WO2016104714A1 - 触媒担体及びその製造方法 - Google Patents
触媒担体及びその製造方法 Download PDFInfo
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- WO2016104714A1 WO2016104714A1 PCT/JP2015/086255 JP2015086255W WO2016104714A1 WO 2016104714 A1 WO2016104714 A1 WO 2016104714A1 JP 2015086255 W JP2015086255 W JP 2015086255W WO 2016104714 A1 WO2016104714 A1 WO 2016104714A1
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- Prior art keywords
- carbon
- catalyst
- catalyst carrier
- particles
- carbon material
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Classifications
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a catalyst carrier, an electrode catalyst, an electrode including the catalyst layer, a membrane electrode assembly including the catalyst layer, and a fuel cell including the membrane electrode assembly.
- an electrode catalyst in which a catalyst metal including platinum is supported on a carbon support is mainly used.
- the carbon support used as a conventional catalyst support is easily oxidized at a high potential operation such as the start / stop operation of the fuel cell, the supported catalyst metal causes aggregation or desorption. It is a major factor in performance degradation.
- Patent Document 1 in order to improve the durability of a carbon support by high-potential operation, the degree of graphitization of the carbon support is increased by heat treatment so that the carbon support is less likely to be oxidized under fuel cell operation.
- a carbon support having a high degree of graphitization is used, although the corrosion resistance is improved, the specific surface area of the carbon support is reduced, so that the power generation performance is reduced.
- Patent Document 2 describes an electrode catalyst in which a carbon support carrying a catalytic metal (platinum) and an acidic oxide are mixed in order to improve durability while maintaining high activity of the catalyst.
- a carbon support carrying a catalytic metal (platinum) and an acidic oxide are mixed in order to improve durability while maintaining high activity of the catalyst.
- carbon supports are highly hydrophobic and acidic oxides are highly hydrophilic, it is very difficult to physically mix catalyst supports having these different physical properties. When coating the catalyst layer or the variation, it may cause performance degradation due to the occurrence of unevenness or cracks.
- Patent Document 3 discloses that a catalyst material containing hydrophilic particles such as zeolite or titanium dioxide is used for the anode in order to maintain battery performance to some extent even in a low humidified operation. However, since these catalyst materials do not have electrical conductivity, the internal resistance of the catalyst layer is expected to increase.
- Patent Document 4 discloses a carrier carbon material for fuel cells in which a moisturizing carbon material and carbon black are mixed. With this technology, water absorption and release of the carbon material by the activated carbon material can be expected to some extent, but in the fuel cell operation under low humidification conditions, the ionomer in the electrolyte membrane and the catalyst layer has water retention. Not enough and high battery output cannot be expected. Further, since the carbon material used in Patent Document 4 is a material in which micropores are introduced in order to provide moisture retention to the carbon material, it is very easily oxidized during high potential operation of the fuel cell, and has a durable property. Problems can also arise.
- Patent Document 5 describes an electrode catalyst obtained by firing zirconium and a carbon material precursor. However, a high battery output cannot be expected with a catalyst containing no precious metal such as Pt.
- An object of the present invention is to provide a catalyst carrier, an electrode catalyst, an electrode containing the catalyst, a membrane electrode assembly having the electrode, and the membrane electrode joint that give a catalyst exhibiting high durability with little degradation in performance even under low humidification conditions
- a fuel cell comprising a body is provided.
- the present invention includes the following inventions [1] to [19].
- [1] containing a carbon material having a chain structure in which carbon particles are continuous, and alumina carbon composite particles formed by including the alumina particles in the carbon material.
- a catalyst carrier having a BET specific surface area of 450 to 1100 m 2 / g.
- the catalyst carrier according to [1] or [2], wherein the alumina particles have an average particle diameter of 5 to 300 nm.
- the metal of the catalyst metal particles is at least one metal selected from the group consisting of platinum, palladium, ruthenium, gold, rhodium, iridium, osmium, iron, cobalt, nickel, chromium, zinc and tantalum, or at least The electrode catalyst according to [6], which is an alloy composed of two kinds of metals.
- An electrode having an electrode substrate and a catalyst layer formed on the electrode substrate and containing the electrode catalyst according to any one of [6] to [8].
- a fuel cell comprising the membrane electrode assembly according to [10].
- the carbon material is a mixture of the carbon material X BET specific surface area of 700 ⁇ 1400m 2 / g, a carbon material Y BET specific surface area of 100 ⁇ 500m 2 / g [12 ] or [ 13].
- the method for producing a catalyst carrier according to [17] wherein the carbon material Y has a primary particle diameter of 5 to 300 nm and a crystallite size of 2.0 to 5.0 nm.
- the present invention it is possible to obtain a catalyst carrier capable of obtaining a catalyst capable of maintaining a high output with little degradation in performance even when operated under low humidification conditions. Further, the fuel cell obtained using this catalyst carrier has high durability against load fluctuations and start / stop operations.
- the catalyst carrier of the present invention includes a carbon material having a chain structure in which carbon particles are linked (carbon particles forming a chain structure may be hereinafter referred to as “carbon particles A”), and the carbon material.
- the contained carbon particles include alumina carbon composite particles (hereinafter sometimes referred to as “carbon particles B”) including alumina particles, and have a BET specific surface area of 450 to 1100 m 2 / g.
- the BET specific surface area of the catalyst carrier is preferably 490 to 1100 m 2 / g, more preferably 700 to 1100 m 2 / g, and 900 to 1100 m 2 / g from the viewpoint of the catalyst performance described later. It is particularly preferred.
- the content of the alumina particles in the catalyst carrier is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and 30 to 70% by mass from the viewpoint of the catalyst performance described later. It is particularly preferred.
- the content of alumina particles in the alumina carbon composite particles is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 25 to 70% by mass.
- the average particle diameter of the alumina particles is preferably 5 to 300 nm, more preferably 5 to 200 nm, and particularly preferably 5 to 100 nm from the viewpoint of enhancing durability and water retention.
- the average particle diameter is an arithmetic average value obtained by measuring the diameters of 50 or more randomly selected alumina particles by observation with a transmission electron microscope.
- the carbon encapsulating the alumina particles may be highly amorphous carbon, carbon having a high graphitization degree, or a mixture of these carbons. From the viewpoint of further improving durability and water retention, graphitized carbon is preferable. Further, the carbon encapsulating the alumina particles may be the same crystalline or different from the carbon material described later.
- Carbon “encapsulates” alumina particles usually means that the alumina particles are completely covered with a carbon coating layer, and a part of the alumina particles may exist on the surface. .
