WO2023047796A1 - 燃料電池用セパレータ - Google Patents
燃料電池用セパレータ Download PDFInfo
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- WO2023047796A1 WO2023047796A1 PCT/JP2022/029141 JP2022029141W WO2023047796A1 WO 2023047796 A1 WO2023047796 A1 WO 2023047796A1 JP 2022029141 W JP2022029141 W JP 2022029141W WO 2023047796 A1 WO2023047796 A1 WO 2023047796A1
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- WIPO (PCT)
- Prior art keywords
- fuel cell
- graphite powder
- cell separator
- average particle
- particle size
- Prior art date
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- 239000000446 fuel Substances 0.000 title claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000002245 particle Substances 0.000 claims abstract description 56
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- 238000005452 bending Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000000465 moulding Methods 0.000 claims abstract description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 239000005011 phenolic resin Substances 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- -1 imidazole compound Chemical class 0.000 claims description 5
- 229920003986 novolac Polymers 0.000 claims description 5
- 238000013001 point bending Methods 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- 238000009661 fatigue test Methods 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 238000005422 blasting Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011812 mixed powder Substances 0.000 description 6
- 238000000748 compression moulding Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910021382 natural graphite Inorganic materials 0.000 description 5
- 239000010680 novolac-type phenolic resin Substances 0.000 description 5
- 239000006061 abrasive grain Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0221—Organic resins; Organic polymers
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0226—Composites in the form of mixtures
-
- 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
Definitions
- the present invention relates to a fuel cell separator.
- the fuel cell separator has a role of making each unit cell conductive, securing a passage for fuel and air (oxygen) supplied to the unit cell, and serving as a boundary wall separating them. . Therefore, separators are required to have various properties such as high electrical conductivity, high gas impermeability, chemical stability, heat resistance and hydrophilicity. In recent years, heat control during operation of fuel cells has come to be emphasized, and accordingly separators are required to have high thermal conductivity.
- Patent Document 1 a polyphenylene sulfide-based resin having a predetermined melt flow rate is used as a binder resin, and two types of large and small graphite particles having different average particle diameters are used to obtain graphite in the separator.
- Fuel cell separators have been proposed in which the porosity of the powder is reduced and the thermal conductivity and fatigue strength are improved.
- the separator of Patent Document 1 uses relatively large graphite particles with an average particle diameter d50 of 100 to 150 ⁇ m as the first graphite particles, so that while having excellent thermal conductivity, bending strength at room temperature is 30 to 36 MPa, and there is a problem that the strength is very poor.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide a fuel cell separator that has good bending strength and bending fatigue properties even in an environment of 70°C.
- the inventors of the present invention have found that, at relatively high temperatures, graphite particles having a predetermined average particle size and an average height within a predetermined range of the average particle size are used.
- the inventors have also found that a fuel cell separator having excellent bending strength and bending fatigue properties can be obtained, and completed the present invention.
- the present invention Molding a composition containing graphite powder and an epoxy resin component containing a main agent, a curing agent and a curing accelerator,
- the average particle size d50 of the graphite powder is 20 to 80 ⁇ m, and the average height of the graphite powder measured with a laser microscope is 30 to 70% of the average particle size d50.
- fuel cell separators 2. 1.
- the fuel cell separator of 1 or 2 which is unbroken up to 10 million cycles under a stress of 20 MPa in a plane bending fatigue test in accordance with ASTM D671 TYPE A in an environment of 70 ° C.; 4. 3.
- the curing agent is a novolac phenolic resin; 6.
- graphite powder having an average particle size d50 of 20 to 80 ⁇ m and an average height of 30 to 70% of the average particle size d50 is used. As a result of being densely filled with, it has excellent bending strength and bending fatigue properties even in an environment of 70°C.
- a fuel cell separator according to the present invention is formed by molding a composition containing graphite powder and an epoxy resin component containing a main agent, a curing agent, and a curing accelerator, and the graphite powder has an average particle size d50 of 20 to 80 ⁇ m. and the average height of the graphite powder measured with a laser microscope is 30 to 70% of the average particle size d50.
