CN1969418A - Liquid composition, method for producing the same, and method for producing membrane electrode assembly for solid polymer fuel cell - Google Patents
Liquid composition, method for producing the same, and method for producing membrane electrode assembly for solid polymer fuel cell Download PDFInfo
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- CN1969418A CN1969418A CNA2005800199442A CN200580019944A CN1969418A CN 1969418 A CN1969418 A CN 1969418A CN A2005800199442 A CNA2005800199442 A CN A2005800199442A CN 200580019944 A CN200580019944 A CN 200580019944A CN 1969418 A CN1969418 A CN 1969418A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
An electrolyte membrane containing cerium ions and composed of a cation-exchange membrane which is made of a polymer compound having a cation-exchange group is used as an electrolyte membrane for solid polymer fuel cells. When the cation-exchange membrane has sulfonic acid groups, cerium ions are preferably contained in an amount of 0.3-20% relative to the -SO3<-> groups contained in the cation-exchange membrane, and for example, the sulfonic acid groups are ion exchanged with the cerium ions. Consequently, there can be provided an electrolyte membrane for solid polymer fuel cells which enables to generate electricity at high energy efficiency and exhibits high power generation performance regardless of the dew point of a supply gas. This electrolyte membrane for solid polymer fuel cells also enables to stably generate electricity for a long time.
Description
Technical field
The present invention relates to the initial stage the output voltage height, can obtain for a long time high output voltage membrane-electrode assembly for polymer electrolyte fuel cell manufacture method and be suitable for its liquid composition.
Background technology
Fuel cell is the battery that the reaction energy as the gas of raw material is converted into electric energy, and the reaction product of hydrogen oxygen fuel cell has only water in theory, to almost not influence of earth environment.Wherein, use solid polymer membrane as electrolytical polymer electrolyte fuel cell owing to developed polyelectrolyte membrane with macroion conductivity, also can work at normal temperatures, can obtain high power density, therefore along with constantly surging in the society, to its power supply as moving vehicle such as used for electric vehicle and small-sized waste-heat power generation system is placed high hopes to the cry of the energy, earth environment problem.
In the polymer electrolyte fuel cell, the amberplex that uses proton-conducting usually is as solid macromolecule electrolyte, particularly by having amberplex that sulfonic perfluocarbon polymer forms in excellence aspect the fundamental characteristics.In the polymer electrolyte fuel cell, at the electrode layer of the two sides of amberplex configuration gas diffusibility, the gas that will contain the hydrogen that acts as a fuel supplies to anode and negative electrode respectively with the gas (air etc.) that contains as the oxygen of oxidant, thereby generates electricity.
The reduction reaction of the oxygen in the negative electrode of polymer electrolyte fuel cell is middle through hydrogen peroxide (H
2O
2) react, therefore owing to the hydrogen peroxide or the peroxide radical that generate in the catalyst layer, may cause the deterioration of dielectric film.In addition, in anode, oxygen molecule is penetrated in the film from negative electrode, therefore equally also may generate hydrogen peroxide or peroxide radical.,, be big problem particularly for long-term running for the stability shortage of free radical with under the situation of hydrocarbon membranes as solid polyelectrolyte membrane.
For example, be when being used as the power supply of U.S.'s Gemini spaceship first with polymer electrolyte fuel cell practicability, used at that time film that styrene-the divinyl benzene polymers sulfonation obtains as dielectric film, but long-term durability existing problems.As the technology of improving such problem, the known interpolation in polyelectrolyte membrane can or have the method (referring to Patent Document 1) of the compound of phenol hydroxyl and the bearing catalyst metallic comes decomposition of hydrogen peroxide in polyelectrolyte membrane method (referring to Patent Document 2) with the transition metal oxide of hydrogen peroxide catalyzed decomposition.But these technology do not attempt suppressing the decomposition of amberplex self for decomposing the technology of the hydrogen peroxide that generates, and therefore have the effect of improvement at first, but may produce bigger problem on the long-term durability.In addition, also there is the high problem of cost.
On the other hand, known to having the amberplex that sulfonic perfluocarbon polymer forms, this polymer phase is for the polymer of hydro carbons, and is very excellent for the stability of free radical.In recent years, the polymer electrolyte fuel cell that uses these amberplexes that formed by perfluocarbon polymer is expected as automobile, and with, the dwelling house power supply with market etc., the cry of practicability improves, and exploitation is in acceleration.Therefore in these purposes, the running under the special requirement high efficiency is not only wished the running under the high voltage more, and is wished cost degradation.In addition, consider the efficient of fuel cell system integral body, most also require low humidification or do not have running under the humidified condition.
Yet, report, for using by fuel cell, though the stability of the running under high humidification is very high with amberplex that sulfonic perfluocarbon polymer forms, but hang down humidification or do not have under the operating condition of humidification voltage deterioration big (non-patent literature 1).That is, think at low humidification or do not have under the operating condition of humidification, by having in the amberplex that sulfonic perfluocarbon polymer forms, because hydrogen peroxide or peroxide radical, the deterioration of dielectric film takes place also.
In addition, the manufacture method of the dielectric film of using as aforesaid fuel cell has method by extrusion molding system film, uses the solution of the resin that constitutes this dielectric film to carry out the method etc. of casting film.During the large-scale film of industrial production, casting film is effective.In addition, report, contain constitute resin with the such film of sulfonic fluorocarbons polymer liquid composition except the manufacturing that is used to membrane material, for the reparation of the film of having made, recovery and as the smears, be very useful (reference example such as patent documentation 3, patent documentation 4).
