CN101944620B - Fuel cell catalyst taking multi-element compound as carrier and preparation method thereof - Google Patents
Fuel cell catalyst taking multi-element compound as carrier and preparation method thereof Download PDFInfo
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- CN101944620B CN101944620B CN2010102425667A CN201010242566A CN101944620B CN 101944620 B CN101944620 B CN 101944620B CN 2010102425667 A CN2010102425667 A CN 2010102425667A CN 201010242566 A CN201010242566 A CN 201010242566A CN 101944620 B CN101944620 B CN 101944620B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a fuel cell catalyst taking multi-element compound as a carrier and a preparation method thereof, relating to a fuel cell catalyst and a preparation method thereof. The fuel cell catalyst of the invention adopts the mixed material of a granular carbon material (C1) and a linear carbon material (C2) as a carbon basal material; a precipitation thermal decompositing method is carried out on the two basal materials to prepare a compound carrier MOx-(C1+C2) of a carbon carrier and an oxide; an in-situ chemical reduction method is carried to prepare a Pt/MOx-(C1+C2) catalyst; MOx is CeO2, SnO2, Co3O4 or NiO; C1 is carbon black, carbon microsphere or mesoporous carbon; C2 is carbon fiber or carbon nanometer tube; the linear carbon material is combined with the granular carbon material to form a three-dimensional compound network structure, so as to increase the three-phase reaction activity area of the catalyst; and the doped metal oxide enhances the anti-CO capacity of the catalyst, and improves the use ratio of platinum.
Description
Technical field
The present invention relates to a kind of fuel-cell catalyst and preparation method.
Background technology
Fuel cell has characteristics such as operating temperature is low, energy efficiency is high, no electrolyte corrosion, is a research focus in electrochemistry and energy science field.Study of Catalyst is one of the most challenging task in the Proton Exchange Membrane Fuel Cells research.Big quantity research proves that the cathode and anode catalyst of the catalyst based battery that acts as a fuel of Pt has shown good catalytic action.Yet the price of metal platinum and the shortage in source have limited the catalyst based application of Pt.Therefore, the amount that reduces the use noble metal catalyst is one of key factor that effectively reduces the fuel cell manufacture cost, and its solution is through using the appropriate carriers material to possess high dispersive and high efficiency catalyst to be arranged.
People generally adopt carbon black as catalyst carrier at present; This is because carbon black has higher specific surface area and has good electrical conductivity and preferable pore structure; Help improving metal platinum microparticulate property; But the utilance of platinum still can be very not high, and an 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 reduce 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; On the other hand in battery operated process and since CO poison platinum or platinum alloy reduced activity.
Summary of the invention
Technical problem to be solved by this invention is that the utilance of raising platinum increases poisoning of anti-CO.
Technical scheme of the present invention:
A kind of the multiple element compound is the fuel-cell catalyst of carrier, and this catalyst is expressed as Pt/MOx-(C1+C2), MO
xBe metal oxide, carrier is the complex of granular carbon material and wire material with carbon element.
Granular carbon material comprises: carbon black, carbosphere or mesoporous carbon, the wire material with carbon element comprises: carbon fiber or CNT.
Metal oxide MO
xComprise: SnO
2, CeO
2, NiO or Co
3O
4
A kind of the multiple element compound is the preparation method of the fuel-cell catalyst of carrier, and this preparation method's step is:
Step 1 is to the pre-treatment of granular carbon material and wire material with carbon element;
Step 2, the preparation molar concentration is the SnCl of 0.01～0.1mol/L
2, (NH
4)
2Ce (NO
3)
6, Ni (NO
3)
2Or Co (NO
3)
2Solution;
Step 3, by granular carbon material: the wire material with carbon element is that 1～10: 1 mass ratio mixes, and joins in the container, adds isopropyl alcohol and water, and its volume ratio is 1: 3, and ultrasonic dispersing is even;
Step 4 slowly drips the metal salt solution that step 2 is prepared, and ultrasonic dispersing is even, and regulating the pH value is 6.5～9.5, ultrasonic stirring, and suction filtration obtains filter cake;
Step 5, filter cake in vacuum is dry, at N
2Decomposed 1～3 hour under following 200 ℃～500 ℃ temperature of gas shiled, promptly get required the multiple element compound carrier MOx-(C1+C2);
Step 6 with the multiple element compound carrier MOx-(C1+C2) of step 5 gained, obtains Pt/MOx-(C1+C2) catalyst through the in-situ chemical reducing process.
