WO2016171082A1 - ガス拡散電極基材およびその製造方法 - Google Patents
ガス拡散電極基材およびその製造方法 Download PDFInfo
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- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8892—Impregnation or coating of the catalyst layer, e.g. by an ionomer
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- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
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- H01M4/88—Processes of manufacture
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- 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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- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
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- H—ELECTRICITY
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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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
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- 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
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells
Definitions
- a fuel cell is a mechanism that electrically extracts energy generated when water is produced by reacting hydrogen and oxygen, and is expected to be clean energy because it has high energy efficiency and has only water.
- the present invention relates to a gas diffusion electrode substrate used for a fuel cell and a method for producing the same, and more particularly, to a gas diffusion electrode substrate used for a polymer electrolyte fuel cell used as a power source for a fuel cell vehicle, etc. It relates to the manufacturing method.
- An electrode used for a polymer electrolyte fuel cell includes a catalyst layer formed on the surface of the polymer electrolyte membrane on both sides of the polymer electrolyte membrane and a gas diffusion layer formed outside the catalyst layer. It has a structure.
- An electrode base material circulates as an individual member for forming a gas diffusion layer on the electrode.
- the performance required for this electrode substrate includes, for example, gas diffusivity, conductivity for collecting electricity generated in the catalyst layer, and drainage for efficiently removing moisture generated on the surface of the catalyst layer. can give.
- a conductive porous base material having both gas diffusibility and conductivity is generally used.
- the conductive porous substrate carbon felt made of carbon fiber, carbon paper, carbon cloth, and the like are used, and among these, carbon paper is most preferable from the viewpoint of mechanical strength.
- a fuel cell is a system that electrically extracts energy generated when hydrogen and oxygen react to produce water
- the electrical load increases, that is, when the current taken out of the cell increases, a large amount of water
- the amount of gas (oxygen or hydrogen) supplied to the catalyst layer decreases, and finally all If the pores are blocked, power generation is stopped. This phenomenon is called flooding.
- the gas diffusion layer is required to have drainage in order to maximize the current value that causes flooding.
- the water repellency is usually increased by using an electrode base material obtained by subjecting the conductive porous base material to a water repellent treatment.
- Patent Documents 1 and 2 are examples of the amount of the water repellent material in the electrode base material continuously decreases from the catalyst layer side toward the other side.
- Patent Document 1 proposes a method of applying a water-repellent liquid while heating the conductive porous substrate in order to suppress the penetration of the water-repellent liquid into the conductive porous substrate.
- the water-repellent liquid is applied while heating the conductive porous substrate, the amount of the water-repellent material on the catalyst layer side of the conductive porous substrate becomes insufficient, and water is condensed at a site with poor water repellency. And hinder the discharge of water outside the system.
- Patent Document 2 proposes a method in which a coating liquid composed of carbon powder and a water repellent material is applied from one side of a conductive porous base material, and the water repellent material in the coating liquid is soaked into the conductive porous base material.
- the conductive porous substrate is not subjected to any treatment, and as a pretreatment, the surfactant solution is impregnated with the conductive porous substrate, so that the coating liquid can easily penetrate into the conductive porous substrate.
- the water repellent material in the coating liquid but also the carbon powder soaks into the conductive porous substrate, thereby blocking the pores and lowering the gas diffusivity and lowering the power generation performance.
- the surface treatment is performed using a surfactant, the water repellent material and the carbon powder reach the side opposite to the side where the coating liquid has been applied, which hinders the discharge of water outside the system. It was.
- the present invention employs the following means in order to solve the above problems.
- the thickness is 110 ⁇ m or more and 240 ⁇ m or less
- the cross section of the gas diffusion electrode substrate is divided into a part having MPL and a part not having MPL, and a part not having MPL is further in contact with MPL (hereinafter referred to as CP1 cross section) and a part not in contact with MPL.
- a gas diffusion electrode having an F / C ratio of the CP1 cross section of 0.03 or more and 0.10 or less and an F / C ratio of the CP2 cross section of less than 0.03 when divided into two equal parts hereinafter referred to as CP2 cross section).
- Base material hereinafter referred to as CP2 cross section.
- F means the mass of fluorine atoms
- C means the mass of carbon atoms
- the fuel cell comprising the gas diffusion layer of the gas diffusion electrode substrate of the present invention has good power generation performance at high current density under the low temperature condition of the fuel cell, that is, the condition where water vapor is condensed inside the fuel cell and water droplets are generated. It will be something.
- the gas diffusion electrode substrate of the present invention has a microporous layer (hereinafter referred to as MPL) disposed on one surface of the electrode substrate.
- MPL microporous layer
- gas diffusion electrode substrate is an individual member corresponding to a gas diffusion layer in a fuel cell electrode.
- electrode substrate means a “conductive porous substrate” containing fluorine atoms.
