CN100544087C - Use in solid polymer fuel cell dielectric film and manufacture method thereof and membrane-electrode assembly for polymer electrolyte fuel cell - Google Patents
Use in solid polymer fuel cell dielectric film and manufacture method thereof and membrane-electrode assembly for polymer electrolyte fuel cell Download PDFInfo
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- CN100544087C CN100544087C CNB2005800199419A CN200580019941A CN100544087C CN 100544087 C CN100544087 C CN 100544087C CN B2005800199419 A CNB2005800199419 A CN B2005800199419A CN 200580019941 A CN200580019941 A CN 200580019941A CN 100544087 C CN100544087 C CN 100544087C
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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
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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
- 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
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Abstract
Will be by the formed cation-exchange membrane of the macromolecular compound with cation exchange base that form and dielectric film that contain cerium ion use as the use in solid polymer fuel cell dielectric film.When above-mentioned cation-exchange membrane has sulfonic group, be preferably, contain and be equivalent to contained in this cation-exchange membrane-SO
3 -0.3～20% cerium ion of the number of base for example carries out ion-exchange with cerium ion p-sulfonic acid base.Can provide and can generate electricity by high dose-effect, no matter the dew point of supply gas all has high power generation performance, and can the use in solid polymer fuel cell film that generate electricity steady in a long-term.
Description
Technical field
The present invention relates to initial stage output voltage height, and still can obtain the dielectric film of the use in solid polymer fuel cell of high output voltage after long-term the use.
Background technology
Fuel cell is the battery that the reaction as the gas of raw material can directly be converted to electric energy, and hydrogen oxygen fuel cell is because its reaction product has only water on the principle, therefore to almost not influence of earth environment.Because having the polyelectrolyte membrane of macroion conductivity is developed out, even also can work and can obtain high power density at normal temperature, therefore be accompanied by the social in recent years raising that the energy, earth environment problem are required, as electrolytical polymer electrolyte fuel cell, be hoped power supply with solid polymer membrane as moving vehicles such as electric automobile, mini thermoelectric heat co-generation system.
In the polymer electrolyte fuel cell, usually the amberplex with proton-conducting uses as solid macromolecule electrolyte, and is especially good by the fundamental characteristics with amberplex that sulfonic perfluocarbon polymer forms.In the polymer electrolyte fuel cell, electrode layer at the two sides of amberplex configuration gas diffusibility, supply with the gas of the hydrogen that acts as a fuel and the oxygenous gas (air etc.) that becomes oxidant by anode and negative electrode respectively, realize generating.
At the negative electrode of polymer electrolyte fuel cell, because the reduction reaction of oxygen is passed through hydrogen peroxide (H in the middle of being
2O
2) reaction is carried out, therefore might cause the deterioration of dielectric film owing to the hydrogen peroxide that in catalyst layer, generates or peroxide radical.In addition, arrive anode in the film, therefore might generate hydrogen peroxide and peroxide radical equally because the oxygen molecule of negative electrode sees through.When particularly the hydrocarbon system film is as solid polyelectrolyte membrane, owing to, therefore have the problem that is difficult to lasting work to the free radical deficient in stability.
For example, the first practicability of polymer electrolyte fuel cell is that power supply as the Gemini spaceship of the U.S. is when using.Be that styrene-divinylbenzene copolymer film of gained after sulfonation is used as dielectric film at that time, but have for a long time lasting problem.As the technology of improving this problem, add transition metal oxide that can the catalytic decomposition hydrogen peroxide in the known oriented polyelectrolyte membrane or have the method (referring to Patent Document 1) of the compound of phenol hydroxyl and, the method for decomposition of hydrogen peroxide (referring to Patent Document 2) at polyelectrolyte membrane internal burden catalyst metals particle.But these technology are the technology of decomposing the hydrogen peroxide that is generated, rather than attempt suppressing the technology that amberplex self decomposes, though therefore have the effect of improvement in the early stage, still big problem might occur for long durability.In addition, also there is the high problem of cost.
On the other hand, for the polymer of hydrocarbon system, as the polymer that free radical is had excellent stability, known have by having the amberplex that sulfonic perfluocarbon polymer forms.In recent years, these polymer electrolyte fuel cells that used the amberplex that is formed by perfluocarbon polymer are expected as automobile, and with, the dwelling house power supply with market etc., its requirement to the practicability improvement is increased, acceleration exploitation.In these purposes, for extra high efficient work, thereby carry out cost degradation when wishing with high voltage operation more.In addition, from the efficient of fuel cell system integral body, also a lot of to hanging down humidification or not having the requirement of working under the humidification.
But, there is report to show, for having used by fuel cell with amberplex that sulfonic perfluocarbon polymer forms, though stability is very high in the work under high humidification, but at low humidification or do not have under the condition of work of humidification, voltage deterioration big (with reference to non-patent literature 1).Promptly think at low humidification or do not have in the condition of work under the humidification, for by having the amberplex that sulfonic perfluocarbon polymer forms, the deterioration of dielectric film is arranged still owing to hydrogen peroxide or peroxide radical.
[patent documentation 1] Japan Patent spy opens 2001-118591 communique (claim 1, the 2nd page of 2～9 row)
[patent documentation 2] Japanese patent laid-open 6-103992 communique (method of dealing with problems, the 2nd page of 33～37 row)
[non-patent literature 1] NEDO is sponsored and is put down into 12 annual solid macromolecule shape fuel cell studies development public lecture summaries, 56 page of 16～24 row
The announcement of invention
At this, the objective of the invention is, at polymer electrolyte fuel cell in vehicle mounted, the practicability of dwelling house with market etc., providing can be with sufficient high energy efficiency generating, be lower than the low humidification of battery temperature or do not have the work under the humidification or under near the temperature of battery temperature, carry out all having high power generation performance in the work of high humidification of humidification at the humidification temperature (dew point) of supply gas, but and the use in solid polymer fuel cell film of stable electric generation still after long-time the use.
The inventor, for the fuel cell that has used the amberplex that forms by macromolecular compound with cation exchange base, deterioration with the film under the condition of work that prevents to hang down humidification or do not have humidification is a purpose, carried out research in earnest, found that by making and contain specific ion in the film and can significantly suppress the deterioration of dielectric film, thereby finished the present invention.
The invention provides the use in solid polymer fuel cell dielectric film, it is characterized in that, formed by cation-exchange membrane, contain cerium ion, this cation-exchange membrane is formed by the macromolecular compound with cation exchange base.In addition, cerium ion can be+3 valencys or+state of 4 valencys, there is no particular limitation in the present invention.
In addition, the present invention also provides the dielectric film of the use in solid polymer fuel cell with following feature, it is characterized in that, form by cation-exchange membrane, this cation-exchange membrane constitutes by the layer that the stacked macromolecular compound by having the cation exchange base more than 2 layers forms, and above-mentioned 2 layers contain cerium ion with at least 1 layer in the upper strata.
