CN100377400C - Catalyst for fuel cell, method for preparation thereof and fuel cell - Google Patents

Catalyst for fuel cell, method for preparation thereof and fuel cell Download PDF

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CN100377400C
CN100377400C CNB038220830A CN03822083A CN100377400C CN 100377400 C CN100377400 C CN 100377400C CN B038220830 A CNB038220830 A CN B038220830A CN 03822083 A CN03822083 A CN 03822083A CN 100377400 C CN100377400 C CN 100377400C
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catalyst
fuel cell
compound
conductive carrier
catalyst layer
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CN1682395A (en
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武井文雄
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Fujitsu Ltd
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Fujitsu Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

A novel catalyst for a fuel cell, which comprises an electroconductive carrier and a Pt group element being attached on the surface of the carrier in such a manner that the surface is covered with the Pt group element; and a method for preparing the catalyst which comprises providing a mixture of a Pt group element compound an electroconductive carrier in the state of a gel or a high viscous material, reducing the Pt group element compound, and firing the resulting product, to form a catalyst layer comprising the Pt group element. A catalyst comprising an electroconductive carrier and a Pt group element being attached on the surface of the carrier has been used conventionally. The reaction rate on the surface of the catalyst has a direct effect on the electric current and thus on the efficiency of power generation, and accordingly, a catalyst capable of achieving a high reaction rate, or a catalyst having a great specific surface area has been required. However, conventional catalyst preparation methods have problems such as one that they have provided a catalyst having particles of a Pt group element attached on an electroconductive carrier only in a dispersal state but no catalyst having particles of the Pt group element attached on the carrier in such a manner that whole the surface of the carrier is covered with such particles, and thus they have failed to provide a catalyst having a great specific surface area.

Description

Catalyst for fuel cell, its manufacture method and fuel cell
Technical field
The present invention relates to catalyst for fuel cell, its manufacture method and fuel cell, particularly adhered to the catalyst of Pt etc. on the conductive carrier surface.
Aerobic-hydrogen battery in the representative example of fuel cell.Owing to utilize the back reaction of water electrolysis, so in case supply with from the outside oxygen as anode (negative pole) active material and hydrogen as negative electrode (positive pole) active material, just can take out electric energy.In cathode active material, also have methyl alcohol, ethanol, methane etc. in addition.
Background technology
The past fuel cell has been developed spaceship, Compact Power Plant, automobile etc. and has been had jumbo fuel cell.But,, the demand of fuel cell is improved constantly in recent years as carry-on information processor batteries such as portable terminal, pocket telephone, notebook PC.
In the fuel cell, there is the methyl alcohol of use to make fuel and directly obtains the direct methanol fuel cell of H+ and make methyl alcohol once decompose the indirect methanol fuel cell that obtains H+ from hydrogen by methyl alcohol.The indirect-type product need at high temperature make its reaction for making Methanol Decomposition, thus be unsuitable in equipment such as portable terminal, adopting, and directly the methanol type product have the advantage that can at room temperature react.
In direct methanol fuel cell, the reaction below producing on the catalyst surface of each electrode of anode and negative electrode:
Anodal (fuel electrodes): CH 3OH+H 2O → CO 2+ 6H ++ 6e -
Negative pole (air pole): 3/2O 2+ 6H ++ 6e -→ 3H 2O
Therefore, can utilize overall reaction
Overall reaction: CH 3OH+3/2O 2→ 2H 2O+CO 2
That is, the electronics that this reaction can be obtained, for example 6 moles of electronics are as electric energy.
Studied in the past and improved the various catalyst that above-mentioned reaction speed is used.Wherein used carrier band on carbon granules and the carbon base plate based on the catalyst of the various metals of platinum.Specifically, be to have on the carbon granules of conductivity, carrier band Pt particulate or Pt alloy particles such as Pt and Ru etc. have the catalyst of the metal particle of electrode catalyst activity.The reaction speed of catalyst surface, directly relevant with the magnitude of current, relate to generating efficiency, so need the fast catalyst of a kind of reaction speed, the promptly suitable big catalyst of surface area (specific area) with unit mass.
Yet existing catalyst manufacture method for example is that carbon granules is dispersed in the aqueous solution that contains the Pt compound, drips alkaline aqueous solution then platinum compounds is reduced, and makes the method for Pt particulate carrier band on carbon granules of separating out.
But, though can make Pt particulate attached on the carbon granules in this method with catalytic action, because its adhesion amount is few, so have the catalytic action deficiency, the problem that the reaction speed in the fuel cell is unhappy.
And in order to improve catalytic action, hope covers all surfaces of carbon granules under the situation that keeps the Pt particle size.But, in case for being increased, the Pt particulate loading of separating out prolongs the recovery time, will Pt combination between Pt particulate adjacent on the surface of carbon granules because of newly separating out, and particle diameter is increased, the problem that catalytic action reduces appears surface area is reduced on the contrary.
Disclosure of an invention
Useful catalyst for fuel cell, its manufacture method and fuel cell is total problem so the present invention is to provide the novelty that has solved above-mentioned problem.
Concrete problem of the present invention is to provide a kind of active reaction speed high, fuel fast catalyst for fuel cell, its manufacture method and the fuel cell that uses this fuel-cell catalyst.
If by a viewpoint of the present invention, a kind of like this catalyst for fuel cell can be provided, wherein have conductive carrier and formedly this conductive carrier is covered and be the catalyst layer of alloy composition by Pt, Ru or Pt.
