WO2016152851A1 - 多孔質炭素電極基材、その製造方法、ガス拡散層、および燃料電池用膜-電極接合体 - Google Patents
多孔質炭素電極基材、その製造方法、ガス拡散層、および燃料電池用膜-電極接合体 Download PDFInfo
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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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
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8817—Treatment of supports before application of the catalytic active composition
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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
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0243—Composites in the form of mixtures
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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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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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
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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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 porous carbon electrode substrate suitably used for a gas diffusion layer or a fuel cell membrane-electrode assembly and a method for producing the same.
- a fuel cell for example, a polymer electrolyte fuel cell, supplies a reaction gas (a fuel gas and an oxidant gas) to a membrane electrode assembly in which a polymer electrolyte membrane is sandwiched between a pair of catalyst layers via a gas diffusion layer.
- a reaction gas a fuel gas and an oxidant gas
- a membrane electrode assembly in which a polymer electrolyte membrane is sandwiched between a pair of catalyst layers via a gas diffusion layer.
- the gas diffusion layer of the fuel cell is formed by subjecting a porous carbon electrode substrate such as carbon paper to water repellent treatment and providing a microporous layer on the surface in contact with the catalyst layer.
- a porous carbon electrode substrate such as carbon paper
- water repellent treatment providing a microporous layer on the surface in contact with the catalyst layer.
- Patent Document 1 discloses a porous carbon electrode base in which a gas is blown onto at least one surface of a porous carbon electrode base material, and carbon short fibers from which the binding by resin carbide has been removed are sufficiently removed. The method of manufacturing the material is shown.
- an insulating member having a plurality of communication holes is disposed on the water repellent layer side of a gas diffusion layer formed by laminating a carbon fiber layer and a water repellent layer, and further insulated from the gas diffusion layer.
- the member is sandwiched between a pair of electrodes, a pair of surface pressure plates are disposed and sandwiched between the back surfaces of the pair of electrodes, and the gas diffusion layer is pressurized by the pair of surface pressure plates.
- Patent Document 3 a sheet having elasticity is arranged on at least one surface of a carbon sheet in which short carbon fibers are bound by carbon, and a linear pressure is 5 kN / m to 30 kN using a continuous pressing means.
- a method of continuously removing carbon powder adhering to a carbon sheet after pressurizing at / m by a method of sweeping with a brush or the like, a method of sucking, or a method of ultrasonic cleaning is shown.
- JP 2010-70433 A JP 2012-33458 A JP 2012-204142 A
- the surface of the gas diffusion layer can be cleaned to some extent, but when the gas diffusion layer is compressed, such as a joining process with a polymer electrolyte membrane, new carbon fiber protrusion occurs. As a result, they pierce the polymer electrolyte membrane and cause a large short-circuit current.
- the present invention overcomes the above-described problems, and is a porous carbon electrode base material in which short carbon fibers that are not easily short-circuited when used in a fuel cell and insufficiently bonded on the surface are sufficiently removed.
- the purpose is to provide.
- a porous carbon electrode base material in which short carbon fibers are bound with resin carbide A porous carbon electrode substrate characterized in that the average value of short-circuit current measured from one surface (referred to as surface A) is 10 mA or less.
- a porous carbon electrode base material in which short carbon fibers are bound with resin carbide A porous carbon electrode substrate characterized by having a short-circuit current of 10 mA or less at a measurement point of 90% or more when a short-circuit current is measured from one surface (referred to as surface A).
- a porous carbon electrode group that heats a composition containing carbon short fibers and a resin having a residual carbon ratio of 35% (mass basis) or more (hereinafter referred to as resin A) to carbonize the resin A.
- a method for producing a material wherein the mass ratio of the short carbon fibers to the resin A in the composition is 70 to 250 parts by mass of the resin A with respect to 100 parts by mass of the short carbon fibers.
- a method for producing a porous carbon electrode substrate according to (2) (4) A microporous layer is provided on one surface of the porous carbon electrode substrate according to (1) or (2). Characteristic gas diffusion layer.
- a membrane-electrode assembly for a fuel cell comprising the porous carbon electrode substrate according to (1) or (2).
- the porous carbon electrode substrate of the present invention is a porous carbon electrode substrate in which short carbon fibers are bound with resin carbide.
- the porous carbon electrode base material whose average value of the short circuit current measured from one surface (it is called surface A) is 10 mA or less is called this invention 1, and when measuring a short circuit current from surface A, 90% or more A porous carbon electrode substrate having a short-circuit current of 10 mA or less at the measurement point is referred to as Invention 2.
- the present invention 1 and the present invention 2 are collectively referred to simply as the present invention.
- carbon fiber such as polyacrylonitrile (PAN), pitch, or rayon
- PAN polyacrylonitrile
- PAN-based or pitch-based, particularly PAN-based carbon fibers because an electrode substrate having excellent mechanical strength and appropriate flexibility can be obtained.
- Such carbon fibers are preferably selected so that the average diameter (average diameter of single fibers) is in the range of 4 to 20 ⁇ m.
- the average diameter of the carbon fibers is preferably 4 to 20 ⁇ m.
- the average diameter of the carbon fiber single fiber is measured from a photograph of a cross-sectional photograph of the carbon fiber single fiber.
- the average value of the major axis and the minor axis is taken as the diameter.
- the average value of the diameter of five single fibers be an average diameter. The same applies when the carbon fiber is a short carbon fiber.
- the short carbon fiber of the present invention means a carbon fiber having an average fiber length of 3 to 20 mm. That is, the short carbon fiber can be obtained by cutting the above-described carbon fiber. At that time, it is important to cut the carbon fiber so that the average fiber length is in the range of 3 to 20 mm.
- carbon fibers having an average fiber length of less than 3 mm are used, mechanical properties such as maximum load and elastic modulus against bending of the obtained porous carbon electrode substrate may be deteriorated.
- carbon fibers having an average fiber length of more than 20 mm are used, dispersibility at the time of papermaking, which will be described later, deteriorates, and variation in the basis weight of the carbon fibers in the obtained porous carbon electrode base material increases, resulting in poor quality. There is.
- the carbon short fiber sheet in which the carbon short fibers are dispersed can be obtained by either the dry paper making method or the wet paper making method.
- the wet paper making method using water as the paper making medium tends to make the carbon short fibers face the sheet surface. Therefore, it is preferable. That is, when the wet papermaking method is used, the short carbon fibers are difficult to be oriented in the direction of passing through the sheet, so it is difficult to cause a short circuit penetrating the fuel cell membrane, and the short circuit current can be kept low. Since a good homogeneous sheet can be obtained, the short-circuit current can be kept low at a large number of measurement points, which is preferable.
- a flameproof yarn, organic fiber, and pulp having the same mass or less as the carbon short fiber may be mixed into the carbon short fiber sheet.
