WO2018070205A1 - 燃料電池緻密質セパレータ用樹脂組成物 - Google Patents
燃料電池緻密質セパレータ用樹脂組成物 Download PDFInfo
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- WO2018070205A1 WO2018070205A1 PCT/JP2017/034032 JP2017034032W WO2018070205A1 WO 2018070205 A1 WO2018070205 A1 WO 2018070205A1 JP 2017034032 W JP2017034032 W JP 2017034032W WO 2018070205 A1 WO2018070205 A1 WO 2018070205A1
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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
- H01M8/02—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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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
- H01M8/02—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
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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
- H01M8/02—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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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- 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 resin composition for a fuel cell dense separator.
- the fuel cell separator plays a role of imparting conductivity to each unit cell, a passage of fuel and air (oxygen) supplied to the unit cell, and a role as a separation boundary wall between them. For this reason, the separator is required to have various properties such as high electrical conductivity, high gas impermeability, chemical stability, heat resistance and hydrophilicity.
- a carbon separator formed from a separator composition containing graphite powder and a resin component is generally formed by heat compression molding the composition in a mold for a predetermined time.
- Patent Document 1 includes an epoxy resin, a curing agent, a curing accelerator, and graphite particles having a ratio of 70 to 80% by mass with respect to the total solid content.
- a method of manufacturing a fuel cell separator includes a step of compression molding a molding material to be molded in a mold for 10 to 30 seconds.
- the productivity is improved, but the retention time in the mold is short, so that the resin composition is cured.
- the fuel cell separator obtained by this manufacturing method has a TOC (total organic carbon) value of 15 ppm or more indicating elution (see Examples in Patent Document 1), which has a problem of adversely affecting battery performance. It was.
- the present invention has been made in view of such circumstances, and for a dense fuel cell separator capable of providing a dense fuel cell separator that satisfies a predetermined performance even when compression-molded in less than 10 seconds. It aims at providing a resin composition.
- the present inventors have obtained a composition comprising a graphite powder having a predetermined spring back and an average particle diameter, and an epoxy resin component containing a predetermined curing accelerator. It has been found that a dense separator for fuel cells having good performance can be obtained even by compression molding in a short time of less than 10 seconds.
- the present invention 1.
- Graphite powder and an epoxy resin component containing a main agent, a curing agent and a curing accelerator, the graphite powder has a spring back of 20 to 70%, an average particle diameter d50 of 30 to 100 ⁇ m, and the curing accelerator
- a resin composition for a dense fuel cell separator which is an imidazole compound having an aryl group at the 2-position; 2.
- a dense separator for a fuel cell of 6 or 7 having a TOC of 7 ppm or less 9.
- a method for producing a dense separator for a fuel cell comprising compression molding the resin composition for a dense fuel cell separator according to any one of 1 to 5, 10. The method for producing a dense separator for a fuel cell according to 9 wherein the compression molding time is less than 10 seconds.
- a dense separator for a fuel cell obtained by using the resin composition of the present invention in a compression molding time of less than 10 seconds has excellent characteristics such as low specific resistance, high glass transition point, and low TOC. .
- a fuel cell dense separator resin composition according to the present invention includes graphite powder and an epoxy resin component containing a main agent, a curing agent and a curing accelerator, and the graphite powder has a spring back of 20 to 70% and an average particle size.
- the diameter d50 is 30 to 100 ⁇ m
- the curing accelerator is an imidazole compound having an aryl group at the 2-position.
- the spring back in the present invention means a spring back of the powder itself.
- the powder is put into a predetermined mold and compressed at a predetermined pressure. This is a value calculated from (Y ⁇ X) / X ⁇ 100 (%) from the powder height X and the powder height Y when the pressure is released.
- the graphite powder of the present invention is not particularly limited as long as it satisfies the spring back as a whole, and any of natural graphite and artificial graphite may be used.
- Artificial graphite may be appropriately selected from those conventionally used for fuel cell separators. Specific examples thereof include artificial graphite obtained by firing acicular coke, artificial graphite obtained by firing massive coke, and the like.
- natural graphite may be appropriately selected from those conventionally used for fuel cell separators. Specific examples thereof include massive natural graphite and scaly natural graphite.
- the spring back of these graphite powders may be measured by the method described later, and the one in the range defined in the present invention may be selected as appropriate.
- These graphite powders may be used alone or in combination of two or more.
- a graphite powder having a spring back of less than 20 to 70% may be used together with the graphite powder having the predetermined spring back.
- a graphite powder having a spring back of less than 20% and a graphite powder having a springback of more than 70% can be used in combination. Examples of such graphite powder include natural graphite and artificial graphite, and these can be used alone or in combination of two or more.
- the springback of the graphite (carbon material) powder used can be adjusted to 20 to 70%
- Other carbon materials such as black and ketjen black may be added. These carbon materials can be used alone or in combination of two or more.
- the content ratio of the graphite powder is that of the graphite powder obtained by mixing.
- the graphite powder of 20 to 70% of the springback contains more than 20% by mass in the total graphite powder. More preferably, it is contained in an amount of 50% by mass or more, and more preferably 90% by mass or more.
- the main component constituting the epoxy resin component is not particularly limited as long as it has an epoxy group.
