CN100413132C - Proton conducter modified fuel cell catalyst using conductive ceramics as carrier and its preparation - Google Patents

Proton conducter modified fuel cell catalyst using conductive ceramics as carrier and its preparation Download PDF

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Publication number
CN100413132C
CN100413132C CNB2006100200060A CN200610020006A CN100413132C CN 100413132 C CN100413132 C CN 100413132C CN B2006100200060 A CNB2006100200060 A CN B2006100200060A CN 200610020006 A CN200610020006 A CN 200610020006A CN 100413132 C CN100413132 C CN 100413132C
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catalyst
proton
carrier
alcohol
conductivity ceramics
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CN1921194A (en
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木士春
尹诗斌
陈磊
潘牧
袁润章
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Wuhan University of Technology WUT
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a fuel battery catalyst which uses proton conductor to decorate conductive ceramic as carrier. Wherein, the carrier of catalyst is the conductive ceramic decorated by proton polymer; compared with traditional carbon carried catalyst, the invention has the advantages that (1) it has better conductive property and corrosion resistance; (2) the conductive ceramic has less surface porous and the expensive metal particle can be anchored on the surface of carrier, to improve the utilization of catalyst; (3) the proton polymer used as adhesive can improve the combine force between metal particle and conductive ceramic; (4) the proton polymer is proton conductor, and the composed catalyst has proton conductive function. The relative preparation comprises that preparing the conductive ceramic carrier decorated by proton polymer, then loading catalyst metal particles on its surface, whose average diameter is 2-5nm. And the catalyst can be prepared into fuel battery chip CCM, with better electric output property.

Description

With proton conductor modified conducting pottery is the fuel-cell catalyst and the preparation of carrier
Technical field
The present invention relates to a kind of catalyst, particularly be applied to the catalyst of fuel cell, the carrier that is characterized in catalyst is through proton superpolymer modified conductivity ceramics.The invention still further relates to this kind Preparation of catalysts method.
Background technology
Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cell is called for short PEMFC) is as a kind of novel energy source device, have plurality of advantages such as working temperature is low, pollution-free, specific power big, startup is rapid, more and more be subjected to people's attention, become the focus that countries in the world are competitively studied.Normally used catalyst is the alloy of precious metal platinum or platinum in fuel cell.But the platinum scarcity of resources costs an arm and a leg, and therefore needs to improve the utilance of platinum, reduces the consumption of platinum, to reach the purpose that reduces the fuel cell cost.People generally adopt carbon black as catalyst carrier at present, and this is because carbon black has higher specific surface area, and has good electrical conductivity and preferable pore structure, the Dispersion of Particles of the metal platinum that helps improving.Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences (CN1165092C) adopts the deadman as chloroplatinic acid such as ammonium chloride, potassium chloride, has made platinum grain and reach equally distributed Pt/C catalyst on the surface in the active carbon hole.Physical Chemistry Technology Inst., Chinese Academy of Sciences (CN1677729A) adopts colloid method at first to prepare PtO xColloid carries out the Pt/C catalyst that vapour phase reduction is prepared uniform particle diameter, high degree of dispersion then.University of Science ﹠ Technology, Beijing (CN1243390C) carries out preliminary treatment with the high alkalinity solution that contains the inferior stannic acid of weak reductant to carbon black support earlier, and the black carbon surface active site is evenly distributed; Join then that reduce deposition obtains the PtRu/C catalyst in chloroplatinic acid and the ruthenic chloride mixed solution.But the utilance of platinum can be very not high among Pt/C, the PtM/C of above method preparation, important reasons is the micropore that a large amount of platinum or platinum alloy particulate enter into carbon surface, because this part platinum or the platinum alloy that are buried can not contact with proton conductor, therefore be difficult to form more three-phase reaction interface, thereby reduced the utilance of platinum.In addition, because platinum or platinum alloy directly link to each other with carbon, in preparation membrane electrode process, proton exchange resins can not enter into the position between platinum or platinum alloy and the carbon.This has reduced the phase reaction district on the one hand, owing to lack cementation, the bond strength between platinum or platinum alloy and the carbon is not high on the other hand.In PEMFC,, thereby make the durability of carbon black be subjected to weakening in addition owing to the work under bad environment of catalyst.And the existence of platinum can quicken the aging of carbon, from and cause coming off of platinum, this also will reduce the durability of catalyst greatly.
