CN1380712A - Anti-CO compound catalystic layer for proteon-exchange membrane fuel cell and its preparation - Google Patents
Anti-CO compound catalystic layer for proteon-exchange membrane fuel cell and its preparation Download PDFInfo
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- CN1380712A CN1380712A CN01110538A CN01110538A CN1380712A CN 1380712 A CN1380712 A CN 1380712A CN 01110538 A CN01110538 A CN 01110538A CN 01110538 A CN01110538 A CN 01110538A CN 1380712 A CN1380712 A CN 1380712A
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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
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- 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 an anti-CO composite catalyst layer used in fuel battieres of the proton exchange membrane. The composite catalyst layer incldues two layers: inner and outer layer. The PtRu/C anti-CO electrocatalyst is adopted in the outer catalyst layer. The Pt/C or Pt black electrocatalyst is adopted in the inner catalyst layer. Weight ratio of catalyst contained in inner and outher layer is 1/2-1/20. The quanta of total precious metal in the composite catalyst layer are not larger than the contents in the electrode prepared by user of traditional method. The composite catalyst layer provided stable structure, good ibnding, not easy to be layered so that the structur can be used to prepare large area electrode.
Description
The present invention relates to a kind of fuel cell, specifically provide a kind of with CO/H
2Be the used in proton exchange membrane fuel cell anti-CO compound catalystic layer of fuel gas and the preparation method of this composite catalytic layer.
Fuel cell is a kind of Blast Furnace Top Gas Recovery Turbine Unit (TRT) that chemical energy in fuel and the oxidant is converted into electric energy.It is without the overheated machine process, so be not subjected to the restriction of Carnot cycle, energy conversion efficiency is very high.Simultaneously, it is again a kind of Blast Furnace Top Gas Recovery Turbine Unit (TRT) of cleanliness without any pollution.Wherein, Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cell is called for short PEMFC) has wide application prospect, its energy cold-starting, and no electrolyte corrosion and leakage, simple in structure, easy to operate; Be acknowledged as the first-selected energy of electric automobile, regional power station, portable power supply, submarine, spacecraft etc., its characteristics that adapt to the oceangoing voyage journey are to the exploitation very attractive of bathyscaph under water such as unmanned battle platform under water.And low other advantage that waits of complete autonomous ability to work that this device itself is had and life cycle cost, because the unmanned battle platform to the requirement of power source is under water: high-energy-density, high-energy-density, anhydrous fully waste discharge down, anhydrous noise down, do not rely on air, to meet " zero center of gravity drift " design principle simultaneously, satisfy the fail safe of height, good recharging property, life cycle cost is few, maintaining simply waits requirement, when this makes under water unmanned battle platform selecting energy form, satisfy very difficulty of above specification requirement fully, and make Proton Exchange Membrane Fuel Cells become a kind of ideal power source of the most promising platform of unmanned battle under water.At present, adopting pure hydrogen is that the energy density of the Proton Exchange Membrane Fuel Cells of fuel can meet the demands, but the storage of hydrogen and the application of carrying to fuel cell bring many inconvenience.If can adopt liquid fuel such as methyl alcohol or gasoline that hydrogen source is provided, then use pure hydrogen that bigger advantage is arranged at aspects such as volume, weight.Liquid fuel can produce the reformation gas of rich hydrogen by reforming.But owing to contain carbon monoxide in the reformation gas, it has extremely strong poisoning effect to the eelctro-catalyst Pt of Proton Exchange Membrane Fuel Cells, and the electrical property of fuel cell is sharply decayed, so press for the anti-CO poisoning problem that solves anode.
At present the CO problem is mainly contained following several processing method: anode is annotated oxygen, the preliminary treatment of reformation gas, is adopted the operating temperature of CO-resistance catalyst and raising battery etc.
It is to mix a spot of oxidant such as O in fuel that anode is annotated oxygen
2With H
2O
2They can be under catalyst action, and a little CO in the fuel is removed in oxidation, and the performance of battery is significantly improved.But oxidant mixes with the direct of fuel, can cause the utilance of fuel to reduce, and has brought the safety issue of system simultaneously.
Preliminary treatment is will contain the reformation gas of a small amount of CO by catalytic reactor, and utilization catalytic reaction wherein further reduces CO concentration; Utilize this method CO concentration can be reduced to below the 10ppm.But this method needs extra operation and energy, can be for the H of the direct low CO concentration of using of PEMFC and will produce
2Very difficult, the requirement of its cost and technology is all very high.
