CN101383416B - A method for improving the anti-CO performance of proton exchange membrane fuel cell - Google Patents
A method for improving the anti-CO performance of proton exchange membrane fuel cell Download PDFInfo
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- CN101383416B CN101383416B CN2007100127144A CN200710012714A CN101383416B CN 101383416 B CN101383416 B CN 101383416B CN 2007100127144 A CN2007100127144 A CN 2007100127144A CN 200710012714 A CN200710012714 A CN 200710012714A CN 101383416 B CN101383416 B CN 101383416B
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- fuel cell
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- proton exchange
- diffusion layer
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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
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Abstract
The invention relates to a method for enhancing the resistance of a proton exchange membrane fuel cell to foreign gas, in particular to a method for enhancing the resistance of the fuel cell to CO. Catalyst which has catalytic action and oxidizing action to the CO gas is born in the anode diffuser layer of the proton exchange membrane fuel cell, under the condition of infusing a small amount of oxygen gas, the CO gas impurities which cause the performance of the proton exchange membrane fuel cell to be attenuated are catalyzed and oxidized when passing through the diffuser layer, and the CO gas impurities react to form CO2 which has small influence to the performance of the cell, therefore, the resistance of the proton exchange membrane fuel cell to the CO is enhanced, and the developmentand the application of the fuel cell are promoted.
Description
Technical field
The present invention relates to improve the method for CO resistance performance of fuel cell with proton exchange film, specifically in the Proton Exchange Membrane Fuel Cells anode diffusion layer, support catalyst Pt or the Au that CO gas is had catalytic action, under the condition of injecting minor amounts of oxygen, the CO gaseous impurity is generated CO2 by catalytic reaction by diffusion layer the time, thereby improve the CO resistance performance of Proton Exchange Membrane Fuel Cells, promoted the development and the application of fuel cell.
Background technology
At present fuel cell is because its high energy conversion efficiency, characteristics such as environmentally friendly are subjected to extensive attention, and characteristics such as Proton Exchange Membrane Fuel Cells also has that room temperature starts fast, no electrolyte loss, life-span are long are considered to the optimal candidate power supply of removable power supply.Yet trace amount of foreign gas may cause eelctro-catalyst to poison in fuel (hydrogen or purification reformation gas) and the oxidant (air or oxygen), battery performance is descended, and these foreign gases is difficult to avoid sometimes.At present, in order to improve the life-span of PEMFC, just improve proton exchange membrane electrode performance and durability, many research institutions are doing a large amount of work aspect the influence of anti-foreign gas.Wherein studying more is that carbon monoxide (CO) causes electrode poisoning problem.In document 1 US Patent 6,689,194, between hydrogen source and anode of fuel cell, add a foreign gas removal device, be filled with adsorbents such as platinum, silver, tungsten, mica, active carbon in this device.When the hydrogen stream that contains foreign gas by this when device, adsorbent can be removed wherein carbon monoxide (CO), carbon dioxide (CO by the method for chemisorbed
2) and other foreign gases.The advantage of the method is can realize than being easier to that by changing a new foreign gas removal device shortcoming is to need to increase extra device after adsorbent absorption is saturated.At document 2 US Patent 4,910, oxygen by inject 2%～6% continuously in the anode fuel porch is proposed in 099, thus under the effect of eelctro-catalyst with the less carbon dioxide (CO of carbon monoxide (CO) oxidation paired electrode influence of 100～500ppm
2).The efficient of the method is higher, and easy operating, but can cause local overheating, destroys proton exchange membrane, shortens battery life, can bring the battery system safety issue simultaneously.In document 3 US Patent 6,500,572, above-mentioned notes oxygen method is improved, do not adopted continuous notes oxygen, but amount of oxygen what the voltage signal that provides by a carbon monoxide (CO) detector control injects.Also can adopt periodicity or the interim method of annotating oxygen.This method can be avoided the decline of local overheating and the excessive battery efficiency that causes of oxygen, and the thermal effect that notes oxygen brings but this method mainly still can not be avoided fully is also broken to catalyst and film, and more complicated.In addition, in document 5 WO 00/36679,, under injecting, significantly strengthened CO resistance performance of fuel cell than a small amount of conditions of air by support the method for Pt, Ru or PtRu catalyst in anode diffusion lamellar field side.
Summary of the invention
The object of the present invention is to provide a kind of method that can improve CO resistance performance of fuel cell with proton exchange film, the method is simple, does not need extra removal device.
For achieving the above object, the technical solution used in the present invention is:
A kind of method that can improve CO resistance performance of fuel cell supports the catalyst that CO gas is had catalysed oxidn in the Proton Exchange Membrane Fuel Cells anode diffusion layer.
