CN1258828C - Process for preparing proton exchange film fuel cell multi component catalyst - Google Patents
Process for preparing proton exchange film fuel cell multi component catalyst Download PDFInfo
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- CN1258828C CN1258828C CNB2004100043041A CN200410004304A CN1258828C CN 1258828 C CN1258828 C CN 1258828C CN B2004100043041 A CNB2004100043041 A CN B2004100043041A CN 200410004304 A CN200410004304 A CN 200410004304A CN 1258828 C CN1258828 C CN 1258828C
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- proton exchange
- oxide
- exchange membrane
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- membrane fuel
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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
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Abstract
The present invention discloses a method for preparing polyatomic catalysts for proton exchange membrane fuel batteries by adopting a hydro-thermal method, which belongs to the technical field of preparing fuel battery material. The preparing method comprises the steps that carriers, one or two kinds of noble metal compounds, one or two kinds of rare earth metal oxide and deionized water are added into a closed vessel and react for 1 to 24 hours under the pressure of 0.3 to 4Mpa at the temperature of 110 to 300 DEG C in the inert atmosphere; after cooling, reduction agents are added; reduction reaction keeps 1 to 10 hours at the temperature of 100 to 200 DEG C, and then, polyatomic catalysts are obtained through washing, filtration and drying. The obtained catalysts have the characteristics of favorable crystallization, little agglomeration, high purity, narrow particle size distribution and controllable shape, and the particle size range is from 0.1 to scores of nanometers. The present invention can be used for preparing catalysts for proton exchange membrane fuel batteries to improve the CO poisoning resisting capability of the catalysts, enhance the output characteristic of batteries, reduce the consumption of noble metal and lower the cost of fuel batteries. The present invention makes the commercial application of proton exchange membrane fuel batteries become possible.
Description
Technical field
The invention belongs to fuel cell material technology of preparing scope, particularly utilize the preparation method of a kind of used in proton exchange membrane fuel cell multicomponent catalyst of hydro thermal method.
Background technology
At present, platinum (Pt), ruthenium noble metals such as (Ru) are as Proton Exchange Membrane Fuel Cells (PEMFC) electrode catalyst, and cost is higher, and scarcity of resources has limited the practicability speed of fuel cell greatly.In order to reduce noble metal dosage, improve the dispersiveness of noble metal, people are by various preparation methods, for contacting with carrier, metal particle provides more specific area as sol-gal process, common dipping, codeposition, colloid method etc., reduce the Pt use amount on the electrode unit are, improve the utilance of Pt.
Hydro thermal method is a kind of wet chemical method of finishing in closed container, compares with other wet chemical methods such as sol-gal process, co-impregnation, coprecipitations, has the advantage that does not need high temperature sintering can directly obtain crystalline powder.Use the Hydrothermal Preparation multicomponent catalyst, metallic is closely contacted with carrier in generative process, interaction strong between metal particle and carrier is fixed on Pt on the reduction reaction original position, prevents the Pt agglomeration of particles.The particle size scope of Hydrothermal Preparation is generally 0.1 micron to several microns, and some can tens nanometers, characteristics such as having advantages of good crystallization, reunite less, purity height, narrow particle size distribution and pattern are controlled.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of used in proton exchange membrane fuel cell multicomponent catalyst.This method is to use the supported carrier noble metal, mix with rare earth metal, pass through hydro thermal method, noble metal can closely be contacted with carrier in generative process with the rare earth metal particle, and by triangular interaction noble metal and rare earth metal are fixed on the reduction reaction original position equably and obtain multicomponent catalyst, it is characterized in that: described preparation process with Hydrothermal Preparation used in proton exchange membrane fuel cell multicomponent catalyst is:
1) with carrier, precious metal chemical complex and rare-earth oxide weight ratio in the noble metal total amount, (5～25): (10～60): the ratio of (10～30) adds in the closed container that loads 70～80% deionized waters, in inert atmosphere, at 110～300 ℃, pressure 0.3～4Mpa reaction down was cooled to room temperature after 1～24 hour;
2) adding is in the reducing agent of the weight ratio (2～20) of noble metal total amount, and under 100～200 ℃, reduction was handled 1～10 hour;
3) centrifugal, dry, obtain multicomponent catalyst.
Described carrier is a kind of in activated carbon, carbon nano-tube, graphite, carbon black or the molecular sieve.
Described precious metal chemical complex is a kind of in chloroplatinic acid, platinum oxide, platinum chloride, ruthenium-oxide, ruthenic chloride, palladium bichloride, palladium oxide, palladium nitrate, carbonate palladium, radium chloride or the rhodium oxide or 2 kinds.
