CN114388839A - Recovery method of coolant polluted membrane electrode - Google Patents
Recovery method of coolant polluted membrane electrode Download PDFInfo
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- CN114388839A CN114388839A CN202111630375.2A CN202111630375A CN114388839A CN 114388839 A CN114388839 A CN 114388839A CN 202111630375 A CN202111630375 A CN 202111630375A CN 114388839 A CN114388839 A CN 114388839A
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- coolant
- membrane electrode
- current density
- polluted
- contaminated
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- 239000012528 membrane Substances 0.000 title claims abstract description 66
- 239000002826 coolant Substances 0.000 title claims abstract description 47
- 238000011084 recovery Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 21
- 238000010926 purge Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 230000010287 polarization Effects 0.000 description 6
- 239000000446 fuel Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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 provides a recovery method of a coolant polluted membrane electrode, which comprises the following steps: respectively introducing air and hydrogen into the cathode and the anode of the membrane electrode polluted by the coolant, and firstly, leading the membrane electrode polluted by the coolant to have a low current density of 10-200 mA/cm2Loading for 10-30 min, and then carrying out high current density of 1000-2000 mA/cm2The operation is constant for 0.5-2 h. The technical scheme of the invention can effectively and quickly recover the membrane electrode polluted by the coolant.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a recovery method of a coolant polluted membrane electrode.
Background
During the operation of the fuel cell, the coolant leaks to the surface of the membrane electrode due to problems such as sealing failure, and the membrane electrode is polluted. At present, methods such as gas purging and the like are mostly adopted for the coolant pollution of the membrane electrode, namely, the ethylene glycol on the surface of the membrane electrode is taken away through the flow of gas. Experiments show that when the time of the membrane electrode polluted by the coolant is short, the problem of coolant pollution can be solved by adopting a gas purging recovery strategy, but the problem of low efficiency exists; when the coolant pollutes for a long time, the coolant can permeate into a catalytic layer of the membrane electrode, and the performance of the membrane electrode cannot be recovered by adopting a gas purging method.
Disclosure of Invention
According to the technical problem that the efficiency of the membrane electrode for recovering the coolant pollution by adopting the gas purging mode is low, and when the coolant is polluted for a long time, the performance of the membrane electrode cannot be completely recovered by adopting the gas purging method, the recovery method for the membrane electrode polluted by the coolant is provided, the mode of low current density loading and high current density constant operation is provided, the efficiency is improved, and the damage of the coolant on the performance of the battery due to the long-time pollution is relieved.
The technical means adopted by the invention are as follows:
a recovery method for a coolant polluted membrane electrode specifically comprises the following steps: and respectively introducing air and hydrogen into the cathode and the anode of the membrane electrode polluted by the coolant, firstly loading the membrane electrode polluted by the coolant for a period of time under low current density, and then constantly operating for a period of time under high current density.
Further, low current density rangeIs 10 to 200mA/cm2。
Furthermore, the low current density loading time is 10-30 min.
Further, the high current density range is 1000-2000 mA/cm2。
Further, the constant operation time under high current density is 0.5-2 h.
Further, the membrane electrode contaminated by the coolant in the recovery process satisfies the condition: the temperature is 65-85 ℃; the cathode air metering ratio is 1.5-2.5; the anode hydrogen metering ratio is 1.5-2.0; air and hydrogen introduced into the cathode and the anode are humidified to 60-100% RH, and the pressure is normal pressure.
Compared with the prior art, the invention has the following advantages:
the recovery method of the membrane electrode polluted by the coolant can effectively and quickly recover the membrane electrode polluted by the coolant, mainly adopts a low current density loading and high current density constant operation mode, and has the advantages of being more effective and quicker.
For the above reasons, the present invention can be widely applied to the fields of fuel cells and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a graph showing the open circuit voltage recovery time of the coolant-contaminated membrane electrode in comparative example 1 and example 1 of the present invention.
Fig. 2 is a polarization curve after recovery of the coolant contaminated membrane electrode in comparative example 1 and example 1 of the present invention and a polarization curve of the membrane electrode in comparative example 3.
Fig. 3 is a graph showing the open circuit voltage recovery time of the coolant contaminated membrane electrode in comparative example 2 and example 2 of the present invention.
FIG. 4 is a polarization curve after recovery of a coolant contaminated membrane electrode in example 2 of the present invention and a polarization curve of a membrane electrode in comparative example 3.
FIG. 5 is a comparative polarization curve after recovery of the coolant contaminated membrane electrode in comparative example 2 and example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a recovery method of a coolant polluted membrane electrode, which comprises the following steps: respectively introducing air and hydrogen into the cathode and the anode of the membrane electrode polluted by the coolant, firstly loading the membrane electrode polluted by the coolant for a period of time under low current density to recover the open-circuit voltage of the membrane electrode to be more than 0.9V, and then constantly operating for a period of time under high current density.
