CN100502109C - Electrode for fuel cell, its preparation method, membrane-electrode assembly for fuel cell comprising the same, fuel cell system - Google Patents

Electrode for fuel cell, its preparation method, membrane-electrode assembly for fuel cell comprising the same, fuel cell system Download PDF

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Publication number
CN100502109C
CN100502109C CNB2007101274206A CN200710127420A CN100502109C CN 100502109 C CN100502109 C CN 100502109C CN B2007101274206 A CNB2007101274206 A CN B2007101274206A CN 200710127420 A CN200710127420 A CN 200710127420A CN 100502109 C CN100502109 C CN 100502109C
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electrode
catalyst
fuel cell
adhesive resin
platinum
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CN101071861A (en
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卢亨坤
金熙卓
李钟基
权镐真
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Samsung SDI Co Ltd
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Samsung SDI Co 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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

Abstract

The electrode for a fuel cell of the invention includes: an electrode substrate; and a catalyst layer having a filler layer formed on the surface of the electrode substrate and a catalyst coating the filler layer.

Description

Electrode of fuel cell and preparation method thereof and the membrane electrode assembly and the fuel cell system that comprise it
The application be that June 8, application number in 2005 are 200510076158.8 the applying date, denomination of invention divides an application for the application of " electrode of fuel cell and preparation method thereof and the membrane electrode assembly and the fuel cell system that comprise it ".
Technical field
The present invention relates to a kind of electrode of fuel cell, comprise the membrane electrode assembly of its fuel cell, comprise its fuel cell system, and a kind of method for preparing the electrode of described fuel cell.More specifically, the present invention relates to a kind of electrode of fuel cell, described electrode comprises the catalyst layer with big surface area, comprises the membrane electrode assembly of the fuel cell of described electrode, the fuel cell system that comprises described electrode, and a kind of method for preparing the electrode of fuel cell.
Background technology
Fuel cell for directly by oxygen and hydrogen or at hydrocarbon materials such as methyl alcohol, the equipment of the which generate electricity by electrochemical reaction of the hydrogen in ethanol or the natural gas.
According to the kind of employed electrolyte, fuel cell can be divided into a kind of in the following type: phosphatic type, fused carbonate type, solid oxide type, polyelectrolyte type or alkalescence.Though every kind of fuel cell is basically according to same basic principle operation, type of fuel cell can be determined the kind of the fuel that utilized, operating temperature, catalyst and electrolyte.
Recently, developed polyelectrolyte film fuel cell (PEMFC), it is compared with the fuel cell of routine, has better power characteristic, lower operating temperature and starts faster and response characteristic.This technology has advantage, because it can be applied to wide field, as is used for the removable power supply of automobile, for example is used for the decentralized power s of family and public building, and is used for the Miniature Power Unit of electronic equipment.
PEMFC is by generator basically, reformer, and tanks and petrolift are formed.Petrolift will be stored in supply of fuel in the tanks in reformer.The reformer fuel reforming produces hydrogen, and with hydrogen supply in generator, make hydrogen and oxygen reaction generation electric energy with electrochemical method.
The another kind of type of fuel cell is direct oxidation fuel cell (DOFC), as direct methanol fuel cell (DMFC), wherein liquid methanol fuel is introduced directly in the generator.DMFC can save reformer, and this is that polymer electrolyte fuel cell is necessary.
According to above-mentioned fuel cell system, the generator for electricity generation in the fuel cell system, and have hierarchy (being called battery pack), it is made up of several to dozens of element cells.Each element cell is made up of membrane electrode assembly (MEA) and two dividing plates (or bipolar plates).In the structure of described MEA, polyelectrolyte film places between anode (being called fuel electrode or oxidizing electrode) and the negative electrode (being called air electrode or reducing electrode).
In MEA, dividing plate not only serves as the required supply of fuel of reaction is fed to the path of negative electrode to anode with oxygen, and conduct connects the conductor of anode and negative electrode continuously.The electrochemical oxidation reactions of fuel occurs in anode, and the electrochemical reducting reaction of oxygen occurs in negative electrode, because the migration of the electronics that in this process, is produced, thereby produce electricity, Re Heshui.
Generally, the anode of fuel cell and negative electrode comprise platinum (Pt) catalyst.Yet because platinum is expensive noble metal, a large amount of use costs are very high.Therefore, used, to reduce employed platinum amount by carbon-supported platinum.
Yet carbon supported platinum catalyst makes described catalyst layer thickening, and has limited memory capacity.And the bad contact between catalyst layer and the electrolyte membrane has reduced fuel cell performance.
