidation catalyst (B ) And carbon dioxide adsorbent (C) to improve the miscibility of the filler to promote the dispersion of the filler so that no defects such as blisters are generated in the film.
  • the acid-modified ethylene resin used in the present invention is an ethylene resin obtained by graft polymerization and / or copolymerization of an unsaturated carboxylic acid or a derivative thereof.
  • unsaturated carboxylic acids include, for example, maleic acid, itaconic acid, fumaric acid
  • derivatives thereof include, for example, maleic acid monoester, maleic acid diester, maleic anhydride, itaconic acid monoester, Examples include itaconic acid diester, itaconic anhydride, fumaric acid monoester, fumaric acid diester, fumaric anhydride and the like.
  • ethylene resin examples include linear polyethylene, ultra-low density polyethylene, high density polyethylene, ethylene-vinyl acetate (VA) copolymer, ethylene-ethyl acrylate (EA) copolymer, and ethylene-methacrylate copolymer. Is mentioned.
  • the acid-modified ethylene resin preferably has an MFR (190 ° C., 21.18 N) of 0.1 to 10 g / 10 min. More preferably, it is 0.2 to 7 g / 10 minutes, and most preferably 0.5 to 5 g / 10 minutes. If the MFR is higher than the above upper limit, the drawability during film formation may be reduced. If the MFR is lower than the lower limit, it may be difficult to adjust the thickness of the film.
  • MFR 190 ° C., 21.18 N
  • acid-modified ethylene resins include Admer (trade name) manufactured by Mitsui Chemicals, Adtex (trade name) manufactured by Nippon Polyolefin Co., Ltd., Polybond (trade name) manufactured by Crompton, and Sumitomo Chemical.
  • Admer trade name
  • Adtex trade name
  • Polybond trade name
  • Bond First trade name manufactured by Co., Ltd.
  • the acid-modified ethylene resin can be used alone or in combination of two or more.
  • the polyethylene resin composition (A) contains 99 to 60% by mass of the ethylene polymer (A-1) and 1 to 40% by mass of the acid-modified ethylene resin (A-2) (where component (A- The total amount of 1) and component (A-2) is 100% by mass). More preferably, they are 97 to 70% by mass of the ethylene polymer (A-1) and 3 to 30% by mass of the acid-modified ethylene resin (A-2), and more preferably, the ethylene polymer (A-1). 95 to 80% by mass and 5 to 20% by mass of the acid-modified ethylene resin (A-2).
  • the acid-modified ethylene resin (A-2) is small (that is, the ethylene polymer (A-1) is large), the filler is not sufficiently dispersed, and a lot of grease is generated during film formation. , Defects such as bumps are likely to occur in the obtained film.
  • the interaction between the acid-modified ethylene resin and the filler becomes very strong, and a compound is produced. Sometimes the kneading load during extrusion and the extrusion load during film formation may be high. Moreover, the tensile elongation of the film obtained may fall.
  • the carbon monoxide oxidation catalyst As the carbon monoxide oxidation catalyst, a composite metal oxide catalyst such as hopcalite (copper-manganese composite oxide) and a supported noble metal catalyst are known. In the present invention, Any of these can be used as component (B) provided it has the specific particle size distribution described below.
  • the supported noble metal catalyst includes a metal oxide-supported noble metal catalyst such as palladium on alumina (a catalyst having a noble metal supported on the metal oxide surface), a noble metal-reducible oxide catalyst such as palladium-cerium oxide, platinum supported on titanium oxide, etc.
  • a composite metal oxide such as hopcalite and a metal oxide-supported noble metal catalyst such as alumina-supported palladium are preferably used.
  • a carbon monoxide oxidation catalyst can be used individually by 1 type or in combination of 2 or more types. Even if the composition is the same as that of hopcalite, it is not in the form of a complex oxide, but in the form of a mixture in which copper (II) oxide and manganese (IV) oxide are simply mixed. Insufficient function.
  • the carbon monoxide oxidation catalyst (B) has a specific particle size distribution, that is, a particle size (D99) of 30 ⁇ m or less and a particle size (D50) of 20 ⁇ m or less, The miscibility can be improved, and therefore a film can be formed well.
  • D99 and D55 refer to the particle diameter at the point where the particle diameter distribution becomes 99 mass% and 50 mass%, respectively, from the smaller particle diameter.
  • D99 is preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less.
  • D50 is preferably 0.01 to 15 ⁇ m, more preferably 0.1 to 10 ⁇ m. Coarse particles that deviate from the above range may be a film defect or foreign matter.
  • the particles may agglomerate to become defects or foreign matter of the film, or if they do not agglomerate, a large amount of air may be included to deteriorate the melt-kneading workability during compound production. .
  • Control of the particle size distribution includes a method in which large particles are produced and then pulverized and sized, and a method in which fine particles are produced and sized from the beginning. Either method may be used as long as the particle size distribution can be controlled within the above range, and is not particularly limited. However, from the viewpoint of extrusion load and film forming property, a method of generating fine particles from the beginning is more preferable.
