WO2010044436A1 - 燃料電池用補強型電解質膜、燃料電池用膜-電極接合体、及びそれを備えた固体高分子形燃料電池 - Google Patents
燃料電池用補強型電解質膜、燃料電池用膜-電極接合体、及びそれを備えた固体高分子形燃料電池 Download PDFInfo
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- WO2010044436A1 WO2010044436A1 PCT/JP2009/067828 JP2009067828W WO2010044436A1 WO 2010044436 A1 WO2010044436 A1 WO 2010044436A1 JP 2009067828 W JP2009067828 W JP 2009067828W WO 2010044436 A1 WO2010044436 A1 WO 2010044436A1
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- fuel cell
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- electrolyte membrane
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- electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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- 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
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a reinforced electrolyte membrane used in a fuel cell, a membrane-electrode assembly for a fuel cell, and a polymer electrolyte fuel cell including the same.
- the polymer electrolyte fuel cell has a structure in which a solid polymer electrolyte membrane is used as an electrolyte and electrodes are joined to both surfaces of the membrane.
- the solid polymer electrolyte membrane When used as a fuel cell, the solid polymer electrolyte membrane needs to have a low membrane resistance. For that purpose, it is desirable that the film thickness be as thin as possible. However, if the film thickness is too thin, there are problems that pinholes are easily formed during film formation, the film is broken during electrode forming, and a short circuit between the electrodes is likely to occur. In addition, since solid polymer electrolyte membranes used in fuel cells are always used in a wet state, durability such as pressure resistance and cross leak during differential pressure operation due to swelling and deformation of the polymer electrolyte membrane due to wetting Problems will arise.
- the longitudinal and transverse tensile yield stresses of the composite are both 12 MPa or more, and the ratio between the longitudinal tensile yield stress and the transverse tensile yield stress (longitudinal direction).
- An electrolyte membrane for a polymer electrolyte fuel cell having a tensile yield stress / lateral tensile yield stress) of 2.0 or less is disclosed.
- Patent Document 2 as an ion-conducting diaphragm having high hardness and dimensional stability, a stretched polytetragon having a morphological structure including a microstructure of ultra-high stretched nodes interconnected by fibrils.
- a composite diaphragm in which an ionomer is absorbed in an integrated composite diaphragm made of fluoroethylene is disclosed.
- the composite diaphragm is also disclosed to exhibit surprisingly increased hardness, thus reducing electrical shorts and improving fuel cell performance and durability.
- porous materials such as expanded polytetrafluoroethylene and electrolyte materials to reduce electrical shorts and improve performance and durability.
- the structure of the porous material is complicated.
- proton conductivity specifically, the performance of the fuel cell
- a membrane made of a composite of a polytetrafluoroethylene porous material and an electrolyte material has an in-plane strength anisotropy, so that distortion is likely to occur inside the fuel cell, and the membrane is likely to be deformed or broken.
- Anode hydrogen electrode: H 2 ⁇ 2H + + 2e ⁇
- Cathode oxygen electrode: 2H + + 2e ⁇ + (1/2) O 2 ⁇ H 2 O
- the hydrogen ions generated by the reaction of the formula (1) at the anode permeate (diffuse) the solid polymer electrolyte membrane in the hydrated state of H + (xH 2 O), and the hydrogen ions that permeate the membrane at the cathode It is used for the reaction (2).
- the electrode reaction at the anode and cathode proceeds at the interface between the catalyst and the solid polymer electrolyte membrane in the electrode catalyst layer with the electrode catalyst layer in close contact with the solid polymer electrolyte membrane as a reaction site.
- a typical example is the generation of hydrogen peroxide (H 2 O 2 ).
- the mechanism of its generation is not necessarily fully understood, but possible mechanisms are: That is, the generation of hydrogen peroxide can occur at either the hydrogen electrode or the oxygen electrode. For example, at the oxygen electrode, it is considered that hydrogen peroxide is generated by the following equation due to incomplete reduction of oxygen. .
- M represents a catalyst metal used for the hydrogen electrode
- MH represents a state in which hydrogen is adsorbed on the catalyst metal.
- a noble metal such as platinum (Pt) is used as the catalyst metal.
- the hydrogen peroxide generated on these electrodes moves away from the electrodes due to diffusion or the like and moves into the electrolyte.
- This hydrogen peroxide is a substance having a strong oxidizing power and oxidizes many organic substances constituting the electrolyte.
- the detailed mechanism is not necessarily clear, in many cases, it is considered that hydrogen peroxide is radicalized, and the generated hydrogen peroxide radical is a direct reactant of the oxidation reaction. That is, it is considered that radicals generated by the reaction represented by the following formula draw hydrogen from the organic substance of the electrolyte or cut other bonds.
- the cause of radicalization is not necessarily clear, but contact with heavy metal ions is considered to have a catalytic action.
- the radical is also formed by heat, light or the like.
- the electrolyte membrane of the fuel cell is required to have both durability (reduction in fluorine emission and prevention of increase in cross leak) and improvement in output (prevention of decrease in proton conductivity).