- the alumina carbon composite particles are contained in the carbon material, and the alumina carbon composite particles are preferably incorporated into a chain structure in which the carbon particles are connected.
- any one carbon material selected from the group consisting of carbon black, graphitized carbon black, graphite, and porous carbon can be preferably used.
- a method for producing graphitized carbon black will be described later.
- the carbon material from the viewpoint of easily obtaining high catalyst performance, a mixture in which any two or more selected from the group consisting of carbon black, graphitized carbon black, graphite, and porous carbon is also preferably used. it can. More preferably, the carbon material is a mixture of carbon black and graphitized carbon black.
- Carbon black is composed of carbon fine particles having a chain structure composed of amorphous carbon, and is classified into furnace black, acetylene black, thermal black, and the like depending on the production method, and any of them can be used as a catalyst carrier. Carbon black has a sufficiently large specific surface area, and when it is contained in a catalyst carrier, a high initial voltage is easily obtained.
- Graphitized carbon black can be obtained by heat-treating commercially available carbon black in an inert or reducing gas atmosphere. Graphitized carbon black has a higher degree of graphitization than carbon black, and when it is contained in a catalyst carrier, durability is easily obtained.
- carbon material a mixture of two or more carbon materials is also preferable. This will be described in detail in the section “Method for producing catalyst carrier”.
- Graphitized carbon black has a microstructure in which a graphite layer overlaps carbon fine particles, and the number of layers in the layered structure is preferably 1 to 30, and more preferably 1 to 20. When the number of layers is in this range, the initial activity is high, and durability under start / stop operation is easily obtained.
- the number of layers is an arithmetic average value of the number of layers in a layered structure in 50 graphitized carbon blacks selected at random by observation with a transmission electron microscope. It can also be confirmed by the degree of graphitization that the graphitized carbon black has a microstructure in which the graphite layer overlaps the carbon fine particles.
- the primary particle diameter of the carbon material is preferably 5 to 300 nm, more preferably 5 to 100 nm, and particularly preferably 5 to 50 nm from the viewpoint of easily obtaining high catalyst performance.
- this primary particle diameter is an arithmetic average value of those measured values obtained by measuring the diameters of the carbon particles A contained in 50 carbon materials selected at random by observation with a transmission electron microscope. .
- the method for producing the catalyst carrier of the present invention is not particularly limited as long as the catalyst carrier can be obtained.
- alumina particles and polyvinyl alcohol are mixed and heat-treated at 500 to 1100 ° C. in a non-oxidizing gas atmosphere.
- a step of obtaining alumina carbon composite particles (hereinafter sometimes referred to as “carbon particles B”) in which carbon encloses alumina particles, and a carbon material having a chain structure in which carbon particles are connected (hereinafter referred to as “carbon particles B”). It may be referred to as “carbon material”) and the carbon particles B are preferably mixed.
- Alumina-carbon composite particle preparation step Mixing of the alumina particles and polyvinyl alcohol may be performed using a solid-phase kneading method.
- a solid phase kneading method a method of uniformly mixing is preferable, and examples thereof include a roll rolling mill, a ball mill, a medium stirring mill, an airflow grinder, a mortar, an automatic kneading mortar, a tank disintegrator, or a jet mill. More preferred is a method using a ball mill.
- Examples of the gas used in the non-oxidizing gas atmosphere include hydrogen gas, which is an inert gas and a reducing gas, and nitrogen gas, argon, and helium are preferable because they are relatively inexpensive and easily available. Further preferred. These gases may be used individually by 1 type, and 2 or more types may be mixed and used for them.
- the heat treatment is desirably performed at the above temperature for 1 to 10 hours, preferably 1 to 6 hours.
- BET specific surface area of the alumina particles from the viewpoint of dispersibility and atomization of catalyst metal to be complexed and supporting of the alumina particles and carbon, preferably from 50 ⁇ 300m 2 / g, 100 ⁇ 300m 2 / More preferably, it is g.
- the average particle diameter is as described above.
- a commercially available thing can be used as polyvinyl alcohol. The amount of polyvinyl alcohol used is appropriately selected according to the amount of alumina particles encapsulated.
- the mixing of the carbon material and the carbon particles B may be performed using a solid phase kneading method.
- a solid phase kneading method a method of uniformly mixing is preferable, and examples thereof include a roll rolling mill, a ball mill, a medium stirring mill, an airflow grinder, a mortar, an automatic kneading mortar, a tank disintegrator, or a jet mill. More preferred is a method using a ball mill.
- the mixing ratio of the carbon material and the carbon particles B may be mixed so that the content of the alumina particles in the final catalyst support is in the above range, and the appropriate ratio is set so that the desired BET specific surface area is obtained. Is selected.
- the DBP oil absorption amount of the carbon material is preferably 350 to 550 mL / 100 g, more preferably 400 to 550 mL / 100 g, more preferably 450 to 550 mL / 100 g from the viewpoint of electronic conductivity and mixing characteristics. Is particularly preferred.
- the BET specific surface area of the carbon material is preferably 700 to 1400 m 2 / g, more preferably 800 to 1400 m 2 / g, more preferably 1000 to 1400 m, from the viewpoint of supporting and dispersibility of the catalyst metal and atomization. Particularly preferred is 2 / g.
- the degree of graphitization of the carbon material is represented by the size Lc of the crystallite in the c-axis direction (hereinafter sometimes referred to as “crystallite size”).
- the carbon material in the present invention preferably has a crystallite size of 0.6 to 2.0 nm, more preferably 0.8 to 2.0 nm, and particularly preferably 0.8 to 1.6 nm. If the crystallite size is 0.6 nm or more, the graphitization degree of the carbon material is high, and it is easy to obtain durability under the load fluctuation and start / stop operation of the fuel cell. When the crystallite size is 2 nm or less, it is easy to obtain a large specific surface area and high catalyst performance is easily obtained.
- the carbon material a mixture of two or more carbon materials can be preferably used from the viewpoint of achieving both durability and initial performance.
- the BET specific surface area of the carbon material X is preferably 700 to 1400 m 2 / g, more preferably 1400m is 2 / g, particularly preferably from 900 ⁇ 1400m 2 / g.
- BET specific surface area of the carbon material Y is preferably 100 ⁇ 500m 2 / g, more preferably from 100 ⁇ 400m 2 / g, particularly preferably 100 ⁇ 350m 2 / g.
