CN1128019C - Process for preparing catalyst of fuel battery with proton exchange membrane - Google Patents
Process for preparing catalyst of fuel battery with proton exchange membrane Download PDFInfo
- Publication number
- CN1128019C CN1128019C CN01127116A CN01127116A CN1128019C CN 1128019 C CN1128019 C CN 1128019C CN 01127116 A CN01127116 A CN 01127116A CN 01127116 A CN01127116 A CN 01127116A CN 1128019 C CN1128019 C CN 1128019C
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- CN
- China
- Prior art keywords
- catalyst
- component
- proton exchange
- preparation
- sodium
- Prior art date
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- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 239000000446 fuel Substances 0.000 title claims abstract description 15
- 239000012528 membrane Substances 0.000 title abstract description 5
- 238000004519 manufacturing process Methods 0.000 title 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 4
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 3
- 239000000725 suspension Substances 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- 229920006324 polyoxymethylene Polymers 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 claims description 2
- 229940075931 sodium dithionate Drugs 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 10
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a method for preparing catalysts of proton exchange membrane fuel batteries, which comprises the steps that a catalyst precursor is first injected into a carbon powder suspension carrier, alkali is added to adjust the pH value to 4.0 to 9.0, and then, a component A is obtained through vacuum drying at low temperature; a solid reducing agent is added into the component A, the component A and the solid reducing agent are fully ground until a solid phase reaction is carried out on metal salt and the reducing agent completely, so metal salt particles generated by reduction are absorbed on a carbon carrier to obtain a component B; after being washed by alkali, acid and water, the component B is dried, and then, a powder catalyst carried by carbon powder is obtained.
Description
One, technical field
The present invention is a kind of proton exchange fuel cell catalyst, belongs to the technical field that catalyst is made.
Two, background technology
Fuel cell becomes following best " clean energy resource " owing to have advantages such as energy conversion efficiency height, environmental pollution are little, and many national government are paid much attention to its research.Particularly Proton Exchange Membrane Fuel Cells because it can be used as the electrical source of power and the portable removable power supply of electric vehicle, and is subjected to extensive concern in recent years.The research work of Proton Exchange Membrane Fuel Cells concentrates on the research of catalyst at present, and be the most effective catalyst of Proton Exchange Membrane Fuel Cells with the multiple catalyzing system of Pt or other metal of Pt+, but, because the price of these metals is extremely expensive, and resource-constrained, thus cause battery to cost an arm and a leg, be difficult to carry out commercialization, therefore, people wish to improve as much as possible the activity of metallic catalyst and the cost that utilization rate reduces catalyst.
At present, people mainly concentrate on the research of catalyst: how on traditional preparation method basis,, further optimize the performance of catalyst by changing the condition of work of battery, and to the research of method for preparing catalyst seldom.But because traditional preparation method, as: liquid phase chemical reduction, electrochemical deposition, high temperature vapour deposition or the like, all exist the factor that some are unfavorable for improving catalyst performance, such as, exist fierce Brownian movement in the liquid-phase system; Particle aggregation under the hot conditions or the like, these factors often cause the catalyst particle diameter bigger, and agglomeration takes place particle easily simultaneously, thereby has reduced the catalytic performance of catalyst.And by the condition of work of change battery and the preparation method of electrode, can not fundamentally improve the performance of catalyst of fuel batter with proton exchange film, therefore seek more appropriate catalyst preparation method, become the task of top priority in the present fuel cell studies work.
Three, summary of the invention
It is simple that purpose of the present invention just provides a kind of technology, and the catalyst particle size of preparation is little, utilization rate height, the preparation method of the catalyst of fuel batter with proton exchange film that activity is high.
Preparation solid yardage method of the present invention is:
1. injecting catalyst presoma in carbon dust suspension carrier at first, and adding alkali, to regulate the pH value be 4.0～9.0, vacuum drying obtains component A at low temperatures then;
2. in component A, add solid reductant,, up to slaine and reducing agent solid phase reaction takes place fully, thereby the slaine particulate that restores is adsorbed on the carbon carrier, obtain component B through fully grinding;
3. with component B drying after alkali cleaning, pickling, washing, promptly make the fine catalyst of carbon dust load.
Catalyst precursor is H
2PtCl
6Or K
2PtCl
6Or the weak solution of the ruthenium of platiniferous, osmium, iridium, above total metal content is 5～35% of a carbon dust amount, wherein the content of platinum accounts for more than 20% of above total metal content.
Solid reductant is one or more in polyformaldehyde, sodium formate, sodium borohydride, sodium sulfite, sodium thiosulfate, the sodium dithionate.
With component B drying after alkali cleaning, pickling, washing is to carry out in air or argon gas or hydrogen or nitrogen or in the atmosphere of oxygen.
The present invention has following advantage:
Theoretically, the particle diameter of catalyst is more little, and then the specific area of catalyst is big more, and the utilization rate of catalyst is just high more; Simultaneously, when activity of such catalysts just high more.And the catalyst that the present invention synthesizes is found through projection Electronic Speculum (TEM) and X-diffraction (XRD) analysis: the diameter of catalyst particle is little of 2-4nm, and system amorphous substance content is higher simultaneously; And the catalyst particle diameter that traditional liquid phase reactor obtains is approximately 10-12nm, and amorphous substance content is relative also lower in the system simultaneously.Electrochemical research methods such as utilization cyclic voltammetry have been studied the catalytic oxidation of catalyst to methyl alcohol, and experimental result is also found: the catalyst that utilizes solid phase reaction to make shows more excellent electrocatalysis characteristic.