According to the present invention, formation is the alloy catalyst layer with stratiform formation with Pt, Ru the conductive carrier surface coverage, that have catalysis or Pt.Therefore, compare, can increase and the unit conductive carrier quality surface area suitable with catalyst quality with the formation situation of existing catalyst particles.In addition, owing to form layered catalyst, so compare with the situation of catalyst particles, the reactive material intermediate that adsorbs on catalyst surface can move to catalyst layer surface more easily, and it is higher that activity becomes.Its result can improve reaction speed.
On the surface of described catalyst layer, can also have by dispersed Pt, Ru or Pt is the metal particle of alloy composition.Can further increase and the quality of conductive carrier and the suitable surface area of quality of catalyst.
And described conductive carrier also can be the conductivity carbon granules.Above-mentioned Pt be alloy also can be with Pt as main component, contain platinum family element except that Pt.The thickness of above-mentioned catalyst layer can be in 0.5nm～20nm scope.
According to another viewpoint of the present invention, a kind of manufacture method of catalyst for fuel cell is provided, comprising: contain the solution of platinum group element compound and the mixture of conductive carrier, make the step that forms on the surface of catalyst layer of forming by platinum family element under gel or the high viscosity state in described conductive carrier with this platinum family compound step of reducing with by calcining.
According to the present invention,,, can suppress the growth of particulate so the platinum family element that is reduced hinders Brownian movement owing under gel or high viscosity state, this platinum family compound is reduced.Make decomposition, evaporations such as gel by calcining in this state, can on the surface of conductive carrier, form the catalyst layer of forming by platinum family element.So this catalyst as mentioned above, can improve reaction speed to such an extent that specific activity is higher.
Can also comprise the step that the particulate be made up of platinum family element is separated out on the surface of above-mentioned catalyst layer.And described platinum family compound, comprise Pt compound, Ru compound or serve as the main platinum family compound that also comprises except that Pt with the Pt compound.And described high viscosity state is meant that viscosity is in 10～1 * 10 4The state of cps scope.
According to other viewpoints of the present invention, a kind of fuel cell is provided, wherein have the fuel electrodes and the air pole of solid electrolyte film, this solid electrolyte film of clamping, this fuel electrodes and air pole are made of collector body and catalysing area, and any layer all comprises and has this conductive carrier is covered and being the catalyst of the catalyst layer of alloy composition by Pt, Ru or Pt of conductive carrier and formation in the catalyst layer of this fuel electrodes and air pole.
According to the present invention, utilization has the catalyst with Pt, Ru the conductive carrier surface coverage, that have catalytic action or Pt alloy catalyst layer that forms with stratiform, can improve the reaction speed of redox reaction in fuel electrodes and the air pole, realize the high fuel cell of generating efficiency.
Brief description of drawings
Figure 1A is the view profile that the catalyst of existing reducing process manufacturing is adopted in expression.
Figure 1B is the view profile of expression recovery time than the catalyst of making under Figure 1A prolongation situation.
Fig. 2 is the view profile of expression catalyst for fuel cell of the present invention.
Fig. 3 is the flow chart of catalyst for fuel cell manufacturing process in expression first kind of execution mode of the present invention.
Fig. 4 is the flow chart of catalyst for fuel cell manufacturing process in expression second kind of execution mode of the present invention.
Fig. 5 is the flow chart of catalyst for fuel cell manufacturing process in expression the third execution mode of the present invention.
Fig. 6 is the view profile of the catalyst for fuel cell of the third execution mode of expression.
Fig. 7 is the schematic diagram of the fuel cell of expression the 4th kind of execution mode of the present invention.
Fig. 8 is the tabulation that the fuel cell luminous efficiency of the catalyst for fuel cell in embodiment and the reference examples is used in expression.
The best mode that carries out an invention
The catalyst for fuel cell of embodiments of the present invention below is described.
The inventor etc. have carried out various tests in order to utilize existing reducing process to improve the Pt activity of such catalysts of carrier band on carbon granules, found that in the catalyst manufacture method that adopts existing reducing process, are difficult to improve active.That is to say, when adopting HRTEM (high-resolution transmission electron microscope) to observe the section of using the Pt catalyst that has the reducing process preparation shown in Figure 1A, find, Pt particulate 12 only with discrete way attached on the surface as the carbon granules 11 of conductive carrier, can not cover the surface of carbon granules 11.Therefore, Pt particulate 12 quality of adhering on carbon granules are little, and promptly the specific area of Pt particulate 12 is little.The catalyst 15 shown in Figure 1B of prolongation recovery time preparation in existing reducing process, though attached to the quality of the Pt particulate 16 on the carbon granules 11 increase is arranged, but owing to the particle diameter of Pt particulate 16 also increases, so specific area can not increase.Therefore by inference, activity can be than the catalyst height shown in Figure 1A.
Reason as this situation, be by inference because the Pt particulate with quantity to a certain degree attached on the carbon granules, the total surface area of Pt particulate will form the energy labile state in case increase, between the Pt particulate mutually apposition growth to become the situation of a particle be stable cause on energy.
Fig. 2 is the view profile of the catalyst for fuel cell of embodiments of the present invention.With reference to Fig. 2, catalyst for fuel cell 20 is made of conductive carrier 21 and the catalyst layer 22 that forms on the surface of conductive carrier 21.Catalyst layer 22 for example is made up of Pt, and conductive carrier 21 for example is made up of the conductivity carbon granules.Therefore owing to form thin Pt layer on conductivity carbon granules surface, so compare with the catalyst of existing reducing process preparation, its surface area increases, the active raising.And it is investigated, because catalyst layer 22 forms on the conductive carrier surface continuously, so the reactive material that adsorbs on catalyst layer 22 surfaces or the intermediate of its reactive material move on catalyst layer 22 surfaces easily, active further raising further improves reaction speed.
