CN101150195A - A method for eliminating impure gas CO influence on the fuel battery performance - Google Patents
A method for eliminating impure gas CO influence on the fuel battery performance Download PDFInfo
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- CN101150195A CN101150195A CNA200610047849XA CN200610047849A CN101150195A CN 101150195 A CN101150195 A CN 101150195A CN A200610047849X A CNA200610047849X A CN A200610047849XA CN 200610047849 A CN200610047849 A CN 200610047849A CN 101150195 A CN101150195 A CN 101150195A
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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
This invention relates to a method for increasing ability of anti-impurity of proton exchange membrane fuel cells, which sets a catalyst catalyzing CO gas on the surface of a flow field of proton exchange membrane fuel cell, thus, gas impurities causing attenuation of performance of fuel cells will be catalyzed to generate substances not causing attenuation so as to increase performance and life of fuel cells.
Description
Technical field
The present invention relates to improve the method for the anti-foreign gas ability of Proton Exchange Membrane Fuel Cells, specifically a kind of method of eliminating impure gas CO to the fuel battery performance influence, fuel cell performance and life-span be can improve, the development and the application of fuel cell promoted.
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 1US 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.Oxygen by inject 2%～6% continuously in the anode fuel porch is proposed in document 2US Patent 4,910,099, 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 3US 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, but this method is primarily aimed at carbon monoxide (CO) gaseous impurity, and more complicated.Adopted an impurity removal means of being made up of porous material and selective absorbing film in document 4WO2005/071785, this device can be removed foreign gas such as the hydrogen sulfide (H in the oxidant (air)
2S), oxysulfide (SO
X) and nitrogen oxide (NO
X).This method scope of application is wider, but needs extra device, and the complicated process of preparation of selective absorbing film.In addition, in document 5WO 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 of eliminating impure gas CO to the fuel battery performance influence, the method is simple, do not need extra removal device, and be applicable to trace amount of foreign gas in removal fuel (hydrogen or purification reformation gas) and the oxidant (air or oxygen) simultaneously.
For achieving the above object, the technical solution used in the present invention is:
A kind of method of eliminating impure gas CO to the fuel battery performance influence supports the catalyst that CO gas is had catalytic action on surface, Proton Exchange Membrane Fuel Cells anode-side flow field.
Said method is not only applicable to the anode-side flow field, is used for the cathode side flow field simultaneously yet, is promptly supporting the catalyst that CO gas is had catalytic action on surface, fuel battery cathode with proton exchange film effluent field.
Described catalyst is that active constituent is that Pt or PtRu support the shape catalyst, and its carrier can be the C+AL of C, C content 〉=50%
2O
3Or the C+Fe of C content 〉=50%
2O
3The weight of active constituent can be 10～60% in the catalyst, when active constituent is PtRu, and Pt and Ru weight ratio 〉=1; Preferred catalysts is Pt/C or PtRu/C, and the weight of active constituent is 20～50%; Described flow field is graphite flow field or metal flow field, and it can be parallel groove flow field, crawl flow field or other form flow fields.
Specific operation process is,
(1) catalyst that will catalytic action be arranged to CO gas and polytetrafluoroethylene (PTFE) aqueous emulsion and organic solvent and water mix, even through ultrasonic oscillation, wherein the mass ratio of catalyst and PTFE aqueous emulsion is 5: 1～1: 1, the mass ratio of catalyst and organic solvent is 1: 500～1: 5000, and the volume ratio of organic solvent and water is 1: 1～1: 3 in the mixed liquor; The concentration of PTFE aqueous emulsion is 20-60%;
(2) with mixed liquor with smearing or method such as spray gun spraying supports on the flow field, thickness is 10～50 μ m, through 240～370 ℃ of sintering, the time is 30～40 minutes.
Described organic solvent can be C1-C4 alcohol, as ethanol, isopropyl alcohol etc.
The present invention has following advantage:
1. method is simple.Because will be on the flow field at the catalyst loading of impure gas CO, will cause pernicious gas impurity oxidized or reduction the time of fuel cell performance decay by the flow field by catalytic reaction, generation does not have influence or the more weak material of influence to fuel battery performance, compares document 1 and document 4 the method do not need extra impurity removal means.Compare document 2, the present invention has avoided anode inlet to annotate the local overheating that oxygen causes continuously, can not bring destruction to eelctro-catalyst and proton exchange membrane.
2. can improve fuel cell performance and life-span.To there be the catalyst of catalytic action to be supported on the Proton Exchange Membrane Fuel Cells flow field to foreign gas by distinct methods, like this those can cause fuel cell performance decay gaseous impurity will when the flow field by catalytic oxidation or reduction, generation does not have influence or the more weak material of influence to fuel battery performance, thereby improve fuel cell performance and life-span, promoted the development and the application of fuel cell.(experimental results show that CO
2Also can team's battery performance influential, but have only when concentration reach 10% or more just influential, but can not say fully do not influence)
3. applied widely, be applicable to simultaneously and remove trace amount of foreign gas in fuel (hydrogen or purification reformation gas) and the oxidant (air or oxygen).
