WO2021132103A1 - 触媒層、固体高分子形燃料電池用膜電極接合体、及び固体高分子形燃料電池 - Google Patents
触媒層、固体高分子形燃料電池用膜電極接合体、及び固体高分子形燃料電池 Download PDFInfo
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- WO2021132103A1 WO2021132103A1 PCT/JP2020/047545 JP2020047545W WO2021132103A1 WO 2021132103 A1 WO2021132103 A1 WO 2021132103A1 JP 2020047545 W JP2020047545 W JP 2020047545W WO 2021132103 A1 WO2021132103 A1 WO 2021132103A1
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- catalyst
- catalyst layer
- carbon
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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
- the present disclosure relates to a catalyst layer, a membrane electrode assembly for a polymer electrolyte fuel cell, and a polymer electrolyte fuel cell.
- a membrane electrode assembly is sandwiched between two separators to form cells, and a plurality of cells are stacked. Further, the membrane electrode assembly includes, for example, an anode having a catalyst layer and a gas diffusion layer, a cathode having a catalyst layer and a gas diffusion layer, and a polymer electrolyte membrane arranged between the anode and the cathode. ..
- the catalyst layer used for the anode and the cathode is composed of, for example, a catalyst carrier in which a catalyst is supported on a carrier and an ionomer which is a polymer electrolyte. Since platinum, which is mainly used as a catalyst, is expensive, it is desired to reduce the amount of the catalyst used. Therefore, in order to efficiently utilize the catalyst, attempts have been made to increase the output of the fuel cell while reducing the amount of catalyst used by coating as many catalyst particles as possible uniformly with ionomer (for example, Patent Documents). 1 to Patent Document 3 etc.).
- Patent Document 1 Japanese Patent Application Laid-Open No. 2010-167379
- Patent Document 2 Japanese Patent Application Laid-Open No. 2010-186678
- Patent Document 3 Japanese Patent Application Laid-Open No. 2011-081977
- the three-phase interface of the catalyst, ionomer, and water, which is the reaction field, is widely formed in the catalyst layer, so that it is as uniform as possible. It has been considered necessary to coat many catalyst particles with ionomers.
- a catalyst containing platinum is used as the catalyst, it is required to further increase the output of the fuel cell while reducing the amount of the catalyst used.
- the present disclosure has been made in view of the above circumstances, and uses a catalyst layer and the catalyst layer that can be used in a polymer electrolyte fuel cell to increase the output of the fuel cell while reducing the amount of catalyst used. It is an object of the present invention to provide a membrane electrode assembly for a polymer electrolyte fuel cell and a polymer electrolyte fuel cell provided with the membrane electrode assembly for a polymer electrolyte fuel cell.
- the catalyst-supported carbon has mesopores having a pore diameter of 2 nm or more and less than 10 nm in the pore distribution obtained by the nitrogen adsorption method. At least a part of the ionomer exists in the mesopores having a pore diameter of 2 nm or more and less than 10 nm.
- the content of ionomer with respect to 100 parts by mass of the carbon carrier is 100 parts by mass or more.
- the catalyst-supporting carbon in the catalyst layer has macropores having a pore diameter of 50 nm or more in the pore distribution obtained by the nitrogen adsorption method in a state where the ionomer is attached, and has 0.03 cm 3 / g catalyst or more.
- ⁇ 4> The catalyst layer according to any one of ⁇ 1> to ⁇ 3>, wherein the catalyst contains at least one selected from the group consisting of platinum particles and platinum alloy particles.
- ⁇ 5> The catalyst layer according to ⁇ 4>, wherein the number average particle size of the catalyst is 1 nm to 20 nm.
- ⁇ 6> The catalyst layer according to any one of ⁇ 1> to ⁇ 5>, wherein the content of the catalyst with respect to the entire catalyst-supporting carbon is 10% by mass to 70% by mass.
- An anode having a first gas diffusion layer and a first catalyst layer provided on one surface side of the first gas diffusion layer.
- a cathode having a second gas diffusion layer and a second catalyst layer provided on one surface side of the second gas diffusion layer, A polymer electrolyte membrane disposed between the first catalyst layer and the second catalyst layer, With A membrane electrode assembly for a polymer electrolyte fuel cell, wherein at least one of the first catalyst layer and the second catalyst layer is the catalyst layer according to any one of ⁇ 1> to ⁇ 6>.
- a polymer electrolyte fuel cell provided with the membrane electrode assembly for a polymer electrolyte fuel cell according to ⁇ 7>.
- a catalyst layer that realizes high output of a fuel cell while reducing the amount of catalyst used by using it in a polymer electrolyte fuel cell, a membrane for a polymer electrolyte fuel cell using the catalyst layer.
- a solid polymer fuel cell including the electrode joint and the membrane electrode joint for the polymer electrolyte fuel cell can be provided.
- the term "process” includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if the process cannot be clearly distinguished from the other process. Is done.
- the numerical values before and after "-" are included as the minimum value and the maximum value, respectively.
- each component may contain a plurality of applicable substances.
- the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
- the catalyst layer in the present embodiment is a catalyst layer containing a catalyst-supported carbon in which a catalyst containing platinum is supported on a carbon carrier and an ionomer.
- the mesopore generally means a pore having a pore diameter of 2 nm or more and less than 50 nm, but in the present embodiment, a specific proportion of volume is provided in the mesopore having a pore diameter of 2 nm or more and less than 10 nm. There is an ionomer to occupy.
- the catalyst-supported carbon has mesopores having a pore diameter of 2 nm or more and less than 10 nm in the pore distribution obtained by the nitrogen adsorption method, and at least a part of the ionomer is in the mesopores having a pore diameter of 2 nm or more and less than 10 nm.
- the content of the ionomer with respect to 100 parts by mass of the carbon carrier is 100 parts by mass or more, and the occupancy of the ionomer in the total volume of the mesopores having a pore diameter of 2 nm or more and less than 10 nm is 50% by volume or less. is there.
- the pore distribution obtained by the nitrogen adsorption method is also simply referred to as “pore distribution”, and pores having a pore size of 2 nm or more and less than 50 nm are also referred to as “mesopores”, and the pore diameter in the pore distribution is 2 nm or more and less than 10 nm.
- the holes are also referred to as “specific mesopores”, and the ionomer occupancy in the total product of the specific mesopores is also referred to as “ionomer occupancy”.
- the “macro pore” described later means a pore having a pore diameter of 50 nm or more and less than 300 nm.
- the sample to be measured is measured by an automatic specific surface area / pore distribution measuring device (for example, manufactured by Shimadzu Corporation, model number: Tristar II 3020, measuring method: nitrogen adsorption method by volumetric method). Obtained by performing analysis by the BJH method. The specific surface area and pore volume of the catalyst-supported carbon described later are calculated from the pore distribution.
- an automatic specific surface area / pore distribution measuring device for example, manufactured by Shimadzu Corporation, model number: Tristar II 3020, measuring method: nitrogen adsorption method by volumetric method.
- the "ionomer occupancy rate" catalyst-carrying carbon that is not the total volume of the specific mesopores
- Samples of catalyst-supporting carbon with attached ionomer obtained by performing the measurement and analysis depositing the P 1, ionomer when the total volume of the specific mesopores for samples obtained by performing the measurement and analysis was P 0, which is a value represented by the following formula (1).
- a coating liquid for forming a catalyst layer is applied on a base film such as a PET film and dried at 80 ° C. to remove the solvent. A work layer is formed, and the obtained coating layer is scraped off to form a powder.
- a mixture of the catalyst-supported carbon and a solvent is applied on a base film such as a PET film and dried to remove the solvent. A coating layer is formed, and the obtained coating layer is scraped off to form a powder.
- PET means polyethylene terephthalate. It is desirable that the above mixture is subjected to the same mixing treatment as the mixing treatment (for example, mixing treatment with a bead mill) performed in the process of preparing the coating liquid for forming the catalyst layer.
- the specific mesopore has a large pore surface area with respect to the pore volume. Therefore, the surface area of the carbon carrier having the specific mesopores becomes very large. For example, even in a carbon carrier in which the ratio of the total pore volume of specific mesopores to the total pore volume of all mesopores and macropores in the carbon carrier is about 30%, the entire mesopores and macropores in the carbon carrier.
- the ratio of the total pore surface area of the specific mesopores to the total pore surface area of the specific mesopores may exceed 85%. That is, in the catalyst-supported carbon in which catalyst particles containing platinum are supported on the surface of the carbon carrier, most of the catalysts are supported on the surface other than the pores of the carbon carrier or the surface of macropores. It is considered that it is supported on the surface of the specific mesopore.
- the content of ionomer with respect to 100 parts by mass of the carbon carrier is 100 parts by mass or more, and the ionomer occupancy is 50% by volume or less while at least a part of the ionomer is present in the specific mesopores.
- the amount of ionomer entering the inside of the specific mesopore is reduced while surrounding the catalyst-supporting carbon with a sufficient amount of ionomer.
- the ionomer that surrounds the catalyst-supported carbon and does not enter the inside of the specific mesopore is in a state of being close to the catalyst supported inside the specific mesopore without contacting the catalyst.
- ionomers in a state of being close to each other without contact form a pseudo three-phase interface through water in a reaction gas (for example, hydrogen, oxygen used for battery operation, etc.) and water generated by the reaction. Be done.
- a reaction gas for example, hydrogen, oxygen used for battery operation, etc.
- the catalytic activity of platinum can be effectively utilized by forming a pseudo three-phase interface while suppressing the decrease in the catalytic activity of platinum due to the direct contact of the ionomer with platinum.
- the catalyst layer of the present embodiment can increase the output of the fuel cell while reducing the amount of catalyst used.
- each component constituting the catalyst layer will be described.
- the catalyst-supported carbon has a carbon carrier having specific mesopores and a catalyst supported on the carbon carrier and containing platinum.
- the carbon carrier and the catalyst will be described respectively.
- the carbon carrier is not particularly limited as long as it is carbon having at least specific mesopores.
- the carbon carrier include activated carbon and carbon black, and from the viewpoint of high chemical durability, those in which at least a part of graphitization is recommended for heat treatment or the like are preferable.