Report is also arranged now with the act as a fuel catalyst carrier of battery of carbon nano-tube (CNT).CNT has carbonization structure, therefore has conductivity and chemical stability preferably; Simultaneously, tube-surface micropore development degree is low, and most of platinum grain can be exposed to tube-surface, has improved the utilance of platinum; CNT has the feature of tubular structure and one dimension extension, and the mechanical strength height can form inierpeneirating network structure in Catalytic Layer, and not only the intensity of Catalytic Layer improves, and conductive capability also is enhanced; In addition, it also has good thermal conductivity.But should see that also the CNT surface is inertia, lack active sites.Therefore influenced the even dispersion of metallic catalyst.Northern Transportation University (CN1414726A) utilization photocatalysis in-situ chemical reduction precipitation method has synthesized CNT and has carried the platinum electrode catalyst, but does not fundamentally solve the agglomeration traits of CNT.The method of Zhejiang University (CN1424150A) utilization carry out microwave radiation heating in the carbon nano tube surface load platinum-ruthenium alloy catalysts.But they have but destroyed the chemical stability of CNT to the surface treatment of CNT.Xiamen University (CN1559686A) is though solved the agglomeration traits of CNT to a certain extent, and they also exist same problem to the surface treatment of CNT.
If pottery has reasonable resist chemical performance usually, therefore as catalyst carrier, can have corrosion resistance preferably.But pottery is non-conductive usually, therefore can not make up the electron channel of catalyst layer as catalyst carrier with it.For this reason, the present invention adopts the conductivity ceramics cell catalyst carrier that acts as a fuel, and proton superpolymer modified in addition, and developing with proton conductor modified conducting pottery is the fuel-cell catalyst of carrier.Compare with background technology, the present invention has the following advantages: 1) possess the favorable conductive ability; 2) possesses excellent corrosion resistance; 3) the conductivity ceramics surface micropore is few, and the catalyst fine particle of noble metal can be anchored on carrier surface.4) proton superpolymer can improve adhesion between catalyst metals particulate and carrier conductive ceramic as binding agent, makes the durability of catalyst be improved; 5) proton superpolymer itself is exactly a proton conductor, and synthetic catalyst also has function of guiding protons.
At present, Shang Weiyou uses the act as a fuel relevant report of cell catalyst carrier of proton superpolymer modified conductivity ceramics.
Summary of the invention
The object of the invention provides a kind of catalyst that is applied to fuel cell, and a kind of this kind Preparation of catalysts method also is provided.
Fuel-cell catalyst of the present invention, catalyst are noble metal, and characteristics are that the carrier of noble metal catalyst is through proton superpolymer modified conductivity ceramics.
Conductivity ceramics carrier of the present invention is TiSi 2, TiB 2, TiC, SiC, PbTiO 3, Ti 3SiC 2, BaPbO 3, LaCrO 3, TiC/Si 3N 4Or TiAl/TiB 2, its particle diameter 10～200 nanometers.
Proton superpolymer of the present invention be in perfluorinated sulfonic resin, SPSF resinoid, sulfonated polyphenyl sulfide resin (SPPS), sulfonated polyphenyl and imidazoles, sulfonation polyphosphazene, sulfonated polyimide resin (SPI), sulfonated polystyrene ion exchange resin and the sulfonated polyether-ether-ketone resin (S-PEEK) any.
Catalyst noble metal of the present invention is precious metal alloys or precious metal simple substance:
Precious metal alloys are M xN yOr M xN yO zWherein M, N, O are respectively the arbitrary metallic element among Pt, Ru, Pd, Rh, Ir, Os, Fe, Cr, Ni, Co, Mn, Cu, Ti, Sn, V, Ga and the Mo, M, N, O three are different, but has a kind of precious metals pt that is at least, x, y and z are respectively the natural number in 0～100, and x+y=100 or x+y+z=100;
Precious metal simple substance is any one among Pt, Ru, Pd, Rh, Ir and the Os.