- a membrane electrode assembly for a polymer electrolyte fuel cell is constructed for the purpose of efficiently decomposing peroxide generated in the battery and suppressing deterioration of the electrode and the electrolyte membrane. It is disclosed that a peroxide decomposition catalyst for decomposing peroxide is disposed with a concentration difference on at least one of a pair of electrodes.
- the peroxide decomposition catalyst is arranged with a concentration difference in the electrode, and the concentration difference may be in the thickness direction of the electrode or in the surface direction of the electrode. It is described that it is desirable to dispose the oxide decomposition catalyst with a concentration difference in the thickness direction of the electrode (paragraphs 0021 and 0022).
- the membrane electrode assembly is sandwiched from both sides for the purpose of suppressing deterioration of the sealing member that seals between the electrolyte membrane and the separator and the electrolyte membrane and improving durability. It is disclosed that a peroxide decomposition catalyst for decomposing peroxide is disposed on a seal member that seals between a separator and an electrolyte membrane.
- the present invention provides a fuel cell electrolyte membrane reinforced with a porous substrate that is excellent in durability and has a reduced cross leak amount due to chemical deterioration of electrolyte membrane components caused by peroxides and radicals.
- the purpose is to do.
- an object of the present invention is to provide a polymer electrolyte fuel cell that has high output and excellent durability under environmental temperature and humidity under high-temperature and low-humidification conditions that are fuel cell operating conditions.
- the present inventors have found that the stability of a perfluorocarbon polymer having a sulfonic acid group as an electrolyte is improved by reinforcement, and the durability is remarkably improved by containing a specific compound group in the electrolyte membrane. I found out. Moreover, a highly durable composite membrane having a constant ionic conductivity was obtained without complicating the fine structure of the porous substrate.
- the present invention includes the following inventions.
- the fuel membrane electrolyte membrane comprising a polymer electrolyte, comprising a porous substrate and a radical scavenger dispersed in the polymer electrolyte.
- the porous substrate is made of polytetrafluoroethylene, polytetrafluoroethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polybromotrifluoroethylene, polytetrafluoroethylene-bromotrifluoroethylene copolymer.
- a porous film made of a polymer, a polytetrafluoroethylene-perfluorovinyl ether copolymer, a polytetrafluoroethylene-hexafluoropropylene copolymer, or a combination of two or more of these materials, The electrolyte membrane for fuel cells as described in 1).
- the radical scavenger is CeO 2 , Ru, Ag, RuO 2 , WO 3 , Fe 3 O 4 , CePO 4 , CrPO 4 , AlPO 4 , FePO 4 , CeF 3 , FeF 3 , Ce 2 (CO 3 ) 3 ⁇ 8H 2 O, Ce (CHCOO) 3 ⁇ H 2 O, CeCl 3 ⁇ 6H 2 O, Ce (NO 3 ) 6 ⁇ 6H 2 O, Ce (NH 4 ) 2 (NO 3 ) 6 , Ce (NH 4) is 4 (SO 4) 4 ⁇ 4H 2 O, Ce (CH 3 COCHCOCH 3) 3 ⁇ 3H 2 O, Fe- porphyrins, and Co- 1 or more selected from porphyrins, (1) - (3 The electrolyte membrane for fuel cells according to any one of 1).
- the electrolyte membrane for a fuel cell according to any one of (1) to (4), which is a perfluorocarbon sulfonic acid resin represented by:
- a fuel cell membrane comprising a pair of electrodes comprising a fuel electrode supplied with fuel gas and an oxygen electrode supplied with oxidant gas, and an electrolyte membrane sandwiched between the pair of electrodes- A fuel cell membrane-electrode assembly, wherein the electrolyte membrane is an electrolyte membrane for a fuel cell according to any one of (1) to (5).
- a polymer electrolyte fuel cell comprising a membrane-electrode assembly having the fuel cell electrolyte membrane according to any one of (1) to (5).
- the present invention also includes the following inventions.
- a reinforced electrolyte membrane for a fuel cell in which a polymer electrolyte dispersion is combined with a porous base material, the electrolyte membrane containing a radical scavenger and a flow direction when processed into a sheet shape
- the elongation ratio when the larger of the flow direction (MD) and MD vertical direction (TD) elongation is the denominator at the maximum tensile strength in the MD (MD) and MD vertical direction (TD) is 0.
- a reinforced electrolyte membrane for a fuel cell which is 4 to 1.0.
- the radical scavenger is CeO 2 , Ru, Ag, RuO 2 , WO 3 , Fe 3 O 4 , CePO 4 , CrPO 4 , AlPO 4 , FePO 4 , CeF 3 , FeF 3 , Ce 2 (CO 3 ) 3 ⁇ 8H 2 O, Ce (CHCOO) 3 ⁇ H 2 O, CeCl 3 ⁇ 6H 2 O, Ce (NO 3 ) 6 ⁇ 6H 2 O, Ce (NH 4 ) 2 (NO 3 ) 6 , Ce (NH 4) 4 (SO 4) 4 ⁇ 4H 2 O, Ce (CH 3 COCHCOCH 3) 3 ⁇ 3H 2 O, Fe- porphyrins, and Co- characterized in that at least one selected from porphyrin [1 ]
- the reinforced electrolyte membrane for a fuel cell according to any one of [4] to [4].