The research of CO-resistance catalyst aspect is based on Pt, mixes other material to reduce the electromotive force of oxidation CO.Because Pt has very strong catalytic activity, for not reducing the catalytic activity of catalyst to fuel, the CO-resistance catalyst that is proposed is that Pt is an alloy substantially.And the CO-resistance catalyst the most ripe, that be most widely used of research at present is to reduce the oxidation potential of CO by the synergy of Pt and Ru, and battery performance under the situation that CO exists is obviously improved.But when being fuel with pure hydrogen, the Pt/Ru activity of such catalysts is starkly lower than the Pt catalyst.
The operating temperature that improves battery is to utilize under higher temperature (as more than 120 ℃), and CO strengthens at the desorption of Pt catalyst surface, thereby makes Pt can have enough active sites to carry out the catalytic oxidation of hydrogen.But because under high temperature so, conventional proton exchange membrane can be dewatered and be made its performance degradation, only can keep the CO resistance performance of very short time usually.
U.S. Pat P4876115 has introduced a kind of manufacture method that is used for the membrane electrode of Proton Exchange Membrane Fuel Cells.At first catalyst and polytetrafluoroethylene (PTFE) are made Catalytic Layer, again the proton conductor polymer is sprayed on the Catalytic Layer surface, with two Catalytic Layer that scribble the proton conductor polymer and a proton exchange membrane hot pressing together, it is three-in-one to form membrane electrode at last.
Another piece USP5211984 has introduced a kind of fuel cell thin layer membrane electrode preparation method.The proton conductor polymer of catalyst and sodium typeization is made ink, be coated in then on the PTFE film, form Catalytic Layer, by hot pressing Catalytic Layer is transferred on the proton exchange membrane again.The proton exchange membrane of this sodium typeization is used to prepare three-in-one membrane electrode assembly after protonated again, the thin layer Catalytic Layer that this method is made, its thickness can be under 5 μ m.
European patent WO0036679 has introduced a kind of compound electrode structure, and the oxygen in conjunction with 1% is blown into the CO poisoning problem that solves.Finish CO and the O that is blown into respectively by different Catalytic Layer
2Between chemical oxidation and hydrogen and negative electrode O
2Electrochemical reaction.Its outer Catalytic Layer contains the Pt catalyst, does not contain proton conductor, thereby not catalytic electrochemical reaction, only catalysis CO be blown into O
2Between directly carry out chemical oxidation, make that the CO concentration in the fuel gas enter internal layer Catalytic Layer 13 is minimized.But, increased the complexity of system operation, but also, reduced the efficient of fuel cell additive decrementation fuel gas owing in fuel gas, be blown into oxygen.
In order to overcome the problems referred to above, the purpose of this invention is to provide a kind of with CO/H
2Be the used in proton exchange membrane fuel cell anti-CO compound catalystic layer of fuel gas and the preparation method of this composite catalytic layer.
To achieve these goals, used in proton exchange membrane fuel cell anti-CO compound catalystic layer provided by the invention, adopting Pt and/or Ru is active component, it is characterized in that by the inside and outside two-layer composite catalytic layer that constitutes, wherein, outer Catalytic Layer adopts the PtRu/C CO-resistance catalyst, and the internal layer Catalytic Layer adopts Pt/C or Pt black appliances catalyst, and the catalyst content weight ratio in the inside and outside two-layer Catalytic Layer is 1/20-1/2.
In above-mentioned used in proton exchange membrane fuel cell anti-CO compound catalystic layer, outer Catalytic Layer adds PTFE, and PTFE content and outer Catalytic Layer volume ratio are 10-50%.
In above-mentioned used in proton exchange membrane fuel cell anti-CO compound catalystic layer, the internal layer Catalytic Layer adds proton conductor, and the weight ratio of internal layer Catalytic Layer and proton conductor is 1: 4--4: 1.And the internal layer Catalytic Layer adds pore creating material, and the weight ratio of pore creating material and internal layer Catalytic Layer is 1: 4--1: 2, internal layer Catalytic Layer adding pore creating material is (NH
4)
2C
2O
4, NaCl and PTFE, internal layer catalyst add PTFE, PTFE content and internal layer Catalytic Layer volume ratio are 1--10%.
