CN100527495C - Activation method for membrane electrode of fuel cell - Google Patents
Activation method for membrane electrode of fuel cell Download PDFInfo
- Publication number
- CN100527495C CN100527495C CNB2006101099626A CN200610109962A CN100527495C CN 100527495 C CN100527495 C CN 100527495C CN B2006101099626 A CNB2006101099626 A CN B2006101099626A CN 200610109962 A CN200610109962 A CN 200610109962A CN 100527495 C CN100527495 C CN 100527495C
- Authority
- CN
- China
- Prior art keywords
- discharge
- fuel cell
- fuel
- battery
- voltage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 161
- 238000000034 method Methods 0.000 title claims abstract description 76
- 230000004913 activation Effects 0.000 title claims description 49
- 239000012528 membrane Substances 0.000 title description 56
- 210000004027 cell Anatomy 0.000 claims description 97
- 210000000170 cell membrane Anatomy 0.000 claims description 23
- 238000007599 discharging Methods 0.000 abstract description 9
- 230000003213 activating effect Effects 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 238000009792 diffusion process Methods 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000036571 hydration Effects 0.000 description 7
- 238000006703 hydration reaction Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 150000003460 sulfonic acids Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 108010041986 DNA Vaccines Proteins 0.000 description 1
- 229940021995 DNA vaccine Drugs 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000020411 cell activation Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003053 immunization Effects 0.000 description 1
- 238000002649 immunization Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Fuel Cell (AREA)
Abstract
This invention relates to a method for activating the membrance electrode of fuel cell. The procedures comprise: the positive pole fuel and negative pole fuel are fed into positive pole chamber and negative pole chamber respectively, thus makes the cell discharging, which is multi-stage discharging, including at least one time-interval between the stages, and the discharging being under constant voltage. This invention method makes the activating operation being fulfilled in a short period, and gives higher outpul power.
Description
Technical field
The invention relates to a kind of activation method of membrane electrode, more particularly, is the activation method about a kind of fuel cell membrane electrode.
Background technology
Fuel cell is a kind of energy conversion device, and it presses electrochemical principle, and the chemical energy that is stored in fuel (as hydrogen, lower alcohol etc.) and the oxidant (oxygen) is changed into electric energy.Fuel cell has energy conversion rate height, advantages of environment protection, and Proton Exchange Membrane Fuel Cells (Proton ExchangeMembrane Fuel Cell, PEMFC) but have more cold operation, specific power advantages of higher, be a kind of novel power source of extensive use.
The anode reaction of the fuel cell that acts as a fuel with hydrogen and the reaction equation of cathode reaction respectively shown in reaction equation (1) and (2), on negative electrode as the oxygen of oxidant usually from air.The proton translocation that anode produces need be finished by the proton exchange membrane of membrane electrode to the ionic conduction of negative electrode.
H
2—2e
-→2H
+ (1)
1/2O
2+2H
++2e
-→H
2O (2)
(Membrane Electrode Assembly is the core component of fuel cell MEA) to membrane electrode, is the position that fuel and oxidant generation electrochemical reaction produce electric energy.As shown in Figure 1, membrane electrode comprises anode 10, negative electrode 11 and the proton exchange membrane 12 between anode 10 and negative electrode 11, anode 10 comprises anode gas diffusion layer 6, anode catalyst layer 7, anode catalyst layer 7 is between anode gas diffusion layer 6 and proton exchange membrane 12, negative electrode 11 comprises cathode gas diffusion layer 8, cathode catalysis layer 9, and cathode catalysis layer 9 is between cathode gas diffusion layer 8 and proton exchange membrane 12.