- the graphite powder has an average particle size d50 of 20 to 80 ⁇ m, preferably 22 to 80 ⁇ m, more preferably 30 to 80 ⁇ m. If the average particle size d50 is less than 20 ⁇ m, the epoxy resin tends to cover the surface of the graphite powder and the contact area between the particles becomes small, resulting in deterioration of the conductivity of the separator itself. On the other hand, when the average particle diameter d50 exceeds 80 ⁇ m, the contact area between the graphite particles and the epoxy resin becomes small, and sufficient mechanical strength cannot be obtained.
- the average particle diameter d50 in the present invention is expressed as a median diameter in particle size distribution measurement by laser diffraction method.
- the average height of graphite powder measured with a laser microscope is 30 to 70% of the average particle size d50, preferably 30 to 68%, more preferably 30 to 67%. If the average height relative to the average particle size d50 is less than 30%, the graphite powder tends to be oriented in the thickness direction during molding of the separator, resulting in insufficient mechanical strength. Moreover, if the average height with respect to the average particle size d50 exceeds 70%, the gaps between the graphite particles during separator molding become large, and sufficient fatigue characteristics cannot be obtained.
- the average height of the graphite powder in the present invention is determined by placing 10 to 20 mg of graphite powder on a glass plate and using a laser microscope VK-X100 manufactured by Keyence Corporation with an objective lens of 50 times magnification (NA value 0.55). The graphite powder on the glass plate is scanned, and then the particle height of the graphite powder is measured by profile measurement of the dedicated analysis application VK-H1XA manufactured by Keyence Corporation, and the average value of 50 randomly selected particles.
- the type etc. are not particularly limited, and natural graphite or artificial graphite can be used.
- the artificial graphite powder can be appropriately selected and used from conventionally used fuel cell separators. Specific examples thereof include artificial graphite obtained by calcining needle coke, artificial graphite obtained by calcining block coke, and the like.
- the natural graphite powder it is also possible to appropriately select and use from those conventionally used in fuel cell separators. Specific examples thereof include massive natural graphite, scale-like natural graphite, and the like.
- graphite powders may be used alone or in combination of two or more.
- graphite powder having a particle size range defined in the present invention may be appropriately selected, and when used in combination of two or more types, a mixed powder of graphite powder having a particle size range specified in the present invention.
- a mixed powder of graphite powder having a particle size range specified in the present invention I wish I could. That is, graphite powders each having a particle size range specified in the present invention may be used in combination, and graphite powder having a particle size outside the range specified in the present invention may be combined with other graphite powder to form a mixed powder of the present invention. It may be used as a graphite powder having a particle size range specified in.
- the main agent constituting the epoxy resin component is not particularly limited as long as it has an epoxy group.
- o-cresol novolak type epoxy resin alone, biphenyl type epoxy resin alone, and mixtures thereof are preferred.
- the epoxy equivalent of the epoxy resin used in the present invention is not particularly limited, it is preferably 180 to 209 g/eq.
- Phenol resin is preferable as the curing agent. Specific examples thereof include novolac-type phenolic resins, cresol novolac-type phenolic resins, resol-type phenolic resins, aralkyl-modified phenolic resins, biphenyl novolac-type phenolic resins, trisphenolmethane-type phenolic resins, and the like. may also be used in combination of two or more. Among these, novolac type phenolic resins are preferred.
- the hydroxyl equivalent weight of the phenolic resin used in the present invention is not particularly limited, but is preferably 95-140 g/eq, more preferably 100-115 g/eq.
- the curing accelerator is not particularly limited as long as it promotes the reaction between the epoxy group and the curing agent, and includes phosphine compounds, amine compounds, imidazole compounds and the like.
- an imidazole compound having an aryl group at the 2-position is preferably used.
- the aryl group include a phenyl group, a tolyl group, a naphthyl group and the like, and a phenyl group is preferred.
- Specific examples of imidazole compounds having an aryl group at the 2-position include 2-phenylimidazole and 2-phenyl-4-methylimidazole.
- composition used in the present invention may optionally contain optional components such as an internal release agent.
