CN101108347B - Method of manufacturing wolfram carbine/platinum compound catalyze material for fuel batter with proton exchange film - Google Patents
Method of manufacturing wolfram carbine/platinum compound catalyze material for fuel batter with proton exchange film Download PDFInfo
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- CN101108347B CN101108347B CN2007101200221A CN200710120022A CN101108347B CN 101108347 B CN101108347 B CN 101108347B CN 2007101200221 A CN2007101200221 A CN 2007101200221A CN 200710120022 A CN200710120022 A CN 200710120022A CN 101108347 B CN101108347 B CN 101108347B
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- tungsten carbide
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- proton exchange
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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 relates to a preparation method of a novel compound catalyst for a proton exchange film fuel battery, which mainly comprises tungsten carbide and Pt, and has higher tolerance capability to the oxidizing environment. The preparation method comprises the following: weighing some processed Vulcan XC-72 carbon powder and putting in three flasks, adding isopropanol, water and H2WO4 solution, stirring and mixing evenly by ultrasonic; dripping excessive NaBH4 solution under the protection of N2 and while mixing by ultrasonic wave to have reduction reaction; filtering, washing and drying after the reaction is finished, reducing and incinerating further to get tungsten carbide; putting the material into a flask, using formaldehyde as reducer and H2PtC16 as Pt precursor, obtaining tungsten carbide or Pt compound catalyst by an in situ reduction method. The invention imports the tungsten carbide material with higher oxidation resistance into the Pt catalyst of proton exchange film fuel batteries, the overall resistance of the catalyst to the oxidizing environment can be substantially improved; the preparation process is simple and needs no complicate equipment, and thus the invention has potential in practical application.
Description
Technical field
The present invention relates to a kind of preparation method of used in proton exchange membrane fuel cell tungsten carbide/platinum compound catalyze material, specifically be that the reduction calcination method prepares tungsten carbide material, and be aided with in-situ reducing Pt, obtain tungsten carbide/Pt compound catalyze material.Used in proton exchange membrane fuel cell tungsten carbide/platinum composite catalyst can obviously improve the oxidation environment tolerance of battery.Belong to catalyst technical field.
Background technology
Mostly adopt carbon black as carrier in the existing PEMFC technology, the Pt particle is loaded into black carbon surface, obtain loaded Pt/C catalyst.Carbon carrier has big specific area, can reduce the use amount of precious metals pt greatly, reduces the battery overall cost.But the problem that oxidation and sinter takes place easily for it also is puzzlement researcher's an important difficult problem.The working environment of fuel battery inside is relatively unique, has higher temperature (50-90 ℃), higher water content, higher acidity (pH＜1) and higher current potential (0.6-1.2V).Under such harsh conditions, and under long-term operating mode, the easier generation of the electrochemical oxidation of carbon, especially all the more so under the very high situation of Pt content.And, when battery moves under unconventional condition, during as bad startup or variable load, the antipole situation might take place, can cause irreversible influence to battery owing to the extreme oxidation of carbon.Usually the oxidizing process of carbon can be represented by (1) formula:
C+2H
2O
→ CO
2+4H
++4e
- E＝0.207Vvs.
NHE (1)
Metallic also may take place to run off or assemble thus, and finally causes the loss of battery performance.Therefore improving the catalyst of fuel batter with proton exchange film work of tolerance under extreme conditions has great importance.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of used in proton exchange membrane fuel cell tungsten carbide/platinum compound catalyze material, its preparation method is simple, need not complex device.
The present invention also aims to provide the tungsten carbide/platinum composite catalyst of described method preparation, and use it in the Proton Exchange Membrane Fuel Cells.
The technical scheme that technical solution problem of the present invention is adopted is: a kind of used in proton exchange membrane fuel cell tungsten carbide/platinum composite catalyst preparation method, comprise following preparation process: take by weighing the Vulcan XC-72 carbon dust of handling and place there-necked flask, add isopropyl alcohol, water, H
2WO
4Solution, ultrasonic wave stirs and fully mixes; At N
2Splash into excessive NaBH under protection and the ultrasonic agitation condition
4Solution carries out reduction reaction, carries out suction filtration, washing, drying after reaction finishes, and through further reduction calcining, obtains tungsten carbide material; This material is placed beaker, is reducing agent with formaldehyde, H
2PtCl
6Be the Pt presoma, adopt local reduction way to make tungsten carbide/platinum composite catalyst.