- a fuel cell including a pair of electrodes each including a fuel electrode supplied with a fuel gas and an oxygen electrode supplied with an oxidant gas, and a polymer electrolyte membrane sandwiched between the pair of electrodes.
- a membrane-electrode assembly for a fuel cell characterized in that the polymer electrolyte membrane is a reinforced electrolyte membrane for a fuel cell according to any one of [1] to [5] body.
- a polymer electrolyte fuel cell comprising a membrane-electrode assembly having the reinforced electrolyte membrane for fuel cells according to any one of [1] to [5].
- the electrolyte membrane for a fuel cell of the present invention has a flow direction (MD) and a MD vertical direction (TD) at the maximum tensile strength in the flow direction (MD) and MD vertical direction (TD) when processed into a sheet shape. It is preferable that the elongation ratio when the larger elongation is used as the denominator is 0.4 to 1.0.
- the electrolyte membrane for a fuel cell of the present invention has a flow direction (MD) and a MD vertical direction (TD) at the maximum tensile strength in the flow direction (MD) and MD vertical direction (TD) when processed into a sheet shape. It is preferable that the elongation ratio when the larger elongation is used as the denominator is 0.4 to 1.0 when the relative humidity is 80 ° C. and the relative humidity is 90%.
- the reinforced electrolyte membrane for a fuel cell of the present invention is a reinforced electrolyte membrane for a high-strength fuel cell excellent in physical deterioration, in which a porous substrate is impregnated with a polymer electrolyte dispersion, and further chemically deteriorated in the polymer electrolyte.
- the fuel cell reinforced electrolyte membrane of the present invention has a maximum tensile strength in the flow direction (MD) and MD vertical direction (TD) of 23 ° C. and a relative humidity of 50% when processed into a sheet shape. is preferably at 65N / mm 2 or more, 23 ° C., and more preferably 70N / mm 2 or more when a relative humidity of 50%.
- the reinforced electrolyte membrane for a fuel cell according to the present invention exhibits excellent durability because the elution amount of fluorine ions is reduced by reinforcement with the reinforcing membrane.
- the reinforced electrolyte membrane for a fuel cell of the present invention has a maximum tensile strength in the flow direction (MD) and MD vertical direction (TD) when processed into a sheet of 80 ° C. and 90% relative humidity. sometimes it is preferably 35N / mm 2 or more, more preferably 80 ° C., is 40N / mm 2 or more when a relative humidity of 90%.
- the reinforced electrolyte membrane for a fuel cell according to the present invention exhibits excellent durability because the elution amount of fluorine ions is reduced by reinforcement with the reinforcing membrane.
- porous base material a wide variety of known reinforcing membranes for fuel cells can be used.
- a porous film made of bromotrifluoroethylene copolymer, polytetrafluoroethylene-perfluorovinyl ether copolymer, polytetrafluoroethylene-hexafluoropropylene copolymer, or a combination of two or more of these materials is suitable. Used for.
- the degree of polymerization and the molecular weight of such a fluororesin are not particularly limited, but the weight average molecular weight of the fluororesin is preferably about 10,000 to 10,000,000 from the viewpoint of strength and shape stability.
- a polytetrafluoroethylene (PTFE) film made porous by a stretching method is preferably exemplified.
- the radical scavenger to be contained in the fuel reinforced electrolyte membrane for a battery of the present invention for example, CeO 2, Ru, Ag, RuO 2, WO 3, Fe 3 O 4, CePO 4, CrPO 4, AlPO 4, FePO 4 , CeF 3 , FeF 3 , Ce 2 (CO 3 ) 3 ⁇ 8H 2 O, Ce (CHCOO) 3 ⁇ H 2 O, CeCl 3 ⁇ 6H 2 O, Ce (NO 3 ) 6 ⁇ 6H 2 O, Ce ( Selected from NH 4 ) 2 (NO 3 ) 6 , Ce (NH 4 ) 4 (SO 4 ) 4 .4H 2 O, Ce (CH 3 COCHCOCH 3 ) 3 .3H 2 O, Fe-porphyrin, and Co-porphyrin One or more of these are preferred. Of these, cerium oxide is particularly preferred.
- the present invention also provides a fuel comprising a pair of electrodes each composed of a fuel electrode to which a fuel gas is supplied and an oxygen electrode to which an oxidant gas is supplied, and a polymer electrolyte membrane sandwiched between the pair of electrodes.
- the polymer electrolyte membrane is the above reinforced electrolyte membrane for a fuel cell.
- the present invention also provides a polymer electrolyte fuel cell comprising a membrane-electrode assembly having the above-described reinforced electrolyte membrane for fuel cells.
- the reinforced electrolyte membrane for fuel cells of the present invention exhibits excellent durability because the elution amount of fluorine ions is reduced by reinforcement with the reinforcing membrane.
- harmful peroxides and radicals generated during operation of the fuel cell can be removed from the electrolyte membrane, and the electrolytes in the electrolyte membrane and the electrode catalyst layer are deteriorated by the peroxide and radicals.