- mesoporous carbon in which the ratio of the total pore volume occupied by the macropores is less than 40% with respect to the total pore volume of the mesopores and the entire macropores is preferable from the viewpoint of suppressing the ionomer occupancy rate to a low level.
- the ratio of the total pore volume occupied by the macropores is preferably 5 to 35%, more preferably 10 to 30%.
- the catalyst is not particularly limited as long as it contains platinum and promotes the redox reaction in the polymer electrolyte fuel cell.
- the catalyst is preferably at least one selected from the group consisting of platinum and platinum alloys, and more preferably contains at least one selected from the group consisting of platinum particles and platinum alloy particles.
- Platinum alloys include platinum group metals other than platinum (lutenium, rhodium, palladium, osmium, iridium), gold, silver, chromium, iron, titanium, manganese, cobalt, nickel, molybdenum, tungsten, aluminum, silicon, zinc, etc.
- An alloy of one or more metals selected from the group consisting of and tin with platinum is preferred.
- the platinum alloy may contain an intermetallic compound of platinum and a metal alloyed with platinum.
- the number average particle diameter of the catalyst is, for example, in the range of 1 nm to 20 nm, from the viewpoint of power generation performance and catalyst durability.
- the range of 2 nm to 10 nm is preferable, and the range of 2 nm to 7 nm is more preferable.
- the number average particle size of the catalyst is the equivalent circle diameter obtained for 300 to 400 particles in an image observed at 300,000 times using a transmission electron microscope (TEM) HT7700 manufactured by Hitachi High-Technologies Corporation. Is a value obtained by averaging the number of particles.
- TEM transmission electron microscope
- the method of supporting the catalyst on the carbon carrier is not particularly limited, and known methods such as a sputtering method, a solution method, an electrolytic precipitation method, and an electroless plating method are used.
- the content of the catalyst in the entire catalyst-supported carbon is, for example, in the range of 10% by mass to 70% by mass, and is preferably in the range of 20% to 60% from the viewpoint of achieving both reduction in the amount of catalyst used and high output. , 30% to 60% is more preferable.
- the content of the catalyst per unit area of the catalyst layer may be 0.20 mg / cm 2 or less.
- the specific surface area of the entire catalyst-supported carbon is preferably in the range of 200 m 2 / g catalyst or more, and more preferably in the range of 250 m 2 / g catalyst or more, from the viewpoint of achieving both reduction in the amount of catalyst used and high output.
- the specific surface area of the entire catalyst-supported carbon means the total surface area of the catalyst-supported carbon per unit mass in the state where the ionomer is not attached.
- the specific surface area of the entire catalyst-supported carbon may be 700 m 2 / g catalyst or less, 500 m 2 / g catalyst or less, or 350 m 2 / g catalyst or less.
- the specific surface area of the entire catalyst-supported carbon is measured by adsorbing nitrogen on the carbon surface with a BET specific surface area device.
- the specific surface area of the mesopores in the catalyst-supported carbon is preferably in the range of 200 m 2 / g catalyst or more, and more preferably in the range of 250 m 2 / g catalyst or more, for example, from the viewpoint of achieving both reduction in the amount of catalyst used and high output. ..
- the specific surface area of the mesopores in the catalyst-supported carbon means the total pore surface area of the mesopores in the catalyst-supported carbon per unit mass in the state where the ionomer is not attached.
- the specific surface area of the entire catalyst-supported carbon may be 700 m 2 / g catalyst or less, 500 m 2 / g catalyst or less, or 350 m 2 / g catalyst or less.
- the specific surface area of the specific mesopores in the catalyst-supported carbon is more preferably in the range of 200 m 2 / g or more from the viewpoint of achieving both reduction in the amount of catalyst used and high output.
- the specific surface area of the specific mesopores in the catalyst-supported carbon means the total pore surface area of the specific mesopores in the catalyst-supported carbon per unit mass in the state where the ionomer is not attached.
- the total pore volume of specific mesopores in the catalyst-supported carbon per unit mass without ionomer is, for example , in the range of 0.1 cm 3 / g catalyst to 0.8 cm 3 / g catalyst, and gas diffusion. in terms of sex and power generation performance is preferably in the range of 0.15 cm 3 / g catalyst ⁇ 0.7 cm 3 / g catalyst, the range of 0.2 cm 3 / g catalyst ⁇ 0.6 cm 3 / g catalyst is more preferable.
- the ratio of the total pore volume of specific mesopores to the total pore volume of all mesopores and macropores in the catalyst-supported carbon with no ionomer attached is, for example, in the range of 20% to 90%, and is generated. From the viewpoint of water drainage and power generation performance, the range of 25% to 80% is preferable, and the range of 30% to 70% is more preferable.
- the total pore capacity of the macropores in the catalyst-supported carbon per unit mass with no ionomer attached is, for example , in the range of 0.05 cm 3 / g or more, which reduces the amount of catalyst used and increases the output. from the viewpoint of both, preferably in the range of 0.07 cm 3 / g catalyst ⁇ 0.50 cm 3 / g catalyst, and more preferably in the range of 0.1 cm 3 / g catalyst ⁇ 0.4 cm 3 / g catalyst.
- the ionomer is not particularly limited as long as it is a polymer compound having an ion exchange group, and among them, a polymer compound having proton conductivity is preferable.
- the polymer compound having an ion exchange group is also referred to as an “ion exchange resin”.
- the “ion exchange group” means a group having H + , a monovalent metal cation, an ammonium ion, or the like.
- Examples of the ion exchange group include a sulfonic acid group, a sulfonimide group, a sulfonamide group, a sulfonmethyl group, a carboxyl group, a phosphoric acid group and the like, and among them, a sulfonic acid group having excellent proton conductivity is preferable.
- One type of ion exchange group may be used alone, or two or more types may be used in combination.
- a fluorine-containing ion exchange resin is preferable from the viewpoint of durability, and a perfluorocarbon polymer having an ion exchange group is more preferable.
- the perfluorocarbon polymer may contain an ethereal oxygen atom.
- the perfluorocarbon polymer is a structural unit derived from a perfluoromonomer having an ion exchange group and a 5-membered ring, which is described in the polymer (H) described later, the polymer (Q) described later, International Publication No. 2011/0135777, and the like.
- Known polymers such as polymers having the above can be mentioned.
- the ionomer preferably contains at least one selected from the group consisting of the polymer (H) and the polymer (Q) from the viewpoint of availability and ease of manufacture.
- the "polymer” means a compound having a structure composed of a plurality of structural units.
- the "constituent unit” means a unit derived from the monomer formed by polymerizing the monomer.
- the structural unit may be a unit directly formed by a polymerization reaction of a monomer, or a unit in which a part of the unit is converted into another structure by processing a polymer.
- monomer is meant a compound having a polymerization-reactive carbon-carbon double bond.
- Polymer (H) The polymer (H) is a polymer having the following unit (U1) (however, the polymer (Q) is excluded).
- Q 3 is a single bond, or an ether of good perfluoroalkylene group which may have an oxygen atom
- R f2 also have an etheric oxygen atom
- a good perfluoroalkyl group X 2 is an oxygen atom, a nitrogen atom, or a carbon atom
- b is 0 if X 2 is an oxygen atom, 1 if X 2 is a nitrogen atom
- Y 2 is a fluorine atom or a monovalent perfluoroorganic group
- t is 0 or 1.
- a single bond means that the carbon atom of CFY 2 and the sulfur atom of SO 2 are directly bonded.
- the organic group means a group containing one or more carbon atoms.
- perfluoroalkylene group represented by Q 3 in the unit (U1) has an etheric oxygen atom, it may be one or may be two or more. Further, the oxygen atom may be inserted between the carbon atoms of the perfluoroalkylene group and the carbon atom bond, or may be inserted at the end of the carbon atom bond.
- the perfluoroalkylene group may be linear or branched. The number of carbon atoms of the perfluoroalkylene group is preferably 1 to 6, and more preferably 1 to 4.
- the perfluoroalkyl group represented by R f2 in the unit (U1) may be linear, may be branched, and is preferably linear.
- the number of carbon atoms of the perfluoroalkyl group is preferably 1 to 6, and more preferably 1 to 4.
- As the perfluoroalkyl group a perfluoromethyl group, a perfluoroethyl group and the like are preferable.
- the ⁇ (SO 2 X 2 (SO 2 R f2 ) b ) ⁇ H + group is an ion exchange group.
- Y 2 in the unit (U1) a fluorine atom or a trifluoromethyl group is preferable.
- the unit (U1) the following unit (U1-1) is preferable, and the following unit (U1-11) and the unit (U1-) are easy to manufacture the polymer (H) and are easy to carry out industrially. 12), unit (U1-13), or unit (U1-14) is more preferred.
- Z is a fluorine atom or a trifluoromethyl group
- t is 0 or 1
- m is an integer of 0 to 3
- n is 1 to 12.
- P is 0 or 1
- the polymer (H) may further have a structural unit derived from another monomer (hereinafter, referred to as another unit).
- the ratio of the other units may be appropriately adjusted so that the ion exchange capacity of the polymer (H) is within a preferable range described later.
- As the other unit a structural unit derived from a perfluoromonomer is preferable, and a structural unit derived from tetrafluoroethylene (hereinafter referred to as TFE) is more preferable from the viewpoint of mechanical strength and chemical durability.
- Polymer (H) is, after obtaining a precursor polymer by polymerizing another monomer, if the following compound (M1) and optionally, by converting the -SO 2 F groups in the precursor polymer to sulfonic acid groups Can be manufactured. Conversion to sulfonic acid groups -SO 2 F groups is performed by hydrolysis and acid type process.
- CF 2 CF- (CF 2 ) t OCF 2- CFY 2- Q 3- SO 2 F ... (M1).
- t, Y 2 and Q 3 in the compound (M1) are synonymous with t, Y 2 and Q 3 in the unit (U1), respectively.
- Polymer (Q) The polymer (Q) is a polymer having at least one of the following units (U2) and the following units (U3).