In fact, in the process of preparation membrane electrode, the structure of membrane electrode does not reach optimization.This be because: (1) Catalytic Layer generally is made up of perfluorinated sulfonic acid (nafion) and two kinds of main matter of catalyst, and perfluorinated sulfonic acid (nafion) plays proton conducting and bond catalysts.In both mixed process, have part activity of such catalysts surface and covered by perfluorinated sulfonic acid (nafion), make anode reaction gas can't reach catalyst surface.(2) in the coating process of catalyst/perfluorinated sulfonic acid (nafion) slurry, along with the volatilization of solvent can make catalyst surface produce a certain amount of space, these spaces have a transmission that is beneficial to gas.But in the preparation process of Catalytic Layer, often need repeatedly to be coated with the catalyst loading that just can reach needs, therefore some space can be blocked in coating process, formed blind hole and semiclosed hole at catalyst surface, and the reaction gas of anode is difficult to enter in these holes and contacts with catalyst.(3) membrane electrode normally forms through hot pressing, in this process, the mixture of catalytic specie and the solution that contains perfluorinated sulfonic acid (removing plasma membrane component of the same race) with solid polymer electrolytic, the catalyst layer that on diffusion layer, forms by means such as coatings, be heated to solid polymer dielectric film and be equal to or higher than electrolytical vitrification point, hot press under certain pressure.Because Catalytic Layer is compressed, and also can seal some holes.Reaction gas mainly is to rely on the hole of membrane electrode inside inwardly to transmit, but because the voidage that the problems referred to above are closed the hole of Catalytic Layer causes Catalytic Layer reduces, increased the transmission obstacle of anode reaction gas, make anode reaction gas can't be fully by catalyst and with the negative electrode fuel reaction, cause fuel cell can't reach desirable power output.And proton exchange membrane only just can demonstrate enough ionic conductances after by hydration, but the manufacturing process of membrane electrode is a process that makes the serious dehydration of proton exchange membrane, this process significantly descends the proton conductivity of proton exchange membrane, therefore, when battery operated, be difficult to obtain high-performance power, for fuel battery energy being reached or reaching optimum Working fast, and the utilance of catalyst in the raising membrane electrode, all need the membrane electrode of fuel cell is activated.General activation method is generally to the reacting gas humidification, to replenish enough moisture to dielectric film, opens partially enclosed hole and makes catalyst layer and proton exchange membrane keep ion channel, improves proton by the diffusion velocity of catalyst surface to the proton film.But, after membrane electrode is placed a period of time,, and the temperature and the humidification amount of supply gas be controlled to a certain degree even battery temperature is maintained set point of temperature, generally also be difficult to make the membrane electrode complete wetting need the very long time in the high performance power of battery output of instantaneous acquisition.
Japanese kokai publication hei 6-196187 discloses a kind of activation method of fuel cell, this method is after the oxygen with the hydrogen of humidification and humidification offers the anode and negative electrode of fuel cell respectively, between two electrodes of fuel cell, apply 1.3 volts or higher voltage, make the fuel cell continuous discharge, in discharge process, the electrolysis of water generates hydrogen and oxygen in the dielectric film, the concentration gradient of water is significantly added, thereby increased the diffusion velocity of water, therefore, dielectric film is by hydration rapidly.Though this method can make the rapid hydration of dielectric film, but adopt single magnitude of voltage activation, be unfavorable for thoroughly carrying out of electrode reaction, the power output of activation back battery is not high, if the number of battery has increased, the voltage that is applied on this fuel cell pile also can raise, and then current density reduces, soak time is prolonged, still can't obtain the fuel cell of higher-wattage output in the short time.
In addition, in order to make battery send high-performance power as early as possible, also attempt to place pure oxygen environment with higher current density generating on battery, or supply with fully that big flow gas carries out current potential restriction so that cell voltage maintains near 0 volt etc. activation method, but this method is relatively more dangerous, because current density is bigger, if control the bad reverse electrode phenomena that is easy to take place, the antipole overlong time influences battery life, if can cause membrane electrode breakdown.
The method that also has remains on the monocell temperature about 80 ℃, the humidification hydrogen and the air (oxygen) that provide temperature to be lower than battery temperature slightly the battery both sides.Under immunization with gD DNA vaccine, the open circuit voltage of battery is greater than 0.98 volt.Then, be 80% in the utilance of hydrogen, the utilance of air (oxygen) is 40%, current density is 0.3 volt/centimetre
2Condition under battery is discharged, the beginning battery can obtain 0.7 volt above voltage, again with the maintenance of the cell voltage more than 0.7 volt more than 5000 hours, cell voltage can not descend, explanation can be generated electricity, thereby membrane electrode is activated.Though this method can make battery send the power of superior performance, has the problem that needs very long soak time.
The soak time of these class methods is very long, and the power output of the fuel cell membrane electrode after the activation is still undesirable.