Simultaneously, use carbon supported platinum catalyst may bring some problems, because in electrode production process, carbon supported platinum catalyst partly is immersed in the adhesive resin, and the catalyst of this immersion can not participate in desirable catalytic reaction.
Therefore, develop that catalyst consumption in the electrode reduces but still electrode with fuel cell of good battery performance is useful.
Summary of the invention
According to one embodiment of the invention, a kind of electrode that is used for fuel cell is provided, described electrode comprises the catalyst with high-specific surface area.
In another embodiment of the invention, a kind of electrode that is used for fuel cell is provided, described electrode has good reactivity, comprises a spot of metallic catalyst simultaneously.
In yet another embodiment of the present invention, provide a kind of membrane electrode assembly that is used for fuel cell, described membrane electrode assembly comprises above-mentioned electrode.
In another embodiment of the present invention, a kind of fuel cell is provided, described battery comprises above-mentioned electrode.
Go back in the embodiment of the present invention, a kind of method for preparing the electrode of fuel cell is provided.
According to one embodiment of the invention, a kind of electrode that is used for fuel cell is provided, described electrode comprises electrode base material and catalyst layer, described catalyst layer comprises and is formed on the lip-deep packing layer of electrode base material and is coated on catalyst on this packing layer.
Membrane electrode assembly comprises polyelectrolyte film and a pair of aforesaid electrode according to embodiments of the present invention, and described arrangement of electrodes is in the both sides of polyelectrolyte film.Fuel cell system comprises fuel supply unit according to embodiments of the present invention, the oxidant feeding unit, and generator unit, described generator unit receives the fuel and the oxidant that comes the autoxidator feeding unit from fuel supply unit, thereby generating, described generator unit comprises at least one membrane electrode assembly and dividing plate, described membrane electrode assembly comprises polyelectrolyte film, and a pair of electrode that is arranged in described polyelectrolyte film both sides, wherein at least one electrode comprises electrode base material and catalyst layer, and described catalyst layer comprises the packing layer of adjacent electrode base material and the catalyst of the described packing layer of coating.
The method for preparing the electrode of fuel cell according to embodiments of the present invention comprises the steps: (a) surface with nano-sized carbon wet coating electrode base material, to form packing layer; And (b) with catalyst coated described packing layer, to form catalyst layer.
The method for preparing the electrode of fuel cell according to embodiments of the present invention comprises the steps: that (a) forms polymer network on the surface of filler particles, way is to form mixture by mixed fillers particle and adhesive resin, side with this mixture coating electrode base material, drying scribbles the electrode base material of this mixture, and heat-treats; Reach the catalyst electrode that (b) preparation has catalyst layer, way is that metal catalyst particles is filled in the gap of described polymer network.
Description of drawings
Introduce and constitute the accompanying drawing of the part of specification, graphic extension embodiment of the present invention, and, be used for explaining principle of the present invention with declaratives, in the accompanying drawing:
Figure 1A is the cross-sectional schematic of the electrode base material before deposited catalyst;
Figure 1B is the cross-sectional schematic according to the electrode of the fuel cell that has deposition catalyst thereon of first embodiment of the invention;
Fig. 2 is the cross-sectional schematic according to the catalyst layer of the electrode of the fuel cell of second embodiment of the invention;
Fig. 3 is the cross-sectional schematic according to the membrane electrode assembly of the electrode that comprises fuel cell of one embodiment of the invention;
Fig. 4 is the schematic diagram according to the fuel cell system of one embodiment of the invention;
Fig. 5 is the decomposition diagram according to the generator unit of the electrode that comprises fuel cell of one embodiment of the invention;
Fig. 6 is the graph of a relation according to the electric current (CPW) of voltage and Unit Weight catalyst in the fuel cell of embodiment 1 and Comparative Examples 1～3 preparation; And
Fig. 7 is fuel cell voltage and the current density graph of a relation according to embodiment 2 and Comparative Examples 4 preparations.
Embodiment
In the following detailed description, certain embodiments of the present invention have been described.Will recognize that the present invention can make amendment in all fields, do not break away from the present invention fully.Therefore, drawing and description are illustrative in itself, rather than restrictive.
In most of the cases, use the act as a fuel metallic catalyst of membrane electrode assembly of battery of expensive noble metal.Wherein, use platinum the most widely.Yet, because its expense is wished to reduce the amount of metallic catalyst, and is kept fuel cell performance.
A method that reduces employed metal catalytic dosage be with catalyst deposit on base material, thereby form catalyst layer.Yet the surface area of described catalyst layer is decided with the surface area of the base material of deposited catalyst.If described catalyst layer has little surface area, the output characteristic of fuel cell descends so.