- Q 1 is a perfluoroalkylene group which may have an ethereal oxygen atom
- Q 2 may have a single bond or an ethereal oxygen atom
- a good perfluoroalkylene group R f1 is a perfluoroalkyl group which may have an ethereal oxygen atom
- X 1 is an oxygen atom, a nitrogen atom, or a carbon atom
- a is X 1 Is 0 when is an oxygen atom
- X 1 is 1 when it is a nitrogen atom
- X 1 is 2 when it is a carbon atom
- Y 1 is a fluorine atom or a monovalent perfluoro organic group, and s is. It is 0 or 1.
- a single bond means that the carbon atom of CY 1 and the sulfur atom of SO 2 are directly bonded.
- the organic group means a group containing one or more carbon atoms.
- the perfluoroalkylene group Q 1, Q 2 has an etheric oxygen atom, it may be one or may be two or more. Further, the oxygen atom may be inserted between the carbon atoms of the perfluoroalkylene group and the carbon atom bond, or may be inserted at the end of the carbon atom bond.
- the perfluoroalkylene group may be linear, may be branched, and is preferably linear.
- the number of carbon atoms of the perfluoroalkylene group is preferably 1 to 6, and more preferably 1 to 4. When the number of carbon atoms is 6 or less, the boiling point of the fluorine-containing monomer as a raw material becomes low, and distillation purification becomes easy.
- Q 2 in the unit (U2) is preferably a perfluoroalkylene group etheric oxygen atoms and 1 carbon atoms which may have a 6. If Q 2 is a perfluoroalkylene group having 1 to 6 carbon atoms which may have an ethereal oxygen atom, the polymer electrolyte fuel cell has been operated for a longer period of time than when Q 2 is a single bond. In particular, it has excellent stability of power generation performance.
- at least one of Q 1, Q 2 is preferably a perfluoroalkylene group having 1 to 6 carbon atoms having an etheric oxygen atom.
- a fluorine-containing monomer having a perfluoroalkylene group having 1 to 6 carbon atoms having an ethereal oxygen atom can be synthesized without undergoing a fluorination reaction with fluorine gas, so that the yield is good and the production is easy.
- the perfluoroalkyl group of R f1 may be linear, may be branched, and is preferably linear.
- the number of carbon atoms of the perfluoroalkyl group is preferably 1 to 6, and more preferably 1 to 4.
- As the perfluoroalkyl group a perfluoromethyl group, a perfluoroethyl group and the like are preferable.
- the R f1 may be the same group or different groups.
- the ⁇ (SO 2 X 1 (SO 2 R f1 ) a ) ⁇ H + group is an ion exchange group.
- the Y 1 in the unit (U2) it is preferable fluorine atom, or a straight-chain perfluoroalkyl group of etheric oxygen atoms and 1 carbon atoms which may have 6.
- the unit (U2) the following unit (U2-1) is preferable, and the following unit (U2-11) and the unit (U2-2) are easy to manufacture the polymer (Q) and are easy to carry out industrially. 12), or the unit (U2-13) is more preferable.
- R F11 is a single bond, or a linear perfluoroalkylene group of etheric 1 carbon atoms which may have an oxygen atom ⁇ 6,
- R F12 is ,
- R F1 and R F2 are each independently a perfluoroalkylene group having 1 to 3 carbon atoms.
- R F1 and R F2 is, -CF 2 -, - CF 2 CF 2 -, - CF (CF 3) -, - CF 2 CF 2 CF 2 -, - CF (CF 2 CF 3) -, -CF (CF 3 ) CF 2- , -CF 2 CF (CF 3 )-, -C (CF 3 ) (CF 3 )-can be mentioned.
- Point raw material is inexpensive, the point easy manufacturing, from viewpoint of higher ion-exchange capacity of the polymer (Q), in each of R F1 and R F2 independently preferably perfluoroalkylene group having 1 or 2 carbon atoms .. In the case of 2 carbon atoms, a straight chain is preferable. Specifically, -CF 2 -, - CF 2 CF 2 - or -CF (CF 3) - are preferred, -CF 2 - or -CF 2 CF 2 - is more preferable, -CF 2 - is particularly preferred.
- the unit (U3) the following unit (U3-1) is preferable.
- the polymer (Q) may have still other units.
- the ratio of the other units may be appropriately adjusted so that the ion exchange capacity of the polymer (Q) is within a preferable range described later.
- a structural unit derived from a perfluoromonomer is preferable, and a structural unit derived from TFE is more preferable, from the viewpoint of mechanical strength and chemical durability.
- the polymer (Q) can be produced, for example, by the method described in International Publication No. 2007/0135333, International Publication No. 2020/116651, and the like.
- the ion exchange capacity of the ionomer is preferably 0.5 mm equivalent / g dry resin to 2.0 mm equivalent / g dry resin, and 0.8 mm equivalent / g dry resin to 1 from the viewpoint of conductivity and gas permeability.
- a .5 mm equivalent / g dry resin is particularly preferred.
- the content of ionomer with respect to 100 parts by mass of the carbon carrier is 100 parts by mass or more, and from the viewpoint of achieving both reduction in the amount of catalyst used and high output, 100 parts by mass to 240 parts by mass is preferable, and 110 parts by mass to 200 parts by mass. Parts by mass are more preferable, and parts by mass of 120 to 180 parts by mass are even more preferable.
- the ionomer occupancy rate is 50% by volume or less, and is preferably 10% by volume to 50% by volume from the viewpoint of achieving both reduction in catalyst usage and high output.
- the ionomer occupancy rate is more preferably 15% by volume to 40% by volume from the viewpoint of achieving both a reduction in the amount of catalyst used and a high output in a low humidity environment (for example, an environment where the humidity is 30%). It is preferable, and 20% by volume to 35% by volume is more preferable.
- a method of adjusting the mixing treatment conditions performed in the process of preparing the coating liquid for forming the catalyst layer As a method of lowering the ionomer occupancy while increasing the content of ionomer, a method of adjusting the mixing treatment conditions performed in the process of preparing the coating liquid for forming the catalyst layer, and a method of adjusting the material used for preparing the coating liquid for forming the catalyst layer. Examples include a method of adjusting the characteristics, and these may be used in combination. Examples of the method of adjusting the mixing treatment conditions include a method of suppressing the shear stress applied in the mixing treatment to a small value, a method of shortening the processing time of the mixing treatment, and the like.
- a method for adjusting the properties of the material As a method for adjusting the properties of the material, a method using a thickening ionomer (for example, an ionomer whose viscosity is increased by adding a fluorine-based solvent), a method using an ionomer having a large molecular weight, and a hydrophilized catalyst-supported carbon (for example). , A method using a catalyst-supported carbon in which the amount of hydrophilic functional groups on the surface is increased by acid treatment) and the like can be mentioned.
- a thickening ionomer for example, an ionomer whose viscosity is increased by adding a fluorine-based solvent
- a method using an ionomer having a large molecular weight for example
- a hydrophilized catalyst-supported carbon for example.
- the catalyst-supported carbon in the catalyst layer preferably has macropores having a pore diameter of 50 nm or more in the pore distribution obtained by the nitrogen adsorption method in a state where ionomers are attached, at 0.03 cm 3 / g or more.
- the total pore volume of macropores per unit weight of the catalyst-carrying carbon in a state in which the ionomer is deposited for example 0.03 cm 3 / g catalyst ⁇ 0.3 cm 3 / g range of the catalyst and the like, reduction of the catalyst consumption
- the range of 0.05 cm 3 / g catalyst to 0.25 cm 3 / g catalyst is preferable, and the range of 0.07 cm 3 / g catalyst to 0.20 cm 3 / g catalyst is more preferable. preferable.
- the thickness of the catalyst layer is not particularly limited, and examples thereof include a range of 0.5 ⁇ m to 10 ⁇ m, preferably a range of 1 ⁇ m to 8 ⁇ m, and more preferably a range of 2 ⁇ m to 6 ⁇ m.
- the thickness of the catalyst layer is measured by observing the cross section of the catalyst layer with a scanning electron microscope or the like.
- the method for producing the catalyst layer is, for example, a preparatory step for preparing a coating liquid for forming a catalyst layer, and a surface or base film of a layer (gas diffusion layer, polymer electrolyte membrane, etc.) in contact with the catalyst layer in a membrane electrode assembly.
- a catalyst layer forming step of forming a catalyst layer by applying a coating liquid for forming a catalyst layer to the surface of the above and drying it is performed.
- a transfer step of transferring the formed catalyst layer to the surface of the layer in contact with the catalyst layer in the membrane electrode assembly may be further performed. ..
- a coating liquid for forming a catalyst layer is prepared by mixing catalyst-supported carbon, ionomer, and if necessary, a solvent.
- the catalyst-supported carbon and ionomer may be each previously dispersed in a solvent. That is, the dispersion liquid in which the catalyst-supported carbon is dispersed and the dispersion liquid in which the ionomer is dispersed may be mixed.
- the solvent include water, alcohol, an aqueous solvent such as a mixture thereof, an organic solvent, and the like, and among them, an aqueous solvent is preferable from the viewpoint of safety during coating and drying.
- the mixing method is not particularly limited, and examples thereof include known mixing methods such as mixing by a bead mill, mixing by a ball mill, mixing by an ultrasonic disperser, and a jet mill, and among them, the viewpoint of lowering the ionomer content. Therefore, a mixing method using a bead mill is preferable.
- the solid content concentration of the coating liquid for forming the catalyst layer is not particularly limited, and examples thereof include a range of 5% by mass to 30% by mass.
- Examples of the base film used in the catalyst layer forming step include PET film, ETFE film, and olefin resin film.
- the above-mentioned "ETFE” means an ethylene tetrafluoride copolymer resin.
- the method for applying the coating liquid for forming the catalyst layer is not particularly limited, and examples thereof include known methods such as the die coating method.
- a known method is used as a method for drying the layer of the coated coating liquid for forming the catalyst layer.
- Examples of the drying temperature include a range of 40 ° C. to 130 ° C., preferably a range of 45 ° C. to 80 ° C.
- Examples of the drying time include a range of 0.5 minutes to 10 minutes, preferably a range of 1 minute to 7 minutes.
- the film electrode junction for a solid polymer fuel cell (hereinafter, also referred to as “film electrode junction”) in the present embodiment is provided on one surface side of the first gas diffusion layer and the first gas diffusion layer.