Described catalyst is Pt or Au catalyst; Wherein the loading of Pt or Au catalyst is 0.1-0.5mg/cm
2, optimum range is 0.1-0.3mg/cm
2
Specific operation process is: 3-5min in the ethanolic solution that will impregnated in 0.03-0.09mol/L chloroplatinic acid or gold chloride as the carbon paper or the charcoal cloth of anode diffusion layer, in 60-100 ℃ of oven dry down, then with impregnated carbon paper under hydrogen atmosphere in 400-800 ℃ of following reductase 12-8 hour, promptly can be used as anode gas diffusion layer and be prepared into anode (hereinafter referred to as modified anode) with carbon paper through above-mentioned processing.
Under the condition of injecting minor amounts of oxygen, can cause the CO gaseous impurity of proton exchange film fuel battery performance decay to react generation to the very little CO of battery performance influence by catalytic oxidation by diffusion layer the time
2Thereby the CO resistance performance of raising Proton Exchange Membrane Fuel Cells has promoted the development and the application of fuel cell.
The present invention has following advantage:
1. method is simple.Owing in will catalyst loading gas diffusion layers, will cause the CO gaseous impurity of fuel cell performance decay oxidized by the flow field time by catalytic reaction, generate to the very little CO of fuel battery performance influence at impure gas CO
2, compare document 1 and document 4 the method do not need extra impurity removal means.
2. can improve fuel cell performance and life-span, compare document 2, because the oxidation of CO is sent out and should be occurred in the gas diffusion layers, avoid anode inlet to annotate the local overheating that oxygen causes continuously among the present invention, can not bring destruction eelctro-catalyst and proton exchange membrane.
3. oxygen utilization rate height, because Pt or Au catalyst have good CO selective oxidation catalytic action in the diffusion layer, the trace oxygen of injection can be effectively with the CO oxidation.
Description of drawings
Fig. 1 is a MEA structural representation catalyst-loaded in anode diffusion layer.When containing the fuel gas process anode diffusion layer of CO, under the effect of catalyst Pt or Au, the trace oxygen of CO and injection reacts, and generates CO
2Thereby, improved CO resistance performance of fuel cell with proton exchange film.
Fig. 2 is the anti-CO MEA of use modified anode preparation and the comparison of conventional MEA performance in 100ppmCO/ hydrogen, 0.1MPa, and anode room temperature humidification, the saturated humidification of negative electrode, battery temperature are 60 ℃, fuel gas flow velocity: 50ml/min; MEA1 wherein, the reduction temperature of MEA2 and MEA3 is respectively 400,600 and 800 ℃.
Fig. 3 is the anti-CO MEA of use modified anode preparation and the comparison of conventional MEA performance in 100ppmCO/ hydrogen, 0.1MPa, anode room temperature humidification, the saturated humidification of negative electrode, battery temperature is 60 ℃, fuel gas flow velocity: 50ml/min, wherein MEA4, Pt catalyst load amount is respectively 0.1,0.2 and 0.3mg/cm in MEA5 and the MEA2 anode diffusion layer
2
Fig. 4 is the anti-CO MEA of use modified anode preparation and the comparison of conventional MEA performance in 100ppmCO/ hydrogen, 0.1MPa, anode room temperature humidification, the saturated humidification of negative electrode, battery temperature is 60 ℃, fuel gas flow velocity: 50ml/min, wherein MEA6, Au catalyst load amount is respectively 0.1,0.2 and 0.3mg/cm in MEA7 and the MEA8 anode diffusion layer
2
Embodiment
Support 0.3mg/cm with the preparation anode diffusion layer
2The MEA of Pt catalyst is example (MEA2 shown in the table 1), gets 77cm
2One of Toray carbon paper, be impregnated in the H of 0.084mol/L
2PtCl
66H
2In the ethanolic solution of O, take out after 3 minutes, and 80 ℃ of oven dry down.Subsequently, will place crystal reaction tube, feed under the condition of hydrogen, and the crystal reaction tube temperature will be elevated to 600 ℃, and keep 2 hours, reduce fully, so just obtain supporting 0.3mg/cm to guarantee the chloroplatinic acid in the carbon paper through the carbon paper of dipping chloroplatinic acid
2The carbon paper of Pt catalyst.For strengthening the hydrophobicity of diffusion layer, be anode diffusion layer with this treated carbon paper, impregnated in after the PTFE emulsion in 330 ℃ of roasts 40 minutes.The carbon paper that has supported catalyst prepares the electro-catalysis layer through hydrophobic processing back by the method that sprays, and obtains diffusion layer and supports 0.3mg/cm
2The modified anode of Pt catalyst.The hot pressing under 140 ℃, 10MPa of modified anode, Nafion 112 films, negative electrode obtained the MEA2 shown in the table 1 in 1 minute.
Change can be controlled the load amount of anode diffusion layer catalyst by changing chloroplatinic acid or gold chloride concentration, can control the size of catalyst granules in the anode diffusion layer to a certain extent by changing reduction temperature.The anode diffusion layer inner catalyst kind of 8 kinds of MEA shown in the table 1, load amount are different with reduction temperature, and its preparation method is identical with said method.