- the primary particle diameter of the carbon material Y having the BET specific surface area is preferably 5 to 300 nm, more preferably 5 to 100 nm, and more preferably 5 to 50 nm from the viewpoint of easily obtaining high catalyst performance. It is particularly preferred.
- this primary particle diameter is those arithmetic average values obtained by measuring the diameter of the carbon particle of 50 or more carbon materials Y selected at random by transmission electron microscope observation.
- the crystallite size of the carbon material Y having the BET specific surface area is preferably 2.0 to 5.0 nm, more preferably 2.0 to 4.5 nm, and 2.5 to 4.5 nm. It is particularly preferred that When the crystallite size is in this range, it is easy to obtain durability under start / stop operation.
- the mixing ratio of X and Y used as the carbon material is in the range of 3: 7 to 7: 3, preferably 4: 6 to 6: 4, so that the effect of Y of the carbon material becomes more remarkable. Can do.
- Increasing the ratio of X can improve the initial voltage characteristics, and increasing the ratio of Y is preferable because the voltage holding ratio can be increased.
- the mixing ratio of Y can be adjusted in accordance with the characteristics of the supported catalyst metal.
- a carbon material composed of fine carbon particles having a chain structure composed of amorphous carbon among commercially available carbon materials can be preferably used.
- the inert or reducing gas atmosphere the aforementioned atmosphere can be used.
- Examples of the carbon material Y having both the primary particle diameter and the crystallite size include graphitized carbon black.
- Such graphitized carbon black can be obtained by heat-treating carbon black in an inert or reducing gas atmosphere, has a higher degree of graphitization than carbon black, and is durable when contained in a catalyst carrier. Easy to obtain.
- the electrode catalyst of the present invention is one in which catalytic metal particles are supported on the catalyst carrier.
- the metal constituting the catalyst metal particles is selected from the group consisting of platinum, palladium, ruthenium, gold, rhodium, iridium, osmium, iron, cobalt, nickel, chromium, zinc and tantalum from the viewpoint of easily obtaining high catalyst performance. It is preferably an alloy composed of at least one kind of metal or two or more kinds of metals, more preferably platinum or a platinum alloy. When the alloy is a platinum alloy, the alloy component other than platinum is at least one metal selected from the group consisting of palladium, ruthenium, gold, rhodium, iridium, osmium, iron, cobalt, nickel, chromium, zinc and tantalum.
- one or more metals selected from the group consisting of palladium, ruthenium, iron and cobalt are preferable, one or more metals selected from the group consisting of palladium and cobalt are more preferable, and cobalt is particularly preferable.
- these as the catalytic metal component good catalytic activity can be easily obtained.
- the average particle diameter of the catalytic metal particles is preferably 2 to 10 nm, and more preferably 3 to 7 nm. An average particle size of this level is preferable because the catalytic activity is good, the stability is easily maintained in the fuel cell environment, and the durability is improved.
- the average particle diameter of the catalyst metal particles is defined in the same manner as the average particle diameter of the oxide particles described above.
- the ratio of the catalytic metal contained in the entire electrode catalyst is preferably 20 to 70% by mass, more preferably 30 to 50% by mass. If it is this range, it will become easy to suppress aggregation and coarsening of a catalyst metal, and it is easy to improve catalyst performance, and is preferable.
- the electrode catalyst can be processed into an ink by the method shown in Examples described later, a conventional method, or the like.
- a catalyst layer containing the electrode catalyst is formed on the electrode substrate surface, and the electrode of the present invention can be obtained. That is, the electrode of the present invention has an electrode substrate and a catalyst layer containing the electrode catalyst formed thereon.
- substrate has a gas diffusion layer on the surface.
- the electrode of the present invention can be used as a cathode and / or an anode.
- the electrode of the present invention is preferably used as a cathode of a fuel cell. In this case, it is possible to obtain a fuel cell with a small decrease in catalyst activity under low humidification conditions and high durability due to load fluctuations and start / stop operations.
- the electrode can also be used as an anode of a fuel cell using hydrogen as a fuel. In this case, it can be set as an electrode with a small fall of hydrogen oxidation activity in a low humidification environment.
- the electrode can be used as an anode of a fuel cell using methanol as a fuel.
- methanol easily wets the electrode surface, and high methanol oxidation activity can be obtained.
- Membrane electrode assembly In the membrane / electrode assembly of the present invention, a cathode and an anode are disposed via an electrolyte membrane, and at least one of the cathode and the anode is composed of the electrode of the present invention.
- a polymer material exhibiting proton conductivity is used for the electrolyte membrane.
- fluorinated or alkylene sulfonated fluorine-based polymers or polystyrenes represented by perfluorocarbon-based sulfonic acid resins and polyperfluorostyrene-based sulfonic acid resins are used. Is mentioned.
- Other examples include materials obtained by sulfonating polysulfones, polyether sulfones, polyether ether sulfones, polyether ether ketones, and hydrocarbon polymers.
- Micro-dispersion of proton conductive inorganic substances such as tungsten oxide hydrate, zirconium oxide hydrate, tin oxide hydrate, silicotungstic acid, silicomolybdic acid, tungstophosphoric acid, molybdophosphoric acid in heat-resistant resin
- the composite solid polymer electrolyte membrane can also be used.
- the other electrode is a conventionally known fuel cell electrode, for example, a platinum-based catalyst such as platinum-supported carbon instead of the composite catalyst.
- a fuel cell electrode can be used.
- the membrane / electrode assembly is obtained by forming the electrode catalyst layer on the electrolyte membrane and / or the gas diffusion layer, sandwiching both surfaces of the electrolyte membrane between the gas diffusion layers with the catalyst layer inside, and hot pressing under known conditions. be able to.
- the temperature during hot pressing is appropriately selected depending on the components in the electrolyte membrane and / or catalyst layer to be used, but is preferably 100 to 160 ° C, more preferably 120 to 160 ° C, and more preferably 120 to 140 More preferably, the temperature is C.
- the pressure during hot pressing is appropriately selected depending on the components in the electrolyte membrane and / or the catalyst layer and the type of the gas diffusion layer, but is preferably 1 to 10 MPa, more preferably 1 to 6 MPa. More preferably, it is ⁇ 5 MPa.
- the hot pressing time is appropriately selected depending on the temperature and pressure during hot pressing, but is preferably 1 to 20 minutes, more preferably 3 to 20 minutes, and further preferably 5 to 20 minutes. preferable. (Fuel cell)
- the fuel cell of the present invention includes the membrane electrode assembly. For this reason, a fuel cell with high output and high durability can be obtained.