Patent documentation 1: the Japan Patent spy opens 2001-118591 communique (claim 1, the 2nd page of the 2nd～9 row)
Patent documentation 2: Japanese patent laid-open 6-103992 communique (method that is used to deal with problems, the 2nd page of the 33rd～37 row)
Patent documentation 3: the Japan Patent spy opens 2003-183467 communique (the 2nd page of the 15th～32 row)
Patent documentation 4: the Japan Patent spy opens 2004-75978 communique (the 5th page of the 24th～41 row)
Non-patent literature 1: NEDO is sponsored, and equals into 12 annual polymer electrolyte fuel cell research and development achievement public lecture summaries, the 56th page of the 16th～24 row
The announcement of invention
The object of the present invention is to provide the use in solid polymer fuel cell film, described film is in to vehicle mounted, the practicability of dwelling house with the polymer electrolyte fuel cell in market etc., can realize the generating under the sufficiently high efficiency, at the humidification temperature (dew point) of the supply gas low humidification lower or do not have running under the humidified condition, under near the temperature of battery temperature, carry out in the running under the high humidified condition of humidification than battery temperature, all have high power generation performance, and can generate electricity steadily in the long term.The present invention also aims to provide the manufacture method of this film to reach to this useful liquid composition.
The invention provides liquid composition, it is characterized in that, contain the cerium of 3 valencys that are selected from or 4 valencys and divalent or 3 valencys manganese the composition more than a kind and have the macromolecular compound of cation exchange base.
In the above-mentioned composition, also contain the liquid (solvent or decentralized medium) that can dissolve or disperse to have the macromolecular compound of cation exchange base.As this solvent or decentralized medium, can exemplify for example alcohols, water etc.In addition, in composition, cerium or manganese can exist with the state of ion, also can exist with the state that disperses as compounds such as oxide, hydroxide.Under the situation that cerium or manganese exist with the state of ion, can carry out ion-exchange with the proton of the cation exchange base of macromolecular compound.
In addition, the present invention also provides the manufacture method of above-mentioned liquid composition, it is characterized in that, make macromolecular compound be dissolved or dispersed in the liquid with cation exchange base after, mix the compound more than a kind be selected from cerium compound and manganese compound therein.Here said liquid is meant solvent or decentralized medium.
In addition, the present invention also provides the manufacture method by above-mentioned liquid composition being carried out the film that casting film obtains and the manufacture method of membrane-electrode assembly for polymer electrolyte fuel cell.The manufacture method of described membrane-electrode assembly is by negative electrode with the catalyst layer that contains catalyst and polyelectrolyte and anode and the manufacture method that is disposed at the membrane-electrode assembly for polymer electrolyte fuel cell that the solid polyelectrolyte membrane between aforementioned negative electrode and the aforesaid anode constitutes, it is characterized in that, make aforementioned solid polyelectrolyte membrane by the manufacture method of above-mentioned film.
In addition, the present invention also provides the manufacture method of membrane-electrode assembly for polymer electrolyte fuel cell, it is by negative electrode with the catalyst layer that contains catalyst and polyelectrolyte and anode and the manufacture method that is disposed at the membrane-electrode assembly for polymer electrolyte fuel cell that the solid polyelectrolyte membrane between aforementioned negative electrode and the aforesaid anode constitutes, it is characterized in that, be coated with by aforementioned catalyst is scattered in the above-mentioned liquid composition, thereby make at least one side in aforementioned negative electrode and the aforesaid anode.
The dielectric film that obtains by the present invention has good tolerability for hydrogen peroxide or peroxide radical.Its reason and unclear, but infer be cerium ion (3 valencys or 4 valencys) or manganese ion (divalent or 3 valencys) with the proton dissociation of cation exchange base after residue (for example-SO
3 -) interaction hydrogen peroxide or peroxide radical tolerance are improved.And, even be contained under the situation in the film with the state of cerium compound or manganese compound, also cerium ion that can obtain to produce or manganese ion by dissociating of trace and-SO
3 -Deng interaction.
In addition, compare with the methods such as processing that the dielectric film that does not contain cerium or manganese be impregnated in the liquid that contains these ions or compound by the dielectric film that manufacture method of the present invention obtains, can with these ions or compound easily, precision is good and be incorporated in the film equably.
Dielectric film of the present invention has good tolerability for hydrogen peroxide or peroxide radical, and the durability of polymer electrolyte fuel cell that therefore possesses the membrane-electrode assembly that dielectric film of the present invention is arranged is good, can be for a long time, generating stably.
The best mode that carries out an invention
As the macromolecular compound before making it contain cerium or manganese among the present invention with cation exchange base, get final product so long as have the cation exchange base function that generates proton of dissociating, be not particularly limited.As the object lesson of cation exchange base, sulfonic group, sulfimide base, phosphate, carboxylic acid group, ketimide base etc. are arranged, good especially is the sulfonic group that acidity is strong, chemical stability is high.Below, be example to have sulfonic macromolecular compound, the present invention will be described.
Liquid composition of the present invention can be dissolved or dispersed in by the compound that makes cerium or manganese to dissolve equably or disperseed to have in the liquid of sulfonic macromolecular compound and obtain.Here, compound as cerium or manganese, can use the compound that dissolves in the solvent in the liquid composition, also can use the compound that is insoluble to this solvent, in order to carry out ion-exchange to having sulfonic macromolecular compound, these compositions are existed more equably, better are that water miscible salt and water are used in combination.
Use water miscible salt, in liquid composition, contain under the situation of water, think that there is the sulfonic group (SO of macromolecular compound in cerium or the manganese state with ion in liquid composition
3H) carried out ion-exchange by cerium ion or manganese ion.In addition, if contain water insoluble in the liquid composition and dissolve in cerium compound or manganese compound and this other solvent of other solvent, then be coated with this liquid composition and in the film that obtains cerium compound or manganese compound exist equably, so be desirable.
In addition, use under the situation for insoluble cerium compound of the solvent in the liquid composition or manganese compound, the particle that must make these compounds equably, be dispersed in the liquid composition well.Therefore, better the dispersion liquid of making this compound under this situation, mix with solution with sulfonic macromolecular compound or dispersion liquid and prepare liquid composition.In addition, also can be in advance the soluble-salt of cerium or manganese be dissolved in solution or the dispersion liquid with sulfonic macromolecular compound, adds the compound of preparing in addition therein, react, make reaction product be contained in liquid composition with the salt of above-mentioned solubility.