Conductive carrier 21 for example can be used electron conduction and the big materials of surface area such as carbon granules, porousness Ni.The BET value of conductive carrier 21 preferably is in 100～2000m 2In/g the scope.In case less than 100m 2/ g, the surface area of catalyst layers such as Pt 22 are just not enough.And in case surpass 2000m 2/ g, conductive carrier 21 will be too small, is difficult in the solution in the aftermentioned manufacture method and disperses.And the ratio resistance of conductive carrier 21, will preferably be in 10 as the transmitting medium this point of electronics that produces because of oxidation methyl alcohol and proton from catalyst -1Ω cm～10 2In the Ω cm scope.Carbon granules for example can use kitchen carbon black EC-600J (trade name of kitchen carbon black International Co., Ltd).
Catalyst layer 22 is not only Pt, also can be that Ru or Pt are alloy, for example with Pt as main component, also added alloy, PtRu, the PtRh etc. of other platinum family elements.PtRu etc. can reduce the toxicity to the carbon monoxide that produces in the fuel cell.And the thickness of catalyst layer 22, preferably measure to form 0.5nm～20nm catalyst layer through the HRTEM crossgraphy.If thinner, then can not fully cover the surface of conductive carrier 21, and can reduce specific area on the contrary in case surpass 20nm than 0.5nm.
The specific area of catalyst for fuel cell 20 with present embodiment of this structure preferably is in 200m with the specific area of pulse CO determination of adsorption method 2/ g～5000m 2In/g the scope.Be lower than 200m 2During/g, the reaction speed in the fuel cell is low, can not obtain sufficient electric current, and in case surpass 5000m 2/ g, the ageing stability of catalyst for fuel cell will reduce.
Below explanation is as the manufacture method of the catalyst for fuel cell of embodiments of the present invention.
Manufacture method of the present invention is characterised in that, to contain the acid of platinum family element or the platinum family compound solution of salt reduces under gel or high viscosity state, the catalyst of separating out is sealed in the three-dimensional mesh structure of gel or heavy viscous material, the restriction Brownian movement, suppress the growth of catalyst particle, on the surface of conductive carrier, form the stratiform catalyst layer through calcining.Compare with reducing process in the existing solution, the specific area suitable with the quality of the quality of catalyst of the present invention and conductive carrier increased, improve reaction speed as catalyst.Below specify manufacture method.
(first kind of execution mode)
Present embodiment relates to the example of reduction platinum family compound manufacturing catalyst for fuel cell under gel state.
Fig. 3 is the flow chart of expression as the catalyst for fuel cell manufacturing process of embodiments of the present invention.Followingly manufacturing process is described with reference to Fig. 3.
Carry out the preparation (S101) of the solution of gel rubber material and platinum family element at first.Specifically, gel rubber material is mixed with predetermined water gaging with platinum family compound, be heated to dissolving fully.
Gel rubber material for example can use monomer, dimer, oligomer and polymer etc.Also can obtain with gelation initator cross-linking reaction by described later.That is to say that also can be the organic polymer material that becomes through cross-linking reaction or organic polymer itself forms the material of tridimensional network with lower-molecular substance.
And platinum family compound, be the acid or the salt of platinum family elements such as Pt, Ru, Rh.The acid or the salt of platinum family elements such as Pt, Ru, Rh for example can use chloroplatinic acid (H 2PtCl 6), platinum chloride (PtCl 4), ruthenic chloride (RuCl 3), radium chloride (RhCl 3) etc.And these compounds can be used in combination.
In the solution that obtains, add the gelation initator of using as crosslinking agent then, and then add conductive carrier, on one side vacuum deaerator conductive carrier is dispersed in (S102) in the solution on one side.Wherein, can adopt homogenizer, ultrasonic disperser etc. that conductive carrier is disperseed.
Specifically, the crosslinking agent selection is suitable for above-mentioned gel rubber material.To itself being the acrylamide of gel rubber material, for example can use bisacrylamide, diacrylate monomer etc.These crosslinking agents have two above reaction bonded positions in a molecule, these positions combine with the reaction bonded position of gel rubber material, form crosslinked combination at the polymeric main interchain, thereby form tridimensional network.
Conductive carrier can be used above-mentioned material.Wherein can also use in case of necessity and promote the loose dispersant of carbon.
Then with nitrogen to this solution air-blowing bubble, the oxygen concentration in the solution is reduced, on one side remove the oxygen of the aftermentioned reducing agent reaction of disinthibiting, on one side with electric hot plate etc. in about 90 ℃ of heating 1 hour down, make its gelling (S103).Specifically heating-up temperature is set in 50～200 ℃, is set in heating time 0.1～5 hour.Resulting gel is from suppressing the viewpoint of catalyst particle growth, the regid gel of preferred agar shape.
After this will be ground into several millimeters square shape gel input with rotary blender etc. and contain in the aqueous solution of reducing agent, about 80 ℃ down heating at room temperature leave standstill (S104) after 2 hours.Reducing agent can use formaldehyde, quinhydrones etc.Specifically, reductant concentration is using under the situation of formaldehyde, and is preferred 0.1～10% from the reaction speed viewpoint, and more preferably 1～3%.And heating-up temperature wherein is set in 50～100 ℃, and time set was at 0.5～10 hour.And the time of repose after the heating, from making the evenly viewpoint of growth of catalyst layer, preferred 8～15 hours.
Then discarded reducing agent after the gel washing, is heated to 150 ℃ and makes gel drying (S106) in atmosphere.
And then with stove etc. with this gel 650 ℃ of 2 hours (S107) of calcining down in atmosphere.The network structure body that forms gel becomes gas because of decomposition, forms the layered catalyst that is imported in the network structure in conductive carrier.