- the gas diffusion layer has a high gas diffusibility for diffusing the gas supplied from the separator to the catalyst, a high drainage property for discharging the water generated by the electrochemical reaction to the separator, and generation. High electrical conductivity is needed to extract the measured current. Therefore, the electrode base material used for the gas diffusion electrode base material for constituting the gas diffusion layer is a conductive porous base material made of a porous body having conductivity and an average pore diameter of usually 10 to 100 ⁇ m. Use.
- the conductive porous substrate specifically, for example, a porous substrate containing carbon fibers such as carbon fiber woven fabric, carbon fiber papermaking body, carbon fiber nonwoven fabric, carbon felt, carbon paper, carbon cloth, It is preferable to use a porous metal substrate such as a foam sintered metal, a metal mesh, or an expanded metal.
- a porous substrate containing carbon fibers since the corrosion resistance is excellent, it is preferable to use a porous substrate containing carbon fibers as the conductive porous substrate, and moreover, a characteristic that absorbs a dimensional change in the thickness direction of the electrolyte membrane, that is, “ Since it is excellent in “spring property”, it is preferable to use carbon paper which is a base material formed by binding a carbon fiber papermaking body with carbide.
- the carbon paper is obtained by impregnating a carbon fiber papermaking body with a resin and carbonizing it.
- Examples of the carbon fiber include polyacrylonitrile (PAN), pitch, and rayon carbon fibers.
- PAN polyacrylonitrile
- pitch rayon carbon fibers.
- PAN-based and pitch-based carbon fibers are preferably used in the present invention because of excellent mechanical strength.
- the thickness of the conductive porous substrate or the electrode substrate is preferably 210 ⁇ m or less. Moreover, it is preferable that the thickness of a conductive porous base material or an electrode base material is 90 micrometers or more.
- the gas diffusion distance in the thickness direction is shortened when this is used as the gas diffusion electrode substrate, and the gas diffusibility is improved.
- the drainage path is shortened, drainage is improved and flooding can be suppressed.
- the conduction path is shortened, the conductivity is improved, and the power generation performance is improved at both high and low temperatures.
- the water repellent material is stained on the other surface when the water repellent treatment is performed from one surface of the conductive porous substrate. Since it does not come out, the F / C ratio of the CP2 cross section becomes 0.01 or less, and since water droplets are smoothly discharged out of the system, drainage is improved, and flooding can be suppressed, so that power generation performance at low temperature is improved.
- the thickness of the conductive porous substrate or electrode substrate is 90 ⁇ m or more, the gas diffusion property in the in-plane direction is improved when the gas diffusion electrode substrate is used, and the separator rib Since the gas can be easily supplied to the catalyst in the above, the power generation performance is improved at both high and low temperatures. Further, when the thickness of the conductive porous substrate or electrode substrate is 90 ⁇ m or more, the mechanical strength of the conductive porous substrate is further improved, and when this is used as a gas diffusion electrode substrate, the electrolyte It becomes easier to support the membrane and catalyst layer.
- the thickness of the conductive porous substrate and the electrode substrate can be determined using a micrometer in a state where the surface pressure is 0.15 MPa. The average of 10 individual measured values is taken as the thickness of the conductive porous substrate or electrode substrate.
- the conductive porous substrate containing fluorine atoms is the electrode substrate.
- an electrode substrate that is a conductive porous substrate containing fluorine atoms is formed.
- fluorine atoms such as fluororesin act as a water repellent material.
- whether or not the conductive porous substrate contains fluorine atoms, that is, whether or not a certain substrate corresponds to the electrode substrate is determined by the F / C ratio of the CP1 cross section and the F / C of the CP2 cross section described later. Determination is made based on whether or not at least one of the ratio and the F / C ratio of the surface opposite to the side on which the MPL is disposed is greater than zero.
- a fluororesin suitable for being applied to the conductive porous substrate is PTFE (polytetrafluoroethylene) (for example, “Teflon” (registered trademark)), FEP (tetrafluoroethylene hexafluoride).
- PTFE polytetrafluoroethylene
- FEP tetrafluoroethylene hexafluoride
- propylene fluoride copolymer PFA (perfluoroalkoxy fluoride resin), ETFA (ethylene tetrafluoroethylene copolymer), PVDF (polyvinylidene fluoride), and PVF (polyvinyl fluoride).
- the viscosity of the fluororesin becomes low when melted, the bias of the fluororesin, that is, the bias of fluorine atoms is reduced, and the power generation performance of the gas diffusion electrode substrate using such an electrode substrate is reduced. improves.
- the fluororesin having a melting point of 200 ° C. or higher and 320 ° C. or lower include FEP and PFA, and FEP is particularly preferable.