- o-cresol novolac type epoxy resins alone, biphenyl type epoxy resins alone, and mixtures thereof are preferable.
- the epoxy equivalent of the epoxy resin used in the present invention is not particularly limited, but is preferably 180 to 209 g / eq.
- the curing agent constituting the epoxy resin component is not particularly limited as long as it is a phenol resin.
- phenol resin include novolak type phenol resins, cresol novolac type phenol resins, resol type phenol resins, and aralkyl-modified phenol resins. , Biphenyl novolac type phenol resin, trisphenol methane type phenol resin, and the like. These may be used alone or in combination of two or more. Among these, a novolac type phenol resin is preferable.
- the hydroxyl equivalent of the phenol resin used in the present invention is not particularly limited, but is preferably 95 to 240 g / eq, more preferably 100 to 115 g / eq.
- an imidazole compound having an aryl group at the 2-position is used as the curing accelerator constituting the epoxy resin component.
- the aryl group include a phenyl group, a tolyl group, and a naphthyl group, and a phenyl group is preferable.
- Specific examples of the imidazole compound having an aryl group at the 2-position include 2-phenylimidazole and 2-phenyl-4-methylimidazole.
- an imidazole compound having a short-chain alkyl group such as 2-methylimidazole is used as a curing accelerator, the curing time is too fast and uniform molding cannot be performed, whereas a long-chain alkyl group such as 2-undecylimidazole is not possible.
- an imidazole compound having a curing accelerator as a curing accelerator, the curing time is too slow and the curing does not end in a short time.
- the amount of the curing accelerator used is not particularly limited, and can be about 0.1 to 5 parts by mass with respect to 100 parts by mass of the mixture of the epoxy resin and the phenol resin. Part by mass is preferred.
- the compounding amount of the epoxy resin component can be about 10.0 to 50.0 parts by mass with respect to 100 parts by mass of the graphite powder. 20 to 40 parts by mass is preferable. In this case, it is preferable to add 0.98 to 1.08 equivalent of phenol resin to epoxy resin, and more preferable to add 0.99 to 1.05 equivalent.
- the internal mold release agent may be appropriately selected from various internal mold release agents conventionally used for molding of separators. Specific examples thereof include stearic acid wax, amide wax, montanic acid wax, carnauba. A wax, polyethylene wax, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.
- the amount of use is not particularly limited, but is preferably 0.01 to 1.5 parts by weight, preferably 0.05 to 1.0 parts by weight with respect to 100 parts by weight of the graphite powder. Part by mass is more preferable.
- the resin composition of the present invention may be prepared, for example, by mixing each of graphite powder, epoxy resin, phenol resin, and curing accelerator in a predetermined ratio in an arbitrary order.
- a planetary mixer for example, a ribbon blender, a Redige mixer, a Henschel mixer, a rocking mixer, a nauter mixer, or the like can be used.
- the compounding order is also arbitrary.
- the dense separator for a fuel cell of the present invention can be obtained by putting the above composition into a predetermined mold and compression molding.
- the mold to be used include a mold for producing a separator for a fuel cell, which can form a groove serving as a gas flow path on one surface or both surfaces of the surface of the molded body.
- the compression molding conditions are not particularly limited, but the mold temperature is 150 to 190 ° C., the molding pressure is 30 to 60 MPa, preferably 30 to 50 MPa.
- a separator having practical characteristics can be obtained in a short compression molding time of less than 10 seconds, and the production efficiency of the separator can be increased.
- the lower limit of the compression molding time may be appropriately set according to the desired performance, but it is preferably 3 seconds or more, and more preferably 5 seconds or more in consideration of obtaining a separator having practical specific resistance and strength. 7 seconds or more is even more preferable.
- the upper limit is not particularly limited, and it can be a compression molding time of about 1 hour as usual, but the performance does not improve so much even if the compression molding time is lengthened. Therefore, about 60 seconds is preferable, and about 30 seconds is more preferable.
- it may be further heated at 150 to 200 ° C. for about 1 to 600 minutes. However, in the resin composition of the present invention, it is practically sufficient even if this step is omitted. A separator having performance can be obtained.
- the dense separator for a fuel cell obtained by compression molding may be subjected to a roughening treatment for the purpose of removing the skin layer and adjusting the surface roughness.
- the surface roughening method is not particularly limited, and may be appropriately selected from conventionally known surface roughening methods such as blasting and polishing, but air blasting, wet blasting, barrel Polishing treatment and brush polishing treatment are preferred, blasting treatment using abrasive grains is more preferred, and wet blasting treatment is even more preferred.
- Alumina, silicon carbide, zirconia, glass, nylon, stainless steel, or the like can be used as the material for the abrasive used in the blast treatment, and these can be used alone or in combination of two or more.
- the discharge pressure at the time of wet blasting varies depending on the grain size of the abrasive grains and cannot be defined unconditionally, but is preferably 0.1 to 1 MPa, more preferably 0.15 to 0.5 MPa.
- the dense separator for a fuel cell obtained by using the resin composition of the present invention has characteristics such as a specific resistance of 15 m ⁇ ⁇ cm or less, a glass transition point of 135 ° C. or more, and a bending strength of 50 MPa or more. Moreover, the value of TOC (total organic carbon) which shows elution is also 7 ppm or less.