Preparation of catalysts method of the present invention is the first proton superpolymer modified conductivity ceramics carrier of preparation, and then on carrier the supported precious metal catalyst particulate, concrete preparation process is as follows:
Step 1, with the conductivity ceramics microparticulate in alcohol solution, the proton superpolymer solution that adds mass concentration 1%～10% then, the mass ratio of conductivity ceramics and proton superpolymer is 1000: 1～2: 1, fully stirs, and makes the dispersion liquid of high polymer modification conductivity ceramics;
Step 2, add the presoma salting liquid of catalyst in the dispersion liquid that step 1 makes, stirred 20～60 minutes, pH value of solution in the course of reaction=8～13 90～100 ℃ of reflux 10～50 minutes, after filtration, drying, make catalyst.
Catalyst precursor salt of the present invention is H 2PtCl 6, RuCl 3, PdCl 2, RhCl 3, IrCl 3, OsCl 3, Fe (NO 3) 3, Cr (NO 3) 3, NiCl 2, Co (NO 3) 2, MnCl 2, CuCl 2, TiCl 3, SnCl 2, VCl 4, Ga (NO 3) 3Or MoCl 5
Alcohol is 0.5～100: 1 with the mass ratio of water in the described alcohol solution, and alcohol is any in methyl alcohol, ethanol, propyl alcohol, ethylene glycol and the isopropyl alcohol.
The eelctro-catalyst of preparation is assembled into monocell, carries out electric performance test:
1, the preparation of fuel cell acp chip CCM (catalyst coated membrane): the eelctro-catalyst of preparation is added in the perfluor sulfoacid resin solution of deionized water and mass concentration 5%, fully stir the furnishing pasty state.Evenly be coated on the Nafion of DU PONT company then @Series membranes (NRE212 or NRE211 etc.) both sides, oven dry makes CCM respectively.
2, monocell assembling and test: the carbon paper that adopts the polytetrafluoroethylene hydrophobic treatment is as gas diffusion layers, wherein the polytetrafluoroethylene mass content 20%～30%, and be compounded with the microporous layers that polytetrafluoroethylene and conductive carbon black particulate are formed in the one side, prepare this composite microporous layer and calcined 20 minutes down through 350 ℃, it mainly acts on is to optimize water and gas passage; Collector plate is a graphite cake, has parallel slot in a side; End plate is gold-plated corrosion resistant plate.CCM, gas diffusion layers, collector plate, end plate and encapsulant are assembled into monocell.The monocell operating condition is:
(1) Proton Exchange Membrane Fuel Cells (PEMFC): H 2/ air, air back pressure are 0; Anode humidification, humidification degree are 0～100%; The monocell working temperature is 60～80 ℃, and the humidification temperature is 60～75 ℃.
(2) straight methanol fuel cell (DMFC): the concentration of anode methyl alcohol is 2 mol, and flow is 5 ml/min, and negative electrode is an air, and back pressure is 0.
Compare with background technology, catalyst of the present invention is a kind of multi-functional fuel-cell catalyst, has following advantage:
(1) adopting the stable conductivity ceramics of chemical property is catalyst carrier, can improve the resistance to corrosion of catalyst, thereby improves the useful life of catalyst.
(2) adopting the less conductivity ceramics particulate of surface micropore is catalyst carrier, thereby the catalyst noble metal can be anchored on the utilance that carrier surface improves catalyst metals.
(3) proton superpolymer can improve adhesion between catalyst metals particulate and conductivity ceramics carrier as binding agent, and the durability of catalyst is improved.