Summary of the invention
The objective of the invention is provides and just can make a kind of within a short period of time battery have the activation method of the fuel cell membrane electrode of big power output for reaching the long defective of the required soak time of big power output in order to overcome existing fuel cell membrane electrode activation method.
The invention provides a kind of activation method of fuel cell membrane electrode, this method comprises anode fuel and negative electrode fuel fed respectively in the anode chamber of fuel cell and the cathode chamber makes fuel cell electric discharge, wherein, described discharge comprises a plurality of discharge regimes, also comprise at least one time interval between a plurality of discharge regimes, and battery discharges with constant voltage all at each discharge regime.
The activation method of fuel cell membrane electrode provided by the invention is in the process that fuel cell is discharged, between described a plurality of discharge regimes, be set at least one time interval, preferably between per two adjacent discharge regimes, all set interval, the described time interval, promptly, make shelving the time that battery stops to discharge, should can guarantee the fully wetting of proton exchange membrane during the water that produces in the battery discharge procedure is to membrane electrode, help the hydration of proton exchange membrane across the time.In addition, method of the present invention can shorten to the soak time of battery and just can make battery have higher power output within 8 hours, more preferably under the situation, the voltage of each discharge regime battery is all between the 0.1-0.7 volt, on the one hand, the distribution of current density that results under different discharge voltages on the membrane electrode is uneven, the regional activation degree of each of membrane electrode is also different, therefore, preferably fuel cell is carried out constant voltage discharge under different voltages, can guarantee area activation more even of membrane electrode, guarantee that fuel battery energy reaches higher power output after the activation of short time; On the other hand, the discharge voltage that makes battery is between the 0.1-0.7 volt, can not make battery owing to brownout, the excessive antipole that takes place of current density influence battery life, can make battery under big relatively current density, carry out fast activating again, further shorten the soak time of battery.
Description of drawings
Fig. 1 is the cutaway view of membrane electrode;
Fig. 2 is the curve chart of the fuel cell membrane electrode cell output voltage under different current densities after adopting method of the present invention and existing method activating.
Embodiment
Method of the present invention comprises anode fuel and negative electrode fuel fed respectively in the anode chamber of fuel cell and the cathode chamber makes fuel cell electric discharge, wherein, described discharge comprises a plurality of discharge regimes, also comprise at least one time interval between a plurality of discharge regimes, and battery discharges with constant voltage all at each discharge regime.
The structure of described fuel cell is conventionally known to one of skill in the art, as, described fuel cell comprises membrane electrode, described membrane electrode is between dividing plate, described membrane electrode comprises anode, negative electrode and the proton exchange membrane between anode and negative electrode, also comprise the anode chamber between described anode and the dividing plate, also comprise cathode chamber between described negative electrode and the dividing plate.According to the present invention, with the method for fuel cell electric discharge is conventionally known to one of skill in the art, as respectively anode fuel and negative electrode fuel being fed in anode chamber and the cathode chamber, and the suitable flow of maintenance fuel, keep proton exchange membrane to be in wetting state all the time, battery is communicated with into the loop with load or external power, makes battery discharge.The working temperature of battery is 20-90 ℃, is preferably 45-85 ℃.
The anode fuel of described fuel cell can be the aqueous solution of hydrogen, alcohol, alcohol, a kind of in organic acid, the organic acid aqueous solution; Described alcohol is selected from one or more in methyl alcohol, ethanol, propyl alcohol, the isopropyl alcohol, and described organic acid is selected from one or more in formic acid, acetate, the propionic acid.Described negative electrode fuel is generally oxygen containing gas, as air or oxygen.In order to guarantee that fuel battery inside has satisfied humidity environment, help the hydration of proton exchange membrane, before being fed battery, fuel preferably described anode fuel and negative electrode fuel are heated, humidification obtains the anode fuel and the negative electrode fuel of humidification, the relative humidity of described anode fuel and negative electrode fuel is preferably 50-100%, for the method for fuel humidification is conventionally known to one of skill in the art, in order to prevent since the temperature of humidification anode fuel of heating and negative electrode fuel too high cause feed temperature be lower than the inside battery of fuel temperature after the fuel airsetting form water droplet, under the preferable case, the humidification temperature of described fuel is lower than the working temperature of battery.It is the 0.01-0.3 MPa that the consumption of described anode fuel and negative electrode fuel makes the pressure in anode chamber and the cathode chamber, and the utilance of anode fuel and negative electrode fuel is respectively 60-100% and 20-100%.