- a fuel cell including the dense separator for a fuel cell of the present invention having such characteristics can maintain stable power generation efficiency over a long period of time.
- a polymer electrolyte fuel cell has a large number of unit cells each composed of a pair of electrodes sandwiching a polymer electrolyte membrane and a pair of separators forming a gas supply / discharge channel sandwiching these electrodes.
- the fuel cell dense separator of the present invention can be used as a part or all of the plurality of separators.
- TOC The test piece was placed in 500 mL of ion exchange water and heated at an internal temperature of 90 ° C. for 1000 hours. After the heating, the test piece was taken out, and the TOC in the ion exchange water was measured with a TOC meter (TOC-L manufactured by Shimadzu Corporation).
- Epoxy resin 1 (o-cresol novolac type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., EOCN) with respect to 100 parts by mass of graphite powder 1 (artificial graphite, needle-shaped, spring back 23%, average particle size (d50) 50 ⁇ m) -1020-65, epoxy equivalent 198 g / eq) 20.4 parts by mass, phenol resin (novolak type phenol resin, Aika SDK Phenol Co., Ltd.
- a dense molded body of ⁇ 240 mm ⁇ 2 mm was obtained.
- Surface treatment was performed to obtain a dense separator for a fuel cell.
- Example 2 A composition was prepared and compression-molded in the same manner as in Example 1 except that the graphite powder 1 was changed to graphite powder 2 (artificial graphite, needle-shaped, springback 30%, average particle size (d50) 50 ⁇ m), A dense separator for a fuel cell was obtained.
- Example 3 A composition was prepared and compression-molded in the same manner as in Example 1 except that the graphite powder 1 was changed to graphite powder 3 (artificial graphite, needle-like, springback 40%, average particle size (d50) 50 ⁇ m), A dense separator for a fuel cell was obtained.
- Example 4 A composition was prepared and compression-molded in the same manner as in Example 1 except that the graphite powder 1 was changed to graphite powder 4 (artificial graphite, lump, springback 45%, average particle size (d50) 30 ⁇ m), and fuel. A dense separator for a battery was obtained.
- Example 5 A composition was prepared and compression-molded in the same manner as in Example 1 except that the graphite powder 1 was changed to graphite powder 5 (artificial graphite, lump, springback 50%, average particle size (d50) 50 ⁇ m), and fuel. A dense separator for a battery was obtained.
- Example 6 A composition was prepared and compression-molded in the same manner as in Example 1 except that the graphite powder 1 was changed to graphite powder 6 (artificial graphite, lump, springback 55%, average particle size (d50) 70 ⁇ m), and fuel. A dense separator for a battery was obtained.
- Example 7 A composition was prepared and compression-molded in the same manner as in Example 1 except that the graphite powder 1 was changed to graphite powder 7 (artificial graphite, lump, springback 60%, average particle size (d50) 100 ⁇ m), and fuel A dense separator for a battery was obtained.
- Example 8 Except for changing 100 parts by mass of graphite powder 1 to 20 parts by mass of graphite powder 1 and 80 parts by mass of graphite powder 9 (artificial graphite, lump, springback 75%, average particle size (d50) 50 ⁇ m). A composition was prepared and compression molded in the same manner as in Example 1 to obtain a dense separator for fuel cells.
- Example 9 Except for changing 100 parts by weight of graphite powder 1 to 30 parts by weight of graphite powder 8 (natural graphite, scaly, spring back 10%, average particle size (d50) 50 ⁇ m) and 970 parts by weight of graphite powder, A composition was prepared and compression molded in the same manner as in Example 1 to obtain a dense separator for fuel cells.
- Example 10 20.4 parts by mass of epoxy resin 1 is added to 19.8 parts by mass of epoxy resin 3 (biphenyl type epoxy resin, manufactured by Mitsubishi Chemical Corporation, jER YX4000, epoxy equivalent 183 g / eq). A composition was prepared and compression-molded in the same manner as in Example 4 except that the amount was changed to 3 parts by mass to obtain a dense separator for a fuel cell.
- epoxy resin 3 biphenyl type epoxy resin, manufactured by Mitsubishi Chemical Corporation, jER YX4000, epoxy equivalent 183 g / eq.
- Example 11 A composition was prepared and compressed in the same manner as in Example 5 except that 20.4 parts by mass of epoxy resin 1 was changed to 19.8 parts by mass of epoxy resin 3 and the addition amount of phenol resin was changed to 11.3 parts by mass. Molding was performed to obtain a dense separator for a fuel cell.
- Example 12 A composition was prepared and compressed in the same manner as in Example 6 except that 20.4 parts by mass of epoxy resin 1 was changed to 19.8 parts by mass of epoxy resin 3 and the addition amount of phenol resin was changed to 11.3 parts by mass. Molding was performed to obtain a dense separator for a fuel cell.
- Example 13 A composition was prepared and compressed in the same manner as in Example 7 except that 20.4 parts by mass of epoxy resin 1 was changed to 19.8 parts by mass of epoxy resin 3 and the addition amount of phenol resin was changed to 11.3 parts by mass. Molding was performed to obtain a dense separator for a fuel cell.
- Example 14 Example except that 20.7 parts by mass of epoxy resin 1 was changed to 10.1 parts by mass of epoxy resin 1 and 10.1 parts by mass of epoxy resin 3 and the addition amount of phenol resin was changed to 11.0 parts by mass.