- the fuel cell which suppressed and improved durability can be obtained.
- Example It shows the result of the check by electron probe microanalyzer of film cross-section of CeO 2 dispersed state in the resulting composite membrane in Example (EPMA). Shows the result of the check by a scanning electron microscope CeO 2 dispersed state membrane section of a composite film obtained in Example (SEM). The results of endurance time of fuel cells using the reinforced electrolyte membrane for fuel cells of Examples and Comparative Examples 1 to 4 are shown.
- the reinforced electrolyte membrane for a fuel cell of the present invention does not necessarily have a conventional special internal fine structure (for example, one having a large aspect ratio of reinforcing membrane portions called nodes connected to each other by fibrils). It is a composite membrane in which an electrolyte membrane made of perfluorocarbon having a sulfonic acid group is reinforced.
- the reinforced electrolyte membrane for a fuel cell of the present invention is a composite membrane that simultaneously improves the Fenton test resistance, which is an indicator of chemical stability of a perfluorocarbon polymer having a sulfonic acid group, by changing the strength of the reinforcement. .
- Either of the maximum tensile strength in the longitudinal direction or the transverse direction in the film surface is 65 N / mm 2 or more at normal temperature (23 ° C., relative humidity 50%), or 35 N at high temperature and high humidity (80 ° C., relative humidity 90%).
- / Mm 2 or more of the complementary membrane can reduce the fluorine ion elution amount in the 80 ° C. Fenton test by 14 to 69% compared to the conventional membrane, and the electrode assembly in which the catalyst layer is formed by a conventional method It has high durability without deteriorating the initial performance of the single cell.
- the porous substrate used in the present invention functions as a carrier for supporting a polymer electrolyte on its surface (especially the surface in the pores), and is a polytetrafluoropolymer that is a fluorine resin excellent in strength and shape stability.
- a porous substrate made of a polymer, a polytetrafluoroethylene-hexafluoropropylene copolymer, or the like is preferably used.
- the degree of polymerization and the molecular weight of such a fluororesin are not particularly limited, but the weight average molecular weight of the fluororesin is preferably about 10,000 to 10,000,000 from the viewpoint of strength and shape stability.
- the average pore diameter and porosity of the porous substrate used in the present invention are not particularly limited, but the average pore diameter is preferably about 0.001 ⁇ m to 100 ⁇ m, and the porosity is preferably about 10% to 99%. If the average pore diameter is less than 0.001 ⁇ m, the introduction of the polymer electrolyte into the pores tends to be inhibited, whereas if it exceeds 100 ⁇ m, the surface area of the porous substrate supporting the polymer electrolyte is insufficient. The proton conductivity tends to decrease. On the other hand, when the porosity is less than 10%, the amount of the polymer electrolyte supported in the pores tends to be insufficient, and the proton conductivity tends to decrease. And shape stability tends to be lowered.
- the shape of the porous substrate used in the present invention is not particularly limited.
- the obtained composite electrolyte can be used as it is as an electrolyte membrane for a fuel cell, a film or membrane is preferred.
- the thickness of the film-like or membrane-like porous substrate is not particularly limited, but is preferably about 1 to 50 ⁇ m. If the thickness of the porous substrate is less than the above lower limit, the strength of the obtained electrolyte membrane tends to decrease, while if it exceeds the above upper limit, the membrane resistance of the obtained electrolyte membrane increases and proton conductivity tends to decrease. It is in.
- Patent Document 5 discloses a method for producing a porous polymer film made of polytetrafluoroethylene, wherein (a) a polytetrafluoroethylene molded product having a crystallinity of about 95% or more is obtained by a paste molding extrusion method.
- Patent Document 6 discloses a porous substrate used in the reinforced electrolyte membrane for fuel cells of the present invention and a method for producing the same.
- Patent Document 6 discloses a composite including a porous polymer film, in which the pores of the film are at least partially filled with a resin, and the room temperature bending elastic modulus of the resin is greater than about 1 GPa.
- a composite comprising a porous polymer film satisfying the following formula: 75 MPa ⁇ (longitudinal membrane tensile elastic modulus + lateral membrane tensile elastic modulus) / 2 is disclosed.
- tetrafluoroethylene it is disclosed that expanded polytetrafluoroethylene is substantially free of knot material.
- Patent Document 6 has the following disclosure more specifically. “Unexpectedly, it has been found that when used in a composite structure, the porous polymer membrane structure according to the present invention contributes significantly to the fracture toughness of the composite.
- the membrane structure is an expanded polytetrafluoroethylene membrane that has minimal material present in a non-fibrillar form called a “node”.
- the membrane is substantially free of node material. Isotropic fibril orientation is preferred when stress is loaded from multiple directions. When the stress is anisotropic, it is preferred that a greater number of fibrils be parallel to the direction of maximum stress. When a multilayer structure is intended, it is desirable to cross-ply the layers to maximize performance.
- the membrane of the present invention has a substantially non-linear membrane-like structure.
- the membrane does not readily wet or adhere to other materials.
- a membrane comprising a polymeric material is preferred.
- Membranes containing stretched polymers are preferred.
