CN101217199B - Method of preserving fuel cell membrane electrode assembly - Google Patents
Method of preserving fuel cell membrane electrode assembly Download PDFInfo
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- CN101217199B CN101217199B CN2008100022791A CN200810002279A CN101217199B CN 101217199 B CN101217199 B CN 101217199B CN 2008100022791 A CN2008100022791 A CN 2008100022791A CN 200810002279 A CN200810002279 A CN 200810002279A CN 101217199 B CN101217199 B CN 101217199B
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- electrode assembly
- closed container
- keeping
- oxygen
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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 a method for keeping the fuel cell used membrane electrode assembly, the method is used for the fuel cell used membrane electrode assembly which is stacked with a catalyst electrode in the two surfaces of the solid polyelectrolyte membrane, and the method has the following characters: the membrane electrode assembly is covered by the soft polymer membrane which hasmoisture permeability for 0.1g/(m<2>.day) or less and oxygen transmissivity for 0.1ml/(m<2>.day.atm) or less, the perimeter of the part protruding from the catalyst electrode on the solid polyelectrolyte membrane is arranged with a space which is filled with inert gas.
Description
The application is that the application number submitted on March 9th, 2005 is 200510054129.1, denomination of invention is divided an application for the Chinese patent application of " keeping method of fuel battery membrane electrode assembly ".
Technical field
The present invention relates to the keeping method of the fuel battery membrane electrode assembly of the stacked oxygen utmost point and fuel electrodes on solid polyelectrolyte membrane.
Background technology
Recently, fuel cell gets most of the attention as cleaner power sources.There is numerous species in this fuel cell, and one of them has solid macromolecular electrolyte type fuel cell.
This solid macromolecular electrolyte type fuel cell, have a plurality of so-called monocell stacked in series as the generating least unit are got up and the so-called fuel cell pack (multi-layer cell) that forms, owing in this fuel cell pack, be equipped with aerobic and the supply mean of fuel and the cooling way of multi-layer cell, thereby the electric power (voltage) that in each monocell, makes hydrogen and oxygen reaction just can obtain to wish.
Above-mentioned monocell and then have fuel battery membrane electrode assembly and the conjugant of space between adjacent and the dividing plate that makes it to conduct electricity during stacked monocell, the main part of managing above-mentioned reaction is a fuel battery membrane electrode assembly.
It is the dielectric film that the macroion exchange membrane of amberplex and so on constitutes that this fuel battery membrane electrode assembly has by containing sulfonic fluororesin, has respectively with the cathode catalysis layer that becomes the oxygen utmost point of stacked state configuration and the anode catalyst layer that becomes fuel electrodes in the both sides of this dielectric film.And anode catalyst layer for example uses the alloy of platinum and ruthenium, and cathode catalysis layer for example uses platinum.
Fuel battery membrane electrode assembly with this spline structure makes oxygen and hydrogen react as following.That is to say, make hydrogen of supplying to fuel electrodes etc. become hydrogen ion, and generate water to the hydrogen ion of oxygen utmost point side shifting at cathode catalysis layer and oxygen and electron reaction by above-mentioned dielectric film with hydration status at above-mentioned anode catalyst layer.Then, by carrying out repeatedly of these reactions, fuel battery membrane electrode assembly just produces electric power (voltage).
In the past, such solid macromolecular electrolyte type fuel cell nearly all be from monocell the installation that is fabricated onto fuel cell pack, produce so continuously to the installation of final fuel battery again, can obtain the desirable performance of fuel cell like this.
The epoch of popularized at these fuel cells, fuel cell being produced with batch mode are in the time of coming, it is generally acknowledged the parts that are necessary under the state that does not make performance degradation before long-term keeping fuel cell is installed, can obtain desirable performance when guaranteeing that fuel cell is finished.For example, under the state of fuel cell pack, can consider in the atmosphere of having removed air (oxygen), to carry out the method for keeping, this method is to remove air (oxygen) by adopting inert gas or water to purify the mode that remains in the air (oxygen) in the runner, wherein runner is arranged on the barrier film, be used to flow through oxygen and hydrogen (for example, opening 2002-93448 communique and the flat 6-251788 communique of Te Kai) with reference to the spy.In addition, as the technology of in the atmosphere of having removed oxygen, carrying out keeping, can consider to use the keeping method (for example, opening the 2000-289380 communique) of oxygen absorber with reference to the spy.