A kind of used in proton exchange membrane fuel cell tungsten carbide/platinum composite catalyst preparation method comprises following preparation process:
Step (1), with Vulcan XC-72 carbon dust with 32% HNO
3Vlil 1 hour is filtered, and spends deionised water to pH=6-7,110 ℃ of freeze-day with constant temperature;
Step (2), take by weighing the Vulcan XC-72 carbon dust that step (1) handled and place there-necked flask, add isopropyl alcohol and water, add H again
2WO
4Solution, the molar ratio of carbon and tungsten 1: 1 fully mixes in the ultrasonic wave, adds hydrogen peroxide and ammoniacal liquor and regulates pH=6-7, places 4-6 hour;
Step (3), at N
2Splash into excessive NaBH under protection and the ultrasonic agitation condition
4Solution carries out reduction reaction, and reaction is carried out suction filtration, washing after finishing, 80 ℃ of vacuum drying 4 hours;
Step (4) places tube furnace with product, at N
2With H
2Calcine under the mixed atmosphere, calcined 2-3 hour for 800 ℃, calcined 3-5 hour for 1150 ℃, get the tungsten carbide powder material;
Step (5), step (4) gained tungsten carbide powder material is put into there-necked flask, add absolute ethyl alcohol, water and isopropyl alcohol successively, ultrasonic mixing adds 10mg/mL H
2PtCl
6The solution ultrasonic wave stirs 30min, uses 1mol/L Na
2CO
3Solution is transferred pH=8-9, leaves standstill 12h, must contain the mixed slurry of tungsten carbide material;
Step (6), slowly drip 37% formalin in step (5) gained slurry, temperature is controlled at 60-70 ℃, and logical nitrogen is as protection gas in the reaction, and ultrasonic wave stirs, and stops ventilation after reaction is finished, and carries out vacuum filtration, spends deionised water to there not being Cl
-, filter cake 80 ℃ of vacuum drying, is obtained tungsten carbide/Pt composite catalyst.
Innovation part of the present invention is to have prepared a kind of tungsten carbide/platinum compound catalyze agent material, this catalysis material has shown the oxidation tolerance performance more more remarkable than conventional Vulcan XC-72 carbon supported platinum catalyst, therefore be expected to substitute existing conventional carbon supported platinum catalyst material, be used for the PEMFC that needs improve the oxidation tolerance, as taking place easily under the situation of weary gas at battery fuel or oxidant, the seriousness loss of energy that the tungsten carbide that oxidation resistance is strong/Pt catalyst can more effectively avoid unexpected situation such as antipole to bring to battery.
Another advantage of the present invention is that the tungsten carbide material particle that makes is tiny, is evenly distributed, and has shown remarkable antioxygenic property.The present invention has introduced the stronger tungsten carbide material of antioxygenic property in Proton Exchange Membrane Fuel Cells Pt catalyst, can obviously improve the whole oxidation environment tolerance of catalyst, and preparation process is simple, need not complex device, and the potentiality of practical application are arranged.
Description of drawings
Fig. 1 is with the transmission electron microscope photo of the tungsten-carbide powder of embodiment 1 preparation;
Fig. 2 is with the transmission electron microscope photo of the tungsten carbide/platinum catalyst of embodiment 1 preparation;
The conventional carbon of Fig. 3 carries the Pt catalyst and novel tungsten carbide/Pt catalyst is made battery, experiences the comparison of identical oxidizing process (1.8V oxidation 5 minutes) back performance degradation; Abscissa is current density, J (mA cm among Fig. 3
-2), ordinate is voltage E (V).
The specific embodiment
Step (1), take by weighing 1g Vulcan XC-72 carbon dust, put into 32% HNO
3In the solution, add hot reflux 1 hour, filter, spend deionised water to pH=6,110 ℃ of freeze-day with constant temperature;
Step (2), the Vulcan XC-72 carbon dust that step (1) was handled place there-necked flask, add isopropyl alcohol and water, add H again
2WO
4Solution, the molar ratio of carbon and tungsten 1: 1 fully mixes in the ultrasonic wave, adds hydrogen peroxide and ammoniacal liquor and regulates pH=6, places 5 hours;
Step (3), at N
2Splash into excessive NaBH under protection and the ultrasonic agitation condition
4Solution carries out reduction reaction; Reaction is carried out suction filtration, washing after finishing, 80 ℃ of vacuum drying 4 hours;
Step (4) places tube furnace with product, at N
2With H
2Calcine under the mixed atmosphere, calcined 2 hours for 800 ℃, calcined 3 hours, and obtained the tungsten carbide powder material for 1150 ℃.
