CN100546089C - The method of the proton exchange film fuel battery performance that the hydrogen that can recover to cure poisons - Google Patents
The method of the proton exchange film fuel battery performance that the hydrogen that can recover to cure poisons Download PDFInfo
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- CN100546089C CN100546089C CNB200610134074XA CN200610134074A CN100546089C CN 100546089 C CN100546089 C CN 100546089C CN B200610134074X A CNB200610134074X A CN B200610134074XA CN 200610134074 A CN200610134074 A CN 200610134074A CN 100546089 C CN100546089 C CN 100546089C
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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
The present invention relates to the recovery of proton exchange film fuel battery performance, the method that specifically a kind of proton exchange film fuel battery performance that the hydrogen that cures is poisoned recovers.By giving the pulse of poisoning battery applying high voltage, can will be adsorbed on hydrogen sulfide or other sulfide oxidations catalyst surface, that cause battery to poison, high-tension value can be 1.0V-1.5V; Because part Pt catalyst is also oxidized at high potential, again by adding low-voltage, with oxidized catalyst reduction, recovers its electro-chemical activity, thereby battery performance is restored, the value of low-voltage can be 0V-0.5V.
Description
Technical field
The present invention relates to the recovery of proton exchange film fuel battery performance, specifically a kind of method that proton exchange film fuel battery performance that the hydrogen that cures poisons is restored, thus promoted the development 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 as at document 1 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).Adopted an impurity removal means of being made up of porous material and selective absorbing film in document 2 WO 2005/071785, this device can be removed foreign gas in the oxidant (air) such as hydrogen sulfide (H2S), oxysulfide (SO
X) and nitrogen oxide (NO
X).How to improve the fuel cell anti-H 2 S, do not have good solution at present, the method for the proton exchange film fuel battery performance that therefore a kind of hydrogen that can recover rapidly, effectively to cure poisons is necessary.
Summary of the invention
The object of the present invention is to provide a kind of method that can make proton exchange film fuel battery performance that the hydrogen that cures poisons obtain fast quick-recovery, this method simple possible.
For achieving the above object, the technical solution used in the present invention is:
1) by to poisoning battery applying high voltage, can hydrogen sulfide or other sulfide oxidations catalyst surface, that cause battery to poison will be adsorbed on; The value of high potential can be 1.0V-1.5V;
2) because part Pt catalyst is also oxidized at high potential,, with oxidized catalyst reduction, recovers its electro-chemical activity, thereby battery performance is restored again by adding low-voltage; The value of electronegative potential can be 0V-0.5V.
The described high potential duration can be 10s-5min, and the duration of electronegative potential can be 10s-5min.
Its specific operation process is as follows,
1) battery that hydrogen poisons that will cure earlier quits work, and feeds inert gas (as nitrogen, helium etc.) in the electrode side of poisoning, and feeds hydrogen at opposite side;
2) add high voltage for the battery of poisoning by external circuit, and the high voltage end of the electrode side joint external circuit of poisoning, will be adsorbed on hydrogen sulfide or other sulfide oxidations catalyst surface, that cause battery to poison;
3) with after-applied low-voltage, make oxidized Pt catalyst reduction, recover its activity.
The present invention has following advantage:
1, the present invention passes through to poisoning battery applying high voltage, can hydrogen sulfide or other sulfide oxidations catalyst surface, that cause battery to poison will be adsorbed on, because part Pt catalyst is also oxidized at high potential, again by adding low-voltage, with oxidized catalyst reduction, recover its electro-chemical activity, thereby the proton exchange film fuel battery performance that the hydrogen that cures poisons is restored, thereby promoted the development of fuel cell industrialization.
2, the present invention is simple, and is applied widely.The fuel cell that hydrogen sulfide in the fuel gas or in the oxidant causes is poisoned and can be recovered by the method.The method is not only applicable to the performance recovery of fuel-cell single-cell, is applicable to the performance recovery of fuel battery (heap) yet.
Description of drawings
Fig. 1 feeds 1%H for fuel-cell single-cell under open-circuit condition
2Battery performance and the performance chart behind over recovery behind the S.
Fig. 2 is that fuel-cell single-cell is at 800mA/cm
2Fuel gas during discharge (hydrogen) switches to and contains 20ppmH
2S/H
2Battery performance and the performance chart behind over recovery after 1 hour.
Fig. 3 poisons for fuel battery 18ppmH2S and recovers polarization curve.
Fig. 4 is the voltage distribution map in fuel battery 18ppmH2S poisoning and the recovery process.
Adopt monocell, the battery effective area is 5cm
2, under the open-circuit condition, the galvanic anode side feeds 1%H
2S/N
2, cathode side feeds hydrogen.Behind the 10min at hydrogen | measure the polarization curve after battery is poisoned under the air system.Afterwards, anode-side feeds nitrogen, and cathode side feeds hydrogen, adds a high voltage by external circuit, and magnitude of voltage is 1.2V, and the duration is 5min, and wherein the external circuit high voltage end links to each other with battery poisoning side (being anode in this example).Subsequently, reduce magnitude of voltage, continue 5min to 0.4V.After battery recovery finishes, again at hydrogen | the polarization curve under the air system behind the measurement battery recovery.