Described discharge comprises a plurality of discharge regimes, can be 2-15 stage, is preferably 5-12 stage, and be 2-60 minute the discharge time of each discharge regime, is preferably 10-30 minute.
In order to increase the activating velocity of fuel cell membrane electrode, each discharge regime, battery all discharges with constant voltage, the method that discharge voltage is controlled to be constant voltage is the method for this area routine, as be included in and apply an external power on the fuel cell, the positive pole with external power is connected with negative electrode with the anode of fuel cell with negative pole respectively, at fuel cell two termination voltmeters, by regulating the electric current of external power, make fuel cell voltage constant; Perhaps with fuel cell with connect with load again after external power is connected, regulate the electric current of external power, the voltage at steady fuel battery two ends by the resistance value of regulating load; Perhaps can also directly fuel cell be connected with load, thereby control the voltage at the discharging current steady fuel battery two ends of fuel cell by the resistance value of regulating or change load; More convenient simple method is for directly being connected to potentiostat the two ends of fuel cell, the voltage that shows on the described potentiostat is the voltage at fuel cell two ends, and can to make the voltage at fuel cell two ends by the voltage of regulating potentiostat be constant voltage output.
In order to guarantee the good activation effect of fuel cell membrane electrode, shorten soak time again, the discharge voltage of described fuel cell is preferably the 0.1-0.7 volt, more preferably the 0.3-0.7 volt.Cell voltage is more near 0 volt, though can produce bigger current density, shorten soak time, but because current density is excessive, if control badly, battery is easy to be punctured by big electric current, and the puncture in the short time can make battery generation reverse electrode phenomena, influence battery life, puncture can cause battery to scrap for a long time; If cell voltage is too high, current density is less, needs the very long cell activation time, just can reach good activation effect, therefore, for the activation effect that improves battery shortens soak time again, the present invention preferably is limited to the discharge voltage of battery between the 0.1-0.7 volt.
In the discharge process of whole fuel cell, the variation of the discharge voltage of different phase battery is not particularly limited, the discharge voltage of different discharge regimes can be identical, also can be different, in order to guarantee the more even of membrane electrode activation, make fuel battery energy after the activation of short time, reach higher power output, under the preferable case, the discharge voltage difference of adjacent two discharge regimes, the rule of variation is not particularly limited, can be for successively decreasing gradually, also can be for increasing progressively gradually, perhaps increasing progressively earlier successively decreases or successively decrease earlier afterwards increases progressively, and under the preferable case, the voltage difference of adjacent two discharge regimes is the 0.1-0.3 volt.
According to the present invention, between described a plurality of discharge regimes, also comprise at least one time interval, the water that the described time interval can make battery produce in discharge process is fully wetting with proton exchange membrane, help the hydration of proton exchange membrane, the described time interval is generally 2 second-10 minute, is preferably 5 second-5 minute.The described time interval can be arranged between any two discharge regimes, in order to guarantee the abundant hydration of proton exchange membrane, under the preferable case, all sets interval between per two adjacent discharge regimes.
Described soak time comprises the discharge time of fuel cell and the time interval between a plurality of discharge regime, i.e. shelving the time of battery, and the time that fuel cell is activated according to method of the present invention was generally 120-900 minute, was preferably 120-420 minute.
Below will the present invention will be further described by specific embodiment.