As long as cerium ion exists as ion, in dielectric film with what state exist all can, can be that a part of cation exchange base in the cation-exchange membrane is carried out ion-exchange by cerium ion, thereby cerium ion is existed as a kind of form.Therefore, the present invention also provides the dielectric film of the use in solid polymer fuel cell with following feature, it is characterized in that, form by the formed cation-exchange membrane of the macromolecular compound with cation exchange base, the part of above-mentioned cation exchange base is carried out ion-exchange by cerium ion, and provide the dielectric film of the use in solid polymer fuel cell with following feature, it is characterized in that, form by cation-exchange membrane, this cation-exchange membrane gets by the layer that the stacked macromolecular compound by having the cation exchange base more than 2 layers forms, and has at least 1 layer of at least a portion by above-mentioned cation exchange base to be got cation-exchange membrane by cerium ion ion-exchange in the above-mentioned layer more than 2 layers and forms.
Dielectric film of the present invention there is no need homogeneous and contains cerium ion.It is by the cation-exchange membrane (stacked film) that forms of layer more than 2 layers, does not need whole layers but at least 1 layer to be carried out ion-exchange by cerium ion, promptly also can contain cerium ion unevenly on thickness direction.Therefore, when particularly needing anode-side, also can be the film formed layer of ion-exchange of only serving as reasons and containing cerium ion from the nearest layer of anode to the high situation of the durability of hydrogen peroxide or peroxide radical.
Among the present invention, the macromolecular compound with cation exchange base is preferably has sulfonic macromolecular compound.
The invention provides the manufacture method of use in solid polymer fuel cell dielectric film, it is characterized in that, will be immersed in the aqueous solution that contains cerium ion by the formed cation-exchange membrane of the macromolecular compound with cation exchange base.
In addition, the invention provides membrane-electrode assembly for polymer electrolyte fuel cell, it is by anode with the catalyst layer that contains catalyst and ion exchange resin and negative electrode, is disposed at the film formed membrane-electrode assembly for polymer electrolyte fuel cell of electrolyte between above-mentioned anode and the above-mentioned negative electrode, it is characterized in that above-mentioned dielectric film is a use in solid polymer fuel cell dielectric film of the present invention.
In addition, the invention provides membrane-electrode assembly for polymer electrolyte fuel cell, it is by anode with the catalyst layer that contains catalyst and ion exchange resin and negative electrode, is disposed at the film formed membrane-electrode assembly for polymer electrolyte fuel cell of electrolyte between above-mentioned anode and the above-mentioned negative electrode, it is characterized in that contained ion exchange resin contains cerium ion among at least one side of above-mentioned anode and above-mentioned negative electrode.
Dielectric film of the present invention has the good patience to hydrogen peroxide or peroxide radical.Its reason is also indeterminate, but infers it is that particularly the part of cation exchange base has been carried out ion-exchange by cerium ion owing to contain cerium ion in the dielectric film, and the residue behind the proton dissociation of cerium ion and cation exchange base (for example-SO
3 -) between interaction the hydrogen peroxide of dielectric film or peroxide radical patience are improved effectively.
Because dielectric film of the present invention has the good patience to hydrogen peroxide or peroxide radical, therefore the durability of polymer electrolyte fuel cell that disposes the membrane-electrode assembly with dielectric film of the present invention is good, can steady in a long-term generate electricity.
The best mode that carries out an invention
Among the present invention, contain the cerium ion macromolecular compound with cation exchange base before as making it, if having the macromolecular compound that the cation exchange base dissociated, generated the function of proton, then there is no particular limitation.As the concrete example of cation exchange base, sulfonic group, sulfimide base, phosphonate group, carboxyl, ketimide base etc. are arranged, the sulfonic group that particularly preferably acidity is strong, chemical stability is high.Below, as example the present invention is described to have sulfonic macromolecular compound.
Contain cerium ion for making to have in the sulfonic macromolecular compound, there is no particular limitation to obtain the method for dielectric film of the present invention, can exemplify following method.(1) in containing the solution of cerium ion dipping by method with film that sulfonic macromolecular compound forms.(2) in having the dispersion liquid of sulfonic macromolecular compound, add the salt that contains cerium ion, make and contain after the cerium ion in the dispersion liquid, the solution that perhaps will contain cerium ion mixes with the dispersion liquid with sulfonic macromolecular compound to be made it to contain after the cerium ion, uses gained solution to wait the method for making film by The tape casting.(3) the organic metal complex salt that makes cerium with contact by having the cation-exchange membrane that sulfonic macromolecular compound forms, make its method that contains cerium ion etc.
Be considered to a sulfonic part by the dielectric film of said method gained and carried out ion-exchange by cerium ion.
At this, cerium ion can also can be+4 valencys for+3 valencys, for the solution that obtains containing cerium ion can use various cerium salt.Contain+salt of the cerium ion of 3 valencys if specifically exemplify, can exemplify as cerous acetate (Ce (CH
3COO)
3H
2O), cerium chloride (CeCl
36H
2O), cerous nitrate (Ce (NO
3)
36H
2O), cerous sulfate (Ce
2(SO
4)
38H
2O), cerous carbonate (Ce
2(CO
3)
38H
2O) etc.As containing+salt of 4 valency cerium ions, can exemplify as cerous sulfate (Ce (SO
4)
24H
2O), nitric acid two ammonium cerium (Ce (NH
4)
2(NO
3)
6), sulfuric acid four ammonium cerium (Ce (NH
4)
4(SO
4)
44H
2O) etc.In addition, as the organic metal complex salt of cerium, can exemplify as acetyl acetone cerium (Ce (CH
3COCHCOCH
3)
33H
2O) etc.Wherein since be water-soluble, handle easily particularly preferably cerous nitrate, cerous sulfate.In addition, owing in their aqueous solution, to having nitric acid or the easy water-soluble solution of sulfuric acid that generates when sulfonic macromolecular compound carries out ion-exchange, can remove, therefore more satisfactory.
When for example cerium ion is the situation of 3 valencys, if sulfonic group is carried out ion-exchange by cerium ion, Ce then as follows
3+With 3-SO
3 -Combine.
Among the present invention, the number of contained cerium ion is preferably in the film-SO in the dielectric film
3 -0.3～20% (following this ratio is called " containing ratio of cerium ion ") of the number of base.When cerium ion becomes above-mentioned structure fully, this with by cerium ion ion-exchange sulfonic group be sulfonic group and by cerium ion ion-exchange 0.9～60% synonym (following this ratio is called " replacement rate ") of sulfonic total amount.The containing ratio of cerium ion is preferably 0.7～16%, and more preferably 1～13%, particularly preferably 1.5～12%, be preferably 2～10%.Above-mentioned replacement rate is preferably 1～60%, and more preferably 2～50%, particularly preferably 3～40%, be preferably 5～30%.
If the containing ratio of cerium ion less than above-mentioned scope, then may not be guaranteed the sufficient stability to hydrogen peroxide or peroxide radical.In addition, if the containing ratio of cerium ion greater than above-mentioned scope, then can not be guaranteed hydrionic sufficient conductibility, film resistance might occur and increase, power generation characteristics descends.