As shown in Figure 1, feed 1% hydrogen sulfide 10min after, and do not compared by the initial performance before being poisoned, the battery performance decay obviously.500mA/cm
2The time, cell voltage has decayed to 0.35V, is 50% of initial voltage value (0.7V).After adding a 1.2V high potential pulse 5min and 0.4V low voltage pulse 5min, battery performance is recovered fully.
Adopt monocell, the battery effective area is 5cm
2, battery is at 800mA/cm
2Fuel gas switches to 20ppmH by pure hydrogen under the situation of constant current work
2S/H
2After 1 hour at hydrogen | measure the polarization curve after battery is poisoned under the air system.Afterwards, anode-side feeds nitrogen, and cathode side feeds hydrogen, adds a high voltage by external circuit, and magnitude of voltage is 1.5V, and the duration is 30s, and wherein the external circuit high voltage end links to each other with battery poisoning side (being anode in this example).Subsequently, reduce magnitude of voltage, continue 30s to 0.2V.After battery recovery finishes, again at hydrogen | the polarization curve under the air system behind the measurement battery recovery.
As shown in Figure 2, even concentration of hydrogen sulfide is very low, have only 20ppm, the influence that fuel cell is brought also is very big.Anode-side feeds 20ppmH
2Behind the S 1 hour, the battery performance decay significantly.After adding a 1.5V high potential pulse 30s and 0.2V low voltage pulse 30s, battery performance is recovered fully.
Adopt fuel battery, single battery effective area 270cm
2, battery pack is in series by the monocell of the same area of 10 joints.Battery is at 600mA/cm
2Fuel gas switches to 18ppmH by pure hydrogen under the situation of constant current work
2S/H
2After 2 hours at hydrogen | measure the polarization curve after battery is poisoned under the air system.Afterwards, anode-side feeds nitrogen, and cathode side feeds hydrogen, all add a high voltage by external circuit for every batteries of forming battery pack, magnitude of voltage is 1.5V, and the duration is 2min, and wherein the external circuit high voltage end links to each other with battery poisoning side (being anode in this example).Subsequently, reduce magnitude of voltage, continue 2min to 0.2V.After battery recovery finishes, again at hydrogen | the polarization curve under the air system behind the measurement battery recovery.
Can be seen with monocell similarly by Fig. 3, the influence that hydrogen sulfide brings fuel battery also is very tangible, and anode feeds 18ppmH
2Behind the S 2 hours, cell voltage is at 400mA/cm
2The time be 0.3V, only be about 40% before not poisoning.After every batteries being added 1.5V high potential pulse (2min) and a 0.2V (2min) low voltage pulse, battery performance is recovered fully.
Can see that by Fig. 4 after the battery pack of hydrogen sulfide poisoning was recovered, each batteries performance all obtained good recovery.
Claims (4)
1, a kind of method that proton exchange film fuel battery performance that the hydrogen that cures poisons is recovered is characterized in that:
1) by to poisoning battery applying high voltage, hydrogen sulfide or other sulfide oxidations catalyst surface, that cause battery to poison will be adsorbed on; High-tension value is 1.0V-1.5V;
2) because part Pt catalyst is also oxidized at high potential,, with oxidized catalyst reduction, recovers its electro-chemical activity, thereby battery performance is restored again by adding low-voltage; The value of low-voltage is 0V-0.5V;
Specific operation process is as follows,
1) battery that hydrogen poisons that will cure earlier quits work, and feeds inert gas in the electrode side of poisoning, and feeds hydrogen in another electrode side;
2) add high voltage for the battery of poisoning by external circuit, and the high voltage end of the electrode side joint external circuit of poisoning, will be adsorbed on hydrogen sulfide or other sulfide oxidations catalyst surface, that cause battery to poison;
3) with after-applied low-voltage, make oxidized Pt catalyst reduction, recover its activity.
2, according to the method for claim 1, it is characterized in that: the described high voltage duration is 10s-5min, and the duration of low-voltage is 10s-5min.
3. according to the method for claim 1, it is characterized in that: described high voltage is a pulse high-voltage, and low-voltage is the pulse low-voltage.
4, in accordance with the method for claim 1, it is characterized in that: described inert gas is nitrogen and/or helium.
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| CNB200610134074XA CN100546089C (en) | 2006-10-27 | 2006-10-27 | The method of the proton exchange film fuel battery performance that the hydrogen that can recover to cure poisons |
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| CNB200610134074XA CN100546089C (en) | 2006-10-27 | 2006-10-27 | The method of the proton exchange film fuel battery performance that the hydrogen that can recover to cure poisons |
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| CN100546089C true CN100546089C (en) | 2009-09-30 |
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| JP5221766B2 (en) * | 2009-09-02 | 2013-06-26 | パナソニック株式会社 | Fuel cell power generation system and operation method thereof |
| CN109449465B (en) * | 2018-09-25 | 2020-10-23 | 全球能源互联网研究院有限公司 | Method for recovering and regenerating alkaline-induced spent membrane electrode of proton exchange membrane fuel cell |
| CN112246289B (en) * | 2020-10-22 | 2022-06-07 | 哈尔滨工业大学 | Regeneration device and regeneration method for eliminating toxic influence of air impurities on oxygen electrode electrocatalyst |
| CN114024010A (en) * | 2021-11-05 | 2022-02-08 | 北京化工大学 | Method for relieving anode poisoning of proton exchange membrane fuel cell by using transient temperature rise |
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