WO2014185491A1 - ガス拡散電極用基材 - Google Patents
ガス拡散電極用基材 Download PDFInfo
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- WO2014185491A1 WO2014185491A1 PCT/JP2014/062954 JP2014062954W WO2014185491A1 WO 2014185491 A1 WO2014185491 A1 WO 2014185491A1 JP 2014062954 W JP2014062954 W JP 2014062954W WO 2014185491 A1 WO2014185491 A1 WO 2014185491A1
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- gas diffusion
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- fiber
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- electrode
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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
- H01M4/8605—Porous electrodes
- H01M4/8626—Porous electrodes characterised by the form
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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
- H01M4/8605—Porous electrodes
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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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- 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
- H01M8/0239—Organic resins; Organic polymers
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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
- H01M2008/1095—Fuel cells with polymeric 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
Definitions
- This invention relates to a gas diffusion electrode substrate.
- Non-Patent Document 1 the fuel cell is a phosphoric acid fuel cell (PAFC), melted, depending on the type of electrolyte used.
- PAFC phosphoric acid fuel cell
- the PEFC has a low temperature range of 100 ° C or lower, the PAFC has a medium temperature range of 180-210 ° C, the MCFC has a temperature of 600 ° C or higher, and the SOFC has a temperature of nearly 1000 ° C It is known to operate in the high temperature region.
- a general PEFC capable of outputting in a low temperature region takes out electric power generated by a combined reaction between hydrogen gas and oxygen gas (or air) as a fuel, but has a relatively small device configuration. Since efficient electric power can be taken out, it is being put to practical use for home use and automobile use.
- FIG. 1 is a schematic cross-sectional view of the main part of a fuel cell showing the basic structure of a conventionally known PEFC.
- the PEFC includes a membrane-electrode assembly (MEA) including a fuel electrode (gas diffusion electrode) 17a, a solid polymer membrane 19, and an air electrode (gas diffusion electrode) 17c as shown in FIG. It has a structure in which a plurality of cell units sandwiched between plates 11a and 11c are stacked.
- MEA membrane-electrode assembly
- the fuel electrode 17a includes a catalyst layer 15a that decomposes into protons and electrons, and a gas diffusion layer 13a that supplies fuel gas to the catalyst layer 15a, and there is moisture between the catalyst layer 15a and the gas diffusion layer 13a.
- a management layer 14a is formed.
- the air electrode 17c includes a catalyst layer 15c that reacts protons, electrons, and an oxygen-containing gas, and a gas diffusion layer 13c that supplies an oxygen-containing gas to the catalyst layer 15c, and the catalyst layer 15c and the gas diffusion layer 13c.
- a moisture management layer 14c is formed between the two.
- the bipolar plate 11a Since the bipolar plate 11a has a groove capable of supplying a fuel gas, when the fuel gas is supplied through the groove of the bipolar plate 11a, the fuel gas diffuses through the gas diffusion layer 13a and permeates the moisture management layer 14a to pass through the catalyst layer 15a. To be supplied. The supplied fuel gas is decomposed into protons and electrons, and the protons move through the solid polymer film 19 and reach the catalyst layer 15c. On the other hand, the electrons pass through an external circuit (not shown) and move to the air electrode 17c.
- the bipolar plate 11c since the bipolar plate 11c has a groove capable of supplying an oxygen-containing gas, when the oxygen-containing gas is supplied through the groove of the bipolar plate 11c, the oxygen-containing gas diffuses through the gas diffusion layer 13c and permeates the moisture management layer 14c. And supplied to the catalyst layer 15c. The supplied oxygen-containing gas reacts with protons that have moved through the solid polymer membrane 19 and electrons that have moved through the external circuit, thereby generating water. The generated water is discharged out of the fuel cell through the moisture management layer 14c. In the fuel electrode, water that has been reversely diffused from the air electrode passes through the moisture management layer 14a and is discharged out of the fuel cell.
- the functions necessary for the gas diffusion layer 13a and the moisture management layer 14a, or the gas diffusion layer 13c and the moisture management layer 14c include a moisture retention property for keeping the solid polymer film 19 moist under a low humidification condition, and a high Under humidified conditions, water accumulates in the fuel cell, and has drainage to prevent flooding.
- Such gas diffusion layer 13a and moisture management layer 14a, or gas diffusion layer 13c and moisture management layer 14c are conventionally impregnated with a conductive porous substrate such as carbon paper with a fluorine-based resin such as polytetrafluoroethylene.
- moisture management layers 14a and 14c in which fluororesin is present or carbon powder and fluororesin are present, and these are not present
- the regions were gas diffusion layers 13a and 13c.
- the moisture management layers 14a and 14c formed in this way are fluorinated resins or carbon powders and fluorinated resins applied to a conductive porous substrate.
- Carbon paper is used, and the carbon fibers that make up this carbon paper have high rigidity, so it penetrates the moisture management layers 14a and 14c and the catalyst layers 15a and 15c, damages the solid polymer film, and shorts. There was a case.
- Patent Document 2 a base material for a gas diffusion electrode including a nonwoven fabric containing conductive fibers containing conductive particles at least inside an organic resin. Since this base material for gas diffusion electrodes is flexible because it is based on an organic resin, the conductive fiber did not directly damage the solid polymer film and short-circuit it. However, since the gas diffusion electrode using the base material for gas diffusion electrode is flexible, the effect of suppressing the swelling and shrinkage of the solid polymer film is low. That is, the solid polymer membrane repeatedly swells and shrinks in accordance with the wet state during power generation of the fuel cell, but the swelling amount and the amount of expansion between the solid polymer membrane and the gas diffusion electrode are caused by this swelling and shrinkage. Stress due to the difference in the amount of shrinkage was generated, resulting in distortion and eventually cracking.
- JP 2008-204945 A International Publication No. 2014/010715 (priority data: Japanese Patent Application No. 2012-158122)
- the present invention has been made under such circumstances, and a gas diffusion electrode capable of suppressing swelling and shrinkage of a solid polymer film without directly damaging the solid polymer film is produced.
- An object of the present invention is to provide a gas diffusion electrode substrate that can be used.
- the present invention is “a gas diffusion electrode base material including a nonwoven fabric containing conductive fibers containing conductive particles at least inside an organic resin, and the specific apparent Young's modulus of the gas diffusion electrode base material is 40”.
- the present invention relates to a gas diffusion electrode substrate characterized by being [MPa / (g / cm 3 )] or more.
- the base material for gas diffusion electrode of the present invention is flexible because the nonwoven fabric constituting the base material for gas diffusion electrode contains conductive fibers containing conductive particles in at least the inside of the organic resin.
- the solid polymer film is not directly damaged as in the case of using a gas diffusion electrode substrate made of glass fiber.