Step (5), step (4) gained tungsten carbide powder material is put into there-necked flask, add absolute ethyl alcohol, water and isopropyl alcohol successively, ultrasonic mixing adds 10mg/mL H
2PtCl
6The solution ultrasonic wave stirs 30min, uses 1mol/L Na
2CO
3Solution is transferred pH=8, leaves standstill 12h, must contain the mixed slurry of tungsten carbide material;
Step (6), slowly drip 37% formalin in step (5) gained slurry, temperature is controlled at 60 ℃, and logical nitrogen is as protection gas in the reaction, and ultrasonic wave stirs, and stops ventilation after reaction is finished, and carries out vacuum filtration, spends deionised water to there not being Cl
-, filter cake 80 ℃ of vacuum drying, is obtained tungsten carbide/Pt composite catalyst.
Tungsten carbide/platinum catalyst is prepared into electrode and constitutes battery, and be that single pond of catalyst compares, relatively see Fig. 3 through the performance after the 1.8V oxidation with carry platinum with conventional carbon.After the 1.8V oxidation, tungsten carbide/Pt is that the decay of battery under each electricity is close of catalyst is significantly less than the Pt/C battery, has proved that this novel composite catalyst has the performance of oxidation environment tolerance preferably.Fig. 3 is that two kinds of catalyst are made the battery original state and through 1.8V oxidation performance degradation (Cell-1:Pt/C catalyst relatively after 5 minutes; Cell-2: tungsten carbide/Pt composite catalyst).
Step (1), take by weighing 1g Vulcan XC-72 carbon dust, put into 32% HNO
3In the solution, add hot reflux 1 hour, filter, spend deionised water to pH=6.5,110 ℃ of freeze-day with constant temperature;
Step (2), the Vulcan XC-72 carbon dust that step (1) was handled place there-necked flask, add isopropyl alcohol and water, add H again
2WO
4Solution, the molar ratio of carbon and tungsten 1: 1 fully mixes in the ultrasonic wave, adds hydrogen peroxide and ammoniacal liquor and regulates pH=6.5, places 5 hours;
Step (3), at N
2Splash into excessive NaBH under protection and the ultrasonic agitation condition
4Solution carries out reduction reaction; Reaction is carried out suction filtration, washing after finishing, 80 ℃ of vacuum drying 4 hours;
Step (4) places tube furnace with product, at N
2With H
2Calcine under the mixed atmosphere, calcined 2.5 hours for 800 ℃, calcined 3.5 hours, and obtained the tungsten carbide powder material for 1150 ℃.
Step (5), step (4) gained tungsten carbide powder material is put into there-necked flask, add absolute ethyl alcohol, water and isopropyl alcohol successively, ultrasonic mixing adds 10mg/mL H
2PtCl
6The solution ultrasonic wave stirs 30min, uses 1mol/L Na
2CO
3Solution is transferred pH=7, leaves standstill 12h, must contain the mixed slurry of tungsten carbide material;
Step (6), slowly drip 37% formalin in step (5) gained slurry, temperature is controlled at 65 ℃, and logical nitrogen is as protection gas in the reaction, and ultrasonic wave stirs, and stops ventilation after reaction is finished, and carries out vacuum filtration, spends deionised water to there not being Cl
-, filter cake 80 ℃ of vacuum drying, is obtained tungsten carbide/Pt composite catalyst.
Tungsten carbide/platinum catalyst is prepared into electrode and constitutes battery, and be assembled into the antioxygenic property of single pond test tungsten carbide/platinum.
Embodiment 3
Step (1), take by weighing 1g Vulcan XC-72 carbon dust, put into 32% HNO
3In the solution, add hot reflux 1 hour, filter, spend deionised water to pH=7,110 ℃ of freeze-day with constant temperature;
Step (2), the Vulcan XC-72 carbon dust that step (1) was handled place there-necked flask, add isopropyl alcohol and water, add H again
2WO
4Solution, the molar ratio of carbon and tungsten 1: 1 fully mixes in the ultrasonic wave, adds hydrogen peroxide and ammoniacal liquor and regulates pH=7, places 6 hours;
Step (3), at N
2Splash into excessive NaBH under protection and the ultrasonic agitation condition
4Solution carries out reduction reaction; Reaction is carried out suction filtration, washing after finishing, 80 ℃ of vacuum drying 4 hours;
Step (4) places tube furnace with product, at N
2With H
2Calcine under the mixed atmosphere, calcined 3 hours for 800 ℃, calcined 5 hours, and obtained the tungsten carbide powder material for 1150 ℃.