- the amount of the water repellent material that is, the amount of fluorine atoms continuously decreases from the catalyst layer side toward the other side. That is, in the gas diffusion electrode substrate of the present invention, as shown in FIG. 1, the cross section of the gas diffusion electrode substrate 1 is divided into a portion having MPL (MPL2) and a portion not having MPL (electrode substrate 3). Further, when the part having no MPL is divided into two parts, a part in contact with the MPL (CP1 cross section 4) and a part not in contact with the MPL (CP2 cross section 5), the F / C ratio of the CP1 cross section is 0.03 or more.
- the F / C ratio of the CP2 cross section is less than 0.03 and the F / C ratio of the CP2 cross section is preferably 0.01 or less.
- F means the mass of fluorine atoms
- C means the mass of carbon atoms.
- the lower limit of the F / C ratio of the CP2 cross section is zero.
- the method for setting the F / C ratio of the CP2 cross section to less than 0.03 is not particularly limited.
- the F / C ratio of the CP2 cross section can be made less than 0.03 by applying a water repellent material from one of the conductive porous substrates having a thickness of 90 ⁇ m or more.
- the method for setting the F / C ratio of the CP1 cross section to 0.03 or more and 0.10 or less is not particularly limited.
- the F / C ratio of the CP1 cross section is 0.03 or more and 0.10.
- F / C ratio is an index indicating the abundance of a fluororesin that is a water repellent material that provides water repellency.
- a large F / C ratio means high water repellency. If the F / C ratio of the CP1 cross section is 0.03 or more, there is sufficient water repellency and water droplets are prevented from staying in CP1. Further, if the F / C ratio of the CP1 cross section is 0.10 or less, it is generated on the surface of the catalyst layer and taken into the electrode base material without pushing back the water droplets that have passed through the MPL toward the CP1. To discharge. If the F / C ratio of the CP2 cross section is less than 0.03, water droplets coming from CP1 toward CP2 are discharged out of the system. If it is 0.03 or more, the water-repellent material inhibits water droplets from being discharged out of the system, and the drainage performance decreases.
- the tip of the portion where MPL is most immersed in the electrode substrate is included.
- it can be determined by drawing a line parallel to the surface of the substrate. Details will be described later.
- the F / C ratio of the surface of the gas diffusion electrode substrate of the present invention on the side opposite to the side on which the MPL is disposed is 0.01 or less, water droplets from CP1 toward CP2 are discharged out of the system. Therefore, it is preferable.
- the lower limit of the F / C ratio on the surface opposite to the side on which the MPL is disposed is zero.
- the method for setting the F / C ratio on the surface opposite to the side on which the MPL is disposed to 0.01 or less is not particularly limited.
- the F / C ratio of the surface of the gas diffusion electrode substrate of the present invention on the side where the MPL is disposed is 0.10 or more, it is preferable because there is sufficient water repellency and water droplets are prevented from staying in the MPL. Further, if the F / C ratio on the surface on which the MPL is disposed is 0.40 or less, the water stays between the catalyst layer and the MPL without pushing back the water droplets coming from the catalyst toward the MPL. It is preferable to prevent it.
- a method of including a fluororesin in the MPL can be mentioned. .
- MPL is disposed on one surface of the electrode substrate.
- MPL has high gas diffusivity in the vertical direction for diffusing the gas supplied from the separator to the catalyst, high drainage for discharging liquid water generated by the electrochemical reaction to the separator, and the generated current. It has high conductivity for taking out. Furthermore, MPL also has a function of accelerating the back diffusion of moisture into the electrolyte membrane and moistening the electrolyte membrane. In the present invention, it is important that the MPL is disposed only on one surface of the electrode substrate. When MPL is arranged on both surfaces of the electrode base material, MPL having high water repellency is also arranged between the electrode base material and the separator. The power generation performance is reduced.
- the method for producing the gas diffusion electrode substrate of the present invention is not particularly limited.
- a production method in which a step of spraying or coating a dispersion containing a fluororesin from one surface of the conductive porous substrate and subsequently placing MPL on the surface is particularly suitable.
- the manufacturing method of the gas diffusion electrode base material of this invention is demonstrated.
- the electrode substrate of the present invention is a conductive porous substrate containing fluorine atoms. This can be obtained by applying a so-called water-repellent treatment for imparting a water-repellent material to the conductive porous substrate.
- the water repellent treatment can be carried out by applying a dispersion containing the fluororesin from one surface of the conductive porous substrate and subsequently performing a heat treatment.
- spraying or the like, or coating with a die coater or the like is preferable.
- the amount of the fluororesin applied during the water repellent treatment is preferably 1 to 5 parts by mass with respect to 100 parts by mass of the conductive porous substrate.
- the electrode substrate When the coating amount of the fluororesin is 1 part by mass or more, the electrode substrate is preferable because it has excellent drainage. Moreover, when the application amount of the fluororesin is 5 parts by mass or less, the electrode base material is preferable because it has excellent conductivity. After the fluororesin coating, drying is preferably performed at 90 ° C. or more and less than 200 ° C.
- the gas diffusion electrode substrate of the present invention is preferably a production method in which MPL is disposed on the surface after water-repellent treatment is performed from one surface of the conductive porous substrate in this way.