Cerium compound as the raw material that is contained in liquid composition can use all cpds such as insoluble compound such as water miscible cerium salt, non-water-soluble cerium salt, oxide or hydroxide.The valence mumber of cerium be+3 valencys or+4 valencys.Contain+salt of the cerium ion of 3 valencys if will specifically exemplify, can exemplify for example 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 the cerium ion of 4 valencys, can exemplify for example 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 acetylacetone,2,4-pentanedione network cerium (Ce (CH
3COCHCOCH
3)
33H
2O) etc.
For example use under the situation of water miscible 3 valency cerium salt, if sulfonic group is carried out ion-exchange, Ce by cerium ion fully
3+With 3-SO
3 -In conjunction with, but in the liquid composition of the present invention, can be not by complete ion-exchange.In the liquid composition of the present invention, can contain cerium with the state of ion or the state of compound.It also is same containing the situation that manganese replaces cerium.
The content of 3 valencys in the liquid composition of the present invention or the cerium of 4 valencys is better for having in the sulfonic macromolecular compound-SO
3 -0.3～30 mole of % (following this ratio is called " containing ratio of cerium ") of molal quantity.Under the situation of cerium compound, the mol ratio of making cerium atom that converts is the containing ratio of cerium.Be more preferably 0.7～20 mole of %, good especially is 1～15 mole of %.
If the containing ratio of cerium then can be guaranteed the enough stability for hydrogen peroxide or peroxide radical less than this scope.In addition, if containing ratio greater than this scope, then can't be guaranteed hydrionic enough conductibility, film resistance increases, and power generation characteristics may descend.
Manganese compound as the raw material that is contained in liquid composition can use all cpds such as insoluble compound such as water miscible manganese salt, non-water-soluble manganese salt, oxide or hydroxide.The valence mumber of manganese is+divalent or+3 valencys.Contain+salt of the manganese ion of divalent if will specifically exemplify, can exemplify for example manganese acetate (Mn (CH
3COO)
24H
2O), manganese chloride (MnCl
24H
2O), manganese nitrate (Mn (NO
3)
26H
2O), manganese sulfate (MnSO
45H
2O), manganese carbonate (MnCO
3NH
2O) etc.As containing+salt of the manganese ion of 3 valencys, can exemplify for example manganese acetate (Mn (CH
3COO)
32H
2O) etc.In addition, as the organic metal complex salt of manganese, can exemplify acetylacetone,2,4-pentanedione network manganese (Mn (CH
3COCHCOCH
3)
2) etc.
The manganese ion in the liquid composition of the present invention or the content of manganese compound are better for having in the sulfonic macromolecular compound-SO
3 -0.5～45 mole of % (following this ratio is called " containing ratio of manganese ") of molal quantity.Under the situation of manganese compound, the mol ratio of making manganese atom that converts is the containing ratio of manganese.Be more preferably 1～30 mole of %, good especially is 1.5～20 moles of %.
If the containing ratio of manganese then can be guaranteed the enough stability for hydrogen peroxide or peroxide radical less than this scope.In addition, if containing ratio greater than this scope, then can't be guaranteed hydrionic enough conductibility, film resistance increases, and power generation characteristics may descend.
When making liquid composition of the present invention, as employed cerium compound or manganese compound, good especially is carbonate.The general most water that is insoluble in of carbonate under the situation of cerous carbonate, manganese carbonate, contains water if make in advance in solution with sulfonic macromolecular compound or the dispersion liquid, easily dissolves when then producing carbonic acid gas.In addition, if use the carbonate of cerium or manganese to prepare liquid composition, be coated with by common The tape casting etc., dry removing desolvated and obtained dielectric film, then can residually not remove-SO in this dielectric film
3 -Anion species beyond the base does not need washing.From the angle of the manufacturing of such film, also better be carbonate.
The method that obtains the method for liquid composition of the present invention and use the liquid composition obtain to obtain dielectric film is not particularly limited, and can exemplify for example following method: at first, make to have sulfonic macromolecular compound and be dissolved or dispersed in the solvent; Add the carbonate of water and cerium or the carbonate of manganese therein, fully mix, obtain liquid composition; Then, the liquid composition casting film by obtaining makes its drying, thereby obtains dielectric film.
The water yield contained in the liquid composition is suitably set according to ion exchange capacity and concentration, the cerium of interpolation or the amount of manganese with sulfonic macromolecular compound.If do not make water, the dissolving meeting of carbonate is very consuming time, so particularly use the situation of carbonate, better is to make to contain water in the liquid composition.
The solid component concentration of liquid composition of the present invention is not particularly limited.Can adjust concentration, viscosity, make it can carry out common curtain coating coating, from this angle, in the mass ratio with respect to the liquid composition gross mass, solid component concentration is preferably 5～50%, and good especially is 10～35%.
Adopt dielectric film of the present invention also can make laminated film, for example can be on the film that liquid composition casting film of the present invention is obtained lamination do not contain the ion of cerium or manganese or the amberplex of compound is made.