- a polymer electrolyte membrane arranged between the first catalyst layer and the second catalyst layer is provided, and at least one of the first catalyst layer and the second catalyst layer is the above-mentioned catalyst layer.
- FIG. 1 shows a schematic cross-sectional view of an example of a form in which the above-mentioned catalyst layer is used as the second catalyst layer, which is the catalyst layer of the cathode, in the membrane electrode assembly of the present embodiment.
- the membrane electrode assembly 10 shown in FIG. 1 has a catalyst between the anode 13 having the catalyst layer 11 and the gas diffusion layer 12, the cathode 14 having the catalyst layer 21 and the gas diffusion layer 22, and the anode 13 and the cathode 14. It includes a polymer electrolyte membrane 15 arranged in contact with the layer 11 and the catalyst layer 21.
- the catalyst layer 21 is the above-mentioned catalyst layer.
- the catalyst layer 21 and the catalyst layer 11 may have the same composition, composition, thickness, or the like, or may be different layers.
- Examples of the catalyst layer 11 include a layer containing catalyst-supported carbon and ionomer.
- the catalyst layer 11 may be the catalyst layer according to the above-described embodiment, or may be a catalyst layer other than the catalyst layer according to the above-mentioned embodiment.
- the gas diffusion layer 12 and the gas diffusion layer 22 have a function of uniformly diffusing the gas and a function of a current collector in the catalyst layer 11 and the catalyst layer 21, respectively.
- the gas diffusion layer 12 and the gas diffusion layer 22 are made of, for example, a gas diffusing base material. Examples of the gas diffusion layer 12 and the gas diffusion layer 22 include carbon paper, carbon cloth, carbon felt and the like.
- the gas diffusion layer 12 and the gas diffusion layer 22 are preferably water-repellent-treated with polytetrafluoroethylene or the like.
- the gas diffusion layer 12 and the gas diffusion layer 22 may have the same composition, composition, thickness, or the like, or may be different layers.
- the anode 13 may have a carbon layer (not shown) as an intermediate layer between the catalyst layer 11 and the gas diffusion layer 12.
- the cathode 14 may also have a carbon layer (not shown) as an intermediate layer between the catalyst layer 21 and the gas diffusion layer 22.
- the carbon layer include a layer containing carbon and a nonionic fluoropolymer.
- the carbon used for the carbon layer include carbon nanofibers having a fiber diameter of 1 nm to 1000 nm and a fiber length of 1000 ⁇ m or less.
- the nonionic fluoropolymer include polytetrafluoroethylene and the like.
- the polymer electrolyte membrane 15 is a membrane containing an ion exchange resin.
- a fluorine-containing ion exchange resin is preferable from the viewpoint of durability, a perfluorocarbon polymer having an ion exchange group is more preferable, the above-mentioned polymer (H) or polymer (Q) is further preferable, and the polymer (H) is more preferable.
- the perfluorocarbon polymer may contain an ethereal oxygen atom.
- the ion exchange capacity of the fluorine-containing ion exchange resin is preferably 0.5 mm equivalent / g dry resin to 2.0 mm equivalent / g dry resin, and 0.8 mm equivalent / g dry resin to 1.5 mm equivalent / g. Dry resins are particularly preferred.
- the ion exchange capacity of the fluorine-containing ion exchange resin can be measured by the same method as the ion exchange capacity of the ionomer.
- the polymer electrolyte membrane 15 may be reinforced with a reinforcing material.
- the reinforcing material include porous materials, fibers, woven fabrics, non-woven fabrics and the like.
- Examples of the material of the reinforcing material include polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer, polyethylene, polypropylene, polyphenylene sulfide and the like.
- the polymer electrolyte membrane 15 may contain one or more atoms selected from the group consisting of cerium and manganese in order to further improve the durability.
- Cerium and manganese decompose hydrogen peroxide, which is a causative substance that causes deterioration of the polymer electrolyte membrane 15.
- Cerium and manganese are preferably present as ions in the polymer electrolyte membrane 15.
- the polymer electrolyte membrane 15 may contain silica, a heteropolyacid (zincyl phosphate, phosphomolybdic acid, phosphotungstic acid, etc.) or the like as a water retention agent for preventing drying.
- the thickness of the polymer electrolyte membrane is preferably 10 ⁇ m to 30 ⁇ m, more preferably 15 ⁇ m to 25 ⁇ m.
- the thickness of the polymer electrolyte membrane is measured by observing the cross section of the polymer electrolyte membrane with a scanning electron microscope or the like.
- the membrane electrode assembly 10 is manufactured, for example, by the following method.
- a catalyst layer 21 is formed on the gas diffusion layer 22 to serve as a cathode 14
- a polymer electrolyte membrane 15 is formed by the anode 13 and the cathode 14. How to pinch.
- the membrane electrode assembly 10 When the membrane electrode assembly 10 has a carbon layer, the membrane electrode assembly 10 is manufactured, for example, by the following method. A dispersion liquid containing carbon and a nonionic fluorine-containing polymer is applied onto the ( ⁇ ) base film and dried to form a carbon layer, and a catalyst layer 11 is formed on the carbon layer. A laminate in which a carbon layer and a catalyst layer 21 are formed in this order is separately produced on the material film, and the catalyst layer 11 and the polymer electrolyte membrane 15 and the catalyst layer 21 and the polymer electrolyte membrane 15 are bonded to each other, and each base material is attached.
- a dispersion liquid containing carbon and a nonionic fluorine-containing polymer is applied onto the ( ⁇ ) base film and dried to form a carbon layer, and a catalyst layer 11 is formed on the carbon layer.
- a laminate in which a carbon layer and a catalyst layer 21 are formed in this order is separately produced on the material film, and the catalyst layer 11 and the polymer electrolyte membrane 15
- ⁇ A dispersion liquid containing carbon and a nonionic fluoropolymer is applied onto the gas diffusion layer 12 and the gas diffusion layer 22, respectively, and dried to form a carbon layer, and a catalyst layer is formed on the polymer electrolyte film 15.
- a method in which a film catalyst layer conjugate forming 11 and a catalyst layer 21 is sandwiched between a gas diffusion layer 12 having a carbon layer and a gas diffusion layer 22 having a carbon layer.
- the polymer electrolyte membrane 15 can be formed, for example, by a method (cast method) in which a liquid composition containing an ion exchange resin is applied onto a base film or a catalyst layer (catalyst layer 11 or catalyst layer 21) and dried.
- a liquid composition containing a liquid medium, a fluoropolymer having a sulfonic acid group, and trivalent or tetravalent cerium ions may be used.
- the above liquid composition it is preferable to perform heat treatment in order to stabilize the polymer electrolyte membrane 15.
- the heat treatment temperature is preferably 130 ° C. to 200 ° C., although it depends on the type of ion exchange resin.
- the ion exchange resin does not contain excessive water.
- the heat treatment temperature is 200 ° C. or lower, the thermal decomposition of the sulfonic acid group is suppressed, and the decrease in the proton conductivity of the polymer electrolyte membrane 15 is suppressed.
- the polymer electrolyte membrane 15 may be treated with hydrogen peroxide solution, if necessary.
- the polymer electrolyte fuel cell in the present embodiment includes the membrane electrode assembly described above.
- a polymer electrolyte fuel cell is manufactured, for example, by forming a cell by sandwiching a membrane electrode assembly between two separators and stacking a plurality of cells.
- the separator include a conductive carbon plate having a groove formed as a passage for an oxidant gas (air, oxygen, etc.) containing fuel gas or oxygen.
- Examples of the type of polymer electrolyte fuel cell include a hydrogen / oxygen fuel cell, a direct methanol fuel cell (DMFC), and the like.
- the methanol or methanol aqueous solution used as the fuel of the DMFC may be a liquid feed or a gas feed.
- Catalyst-supported carbon As the catalyst-supported carbon, the following catalyst-supported carbon (1), catalyst-supported carbon (2), and catalyst-supported carbon (3) were prepared.
- Catalyst-supported carbon (3) catalyst: platinum particles, catalyst content with respect to the entire catalyst-supported carbon: 20% by mass, number average particle size of platinum particles: 2.5 nm
- a general platinum-supported carbon catalyst having a platinum-supporting ratio of 20% was used.
- the characteristics of the catalyst-supported carbon (1) are as follows. Overall specific surface area: 283 m 2 / g Total pore volume of specific mesopores: 0.15 cm 3 / g Ratio of total pore volume of specific mesopores to total mesopores and macropores: 28% Total pore volume of macropores: 0.25 cm 3 / g catalyst
- the characteristics of the catalyst-supported carbon (2) are as follows. Overall specific surface area: 410 m 2 / g Total pore volume of specific mesopores: 0.15 cm 3 / g Ratio of total pore volume of specific mesopores to total mesopores and macropores: 50% Total pore volume of macropores: 0.25 cm 3 / g catalyst
- Coating liquid (a1) 50.0 g of catalyst-supported carbon (1) was added to 363 g of distilled water and stirred well. Further, 177 g of ethanol and 65 g of 2-propanol were added and stirred well. 56.0 g of the polymer (H1) dispersion liquid (A) is added thereto, and 1 mm of zirconia beads are used in a bead mill (LZ015 manufactured by Ashizawa Finetech) so that the peripheral speed is 6 m / s and the residence time is 1.1 minutes. This was used as the coating liquid (a1).
- Coating liquid (c1) 21.0 g of ethanol and 24.0 g of distilled water are added to 10.0 g of vapor-grown carbon fiber (manufactured by Showa Denko Co., Ltd., trade name: VGCF-H, average fiber diameter: about 150 nm, fiber length: 10 to 20 ⁇ m). It was added and stirred well. To this, 20.0 g of the polymer (H1) dispersion liquid (A) was added, stirred well, mixed and pulverized using a homogenizer, and this was used as a coating liquid (c1).
- Example C1> Apply the coating liquid (c1) on the gas diffusion layer base material (NOK, H2315 T10X6) without a sealing layer with a die coater so that the solid content is 3.0 mg / cm 2, and dry it on top of it. Further, the coating liquid (a1) was coated with a die coater so that the amount of platinum was 0.20 mg / cm 2, and dried to obtain a cathode (gc1).
- the "platinum amount” means the content of the catalyst per unit area of the catalyst layer.