- MPL comprises conductive fine particles such as carbon black, carbon nanotubes, carbon nanofibers, chopped fibers of carbon fibers, graphene, and graphite.
- conductive fine particles carbon black, carbon nanotubes, carbon nanofibers, and graphene are particularly preferably used.
- carbon black acetylene black is preferably used because it has few impurities and hardly reduces the activity of the catalyst.
- the MPL also requires properties such as conductivity, gas diffusivity, water drainage, moisture retention and thermal conductivity, as well as strong acid resistance on the anode side inside the fuel cell and oxidation resistance on the cathode side. It is done. Therefore, the MPL preferably contains a water-repellent resin such as a fluororesin in addition to the conductive fine particles.
- a fluororesin used for MPL PTFE, FEP, PFA, ETFA, etc. are suitable like the fluororesin used for an electrode substrate.
- PTFE is preferable because it has the highest water repellency.
- PTFE has a high melting point of around 330 ° C., there is a drawback that the sintering temperature described later must be 350 ° C.
- a fluororesin having a melting point of 300 ° C. or lower such as FEP.
- the lower limit of the melting point is not less than the boiling point of the solvent and substantially about 100 ° C., preferably 150 ° C. or more.
- MPL coating liquid a coating liquid for forming MPL (hereinafter referred to as MPL coating liquid) to one surface of the electrode base material.
- the MPL coating liquid usually contains the above-mentioned conductive fine particles and a solvent such as water or alcohol, and is often blended with a surfactant for dispersing the conductive fine particles. Further, in order to include the water repellent resin in the MPL, the water repellent resin is previously blended in the MPL coating liquid.
- the coating of the MPL coating liquid on the electrode substrate can be performed using various commercially available coating apparatuses.
- As the coating method screen printing, rotary screen printing, spray spraying, intaglio printing, gravure printing, die coater coating, bar coating, blade coating and the like can be used. Since the amount of coating can be quantified regardless of the surface roughness of the electrode substrate, coating with a die coater is preferred.
- the coating methods exemplified above are only for illustrative purposes, and are not necessarily limited thereto.
- sintering is performed for the purpose of removing the surfactant used for dispersing the conductive fine particles and for binding the conductive fine particles by dissolving the fluororesin once.
- the sintering temperature is higher than the boiling point or decomposition temperature of the surfactant and the melting temperature of the fluororesin.
- sintering should be performed at a sintering temperature of 330 ° C. or higher, preferably 350 ° C. or higher for 30 seconds or longer.
- the upper limit is usually about 400 ° C.
- the upper limit of the sintering time is usually about 60 minutes from the viewpoint of productivity.
- a nonionic surfactant is generally used in that it has few impurities.
- Octylphenoxypolyethoxyethanol (“TRITON (registered trademark)" X-100 manufactured by Nacalai Tesque, Inc.), polyoxyethylene alkyl ether, polyvinyl alcohol, and the like can be used.
- the preferred production method of the present invention includes a step of applying the dispersion containing the fluororesin from one surface of the conductive porous substrate, and subsequently applying the MPL coating solution from the surface side. It is preferable to work.
- moisture generated by the reaction is generated in the catalyst layer. That is, in the gas diffusion electrode substrate, moisture is generated on the side where the MPL is provided.
- the generated moisture is condensed into water droplets, the water droplets move from a region with high water repellency to a region with low water repellency. Therefore, it is preferable to provide the MPL on the surface of the electrode substrate having a high water repellency because generated water droplets can be easily removed to the separator side.
- the thickness of the gas diffusion electrode substrate is 240 ⁇ m or less.
- the thickness of the gas diffusion electrode substrate is 110 ⁇ m or more.
- the gas diffusion distance in the thickness direction is shortened and gas diffusibility is improved, and the drainage path is shortened to improve drainage and suppress flooding.
- the conductive path is shortened, the conductivity is improved, and the power generation performance is improved at both high and low temperatures.
- the thickness of the gas diffusion electrode substrate is 110 ⁇ m or more, the gas diffusibility in the in-plane direction is improved, and the gas can be more easily supplied to the catalyst under the ribs of the separator. In any case, the power generation performance is improved.
- a gas diffusion electrode substrate having such a thickness can be obtained by controlling the thickness of the conductive porous substrate and the thickness of the MPL.
- the thickness of the gas diffusion electrode substrate can be determined using a micrometer in a state where the surface pressure is 0.15 MPa, and the average of 10 individual measured values can be obtained as the gas diffusion electrode. The thickness of the substrate.
- the gas diffusibility in the thickness direction of the gas diffusion electrode substrate is preferably 30% or more.
- the gas diffusibility is 30% or more, high power generation performance can be obtained at both high and low temperatures.
- the higher the gas diffusivity in the thickness direction the better.
- the upper limit of gas diffusivity is considered to be about 40%.