Further, the low current density range is 10 to 200mA/cm2。
Furthermore, the low current density loading time is 10-30 min.
Further, the high current density range is 1000-2000 mA/cm2。
Further, the constant operation time under high current density is 0.5-2 h.
Further, the membrane electrode contaminated by the coolant in the recovery process satisfies the condition: the temperature is 65-85 ℃; the cathode air metering ratio is 1.5-2.5; the anode hydrogen metering ratio is 1.5-2.0; air and hydrogen introduced into the cathode and the anode are humidified to 60-100% RH, and the pressure is normal pressure.
Coolant contamination can cause the membrane electrodeThe open-circuit voltage is below 0.6V, and the specific reason is that: as can be seen from the anodic oxidation equation (1) for ethylene glycol, when the potential is higher than-0.008V, ethylene glycol is oxidized into CO on the surface of Pt catalyst2However, it produces an intermediate CHO during the electro-oxidation processads/COadsIt can cause the Pt surface of the catalyst to be poisoned and lose the catalytic reaction activity.
To eliminate intermediate CHOads/COadsTo convert it into the final product CO which has no poisoning effect on the catalyst2Increase of OH on Pt surfaceadsSurface coverage of (a).
C2H6O2+2H2O→2CO2+10H++10e- E＝-0.008V(vs.SHE) (1)
CHOads+OHads→CO2+2H++2e- (2)
COads+OHads→CO2+H++2e- (3)
The recovery method of the coolant polluted membrane electrode provided by the invention comprises the steps of firstly adopting a low-current loading mode to increase OH on the surface of PtadsThe surface coverage of the Pt substrate enables a poisoning intermediate product on the surface of the Pt to be oxidized, and the open-circuit voltage is recovered to be more than 0.9V; then the membrane electrode is operated under high current density and constant, and residual glycol and other intermediate products and final products CO in micropores of the membrane electrode are taken away through high flux of gas and water2The problem of performance recovery of the membrane electrode after long-time pollution by the coolant is effectively solved, and the efficiency of membrane electrode performance recovery is improved.
The recovery effect of the method provided by the present invention on the coolant-contaminated membrane electrode will be specifically described below with reference to examples 1 to 2 and comparative examples 1 to 3.
The coolant used in examples 1-2 and comparative examples 1-2 was a mixture of ethylene glycol and deionized water, with an ethylene glycol concentration of about 20% to 80%. As shown in Table 1, the membrane electrodes used in examples 1-2 and comparative examples 1-2 were coolant-contaminated membrane electrodes, except that the membrane electrodes were impregnated with coolants having different ethylene glycol contentsSoaking for different time and adopting different recovery modes, and comparative examples 1-2 adopt first purging and then continuously loading current density to 1000-1500 mA/cm2The embodiment 1-2 adopts the recovery method provided by the present invention. Comparative example 3 is a membrane electrode that was not contaminated with ethylene glycol.
Table 1: examples 1-2 and comparative examples 1-3 protocols
| Numbering | Content of ethylene glycol in the coolant/%) | Coolant soak time/h | Recovery mode |
| Example 1 | 80％ | 0.5h | Low current density loading, high current density operation |
| Example 2 | 60％ | 20h | Low current density loading, high current density operation |
| Comparative example 1 | 80％ | 0.5h | Purging, loading |
| Comparative example 2 | 20％ | 20h | Purging, loading |
| Comparative example 3 | 0 | 0 | -- |
The open-circuit voltage recovery time of the membrane electrode is shown in fig. 1 and fig. 3, when the membrane electrode is polluted by coolant for a short time, the open-circuit voltage can be recovered by both methods, but the open-circuit voltage can be recovered to be more than 0.9V more quickly by adopting the method provided by the invention; the recovery method employed in comparative examples 1-2 could not recover the open circuit voltage of the membrane electrode to 0.9V or more after the membrane electrode was contaminated with the coolant for a long time.
The non-contaminated membrane electrode of comparative example 3 and the recovery-treated membrane electrodes of examples 1 to 2 and comparative examples 1 to 2 were subjected to a polarization curve test under 100% RH conditions: the test results are shown in fig. 2, 4 and 5; as can be seen from fig. 2, both the recovery method adopted in comparative example 1 and the method provided by the present invention can recover the original performance of the contaminated membrane electrode when the time for contaminating the membrane electrode with the coolant is short; however, when the time for which the membrane electrode was contaminated with the coolant was long, as shown in fig. 4 and 5, the recovery method employed in comparative example 2 did not allow the membrane electrode to recover in performance.