The electrode of first embodiment of the present invention comprises electrode base material and catalyst layer, and described catalyst layer has lip-deep packing layer that is formed on described electrode base material and the catalyst that is coated with described packing layer.
According to one embodiment of the invention, by on electrode base material, forming the nanometer carbon-coating, follow deposited catalyst thereon, make the surface area maximization of the electrode of fuel cell.The result obtains having the thin catalyst layer of high-specific surface area.
Figure 1A is the cross-sectional schematic with electrode base material of maximum surface area.Figure 1B is deposited on the cross-sectional schematic of electrode that lip-deep catalyst has the fuel cell of maximum surface area for first embodiment according to the present invention has.
With reference to Figure 1A and 1B, the electrode 100 of fuel cell comprises electrode base material 101 and the lip-deep nanometer carbon-coating 102 that is formed on described electrode base material 101, and the catalyst 103 of the described nanometer carbon-coating 102 of coating, wherein said nanometer carbon-coating 102 and catalyst 103 form catalyst layer 105 together.
Electrode base material 101 is the supporter of electrode 100, simultaneously, provides migration fuel and the oxygen path to catalyst 105.The example that is used for the material of described electrode base material 101 comprises carbon paper or charcoal cloth, and the electrode base material 101 that is made of carbon paper or charcoal cloth is commonly referred to as gas diffusion layers.
Comprise the electrode base material 101 of the gas diffusion layers that contains carbon paper or charcoal cloth, not only comprise gas diffusion layers, but also can comprise microporous layer.Described microporous layer scatters fuel and the oxygen through described gas diffusion layers migration, and helps the gas contact catalyst.The suitable material of microporous layer is the carbon that has micropore, and exemplary material with carbon element comprises graphite, fullerene (C60), active carbon and carbon black.
In one embodiment of the invention, the thickness of the gas diffusion layers of electrode base material is 10～1000 μ m, and the thickness of microporous layer is 1～100 μ m.When the thickness of described gas diffusion layers was lower than 10 μ m, it can not serve as supporter.When its thickness during greater than 1000 μ m, fuel supplying and oxygen reposefully.Simultaneously, when the thickness of described microporous layer was lower than 1 μ m, fuel and gas can not spread fully, and can not contact described catalyst layer equably.When its thickness during greater than 100 μ m, fuel supplying and oxygen reposefully.
In one embodiment of the invention, the thickness that is formed on the nanometer carbon-coating on the described electrode base material is 0.05～10 μ m.When its thickness was lower than 0.05 μ m, the effect that surface area increases can be ignored.When its thickness during greater than 10 μ m, the effect that can not bring further surface area to increase, and electrode thickening, this is undesirable.
The suitable nano-carbon material of nanometer carbon-coating comprises and is selected from following material with carbon element: carbon nano-tube, carbon nano-fiber, carbon nanocoils, Carbon Nanohorn (nanohom) and carbon nano ring.
In one embodiment, the diameter of preferred nano-sized carbon is 1～500nm, and length is 50～5000nm.Generally, more the nano-sized carbon of minor diameter provides better result.Yet,, make difficulty when diameter during less than 1nm.When diameter during greater than 500nm, it is little that surface area increases effect.When nano-sized carbon be shorter in length than 50nm the time because the dense arrangement of nano-sized carbon, porosity reduces, this makes and is difficult to fuel supplying.When nano-sized carbon length is longer than 500nm, in the time of the preparation slurry, be difficult to dispersing nanometer carbon.
In one embodiment, the amount of providing of catalyst is per unit area 0.001～0.5mg/cm in described catalyst layer 2, preferably, be 0.01～0.05mg/cm 2When the amount of catalyst in described catalyst layer is lower than 0.001mg/cm 2The time, fuel cell does not have enough efficient.When catalyst content surpasses 0.5mg/cm 2The time, can not get beneficial effect of the present invention.
In one embodiment, the preferred specific area of the catalyst of per unit weight is 10～500m in described catalyst layer 2/ g.Because the oxidation/reduction reaction of fuel cell occurs in the surface of catalyst, so when its per unit weight had high specific area, fuel cell had good efficient.By contrast, when the specific area of per unit weight less than 10m 2During/g, the efficient of fuel cell is poor.Yet, when the specific area of per unit weight greater than 500m 2During/g, the preparation fuel cell has some problems.
The suitable catalyst of described catalyst layer comprises and is selected from following catalyst: platinum; Ruthenium; Osmium; Platinum-ruthenium alloy; Platinum-osmium alloy; Platinum-palldium alloy and platinum-M alloy, wherein M is selected from following transition metal: Ga, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, and combination.Preferred catalyst comprises and is selected from following catalyst: platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palldium alloy, platinum-cobalt alloy and platinum-nickel alloy.