But, after the battery pile that the acts as a fuel assembling, it is generally acknowledged that the method with existing example is possible for a long time certainly, but, for example, just can not be fit to only produce the keeping of fuel battery membrane electrode assembly and the conjugant single body of needs when transport in a distant place along with the generalization of fuel cell.
Summary of the invention
So the present inventor has carried out research with great concentration repeatedly in view of existing technology, found out that at last the reason of unfavorable condition takes place when taking care of the single body of electrode for fuel cell conjugant.
Promptly in the manufacturing process of the Catalytic Layer of membrane-electrode assembly, used alcohol.For example, manufacturing process as Catalytic Layer, with the acetylene black that is loaded with platinum one ruthenium alloy particle or platinum particles is that carbon dust is a catalyst fines, this catalyst fines is dispersed in the ethanol that contains perfluorinated sulfonic acid (perfluorocarbonsulfonic acid) powder and makes the catalyst of pasty state.One side at carbon system nonwoven fabrics applies this pasty state catalyst then, forms Catalytic Layer thus.One side that then will be coated with catalyst is clamped between two Catalytic Layer dielectric film towards dielectric film, has so just made membrane-electrode assembly.
But even above-mentioned alcohol after membrane-electrode assembly is made, also can remain on the nonwoven fabrics, if directly preserve like this, then airborne oxygen and this alcohol react and oxides such as generation acetic acid, and catalyst is produced harmful effect.And recognize that long-term keeping will cause the rotten of catalyst itself.
Also recognize in addition: be in the environment such as factory or warehouse, dusts such as the organic substance that contains in the air tend to attached on the membrane-electrode assembly, when unnecessary organic substance during for a long time attached to catalyst, will make Catalytic Layer rotten.
In addition, when metal (particularly transition metal) particulate arrives on the dielectric film, because the highly acid of dielectric film, ionization will take place in metallic.And the dielectric film that adheres to when Ionized metallic is used on the fuel cell and when making this fuel cell running, gas of coming by the dielectric film seepage or the hydrogen peroxide that generates because of the influence of side reaction and the above-mentioned ionized metal that adheres to react and produce hydroxyl radical free radical, because the effect of this free radical, dielectric film is decomposed.Recognize in addition: in a single day dielectric film is decomposed, and then seepage increases, and decomposes and quickens, and the thickness of dielectric film reduces, and finally just can not keep and generate electricity.
Also learn in addition: be exposed in the oxygen in the air, each Catalytic Layer reaches the high voltage near 1V, this has promoted the oxidation of metallic catalysts such as the carrier carbon in the Catalytic Layer, platinum and ruthenium and has lost function as catalyst, perhaps catalyst stripping and produce damaged from Catalytic Layer.
Further also find: because of the ambient humidity of taking care of fuel battery membrane electrode assembly changes, dielectric film expands repeatedly and shrinks, and causes the damage of dielectric film itself or Catalytic Layer.
And found out already: under above-mentioned at least a arbitrarily state, in a single day fuel battery membrane electrode assembly goes wrong, the fuel cell that constitutes by this fuel battery membrane electrode assembly, its initial characteristic such as voltage-current characteristic will reduce, and can see that perhaps reducing appears in the long durability of fuel cell itself.
Further also find: because of the expansion and the contraction of dielectric film, its size changes, and causes the assembling difficulty of monocell or becomes impossible.
In addition, in the low packing container of oxygen permeability, enclose oxygen-absorbing substance, when under such state, taking care of, owing to can under the low oxygen concentration state, take care of, thereby can avoid the generation of above-mentioned problem of oxidation, but, the material that quickens the dielectric film decomposition discharges from oxygen-absorbing substance sometimes, so the selection of oxygen-absorbing substance also is important.
The present invention is in view of former problem and inventor's opinion and finish, purpose is to provide a kind of keeping method of fuel battery membrane electrode assembly, even this method is only taken care of fuel battery membrane electrode assembly for a long time, also can suppress the decline of the characteristics of fuel cells that constitutes by the conjugant after the keeping.
For achieving the above object, the keeping method of fuel battery membrane electrode assembly of the present invention is the keeping method at the fuel battery membrane electrode assembly of two surperficial inner stacks catalyst electrodes of solid polyelectrolyte membrane, it is characterized in that: described membrane-electrode assembly has solid polyelectrolyte membrane, at anode catalyst layer stacked on this solid polyelectrolyte membrane and cathode catalysis layer and the gas diffusion layers that is provided with on described Catalytic Layer separately, and the outer surface moisture permeability of wherein said gas diffusion layers is 0.1g/ (m
2D) or following, oxygen permeability be 0.1ml/ (m
2Datm) or the macromolecule membrane of following softness cover, with described membrane-electrode assembly with sealing state keeping in closed container that the material of anti-block, moisture and infringement performance flows into or the closed container that constitutes by described macromolecule membrane, in described closed container, be filled with inert gas.