- DBP oil absorption was measured by converting the DBP addition amount at 70% of the maximum torque as the DBP oil absorption per 100 g of the sample using an absorber meter (manufactured by Branbender).
- BET specific surface area measurement For BET specific surface area measurement, Max Soap (manufactured by Mountec Co., Ltd.) was used, and the specific surface area of the sample was calculated using nitrogen gas. The pretreatment time and pretreatment temperature for measurement were set to 200 ° C. for 30 minutes, respectively.
- H9500 acceleration voltage 300 kV
- Crystallite size Powder X-ray diffraction of the sample was performed using a rotor flex made by Rigaku Corporation. As the X-ray diffraction measurement conditions, analysis was performed in a measurement range of 10 to 90 ° using 50 kW of Cu—K ⁇ ray. At this time, the peak appearing at 20 ° ⁇ 2 ⁇ ⁇ 30 ° was calculated according to Scherrer's formula to obtain the crystallite size.
- Example 1 (Production of carbon particles B (1)) 5 g of alumina particles (prepared by the method described in International Publication WO01 / 47812, average primary particle diameter 15 nm, average secondary particle diameter 70 nm) and 5 g of polyvinyl alcohol powder (manufactured by Kanto Chemical Co., Inc.) Using a ball mill, the mixture was uniformly mixed to obtain a solid mixed powder. This powder is put into a tubular furnace, heated to 700 ° C. in a mixed gas atmosphere of hydrogen and nitrogen containing 4% by volume of hydrogen, heat-treated at 700 ° C. for 1 hour, and alumina carbon in which carbon particles enclose alumina particles. Composite particles (hereinafter also referred to as “carbon particles B (1)”) were obtained.
- the suspension was stirred for 3 hours while maintaining the temperature of the suspension at 80 ° C.
- 60 ml of an aqueous solution containing 0.583 g of sodium borohydride was dropped into the suspension over 30 minutes.
- the suspension was stirred for 1 hour while maintaining the liquid temperature at 80 ° C.
- the suspension was cooled to room temperature, and the black powder was separated by filtration and dried.
- Electrode catalyst (1) An electrode catalyst carrying this alloy as a catalyst metal was obtained.
- cathode ink Electrocatalyst 35 mg, proton conductive material (aqueous solution (5% Nafion aqueous solution, manufactured by Wako Pure Chemical Industries) containing 15.8 mg of Nafion (registered trademark)) 315 g, 2.0 mL of pure water and 2.0 mL of 2-propanol were weighed into a vial, and subjected to ultrasonic washing irradiation in ice water for 30 minutes to prepare a cathode ink (1).
- aqueous solution 5% Nafion aqueous solution, manufactured by Wako Pure Chemical Industries
- Nafion registered trademark
- a gas diffusion layer (carbon paper (TGP-H-060 manufactured by Toray Industries, Inc.)) was degreased by immersing it in acetone for 30 seconds, dried, and then 10% polytetrafluoroethylene (PTFE) aqueous solution For 30 seconds. The immersion material was dried at room temperature and then heated at 350 ° C. for 1 hour to obtain a gas diffusion layer (hereinafter also referred to as “GDL”) having PTFE dispersed in the carbon paper and having water repellency.
- GDL gas diffusion layer
- cathode (1) was applied to the surface of the GDL having a size of 5 cm ⁇ 5 cm by an automatic spray coating apparatus (manufactured by Sanei Tech Co., Ltd.) at 80 ° C., and the total amount of the electrode catalyst (1) was An electrode having a cathode catalyst layer of 0.20 mg / cm 2 per unit area on the GDL surface (hereinafter also referred to as “cathode (1)”) was produced.
- anode GDL having a size of 5 cm ⁇ 5 cm was obtained in the same manner as the production of the cathode described above, and the anode ink was applied to the surface of this GDL at 80 ° C. by an automatic spray coating device (manufactured by Saneitec). (1) was applied, and an electrode (hereinafter also referred to as “anode (1)”) having an anode catalyst layer having a total amount of platinum-supported carbon catalyst of 1.00 mg / cm 2 on a GDL surface was prepared.
- a Nafion (registered trademark) membrane (NR-212, manufactured by DuPont) was prepared as an electrolyte membrane, a cathode (1) as a cathode, and an anode (1) as an anode.
- a fuel cell membrane electrode assembly (hereinafter also referred to as “MEA”) in which the electrolyte membrane was disposed between the cathode (1) and the anode (1) was produced as follows. The electrolyte membrane is sandwiched between the cathode (1) and the anode (1), and the temperature is 140 ° C. using a hot press machine so that the cathode catalyst layer (1) and the anode catalyst layer (1) are in close contact with the electrolyte membrane. These were thermocompression bonded at a pressure of 3 MPa over 7 minutes to prepare MEA (1).
- single cell MEA (1) Manufacture of single cell MEA (1), two sealing materials (gaskets), two separators with gas flow path, The current collector plate and two rubber heaters are sandwiched in order and the surroundings are fixed with bolts. The bolts are tightened to a predetermined surface pressure (4 N), and a single cell of a polymer electrolyte fuel cell (Hereinafter also referred to as “single cell (1)”) (cell area: 25 cm 2 ).
- single cell (1) a polymer electrolyte fuel cell (Hereinafter also referred to as “single cell (1)”) (cell area: 25 cm 2 ).
- Fuel cell evaluation under normal humidification conditions is as follows: single cell (1) at 80 ° C., anode humidifier at 80 ° C., cathode humidifier Was adjusted to 80 ° C. Thereafter, hydrogen was supplied as fuel to the anode side and air was supplied to the cathode side, and the current-voltage (IV) characteristics of the single cell (1) were evaluated.
- the fuel cell evaluation under low humidification conditions was carried out by adjusting the temperature of the single cell (1) to 65 ° C., the anode humidifier to 65 ° C., and the cathode to 65 ° C. with no humidification. ) The characteristics were evaluated.
- the voltage holding ratio is defined as the ratio (%) of voltage values obtained from current-voltage measurement at 0.2 A / cm 2 before and after potential cycle application.
- Voltage holding ratio (voltage value after application of potential cycle) / (voltage value before application of potential cycle) ⁇ 100
- the voltage value at a certain current density is an index of the power generation performance of the fuel cell. That is, the higher the initial voltage, the higher the initial power generation performance of the fuel cell, and thus the higher the catalytic activity of the oxygen reduction catalyst.
- the higher the voltage holding ratio the less the power generation performance of the fuel cell, and consequently the catalytic activity of the oxygen reduction catalyst, that is, the higher the durability.
