CN1909272A - Proton conductor modified fuel cell catalyst which uses conductive ceramics as carrying agent and preparation - Google Patents
Proton conductor modified fuel cell catalyst which uses conductive ceramics as carrying agent and preparation Download PDFInfo
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- CN1909272A CN1909272A CNA2006100200075A CN200610020007A CN1909272A CN 1909272 A CN1909272 A CN 1909272A CN A2006100200075 A CNA2006100200075 A CN A2006100200075A CN 200610020007 A CN200610020007 A CN 200610020007A CN 1909272 A CN1909272 A CN 1909272A
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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
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- 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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Abstract
The invention relates to a fuel battery catalyst which is decorated by proton conductor and uses conductive ceramic as carrier, wherein compared with carbon-black carrier catalyst, it has the advantages that: (1) it has better conductive property and anti-corrosion property; (2) the surface of conductive ceramic has less holes, therefore, the expensive metal catalyst particles can be anchored on the carrier to improve the utilization of catalyst; (3) the conductive proton polymer is used as adhesive to improve the adhesive force between the metal particle and the carrier conductive ceramic; (4) since the conductive proton polymer is conductor, the composed catalyst has conductive proton function. The invention is multifunctional fuel battery catalyst. And its preparation comprises: first, preparing the catalyst nanometer expensive metal rubber decorated by conductive proton; then depositing the rubber on the carrier; the average diameter of catalyst expensive metal is 2-5 nanometers; and using catalyst to produce fuel battery chip CCM, to form single battery, with better electric output property.
Description
Technical field
The present invention relates to a kind of fuel-cell catalyst, particularly have the fuel-cell catalyst of function of guiding protons.It is characterized in that the catalyst fine particle of noble metal is modified by proton superpolymer, the carrier of catalyst is a conductivity ceramics.The invention still further relates to this 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.Therefore need to improve the utilance of platinum, reduce 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 microparticulate 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 particulate equally distributed Pt/C catalyst on the surface early 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 particulate 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 the uniformity that has influenced metallic catalyst is disperseed.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 will can not make up the electron channel of catalyst layer with it as catalyst carrier.For this reason, the present invention adopts the conductivity ceramics cell catalyst carrier that acts as a fuel, and adopts proton superpolymer modified noble metal catalyst simultaneously, develops modified by proton conductor and is the fuel-cell catalyst of carrier with the conductivity ceramics.Catalyst of the present invention is compared with background technology and is had 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, modified by proton conductor and be the relevant report of the fuel-cell catalyst of carrier with the conductivity ceramics is not arranged as yet.
Summary of the invention
The object of the invention provides a kind of fuel-cell catalyst, particularly has function of guiding protons and is the fuel-cell catalyst of carrier with the conductivity ceramics.The present invention also provides a kind of this Preparation of catalysts method.
A kind of fuel-cell catalyst of the present invention, catalyst is a fine particle of noble metal, it is characterized in that, and carrier is a conductivity ceramics, and the catalyst fine particle of noble metal that is carried on the conductivity ceramics carrier is modified by proton superpolymer.
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.
Conductivity ceramics of the present invention is TiSi
2, TiB
2, TiC, TiO
2, SiC, PbTiO
3, Ti
3SiC
2, BaPbO
3, LaCrO
3, TiC/Si
3N
4Or TiAl/TiB
2, its particle diameter 10～200 nanometers.
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 that preparation supports it on conductivity ceramics carrier then with proton superpolymer modified nanoscale fine particle of noble metal colloid earlier, makes the catalyst with function of guiding protons.Concrete preparation method's step is:
Step 1, be that 1%～10% proton superpolymer solution adds in the alcohol-water mixture with mass concentration, after the stirring, the aqueous solution that adds the presoma salt of catalyst, wherein the mass ratio of noble metal and proton superpolymer is 1000～1: 10, keep solution PH=8～13 in the course of reaction, 90～100 ℃ of reflux 10～50 minutes are prepared and are led the polymer-modified catalyst noble metal nano colloid of proton;
Step 2, the conductivity ceramics particulate fully disperseed after, join in the prepared colloidal solution of step 1, continue to stir 1～2 hour, make catalyst with function of guiding protons.