- a coating liquid (a7) is coated on a gas diffusion layer base material with a sealing layer (25BC manufactured by SGL Carbon Co., Ltd.) with a die coater so that the amount of platinum is 0.05 mg / cm 2, and the anode (Anode) ( ga1) was obtained.
- a 20 ⁇ m-thick ion exchange membrane manufactured by Asahi Glass Co., Ltd., trade name: Flemion, ion exchange capacity: 1.1 mm equivalent / g dry resin
- Flemion, ion exchange capacity: 1.1 mm equivalent / g dry resin made of a perfluorocarbon polymer having a sulfonic acid group.
- the polymer electrolyte membrane is sandwiched between the anode (ga1) and the cathode (ggc1), and the catalyst layers of the cathode (ga1) and the anode (ggc1) are pressure-bonded to the polymer electrolyte membrane by a hot press method to form a membrane electrode assembly (electrode area). : 25 cm 2 ) was obtained.
- Example 1> Apply the coating liquid (c1) on the gas diffusion layer base material (NOK, H2315 T10X6) without a sealing layer with a die coater so that the solid content is 3.0 mg / cm 2, and dry it on top of it. Further, the coating liquid (a2) was coated with a die coater so that the amount of platinum was 0.20 mg / cm 2, and dried to obtain a cathode (gc2). A membrane electrode assembly was obtained in the same manner as in Example C1 except that the cathode (gc2) was used instead of the cathode (gc1).
- Example 2> Apply the coating liquid (c1) on the gas diffusion layer base material (NOK, H2315 T10X6) without a sealing layer with a die coater so that the solid content is 3.0 mg / cm 2, and dry it on top of it. Further, the coating liquid (a3) was coated with a die coater so that the amount of platinum was 0.20 mg / cm 2, and dried to obtain a cathode (gc3). A membrane electrode assembly was obtained in the same manner as in Example C1 except that a cathode (gc3) was used instead of the cathode (gc1).
- Example C2> Apply the coating liquid (c1) on the gas diffusion layer base material (NOK, H2315 T10X6) without a sealing layer with a die coater so that the solid content is 3.0 mg / cm 2, and dry it on top of it. Further, the coating liquid (a4) was coated with a die coater so that the amount of platinum was 0.20 mg / cm 2, and dried to obtain a cathode (gc4). A membrane electrode assembly was obtained in the same manner as in Example C1 except that a cathode (gc4) was used instead of the cathode (gc1).
- Example 3> Apply the coating liquid (c1) on the gas diffusion layer base material (NOK, H2315 T10X6) without a sealing layer with a die coater so that the solid content is 3.0 mg / cm 2, and dry it on top of it. Further, the coating liquid (a5) was coated with a die coater so that the amount of platinum was 0.20 mg / cm 2, and dried to obtain a cathode (gc5). A membrane electrode assembly was obtained in the same manner as in Example C1 except that a cathode (gc5) was used instead of the cathode (gc1).
- Example C3> Apply the coating liquid (c1) on the gas diffusion layer base material (NOK, H2315 T10X6) without a sealing layer with a die coater so that the solid content is 3.0 mg / cm 2, and dry it on top of it. Further, the coating liquid (a6) was coated with a die coater so that the amount of platinum was 0.20 mg / cm 2, and dried to obtain a cathode (gc6). A membrane electrode assembly was obtained in the same manner as in Example C1 except that the cathode (gt6) was used instead of the cathode (gt1).
- Example 4> Apply the coating liquid (c1) on the gas diffusion layer base material (NOK, H2315 T10X6) without a sealing layer with a die coater so that the solid content is 3.0 mg / cm 2, and dry it on top of it. Further, the coating liquid (a8) was coated with a die coater so that the amount of platinum was 0.10 mg / cm 2, and dried to obtain a cathode (gc7). A membrane electrode assembly was obtained in the same manner as in Example C1 except that a cathode (gc7) was used instead of the cathode (gc1).
- ⁇ Power generation performance (2)> The membrane electrode assembly obtained in the above example is incorporated into a power generation cell, hydrogen (utilization rate 70%) / air (utilization rate 50%) is supplied at normal pressure, and the current density is at a cell temperature of 80 ° C. : The cell voltage (V) at the initial stage of operation at 1.0 A / cm 2 was measured. Hydrogen having a dew point of 53 ° C. was supplied to the anode side, and air having a dew point of 53 ° C. was supplied to the cell (relative humidity in the cell: 30% RH). The results are shown in Table 1 (“30% RH cell voltage” in Table 1).
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Abstract
Description
また、膜電極接合体は、例えば、触媒層及びガス拡散層を有するアノードと、触媒層及びガス拡散層を有するカソードと、アノードとカソードとの間に配置された高分子電解質膜と、を備える。
触媒として主に用いられている白金は高価であるため、触媒の使用量を削減することが望まれている。そのため、触媒を効率的に活用するため、できるだけ均一に多くの触媒粒子をイオノマーで被覆することで、触媒の使用量を削減しつつ燃料電池を高出力化する試みがなされている(例えば特許文献1~特許文献3等)。
特許文献2: 特開2010-186678号公報
特許文献3: 特開2011-081977号公報
しかしながら、触媒として白金を含む触媒を用いる場合において、触媒使用量を削減しつつ、さらなる燃料電池の高出力化が要求されている。