In conclusion, the invention adopts a low current density loading and high current density constant operation mode, and has important significance for the effective and rapid recovery of the fuel coolant polluted membrane electrode.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. A recovery method for a coolant polluted membrane electrode is characterized by comprising the following steps: and respectively introducing air and hydrogen into the cathode and the anode of the membrane electrode polluted by the coolant, firstly loading the membrane electrode polluted by the coolant for a period of time under low current density, and then constantly operating for a period of time under high current density.
2. The method for recovering a coolant-contaminated membrane electrode assembly according to claim 1, wherein the low current density is in the range of 10 to 200mA/cm2。
3. The method for recovering a coolant-contaminated membrane electrode according to claim 1, wherein the low current density loading time is 10 to 30 min.
4. The method for recovering a coolant-contaminated membrane electrode assembly according to claim 1, wherein the high current density is in the range of 1000 to 2000mA/cm2。
5. The method for recovering a coolant-contaminated membrane electrode according to claim 1, wherein the constant operation time is 0.5 to 2 hours at a high current density.
6. The recovery method of a coolant-contaminated membrane electrode according to claim 1, wherein the membrane electrode contaminated with the coolant during the recovery process satisfies the condition: the temperature is 65-85 ℃; the cathode air metering ratio is 1.5-2.5; the anode hydrogen metering ratio is 1.5-2.0; air and hydrogen introduced into the cathode and the anode are humidified to 60-100% RH, and the pressure is normal pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111630375.2A CN114388839A (en) | 2021-12-28 | 2021-12-28 | Recovery method of coolant polluted membrane electrode |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111630375.2A CN114388839A (en) | 2021-12-28 | 2021-12-28 | Recovery method of coolant polluted membrane electrode |
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| CN114388839A true CN114388839A (en) | 2022-04-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100805458B1 (en) * | 2006-12-11 | 2008-02-20 | 현대자동차주식회사 | A one body type membrane electrode assembly with gasket of multiple sealing structure for a fuel cell |
| CN101140997A (en) * | 2006-09-08 | 2008-03-12 | 新源动力股份有限公司 | Fuel batter with proton exchange film disabled membrane electrode recovery regenerated method |
| CN102044689A (en) * | 2009-10-16 | 2011-05-04 | 通用汽车环球科技运作公司 | In-situ fuel cell stack reconditioning |
| CN103474683A (en) * | 2013-09-24 | 2013-12-25 | 上海空间电源研究所 | Membrane electrode assembly for improving performance of integrated regenerative fuel cell and preparation method of membrane electrode assembly |
| KR20150015635A (en) * | 2013-07-31 | 2015-02-11 | 울산대학교 산학협력단 | Recovery method of coolant leak in polymer electrolyte membrane fuel cell |
| CN110571446A (en) * | 2019-09-02 | 2019-12-13 | 武汉中极氢能产业创新中心有限公司 | Method for activating fuel cell and preventing/improving dry film |
| CN111525164A (en) * | 2020-04-30 | 2020-08-11 | 郑州帅先新能源科技有限公司 | Fuel cell regeneration control method and fuel cell system |
| CN112864415A (en) * | 2020-12-24 | 2021-05-28 | 上海神力科技有限公司 | Method for eliminating pollution of fuel cell cooling liquid |
-
2021
- 2021-12-28 CN CN202111630375.2A patent/CN114388839A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101140997A (en) * | 2006-09-08 | 2008-03-12 | 新源动力股份有限公司 | Fuel batter with proton exchange film disabled membrane electrode recovery regenerated method |
| KR100805458B1 (en) * | 2006-12-11 | 2008-02-20 | 현대자동차주식회사 | A one body type membrane electrode assembly with gasket of multiple sealing structure for a fuel cell |
| CN102044689A (en) * | 2009-10-16 | 2011-05-04 | 通用汽车环球科技运作公司 | In-situ fuel cell stack reconditioning |
| KR20150015635A (en) * | 2013-07-31 | 2015-02-11 | 울산대학교 산학협력단 | Recovery method of coolant leak in polymer electrolyte membrane fuel cell |
| CN103474683A (en) * | 2013-09-24 | 2013-12-25 | 上海空间电源研究所 | Membrane electrode assembly for improving performance of integrated regenerative fuel cell and preparation method of membrane electrode assembly |
| CN110571446A (en) * | 2019-09-02 | 2019-12-13 | 武汉中极氢能产业创新中心有限公司 | Method for activating fuel cell and preventing/improving dry film |
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| CN112864415A (en) * | 2020-12-24 | 2021-05-28 | 上海神力科技有限公司 | Method for eliminating pollution of fuel cell cooling liquid |
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