- the internal mold release agent may be appropriately selected from various internal mold release agents conventionally used for molding separators. Specific examples thereof include stearic acid wax, amide wax, montanic acid wax, carnauba Wax, polyethylene wax and the like can be mentioned, and these can be used alone or in combination of two or more.
- the amount of the epoxy resin component is not particularly limited, and is preferably 10 to 50 parts by mass with respect to 100 parts by mass of graphite powder. ⁇ 40 parts by mass is more preferable. In this case, it is preferable to blend 0.98 to 1.08 equivalents, more preferably 0.99 to 1.05 equivalents, of the curing agent with respect to the main agent.
- the amount of the curing accelerator used is not particularly limited, and is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass, with respect to 100 parts by mass of the mixture of the main agent and the curing agent. preferable.
- the amount used is not particularly limited, but is preferably 0.01 to 3.0 parts by mass, more preferably 0.05 to 1.0 part by mass, based on 100 parts by mass of the graphite powder. 5 parts by mass is more preferred.
- the composition used in the present invention may be prepared, for example, by mixing graphite powder, a main agent, a curing agent and a curing accelerator in an arbitrary order and in predetermined proportions.
- a mixer for example, a planetary mixer, a ribbon blender, a Loedige mixer, a Henschel mixer, a rocking mixer, a Nauta mixer, or the like can be used.
- the mixing order is also arbitrary.
- the fuel cell separator of the present invention is preferably obtained by putting the composition into a predetermined mold and compression-molding it.
- the mold to be used include a mold for manufacturing a fuel cell separator, which can form grooves that serve as gas flow paths on one or both surfaces of the molded body.
- Conditions for compression molding are not particularly limited, but the mold temperature is 150 to 190° C. and the molding pressure is 30 to 60 MPa, preferably 30 to 50 MPa.
- the compression molding time is not particularly limited, and can be appropriately set from 3 seconds to 1 hour. After the compression molding, it may be further heated at 150 to 200° C. for 1 to 600 minutes for the purpose of accelerating thermosetting.
- the fuel cell separator (molded body) obtained by compression molding may be roughened for the purpose of removing the skin layer and adjusting the surface roughness.
- the method of roughening treatment is not particularly limited, and may be appropriately selected from various roughening methods such as conventionally known blasting treatment and polishing treatment, but air blasting, wet blasting, barrel Polishing treatment and brush polishing treatment are preferable, blasting treatment using abrasive grains is more preferable, and wet blasting treatment is even more preferable.
- the material of the abrasive grains used in blasting is not particularly limited, and for example, alumina, silicon carbide, zirconia, glass, nylon, stainless steel, etc. can be used, and each of these can be used alone or in combination of two or more. They can be used in combination.
- the ejection pressure during the wet blasting process varies depending on the grain size of the abrasive grains, so it cannot be defined unconditionally.
- the fuel cell separator of the present invention preferably has a bending strength of 45 MPa or more in a 70° C. environment in a three-point bending test conforming to ASTM D790, and a plane bending fatigue test conforming to ASTM D671 TYPE A. , 70° C., the number of repetitions at a stress of 20 MPa is preferably at least 10,000,000 times without breakage. Moreover, in the above three-point bending test, it is preferable that the bending strength in an environment of 23° C. is 55 MPa or more.
- a fuel cell equipped with the fuel cell separator of the present invention having such bending strength and bending fatigue characteristics can maintain stable power generation efficiency over a long period of time.
- polymer electrolyte fuel cells consist of a pair of electrodes sandwiching a polymer electrolyte membrane, and a pair of separators sandwiching these electrodes to form a gas supply and discharge flow path.
- the fuel cell separator of the present invention can be used as part or all of the plurality of separators.
- Average particle size d50 of graphite powder The median diameter was measured by a laser diffraction method using a particle size distribution analyzer (manufactured by Nikkiso Co., Ltd. MT3000).
- Average height of graphite powder 10 to 20 mg of graphite powder is placed on a glass plate, and a laser microscope VK-X100 manufactured by Keyence Corporation is used to obtain a glass plate with an objective lens (NA value 0.55) at a magnification of 50 times. Scan the graphite powder above, then measure the particle height of the graphite powder by profile measurement of the dedicated analysis application VK-H1XA manufactured by Keyence Corporation, calculate the average value of 50 randomly selected particles, and obtain the average height Satoshi.