The keeping method of another kind of the present invention fuel battery membrane electrode assembly of stacked catalyst electrode on solid polyelectrolyte membrane, it is characterized in that: fuel battery membrane electrode assembly is placed on prevents that block, moisture and infringement keep in the closed container that the material of performance flows into, under sealing state, take care of.
Thus, can keep certain atmosphere in the closed container of sealing back, can suppress fuel battery membrane electrode assembly and the degeneration of performance or adhering to of unnecessary material take place because of keeping.
Above-mentioned keeping method further also can be set at the atmosphere in the above-mentioned closed container than air lower oxygen concentration.
Thus, can prevent from because of the oxidation of membrane-electrode assembly itself or remain in organic oxidation in the membrane-electrode assembly etc. Catalytic Layer is caused damage or makes the Catalytic Layer performance degradation.
Above-mentioned keeping method further also can make the concentration ratio air height of the fuel gas of atmosphere in the above-mentioned closed container of firm sealing.
Thus, because of the catalytic action of membrane-electrode assembly, fuel gas and residual oxygen reaction and become hypoxic atmosphere.In addition,, the current potential of Catalytic Layer in the container is reduced near the hydrogen normal potential 0V, also can prevents from Catalytic Layer to be caused damage or makes the Catalytic Layer performance degradation because of Catalytic Layer remains on high potential owing to remain in the effect of hydrogen in the container.
Above-mentioned keeping method further also can be at closed container internal configurations deoxidier.
Thus, just can make easily to be in hypoxia in the closed container, just can suppress the performance of membrane-electrode assembly easily and degenerate in time.
Above-mentioned keeping method further also can make the inert gas concentration of atmosphere in the above-mentioned closed container than air height.
Thus, the concentration of other gas such as oxygen is relatively low, can obtain and the same action effect of above-mentioned low oxygen concentration atmosphere.
Above-mentioned keeping method is in keeping during membrane-electrode assembly, further also can take in atmosphere in the closed container of membrane-electrode assembly with gas purification with keeping, thereby closed container is sealed.
If adopt this method, just can make becomes desirable environment and the keeping membrane-electrode assembly in the closed container, can suppress the performance degradation that causes because of keeping.
Above-mentioned keeping with the humidity of gas be preferably set to purify before the interior humidity of closed container identical.
Thus,, also can suppress the variation of humidity even when the keeping of membrane-electrode assembly begins, thus can prevent the starting stage change in size, prevent the degeneration of performances such as initial characteristic that membrane-electrode assembly causes because of long-term keeping and durability.
Above-mentioned keeping method further also can seal the closed container of taking in membrane-electrode assembly in taking care of with gas atmosphere when the keeping membrane-electrode assembly.
If adopt this method, just can make becomes desirable environment and the keeping membrane-electrode assembly in the closed container, thereby can suppress because of the performance degradation that causes of keeping.
Above-mentioned keeping is preferably set to the humidity of gas atmosphere and puts into this atmosphere with fuel battery membrane electrode assembly the humidity of residing atmosphere is identical before.
Thus,, also can suppress the variation of humidity, thereby can prevent the change in size of starting stage, prevent the degeneration of membrane-electrode assembly because of performances such as long-term initial characteristic that causes certainly and durability even when the keeping of membrane-electrode assembly begins.
The oxygen permeability of above-mentioned closed container is preferably 0.1ml/ (m
2Datm) or below, and moisture permeability is preferably 0.1g/ (m
2D) or below.
Thus, can special provision make the long preservation of membrane-electrode assembly become the performance of possible concrete closed container, thereby can effectively prevent the inflow of block, moisture.
The Catalytic Layer surface of fuel battery membrane electrode assembly also can cover with the high diaphragm of oxygen isolation.
Thus, because direct contacting of barrier film assembly of electrode and oxygen, and then can prevent degeneration because of performances such as the caused initial characteristic of long-term keeping of membrane-electrode assembly and durability.And since the resiliency of film can also prevent from effectively to make the damaged of membrane-electrode assembly generation because of impact or the contact between the membrane-electrode assembly from the outside.
Description of drawings
These and other objects of the present invention, advantage and characteristic will become obvious from the explanation of they being carried out below in conjunction with accompanying drawing.What described accompanying drawing was represented is particular of the present invention.Among the accompanying drawing:
Fig. 1 is the schematic diagram of the keeping method of fuel cell pack before the expression.