<1> 白金を含む触媒がカーボン担体に担持された触媒担持カーボンと、イオノマーと、を含有する触媒層であり、
前記触媒担持カーボンは、窒素吸着法により得られる細孔分布における細孔直径2nm以上10nm未満のメソ孔を有し、
前記イオノマーの少なくとも一部は、前記細孔直径2nm以上10nm未満のメソ孔内に存在し、
前記カーボン担体100質量部に対するイオノマーの含有量が100質量部以上であり、
前記細孔直径2nm以上10nm未満のメソ孔の全体積に占める前記イオノマーの占有率が50体積%以下である触媒層。
<2> 触媒層中における前記触媒担持カーボンは、前記イオノマーが付着した状態で、窒素吸着法により得られる細孔分布における細孔直径50nm以上のマクロ孔を0.03cm3/g触媒以上有する<1>に記載の触媒層。
<3> 触媒層の単位面積あたりにおける前記触媒の含有量は、0.2mg/cm2以下である<1>又は<2>に記載の触媒層。
<4> 前記触媒は、白金の粒子及び白金合金の粒子からなる群より選択される少なくとも一種を含む<1>~<3>のいずれか一つに記載の触媒層。
<5> 前記触媒の個数平均粒子径は、1nm~20nmである<4>に記載の触媒層。
<6> 前記触媒担持カーボン全体に対する前記触媒の含有率は、10質量%~70質量%である<1>~<5>のいずれか一つに記載の触媒層。
<7> 第1のガス拡散層と前記第1のガス拡散層における一方の面側に設けられた第1の触媒層とを有するアノードと、
第2のガス拡散層と前記第2のガス拡散層における一方の面側に設けられた第2の触媒層とを有するカソードと、
前記第1の触媒層と前記第2の触媒層との間に配置された高分子電解質膜と、
を備え、
前記第1の触媒層及び前記第2の触媒層の少なくとも一方が、<1>~<6>のいずれか一つに記載の触媒層である、固体高分子形燃料電池用膜電極接合体。
<8> <7>に記載の固体高分子形燃料電池用膜電極接合体を備えた固体高分子形燃料電池。
本明細書において「~」を用いて示された数値範囲には、「~」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本明細書において各成分は該当する物質を複数種含んでいてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本明細書において実施形態を図面を参照して説明する場合、当該実施形態の構成は図面に示された構成に限定されない。また、各図における部材の大きさは概念的なものであり、部材間の大きさの相対的な関係はこれに限定されない。
本実施形態における触媒層は、白金を含む触媒がカーボン担体に担持された触媒担持カーボンと、イオノマーと、を含有する触媒層である。
メソ孔は、一般的に細孔直径が2nm以上50nm未満である細孔を意味するが、本実施形態においては、その中でも細孔直径2nm以上10nm未満のメソ孔内に、特定割合の体積を占有するイオノマーが存在する。すなわち、前記触媒担持カーボンは窒素吸着法により得られる細孔分布における細孔直径2nm以上10nm未満のメソ孔を有し、前記イオノマーの少なくとも一部は前記細孔直径2nm以上10nm未満のメソ孔内に存在し、前記カーボン担体100質量部に対するイオノマーの含有量が100質量部以上であり、前記細孔直径2nm以上10nm未満のメソ孔の全体積に占める前記イオノマーの占有率が50体積%以下である。
上記「細孔分布」は、測定対象の試料を、自動比表面積/細孔分布測定装置(例えば、島津製作所製、型番:トライスターII 3020、測定方式:定容法による窒素吸着法)により、BJH法による解析を行うことで得られる。なお、後述する触媒担持カーボンについての比表面積及び細孔容量は、上記細孔分布から算出される。
イオノマー占有率(体積%)=(P0-P1)×100/P0 ・・・・(1)
また、上記イオノマーを付着させていない触媒担持カーボンの試料としては、例えば、触媒担持カーボンと溶媒との混合物を、PETフィルム等の基材フィルム上に塗布し、乾燥させて溶媒を除去することで塗工層を形成し、得られた塗工層を掻きとって粉体としたものを用いる。ここで、上記「PET」は、ポリエチレンテレフタレートを意味する。なお、上記混合物は、触媒層形成用塗布液を調製する過程で行う混合処理(例えばビーズミルによる混合処理等)と同じ混合処理を行ったものであることが望ましい。
特定メソ孔は、細孔容量に対して細孔表面積が大きい。そのため、特定メソ孔を有するカーボン担体の表面積は非常に大きくなる。例えば、カーボン担体におけるメソ孔及びマクロ孔全体の合計細孔容量に占める特定メソ孔の合計細孔容量の割合が30%程度であるカーボン担体であっても、カーボン担体におけるメソ孔及びマクロ孔全体の合計細孔表面積に占める特定メソ孔の合計細孔表面積の割合は85%を超えることがある。つまり、白金を含む触媒の粒子がカーボン担体の表面に担持された触媒担持カーボンでは、カーボン担体における細孔以外の表面又はマクロ孔の表面等に担持された触媒も存在するものの、触媒の多くが特定メソ孔の表面に担持されていると考えられる。
しかしながら、イオノマーが白金触媒粒子に接触すると、イオノマーが有する酸性の官能基によって被毒し、白金の触媒活性がむしろ低下してしまうことがあることが分かってきた。
以上の理由により、本実施形態の触媒層では、触媒使用量を削減しつつ燃料電池の高出力化が実現されるものと推測される。
以下、触媒層を構成する各成分についてそれぞれ説明する。
触媒担持カーボンは、特定メソ孔を有するカーボン担体と、カーボン担体に担持され白金を含む触媒と、を有する。以下、カーボン担体及び触媒についてそれぞれ説明する。
カーボン担体としては、活性炭、カーボンブラック等が挙げられ、化学的耐久性が高い点から、熱処理等に少なくとも一部グラファイト化をすすめたものが好ましい。また、カーボン担体としては、イオノマー占有率を低く抑える観点から、マクロ孔の占める合計細孔容量の割合がメソ孔及びマクロ孔全体の合計細孔容量に対し、40%未満のメソポーラスカーボンが好ましい。マクロ孔の占める合計細孔容量の割合は、5~35%が好ましく、10~30%がより好ましい。
白金合金としては、白金を除く白金族の金属(ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム)、金、銀、クロム、鉄、チタン、マンガン、コバルト、ニッケル、モリブデン、タングステン、アルミニウム、ケイ素、亜鉛、及びスズからなる群から選ばれる1種以上の金属と、白金と、の合金が好ましい。該白金合金には、白金と合金化される金属と、白金と、の金属間化合物が含まれていてもよい。
なお、上記触媒の個数平均粒子径は、日立ハイテクノロジーズ社製透過型電子顕微鏡(TEM) HT7700を使用して、30万倍で観察した画像において、300~400個の粒子について求めた円相当径を個数平均して求めた値である。
触媒層の単位面積あたりにおける触媒の含有量は、電極反応を効率よく行うための触媒層の最適な厚さの点から、0.01mg/cm2~0.50mg/cm2が好ましく、原料のコストと性能とのバランスの点から、0.05mg/cm2~0.35mg/cm2がより好ましい。特に、本実施形態の触媒層では、触媒使用量を削減しつつ高出力化できるため、触媒層の単位面積あたりにおける触媒の含有量は、0.20mg/cm2以下であってもよい。
また、触媒担持カーボン全体の比表面積は、700m2/g触媒以下であってもよく、500m2/g触媒以下であってもよく、350m2/g触媒以下であってもよい。
上記触媒担持カーボン全体の比表面積は、BET比表面積装置により、カーボン表面への窒素吸着により測定する。
イオノマーが付着していない状態の触媒担持カーボンにおけるメソ孔及びマクロ孔全体の合計細孔容量に占める特定メソ孔の合計細孔容量の割合は、例えば20%~90%の範囲が挙げられ、生成水の排水性と発電性能の観点から25%~80%の範囲が好ましく、30%~70%の範囲がより好ましい。
イオノマーは、イオン交換基を有する高分子化合物であれば特に限定するものではなく、その中でもプロトン伝導性を有する高分子化合物が好ましい。以下、イオン交換基を有する高分子化合物を「イオン交換樹脂」ともいう。「イオン交換基」とは、H+、一価の金属カチオン、アンモニウムイオン等を有する基を意味する。
イオン交換基としては、スルホン酸基、スルホンイミド基、スルホンアミド基、スルホンメチド基、カルボキシル基、リン酸基等が挙げられ、中でもプロトン伝導性に優れるスルホン酸基が好ましい。イオン交換基は1種を単独で又は2種以上を組み合わせて用いられる。
該ペルフルオロカーボンポリマーとしては、後述するポリマー(H)、後述するポリマー(Q)、国際公開第2011/013577号等に記載された、イオン交換基及び5員環を有するペルフルオロモノマーに由来する構成単位を有するポリマー等の公知のポリマーが挙げられる。イオノマーは、入手のしやすさ及び製造のしやすさの点から、ポリマー(H)及びポリマー(Q)からなる群より選択される少なくとも1種を含むことが好ましい。
ポリマー(H)は、下記単位(U1)を有するポリマーである(ただし、ポリマー(Q)を除く)。
ペルフルオロアルキレン基は、直鎖状であってもよく、分岐状であってもよい。
ペルフルオロアルキレン基の炭素数は、1~6が好ましく、1~4がより好ましい。
ペルフルオロアルキル基の炭素数は、1~6が好ましく、1~4がより好ましい。ペルフルオロアルキル基としては、ペルフルオロメチル基、ペルフルオロエチル基等が好ましい。
上記単位(U1)中の-(SO2X2(SO2Rf2)b)-H+基としては、スルホン酸基(-SO3 -H+基)、スルホンイミド基(-SO2N(SO2Rf2)-H+基)、又はスルホンメチド基(-SO2C(SO2Rf2)2)-H+基)が挙げられる。
上記単位(U1)中のY2としては、フッ素原子又はトリフルオロメチル基が好ましい。
他の単位としては、機械的強度及び化学的な耐久性の点から、ペルフルオロモノマーに由来する構成単位が好ましく、テトラフルオロエチレン(以下、TFEと記す。)に由
来する構成単位がより好ましい。
CF2=CF-(CF2)tOCF2-CFY2-Q3-SO2F・・・(M1)。
なお、上記化合物(M1)中のt、Y2、及びQ3は、それぞれ前記単位(U1)中のt、Y2、及びQ3と同義である。
ポリマー(Q)は、下記単位(U2)及び下記単位(U3)の少なくとも一方を有するポリマーである。
ペルフルオロアルキレン基は、直鎖状であってもよく、分岐状であってもよく、直鎖状であることが好ましい。
ペルフルオロアルキレン基の炭素数は、1~6が好ましく、1~4がより好ましい。炭素数が6以下であれば、原料の含フッ素モノマーの沸点が低くなり、蒸留精製が容易となる。
上記単位(U2)中、Q1、Q2の少なくとも一方は、エーテル性の酸素原子を有する炭素数1~6のペルフルオロアルキレン基であることが好ましい。エーテル性の酸素原子を有する炭素数1~6のペルフルオロアルキレン基を有する含フッ素モノマーは、フッ素ガスによるフッ素化反応を経ずに合成できるため、収率が良好で、製造が容易である。
ペルフルオロアルキル基の炭素数は、1~6が好ましく、1~4がより好ましい。ペルフルオロアルキル基としては、ペルフルオロメチル基、ペルフルオロエチル基等が好ましい。
単位(U2)が2つ以上のRf1を有する場合、Rf1は、それぞれ同じ基であってもよく、それぞれ異なる基であってもよい。