- the total content of the flameproof yarn, the organic fiber, and the pulp is 100 mass of the short carbon fiber in the porous carbon electrode base material. The amount is preferably 0 part by mass or more and 50 parts by mass or less with respect to part by mass.
- an organic binder such as polyvinyl alcohol, cellulose, polyester, epoxy resin, phenol resin, acrylic resin in the carbon short fiber sheet, in that case The total of these is preferably in the range of 1 to 30% by mass.
- the basis weight of the short carbon fiber in the short carbon fiber sheet is preferably 10 to 50 g / m 2 .
- the resulting porous carbon electrode substrate has excellent mechanical strength, and at the same time, sufficient flexibility can be maintained. it can.
- the basis weight of the short carbon fiber in the short carbon fiber sheet is set to 10 to 50 g / m 2 .
- the basis weight of the short carbon fibers in the short carbon fiber sheet is more preferably 15 to 35 g / m 2 .
- the obtained carbon short fiber sheet is impregnated with a resin having a residual carbon ratio of 35% (mass basis) or more (hereinafter referred to as “resin A”).
- resin A a resin having a residual carbon ratio of 35% (mass basis) or more
- a porous carbon electrode substrate can be obtained by preparing a composition containing the mixture and heating the composition to carbonize the resin A.
- the resin A is carbonized by heating in an inert atmosphere, and becomes a resin carbide that binds the short carbon fibers.
- the resin A that is a resin having a residual carbon ratio of 35% (mass basis) or more include a phenol resin, an epoxy resin, a furan resin, and a melamine resin.
- a thermosetting resin is used as the resin A, it is cured by heating under conditions suitable for each resin before raising the temperature to 800 ° C. In the production conditions of the porous carbon electrode base material, heating exceeding 2000 ° C. may be performed, but since the resin mass decrease mainly occurs up to 800 ° C., in the present invention, by the method of heating to 800 ° C. Define the remaining coal rate.
- porous carbon plate heated and carbonized at a temperature of 2000 ° C. or more is impregnated with resin A. If the porous carbon plate contains a solvent, the solvent is dried and removed as necessary. After the resin A is cured, it is carbonized under the above conditions.
- the porous carbon plate carbonized at 2000 ° C. or more is a material substantially made of carbon.
- a porous carbon electrode base material in which short carbon fibers are bound with resin carbide can be used. Since the porous carbon plate carbonized at 2000 ° C.
- the porous carbon plate impregnated with resin A is carbonized before and after carbonization of the porous carbon plate impregnated with resin A. By subtracting the mass, the mass of the resin A before and after carbonization can be obtained.
- a carbon short fiber sheet containing resin A (this is called a composite sheet) is used as a composition containing carbon short fibers and resin A, it is formed by heating and pressurizing before carbonization by heating of the sheet. It is also preferable to keep it.
- the thickness and porosity of the porous carbon electrode substrate can be set to more appropriate values.
- the molding temperature is preferably 100 to 250 ° C.
- the applied pressure is preferably 0.01 to 5 MPa.
- surface A the average value of the short-circuit current measured from one surface
- the porous carbon electrode base material of this invention 2 it is preferable that the average value of the short circuit current measured from the surface A is 10 mA or less.
- the short-circuit current defined in the present invention means a value specified by the following procedures (1) to (3).
- the polymer electrolyte membrane “Nafion” (registered trademark) NR211 (manufactured by DuPont) with a film thickness of 25 ⁇ m is superimposed on one surface (referred to as surface A) of the porous carbon electrode substrate.
- the porous carbon electrode base material is a square with a side of 4 cm
- the polymer electrolyte membrane is a square with a side of 5.5 cm or more
- each side of the polymer electrolyte membrane is parallel to each side of the porous carbon electrode base material.
- the polymer electrolyte membrane and the porous carbon electrode base material are overlapped so that the center thereof coincides with the center of the porous carbon electrode substrate.
- the average value of the short-circuit current is obtained by changing the measurement sample of the porous carbon electrode base material, repeating the procedures (1) to (3) 20 times, and averaging the obtained 20 short-circuit current values. .
- This short-circuit current measurement method is a test method that simulates a short circuit of a polymer electrolyte membrane on one surface of a porous carbon electrode substrate in a fuel cell.
- a microporous layer and a catalyst layer exist between the porous carbon electrode substrate and the polymer electrolyte membrane, the test conditions are more emphasized than the actual fuel cell.
- each side described in the items (1) and (2) is a porous carbon electrode substrate in which the entire surface of a porous carbon electrode substrate that is a square with a side of 4 cm overlaps the polymer electrolyte membrane, and the porous carbon electrode The entire surface of the porous carbon electrode substrate is covered by covering the entire surface of the base material with the stainless block electrode and covering the entire surface of the stainless block electrode with a square of 5 cm on each side with a polymer electrolyte membrane. This is to prevent contact between the two stainless steel blocks at the same time as the pressure is applied.
- the porous carbon electrode substrate of the present invention 1 that the average value of the short-circuit current measured from the surface A is 10 mA or less.
- the porous carbon electrode base material of this invention 2 is 10 mA or less in average value of the short circuit current measured from the surface A.
- the average value of the short-circuit current measured from the surface A of the porous carbon electrode substrate is preferably 0 mA or more and 5 mA or less, more preferably 0 mA or more and 1 mA or less from the viewpoint of suppressing a decrease in power generation performance. .
- the porous carbon electrode substrate of the present invention 2 it is important that the short-circuit current is 10 mA or less at 90% or more measurement points when the short-circuit current is measured from one surface (referred to as surface A).
- the short-circuit current at 90% or more of the measurement points specified in the present invention is 10 mA or less
- the measurement sample is changed, and the procedure of (1) to (3) in the measurement of the short-circuit current is performed 20 times. Repeatedly, it means that 90% or more of the obtained 20 short-circuit current values (that is, 18 or more short-circuit current values) is 10 mA or less.
- the porous carbon electrode substrate of the present invention 2 can suppress a decrease in power generation performance by setting the short-circuit current to 10 mA or less at a measurement point of 90% or more. .
- the porous carbon electrode substrate of the present invention 1 further suppresses the decrease in power generation performance by setting the short-circuit current to 10 mA or less at a measurement point of 90% or more. This is preferable.
- the short-circuit current is more preferably 10 mA or less at a measurement point of 95% or more and 100% or less.
- the method for suppressing the short-circuit current to be low and further suppressing the short-circuit current at a large number of measurement points can be achieved by increasing the ratio of the resin carbide binding the short carbon fibers in the porous carbon electrode base material, although it is possible by increasing the density of the material, on the other hand, means for reducing the gas permeability of the porous carbon electrode substrate is not preferred.