According to second embodiment of the present invention as shown in Figure 2, the electrode of fuel cell comprises catalyst layer 205, described catalyst layer is made of with polymer network 106 a plurality of filler particles 104, described polymer network 106 is formed on the surface of each filler particles 104, and is limited to the gap 107 in the polymer network 106.Catalyst granules 108 is arranged in some gap 107 of described polymer network.
Because described catalyst granules 108 is arranged in the gap 107 of described polymer network 106, can obtain good reactivity with a spot of catalyst.
For second embodiment of the present invention, the suitable catalyst of described catalyst granules is described in the first embodiment catalyst.
For second embodiment of the present invention, the average diameter of catalyst granules can be 1～1000nm, and preferably, the average particulate diameter of catalyst granules is 1～100nm.When average particulate diameter during less than 1nm, the preparation difficulty of catalyst granules.When average particulate diameter during greater than 1000nm, fuel cell performance may descend.
For second embodiment, the preferred amount of catalyst granules is per unit area 0.0001～0.4mg/cm in described catalyst layer 2, 0.01～0.3mg/cm more preferably 2When the amount of metal catalyst particles is lower than 0.0001mg/cm 2The time, the reactivity of fuel cell reduces.When the amount of metal catalyst particles greater than 0.4mg/cm 2The time, obtain few beneficial effect.
According to second embodiment of the present invention, be included in the suitable material of filler particles in the catalyst layer of fuel cell electrode, comprise carbon granule, inorganic particle, and combination.Exemplary carbon granule is selected from: graphite, nano-sized carbon, and combination.Suitable inorganic particle is selected from: aluminium oxide, silica, and combination.
The lip-deep polymer network that is formed on filler particles can constitute by being selected from following adhesive resin: fluorine-based adhesive resin, the benzimidazolyl adhesive resin, ketone group adhesive resin, ester group adhesive resin, amide groups adhesive resin and imide adhesive resin.In certain embodiments of the invention, described adhesive resin can comprise at least a polymer that is selected from following proton conductive: poly-(perfluorinated sulfonic acid), poly-(perfluorocarboxylic acid), tetrafluoroethene and the copolymer that contains sulfonic fluroxene, the polyether-ketone sulfide of defluorinate, aryl ketones, poly-(2,2 '-(-phenylene)-5,5 '-bisbenzimidazole), and poly-(2, the 5-benzimidazole).Yet this adhesive resin only is exemplary, is not restrictive.
With reference to figure 3, the cross-sectional schematic of membrane electrode assembly 10 according to the anode 100 of the fuel cell of first and second embodiments of the present invention and negative electrode 100 ' be arranged in the both sides of polyelectrolyte film 110, thereby forms membrane electrode assembly.Described electrode 100 and 100 ' respectively comprise electrode base material 101 and 101 ' with separately catalyst layer 105 and 105 '.
At anode, the fuel oxidation reaction takes place, produce proton H +With electronics e -The proton that described polyelectrolyte film 110 migrations are produced is to negative electrode.At negative electrode, with electrochemical method the proton that moved and the oxygen of supply are reacted, generate water.
Described polyelectrolyte film 110 comprises the polymer of at least a proton conductive.The polymer of suitable proton conductive is selected from: the perfluor based polyalcohol, benzimidazole-based polymer, the polyimides based polyalcohol, the polyetherimide amine based polymer, polyphenylene sulfide based polyalcohol, polysulfones based polyalcohol, the polyether sulfone based polyalcohol, the polyether-ketone based polyalcohol, polyether-ether-ketone based polyalcohol, and polyphenyl quinoxalinyl polymer.The polymer of preferred proton conductive comprises and is selected from those following polymer: poly-(perfluorinated sulfonic acid), poly-(perfluorocarboxylic acid), tetrafluoroethene and the copolymer that contains sulfonic fluroxene, the polyether-ketone sulfide of defluorinate, aryl ketones, poly-(2,2 '-(-phenylene)-5,5 '-bisbenzimidazole), and poly-(2, the 5-benzimidazole).Yet according to the present invention, the polymer that is included in the proton conductive in the polyelectrolyte film of fuel cell is not limited to these polymer.
Membrane electrode assembly can be used for various types of fuel cells, comprises polyelectrolyte film fuel cell (PEMFC) and direct oxidation fuel cell (DOFC).Because this membrane electrode assembly has high-specific surface area, so they provide good performance.
Fig. 4 is the schematic diagram according to the fuel cell system of one embodiment of the invention, and Fig. 5 is the decomposition diagram according to the generator unit that comprises fuel cell electrode of one embodiment of the invention.