The presoma of catalyst 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
The alcohol in the described alcohol-water mixture and the mass ratio of water are 0.5～100: 1, 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 deionized water and mass concentration 5% perfluor sulfoacid resin solution, fully stir the furnishing pasty state.Evenly be coated on the Nafion of DUPONT 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, (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:
(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 noble metal catalyst particulate 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
2Conductivity ceramics particulate, particle diameter 10 nanometers～50 nanometers, purity be greater than 95%, joins in the mixed liquor 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 5 minutes TiB
2The conductivity ceramics dispersion liquid.Get the Nafion of 4 milliliters of mass concentrations 5%
@Solution joins in the mixed liquor of 240 milliliters of absolute ethyl alcohols and water, and the mass ratio of absolute ethyl alcohol and water 1: 1 stirred after 10 minutes, adds the H of 40 milliliter of 4 grams per liter
2PtCl
6Solution continue to stir, and transfers the pH=8 of solution with NaOH, 80 ℃ of reflux, and solution is by light yellow blackening gradually, and finally becomes aterrimus, makes stable Pt colloid.Then with TiB
2The conductivity ceramics dispersant liquid drop is added in the made Pt colloid, continues to stir 2 hours, makes Nafion
@The 40%Pt/TiB that modifies
2Catalyst.Average grain diameter 2 nanometers of Pt wherein, and dispersed fine.
The preparation of fuel cell acp chip CCM: the catalyst of preparation is added deionized water and mass concentration 5% 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.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 be compounded with the microporous layers that polytetrafluoroethylene and conductive carbon black particulate 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: H
2/ air, air back pressure are 0, anode 100% humidification, and the monocell working temperature is 70 ℃, the humidification temperature is 70 ℃.Test result shows that the electricity output of monocell reaches 0.801 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 liquor of 20 milliliters isopropyl alcohol and water, the mass ratio of isopropyl alcohol and water is 1: 1, and ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 10 minutes, obtained TiC conductivity ceramics dispersion liquid.Sulfonated polyphenyl sulfide resin (SPPS) solution of getting 4 milliliters of mass content 5% joins in the mixed liquor of 240 milliliters of isopropyl alcohols and water, and the mass ratio of isopropyl alcohol and water is 1: 1, stirs after 5 minutes, adds the H of 40 milliliter of 4 grams per liter
2PtCl
6Solution continue to stir, and transfers the pH=10 of solution with NaOH, 100 ℃ of reflux, and solution is by light yellow blackening gradually, and finally becomes aterrimus, makes stable Pt colloid.Then TiC conductivity ceramics dispersant liquid drop is added in the made Pt glue, continues to stir 3 hours, make the 40%Pt/TiC catalyst that SPPS modifies.Average grain diameter 3 nanometers of Pt wherein, and dispersed fine.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1, adopt the catalyst of present embodiment preparation.Test result shows that the electricity output of monocell reaches 0.765 volt/cm
2The @300 milliampere/centimetre
2
Embodiment 3
Get 116 milligrams BaPbO
3Conductivity ceramics particulate, particle diameter 100～120 nanometers, purity be greater than 90%, joins in 20 milliliters the mixed liquor of first alcohol and water, and the mass ratio of first alcohol and water is 100: 1, and ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 6 minutes, obtained BaPbO
3The conductivity ceramics dispersion liquid.Sulfonated polyimide resin (SPI) solution of getting 4 milliliters of mass content 5% joins in the mixed liquor of 240 ml methanol and water, and the mass ratio of first alcohol and water is 100: 1, stirs after 6 minutes, adds the H of 40 milliliter of 4 grams per liter
2PtCl
6Solution continue to stir, and adjusts the pH=9 of solution with NaOH, 90 ℃ of reflux, and solution is by light yellow blackening gradually, and finally becomes aterrimus, makes stable Pt colloid.Then with BaPbO
