CN1917260A - Fuel cell catalyst with function of guiding protons, and prepartion method - Google Patents
Fuel cell catalyst with function of guiding protons, and prepartion method Download PDFInfo
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- CN1917260A CN1917260A CNA2006100200041A CN200610020004A CN1917260A CN 1917260 A CN1917260 A CN 1917260A CN A2006100200041 A CNA2006100200041 A CN A2006100200041A CN 200610020004 A CN200610020004 A CN 200610020004A CN 1917260 A CN1917260 A CN 1917260A
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Abstract
Nano fine particles of noble metal in catalyst are modified by high polymer of guiding protons. Inductive the said high polymer can increase steric hindrance of fine particles of noble metal in order to anchor fine particles of noble metal in catalyst on surface of carrier so as to raise use ratio of catalyst. Farther, the high polymer of guiding protons is a better bonding agent also. Better binding force is existed between Nano fine particles of noble metal modified by the high polymer and carrier. The synthesized catalyst possesses function of guiding protons. The method for preparing the catalyst includes steps: preparing colloid of Nano noble metal modified by the said high polymer in advance; then, depositing the prepared colloid on carbon carrier. Average particle diameter of noble metal in catalyst is 2-5 Nano, and diameters are distributed evenly. Battery produced from the catalyst possesses better performance of electric output.
Description
Technical field
The present invention relates to a kind of catalyst of fuel cell field, particularly have the fuel-cell catalyst of function of guiding protons.Be characterized in that the catalyst nano fine particle of noble metal is by proton superpolymer modified.The invention still further relates to this Preparation of catalysts method.
Background technology
Proton Exchange Membrane Fuel Cells (PEM Fuel Cell) has advantages such as working temperature is low, pollution-free, specific power big, startup is rapid as a kind of novel energy, more and more is subjected to people's attention, has become the focus that countries in the world are competitively studied.What fuel cell used is noble metal platinum or platinum alloy catalyst.Platinum is rare metal, and resource scarcity costs an arm and a leg.So improve the utilance of Pt, reduce the Pt carrying capacity, be a pith that reduces the fuel cell cost.People generally use the carrier of carbon black as Pt at present, and this is because carbon black has higher specific surface area, helps improving the dispersiveness of metal platinum particulate.
Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences (CN1165092C) adopts the deadman as chloroplatinic acid such as ammonium chloride, potassium chloride, made the platinum particulate in the active carbon hole with lip-deep equally distributed Pt/C catalyst.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, the black carbon surface active site is evenly distributed, joins afterwards that reduce deposition obtains the PtRu/C catalyst in chloroplatinic acid and the ruthenic chloride mixed solution.But it is not high that the carbon of above method preparation carries the Pt utilance of Pt or Pt alloy catalyst.One of them major reason is that a large amount of platinum or platinum alloy particulates enters in the micropore of carbon surface, this part platinum that is buried or platinum alloy particulate are owing to can not contact with proton conductor and reacting gas, therefore be difficult to form effective three-phase reaction interface, thereby reduced the utilance of platinum.In addition, because Pt or Pt alloy directly link to each other with carbon, in preparation membrane electrode process, proton exchange resins can not enter into the position between Pt or Pt alloy and the carbon.This has reduced three-phase reaction interface on the one hand, owing to lack cementation, the bond strength between Pt or Pt alloy and the carbon is low on the other hand.
In order to overcome above shortcoming, the present invention adopts proton superpolymer modified catalyst fine particle of noble metal, to increase the steric hindrance of catalyst metals particulate, make it be difficult for entering into the micropore of porous carbon carrier, simultaneously, owing to fine particle of noble metal directly contacts with proton superpolymer, when it is carried on the carrier, be easy to form more three-phase reaction interface, thereby improve the catalytic efficiency of catalyst; Proton superpolymer itself is exactly a proton conductor, and therefore synthetic catalyst also has function of guiding protons; In addition, stronger adhesion is also arranged between carbon carrier and proton superpolymer, thus the useful life of having improved catalyst.
The pertinent literature report that the type catalyst is not arranged at present as yet.
Summary of the invention
The purpose of this invention is to provide a kind of preparation fuel-cell catalyst, particularly have the fuel-cell catalyst of function of guiding protons.Another object of the present invention provides this kind Preparation of catalysts method.