Adopt the manufacture method of present embodiment, owing under gel state platinum family compound is reduced, the platinum family element that reduction is separated out forms the tridimensional network of gel, because Brownian movement is subjected to the restriction of this structure, so can suppress particle growth.Therefore, make the tridimensional network decomposition evaporation, on the surface of conductive carrier, form the stratiform catalyst layer by calcining.Its result can improve the specific area of the catalyst suitable with the unit mass conductive carrier with the unit mass catalyst, can make activity stronger.
Wherein as gel rubber material, can also enumerate for example casein of animal protein, gelatin and ossein, vegetable protein is aleuronat for example, soybean protein, cellulose is wood pulp cellulose for example, the stickum that comes from vegetable seeds for example Yu is created wooden fat (Network ア ガ system), locust tree beanpod glue (ロ one カ ス ト PVC Application ガ system), the stickum that comes from marine alga is agar for example, carrageenan (カ ラ ギ one Na Application), the stickum of plant leaf is Arabic gum for example, bassora gum, the stickum of fruit is pectin for example, the stickum that comes from plant roots and stems is mannosan for example, the stickum of micro-organisms is pulullan polysaccharide (プ Le ラ Application) for example, xanthans, glucan, cellulose derivative is methylcellulose for example, ethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, carboxymethylethylcellulose, methylcellulose, cellulosic phthalic acetate, HPMCP and starch derivatives be soluble starch for example, CMS etc.Utilize these gel rubber materials to form the method for gel state, need not above-mentioned crosslinking agent, for example, in platinum family compound solution, add gel rubber material, in case be cooled to below the gelation temperature, just the casein of energy gelling, agar etc. perhaps just are gelation colloid etc. in case be in the above temperature of gelling, should set the heating-up temperature of step S103 and the temperature after the heat treatment according to the gelling conditions such as gelation temperature of gel rubber material.Wherein, also can use these gel rubber materials as tackifier described later according to heating-up temperature and use level.In addition, can also use the gelinite of polyvinyl alcohol poly ion complexes composition as gel rubber material.
(second kind of execution mode)
Present embodiment is the example that the reduction platinum family compound is made catalyst for fuel cell under high viscosity state.
Fig. 4 is the flow chart of expression as catalyst for fuel cell of the present invention manufacturing process.Followingly manufacturing process is described with reference to Fig. 4.
Carry out the preparation (S201) of tackifier and platinum family compound solution at first.Specifically, the scheduled volume platinum family compound slowly is added in the aqueous solution that has dissolved tackifier, mixes with water while be heated to about 60 ℃, just it dissolves fully in heating.
It itself is the polyethylene glycol of polyoxyethylene compound that tackifier can be enumerated, poly(ethylene oxide), the epoxyalkane of polyalcohols is oxirane for example, the addition product of expoxy propane, polyoxyethylene hydroxyl propylene glycol is the block or the random copolymer of oxirane and expoxy propane for example, itself be that propylene is the polyacrylamide of water tackifying polymer, PMAm, polyacrylic acid or its salt, polymethylacrylic acid or its salt, 2-alkyl-2-acrylamide propane sulfonic acid or its salt is 2-alkyl-2-acrylamide propane sulfonic acid sodium salt for example, (methyl) acrylic alkyl trialkyl ammonium quaternary amine is the methacrylic acid group ethyl-trimethyl salmiac for example, (methyl) acrylic dialkyl group dialkyl group amine salt is the tertiary ammonium salt or the quaternary amine of diethylamino methyl acrylic ethyl ester for example, and the mixture of the two or more materials in these materials etc.And platinum family compound, can use and first kind of acid or salt that execution mode is same.
In the solution that obtains, add conductive carrier then, vacuum deaerator and meanwhile conductive carrier is dispersed in (S202) in the solution.Wherein, can use homogenizer, ultrasonic disperser etc. for the dispersed electro-conductive carrier.Conductive carrier can be used and same those of first kind of execution mode.
And then the aqueous solution that will contain reducing agent slowly adds in this solution, about 80 ℃ stir about 2 hours down after, at room temperature leave standstill (S203).Reducing agent is identical with first kind of execution mode.And this moment heating-up temperature be 50～95 ℃, be set at 0.1～5 hour heating time.Time of repose after heating in addition, the viewpoint from the growth of catalyst layer homogeneous is preferably 8～15 hours.The viscosity under 80 ℃ for example during heating, the numerical value that records with Brookfield viscometer is preferably 10～1 * 10 4Cps.And the viscosity under the room temperature after slowly cooling off, the numerical value that records with Brookfield viscometer is preferably 100～1 * 10 5Cps.
The aqueous solution after then with rotary evaporator etc. this reduction reaction being stopped is concentrated into dried, and then is heated to bone dry (S204) under about 150 ℃.
Then, with stove etc. with this dry thing 650 ℃ of about 2 hours (S205) of calcining down in atmosphere.Make the substance decomposition evaporation that forms high viscosity state, be imported into catalyst in the conductive carrier with netted formation.Specifically, calcining heat is set in 500～800 ℃, calcination time was set in 1～5 hour.Be higher than under 800 ℃ the calcining heat, the surperficial oxidized grade of catalyst layer becomes just like toxic state, and catalytic action reduces.Be lower than under 500 ℃ the calcining heat, heavy viscous material is fully decomposed and evaporate.
Adopt the manufacture method of present embodiment, owing to be under high viscosity state with the platinum family compound reduction, so the platinum family element that reduction is separated out can suppress particle growth because of the viscosity height is restricted Brownian movement.Therefore, realized full-bodied substance decomposition evaporation, on the surface of conductive carrier, formed the stratiform catalyst layer by calcining.Its result can improve the specific area of the catalyst suitable with the unit mass conductive carrier with the unit mass catalyst, can obtain stronger activity.