  • the amount of component (B) is 1 to 150 parts by weight, preferably 3 to 120 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of component (A). If the amount is less than the above lower limit, the function of oxidizing carbon monoxide becomes unsatisfactory, and if the upper limit is exceeded, melt kneading and film formation at the time of compound production may be difficult.
  • Carbon dioxide adsorbent Any carbon dioxide adsorbent (C) in the present invention can be used as long as it has the same particle size distribution as that described for component (B). Examples thereof include zeolites having a pore diameter of 0.4 nm or more (for example, molecular sieve 4A and molecular sieve 5A) and alkaline earth metal oxides such as strontium oxide.
  • the component (C) is preferably one that does not substantially require water for carbon dioxide adsorption (does not require more than about 1 mg / L of absolute humidity).
  • the component (C) is preferably one that does not substantially require water for carbon dioxide adsorption (does not require more than about 1 mg / L of absolute humidity).
  • magnesium oxide requires water in the carbon dioxide adsorption mechanism.
  • the compounding amount of the carbon dioxide adsorbent (C) is 1 to 200 parts by mass, preferably 5 to 150 parts by mass, more preferably 10 to 120 parts by mass with respect to 100 parts by mass of the component (A). If it is less than the above lower limit, the function of adsorbing carbon dioxide becomes unsatisfactory, and if it exceeds the above upper limit, melt kneading and film formation at the time of compound production may be difficult.
  • the resin composition in the present invention preferably further contains a slip agent.
  • a slip agent examples include metal soaps such as calcium stearate, fatty acid amides such as oleic acid amide and erucic acid amide, polyethylene wax, silicone gum, and silicone oil.
  • a preferable amount of the slip agent to be added is 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component (A).
  • the resin composition in the present invention is optionally provided with a phosphorus-based, phenol-based or sulfur-based antioxidant, an anti-aging agent, a light stabilizer, a weathering agent such as an ultraviolet absorber, a copper damage inhibitor, an aromatic Group nucleating agents such as metal phosphates and gelols, antistatic agents such as glycerin fatty acid monoesters, coloring agents, fragrances, antibacterial agents, magnesium oxide, zinc oxide, calcium carbonate, talc, metal hydrates, etc. And additives such as plasticizers such as filler, glycerin fatty acid ester, paraffin oil, phthalic acid and ester.
  • the resin composition in the present invention can be obtained by melt-kneading the above components (A-1), (A-2), (B) and (C) and optionally an optional additive.
  • the melt-kneading can be performed using a conventional apparatus such as a twin screw extruder or a Banbury mixer.
  • the kneading temperature is preferably higher than the film-forming temperature in order to avoid moisture-absorbing foaming troubles during film formation.
  • the resulting composition can be pelletized by a granulator and then subjected to normal film formation using a T die or the like. In that case, the pelletization is performed using water such as a hot cut method. It is preferable to carry out by a method that does not intervene.
  • a vacuum vent may be provided or a gear pump or the like may be used.
  • a method in which film formation is directly performed without pelletization for example, a method in which a composition obtained by melt kneading is directly sent to a T die via a gear pump or the like to form a film.
  • the film of the present invention preferably has a thickness of 1 to 1000 ⁇ m. More preferably, it is 10 to 500 ⁇ m, and further preferably 20 to 200 ⁇ m. If the film is too thin, the waist / stiffness will be insufficient, and it will take time to assemble the storage element in the non-aqueous electrolyte secondary battery or the electric double layer capacitor in which the storage element is enclosed. If the film is too thick, the film cannot be disposed in a small gap in the container of the nonaqueous electrolyte secondary battery or the electric double layer capacitor.
  • the film of the present invention can oxidize and adsorb carbon monoxide to carbon dioxide in the absence of gaseous oxygen, has excellent heat resistance, and encloses storage elements in non-aqueous electrolyte secondary batteries and electric double layer capacitors Particularly useful in a used container.
  • Examples 1 to 4 and Comparative Examples 1 to 13 The components (parts by mass) shown in Table 1 were dry blended and melt-kneaded with a twin screw extruder TEX28 of Nippon Steel, Ltd., and then directly through a gear pump, manufactured by Toshiba Machine Co., Ltd. The film was sent to a single layer T die to form a film having a thickness of 50 ⁇ m.
  • the resin temperature at the exit of the twin screw extruder was 220 ° C. (using a vacuum vent), and the resin temperature at the exit of the gear pump was 220 ° C.
  • Film formation was performed using a vacuum vent under conditions of a T-die outlet resin temperature of 220 ° C., a chill roll temperature of 40 ° C., and a take-off speed of 10 m / min.
  • the obtained film was stored in a gas substitution type glove box (SG-1000 manufactured by ASONE Co., Ltd.) having a dew point temperature of ⁇ 50 ° C. or lower.
  • the obtained film was subjected to the following evaluation test. The results are shown in Table 1.
  • the DSC measurement was held at 230 ° C. for 5 minutes, then cooled to ⁇ 10 ° C. at a rate of temperature decrease of 10 ° C./min, held at ⁇ 10 ° C. for 5 minutes, This was performed using a temperature program of heating to 230 ° C. at a rate of temperature increase of ° C./min.