The method of used in proton exchange membrane fuel cell anti-CO compound catalystic layer provided by the invention, press following step:
(1) outer Catalytic Layer adopts the coating method preparation, adds PTFE and makes gas passage, and PTFE content is 10%～50% (volume ratio), fires 20～50 minutes under 320～370 ℃ of temperature, inert atmosphere, treats that temperature reduces to below 100 ℃, takes out this Catalytic Layer;
(2) the internal layer Catalytic Layer is with changeing the platen press preparation, eelctro-catalyst is that Pt/C or Pt are black, add proton conductor, the weight ratio of catalyst and proton conductor is 1: 4～4: 1, and the weight ratio of pore creating material and catalyst is 1: 4～1: 2, adopts spraying method that mixed liquor is sprayed on the poly tetrafluoroethylene, then at 6～15MPa, change being pressed onto on the proton exchange membrane of Na typeization under 160～200 ℃, throw off the PTFE film, make the Na type proton exchange membrane that has the internal layer Catalytic Layer;
(3) proton exchange membrane one that will have a catalyst is sidelong and is put outer Catalytic Layer, opposite side is placed an oxygen cathode, in hydraulic press, be forced into 6～10MPa, the three-in-one membrane electrode assembly with composite anode Catalytic Layer is made in pressing, and the catalyst content weight ratio in the inside and outside two-layer Catalytic Layer is 1/2～1/20 in the composite anode.
In the preparation method of above-mentioned used in proton exchange membrane fuel cell anti-CO compound catalystic layer, after the internal layer Catalytic Layer of described (2) preparation, with this film with 0.2～2MH
2SO
470～90 ℃ protonated again, put into ultra-pure water, obtain the internal layer Catalytic Layer.
In the above-mentioned preparation method who states the used in proton exchange membrane fuel cell anti-CO compound catalystic layer, also can add 1～10% PTFE emulsion in the internal layer Catalytic Layer, to strengthen the gas transfer passage.Be about to eelctro-catalyst and ethanol, PTFE emulsion and in ultrasonic wave, mix, be sprayed onto on the metal forming, behind high-temperature firing with spray gun, at 140～160 ℃, hot pressing is 1～3 minute under 10～12MPa, and the internal layer Catalytic Layer is transferred on the proton exchange membrane, and this proton exchange membrane need not the Na typeization.
In the preparation method of above-mentioned used in proton exchange membrane fuel cell anti-CO compound catalystic layer, also available coating process of internal layer Catalytic Layer or spraying process or sputtering method are made, the mixed liquor (wherein the content of PTFE is 1%～10%) of catalyst and PTFE is coated on the Manufactured outer Catalytic Layer, carries out sintering then and form composite catalytic layer.
In addition, the present invention provides a kind of membrane electrode again, is being composite anode, former proton exchange and composite anode, oxygen cathode hot pressing are formed the three-in-one membrane electrode assembly with composite anode Catalytic Layer by the made composite catalytic layer of the preparation method of above-mentioned used in proton exchange membrane fuel cell anti-CO compound catalystic layer.
The used in proton exchange membrane fuel cell anti-CO compound catalystic layer of the invention described above owing to adopt double-deck Catalytic Layer, has following advantage.
1. adopt the CO-resistance catalysts such as PtRu/C that CO had better activity in outer Catalytic Layer, to there be the CO of poisoning effect to carry out electrochemical oxidation to Pt/C earlier, thereby alleviated the poisoning effect of CO, kept the internal layer Catalytic Layer H to the Pt/C catalyst in the internal layer Catalytic Layer
2Higher activity is arranged.
In the internal layer Catalytic Layer owing to there is hydrophilic proton conductor Nafion, so Catalytic Layer combines closely with proton exchange membrane and outer Catalytic Layer, guaranteed that simultaneously outer Catalytic Layer and proton exchange membrane have proton conductor to be communicated with, and carry out electrochemical reaction.
3. the present invention compares with conventional electrodes, internal layer Catalytic Layer attenuate, and the utilance of catalyst improves.
4. the lophophore amount of eelctro-catalyst is no more than conventional electrodes in the double-deck Catalytic Layer, and the ability that anti-CO poisons increases substantially.