3The conductivity ceramics dispersant liquid drop is added in the made Pt glue, continues to stir 3 hours, makes the 40%Pt/BaPbO that SPI modifies
3Catalyst.Average grain diameter 4 nanometers of Pt wherein, and dispersed fine.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1, adopt the catalyst of present embodiment preparation.Test result shows that the electricity output of monocell reaches 0.785 volt/cm
2The @300 milliampere/centimetre
2
Embodiment 4
Get 116 milligrams TiAl/TiB
2Conductivity ceramics particulate, particle diameter 120～150 nanometers, purity be greater than 92%, joins in the mixed liquor of 20 milliliters absolute ethyl alcohol and water, and the mass ratio of absolute ethyl alcohol and water is 1: 1, and ultrasonic (the ultrasonic cell pulverization machine of R-S150) disperseed 10 minutes, obtained TiAl/TiB
2The conductivity ceramics dispersion liquid.Sulfonated polyether-ether-ketone resin (S-PEEK) solution of getting 4 milliliters of mass content 5% joins in the mixed liquor of 240 milliliters of absolute ethyl alcohols and water, and the mass ratio of absolute ethyl alcohol and water is 1: 1, stirs after 8 minutes, adds the H of 40 milliliter of 4 grams per liter
2PtCl
6Solution, the RuCl of 40 milliliter of 4 grams per liter
3Solution continue to stir, and adjusts the pH=11 of solution with NaOH, 100 ℃ of reflux, and solution is by light yellow blackening gradually, and finally becomes aterrimus, makes stable PtRu colloid.Then with TiAl/TiB
2The conductivity ceramics dispersant liquid drop is added in the made PtRu glue, continues to stir the 40%Pt that made the S-PEEK modification in 2 hours
50Ru
50/ TiAl-TiB
2Catalyst.Metal particle average grain diameter 5 nanometers wherein, and dispersed fine.
The preparation of fuel cell acp chip CCM: the eelctro-catalyst of preparation is added deionized water and mass concentration 5% 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 PTFE and conductive carbon black particulate 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 that 2 mol, flow are: 5 ml/min, negative electrode are air, and back pressure is 0.Test result shows, the electricity output of monocell reach 245 milliwatts/centimetre
2The @400 milliampere/centimetre
2
Embodiment 5
Get 116 milligrams TiC/Si
3N
4Conductivity ceramics particulate, particle diameter 150～200 nanometers, purity be greater than 85%, joins in the mixed liquor of 20 milliliters absolute ethyl alcohol and water, and 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, obtained TiC/Si
3N
4The conductivity ceramics dispersion liquid.Get the Nafion of 4 milliliters of mass content 5%
@Solution joins in the mixed liquor of 240 milliliters of absolute ethyl alcohols and water, and the mass ratio of absolute ethyl alcohol and water is 1: 1, stirs after 10 minutes, adds 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 continue to stir, and transfers the pH=9 of solution with NaOH, 100 ℃ of reflux, and solution is by light yellow blackening gradually, and finally becomes aterrimus, makes stable colloid.Then with TiC/Si
3N
4The conductivity ceramics dispersant liquid drop is added in the made colloid, continues to stir 2 hours, makes Nafion
@The 40%Pt that modifies
50Ru
25Sn
25/ TiC/Si
3N
4Catalyst.Metal particle average grain diameter 4.5 nanometers wherein, and dispersed fine.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 4, adopt the catalyst of present embodiment preparation.Test result shows, the electricity output of monocell reach 276 milliwatts/centimetre
2The @400 milliampere/centimetre
2
Claims (5)
1, a kind of fuel-cell catalyst, catalyst is a fine particle of noble metal, it is characterized in that, and carrier is a conductivity ceramics, and the catalyst fine particle of noble metal that is carried on the conductivity ceramics carrier is modified by proton superpolymer.
2, fuel-cell catalyst according to claim 1, it is characterized in that, described proton superpolymer be in perfluorinated sulfonic resin, SPSF resinoid, sulfonated polyphenyl sulfide resin, sulfonated polyphenyl and imidazoles, sulfonation polyphosphazene, sulfonated polyimide resin, sulfonated polystyrene ion exchange resin and the sulfonated polyether-ether-ketone resin any.
