CN100433437C - Method for recovering performance of poisoned proton exchange membrane fuel cell - Google Patents
Method for recovering performance of poisoned proton exchange membrane fuel cell Download PDFInfo
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- CN100433437C CN100433437C CNB2005101367485A CN200510136748A CN100433437C CN 100433437 C CN100433437 C CN 100433437C CN B2005101367485 A CNB2005101367485 A CN B2005101367485A CN 200510136748 A CN200510136748 A CN 200510136748A CN 100433437 C CN100433437 C CN 100433437C
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- fuel cell
- electrode
- cyclic voltammetry
- performance
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- 239000000446 fuel Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000012528 membrane Substances 0.000 title claims abstract description 11
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 21
- 239000002574 poison Substances 0.000 claims abstract description 14
- 231100000614 poison Toxicity 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 8
- 238000003795 desorption Methods 0.000 claims description 7
- 238000009423 ventilation Methods 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 230000010287 polarization Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 9
- 230000000607 poisoning effect Effects 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 208000005374 Poisoning Diseases 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 206010017740 Gas poisoning Diseases 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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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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- Fuel Cell (AREA)
Abstract
This invention relates to a proton exchange membrane fuel cell, specifically, a method to restore the poison proton exchange membrane fuel cell performance, which uses cyclic voltammetry to the proton exchange membrane fuel cell electrodes poisoned by the impurity gas in the air, making impurities absorbed by the electric catalyst being oxidation desorbed, and restoring the catalytic activity, thus restoring the electrode performance; in which: the said cyclic voltammetry processes cyclic scan to the proton exchange membrane fuel cell bipolar in the certain potential range. The method of the invention can restore the electrode performance, and meanwhile effectively solve the problems of the poisoned fuel cell electrode that the performance reduced, and the life shortened, thereby promoting the development of fuel cell.
Description
Technical field
The present invention relates to Proton Exchange Membrane Fuel Cells, is the method that a kind of making alive recovers the proton exchange film fuel battery performance of negative electrode foreign gas poisoning; A kind of specifically cyclic voltammetry that adopts applies high voltage with the poisoning impurity of chemisorbed on electrode, makes the method for the proton exchange film fuel battery performance recovery of the impurity desorption that is adsorbed on the electrode.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) removes the general characteristic with fuel cell, and as energy transformation efficiency height, environmental friendliness etc. start fast but also have room temperature simultaneously, no electrolyte loss, and the life-span is long, outstanding features such as specific power and specific energy height.Therefore, it not only can be used for building the dispersion power station, also be suitable for especially as removable power source, be electric motor car and do not rely on air to advance one of ideal candidates power supply of submarine, be the general a kind of novel removable power sources of the army and the people, future with the hydrogen energy era of hydrogen as main energy carrier, it is best family power source.
Along with going deep into of Proton Exchange Membrane Fuel Cells research, the endurance issues of battery is subjected to researcher's extensive concern and attention day by day, and ambiance adaptability is importance wherein.Because many employing surrounding airs in the Proton Exchange Membrane Fuel Cells running, so the performance and the life-span of various foreign gases that contained in the air and battery are closely related.
NO, NO
2, H
2S, SO
2Deng all being major pollutants in the atmosphere, be mostly that industrial waste gas and motor vehicle exhaust emission cause.In a single day airborne foreign gas enter battery, will produce absorption on eelctro-catalyst.Absorption is divided into two kinds, NO, NO
2Deng the physical absorption that is adsorbed as on eelctro-catalyst, H
2S, SO
2On eelctro-catalyst, be adsorbed as chemisorbed.In a single day impurity adsorbs on eelctro-catalyst, will occupy the active sites of Pt.And acquire a certain degree when adsorbing, when requiring of hydrogen-oxygen catalytic reaction can't be satisfied in the residual activity position, the performance of battery will descend.And battery performance will be in case the performance degradation that decline, the especially impurity of chemisorbed cause will be difficult to recovery by battery self.
About negative electrode foreign gas on eelctro-catalyst adsorption mechanism and to the influence degree of battery, existing a few patents report.But performance how to recover to have been poisoned electrode is not seen relevant report as yet.