Fig. 2 is the stereogram of keeping state of schematically representing the membrane-electrode assembly of embodiment of the present invention.
Fig. 3 is the profile of keeping state of schematically representing the membrane-electrode assembly of embodiment of the present invention.
Fig. 4 is the profile that schematically is illustrated in the state of a plurality of membrane-electrode assemblies of keeping in the closed container.
Fig. 5 is a profile of schematically representing the keeping state of the membrane-electrode assembly that covers with diaphragm.
Fig. 6 is the profile that schematically is illustrated in a plurality of membrane-electrode assembly states that cover with diaphragm of keeping in the closed container.
Fig. 7 is that expression is used for the schematic diagram of keeping with the device of gas purification closed container inside.
Fig. 8 is the schematic diagram that expression is used for being full of with gas with keeping the device of closed container inside.
Fig. 9 represents that being used to make the closed container internal atmosphere is the profile of hypoxia.
Figure 10 represents that cell voltage over time.
Embodiment
Followingly describe with regard to embodiment of the present invention with reference to drawing.
(embodiment 1)
Fig. 2 is the stereogram of keeping state of the fuel battery membrane electrode assembly of expression embodiment of the present invention.
Fig. 3 is the profile the when membrane-electrode assembly in closed container 21 11 cuts off certainly with representing imagination.
Just as shown in these figures, membrane-electrode assembly 11 is taken care of in the bag shape closed container 21 that is made of resin with sealing state.
Membrane-electrode assembly 11 is fuel battery membrane electrode assemblies, and its structure is that each face at solid polyelectrolyte membrane 12 is laminated with anode catalyst layer 13 and cathode catalysis layer 14.In addition, Catalytic Layer 13,14 structure separately is to be loaded with catalyst on the net of carbon, and it is frangible and not shock-resistant.In addition, as Fig. 3 show in detail, each face of Catalytic Layer 13,14 is respectively arranged with gas diffusion layers 15.
Specifically, the moisture permeability of closed container 21 is necessary for 0.1[g/m
2D] or below, and oxygen permeability is necessary for 0.1[cc/m
2Datm] or below.This be because: if do not satisfy this two conditions, then membrane-electrode assembly 11 degeneration in time will become obvious.And moisture permeability is preferably set to 0.01[g/m
2D] or below, and oxygen permeability is preferably set to 0.01[cc/m
2Datm] or below.Because if satisfy this condition, just can withstand long-term keeping.
In addition, as the material of closed container 21, can from the following material of enumerating, select.
The candidate material of closed container 21: polyvinyl chloride (PVDC) is, ethene one vinyl alcohol (EVOA) is, polyvinyl alcohol (PVA) be with polyamide (PA) be the single body of plastic film and ceramic evaporated film, aluminium-vapour deposition film, laminate aluminium foil film or stacked a plurality of barrier material and the film that uses, perhaps they are used for barrier layer and film that compound other macromolecule membrane became.
In addition, the typical example as above-mentioned macromolecule membrane has: PET, the glassine paper of coating PVDC, EVOH film, stretching PVA film, the coating of ONY, the multilayer barrier layer ONY (MXD, EVOH co-extrusion pressure) of the OPP of the OPP of coating PVDC, coating PVA system, OPP, the coating PVDC of EVOH co-extrusion pressure, the PET of coating PVDC, coating P VA system mix film, the aluminium oxide evaporated film (aluminium oxide (AL of barrier layer
2O
3) evaporation PET, silica (SiO
X) evaporation PET, aluminium oxide evaporation ONY, aluminium oxide evaporation OPP), aluminium-vapour deposition film (aluminium-vapour deposition PET, aluminium-vapour deposition CPP, aluminium-vapour deposition OPP, aluminium-vapour deposition ONY, aluminium-vapour deposition PE) etc.
So-called OPP is meant biaxial stretch-formed polypropylene, and ONY is meant Biaxially oriented polyamide fiber (nylon), and CPP is meant no oriented polypropylene, and MXD is meant the barrier polyamide, and PET is meant PETG.
In addition, above-mentioned material is used in qualification that the thickness of closed container 21 has nothing special, as long as thickness can guarantee that moisture permeability is 0.1[g/m
2D] or following and oxygen permeability be 0.1[cc/m
2Datm] or just following.If particularly AM aluminum metallization on the film that is made of above-mentioned material just can significantly reduce moisture permeability and oxygen permeability, thickness that can attenuate closed container 21.