5. when adopting pure hydrogen to be fuel, utilizing the performance of the prepared Proton Exchange Membrane Fuel Cells of the present invention to be higher than conventional is the Proton Exchange Membrane Fuel Cells of anode electrocatalyst with PtRu/C, and suitable with the Proton Exchange Membrane Fuel Cells that with Pt/C is anode electrocatalyst.
6. adopt double-deck Catalytic Layer membrane electrode, can change the catalyst distribution of Catalytic Layer,, improve battery performance, improve anti-CO ability with under the constant situation of catalyst load amount at different fuel gas.
Also give further instruction to technology of the present invention in conjunction with the accompanying drawings below by embodiment.
Fig. 1 is an anode composite catalyst structural representation of the present invention.
Among the figure, 1-gas diffusion layers, 2-outer Catalytic Layer, 3-internal layer Catalytic Layer, 4-Nafion film.
Fig. 2 is with pure H
2During for fuel gas, the monocell performance comparison curve chart of composite anode of the present invention and conventional anode.
Fig. 3 is with 50ppmCO/H
2During for fuel gas, the monocell performance comparison curve chart of composite anode of the present invention and conventional anode.
As shown in Figure 1, anode composite catalytic layer of the present invention is by outer Catalytic Layer 2 and internal layer Catalytic Layer 3 two-layer Catalytic Layer.Outside outer Catalytic Layer 2 is gas diffusion layers, and is the Nafion film outside internal layer Catalytic Layer 3.And constitute the anode composite catalytic layer by said structure.
Embodiment 1
Adopt the one-level balance to take by weighing Pt/C catalyst 0.1mg, 20ml mixes with isopropyl alcohol.Vibration is 30 minutes in ultrasonic wave; After mixing, add 5% Nafion solution 40mg, vibration is 30 minutes in ultrasonic wave; After mixing, add (the NH of 100mg again
4)
2C
2O
4The aqueous solution, vibration is 30 minutes in ultrasonic wave, after mixing, adds 5～10%NaOH solution 40mg, and vibration is 30 minutes in ultrasonic wave, mixes.Mixed liquor is sprayed on the PTFE film of a cleaning with spray gun.Catalytic Layer effective area on the PTFE film is 5cm
2The PTFE film that will scribble catalyst after the spraying dries naturally, and it is standby to put into drier.
The Nafion112 film of Na typeization is placed between the PTFE film of the above-mentioned PTFE film that is sprayed with catalyst and another blank, places hydraulic press hot pressing, temperature is 160～200 ℃, and pressure is 10MPa.After taking out cooling, the PTFE film is taken off, a side have the proton exchange membrane of Catalytic Layer, this Catalytic Layer is the internal layer Catalytic Layer of composite anode.With the H of this film with 0.5M
2SO
4Again after protonated and clean, it is standby to put into deionized water.
With the 1.4mg/cm that contains for preparing according to a conventional method
2(bullion content is 0.28mg/cm to the anode of PtRu/C
2), 2.5mg/cm
2(bullion content is 0.5mg/cm to Pt/C
2) negative electrode be placed on again the side that protonated Nafion film has catalyst and catalyst-free respectively, this assembly is put into hydraulic press hot pressing, promptly get the three-in-one membrane electrode assembly that contains the composite catalytic layer anode.
Above-mentioned three-in-one membrane electrode assembly and two stainless steel end plates are assembled into battery, are 80 ℃ in battery operated temperature, respectively with H
2, 50ppmCO/H
2With O
2Be fuel gas and oxidant, the operating pressure of fuel gas and oxidant is 0.2MPa, and the humidification temperature of fuel gas and oxidant is 85 ℃, and the utilance of fuel gas and oxidant is 50%, carries out the fuel cell electric discharge experiment.(PtRu/C content is 1.5mg/cm to the anode for preparing with conventional method in addition
2, bullion content is 0.3mg/cm
2) make membrane electrode assembly and assembled battery by above-mentioned condition, carry out the monocell experiment.Composite anode monocell and conventional anode monocell contrast properties that the present invention proposes are seen Fig. 3 and Fig. 4.Wherein, Fig. 3, Fig. 4 are respectively with pure hydrogen or 50ppmCO/H
2The composite anode that the present invention proposes during for fuel gas and single pond performance comparison of conventional anode, composite anode of the present invention as can be known from Fig. 3 is when pure hydrogen is fuel, performance is higher than conventional PtRu/C anode; And by Fig. 4 with 50ppmCO/H
2During for fuel gas, the performance of composite anode of the present invention is also good than conventional PtRu/C anode, illustrates that composite anode structure that the present invention proposes can make battery performance with pure hydrogen and CO/H
2All be improved during for fuel gas.