As making it contain the sulfonic macromolecular compound that has before cerium or the manganese among the present invention, be not particularly limited, ion exchange capacity is preferably 0.5～3.0 milliequivalent/g dry resin, 0.7～2.5 milliequivalent/g dry resin more preferably, and good especially is 1.0～2.5 milliequivalents/g dry resin.If ion exchange capacity is low excessively, after then sulfonic group carries out ion-exchange with cerium ion or manganese ion, can't guarantee hydrionic enough conductibility, film resistance increases, and power generation characteristics may descend.In addition, if ion exchange capacity is too high, then the resistance to water of film and intensity may descend.In addition, from the angle of durability, this macromolecular compound better is a fluoropolymer, and good especially is to have sulfonic perfluocarbon polymer (oxygen atom that can contain ehter bond).As perfluocarbon polymer, be not particularly limited, better be to contain based on CF
2=CF-(OCF
2CFX)
m-O
p-(CF
2)
n-SO
3The polymerized unit of the perfluorinated ethenyl compound (m represents 0～3 integer, and n represents 1～12 integer, and p represents 0 or 1, and X represents fluorine atom or trifluoromethyl) that H is represented and based on the copolymer of the polymerized unit of tetrafluoroethene.
If will more specifically exemplify the preferred example of above-mentioned perfluorinated ethenyl compound, can exemplify the compound shown in the following formula (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)
Use has under the situation of sulfonic perfluocarbon polymer, can use the polymer that the end of polymer has been carried out fluorination treatment after polymerization by fluoridizing.If the end of polymer is fluoridized, then better to the stability of hydrogen peroxide and peroxide radical, so durability improves.
In addition, as making it contain the sulfonic macromolecular compound that has before cerium or the manganese, also can use the compound that has beyond the sulfonic perfluocarbon polymer, for example can preferably use to possess to have aromatic ring on high molecular main chain or main chain and the side chain, in this aromatic ring, imported sulfonic structure and ion exchange capacity is the macromolecular compound of 0.5～3.0 milliequivalent/g dry resin.Specifically, can use for example following macromolecular compound.
Sulfonation polyarylene, sulfonated polyphenyl and azoles, 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 and disposed the anode with the catalyst layer that contains catalyst and ion exchange resin and the membrane-electrode assembly of negative electrode on the two sides of dielectric film of the present invention.The anode of membrane-electrode assembly and negative electrode better are the gas diffusion layers that the outside (with the film opposition side) configuration at catalyst layer is made of carbon cloth or carbon paper etc.Its structure is: the ditch that is formed with the path of act as a fuel gas or oxidant gas on the two sides of membrane-electrode assembly, the configuration isolation layer, by multilayer laminated storehouse, hydrogen is fed to anode-side to formation across the separator membrane-electrode assembly, and oxygen or air are fed to cathode side.Take place in the anode
Reaction, take place in the negative electrode
Reaction, chemical energy is converted into electric energy.
In addition, dielectric film of the present invention also can be used for the direct methanol fuel cell that anode side is supplied with methyl alcohol rather than fuel gas.
Above-mentioned catalyst layer can obtain by for example following operation according to usual way.At first, the conductive carbon black powder that is carrying platinum catalyst or platinum alloy catalyst particulate is mixed with the solution with sulfonic perfluocarbon polymer, obtain the dispersion liquid of homogeneous, form gas-diffusion electrode, obtain membrane-electrode assembly by any for example following method.
The 1st kind of method is, after above-mentioned dispersion liquid of the two sided coatings of dielectric film and drying, with the method for two sides with 2 blocks of carbon cloths or carbon paper adhesion.The 2nd kind of method be, be coated on above-mentioned dispersion liquid on 2 blocks of carbon cloths or the carbon paper and drying after, clamp from the two sides of above-mentioned amberplex, make the face that has been coated with dispersion liquid and the method for above-mentioned amberplex driving fit.Here, carbon cloth or carbon paper have as the function of the gas diffusion layers of the layer that is used to that gas is diffused into more equably and contains catalyst with as the function of collector body.In addition, also can use the above-mentioned dispersion liquid of coating on the base material of preparing in addition and make catalyst layer, after making it and dielectric film engages by methods such as transfer printings, peel off base material, with the method for above-mentioned gas diffusion layers clamping.
Ion exchange resin contained in the catalyst layer is not particularly limited, and better is to have sulfonic macromolecular compound, is more preferably to have sulfonic perfluocarbon polymer.Ion exchange resin in the catalyst layer can similarly contain cerium or manganese with the state of ion or the state of compound with dielectric film of the present invention.Such resin can be used for male or female, and the decomposition of resin is effectively suppressed, so the durability of polymer electrolyte fuel cell further improves.In addition, can use the ion exchange resin that does not contain cerium or manganese, only make the ion exchange resin in the catalyst layer contain cerium or manganese as dielectric film.
When making the ion that contains cerium or manganese in the catalyst layer or compound, dispersed catalyst in liquid composition of the present invention and, getting final product to form catalyst layer with above-mentioned same method as coating fluid.Under this situation, can only the either party in negative electrode and the anode be made with liquid composition of the present invention, also can negative electrode and negative electrode all use liquid composition to make.At this moment, also can use the different liquid composition of content of cerium or manganese in negative electrode and anode, the content of regulating the cerium that makes negative electrode and anode or manganese is different.Particularly, if contain in the anode have sulfonic macromolecular compound contained-SO
3 -The cerium of 10～30 moles of % of base contains the cerium of 3～10 moles of % in the negative electrode, then the decomposition of the ion exchange resin in the catalyst layer also can effectively be suppressed, so consider the raising of durability, is more preferably.
According to same reason, contain under the situation of the ion of manganese or compound, better be contain in the anode have sulfonic macromolecular compound contained-SO
3 -The manganese of 15～45 moles of % of base contains the manganese of 5～15 moles of % in the negative electrode.Here, under the situation that is cerium compound or manganese compound, the content of cerium or manganese is represented the ratio in the molal quantity that is converted into cerium or manganese.
The dielectric film that obtains by the present invention can be only by the state with ion or compound contain cerium or manganese, have the film that sulfonic macromolecular compound constitutes, also can contain other composition.For example, also the film that the fiber by other resins such as polytetrafluoroethylene (following note is made PTFE) or perfluoroalkyl ethers etc., woven cloth, nonwoven fabrics, porous body etc. are strengthened can be used to adopt the method for liquid composition system film of the present invention.When strengthening dielectric film, can strengthen whole film, also can strengthen with film, sheet etc. near the margo frontalis shape ground periphery of film.If margo frontalis shape ground strengthening membrane, then the intensity of periphery increases, so the property handled raising.Can also strengthen with the high reinforcement material of voidage whole film, only periphery with voidage low or void-free reinforcement material strengthen.