- the composition was prepared and compression molded in the same manner as in Example 5 to obtain a dense separator for fuel cells.
- Example 15 20.7 parts by mass of epoxy resin 1 14.4 parts by mass of epoxy resin 1 and epoxy resin 2 (o-cresol novolak type epoxy resin, Nippon Kayaku Co., Ltd., EOCN-103S, epoxy equivalent 214 g / eq) 6 A composition was prepared and compression-molded in the same manner as in Example 5 except that the addition amount of phenolic resin was changed to 10.6 parts by mass in the combination of 2 parts by mass, and a dense separator for fuel cells was obtained. .
- Example 16 Example except that 20.7 parts by mass of epoxy resin 1 was changed to 5.0 parts by mass of epoxy resin 2 and 15.1 parts by mass of epoxy resin 3 and the addition amount of phenol resin was changed to 11.0 parts by mass.
- the composition was prepared and compression molded in the same manner as in Example 5 to obtain a dense separator for fuel cells.
- Example 1 A composition was prepared and compression-molded in the same manner as in Example 1 except that the graphite powder 1 was changed to the graphite powder 8 to obtain a dense separator for fuel cells.
- Example 2 A composition was prepared and compression-molded in the same manner as in Example 1 except that the graphite powder 1 was changed to the graphite powder 9 to obtain a dense fuel cell separator.
- Example 3 A composition was prepared and compression-molded in the same manner as in Example 1 except that the graphite powder 1 was changed to graphite powder 10 (artificial graphite, lump, springback 40%, average particle size (d50) 20 ⁇ m), and fuel. A dense separator for a battery was obtained.
- Example 4 A composition was prepared and compression-molded in the same manner as in Example 1 except that the graphite powder 1 was changed to graphite powder 11 (artificial graphite, lump, springback 65%, average particle size (d50) 110 ⁇ m), and fuel A dense separator for a battery was obtained.
- Example 1 except that graphite powder 1 was changed to graphite powder 9, 20.4 parts by mass of epoxy resin 1, 19.8 parts by mass of epoxy resin 3 and 11.3 parts by mass of phenol resin.
- the composition was prepared and compression molded in the same manner as above to obtain a dense separator for fuel cells.
- Example 1 except that graphite powder 1 was changed to graphite powder 10, 20.4 parts by mass of epoxy resin 1, 19.8 parts by mass of epoxy resin 3 and 11.3 parts by mass of phenol resin.
- the composition was prepared and compression molded in the same manner as above to obtain a dense separator for fuel cells.
- Example 7 Example 1 except that graphite powder 1 was changed to graphite powder 11, 20.4 parts by mass of epoxy resin 1, 19.8 parts by mass of epoxy resin 3, and 11.3 parts by mass of the phenol resin added. The composition was prepared and compression molded in the same manner as above to obtain a dense separator for fuel cells.
- the separators of Examples 1 to 16 obtained from the compositions in which the graphite springback and the average particle size are within the range defined in the present invention have a specific resistance of 15 m ⁇ ⁇ cm.
- Tg is 135 ° C. or more
- bending strength is 50 MPa or more
- bending elastic modulus is 9.5 GPa or more
- TOC is 7 ppm or less, which are suitable values for a dense separator for a fuel cell.
- the separators of Comparative Examples 1 to 8 use a graphite springback or a composition having an average particle size outside the range defined in the present invention, the specific resistance and / or strength is insufficient. I understand.
- Comparative Example 1 since the spring back of the graphite powder is too low, it is considered that the resin has been cured (glass transition point 167 ° C.), but the bending strength is low.
- Comparative Example 2 and Comparative Example 5 since the spring back of the graphite powder is too high, the curing of the resin is not completed at a molding time of 9 seconds (glass transition point 125 ° C.), and the specific resistance and TOC are high.
- Comparative Example 3 and Comparative Example 6 since the particle size of the graphite powder is too small, it is considered that the curing of the resin is finished, but the specific resistance is high.
- Comparative Example 4 and Comparative Example 7 since the particle size of the graphite powder is too large, it is considered that the curing of the resin is finished, but the bending strength is low.
- Example 17 A composition was prepared and compression-molded in the same manner as in Example 5 except that the curing accelerator 2PZ was changed to 2-phenyl-4-methylimidazole (hereinafter 2P4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.). A dense separator for a battery was obtained.
- 2P4MZ 2-phenyl-4-methylimidazole
- Example 18 The composition was prepared and compression-molded in the same manner as in Example 5 except that 2PZ0.25 parts by weight of the curing accelerator was changed to a combination of 0.125 parts by weight of 2PZ and 0.125 parts by weight of 2P4MZ. A separator was obtained.
- Example 19 The composition was prepared and compression-molded in the same manner as in Example 5 except that 2PZ0.25 parts by weight of the curing accelerator was changed to a combination of 0.075 parts by weight of 2PZ and 0.175 parts by weight of 2P4MZ. A separator was obtained.
- Example 20 The composition was prepared and compression-molded in the same manner as in Example 5 except that 2PZ0.25 parts by weight of the curing accelerator was changed to a combination of 0.175 parts by weight of 2PZ and 0.075 parts by weight of 2P4MZ. A separator was obtained.