In addition, when dielectric film of the present invention is formed by stacked film, with respect to dielectric film integral body-SO
3 -The ratio of cerium ion of base get final product in above-mentioned scope, and layer self the containing ratio of cerium ion that contains cerium ion can be higher than above-mentioned scope.In addition as the manufacture method of stacked film, for example comparatively ideally be, any method by above-mentioned (1)～(3) produces the cation-exchange membrane that contains cerium ion in advance, and through making with the operation of the cation exchange film-stack that does not contain cerium ion, still there is no particular limitation again.
In addition, if the preferable range of the amount of cerium ion is represented with the ratio with respect to the quality of dielectric film, then, be preferably 0.02～8% as quality with respect to the cerium of dielectric film total quality, more preferably 0.05～6.6%, particularly preferably 0.07～5.3%.
Among the present invention, there is no particular limitation for making it to contain the cerium ion sulfonic macromolecular compound that has before, ion exchange capacity is preferably 0.5～3.0 milliequivalent/g dry resin, more preferably 0.7～2.5 milliequivalent/g dry resin, particularly preferably 1.0～2.5 milliequivalents/g dry resin.If ion exchange capacity is low excessively, then can not guarantee hydrionic sufficient conductibility during by cerium ion ion-exchange at sulfonic group, film resistance might occur and increase, power generation characteristics reduces.In addition, if ion exchange capacity is too high, the resistance to water or the intensity that film then might occur reduce.In addition, consider that this macromolecular compound is preferably fluoropolymer, particularly preferably have sulfonic perfluocarbon polymer (oxygen atom that also can contain ehter bond) from the angle of durability.There is no particular limitation as perfluocarbon polymer, is preferably to contain based on CF
2=CF-(OCF
2CFX)
m-O
p-(CF
2)
n-SO
3The polymerized unit of perfluorinated ethenyl compound shown in the H (m represents that 0～3 integer, n represent that 1～12 integer, p represent 0 or 1, X represent fluorine atom or trifluoromethyl) and based on the copolymer of the polymerized unit of tetrafluoroethene.
If more specifically the preferred exemplary of the above-mentioned perfluorinated ethenyl compound of example then can exemplify as shown in the formula the compound shown in (i)～(iii).In the following formula, q represents 1～8 integer, and r represents 1～8 integer, and t represents 1～3 integer.
CF
2＝CFO(CF
2)
q-SO
3H …(i)
CF
2＝CFOCF
2CF(CF
3)O(CF
2)
r-SO
3H …(ii)
CF
2＝CF(OCF
2CF(CF
3))
tO(CF
2)
2-SO
3H …(iii)
When use has sulfonic perfluocarbon polymer, also can use after polymerization and carry out the polymer that fluorination treatment gets by the end of fluoridizing polymer.If the end of polymer is fluoridized,, therefore further improved durability then owing to better for the stability of hydrogen peroxide or peroxide radical.
In addition, the sulfonic macromolecular compound that has as making it to contain before the cerium ion also can use the compound that has outside the sulfonic perfluocarbon polymer.For example better use and have at high molecular main chain, perhaps aromatic rings is arranged at main chain and side chain, have the macromolecular compound that in this aromatic rings, has imported sulfonic structure, and the ion exchange capacity of this macromolecular compound is 0.8～3.0 milliequivalent/g dry resin.Specifically, for example can use following macromolecular compound.
Sulfonation polyarylene, sulfonated polyphenyl Bing oxazole, sulfonated polyphenyl and thiazole, sulfonated polyphenyl and imidazoles, SPSF, sulfonated polyether sulfone, sulfonated polyether ether sulfone, sulfonated polyphenyl sulfone, sulfonated poly (phenylene oxide), sulfonated polyphenyl sulfoxide, sulfonated polyphenyl thioether, sulfonated polyphenyl thioether sulfone, sulfonated polyether ketone, sulfonated polyether-ether-ketone, sulfonated polyether ketone ketone, sulfonated polyimide etc.
Polymer electrolyte fuel cell with dielectric film of the present invention for example is following structure.That is, possess membrane-electrode assembly, this membrane-electrode assembly has disposed anode and negative electrode with the catalyst layer that contains catalyst and ion exchange resin and has formed on the two sides of dielectric film of the present invention.The outside (with the opposition side of film) that the anode of membrane-electrode assembly and negative electrode are preferably at catalyst layer is provided with the gas diffusion layers that is formed by charcoal cloth or carbon paper etc.The separator of the ditch of the path that is formed with act as a fuel gas or oxidant gas is set on the two sides of membrane-electrode assembly.Formation across a plurality of membrane-electrode assemblies of separator stacked and storehouse (ス Star Network), the anode side hydrogen supply is supplied with oxygen or air to cathode side.H takes place at anode
2→ 2H
++ 2e
-Reaction, 1/2O takes place at negative electrode
2+ 2H
++ 2e
-→ H
2The reaction of O changes into electric energy with chemical energy.
In addition, dielectric film of the present invention also can use at anode side fueling gas not but supply with in the direct methanol fuel cell of methyl alcohol.
Above-mentioned catalyst layer can pass through usual way, is for example got by following method.At first, load there is the conductive carbon black powder of platinum catalyst or platinum alloy catalyst particulate mix with solution with sulfonic perfluocarbon polymer, obtain the dispersion liquid of homogeneous, for example form gas-diffusion electrode, obtain membrane-electrode assembly by any following method.
The 1st method is after the above-mentioned dispersion liquid of the two sided coatings of dielectric film, drying, sticks to method on the two sides with 2 charcoal cloth or carbon paper.The 2nd method is after the above-mentioned dispersion liquid drying of coating on 2 charcoal cloth or the carbon paper, and they are clamped this amberplex from the two sides of above-mentioned amberplex respectively, and makes the face that is coated with dispersion liquid and the method for above-mentioned amberplex driving fit.In addition, play as the function of the gas diffusion layers of the layer that is used to that gas is diffused to more equably and contains catalyst and as the function of collector body at this charcoal cloth or carbon paper.Also can use in addition, the above-mentioned dispersion liquid of coating is made catalyst layer on the base material that other prepares, and makes it to peel off base material with after dielectric film engages by methods such as transfer printings again, clamps its method with above-mentioned gas diffusion layers.
There is no particular limitation to the ion exchange resin that contains in the catalyst layer, is preferably to have sulfonic macromolecular compound, more preferably has sulfonic perfluocarbon polymer.Ion exchange resin in the catalyst layer can contain cerium ion equally with dielectric film of the present invention.The ion exchange resin that contains cerium ion all can use in anode and negative electrode, owing to can suppress the decomposition of resin effectively, so polymer electrolyte fuel cell is paid better durability.In addition, also can use the ion exchange resin that does not contain cerium ion, only make the ion exchange resin in the catalyst layer contain cerium ion as dielectric film.