Below by example in detail the present invention is described in detail, the objectionable impurities gas in example in the fuel gas is the CO of 50ppm and 10ppm.
Description of drawings
Fig. 1 is at the catalyst-loaded battery structure schematic diagram of anode flow field, wherein: the 1-battery pole plates; The 2-graphite flow field; The Catalytic Layer that is supported on the 3-flow field; 4-carbon paper diffusion layer; 5-anode electrocatalyst layer, Pt load amount is 0.3mg/cm
26-Nafion 112 proton exchange membrane; 7-cathodic electricity Catalytic Layer, Pt load amount is 0.5mg/cm
2
Fig. 2 is for supporting the battery polarization curve of Pt catalyst on the flow field, fuel gas adopts pure hydrogen.
Fig. 3 (a) and (b) for support the battery polarization curve of Pt catalyst on the flow field, fuel gas adopts the hydrogen that contains 50ppm and 100ppmCO, and injects 3% air in fuel gas battery porch.
Fig. 4 is for supporting the battery polarization curve of PtRu catalyst on the flow field, fuel gas adopts pure hydrogen.
Fig. 5 (a) and (b) for support the battery polarization curve of PtRu catalyst on the flow field, fuel gas adopts the hydrogen that contains 50ppm and 100ppmCO, and injects 3% air in fuel gas battery porch.
Take by weighing 5mg Pt/C (20%), add 1～2ml deionized water and 2～5ml ethanol, evenly mix the back and add a certain amount of PTFE aqueous solution (30%), wherein the mass ratio of the PTFE aqueous solution and catalyst is 1: 1.Use spray gun to spray to area after in ultrasonic wave, vibrating 15 minutes and be 10cm
2The flow field on, spraying finishes the back 240 ℃ of insulations 40 minutes, 340 ℃ of roasts 40 minutes, obtaining the catalyst Pt loading was 0.1mg/cm then
2The flow field.Use and prepare the Pt loading with quadrat method and be 0.2mg/cm
2And 0.3mg/cm
2The flow field.
According to assembled battery shown in Figure 1, the battery effective area is 5cm
2, T
Cell=T
The hydrogen humidification=T
Air humidification, air mass flow is 800ml/min.Fuel gas is under the condition of purified hydrogen, obtains polarization curve as shown in Figure 2, wherein:
The ref-reference cell, the flexible graphite flow field is adopted in the flow field, and is not modified;
F-Pt0.1-galvanic anode flow field supports 0.1mg/cm
2The Pt catalyst;
F-Pt0.2-galvanic anode flow field supports 0.2mg/cm
2The Pt catalyst;
F-Pt0.3-galvanic anode flow field supports 0.3mg/cm
2The Pt catalyst;
The PtRu-battery uses the PtRu electrode of anti-CO, but the flow field is not modified;
As shown in Figure 2, the catalyst-loaded battery performance that can't cause under the condition of the pure hydrogen of use descends in the flow field.
Fuel gas is switched to the hydrogen that contains 50ppmCO and 100ppmCO, and in fuel gas, inject 3% air, obtain polarization curve shown in Figure 3.Use the battery in the flow field of process modification obviously to be promoted as seen from the figure, and be better than the battery that uses the anti-CO electrode of PtRu with respect to the reference cell performance.When use contains the hydrogen of 100ppmCO and 3% air, battery 800mA/cm
2During constant-current discharge, use the battery of modifying the flow field to obtain the performance boost of 150～200mV with respect to reference cell.
Take by weighing 5mg PtRu/C (Pt 20%, and Ru 10%), add 1～2ml deionized water and 2～5ml ethanol, evenly mix the back and add a certain amount of PTFE aqueous solution (30%), wherein the mass ratio of the PTFE aqueous solution and catalyst is 1: 1.Use spray gun to spray to area after in ultrasonic wave, vibrating 15 minutes and be 10cm
2The flow field on, spraying finishes the back 240 ℃ of insulations 40 minutes, then 340 ℃ of roasts 40 minutes.Take by weighing the amount of PtRu/C and the area of the graphite flow field that uses by control, obtaining catalyst Pt Ru loading is 0.1mg/cm
2The flow field.Use and obtain the PtRu loading with quadrat method and be 0.2mg/cm
2And 0.3mg/cm
2The flow field.
According to assembled battery shown in Figure 1, the battery effective area is 5cm
2, T
Cell=T
The hydrogen humidification=T
Air humidification, air mass flow is 800ml/min.Fuel gas is under the condition of purified hydrogen, obtains polarization curve as shown in Figure 4, wherein:
The ref-reference cell, the flexible graphite flow field is adopted in the flow field, and is not modified;
F-PtRu0.1-galvanic anode flow field supports 0.1mg/cm
2The PtRu catalyst;
F-PtRu0.2-galvanic anode flow field supports 0.2mg/cm
2The PtRu catalyst;
F-PtRu0.3-galvanic anode flow field supports 0.3mg/cm
2The PtRu catalyst;
The PtRu-battery uses the PtRu electrode of anti-CO, but the flow field is not modified;
It is similar to support the Pt catalyst with the flow field, and supporting the PtRu catalyst in the flow field can not influence battery performance yet.