At high temperature durability is also good to have the polymer electrolyte fuel cell of the membrane-electrode assembly that obtains by the present invention, so the generating of can turning round under the temperature more than 100 ℃.When the gas that acts as a fuel used the hydrogen that modification such as methyl alcohol, natural gas, gasoline is obtained, even trace contains carbon monoxide, electrode catalyst also can be poisoned, and the output of fuel cell descends easily.If operating temperature is reached more than 100 ℃, then poison and to be inhibited.Be more preferably operating temperature is reached more than 120 ℃, suppress the better effects if of poisoning.
In addition, liquid composition of the present invention can also be preferably used for various transducers, signals such as film that water electrolysis uses and humidity sensor and transmit medium etc. except the making of the dielectric film that can be used for fuel cell and use, catalyst layer.
Embodiment
Below, use embodiment (example 1～5,8～11) and comparative example (example 6～7), the present invention is specifically described, but the present invention is not limited to these embodiment.
[preparation] with solution of sulfonic perfluocarbon polymer
With 300g CF
2=CF
2/ CF
2=CFOCF
2CF (CF
3) O (CF
2)
2SO
3H copolymer (ion exchange capacity is 1.1 milliequivalents/g dry resin), 420g ethanol and 280g water join in the 2L autoclave, carry out airtightly, mix down at 105 ℃ by the double helix blade and to stir 6 hours, obtain the solution (hereinafter referred to as solution A) of homogeneous.The solid component concentration of solution A is 30 quality %.
[preparation] with solution of sulfonic aromatic polymer
Commercially available polyether-ether-ketone (the Britain Victrex corporate system that 60g is granular, PEEK-450P) at room temperature add to one by one in the sulfuric acid of 1200g 98 quality % on a small quantity, at room temperature stir 60 hours, thereby obtain in polyether-ether-ketone, having imported the uniform solution of sulfonic macromolecular compound.Then, on one side this solution is cooled off,, have sulfonic polyether-ether-ketone and separate out isolated by filtration thereby make Yi Bian slowly splash in the distilled water of 5L.Then, it is cleaned to cleaning fluid with distilled water reach neutral, under 80 ℃ of vacuum dry 24 hours then, obtain 48g and have sulfonic polyether-ether-ketone.Ion exchange capacity is 1.6 milliequivalents/g dry resin.
Then, 40g should be had sulfonic polyether-ether-ketone be dissolved in 360g N-N-methyl-2-2-pyrrolidone N-(NMP), obtain the solution (hereinafter referred to as solution B) of 10 quality %.
[example 1]
In 300mL glass round-bottomed flask, add 100g solution A and 1.00g cerous carbonate hydrate (Ce
2(CO
3)
38H
2O), at room temperature stirred 8 hours by polytetrafluoroethylene (PTFE) system semilune blade.Begin from stirring, produce because of generating CO
2And the bubble that causes, but finally obtain the liquid composition (hereinafter referred to as liquid composition C) of transparent and homogeneous.The solid component concentration of the liquid composition C that obtains is 30.2 quality %.Said composition is applied to ethylene-tetrafluoroethylene copolymer (ETFE) sheet (trade name: ア Off レ Star Network ス 100N of 100 μ m with mold pressing coating machine curtain coating, the Asahi Glass corporate system) on, after under 80 ℃ predrying 10 minutes, drying is 10 minutes under 120 ℃, carry out 150 ℃, 30 minutes calcining again, obtain the solid polyelectrolyte membrane of thickness 50 μ m.
Cut the film of 5cm * 5cm size from this polyelectrolyte membrane, place in drying nitrogen after 16 hours, accurately the weighing quality is immersed in the HCl aqueous solution of 0.1 equivalent, the liquid that has obtained the complete extracting of cerium ion.This liquid is measured by inductively coupled plasma (ICP) luminesceence analysis, thereby the cerium in the polyelectrolyte membrane is carried out quantitatively, the result is the cerium amount with respect to the quality of film is 1.5%, and the cerium containing ratio is 10 moles of %.
Then, 50% platinum in 1.0g catalyst gross mass is carried on carbon carrier (specific area 800m
2Mix 5.1g distilled water in the/catalyst fines (N.E.CHEMCAT corporate system) that g) obtains.In this mixed liquor, mix 5.6g and make CF
2=CF
2/ CF
2=CFOCF
2CF (CF
3) O (CF
2)
2SO
3H copolymer (ion exchange capacity is 1.1 milliequivalents/g dry resin) is scattered in the liquid of the solid component concentration 9 quality % that ethanol obtains.Use homogenizer (trade name: POLYTRON, KINEMATICA corporate system) to make this mixture mix, pulverize, make catalyst layer formation coating fluid.
After being coated with on the base material film that device is coated on polypropylene system with rod this coating fluid,, make catalyst layer 80 ℃ drier inner dryings 30 minutes.The quality of the base material film after quality by the only base material film before measuring catalyst layer and forming and catalyst layer form is calculated the platinum amount of the contained unit are of catalyst layer, and the result is 0.5mg/cm
2
Then, use the above-mentioned polyelectrolyte membrane that contains cerium, two sides at this film disposes the catalyst layer that is formed on the above-mentioned base material film respectively, by pressure sintering catalyst layer is transferred on the film, join anode catalyst layer and cathode catalyst layer the two sides of polyelectrolyte membrane to respectively, thereby obtain the film catalyst layer assembly.Electrode area is 16cm
2
This film catalyst layer assembly is clipped between 2 gas diffusion layers that are made of the carbon cloth of thick 350 μ m, makes membrane-electrode assembly, battery is used in its generating of packing into, carry out open circuit test (OCV test) as accelerated test.In the test, under normal pressure, will be equivalent to current density 0.2A/cm
2Hydrogen (utilance 70%) and air (utilance 40%) feed to anode and negative electrode respectively, battery temperature is made as 90 ℃, the dew point of anodic gas is made as 60 ℃, the dew point of cathode gas is made as 60 ℃, do not generate electricity, operation is 100 hours under open-circuit condition, measures change in voltage therebetween.In addition, before and after test, the anode hydrogen supply is supplied with nitrogen to negative electrode, analyzes by film and escapes to the amounts of hydrogen of negative electrode from anode, investigates the degradation of film.The results are shown in table 1.