Desire to make when containing the situation of cerium ion among two sides of ion exchange resin in the catalyst layer and dielectric film, for example can at first make the conjugant of catalyst layer and dielectric film, this conjugant is immersed in the solution that contains cerium ion makes again.In addition, when making the situation that contains cerium ion in the catalyst layer, also can will catalyst be scattered in contain in the dispersion liquid with sulfonic macromolecular compound and cerium ion and solution as coating fluid, form catalyst layer according to the method described above.During this situation, can only make the either party of negative electrode and anode contain cerium ion, also can make negative electrode, anode all contain cerium ion.At this moment, also can negative electrode and anode use the different dispersion liquid of cerium ion amount, be adjusted to the cerium ion amount of negative electrode and anode inequality.If particularly in anode, contain contained in having sulfonic macromolecular compound-SO
3 -The cerium ion of 10～30 moles of % of base, when in negative electrode, containing the cerium ion of 3～10 moles of % owing to can suppress the decomposition of the ion exchange resin in the catalyst layer effectively, therefore the angle that improves from durability is even more ideal.
Dielectric film of the present invention, can be a part contain cerium ion, only by having the film that sulfonic macromolecular compound forms, also can contain other composition, also can be by polytetrafluoroethylene or perfluorinated alkyl ether etc. other resin etc. fiber, weave cotton cloth, the film of reinforcement such as nonwoven fabrics, porous body.For when the situation of the film of reinforcement, also obtain dielectric film of the present invention in the solution that contains cerium ion by being immersed in through the sulfonic cation-exchange membrane of having of reinforcement.In addition, also can adopt to use and contain the method for dispersion liquid system film that useful cerium ion has carried out the macromolecular compound of ion-exchange.In addition, for the situation of reinforcement dielectric film, the film integral reinforcement also can be carried out the frame reinforcement with film material or sheet material near the periphery with film.If film is carried out the frame reinforcement, then the property handled increases because therefore the intensity of periphery increase.Also can be that film is whole with the high supporting material reinforcement of voidage, and only in periphery low or void-free supporting material reinforcement with voidage.
Even be provided with the polymer electrolyte fuel cell of membrane-electrode assembly of the present invention, therefore under the temperature more than 100 ℃, work and also can generate electricity because at high temperature durability is also good.When the gas that acts as a fuel uses the hydrogen that upgradings such as methyl alcohol, natural gas, gasoline are obtained,, also occur electrode catalyst easily and poison, the phenomenon that the output of fuel cell descends if even contain the carbon monoxide of trace.If working temperature is more than 100 ℃ then can suppress to poison.Working temperature suppresses the better effects if of poisoning so better more than 120 ℃.
Embodiment
Below, exemplify embodiment (example 1～5,10,12～15) and comparative example (example 6～9,11) illustrates in greater detail the present invention, but the invention is not restricted to this.
[example 1]
As solid polyelectrolyte membrane, the thickness with sulfonic perfluocarbon polymer formation of serving as reasons is the amberplex (trade name: Off レ ミ オ Application, Asahi Glass society system, ion exchange capacity 1.1 milliequivalents/g dry resin) of 50 μ m, and the size of using is 5cm * 5cm (area 25cm
2).This film integral body was placed in the drying nitrogen after 16 hours, and the weight that records this film integral body in drying nitrogen is 0.251g.The sulfonic amount of this film is tried to achieve by following formula.
0.251 (g) * 1.1 (milliequivalent/g dry resin)=0.276 (milliequivalent).
Then, with cerous nitrate (Ce (NO
3)
36H
2O) 12.0mg is dissolved in the distilled water of 500mL, make it to contain the cerium ion (+3 valency) of 30% amount (equivalent) of the sulfonic acid base unit weight that is equivalent to this film, flood above-mentioned amberplex therein, at room temperature stirred 40 hours, make and contain cerium ion in the amberplex with blender.In addition, cerous nitrate solution energising sense coupled plasma (ICP) luminesceence analysis before and after the dipping is analyzed, the cerium ion containing ratio of this amberplex of results verification (with respect in the film-SO
3 -The ratio of the cerium ion of radix) be 9.3%.
Afterwards, loaded on charcoal carrier (specific area 800m to platinum with 50% amount of catalyst gross mass
2/ g) upward among catalyst fines (the エ ヌ イ-ケ system キ ヤ Star ト society system) 1.0g that gets, mix distilled water 5.1g.In this mixed liquor, sneak into and make CF
2=CF
2/ CF
2=CFOCF
2CF (CF
3) O (CF
2)
2SO
3H copolymer (ion exchange capacity 1.1 milliequivalents/g dry resin) in ethanol, disperse and the liquid 5.6g of solid component concentration 9 quality %.Use even matter device (trade name: Port リ ト ロ Application, キ ネ マ チ カ society system) to make mixture mix, pulverize, make catalyst layer formation coating fluid.
This coating fluid is coated on the base material film of polypropylene system with rod coater after, in 80 ℃ drier, make it to make in dry 30 minutes catalyst layer.In addition, the quality of the base material film after quality by the independent base material film before measuring catalyst layer and forming and catalyst layer form calculates the amount of the platinum of the per unit area that contains in the catalyst layer, and the result is 0.5mg/cm
2
Then, use the above-mentioned amberplex that contains cerium ion, two sides at this film is configured in the catalyst layer that forms on the base material film respectively, carry out transfer printing by pressure sintering anode catalyst layer and cathode catalyst layer are bonded on the two sides of amberplex respectively, obtain the film catalyst layer assembly.In addition, electrode area is 16cm
2
This film catalyst layer assembly is clipped between the gas diffusion layers that is formed by charcoal cloth that 2 thickness are 350 μ m forms membrane-electrode assembly, it is assembled into generating with in the battery, carry out open voltage test (OCV test) as accelerated test.Test is: anode and negative electrode are supplied with and are equivalent to current density 0.2A/cm respectively under normal pressure
2Hydrogen (utilance 70%) and air (utilance 40%), making battery temperature is 90 ℃, the dew point of anodic gas is 60 ℃, the dew point of cathode gas is 60 ℃, does not generate electricity with open-circuit condition work 100 hours, measures change in voltage during this period.In addition, anode hydrogen supply before and after the test, supply with nitrogen, analyze by film and sew amounts of hydrogen, investigate the degradation of film to negative electrode from anode to negative electrode.The results are shown in table 1.
Then, with above-mentioned same manufacturing membrane-electrode assembly and be assembled to generating, carry out the long duration test under low humidification condition of work with in the battery.Experimental condition is hydrogen supply under normal pressure (utilance 70%)/air (utilance 40%), carries out current density 0.2A/cm under 80 ℃ of battery temperatures
2The time the initial stage evaluating characteristics and the durability evaluation of polymer electrolyte fuel cell.By the dew point that makes anode-side is that 80 ℃, the dew point of cathode side are 50 ℃, will be supplied in the battery after hydrogen and the air wetting respectively, measures cell voltage and the elapsed-time standards after the work beginning and the relation between the cell voltage at work initial stage.The results are shown in table 2.In addition, in the appreciation condition of above-mentioned battery, change into 80 ℃,, measure cell voltage and the elapsed-time standards after the work beginning and the relation of cell voltage at work initial stage with above-mentioned same operation except dew point with cathode side.Evaluation result is shown in table 3.