Fuel gas is switched to the hydrogen that contains 50ppmCO and 100ppmCO, and in fuel gas, inject 3% air, obtain polarization curve shown in Figure 5.Use the battery in the flow field of process modification obviously to be promoted as seen from the figure, and be better than the battery that uses the anti-CO electrode of PtRu equally with respect to the reference cell performance.When use contains the hydrogen of 100ppmCO and 3% air, battery 800mA/cm
2During constant-current discharge, use the battery of modifying the flow field to obtain the performance boost of 120～150mV with respect to reference cell.
It is effective and feasible strengthening the battery CO resistance performance in the catalyst-loaded method of fuel battery flow field as can be known by example.The method can also be used to strengthening the performance of anti-other objectionable impurities gases of battery.
Claims (8)
1. a method of eliminating impure gas CO to the fuel battery performance influence is characterized in that: support the catalyst that CO gas is had catalytic action on surface, Proton Exchange Membrane Fuel Cells anode-side flow field.
2. it is characterized in that in accordance with the method for claim 1: support the catalyst that CO gas is had catalytic action on surface, fuel battery cathode with proton exchange film effluent field.
3. in accordance with the method for claim 1, it is characterized in that: described catalyst is that active constituent is that Pt or PtRu support the shape catalyst, and its carrier can be the C+AL of C or C content 〉=50%
2O
3
4. in accordance with the method for claim 3, it is characterized in that: the weight of active constituent is 10～60% in the catalyst, when active constituent is PtRu, and Pt and Ru weight ratio 〉=1.
5. in accordance with the method for claim 3, it is characterized in that: described catalyst is Pt/C or PtRu/C, and the weight of active constituent is 20～50%.
6. in accordance with the method for claim 3, it is characterized in that: described flow field is graphite flow field or metal flow field, and it can be parallel groove flow field, crawl flow field or other form flow fields.
7. in accordance with the method for claim 1, it is characterized in that: specific operation process is,
(1) catalyst that will catalytic action be arranged to CO gas and polytetrafluoroethylene PTFE aqueous emulsion and organic solvent and water mix, even through ultrasonic oscillation, wherein the mass ratio of catalyst and PTFE aqueous emulsion is 5: 1～1: 1, the mass ratio of catalyst and organic solvent is 1: 500～1: 5000, and the volume ratio of organic solvent and water is 1: 1～1: 3 in the mixed liquor; The concentration of PTFE aqueous emulsion is 20-60%;
(2) with mixed liquor with smearing or spraying method supports on the flow field, thickness is 10～50 μ m, through 240～370 ℃ of sintering, the time is 30～40 minutes.
8. it is characterized in that in accordance with the method for claim 7: described organic solvent can be C1-C4 alcohol.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336383A (en) * | 2018-01-10 | 2018-07-27 | 江苏乾景新能源产业技术研究院有限公司 | A method of enhancing high temperature film fuel battery performance stability |
| CN111082108A (en) * | 2019-12-30 | 2020-04-28 | 上海神力科技有限公司 | Device and method for testing start-stop accelerated life of fuel cell |
| CN113690473A (en) * | 2021-07-06 | 2021-11-23 | 清华大学 | Fuel cell stack |
| CN115241480A (en) * | 2022-08-22 | 2022-10-25 | 海卓动力(北京)能源科技有限公司 | Flow field type hydrogen fuel electric pile catalyst structure adjusting reactor |
| WO2023103812A1 (en) * | 2021-12-08 | 2023-06-15 | 嘉庚创新实验室 | Electrochemical reaction device, and method for producing oxygen |
-
2006
- 2006-09-22 CN CN200610047849A patent/CN100576616C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336383A (en) * | 2018-01-10 | 2018-07-27 | 江苏乾景新能源产业技术研究院有限公司 | A method of enhancing high temperature film fuel battery performance stability |
| CN111082108A (en) * | 2019-12-30 | 2020-04-28 | 上海神力科技有限公司 | Device and method for testing start-stop accelerated life of fuel cell |
| CN113690473A (en) * | 2021-07-06 | 2021-11-23 | 清华大学 | Fuel cell stack |
| CN113690473B (en) * | 2021-07-06 | 2023-02-03 | 清华大学 | Fuel cell stack |
| WO2023103812A1 (en) * | 2021-12-08 | 2023-06-15 | 嘉庚创新实验室 | Electrochemical reaction device, and method for producing oxygen |
| CN115241480A (en) * | 2022-08-22 | 2022-10-25 | 海卓动力(北京)能源科技有限公司 | Flow field type hydrogen fuel electric pile catalyst structure adjusting reactor |
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|---|---|
| CN100576616C (en) | 2009-12-30 |
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