Fuel-cell catalyst of the present invention is the carbon supported noble metal particle catalyst, it is characterized in that fine particle of noble metal is by proton superpolymer modified in the catalyst.
Proton superpolymer of the present invention is any 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).
Carbon carrier of the present invention is nano-sized carbon or mesoporous carbon microballoon, and described nano-sized carbon comprises nanometer carbon black and nano-graphite ball, and its particle grain size is 10～100 nanometers, and described mesoporous carbon microballoon pore size is the 2-50 nanometer.
Noble metal catalyst 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 carbon carrier then with proton superpolymer modified nanoscale fine particle of noble metal colloid earlier, makes the catalyst with function of guiding protons.Concrete preparation process is:
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
5The alcohol in the described alcohol-water mixture and the mass ratio of water are 0.5～100: 1, and wherein alcohol is any in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol and the polyalcohol, and polyalcohol is ethylene glycol, glycerol or butanediol.
The catalyst of preparation is assembled into monocell, carries out electric performance test, test process is as follows:
1, the preparation of fuel cell acp chip CCM (catalyst coated membrane): the catalyst of preparation is joined in deionized water and perfluorinated sulfonic resin (Nafion and Pt/C mass ratio are 1: the 5) mixed liquor, fully stir the furnishing pasty state, evenly be coated on the Nafion of DU PONT company then
@Series membranes (NRE212, NRE211 etc.) both sides, oven dry makes CCM respectively.
2, monocell assembling and test: the carbon paper that adopts hydrophobic treatment is as gas diffusion layers, wherein the polytetrafluoroethylene mass content 20%～50%, and be compounded with the microporous layers that polytetrafluoroethylene and conductive carbon black particle are formed in the one side, compound this microporous layers was calcined 20 minutes down through 350 ℃, and 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.
With existing be that the catalyst of carrier is compared with carbon, the present invention has following advantage:
1, since the fine particle of noble metal finishing proton superpolymer, the fine particle of noble metal steric hindrance increases, make that colloid is difficult for when supporting on the carbon carrier entering in the micropore of porous carbon carrier, simultaneously the catalyst metals particulate directly and proton superpolymer contact, be easy to form three-phase reaction interface, thereby improved the catalytic efficiency of catalyst.
2, have adhesion preferably between carbon carrier and high polymer, can improve the durability of catalyst.
3, proton superpolymer itself is exactly a proton conductor, and therefore synthetic catalyst also has function of guiding protons.
Description of drawings
What Fig. 1 was traditional is carrier fuel-cell catalyst structural representation with the carbon black
Fine particle of noble metal is at the occurrence status schematic diagram of carrier surface in Fig. 2 conventional fuel cell catalyst
Fig. 3 is of the present invention through proton superpolymer modified fuel-cell catalyst structural representation
Fig. 4 is of the present invention through the occurrence status schematic diagram of proton superpolymer modified fine particle of noble metal on the carbon carrier surface
Among the figure: the 1-carbon carrier; The 2-fine particle of noble metal; The 3-proton superpolymer.
Embodiment
Below by embodiment in detail the present invention is described in detail.
The Nafion solution of getting 2 milliliters of mass concentrations 5% joins in ethanol and the mixed liquor of water quality than 0.5: 1, stirs after 5～10 minutes, adds the H of 32 milligrams of platiniferous
2PtCl
6Solution continue to stir, and transfers the pH=8 of solution with NaOH, 90 ℃ of reflux, and solution is by light yellow blackening gradually, and finally becomes aterrimus, makes the stable Pt colloidal solution that contains.Take by weighing 80 milligrams carrier XC-72 (specific area is 250 meters squared per gram) then, join after fully disperseing with above-mentioned ethanol and water mixed liquid and contain in the Pt colloidal solution, continue to stir and made the Pt/C catalyst that Nafion modifies in 3～5 hours.Pt particulate average grain diameter 2 nanometers wherein, and dispersed fine.