(the third execution mode)
Present embodiment is to make the platinum family element particulate with catalytic action separate out the example of carrier band at the lip-deep manufacturing catalyst for fuel cell of the catalyst for fuel cell that adopts first and second kinds of execution modes to obtain.
Fig. 5 is the flow chart of expression as the catalyst for fuel cell manufacturing process of present embodiment.Followingly manufacturing process is described with reference to Fig. 5.
The solution of initial preparation platinum family compound adds first and second kinds of catalyst that execution mode obtains, and utilizes homogenizer with its dispersion (S301).
Slowly add reducing agent to this mixed solution then, leave standstill (S302) under the room temperature after about 2 hours in heating under about 80 ℃.
After this sediment centrifugation washing, 300 ℃ are heated down after about 2 hours in nitrogen atmosphere, form catalyst (S303).
Fig. 6 is the view profile of present embodiment catalyst for fuel cell.With reference to Fig. 6, make the catalyst particles that constitutes by platinum family element on the catalyst layer that first and second kinds of execution modes obtain, separate out, adhere to.Utilize these catalyst particles can improve the specific area of the catalyst suitable with the unit mass conductive carrier, can obtain stronger activity with the unit mass catalyst.
Adopt present embodiment, as mentioned above, on the catalyst layer that forms on the surface by the conductive carrier that obtains at first and second kinds of execution modes, further form catalyst particles, the specific area of the catalyst suitable with the unit mass conductive carrier can be improved by means of these catalyst particles, stronger activity can be obtained with the unit mass catalyst.
(the 4th kind of execution mode)
Fig. 7 is the view of the fuel cell of expression present embodiment.With reference to Fig. 7 as can be known, the fuel cell of present embodiment, substantially by solid electrolyte film 31, the fuel electrodes 32 and the air pole 33 that are in solid electrolyte film 31 both sides, hold these shell 34, take out electric power and the external circuit 35 that is connected with load etc. constitutes from fuel cell.
Solid electrolyte film 31 is made by the macromolecular material with proton conductive, for example can use the Nafion-115 (Na Off イ オ Application-115, trade name) of E.I.Du Pont Company's manufacturing etc.
Fuel electrodes 32 and air pole 33 are made of collector body 36 and the catalyst layer 38 that is coated on the carbon paper 37, and catalyst layer 38 is connected with above-mentioned solid electrolyte film 31.This catalyst layer 38 can use the catalyst for fuel cell that obtains in first～the third execution mode.The catalyst for fuel cell that about 2 grams obtain in first～the third execution mode is mediated with the Nafion solution of 20 grams 5%, made pasty state, utilize cutter to be coated with method or rod and be coated with method and set to such an extent that to make thickness be about 50 μ m～300 μ m being coated with on the carbon paper.
Collector body 36A, 36B are made by the strong alloy network of corrosion resistances such as stainless steel, and the electronics that produces at the catalyst layer of fuel electrodes 32 is captured by carbon paper 37A, perhaps will supply with catalyst layer 38B from the electronics that external circuit 35 flows out.
Supply with methanol aqueous solution to fuel electrodes 32 sides, on the catalyst surface of catalyst layer 38A, produce reaction:
CH 3OH+H 2O→CO 2+6H ++6e -
The proton that produces conducts in solid electrolyte film 31, after electronics flows through the load that is connected with external circuit 35, arrives air pole 33.Oxygen in air pole 33 side air supplies produces reaction on the catalyst surface of catalyst layer 38B:
3/2O 2+6H ++6e -→3H 2O
Form water by oxygen and proton and electronics.
The fuel cell of present embodiment is characterised in that to having the catalyst of catalyst layer.The carbon grain surface of carrier is owing to covered by the stratiform catalyst, thus big with respect to the specific area of the catalyst quality of catalyst layer, the contact probability height of reactive material and catalyst, promptly reaction speed is fast, the generating efficiency raising.
Below the embodiment that the present invention relates to of explanation and the present invention not have the reference examples of employing.
Embodiment 1
With the bisacrylamide aqueous solution of 200 milliliter 30% acrylamide aqueous solution and 200 milliliter 2%, add 1.5 gram chloroplatinic acids again, under 60 ℃, be heated to dissolving fully.After adding 40 milliliter 10% persulfate aqueous solution then, drop into the carbon granules of the black EC-600J in 0.6 gram kitchen, reduce pressure, deaeration and stirring as conductive carrier.With nitrogen bubble the oxygen concentration in the solution is reduced on one side, with electric hot plate this solution at 90 ℃ down heated 1 hour on one side, gel obtained.
Then above-mentioned gel is ground into several millimeters square back and drops in 1000 milliliter 3.5% the formalin, 80 ℃ down heating left standstill under the room temperature 10 hours after 2 hours.Then discharge formalin, water washs gently, under 150 ℃ gel is heated 3 hours in atmosphere, makes gel drying.And then under 650 ℃, in atmosphere, this gel was calcined 2 hours, obtained the Pt catalyst of present embodiment.
Finding that the thickness of PT catalyst layer is 2 nanometers when observing the section of Pt catalyst of present embodiment with HRTEM, is 1200m with the specific area of pulse CO determination of adsorption method 2/ g.
Embodiment 2
1.5 gram chloroplatinic acids are heated to 60 ℃ it slowly are added in 500 milliliter 10% PVP (K-90) aqueous solution after down, it is dissolved fully.Drop into the black EC-600J in 0.6 gram kitchen then as the carrier carbon granules, one side vacuum deaerator stir on one side.1000 milliliter 3.5% formalin is slowly added in this solution, left standstill under the room temperature 10 hours after 2 hours in heating under 80 ℃ while stirring.Viscosity when wherein heating for 80 ℃ times is 2500cps.