- the specific apparent Young's modulus of the gas diffusion electrode base material is 40 [MPa / (g / cm 3 )] or more, and a gas containing conductive fibers containing conductive particles at least inside a conventional organic resin Since the rigidity is higher than that of the diffusion electrode base material and swelling and shrinkage of the solid polymer film can be suppressed, cracks due to swelling and shrinkage of the solid polymer film can be prevented.
- FIG. 1 is a schematic cross-sectional view showing a schematic configuration of a solid polymer fuel cell.
- the base material for gas diffusion electrode of the present invention includes a non-woven fabric containing conductive fibers containing conductive particles at least inside an organic resin. Since the conductive fibers of the nonwoven fabric are flexible because they contain an organic resin, the conductive fibers do not directly damage and short-circuit the solid polymer film.
- the “organic resin” of the present invention does not include diamond, graphite, and amorphous carbon.
- the organic resin constituting the conductive fiber may be a hydrophobic organic resin, a hydrophilic organic resin, a mixture or a composite thereof, and is not particularly limited.
- a hydrophobic organic resin When the former hydrophobic organic resin is contained, excellent water permeability is exhibited without impregnating with a hydrophobic resin such as a fluorine-based resin, and excellent drainage is exhibited.
- a hydrophilic organic resin when a hydrophilic organic resin is contained, moisture can be retained, so that the solid polymer film can be kept in a wet state even under low humidity, and even under low humidity It is possible to produce a polymer electrolyte fuel cell that can exhibit excellent power generation performance.
- the “hydrophobic organic resin” is an organic resin having a contact angle with water of 90 ° or more.
- polytetrafluoroethylene PTFE
- PCTFE polychlorotrifluoroethylene
- PVDF polyvinylidene fluoride
- PVDF polyvinylidene fluoride
- PVDF Polyvinyl fluoride
- PFA perfluoroalkoxy fluororesin
- FEP tetrafluoroethylene / hexafluoropropylene copolymer
- FEP ethylene / tetrafluoroethylene copolymer
- PE polyethylene
- PP polypropylene
- PP polypropylene
- the “hydrophilic organic resin” is an organic resin having a contact angle with water of less than 90 °, for example, cellulose such as rayon; acrylic type such as polyacrylonitrile, acrylic oxide, polyacrylic acid, and polymethacrylic acid. Resins; polyamide resins such as nylon 6 and nylon 66; polyvinyl alcohol resins; hydrophilic polyurethanes; polyvinyl pyrrolidone; hydrophilic resins such as thermosetting resins such as phenol resins, urea resins, melamine resins, unsaturated polyester resins, and epoxy resins And resins having a functional group (amide group, carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc.). Moreover, these hydrophilic organic resins can also be used independently and can also be used in mixture of 2 or more types or in combination.
- thermosetting resin can suppress the swelling and shrinkage of the solid polymer film and prevent the solid polymer film from cracking due to the high rigidity of the conductive fiber and consequently the high rigidity of the electrode substrate.
- thermosetting resins a phenol resin or an epoxy resin is preferable because it has heat resistance and acid resistance and can increase the rigidity of the electrode substrate by heat treatment.
- the conductive fiber of the present invention When the conductive fiber of the present invention is used as a gas diffusion electrode, it contains conductive particles at least inside the organic resin so that the electron mobility is excellent. In other words, when the conductive particles are present only on the outer surface of the organic resin, the organic resin component becomes a resistance component, which is inferior in conductivity in the thickness direction of the gas diffusion electrode. Since the organic resin contains conductive particles, the conductivity is excellent in the thickness direction of the gas diffusion electrode. From the viewpoint of conductivity, the conductive particles are preferably exposed from the organic resin. “Containing conductive particles inside” does not only mean that the conductive particles are completely buried in the organic resin, but a part of the conductive particles is made of the organic resin. It also means an exposed state. Such conductive fibers containing conductive particles at least inside the organic resin can be produced, for example, by spinning a spinning solution containing the organic resin and conductive particles.
- the conductive particles are not particularly limited, and examples thereof include carbon black, carbon nanotubes, carbon nanofibers, metal particles, and metal oxide particles. Among these, carbon black is preferable in terms of chemical resistance, conductivity, and dispersibility.
- the particle size of the carbon black which is suitable is not particularly limited, but preferably the average primary particle size is 5 nm to 200 nm, more preferably 10 nm to 100 nm.
- the average primary particle diameter of the conductive particles is smaller than the fiber diameter of the conductive fibers to be described later so that the average primary particle diameter does not easily fall off and easily forms a fiber form.
- carbon nanofibers such as vapor grown carbon fiber are suitable because they are in the form of fibers, so that the specific apparent Young's modulus of the electrode substrate can be easily increased.
- the mass ratio between the conductive particles and the organic resin is not particularly limited, but is preferably 10 to 90:90 to 10, more preferably 20 to 80:80 to 20, and 30 It is more preferably from 70 to 70 to 30, still more preferably from 35 to 65:65 to 35, and still more preferably from 40 to 60:60 to 40. This is because if the amount of the conductive particles is less than 10 mass%, the conductivity tends to be insufficient, and if the amount of the conductive particles exceeds 90 mass%, the fiber forming property tends to decrease.
- the conductive particles preferably occupy 10 to 90 mass%, more preferably 20 to 80 mass% of the non-woven fabric (electrode base material) so as to have excellent conductivity, and 30 to 70 mass%. %, More preferably 35 to 65 mass%, and even more preferably 40 to 60 mass%.
- the average fiber diameter of the conductive fiber of the present invention is not particularly limited, but is preferably 10 nm to 10 ⁇ m, more preferably 50 nm to 5 ⁇ m, and still more preferably 50 nm to 1 ⁇ m.
- the average fiber diameter exceeds 10 ⁇ m, there are few contact points between the fibers in the electrode substrate, and the conductivity tends to be insufficient.
- the average fiber diameter is less than 10 nm, it tends to be difficult to contain conductive particles inside the fiber. Because there is.
- the average fiber diameter of a conductive fiber is 5 times or more of the primary particle diameter of an electroconductive particle so that an electroconductive particle cannot drop out easily.
- the conductive fibers having such an average fiber diameter were discharged from a liquid discharge unit such as an electrostatic spinning method, a spunbond method, a melt blow method, or disclosed in JP-A-2009-287138. It can be produced by a method in which a gas is discharged in parallel to the spinning solution, and a fiber is formed by applying a shearing force to the spinning solution in a straight line.
- a liquid discharge unit such as an electrostatic spinning method, a spunbond method, a melt blow method, or disclosed in JP-A-2009-287138.