Step (5), step (4) gained tungsten carbide powder material is put into there-necked flask, add absolute ethyl alcohol, water and isopropyl alcohol successively, ultrasonic mixing adds 10mg/mL H
2PtCl
6The solution ultrasonic wave stirs 30min, uses 1mol/L Na
2CO
3Solution is transferred pH=9, leaves standstill 12h, must contain the mixed slurry of tungsten carbide material;
Step (6), slowly drip 37% formalin in step (5) gained slurry, temperature is controlled at 70 ℃, and logical nitrogen is as protection gas in the reaction, and ultrasonic wave stirs, and stops ventilation after reaction is finished, and carries out vacuum filtration, spends deionised water to there not being Cl
-, filter cake 80 ℃ of vacuum drying, is obtained tungsten carbide/Pt composite catalyst.And be assembled into the antioxygenic property of single pond test tungsten carbide/platinum.
Claims (1)
1. a used in proton exchange membrane fuel cell tungsten carbide/platinum compound catalyze material prepares the method for battery, it is characterized in that comprising following preparation process: take by weighing the Vulcan XC-72 carbon dust of handling and place there-necked flask, add isopropyl alcohol, water, H
2WO
4Solution, ultrasonic wave stirs and fully mixes; At N
2Splash into excessive NaBH under protection and the ultrasonic agitation condition
4Solution carries out reduction reaction, carries out suction filtration, washing, drying after reaction finishes, and through further reduction calcining, obtains tungsten carbide material; This material is placed beaker, is reducing agent with formaldehyde, H
2PtCl
6Be the Pt presoma, adopt local reduction way to make tungsten carbide/platinum composite catalyst; Concrete steps are as follows:
Step (1), with Vulcan XC-72 carbon dust with 32% HNO
3Vlil 1 hour is filtered, and spends deionised water to pH=6-7,110 ℃ of freeze-day with constant temperature;
Step (2), take by weighing the Vulcan XC-72 carbon dust that step (1) handled and place there-necked flask, add isopropyl alcohol and water, add H again
2WO
4Solution, the molar ratio of carbon and tungsten 1: 1 fully mixes in the ultrasonic wave, adds hydrogen peroxide and ammoniacal liquor and regulates pH=6-7, places 4-6 hour;
Step (3), at N
2Splash into excessive NaBH under protection and the ultrasonic agitation condition
4Solution carries out reduction reaction, and reaction is carried out suction filtration, washing after finishing, 80 ℃ of vacuum drying 4 hours;
Step (4) places tube furnace with product, at N
2With H
2Calcine under the mixed atmosphere, calcined 2-3 hour for 800 ℃, calcined 3-5 hour for 1150 ℃, get the tungsten carbide powder material;
Step (5), step (4) gained tungsten carbide powder material is put into there-necked flask, add absolute ethyl alcohol, water and isopropyl alcohol successively, ultrasonic mixing adds 10mg/mL H
2PtCl
6The solution ultrasonic wave stirs 30min, uses 1mol/L Na
2CO
3Solution is transferred pH=8-9, leaves standstill 12h, must contain the mixed slurry of tungsten carbide material;
Step (6), slowly drip 37% formalin in step (5) gained slurry, temperature is controlled at 60-70 ℃, and logical nitrogen is as protection gas in the reaction, and ultrasonic wave stirs, and stops ventilation after reaction is finished, and carries out vacuum filtration, spends deionised water to there not being Cl
-, filter cake 80 ℃ of vacuum drying, is obtained tungsten carbide/platinum composite catalyst;
Tungsten carbide/platinum catalyst is prepared into electrode and constitutes battery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101200221A CN101108347B (en) | 2007-08-07 | 2007-08-07 | Method of manufacturing wolfram carbine/platinum compound catalyze material for fuel batter with proton exchange film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101200221A CN101108347B (en) | 2007-08-07 | 2007-08-07 | Method of manufacturing wolfram carbine/platinum compound catalyze material for fuel batter with proton exchange film |
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| CN101108347B true CN101108347B (en) | 2010-09-29 |
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| KR20120115559A (en) * | 2010-02-05 | 2012-10-18 | 바스프 에스이 | Process for producing a catalyst and catalyst |
| CN105251487B (en) * | 2015-11-06 | 2018-01-26 | 上海电力学院 | A kind of preparation method of fuel cell W@Pt/C catalyst with core-casing structure |
| CN106995928A (en) * | 2016-01-23 | 2017-08-01 | 西南大学 | Preparation method based on the nano combined liberation of hydrogen catalyst of AuPdPt-WC/C in simulated seawater |
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Granted publication date: 20100929 Termination date: 20130807 |