Then, also with the above-mentioned membrane-electrode assembly of similarly making, battery is used in packing into generating, hangs down the endurance test under the operating condition of humidification.Experimental condition is hydrogen supply under the normal pressure (utilance 70%)/air (utilance 40%), 80 ℃ of battery temperatures, current density 0.2A/cm
2, carry out the initial stage evaluating characteristics and the durability evaluation of the polymer electrolyte fuel cell under this condition.Respectively hydrogen and air are carried out supplying in the battery behind the humidification, the dew point that makes anode-side is 80 ℃, and the dew point of cathode side is 50 ℃, measures the relation of cell voltage and the running beginning back elapsed time and the cell voltage of start of run.The results are shown in table 2.In addition, in the appreciation condition of above-mentioned battery,, similarly operate, measure the relation of cell voltage and the running beginning back elapsed time and the cell voltage of start of run except the dew point with cathode side changes to 80 ℃.Evaluation result is shown in table 3.
[example 2]
Except with cerous carbonate hydrate (Ce in the example 1
2(CO
3)
38H
2O) amount changes into outside the 498mg, similarly operates with example 1, and the containing ratio that obtains cerium is the film of 5 moles of %.Then, use this film, similarly operate, obtain the film catalyst layer assembly, and then obtain membrane-electrode assembly with example 1.Carry out the evaluation same with example 1 for this membrane-electrode assembly, the result is shown in table 1～3.
[example 3]
Except with cerous carbonate hydrate (Ce in the example 1
2(CO
3)
38H
2O) amount changes into outside the 166mg, similarly operates with example 1, and the containing ratio that obtains cerium is the film of 1.7 moles of %.Then, use this film, similarly operate, obtain the film catalyst layer assembly, and then obtain membrane-electrode assembly with example 1.Carry out the evaluation same with example 1 for this membrane-electrode assembly, the result is shown in table 1～3.
[example 4]
Except using 422mg manganese carbonate hydrate (MnCO
3NH
2O, the content of manganese be gross mass 41～46%) replace similarly operating with example 1 outside the cerous carbonate hydrate used in the example 1, the containing ratio that obtains manganese is the film of 10 moles of %.Then, use this film, similarly operate, obtain the film catalyst layer assembly, and then obtain membrane-electrode assembly with example 1.Carry out the evaluation same with example 1 for this membrane-electrode assembly, the result is shown in table 1～3.
[example 5]
In 300mL glass round-bottomed flask, add 100g solution B, 20g water and 484mg cerous carbonate hydrate (Ce
2(CO
3)
38H
2O), stirred 8 hours down at 70 ℃ by PTFE system semilune blade.In the stirring, produce because of generating CO
2And the bubble that causes, but finally obtain the liquid of transparent and homogeneous.The solid component concentration of the liquid composition that obtains is 8.3%.Use said composition under the room temperature on PTFE system base material casting film, in nitrogen atmosphere,, make the evaporation of NMP and water, thereby obtain the film of thick 50 μ m in 100 ℃ of dryings 10 hours.By measuring with the same ICP of example 1, the containing ratio of the cerium of this film is 10 moles of %.
Then, use this film, similarly operate, obtain the film catalyst layer assembly, and then obtain membrane-electrode assembly with example 1.Carry out the evaluation same with example 1 for this membrane-electrode assembly, the result is shown in table 1～3.
[example 6]
In solution A, do not add any composition, carry out casting film, obtain solid polyelectrolyte membrane.Except using this film as the dielectric film, similarly operate with example 1, obtain the film catalyst layer assembly, and then 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 7]
Cerous carbonate in not adding example 5 and water and directly use the solution B are similarly operated with example 5, obtain the film catalyst layer assembly, and then 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 8]
Except in the 100g of example 1 solution A with change the cerous carbonate hydrate (Ce of 249mg into
2(CO
3)
38H
2O) add 170mg manganese carbonate hydrate (MnCO in again
3NH
2O, the content of manganese be gross mass 41～46%) outside, similarly operate with example 1, obtain liquid composition, obtain containing perfluocarbon polymer in the film contained-SO
3 -The film of the cerium of 2.5 moles of % of base and the manganese of 3.75 moles of %.Then, use this film, similarly operate, obtain the film catalyst layer assembly, and then obtain membrane-electrode assembly with example 1.Carry out the evaluation same with example 1 for this membrane-electrode assembly, the result is shown in table 1～3.
[example 9]
Solution A is applied to the ETFE sheet (trade name: ア Off レ Star Network ス 100N of 100 μ m with the mold pressing coating machine, the Asahi Glass corporate system) on, after under 80 ℃ predrying 10 minutes, drying is 10 minutes under 120 ℃, carry out 150 ℃, 30 minutes calcining again, obtain the dielectric film of thickness 50 μ m, 5cm * 5cm size.
Then, the containing ratio that makes the cerium of making in the use-case 1 is the liquid composition C of 10 moles of %, the following anode catalyst layer of making.50% platinum in 1.0g catalyst gross mass is carried on carbon carrier (specific area 800m
2Mix 5.1g distilled water in the/catalyst fines (N.E.CHEMCAT corporate system) that g) obtains.Mixing 5.6g in this mixed liquor, above-mentioned liquid composition C is made solid component concentration with the ethanol dilution is the liquid of 9 quality %.Use homogenizer to make this mixture mix, pulverize, make and form the anode catalyst layer coating fluid.