- Comparative Example 8 A composition was prepared and compression-molded in the same manner as in Example 5 except that the curing accelerator 2PZ was changed to 2-ethyl-4-methylimidazole (hereinafter 2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.). A dense separator for a battery was obtained.
- 2E4MZ 2-ethyl-4-methylimidazole
- Example 9 A composition was prepared and compression-molded in the same manner as in Example 5 except that the curing accelerator 2PZ was changed to 2-methylimidazole (hereinafter, 2MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.). A separator was obtained.
- 2MZ 2-methylimidazole
- Example 10 A composition was prepared and compression-molded in the same manner as in Example 5 except that the curing accelerator 2PZ was changed to 2-undecylimidazole (hereinafter, C11Z, manufactured by Shikoku Kasei Kogyo Co., Ltd.). A quality separator was obtained.
- the curing accelerator 2PZ was changed to 2-undecylimidazole (hereinafter, C11Z, manufactured by Shikoku Kasei Kogyo Co., Ltd.).
- C11Z 2-undecylimidazole
- Example 11 A composition was prepared and compression-molded in the same manner as in Example 5 except that the curing accelerator 2PZ was changed to 2-heptadecylimidazole (hereinafter, C17Z, manufactured by Shikoku Kasei Kogyo Co., Ltd.). A quality separator was obtained.
- the curing accelerator 2PZ was changed to 2-heptadecylimidazole (hereinafter, C17Z, manufactured by Shikoku Kasei Kogyo Co., Ltd.).
- C17Z 2-heptadecylimidazole
- composition was prepared and compression-molded in the same manner as in Example 5 except that the curing accelerator 2PZ was changed to triphenylphosphine (hereinafter, TPP) to obtain a dense fuel cell separator.
- TPP triphenylphosphine
- the separators of Examples 17 to 20 obtained from the composition containing an imidazole compound having a phenyl group at the 2-position as a curing accelerator had a specific resistance of 13 m ⁇ ⁇ cm or less and a Tg of 160 ° C.
- the bending strength is 60 MPa or more
- the bending elastic modulus is 11 GPa or more
- the TOC is 7 ppm or less, which are suitable values for a dense separator for a fuel cell.
- the separators of Comparative Examples 8 to 12 have high specific resistance and low strength because an imidazole compound or triphenylphosphine having no phenyl group at the 2-position is used as a curing accelerator.
- Comparative Example 8 and Comparative Example 9 since the activity of the curing accelerator is too high, a viscosity increase due to an abrupt curing reaction occurs in the mold, resulting in a defective molding and a high specific resistance. Yes.
- Comparative Examples 10 to 12 since the activity of the curing accelerator is too low, the molding is not completed in 9 seconds, the glass transition point is lowered, the specific resistance and TOC are high, and the bending strength is low.
- Examples 21 and 22 and Comparative Examples 13 and 14 Using the resin compositions prepared in Example 1, Example 5, Comparative Example 1 and Comparative Example 2, the compression time was changed to 3 seconds, 5 seconds, 7 seconds, 12 seconds, 15 seconds, 20 seconds and 30 seconds. A dense separator for a fuel cell was produced in the same manner as in Example 1 except that the above was performed. About each obtained separator, specific resistance, bending strength, and TOC were measured. The results are shown in Tables 4-6. In each table, the results of Examples 1 and 5 and Comparative Examples 1 and 2 (molding time 9 seconds) are also shown. These results are shown in FIGS.