With reference to Figure 4 and 5, fuel cell system of the present invention comprises fuel supply unit 2, described fuel supply unit 2 supplies comprise the fuel of hydrogen, with oxidant feeding unit 3, described oxidant feeding unit 3 supply oxidants such as oxygen containing air are in generator unit 1, and described generator unit 1 is by the which generate electricity by electrochemical reaction between fuel and the oxidant.
Generator unit 1 of the present invention comprises at least one element cell 30, described element cell 30 comprises membrane electrode assembly 10 and dividing plate 20, described membrane electrode assembly 10 comprises polyelectrolyte film, and is arranged in the anode and the negative electrode of the side of described polyelectrolyte film.And at least one of negative electrode and anode comprises electrode base material and catalyst layer, and described catalyst layer comprises the packing layer of adjacent electrode base material and the catalyst of the described packing layer of coating.
According to first embodiment of the present invention, a kind of method for preparing the electrode of fuel cell comprises the following steps: that (a) by the surface with nano-sized carbon wet coating electrode base material, forms the nanometer carbon-coating; And, form catalyst layer (b) by with catalyst coated described nanometer carbon-coating.
As for electrode base material, can use the gas diffusion layers (GDL) that is selected from carbon paper and charcoal cloth.If necessary, electrode base material can also comprise the lip-deep microporous layer that is formed on described gas diffusion layers.
According to an embodiment, the thickness of gas diffusion layers is 10～1000 μ m, and the thickness of microporous layer is 1～100 μ m.
Microporous layer can be the carbon-coating that has micropore, and the preferred material of described microporous layer comprises and is selected from following material: graphite, fullerene (C60), active carbon, carbon black, and combination.
Adopt the wet coating method, with the surface of nanometer carbon-coating coating electrode base material, the section that scribbles the electrode base material of nanometer carbon-coating is shown among Figure 1A.The example of wet coating method is a slurry methods, wherein nano-sized carbon mixed with organic solvent and adhesive, and with described nano-sized carbon mixture coated substrate; Method for printing screen; Scraping blade method and spraying method.Yet in the present invention, the method that forms the nanometer carbon-coating is not limited to above-mentioned method.
Because described wet coating method is well-known technology, so its detailed description just is not provided here.If the use adhesive, so Shi Yi adhesive is the polymer of proton conductive.The example of the polymer of proton conductive is described in the polyelectrolyte film in the above and is mentioned.Yet can use other is not the adhesive of routine of the polymer of proton conductive, as polytetrafluoroethylene, and polyvinylidene fluoride, polyvinyl alcohol, polyvinyl chloride, PSB and cellulose.Yet the adhesive that is used in the wet coating of the present invention is not limited to above-mentioned example.
The solvent that is used in the wet coating method does not have concrete restriction.The suitable solvent comprises water, and is pure as methyl alcohol, ethanol or isopropyl alcohol, aromatic alcohol such as terpineol, ether, ketone, benzene, acid amides and ester.
The thickness of the nanometer carbon-coating that is preferably formed in one embodiment, is 0.05～10 μ m.
The suitable nano-sized carbon that is included in the described nanometer carbon-coating is selected from: carbon nano-tube (CNT), carbon nano-fiber, carbon nanocoils, Carbon Nanohorn and carbon nano ring.
In one embodiment, the diameter of described nano-sized carbon is 1～500nm, and length is 50～5000nm.
On the nanometer carbon-coating of the electrode base material that as above prepares, can form described catalyst layer by deposited catalyst.In one embodiment, the content of preferred catalyst is per unit area 0.01～0.5mg/cm 2, more preferably, per unit area 0.01～0.05mg/cm 2In this embodiment, the specific area that also preferably is contained in the catalyst per unit weight in the described catalyst layer is 10～500m 2/ g.
Described catalyst layer can form by using conventional deposition process.Suitable deposition process is selected from: sputtering method, physical vapor deposition (PVD) method, thermal chemical vapor deposition (CVD) method, plasma enhanced CVD (PECVD) method, thermal evaporation method, electrochemical deposition method and electron beam evaporation method.Yet, be used in deposition process of the present invention and be not limited to above-mentioned deposition process, if necessary, may mix the two or more method of using.
Suitable catalyst is selected from: platinum; Ruthenium; Osmium; Platinum-ruthenium alloy; Platinum-osmium alloy; Platinum-palldium alloy; And platinum-M alloy, wherein M is selected from following transition metal: Ga, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, and combination.Preferred catalyst is selected from: platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palldium alloy, platinum-cobalt alloy and platinum-nickel alloy.