Use the above-mentioned material manufacturing can guarantee that moisture permeability is 0.1[g/m
2D] or following closed container 21, can prevent that steam from coming out from the container internal leakage, can prevent the variation of the internal tank water yield.But, if the rapid variations in temperature of closed container 21 outside generations, closed container 21 inner meetings produce condensation so, great changes will take place to make humidity, so, should temperature can place jumpy, can be with temperature maintenance place within the specific limits keeping membrane-electrode assembly 11 in constant temperature and humidity cabinet for example.The variation of the water yield in the polyelectrolyte can be prevented by this, the degeneration of polyelectrolyte membrane can be prevented.
In addition,, can also prevent, thereby can prevent because of the reduction of the material of infringement performance attached to the fuel battery performance that produces on the membrane-electrode assembly 11 from the sneaking into of the material of the infringement performance of outside by means of closed container 21.
Here, the material of so-called infringement performance for example is meant metallic atoms such as organic substance, iron and transition metal, metal particle etc., the performance that not only comprises the membrane-electrode assembly 11 self that makes long-term keeping produces the material of degenerating, and comprises because of attached to the material that makes the decreased performance when acting as a fuel battery operation on the membrane-electrode assembly 11.
In addition; when there is not the membrane-electrode assembly 11 (state that promptly has only the solid polymer membrane 12 in the assembling) of Catalytic Layer 13,14 in keeping; by covering solid polymer membrane 12 with diaphragm 16 and taking care of in closed container 21 inside with sealing state; also can prevent the contacting and keep constant water content of material of block and infringement performance; even so long preservation solid polymer membrane 12 also can prevent its performance decrease.
Fig. 4 is the profile that expression is piled up a plurality of fuel battery membrane electrode assemblies 11 when keeping.
In the inside of closed container 21, a plurality of membrane-electrode assemblies 11 overlap with state of contact between the gas diffusion layers 15 with the overlap condition good seal.
Like this, also can in closed container 21, once take care of a plurality of membrane-electrode assemblies 11.
If by above-mentioned such keeping, just can be in the closed container 21 of the material permeance of preventing block, moisture and infringement performance, in the atmosphere of removing oxygen and with the state that the water content (humidity) that prevents in the container changes, take care of fuel battery membrane electrode assembly 11 single bodies, so when keeping fuel battery membrane electrode assembly 11, can prevent the reduction of power generation performance, can not make the performance degradation of membrane-electrode assembly 11 single bodies for a long time.
In addition, the inside that water is filled closed container 21 also is possible, in closed container, can pass through to inject water and the oxygen of amount discharge container, owing to all become water around the membrane-electrode assembly 11, so can prevent that also the water content in the polyelectrolyte membrane from changing.In water in order not sneak into the material of infringement performance, preferably with pure water or distilled water as filling water.
(embodiment 2)
Followingly describe with regard to the 2nd embodiment of the present invention with reference to drawing.
Fig. 5 is the profile that expression is in the keeping state of the membrane-electrode assembly 11 of using diaphragm 16 to cover the outer surface states.
About membrane-electrode assembly 11 and closed container 21, because of same as described above, so omit its explanation.
Contacting of the material of oxygen during diaphragm 16 plays and directly prevents membrane-electrode assembly 11 and remain in closed container 21 and infringement performance also has the effect of the padded coaming that prevents the catalyst surface damage simultaneously.As the material of this diaphragm 16, can use the high macromolecular film resin of oxygen isolation.The material of diaphragm 16 also can be identical with the material of above-mentioned closed container 21.
In addition, membrane-electrode assembly 11 has the structure of stacked anode catalyst layer 13 and cathode catalysis layer 14 on solid polymer membrane 12.And Catalytic Layer separately 13,14 is provided with gas diffusion layers 15.
Even have at membrane-electrode assembly 11 under the situation of gas diffusion layers 15; by using diaphragm 16 covering surfaces; can further reduce oxygen and the infringement material of performance and contacting of catalyst surface, also can further reduce the variation of the water content of catalyst surface simultaneously.This is because gas diffusion layers itself also can be brought into play the function of diaphragm, thereby can further prevent because of taking care of the decline of the power generation performance of the membrane-electrode assembly 11 that causes for a long time.Therefore membrane-electrode assembly 11 is preferably taken care of under the state that sets diffusion layer 15.
Fig. 6 is the profile when schematically being illustrated in a plurality of membrane-electrode assembly 11 of keeping in the closed container 21.