Then this mixed aqueous solution is concentrated into rotary evaporator dried, and then 150 ℃ down heating made its bone dry in 3 hours.650 ℃ under in atmosphere in calcine this solidfied material 2 hour after, obtained the Pt catalyst of present embodiment thereafter.
Finding that the thickness of PT catalyst layer is 3 nanometers when observing the section of Pt catalyst of present embodiment with HRTEM, is 1100m with the specific area of pulse CO determination of adsorption method 2/ g.
Embodiment 3
After being dispersed in the Pt catalyst of 1 gram embodiment 1 in 100 milliliter 1% the chloroplatinic acid aqueous solution, slowly add 200 milliliter 3.5% formalin, 80 ℃ keep down leaving standstill under the room temperature 10 hours after 2 hours.The sediment that centrifugation obtains after the washing, heated 2 hours down in 300 ℃ in the stove under the nitrogen atmosphere, had obtained the Pt catalyst of embodiment 3.
Finding that the thickness of PT catalyst layer is 5 nanometers when observing the section of Pt catalyst of present embodiment with HRTEM, is 1800m with the specific area of pulse CO determination of adsorption method 2/ g.
Embodiment 4
After being dispersed in the Pt catalyst of 1 gram embodiment 2 in 100 milliliter 1% the chloroplatinic acid aqueous solution, slowly add 200 milliliter 3.5% formalin, 80 ℃ keep down leaving standstill under the room temperature 10 hours after 2 hours.The sediment that centrifugation obtains, heated 2 hours down in 300 ℃ in the stove under the nitrogen atmosphere washing back, has obtained the Pt catalyst of embodiment 4.
Finding that the thickness of PT catalyst layer is 6 nanometers when observing the section of Pt catalyst of present embodiment with HRTEM, is 1700m with the specific area of pulse CO determination of adsorption method 2/ g.
Embodiment 5
With 200 milliliter 20% 2-acrylamide-2-methyl propane sulfonic acid aqueous solution and 200 milliliter 2% bisacrylamide aqueous solution, add 1.5 gram chloroplatinic acids again, under 60 ℃, be heated to dissolving fully.After adding 10% aqueous solution of 40 milliliters of potassium peroxydisulfates then, drop into the black EC-600J in 0.6 gram kitchen, reduce pressure, deaeration and stirring as carrier carbon.Following operation has obtained the Pt catalyst of present embodiment similarly to Example 1.
Embodiment 6
With 20% aqueous solution of 200 milliliters of 2-hydroxyethyl meth acrylates and 200 milliliter 4,2% aqueous solution of 4 '-bisphenol-A-diacrylate is added 1.5 gram chloroplatinic acids again, is heated to dissolving fully under 60 ℃.After adding 10% aqueous solution of 40 milliliters of potassium peroxydisulfates then, drop into the black EC-600J in 0.6 gram kitchen, reduce pressure, deaeration and stirring as carrier carbon.Following operation has obtained the Pt catalyst of present embodiment similarly to Example 1.
Embodiment 7
(four Grade ス チ Le バ ゾ リ ウ system bases add 1.5 gram chloroplatinic acids in 15% aqueous solution of polyvinyl alcohol tetra-stilbazolium), be heated to dissolving fully under 60 ℃ to have imported stibazole father-in-law base to 400 milliliters.After adding 10% aqueous solution of 40 milliliters of potassium peroxydisulfates then, drop into the black EC-600J in 0.6 gram kitchen, reduce pressure, deaeration and stirring as carrier carbon.Following operation has obtained the Pt catalyst of present embodiment similarly to Example 1.
Embodiment 8
In 20% aqueous solution of 200 milliliters of kayexalates, add 1.5 gram chloroplatinic acids, slowly be heated to 60 ℃ it is dissolved fully.Drop into the black EC-600J in 0.6 gram kitchen then as carrier carbon, reduce pressure, deaeration and stirring.20% aqueous solution that in this solution, adds 200 milliliters poly-(4-ethylethylene yl pyridines), with blender stirring on one side mix on one side, make its gelling 10 minutes.Following operation has obtained the Pt catalyst of present embodiment similarly to Example 1.
Embodiment 9
With 20% aqueous solution of 200 milliliters of PAAs and 200 milliliter 4,2% aqueous solution of 4 '-bisphenol-A-diacrylate is added 1.5 gram chloroplatinic acids again, is heated to dissolving fully under 60 ℃.After adding 10% aqueous solution of 40 milliliters of potassium peroxydisulfates then, drop into the black EC-600J in 0.6 gram kitchen, reduce pressure, deaeration and stirring as carrier carbon.Following operation has obtained the Pt catalyst of present embodiment similarly to Example 1.
Embodiment 10
With 20% aqueous solution of 200 milliliters of vinyl pyrrolidones and 200 milliliter 4,2% aqueous solution of 4 '-bisphenol-A-diacrylate is added 1.5 gram chloroplatinic acids again, is heated to dissolving fully under 60 ℃.After adding 10% aqueous solution of 40 milliliters of potassium peroxydisulfates then, drop into the black EC-600J in 0.6 gram kitchen, reduce pressure, deaeration and stirring as carrier carbon.Following operation has obtained the Pt catalyst of present embodiment similarly to Example 1.
Embodiment 11
In 8% aqueous solution of gelatin, add 1.5 gram chloroplatinic acids, under 90 ℃, be heated to dissolving fully.Drop into the black EC-600J in 0.6 gram kitchen then as carrier carbon, reduce pressure, deaeration and stirring.With this solution slowly behind the cool to room temperature,, obtained gel in 4 ℃ of coolings 3 hours down.Following operation has obtained the Pt catalyst of present embodiment similarly to Example 1.