[example 2]
Except the cerous nitrate aqueous solution that will use in the example 1 replaces to and will contain the cerous sulfate (Ce of cerium ion (+3 valency)
2(SO
4)
38H
2O) 9.8mg be dissolved in the distilled water of 500mL and the aqueous solution outside, operate equally with example 1, to example 1 in the identical commercially available amberplex of use handle, the containing ratio that obtains cerium ion is 9.3% film.Then, use this film and example 1 to operate equally, obtain the film catalyst layer assembly, further obtain membrane-electrode assembly again.This membrane-electrode assembly is carried out the evaluation identical with example 1, and the result is shown in table 1～3.
[example 3]
Except using with cerous nitrate (Ce (NO
3)
36H
2O) 8.0mg be dissolved in the distilled water of 500mL and the aqueous solution replace outside the cerous nitrate aqueous solution used in the example 1, operate equally with example 1, to with example 1 in the identical commercially available amberplex that uses handle, the containing ratio that obtains cerium ion is 6.3% film.Then, use this film and example 1 same operation to obtain the film catalyst layer assembly, further obtain membrane-electrode assembly.This membrane-electrode assembly is carried out the evaluation same with example 1, and the result is shown in table 1～3.
[example 4]
Except using with cerous nitrate (Ce (NO
3)
36H
2O) the 4.0mg aqueous solution that is dissolved in the distilled water gained of 500mL replaces operate equally with example 1 outside the used cerous nitrate aqueous solution of example 1, to example 1 in the identical commercially available amberplex of use handle, the containing ratio that obtains cerium ion is 3.3% film.Then, use this film and example 1 same operation to obtain the film catalyst layer assembly, further obtain membrane-electrode assembly.This membrane-electrode assembly is carried out the evaluation identical with example 1, and the result is shown in table 1～3.
[example 5]
As solid polyelectrolyte membrane, by having sulfonic polyether-ether-ketone, it is the amberplex of 50 μ m that a sulfonic part has been carried out the thickness that the macromolecular compound of ion-exchange forms with cerium ion according to manufacturing as described below.Promptly, by granular commercially available polyether-ether-ketone (Britain Victrex society system, PEEK-450P) 60g at room temperature being added into several times slightly among 98% the sulfuric acid 1200g, at room temperature stir and obtained the solution of homogeneous in 60 hours, thereby obtain in polyether-ether-ketone, having imported the solution of sulfonic macromolecular compound.Then,,, make to have sulfonic polyether-ether-ketone and separate out, carry out filter analysis Yi Bian slowly splash into to the distilled water of 5L Yi Bian cool off this solution.Then it is cleaned until neutrality with distilled water, under 80 ℃ of vacuum, carry out 24 hours dryings afterwards, obtain the sulfonic polyether-ether-ketone of having of 48g.
Afterwards, after the about 1g of this compound of precision weighing, it is flooded in 1 centinormal 1 sodium-chloride water solution 500mL, make it to carry out the ion-exchange of sulfonic proton and sodium ion in 24 hours 60 ℃ of reactions.This test portion is cooled to room temperature, fully cleans, the distilled water after sodium-chloride water solution after the ion-exchange and the cleaning is carried out titration with 0.01 centinormal 1 NaOH, try to achieve ion exchange capacity with distilled water.Ion exchange capacity is 1.6 milliequivalents/g dry resin.
Then, to have this sulfonic polyether-ether-ketone is dissolved in the N-N-methyl-2-2-pyrrolidone N-(NMP), obtain the solution of about 10 quality %, with it after on the base material that forms by polytetrafluoroethylene, carrying out casting film under the room temperature, under nitrogen atmosphere, made the NMP evaporation in 10 hours, obtain the film that thickness is 50 μ m 100 ℃ of dryings.Afterwards, this film is cut into size and be 5cm * 5cm (area 25cm
2), the weight such as the example 1 of this film integral body are measured equally, the result is 0.168g.The sulfonic amount of this film can be tried to achieve by following formula.
0.168 (g) * 1.6 (milliequivalent/g dry resin)=0.269 (milliequivalent).
Cerous nitrate (Ce (the NO that is inciting somebody to action
3)
36H
2O) 12.0mg is dissolved in the above-mentioned amberplex of dipping in Ce ion (+3 valency) aqueous solution of about 30% amount (equivalent) of sulfonic acid base unit weight that containing of gained in the distilled water of 500mL be equivalent to this film, use blender at room temperature to stir 40 hours, the containing ratio that obtains cerium ion is 10.3% film.Then, use this film and example 1 same operation to obtain the film catalyst layer assembly, further obtain membrane-electrode assembly.This membrane-electrode assembly is carried out the evaluation same with example 1, the results are shown in table 1～3.
[example 6]
To be left intact with the identical commercially available amberplex of use in the example 1 and directly use, and then, use this film and example 1 same operation to obtain the film catalyst layer assembly, further obtain membrane-electrode assembly as solid polyelectrolyte membrane.This membrane-electrode assembly is carried out the evaluation same with example 1, the results are shown in table 1～3.
[example 7]
Operate equally with example 1, will be immersed in calcium nitrate (Ca (NO with the identical commercially available amberplex that example 1 is used
3)
24H
2O) 9.8mg is dissolved in the aqueous solution that contains calcium ion (+divalent) of distilled water gained of 500mL, and the containing ratio that obtains calcium ion is 10.3% film.Then, use this film and example 1 same operation to obtain the film catalyst layer assembly, further obtain membrane-electrode assembly.Carry out the evaluation same for this membrane-electrode assembly, the results are shown in table 1～3 with example 1.
[example 8]
Operate equally with example 1, will be immersed in copper sulphate (CuSO with the identical commercially available amberplex that example 1 is used
45H
2O) 10.3mg be dissolved in 500mL distilled water and the aqueous solution that contains copper ion (+divalent) in, the containing ratio that obtains copper ion is 9.7% film.Then, utilize this film and example 1 same operation to obtain the film catalyst layer assembly, further obtain membrane-electrode assembly.Carry out the evaluation same with example 1 for this membrane-electrode assembly, the result is shown in table 1～3.
[example 9]
Except to not the adopting the processing of cerium ion of example 5 gained by having the amberplex that sulfonic polyether-ether-ketone forms, obtaining the film catalyst layer assembly with example 5 same operations, further obtain membrane-electrode assembly.Carry out the evaluation same with example 1 for this membrane-electrode assembly, the result is shown in table 1～3.
[example 10]
Except using with cerous nitrate (Ce (NO
3)
36H
2O) 6.0mg be dissolved in 500mL distilled water and the aqueous solution replace operate equally with example 1 outside the used cerous nitrate aqueous solution of example 1, to example 1 in the identical commercially available amberplex of use handle, the containing ratio that obtains cerium ion is 4.7% film.Then, use this film and example 1 same operation to obtain the film catalyst layer assembly.