The present invention compares the beneficial effect that is had with prior art: the present invention adopts the composite material of wire material with carbon element and granular carbon material as catalyst carrier, on these two kinds of basis materials, adopts the precipitation heat decomposition method to prepare the complex carrier MO of carbon carrier and oxide
x-(C1+C2), and then adopt in-situ chemical reduction method for preparing Pt/MO
x-(C1+C2) catalyst; Have like this between wire material with carbon element and the granular carbon material and the Pt of bigger draw ratio and formed three-dimensional composite network structure; Active material Pt and collector and intermembranous being in contact with one another of proton have been increased; The composite catalyzing agent carrier of processing at some metal oxides that mix on the carbon back can promote the absorption of active OH on the Pt electrode and the desorption of CO, has increased poisoning of anti-CO, has improved the utilance of platinum.
Embodiment
A kind of the multiple element compound is the fuel-cell catalyst of carrier, and this catalyst is expressed as Pt/MOx-(C1+C2), MO
xBe metal oxide, support C is the complex of granular carbon material C1 and wire material with carbon element C2.
Described granular carbon material C1 comprises: carbon black, carbosphere or mesoporous carbon, wire material with carbon element C2 comprises: carbon fiber or CNT.
Described metal oxide MO
xComprise: SnO
2, CeO
2, NiO or Co
3O
4
A kind of the multiple element compound is preparation method's the execution mode of the fuel-cell catalyst of carrier:
Embodiment one
A kind of the multiple element compound is the preparation method of the fuel-cell catalyst of carrier, and this preparation method may further comprise the steps:
Step 1 is the pre-treatment of carbon black (ValcanXC-72) to granular carbon material C1:
With the granular carbon material ValcanXC-72 0.5h that in acetone, refluxes; Filter then, wash, after the drying, with 2mol/L nitric acid dousing 24h, then with deionized water wash to neutral; Use 5% hydrogen peroxide backflow 2h again, filter, washing, dry, grind subsequent use.
To wire material with carbon element C2 is the pre-treatment of CNT (CNTS):
CNTS at room temperature is soaked in the red fuming nitric acid (RFNA), stirs 12h, at 80 ℃ of refluxed 2h, with the mixed liquor natural cooling, filter then, vacuumize 12h grinds subsequent use.
Step 2, the preparation molar concentration is the SnCl of 0.01mol/L
2Solution;
Step 3 is got the ValcanXC-7230mg that step 1 handles by 1: 1 mass ratio and mixed with CNTS 30mg, joins in the there-necked flask of 150ml the adding isopropyl alcohol: the 40ml isopropanol water solution of water=1: 3, ultrasonic dispersing is even.
Step 4 slowly drips the SnCl that step 2 is prepared
2Solution, ultrasonic dispersing is even, and regulating the pH value is 9.5, ultrasonic stirring, suction filtration obtains filter cake;
Step 5, filter cake in vacuum is dry, at N
2Decomposed 1 hour under the following 500 ℃ temperature of gas shiled, promptly get complex carrier SnO
2-(ValcanXC-72R+CNTS);
Step 6 obtains Pt/SnO with step 5 gained complex carrier through the in-situ chemical reducing process
2-(ValcanXC-72+CNTS) catalyst.
Embodiment two
A kind of the multiple element compound is the preparation method of the fuel-cell catalyst of carrier, and this preparation method comprises that step is:
Step 1 is the pre-treatment of carbosphere to granular carbon material C1:
With the carbosphere 0.5h that in acetone, refluxes, filter then, wash, after the drying, with 2mol/L nitric acid dousing 24h, then with deionized water wash to neutral, use 5% hydrogen peroxide backflow 2h again, filter, washing, dry, grind subsequent use.