Embodiment 12
In 5% aqueous solution of agar, add 1.5 gram chloroplatinic acids, under 90 ℃, be heated to dissolving fully.Drop into the black EC-600J in 0.6 gram kitchen then as carrier carbon, reduce pressure, deaeration and stirring.With this solution slowly behind the cool to room temperature,, obtained gel in 4 ℃ of coolings 3 hours down.Following operation has obtained the Pt catalyst of present embodiment similarly to Example 1.
Embodiment 13
With 20% aqueous solution and 200 milliliters of oligomeric (oxirane) acrylate 4 of 200 milliliters of carboxymethyl celluloses, 2% aqueous solution of 4 '-bisphenol-A-diacrylate is added 1.5 gram chloroplatinic acids again, is heated to dissolving fully under 60 ℃.After adding 10% aqueous solution of 40 milliliters of potassium peroxydisulfates then, drop into the black EC-600J in 0.6 gram kitchen, reduce pressure, deaeration and stirring as carrier carbon.Following operation has obtained the Pt catalyst of present embodiment similarly to Example 1.
Embodiment 14
With 20% aqueous solution and 200 milliliters of oligomeric (oxirane) acrylate 4 of 200 milliliters of poly(ethylene oxide)-acrylate, 2% aqueous solution of 4 '-bisphenol-A-diacrylate is added 1.5 gram chloroplatinic acids again, is heated to dissolving fully under 60 ℃.After adding 10% aqueous solution of 40 milliliters of potassium peroxydisulfates then, drop into the black EC-600J in 0.6 gram kitchen, reduce pressure, deaeration and stirring as carrier carbon.Following operation has obtained the Pt catalyst of present embodiment similarly to Example 1.
Embodiment 15
In 10% aqueous solution of 500 milliliters of gelatin 1.5 gram chloroplatinic acids slowly being heated to 60 ℃ dissolves it fully.Drop into the black EC-600J in 0.6 gram kitchen then as carrier carbon, reduce pressure, deaeration and stirring.Following operation has obtained the Pt catalyst of present embodiment similarly to Example 2.
Embodiment 16
In 10% aqueous solution of 500 milliliters of polyethylene glycol (molecular weight 5000) 1.5 gram chloroplatinic acids slowly being heated to 60 ℃ dissolves it fully.Drop into the black EC-600J in 0.6 gram kitchen then as carrier carbon, reduce pressure, deaeration and stirring.Following operation has obtained the Pt catalyst of present embodiment similarly to Example 2.
Embodiment 17
In 10% aqueous solution of 500 ml polypropylene acid amides (molecular weight 2000) 1.5 gram chloroplatinic acids slowly being heated to 60 ℃ dissolves it fully.Drop into the black EC-600J in 0.6 gram kitchen then as carrier carbon, reduce pressure, deaeration and stirring.Following operation has obtained the Pt catalyst of present embodiment similarly to Example 2.
Embodiment 18
With 2% aqueous solution of 30% aqueous solution and 200 milliliters of bisacrylamides of 200 milliliters of acrylamides, add 0.3 gram ruthenium trichloride again, under 60 ℃, be heated to dissolving fully.After adding 10% aqueous solution of 40 milliliters of potassium peroxydisulfates then, drop into the black EC-600J in 0.6 gram kitchen, reduce pressure, deaeration and stirring as carrier carbon.After following operation is handled similarly to Example 1, handle equally, obtained the Pt catalyst of forming by Ru and Pt with the third execution mode.
Embodiment 19
With 2% aqueous solution of 30% aqueous solution and 200 milliliters of bisacrylamides of 200 milliliters of acrylamides, and then add 1.00 gram chloroplatinic acids and 0.25 gram ruthenium trichloride, make that mol ratio reaches 2: 1 between Pt and Ru, under 60 ℃, be heated to dissolving fully.After adding 10% aqueous solution of 40 milliliters of potassium peroxydisulfates then, drop into the black EC-600J in 0.6 gram kitchen, reduce pressure, deaeration and stirring as carrier carbon.Following operation has obtained the Pt-Ru alloy catalyst of present embodiment similarly to Example 1.
Reference examples
In 400 ml waters, add 1.5 gram chloroplatinic acids, under 60 ℃, be heated to dissolving fully.Drop into the carbon granules of the black EC-600J in 0.6 gram kitchen then, reduce pressure, deaeration and stirring as conductive carrier.Make this solution bubbling with nitrogen, the oxygen concentration in the solution is reduced.
3.5% aqueous solution that then slowly adds 1000 milliliters of formaldehyde in this mixture, 80 ℃ are heated after 2 hours down, at room temperature left standstill 10 hours.Then discharge formalin, slowly wash, obtained the Pt catalyst of this reference examples behind the suction filtration.
(evaluation)
With the catalyst of the foregoing description 1～embodiment 19 and reference examples, made fuel cell.In each 2 gram catalyst, add the 5 weight % solution of 20 gram Nafion and mediate, make pasty state.Be coated with method with cutter then and be coated with to such an extent that thickness reaches 60 microns on carbon paper (200 square centimeters of areas), evaporation moisture content sticks on it on one side of polymer solid electrolyte film (Nafion-115 (237 microns of thickness) that E.I.Du Pont Company makes).On another side, paste the same air pole electrode of making.Screen cloth is pressed in makes collector body on the two poles of the earth.It is contained in the propylene shell, the fuel electrodes side is supplied with the 10 weight % aqueous solution of methyl alcohol with 30 ml/min speed, with 50 ml/min speed to the air pole air supply.
Load is connected on this fuel cell, has measured generating efficiency.
Fig. 8 is the form of the generating efficiency of each embodiment of expression and reference examples.Generating efficiency, with the unit electrode surface area of fuel cell suitable electric power (watt/square centimeter) expression.