- the gas diffusion electrode substrate of the present invention is pressure-bonded so that the catalyst layer and the MPL of the gas diffusion electrode substrate are in contact with both sides of the electrolyte membrane provided with the catalyst layer on both sides, and further, a member such as a separator is assembled.
- the battery is assembled and used as a fuel cell.
- thermosetting resin using a resin in which a resol type phenolic resin and a novolac type phenolic resin are mixed at a mass ratio of 1: 1 as a thermosetting resin, scaly graphite (average particle size 5 ⁇ m) as a carbon filler, and methanol as a solvent.
- Carbon-based filler / solvent 10 parts by mass / 5 parts by mass / 85 parts by mass
- the paper body cut into 15 cm ⁇ 12.5 cm is immersed in a resin composition filled with aluminum bat, and the resin component (thermosetting resin + carbon filler) becomes 130 parts by mass with respect to 100 parts by mass of the carbon fibers. After impregnating in this manner, it was dried by heating at 100 ° C. for 5 minutes to prepare a pre-impregnated body. Next, it heat-processed for 5 minutes at 180 degreeC, pressing with a flat plate press. In addition, the space
- the base material obtained by heat-treating the pre-impregnated body was introduced into a heating furnace having a maximum temperature of 2400 ° C. maintained in a nitrogen gas atmosphere in a heating furnace to obtain a conductive porous base material.
- MPL was formed on the surface of the electrode base material coated with FEP using a slit die coater.
- MPL coating liquid used here acetylene black (“DENKA BLACK” (registered trademark) manufactured by Denki Kagaku Kogyo Co., Ltd.), which is a kind of carbon black, is used as the conductive fine particles, and PTFE (Daikin Industries, Ltd.) is used as the fluororesin.
- DENKA BLACK registered trademark
- PTFE Denki Kagaku Kogyo Co., Ltd.
- Polyflon registered trademark
- D-1E manufactured by Nacalai Tesque Co., Ltd. was used as a surfactant, and purified water was used as a dispersion medium.
- the F / C ratio of the surface of the gas diffusion electrode substrate on the side where the MPL was disposed and the surface opposite to the side where the MPL was disposed were measured as follows.
- the gas diffusion electrode substrate was cut to 5 ⁇ 5 mm. A part of the gas diffusion electrode base material cut to 5 ⁇ 5 mm using SEM-EDX (energy dispersive fluorescent X-ray) was magnified 200 times. Elemental analysis of the surface to be measured was performed with an acceleration voltage of 5 KeV, a scan width of 20 ⁇ m, and a line scan interval of 50 ⁇ m. The X-ray dose (count number) corresponding to fluorine and carbon was quantified to determine the F / C ratio.
- SEM-EDX energy dispersive fluorescent X-ray
- the F / C ratio of the cross section of the gas diffusion electrode substrate was measured as follows.
- the gas diffusion electrode base material was placed horizontally and sliced perpendicularly to the horizontal plane using a single blade to give a cross section.
- SEM-EDX energy dispersive X-ray fluorescence
- the magnification was adjusted so that the field of view (overall field of view) from the portion close to one surface to the portion close to the other surface was within the monitor screen.
- Elemental analysis of the cross section of the gas diffusion electrode substrate was performed at an acceleration voltage of 5 KeV, a scan width of 20 ⁇ m, and a line scan interval of 50 ⁇ m.
- the X-ray dose (count number) corresponding to fluorine and carbon was quantified to determine the F / C ratio.
- the measurement of the F / C ratio of the cross section was performed for each of the CP1 cross section and the CP2 cross section, which are portions having no MPL, in the cross section of the gas diffusion electrode substrate.
- the boundary 6 between the portion having MPL and the portion not having MPL was drawn in parallel with the surface of the base material so that the MPL includes the tip of the portion most penetrating into the electrode base material. A line.
- SEM-EDX an apparatus obtained by adding an energy dispersive X-ray fluorescence spectrometer SEMEDEX Type-H to SEM H-3000 manufactured by Hitachi was used.
- ⁇ Gas diffusivity evaluation in the thickness direction> A gas water vapor permeation diffusion evaluation apparatus (MVDP-200C) manufactured by Seika Sangyo was used. A gas whose diffusibility is to be measured was flowed to one (primary side) of the gas diffusion electrode substrate, and nitrogen gas was flowed to the other (secondary side). The differential pressure between the primary side and the secondary side was controlled in the vicinity of 0 Pa (0 ⁇ 3 Pa). That is, there was almost no gas flow due to the pressure difference, and the gas movement phenomenon was caused only by molecular diffusion. The gas concentration when the equilibrium was reached was measured with a gas concentration meter on the secondary side, and this value (%) was defined as gas diffusivity in the thickness direction.
- MVDP-200C gas water vapor permeation diffusion evaluation apparatus manufactured by Seika Sangyo was used.