- the “average fiber diameter” means the arithmetic average value of the fiber diameters at 40 points, and the “fiber diameter” is a value measured based on a micrograph, and the conductive particle exposed conductive particles. In the case of being composed only of conductive fibers, it means the diameter including the exposed conductive particles, and does not contain conductive fibers with exposed conductive particles or conductive fibers with exposed conductive particles In the case where it is configured to include a conductive fiber having a portion where the conductive particles are not exposed, the diameter at the portion where the conductive particles are not exposed is meant.
- the conductive fiber of the present invention is preferably a continuous fiber so that the mobility of electrons is excellent and the end of the conductive fiber is small and the solid polymer film is hardly damaged.
- Such conductive continuous fibers can be produced, for example, by an electrostatic spinning method or a spunbond method.
- the mass content ratio of the conductive fibers in the nonwoven fabric constituting the electrode substrate of the present invention is preferably 10% or more, more preferably 50% or more, and more preferably 70% or more so that the mobility of electrons is excellent. More preferably, it is more preferably 90% or more, and most preferably composed only of conductive fibers.
- the fibers other than the conductive fibers include hydrophobic organic fibers such as fluorine fibers and polyolefin fibers, acrylic fibers, nylon fibers (for example, nylon 6 and nylon 66), and hydrophilic organic fibers such as phenol fibers. be able to.
- the nonwoven fabric constituting the electrode substrate of the present invention can contain fibers other than conductive fibers, but the electrode substrate has an electric resistance of 150 m ⁇ ⁇ cm 2 or less so as to be excellent in conductivity. are preferred, more preferably at 100 m [Omega ⁇ cm 2 or less, and even more preferably 50 m [Omega ⁇ cm 2 or less.
- the nonwoven fabric which comprises the electrode base material of this invention may be couple
- suitable organic resin bonds include entanglement of fibers, bonding by plasticization with a solvent, and bonding by heat fusion.
- the basis weight of the nonwoven fabric constituting the electrode substrate of the present invention is not particularly limited, but is preferably 0.5 to 200 g / m 2 from the viewpoint of drainage, gas diffusibility, handleability and productivity, It is more preferably 0.5 to 100 g / m 2 , and still more preferably 0.5 to 50 g / m 2 .
- the thickness is not particularly limited, it is preferably 1 to 1000 ⁇ m, more preferably 1 to 500 ⁇ m, further preferably 30 to 300 ⁇ m, and further preferably 50 to 250 ⁇ m. .
- Weight in the present invention is a value obtained by measuring the mass of a sample cut into a 10 cm square and converting it to a mass of 1 m 2.
- Thiickness is a thickness gauge (manufactured by Mitutoyo Corporation: Code No.) .547-401: Measurement force 3.5N or less).
- the electrode substrate of the present invention includes a nonwoven fabric containing conductive fibers as described above, and has a specific apparent Young's modulus of 40 [MPa / (g / cm 3 )] or more, at least inside a conventional organic resin. Since it has higher rigidity than an electrode substrate containing conductive fibers containing conductive particles and can suppress swelling and shrinkage of the solid polymer film, it prevents cracks due to swelling and shrinkage of the solid polymer film. It is something that can be done.
- this specific apparent Young's modulus is a value obtained by dividing the apparent Young's modulus, which is an index of the rigidity of the electrode substrate, by the apparent density of the electrode substrate.
- the apparent Young's modulus is the same, when the apparent density is high and low, the lower apparent density is the same apparent Young's modulus even though the amount of conductive fibers is small.
- the rigidity of each conductive fiber is high, and as a result, it means that the solid polymer membrane is excellent in suppressing the swelling and shrinkage.
- Is expressed by a specific apparent Young's modulus which is a value obtained by dividing the apparent Young's modulus of the electrode substrate by the apparent density.
- the specific apparent Young's modulus is too high, the solid polymer film may be directly damaged by the rigidity of the conductive fiber, and therefore it is 1000 [MPa / (g / cm 3 )] or less. Is preferably 900 [MPa / (g / cm 3 )] or less, more preferably 700 [MPa / (g / cm 3 )] or less, and 500 [MPa / (g / cm 3). )] The following is more preferable.
- the specific apparent Young's modulus of the carbon paper and the glass nonwoven fabric electrode base material both well exceeds 1000 [MPa / (g / cm 3 )].
- the “specific apparent Young's modulus” of the present invention is a value obtained by the following procedure. (1) The apparent density (g / cm 3 ) is calculated by dividing the basis weight (g / cm 2 ) of the electrode base material to be evaluated by the thickness (cm). (2) The electrode substrate was cut into a rectangular shape of 50 mm in the vertical direction and 5 mm in the vertical direction, and 10 vertical direction test pieces cut into a rectangular shape of 5 mm in the horizontal direction and 50 mm in the horizontal direction. Ten test specimens each having a horizontal direction are collected.
- the apparent Young's modulus is obtained by dividing the tensile stress by the strain at the maximum point (dimensionalless) [elongation length of the test piece (mm) ⁇ initial test piece length (mm)]. Then, the arithmetic average value of the apparent Young's modulus of the 20 test pieces is calculated and set as the “average apparent Young's modulus”. (5) The “average apparent Young's modulus” is calculated by dividing the average apparent Young's modulus by the apparent density.
- the electrode substrate of the present invention preferably has a specific tensile strength (MPa) of 0.5 MPa or more so that it is excellent in handling properties during production of the gas diffusion electrode without being limited by thickness or production cost. It is more preferably 2 MPa or more, further preferably 4 MPa or more, further preferably 5 MPa or more, further preferably 6 MPa or more, and further preferably 7 MPa or more.
- the specific tensile strength is a value obtained by dividing the breaking strength, which is the strength of the electrode base material, by the apparent density of the electrode base material, as can be understood from the measurement method described later.
- the same tensile strength means that This means that the tensile strength of each conductive fiber is strong or the bond between the conductive fibers is strong, and as a result, the amount of fiber (weight per unit area) necessary to secure the tensile strength required during production is adjusted. It means you can do it.
- This “specific tensile strength” is a value obtained by the following procedure.
- the apparent density (g / cm 3 ) is calculated by dividing the basis weight (g / cm 2 ) of the electrode base material to be evaluated by the thickness (cm).
- the electrode substrate was cut into a rectangular shape of 50 mm in the vertical direction and 5 mm in the vertical direction, and 10 vertical direction test pieces cut into a rectangular shape of 5 mm in the horizontal direction and 50 mm in the horizontal direction. Ten test specimens are collected.
- the tensile shear test of each test piece was carried out using a small tensile tester (manufactured by Search, TSM-op01) with a distance between chucks of 20 mm and a pulling speed of 20 mm / min.
- the breaking strength (N) is measured.