Summary of the invention
For remedying the deficiencies in the prior art, the method that the object of the present invention is to provide a kind of proton exchange film fuel battery performance that can make fuel cell electrode poisoning back performance recovery and can increase the service life to recover.
For achieving the above object, technical scheme of the present invention is: adopt cyclic voltammetry, the electrode that the foreign gas that is contained in the air is poisoned imposes high voltage, makes the oxidized desorption of the impurity that adsorbs on the eelctro-catalyst, recover catalytic activity, thereby recover electrode performance.
The method concrete steps that proton exchange film fuel battery performance recovers are as follows:
(1) cell cathode that will have been poisoned feeds nitrogen, and anode feeds hydrogen.
(2) poison the battery ventilation after 60 minutes with described, treat that voltage is stable, it is carried out cyclic voltammetry scan.
Wherein: sweep limits is: cathode voltage is 0.05V～1.45V, and sweep speed Wei 5mV/s, 10mV/s, 15mV/s; The still logical hydrogen of anode in the scanning process, the still logical nitrogen of negative electrode.
The principle of the invention is: to contain H
2The air of S impurity is an example.With pure air operation battery the time, battery performance is stable.Contain H when switching to
2Behind the air of the S foreign gas operation battery, battery performance very short time the sharp fall of having to go to the toilet low, H is described
2S foreign gas has tangible poisoning effect to the PEMFC electrode.After adopting cyclic voltammetry, in the cyclic voltammetry scan process, in the anode scanning potential range of first lap more than 0.9V, at 0.92V and 1.12V place two tangible oxidation peak have appearred, and the most outstanding with the oxidation peak at 1.12V place.This is because following reaction takes place on the Pt electrode S:
In second circle and later several circles scanning, degenerating fast in two such peaks, disappears substantially during to the 5th circle.The good oxidation desorption of cyclic voltammetric the has been described impurity of chemisorbed on eelctro-catalyst, electrode performance obtains good recovery.
The present invention has following advantage:
1. prolonged the useful life of fuel cell electrode.Adopt method of the present invention can recover electrode performance, efficiently solve fuel cell electrode poisoning back decreased performance, lost of life problem, thereby can promote the development of fuel cell.
2. method is simple.The present invention is easy and simple to handle, takes effect rapidly, and electrode performance is recovered at short notice fully.
3. solved the environmental suitability problem of PEMFC.PEMFC is under abominable air ambient, and performance can obviously descend.Adopt this method, can recover electrode performance rapidly, thereby better adapt to different environment.
Description of drawings
Fig. 1 be under the embodiment of the invention different operating condition cell voltage with the result of variations figure of cumulative time;
The polarization curve comparison diagram of Fig. 2 for obtaining under the embodiment of the invention different condition;
Fig. 3 feeds 200ppmH for the embodiment of the invention
2The cyclic voltammetric spectrogram that obtains behind the S;
Among the figure: Recover with air: recover CV with air: cyclic voltammetric, IVtest: polarization curve test, Accumulative running time: Cumulative Elapsed Time.Voltage: voltage, Current density: current density, Potential vs.SHE: with respect to the voltage of standard hydrogen electrode.
Embodiment:
Illustrate: present embodiment is by accelerated tests, and negative electrode feeds and contains higher concentration (200ppm) H
2The air of S makes battery poison at short notice.Again feed pure air, battery performance can not recover voluntarily.Adopt the cyclic voltammetric method this moment, and electrode is imposed higher voltage, then can recover battery performance.
Embodiment 1
1. toxicity processing test:
(1) assembling monocell: anode reaction gas is a pure hydrogen, and cathode reaction gas is a pure air.
Polarization curve test: 1. with pure air constant current density (700mA/cm
2) polarization operation battery a period of time, recording voltage-time graph (referring to Fig. 1).
2. move the above-mentioned battery that assembles, treat the stable back test of battery performance polarization curve.Wherein: adopt the steady-state polarization mode during test polarization curve, each measuring current density points is measured 5 minutes (referring to Fig. 2) approximately.
(2) poison monocell: anode reaction gas is a pure hydrogen, and cathode reaction gas is 200ppmH
2The air of S foreign gas.