- a preferable method for suppressing the short-circuit current to be low and further suppressing the short-circuit current at a large number of measurement points is to heat the composition containing the short carbon fibers and the resin A to carbonize the resin A to form a porous carbon electrode substrate.
- there is a method of increasing the temperature rising rate during heating When the rate of temperature increase is increased, the amount of shrinkage in thickness during heating and carbonization of the porous carbon electrode substrate is reduced, and the binding between the carbide of resin A and the short carbon fibers is less likely to come off.
- the heating rate during heating and carbonization is preferably such that the average heating rate from the furnace inlet (room temperature) to the maximum temperature in the furnace is 2000 to 15000 ° C./min.
- the furnace inlet room temperature
- the maximum temperature in the furnace is 2000 to 15000 ° C./min.
- the linear pressure for calendering is preferably 80 to 150 N / cm. If the pressure is too low, the effect of folding the short carbon fibers is small, and if the pressure is too high, the porous carbon electrode substrate may be broken, and the short carbon fibers may fall off and fuzz. After the calendering process, the carbon short fibers that are broken or broken are removed by blowing or sucking air to efficiently remove the burned carbon short fibers by Joule heat of the next current. be able to. By carrying out calendering before removal by combustion, the short carbon fibers protruding on the surface of the porous carbon electrode substrate are damaged near the roots of the short carbon fibers that are closer to the resin carbide than the supple fibers.
- the damaged portion in the vicinity of the root has a high electric resistance value, and thus is easily cut off by energized combustion.
- by making the thickness of the porous carbon electrode base material uniform by calendering it is possible to prevent overcurrent caused by thickness variation.
- Over-energization is a phenomenon in which short carbon fibers are not burnt out even when current flows when a large number of energized locations occur in the thick part of the porous carbon electrode substrate, and this is prevented by calendering. can do.
- the average value of the short circuit current of the surface A can be made 10 mA or less, and the short circuit current can be made 10 mA or less at the measurement points of 90% or more of the surface A.
- the porous carbon electrode substrate of the present invention is a method for producing a porous carbon electrode substrate, wherein the composition containing carbon short fibers and the resin A is heated to carbonize the resin A.
- the mass ratio of the short carbon fibers to the resin A is preferably obtained by a production method in which the resin A is 70 to 250 parts by mass with respect to 100 parts by mass of the short carbon fibers. Since the porous carbon electrode base material obtained by such a method has a strong bond between the carbide of the resin A and the short carbon fibers, and the short carbon fibers are less likely to fall off from the porous carbon electrode base material, It can be kept low.
- the mass ratio of the short carbon fibers to the resin A in the composition is 100 to 150 parts by mass of the resin A with respect to 100 parts by mass of the short carbon fibers.
- the resin A preferably contains carbon powder such as graphite powder, carbon black, carbon nanotube, graphene, and the like.
- carbon powder such as graphite powder, carbon black, carbon nanotube, graphene, and the like.
- the obtained porous carbon electrode base material also contains the carbon powder, and shrinkage and crack generation when the resin A is carbonized are suppressed. It is possible to prevent the short carbon fibers from dropping and the polymer electrolyte membrane from being short-circuited due to the decrease in fiber binding, and as a result, the short-circuit current can be kept low.
- the carbon powder preferably has an average particle size (average particle size D50 by laser diffraction method) of 1 to 10 ⁇ m.
- the porous carbon electrode substrate of the present invention is a method for producing a porous carbon electrode substrate, in which a composition containing carbon short fibers, resin A, and carbon powder is heated to carbonize resin A.
- the content of carbon powder in the product is preferably obtained by a production method in which carbon powder is 5 to 70 parts by mass with respect to 100 parts by mass of resin A in the composition.
- the porous carbon electrode substrate obtained by such a method can suppress the shrinkage and crack generation during carbonization of the resin A, and further make the resin A carbide an appropriate amount when binding the carbon short fibers or the carbon powder. be able to.
- the amount of the carbon powder with respect to 100 parts by mass of the resin A in the composition is more preferably 11 to 30 parts by mass.
- the amount is preferably 50 to 220 parts by mass of the short carbon fibers and the carbon powder with respect to 100 parts by mass of the resin A in the composition.
- the bulk density of a porous carbon electrode base material can suppress that the bulk density of a porous carbon electrode base material becomes high too much, and can be set as the porous carbon electrode base material which has the outstanding gas permeability and electric power generation performance. Furthermore, it can be set to an amount suitable for binding of carbon short fibers and carbon powder by the carbide of resin A.
- the total of the short carbon fibers and the carbon powder with respect to 100 parts by mass of the resin A is more preferably 80 to 130 parts by mass.
- the bulk density of the porous carbon electrode substrate is preferably 0.20 to 0.50 g / cm 3 .
- the bulk density is calculated from the mass and thickness of a sample cut into a 10 cm square. The thickness is measured using a dial gauge having a diameter of 5 mm ⁇ , and the measurement pressure is 0.15 MPa.
- the bulk density of the porous carbon electrode substrate By setting the bulk density of the porous carbon electrode substrate to 0.20 to 0.50 g / cm 3 , the short carbon fibers can be prevented from falling off, the short circuit current can be kept low, and the gas permeability and power generation performance can be reduced. Can be made an excellent value.
- the bulk density is more preferably 0.25 to 0.40 g / cm 3 , further preferably 0.25 to 0.35 g / cm 3 .
- the porous carbon electrode substrate is faced About the layer obtained by equally dividing into 3 in the straight direction (thickness direction), it is preferable that the layer filling rate is different between the layer close to one surface and the layer close to the other surface.
- the 50% filling rate refers to the surface filling rate obtained by measuring the surface filling rate for each fixed length from one surface of the porous carbon electrode substrate to the other surface. The average value is obtained, and 50% of the obtained average value.
- the layer filling rate means an average value obtained by using the filling rate of the surface on which the layer is formed.
- the porous carbon electrode base For the layer obtained by dividing the material into three equal parts in the direction perpendicular to the surface, the layer having the largest layer filling rate near one surface is the layer X, and the layer near the other surface having a smaller layer filling rate than the layer X
- the layer located between the layer Y and the layer X and the layer Y is the layer Z
- it is preferable that the filling rate of the layer becomes smaller in the order of the layer X, the layer Y, and the layer Z.
- the filling rate of layer Y is set to 1. Sometimes it is more preferred that the packing rate of layer X is 1.03 or more.
- the filling rate of the layer Y is 1, it is more preferable that the filling rate of the layer X is 1.03 or more and the filling rate of the layer Z is 0.97 or less. More preferably, the filling factor of the layer X is 1.05 or more and the filling factor of the layer Z is 0.90 or less.
- the filling rate of layer X, layer Y, and layer Z is obtained by three-dimensional measurement X-ray CT.