- the tensile strength (MPa) is obtained by dividing the breaking strength (N) by the cross-sectional area [thickness (T) ⁇ 5] (unit: mm 2 ) of the test piece before the tensile shear test.
- the arithmetic average value of the tensile strength of the 20 test pieces is calculated and is defined as “average tensile strength”.
- the electrode base material of the present invention includes the nonwoven fabric as described above, since the nonwoven fabric is porous, when nothing is filled in the voids of the nonwoven fabric, drainage and gas diffusibility are also achieved in the surface direction. An excellent fuel cell with high power generation performance can be produced.
- This porosity preferably has a porosity of 20% or more, more preferably a porosity of 30% or more. More preferably, the porosity is 50% or more, more preferably the porosity is 60% or more, more preferably the porosity is 70% or more. More preferably, the porosity is 80% or more.
- the upper limit of the porosity is not particularly limited, but is preferably 99% or less, more preferably 95% or less, and still more preferably 90% or less from the viewpoint of form stability.
- Frn indicates the filling rate (unit:%) of component n constituting the nonwoven fabric, and is a value obtained from the following formula.
- M M ⁇ Prn / (T ⁇ SGn) ⁇ 100
- M is the basis weight of the nonwoven fabric (unit: g / cm 2 )
- T is the thickness (cm) of the nonwoven fabric
- Prn is the mass ratio of component n (for example, organic resin, conductive particles) in the nonwoven fabric
- SGn It means the specific gravity (unit: g / cm 3 ) of component n.
- the electrode base material of the present invention is preferably filled with no voids in the nonwoven fabric so that a fuel cell having excellent drainage and gas diffusibility in the surface direction and having high power generation performance can be produced.
- the surface of the nonwoven fabric and / or the voids may contain a fluorine-based resin and / or carbon within a range that does not impair drainage and gas diffusibility in the surface direction.
- fluororesin examples include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), perfluoroalkoxy fluororesin (PFA), tetrafluoroethylene.
- PTFE polytetrafluoroethylene
- PCTFE polychlorotrifluoroethylene
- PVDF polyvinylidene fluoride
- PVDF polyvinyl fluoride
- PVF polyvinyl fluoride
- PFA perfluoroalkoxy fluororesin
- Ethylene / hexafluoropropylene copolymer FEP
- Ethylene / hexafluoropropylene copolymer Ethylene / hexafluoropropylene copolymer
- ETFE ethylene / tetrafluoroethylene copolymer
- ECTFE ethylene / chlorotrifluoroethylene copolymer
- examples thereof include a propylene copolymer and a copolymer of various monomers constituting the resin
- examples of the carbon include carbon black, carbon nanotube, and carbon nanofiber.
- the electrode substrate of the present invention can be manufactured, for example, as follows.
- a fiber web is formed by spinning using a spinning solution in which an organic resin and conductive particles are mixed to form conductive fibers, and collecting and collecting the conductive fibers directly.
- thermosetting resin especially phenol resin or epoxy resin
- the organic resin so that the conductive fiber is stronger than the conductive fiber containing conductive particles at least inside the conventional organic resin. It is preferable.
- the fiber web can be used as a non-woven fabric (electrode substrate) as it is, and in order to impart or improve strength, plasticizing with a solvent, fusion with heat, adhesion with an adhesive, etc. It can combine and can also be set as a nonwoven fabric (electrode base material).
- a suitable thermosetting resin it is preferable to increase the rigidity of the conductive fiber by curing with heat.
- the conditions for curing the thermosetting resin differ depending on the type of the thermosetting resin, they are appropriately set according to the type of the thermosetting resin.
- the fibers constituting the fiber web formed by collecting and accumulating the conductive fibers directly are continuous long fibers. This is because the continuous long fibers are not only excellent in terms of conductivity and strength, but also have few fiber ends and are difficult to damage the solid polymer film.
- an electrostatic spinning method for example, an electrostatic spinning method, a spunbond method, a melt blow method, or a spinning solution discharged from a liquid discharge unit as disclosed in JP-A-2009-287138 is used.
- a method in which gas is discharged in parallel and a fiber is formed by applying a shearing force to the spinning solution in a straight line there can be mentioned a method in which gas is discharged in parallel and a fiber is formed by applying a shearing force to the spinning solution in a straight line.
- the electrostatic spinning method or the method disclosed in Japanese Patent Application Laid-Open No. 2009-287138 conductive fibers having a small fiber diameter can be spun, so that a thin non-woven fabric can be produced, resulting in the resistance of the fuel cell. This is preferable because the volume of the fuel cell can be reduced.
- the electrospinning method is suitable because continuous conductive fibers can be formed, and therefore there are few ends of the fibers and the solid polymer film is hardly damaged.
- a fiber web is formed by a known dry method or wet method, and plasticization with a solvent, heat It can also be made into a non-woven fabric by bonding by fusing, bonding with an adhesive or the like.
- the conductive fibers constituting the nonwoven fabric are preferably continuous fibers
- the nonwoven fabric is derived from a fiber web formed by collecting and collecting the continuous conductive fibers directly. preferable.
- the organic resin constituting the conductive fibers is acrylic oxide
- a spinning solution in which acrylic resin and conductive particles are mixed is spun to form conductive fibers, and the fiber web containing the conductive fibers is directly formed.
- the conductive property of the nonwoven fabric can be further increased by forming the acrylic resin as an acrylic oxide by heating it at a temperature of 200 to 300 ° C. in the air after it is formed indirectly or indirectly.
- conductive fibers spun using a spinning solution in which acrylic resin and conductive particles are mixed are heated in air at a temperature of 200 to 300 ° C. to make the acrylic resin acrylic oxide, and then acrylic oxide and It is also possible to form a nonwoven fabric using conductive fibers made of conductive particles.
- the nonwoven fabric When the organic resin constituting the conductive fiber contains a heat-resistant organic resin having a melting point exceeding 350 ° C., the nonwoven fabric is immersed in a fluorine-based dispersion such as polytetrafluoroethylene dispersion, and the nonwoven fabric is fluorinated. After applying the resin, sintering at a temperature of 300 to 350 ° C. can form an electrode substrate with improved water repellency.
- a fluorine-based dispersion such as polytetrafluoroethylene dispersion
- the electrode base material of the present invention is used, a gas diffusion electrode in which a catalyst is supported on the electrode base material can be produced. Since this gas diffusion electrode uses the electrode base material of the present invention, it is possible to suppress swelling and shrinkage of the solid polymer film without directly damaging the solid polymer film.
- the gas diffusion electrode has a catalyst supported on the surface of the conductive fiber, and not only the electron conduction by contact between the catalysts but also the electron conduction path by the conductive fiber is formed. Less is.