(4) proton superpolymer itself is exactly a proton conductor, and synthetic catalyst also has function of guiding protons.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
Get 116 milligrams TiB 2The conductivity ceramics particulate, particle diameter 10 nanometers～50 nanometers, purity is greater than 95%, join in the mixed solution of 20 milliliters absolute ethyl alcohol and water, the mass ratio of absolute ethyl alcohol and water is 1: 1, and ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 5 minutes, then it is joined in 240 milliliters pure water (mass ratio of absolute ethyl alcohol and water is 1: the 1) mixed liquor, in mixed solution, add the perfluor sulfoacid resin solution of 4 milliliters of mass concentrations 5% again, stirred 20 minutes, add the H of 4 grams per liters 2PtCl 640 milliliters, adjust pH=8 with NaOH, 100 ℃ of reflux 20 minutes, through clean, drying obtains Pt/TiB of the present invention 2Catalyst.The average grain diameter of Pt catalyst is 2 nanometers.
The preparation of fuel cell acp chip CCM: the catalyst of preparation is added in the perfluor sulfoacid resin solution of a certain amount of deionized water and mass concentration 5%, fully stir the furnishing pasty state.Evenly be coated on the Nafion of DU PONT company then @Series membranes NRE211 both sides, oven dry makes CCM.Pt carrying capacity in the Catalytic Layer of CCM yin, yang the two poles of the earth adds up to: 0.42 milligram/centimetre 2
Monocell assembling and test: the carbon paper that adopts the polytetrafluoroethylene hydrophobic treatment is as gas diffusion layers, wherein the polytetrafluoroethylene mass content 20%, and being compounded with the microporous layers that polytetrafluoroethylene and conductive carbon black particle form (through 350 ℃ of calcinings 20 minutes down) in the one side, it mainly acts on is to optimize water and gas passage; Collector plate is a graphite cake, has parallel slot in a side; End plate is gold-plated corrosion resistant plate.CCM, gas diffusion layers, collector plate, end plate and encapsulant are assembled into monocell.The monocell operating condition is: H 2/ air, air back pressure are 0; Anode 100% humidification; The monocell working temperature is 70 ℃, and the humidification temperature is 70 ℃.Test result shows that the electricity output of monocell reaches 0.794 volt/cm 2The @300 milliampere/centimetre 2
Embodiment 2
Get 116 milligrams TiC conductivity ceramics particulate, particle diameter 50～100 nanometers, purity is greater than 92%, join in the mixed solution of 20 milliliters isopropyl alcohol and water, the mass ratio of isopropyl alcohol and water is 1: 1, ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 10 minutes, then it is joined in the mixed liquor of 240 milliliters of isopropyl alcohols and water, the mass ratio of isopropyl alcohol and water is 1: 1, the sulfonated polyphenyl sulfide resin solution that in mixed solution, adds 4 milliliters of mass concentrations 5% again, stirred 60 minutes, and added the H of 4 grams per liters 2PtCl 640 milliliters, adjust pH=10 with NaOH, 100 ℃ of reflux 10 minutes, through clean, drying obtains Pt/TiC catalyst of the present invention.The average grain diameter of Pt catalyst is 3 nanometers, and the preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1, adopts the catalyst of present embodiment preparation.Test result shows that the electricity output of monocell reaches 0.764 volt/cm 2The @300 milliampere/centimetre 2
Embodiment 3
Get 116 milligrams BaPbO 3The conductivity ceramics particulate, particle diameter 100～120 nanometers, purity is greater than 90%, joins in 20 milliliters the mixed solution of first alcohol and water, and the mass ratio of first alcohol and water is 100: 1, ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 6 minutes, then it is joined in the mixed liquor of 240 ml methanol and water, the mass ratio of first alcohol and water is 100: 1, adds the sulfonated polyimide resin solution of 4 milliliters of mass concentrations 5% again in mixed solution, stirred 30 minutes, and added the H of 4 grams per liters 2PtCl 640 milliliters, adjust pH=9 with NaOH, 100 ℃ of reflux 25 minutes, through clean, drying obtains Pt/BaPbO of the present invention 3Catalyst.The average grain diameter of Pt catalyst is 4.5 nanometers, and the preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1, adopts the catalyst of present embodiment preparation.Test result shows that the electricity output of monocell reaches 0.778 volt/cm 2The @300 milliampere/centimetre 2
Embodiment 4
Get 116 milligrams TiAl/TiB 2The conductivity ceramics particulate, particle diameter 120～150 nanometers, purity is greater than 92%, join in the mixed solution of 20 milliliters absolute ethyl alcohol and water, the mass ratio of absolute ethyl alcohol and water is 1: 1, ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 5 minutes, then it is joined in the mixed liquor of 240 milliliters of absolute ethyl alcohols and water, the mass ratio of absolute ethyl alcohol and water is 1: 1, the sulfonated polyether-ether-ketone resin solution that in mixed solution, adds 4 milliliters of mass concentrations 5% again, stirred 40 minutes, and added the H of 40 milliliter of 4 grams per liter 2PtCl 6Solution, the RuCl of 40 milliliter of 4 grams per liter 3Solution is adjusted pH=9 with NaOH, 100 ℃ of reflux 20 minutes, through clean, drying obtains Pt of the present invention 50Ru 50/ TiAl-TiB 2Catalyst.The average grain diameter of metal particle is 4 nanometers.