Embodiment 1
This embodiment illustrates the activation method of fuel cell membrane electrode provided by the invention
1, the preparation of membrane electrode
(1) with 0.2 weight portion carbon black (Vulcan XC72R, Cabot company) and 0.1 weight portion solid content be the PTFE emulsion (FR303A of 60 weight %, Shanghai Sanaifu New Material Co., Ltd), 10 parts by weight of deionized water are mixed, ultrasonic dispersion 30 minutes, obtain the carbon dispersion liquid, then the carbon dispersion liquid is coated on the carbon paper (TGP-H-90, Toray company), 100 ℃ of dry back carbon paper gains in weight are 1 milligram/centimetre
2, place the interior 350 ℃ of oven dry of high temperature oven 20 minutes then, obtain gas diffusion layers;
(2) be that Pt/C catalyst (Hispec8100, Johnson Matthey company product) and the 2 weight portion nafion dispersion liquids (DE520, DUPONT company product) of 47.7 weight % mix with 0.2 weight portion platinum loading.Ultrasonic dispersion 30 minutes obtains the catalyst dispersion liquid, then dispersion liquid is coated on the inner face of gas diffusion layers, reaches 0.5 milligram/centimetre until the platinum carrying capacity
2, 100 ℃ of dryings 2 hours obtain gas-diffusion electrode;
(3) two above-mentioned gas-diffusion electrodes that obtain are cut into the square of 5 centimetres of 5 cm x, be clipped in the nafion film (NRE212 of area respectively greater than gas-diffusion electrode, DUPONT company product) 130 ℃ of hot presses, 2 MPa hot pressing 2 minutes are sent in central both sides, obtain membrane electrode.The active area of membrane electrode is 25 centimetres
2
2, the activation of fuel cell membrane electrode
(1) with battery separator above-mentioned membrane electrode is clipped in the middle and is assembled into fuel cell, described dividing plate inboard comprises anode chamber and cathode chamber respectively.
(2) feed humidification hydrogen (70 ℃, relative humidity is 100%) from the anode of fuel cell import, and the holding anode room pressure is 0.1 MPa, control anode export hydrogen flowing quantity keeps under the different current densities, and the utilance of hydrogen is 95%; From cathode inlet bubbling air (70 ℃, relative humidity is 100%), and to keep the cathode chamber internal pressure be 0.1 MPa, and the flow of control cathode outlet air keeps under the different current densities, and air utilization ratio is 40%, and the control battery temperature is 75 ℃.
(3) positive pole and the negative pole with external power is communicated with the anode and the negative electrode of fuel cell respectively, and at fuel cell two termination voltmeters, closed external power switch, the electric current of regulating external power makes fuel cell voltage stabilize to 0.6 volt, made fuel cell electric discharge 20 minutes, disconnect external power then, make fuel cell stop discharge, shelved for 10 seconds, and then closed external power switch, regulating the external power electric current makes fuel cell voltage stabilize to 0.3 volt, made fuel cell electric discharge 20 minutes, disconnect external power then, make fuel cell stop discharge, shelved for 30 seconds, repeat above-mentioned steps again, make the discharge voltage of fuel cell be stabilized in 0.6 volt respectively once more, 0.4 volt and 0.6 volt discharged 30 minutes, 30 minutes and 30 minutes, the battery time of shelving between per two discharge regimes was 2 minutes, and the discharge current density of fuel cell is stabilized in 0.5 ampere/centimetre afterwards
2, and keep no significant change in 5 minutes, finish activation act.The total soak time of battery is 2 hours 14 minutes 40 seconds.
This embodiment illustrates the activation method of fuel cell membrane electrode provided by the invention
Method preparation and activation membrane electrode according to embodiment 1, different is, the temperature of battery is controlled to be 80 ℃, and the resistance value of connecting between external power and fuel cell is 2 ohm a slide rheostat, the slip slide rheostat, the electric current of regulating external power makes fuel cell voltage stabilize to 0.6 volt, made fuel cell electric discharge 30 minutes, the electric current that continues the adjusting external power then makes fuel cell voltage stabilize to 0.4 volt, makes fuel cell electric discharge 30 minutes, disconnects external power then, make fuel cell stop discharge, shelved 1 minute, and then after repeating above-mentioned steps 5 times, the discharge current density of fuel cell stabilizes to 0.5 ampere/centimetre afterwards
2, and keep no significant change in 5 minutes, finish activation act.The total soak time of battery is 5 hours 4 minutes.