- the electrode base material is a non-woven porous body and has excellent drainage and gas diffusivity, so that gas can be supplied sufficiently stably to the three-phase interface (reaction field where gas, catalyst, and electrolyte resin meet). be able to. For these reasons, the catalyst can be used efficiently and the amount of catalyst can be reduced.
- the gas diffusion electrode has the same structure as that of a conventional gas diffusion electrode except that the gas diffusion electrode includes the electrode substrate of the present invention.
- the catalyst include platinum, platinum alloy, palladium, palladium alloy, titanium, manganese, magnesium, lanthanum, vanadium, zirconium, iridium, rhodium, ruthenium, gold, nickel-lanthanum alloy, titanium-iron alloy, and the like. It is possible to carry one or more kinds of catalysts selected from these.
- an electron conductor and a proton conductor are included, and as the electron conductor, conductive particles similar to the conductive particles contained in conductive fibers such as carbon black are suitable.
- the catalyst may be supported on the conductive particles.
- an ion exchange resin is suitable as the proton conductor.
- Such a gas diffusion electrode can be produced, for example, by the following method.
- a catalyst for example, carbon powder carrying a catalyst such as platinum
- a catalyst for example, carbon powder carrying a catalyst such as platinum
- a single or mixed solvent composed of ethyl alcohol, propyl alcohol, butyl alcohol, ethylene glycol dimethyl ether, etc.
- the solution is added and mixed uniformly by ultrasonic dispersion or the like to obtain a catalyst dispersion suspension.
- the catalyst dispersion suspension can be coated or dispersed on the electrode substrate of the present invention, and dried to produce a gas diffusion electrode.
- a membrane-electrode assembly can be formed using the electrode substrate of the present invention. Since this membrane-electrode assembly uses the electrode substrate of the present invention, swelling and shrinkage of the solid polymer membrane can be suppressed without directly damaging the solid polymer membrane.
- the membrane-electrode assembly can be exactly the same as the conventional membrane-electrode assembly except that the membrane-electrode assembly includes the electrode substrate of the present invention.
- Such a membrane-electrode assembly is obtained, for example, by sandwiching a solid polymer membrane between the respective catalyst-supporting surfaces of a pair of gas diffusion electrodes produced using the electrode base material of the present invention and hot pressing. Can be manufactured by joining.
- the catalyst layer is transferred to a solid polymer film, and then the electrode substrate of the present invention is laminated on the catalyst layer.
- the catalyst layer can also be manufactured by a hot pressing method.
- solid polymer film for example, a perfluorocarbon sulfonic acid resin film, a sulfonated aromatic hydrocarbon resin film, an alkylsulfonated aromatic hydrocarbon resin film, or the like can be used.
- the polymer electrolyte fuel cell using the electrode base material of the present invention uses the electrode base material of the present invention, the solid polymer film is not directly damaged, and the solid polymer film is not damaged. Therefore, the fuel cell has a long life.
- This fuel cell can be exactly the same as a conventional fuel cell except that it comprises the electrode substrate of the present invention.
- it has a structure in which a plurality of cell units each having a membrane-electrode assembly sandwiched between a pair of bipolar plates are stacked.
- a plurality of cell units can be stacked and fixed.
- the bipolar plate is not particularly limited as long as the bipolar plate has high conductivity, does not transmit gas, and has a flow path capable of supplying gas to the gas diffusion electrode.
- Carbon-resin composite materials, metal materials, and the like can be used.
- carbon black (Denka Black granular product, manufactured by Denki Kagaku Kogyo Co., Ltd., average primary particle size: 35 nm) is used as the conductive particles
- phenol resin (Bellepearl, Air Water Bellpearl Co., Ltd.) is used as the thermosetting resin. Is mixed with the above solution, stirred, diluted by adding DMF, carbon black and phenol resin are dispersed, and the solid mass of carbon black, phenol resin, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene copolymer A first spinning solution having a ratio of 40:10:50 and a solid content concentration of 10 mass% was prepared.
- the solid content concentration was 10 mass% in the same manner as in the first spinning solution except that the solid mass ratio of carbon black, phenol resin, and vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer was 40:20:40.
- a second spinning solution was prepared.
- the solid content concentration was 10 mass% in the same manner as in the first spinning solution except that the solid mass ratio of carbon black, phenol resin, and vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer was 40:30:30.
- a third spinning solution was prepared.
- the solid content concentration was 10 mass% in the same manner as in the first spinning solution except that the solid mass ratio of carbon black, phenol resin, and vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer was 50:10:40.
- a fourth spinning solution was prepared.
- the solid content concentration was 10 mass% in the same manner as in the first spinning solution except that the solid mass ratio of carbon black, phenol resin, and vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer was 50:20:30.
- a fifth spinning solution was prepared.
- the solid content concentration was 10 mass% in the same manner as in the first spinning solution except that the solid mass ratio of carbon black, phenol resin, and vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer was 60:10:30.
- a sixth spinning solution was prepared.
- VGCF vapor-grown carbon fiber
- the blending ratio of the first spinning solution to the eighth spinning solution was as shown in Table 1.
- CB represents carbon black
- P represents a phenol resin
- PV / TF / HFP represents a vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer.
- the blending ratio of the ninth spinning solution to the tenth spinning solution was as shown in Table 2.
- CB represents carbon black
- CF represents vapor grown carbon fiber
- PV, TF, and HFP represent vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer, respectively.
- Example 1 Conductive fibers obtained by spinning the first spinning solution by the electrostatic spinning method were directly accumulated on a stainless drum as a counter electrode to prepare a fiber web composed only of continuous conductive fibers. This fiber web was heat-treated at a temperature of 140 ° C. for 1 hour to cure the phenol resin, and an electrode substrate (36 g / m 2 in weight, thickness 160 ⁇ m, porosity 87%, average fiber diameter: 830 nm, electrical resistance: 33 m ⁇ ⁇ cm) 2 ) was produced. A part of the carbon black constituting this conductive fiber was present inside the conductive fiber, a part was exposed from the fiber surface, and the fibers were bonded together.
- the electrospinning conditions were as follows.
- Electrode Metal nozzle (inner diameter: 0.33 mm) and stainless steel drum Discharge amount: 2 g / hour Distance between nozzle tip and stainless steel drum: 10 cm Applied voltage: 15 kV Temperature / humidity: 25 ° C / 30% RH
- Example 2 The same procedure as in Example 1 was performed except that the second spinning solution was used, and an electrode substrate (weight per unit area: 34 g / m 2 , thickness: 180 ⁇ m, porosity: 89%, average fiber diameter: 360 nm, electric resistance: 39 m ⁇ ⁇ cm) 2 ) was produced. A part of the carbon black constituting this conductive fiber was present inside the conductive fiber, a part was exposed from the fiber surface, and the fibers were bonded together.