- Most preferred is a membrane comprising expanded PTFE.
- the polymer membrane may be substantially any polymeric material such as vinyl polymer, styrene, acrylate, methacrylate, polyethylene, polypropylene, polyacrylonitrile, polyacrylamide, polyvinyl chloride, fluoropolymer, such as PTFE, condensation polymer, polysulfone.
- polymeric material such as vinyl polymer, styrene, acrylate, methacrylate, polyethylene, polypropylene, polyacrylonitrile, polyacrylamide, polyvinyl chloride, fluoropolymer, such as PTFE, condensation polymer, polysulfone.
- the porous polymer film can be produced by a known method.
- a nodeless ePTFE membrane is preferred.
- Such an ePTFE membrane can be manufactured, for example, according to the teaching of Patent Document 7 above.
- Such membranes are formed by being highly fibrillated by biaxial stretching of PTFE and eliminating a substantially coarse nodule structure.
- the structure includes a very strong web of fine fibrils that intersect at the fibril intersection.
- the expanded PTFE material according to Patent Document 7 can be produced as follows.
- a PTFE fine powder having a low amorphous content and a crystallinity of at least 98% is used as a raw material.
- Suitable PTFE fine powders include, for example, FLUON® CD-123 and FLUON® CD-1 fine powder manufactured by ICI Americas, and E.I. I. Examples include TEFLON (registered trademark) fine powder manufactured by duPont de Nemours.
- the PTFE fine powder is first solidified and then lubricated with a hydrocarbon extrusion aid, preferably odorless mineral spirits such as ISOPAR® K (manufactured by Exxon).
- the lubricated powder is compressed into a cylindrical shape and extruded with a ram extruder to form a tape.
- Two or more layers of tape are laminated together and compressed between two rolls.
- the tape (single or plural) is compressed between rolls to a suitable thickness, for example, 0.1-1 mm. Stretch the wet tape in the transverse direction to 1.5 to 5 times its initial width. Heat to remove the extrusion aid.
- the dried tape is then stretched longitudinally in the space between the roll rows heated to a temperature below the melting point of the polymer (327 ° C.). Longitudinal stretching has a ratio of the speed of the second row of rolls to the speed of the first row of rolls of 10 to 100: 1.
- the machine direction stretching is repeated at a ratio of 1 to 1.5: 1.
- the longitudinally stretched tape is at a temperature of less than 327 ° C. while preventing the membrane from shrinking in the machine direction, at least 1.5 times, preferably 6 to 15 times the width of the first extrudate. Stretch in the transverse direction. While still constrained, the membrane is preferably heated above the melting point of the polymer (327 ° C.) and then cooled.
- a particularly preferred membrane is a nodeless ePTFE membrane with a high density of fibrils oriented in the direction of maximum stress in the intended composite body. Isotropic fibril orientation is preferred when stress is loaded from multiple directions.
- the ePTFE membrane can have a suitable void fraction. According to one aspect of the invention, the void fraction of the membrane is from about 1 to about 99.5% by volume.
- the void fraction can be about 50 to about 90%.
- a preferred void fraction is about 70-90%.
- the film may be treated as necessary to facilitate adhesion to the resin component or to facilitate adhesion to the resin component. Examples of the treatment include corona, plasma, and chemical oxidation.
- the resin is absorbed into at least a portion of the membrane pores.
- a polymer resin is preferable, and examples thereof include a thermoplastic resin, a thermosetting resin, and combinations or mixtures thereof.
- the resin is a polymer and the glass transition temperature of the amorphous component is> 80 ° C.
- the polymer electrolyte is impregnated and applied to the porous substrate in the form of a liquid dispersed or dissolved in a solvent. By removing the solvent by evaporating the solvent, the reinforced electrolyte membrane for a fuel cell of the present invention is obtained.
- Solvents for dispersing or dissolving the polymer electrolyte are water, methanol, ethanol, n-propanol, iso-propanol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, propylene glycol, 1, 2 and 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1,2 and 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, and C4-C8 linear, branched or cyclic alcohols such as 4-methyl-1-pentanol (especially ethanol or 1-propanol is preferred), hydrocarbon solvents such as n-hexane, tetrahydrofuran, dioxane, etc.
- Ether solvents dimethyl sulfoxide, diethyls Sulfoxide solvents such as oxoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, N-methyl-2 -Pyrrolidone solvents such as pyrrolidone and N-vinyl-2-pyrrolidone, 1,1,2,2-tetrachloroethane, 1,1,1,2-tetrachloroethane, 1,1,1-trichloroethane, 1,2- Examples include dichloroethane, trichloroethylene, tetrachloroethylene, dichloromethane, chloroform and the like. These water and solvent may be used alone or in combination of two or more.
- the electrolyte in the fuel cell membrane-electrode assembly of the present invention may be a laminate of a plurality of reinforcing porous substrates.
- at least one porous substrate among the plurality of porous substrates is the reinforced electrolyte membrane of the present invention.
- the electrolyte membrane to be laminated is not particularly limited as long as it is a polymer membrane that can be used as an electrolyte.
- the laminated electrolyte membranes may be the same electrolyte membrane, or different types of electrolyte membranes may be mixed and used.