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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。
近年、燃料電池セパレータの低コスト化のために、その生産効率の向上が求められており、圧縮成形時間の短縮等、製造工程における時間の短縮化が望まれている。
しかし、特許文献1の製造方法において、金型内で圧縮成形時間として採用されている10~30秒では、生産性は向上するものの、金型内での保持時間が短いため樹脂組成物の硬化が終了しておらず、硬化を完了させるために、さらに押圧下での加熱処理が必要となるのみならず、そのための設備も必要となるなど、生産効率という点で改良の余地がある。
しかも、この製造方法で得られた燃料電池セパレータは、溶出性を示すTOC(全有機炭素)の値が15ppm以上であり(特許文献1実施例参照)、電池性能に悪影響を及ぼすという問題があった。
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み、前記黒鉛粉末のスプリングバックが20~70%、かつ、平均粒径d50が30~100μmであり、前記硬化促進剤が、2位にアリール基を有するイミダゾール化合物であることを特徴とする燃料電池緻密質セパレータ用樹脂組成物、
2. 前記スプリングバックが、20~65%である1の燃料電池緻密質セパレータ用樹脂組成物、
3. 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または2の燃料電池緻密質セパレータ用樹脂組成物、
4. 前記硬化剤が、ノボラック型フェノール樹脂である1~3のいずれかの燃料電池緻密質セパレータ用樹脂組成物、
5. 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である1~4のいずれかの燃料電池緻密質セパレータ用樹脂組成物、
6. 1~5のいずれかの燃料電池緻密質セパレータ用樹脂組成物を成形してなる燃料電池用緻密質セパレータ、
7. 固有抵抗が15mΩ・cm以下、ガラス転移点135℃以上、かつ、曲げ強度50MPa以上である6の燃料電池用緻密質セパレータ、
8. TOCが、7ppm以下である6または7の燃料電池用緻密質セパレータ、
9. 1~5のいずれかの燃料電池緻密質セパレータ用樹脂組成物を、圧縮成形することを特徴とする燃料電池用緻密質セパレータの製造方法、
10. 前記圧縮成形の時間が、10秒未満である9の燃料電池用緻密質セパレータの製造方法
を提供する。
また、本発明の樹脂組成物を用い、10秒未満の圧縮成形時間で得られた燃料電池用緻密質セパレータは、低固有抵抗、高ガラス転移点、低TOCという優れた特性を有している。
本発明に係る燃料電池緻密質セパレータ用樹脂組成物は、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み、黒鉛粉末のスプリングバックが20~70%、かつ、平均粒径d50が30~100μmであり、硬化促進剤が、2位にアリール基を有するイミダゾール化合物であることを特徴とする。
本発明者らは、スプリングバックの低い黒鉛粉末を用いることにより、成形温度、成形圧力を上げたのと同様の効果が得られ、圧縮成形時間を短くできること、およびスプリングバックが低すぎると得られるセパレータの強度が弱くなることを知見した。
このような観点から、本発明では、その粉末全体のスプリングバックが20~70%の黒鉛粉末を用いる。この範囲のスプリングバックの黒鉛を採用することで、圧縮成形時間を短くできるとともに、薄肉で均一なセパレータを得ることができる。
人造黒鉛としては、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ればよい。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ればよい。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。
いずれにおいても、後述の手法によってこれら黒鉛粉末のスプリングバックを測定し、本発明に規定される範囲のものを適宜選択すればよい。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。
そのような黒鉛粉末としては、天然黒鉛、人造黒鉛が挙げられ、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。
さらに、本発明では、用いる黒鉛(炭素材料)粉末全体のスプリングバックが20~70%に調整できる限り、電極を粉砕したもの、石炭系ピッチ、石油系ピッチ、コークス、活性炭、ガラス状カーボン、アセチレンブラック、ケッチェンブラック等のその他の炭素材料を添加してもよい。これらの炭素材料は、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。
また、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ないが、95~240g/eqが好ましく、100~115g/eqがより好ましい。
アリール基の具体例としては、フェニル基、トリル基、ナフチル基等が挙げられるが、フェニル基が好ましい。
2位にアリール基を有するイミダゾール化合物の具体例としては、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール等が挙げられる。
なお、2-メチルイミダゾール等の短鎖アルキル基を有するイミダゾール化合物を硬化促進剤として用いると、硬化時間が速すぎて均一な成形ができず、一方、2-ウンデシルイミダゾール等の長鎖アルキル基を有するイミダゾール化合物を硬化促進剤として用いると、硬化時間が遅すぎて短時間では硬化が終了しない。
この場合、エポキシ樹脂に対してフェノール樹脂を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。
内部離型剤を用いる場合、その使用量としては、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0.01~1.5質量部が好ましく、0.05~1.0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。
上述したとおり、本発明の樹脂組成物を用いることで、10秒未満という短い圧縮成形時間で実用可能な特性を有するセパレータを得ることができ、セパレータの生産効率を上げることができる。
圧縮成形時間の下限は、所望の性能に応じて適宜設定すればよいが、実用的な固有抵抗および強度等を有するセパレータを得ることを考慮すると、3秒以上が好ましく、5秒以上がより好ましく、7秒以上がより一層好ましい。一方、上限については、特に限定されるものではなく、従来どおりの1時間程度の圧縮成形時間とすることもできるが、圧縮成形時間を長くしても性能はそれほど向上しないため、実用上の観点から、60秒程度が好ましく、30秒程度がより好ましい。
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が、本発明の樹脂組成物ではこの工程を省略しても実用上十分な性能を有するセパレータを得ることができる。