上記単位(U2)中の-(SO2X1(SO2Rf1)a)-H+基としては、スルホン酸基(-SO3 -H+基)、スルホンイミド基(-SO2N(SO2Rf1)-H+基)、又はスルホンメチド基(-SO2C(SO2Rf1)2)-H+基)が挙げられる。
上記単位(U2)中のY1としては、フッ素原子、又はエーテル性の酸素原子を有していてもよい炭素数1~6の直鎖のペルフルオロアルキル基であることが好ましい。
RF1及びRF2の具体例としては、-CF2-、-CF2CF2-、-CF(CF3)-、-CF2CF2CF2-、-CF(CF2CF3)-、-CF(CF3)CF2-、-CF2CF(CF3)-、-C(CF3)(CF3)-が挙げられる。
原料が安価である点、製造が容易である点、ポリマー(Q)のイオン交換容量をより高くできる点から、RF1及びRF2はそれぞれ独立に、炭素数1又は2のペルフルオロアルキレン基が好ましい。炭素数2の場合は、直鎖が好ましい。具体的には、-CF2-、-CF2CF2-又は-CF(CF3)-が好ましく、-CF2-又は-CF2CF2-がより好ましく、-CF2-が特に好ましい。
単位(U3)としては、下記単位(U3-1)が好ましい。
他の単位としては、機械的強度及び化学的な耐久性の点から、ペルフルオロモノマーに由来する構成単位が好ましく、TFEに由来する構成単位がより好ましい。
イオノマー占有率は、50体積%以下であり、触媒使用量の削減と高出力化とを両立する観点から、10体積%~50体積%が好ましい。また、イオノマー占有率は、さらに低湿環境下(例えば湿度が30%である環境下)における触媒使用量の削減と高出力化との両立を実現する観点から、15体積%~40体積%がより好ましく、20体積%~35体積%がさらに好ましい。
混合処理条件を調整する方法としては、混合処理において加えるせん断応力を小さく抑える方法、混合処理の処理時間を短くする方法等が挙げられる。
材料の特性を調整する方法としては、増粘イオノマー(例えば、フッ素系の溶剤を添加することで粘度を高くしたイオノマー)を用いる方法、分子量の大きなイオノマーを用いる方法、親水化触媒担持カーボン(例えば、酸処理により表面の親水性官能基量を多くした触媒担持カーボン)を用いる方法等が挙げられる。
イオノマーが付着した状態における触媒担持カーボンの単位質量あたりにおけるマクロ孔の合計細孔容量は、例えば0.03cm3/g触媒~0.3cm3/g触媒の範囲が挙げられ、触媒使用量の削減と高出力化とを両立する観点から、0.05cm3/g触媒~0.25cm3/g触媒の範囲が好ましく、0.07cm3/g触媒~0.20cm3/g触媒の範囲がより好ましい。
触媒層の厚さは、触媒層の断面を走査型電子顕微鏡等によって観察することにより測定する。
触媒層の製造方法は、例えば、触媒層形成用塗布液を準備する準備工程と、膜電極接合体において触媒層と接触する層(ガス拡散層、高分子電解質膜等)の表面又は基材フィルムの表面に触媒層形成用塗布液を塗布し、乾燥させることで触媒層を形成する触媒層形成工程と、を経る。
なお、基材フィルムの表面に触媒層形成用塗布液を塗布する場合は、形成された触媒層を、膜電極接合体において触媒層と接触する層の表面に転写する転写工程をさらに経てもよい。
溶媒としては、水、アルコール、それらの混合物等の水系溶媒、有機溶媒等が挙げられ、その中でも塗工・乾燥時の安全性の観点から水系溶媒が好ましい。
混合方法は、特に限定されるものではなく、例えば、ビーズミルによる混合、ボールミルによる混合、超音波分散機による混合、ジェットミル等の公知の混合方法が挙げられ、その中でもイオノマー含有率を低くする観点からビーズミルによる混合方法が好ましい。
触媒層形成用塗布液の固形分濃度は、特に限定されるものではなく、例えば5質量%~30質量%の範囲が挙げられる。
触媒層形成用塗布液を塗布する方法は、特に限定されるものではなく、例えば、ダイコート法等の公知の方法が挙げられる。
塗布された触媒層形成用塗布液の層を乾燥する方法は、公知の方法が用いられる。乾燥温度としては、例えば40℃~130℃の範囲が挙げられ、45℃~80℃の範囲が好ましい。乾燥時間としては、例えば0.5分~10分の範囲が挙げられ、1分~7分の範囲が好ましい。
本実施形態における固体高分子形燃料電池用膜電極接合体(以下、「膜電極接合体」ともいう)は、第1のガス拡散層と第1のガス拡散層における一方の面側に設けられた第1の触媒層とを有するアノードと、第2のガス拡散層と第2のガス拡散層における一方の面側に設けられた第2の触媒層とを有するカソードと、第1の触媒層と第2の触媒層との間に配置された高分子電解質膜と、を備え、第1の触媒層及び第2の触媒層の少なくとも一方が、前述の触媒層である。
以下、図面を用いて本実施形態における膜電極接合体について説明する。
図1に示す膜電極接合体10は、触媒層11及びガス拡散層12を有するアノード13と、触媒層21及びガス拡散層22を有するカソード14と、アノード13とカソード14との間に、触媒層11及び触媒層21に接した状態で配置された高分子電解質膜15とを具備する。
そして、触媒層21が、前述の触媒層である。
触媒層11は、例えば触媒担持カーボンとイオノマーとを含む層が挙げられる。触媒層11は、前述の実施形態に係る触媒層であってもよく、前述の実施形態に係る触媒層以外の触媒層であってもよい。なお、触媒層11における触媒担持カーボン及びイオノマーとしては、前述の実施形態に係る触媒層における触媒担持カーボン及びイオノマーと同様のものを用いてもよい。
カーボン層としては、例えば、カーボンと非イオン性含フッ素ポリマーとを含む層が挙げられる。カーボン層に用いるカーボンとしては、例えば、繊維径1nm~1000nm、繊維長1000μm以下のカーボンナノファイバーが挙げられる。非イオン性含フッ素ポリマーとしては、例えば、ポリテトラフルオロエチレン等が挙げられる。
含フッ素イオン交換樹脂のイオン交換容量は、0.5ミリ当量/g乾燥樹脂~2.0ミリ当量/g乾燥樹脂が好ましく、0.8ミリ当量/g乾燥樹脂~1.5ミリ当量/g乾燥樹脂が特に好ましい。
なお、含フッ素イオン交換樹脂のイオン交換容量は、イオノマーのイオン交換容量と同様の方法で測定できる。
高分子電解質膜15は、耐久性をさらに向上させるために、セリウム及びマンガンからなる群から選ばれる1種以上の原子を含んでいてもよい。セリウム、マンガンは、高分子電解質膜15の劣化を引き起こす原因物質である過酸化水素を分解する。セリウム、マンガンは、イオンとして高分子電解質膜15中に存在することが好ましい。
高分子電解質膜15は、乾燥を防ぐための保水剤として、シリカ、ヘテロポリ酸(リン酸ジルコニウム、リンモリブデン酸、リンタングステン酸等)などを含んでいてもよい。
高分子電解質膜の厚さは、高分子電解質膜の断面を走査型電子顕微鏡等によって観察することにより測定する。
膜電極接合体10は、例えば、下記の方法にて製造される。
(α)高分子電解質膜15上に触媒層11及び触媒層21を形成して膜触媒層接合体とし、該膜触媒層接合体をガス拡散層12とガス拡散層22とで挟み込む方法。
(β)ガス拡散層12上に触媒層11を形成してアノード13とし、ガス拡散層22上に触媒層21を形成してカソード14とし、高分子電解質膜15をアノード13とカソード14とで挟み込む方法。
(γ)基材フィルム上に、カーボン及び非イオン性含フッ素ポリマーを含む分散液を塗布し、乾燥させてカーボン層を形成し、カーボン層上に触媒層11を形成し、同様の方法で基材フィルム上にカーボン層、触媒層21の順に形成された積層体を別途作製し、触媒層11と高分子電解質膜15、触媒層21と高分子電解質膜15、をそれぞれ貼り合わせ、各基材フィルムを剥離して、カーボン層を有する膜触媒層接合体とし、該膜触媒層接合体をガス拡散層12及びガス拡散層22で挟み込む方法。
(δ)ガス拡散層12及びガス拡散層22上に、カーボン及び非イオン性含フッ素ポリマーを含む分散液をそれぞれ塗布し、乾燥させてカーボン層を形成し、高分子電解質膜15上に触媒層11及び触媒層21を形成した膜触媒層接合体を、カーボン層を有するガス拡散層12とカーボン層を有するガス拡散層22とで挟み込む方法。
高分子電解質膜15を形成する際には、例えば、液状媒体と、スルホン酸基を有する含フッ素ポリマーと、3価又は4価のセリウムイオンと、を含む液状組成物を用いてもよい。
上記液状組成物を用いる場合、高分子電解質膜15を安定化させるために、熱処理を行うことが好ましい。熱処理の温度は、イオン交換樹脂の種類にもよるが、130℃~200℃が好ましい。熱処理の温度が130℃以上であれば、イオン交換樹脂が過度に含水しなくなる。熱処理の温度が200℃以下であれば、スルホン酸基の熱分解が抑えられ、高分子電解質膜15のプロトン伝導性の低下が抑えられる。高分子電解質膜15は、必要に応じて過酸化水素水で処理してもよい。
本実施形態における固体高分子形燃料電池は、前述の膜電極接合体を備える。
固体高分子形燃料電池は、例えば、2つのセパレータの間に膜電極接合体を挟んでセルを形成し、複数のセルをスタックすることにより製造される。
セパレータとしては、燃料ガス又は酸素を含む酸化剤ガス(空気、酸素等)の通路となる溝が形成された導電性カーボン板等が挙げられる。
固体高分子形燃料電池の種類としては、水素/酸素型燃料電池、直接メタノール型燃料電池(DMFC)等が挙げられる。DMFCの燃料に用いるメタノール又はメタノール水溶液は、液フィードであってもよく、ガスフィードであってもよい。
触媒担持カーボンとして、下記触媒担持カーボン(1)、触媒担持カーボン(2)、及び触媒担持カーボン(3)を準備した。
触媒担持カーボン(1):触媒:白金粒子、触媒担持カーボン全体に対する触媒含有率:60質量%、白金粒子の個数平均粒子径:4.8nm
触媒担持カーボン(2):触媒:白金粒子、触媒担持カーボン全体に対する触媒含有率:50質量%、白金粒子の個数平均粒子径:3.3nm
触媒担持カーボン(3):触媒:白金粒子、触媒担持カーボン全体に対する触媒含有率:20質量%、白金粒子の個数平均粒子径:2.5nm
なお、触媒担持カーボン(3)としては、白金担持率20%の一般的な白金担持カーボン触媒を使用した。
全体の比表面積:283m2/g触媒
特定メソ孔の合計細孔容量:0.15cm3/g触媒
メソ孔及びマクロ孔全体に占める特定メソ孔の合計細孔容量の割合:28%
マクロ孔の合計細孔容量:0.25cm3/g触媒
全体の比表面積:410m2/g触媒
特定メソ孔の合計細孔容量:0.15cm3/g触媒
メソ孔及びマクロ孔全体に占める特定メソ孔の合計細孔容量の割合:50%
マクロ孔の合計細孔容量:0.25cm3/g触媒
イオノマーとして、TFEに由来する構成単位と前記単位(U1-11)とを有するポリマー(H1)(イオン交換容量:1.1ミリ当量/g乾燥樹脂)を準備した。
ポリマー(H1)をエタノール/水=6/4(質量比)の分散媒に分散させ、固形分濃度:25.0質量%のポリマー(H1)分散液(A)を調製した。
<塗工液(a1)>
触媒担持カーボン(1)の50.0gを、蒸留水の363gに添加し、よく撹拌した。さらにエタノールの177g、2-プロパノールの65gを添加し、よく撹拌した。これにポリマー(H1)分散液(A)の56.0gを添加し、ビーズミル(アシザワ・ファインテック製LZ015)でジルコニアビーズ1mmを用い、周速6m/s、滞留時間1.1分になるように分散し、これを塗工液(a1)とした。