After being coated with on the base material film that device is coated on polypropylene system with rod this coating fluid, 80 ℃ drier inner dryings 30 minutes, make the perfluocarbon polymer that contains in the catalyst layer contained-SO
3 -The anode catalyst layer of the cerium of 10 moles of % of base.The quality of the base material film after quality by the only base material film before measuring catalyst layer and forming and catalyst layer form is calculated the platinum amount of the contained unit are of catalyst layer, and the result is 0.5mg/cm
2
In addition, replace similarly operating with anode catalyst layer the above-mentioned liquid composition C, make the cathode catalyst layer that does not contain cerium except using above-mentioned solution A.
Then, two sides at the dielectric film that uses solution A to make disposes anode catalyst layer and the cathode catalyst layer that is formed on the above-mentioned base material film respectively, by pressure sintering catalyst layer is transferred on the film, will contain perfluocarbon polymer in the catalyst layer contained-SO
3 -The anode catalyst layer of the cerium of 10 moles of % of base and the cathode catalyst layer that does not contain cerium join the two sides of polyelectrolyte membrane respectively to, thereby obtain the film catalyst layer assembly.Electrode area is 16cm
2
Similarly operate with example 1, obtain membrane-electrode assembly by this film catalyst layer assembly again.This membrane-electrode assembly is carried out the open circuit test same with example 1.The results are shown in table 1.In addition, make and above-mentioned same membrane-electrode assembly, battery is used in packing into generating, carries out the endurance test under the operating condition with same low humidification of example 1 and high humidification, and the result is shown in table 2,3.
[example 10]
Except in the making of the liquid composition C of example 1, adding 2.00g cerous carbonate hydrate (Ce
2(CO
3)
38H
2O) outside, similarly operate with example 1, the containing ratio of making cerium is the liquid composition of 20 moles of %.Except this liquid composition being used for the formation of anode catalyst layer, similarly operate with example 9, will contain perfluocarbon polymer in the catalyst layer contained-SO
3 -The anode catalyst layer of the cerium of 20 moles of % of base and the cathode catalyst layer that does not contain cerium join the two sides of polyelectrolyte membrane respectively to, thereby obtain the film catalyst layer assembly.
Similarly operate with example 1, obtain membrane-electrode assembly by this film catalyst layer assembly again.This membrane-electrode assembly is carried out the open circuit test same with example 1.The results are shown in table 1.In addition, make and above-mentioned same membrane-electrode assembly, battery is used in packing into generating, carries out the endurance test under the operating condition with same low humidification of example 1 and high humidification, and the result is shown in table 2,3.
[example 11]
Except in the making of the liquid composition C of example 1, adding 844mg manganese carbonate hydrate (MnCO
3NH
2O, the content of manganese be gross mass 41～46%) replace similarly operating with example 1 outside the cerous carbonate hydrate, the containing ratio of making manganese is the liquid composition of 20 moles of %.Except this liquid composition being used for the formation of anode catalyst layer, similarly operate with example 8, will contain perfluocarbon polymer in the catalyst layer contained-SO
3 -The anode catalyst layer of the manganese of 20 moles of % of base and the cathode catalyst layer that does not contain manganese join the two sides of polyelectrolyte membrane respectively to, thereby obtain the film catalyst layer assembly.
Similarly operate with example 1, obtain membrane-electrode assembly by this film catalyst layer assembly again.This membrane-electrode assembly and example 1 are similarly estimated, and the result is shown in table 1～3.
[table 1]
| Open circuit voltage (V) | Spill hydrogen (ppm) | |||
| Initial stage | After 100 hours | Initial stage | After 100 hours | |
| Example 1 | 0.99 | 0.98 | 710 | 720 |
| Example 2 | 0.99 | 0.96 | 700 | 710 |
| Example 3 | 0.97 | 0.96 | 730 | 780 |
| Example 4 | 0.97 | 0.94 | 750 | 790 |
| Example 5 | 0.96 | 0.92 | 850 | 1100 |
| Example 6 | 0.96 | 0.75 | 1100 | 12000 |
| Example 7 | 0.94 | 0.51 | 1300 | 70000 |
| Example 8 | 0.99 | 0.98 | 750 | 790 |
| Example 9 | 0.99 | 0.96 | 710 | 720 |
| Example 10 | 0.99 | 0.98 | 700 | 710 |
| Example 11 | 0.99 | 0.97 | 730 | 780 |
[table 2]
| The output voltage at initial stage (V) | Durability/output voltage (V) | ||
| After 500 hours | After 2000 hours | ||
| Example 1 | 0.77 | 0.77 | 0.76 |
| Example 2 | 0.77 | 0.76 | 0.76 |
| Example 3 | 0.76 | 0.75 | 0.75 |
| Example 4 | 0.76 | 0.75 | 0.74 |
| Example 5 | 0.75 | 0.73 | 0.72 |
| Example 6 | 0.77 | 0.70 | 0.65 |
| Example 7 | 0.73 | 0.58 | 0.50 |
| Example 8 | 0.76 | 0.76 | 0.76 |
| Example 9 | 0.77 | 0.76 | 0.75 |
| Example 10 | 0.77 | 0.76 | 0.76 |
| Example 11 | 0.76 | 0.75 | 0.75 |
[table 3]
| The output voltage at initial stage (V) | Durability/output voltage (V) | ||
| After 500 hours | After 2000 hours | ||
| Example 1 | 0.78 | 0.78 | 0.78 |
| Example 2 | 0.78 | 0.78 | 0.77 |
| Example 3 | 0.78 | 0.77 | 0.77 |
| Example 4 | 0.78 | 0.77 | 0.77 |
| Example 5 | 0.76 | 0.75 | 0.74 |
| Example 6 | 0.77 | 0.73 | 0.70 |
| Example 7 | 0.74 | 0.65 | 0.60 |
| Example 8 | 0.78 | 0.77 | 0.77 |
| Example 9 | 0.78 | 0.77 | 0.76 |
| Example 10 | 0.78 | 0.77 | 0.76 |
| Example 11 | 0.78 | 0.77 | 0.77 |
By the result of the foregoing description and comparative example as can be known, in the open circuit test (OCV test) as the high temperature of accelerated test, low humidification, dielectric film deterioration in the past, hydrogen spills increase, and dielectric film of the present invention shows obviously better durability.