The preparation of fuel cell acp chip CCM: the catalyst of preparation is joined in deionized water and perfluorinated sulfonic resin (Nafion and Pt/C mass ratio are 1: the 5) mixed liquor, 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: 0.40 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 is 50%, 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: H
2/ air, air back pressure are 0; Anode 100% humidification, humidification temperature are 70 ℃; The monocell working temperature is 65 ℃.Test result shows that the electricity output of monocell reaches 0.795 volt/cm
2The @300 milliampere/centimetre
2
Get the SPEEK solution of 3 milliliters of mass concentrations 5%, join in ethanol and the mixed liquor of water quality, stir after 5～10 minutes, add the H of 60 milligrams of platiniferous than 100: 1
2PtCl
6Solution continue to stir, and transfers the pH=13 of solution with NaOH, 90 ℃ of reflux, and solution is by light yellow blackening gradually, and finally becomes aterrimus, makes the stable Pt colloidal solution that contains.Take by weighing 90 milligrams carrier mesoporous carbon microballoon then, its aperture is 3～6 nanometers, joins after fully disperseing with above-mentioned ethanol and water mixed liquid to contain in the Pt colloidal solution, continues to stir the Pt/C catalyst that made the SPEEK modification in 3～5 hours.Wherein Pt particulate average grain diameter 3.5 nanometers are dispersed fine.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the electricity output of monocell reaches 0.772 volt/cm
2The @300 milliampere/centimetre
2
Get the sulfonated polystyrene ion exchange resin solution of 10 milliliters of mass concentrations 5%, join in methyl alcohol and the mixed liquor of water quality, stir after 5～10 minutes, add the H of 32 milligrams of platiniferous than 10: 1
2PtCl
6Solution continue to stir, and transfers the pH=8 of solution with NaOH, 100 ℃ of reflux, and solution is by light yellow blackening gradually, and finally becomes aterrimus, makes the stable Pt colloidal solution that contains.Take by weighing 80 milligrams carrier nano-graphite ball then, its grain diameter is 40～55 nanometers, after fully disperseing with above-mentioned methyl alcohol and water mixed liquid, join and contain in the Pt colloidal solution, continue to stir and made the Pt/C catalyst that sulfonated polystyrene ion exchange resin is modified in 3～5 hours.Average grain diameter 3 nanometers of Pt particulate wherein, and dispersed fine.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the electricity output of monocell reaches 0.763 volt/cm
2The @300 milliampere/centimetre
2
Embodiment 4
Get the SPPS solution of 10 milliliters of mass concentrations 5%, join in methyl alcohol and the mixed liquor of water quality, stir after 5～10 minutes, add the H of 32 milligrams of platiniferous than 10: 1
2PtCl
6Solution continue to stir, and transfers the pH=8 of solution with NaOH, 100 ℃ of reflux, and solution is by light yellow blackening gradually, and finally becomes aterrimus, makes stable Pt colloidal solution.Take by weighing 80 milligrams carrier nano-graphite ball then, its grain diameter is 40～55 nanometers, joins after fully disperseing with above-mentioned methyl alcohol and water mixed liquid to contain in the Pt colloidal solution, continues to stir the Pt/C catalyst that made the SPPS modification in 3～5 hours.Average grain diameter 3 nanometers of Pt particulate wherein, and dispersed fine.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 1.Test result shows that the electricity output of monocell reaches 0.765 volt/cm
2The @300 milliampere/centimetre
2
Embodiment 5
Get the Nafion solution of 5 milliliters of mass concentrations 5%, join in propyl alcohol and the mixed liquor of water quality, stir after 5～10 minutes, add the H of 72 milligrams of platiniferous than 1: 1
2PtCl
6Solution and the RuCl that contains 32 milligrams of rutheniums
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 alloy colloid solution.Take by weighing 80 milligrams carrier XC-72 then, join in the alloy colloid solution after fully disperseing with above-mentioned propyl alcohol and water mixed liquid, continue to stir the Pt that made the Nafion modification in 3～5 hours
70Ru
30/ C catalyst.Average grain diameter 4 nanometers of alloy particle wherein, and dispersed fine.