- Three-dimensional data of the carbon sheet is acquired by scanning the entire area in the perpendicular direction with a three-dimensional X-ray CT for each fixed length from one surface of the carbon sheet to the other surface. By analyzing such three-dimensional data, the filling rate in the measured surface can be acquired, and the filling rate in a specific layer can be obtained.
- the above-mentioned fixed length (henceforth a slice pitch) can be set arbitrarily, it shall be 1/3 or less of the average diameter of the carbon short fiber which comprises a carbon sheet.
- the filling ratio of the surface at a predetermined position in the direction perpendicular to the surface of the carbon sheet is determined by using the image processing program “J-trim” for the slice image at the position in the three-dimensional data, and the maximum and minimum brightness in brightness.
- the image is divided into 256 levels, and binarization is performed using the minimum 175 gradation steps as a threshold value.
- the ratio of the area on the bright side binarized in the entire area is the filling ratio of the surface at a predetermined position.
- the filling rate of the surface at this predetermined position is determined for each fixed length from one surface of the carbon sheet to the other surface, and the distribution of the filling rate of the surface for each fixed length in the perpendicular direction is calculated. obtain.
- An average value is obtained using the filling rate values of all the surfaces thus obtained, and a value of 50% (1/2) of the average value is defined as a 50% filling rate.
- the layer obtained by equally dividing the carbon sheet into three in the perpendicular direction The average value obtained using the filling rate of the surface on which the layer is formed is taken as the filling rate of the layer.
- the layer having the highest packing ratio near one surface is the layer X
- the layer near the other surface and having a lower packing ratio than the layer X is the layer Y
- the layer positioned between the layers X and Y is the layer Let it be Z.
- one measurement visual field for calculating the filling rate of the surface depends on the slice pitch
- a plurality of measurements are performed so that the total of the measurement visual fields is 5 mm 2 or more, and an average value is obtained to fill the layer. Find the rate.
- the three-dimensional X-ray CT used for measurement is SMX-160CTS manufactured by Shimadzu Corporation or an equivalent apparatus.
- the slice pitch is 2.1 ⁇ m
- the measurement visual field is 1070 ⁇ m
- the measurement visual field is 5 mm 2 or more
- the filling factor of the surface is obtained.
- the number of measurements for determining the filling rate was 7 times.
- the porous carbon electrode substrate of the present invention in which the packing ratio of the layers is made smaller in the order of layer X, layer Y, and layer Z is the average diameter of the short carbon fibers constituting the porous carbon electrode substrate and the porous carbon electrode substrate. Is obtained by a method of controlling the distribution of the resin A in the composite sheet before carbonization, heating, and carbonization in the direction perpendicular to the plane (thickness direction), but it is more preferable to control the distribution of the resin A.
- the method of controlling the distribution of the resin A in the direction perpendicular to the surface is prepared by preparing three composite sheets having different resin A impregnation amounts in the composite sheet in which the carbon short fiber sheet is impregnated with the resin A, and laminating them.
- Resin by using a method obtained by carbonization after molding and joining, or a resin application method in which a distribution is formed in the amount of resin A deposited when impregnating resin A into a porous body such as a carbon short fiber sheet It may be obtained by preparing a single composite sheet having a distribution in the amount of adhesion, and molding and carbonizing without laminating, but when obtaining by laminating composite sheets having different resin A impregnation amounts, Since a rapid change in the filling rate is likely to occur at the lamination interface, a method of producing from one composite sheet is preferable.
- the method of producing from one composite sheet is suitable for adjusting the thickness to a preferred range because it is easy to reduce the thickness of the obtained porous carbon electrode substrate.
- the preferred thickness range is 50 ⁇ m to 200 ⁇ m, more preferably 90 ⁇ m to 150 ⁇ m.
- the thickness is small, the porous carbon electrode substrate is fragile and difficult to handle.
- the output of the fuel cell is low because the permeability of hydrogen and oxygen is low.
- a microporous layer can be provided on one surface of the porous carbon electrode substrate to form a gas diffusion layer for a fuel cell.
- the microporous layer is composed of carbon particles and a fluororesin, and is provided on the surface of the porous carbon electrode substrate.
- the carbon particles are not particularly limited, but carbon particles such as carbon black, “VGCF” (registered trademark) (manufactured by Showa Denko KK), carbon nanotubes, etc., having at least one dimension of 1 ⁇ m or less among the three dimensions indicating the size. (This is referred to as carbon fine particles).
- the fluororesin is not particularly limited, but a fully fluorinated resin such as PTFE, FEP, PFA and the like is preferable.
- the gas diffusion layer may form a microporous layer on any surface of the porous carbon electrode substrate, but preferably has a microporous layer on the surface A of the porous carbon electrode substrate. Since surface A has few protrusions such as carbon short fibers, surface A is a smooth surface with few convex portions. Therefore, by forming a microporous layer on surface A, the resulting microporous layer of the gas diffusion layer can be further increased. As a result, the fuel cell obtained by using such a gas diffusion layer is less likely to cause a short circuit.
- a part of the microporous layer may penetrate into the porous carbon electrode substrate.
- a microporous layer is provided on the A surface of the porous carbon electrode substrate, and further, the microporous layer is incorporated in the fuel cell so as to face the polymer electrolyte membrane with the catalyst layer interposed therebetween. It can contribute to improvement of moisture retention and drainage and prevention of short circuit of the membrane.
- the membrane-electrode assembly of the present invention includes the porous carbon electrode substrate of the present invention. That is, the catalyst layer on both sides of the polymer electrolyte membrane, the outer surface of the catalyst layer (the surface of the catalyst layer different from the surface in contact with the polymer electrolyte membrane), and the outer surface of the microporous layer (microporous) A membrane-electrode assembly for a fuel cell in which a porous carbon electrode base material is provided on a layer different from the surface in contact with the catalyst layer). At that time, by providing a microporous layer on the A surface of the porous carbon electrode substrate, it is possible to contribute to improvement of moisture retention and drainage of the fuel cell and prevention of short circuit of the membrane.
- OCV open circuit voltage
- a catalyst solution was applied to 9001 (manufactured by Nichias Co., Ltd.) by spraying and dried at room temperature to prepare a PTFE sheet with a catalyst layer having a platinum amount of 0.3 mg / cm 2 .
- a solid polymer electrolyte membrane “Nafion” (registered trademark) NR-211 (manufactured by DuPont) cut to 8 cm ⁇ 8 cm is sandwiched between two PTFE sheets with a catalyst layer, and pressed to 5 MPa with a flat plate press.
- the catalyst layer was transferred to a solid polymer electrolyte membrane by pressing at a temperature of 130 ° C. for 5 minutes. After pressing, the PTFE sheet was peeled off to produce a solid polymer electrolyte membrane with a catalyst layer.