- Graphite powder 1 (artificial graphite, average particle size d50: 23 ⁇ m, average height: 8 ⁇ m) is added to 100 parts by mass of epoxy resin (o-cresol novolak type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., EOCN-1020-65 , epoxy equivalent 198 g / eq) 20.4 parts by mass, phenolic resin (novolac type phenolic resin, Aika SDK Phenol Co., Ltd.
- epoxy resin o-cresol novolak type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., EOCN-1020-65 , epoxy equivalent 198 g / eq
- phenolic resin novolac type phenolic resin, Aika SDK Phenol Co., Ltd.
- a planarization treatment was applied to obtain a fuel cell separator.
- Example 2 A fuel cell separator was obtained in the same manner as in Example 1, except that graphite powder 1 was changed to graphite powder 2 (artificial graphite, average particle size d50: 35 ⁇ m, average height: 23 ⁇ m).
- Example 3 A fuel cell separator was obtained in the same manner as in Example 1, except that graphite powder 1 was changed to graphite powder 3 (artificial graphite, average particle diameter d50: 50 ⁇ m, average height: 15 ⁇ m).
- Example 4 A fuel cell separator was obtained in the same manner as in Example 1, except that graphite powder 1 was changed to graphite powder 4 (artificial graphite, average particle diameter d50: 80 ⁇ m, average height: 25 ⁇ m).
- Example 5 A fuel cell separator was obtained in the same manner as in Example 1, except that graphite powder 1 was changed to graphite powder 5 (artificial graphite, average particle diameter d50: 50 ⁇ m, average height 30 ⁇ m).
- Example 6 A fuel cell separator was obtained in the same manner as in Example 1, except that graphite powder 1 was changed to graphite powder 6 (artificial graphite, average particle size d50: 80 ⁇ m, average height 44 ⁇ m).
- Example 7 Graphite powder 1 (100 parts by mass) was changed to a mixed powder (average particle size d50: 41 ⁇ m, average height 20 ⁇ m) of graphite powder 2 (70 parts by mass) and graphite powder 3 (30 parts by mass). A fuel cell separator was obtained in the same manner as in Example 1.
- Example 8 Graphite powder 1 (100 parts by mass) was changed to a mixed powder (average particle size d50: 39 ⁇ m, average height 12 ⁇ m) of graphite powder 1 (70 parts by mass) and graphite powder 4 (30 parts by mass). A fuel cell separator was obtained in the same manner as in Example 1.
- Example 1 A fuel cell separator was obtained in the same manner as in Example 1, except that graphite powder 1 was changed to graphite powder 7 (artificial graphite, average particle size d50: 18 ⁇ m, average height 3 ⁇ m).
- Example 2 A fuel cell separator was obtained in the same manner as in Example 1, except that graphite powder 1 was changed to graphite powder 8 (natural graphite, average particle diameter d50: 100 ⁇ m, average height 10 ⁇ m).
- Example 3 A fuel cell separator was obtained in the same manner as in Example 1, except that graphite powder 1 was changed to graphite powder 9 (artificial graphite, average particle size d50: 50 ⁇ m, average height 40 ⁇ m).
- the fuel cell separators produced in Examples 1 to 8 had an average particle size d50 of 20 to 80 ⁇ m and an average height of d50 as graphite powder or a mixed powder of graphite. Since the content is in the range of 30 to 70%, compared to the fuel cell separators produced in Comparative Examples 1 to 4, it can be seen that they have excellent bending strength and bending fatigue characteristics even in an environment of 70 ° C. .