Inside at closed container 21; a plurality of membrane-electrode assembly 11 superimposed inclosures, still, by covering the diaphragm 16 on membrane-electrode assembly 11 surfaces separately; each membrane-electrode assembly 11 can not contact, damage, and can take care of a plurality of membrane-electrode assemblies 11 in a closed container 21.
In addition, in the present embodiment, each membrane-electrode assembly 11 has gas diffusion layers 15, but also can take care of the membrane-electrode assembly 11 with gas diffusion layers 15.
(the formation method 1 of atmosphere in the closed container 21)
Below, be illustrated as the method that the atmosphere that makes in the closed container 21 becomes the atmosphere of low oxygen concentration.
At first, insert membrane-electrode assembly 11 in the inside of the bag shape closed container 21 of a part of opening.
Secondly, as shown in Figure 7, Yi Bian press the peristome of the closed container 21 that has inserted membrane-electrode assembly 11, Yi Bian insert the blast pipe 31 of discharging closed container 21 gas inside and supply with the air supply pipe 32 of keeping with gas.
Then, open vent valve 34, the air of sucking-off closed container 21 inside makes closed container 21 inner for behind the vacuum state, and the open state of switching vent valve 34 and steam supply valve 36 charges into keeping gas in closed container 21.
At last, transfer to when managing 31,32, the heat seal peristome makes closed container 21 be in sealing state.
In addition, blast pipe 31 and air supply pipe 32 both can use same pipe, also can use separately independently pipe.When using same pipe, on pipeline, use changeable exhaust usefulness and air feed valve with pipeline.
Using gas as above-mentioned keeping, can be the gas of low oxygen concentration, and preferred especially is the gas of main component with the inert gas.And be main component with the inert gas, also can contain fuel gas.
In addition, so-called fuel gas is meant the gas that supplies to anode one side in fuel cell, mainly is hydrogen.
When keeping as above contains fuel gas like that with gas, keeping is with the oxygen of the trace interior minimal residue of the fuel gas that contains in the gas and closed container or that go into from the container outer flow, consumes by combustion reaction in the Catalytic Layer of membrane-electrode assembly 11.Therefore, oxygen can not remain in internal tank, and Catalytic Layer can not remain on high potential because of the oxidation or the oxygen of membrane-electrode assembly 11, thereby can prevent that the function of membrane-electrode assembly from reducing.
So-called above-mentioned inert gas comprises nitrogen, also can be helium or argon.
Furtherly, also can adopt in the mode that charges into fuel gas after the inert gas purge or after charging into fuel gas in the mode of inert gas purge, the atmosphere that makes closed container 21 inside is the inert gas that contains fuel gas.At this moment, use the pipe that charges into the pipe of inert gas and charge into fuel gas respectively,, can charge into gas separately when closed container is inflated, passing through transfer valve.
And then the keeping that makes supply has humidity identical when making with membrane electrode, the variation that can prevent to produce humidity by this when gas purification with gas.
In addition, though the sealing of peristome has been described,, can use clamping mode, pressuring method as other encapsulating method with the hot pressing method.And hot pressing mode sealing height, simple to operate, so be preferred mode.
By above-mentioned method, can be enough keeping with gas purification closed container 21 inside, the atmosphere that can make closed container 21 inside is atmosphere arbitrarily.
(the formation method 2 of atmosphere in the closed container 21)
The following describes to making closed container 21 interior atmosphere become other method of low oxygen concentration atmosphere.
At first, insert membrane-electrode assembly 11 in the inside of the bag shape closed container 21 of a part of opening.
Secondly, in tun shown in Figure 8 51, dispose the closed container 21 that has inserted membrane-electrode assembly 11.
Fuel battery membrane electrode assembly 11 is inserted in the closed container 21 under the state that is coated with diaphragm 16.Membrane-electrode assembly 11 can be in the state that diffusion layer 15 is arranged that engages, and perhaps is the state of stacked Catalytic Layer 13,14 on polyelectrolyte membrane 12.
Secondly, controlled opening/closing valve 34,36 is extracted the air of container 51 inside out and after becoming vacuum state, is contained the inert gas of burning gases to container 51 internal feeds.In addition, the pressure behind the air feed is 1 air pressure.
At last, seal the peristome of closed container 21 and make it to be in sealing state with methods such as hot pressings in container 51 inside.
If adopt this method, then can in taking care of, seal a plurality of membrane-electrode assemblies 11 simultaneously, so this method is preferred according to the volume of container 51 with the atmosphere of gas.In addition, even when being in vacuum state, atmospheric pressure can not act directly on the membrane-electrode assembly 11 yet, thereby can avoid damage of the Catalytic Layer 13,14 that causes because of atmospheric pressure etc.