Described rare-earth oxide is a kind of in samarium oxide, cerium oxide, yittrium oxide or the scandium oxide or 2 kinds.
Described reducing agent is any one in sodium thiosulfate, sodium dithionite, hydrazine hydrate, sodium formate or the formaldehyde.
Described inert gas is nitrogen or argon gas.
The invention has the beneficial effects as follows by hydro thermal method, noble metal can closely be contacted with carrier in generative process with the rare earth metal particle, noble metal and rare earth metal are fixed on the reduction reaction original position equably, prevent particle aggregation.When being used for the catalyst of Proton Exchange Membrane Fuel Cells, can improve the anti-CO poisoning capability of catalyst, improve the output characteristic of battery, reduce noble metal dosage, reduce the cost of fuel cell.Adopt the catalyst of this method preparation to have advantages of good crystallization, reunite less, the characteristics of purity height, narrow particle size distribution,
Concrete embodiment
The present invention is a kind of preparation method of used in proton exchange membrane fuel cell multicomponent catalyst.Carrier, precious metal chemical complex, rare-earth oxide and deionized water are joined in the closed container, pass through hydro thermal method, noble metal can closely be contacted with carrier in generative process with the rare earth metal particle, add after the reducing agent reduction handles, centrifugal, be drying to obtain multicomponent catalyst; Its preparation process is:
1) with carrier be a kind of in activated carbon, carbon nano-tube, graphite, carbon black or the molecular sieve: precious metal chemical complex is a kind of in chloroplatinic acid, platinum oxide, platinum chloride, ruthenium-oxide, ruthenic chloride, palladium bichloride, palladium oxide, palladium nitrate, carbonate palladium, radium chloride or the rhodium oxide or 2 kinds: rare-earth oxide is a kind of in samarium oxide, cerium oxide, yittrium oxide or the scandium oxide or 2 kinds, weight ratio (5～25) in the noble metal total amount: (10～60): the ratio of (10～30) joins in the closed container that loads 70～80% deionized waters, forms pre-composition;
2) in the inert atmosphere of nitrogen or argon gas, at 110～300 ℃, pressure 0.3～4Mpa reaction down was cooled to room temperature after 1～24 hour;
3) adding with a kind of in sodium thiosulfate, sodium dithionite, hydrazine hydrate, sodium formate or the formaldehyde then is 2～20 parts of reducing agents (weight ratio is in the noble metal total amount), handles 1～10 hour at 100～200 ℃;
4) slurries filtration, washing, the drying that obtains more than the general gets multicomponent catalyst.
Lifting instantiation is below further specified the present invention:
Example 1:
1) 20 parts of activated carbon, 30 parts of chloroplatinic acids, 30 parts of ruthenium trichlorides, 20 parts of cerium oxide are added in the closed container that loads 75% deionized water, form pre-composition;
2) this pre-composition is in nitrogen atmosphere, and 200 ℃, pressure 2.5Mpa reaction down was cooled to room temperature after 6 hours;
3) add 2 parts of sodium thiosulfate, handled 4 hours, platinum, ruthenium and cerium are fixed on the reduction reaction original position equably for 140 ℃;
4) with slurries filtration, washing, the drying of above formation, obtain the PtRuCe/C multicomponent catalyst.
Example 2:
1) 25 parts of carbon nano-tube, 50 parts of platinum chlorides, 10 parts of ruthenium-oxide, 15 parts of samarium oxides are added in the closed container that adds 80% deionized water, form pre-composition;
2) this pre-composition is in argon gas atmosphere, and 150 ℃, pressure 2Mpa reaction down was cooled to room temperature after 8 hours;
3) add 4 parts of sodium dithionites, handled 6 hours, platinum, ruthenium and samarium are fixed on the reduction reaction original position equably for 120 ℃;
4) with slurries filtration, washing, the drying of above formation, obtain the PtRuSm/C multicomponent catalyst.
Example 3:
1) 20 parts of activated carbon, 25 parts of platinum oxides, 25 parts of ruthenium-oxide, 30 parts of yittrium oxide are added in the closed container that adds 80% deionized water, form pre-composition;
2) this pre-composition is in nitrogen atmosphere, and 300 ℃, pressure 2Mpa reaction down was cooled to room temperature after 6 hours;
3) add 2 parts of sodium formates, handled 2 hours, platinum, ruthenium and yttrium are fixed on the reduction reaction original position equably for 200 ℃;
4) with slurries filtration, washing, the drying of above formation, obtain the PtRuY/C multicomponent catalyst.