Embodiment 2
Adopt the one-level balance to take by weighing Pt/C catalyst 0.1mg, 15ml mixes with absolute ethyl alcohol.Vibration is 30 minutes in ultrasonic wave, after mixing, adds 5% the PTFE emulsion of 1mg again, and vibration is 30 minutes in ultrasonic wave, mixes.Mixed liquor is sprayed to spray gun on the aluminium foil of a cleaning, and the effective area of Catalytic Layer is 5cm on the aluminium foil
2After the spraying aluminium foil is inserted in the muffle furnace, 320～360 ℃ of temperature sintering 20 minutes, took out the back of waiting to lower the temperature under protective atmosphere, and it is standby to put into drier.
Will be through H
2O
2, H
2SO
4The Nafion112 film of handling is placed between the PTFE film of the above-mentioned aluminium foil that is sprayed with catalyst and another blank, places hydraulic press hot pressing, and temperature is 130～160 ℃, and pressure is 10MPa.After taking out cooling, the PTFE film is taken off, a side have the proton exchange membrane of Catalytic Layer, this Catalytic Layer is the internal layer Catalytic Layer of composite anode.
With the 1.0mg/cm that contains for preparing according to a conventional method
2The anode of CO-resistance catalysts such as PtRu/C, 1.5mg/cm
2The negative electrode of Pt/C is placed on again the side that protonated Nafion film has catalyst and catalyst-free respectively, and this assembly is put into hydraulic press hot pressing, promptly gets the three-in-one membrane electrode assembly that contains the composite catalytic layer anode.
Above-mentioned three-in-one membrane electrode assembly and two stainless steel end plates are assembled into battery, are 80 ℃ at battery temperature, respectively with H
2, 50ppmCO/H
2With O
2Be fuel gas and oxidant, the operating pressure of fuel gas and oxidant is 0.2MPa, and the humidification temperature of fuel gas and oxidant is 85 ℃, and the utilance of fuel gas and oxidant is 50%, carries out the fuel cell electric discharge experiment.
Embodiment 3
Preparation contains 1.0mg/cm according to a conventional method
2PtRuWO
3The anode of/C: adopt the one-level balance to take by weighing PtRu/C catalyst 5.0mg, 15ml mixes with absolute ethyl alcohol.Vibration is 30 minutes in ultrasonic wave, after mixing, adds 20% the PTFE aqueous solution of 20～40mg again, and vibration is 30 minutes in ultrasonic wave, mixes.Mixed liquor is heated in 100 ℃ of water-baths and stirred 3～5 minutes, it is 5cm that this mixed liquor is coated to a slice area
2Diffusion layer on, form outer Catalytic Layer.This Catalytic Layer under protective atmosphere, was burnt 30 minutes 340 ℃ of temperature, remove the surfactant among the PTFE and make the PTFE commissure form gas passage.
Adopt the one-level balance to take by weighing Pt/C catalyst 0.5mg/cm
2, 15ml mixes with absolute ethyl alcohol.Vibration is 30 minutes in ultrasonic wave, after mixing, adds 20% the PTFE aqueous solution of 20～40mg again, and vibration is 30 minutes in ultrasonic wave, mixes.Mixed liquor is heated in 100 ℃ of water-baths and stirred 3～5 minutes, this mixed liquor is coated on the aforesaid outer Catalytic Layer, form the internal layer Catalytic Layer.Still under protective atmosphere, burnt 30 minutes then, form anti-CO anode with composite catalytic layer in 340 ℃ of temperature.
The Nafion112 film is placed between above-mentioned anode and the conventional oxygen cathode of a slice, and hot pressing is 1～2 minute in hydraulic press, and temperature is 130～150 ℃, and pressure is 2MPa.Form three-in-one membrane electrode assembly.