Four, the specific embodiment
Example one: take by weighing the Vulcan XC-72R activated carbon powder of 40mg Cabot company, add 1.3ml0.0386mol/L H
2PtCL
6Solution, and add 0.9974mol/L NaOH solution 3.2ml, in agate mortar, mix, ground 10 minutes.Then, the gained mixture is placed vacuum drying chamber, in 50 ℃ of vacuum drying 10-12 hours, till system moisture removes fully.
Be cooled to room temperature under vacuum protection, constantly gradation adds polyformaldehyde on a small quantity, grinds approximately more than 4 hours, makes slaine and reducing agent complete reaction.
With small amount of thermal dilute NaOH solution washing said mixture, remove unreacted polyformaldehyde, unreacted a small amount of salt is reduced fully.Pickling again, washing repeatedly with the liquor argenti nitratis ophthalmicus check, does not have chlorion in eluate repeatedly.
90 ℃ of dryings promptly make the Pt/C catalyst under air conditions, and wherein the size of Pt particle is 2-4nm.
Experiment two: take by weighing the Vulcan XC-72R activated carbon powder of 40mgCabot company, add 1.5ml0.0386mol/L H
2PtCl
6With 0.6ml 0.09635mol/L RuCl
3Solution adds 0.9974mol/L NaOH solution, mixes in agate mortar, grinds 10 minutes.The gained mixture is placed vacuum drying chamber, in 50 ℃ of vacuum drying 10-12 hours, till system moisture removes fully.
Be cooled to room temperature under vacuum protection, constantly gradation adds polyformaldehyde on a small quantity, grinds 4-5 hour, makes slaine and reducing agent complete reaction.
With small amount of thermal dilute NaOH solution washing said mixture, remove unreacted polyformaldehyde, unreacted a small amount of salt is reduced fully.Pickling again, washing repeatedly with the liquor argenti nitratis ophthalmicus check, does not have chlorion in eluate repeatedly.
90 ℃ of dryings are promptly made the Pt-Ru/c catalyst under air conditions, and its catalyst particle size is about 2-4nm.
Claims (4)
1. the preparation method of a catalyst of fuel batter with proton exchange film is characterized in that the method for preparing is:
1. injecting catalyst presoma in carbon dust suspension carrier at first, and adding alkali, to regulate the pH value be 4.0～9.0, vacuum drying obtains component A at low temperatures then;
2. in component A, add solid reductant,, up to slaine and reducing agent solid phase reaction takes place fully, thereby the slaine particulate that restores is adsorbed on the carbon carrier, obtain component B through fully grinding;
3. with component B drying after alkali cleaning, pickling, hand washing, promptly make the fine catalyst of carbon dust load.
2. according to the preparation method of claim 1 described catalyst of fuel batter with proton exchange film, it is characterized in that catalyst precursor is H
2PtCl
6Or K
2PtCl
6Or the weak solution of the ruthenium of platiniferous, osmium, iridium, above total metal content is 5～35% of a carbon dust amount, wherein the content of platinum accounts for more than 20% of above total metal content.
3. according to the preparation method of claim 1 described catalyst of fuel batter with proton exchange film, it is characterized in that solid reductant is one or more in polyformaldehyde, sodium formate, sodium borohydride, sodium sulfite, sodium thiosulfate, the sodium dithionate.
4. according to the preparation method of claim 1 described catalyst of fuel batter with proton exchange film, it is characterized in that be to carry out component B through drying after alkali cleaning, pickling, the hand washing in the atmosphere of air or argon gas or hydrogen or nitrogen or oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01127116A CN1128019C (en) | 2001-08-17 | 2001-08-17 | Process for preparing catalyst of fuel battery with proton exchange membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01127116A CN1128019C (en) | 2001-08-17 | 2001-08-17 | Process for preparing catalyst of fuel battery with proton exchange membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1346706A CN1346706A (en) | 2002-05-01 |
| CN1128019C true CN1128019C (en) | 2003-11-19 |
Family
ID=4667109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01127116A Expired - Fee Related CN1128019C (en) | 2001-08-17 | 2001-08-17 | Process for preparing catalyst of fuel battery with proton exchange membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1128019C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100531914C (en) * | 2006-08-09 | 2009-08-26 | 华南理工大学 | solid phase reduction preparation method for platinum, carbon catalyst of fuel cell |
| JP6608800B2 (en) * | 2016-12-09 | 2019-11-20 | トヨタ自動車株式会社 | Fuel cell electrode catalyst |
| CN110556547B (en) * | 2018-05-30 | 2023-01-13 | 中国科学院深圳先进技术研究院 | Noble metal nano cage catalyst and preparation method and application thereof |
-
2001
- 2001-08-17 CN CN01127116A patent/CN1128019C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1346706A (en) | 2002-05-01 |
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