- a solid polymer electrolyte membrane with a catalyst layer is sandwiched between two gas diffusion layers cut to 5 cm x 5 cm, pressed for 5 minutes at a temperature of 130 ° C while pressing to 3 MPa with a flat plate press, and membrane-electrode bonding The body was made.
- the gas diffusion layer was disposed so that the surface having the microporous layer was in contact with the catalyst layer side.
- a single cell for fuel cell evaluation was assembled using the obtained membrane-electrode assembly and a separator.
- a serpentine type separator having a single flow path of 1.0 mm was used for each of the groove width, groove depth, and rib width.
- the cell temperature was 80 ° C.
- non-pressurized hydrogen was supplied to the anode side
- non-pressurized air was supplied to the cathode side. Both hydrogen and air were humidified by a humidification pot set at a temperature of 40 ° C.
- the anode-side separator and the cathode-side separator were not electrically connected by an external circuit. Hydrogen and air were supplied for 2 hours in an open circuit state, and then the potential difference (OCV) between the anode and the cathode was measured.
- OCV potential difference
- Example 1 A PAN-based carbon fiber “Torayca” (registered trademark) T300 (average diameter: 7 ⁇ m) manufactured by Toray Industries, Inc. was cut into an average length of 12 mm of short fibers, dispersed in water, and continuously made by wet paper making. Furthermore, a 10% by mass aqueous solution of polyvinyl alcohol as a binder was applied to the paper and dried to prepare a carbon short fiber sheet having a carbon short fiber basis weight of 30 g / m 2 . The adhesion amount of polyvinyl alcohol was 22 parts by mass with respect to 100 parts by mass of the carbon fiber.
- the residual carbon ratio of the phenol resin obtained by mixing the resol type phenol resin and the novolak type phenol resin so that the non-volatile content was a mass ratio of 1: 1 was 59%. Furthermore, carbon powder became 50 mass parts with respect to 100 mass parts of resin A in a composition.
- the carbon short fiber sheet was immersed in a mixed solution of the resin composition and squeezed by being sandwiched between rolls. At this time, two rolls were arranged horizontally with a certain clearance, and the carbon short fiber sheet was pulled up vertically to adjust the total amount of the resin composition.
- one of the two rolls was a smooth metal roll having a structure capable of removing excess resin composition with a doctor blade, and the other roll was a roll having a rugged gravure roll. .
- sandwiching one surface side of the carbon short fiber sheet with a metal roll and the other surface side with a gravure roll and squeezing the impregnating solution of the resin composition the resin composition of one surface and the other surface of the carbon short fiber sheet A difference was made in the amount of deposits.
- the composite sheet which is a carbon short fiber sheet containing a phenol resin.
- the adhesion amount of the phenol resin in the composite sheet is 120 parts by mass with respect to 100 parts by mass of the short carbon fibers.
- molding was performed by heating for 5 minutes at a temperature of 180 ° C. while pressing with a flat plate press. A spacer was placed on the flat plate press during the pressurization, and the distance between the upper and lower press face plates was adjusted so that the thickness of the composite sheet after molding was 195 ⁇ m.
- the base material obtained by heat-treating the composite sheet after molding was introduced into a heating furnace having a maximum temperature of 2400 ° C. maintained in a nitrogen gas atmosphere to obtain a porous carbon electrode base material. Heating was performed in two stages in a low temperature furnace having a maximum temperature of 750 ° C. and a high temperature furnace having a maximum temperature of 2400 ° C. At this time, the average temperature increase rate in the low temperature furnace was 2900 ° C./min, and the average temperature increase rate in the high temperature furnace was 4200 ° C./min.
- Kraft paper (weighing 70 g / m 2 ) was placed on both sides of this porous carbon electrode substrate, and calendering was performed at a linear pressure of 85 N / cm.
- static air 08 type on the porous carbon electrode substrate subjected to calendering
- the removal process of the carbon short fiber which protruded by one side combustion surface which the gravure roll contacted at the time of resin squeezing
- electrical combustion was performed according to the procedure described later.
- the thickness of the porous carbon electrode substrate after energization combustion was 143 ⁇ m, and the filling rates of layers X, Z, and Y were different.
- the physical properties are shown in Table 1.
- the short-circuit current was measured with the surface on the side where the electric combustion was performed as the surface A.
- the surface A was the layer X layer side with a high filling rate.
- the graphite rod passes through the porous carbon electrode substrate with a gap of 30 ⁇ m, and the carbon short fiber protruding more than 30 ⁇ m from the surface of the porous carbon electrode substrate. An electric current flows and is removed by combustion.
- Example 2 A porous carbon electrode substrate was obtained in the same manner as in Example 1 except that a large amount of the resin composition mixture was removed from the whole. The physical properties are shown in Table 1.
- Example 2 the short-circuit current was measured with the surface on the side subjected to electro-combustion in the same manner as in Example 1, and the value was listed in the table.
- the average value of the short-circuit current measured from the surface on the different side was 12.0 mA, and the ratio of the short-circuit current of 10 mA or less measured from the surface on the side different from the surface subjected to the energization combustion was 70%.
- Example 3 A porous carbon electrode base material was obtained in the same manner as in Example 1 except that a large amount of the resin composition mixture was removed from the whole, and drying at the time of preparing the composite sheet was performed at a higher temperature. The purpose of drying at a higher temperature is to suppress resin movement in the thickness direction during drying. The physical properties are shown in Table 1.
- Example 4 A porous carbon electrode substrate was obtained in the same manner as in Example 3 except that much of the mixed liquid of the resin composition was removed from the surface Y, and drying at the time of preparing the composite sheet was performed at a higher temperature. The purpose of drying at a higher temperature is to suppress resin movement in the thickness direction during drying. The physical properties are shown in Table 1.
- LLKP hardwood bleached kraft pulp
- the mixing ratio of parts by mass / 77 parts by mass, the two rolls for squeezing the impregnated resin liquid are smooth metal rolls, and the composite sheet is 110 parts by mass of phenol resin with respect to 100 parts by mass of carbon short fibers.
- the same surface of the two composite sheets facing each other when pressed with a flat plate press, and the composite sheet after molding (two composite sheets bonded to form a single sheet) of A porous carbon electrode base material was obtained in the same manner as in Example 1 except that the interval between the upper and lower press face plates was adjusted so that the thickness was 165 ⁇ m, and that the electric combustion was performed on the lower face during pressing. .
- the physical properties are shown in Table 1.
- the average value of the short circuit current of Examples 1 to 5 is significantly lower than the surface on the side different from the surface where the electric combustion was performed in Example 2, and the short circuit current is 10 mA or less.
- the ratio is markedly high.