Embodiment 3
This embodiment illustrates the activation method of fuel cell membrane electrode provided by the invention
According to preparation of the method for embodiment 1 and activation membrane electrode, different is, the temperature of battery is controlled to be 55 ℃, and the temperature of described humidification hydrogen, humidification air is 50 ℃.And directly with potentiostat (the special Electronics Co., Ltd. of Shenzhen's easy thing, D.C. regulated power supply) is connected to the two ends of fuel cell, the voltage of regulating the constant voltage potentiometer makes fuel cell voltage stabilize to 0.6 volt, made fuel cell electric discharge 10 minutes, it is 0.4 volt that voltage that continue to regulate the constant voltage potentiometer then makes fuel cell voltage, made fuel cell electric discharge 30 minutes, disconnect external power then, make fuel cell stop discharge, shelved 2 minutes, and then the voltage of regulating the constant voltage potentiometer makes fuel cell voltage stabilize to 0.7 volt, makes fuel cell electric discharge 50 minutes, and the voltage that continues adjusting constant voltage potentiometer makes fuel cell voltage stabilize to 0.5 volt, made fuel cell electric discharge 40 minutes, the voltage that continues adjusting constant voltage potentiometer makes fuel cell voltage stabilize to 0.4 volt, makes fuel cell electric discharge 40 minutes, cuts off electric current then, stop discharge, battery was shelved 4 minutes, repeated above-mentioned steps 1 time, the discharge current density of fuel cell stabilizes to 0.5 ampere/centimetre afterwards
2, and keep no significant change in 5 minutes, finish activation act.The total soak time of battery is 5 hours 48 minutes.
This embodiment illustrates the activation method of fuel cell membrane electrode provided by the invention
According to preparation of the method for embodiment 1 and activation membrane electrode, different is, the temperature of battery is controlled to be 60 ℃, and the temperature of described humidification hydrogen, humidification air is 58 ℃.The electric current of regulating external power earlier makes fuel cell voltage stabilize to 0.6 volt, made fuel cell electric discharge 30 minutes, it is 0.4 volt that electric current that continue to regulate external power then makes fuel cell voltage, made fuel cell electric discharge 30 minutes, it is 0.2 volt that electric current that continue to regulate external power then makes fuel cell voltage, made fuel cell electric discharge 30 minutes, disconnect external power then, make fuel cell stop discharge, shelved 5 minutes, and then the electric current of regulating external power makes fuel cell voltage stabilize to 0.7 volt, made fuel cell electric discharge 30 minutes, the electric current that continues the adjusting external power makes fuel cell voltage stabilize to 0.5 volt, made fuel cell electric discharge 30 minutes, the electric current that continues the adjusting external power makes fuel cell voltage stabilize to 0.3 volt, makes fuel cell electric discharge 30 minutes, and the discharge current density of fuel cell stabilizes to 0.5 ampere/centimetre afterwards
2, and keep no significant change in 5 minutes, finish activation act.The total soak time of battery is 3 hours 5 minutes.
Comparative Examples 1
The activation method of the existing fuel cell membrane electrode of this Comparative Examples explanation
According to preparation of the method for embodiment 1 and activation membrane electrode, different is, earlier under the discharge voltage of fuel cell not with fuel cell electric discharge after 2 minutes, battery is no abnormal, is that 0.7 volt, current density are 0.5 ampere/centimetre at discharge voltage again
2Make battery discharge under the condition 24 hours, and finished the activation act of battery.
Embodiment 5-8
The performance of the battery after the method activation provided by the invention is adopted in the following examples explanation
Fuel cell membrane electrode the output voltage under different current densities of mensuration after according to the activation of the method for embodiment 1-4, assay method is as follows: feed (70 ℃ of humidification hydrogen from the anode of fuel cell import, relative humidity is 100%), and the holding anode room pressure is 0.1 MPa, control anode export hydrogen flowing quantity, keep under the different current densities, the utilance of hydrogen is 95%; From cathode inlet bubbling air (70 ℃, relative humidity is 100%), and to keep the cathode chamber internal pressure be 0.1 MPa, and the flow of control cathode outlet air keeps under the different current densities, and air utilization ratio is 40%.Fuel cell connected with one 3 ohm resistance make battery constitute the loop, battery begins discharge, the working temperature of control battery is 75 ℃, after discharge a period of time, behind the output voltage stabilization of battery, be recorded as initial voltage, change the discharge current density of battery then, the record output voltage of battery under different discharge current densities, and with current density (ampere/centimetre
2) be abscissa, output voltage (volt) is the ordinate mapping.The result as shown in Figure 2, wherein, curve 1 is the output voltage curve chart of method activation back membrane electrode under different discharging current sealings according to embodiment 1, curve 2 is the output voltage curve chart of method activation back membrane electrode under different discharging current sealings according to embodiment 2, curve 3 is the output voltage curve chart of method activation back membrane electrode under different discharging current sealings according to embodiment 3, and curve 4 is the output voltage curve chart of method activation back membrane electrode under different discharging current sealings according to embodiment 4.