- an electrode substrate weight per unit area: 34 g / m 2 , thickness: 180 ⁇ m, porosity: 89%, average fiber diameter: 360 nm, electric resistance: 39 m ⁇ ⁇ cm
- Example 3 The same procedure as in Example 1 was performed except that the third spinning solution was used, and an electrode substrate (weight per unit: 37 g / m 2 , thickness: 200 ⁇ m, porosity: 89%, average fiber diameter: 270 nm, electric resistance: 44 m ⁇ ⁇ cm) 2 ) was produced. A part of the carbon black constituting this conductive fiber was present inside the conductive fiber, a part was exposed from the fiber surface, and the fibers were bonded together.
- Example 4 The same procedure as in Example 1 was performed except that the fourth spinning solution was used, and an electrode substrate (weight per unit area: 18 g / m 2 , thickness: 100 ⁇ m, porosity: 90%, average fiber diameter: 550 nm, electric resistance: 26 m ⁇ ⁇ cm) 2 ) was produced. A part of the carbon black constituting this conductive fiber was present inside the conductive fiber, a part was exposed from the fiber surface, and the fibers were bonded together.
- Example 5 The same procedure as in Example 1 was performed except that the fifth spinning solution was used.
- the electrode substrate (weight per unit area: 17 g / m 2 , thickness: 77 ⁇ m, porosity: 87%, average fiber diameter: 320 nm, electric resistance: 30 m ⁇ ⁇ cm 2 ) was produced. A part of the carbon black constituting this conductive fiber was present inside the conductive fiber, a part was exposed from the fiber surface, and the fibers were bonded together.
- Example 6 The same procedure as in Example 1 was performed except that the sixth spinning solution was used, and the electrode substrate (weight per unit area: 20 g / m 2 , thickness: 100 ⁇ m, porosity: 88%, average fiber diameter: 720 nm, electric resistance: 21 m ⁇ ⁇ cm) 2 ) was produced. A part of the carbon black constituting this conductive fiber was present inside the conductive fiber, a part was exposed from the fiber surface, and the fibers were bonded together.
- Example 7 The same procedure as in Example 1 was performed except that the ninth spinning solution was used, and an electrode substrate (weight per unit area 90 g / m 2 , thickness 185 ⁇ m, porosity 70%, average fiber diameter: 620 nm, electrical resistance: 45 m ⁇ ⁇ cm) 2 ) was produced. A part of the carbon black constituting this conductive fiber was present inside the conductive fiber, a part was exposed from the fiber surface, and the fibers were bonded together.
- Example 8> The same procedure as in Example 1 was carried out except that the 10th spinning solution was used, and the electrode substrate (weight per unit 42 g / m 2 , thickness 150 ⁇ m, porosity 82%, average fiber diameter: 720 nm, electrical resistance: 40 m ⁇ ⁇ cm) 2 ) was produced. A part of the vapor grown carbon fiber constituting this conductive fiber was present inside the conductive fiber, a part was exposed from the fiber surface, and the fibers were bonded together.
- Example 1 The same procedure as in Example 1 was conducted except that the heat treatment was not performed, and an electrode substrate (weight per unit area: 22 g / m 2 , thickness: 100 ⁇ m, porosity: 88%, average fiber diameter: 700 nm, electric resistance: 35 m ⁇ ⁇ cm 2 ) was made. A part of the carbon black constituting this conductive fiber was present inside the conductive fiber, a part was exposed from the fiber surface, and the fibers were bonded together.
- an electrode substrate weight per unit area: 22 g / m 2 , thickness: 100 ⁇ m, porosity: 88%, average fiber diameter: 700 nm, electric resistance: 35 m ⁇ ⁇ cm 2 .
- Comparative example 2 The same procedure as in Comparative Example 1 was conducted except that the seventh spinning solution was used, and an electrode substrate (weight per unit area: 18 g / m 2 , thickness: 90 ⁇ m, porosity: 90%, average fiber diameter: 900 nm, electric resistance: 43 m ⁇ ⁇ cm) 2 ) was produced. A part of the carbon black constituting this conductive fiber was present inside the conductive fiber, a part was exposed from the fiber surface, and the fibers were bonded together.
- an electrode substrate weight per unit area: 18 g / m 2 , thickness: 90 ⁇ m, porosity: 90%, average fiber diameter: 900 nm, electric resistance: 43 m ⁇ ⁇ cm
- SRS is specific tensile strength [unit: MPa / (g / cm 3 )]
- AY is apparent Young's modulus (unit: MPa)
- SAY is relative apparent Young's modulus [unit: MPa / (g / cm 3 )].
- the electrode base materials of Examples 1 to 8 of the present invention are the electrode base materials made of non-woven fabric containing conductive fibers containing the conventional organic resin and conductive particles of Comparative Examples 2 to 4. Furthermore, since the specific Young's modulus is high and the rigidity is high, the effect of suppressing the swelling and shrinkage of the solid polymer film can be expected.
- the base material for gas diffusion electrode of the present invention is more rigid than the base material for gas diffusion electrode made of a nonwoven fabric containing conductive fibers containing conventional organic resin and conductive particles, the swelling of the solid polymer film And shrinkage can be suppressed.
- the base material for gas diffusion electrodes of this invention is more flexible than the base material for gas diffusion electrodes which consists of conventional carbon paper and glass fiber, it does not damage a solid polymer film directly. Therefore, it can be suitably used for polymer electrolyte fuel cell applications.