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Abstract
Description
このため、セパレータには、高電気導電性、高ガス不浸透性、化学的安定性、耐熱性および親水性などの諸特性が要求される。
また、近年の燃料電池は運転中の熱コントロールが重視されるようになり、それに伴いセパレータには高い熱伝導率が要求される。
1. 黒鉛粉末、並びに主剤、硬化剤および硬化促進剤を含むエポキシ樹脂成分を含む組成物を成形してなり、
前記黒鉛粉末の平均粒径d50が、20~80μmであり、かつ、前記黒鉛粉末のレーザ顕微鏡で測定される平均高さが、前記平均粒径d50の30~70%であることを特徴とする燃料電池用セパレータ、
2. ASTM D790に準拠する3点曲げ試験において、70℃の環境下での曲げ強度が、45MPa以上である1の燃料電池用セパレータ、
3. ASTM D671 TYPE Aに準拠する平面曲げ疲労試験において、70℃の環境下、応力20MPaでの繰り返し数が1000万回まで未破断である1または2の燃料電池用セパレータ、
4. 前記主剤が、クレゾールノボラック型エポキシ樹脂およびビフェニル型エポキシ樹脂から選ばれる少なくとも1種である1~3のいずれかの燃料電池用セパレータ、
5. 前記硬化剤が、ノボラック型フェノール樹脂である1~4のいずれかの燃料電池用セパレータ、
6. 前記硬化促進剤が、2位にフェニル基を有するイミダゾール化合物を含む1~5のいずれかの燃料電池用セパレータ、
7. 前記黒鉛粉末100質量部に対し、前記エポキシ樹脂成分が25~40質量部含まれる1~6のいずれかの燃料電池用セパレータ
を提供する。
本発明に係る燃料電池用セパレータは、黒鉛粉末、並びに主剤、硬化剤および硬化促進剤を含むエポキシ樹脂成分を含む組成物を成形してなり、黒鉛粉末の平均粒径d50が、20~80μmであり、かつ、黒鉛粉末のレーザ顕微鏡で測定される平均高さが、平均粒径d50の30~70%であることを特徴とする。
なお、本発明における平均粒径d50は、レーザ回折法による粒度分布測定におけるメジアン径として表される。
人造黒鉛粉末としては、従来、燃料電池用セパレータに用いられるものから適宜選択して用いることができる。その具体例としては、針状コークスを焼成した人造黒鉛、塊状コークスを焼成した人造黒鉛等が挙げられる。
一方、天然黒鉛粉末としても、従来、燃料電池用セパレータに用いられるものから適宜選択して用いることができる。その具体例としては、塊状天然黒鉛、鱗片状天然黒鉛等が挙げられる。
なお、これらの黒鉛粉末は、単独で用いても2種以上組み合わせて用いてもよい。単独で用いる場合は、本発明に規定される粒径範囲の黒鉛粉末を適宜選択すればよく、2種以上組み合わせて用いる場合は、黒鉛粉末の混合紛として本発明に規定される粒径範囲となればよい。すなわち、それぞれ本発明に規定される粒径範囲の黒鉛粉末を組み合わせて用いてもよく、また本発明に規定される粒径範囲から外れる黒鉛粉末を他の黒鉛粉末と組合せ、混合粉として本発明に規定される粒径範囲となる黒鉛粉末として用いてもよい。
本発明で用いるエポキシ樹脂のエポキシ当量は、特に限定されるものではないが、180~209g/eqが好ましい。
本発明で用いるフェノール樹脂の水酸基当量は、特に限定されるものではないが、95~140g/eqが好ましく、100~115g/eqがより好ましい。
内部離型剤としては、従来、セパレータの成形に用いられている各種内部離型剤から適宜選択すればよく、その具体例としては、ステアリン酸系ワックス、アマイド系ワックス、モンタン酸系ワックス、カルナバワックス、ポリエチレンワックス等が挙げられ、これらはそれぞれ単独で、または2種以上組み合わせて用いることができる。
この場合、主剤に対して硬化剤を0.98~1.08当量配合することが好ましく、0.99~1.05当量配合することがより好ましい。