- perfluorinated sulfonic acid films perfluorinated phosphonic acid films, perfluorinated carboxylic acid films, and perfluorinated films such as PTFE composite films in which polytetrafluoroethylene (PTFE) is compounded with these perfluorinated films.
- PTFE polytetrafluoroethylene
- a liquid obtained by dispersing or dissolving an electrolyte membrane, a fluorine-containing hydrocarbon-based graft membrane, a hydrocarbon-based electrolyte membrane such as a wholly hydrocarbon-based graft membrane, or a wholly aromatic membrane in a solvent can be used.
- the polymer electrolyte fuel cell of the present invention is a polymer electrolyte fuel cell using the above-described fuel cell membrane-electrode assembly of the present invention. Except for using the membrane-electrode assembly for a fuel cell of the present invention, the configuration of a generally known polymer electrolyte fuel cell may be followed. By using the fuel cell membrane-electrode assembly of the present invention, the polymer electrolyte fuel cell of the present invention is a solid polymer fuel cell having a large output, low cost and high durability.
- porous substrate used in Examples and Comparative Examples was prepared by biaxially stretching a PTFE tape and highly fibrillating by the following method.
- Extrusion aid (IsoperK, manufactured by Exxon) was added to PTFE fine powder (PTFE601A, manufactured by Dupont) in an amount of 285 mg per kg of PTFE fine powder.
- the PTFE fine powder to which the extrusion aid was added was compressed into a cylindrical shape, which was extruded with a ram extruder to form a tape shape.
- the extruded tape was rolled to a thickness of about 20 ⁇ m between rolling rolls. The extruded tape was removed from the rolled tape at 210 ° C. in a blowing oven.
- the temperature was adjusted to the stretching temperature in the length direction shown in Table 1 below.
- the film is stretched in the length direction between the roll rows in the heating zone, and then in the transverse direction in the heating zone adjusted to the stretching temperature in the width direction shown in Table 1 while preventing the film from shrinking in the longitudinal direction.
- Drawing was performed. Thereafter, heat treatment was performed at 380 ° C. in a state where the membrane was fixed so as not to shrink, and a porous substrate was obtained.
- porous base material used for an Example and the comparative example 4 was obtained by changing the extending
- the porous substrate used in Comparative Example 4 is the same as that in the example.
- porous substrates used in Comparative Examples 1 to 3 were obtained under the following conditions.
- CeO 2 powder (product name “CEO05PB”, average particle size 0.2 ⁇ m, manufactured by High-Purity Chemical Laboratory Co., Ltd.) obtained by weighing the prepared porous base material in advance so as to be 7 ⁇ mg / cm 2 in the membrane was perfluorocarbon. It was impregnated with a liquid dispersed in a mixed solution of sulfonic acid resin (Nafion solution (DE2020)) / alcohol solvent (ethanol or 1-propanol) and water (referred to as a polymer electrolyte dispersion).
- sulfonic acid resin Nafion solution (DE2020)
- alcohol solvent ethanol or 1-propanol
- water referred to as a polymer electrolyte dispersion
- the porous substrate was fixed to a fixed frame so as not to shrink, the polymer electrolyte dispersion containing the CeO 2 powder was applied to both sides of the porous substrate, and then dried with a hair dryer to remove the solvent. .
- the porous substrate and the fixed frame were dried in an oven at 180 ° C. for 8 minutes. The porous substrate and the fixed frame were removed from the oven, and the porous substrate was removed from the fixed frame.
- the taken-out porous substrate / polymer electrolyte composite membrane was transparent, and complete impregnation of the porous substrate with the polymer electrolyte was confirmed.
- the thickness of the obtained composite film was about 20 ⁇ m, and the Ce content in the film was quantified by high-frequency plasma mass spectrometry (ICP-MS), and was about 7 ⁇ g / cm 2 .
- Table 2 shows the results of conducting a tensile test under normal temperature conditions of the composite films obtained in Examples and Comparative Example 4, results of conducting a tensile test under high temperature and high humidity conditions, and ionic conductivity. Each test was performed according to the following procedure.
- a test piece having a width of 10 mm is attached to a jig with a platinum electrode having a distance between electrodes of 5 mm, and the whole jig is immersed in distilled water at 30 ⁇ 0.5 ° C. for 1 hour. Thereafter, the impedance is measured using a LCR meter at a measurement frequency of 100 kHz. Thereafter, the proton conductivity is calculated using the following formula.
- ⁇ (S / cm) 1 / impedance ( ⁇ ) ⁇ terminal distance (cm) / sample cross-sectional area (cm 2 )
- Tables 3 to 5 show the results of conducting a tensile test under normal temperature conditions on the composite membranes obtained in Comparative Examples 1 to 3, results of conducting a tensile test under high temperature and high humidity conditions, and ionic conductivity.
- FIG. 1 shows the result of confirming the CeO 2 dispersion state in the composite film obtained in the example by an electron probe microanalyzer (EPMA) of the film cross section
- FIG. 2 shows in the composite film obtained in the example. shows the result of the check by a scanning electron microscope of CeO 2 dispersed state of the film cross section (SEM).