The possibility of utilizing on the industry
Very excellent for the durability of the hydrogen peroxide that is generated by the generating of fuel cell or peroxide radical by the dielectric film that the aqueous composition of electrolyte of the present invention obtains. Therefore, the polymer electrolyte fuel cell that possesses the membrane-electrode assembly with dielectric film of the present invention all has long-term durability under the condition that low humidification generating and high humidification generate electricity.
Quote the full content of Japanese patent application 2004-204704 number of filing an application on July 12nd, Japanese patent application 2004-183712 number 1 of filing an application on June 22nd, 2004 and Japanese patent application 2004-265176 number the specification of filing an application on September 13rd, 2004, claims, drawing and description summary here, adopt as the announcement of specification of the present invention.
Claims (15)
1. liquid composition is characterized in that, contain the cerium of 3 valencys that are selected from or 4 valencys and divalent or 3 valencys manganese the composition more than a kind and have the macromolecular compound of cation exchange base.
2. liquid composition as claimed in claim 1, wherein, the cation exchange base is a sulfonic group.
3. liquid composition as claimed in claim 1 or 2 wherein, contains water.
4. as claim 2 or 3 described liquid compositions, wherein, aforementioned macromolecular compound forms by having sulfonic perfluocarbon polymer, and described polymer can contain etheric oxygen atom.
5. as each described liquid composition in the claim 2～4, wherein, the content of the cerium of 3 valencys or 4 valencys is in the aforementioned macromolecular compound-SO
3 -0.3～30 mole of % of molal quantity.
6. as each described liquid composition in the claim 2～4, wherein, the content of the manganese of divalent or 3 valencys is in the aforementioned macromolecular compound-SO
3 -0.5～45 mole of % of molal quantity.
7. as each described liquid composition in the claim 2～6, wherein, the ion exchange capacity of aforementioned macromolecular compound is 0.5～3.0 milliequivalent/g dry resin.
8. as each described liquid composition in the claim 2～7, wherein, aforementioned macromolecular compound is to contain based on the repetitive of tetrafluoroethene with based on CF
2=CF-(OCF
2CFX)
m-O
p-(CF
2)
n-SO
3The copolymer of the repetitive of the perfluorinated ethenyl compound that H is represented, X are represented fluorine atom or trifluoromethyl, and m represents 0～3 integer, and n represents 1～12 integer, and p represents 0 or 1.
9. the manufacture method of each described liquid composition in the claim 1～8, it is characterized in that, after making macromolecular compound be dissolved or dispersed in the liquid, mix the compound more than a kind that is selected from cerium compound and manganese compound therein with cation exchange base.
10. the manufacture method of liquid composition as claimed in claim 9 wherein, contains water in the aforementioned liquids, and the compound more than a kind that is selected from aforementioned cerium compound and aforementioned manganese compound is a carbonate.
11. the manufacture method of film is characterized in that, each described liquid composition in the claim 1～8 is carried out casting film.
12. the manufacture method of film as claimed in claim 11 wherein, after making the macromolecular compound dissolving with cation exchange base or being dispersed in the moisture liquid, makes the dissolves carbonate of the carbonate or the manganese of cerium, and obtains aforementioned liquid composition.
13. the manufacture method of membrane-electrode assembly for polymer electrolyte fuel cell, it is by negative electrode with the catalyst layer that contains catalyst and polyelectrolyte and anode and the manufacture method that is disposed at the membrane-electrode assembly for polymer electrolyte fuel cell that the solid polyelectrolyte membrane between aforementioned negative electrode and the aforesaid anode constitutes, it is characterized in that, make aforementioned solid polyelectrolyte membrane by claim 11 or 12 described methods.
14. the manufacture method of membrane-electrode assembly for polymer electrolyte fuel cell, it is by negative electrode with the catalyst layer that contains catalyst and polyelectrolyte and anode and the manufacture method that is disposed at the membrane-electrode assembly for polymer electrolyte fuel cell that the solid polyelectrolyte membrane between aforementioned negative electrode and the aforesaid anode constitutes, it is characterized in that, be coated with in each described liquid composition by aforementioned catalyst is scattered in the claim 1～8, thereby make the catalyst layer of at least one side in aforementioned negative electrode and the aforesaid anode.
15. the manufacture method of membrane-electrode assembly for polymer electrolyte fuel cell as claimed in claim 13, wherein, be coated with in each described liquid composition by aforementioned catalyst is scattered in the claim 1～8, thereby make the catalyst layer of at least one side in aforementioned negative electrode and the aforesaid anode.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004183712 | 2004-06-22 | ||
| JP183712/2004 | 2004-06-22 | ||
| JP204704/2004 | 2004-07-12 | ||
| JP265176/2004 | 2004-09-13 |
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| CNB2005800199419A Active CN100544087C (en) | 2004-06-22 | 2005-06-22 | Use in solid polymer fuel cell dielectric film and manufacture method thereof and membrane-electrode assembly for polymer electrolyte fuel cell |
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| CN100466348C (en) | 2009-03-04 |
| CN100544087C (en) | 2009-09-23 |
| CN1969417A (en) | 2007-05-23 |
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