The preparation of fuel cell acp chip CCM: the eelctro-catalyst of preparation is joined in deionized water and the perfluorinated sulfonic resin mixed liquor, 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 catalyst of present embodiment system, and the Pt carrying capacity is 1 milligram/centimetre
2, negative electrode uses the Pt/C catalyst of E-TEK company, and the Pt carrying capacity is 0.6 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 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.Straight methanol fuel cell (DMFC) test: 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 reach 265 milliwatts/centimetre
2The @400 milliampere/centimetre
2
Embodiment 6
Get the SPEEK solution of 3 milliliters of mass concentrations 5%, join in isopropyl alcohol and the mixed liquor of water quality, stir after 5～10 minutes, add the H of 72 milligrams of platiniferous than 10: 1
2PtCl
6Solution and the RuCl that contains 32 milligrams of rutheniums
3Solution continue to stir, and transfers the pH=10 of solution with NaOH, 90 ℃ of reflux, and solution is by light yellow blackening gradually, and finally becomes aterrimus, makes stable alloy colloid solution.Take by weighing 80 milligrams carrier XC-72 then, join in the alloy colloid solution after fully disperseing with above-mentioned isopropyl alcohol and water mixed liquid, continue to stir the Pt that made the SPEEK modification in 3～5 hours
70Ru
30/ C catalyst.Average grain diameter 3.5 nanometers of alloy particle wherein, and dispersed fine.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 5, and anode uses the catalyst of present embodiment system.Test result shows, the electricity output of monocell reach 210 milliwatts/centimetre
2The @400 milliampere/centimetre
2
Embodiment 7
Get the sulfonation polyphosphazene solution of 3 milliliters of mass concentrations 5%, join in ethanol and the mixed liquor of water quality, stir after 5～10 minutes, add the H of 72 milligrams of platiniferous than 10: 1
2PtCl
6Solution and the RuCl that contains 32 milligrams of rutheniums
3Solution continue to stir, and transfers the pH=10 of solution with NaOH, 90 ℃ of reflux, and solution is by light yellow blackening gradually, and finally becomes aterrimus, makes stable alloy colloid solution.Take by weighing 80 milligrams carrier XC-72 then, join in the alloy colloid solution after fully disperseing with above-mentioned ethanol and water mixed liquid, continue to stir the Pt that made the modification of sulfonation polyphosphazene in 3～5 hours
70Ru
30/ C catalyst.Average grain diameter 5 nanometers of alloy particle wherein, and dispersed fine.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 5, and anode uses the catalyst of present embodiment system.Test result shows, the electricity output of monocell reach 215 milliwatts/centimetre
2The @400 milliampere/centimetre
2
Embodiment 8
Get the Nafion solution of 3 milliliters of mass concentrations 5%, join in ethylene glycol and the mixed liquor of water quality, stir after 5～10 minutes, add the H of 60 milligrams of platiniferous than 10: 1
2PtCl
6Solution, contain the RuCl of 20 milligrams of rutheniums
3Solution and the CrCl that contains 10 milligrams of chromium
3Solution continue to stir, and transfers the pH=10 of solution with NaOH, 90 ℃ of reflux, and solution is by light yellow blackening gradually, and finally becomes aterrimus, makes stable alloy colloid solution.Take by weighing 80 milligrams carrier XC-72 then, join in the colloidal solution after fully disperseing with above-mentioned ethylene glycol and water mixed liquid, continue to stir the Pt that made the Nafion modification in 3～5 hours
70Ru
20Cr
10/ C catalyst.Average grain diameter 3.5 nanometers of alloy particle wherein, and dispersed fine.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 5, and anode uses the catalyst of present embodiment system.Test result shows, only the output of the electricity of battery reach 270 milliwatts/centimetre
2The @400 milliampere/centimetre
2
Embodiment 9
Get the sulfonated polyimide resin solution of 3 milliliters of mass concentrations 5%, join in glycerol and the mixed liquor of water quality, stir after 5～10 minutes, add the H of 60 milligrams of platiniferous than 1: 1
2PtCl
6Solution, contain the RuCl of 20 milligrams of rutheniums
3Solution and the CrCl that contains 10 milligrams of chromium
3Solution continue to stir, and transfers the pH=10 of solution with NaOH, 90 ℃ of reflux, and solution is by light yellow blackening gradually, and finally becomes aterrimus, makes stable alloy colloid solution.Take by weighing 80 milligrams carrier XC-72 then, join in the alloy colloid solution after fully disperseing with above-mentioned glycerol and water mixed liquid, continue to stir the Pt that made the sulfonated polyimide resin modification in 3～5 hours
70Ru
20Cr
10/ C catalyst.Average grain diameter 3.5 nanometers of alloy particle wherein, and dispersed fine.The preparation technology of fuel cell acp chip CCM, monocell assembling and test condition are identical with embodiment 5, and anode uses the catalyst of present embodiment system.Test result shows, only the output of the electricity of battery reach 240 milliwatts/centimetre
2The @400 milliampere/centimetre
2
Claims (3)
1, a kind of fuel-cell catalyst, be the carbon supported noble metal particle catalyst, it is characterized in that being carried on catalyst fine particle of noble metal on the carbon carrier by proton superpolymer modified, 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; Described carrier carbon is nano-sized carbon or mesoporous carbon microballoon, and described nano-sized carbon comprises nanometer carbon black and nano-graphite ball, and its particle grain size is 10～100 nanometers, and described mesoporous carbon microballoon pore size is the 2-50 nanometer.