- a gas whose diffusibility is to be measured was flowed to one (primary side) of the gas diffusion electrode substrate, and nitrogen gas was flowed to the other (secondary
- the obtained gas diffusion electrode base material is an electrolyte membrane / catalyst layer integrated product (Nippon Gore's electrolyte membrane “Gore Select (registered trademark)” and Nihon Gore's catalyst layer “PRIMEA (registered trademark)” on both sides.
- a membrane electrode assembly (MEA) was produced by sandwiching the catalyst layer and the MPL so that the MPL was in contact with both sides of the formed product and hot pressing. This membrane electrode assembly is incorporated into a single cell for a fuel cell.
- the battery temperature is 57 ° C.
- the fuel utilization efficiency is 70%
- the air utilization efficiency is 40%
- the hydrogen on the anode side and the air on the cathode side have dew points of 57 ° C. and 57 ° C., respectively.
- Humidification was performed so that the temperature reached °C, and power was generated.
- the output voltage when the current density was 1.9 A / cm 2 was used as an indicator of flooding resistance.
- Example 1 A gas diffusion electrode substrate was obtained according to the methods described in ⁇ Preparation of electrode substrate> and ⁇ Formation of MPL>. As a result of evaluating the power generation performance of this gas diffusion electrode substrate, as shown in Table 1, the output voltage is 0.40 V (operating temperature 57 ° C., humidification temperature 57 ° C., current density 1.9 A / cm 2 ), The flooding resistance was also good. The other measurement results were as shown in Table 1.
- Example 2 In ⁇ Preparation of Electrode Base>, 5 parts by mass of FEP is sprayed from one side of the conductive porous base with 95 parts by weight of the conductive porous base, and heated at 100 ° C. for 5 minutes.
- a gas diffusion electrode base material was obtained according to the method described in ⁇ Preparation of electrode base material> and ⁇ Formation of MPL> except that the electrode base material was prepared by heat treatment.
- the output voltage was 0.42 V (operating temperature 57 ° C., humidification temperature 57 ° C., current density 1.9 A / cm 2 ), The flooding resistance was also good.
- the other measurement results were as shown in Table 1.
- Example 3 In ⁇ Preparation of Electrode Base>, 5 parts by mass of FEP is applied from one side of the conductive porous base with a die coater to 95 parts by weight of the conductive porous base, and at 100 ° C. for 5 minutes.
- a gas diffusion electrode substrate was obtained according to the methods described in ⁇ Preparation of electrode substrate> and ⁇ Formation of MPL> except that the electrode substrate was prepared by heat treatment.
- the output voltage is 0.41 V (operating temperature 57 ° C., humidification temperature 57 ° C., current density 1.9 A / cm 2 ), The flooding resistance was also good.
- the other measurement results were as shown in Table 1.
- Example 4 ⁇ Preparation of electrode substrate> In 93 parts by mass of the conductive porous substrate, 7 parts by mass of FEP was applied from one surface of the conductive porous substrate by a die coater, and the coating was performed at 100 ° C. for 5 minutes.
- a gas diffusion electrode substrate was obtained according to the methods described in ⁇ Preparation of electrode substrate> and ⁇ Formation of MPL> except that the electrode substrate was prepared by heat treatment.
- the output voltage is 0.40 V (operating temperature 57 ° C., humidification temperature 57 ° C., current density 1.9 A / cm 2 ), The flooding resistance was also good.
- the other measurement results were as shown in Table 1.
- CP1 F / C ratio is the F / C ratio of the CP1 cross section
- CP2 F / C ratio is the F / C ratio of the CP2 cross section
- MPL surfaceLF / C ratio is “MPL.
- the F / C ratio of the surface on the side, “MPL opposite surface F / C ratio” means the F / C ratio of the surface opposite to the side on which the MPL is disposed.