Example 4:
1) 20 parts of activated carbon, 25 parts of palladium bichlorides, 15 parts of ruthenium trichlorides, 40 parts of scandium oxides are added in the closed container that adds 70% deionized water, form pre-composition;
2) this pre-composition is in argon gas atmosphere, and 110 ℃, pressure 3Mpa reaction down was cooled to room temperature after 10 hours;
3) add 6 parts of formaldehyde, handled 8 hours, palladium, ruthenium and scandium are fixed on the reduction reaction original position equably for 100 ℃;
4) with slurries filtration, washing, the drying of above formation, obtain the PdRuSc/C multicomponent catalyst.
Claims (6)
1. the preparation method of a used in proton exchange membrane fuel cell multicomponent catalyst, this method is to use the supported carrier noble metal, mix with rare earth metal, pass through hydro thermal method, noble metal can closely be contacted with carrier in generative process with the rare earth metal particle, and by triangular interaction noble metal and rare earth metal are fixed on the reduction reaction original position equably and obtain multicomponent catalyst, it is characterized in that: described preparation process with Hydrothermal Preparation used in proton exchange membrane fuel cell multicomponent catalyst is:
1) carrier, precious metal chemical complex and the rare-earth oxide ratio in the weight ratio 5～25: 10～60: 10～30 of noble metal total amount is added in the closed container of 70～80% deionized waters that are mounted with the closed container volume, in inert atmosphere, at 110～300 ℃, pressure 0.3～4Mpa reaction down was cooled to room temperature after 1～24 hour;
2) adding is in the reducing agent of the weight ratio 2～20 of noble metal total amount, and under 100～200 ℃, reduction was handled 1～10 hour;
3) centrifugal, dry, obtain multicomponent catalyst.
2. according to the preparation method of the described used in proton exchange membrane fuel cell multicomponent catalyst of claim 1, it is characterized in that: described carrier is a kind of in activated carbon, carbon nano-tube, graphite, carbon black or the molecular sieve.
3. according to the preparation method of the described used in proton exchange membrane fuel cell multicomponent catalyst of claim 1, it is characterized in that: described precious metal chemical complex is a kind of in chloroplatinic acid, platinum oxide, platinum chloride, ruthenium-oxide, ruthenic chloride, palladium bichloride, palladium oxide, palladium nitrate, carbonate palladium, radium chloride or the rhodium oxide or 2 kinds.
4. according to the preparation method of the described used in proton exchange membrane fuel cell multicomponent catalyst of claim 1, it is characterized in that: described rare-earth oxide is a kind of in samarium oxide, cerium oxide, yittrium oxide or the scandium oxide or 2 kinds.
5. according to the preparation method of the described used in proton exchange membrane fuel cell multicomponent catalyst of claim 1, it is characterized in that: described reducing agent is any one in sodium thiosulfate, sodium dithionite, hydrazine hydrate, sodium formate or the formaldehyde.
6. according to the preparation method of the described used in proton exchange membrane fuel cell multicomponent catalyst of claim 1, it is characterized in that: described inert gas is nitrogen or argon gas.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100043041A CN1258828C (en) | 2004-02-13 | 2004-02-13 | Process for preparing proton exchange film fuel cell multi component catalyst |
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| CNB2004100043041A CN1258828C (en) | 2004-02-13 | 2004-02-13 | Process for preparing proton exchange film fuel cell multi component catalyst |
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| CN1258828C true CN1258828C (en) | 2006-06-07 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100359044C (en) * | 2005-09-08 | 2008-01-02 | 陕西科技大学 | Hydrothermal Sm2O3 film preparing process |
| KR20100053672A (en) | 2007-08-27 | 2010-05-20 | 테크니온 리서치 엔드 디벨로프먼트 화운데이션 엘티디. | Ph gradients controlled by electrolysis, and their use in isoelectric focusing |
| US8864970B2 (en) | 2009-08-18 | 2014-10-21 | Technion Research & Development Foundation Limited | Methods and devices of separating molecular analytes |
| WO2011021196A2 (en) | 2009-08-18 | 2011-02-24 | Technion Research & Development Foundation Ltd. | Proton concentration topographies, methods and devices for producing the same |
| CN101714637B (en) * | 2009-11-19 | 2011-08-17 | 山西大学 | Fuel-cell anode catalyst and preparation method thereof |
| CN102836705B (en) * | 2011-06-24 | 2014-07-16 | 南京理工大学 | Compounding method for platinum-graphene structural carbon material combined electrode catalyst |
| CN103296288A (en) * | 2013-06-07 | 2013-09-11 | 苏州诺信创新能源有限公司 | Preparation method of catalyst electrode of microorganism fuel cell |
| CN110635142B (en) * | 2019-10-11 | 2021-08-31 | 燕山大学 | Platinum-rhodium-yttrium nanowire and preparation method and application thereof |
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