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 catalyst of claim 1 is characterized in that, preparation process is as follows:
Step 1, be that 1%～10% proton superpolymer solution adds in the alcohol-water mixture with mass concentration, after the stirring, the precursor salting liquid that adds catalyst, wherein the mass ratio of noble metal and proton superpolymer is 1000～1: 10, solution PH in the course of reaction=8～13,90～100 ℃ of reflux 10～50 minutes make and lead the catalyst noble metal nano colloidal solution that the proton high polymer is modified;
Step 2, carrier carbon fully disperseed after, join in the prepared colloidal solution of step 1, continue to stir 3～5 hours, make proton superpolymer modified catalyst with function of guiding protons;
Wherein, alcohol is 0.5～100: 1 with the mass ratio of water in the described alcohol-water mixture, and alcohol is any in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol and the polyalcohol, and wherein polyalcohol is ethylene glycol, butanediol or glycerol.
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|---|---|---|---|
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|---|---|---|---|
| CNB2006100200041A CN100399612C (en) | 2006-08-17 | 2006-08-17 | Fuel cell catalyst with function of guiding protons, and prepartion method |
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| CN100399612C CN100399612C (en) | 2008-07-02 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462076B (en) * | 2009-01-06 | 2011-01-19 | 上海汽车工业(集团)总公司 | Novel use of hydrophobing agent/conductive carbon material composite body |
| CN101664698B (en) * | 2008-09-03 | 2012-01-25 | 中国科学院大连化学物理研究所 | Unsupported fuel cell catalyst slurry and preparation method thereof |
| CN101722049B (en) * | 2009-11-25 | 2013-08-07 | 武汉理工大学 | Catalyst modified by proton conductor and using conductive polymer as carrier and preparation method thereof |
| CN110957496A (en) * | 2019-12-30 | 2020-04-03 | 一汽解放汽车有限公司 | Fuel cell catalyst, preparation method thereof and application thereof in fuel cell |
| CN114824329A (en) * | 2022-05-20 | 2022-07-29 | 南京师范大学 | Iron-containing monatomic catalyst and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05144444A (en) * | 1991-11-25 | 1993-06-11 | Toshiba Corp | Fuel cell and electrode manufacturing method |
| JP3649009B2 (en) * | 1998-12-07 | 2005-05-18 | 日本電池株式会社 | Fuel cell electrode and method of manufacturing the same |
| CN1299374C (en) * | 2001-09-10 | 2007-02-07 | 旭化成株式会社 | Electrode catalyst layer for fuel cell |
-
2006
- 2006-08-17 CN CNB2006100200041A patent/CN100399612C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101664698B (en) * | 2008-09-03 | 2012-01-25 | 中国科学院大连化学物理研究所 | Unsupported fuel cell catalyst slurry and preparation method thereof |
| CN101462076B (en) * | 2009-01-06 | 2011-01-19 | 上海汽车工业(集团)总公司 | Novel use of hydrophobing agent/conductive carbon material composite body |
| CN101722049B (en) * | 2009-11-25 | 2013-08-07 | 武汉理工大学 | Catalyst modified by proton conductor and using conductive polymer as carrier and preparation method thereof |
| CN110957496A (en) * | 2019-12-30 | 2020-04-03 | 一汽解放汽车有限公司 | Fuel cell catalyst, preparation method thereof and application thereof in fuel cell |
| CN114824329A (en) * | 2022-05-20 | 2022-07-29 | 南京师范大学 | Iron-containing monatomic catalyst and application thereof |
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| Publication number | Publication date |
|---|---|
| CN100399612C (en) | 2008-07-02 |
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