Above-mentioned three-in-one membrane electrode assembly and two stainless steel end plates are assembled into battery, are 80 ℃ at battery temperature, respectively with H
2, 50ppmCO/H
2With O
2Be fuel gas and oxidant, the operating pressure of fuel gas and oxidant is 0.2MPa, and the humidification temperature of fuel gas and oxidant is 85 ℃, and the utilance of fuel gas and oxidant is 50%, carries out the fuel cell electric discharge experiment.
From the above, adopt composite catalytic layer mea of the present invention to dress up battery and have better electrode performance than the battery of conventional electrodes assembling.In addition, composite catalytic layer of the present invention can be with Catalytic Layer layering preparation, form catalyst along battery shaft to Gradient distribution.The load amount of total noble metal catalyst is less than or equal to the electrode of conventional method preparation in the prepared composite catalytic layer.The composite catalytic layer Stability Analysis of Structures in conjunction with good, is difficult for layering, can make broad-area electrode.Form at different fuel gas, both can when pure hydrogen fuel, obtain higher battery performance, also can when use contains CO fuel gas, keep the quite cell discharge performance of level.During battery operation, need not to be blown into oxygen, simple to operate, safe and reliable.
Claims (11)
1. used in proton exchange membrane fuel cell anti-CO compound catalystic layer, adopting Pt and/or Ru is active component, it is characterized in that by the inside and outside two-layer composite catalytic layer that constitutes, wherein, outer Catalytic Layer adopts the PtRu/C CO-resistance catalyst, the internal layer Catalytic Layer adopts Pt/C or Pt black appliances catalyst, and the catalyst content weight ratio in the inside and outside two-layer Catalytic Layer is 1/2-1/20.
2. used in proton exchange membrane fuel cell anti-CO compound catalystic layer according to claim 1 is characterized in that outer Catalytic Layer adds PTFE, and PTFE content and outer Catalytic Layer volume ratio are 10-50%.
3. used in proton exchange membrane fuel cell anti-CO compound catalystic layer according to claim 1 is characterized in that the internal layer Catalytic Layer adds proton conductor, and the weight ratio of internal layer Catalytic Layer and proton conductor is 1: 4--4: 1.
4. used in proton exchange membrane fuel cell anti-CO compound catalystic layer according to claim 1 is characterized in that the internal layer Catalytic Layer adds pore creating material, and the weight ratio of pore creating material and internal layer Catalytic Layer is 1: 4--1: 2.
5. used in proton exchange membrane fuel cell anti-CO compound catalystic layer according to claim 4 is characterized in that it is (NH that the internal layer Catalytic Layer adds pore creating material
4)
2C
2O
4, NaCl or PTFE.
6. used in proton exchange membrane fuel cell anti-CO compound catalystic layer according to claim 4 is characterized in that internal layer catalyst adds PTFE, and PTFE content and internal layer Catalytic Layer volume ratio are 1-10%.
7. the preparation method of a used in proton exchange membrane fuel cell anti-CO compound catalystic layer is characterized in that by following step:
(1) outer Catalytic Layer adopts the coating method preparation, adds PTFE and makes gas passage, and PTFE content is 10%～50% (volume ratio), fires 20～50 minutes under 320～370 ℃ of temperature, inert atmosphere, treats that temperature reduces to below 100 ℃, takes out this Catalytic Layer;
(2) the internal layer Catalytic Layer is with changeing the platen press preparation, eelctro-catalyst is that Pt/C or Pt are black, add proton conductor, the weight ratio of catalyst and proton conductor is 1: 4～4: 1, and the weight ratio of pore creating material and catalyst is 1: 4～1: 2, adopts spraying method that mixed liquor is sprayed on the poly tetrafluoroethylene, then at 6～15MPa, change being pressed onto on the proton exchange membrane of Na typeization under 160～200 ℃, throw off the PTFE film, make the Na type proton exchange membrane that has the internal layer Catalytic Layer;
(3) proton exchange membrane one that will have a catalyst is sidelong and is put outer Catalytic Layer, opposite side is placed an oxygen cathode, in hydraulic press, be forced into 6～10MPa, the three-in-one membrane electrode assembly with composite anode Catalytic Layer is made in pressing, and the catalyst content weight ratio in the inside and outside two-layer Catalytic Layer is 1/2～1/20 in the composite anode.