- Table 1 shows the initial voltage and voltage holding ratio under humidification conditions and low humidification conditions at 0.2 A / cm 2 .
- Example 2 Similarly to Example 1, carbon particles B (1) were obtained, and the carbon material (1) and the carbon particles B (1) were mixed to obtain a catalyst carrier (2). However, the proportion of alumina particles was 60% by mass with respect to the total mass of the catalyst carrier (2).
- Example 3 Similarly to Example 1, carbon particles B (1) were obtained, and the carbon material (1) and the carbon particles B (1) were mixed to obtain a catalyst carrier (3). However, the proportion of alumina particles was 25% by mass with respect to the total mass of the catalyst carrier (3).
- Example 4 Instead of the carbon material (1), a commercially available carbon material (BET specific surface area 563 m 2 / g, DBP oil absorption 295 mL / 100 g, crystallite size 3.2 nm, carbon nano particles having a chain structure, Using the carbon material (2), the same operation as in Example 1 was performed to obtain a catalyst carrier (4). However, the proportion of alumina particles was 40% by mass with respect to the total mass of the catalyst carrier (4).
- BET specific surface area 563 m 2 / g, DBP oil absorption 295 mL / 100 g, crystallite size 3.2 nm, carbon nano particles having a chain structure Using the carbon material (2), the same operation as in Example 1 was performed to obtain a catalyst carrier (4). However, the proportion of alumina particles was 40% by mass with respect to the total mass of the catalyst carrier (4).
- Example 5 In Example 1, instead of the carbon material (1), the carbon material (1) and the carbon material (3) (graphitized carbon black obtained by firing a commercially available carbon black at 2200 ° C.
- Example 7 (Production of carbon particles B (2)) In Example 1, carbon particles B (2) were obtained using nitrogen gas containing 100% by volume of nitrogen instead of a mixed gas of hydrogen and nitrogen containing 4% by volume of hydrogen.
- Example 2 Using the carbon particle B (2) instead of the carbon particle B (1), the same operation as in Example 1 was performed to obtain a catalyst carrier (7). However, the proportion of alumina particles was 40% by mass with respect to the total mass of the catalyst carrier (7).
- Example 1 platinum and cobalt are supported on the catalyst carrier (7), and heat treatment is performed to alloy platinum and cobalt to obtain an electrode catalyst (7). went.
- the results are shown in Table 1.
- Comparative Example 1 A catalyst carrier (8) was obtained in the same manner as in Example 1, except that the alumina particles used as the raw material for the carbon particles B (1) in Example 1 were used instead of the carbon particles B (1). Further, the proportion of alumina particles to the total mass of the catalyst carrier (8) was 50 mass%.
- Example 2 Thereafter, as in Example 1, platinum and cobalt are supported on the catalyst carrier (8), and heat treatment is performed to alloy platinum and cobalt to obtain an electrode catalyst (8). went. The results are shown in Table 1. Comparative Example 2: An electrode catalyst (9) was obtained in the same manner as in Example 1, except that the carbon material (1) was used as the catalyst carrier (9) instead of the catalyst carrier (1).
- Comparative Example 3 An electrode catalyst (10) was obtained in the same manner as in Example 1, except that carbon particles B (1) were used as the catalyst carrier (10) instead of the catalyst carrier (1).
- Example 1 An electrode catalyst (11) was obtained in the same manner as in Example 1, except that the carbon material (3) was used as the catalyst support (11) instead of the catalyst support (1).
- Example 1 a catalyst carrier (12) was obtained in the same manner as in Example 1 except that the carbon material (3) was used instead of the carbon material (1). However, the proportion of alumina particles was 42% by mass with respect to the total mass of the catalyst carrier (12).
- Example 1 Preparation of carbon particle B (3)
- alumina particles instead of alumina particles, commercially available iron (III) particles (average particle size: 10 to 15 nm) were used, and the iron (III) particles were coated with carbon in the same manner as in Example. Particles (hereinafter also referred to as “carbon particles B (3)”).
- Example 2 Using the carbon particle B (3) instead of the carbon particle B (1), the same operation as in Example 1 was performed to obtain a catalyst carrier (13). However, the proportion of iron oxide particles was 42% by mass with respect to the total mass of the catalyst carrier (13).
- Example 1 platinum and cobalt were supported on the catalyst carrier (13), and heat treatment was performed to alloy platinum and cobalt to obtain an electrode catalyst (13). went. The results are shown in Table 1.
- Examples 1 to 7 showed high activity under normal and low humidification conditions. This is presumably because a carbon material having a BET specific surface area, a DBP oil absorption amount and a crystallite size that are appropriate for the present invention was selected and used.
- Example 5 showed particularly high initial voltage and durability. This is considered to be because two types of carbon materials having different BET specific surface areas, primary particle diameters, and crystallite sizes were appropriately selected and mixed. ⁇ Industrial applicability> Since the electrode catalyst of the present invention has a small performance drop under low humidification conditions and high durability, a fuel cell excellent in power generation efficiency and reliability can be obtained. The fuel cell can be used as a power source for electric vehicles and household cogeneration.