Comparative Examples 2
The performance of the battery after the existing method activation is adopted in the explanation of this Comparative Examples
Measure according to the output voltage of fuel cell membrane electrode under different current densities after the method activation of Comparative Examples 1 according to the method for embodiment 5-8, obtain activating the output voltage curve chart of back membrane electrode under different discharging current sealings, shown in curve among Fig. 25.
As can be seen from Figure 2, adopt the fuel cell membrane electrode after existing method activates to compare with adopting the fuel cell membrane electrode after activation method of the present invention activates, (it is 70 ℃ that anode feeds temperature under identical condition determination, relative humidity is 100% humidification hydrogen, anode chamber's internal pressure is 0.1 MPa, and the utilance of hydrogen is 95%; The negative electrode bubbling air, the cathode chamber internal pressure is 0.1 MPa, air utilization ratio is 40%, the working temperature of control battery is 70 ℃), under same current density, the output voltage of the fuel cell of the output voltage that adopts the fuel cell membrane electrode after the method for the present invention activation after the method activation of adopting Comparative Examples 1 illustrate the power of battery that adopts after method of the present invention the activates power of battery apparently higher than Comparative Examples 1, in addition, soak time of the present invention shortens greatly.
Claims (11)
1, a kind of activation method of fuel cell membrane electrode, this method comprises anode fuel and negative electrode fuel fed respectively in the anode chamber of fuel cell and the cathode chamber makes fuel cell electric discharge, it is characterized in that, described discharge comprises a plurality of discharge regimes, also comprise at least one time interval between a plurality of discharge regimes, and all with the constant voltage discharge, described discharge voltage is the 0.1-0.7 volt to battery at each discharge regime.
2, method according to claim 1, wherein, described discharge voltage is the 0.3-0.7 volt.
3, method according to claim 1, wherein, the described time interval is a plurality of, each time interval is between different two adjacent discharge regimes.
4, method according to claim 3 wherein, all comprises the time interval between per two adjacent discharge regimes.
5, according to any described method in the claim 1,3 and 4, wherein, the described time interval is 2 second-10 minute.
6, method according to claim 5, wherein, the described time interval is 5 second-5 minute.
7, method according to claim 1, wherein, discharge regime is 2-15, be 2-60 minute the discharge time of each discharge regime.
8, method according to claim 7, wherein, discharge regime is 5-12, be 10-30 minute the discharge time of each discharge regime.
9, method according to claim 1, wherein, the difference of the discharge voltage of two adjacent discharge regimes is the 0.1-0.3 volt.
10, method according to claim 1, wherein, the relative humidity of described anode fuel and negative electrode fuel is 50-100%, the working temperature of battery is 20-90 ℃.