This film catalyst layer assembly is clipped between the gas diffusion layers that is formed by charcoal cloth that 2 thickness are 350 μ m makes membrane-electrode assembly, it is assembled in generating with in the battery, as followsly under low humidification, 120 ℃ condition of work, carry out long duration test.Antianode and negative electrode all are forced into 200kPa, hydrogen supply (utilance 50%)/air (utilance 50%), and carrying out current density under 120 ℃ of battery temperatures is 0.2A/cm
2The time the initial stage evaluating characteristics and the durability evaluation of polymer electrolyte fuel cell.By the dew point that makes anode-side is that 100 ℃, the dew point of cathode side are 100 ℃, will be supplied in the battery after hydrogen and the air wetting respectively, measures cell voltage and the elapsed-time standards after the work beginning and the relation between the cell voltage at work initial stage.The results are shown in table 4.
[example 11]
Identical commercially available amberplex with example 1 use is not carried out any processing, use, then, use this film and example 1 same operation to obtain the film catalyst layer assembly, further obtain membrane-electrode assembly as solid polyelectrolyte membrane.This membrane-electrode assembly is carried out the evaluation identical with example 10, and generating voltage sharply drops to 0V after 110 hours, can not generate electricity.The test back is taken out film and is investigated, and found that large perforation in the film, and this becomes the reason that voltage sharply descends.
[modulation] with solution of sulfonic perfluocarbon polymer
In the 2L reactor, add CF
2=CF
2/ CF
2=CFOCF
2CF (CF
3) O (CF
2)
2SO
3Behind H copolymer (ion exchange capacity 1.1 milliequivalents/g dry resin) 300g, ethanol 420g and the water 280g, seal, use the double helix blade to mix and stir the solution that obtained homogeneous in 6 hours (below, be called solution A) at 105 ℃.The solid formation branch concentration of solution A is 30 quality %.
[containing the modulation of the solution with sulfonic perfluocarbon polymer of cerium ion]
In 300mL glass round-bottomed flask, add solution A 100g, cerous carbonate hydrate (Ce
2(CO
3)
38H
2O) 1.00g at room temperature stirred 8 hours with polytetrafluoroethylene (PTFE) system semilune blade.Begin to have stirred and occurred owing to produce CO
2And the bubble that generates, but finally obtain the liquid composition (hereinafter referred to as solution B) of transparent and homogeneous.The solid shape branch concentration of solution B is 30.2 quality %.
Adjust the containing ratio of the cerium ion of this solution B according to the following stated.Go up by die head coating machine curtain coating coating solution B at ethylene-tetrafluoroethylene copolymer (ETFE) sheet (trade name: ア Off レ Star Network ス 100N, Asahi Glass society system) of 100 μ m, under 80 ℃, carry out 10 minutes predrying after, drying is 10 minutes under 120 ℃, in 150 ℃ of annealing of carrying out 30 minutes, obtain the dielectric film of thickness 50 μ m again.Cut out the film of 5cm * 5cm size from this dielectric film, after it was placed 16 hours in drying nitrogen, accurate its quality of weighing, impregnation in the 0.1 centinormal 1 HCl aqueous solution obtains the liquid that cerium ion is extracted fully.By this liquid is carried out the ICP luminesceence analysis, the cerium in the dielectric film is carried out quantitatively, the cerium ion amount is 1.5% with respect to the quality of film, the containing ratio of cerium ion with respect to contain in the perfluocarbon polymer-SO
3 -The quantity of base is 10%.
[example 12]
With the curtain coating coating on the ETFE sheet of 100 μ m of above-mentioned solution A, after 80 ℃ are carried out 10 minutes predrying, carry out 10 minutes dryings by the die head coating machine,, obtain the dielectric film of thickness 25 μ m again in 150 ℃ of annealing of carrying out 30 minutes at 120 ℃.Equally, by the die head coating machine above-mentioned solution B is carried out the curtain coating coating on the ETFE sheet of 100 μ m, 80 ℃ carry out 10 minutes predrying after, carry out 10 minutes dryings at 120 ℃, carry out annealing in 30 minutes in 150 ℃ again, the containing ratio that obtains cerium ion is that 10% thickness is the dielectric film of 25 μ m.Then, this film is carried out hot pressing at 150 ℃, obtain that the inhomogenous thickness of the containing ratio of cerium ion is the composite membrane of the solid macromolecule electrolyte of 50 μ m on film thickness direction.
Afterwards, loaded on charcoal carrier (specific area 800m to platinum with 50% amount of catalyst gross mass
2/ g) upward among catalyst fines (the エ ヌ イ-ケ system キ ヤ Star ト society system) 1.0g that gets, mix distilled water 5.1g.In this mixed liquor, mix with above-mentioned solution A with ethanol be diluted to solid formation branch concentration be 9 quality % get liquid 5.6g.Use even matter device that this mixture is mixed, pulverizes, make catalyst layer formation coating fluid.
Use after rod coater is coated on this coating fluid on the base material film of polypropylene system, in 80 ℃ drier, make it to make in dry 30 minutes catalyst layer.In addition, the quality of the base material film after quality by the independent base material film before measuring catalyst layer and forming and catalyst layer form calculates the amount of the platinum of the per unit area that contains in the catalyst layer, and the result is 0.5mg/cm
2
Then, use above-mentioned composite membrane to be configured in the catalyst layer that forms on the above-mentioned base material film on the face of cerium ion as anode containing, be configured in the catalyst layer that forms on the above-mentioned base material film on the face that does not contain cerium ion as negative electrode, carry out transfer printing by pressure sintering anode catalyst layer and cathode catalyst layer are bonded on the two sides of amberplex respectively, obtain the film catalyst layer assembly.In addition, electrode area is 16cm
2
Operate equally with example 1, obtain membrane-electrode assembly by this film catalyst layer assembly again.Carry out the open voltage test same with example 1 for this membrane-electrode assembly, the result is as shown in table 1.
Then,, it is assembled in generating with in the battery with the above-mentioned membrane-electrode assembly of making equally, carry out with the same low humidification high temperature of example 10 under condition of work in long duration test.Be that antianode and negative electrode all are forced into 200kPa, hydrogen supply (utilance 50%)/air (utilance 50%) carries out current density 0.2A/cm under the condition of 120 ℃ of battery temperatures
2The time the initial stage evaluating characteristics and the durability evaluation of polymer electrolyte fuel cell.By the dew point that makes anode-side is that 100 ℃, the dew point of cathode side are 100 ℃, will be supplied in the battery after hydrogen and the air wetting respectively, measures cell voltage and the elapsed-time standards after the work beginning and the relation between the cell voltage at work initial stage.The results are shown in table 4.