To wire material with carbon element C2 is the pre-treatment of carbon fiber:
Carbon fiber at room temperature is soaked in the red fuming nitric acid (RFNA), stirs 12h, at 80 ℃ of refluxed 2h, with the mixed liquor natural cooling, filter then, vacuumize 12h grinds subsequent use.
Step 2, the preparation molar concentration is the (NH of 0.1mol/L
4)
2Ce (NO
3)
6Solution;
Step 3 is got the carbosphere 100mg that step 1 handles by 10: 1 mass ratio and mixed with carbon fiber 1mg, joins in the there-necked flask of 150ml the adding isopropyl alcohol: the 40ml isopropanol water solution of water=1: 3, ultrasonic dispersing is even.
Step 4 slowly drips (the NH that step 2 is prepared
4)
2Ce (NO
3)
6Solution, ultrasonic dispersing is even, and regulating the pH value is 6.5, ultrasonic stirring, suction filtration obtains filter cake;
Step 5, filter cake in vacuum is dry, at N
2Decomposed 2 hours under the following 200 ℃ temperature of gas shiled, promptly get complex carrier CeO
2-(carbosphere+carbon fiber);
Step 6 obtains Pt/CeO with step 5 gained complex carrier through the in-situ chemical reducing process
2-(carbosphere+carbon fiber) catalyst.
Embodiment three
A kind of the multiple element compound is the preparation method of the fuel-cell catalyst of carrier, and this preparation method comprises that step is:
Step 1 is the pre-treatment of mesoporous carbon to granular carbon material C1:
With the mesoporous carbon 0.5h that in acetone, refluxes, filter then, wash, after the drying, with 2mol/L nitric acid dousing 24h, then with deionized water wash to neutral, use 5% hydrogen peroxide backflow 2h again, filter, washing, dry, grind subsequent use.
To wire material with carbon element C2 is the pre-treatment of CNT (CNTS):
CNTS at room temperature is soaked in the red fuming nitric acid (RFNA), stirs 12h, at 80 ℃ of refluxed 2h, with the mixed liquor natural cooling, filter then, vacuumize 12h grinds subsequent use.
Step 2, the preparation molar concentration is the Ni (NO of 0.05mol/L
3)
2Solution;
Step 3 is got the mesoporous carbon 50mg that step 1 handles by 5: 1 mass ratio and mixed with CNTS 10mg, joins in the there-necked flask of 150ml the adding isopropyl alcohol: the 40ml isopropanol water solution of water=1: 3, ultrasonic dispersing is even.
Step 4 slowly drips the Ni (NO that step 2 is prepared
3)
2Solution, ultrasonic dispersing is even, and regulating the pH value is 9.5, ultrasonic stirring, suction filtration obtains filter cake;
Step 5, filter cake in vacuum is dry, at N
2Decomposed 3 hours under the following 300 ℃ temperature of gas shiled, promptly get complex carrier NiO-(mesoporous carbon+CNTS);
Step 6 obtains the Pt/NiO-(catalyst of mesoporous carbon+CNTS) with step 5 gained complex carrier through the in-situ chemical reducing process
Embodiment four
A kind of the multiple element compound is the preparation method of the fuel-cell catalyst of carrier, and this preparation method comprises that step is:
Step 1 is the pre-treatment of carbosphere to granular carbon material C1:
With the carbosphere 0.5h that in acetone, refluxes, filter then, wash, after the drying, with 2mol/L nitric acid dousing 24h, then with deionized water wash to neutral, use 5% hydrogen peroxide backflow 2h again, filter, washing, dry, grind subsequent use.
To wire material with carbon element C2 is the pre-treatment of carbon fiber:
Carbon fiber at room temperature is soaked in the red fuming nitric acid (RFNA), stirs 12h, at 80 ℃ of refluxed 2h, with the mixed liquor natural cooling, filter then, vacuumize 12h grinds subsequent use.