  • the films of Examples 1 to 4 according to the present invention are excellent in appearance, film thickness stability and heat resistance. Further, the carbon monoxide concentration after 24 hours in the N 2 —CO mixed gas and in the N 2 —O 2 —CO mixed gas was 1.1 vol% or less, and carbon dioxide was not detected. This shows that the film of the present invention can oxidize carbon monoxide well to carbon dioxide and adsorb as carbon dioxide even in the absence of oxygen.
  • Comparative Examples 1 and 2 not containing the component (B) the carbon monoxide concentration after 24 hours in the N 2 —CO mixed gas and in the N 2 —O 2 —CO mixed gas was almost the same as that of the blank. Yes, indicating that no oxidation of carbon monoxide to carbon dioxide occurred.
  • the film of Comparative Example 3 containing no component (C) was able to oxidize carbon monoxide to carbon dioxide, but could not adsorb carbon dioxide.
  • Comparative Example 4 containing a large amount of Component (B)
  • Comparative Example 5 containing a large amount of Component (C)
  • Comparative Example 6 using a component (B) that does not have the particle size distribution of the present invention, Since the film property was poor and a film could not be obtained, other tests were not conducted.
  • the film of Comparative Example 12 in which the amount of component (A-2) is too large has a very high extrusion load at the time of film formation, the discharge amount becomes unstable, and the film thickness stability is poor.
  • the filler was not sufficiently dispersed, and grease was generated during film formation, and fine irregularities remained on the film.
  • the film thickness stability was also insufficient.

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Abstract

L'invention concerne un film qui présente une excellente résistance à la chaleur, qui est capable d'oxyder du monoxyde de carbone en dioxyde de carbone et d'adsorber le dioxyde de carbone en l'absence d'oxygène gazeux. L'invention concerne spécifiquement un film qui est formé à partir d'une composition de résine qui contient : (A) 100 parties en masse d'une composition de résine d'éthylène contenant (A-1) 99 à 60 % en masse d'un polymère d'éthylène qui présente (i) un point de fusion au sommet du pic (Tm) du côté des températures les plus élevées sur la courbe de fusion DSC supérieur ou égal à 110 °C, (ii) une enthalpie de fusion (∆H) sur la courbe de fusion DSC de 90 à 180 J/g, (iii) une fraction de cristallisation à 110 °C (Xc110) de 10 à 60 %, et (iv) un MFR (190 °C, 21,18 N) de 0,1 à 10 g/10 min, et (A-2) 1 à 40 % en masse d'une résine d'éthylène modifiée par un acide (le total de (A-1) et (A-2) étant de 100 % en masse) ; (B) 1 à 150 parties en masse de particules d'un catalyseur d'oxydation du monoxyde de carbone ; et (C) 1 à 200 parties en masse de particules adsorbant le dioxyde de carbone. Le composant (B) et le composant (C) ont respectivement un diamètre de particule (D99) inférieur ou égal à 30 µm et un diamètre de particule (D50) inférieur ou égal à 20 µm.
PCT/JP2010/051452 2009-02-04 2010-02-02 Film capable d'oxyder du monoxyde de carbone et son utilisation Ceased WO2010090193A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107681123A (zh) * 2016-08-01 2018-02-09 宁德新能源科技有限公司 正极材料及其制备方法、正极极片及锂离子电池

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JPH11124446A (ja) * 1997-10-23 1999-05-11 Okura Ind Co Ltd 熱収縮性フィルム
JP2003197487A (ja) * 2001-12-28 2003-07-11 Nec Tokin Corp 電気二重層キャパシタ
WO2005120686A1 (fr) * 2004-06-08 2005-12-22 National Institute Of Advanced Industrial Science And Technology Catalyseur pour extraction de monoxyde de carbone et procédé d’extraction de monoxyde de carbone avec le catalyseur
JP2006512186A (ja) * 2002-09-05 2006-04-13 ビーエーエスエフ　アクチェンゲゼルシャフト 物質流から一酸化炭素を除去する吸着組成物、及びその除去方法
JP2006216547A (ja) * 2005-02-02 2006-08-17 Samsung Sdi Co Ltd オールインワンタイプのハイブリッド燃料電池システム
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WO2005120686A1 (fr) * 2004-06-08 2005-12-22 National Institute Of Advanced Industrial Science And Technology Catalyseur pour extraction de monoxyde de carbone et procédé d’extraction de monoxyde de carbone avec le catalyseur
JP2006216547A (ja) * 2005-02-02 2006-08-17 Samsung Sdi Co Ltd オールインワンタイプのハイブリッド燃料電池システム
WO2007066372A2 (fr) * 2005-12-06 2007-06-14 Saes Getters S.P.A. Condensateurs electrolytiques comprenant des moyens se presentant sous la forme d'une feuille polymere multicouche destinee a la sorption de substances nuisibles
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107681123A (zh) * 2016-08-01 2018-02-09 宁德新能源科技有限公司 正极材料及其制备方法、正极极片及锂离子电池

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