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、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、溶出性を示すTOC(全有機炭素)の値が、7ppm以下という特性をも有している。
このような特性を有する本発明の燃料電池用緻密質セパレータを備えた燃料電池は、長期に亘って安定した発電効率を維持することができる。
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緻密質セパレータを用いることができる。
[1]黒鉛粉末のスプリングバック
図1(A)に示される内径15mmの金型に測定試料である黒鉛粉末2gを入れ、試料の上面を平らにした後、上型に5秒で5.4tの荷重がかかるようプレス機で圧縮した(図1(B)参照)。圧縮状態を30秒間保持したのち、荷重を一気に解放した。ハイトゲージで各状態の上型上面の高さを測定し、次の計算式によりスプリングバックを求めた。
L0:測定試料が入っていない状態の上型の高さ(mm)
L1:荷重をかけた状態の上型の高さ(mm)
L2:荷重を解放した状態の上型の高さ(mm)
スプリングバック(%)=(L2-L1)/(L1-L0)×100
[2]平均粒径
粒度分布測定装置(日機装(株)製)により測定した。
[3]固有抵抗
JIS H0602(シリコン単結晶およびシリコンウエーハの4探針による抵抗率測定方法)に基づいて測定した。
[4]ガラス転移点
熱分析装置(TAインスツルメンツ社製、Q400TMA)を使用し、昇温速度1℃/min、荷重5gの条件で測定を行い、得られた熱膨張係数の変曲点をガラス転移点とした。
[5]強度試験(曲げ強度、曲げ弾性率、曲げひずみ)
セパレータから切り出した100×20×2mmの試験片を用い、JIS K 6911「熱硬化性プラスチックの一般試験方法」に準じて、支点間距離40mmで3点曲げ試験を行い、曲げ強度、曲げ弾性率、曲げひずみを測定した。
[6]TOC
上記試験片をイオン交換水500mL中に入れ、内温90℃で1000時間加熱した。加熱終了後に試験片を取り出し、イオン交換水中のTOCをTOC計((株)島津製作所製 TOC-L)により測定した。
黒鉛粉末1(人造黒鉛、針状、スプリングバック23%、平均粒径(d50)50μm)100質量部に対し、エポキシ樹脂1(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、燃料電池緻密質セパレータ用樹脂組成物を調製した。
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、燃料電池用緻密質セパレータを得た。
黒鉛粉末1を、黒鉛粉末2(人造黒鉛、針状、スプリングバック30%、平均粒径(d50)50μm)に変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
黒鉛粉末1を、黒鉛粉末3(人造黒鉛、針状、スプリングバック40%、平均粒径(d50)50μm)に変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
黒鉛粉末1を、黒鉛粉末4(人造黒鉛、塊状、スプリングバック45%、平均粒径(d50)30μm)に変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
黒鉛粉末1を、黒鉛粉末5(人造黒鉛、塊状、スプリングバック50%、平均粒径(d50)50μm)に変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
黒鉛粉末1を、黒鉛粉末6(人造黒鉛、塊状、スプリングバック55%、平均粒径(d50)70μm)に変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
黒鉛粉末1を、黒鉛粉末7(人造黒鉛、塊状、スプリングバック60%、平均粒径(d50)100μm)に変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
黒鉛粉末1 100質量部を、黒鉛粉末1 20質量部と、黒鉛粉末9(人造黒鉛、塊状、スプリングバック75%、平均粒径(d50)50μm)80質量部の組み合わせに変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
黒鉛粉末1 100質量部を、黒鉛粉末8(天然黒鉛、鱗片状、スプリングバック10%、平均粒径(d50)50μm)30質量部と、黒鉛粉末9 70質量部の組み合わせに変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
エポキシ樹脂1 20.4質量部を、エポキシ樹脂3(ビフェニル型エポキシ樹脂、三菱化学(株)製、jER YX4000、エポキシ当量183g/eq)19.8質量部に、フェノール樹脂の添加量を11.3質量部に変更した以外は、実施例4と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
エポキシ樹脂1 20.4質量部を、エポキシ樹脂3 19.8質量部に、フェノール樹脂の添加量を11.3質量部に変更した以外は、実施例5と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
エポキシ樹脂1 20.4質量部を、エポキシ樹脂3 19.8質量部に、フェノール樹脂の添加量を11.3質量部に変更した以外は、実施例6と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
エポキシ樹脂1 20.4質量部を、エポキシ樹脂3 19.8質量部に、フェノール樹脂の添加量を11.3質量部に変更した以外は、実施例7と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
エポキシ樹脂1 20.7質量部を、エポキシ樹脂1 10.1質量部およびエポキシ樹脂3 10.1質量部の組み合わせに、フェノール樹脂の添加量を11.0質量部に変更した以外は、実施例5と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
エポキシ樹脂1 20.7質量部を、エポキシ樹脂1 14.4質量部およびエポキシ樹脂2(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-103S、エポキシ当量214g/eq)6.2質量部の組み合わせに、フェノール樹脂の添加量を10.6質量部に変更した以外は、実施例5と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
エポキシ樹脂1 20.7質量部を、エポキシ樹脂2 5.0質量部およびエポキシ樹脂3 15.1質量部の組み合わせに、フェノール樹脂の添加量を11.0質量部に変更した以外は、実施例5と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
黒鉛粉末1を、黒鉛粉末8に変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
黒鉛粉末1を、黒鉛粉末9に変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
黒鉛粉末1を、黒鉛粉末10(人造黒鉛、塊状、スプリングバック40%、平均粒径(d50)20μm)に変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