触媒担持カーボン(1)の50.0gを、蒸留水の389gに添加し、よく撹拌した。さらにエタノールの188g、2-プロパノールの71gを添加し、よく撹拌した。これにポリマー(H1)分散液(A)の80.0gを添加し、ビーズミル(アシザワ・ファインテック製LZ015)でジルコニアビーズ1mmを用い、周速6m/s、滞留時間1.1分になるように分散し、これを塗工液(a2)とした。
触媒担持カーボン(1)の50.0gを、蒸留水の431gに添加し、よく撹拌した。さらにエタノールの207g、2-プロパノールの81gを添加し、よく撹拌した。これにポリマー(H1)分散液(A)の120gを添加し、ビーズミル(アシザワ・ファインテック製LZ015)でジルコニアビーズ1mmを用い、周速6m/s、滞留時間1.1分になるように分散し、これを塗工液(a3)とした。
触媒担持カーボン(1)の50.0gを、蒸留水の363gに添加し、よく撹拌した。さらにエタノールの177g、2-プロパノールの65gを添加し、よく撹拌した。これにポリマー(H1)分散液(A)の56.0gを添加し、ビーズミル(アシザワ・ファインテック製LZ015)でジルコニアビーズ0.5mmを用い、周速8m/s、滞留時間5.5分になるように分散し、これを塗工液(a4)とした。
触媒担持カーボン(1)の50.0gを、蒸留水の389gに添加し、よく撹拌した。さらにエタノールの188g、2-プロパノールの71gを添加し、よく撹拌した。これにポリマー(H1)分散液(A)の80.0gを添加し、ビーズミル(アシザワ・ファインテック製LZ015)でジルコニアビーズ0.5mmを用い、周速8m/s、滞留時間5.5分になるように分散し、これを塗工液(a5)とした。
触媒担持カーボン(1)の50.0gを、蒸留水の431gに添加し、よく撹拌した。さらにエタノールの207g、2-プロパノールの81gを添加し、よく撹拌した。これにポリマー(H1)分散液(A)の120gを添加し、ビーズミル(アシザワ・ファインテック製LZ015)でジルコニアビーズ0.5mmを用い、周速8m/s、滞留時間5.5分になるように分散し、これを塗工液(a6)とした。
触媒担持カーボン(3)の50.0gを、蒸留水の357gに添加し、よく撹拌した。さらにエタノールの376gを添加し、よく撹拌した。これにポリマー(H1)分散液(A)の128gを添加し、ビーズミル(アシザワ・ファインテック製LZ015)でジルコニアビーズ1.0mmを用い、周速6m/s、滞留時間4.3分になるように分散し、これを塗工液(a7)とした。
触媒担持カーボン(2)の50.0gを、蒸留水の375gに添加し、よく撹拌した。さらにエタノールの397gを添加し、よく撹拌した。これにポリマー(H1)分散液(A)の150gを添加し、ビーズミル(アシザワ・ファインテック製LZ015)でジルコニアビーズ1.0mmを用い、周速6m/s、滞留時間1.1分になるように分散し、これを塗工液(a8)とした。
<塗工液(c1)>
気相成長炭素繊維(昭和電工社製、商品名:VGCF-H、平均繊維径:約150nm、繊維長:10~20μm)の10.0gにエタノールの21.0g、蒸留水の24.0gを添加し、よく撹拌した。これにポリマー(H1)分散液(A)の20.0gを添加し、よく撹拌し、さらにホモジナイザーを用いて混合、粉砕し、これを塗工液(c1)とした。
<例C1>
目止め層なしガス拡散層基材(NOK製、H2315 T10X6)上に塗工液(c1)を固形分で3.0mg/cm2となるようにダイコーターで塗工、乾燥し、その上にさらに塗工液(a1)を白金量で0.20mg/cm2となるようにダイコーターで塗工、乾燥し、カソード(gc1)を得た。なお、上記「白金量」は、触媒層の単位面積あたりにおける触媒の含有量を意味する。
目止め層付きガス拡散層基材(SGLカーボン社製、25BC)上に塗工液(a7)を白金量で0.05mg/cm2となるようにダイコーターで塗工、乾燥し、アノード(ga1)を得た。
高分子電解質膜をアノード(ga1)及びカソード(gc1)で挟み、ホットプレス法によりカソード(ga1)及びアノード(gc1)の触媒層を高分子電解質膜に圧着することで膜電極接合体(電極面積:25cm2)を得た。
目止め層なしガス拡散層基材(NOK製、H2315 T10X6)上に塗工液(c1)を固形分で3.0mg/cm2となるようにダイコーターで塗工、乾燥し、その上にさらに塗工液(a2)を白金量で0.20mg/cm2となるようにダイコーターで塗工、乾燥し、カソード(gc2)を得た。
カソード(gc1)の代わりにカソード(gc2)を用いた以外は、例C1と同様にして膜電極接合体を得た。
目止め層なしガス拡散層基材(NOK製、H2315 T10X6)上に塗工液(c1)を固形分で3.0mg/cm2となるようにダイコーターで塗工、乾燥し、その上にさらに塗工液(a3)を白金量で0.20mg/cm2となるようにダイコーターで塗工、乾燥し、カソード(gc3)を得た。
カソード(gc1)の代わりにカソード(gc3)を用いた以外は、例C1と同様にして膜電極接合体を得た。
目止め層なしガス拡散層基材(NOK製、H2315 T10X6)上に塗工液(c1)を固形分で3.0mg/cm2となるようにダイコーターで塗工、乾燥し、その上にさらに塗工液(a4)を白金量で0.20mg/cm2となるようにダイコーターで塗工、乾燥し、カソード(gc4)を得た。
カソード(gc1)の代わりにカソード(gc4)を用いた以外は、例C1と同様にして膜電極接合体を得た。
目止め層なしガス拡散層基材(NOK製、H2315 T10X6)上に塗工液(c1)を固形分で3.0mg/cm2となるようにダイコーターで塗工、乾燥し、その上にさらに塗工液(a5)を白金量で0.20mg/cm2となるようにダイコーターで塗工、乾燥し、カソード(gc5)を得た。
カソード(gc1)の代わりにカソード(gc5)を用いた以外は、例C1と同様にして膜電極接合体を得た。
目止め層なしガス拡散層基材(NOK製、H2315 T10X6)上に塗工液(c1)を固形分で3.0mg/cm2となるようにダイコーターで塗工、乾燥し、その上にさらに塗工液(a6)を白金量で0.20mg/cm2となるようにダイコーターで塗工、乾燥し、カソード(gc6)を得た。
カソード(gc1)の代わりにカソード(gc6)を用いた以外は、例C1と同様にして膜電極接合体を得た。
目止め層なしガス拡散層基材(NOK製、H2315 T10X6)上に塗工液(c1)を固形分で3.0mg/cm2となるようにダイコーターで塗工、乾燥し、その上にさらに塗工液(a8)を白金量で0.10mg/cm2となるようにダイコーターで塗工、乾燥し、カソード(gc7)を得た。
カソード(gc1)の代わりにカソード(gc7)を用いた以外は、例C1と同様にして膜電極接合体を得た。
<カーボン担体100質量部に対するイオノマーの含有量>
上記例のカソードにおける、カーボン担体100質量部に対するイオノマーの含有量(質量部)を、それぞれ表1(表1中の「イオノマー含有量」)に示す。
上記例のカソードの形成に用いた塗工液を、PETフィルム上に塗布し、乾燥した後、塗工層をかき取ることで得られた粉体を「イオノマーを付着させた触媒担持カーボンの試料」として用いた。また、イオノマーを含まない塗工液(つまり、触媒担持カーボンと溶媒との混合液)を、PETフィルム上に塗布し、乾燥した後、塗工層をかき取ることで得られた粉体を「イオノマーを付着させていない触媒担持カーボンの試料」として用いた。これらの試料を用い、前述の方法によりそれぞれ細孔分布を求め、各例におけるイオノマー占有率(%)を算出した。結果をそれぞれ表1に示す。
各例における上記「イオノマーを付着させた触媒担持カーボンの試料」の細孔分布から、イオノマーが付着した状態における触媒担持カーボンの単位質量あたりにおけるマクロ孔の合計細孔容量(cm3/g触媒)を求めた。結果をそれぞれ表1(表1中の「マクロ孔細孔容量」)に示す。
上記例において得られた膜電極接合体を、発電用セルに組み込み、常圧にて、水素(利用率70%)/空気(利用率50%)を供給し、セル温度:80℃において電流密度:1.0A/cm2における運転初期のセル電圧(V)を測定した。なお、アノード側には露点80℃の水素を供給し、カソード側は露点80℃の空気をそれぞれセル内に供給した(セル内の相対湿度:100%RH)。結果を表1(表1中の「100%RHセル電圧」)に示す。
上記実例において得られた膜電極接合体を、発電用セルに組み込み、常圧にて、水素(利用率70%)/空気(利用率50%)を供給し、セル温度:80℃において電流密度:1.0A/cm2における運転初期のセル電圧(V)を測定した。なお、アノード側には露点53℃の水素を供給し、カソード側は露点53℃の空気をそれぞれセル内に供給した(セル内の相対湿度:30%RH)。結果を表1(表1中の「30%RHセル電圧」)に示す。
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に取り込まれる。
Claims (8)
- 白金を含む触媒がカーボン担体に担持された触媒担持カーボンと、イオノマーと、を含有する触媒層であり、
前記触媒担持カーボンは、窒素吸着法により得られる細孔分布における細孔直径2nm以上10nm未満のメソ孔を有し、
前記イオノマーの少なくとも一部は、前記細孔直径2nm以上10nm未満のメソ孔内に存在し、
前記カーボン担体100質量部に対するイオノマーの含有量が100質量部以上であり、
前記細孔直径2nm以上10nm未満のメソ孔の全体積に占める前記イオノマーの占有率が50体積%以下である触媒層。 - 触媒層中における前記触媒担持カーボンは、前記イオノマーが付着した状態で、窒素吸着法により得られる細孔分布における細孔直径50nm以上のマクロ孔を0.03cm3/g触媒以上有する請求項1に記載の触媒層。
- 触媒層の単位面積あたりにおける前記触媒の含有量は、0.2mg/cm2以下である請求項1又は請求項2に記載の触媒層。
- 前記触媒は、白金の粒子及び白金合金の粒子からなる群より選択される少なくとも一種を含む請求項1~請求項3のいずれか一項に記載の触媒層。
- 前記触媒の個数平均粒子径は、1nm~20nmである請求項4に記載の触媒層。
- 前記触媒担持カーボン全体に対する前記触媒の含有率は、10質量%~70質量%である請求項1~請求項5のいずれか一項に記載の触媒層。
- 第1のガス拡散層と前記第1のガス拡散層における一方の面側に設けられた第1の触媒層とを有するアノードと、
第2のガス拡散層と前記第2のガス拡散層における一方の面側に設けられた第2の触媒層とを有するカソードと、
前記第1の触媒層と前記第2の触媒層との間に配置された高分子電解質膜と、
を備え、
前記第1の触媒層及び前記第2の触媒層の少なくとも一方が、請求項1~請求項6のいずれか一項に記載の触媒層である、固体高分子形燃料電池用膜電極接合体。 - 請求項7に記載の固体高分子形燃料電池用膜電極接合体を備えた固体高分子形燃料電池。
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US20220328847A1 (en) | 2022-10-13 |
KR20220113412A (ko) | 2022-08-12 |
CN114902453A (zh) | 2022-08-12 |
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