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Abstract
Description
[1]炭素粒子が連なった鎖状構造を有する炭素材料と
該炭素材料中に含まれる、炭素粒子がアルミナ粒子を内包してなるアルミナ炭素複合粒子とを含有する、
BET比表面積が450~1100m2/gである触媒担体。
[2]前記アルミナ粒子の含有量が10~90質量%である[1]に記載の触媒担体。
[3]前記アルミナ粒子は、平均粒子径が5~300nmである[1]または[2]に記載の触媒担体。
[5]前記炭素材料が、カーボンブラック、グラファイト化カーボンブラック、グラファイトおよび多孔性カーボンからなる群から選ばれるいずれか2種以上の混合物である[1]~[4]のいずれかに記載の触媒担体。
[6][1]~[5]のいずれかに記載の触媒担体に触媒金属粒子が担持されてなる電極触媒。
[8]BET比表面積が200~800m2/gである[6]または[7]に記載の電極触媒。
[9]電極基体と、該電極基体上に形成された、[6]~[8]のいずれかに記載の前記電極触媒を含む触媒層とを有する電極。
前記カソード及び前記アノードの少なくともいずれか一方が[9]に記載の電極である膜電極接合体。
[11][10]に記載の膜電極接合体を備える燃料電池。
[12]アルミナ粒子とポリビニルアルコールとを混合し、非酸化性ガスの雰囲気下500~1100℃で熱処理を行い、炭素がアルミナ粒子を内包してなるアルミナ炭素複合 粒子を得る工程、及び、
炭素粒子が連なった鎖状構造を有する炭素材料と前記アルミナ炭素複合粒子とを混合する工程を有する触媒担体の製造方法。
[14]前記炭素材料のジブチルフタレート吸油量が、350~550mL/100gである[12]または[13]に記載の触媒担体の製造方法。
[15]前記炭素材料のBET比表面積が、700~1400m2/gである[12]~[14]のいずれかに記載の触媒担体の製造方法。
[17] 前記炭素材料が、BET比表面積が700~1400m2/gである炭素材料Xと、BET比表面積が100~500m2/gである炭素材料Yとの混合物である[12]または[13]に記載の触媒担体の製造方法。
[18]前記炭素材料Yは、一次粒子径が5~300nmであり、かつ結晶子サイズが2.0~5.0nmである[17]に記載の触媒担体の製造方法。
[19]前記混合が、ボールミルで行われる[12]~[18]のいずれかに記載の触媒担体の製造方法。
本発明の触媒担体は、炭素粒子が連なった鎖状構造(鎖状構造を形成する炭素粒子を、以下「炭素粒子A」と言うことがある。)を有する炭素材料と、該炭素材料中に含まれる炭素粒子がアルミナ粒子を内包してなるアルミナ炭素複合粒子(以下「炭素粒子B」と言うことがある。)とを含み、BET比表面積が450~1100m2/gである。
本発明の触媒担体の製造方法は、前記触媒担体が得られればよく、特に限定されないが、例えば、アルミナ粒子とポリビニルアルコールとを混合し、非酸化性ガス雰囲気下500~1100℃で熱処理を行うことにより、炭素がアルミナ粒子を内包してなるアルミナ炭素複合粒子(以下「炭素粒子B」と言うことがある。)を得る工程、及び炭素粒子が連なった鎖状構造を有する炭素材料(以下「炭素材料」と言うことがある。)と前記炭素粒子Bとを混合する工程を有することが好ましい。
アルミナ粒子とポリビニルアルコールとの混合は、固相混練法を用いて行う方法が挙げられる。固相混練法としては、均一に混合される方法が好ましく、例えば、ロール転動ミル、ボールミル、媒体撹拌ミル、気流粉砕機、乳鉢、自動混練乳鉢、槽解機またはジェトミルを用いる方法が挙げられ、より好ましくはボールミルを用いる方法が挙げられる。
通常、疎水性の導電性カーボン粒子と、アルミナのような親水性粒子とを均一に混合することは困難であるが、本発明で用いるアルミナ粒子は炭素に内包されているので、両者は均一に混合されやすい。このため、混合時間は、通常10分~10時間程度で十分である。また、両者は均一に混合されるため、後述する電極内での湿度の維持及び電子導電性の向上や、負荷変動及び起動停止運転による触媒の劣化が少なく、低加湿条件下でも触媒性能の低下が小さいことが期待される。
(電極触媒)
本発明の電極触媒は、前記触媒担体に触媒金属粒子を担持させたものである。
(電極)
前記電極触媒を、後述する実施例に示した方法や常法等によりインクに加工することができる。得られたインクを電極基体に塗布などすることにより、電極基体表面に前記電極触媒を含む触媒層を形成し、本発明の電極を得ることができる。すなわち、本発明の電極は、電極基体と、その上に形成された前記電極触媒を含む触媒層を有する。なお、本発明の電極を燃料電池の電極として用いる場合は、電極基体は表面にガス拡散層を有することが好ましい。また、本発明の電極は、カソード及び/又はアノードとして用いることができる。
(膜電極接合体)
本発明の膜電極接合体は、電解質膜を介してカソードとアノードとが配置され、前記カソード及び前記アノードの少なくともいずれかが前記本発明の電極で構成される。
(燃料電池)
本発明の燃料電池は、前記膜電極接合体を備える。このため、高出力で耐久性の高い燃料電池を得ることができる。
試料約40mgをビーカーに秤量し、王水、次いで硫酸を加えて加熱分解した。この加熱分解物を超純水で定容後、適宜希釈し、ICP発光分析装置(SII社製VISTA-PRO)を用いて金属元素を定量した。
DBP吸油量は、アブソープトメーター(Branbender社製)を用いて、最大トルクの70%時のDBP添加量を、試料100g当たりのDBP吸油量として換算して測定を行った。
BET比表面積測定は、マックソープ(株式会社マウンテック製)を使用し、窒素ガスを用いて、試料の比表面積を算出した。測定の前処理時間、前処理温度はぞれぞれ30分、200℃に設定した。
透過型電子顕微鏡(TEM)観察は、日立製作所製H9500(加速電圧300kV)を用いて行った。観察試料は、試料粉末をエタノール中に超音波分散させて得られた分散液を、TEM観察用グリッド上に滴下することで作製した。
理学電機株式会社製ロータフレックスを用いて、試料の粉末X線回折を行った。X線回折測定条件としては、Cu-Kα線の50kWを用いて10~90°の測定範囲で分析を行った。このとき、20°<2θ<30°に現れるピークをシェラーの式により算出し、結晶子サイズを求めた。
実施例1:
(炭素粒子B(1)の作製)
アルミナ粒子(国際公開WO01/47812号に記載の方法で作成し、平均一次粒子径15nm、平均二次粒子径が70nmであった。)5gとポリビニルアルコール粉末(関東化学株式会社製)5gとをボールミルを用いて均一に混合し、固体混合粉末を得た。この粉末を管状炉に入れ、水素を4体積%含む水素と窒素の混合ガス雰囲気下で700℃まで加熱し、700℃で1時間熱処理を行い、炭素粒子がアルミナ粒子を内包してなるアルミナ炭素複合粒子(以下、「炭素粒子B(1)」とも記す。)を得た。