3, fuel-cell catalyst according to claim 1 is characterized in that, described conductivity ceramics is TiSi
2, TiB
2, TiC, TiO
2, SiC, PbTiO
3, Ti
3SiC
2, BaPbO
3, LaCrO
3, TiC/Si
3N
4Or TiAl/TiB
2, particle diameter is 10～200 nanometers.
4, 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.
5, the preparation method of the described fuel cell electro-catalyst of claim 1 is characterized in that preparation process is:
Step 1, be that 1%～10% proton superpolymer solution adds in the alcohol-water mixture with mass concentration, after the stirring, the aqueous solution that adds the presoma salt of catalyst, wherein the mass ratio of noble metal and proton superpolymer is 1000～1: 10, pH value of solution in the course of reaction=8～13,90～100 ℃ of reflux 10～50 minutes are prepared and are led the polymer-modified catalyst noble metal nano colloid of proton;
Step 2, the conductivity ceramics particulate fully disperseed after, join in the prepared colloidal solution of step 1, continue to stir 1～2 hour, after filtration, drying makes catalyst of the present invention;
The alcohol in the wherein said alcohol-water mixture and the mass ratio of water are 0.5～100: 1, and alcohol is any in methyl alcohol, ethanol, propyl alcohol, ethylene glycol and the isopropyl alcohol.
Priority Applications (1)
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|---|---|---|---|
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|---|---|---|---|
| CNB2006100200075A CN100428545C (en) | 2006-08-17 | 2006-08-17 | Proton conductor modified fuel cell catalyst which uses conductive ceramics as carrying agent and preparation |
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| CN100428545C CN100428545C (en) | 2008-10-22 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101442128B (en) * | 2007-11-21 | 2011-06-29 | 中国科学院大连化学物理研究所 | Diffusion layer for integral regeneratable fuel cell and preparation thereof |
| CN102728397A (en) * | 2012-06-28 | 2012-10-17 | 山西大学 | Preparation method for silicon carbide loaded metal nanoparticle catalyst |
| CN103263918A (en) * | 2013-04-25 | 2013-08-28 | 浙江大学 | Preparation method of Pt-PbTiO3 nano-catalyst for CO catalytic oxidation |
| CN111167496A (en) * | 2020-01-09 | 2020-05-19 | 南开大学 | Visible light catalytic material and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05144444A (en) * | 1991-11-25 | 1993-06-11 | Toshiba Corp | Fuel cell and electrode manufacturing method |
| JP4390558B2 (en) * | 2001-09-10 | 2009-12-24 | 旭化成イーマテリアルズ株式会社 | Electrocatalyst layer for fuel cells |
| CN1226086C (en) * | 2001-12-11 | 2005-11-09 | 中国科学院大连化学物理研究所 | Solid supported noble metal catalyst and its preparing method |
| KR100599814B1 (en) * | 2004-10-28 | 2006-07-12 | 삼성에스디아이 주식회사 | Catalyst for fuel cell, method of preparation same, and fuel cell system comprising same |
-
2006
- 2006-08-17 CN CNB2006100200075A patent/CN100428545C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101442128B (en) * | 2007-11-21 | 2011-06-29 | 中国科学院大连化学物理研究所 | Diffusion layer for integral regeneratable fuel cell and preparation thereof |
| CN102728397A (en) * | 2012-06-28 | 2012-10-17 | 山西大学 | Preparation method for silicon carbide loaded metal nanoparticle catalyst |
| CN103263918A (en) * | 2013-04-25 | 2013-08-28 | 浙江大学 | Preparation method of Pt-PbTiO3 nano-catalyst for CO catalytic oxidation |
| CN103263918B (en) * | 2013-04-25 | 2015-04-15 | 浙江大学 | Preparation method of Pt-PbTiO3 nano-catalyst for CO catalytic oxidation |
| CN111167496A (en) * | 2020-01-09 | 2020-05-19 | 南开大学 | Visible light catalytic material and preparation method and application thereof |
| CN111167496B (en) * | 2020-01-09 | 2020-12-25 | 南开大学 | Visible light catalytic material and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN100428545C (en) | 2008-10-22 |
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