また、硬化促進剤の使用量は特に限定されるものではなく、主剤と硬化剤との混合物100質量部に対して、0.1~5質量部が好ましく、0.5~2質量部がより好ましい。
さらに、内部離型剤を用いる場合、その使用量は、特に限定されるものではないが、黒鉛粉末100質量部に対して0.01~3.0質量部が好ましく、0.05~1.5質量部がより好ましい。
なお、内部離型剤を用いる場合、その配合順序も任意である。
圧縮成形の条件は、特に限定されるものではないが、型温度が150~190℃、成形圧力30~60MPa、好ましくは30~50MPaである。
圧縮成形時間は、特に限定されるものではなく、3秒から1時間程度で適宜設定することができる。
なお、圧縮成形後、熱硬化を促進させる目的で、さらに150~200℃で1~600分程加熱してもよい。
粗面化処理の手法としては、特に限定されるものでははく、従来公知のブラスト処理や研磨処理などの各種粗面化法から適宜選択すればよいが、エアブラスト処理、ウェットブラスト処理、バレル研磨処理、ブラシ研磨処理が好ましく、砥粒を用いたブラスト処理がより好ましく、ウェットブラスト処理がより一層好ましい。
ブラスト処理で使用する砥粒の材質としては特に限定されるものではなく、例えば、アルミナ、炭化珪素、ジルコニア、ガラス、ナイロン、ステンレス等を用いることができ、これらはそれぞれ単独で、または2種以上組み合わせて用いることができる。
ウェットブラスト処理時の吐出圧力は、砥粒の粒径等に応じて変動するものであるため一概に規定できないが、0.1~1MPaが好ましく、0.15~0.5MPaがより好ましい。
また、上記3点曲げ試験において、23℃の環境下での曲げ強度が55MPa以上であることが好ましい。
一般的に固体高分子型燃料電池は、固体高分子膜を挟む一対の電極と、これらの電極を挟んでガス供給排出用流路を形成する一対のセパレータとから構成される単位セルが多数併設されてなるものであるが、これら複数個のセパレータの一部または全部として本発明の燃料電池用セパレータを用いることができる。
粒度分布測定装置(日機装(株)製 MT3000)を用い、レーザ回折法によりメジアン径を測定した。
[2]黒鉛粉末の平均高さ
黒鉛粉末10~20mgをガラス板に載せ、(株)キーエンス製レーザ顕微鏡VK-X100を用いて、倍率50倍の対物レンズ(NA値0.55)でガラス板上の黒鉛粉末をスキャンし、次いで、(株)キーエンス製専用解析アプリケーションVK-H1XAのプロファイル計測により黒鉛粉末の粒子高さを測定し、無作為に選んだ50粒子の平均値を求め、平均高さとした。
[3]曲げ強度
23℃および70℃の環境下で、ASTM D790に準拠した3点曲げ試験により測定した。
[4]曲げ疲労
(1)試験片の作製
厚さ2mmの燃料電池用セパレータの平板を、ASTMD671タイプAの形状に機械加工し、試験片とした。
(2)曲げ疲労測定
繰り返し振動疲労試験機((株)東洋精機製作所製、B50型)を用いて、70℃の環境下で周波数30Hz、応力20MPaで試験片が破断に至るまでの繰り返し数を測定した(最大1000万回)。
黒鉛粉末1(人造黒鉛、平均粒径d50:23μm、平均高さ:8μm)100質量部に対し、エポキシ樹脂(o-クレゾールノボラック型エポキシ樹脂、日本化薬(株)製、EOCN-1020-65、エポキシ当量198g/eq)20.4質量部、フェノール樹脂(ノボラック型フェノール樹脂、アイカSDKフェノール(株)製ショウノールBRG-566、水酸基当量103g/eq)10.7質量部、および2-フェニルイミダゾール(以下、2PZ、四国化成工業(株)製)0.25質量部からなるエポキシ樹脂成分をヘンシェルミキサ内に投入し、800rpmで3分間混合して、組成物を調製した。
得られた組成物を燃料電池用セパレータ作製用の金型内に投入し、金型温度185℃、成形圧力36.6MPa、成形時間9秒の条件で圧縮成形し、ガス流路溝を有する240mm×240mm×2mmの緻密質成形体を得た。