- the average value of the short-circuit current of Examples 1 to 4 is low, the ratio of the short-circuit current of 10 mA or less is high, and the average value of the short-circuit current equivalent to that of Examples 1 and 2 is particularly high even in Examples 3 and 4 where the density is low.
- the ratio of the short circuit current of 10 mA or less is shown.
- Example 6 Using the porous carbon electrode substrate of Example 5, a microporous layer was formed by the following procedure to produce a gas diffusion layer.
- Carbon powder A Acetylene black: “DENKA BLACK” (registered trademark) (manufactured by Denki Kagaku Kogyo Co., Ltd.)
- B Water repellent material: Aqueous dispersion of PTFE resin ("Polyflon” (registered trademark) PTFE dispersion D-210C (manufactured by Daikin Industries))
- Material C Surfactant “TRITON” (registered trademark) X-100 (manufactured by Nacalai Tesque)
- the above materials and purified water were mixed using a disperser to form a carbon powder-containing coating solution.
- the thickness and basis weight are values as the gas diffusion layer.
- the average value of the short circuit current and the ratio of the short circuit current of 10 mA or less indicate values measured from the surface of the gas diffusion layer having the microporous layer (that is, the surface of the microporous layer in the gas diffusion layer).
- a fuel cell membrane-electrode is formed by stacking one catalyst electrolyte membrane with a catalyst and two gas diffusion layers so that the catalyst layer and the microporous layer face each other and heating and pressurizing at 3 MPa and 130 ° C for 5 minutes with a flat plate press It can be set as a joined body.
- the average value of the short circuit current measured from one surface (referred to as surface A) of the porous carbon electrode substrate of the present invention is 10 mA or less, and in many cases, the ratio of the short circuit current of 10 mA is 90%.
- surface A the average value of the short circuit current measured from one surface of the porous carbon electrode substrate of the present invention
- Such membrane-electrode assemblies are subject to rapid deterioration of performance due to thinning of the membrane and short-circuiting due to repeated start-up and stop of power generation, and the effect of this in a fuel cell stack in which many membrane-electrode assemblies are connected in series Becomes even more prominent.
- the durability of power generation is improved.
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Abstract
Description
(1) 炭素短繊維が樹脂炭化物で結着された多孔質炭素電極基材であって、
一方の表面(面Aという)から測定した短絡電流の平均値が10mA以下であることを特徴とする、多孔質炭素電極基材。
(2) 炭素短繊維が樹脂炭化物で結着された多孔質炭素電極基材であって、
一方の表面(面Aという)から短絡電流を測定した場合において、90%以上の測定点において短絡電流が10mA以下であることを特徴とする、多孔質炭素電極基材。
(3) 炭素短繊維、及び、残炭率35%(質量基準)以上の樹脂(以下、樹脂Aとする)を含む組成物を加熱して、前記樹脂Aを炭化させる、多孔質炭素電極基材の製造方法であって、前記組成物中の炭素短繊維と樹脂Aの質量比率が、炭素短繊維100質量部に対して樹脂Aが70~250質量部であることを特徴とする、(1)又は(2)に記載の多孔質炭素電極基材の製造方法
(4) (1)又は(2)に記載の多孔質炭素電極基材の一方の表面に、マイクロポーラス層を有することを特徴とする、ガス拡散層。
(5) (1)又は(2)に記載の多孔質炭素電極基材を含むことを特徴とする、燃料電池用膜-電極接合体。
本発明1の多孔質炭素電極基材は、一方の表面(面Aという)から測定した短絡電流の平均値が10mA以下であることが重要である。そして、本発明2の多孔質炭素電極基材は、面Aから測定した短絡電流の平均値が10mA以下であることが好ましい。
本発明2の多孔質炭素電極基材は、一方の表面(面Aという)から短絡電流を測定した場合に、90%以上の測定点において短絡電流が10mA以下であることが重要である。そして、本発明1の多孔質炭素電極基材は、面Aから短絡電流を測定した場合に、90%以上の測定点において短絡電流が10mA以下であることが好ましい。
多孔質炭素電極基材のかさ密度は0.20~0.50g/cm3が好ましい。かさ密度は10cm角に切り出したサンプルの質量と厚さから算出する。厚さの測定は、直径5mmφの測定子のダイヤルゲージを用い、測定圧力は0.15MPaとする。多孔質炭素電極基材のかさ密度を0.20~0.50g/cm3とすることで、炭素短繊維の脱落を抑制し、短絡電流を低く抑えることができ、さらに気体透過性および発電性能を優れた値とすることができる。かさ密度は0.25~0.40g/cm3がより好ましく、0.25~0.35g/cm3がさらに好ましい。
東レ(株)製PAN系炭素繊維“トレカ”(登録商標)T300(平均直径:7μm)を短繊維の平均長さ12mmにカットし、水中に分散させて湿式抄紙法により連続的に抄紙した。さらに、バインダーとしてポリビニルアルコールの10質量%水溶液を当該抄紙に塗布して乾燥させ、炭素短繊維の目付が30g/m2の炭素短繊維シートを作製した。ポリビニルアルコールの付着量は、炭素繊維100質量部に対して22質量部であった。
(1)鉄板上に多孔質炭素電極基材を置き、端部を粘着テープで固定した。多孔質炭素電極基材は、樹脂絞り時にグラビアロールと接触した面を上に向けて置いた。
樹脂組成物の混合液を全体から多く取り除いた以外は実施例1と同様にして多孔質炭素電極基材を得た。物性を表1に示す。
