CN101874322A - Composite electrolyte membrane, membrane-electrode assembly, fuel cell, and methods for manufacturing same - Google Patents
Composite electrolyte membrane, membrane-electrode assembly, fuel cell, and methods for manufacturing same Download PDFInfo
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- CN101874322A CN101874322A CN200880117847A CN200880117847A CN101874322A CN 101874322 A CN101874322 A CN 101874322A CN 200880117847 A CN200880117847 A CN 200880117847A CN 200880117847 A CN200880117847 A CN 200880117847A CN 101874322 A CN101874322 A CN 101874322A
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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
-
- 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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- Fuel Cell (AREA)
- Conductive Materials (AREA)
Abstract
A method for manufacturing a composite electrolyte membrane including: a first folding process of folding a laminate (10A) obtained by laminating and integrating an electrolyte sheet (11) having an electrolyte as an electrolyte layer and a reinforcing sheet (12) having a porous polymer material as a reinforcing layer, so that a part of a surface of the laminate (10A) lies on another part of the surface; an impregnation process of impregnating the electrolyte of the folded laminate (10B) into the reinforcing layer; and a hydrolysis process of hydrolyzing the electrolyte impregnated in the laminate (10C).
Description
Technical field
The present invention relates to composite electrolyte membrane, membrane electrode assembly, fuel cell and be used to make their method, relate more particularly to have at least the dielectric substrate that constitutes by electrolyte and wherein porous polymer material be impregnated with composite electrolyte membrane, membrane electrode assembly, the fuel cell of described electrolytical reinforced layer and be used to make their method.
Background technology
Adopt the solid polymer type fuel battery of dielectric film to be studied and be applied to movable body, automobile for example is because this fuel cell can be worked at low temperatures and be had little size and weight.Especially, fuel cell car that solid polymer type fuel battery the is installed degree of social concern as the ecological, environmental protective car is being increased.
As shown in figure 14, solid polymer type fuel battery has the membrane electrode assembly (MEA) 95 as the main structure element.The single fuel cell 90 that is called as element cell is by forming between the dividing plate 96 that membrane electrode assembly is clipped in (hydrogen) gas flow path that has fuel and air flow circuit.Membrane electrode assembly 95 has such structure, wherein anode side electrode (anode catalyst layer) 93a is layered in the side as the dielectric film 91 of amberplex, and cathode side electrode (cathode catalyst layer) 93b is layered in opposite side, and corresponding diffusion layer 94a, 94b are configured in anode catalyst layer 93a and cathode catalyst layer 93b place.
In order to ensure film strength, dielectric film 91 has the reinforced layer that is made of porous polymer material such as polytetrafluoroethylene (PTFE), and this reinforced layer is impregnated with electrolyte.This composite electrolyte membrane with reinforced layer forms method manufacturing by the casting films shown in Figure 13 A (cast film), and it is open in Japanese patent application 2006-147257 communique (JP-A-2006-147257).
More specifically, at first, will comprise that the electrolyte of electrolytic polymer and solvent is coated on the side of the end liner plate 81 that just is being transmitted, and make the electrolyte drying.On the surface of the dielectric substrate that then, will be configured in dry by the reinforcement plate 82 that porous polymer material constitutes.At least by under this configuration status to dielectric substrate and strengthen plate 82 exert pressure make electrolyte from a surface impregnation strengthening plate 82 to porous polymer material.Then, electrolyte is coated in another surface of strengthening plate 82 to be gone up and drying, just can produce composite electrolyte membrane 91 thus, wherein be arranged on the end liner plate 81 by porous polymer material reinforced layer that constitutes and the electrolyte that is immersed in the reinforced layer at least.
In the composite electrolyte membrane of making in the above described manner 91, shown in Figure 13 B, for example, the anode catalyst layer 93a and the cathode catalyst layer 93b that have been formed on the end liner plate 81 shift by utilizing instrument and employing heating and pressurization, and catalyst layer 93a, 93b further are formed on the surface of composite electrolyte membrane 91.
But in above-mentioned casting films formation method, electrolyte is impregnated in different operations in two surfaces strengthening plate.As a result, though what use is the identical electrolyte that comprises electrolytic polymer and solvent, (difference spread), and is difficult to obtain the characteristic of homogeneous may to produce the dispersion of membrane property between two face side of composite electrolyte membrane.
In addition, go up coated electrolyte and make solvent seasoning because this manufacture process is included in each surface, so be difficult to obtain to have the dielectric film of high-precision homogeneous film thickness sometimes.In addition, with the precision of manufacturing equipment accordingly, strengthening plate may be from the offset of expectation with respect to coated electrolytical position.This skew takes place in the configuration of anode and cathode catalyst layer especially easily.
Like this, when not obtaining the membrane property of homogeneous on two surfaces at dielectric film, and when the position of the thickness of dielectric film and catalyst layer is not in the expected accuracy scope, in the battery manufacture process, may cause bad assembling, perhaps during generating electricity, may produce the dispersion of fuel battery performance.