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Abstract
Description
厚さが110μm以上240μm以下であり、
ガス拡散電極基材の断面を、MPLを有する部分とMPLを有さない部分とに分け、さらにMPLを有さない部分を、MPLと接する部分(以下、CP1断面という)とMPLと接しない部分(以下、CP2断面という)に2等分したときに、CP1断面のF/C比が0.03以上0.10以下、CP2断面のF/C比が0.03未満である、ガス拡散電極基材。
東レ(株)製ポリアクリルニトリル系炭素繊維“トレカ”(登録商標)T300(平均炭素繊維径:7μm)を平均長さ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、乾燥させ、抄紙体を作製した。ポリビニルアルコールの塗布量は、抄紙体100質量部に対して、22質量部であった。
スリットダイコーターを用いて電極基材のFEPを塗布した面にMPLを形成した。ここで用いたMPL塗液には、導電性微粒子としてカーボンブラックの一種であるアセチレンブラック(電気化学工業株式会社製“デンカ ブラック”(登録商標))を用い、フッ素樹脂としてPTFE(ダイキン工業株式会社製“ポリフロン”(登録商標)D-1E)を用い、界面活性剤としてナカライテスク株式会社製“TRITON”(登録商標)X-100を用い、分散媒として精製水を用いた。導電性微粒子7.7質量部、フッ素樹脂4質量部、界面活性剤14質量部、分散媒74.3質量部となるよう調整して配合した。ダイコーターを用いて電極基材にMPL塗液を塗工後、100℃で5分間、380℃で10分間加熱(焼結)し、厚さ194μmのガス拡散電極基材を作製した。
ガス拡散電極基材のMPLを配置させた側の表面およびMPLを配置させた側とは反対側の表面のF/C比を以下のようにして測定した。
西華産業製ガス水蒸気透過拡散評価装置(MVDP-200C)を用いた。ガス拡散電極基材の一方(1次側)に拡散性を測定したいガスを流し、他方(2次側)に窒素ガスを流した。1次側と2次側の差圧を0Pa近傍(0±3Pa)に制御した。すなわち圧力差によるガスの流れがほとんどなく、分子拡散によってのみガスの移動現象が起こる状態としておいた。2次側のガス濃度計により、平衡に達したときのガス濃度を測定し、この値(%)を厚み方向のガス拡散性とした。
得られたガス拡散電極基材を、電解質膜・触媒層一体化品(日本ゴア製の電解質膜“ゴアセレクト(登録商標)”に、日本ゴア製触媒層“PRIMEA(登録商標)”を両面に形成したもの)の両側に、触媒層とMPLが接するように挟み、ホットプレスすることにより、膜電極接合体(MEA)を作製した。この膜電極接合体を燃料電池用単セルに組み込み、電池温度57℃、燃料利用効率を70%、空気利用効率を40%、アノード側の水素、カソード側の空気をそれぞれ露点が57℃、57℃となるように加湿して発電させた。電流密度が1.9A/cm2のときの出力電圧を耐フラッディング性の指標とした。
<電極基材の作製>および<MPLの形成>に記載した方法に従って、ガス拡散電極基材を得た。このガス拡散電極基材の発電性能を評価した結果、表1に記載のように、出力電圧0.40V(運転温度57℃、加湿温度57℃、電流密度1.9A/cm2)であり、耐フラッディング性も良好であった。その他の測定結果は表1に記載のとおりであった。
<電極基材の作製>において、導電性多孔質基材95質量部に対し、5質量部のFEPをスプレーにより導電性多孔質基材の一方の面より噴霧し、100℃で5分間加熱して熱処理させて電極基材を作製したこと以外は、<電極基材の作製>および<MPLの形成>に記載した方法に従って、ガス拡散電極基材を得た。このガス拡散電極基材の発電性能を評価した結果、表1に記載のように、出力電圧0.42V(運転温度57℃、加湿温度57℃、電流密度1.9A/cm2)であり、耐フラッディング性も良好であった。その他の測定結果は表1に記載のとおりであった。
<電極基材の作製>において、導電性多孔質基材95質量部に対し、5質量部のFEPをダイコーターにより導電性多孔質基材の一方の面より塗工し、100℃で5分間熱処理させて電極基材を作製したこと以外は、<電極基材の作製>および<MPLの形成>に記載した方法に従って、ガス拡散電極基材を得た。このガス拡散電極基材の発電性能を評価した結果、表1に記載のように、出力電圧0.41V(運転温度57℃、加湿温度57℃、電流密度1.9A/cm2)であり、耐フラッディング性も良好であった。その他の測定結果は表1に記載のとおりであった。
<電極基材の作製>において、導電性多孔質基材93質量部に対し、7質量部のFEPをダイコーターにより導電性多孔質基材の一方の面より塗工し、100℃で5分間熱処理させて電極基材を作製したこと以外は、<電極基材の作製>および<MPLの形成>に記載した方法に従って、ガス拡散電極基材を得た。このガス拡散電極基材の発電性能を評価した結果、表1に記載のように、出力電圧0.40V(運転温度57℃、加湿温度57℃、電流密度1.9A/cm2)であり、耐フラッディング性も良好であった。その他の測定結果は表1に記載のとおりであった。
<電極基材の作製>において、撥水加工を行わず、<MPLの形成>において、電極基材ではなく導電性多孔質基材の一方の面にMPLを形成した以外は、<電極基材の作製>および<MPLの形成>に記載した方法に従って、ガス拡散電極基材を得た。このガス拡散電極基材の発電性能を評価した結果、表1に記載のように、出力電圧0.38V(運転温度57℃、加湿温度57℃、電流密度1.9A/cm2)であり、耐フラッディング性がやや劣る結果であった。その他の測定結果は表1に記載のとおりであった。