(the formation method 3 of atmosphere in the closed container 21)
Fig. 9 is the profile that is illustrated in the state of keeping membrane-electrode assembly 11 in the closed container 21 of enclosing deoxidier 3.
When using deoxidier 3, in closed container 21, put into deoxidier 3, can be like this direct hermetically closed container 21 in atmosphere.
Like this, if in closed container 21, put into deoxidier 3, just can make closed container 21 interior atmosphere be in the state of low oxygen concentration simply.
When using deoxidier 3, also can remove the oxygen that bleeds from the outside selectively,, continue the oxygen in the removal closed container 21 in also can be during predetermined even the sealing of closed container 21 is low.
As deoxidier, preferably use the organic system deoxidier of autoreaction type.The organic system deoxidier of autoreaction type need be from the moisture of outside, so can prevent the variation of water content in the container.The iron series deoxidizers oxygen uptake is fast and economical, and on the other hand, its shortcoming is a moisture dependent form, can change the water content in the closed container, and iron becomes the material of the infringement performance that makes the power generation performance degeneration in fuel cell, thereby does not preferably use.
(embodiment)
Below based on Figure 10, illustrate and adopt keeping method of the present invention, prevent the checking result that is achieved by the target that the power generation performance of the membrane-electrode assembly 11 of keeping and endurance quality descend.
At first, prepare can make at least a plurality of membrane-electrode assemblies of 3 fuel cells, the A group was placed 1 year in the inert atmosphere in closed container 21 behind the membrane-electrode assembly that covers with the EVOH film separately.B group is placed on membrane-electrode assembly in the inert atmosphere in the closed container 21 and placed 1 year.The C group is only used polyethylene film packaging film assembly of electrode, places 1 year with this state.
Then, every group of membrane-electrode assembly and carrier ring of all inciting somebody to action separately stacked and make fuel cell.
In confirmatory experiment, the anode hydrogen supply acts as a fuel, and contains the gas of oxidant to the conduct of negative electrode air supply.Service conditions is: about 70 ℃ of the temperature of battery, and fuel availability is about 70%, and air utilization ratio is about 40%, the about 0.2A/cm of current density
2
Figure 10 represent to reach running time 3000 hours cell voltage over time.In addition, the dotted line among this figure is for the ease of relatively, the result of the fuel cell power generation that expression is made of the membrane-electrode assembly after just making.
The cell voltage of the membrane-electrode assembly 11 (C) of the membrane-electrode assembly 11 (A, B) that obtains with keeping method of the present invention and the keeping method acquisition of prior art, the cell voltage height of the membrane-electrode assembly that obtains with method of the present invention in the time of in the early stage, the cell voltage with by 11 generatings of the membrane-electrode assembly after just making the time is equal.In addition, observing one and be issued to 3000 hours voltage reduced rate, also is that the reduced rate of cell voltage of the membrane-electrode assembly that obtains with method of the present invention is little, identical with the reduced rate of the cell voltage that is generated electricity by the membrane-electrode assembly after just making 11.Further also confirm: when continuing generating for a long time, use the battery of the membrane-electrode assembly 11 of common keeping method acquisition, the degeneration of its polyelectrolyte membrane is than development quickly usually, compare with the cell power generation situation of using the membrane-electrode assembly 11 after just having made, in the time more early, rapid voltage takes place descend, to such an extent as to can not generate electricity.Also confirm in addition: the A group that covers keeping with the EVOH film is compared with the B group, can keep higher cell voltage usually.The placement condition of present embodiment can also be confirmed: extraneous atmosphere all has same effect under normal temperature (20 ℃～30 ℃), high temperature (50 ℃～60 ℃), low temperature (0 ℃～10 ℃).
Therefore,, compare, can prevent because of taking care of the power generation performance of the membrane-electrode assembly 11 that causes and the reduction of endurance quality for a long time with the situation of carrying out keeping with former method according to keeping method of the present invention.
Claims (2)
1. the keeping method of a fuel battery membrane electrode assembly, it is the keeping method at the fuel battery membrane electrode assembly of two surperficial inner stacks catalyst electrodes of solid polyelectrolyte membrane, it is characterized in that: described membrane-electrode assembly (11) has solid polyelectrolyte membrane (12), go up stacked anode catalyst layer (13) and cathode catalysis layer (14) at this solid polyelectrolyte membrane (12), and in described Catalytic Layer (13 separately, 14) go up the gas diffusion layers (15) that is provided with, the outer surface moisture permeability of wherein said gas diffusion layers (15) is 0.1g/ (m
2D) following, oxygen permeability is 0.1ml/ (m
2Datm) macromolecule membrane of Yi Xia softness (16) covers, and described membrane-electrode assembly (11) is taken care of in the closed container that is made of described macromolecule membrane (21) with sealing state, is filled with inert gas in described closed container (21).