11, method according to claim 1, wherein, it is the 0.01-0.3 MPa that the consumption of described anode fuel and negative electrode fuel makes the pressure in anode chamber and the cathode chamber, the utilance of anode fuel and negative electrode fuel is respectively 60-100% and 20-100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101099626A CN100527495C (en) | 2006-08-25 | 2006-08-25 | Activation method for membrane electrode of fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101099626A CN100527495C (en) | 2006-08-25 | 2006-08-25 | Activation method for membrane electrode of fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101132068A CN101132068A (en) | 2008-02-27 |
| CN100527495C true CN100527495C (en) | 2009-08-12 |
Family
ID=39129233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101099626A Expired - Fee Related CN100527495C (en) | 2006-08-25 | 2006-08-25 | Activation method for membrane electrode of fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100527495C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102157744B (en) * | 2011-03-14 | 2012-12-26 | 广东省电子技术研究所 | Constant voltage discharge adjusting device of fuel cell and adjusting method thereof |
| CN105552405B (en) * | 2016-01-28 | 2017-09-01 | 新源动力股份有限公司 | A kind of method for lifting activation of fuel cell efficiency |
| CN105895938B (en) * | 2016-07-05 | 2018-11-16 | 弗尔赛（上海）能源科技有限公司 | A kind of activation method of proton exchange film fuel cell electric piling |
| CN109786789A (en) * | 2018-12-27 | 2019-05-21 | 武汉喜玛拉雅光电科技股份有限公司 | A kind of test method of fuel cell membrane electrode activation method and polarization curve |
| CN111600048A (en) * | 2019-02-20 | 2020-08-28 | 北京中氢绿能科技有限公司 | Method for quickly activating proton exchange membrane fuel cell |
| CN110690482B (en) * | 2019-09-20 | 2021-03-30 | 一汽解放汽车有限公司 | Activation method of proton exchange membrane fuel cell |
| CN110649291B (en) * | 2019-09-27 | 2022-08-02 | 先进储能材料国家工程研究中心有限责任公司 | Rapid activation method for proton exchange membrane fuel cell |
| CN110911714A (en) * | 2019-10-23 | 2020-03-24 | 浙江高成绿能科技有限公司 | Proton exchange membrane fuel cell stack activation method |
| CN110911716B (en) * | 2019-11-25 | 2023-01-13 | 浙江锋源氢能科技有限公司 | Constant-voltage activation method of fuel cell stack |
| CN113871633B (en) * | 2021-09-26 | 2023-06-30 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Method for efficiently activating membrane electrode of proton exchange membrane fuel cell in situ |
| CN114284529B (en) * | 2021-12-27 | 2024-07-16 | 深圳市贝特瑞新能源技术研究院有限公司 | Battery activation method and battery activation device |
-
2006
- 2006-08-25 CN CNB2006101099626A patent/CN100527495C/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 质子交换膜燃料电池膜电极活化工艺及机理. 朱科，陈延禧等.电源技术，第26卷第4期. 2002 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101132068A (en) | 2008-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100539267C (en) | The activation method of fuel cell membrane electrode | |
| CN100527495C (en) | Activation method for membrane electrode of fuel cell | |
| CN101098009B (en) | Method for activating membrane electrode of fuel cell | |
| US8617770B2 (en) | Electrodes containing oxygen evolution reaction catalysts | |
| CN100508266C (en) | Membrane electrode unit | |
| CN101212054A (en) | Fuel cell membrane electrode and its preparation method | |
| US7955745B2 (en) | Fuel cell system and activation method for fuel cell | |
| JP2002289230A (en) | Polymer electrolyte fuel cell | |
| CN100521317C (en) | Membrane-electrode unit for direct methanol fuel cells and method for the production thereof | |
| CN101000963A (en) | Manufacturing method of membrane electrode of fuel cell | |
| CN101427409A (en) | Method and apparatus for measuring crossover loss of fuel cell | |
| KR100765088B1 (en) | Hybrid membrane-electrode assembly with minimal interfacial resistance and preparation method thereof | |
| KR20170069783A (en) | Catalyst slurry composition for polymer electrolyte fuel cell, membrane electrode assembly, and manufacturing methode of membrane electrode assembly | |
| JP2007018858A (en) | Fuel cell system | |
| US10923749B2 (en) | Method for operating a fuel cell and fuel cell system | |
| KR100311731B1 (en) | Method for manufacturing electrode for direct methanol feul cell | |
| CN201956423U (en) | Spraying heating vacuum sucker for membrane electrodes of proton exchange membrane fuel cells | |
| JP4068372B2 (en) | Fuel cell operating method and fuel cell system | |
| JP2010021114A (en) | Direct oxidation type fuel cell | |
| KR100907183B1 (en) | Gas diffusion layer of fuel cell, membrane-electrode assembly of fuel cell and fuel cell | |
| JPH1116586A (en) | Manufacture of high polymer electrolyte film-gas diffusion electrode body | |
| CN108390083B (en) | Discharge working mode starting method of combined regenerative fuel cell system | |
| US20050136298A1 (en) | Methods of treating fuel cells and fuel cell systems | |
| KR20150138103A (en) | Electrode for fuel cell, membrane electrode assembly comprising the same and fuel cell comprising the membrane electrode assembly | |
| KR100599811B1 (en) | Membrane/electrode for fuel cell and fuel cell system comprising same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090812 |