According to second embodiment of the present invention, a kind of method for preparing the electrode of fuel cell, comprise the following steps: that (a) is by mixed fillers particle and adhesive resin, on the surface of filler particles, form polymer network, with a side of described mixture coating electrode base material, drying scribbles the electrode base material of described mixture and heat-treats; And (b) by filling metal catalyst particles in the gap of described polymer network, preparation has the catalyst electrode of catalyst layer.
Polymer network can prepare by following method: described filler particles of dissolving and adhesive resin in solvent, thus make mixture, with a side of described mixture coating electrode base material, drying scribbles the electrode base material of mixture, and heat-treats.The polymer network that makes through said process has the good gap that is formed on wherein.
Be used in the suitable filler particles that catalyst layer forms, comprise carbon granule, inorganic particle, and combination.Suitable carbon granule is selected from: graphite, carbon, nano-sized carbon, and combination.Suitable inorganic particle is selected from: aluminium oxide, silica, and combination.
Use is selected from following at least a adhesive resin: fluorine-based adhesive resin, the benzimidazolyl adhesive resin, the ketone group adhesive resin, the ester group adhesive resin, amide groups adhesive resin and imide adhesive resin can make the lip-deep polymer network that is formed on filler particles.Described adhesive resin can also be the polymer that is selected from following proton conductive: poly-(perfluorinated sulfonic acid), poly-(perfluorocarboxylic acid), tetrafluoroethene and the copolymer that contains sulfonic fluroxene, the polyether-ketone sulfide of defluorinate, aryl ketones, poly-(2,2 '-(-phenylene)-5,5 '-bisbenzimidazole) and poly-(2, the 5-benzimidazole).Yet according to the present invention, described adhesive resin is not limited to these.
Because the example of electrode base material is identical with the example of first embodiment, just do not provide detailed description here to them.
According to second embodiment of the present invention, the polymer network of the electrode of fuel cell has the gap, and passes through the catalyst filling particle in described gap, forms catalyst layer.Described catalyst electrode can form by following method: directly spread catalyst granules; By deposition process, or the method for use dispersed catalyst dispersion soln, described catalyst dispersion soln is included in the catalyst in the organic solvent, is coated with described polymer network with catalyst granules; With described catalyst dispersion soln impregnated polymer network, and the described solvent of evaporation.The suitable organic solvent that is used for described catalyst dispersion soln is not limited to the solvent of concrete kind, can use any solvent, as long as it can disperse described metallic catalyst.
The example of catalyst that is used to form described catalyst layer is identical with in the first embodiment example, will omit its detailed description.
In one embodiment, preferred catalyst is to have the metallic catalyst that average particulate diameter is the particle of 1～1000nm, more preferably, and 1～100nm.When the average particulate diameter of catalyst granules during, be difficult to make described catalyst less than 1nm.When average particulate diameter during greater than 1000nm, catalytic performance may descend.
In another embodiment, the amount of the catalyst granules in the gap of described polymer network is per unit area 0.0001～0.4mg/cm 2, be preferably 0.1～0.3mg/cm 2When the amount of catalyst granules is lower than per unit area 0.0001mg/cm 2The time, the reactivity of fuel cell descends.When the amount of metal catalyst particles greater than 0.4mg/cm 2The time, catalytic performance descends.
In the both sides of polyelectrolyte film, can make membrane electrode assembly by the electrode arranging and connect fuel cell.
The polyelectrolyte film that is used for membrane electrode assembly can comprise the polymer of any proton conductive.The polymer of suitable proton conductive is selected from: the perfluor based polyalcohol, benzimidazole-based polymer, the polyimides based polyalcohol, the polyetherimide amine based polymer, polyphenylene sulfide based polyalcohol, polysulfones based polyalcohol, the polyether sulfone based polyalcohol, the polyether-ketone based polyalcohol, polyether-ether-ketone based polyalcohol, and polyphenyl quinoxalinyl polymer.In one embodiment, the polymer of described proton conductive can include, but not limited to be selected from following polymer: poly-(perfluorinated sulfonic acid), poly-(perfluorocarboxylic acid), tetrafluoroethene and the copolymer that contains sulfonic fluroxene, the polyether-ketone sulfide of defluorinate, aryl ketones, poly-(2,2 '-(-phenylene)-5,5 '-bisbenzimidazole) and poly-(2, the 5-benzimidazole).Yet according to the present invention, the polymer of described proton conductive is not limited to these polymer.
The following examples illustrate in greater detail the present invention.Yet, should be appreciated that the present invention is not limited by these embodiment.