Summary of the invention
The invention provides a kind of composite electrolyte membrane, wherein the homogeneity of the electrolyte characteristic in the film improves, and it can be manufactured with stable dimensional accuracy, a kind of membrane electrode assembly, a kind of fuel cell also is provided and has been used to make their method.
Comprise duplexer is folded into making the part on surface of described duplexer be positioned at first folding process on this surperficial another part that described duplexer is by making as electrolytical electrolyte plate of having of dielectric substrate and integrated acquisition of stiffener lamella superimposition that comprises porous polymer material as reinforced layer according to the method that is used to make composite electrolyte membrane of first aspect present invention; The dipping operation of the described electrolyte-impregnated that makes the described duplexer that is folded in the described reinforced layer; With the hydrolyzing process that makes the described electrolyte hydrolysis of flooding in the described duplexer.
In addition, in the method that is used for making composite electrolyte membrane, in described stacked operation, can form described duplexer by heating and stacked described electrolyte plate and described reinforcement plate according to first aspect.
In addition, in the method that is used for making composite electrolyte membrane, in described dipping operation, can heat the described duplexer that is folded up to described electrolyte dissolution, and can make described electrolyte-impregnated in described reinforced layer according to first aspect.
By the method that is used to make composite electrolyte membrane according to above-mentioned aspect, comprise the duplexer of reinforced layer and dielectric substrate can be in stacked operation by make the electrolyte plate with strengthen plate by means of engaging integrated formation.Be used to make two stacked methods of plate to be not particularly limited, as long as can form duplexer, and the part of electrolyte plate can be by being impregnated in the surface strengthening plate heating of electrolyte plate and pressurization.
In addition, in described first folding process, duplexer is folded into makes the part on surface of described duplexer be positioned on another part, that is to say, each several part on the surface of reinforced layer side is positioned at each other at least to be gone up, and perhaps the each several part on the surface of dielectric substrate side is positioned at each other at least and goes up.In the operation of folding duplexer, can engage by heating and pressurization by the folding surface that contacts.Preferably, central axis around duplexer folds, make the surface of two equalizations be positioned at each other and go up, but foldable number and method for folding are not particularly limited, if after having implemented the second following folding process two lip-deep electrolyte homogeneous of dielectric film.
In described dipping operation, the described duplexer that heating is folded dissolves up to described electrolyte at least, and makes described electrolyte-impregnated in the reinforced layer of porous.In this dipping operation, can carry out with heating the pressurization of duplexer.As a result, the electrolyte of the single electrolyte plate that adopts in stacked stage is configured on two surfaces of duplexer.In described hydrolyzing process, can give electrolyte with ion exchanging function by making the electrolyte hydrolysis of flooding in the described duplexer.
By this method that is used to make composite electrolyte membrane, needn't be three plates in location on two surfaces strengthening plate that the electrolyte plate is clipped in the middle.Therefore, positioning accuracy increases to some extent, and the quality of dielectric film is stablized.In addition, because duplexer is folded and the electrolyte of single electrolyte plate is impregnated, so can on two surfaces of composite electrolyte membrane (dielectric film), dispose the electrolyte of homogeneous.In addition, the thickness of dielectric film is also stablized.Like this, the homogeneity of electrolyte characteristic is improved in dielectric film, can obtain high-precision dielectric film, and fuel battery performance can be stablized.
In addition, be not particularly limited as the shape of " electrolyte plate " alleged in the description of this invention and " reinforcement plate ", thickness etc., as long as they can be folded after stacked, its implication comprises film, film or the like.Alleged as this paper, the plate that " reinforcement plate " constituted, adopted for the purpose of strengthening dielectric film by porous polymer material, " reinforced layer " is the layer that has porous polymer material and form on the thickness direction of dielectric film at least for the purpose of strengthening dielectric film, and its implication also comprises the layer by being obtained with the electrolyte-impregnated polymeric material.In addition, " composite electrolyte membrane " is meant the layer that comprises dielectric substrate and reinforced layer at least, and described dielectric substrate comprises electrolyte, and porous polymer material is impregnated with electrolyte in described reinforced layer.
In the method that is used for making composite electrolyte membrane, in described first folding process, described duplexer can be folded into a part that makes in the described duplexer on the surface of described dielectric substrate side and be positioned on this surperficial another part according to first aspect.According to above-mentioned aspect, because duplexer is folded into a part that makes in the duplexer on the surface of dielectric substrate side and is positioned on this surperficial another part and the reinforced layer side becomes the dielectric film surface in first folding process, so reinforced layer is configurable in the surface layer part near the surface on the thickness direction of dielectric film in the dipping operation.As a result, can improve creep (creep) performance of dielectric film when operation of fuel cells.