次いで、得られた緻密質成形体の全表面に対し、アルミナ研創材(平均粒径:d50=6μm)を用いて吐出圧力0.25MPa、搬送速度1.5m/分の条件でウェットブラストによる粗面化処理を施し、燃料電池用セパレータを得た。
黒鉛粉末1を、黒鉛粉末2(人造黒鉛、平均粒径d50:35μm、平均高さ:23μm)に変更した以外は、実施例1と同様にして燃料電池用セパレータを得た。
黒鉛粉末1を、黒鉛粉末3(人造黒鉛、平均粒径d50:50μm、平均高さ:15μm)に変更した以外は、実施例1と同様にして燃料電池用セパレータを得た。
黒鉛粉末1を、黒鉛粉末4(人造黒鉛、平均粒径d50:80μm、平均高さ:25μm)に変更した以外は、実施例1と同様にして燃料電池用セパレータを得た。
黒鉛粉末1を、黒鉛粉末5(人造黒鉛、平均粒径d50:50μm、平均高さ30μm)に変更した以外は、実施例1と同様にして燃料電池用セパレータを得た。
黒鉛粉末1を、黒鉛粉末6(人造黒鉛、平均粒径d50:80μm、平均高さ44μm)に変更した以外は、実施例1と同様にして燃料電池用セパレータを得た。
黒鉛粉末1(100質量部)を、黒鉛粉末2(70質量部)および黒鉛粉末3(30質量部)の混合粉末(平均粒径d50:41μm、平均高さ20μm)に変更した以外は、実施例1と同様にして燃料電池用セパレータを得た。
黒鉛粉末1(100質量部)を、黒鉛粉末1(70質量部)および黒鉛粉末4(30質量部)の混合粉末(平均粒径d50:39μm、平均高さ12μm)に変更した以外は、実施例1と同様にして燃料電池用セパレータを得た。
黒鉛粉末1を、黒鉛粉末7(人造黒鉛、平均粒径d50:18μm、平均高さ3μm)に変更した以外は、実施例1と同様にして燃料電池用セパレータを得た。
黒鉛粉末1を、黒鉛粉末8(天然黒鉛、平均粒径d50:100μm、平均高さ10μm)に変更した以外は、実施例1と同様にして燃料電池用セパレータを得た。
黒鉛粉末1を、黒鉛粉末9(人造黒鉛、平均粒径d50:50μm、平均高さ40μm)に変更した以外は、実施例1と同様にして燃料電池用セパレータを得た。
黒鉛粉末1(100質量部)を、黒鉛粉末1(70質量部)および黒鉛粉末7(30質量部)の混合粉末(平均粒径d50:21μm、平均高さ4μm)に変更した以外は、実施例1と同様にして燃料電池用セパレータを得た。
Claims (7)
- 黒鉛粉末、並びに主剤、硬化剤および硬化促進剤を含むエポキシ樹脂成分を含む組成物を成形してなり、
前記黒鉛粉末の平均粒径d50が、20~80μmであり、かつ、前記黒鉛粉末のレーザ顕微鏡で測定される平均高さが、前記平均粒径d50の30~70%であることを特徴とする燃料電池用セパレータ。 - ASTM D790に準拠する3点曲げ試験において、70℃の環境下での曲げ強度が、45MPa以上である請求項1記載の燃料電池用セパレータ。
- ASTM D671 TYPE Aに準拠する平面曲げ疲労試験において、70℃の環境下、応力20MPaでの繰り返し数が1000万回まで未破断である請求項1または2記載の燃料電池用セパレータ。
- 前記主剤が、クレゾールノボラック型エポキシ樹脂およびビフェニル型エポキシ樹脂から選ばれる少なくとも1種である請求項1~3のいずれか1項記載の燃料電池用セパレータ。
- 前記硬化剤が、ノボラック型フェノール樹脂である請求項1~4のいずれか1項記載の燃料電池用セパレータ。
- 前記硬化促進剤が、2位にフェニル基を有するイミダゾール化合物を含む請求項1~5のいずれか1項記載の燃料電池用セパレータ。
- 前記黒鉛粉末100質量部に対し、前記エポキシ樹脂成分が25~40質量部含まれる請求項1~6のいずれか1項記載の燃料電池用セパレータ。
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