The preparation of fuel cell acp chip CCM: the eelctro-catalyst of preparation is added in deionized water and the perfluor sulfoacid resin solution, fully stir the furnishing pasty state.Evenly be coated on the Nafion of DU PONT company then @Series membranes NRE211 both sides, oven dry makes CCM.Anode uses the homemade catalyst of the present invention, and the Pt carrying capacity is 1 milligram/centimetre 2, negative electrode uses the Pt/C catalyst of JM company, and the Pt carrying capacity is 1 milligram/centimetre 2
Monocell assembling and test: the carbon paper that adopts the polytetrafluoroethylene hydrophobic treatment is as gas diffusion layers, wherein the polytetrafluoroethylene mass content 30%, and be compounded with the microporous layers that polytetrafluoroethylene and conductive carbon black particle are formed in the one side, (calcining 20 minutes down) through 350 ℃, it mainly acts on is to optimize water and gas passage; Collector plate is a graphite cake, has parallel slot in a side; End plate is gold-plated corrosion resistant plate.CCM, gas diffusion layers, collector plate, end plate and encapsulant are assembled into monocell.The monocell operating condition is: the concentration of anode methyl alcohol is 2 mol, and flow is 5 ml/min, and negative electrode is an air, and back pressure is 0.Test result shows, the electricity output of monocell reaches 245 milliwatts/centimetre 2@400 milliampere/centimetres 2.
Embodiment 5
Get 116 milligrams conductivity ceramics carrier TiC/Si 3N 4Particle diameter 150～200 nanometers, purity is greater than 85%, joins in the mixed solution of 20 milliliters absolute ethyl alcohol and water, and the mass ratio of absolute ethyl alcohol and water is 1: 1, ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 8 minutes, then it is joined in the mixed liquor of 240 milliliters of absolute ethyl alcohols and water, the mass ratio of absolute ethyl alcohol and water is 1: 1, adds the perfluor sulfoacid resin solution of 4 milliliters of mass concentrations 5% again in mixed solution, stirred 20 minutes, and added the H of 40 milliliter of 4 grams per liter 2PtCl 6Solution, the RuCl of 20 milliliter of 4 grams per liter 3Solution, the SnCl of 20 milliliter of 4 grams per liter 3Solution is adjusted pH=10 with NaOH, 100 ℃ of reflux 50 minutes, through clean, drying obtains Pt of the present invention 50Ru 25Sn 25/ TiC/Si 3N 4Catalyst.The average grain diameter of metallic catalyst is 3.5 nanometers, and the preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 4, adopts the catalyst of present embodiment preparation.Test result shows, the electricity output of monocell reach 266 milliwatts/centimetre 2The @400 milliampere/centimetre 2

Claims (3)

1. fuel-cell catalyst, catalyst is a noble metal, it is characterized in that, and the carrier of noble metal catalyst is proton superpolymer modified conductivity ceramics, and wherein, described conductivity ceramics is TiB 2, TiC, BaPbO 3, TiC/Si 3N 4Or T 1Al/TiB 2, particle diameter is 10～200 nanometers, described proton superpolymer be in perfluorinated sulfonic resin, sulfonated polyphenyl sulfide resin, sulfonated polyimide resin and the sulfonated polyether-ether-ketone resin any.