With reference to Fig. 8, embodiment 1 compares with the reference examples that adopts existing Pt catalyst with embodiment 2, and generating efficiency has improved more than 1.55～1.65 times.And with respect to embodiment and embodiment 2, in embodiment 3 that further makes catalyst particles separate out, adhere to and embodiment 4, generating efficiency has been improved 1.90～1.95 times with respect to reference examples.
Though more than describe the preferred embodiments of the present invention in detail, the present invention is not limited on the related specific embodiment, can make various changes and variation in the scope of the invention of Patent right requirement record.
For example, can be with embodiment 18, with embodiment 1～embodiment 17 appropriate combination except that embodiment 3 and embodiment 4.And can be with embodiment 1,2,5～18, with embodiment 3,4 combinations.In addition, the precious metal element in catalyst layer or the catalyst particles can also be made up.
The possibility of utilizing on the industry
According to the present invention, form catalyst layer by the surface in conductive carrier, a kind of work can be provided The property height, with fast catalyst for fuel cell, its manufacture method of the reaction speed of fuel with use this fuel electricity The pond fuel cell of catalyst.

Claims (21)

1. a catalyst for fuel cell wherein has
Conductive carrier and
Form continuously on the surface of this conductive carrier by covering this conductive carrier, and be the catalyst layer that alloy is formed by Pt, Ru or Pt.
2. the described catalyst for fuel cell of claim 1 wherein further has on the surface of described catalyst layer by being the metal particle that alloy is formed by dispersed Pt, Ru or Pt.
3. the described catalyst for fuel cell of claim 1 is characterized in that described conductive carrier is the conductivity carbon granules.
4. the described catalyst for fuel cell of claim 3 is characterized in that the BET value of described carbon granules is in 100m 2/ g～2000m 2In/g the scope.
5. the described catalyst for fuel cell of claim 1, it is characterized in that described Pt be alloy with Pt as main component, contain the platinum family element except that Pt.
6. the described catalyst for fuel cell of claim 1 is characterized in that being in 200m with the specific area of pulse CO determination of adsorption method 2/ g～5000m 2In/g the scope.
7. the described catalyst for fuel cell of claim 1 is characterized in that the thickness of described catalyst layer is in 0.5nm～20nm scope.
8. the manufacture method of a catalyst for fuel cell, comprising:
The mixture that will contain the solution of platinum group element compound and conductive carrier forms the step of gel;
Pulverize above-mentioned gel, add reducing agent and make this platinum family compound step of reducing; And
Calcine the gel that this platinum family compound has been reduced, make the step that the catalyst layer be made up of platinum family element forms on the surface of above-mentioned conductive carrier.
9. the manufacture method of the described catalyst for fuel cell of claim 8 is characterized in that also being included in after the step that forms above-mentioned catalyst layer, the step that the particulate be made up of platinum family element is separated out on the surface of above-mentioned catalyst layer.
10. the manufacture method of the described catalyst for fuel cell of claim 8 is characterized in that, in the step that forms above-mentioned gel, utilizes gel rubber material and gel initator to realize the state of described gel.
11. the manufacture method of the described catalyst for fuel cell of claim 8 is characterized in that described platinum family compound, comprises Pt compound, Ru compound or based on the Pt compound and comprise the compound of the Pt family element except that Pt.
12. the manufacture method of a catalyst for fuel cell, comprising:
Heat adding reducing agent in the mixture of the solution that contains the platinum group element compound and conductive carrier and tackifier when, viscosity is in 10cps～1 * 10 in the time of 80 ℃ 4The state of cps scope is this platinum family compound of reduction down; And
Calcine the mixture that this platinum family compound has been reduced, make the step that the catalyst layer be made up of platinum family element forms on the surface of above-mentioned conductive carrier.
13. the manufacture method of the described catalyst for fuel cell of claim 12 is characterized in that also being included in after the step that forms above-mentioned catalyst layer, the step that the particulate be made up of platinum family element is separated out on the surface of above-mentioned catalyst layer.
14. the manufacture method of the described catalyst for fuel cell of claim 12 is characterized in that described platinum family compound, comprises Pt compound, Ru compound or based on the Pt compound and comprise the compound of the Pt family element except that Pt.
15. a fuel cell is characterized in that it has
Solid electrolyte film and
The fuel electrodes of this solid electrolyte film of clamping and air pole,
This fuel electrodes and air pole are made of collector body and catalysing area,
Any one deck in the catalyst layer of this fuel electrodes and air pole comprise have conductive carrier and form continuously on the surface of this conductive carrier by covering this conductive carrier and be the catalyst of the catalyst layer of alloy composition by Pt, Ru or Pt.
16. the described fuel cell of claim 15 is characterized in that also further having by Pt, Ru or Pt on the surface of described catalyst layer is the metal particle of alloy composition.
17. the described fuel cell of claim 15 is characterized in that described conductive carrier is the conductivity carbon granules.
18. the described fuel cell of claim 17 is characterized in that the BET value of described carbon granules is in 100m 2/ g～2000m 2In/g the scope.
19. the described fuel cell of claim 15 is characterized in that described Pt is an alloy, as main component, contains the platinum family element except that Pt with Pt.
20. the described fuel cell of claim 15 is characterized in that being in 200m with the specific area of pulse CO determination of adsorption method 2/ g～5000m 2In/g the scope.
21. the described fuel cell of claim 15 is characterized in that the thickness of described catalyst layer is in 0.5nm～20nm scope.
CNB038220830A 2002-09-19 2003-07-10 Catalyst for fuel cell, method for preparation thereof and fuel cell Expired - Lifetime CN100377400C (en)

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