Embodiment 1
By mixing average diameter is that 30nm, average length are the carbon nano-tube (CNT) of 1000nm and gather (perfluorinated sulfonic acid) solution (by the Nafion of DuPont company production TMSolution), make the carbon nano-tube slurry.Then, make the electrode base material that has at the thick active carbon layer of the lip-deep 20 μ m of the thick charcoal cloth of 280 μ m.Be coated with the surface of the active carbon layer of described electrode base material with the carbon nano-tube slurry, dry then, thus form the nanometer carbon-coating.Then, by sputter per unit area 0.05mg/cm 2Platinum on the surface of the nanometer carbon-coating of described electrode base material, make electrode according to the fuel cell of first embodiment of the present invention.Subsequently, by the electrode arranging and connect fuel cell at Nafion TMThe side of poly-(perfluorinated sulfonic acid) film makes membrane electrode assembly.By arranging that dividing plate in the both sides of membrane electrode assembly, makes fuel cell.
Comparative Examples 1
According to as in embodiment 1 same method, make fuel cell, different is, by sputter per unit area 0.05mg/cm 2Platinum on the surface of the thick charcoal cloth of 280 μ m, the preparation fuel cell electrode.
Comparative Examples 2
According to as in embodiment 1 same method, make fuel cell, different is, by sputter per unit area 0.05mg/cm 2Platinum on the surface of the active carbon layer of electrode base material, described electrode base material comprises the thick active carbon layer of 20 μ m that is formed on the thick charcoal cloth of 280 μ m, makes the electrode of fuel cell.
Comparative Examples 3
By mixing the Nafion of 3g by carbon-supported platinum catalyst (its platinum content is 20wt%) and 1g TMPoly-(perfluorinated sulfonic acid) solution makes slurry.According to as in embodiment 1 same method, make fuel cell, different is, by be coated with the surface of the active carbon layer of electrode base material with described slurry, described electrode base material comprises the thick active carbon layer of 20 μ m that is formed on the thick charcoal cloth of 280 μ m, and the dry electrode base material that scribbles slurry, make the electrode of fuel cell.Here, the content that is included in the platinum catalyst in the described catalyst layer is per unit area 0.4mg/cm 2For the fuel cell according to embodiment 1 and Comparative Examples 1～3 preparation, the electric current of the catalyst of measuring voltage and Unit Weight (CPW) the results are shown among Fig. 6.
As shown in Figure 6, fuel cell according to embodiments of the invention 1 preparation provides good performance, be included in according to 1/8th of the catalyst in the fuel cell of Comparative Examples 3 preparations and only contain, and showing the fuel cell performance that is better than Comparative Examples 1 and 2, Comparative Examples 1 and 2 does not comprise the nanometer carbon-coating and does not have deposition catalyst thereon.The electrode of the fuel cell that proposes in first embodiment of the present invention has the high-specific surface area of catalyst, thereby advantage is arranged, and promptly just can improve fuel cell performance with a spot of catalyst.
Embodiment 2
By in the isopropyl alcohol of 100 weight portions, the average particulate diameter that mixes 30 weight portions is carbon and the 10 weight portion polytetrafluoroethylene of 100nm, makes the slurry that forms catalyst layer.With described slurry coating a slice carbon paper, dry then and heat treatment scribbles the carbon paper of described slurry, thereby forms polymer network on the surface of carbon granule.
Then, by disperseing 1 weight portion platinum in 100 weight portion butanols, make the platinum dispersion soln.Flood prepared catalyst electrode with described platinum dispersion soln, and dry, thereby fill the gap of described polymer network and make catalyst electrode according to second embodiment of the present invention with platinum grain.The content that is included in the catalyst in the catalyst layer of catalyst electrode is per unit area 0.05mg/cm 2
By connecting two catalyst electrodes that make as previously mentioned and poly-(perfluorinated sulfonic acid) electrolyte membrane, make membrane electrode assembly.Here, arrange the catalyst layer of catalyst electrode, make the both sides of its contact electrolyte membrane.The dividing plate that has runner is respectively adhered in the both sides of the membrane electrode assembly that makes in the above, thereby makes fuel cell.
Comparative Examples 4
By in 100 weight portion isopropyl alcohols, mix producing and comprise by Johnson Matthey company and the carbon supported platinum catalyst (Pt/C) of 10wt% platinum, making the slurry that forms catalyst layer of 40 weight portions with 10 weight portion polytetrafluoroethylene.With described slurry coating a slice carbon paper, dry then and heat treatment scribbles the carbon paper of described slurry, thereby forms catalyst electrode.The content that is included in the catalyst in the catalyst layer of described catalyst electrode is per unit area 0.05mg/cm 2
By connecting two catalyst electrodes that make as mentioned above and poly-(perfluorinated sulfonic acid) electrolyte membrane, make membrane electrode assembly.Here, arrange the catalyst layer of described catalyst electrode, make the both sides of its contact electrolyte membrane.