- this invention was demonstrated along the specific aspect, the deformation
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Abstract
Description
(1)評価対象の電極基材の目付(g/cm2)を厚さ(cm)で除して、見掛密度(g/cm3)を算出する。
(2)電極基材を、たて方向に50mmで、よこ方向に5mmの長方形状に裁断したたて方向試験片10枚、及びよこ方向に50mmで、たて方向に5mmの長方形状に裁断したよこ方向試験片10枚を、それぞれ採取する。
(3)前記各試験片の引張りせん断試験を、小型引張り試験機(サーチ社製、TSM-op01)を用い、チャック間距離20mm、引張り速度20mm/min.の条件で実施し、各々荷重-伸び曲線を描く。
(4)前記各々の荷重-伸び曲線における原点近くで伸長変化に対する荷重変化の最大点(接線角の最大点)における荷重(N)を、引張りせん断試験をする前の試験片の断面積[厚さ(T)×5](単位:mm2)で除して、引張り応力(MPa)を算出する。続いて、引張り応力を最大点におけるひずみ(無次元)[試験片の伸び長さ(mm)÷初期試験片長さ(mm)]で除することで、見掛けヤング率を各々求める。そして、20枚の試験片の見掛けヤング率の算術平均値を算出し、「平均見掛けヤング率」とする。
(5)前記平均見掛けヤング率を前記見掛密度で除して、「比見掛ヤング率」を算出する。
(1)評価対象の電極基材の目付(g/cm2)を厚さ(cm)で除して、見掛密度(g/cm3)を算出する。
(2)電極基材を、たて方向に50mmで、よこ方向に5mmの長方形状に裁断したたて方向試験片10枚、及びよこ方向に50mmで、たて方向に5mmの長方形状に裁断したよこ方向試験片10枚を採取する。
(3)前記各試験片の引張りせん断試験を、小型引張り試験機(サーチ社製、TSM-op01)を用い、チャック間距離20mm、引張り速度20mm/min.の条件で実施し、破断強度(N)を各々測定する。
(4)破断強度(N)を、引張りせん断試験をする前の試験片の断面積[厚さ(T)×5](単位:mm2)で除して、引張り強度(MPa)を各々求め、20枚の試験片の引張り強度の算術平均値を算出し、「平均引張り強度」とする。
(5)前記平均引張り強度を前記見掛密度で除して、「比引張り強度」を算出する。
P=100-(Fr1+Fr2+・・+Frn)
ここで、Frnは不織布を構成する成分nの充填率(単位:%)を示し、次の式から得られる値をいう。
Frn=M×Prn/(T×SGn)×100
ここで、Mは不織布の目付(単位:g/cm2)、Tは不織布の厚さ(cm)、Prnは不織布における成分n(例えば、有機樹脂、導電性粒子)の存在質量比率、SGnは成分nの比重(単位:g/cm3)をそれぞれ意味する。
<第1紡糸溶液の調製>
フッ化ビニリデン・テトラフルオロエチレン・ヘキサフルオロプロピレン共重合物をN,N-ジメチルホルムアミド(DMF)に加え、ロッキングミルを用いて溶解させ、濃度10mass%の溶液を得た。
カーボンブラックとフェノール樹脂とフッ化ビニリデン・テトラフルオロエチレン・ヘキサフルオロプロピレン共重合物の固形質量比を40:20:40としたこと以外は第1紡糸溶液と同様にして、固形分濃度が10mass%の第2紡糸溶液を調製した。
カーボンブラックとフェノール樹脂とフッ化ビニリデン・テトラフルオロエチレン・ヘキサフルオロプロピレン共重合物の固形質量比を40:30:30としたこと以外は第1紡糸溶液と同様にして、固形分濃度が10mass%の第3紡糸溶液を調製した。
カーボンブラックとフェノール樹脂とフッ化ビニリデン・テトラフルオロエチレン・ヘキサフルオロプロピレン共重合物の固形質量比を50:10:40としたこと以外は第1紡糸溶液と同様にして、固形分濃度が10mass%の第4紡糸溶液を調整した。
カーボンブラックとフェノール樹脂とフッ化ビニリデン・テトラフルオロエチレン・ヘキサフルオロプロピレン共重合物の固形質量比を50:20:30としたこと以外は第1紡糸溶液と同様にして、固形分濃度が10mass%の第5紡糸溶液を調製した。
カーボンブラックとフェノール樹脂とフッ化ビニリデン・テトラフルオロエチレン・ヘキサフルオロプロピレン共重合物の固形質量比を60:10:30としたこと以外は第1紡糸溶液と同様にして、固形分濃度が10mass%の第6紡糸溶液を調製した。
フェノール樹脂を加えなかったこと以外は第1紡糸溶液と同様にして、カーボンブラックとフッ化ビニリデン・テトラフルオロエチレン・ヘキサフルオロプロピレン共重合物の固形質量比が40:60で、固形分濃度が10mass%の第7紡糸溶液を調製した。
カーボンブラックとフッ化ビニリデン・テトラフルオロエチレン・ヘキサフルオロプロピレン共重合物の比率を変えたこと以外は、第7紡糸溶液と同様にして、カーボンブラックとフッ化ビニリデン・テトラフルオロエチレン・ヘキサフルオロプロピレン共重合物の固形質量比が60:40で、固形分濃度が10mass%の第8紡糸溶液を調製した。
フェノール樹脂に替えて、クレゾールノボラックエポキシ樹脂を主剤とし、ノボラック型フェノール樹脂を硬化剤とするエポキシ樹脂を使用し、固形分濃度を16mass%に変更したこと以外は、第3紡糸溶液と同様にして、第9紡糸溶液を調製した。
カーボンブラックに替えて、気相法炭素繊維(VGCF、登録商標、昭和電工(株)製)を使用したこと以外は、第9紡糸溶液と同様にして、第10紡糸溶液を調製した。
第1紡糸溶液を静電紡糸法により紡糸して得た導電性繊維を、対向電極であるステンレスドラム上に、直接、集積して、連続した導電性繊維のみからなる繊維ウエブを作製した。この繊維ウエブを温度140℃で1時間熱処理し、フェノール樹脂を硬化させ、電極基材(目付36g/m2、厚さ160μm、空隙率87%、平均繊維径:830nm、電気抵抗:33mΩ・cm2)を作製した。この導電性繊維を構成するカーボンブラックの一部は導電性繊維内部に存在し、一部は繊維表面から露出した状態にあり、繊維同士は集積時に結合した状態にあった。なお、静電紡糸条件は次の通りとした。
吐出量:2g/時間
ノズル先端とステンレスドラムとの距離:10cm
印加電圧:15kV
温度/湿度:25℃/30%RH
第2紡糸溶液を用いたこと以外は実施例1と同様に実施し、電極基材(目付34g/m2、厚さ180μm、空隙率89%、平均繊維径:360nm、電気抵抗:39mΩ・cm2)を作製した。この導電性繊維を構成するカーボンブラックの一部は導電性繊維内部に存在し、一部は繊維表面から露出した状態にあり、繊維同士は集積時に結合した状態にあった。
第3紡糸溶液を用いたこと以外は実施例1と同様に実施し、電極基材(目付37g/m2、厚さ200μm、空隙率89%、平均繊維径:270nm、電気抵抗:44mΩ・cm2)を作製した。この導電性繊維を構成するカーボンブラックの一部は導電性繊維内部に存在し、一部は繊維表面から露出した状態にあり、繊維同士は集積時に結合した状態にあった。
第4紡糸溶液を用いたこと以外は実施例1と同様に実施し、電極基材(目付18g/m2、厚さ100μm、空隙率90%、平均繊維径:550nm、電気抵抗:26mΩ・cm2)を作製した。この導電性繊維を構成するカーボンブラックの一部は導電性繊維内部に存在し、一部は繊維表面から露出した状態にあり、繊維同士は集積時に結合した状態にあった。