Then,, it is assembled into generating uses battery with the above-mentioned membrane-electrode assembly of making equally, carry out with the same high humidification of example 1 under condition of work in long duration test.That is, experimental condition is: under normal pressure, hydrogen supply (utilance 70%)/air (utilance 40%) under 80 ℃ of battery temperatures, carries out current density 0.2A/cm
2Under the initial stage evaluating characteristics and the durability evaluation of polymer electrolyte fuel cell.By the dew point that makes anode-side is 80 ℃, and the dew point of cathode side is 80 ℃, will be supplied in the battery after hydrogen and the air wetting respectively, measures cell voltage and the elapsed-time standards after the work beginning and the relation of cell voltage at work initial stage.The results are shown in table 3.
[example 13]
Above-mentioned solution A curtain coating is coated on the ETFE sheet of 100 μ m by the die head coating machine, 80 ℃ carry out 10 minutes predrying after, carry out 10 minutes dryings at 120 ℃, again in 150 ℃ of annealing of carrying out 30 minutes, obtaining thickness is the dielectric film of 50 μ m, 5cm * 5cm size.
Afterwards, loaded on charcoal carrier (specific area 800m to platinum with 50% amount of catalyst gross mass
2/ g) upward among catalyst fines (the エ ヌ イ-ケ system キ ヤ Star ト society system) 1.0g that gets, mix distilled water 5.1g.In this mixed liquor, mix with above-mentioned solution B with ethanol be diluted to solid formation branch concentration be 9 quality % get liquid 5.6g.Use even matter device that this mixture is mixed, pulverizes, make catalyst layer formation coating fluid.
This coating fluid is coated on the base material film of polypropylene system with rod coater after, in 80 ℃ drier, make it dry 30 minutes, make amount and be contained-SO in the perfluocarbon polymer in the catalyst layer
3 -The anode catalyst layer of the cerium ion of 10 moles of % of base.In addition, the quality of the base material film after quality by the independent base material film before measuring catalyst layer and forming and catalyst layer form calculates the amount of the platinum of the per unit area that contains in the catalyst layer, and the result is 0.5mg/cm
2
On the other hand, substitute the above-mentioned solution B, operate equally, make the cathode catalyst layer that does not contain cerium with anode catalyst layer except using above-mentioned solution A.
Then, two sides at the dielectric film that uses solution A to make is configured in anode catalyst layer and the cathode catalyst layer that forms on the above-mentioned base material film respectively, by pressure sintering catalyst layer is transferred to film, obtain the film catalyst layer assembly, engage contained in the perfluocarbon polymer that contains in the catalyst layer-SO respectively on the two sides of the polyelectrolyte membrane of this film catalyst layer assembly
3 -The anode catalyst layer of the cerium ion of 10 moles of % of base, and the cathode catalyst layer that does not contain cerium ion.In addition, electrode area is 16cm
2
Operate equally with example 1, further obtain membrane-electrode assembly by this film catalyst layer assembly.This membrane-electrode assembly is carried out the open voltage test identical with example 1.The results are shown in table 1.In addition, make with above-mentioned same membrane-electrode assembly after it is assembled in generating with in the battery, with example 1 same low humidification and the condition of work under the high humidification under, carry out endurance test, the result is shown in table 2,3.
[example 14]
In the manufacturing of above-mentioned solution B, except cerous carbonate hydrate (Ce
2(CO
3)
38H
2O) amount is that other is identical outside the 2.00g, and the containing ratio that obtains cerium ion is with respect to contained in the perfluocarbon polymer-SO
3 -The quantity of base is 20% solution.Then, except using this solution in the formation of anode catalyst layer, other and example 13 are operated equally, obtain the film catalyst layer assembly, engage contained in the perfluocarbon polymer that contains in the catalyst layer-SO respectively on the two sides of the polyelectrolyte membrane of this film catalyst layer assembly
3 -The anode catalyst layer of the cerium ion of 20 moles of % of base, and the cathode catalyst layer that does not contain cerium ion.
Operate equally with example 1, further obtain membrane-electrode assembly by this film catalyst layer assembly.This membrane-electrode assembly is carried out the open voltage test same with example 1.The results are shown in table 1.In addition, make with above-mentioned same membrane-electrode assembly after it is assembled in generating with in the battery, with the condition of work of same low humidification of example 1 and high humidification under, carry out endurance test, the result is shown in table 2,3.
[example 15]
In example 13,, operate equally, obtain the film catalyst layer assembly with example 13 except using the solution A manufacturing not contain the anode catalyst layer of cerium ion.This film catalyst layer assembly is immersed in is dissolved with cerous nitrate (Ce (NO
3)
36H
2O) in the aqueous solution, obtain the sulfonic part of the perfluocarbon polymer in film and the catalyst layer has been carried out with cerium ion the film catalyst layer assembly of ion-exchange.Ion-exchange is tried to achieve by following method.
At first, the film integral body that above-mentioned casting film is made is placed 16 hours in drying nitrogen after, measure the weight of film integral body in drying nitrogen, the result is 0.251g.The sulfonic amount of this film can be undertaken by following method.
0.251 (g) * 1.1 (milliequivalent/g dry resin)=0.276 (milliequivalent).
Then, with cerous nitrate (Ce (NO
3)
36H
2O) 12.0mg is dissolved in 500mL distilled water, makes it to contain the cerium ion (+3 valency) of 10% amount of the sulfonic acid radix of the membrane portions that is equivalent to this film catalyst layer assembly.Flood above-mentioned film catalyst layer assembly therein, at room temperature stirred 40 hours with blender, the sulfonic part of the perfluocarbon polymer in the film catalyst layer assembly is carried out ion-exchange by cerium ion, make in the integral body of film catalyst layer assembly and contain cerium ion.In addition, analyze cerous nitrate solution before and after the dipping by the ICP luminesceence analysis, membrane portions that the film catalyst layer assembly contains is equivalent to the film catalyst layer assembly that the result is clear and definite-SO
3 -The cerium ion of 9.3% amount of radix.
Operate equally with example 1, further obtain membrane-electrode assembly by this film catalyst layer assembly.This membrane-electrode assembly is carried out the open voltage test same with example 1.The results are shown in table 1.In addition, make with above-mentioned same membrane-electrode assembly after it is assembled in generating with in the battery, under the condition of work of low humidification identical and high humidification, carry out endurance test with example 1, the result is shown in table 2,3.
[table 1]
[table 2]
[table 3]
[table 4]
By the result of the foregoing description and comparative example as can be known, high temperature in accelerated test hangs down in the open voltage test (OCV test) of humidification, because hydrogen peroxide or peroxide radical in anode and negative electrode generation, dielectric film deterioration hydrogen is in the past sewed increase, but dielectric film of the present invention has shown very good durability.
The possibility of utilizing on the industry
Hydrogen peroxide or peroxide that dielectric film of the present invention generates for the generating owing to fuel cell The durability of compound free radical is extremely good. Therefore, dispose the membrane electrode with dielectric film of the present invention The polymer electrolyte fuel cell of conjugant generates electricity or any situation of high humidification generating at low humidification, Perhaps generating all has long-term durability under the high temperature more than 100 ℃.