The dividing plate with runner is adhered in the both sides of Zhi Bei membrane electrode assembly in the above, thereby makes fuel cell.
As for fuel cell according to embodiment 2 and Comparative Examples 4 preparations, measuring voltage and current density, the result provides in Fig. 7.From the result, as can be seen, promptly use a spot of catalyst, comprise that the membrane electrode assembly of the electrode of the fuel cell for preparing according to second embodiment also has good reactivity.

Claims (20)

1. electrode that is used for fuel cell, described electrode comprises electrode base material and catalyst layer, described catalyst layer comprises:
Filler particles, this filler particles are formed on the surface of electrode base material;
Be positioned at the lip-deep polymer network of this filler particles, this polymer network limits a plurality of gaps; And catalyst granules, this catalyst granules is arranged at least some gaps of polymer network.
2. according to the electrode of claim 1, wherein said catalyst granules comprises and is selected from following catalyst: platinum; Ruthenium; Osmium; Platinum-ruthenium alloy; Platinum-osmium alloy; Platinum-palldium alloy; Platinum-M alloy; And combination, wherein M is selected from following transition metal: Ga, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, and combination.
3. according to the electrode of claim 1, the average diameter of wherein said catalyst granules is 1～1000nm.
4. according to the electrode of claim 1, wherein said catalyst layer comprises that quantity is per unit surface area 0.0001～0.4mg/cm 2Catalyst granules.
5. according to the electrode of claim 1, wherein said filler particles comprises the particle that is selected from inorganic particle.
6. according to the electrode of claim 5, wherein said inorganic particle is a carbon granule.
7. according to the electrode of claim 6, wherein said filler particles comprises and is selected from following carbon granule: graphite, nano-sized carbon, and combination.
8. according to the electrode of claim 5, wherein said filler particles comprises and is selected from following inorganic particle: aluminium oxide, silica, and combination.
9. according to the electrode of claim 1, wherein said polymer network comprises and is selected from following adhesive resin: fluorine-based adhesive resin, benzimidazolyl adhesive resin, the ketone group adhesive resin, the ester group adhesive resin, amide groups adhesive resin, and imide adhesive resin.
10. according to the electrode of claim 9, wherein said polymer network comprises and is selected from following material: poly-(perfluorinated sulfonic acid), poly-(perfluorocarboxylic acid), tetrafluoroethene and contain the copolymer of sulfonic fluroxene, the polyether-ketone sulfide of defluorinate, aryl ketones, poly-(2,2 '-(-phenylene)-5,5 '-bisbenzimidazole), poly-(2, the 5-benzimidazole), and combination.
11. a method for preparing the electrode of fuel cell comprises:
On electrode base material, form the polymer network that limits a plurality of gaps, way is to form mixture by mixing a plurality of filler particles and adhesive resin, form the electrode base material of coating with a side of this mixture coating electrode base material, the dry electrode base material that is coated with, and the electrode base material that heat treatment was coated with; And
Fill at least some gaps of described polymer network with catalyst granules, on electrode base material, to form catalyst layer.
12. method according to claim 11, wherein said polymer network comprises and is selected from following adhesive resin: fluorine-based adhesive resin, the benzimidazolyl adhesive resin, the ketone group adhesive resin, the ester group adhesive resin, the amide groups adhesive resin, imide adhesive resin, and combination.
13. method according to claim 12, wherein said polymer network comprises and is selected from following material: poly-(perfluorinated sulfonic acid), poly-(perfluorocarboxylic acid), tetrafluoroethene and contain the copolymer of sulfonic fluroxene, the polyether-ketone sulfide of defluorinate, aryl ketones, poly-(2,2 '-(-phenylene)-5,5 '-bisbenzimidazole), poly-(2, the 5-benzimidazole), and combination.
14. according to the method for claim 11, wherein said filler particles comprises the material that is selected from inorganic particle.
15. according to the method for claim 14, wherein said inorganic particle is a carbon granule.
16. according to the method for claim 15, wherein said filler particles comprises and is selected from following carbon granule: graphite, nano-sized carbon, and combination.
17. according to the method for claim 14, wherein said filler particles comprises and is selected from following inorganic particle: aluminium oxide, silica, and combination.
18. according to the method for claim 11, wherein said catalyst granules is selected from: platinum; Ruthenium; Osmium; Platinum-ruthenium alloy; Platinum-osmium alloy; Platinum-palldium alloy; Platinum-M alloy; And combination, wherein M is selected from following transition metal: Ga, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, and combination.
19. according to the method for claim 11, the amount of providing of wherein said catalyst granules is per unit surface area 0.0001～0.4mg/cm 2
20. according to the method for claim 11, the average diameter of wherein said catalyst granules is 1～1000nm.
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