Polarization curve test: 1. to contain H
2Air constant current density polarization operation a period of time of S foreign gas, write down constant current density (700mA/cm equally
2) polarization curve.
2. treat to test H with the steady-state polarization mode after battery performance is stablized
2Battery polarization curve (referring to Fig. 2) after S poisons.
(3) detection poisons monocell: anode reaction gas is a pure hydrogen, and cathode reaction gas switches to pure air once more, and constant current density polarization operation battery also writes down the steady-state polarization that the constant current density polarization curve is measured battery subsequently once more.
2. adopt cyclic voltammetry to recover battery performance
1. the above-mentioned cell cathode that has been poisoned is fed nitrogen, anode feeds hydrogen.
2. poison the battery ventilation after 60 minutes with described, treat that voltage is stable, it is carried out cyclic voltammetry scan.
Wherein: sweep limits is: cathode voltage is 0.05V～1.45V, sweep speed 10mV/s; The still logical hydrogen of anode in the scanning process, the still logical nitrogen of negative electrode.
So-called cyclic voltammetric is meant to apply the current potential that increases (or minimizing) with certain step gradually on electrode.When arriving maximum (or minimum) current potential of wishing, the direction counter-rotating of " scanning ".Measure the electric current of every step, draw the figure of electric current then current potential.
3. polarization curve test: measure the steady-state polarization that battery constant current density operation polarization curve is also measured battery subsequently.
(3) interpretation of result:
As seen from Figure 1, with pure air operation battery the time, battery performance is stable.Contain H when switching to
2Behind the air of S foreign gas, battery performance very short time have to go to the toilet the sharp fall low, H is described
2S foreign gas has tangible poisoning effect to the PEMFC electrode.And after the employing cyclic voltammetry, battery performance almost returns to initial level.
From Fig. 2, can obviously find out, contain H in employing
2Behind the air operation battery of S, battery performance descends greatly, and this illustrates H once more
2S is obvious to the battery performance poisoning effect.And after the employing cyclic voltammetry, the performance of electrode is significantly improved.
From Fig. 3, can see, in the cyclic voltammetry scan process, in the anode scanning potential range of first lap more than 0.9V, two tangible oxidation peak occur at 0.92V and 1.12V place, and the most outstanding with the oxidation peak at 1.12V place.This is because following reaction takes place on the Pt electrode S:
In second circle and later several circles scanning, degenerating fast in two such peaks, disappears substantially during to the 5th circle.The good oxidation desorption of cyclic voltammetric the has been described impurity of chemisorbed on eelctro-catalyst.Can see also that from Fig. 1, Fig. 2 electrode performance obtains good recovery.
Embodiment 2
Difference from Example 1 is:
1. adopt cyclic voltammetry to recover battery performance
1. the above-mentioned cell cathode that has been poisoned is fed nitrogen, anode feeds hydrogen.
2. poison the battery ventilation after 60 minutes with described, treat that voltage is stable, it is carried out cyclic voltammetry scan.
Wherein: sweep limits is: cathode voltage is 0.05V～1.45V, sweep speed 5mV/s; The still logical hydrogen of anode in the scanning process, the still logical nitrogen of negative electrode.
Embodiment 3
Difference from Example 1 is:
1. adopt cyclic voltammetry to recover battery performance
1. the above-mentioned cell cathode that has been poisoned is fed nitrogen, anode feeds hydrogen.
2. poison the battery ventilation after 60 minutes with described, treat that voltage is stable, it is carried out cyclic voltammetry scan.
Wherein: sweep limits is: cathode voltage is 0.05V～1.45V, sweep speed 15mV/s; The still logical hydrogen of anode in the scanning process, the still logical nitrogen of negative electrode.
By this example as can be seen, at relatively poor, the H of PEMFC process air quality
2During higher regional of S content, battery performance can be decayed.Even return to area with fresh air, battery performance also can't recover.Adopt alive way this moment, can make the oxidized desorption of the impurity that is adsorbed on the electrode, thereby recover the activity of eelctro-catalyst, and battery performance is also restored.