<電極基材の作製>において、導電性多孔質基材99質量部に対し、1質量部のFEPとなるように含浸撥水を行い、100℃で5分間加熱して乾燥させて電極基材を作製したこと以外は、<電極基材の作製>および<MPLの形成>に記載した方法に従って、ガス拡散電極基材を得た。このガス拡散電極基材の発電性能を評価した結果、表1に記載のように、出力電圧0.35V(運転温度57℃、加湿温度57℃、電流密度1.9A/cm2)であり、耐フラッディング性がやや劣る結果であった。その他の測定結果は表1に記載のとおりであった。
<電極基材の作製>において、厚さ70μmの電極基材となるように平板プレスにスペーサーを配置して上下プレス面板の間隔を調整したこと以外は、<電極基材の作製>および<MPLの形成>に記載した方法に従って、ガス拡散電極基材を得た。このガス拡散電極基材の発電性能を評価した結果、表1に記載のように、出力電圧0.30V(運転温度57℃、加湿温度57℃、電流密度1.9A/cm2)であり、耐フラッディング性がやや劣る結果であった。その他の測定結果は表1に記載のとおりであった。
<電極基材の作製>において、厚さ230μmの電極基材となるように平板プレスにスペーサーを配置して上下プレス面板の間隔を調整したこと以外は、<電極基材の作製>および<MPLの形成>に記載した方法に従って、ガス拡散電極基材を得た。このガス拡散電極基材の発電性能を評価した結果、表1に記載のように、出力電圧0.25V(運転温度57℃、加湿温度57℃、電流密度1.9A/cm2)であり耐フラッディング性がやや劣る結果であった。その他の測定結果は表1に記載のとおりであった。
2 MPL
3 電極基材
4 CP1断面
5 CP2断面
6 MPLを有する部分と有さない部分の境界
Claims (7)
- 電極基材の一方の表面に、マイクロポーラス層(以下、MPLという)を配置させたガス拡散電極基材であって、
厚さが110μm以上240μm以下であり、
ガス拡散電極基材の断面を、MPLを有する部分とMPLを有さない部分とに分け、さらにMPLを有さない部分を、MPLと接する部分(以下、CP1断面という)とMPLと接しない部分(以下、CP2断面という)に2等分したときに、CP1断面のF/C比が0.03以上0.10以下、CP2断面のF/C比が0.03未満である、ガス拡散電極基材。
ここで「F」とはフッ素原子の質量を意味し、「C」とは炭素原子の質量を意味する。 - 前記CP2断面のF/C比が0.01以下である、請求項1に記載のガス拡散電極基材。
- 前記ガス拡散電極基材の、MPLを配置させた側とは反対側の表面のF/C比が、0.01以下である、請求項1に記載のガス拡散電極基材。
- 前記ガス拡散電極基材の、MPLを配置させた側の表面のF/C比が、0.10以上0.40以下である、請求項1または2に記載のガス拡散電極基材。
- 厚み方向のガス拡散性が30%以上である、請求項1~3のいずれかに記載のガス拡散電極基材。
- 請求項1~5のいずれかに記載のガス拡散電極基材を製造する方法であって、導電性多孔質基材の一方の表面からフッ素樹脂を含む分散液を噴霧する工程を有し、続いて当該表面にMPLを配置させることを特徴とする、ガス拡散電極基材の製造方法。
- 請求項1~5のいずれかに記載のガス拡散電極基材を製造する方法であって、導電性多孔質基材の一方の表面からフッ素樹脂を含む分散液を塗工する工程を有し、続いて当該表面にMPLを配置させることを特徴とする、ガス拡散電極基材の製造方法。
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JP2005116338A (ja) * | 2003-10-08 | 2005-04-28 | Matsushita Electric Ind Co Ltd | 高分子電解質型燃料電池及びそのガス拡散電極の製造方法 |
WO2014030553A1 (ja) * | 2012-08-24 | 2014-02-27 | 東レ株式会社 | 燃料電池用ガス拡散電極基材 |
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JP2018156818A (ja) * | 2017-03-17 | 2018-10-04 | 東レ株式会社 | ガス拡散電極、および、燃料電池 |
JP7114858B2 (ja) | 2017-03-17 | 2022-08-09 | 東レ株式会社 | ガス拡散電極、および、燃料電池 |
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CA2980461C (en) | 2023-05-16 |
CN107534156A (zh) | 2018-01-02 |
CN107534156B (zh) | 2020-11-27 |
TW201703327A (zh) | 2017-01-16 |
JP6135826B2 (ja) | 2017-05-31 |
EP3288106A1 (en) | 2018-02-28 |
CA2980461A1 (en) | 2016-10-27 |
JPWO2016171082A1 (ja) | 2017-05-18 |
KR20170141710A (ko) | 2017-12-26 |
US20180102552A1 (en) | 2018-04-12 |
KR102587488B1 (ko) | 2023-10-11 |
US10680250B2 (en) | 2020-06-09 |
ES2767928T3 (es) | 2020-06-19 |
EP3288106A4 (en) | 2018-09-19 |
EP3288106B1 (en) | 2019-12-11 |
TWI668908B (zh) | 2019-08-11 |
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