- SEM scanning electron microscope
- a fuel cell was produced by a conventional method, and the initial performance and durability were evaluated.
- the initial voltage was evaluated as follows.
- the operating temperature was set at 80 ° C, the hydrogen bubbler temperature and the air bubbler temperature at 50 ° C.
- Hydrogen was supplied to the fuel electrode as a fuel gas at a back pressure of about 0.1 MPa and 2.0 times the stoichiometric ratio.
- Air was supplied to the oxygen electrode as an oxidant gas at a back pressure of about 0.1 MPa and a stoichiometric ratio of 2.5 times.
- the load was discharged at 0.84 A / cm 2 and the voltage value after 20 minutes was taken as the initial voltage.
- the endurance time was the time when the amount of hydrogen cross-leakage from the anode to the cathode increased by 0.01 MPa or more due to the pressure difference due to repeated film on-off in the above-described environment.
- FIG. 3 shows the results of the endurance time of the fuel cells using the composite membranes of Examples and Comparative Examples 1 to 4. From the results shown in FIG. 3, the CeO 2 -added film (Example) does not increase the amount of cross leak of hydrogen from the anode to the cathode even after the maximum test time of 6000 hours, and the CeO 2 -free film (Comparative Example 1). Compared with (4) to (4), the durability was improved at least 2.4 times to 8.5 times.
- a fuel cell using an electrolyte membrane (thickness 50 ⁇ m) manufactured using Nafion 112 and an electrolyte membrane (thickness 50 ⁇ m) manufactured by adding CeO 2 to Nafion 112 was prepared.
- the same durability test as above was performed.
- the results are also shown in FIG. From these results, it can be seen that the durability of the fuel cell is improved by adding CeO 2 even for an electrolyte membrane that is not reinforced by the porous substrate.
- Example and Comparative Example 4 in the electrolyte membrane reinforced by the porous substrate, the durability of the fuel cell exceeded the expectation by adding CeO 2. It turns out that it improved notably.
- FIG. 4 shows the endurance time of the fuel cell using the Example, Comparative Example 4, Nafion 112 (thickness 50 ⁇ m), and an electrolyte membrane (thickness 50 ⁇ m) obtained by adding CeO 2 to Nafion 112 and changes in the sealing pressure of the electrolyte membrane. The relationship of quantity is shown. From the results of FIG. 4, the electrolyte membranes other than this example deteriorated in an early time and the amount of cross leak increased rapidly, whereas the electrolyte membrane of this example exceeded the maximum test time of 6000 hours. However, it does not deteriorate, and it can be seen that the initial small change in sealing pressure is maintained.
- the durability ratio of the reinforced electrolyte membrane for fuel cells is excellent in the range of 0.4 to 1.0.
- an electrolyte membrane under high temperature and high humidity conditions has a larger denominator of the maximum tensile strength in the flow direction (MD) and MD vertical direction (TD) when processed into a sheet shape.
- the durability time is long when the elongation is 0.4 or more.
- the electrolyte membrane for a fuel cell of the present invention does not generate cross leak even after 6000 hours and has extremely improved durability, and it is possible to improve the durability of a fuel cell using this. This contributes to the practical use of fuel cells.
Abstract
Description
カソード(酸素極):2H++2e-+(1/2)O2→H2O …(2)