樹脂組成物の混合液を全体から多く取り除き、さらに複合シート作成時の乾燥をより高温で行った以外は実施例1と同様にして多孔質炭素電極基材を得た。乾燥をより高温で行ったのは、乾燥時の厚さ方向への樹脂移動を抑制する目的である。物性を表1に示す。
樹脂組成物の混合液を面Yから多く取り除き、さらに複合シート作成時の乾燥をより高温で行った以外は実施例3と同様にして多孔質炭素電極基材を得た。乾燥をより高温で行ったのは、乾燥時の厚さ方向への樹脂移動を抑制する目的である。物性を表1に示す。
抄紙する炭素短繊維の平均長さを6mmとしたこと、炭素短繊維100質量部に対して広葉樹晒クラフトパルプ(LBKP)40質量部を混合して抄紙したこと、抄紙時の炭素短繊維の目付が14g/m2であること、ポリビニルアルコールの付着量が炭素短繊維100質量部に対して33質量部であること、熱硬化性樹脂(不揮発分)/炭素粉末/溶媒=20質量部/3質量部/77質量部の配合比としたこと、含浸した樹脂液を絞る2本のロールが平滑な金属ロールであること、複合シートは炭素短繊維100質量部に対してフェノール樹脂を110質量部としたこと、平板プレスで加圧する際に2枚の複合シートの同じ面を向かい合わせて重ねたこと、成形後の複合シート(成形により2枚の複合シートが接着し1枚になったもの)の厚さが165μmになるように、上下プレス面板の間隔を調整したこと、プレス時の下面に対し通電燃焼を行ったこと以外は実施例1と同様にして、多孔質炭素電極基材を得た。物性を表1に示す。
カレンダー加工と通電燃焼による突き出し毛羽除去処理を行わなかった以外は実施例1~5と同様にして多孔質炭素電極基材を得た。そして両面について短絡電流の平均値を測定したが、表においては平均値が小さな値を示した側の面の値を記す。具体的には、比較例1~4はグラビアロールが接する側の面を、比較例5はプレス時の下面について短絡電流を測定した際の値を表に記す。
実施例5の多孔質炭素電極基材を用い、以下の手順でマイクロポーラス層を形成してガス拡散層を製造した。
[材料]
・炭素粉末A:アセチレンブラック:“デンカ ブラック”(登録商標)(電気化学工業(株)製)
・材料B:撥水材:PTFE樹脂の水分散液(“ポリフロン”(登録商標)PTFEディスパージョンD-210C(ダイキン工業(株)製))
・材料C:界面活性剤“TRITON”(登録商標)X-100(ナカライテスク(株)製)
上記の各材料と精製水を分散機を用いて混合し、炭素粉末含有塗液を形成した。この炭素粉末含有塗液をスリットダイコーターを用いて、撥水材を含む多孔質炭素電極基材(実施例5の多孔質炭素電極基材)の一方の表面(通電燃焼を行った側の面)に面状に塗布した後、120℃の温度で10分間、続いて380℃の温度で10分間加熱した。このようにして、撥水材を含む多孔質炭素電極基材上にマイクロポーラス層を形成して、ガス拡散層を作製した。面A側にマイクロポーラス層を設けることで短絡電流を小さくすることができる。
Claims (12)
- 炭素短繊維が樹脂炭化物で結着された多孔質炭素電極基材であって、
一方の表面(面Aという)から測定した短絡電流の平均値が10mA以下であることを特徴とする、多孔質炭素電極基材。 - 面Aから短絡電流を測定した場合において、90%以上の測定点において短絡電流が10mA以下であることを特徴とする、請求項1に記載の多孔質炭素電極基材。
- 炭素短繊維が樹脂炭化物で結着された多孔質炭素電極基材であって、
一方の表面(面Aという)から短絡電流を測定した場合において、90%以上の測定点において短絡電流が10mA以下であることを特徴とする、多孔質炭素電極基材。 - 面Aから測定した短絡電流の平均値が10mA以下であることを特徴とする、請求項3に記載の多孔質炭素電極基材。
- かさ密度が0.20~0.50g/cm3であることを特徴とする、請求項1~4のいずれかに記載の多孔質炭素電極基材。
- 一方の表面にもっとも近い50%充填率を有する面から、他方の表面にもっとも近い50%充填率を有する面までの区間において、前記多孔質炭素電極基材を面直方向に3等分して得られる層について、一方の表面に近い層と他方の表面に近い層とで、層の充填率が異なることを特徴とする、請求項1~5のいずれかに記載の多孔質炭素電極基材。
- 一方の表面にもっとも近い50%充填率を有する面から、他方の表面にもっとも近い50%充填率を有する面までの区間において、前記多孔質炭素電極基材を面直方向に3等分して得られる層について、一方の表面に近く層の充填率が最も大きい層を層X、他方の表面に近く層の充填率が層Xよりも小さい層を層Y、層Xと層Yの間に位置する層を層Zとすると、層の充填率が、層X、層Y、層Zの順に小さくなることを特徴とする、請求項1~6のいずれかに記載の多孔質炭素電極基材。
- 層Yの充填率を1とした時に、層Xの充填率が1.03以上であり、層Zの充填率が0.97以下である、請求項7に記載の多孔質炭素電極基材。
- 炭素短繊維、及び、残炭率35%(質量基準)以上の樹脂(以下、樹脂Aとする)を含む組成物を加熱して、前記樹脂Aを炭化させる、多孔質炭素電極基材の製造方法であって、
前記組成物中の炭素短繊維と樹脂Aの質量比率が、炭素短繊維100質量部に対して樹脂Aが70~250質量部であることを特徴とする、請求項1~8のいずれかに記載の多孔質炭素電極基材の製造方法。 - 炭素短繊維、残炭率35%(質量基準)以上の樹脂(以下、樹脂Aとする)、及び炭素粉末を含む組成物を加熱して、前記樹脂Aを炭化させる、多孔質炭素電極基材の製造方法であって、
前記組成物中の樹脂Aと炭素粉末の質量比率が、樹脂A 100質量部に対して炭素粉末が5~70質量部であることを特徴とする、請求項1~8のいずれかに記載の多孔質炭素電極基材の製造方法。 - 請求項1~8のいずれかに記載の多孔質炭素電極基材の一方の表面に、マイクロポーラス層を有することを特徴とする、ガス拡散層。
- 請求項1~8のいずれかに記載の多孔質炭素電極基材を含むことを特徴とする、燃料電池用膜-電極接合体。
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Application Number | Priority Date | Filing Date | Title |
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JP2016527487A JP6729373B2 (ja) | 2015-03-25 | 2016-03-22 | 多孔質炭素電極基材、その製造方法、ガス拡散層、および燃料電池用膜−電極接合体 |
EP16768754.0A EP3276718B1 (en) | 2015-03-25 | 2016-03-22 | Porous carbon electrode base material, method for manufacturing same, gas diffusion layer, and membrane-electrode assembly for fuel cell |
CA2977344A CA2977344A1 (en) | 2015-03-25 | 2016-03-22 | Porous carbon electrode substrate, method for manufacturing same, gas diffusion layer, and membrane-electrode assembly for fuel cell |
US15/558,456 US10651477B2 (en) | 2015-03-25 | 2016-03-22 | Porous carbon electrode substrate, method of manufacturing same, gas diffusion layer, and membrane-electrode assembly for fuel cell |
CN201680015135.2A CN107408706B (zh) | 2015-03-25 | 2016-03-22 | 多孔碳电极基材、其制造方法、气体扩散层、以及燃料电池用膜-电极接合体 |
KR1020177028668A KR102564231B1 (ko) | 2015-03-25 | 2016-03-22 | 다공질 탄소 전극 기재, 그의 제조 방법, 가스 확산층 및 연료 전지용 막-전극 접합체 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018085333A (ja) * | 2016-11-11 | 2018-05-31 | 三菱ケミカル株式会社 | 多孔質電極基材及び、ガス拡散層、及びガス拡散電極とその製造方法 |
WO2019049934A1 (ja) * | 2017-09-07 | 2019-03-14 | 東洋紡株式会社 | 燃料電池用ガス拡散層基材、燃料電池用ガス拡散層、燃料電池 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US10790516B2 (en) * | 2015-12-24 | 2020-09-29 | Toray Industries, Inc. | Gas diffusion electrode and method for manufacturing same |