8. the preparation method of used in proton exchange membrane fuel cell anti-CO compound catalystic layer according to claim 7 is characterized in that after the internal layer Catalytic Layer of described (2) preparation, with this film with 0.2～2MH
2SO
470～90 ℃ protonated again, put into ultra-pure water, obtain the internal layer Catalytic Layer.
9. the preparation method of used in proton exchange membrane fuel cell anti-CO compound catalystic layer according to claim 7, it is characterized in that also can adding in the internal layer Catalytic Layer 1～10% PTFE emulsion, to strengthen the gas transfer passage, being about to eelctro-catalyst and ethanol, PTFE emulsion mixes in ultrasonic wave, be sprayed onto on the metal forming with spray gun, behind high-temperature firing, at 140～160 ℃, hot pressing is 1～3 minute under 10～12MPa, the internal layer Catalytic Layer is transferred on the proton exchange membrane, and this proton exchange membrane need not the Na typeization.
10. the preparation method of used in proton exchange membrane fuel cell anti-CO compound catalystic layer according to claim 7, it is characterized in that also available coating process of internal layer Catalytic Layer or spraying process or sputtering method make, the mixed liquor (wherein the content of PTFE is 1%～10%) of catalyst and PTFE is coated on the Manufactured outer Catalytic Layer, carries out sintering then and form composite catalytic layer.
11. a membrane electrode is characterized in that being composite anode, former proton exchange and composite anode, oxygen cathode hot pressing are formed the three-in-one membrane electrode assembly with composite anode Catalytic Layer by the made composite catalytic layer of the preparation method of claim 7,9 or 10 described used in proton exchange membrane fuel cell anti-CO compound catalystic layers.
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|---|---|---|---|
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| CN1299375C (en) * | 2005-02-01 | 2007-02-07 | 哈尔滨工业大学 | Method for preparing Pt-Ru/C catalyst in use for direct methanol fuel cell |
| CN101496208B (en) * | 2005-05-06 | 2012-06-13 | 俄亥俄州立大学 | Electrocatalysts and additives for the oxidation of solid fuels |
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| CN107658485A (en) * | 2017-09-22 | 2018-02-02 | 深圳先进储能材料国家工程研究中心有限公司 | Membrane electrode of fuel batter with proton exchange film and preparation method thereof |
| CN110085875A (en) * | 2019-04-19 | 2019-08-02 | 同济大学 | A kind of multilayer Catalytic Layer and preparation method thereof for alleviating the decaying of Catalytic Layer containing alloy |
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2001
- 2001-04-10 CN CNB011105380A patent/CN1181583C/en not_active Expired - Lifetime
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| CN1299375C (en) * | 2005-02-01 | 2007-02-07 | 哈尔滨工业大学 | Method for preparing Pt-Ru/C catalyst in use for direct methanol fuel cell |
| CN101496208B (en) * | 2005-05-06 | 2012-06-13 | 俄亥俄州立大学 | Electrocatalysts and additives for the oxidation of solid fuels |
| CN106338459A (en) * | 2016-08-26 | 2017-01-18 | 上海交通大学 | Method for measuring oxygen effective diffusion coefficient in fuel cell catalyst layer |
| CN107658485A (en) * | 2017-09-22 | 2018-02-02 | 深圳先进储能材料国家工程研究中心有限公司 | Membrane electrode of fuel batter with proton exchange film and preparation method thereof |
| CN110085875A (en) * | 2019-04-19 | 2019-08-02 | 同济大学 | A kind of multilayer Catalytic Layer and preparation method thereof for alleviating the decaying of Catalytic Layer containing alloy |
| CN112825366A (en) * | 2019-11-21 | 2021-05-21 | 中国科学院大连化学物理研究所 | High-temperature proton membrane fuel cell membrane electrode based on hydrogen-poor reformed gas feeding, preparation and application |
| CN112083041A (en) * | 2020-09-15 | 2020-12-15 | 中国科学院大连化学物理研究所 | Online testing method for resin content of catalyst layer of fuel cell |
| CN112083041B (en) * | 2020-09-15 | 2021-06-01 | 中国科学院大连化学物理研究所 | Online testing method for resin content of catalyst layer of fuel cell |
| CN114171744A (en) * | 2022-02-11 | 2022-03-11 | 北京新研创能科技有限公司 | Polar plate of fuel cell, preparation method of polar plate, fuel cell stack, fuel cell system and cold start method of fuel cell system |
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