Step 2, the preparation molar concentration is the Co (NO of 0.1mol/L
3)
2Solution;
Step 3 is got the carbosphere 30mg that step 1 handles by 3: 1 mass ratio and mixed with carbon fiber 10mg, joins in the there-necked flask of 150ml the adding isopropyl alcohol: the 40ml isopropanol water solution of water=1: 3, ultrasonic dispersing is even.
Step 4 slowly drips the Co (NO that step 2 is prepared
3)
2Solution, ultrasonic dispersing is even, and regulating the pH value is 8, ultrasonic stirring, suction filtration obtains filter cake;
Step 5, filter cake in vacuum is dry, at N
2Decomposed 2 hours under the following 300 ℃ temperature of gas shiled, promptly get complex carrier Co
3O
4(carbosphere+carbon fiber);
Step 6 obtains Pt/Co with step 5 gained complex carrier through the in-situ chemical reducing process
3O
4-(carbosphere+carbon fiber) catalyst.
Carbosphere, mesoporous carbon are from Beijing University of Chemical Technology, and carbon fiber and CNT are from Tsing-Hua University.
The method of the patent that the described in-situ chemical reducing process of the step 6 in all execution modes all adopts (02155256.8 and 02155255.X) record realizes.
Claims (1)
1. the preparation method that the multiple element compound is the fuel-cell catalyst of carrier is characterized in that, this preparation process is:
Step 1 is to the pre-treatment of granular carbon material (C1) and wire material with carbon element (C2);
Step 2, the preparation molar concentration is the SnCl of 0.01～0.1mol/L
2, (NH
4)
2Ce (NO
3)
6, Ni (NO
3)
2Or Co (NO
3)
2Solution;
Step 3, by granular carbon material C1: wire material with carbon element C2 is that the mass ratio of 1～10:1 mixes, and joins in the container, adds isopropyl alcohol and water, and its volume ratio is 1:3, and ultrasonic dispersing is even;
Step 4 slowly drips the metal salt solution that step 2 is prepared, and ultrasonic dispersing is even, and regulating the pH value is 6.5～9.5, ultrasonic stirring, and suction filtration obtains filter cake;
Step 5, filter cake in vacuum is dry, at N
2Decomposed 1～3 hour under following 200 ℃～500 ℃ temperature of gas shiled, promptly get required the multiple element compound carrier MOx-(C1+C2), the M among the MOx represents Sn, Ce, Ni or Co;
Step 6 with the multiple element compound carrier MOx-(C1+C2) of step 5 gained, obtains Pt/ MOx-(C1+C2) catalyst through the in-situ chemical reducing process.
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|---|---|---|---|
| CN2010102425667A CN101944620B (en) | 2010-08-02 | 2010-08-02 | Fuel cell catalyst taking multi-element compound as carrier and preparation method thereof |
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| CN101944620B true CN101944620B (en) | 2012-10-31 |
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| CN103191755A (en) * | 2012-01-16 | 2013-07-10 | 曲阜师范大学 | Pt/Fe3O4-CeO2 composite material and its preparation method and use |
| CN102780009A (en) * | 2012-08-03 | 2012-11-14 | 上海锦众信息科技有限公司 | Membrane electrode preparation method of fuel battery |
| CN102773095A (en) * | 2012-08-03 | 2012-11-14 | 上海锦众信息科技有限公司 | Method for preparing platinum-based catalyst for fuel cell |
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| CN103657629B (en) * | 2013-12-30 | 2016-03-30 | 北京化工大学 | High dispersancy nano Pt-SnO 2the preparation method of/C catalyst |
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| CN110364742B (en) * | 2019-06-25 | 2020-12-18 | 北方民族大学 | Anode catalyst for direct borohydride fuel cell, anode material, preparation method of anode material and fuel cell |
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| CN113611874A (en) * | 2021-06-17 | 2021-11-05 | 苏州欣和智达能源科技有限公司 | Composite carbon carrier alloy catalyst and preparation method and application thereof |
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