市販の炭素材料(BET比表面積1350m2/g、DBP吸油量490mL/100g、結晶子サイズ1.5nm、炭素粒子(以下「炭素粒子A(1)」とも記す。)が連なって鎖状構造を有する炭素材料。)(以下、「炭素材料(1)」とも記す。)と、炭素粒子B(1)とを、ボールミルを用いて混合し、触媒担体(1)を得た。なお、触媒担体(1)の総質量に対して、前記アルミナ粒子の占める割合を40質量%にした。
純水1Lに、触媒担体(1)0.20gを添加し、超音波洗浄機で30分以上振とうさせた。得られた懸濁液を、液温80℃に維持し、30分以上攪拌した。ここに、塩化白金酸六水和物0.517g(白金として0.195g)と、酢酸コバルト(II)四水和物0.083g(コバルトとして0.020g)とを含む水溶液40mLを、1時間かけて滴下した。この際、1.0mol/L水酸化ナトリウム水溶液を適宜滴下することで、懸濁液のpHを約7.0に保持した。この後、懸濁液の温度を80℃に維持したまま、3時間攪拌した。次に、0.583gの水素化ホウ素ナトリウムを含む水溶液60mlを、上記懸濁液に30分かけて滴下した。その後、懸濁液の液温を、80℃に維持したまま、1時間攪拌した。反応終了後、上記懸濁液を室温まで冷却し、ろ過により黒色粉末を濾別し、乾燥した。
前記黒色粉末を石英管状炉に入れ、水素ガスを4体積%含む水素ガスと窒素ガスの混合ガス雰囲気下で、昇温温度10℃/minで700℃まで加熱し、700℃で30分間熱処理することにより、白金とコバルトとを合金化させてPt-Co合金とし、この合金を触媒金属として担持した電極触媒(以下「電極触媒(1)」とも記す。)を得た。
(1)カソード用インクの調製
電極触媒(1)35mg、プロトン伝導性材料(ナフィオン(NAFION)(登録商標))15.8mgを含有する水溶液(5%ナフィオン水溶液、和光純薬製))0.315g、純水2.0mL、2-プロパノール2.0mLをバイアルに秤量し、氷水中で30分間超音波洗照射することにより、カソード用インク(1)を調製した。
ガス拡散層(カーボンペーパー(東レ製TGP-H-060))を、アセトンに30秒間浸漬して脱脂した後、乾燥させ、次いで10%のポリテトラフルオロエチレン(PTFE)水溶液に30秒間浸漬した。浸漬物を、室温乾燥後、350℃で1時間加熱することにより、カーボンペーパー内部にPTFEが分散し撥水性を有するガス拡散層(以下「GDL」とも記す。)を得た。次に、5cm×5cmの大きさとした前記GDLの表面に、自動スプレー塗布装置(サンエイテック社製)により、80℃で、カソード用インク(1)を塗布し、電極触媒(1)の総量が単位面積あたり0.20mg/cm2であるカソード触媒層をGDL表面に有する電極(以下「カソード(1)」とも記す。)を作製した。
純水50mlに、白金担持カーボン触媒(田中貴金属工業製TEC10E70TPM)0.6gと、プロトン伝導性材料0.25gを含有する水溶液(5%ナフィオン水溶液、和光純薬製))5gを添加し、超音波分散機で1時間混合することにより、アノード用インク(1)を調製した。
前述のカソードの作製と同様に5cm×5cmの大きさとしたGDLを得、このGDL表面に、自動スプレー塗布装置(サンエイテック社製)により、80℃で、上記アノード用インク(1)を塗布し、白金担持カーボン触媒の総量が単位面積あたり1.00mg/cm2であるアノード触媒層をGDL表面に有する電極(以下「アノード(1)」とも記す。)を作製した。
電解質膜としてナフィオン(登録商標)膜(NR-212、DuPont社製)を、カソードとしてカソード(1)を、アノードとしてアノード(1)をそれぞれ準備した。カソード(1)とアノード(1)との間に前記電解質膜を配置した燃料電池用膜電極接合体(以下「MEA」とも記す。)を次のように作製した。前記電解質膜をカソード(1)およびアノード(1)で挟み、カソード触媒層(1)およびアノード触媒層(1)が前記電解質膜に密着するように、ホットプレス機を用いて、温度140℃、圧力3MPaで7分間かけてこれらを熱圧着し、MEA(1)を作製した。
MEA(1)を、2つのシール材(ガスケット)、2つのガス流路付きセパレーター、
2つの集電板および2つのラバーヒータで順次挟んで周囲をボルトで固定し、これらを所
定の面圧(4N)になるように前記ボルトを締め付けて、固体高分子形燃料電池の単セル
(以下「単セル(1)」とも記す。)を作製した(セル面積:25cm2)。
通常の加湿条件(以下、単に「加湿条件」とも記す)下での燃料電池評価は、単セル(1)を80℃、アノード加湿器を80℃、カソード加湿器を80℃に温度調節した。この後、アノード側に燃料として水素を、カソード側に空気をそれぞれ供給し、単セル(1)の電流―電圧(I-V)特性を評価した。また、低加湿条件下での燃料電池評価は、上記単セル(1)を65℃、アノード加湿器を65℃、カソードは無加湿の65℃に温度調整して、電流―電圧(I-V)特性を評価した。
電位サイクル耐久性試験は、以下の条件で行った。
ここで、燃料電池のI-V特性において、ある一定の電流密度における電圧値は、当該燃料電池の発電性能の指標となる。すなわち、前記初期電圧が高いほど、燃料電池の初期発電性能が高いことを意味し、ひいては酸素還元触媒の触媒活性が高いことを示す。また、前記電圧保持率が高いほど、燃料電池の発電性能、ひいては酸素還元触媒の触媒活性が劣化しにくく、すなわち耐久性が高いことを示す。0.2A/cm2における加湿条件及び低加湿条件下での初期電圧および電圧保持率を表1に示す。
実施例2:
実施例1と同様に、炭素粒子B(1)を得、炭素材料(1)と炭素粒子B(1)とを混合して触媒担体(2)を得た。ただし、触媒担体(2)の総質量に対して、アルミナ粒子の占める割合を60質量%にした。
実施例3:
実施例1と同様に、炭素粒子B(1)を得、炭素材料(1)と炭素粒子B(1)とを混合して触媒担体(3)を得た。ただし、触媒担体(3)の総質量に対して、アルミナ粒子の占める割合を25質量%にした。
実施例4:
炭素材料(1)の代わりに、市販の炭素材料(BET比表面積563m2/g、DBP吸油量295mL/100g、結晶子サイズ3.2nm、炭素ナノ粒子が鎖状構造を有する炭素材料、以下、炭素材料(2)とする)を用い、実施例1と同様に操作をして触媒担体(4)を得た。ただし、触媒担体(4)の総質量に対して、アルミナ粒子の占める割合を40質量%にした。
実施例5:
実施例1において、炭素材料(1)の代わりに、炭素材料(1)と炭素材料(3)(市販のカーボンブラックをN2雰囲気下で2200℃4時間焼成して得たグラファイト化カーボンブラック、BET比表面積170m2/g、一次粒子径40nm、結晶子サイズ3.5nm、炭素ナノ粒子が鎖状構造を有する炭素材料)との混合物(質量比は、炭素材料(1):炭素材料(3)=5:5、BET比表面積760m2/g)(以下、「炭素材料(4)」とも記す。)を用い、実施例1と同様に操作をして触媒担体(5)を得た。ただし、触媒担体(5)の総質量に対して、アルミナ粒子の占める割合を25質量%にした。
実施例6:
実施例1において、炭素材料(1)の代わりに、市販の炭素材料(BET比表面積1350m2/g)と炭素材料(3)の混合物(質量比は、市販の炭素材料:炭素材料(3)=2:1、BET比表面積955m2/g)(以下、「炭素材料(5)」とも記す。)を用い、実施例1と同様に操作をして触媒担体(6)を得た。ただし、触媒担体(6)の総質量に対して、アルミナ粒子の占める割合を60質量%にした。
実施例7:
(炭素粒子B(2)の作製)
実施例1において、水素を4体積%含む水素と窒素との混合ガスの代わりに、窒素が100体積%である窒素ガスを用いて炭素粒子B(2)を得た。
比較例1:
炭素粒子B(1)の代わりに、実施例1において炭素粒子B(1)の原料に用いたアルミナ粒子を用いて、実施例1と同様にして触媒担体(8)を得た。また、触媒担体(8)の総質量に対してアルミナ粒子の占める割合を50質量%にした。
比較例2:
触媒担体(1)の代わりに炭素材料(1)を触媒担体(9)として用いたこと以外は実施例1と同様の操作をして電極触媒(9)を得た。
比較例3:
触媒担体(1)の代わりに炭素粒子B(1)を触媒担体(10)として用いたこと以外は実施例1と同様の操作をして電極触媒(10)を得た。
比較例4:
実施例1において、触媒担体(1)の代わりに炭素材料(3)を触媒担体(11)として用いたこと以外は実施例1と同様の操作をして電極触媒(11)を得た。
比較例5:
実施例1において、炭素材料(1)の代わりに、炭素材料(3)を用いたこと以外は実施例1と同様に操作をして触媒担体(12)を得た。ただし、触媒担体(12)の総質量に対して、アルミナ粒子の占める割合を42質量%にした。
比較例6:
(炭素粒子B(3)の作製)
実施例1において、アルミナ粒子の代わりに市販の酸化鉄(III)粒子(平均粒径10~15nm)を用い、実施例と同様の操作をして、酸化鉄(III)粒子を炭素で被覆してなる粒子(以下、「炭素粒子B(3)」とも記す。)を得た。
<産業上の利用可能性>
本発明の電極触媒は、低加湿条件下で性能低下が小さく、高い耐久性を示すため、発電効率及び信頼性が優れた燃料電池が得られる。該燃料電池は、電気自動車用電源、家庭用コージェネレーションなどの電源として利用できる。
Claims (19)
- 炭素粒子が連なった鎖状構造を有する炭素材料と
該炭素材料中に含まれる、炭素粒子がアルミナ粒子を内包してなるアルミナ炭素複合粒子とを含有する、
BET比表面積が450~1100m2/gである触媒担体。 - 前記アルミナ粒子の含有量が10~90質量%である請求項1に記載の触媒担体。
- 前記アルミナ粒子は、平均粒子径が5~300nmである請求項1または2に記載の触媒担体。
- 前記炭素材料が、カーボンブラック、グラファイト化カーボンブラック、グラファイトおよび多孔性カーボンからなる群から選ばれるいずれか1種である請求項1~3のいずれかに記載の触媒担体。
- 前記炭素材料が、カーボンブラック、グラファイト化カーボンブラック、グラファイトおよび多孔性カーボンからなる群から選ばれるいずれか2種以上の混合物である請求項1~4のいずれかに記載の触媒担体。
- 請求項1~5のいずれかに記載の触媒担体に触媒金属粒子が担持されてなる電極触媒。
- 前記触媒金属粒子の金属が、白金、パラジウム、ルテニウム、金、ロジウム、イリジウム、オスミウム、鉄、コバルト、ニッケル、クロム、亜鉛及びタンタルからなる群から選ばれる少なくとも1種の金属、または少なくとも2種の金属からなる合金である請求項6に記載の電極触媒。
- BET比表面積が200~800m2/gである請求項6または7に記載の電極触媒。
- 電極基体と、該電極基体上に形成された、請求項6~8のいずれかに記載の前記電極触媒を含む触媒層とを有する電極。
- 電解質膜を介してカソードとアノードとが配置されてなる膜電極接合体であって、
前記カソード及び前記アノードの少なくともいずれか一方が請求項9に記載の電極である膜電極接合体。 - 請求項10に記載の膜電極接合体を備える燃料電池。
- アルミナ粒子とポリビニルアルコールとを混合し、非酸化性ガスの雰囲気下500~1100℃で熱処理を行い、炭素がアルミナ粒子を内包してなるアルミナ炭素複合粒子を得る工程、及び、
炭素粒子が連なった鎖状構造を有する炭素材料と前記アルミナ炭素複合粒子とを混合する工程を有する触媒担体の製造方法。 - 前記アルミナ粒子のBET比表面積が、50~300m2/gである請求項12に記載の触媒担体の製造方法。
- 前記炭素材料のジブチルフタレート吸油量が、350~550mL/100gである請求項12または13に記載の触媒担体の製造方法。
- 前記炭素材料のBET比表面積が、700~1400m2/gである請求項12~14のいずれかに記載の触媒担体の製造方法。
- 前記炭素材料の結晶子サイズが、0.6~2.0nmである請求項12~15のいずれかに記載の触媒担体の製造方法。
- 前記炭素材料が、BET比表面積が700~1400m2/gである炭素材料Xと、BET比表面積が100~500m2/gである炭素材料Yとの混合物である請求項12または13に記載の触媒担体の製造方法。
- 前記炭素材料Yは、一次粒子径が5~300nmであり、かつ結晶子サイズが2.0~5.0nmである請求項17に記載の触媒担体の製造方法。
- 前記混合が、ボールミルで行われる請求項12~18のいずれかに記載の触媒担体の製造方法。
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JP2016566518A JP6165359B2 (ja) | 2014-12-25 | 2015-12-25 | 触媒担体及びその製造方法 |
CN201580069903.8A CN107107032B (zh) | 2014-12-25 | 2015-12-25 | 催化剂载体及其制造方法 |
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US20220339128A1 (en) * | 2018-08-30 | 2022-10-27 | Mayo Foundation For Medical Education And Research | Methods and materials for treating cytokine release syndrome |
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