Claims (3)
1. method that the proton exchange film fuel battery performance that poisons is recovered, it is characterized in that: the proton exchange membrane fuel cell electrode that the foreign gas that is contained in the air is poisoned adopts cyclic voltammetry, make the oxidized desorption of the impurity that adsorbs on the eelctro-catalyst, recover catalytic activity, thereby recover electrode performance;
Wherein: described cyclic voltammetry is meant carries out scan round to electrode in certain potential range;
Adopt the cyclic voltammetry concrete steps to be:
(1) cell cathode that will have been poisoned feeds nitrogen, and anode feeds hydrogen;
(2) poison the battery ventilation after 60 minutes with described, treat that voltage is stable, it is carried out cyclic voltammetry scan;
Sweep limits is: cathode voltage is 0.05V～1.45V, and sweep speed is respectively 5mV/s, 10mV/s, 15mV/s; The still logical hydrogen of anode in the scanning process, the still logical nitrogen of negative electrode.
2. according to the described method that makes the proton exchange film fuel battery performance recovery that poisons of claim 1, its feature also is: described cyclic voltammetry is that the foreign gas of chemisorbed on the Pt catalyst in the proton exchange membrane fuel cell electrode is carried out the oxidation desorption.
3. according to the described method that makes the proton exchange film fuel battery performance recovery that poisons of claim 1, its feature also is: the foreign gas that contains in the described air is H
2S, SO
2, NO or NO
2
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| CNB2005101367485A CN100433437C (en) | 2005-12-29 | 2005-12-29 | Method for recovering performance of poisoned proton exchange membrane fuel cell |
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|---|---|---|---|
| CNB2005101367485A CN100433437C (en) | 2005-12-29 | 2005-12-29 | Method for recovering performance of poisoned proton exchange membrane fuel cell |
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| CN1992412A CN1992412A (en) | 2007-07-04 |
| CN100433437C true CN100433437C (en) | 2008-11-12 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5401867B2 (en) * | 2008-08-07 | 2014-01-29 | 日産自動車株式会社 | Fuel cell system and method for recovering characteristics of fuel cell |
| CN109950581B (en) * | 2019-01-28 | 2021-11-05 | 江苏乾景新能源产业技术研究院有限公司 | Rapid activation method for phosphoric acid doped polybenzimidazole high-temperature membrane electrode of fuel cell |
| CN115832361B (en) * | 2022-12-05 | 2024-06-21 | 江苏耀扬新能源科技有限公司 | Performance recovery method based on output power attenuation ratio of fuel cell |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040086772A1 (en) * | 2002-09-06 | 2004-05-06 | Board Of Regents, The University Of Texas System | Fuel cell electrode comprising CO and sulfur tolerant metal compound hydrogen activation catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040086772A1 (en) * | 2002-09-06 | 2004-05-06 | Board Of Regents, The University Of Texas System | Fuel cell electrode comprising CO and sulfur tolerant metal compound hydrogen activation catalyst |
Non-Patent Citations (6)
| Title |
|---|
| Assessing durability of cathodes exposed tocommon air impurites. R. Wohtadi, W.-k. Lee, J.W.Van Zee.Journal of Power Sources,Vol.138 . 2004 |
| Assessing durability of cathodes exposed tocommon air impurites. R.Wohtadi, W.-k. Lee, J.W.Van Zee.Journal of Power Sources,Vol.138. 2004 * |
| CO/H2燃料气的质子交换膜燃料电池性能研究. 俞红梅，候中军，衣宝廉，毕可万，张景新，林治银，韩明.电化学，第7卷第2期. 2001 |
| CO/H2燃料气的质子交换膜燃料电池性能研究. 俞红梅，候中军，衣宝廉，毕可万，张景新，林治银，韩明.电化学，第7卷第2期. 2001 * |
| 质子交换膜燃料电池抗CO催化剂PtRu/C的研究. 许韵华，晋丽叶，陈敏，王永生，朱红.可持续发展的中国交通－2005全国博士生学术论坛（交通运输工程学科）论文集（下册）. 2005 |
| 质子交换膜燃料电池抗CO催化剂PtRu/C的研究. 许韵华，晋丽叶，陈敏，王永生，朱红.可持续发展的中国交通－2005全国博士生学术论坛(交通运输工程学科)论文集(下册). 2005 * |
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