第5紡糸溶液を用いたこと以外は実施例1と同様に実施し、電極基材(目付17g/m2、厚さ77μm、空隙率87%、平均繊維径:320nm、電気抵抗:30mΩ・cm2)を作製した。この導電性繊維を構成するカーボンブラックの一部は導電性繊維内部に存在し、一部は繊維表面から露出した状態にあり、繊維同士は集積時に結合した状態にあった。
第6紡糸溶液を用いたこと以外は実施例1と同様に実施し、電極基材(目付20g/m2、厚さ100μm、空隙率88%、平均繊維径:720nm、電気抵抗:21mΩ・cm2)を作製した。この導電性繊維を構成するカーボンブラックの一部は導電性繊維内部に存在し、一部は繊維表面から露出した状態にあり、繊維同士は集積時に結合した状態にあった。
第9紡糸溶液を用いたこと以外は実施例1と同様に実施し、電極基材(目付90g/m2、厚さ185μm、空隙率70%、平均繊維径:620nm、電気抵抗:45mΩ・cm2)を作製した。この導電性繊維を構成するカーボンブラックの一部は導電性繊維内部に存在し、一部は繊維表面から露出した状態にあり、繊維同士は集積時に結合した状態にあった。
第10紡糸溶液を用いたこと以外は実施例1と同様に実施し、電極基材(目付42g/m2、厚さ150μm、空隙率82%、平均繊維径:720nm、電気抵抗:40mΩ・cm2)を作製した。この導電性繊維を構成する気相法炭素繊維の一部は導電性繊維内部に存在し、一部は繊維表面から露出した状態にあり、繊維同士は集積時に結合した状態にあった。
熱処理を行わなかったこと以外は実施例1と同様に実施し、電極基材(目付22g/m2、厚さ100μm、空隙率88%、平均繊維径:700nm、電気抵抗:35mΩ・cm2)を作製した。この導電性繊維を構成するカーボンブラックの一部は導電性繊維内部に存在し、一部は繊維表面から露出した状態にあり、繊維同士は集積時に結合した状態にあった。
第7紡糸溶液を用いたこと以外は比較例1と同様に実施し、電極基材(目付18g/m2、厚さ90μm、空隙率90%、平均繊維径:900nm、電気抵抗:43mΩ・cm2)を作製した。この導電性繊維を構成するカーボンブラックの一部は導電性繊維内部に存在し、一部は繊維表面から露出した状態にあり、繊維同士は集積時に結合した状態にあった。
比較例2と同様に実施し、電極基材(目付65g/m2、厚さ180μm、空隙率80%、平均繊維径:680nm、電気抵抗:39mΩ・cm2)を作製した。この導電性繊維を構成するカーボンブラックの一部は導電性繊維内部に存在し、一部は繊維表面から露出した状態にあり、繊維同士は集積時に結合した状態にあった。
第8紡糸溶液を用いたこと以外は比較例2と同様に実施し、電極基材(目付21g/m2、厚さ120μm、空隙率87%、平均繊維径:880nm、電気抵抗:25mΩ・cm2)を作製した。この導電性繊維を構成するカーボンブラックの一部は導電性繊維内部に存在し、一部は繊維表面から露出した状態にあり、繊維同士は集積時に結合した状態にあった。
実施例1~8及び比較例1~4の電極基材に関して、前述の方法により、破断強度、比引張り強度、見掛ヤング率及び比見掛ヤング率を、それぞれ計測した。これらの結果は表3に示す通りであった。なお、表中、Mは目付(単位:g/m2)、Tは厚さ(単位:μm)、ADは見掛密度(単位:g/cm3)、RSは破断強度(単位:MPa)、SRSは比引張り強度[単位:MPa/(g/cm3)]、AYは見掛ヤング率(単位:MPa)、SAYは比見掛ヤング率[単位:MPa/(g/cm3)]を、それぞれ表す。
以上、本発明を特定の態様に沿って説明したが、当業者に自明の変形や改良は本発明の範囲に含まれる。
11c (空気極側)バイポーラプレート
13a (燃料極側)ガス拡散層
13c (空気極側)ガス拡散層
14a (燃料極側)水分管理層
14c (空気極側)水分管理層
15a (燃料極側)触媒層
15c (空気極側)触媒層
17a 燃料極(ガス拡散電極)
17c 空気極(ガス拡散電極)
19 固体高分子膜
Claims (1)
- 有機樹脂の少なくとも内部に導電性粒子を含有する導電性繊維を含有する不織布を含むガス拡散電極用基材であり、前記ガス拡散電極用基材の比見掛ヤング率が40[MPa/(g/cm3)]以上であることを特徴とする、ガス拡散電極用基材。
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US14/891,025 US9685663B2 (en) | 2013-05-15 | 2014-05-15 | Base material for gas diffusion electrode |
JP2015517131A JP6251737B2 (ja) | 2013-05-15 | 2014-05-15 | ガス拡散電極用基材 |
EP14797557.7A EP2999038A4 (en) | 2013-05-15 | 2014-05-15 | BASIC MATERIAL FOR GAS DIFFUSION ELECTRODE |
KR1020157034453A KR20160009584A (ko) | 2013-05-15 | 2014-05-15 | 가스 확산 전극용 기재 |
CN201480027353.9A CN105190970B (zh) | 2013-05-15 | 2014-05-15 | 气体扩散电极用基材 |
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WO2015146984A1 (ja) * | 2014-03-27 | 2015-10-01 | 日本バイリーン株式会社 | 導電性多孔体、固体高分子形燃料電池、及び導電性多孔体の製造方法 |
JP2016169450A (ja) * | 2015-03-12 | 2016-09-23 | 日本バイリーン株式会社 | 導電性繊維シ−ト、ガス拡散電極、膜−電極接合体、固体高分子形燃料電池、及び導電性繊維シートの製造方法 |
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JP6814045B2 (ja) * | 2014-06-17 | 2021-01-13 | オーシーヴィー インテレクチュアル キャピタル リミテッド ライアビリティ カンパニー | 鉛蓄電池用の抗−サルフェーション性貼付マット |
KR102169179B1 (ko) * | 2016-03-31 | 2020-10-21 | 주식회사 엘지화학 | 바이폴라 플레이트 및 이를 포함하는 레독스 흐름 전지 |
CN113410486A (zh) * | 2021-06-03 | 2021-09-17 | 大连海事大学 | 一种液流电池双极板材料及其制备方法 |
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US9685663B2 (en) | 2017-06-20 |
EP2999038A4 (en) | 2016-10-12 |
CN105190970A (zh) | 2015-12-23 |
KR20160009584A (ko) | 2016-01-26 |
JP6251737B2 (ja) | 2017-12-20 |
EP2999038A1 (en) | 2016-03-23 |
CN105190970B (zh) | 2017-12-29 |
US20160118669A1 (en) | 2016-04-28 |
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