Table 1 changes 8 kinds of MEA of anode diffusion layer inner catalyst kind, load amount and reduction temperature preparation
| Sample | Catalyst load amount (mg cm in the anode diffusion layer -2) | Reduction temperature (℃) | Used chloroplatinic acid or chlorauric acid solution concentration (mol/L) |
| MEA-1 MEA-2 MEA-3 MEA-4 MEA-5 MEA-6 MEA-7 MEA-8 | Pt：0.3mg?cm
-2Pt：0.3mg?cm
-2Pt：0.3mg?cm
-2Pt：0.1mg?cm
-2Pt：0.2mg?cm
-2Au：0.1mg?cm
-2Au：0.2mg?cm
-2Au：0.3mg? |
400 |
0.0840.0840.0840.0280.0560.0250.0500.075 |
Adopt monocell, the battery effective area is 5cm
2, fuel gas (100ppmCO/H
2) and air mass flow be respectively 50ml/min and 600ml/min, operating pressure is 0.1MPa, battery temperature is 60 ℃, anode and negative electrode humidification temperature are respectively: 25 and 60 ℃.After battery activates, feed 100ppm/H in pure hydrogen
2, the CO resistance performance of 8 kinds of MEA in the investigation table 1.
Fig. 2 is anti-CO MEA and the battery polarization curve of conventional MEA under 100ppmCO, can see that by Fig. 2 battery performance is obviously decayed after feeding contains the hydrogen of 100ppmCO, and decay is especially remarkable in the low current density scope.It is that a kind of efficient and simple method improves the battery CO resistance performance that anode is annotated oxygen, even adopt conventional MEA as seen from Figure 2, after injecting 2% air in the fuel gas, battery performance obtains part and recovers, but still not ideal enough, at 900mA/cm
2The time, voltage only is about 0.3V.By improving electrode structure, promptly some Pt particles of preparation in diffusion layer injecting under the constant situation of amount of oxygen, can effectively improve battery performance.As MEA2 (reduction temperature: 600 ℃) at 900mA/cm
2The time, voltage can reach 0.566V (respective value of reference MEA in pure hydrogen is 0.606V).
Fig. 3 is the different antagonism of a Pt load amount CO Effect on Performance in the diffusion layer, MEA4 wherein, among MEA5 and the MEA2 in the diffusion layer Pt load amount be respectively 0.1mg/cm
2, 0.2mg/cm
2And 0.3mg/cm
2As can see from Figure 3, Pt load amount is 0.2 and 0.3mg/cm in the diffusion layer
2The time, battery has good CO resistance performance, and all being better than Pt load amount is 0.1mg/cm
2MEA4.
Fig. 4 for the anti-CO MEA that supports Au in the anode diffusion layer and conventional MEA at 100ppmCO/H
2In battery performance.As we can see from the figure, compare and support Pt in the diffusion layer, the change of the interior Au load amount of diffusion layer is less to the influence of battery CO resistance performance, MEA6 (Au:0.1mg/cm
2), MEA7 (Au:0.2mg/cm
2) and MEA8 (Au:0.3mg/cm
2) at 100ppmCO/H
2In battery performance more approaching, but CO resistance performance all far is better than conventional MEA.
Claims (2)
1. a method that improves CO resistance performance of fuel cell is characterized in that: support the catalyst that CO gas is had catalysed oxidn in the Proton Exchange Membrane Fuel Cells anode diffusion layer;
Described catalyst is Pt or Au catalyst; Wherein the loading of Pt or Au catalyst is 0.1-0.5mg/cm
2
Specific operation process is: will impregnated in 3-5min in the ethanolic solution of 0.03-0.09mol/L chloroplatinic acid or gold chloride as the carbon paper of anode diffusion layer, in 60-100 ℃ of oven dry down, then with impregnated carbon paper under hydrogen atmosphere in 400-800 ℃ of following reductase 12-8 hour, promptly can be used as anode gas diffusion layer with carbon paper through above-mentioned processing.
2. according to the method for the described raising CO resistance performance of fuel cell of claim 1, it is characterized in that: the loading of described Pt or Au catalyst is 0.1-0.3mg/cm
2
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| CN101383416B true CN101383416B (en) | 2010-12-08 |
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| KR20220005552A (en) * | 2019-05-07 | 2022-01-13 | 필립스 66 컴퍼니 | Evaluation of Solid Oxide Fuel Cell Cathode Materials |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202984A (en) * | 1995-11-28 | 1998-12-23 | 德国赫彻斯特研究技术两合公司 | Gas diffusion electrode for polymer electrolyte membrane fuel cells |
| CN1885599A (en) * | 2005-06-22 | 2006-12-27 | 中国科学院大连化学物理研究所 | Anti-carbon monoxide composite anode electrode catalyst layer structure and preparation method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202984A (en) * | 1995-11-28 | 1998-12-23 | 德国赫彻斯特研究技术两合公司 | Gas diffusion electrode for polymer electrolyte membrane fuel cells |
| CN1885599A (en) * | 2005-06-22 | 2006-12-27 | 中国科学院大连化学物理研究所 | Anti-carbon monoxide composite anode electrode catalyst layer structure and preparation method |
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