黒鉛粉末1を、黒鉛粉末11(人造黒鉛、塊状、スプリングバック65%、平均粒径(d50)110μm)に変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
黒鉛粉末1を、黒鉛粉末9に、エポキシ樹脂1 20.4質量部を、エポキシ樹脂3 19.8質量部に、フェノール樹脂の添加量を11.3質量部に変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
黒鉛粉末1を、黒鉛粉末10に、エポキシ樹脂1 20.4質量部を、エポキシ樹脂3 19.8質量部に、フェノール樹脂の添加量を11.3質量部に変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
黒鉛粉末1を、黒鉛粉末11に、エポキシ樹脂1 20.4質量部を、エポキシ樹脂3 19.8質量部に、フェノール樹脂の添加量を11.3質量部に変更した以外は、実施例1と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
比較例1~8のセパレータは、黒鉛のスプリングバックまたは平均粒径が本発明に規定される範囲外である組成物を用いているため、固有抵抗もしくは強度、またはその双方において不十分であることがわかる。
具体的には、比較例1では、黒鉛粉末のスプリングバックが低すぎるため、樹脂の硬化は終了していると考えられるが(ガラス転移点167℃)、曲げ強度が低くなっている。
比較例2および比較例5では、黒鉛粉末のスプリングバックが高すぎるため、成形時間9秒では樹脂の硬化が終了せず(ガラス転移点125℃)、固有抵抗、TOCが高くなっている。
比較例3および比較例6では、黒鉛粉末の粒径が小さすぎるため、樹脂の硬化は終了していると考えられるが、固有抵抗が高くなっている。
比較例4および比較例7では、黒鉛粉末の粒径が大きすぎるため、樹脂の硬化は終了していると考えられるが、曲げ強度が低くなっている。
硬化促進剤2PZを、2-フェニル-4-メチルイミダゾール(以下、2P4MZ、四国化成工業(株)製)に変更した以外は、実施例5と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
硬化促進剤2PZ0.25質量部を、2PZ0.125質量部および2P4MZ0.125質量部の組み合わせに変更した以外は、実施例5と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
硬化促進剤2PZ0.25質量部を、2PZ0.075質量部および2P4MZ0.175質量部の組み合わせに変更した以外は、実施例5と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
硬化促進剤2PZ0.25質量部を、2PZ0.175質量部および2P4MZ0.075質量部の組み合わせに変更した以外は、実施例5と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
硬化促進剤2PZを、2-エチル-4-メチルイミダゾール(以下、2E4MZ、四国化成工業(株)製)に変更した以外は、実施例5と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
硬化促進剤2PZを、2-メチルイミダゾール(以下、2MZ、四国化成工業(株)製)に変更した以外は、実施例5と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
硬化促進剤2PZを、2-ウンデシルイミダゾール(以下、C11Z、四国化成工業(株)製)に変更した以外は、実施例5と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
硬化促進剤2PZを、2-ヘプタデシルイミダゾール(以下、C17Z、四国化成工業(株)製)に変更した以外は、実施例5と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
硬化促進剤2PZを、トリフェニルホスフィン(以下、TPP)に変更した以外は、実施例5と同様にして組成物を調製、圧縮成形し、燃料電池用緻密質セパレータを得た。
比較例8~12のセパレータは、硬化促進剤として2位にフェニル基を有しないイミダゾール化合物またはトリフェニルホスフィンを用いているため、固有抵抗が高く、また、強度も低いことがわかる。
具体的には、比較例8および比較例9では、硬化促進剤の活性が高すぎるため、金型内で急激な硬化反応による粘度上昇が起きて成形不良が発生し、固有抵抗が高くなっている。
比較例10~12では、硬化促進剤の活性が低すぎるため、9秒では成形が終了せず、ガラス転移点が低くなり、固有抵抗、TOCが高く、曲げ強度が低くなっている。
上記実施例1、実施例5、比較例1および比較例2で調製した樹脂組成物を用い、圧縮時間を3秒、5秒、7秒、12秒、15秒、20秒、30秒と変化させた以外は実施例1と同様にして燃料電池用緻密質セパレータを作製した。
得られた各セパレータについて、固有抵抗、曲げ強度およびTOCを測定した。
結果を表4~6に示す。なお、各表には、実施例1,5および比較例1,2の結果(成形時間9秒)も併記する。また、これらの結果を図2~4に示す。
一方、スプリングバックが75%の黒鉛粉末9を含む樹脂組成物を用いた場合、成形時間が10秒未満であると、固有抵抗およびTOCが高くなることがわかる。
これらに対し、スプリングバックが23%および50%の黒鉛粉末1,5を含む樹脂組成物を用いた場合、成形時間が10秒未満でも、固有抵抗、曲げ強度およびTOCのいずれの特性も良好なセパレータが得られていることがわかる。
以上のことから、短時間の成形で特性の良好な燃料電池緻密質セパレータを得るためには、スプリングバック20~70%の黒鉛粉末を用いることが好適であることがわかる。
Claims (10)
- 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み、
前記黒鉛粉末のスプリングバックが20~70%、かつ、平均粒径d50が30~100μmであり、
前記硬化促進剤が、2位にアリール基を有するイミダゾール化合物であることを特徴とする燃料電池緻密質セパレータ用樹脂組成物。 - 前記スプリングバックが、20~65%である請求項1記載の燃料電池緻密質セパレータ用樹脂組成物。
- 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または2記載の燃料電池緻密質セパレータ用樹脂組成物。
- 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1~3のいずれか1項記載の燃料電池緻密質セパレータ用樹脂組成物。
- 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である請求項1~4のいずれか1項記載の燃料電池緻密質セパレータ用樹脂組成物。
- 請求項1~5のいずれか1項記載の燃料電池緻密質セパレータ用樹脂組成物を成形してなる燃料電池用緻密質セパレータ。
- 固有抵抗が15mΩ・cm以下、ガラス転移点135℃以上、かつ、曲げ強度50MPa以上である請求項6記載の燃料電池用緻密質セパレータ。
- TOCが、7ppm以下である請求項6または7記載の燃料電池用緻密質セパレータ。
- 請求項1~5のいずれか1項記載の燃料電池緻密質セパレータ用樹脂組成物を、圧縮成形することを特徴とする燃料電池用緻密質セパレータの製造方法。
- 前記圧縮成形の時間が、10秒未満である請求項9記載の燃料電池用緻密質セパレータの製造方法。
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