In addition, quote the Japanese patent application 2004-183712 that filed an application on June 22nd, 2004 at this Number, Japanese patent application 2004-225706 number, in September, 2004 of filing an application on August 2nd, 2004 The Japanese patent application 2004-265176 that filed an application in 13rd number and filed an application on April 15th, 2005 Scope, accompanying drawing and the summary of Japanese patent application 2005-118412 number specification, claim Whole contents are as the disclosure of specification of the present invention.
Claims (13)
1. use in solid polymer fuel cell dielectric film, it is characterized in that, be made of the formed cation-exchange membrane of sulfonic macromolecular compound that has as the cation exchange base, contain cerium ion, the content of described cerium ion is contained in the described cation-exchange membrane-SO
3 -0.3～20% of the number of base.
2. use in solid polymer fuel cell dielectric film as claimed in claim 1 is characterized in that the part of described cation exchange base has been carried out ion-exchange by cerium ion.
3. use in solid polymer fuel cell dielectric film as claimed in claim 1, it is characterized in that, described cation-exchange membrane is by stacked get by having the layer that sulfonic macromolecular compound forms more than 2 layers, described more than 2 layers layer in have at least 1 layer to contain cerium ion.
4. use in solid polymer fuel cell dielectric film as claimed in claim 3 is characterized in that, has at least 1 layer of at least a portion by described cation exchange base to be formed by the cation-exchange membrane of cerium ion ion-exchange in the described layer more than 2 layers.
5. as each described use in solid polymer fuel cell dielectric film in the claim 1～4, it is characterized in that described to have sulfonic macromolecular compound be to have sulfonic perfluocarbon polymer.
6. use in solid polymer fuel cell dielectric film as claimed in claim 5 is characterized in that described perfluocarbon polymer is to contain based on CF
2=CF-(OCF
2CFX)
m-O
p-(CF
2)
n-SO
3The polymerized unit of perfluorinated ethenyl compound shown in the H and based on the copolymer of the polymerized unit of tetrafluoroethene, in the following formula, m represents 0～3 integer, and n represents 1～12 integer, and p represents 0 or 1, and X represents fluorine atom or trifluoromethyl.
7. as each described use in solid polymer fuel cell dielectric film in the claim 1～4, it is characterized in that, described have sulfonic macromolecular compound and have and have aromatic rings on the high molecular main chain or on main chain and the side chain and imported sulfonic structure in this aromatic rings, and its ion exchange capacity is 0.8～3.0 milliequivalent/g dry resin.
8. use in solid polymer fuel cell dielectric film as claimed in claim 1 is characterized in that, described film is the dielectric film through reinforcement.
9. the manufacture method of use in solid polymer fuel cell dielectric film, it is the manufacture method of each described dielectric film in the claim 1～8, it is characterized in that, will be immersed in the aqueous solution that contains cerium ion by the formed cation-exchange membrane of the macromolecular compound with cation exchange base.
10. the manufacture method of dielectric film as claimed in claim 9 is characterized in that, the described aqueous solution that contains cerium ion is the cerous nitrate aqueous solution or the cerous sulfate aqueous solution.
11. membrane-electrode assembly for polymer electrolyte fuel cell, it is by anode with the catalyst layer that contains catalyst and ion exchange resin and negative electrode, and the film formed membrane-electrode assembly for polymer electrolyte fuel cell of electrolyte that between described anode and described negative electrode, disposes, it is characterized in that described dielectric film is each described dielectric film in the claim 1～8.
12. membrane-electrode assembly for polymer electrolyte fuel cell, it is by anode with the catalyst layer that contains catalyst and ion exchange resin and negative electrode, and the film formed membrane-electrode assembly for polymer electrolyte fuel cell of electrolyte that between described anode and described negative electrode, disposes, it is characterized in that, contained ion exchange resin has sulfonic group among at least one side of described anode and described negative electrode, and containing cerium ion, the content of described cerium ion is-SO
3 -0.3～20% of the number of base.
13. membrane-electrode assembly for polymer electrolyte fuel cell as claimed in claim 11 is characterized in that, contained ion exchange resin contains cerium ion among at least one side of described anode and described negative electrode.
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|---|---|---|---|
| JP183712/2004 | 2004-06-22 | ||
| JP2004183712 | 2004-06-22 | ||
| JP225706/2004 | 2004-08-02 | ||
| JP265176/2004 | 2004-09-13 | ||
| JP118412/2005 | 2005-04-15 |
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| US7572534B2 (en) * | 2004-09-20 | 2009-08-11 | 3M Innovative Properties Company | Fuel cell membrane electrode assembly |
| US8906573B2 (en) * | 2007-08-10 | 2014-12-09 | W. L. Gore & Associates, Co., Ltd. | Reinforced solid polymer electrolyte composite membrane, membrane electrode assembly for solid polymer fuel cell, and solid polymer fuel cell |
| EP2218130B1 (en) * | 2007-11-09 | 2017-04-19 | 3M Innovative Properties Company | Polymer electrolytes including heteropolyacids |
| US7989115B2 (en) * | 2007-12-14 | 2011-08-02 | Gore Enterprise Holdings, Inc. | Highly stable fuel cell membranes and methods of making them |
| US8137828B2 (en) * | 2007-12-27 | 2012-03-20 | 3M Innovative Properties Company | Durable fuel cell membrane electrode assembly with combined additives |
| US8802314B2 (en) * | 2008-10-17 | 2014-08-12 | Toyota Jidosha Kabushiki Kaisha | Reinforced electrolyte membrane for fuel cell, membrane-electrode assembly for fuel cell, and polymer electrolyte fuel cell comprising the same |
| EP2559097B1 (en) * | 2010-04-13 | 2018-05-30 | Fluidic, Inc. | Metal-air electrocemical cell with high energy efficiency mode |
| WO2013031479A1 (en) * | 2011-08-26 | 2013-03-07 | 旭硝子株式会社 | Solid polymer electrolyte membrane, and membrane electrode assembly for use in solid polymer fuel cell |
| EP2743935B1 (en) * | 2011-09-21 | 2018-01-24 | Toray Industries, Inc. | Molded article of polymer electrolyte composition and solid polymer type fuel cell using same |
| CN103736405B (en) * | 2013-12-17 | 2016-04-20 | 中国科学技术大学 | A kind of preparation method with the cation-exchange membrane of a polyvalent cation Selective Separation function |
| WO2015108193A1 (en) * | 2014-01-20 | 2015-07-23 | 旭硝子株式会社 | Liquid composition, method for manufacturing same, and method for manufacturing membrane electrode assembly for polymer electrolyte fuel cell |
| CN106654328B (en) * | 2016-12-29 | 2019-05-28 | 山东东岳未来氢能材料有限公司 | A kind of fuel cell exchange membrane containing fluorine and preparation method thereof |
| CN111900419A (en) * | 2020-09-07 | 2020-11-06 | 重庆新申世纪新材料科技有限公司 | Preparation method of manganese oxide in-situ composite air electrode |
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