2. fuel-cell catalyst according to claim 1 is characterized in that, described catalyst noble metal is precious metal alloys or precious metal simple substance:
Precious metal alloys are M xN yOr M xN yO zWherein M, N, O are respectively the arbitrary metallic element among Pt, Ru, Pd, Rh, Ir, Os, Fe, Cr, Ni, Co, Mn, Cu, Ti, Sn, V, Ga and the Mo, M, N, O three are different, but has a kind of precious metals pt that is at least, x, y and z are respectively the natural number in 0～100, and x+y=100 or x+y+z=100;
Precious metal simple substance is any one among Pt, Ru, Pd, Rh, Ir and the Os.
3. the preparation method of the described fuel cell electro-catalyst of claim 1 is characterized in that, preparation process is
Step 1, with the conductivity ceramics microparticulate in alcohol solution, the proton superpolymer solution that adds mass concentration 1%～10% then, the mass ratio of conductivity ceramics and proton superpolymer is 1000: 1～2: 1, fully stirs, and makes the dispersion liquid of high polymer modification conductivity ceramics;
Step 2, add the presoma salting liquid of catalyst in the dispersion liquid that step 1 makes, stirred 20～60 minutes, pH value of solution in the course of reaction=8～13 90～100 ℃ of reflux 10～50 minutes, after filtration, drying, make catalyst;
Alcohol is 0.5～100: 1 with the mass ratio of water in the wherein said alcohol solution, and alcohol is any in methyl alcohol, ethanol, propyl alcohol, ethylene glycol and the isopropyl alcohol.
CNB2006100200060A 2006-08-17 2006-08-17 Proton conducter modified fuel cell catalyst using conductive ceramics as carrier and its preparation Expired - Fee Related CN100413132C (en)

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CN102728397A (en) * 2012-06-28 2012-10-17 山西大学 Preparation method for silicon carbide loaded metal nanoparticle catalyst
CN108043437B (en) * 2017-11-09 2023-09-22 国家电网公司 Preparation method of hollow SiC carrier type Ir-Ru catalyst

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1425499A (en) * 2001-12-11 2003-06-25 中国科学院大连化学物理研究所 Solid supported noble metal catalyst and its preparing method
CN1464580A (en) * 2002-06-19 2003-12-31 中国科学院大连化学物理研究所 Process for preparing self-humidifying composite proton exchange film for fuel cell
JP2005108551A (en) * 2003-09-29 2005-04-21 Tomoegawa Paper Co Ltd Catalyst film for solid polymer fuel cells, its manufacturing method and fuel cell using the same
CN1684292A (en) * 2005-02-21 2005-10-19 武汉理工大学 Method for preparing electric catalyst using one dimension nano carbon as carrier
US20050245389A1 (en) * 2001-03-24 2005-11-03 Patrick Bachinger Production of a securely adhering, hydrophobic catalyst layer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050245389A1 (en) * 2001-03-24 2005-11-03 Patrick Bachinger Production of a securely adhering, hydrophobic catalyst layer
CN1425499A (en) * 2001-12-11 2003-06-25 中国科学院大连化学物理研究所 Solid supported noble metal catalyst and its preparing method
CN1464580A (en) * 2002-06-19 2003-12-31 中国科学院大连化学物理研究所 Process for preparing self-humidifying composite proton exchange film for fuel cell
JP2005108551A (en) * 2003-09-29 2005-04-21 Tomoegawa Paper Co Ltd Catalyst film for solid polymer fuel cells, its manufacturing method and fuel cell using the same
CN1684292A (en) * 2005-02-21 2005-10-19 武汉理工大学 Method for preparing electric catalyst using one dimension nano carbon as carrier

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