2. the keeping method of fuel battery membrane electrode assembly as claimed in claim 1, it is characterized in that: described inert gas is a nitrogen.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP065196/2004 | 2004-03-09 | ||
| JP2004065196A JP4543708B2 (en) | 2004-03-09 | 2004-03-09 | Membrane electrode assembly of polymer electrolyte fuel cell |
| JP245566/2004 | 2004-08-25 | ||
| JP2004245566A JP4543825B2 (en) | 2004-08-25 | 2004-08-25 | Storage method of fuel cell membrane electrode assembly |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005100541291A Division CN100442584C (en) | 2004-03-09 | 2005-03-09 | Method of preserving fuel cell membrane electrode assembly |
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| CN101217199A CN101217199A (en) | 2008-07-09 |
| CN101217199B true CN101217199B (en) | 2010-06-02 |
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| CN2008100022791A Expired - Fee Related CN101217199B (en) | 2004-03-09 | 2005-03-09 | Method of preserving fuel cell membrane electrode assembly |
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| JP (1) | JP4543708B2 (en) |
| CN (1) | CN101217199B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9093698B2 (en) | 2005-10-20 | 2015-07-28 | Toyota Jidosha Kabushiki Kaisha | Fuel cell stack casing |
| JP5130627B2 (en) * | 2006-01-17 | 2013-01-30 | パナソニック株式会社 | Fuel cell power generator |
| KR101169977B1 (en) | 2010-04-06 | 2012-07-31 | 지에스나노텍 주식회사 | Thin film battery having improved durability |
| JP6212154B2 (en) * | 2016-03-18 | 2017-10-11 | 本田技研工業株式会社 | Manufacturing method of membrane electrode assembly for fuel cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5178969A (en) * | 1990-07-06 | 1993-01-12 | Kabushiki Kaisha Toshiba | Fuel cell powerplant system |
| US6322920B1 (en) * | 1999-08-26 | 2001-11-27 | Plug Power, Inc. | Fuel cell isolation system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0688616B2 (en) * | 1988-11-18 | 1994-11-09 | 株式会社日本触媒 | How to store green sheets |
| JP3297125B2 (en) * | 1993-02-25 | 2002-07-02 | 三菱重工業株式会社 | Shutdown storage method of solid polymer electrolyte fuel cell |
| US5547911A (en) * | 1994-10-11 | 1996-08-20 | E. I. Du Pont De Nemours And Company | Process of imprinting catalytically active particles on membrane |
| JP2002104539A (en) * | 2000-09-28 | 2002-04-10 | Kawasumi Lab Inc | Packaging of medical appliance, and manufacturing method thereof |
| JP2003034552A (en) * | 2001-07-19 | 2003-02-07 | Asahi Glass Co Ltd | Protection method of substrate surface and functional thin film, and electro-conductive antireflection material with protective film |
| JP4394873B2 (en) * | 2001-12-19 | 2010-01-06 | 武田薬品工業株式会社 | Solid composition containing oxygen labile compound and method for stabilizing the same |
| KR100442843B1 (en) * | 2002-03-13 | 2004-08-02 | 삼성에스디아이 주식회사 | Membrane and electrode assembly(MEA), production method of the same and fuel cell employing the same |
| JP4292361B2 (en) * | 2002-03-14 | 2009-07-08 | 日本ゼオン株式会社 | Precision substrate protective film |
| US20040042789A1 (en) * | 2002-08-30 | 2004-03-04 | Celanese Ventures Gmbh | Method and apparatus for transferring thin films from a source position to a target position |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5178969A (en) * | 1990-07-06 | 1993-01-12 | Kabushiki Kaisha Toshiba | Fuel cell powerplant system |
| US6322920B1 (en) * | 1999-08-26 | 2001-11-27 | Plug Power, Inc. | Fuel cell isolation system |
Non-Patent Citations (1)
| Title |
|---|
| JP平6-251788A 1994.09.09 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101217199A (en) | 2008-07-09 |
| JP2005259360A (en) | 2005-09-22 |
| JP4543708B2 (en) | 2010-09-15 |
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