JP7209221B2 (ja) * | 2018-07-23 | 2023-01-20 | パナソニックIpマネジメント株式会社 | 電気化学式水素ポンプ |
KR102169124B1 (ko) * | 2018-12-19 | 2020-10-22 | 주식회사 제이앤티지 | 흑연화 탄소 기재 및 이를 채용한 기체확산층 |
US11804606B2 (en) * | 2019-07-29 | 2023-10-31 | Toray Industries, Inc. | Gas diffusion electrode, method for producing the same and membrane electrode assembly |
CN111762771A (zh) * | 2020-07-10 | 2020-10-13 | 山东理工大学 | 一种高长径比纤维碳的自焊接工艺 |
CN115101771A (zh) * | 2022-06-28 | 2022-09-23 | 广东德氢氢能科技有限责任公司 | 燃料电池气体扩散层及其制备方法、燃料电池膜电极 |
DE102022127234A1 (de) | 2022-10-18 | 2024-04-18 | Carl Freudenberg Kg | Gasdiffusionslage mit geringer plastischer Verformbarkeit und hoher Oberflächengüte und Verfahren zu ihrer Herstellung |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010070433A (ja) * | 2008-09-22 | 2010-04-02 | Toray Ind Inc | 多孔質炭素シートおよびその製造方法 |
JP2012033458A (ja) * | 2010-07-05 | 2012-02-16 | Nippon Soken Inc | 燃料電池のガス拡散層の製造方法、製造装置および燃料電池 |
JP2013065413A (ja) * | 2011-09-15 | 2013-04-11 | Toyota Motor Corp | 燃料電池 |
JP2013145640A (ja) * | 2012-01-13 | 2013-07-25 | Toyota Motor Corp | 燃料電池用拡散層の製造方法および燃料電池用拡散層 |
JP2015041456A (ja) * | 2013-08-21 | 2015-03-02 | 凸版印刷株式会社 | 触媒層の製造装置及び触媒層の製造方法並びに固体高分子形燃料電池用膜・電極接合体 |
WO2016060044A1 (ja) * | 2014-10-17 | 2016-04-21 | 東レ株式会社 | 炭素シート、ガス拡散電極基材、および燃料電池 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100527496C (zh) * | 2004-06-21 | 2009-08-12 | 三菱丽阳株式会社 | 多孔质电极基材及其制造方法 |
CA2767211C (en) * | 2009-11-24 | 2018-07-31 | Mitsubishi Rayon Co., Ltd. | Porous electrode substrate and method for producing the same |
KR101571227B1 (ko) * | 2011-01-27 | 2015-11-23 | 미쯔비시 레이온 가부시끼가이샤 | 다공질 전극 기재, 그의 제조 방법, 전구체 시트, 막-전극 접합체 및 고체 고분자형 연료 전지 |
JP5485212B2 (ja) * | 2011-03-25 | 2014-05-07 | 三菱レイヨン株式会社 | 多孔質炭素電極基材及びその製造方法 |
JP2013143317A (ja) * | 2012-01-12 | 2013-07-22 | Toyota Motor Corp | ガス拡散層基材およびガス拡散層基材の製造方法 |
KR101484762B1 (ko) * | 2012-06-29 | 2015-01-21 | 주식회사 제이앤티씨 | 기체확산층용 탄소기재, 이를 이용한 기체확산층, 및 이를 포함하는 연료전지용 전극 |
US10790516B2 (en) | 2015-12-24 | 2020-09-29 | Toray Industries, Inc. | Gas diffusion electrode and method for manufacturing same |
-
2016
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- 2016-03-22 CN CN201680015135.2A patent/CN107408706B/zh active Active
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010070433A (ja) * | 2008-09-22 | 2010-04-02 | Toray Ind Inc | 多孔質炭素シートおよびその製造方法 |
JP2012033458A (ja) * | 2010-07-05 | 2012-02-16 | Nippon Soken Inc | 燃料電池のガス拡散層の製造方法、製造装置および燃料電池 |
JP2013065413A (ja) * | 2011-09-15 | 2013-04-11 | Toyota Motor Corp | 燃料電池 |
JP2013145640A (ja) * | 2012-01-13 | 2013-07-25 | Toyota Motor Corp | 燃料電池用拡散層の製造方法および燃料電池用拡散層 |
JP2015041456A (ja) * | 2013-08-21 | 2015-03-02 | 凸版印刷株式会社 | 触媒層の製造装置及び触媒層の製造方法並びに固体高分子形燃料電池用膜・電極接合体 |
WO2016060044A1 (ja) * | 2014-10-17 | 2016-04-21 | 東レ株式会社 | 炭素シート、ガス拡散電極基材、および燃料電池 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018085333A (ja) * | 2016-11-11 | 2018-05-31 | 三菱ケミカル株式会社 | 多孔質電極基材及び、ガス拡散層、及びガス拡散電極とその製造方法 |
JP7052301B2 (ja) | 2016-11-11 | 2022-04-12 | 三菱ケミカル株式会社 | 多孔質電極基材及び、ガス拡散層、及びガス拡散電極とその製造方法 |
JP2022082646A (ja) * | 2016-11-11 | 2022-06-02 | 三菱ケミカル株式会社 | 多孔質電極基材及び、ガス拡散層、及びガス拡散電極とその製造方法 |
JP7355143B2 (ja) | 2016-11-11 | 2023-10-03 | 三菱ケミカル株式会社 | 多孔質電極基材及び、ガス拡散層、及びガス拡散電極とその製造方法 |
WO2019049934A1 (ja) * | 2017-09-07 | 2019-03-14 | 東洋紡株式会社 | 燃料電池用ガス拡散層基材、燃料電池用ガス拡散層、燃料電池 |
JPWO2019049934A1 (ja) * | 2017-09-07 | 2020-10-15 | 東洋紡株式会社 | 燃料電池用ガス拡散層基材、燃料電池用ガス拡散層、燃料電池 |
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EP3276718A1 (en) | 2018-01-31 |
JP6729373B2 (ja) | 2020-07-22 |
KR102564231B1 (ko) | 2023-08-08 |
US10651477B2 (en) | 2020-05-12 |
TWI705610B (zh) | 2020-09-21 |
CN107408706B (zh) | 2020-10-27 |
TW201701521A (zh) | 2017-01-01 |
CN107408706A (zh) | 2017-11-28 |
KR20170130460A (ko) | 2017-11-28 |
EP3276718B1 (en) | 2023-02-22 |
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