アノードで式(1)の反応により生成した水素イオンは、H+(xH2O)の水和状態で固体高分子電解質膜を透過(拡散)し、膜を透過した水素イオンは、カソードで式(2)の反応に供される。このアノード及びカソードにおける電極反応は、固体高分子電解質膜に密着した電極触媒層を反応サイトとし、当該電極触媒層における触媒と固体高分子電解質膜との界面で進行する。
また、水素極では、ガス中に不純物としてあるいは意図的に混ぜることによって入っている酸素、若しくは酸素極で電解質にとけ込み水素極に拡散してきた酸素が反応に関与すると考えられ、その反応式は上記(3)式と同一か、若しくは次に示した式で表されると考えられる。
ここで、Mは、水素極に用いられている触媒金属を示し、M-Hはその触媒金属に水素が吸着した状態を示す。通常触媒金属には白金(Pt)等の貴金属が用いられる。
又は
H2O2→・H+・OOH
このように、燃料電池の電解質膜には、耐久性(フッ素排出低減やクロスリーク増加の防止)と出力向上(プロトン伝導度の低下の防止)の両方が求められている。
で表されるパーフルオロカーボンスルホン酸樹脂である、(1)~(4)のいずれか1項に記載の燃料電池用電解質膜。
作製した多孔質基材を、予め膜中で7μmg/cm2となるように秤量したCeO2パウダー(高純度化学研究所社製、製品名「CEO05PB」、平均粒径0.2μm)をパーフルオロカーボンスルホン酸樹脂(ナフィオン溶液(DE2020))/アルコール溶媒(エタノールあるいは1-プロパノール)と水との混合液(これを高分子電解質分散液と呼ぶ)に分散した液に含浸させた。
比較のために、CeO2パウダーを含まない高分子電解質分散液を用いた他は実施例と同様にして、多孔質基材/高分子電解質複合膜を調製した。得られた複合膜の厚みは比較例1~3では約45μm、比較例4では約20μmとなった。
引っ張り試験機にて、常温条件での環境温湿度(23℃、50%RH)又は高温多湿条件での環境温湿度(80℃、90%RH)において、初期チャック間距離:80mm、試験片形状:10mm幅矩形、引張速度200mm/minにて測定を行い、強度が最大になった時点での強度及び伸度を求めた。また、弾性率は伸度が2%の際の値を用いた。
10mm幅の試験片を電極間距離5mmの白金電極の付いた治具に取り付け、治具ごと30±0.5℃の蒸留水に1時間浸漬させる。その後に、LCRメーターを用いて測定周波数100kHzにてインピーダンスを測定する。その後、次式を用いてプロトン伝導度を計算する。
Claims (6)
- 多孔質基材に高分子電解質分散液を複合化した燃料電池用補強型電解質膜であって、該電解質膜はラジカル捕捉剤を含有しており、シート状に加工する際の流れ方向(MD)及びMDの垂直方向(TD)の最大引張強度のいずれか一方が、80℃、相対湿度90%の時に35N/mm2以上であることを特徴とする燃料電池用補強型電解質膜。
- 前記電解質膜の、シート状に加工する際の流れ方向(MD)及びMDの垂直方向(TD)の最大引張強度時の、流れ方向(MD)及びMDの垂直方向(TD)伸度のいずれか大きい方を分母とした時の伸度比が、80℃、相対湿度90%の時に0.4~1.0であることを特徴とする請求項1に記載の燃料電池用補強型電解質膜。
- 前記多孔質基材が、延伸法によって多孔質化されたポリテトラフルオロエチレン(PTFE)膜であることを特徴とする請求項1または2に記載の燃料電池用補強型電解質膜。
- 前記ラジカル捕捉剤が、CeO2、Ru、Ag、RuO2、WO3、Fe3O4、CePO4、CrPO4、AlPO4、FePO4、CeF3、FeF3、Ce2(CO3)3・8H2O、Ce(CHCOO)3・H2O、CeCl3・6H2O、Ce(NO3)6・6H2O、Ce(NH4)2(NO3)6、Ce(NH4)4(SO4)4・4H2O、Ce(CH3COCHCOCH3)3・3H2O、Fe-ポルフィリン、及びCo-ポルフィリンから選択される1種以上であることを特徴とする、請求項1~3のいずれか1項に記載の燃料電池用補強型電解質膜。
- 燃料ガスが供給される燃料極と酸化剤ガスが供給される酸素極とからなる一対の電極と、前記一対の電極の間に挟装された電解質膜とを含む燃料電池用膜-電極接合体であって、前記電解質膜は、請求項1~4のいずれか1項に記載の燃料電池用補強型電解質膜であることを特徴とする燃料電池用膜-電極接合体。
- 請求項1~4のいずれか1項に記載の燃料電池用補強型電解質膜を有する膜-電極接合体を備えた固体高分子形燃料電池。
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DE112009002507.2T DE112009002507B8 (de) | 2008-10-17 | 2009-10-15 | Verstärkte brennstoffzellen-elektrolytmembran, membran-elektroden-anordnung und polymerelektrolytbrennstoffzelle, diese enthaltend und herstellungsverfahren dazu |
CN200980140877.8A CN102187507B (zh) | 2008-10-17 | 2009-10-15 | 燃料电池用补强型电解质膜、燃料电池用膜-电极接合体以及具备该燃料电池用膜-电极接合体的固体高分子型燃料电池 |
JP2010533917A JP5331122B2 (ja) | 2008-10-17 | 2009-10-15 | 燃料電池用補強型電解質膜、燃料電池用膜−電極接合体、及びそれを備えた固体高分子形燃料電池 |
US13/124,602 US8802314B2 (en) | 2008-10-17 | 2009-10-15 | Reinforced electrolyte membrane for fuel cell, membrane-electrode assembly for fuel cell, and polymer electrolyte fuel cell comprising the same |
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US10355299B2 (en) | 2015-12-21 | 2019-07-16 | Korea Institute Of Energy Research | Reinforced composite membranes and method for manufacturing the same |
JP2020149839A (ja) * | 2019-03-13 | 2020-09-17 | ダイハツ工業株式会社 | 膜電極接合体 |
JP7341680B2 (ja) | 2019-03-13 | 2023-09-11 | ダイハツ工業株式会社 | 膜電極接合体 |
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Also Published As
Publication number | Publication date |
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CN102187507A (zh) | 2011-09-14 |
DE112009002507B8 (de) | 2018-08-30 |
JPWO2010044436A1 (ja) | 2012-03-15 |
DE112009002507T8 (de) | 2012-06-14 |
US8802314B2 (en) | 2014-08-12 |
US20110287335A1 (en) | 2011-11-24 |
JP5331122B2 (ja) | 2013-10-30 |
DE112009002507T5 (de) | 2012-01-19 |
DE112009002507B4 (de) | 2018-05-24 |
CN102187507B (zh) | 2014-06-04 |
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