In the method that is used for making composite electrolyte membrane, in described first folding process, described duplexer can be folded into a part that makes in the described duplexer on the surface of described reinforced layer side and be positioned on this surperficial another part according to first aspect.According to above-mentioned aspect, because duplexer is folded into a part that makes in the duplexer on the surface of reinforced layer side and is positioned on this surperficial another part and the dielectric substrate side becomes the dielectric film surface in first folding process, so dielectric substrate is formed in the superficial layer on the thickness direction and the position of reinforced layer is stablized in the dipping operation.As a result, in being equipped with the fuel cell of described dielectric film, the dielectric substrate of superficial layer has suppressed water and has moved dispersion in the surface of dielectric film during generating electricity.In addition, the adhesion of dielectric substrate and catalyst layer can improve, and performance can be stablized.
Any polymer that dissolves all can be used as the electrolyte (precursor polymer) according to the foregoing description, as long as its thermal degradation when and can give ion exchanging function after hydrolysis not.The example of the polymer that can advantageously be used comprises the perfluor proton exchange resins of the fluoroalkyl copolymer with fluoroalkyl ether side chain and perfluoroalkyl main chain.Concrete example comprises Nafion (trade (brand) name, Du Pont Co. manufacturing), Aciplex (trade (brand) name, Asahi Chemical Industry Co., Ltd. manufacturing), Fremion (trade (brand) name, Asahi Glass Co. makes) and Goaselect (trade (brand) name, Japan Goatex Co., Ltd. makes).Other example comprises the part fluororesin, for example the polymer of trifluorostyrene sulfonic acid and sulfonic group introduced the polymer that is obtained in the poly-fluorine ethenylidene.Also can use sulfonic group wherein to be introduced into hydrocarbon proton exchange resins, polyimide resin of styrene diethylene benzene copoly mer or the like.Polymer must suitably be selected according to the purposes or the environment that use fuel cell, and still from the viewpoint of fuel battery service life, perfluorinated resin is preferred.
It is necessary that the reinforcement plate does not dissolve in the electrolyte-impregnated operation.The reinforcement plate that comprises waterproof polymer is particularly preferred.The reinforcement plate that comprises waterproof polymer can prevent to have condensed in solid polymer type fuel battery effectively and the water that gathers supplies to the electrode reaction product.Fluororesin such as polytetrafluoroethylene (PTFE), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP) and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) are particularly preferred, because they have high waterproof ability.Also can use floride-free film, for example PETG, polyethylene, polypropylene and polyimides.
In the method that is used for making composite electrolyte membrane according to first aspect, when in folding process, duplexer being folded into as mentioned above when making the part on surface of reinforced layer side be positioned on this surperficial another part, in described stacked operation, after described duplexer has formed, can on the surface of described reinforced layer, dispose hydrogen peroxide decomposes Cheng Shui and oxygen and suppress free radical inhibitors that hydroxy radical produces and in the water-keeping material at least one.
In addition, in the method that is used for making composite electrolyte membrane according to first aspect, when in folding process, duplexer being folded into as mentioned above when making the part on surface of reinforced layer side be positioned on this surperficial another part, in described stacked operation, can between described electrolyte plate and described reinforcement plate, dispose hydrogen peroxide decomposes Cheng Shui and oxygen and suppress free radical inhibitors that hydroxy radical produces and in the water-keeping material at least one.
According to above-mentioned aspect, in first folding process, be sandwiched in the centre from least a additive among free radical inhibitors and the water-keeping material, additive is added to electrolyte at the center of dielectric film on thickness direction in the dipping operation then.Therefore, additive can be fixed.
As a result, during fuel cell power generation, can prevent additive moving or flow out because of water.When using free radical inhibitors, free radical inhibitors utilizes mobile hydrogen peroxide decomposes Cheng Shui and the oxygen that will fuel cell power generation during as accessory substance produce of water in dielectric film in hydrolyzing process.As a result, can suppress the generation of hydroxy radical, dielectric film is stablized, and can suppress its deterioration.On the other hand, when configuration be water-keeping material the time, can obtain its water and keep and diffusion effect, and can suppress the low of fuel battery performance that the deterioration by proton-conducting causes effectively.
Free radical inhibitors alleged in the description of this invention is " be used for hydrogen peroxide decomposes Cheng Shui and the oxygen that will produce as accessory substance and suppress the material that hydroxy radical produces during fuel cell power generation ".Its example comprises the oxide of transition metal (as cerium, ruthenium, silver, tungsten, palladium, rhodium, zirconium, yttrium, manganese, molybdenum, lead, vanadium and titanium).Water-keeping material is not particularly limited, as long as it can absorb water.Its example comprises particle or the fiber that is made of water absorbent polymer material such as polystyrolsulfon acid and cellulose and suction inorganic material such as silica and titanium oxide.
This free radical inhibitors and water-keeping material can apply (diecoating) or spraying and physical vapor deposition (PVD) technology such as sputter by coating processes such as pattern and be configured in equably on the surface of reinforced layer.Owing in the middle of free radical inhibitors and water-keeping material are sandwiched in first folding process as mentioned above,, reach the degree that during folding, can not break away from the reinforced layer as long as they can be sandwiched in so its collocation method is not particularly limited.
When using fine-powdered material as free radical inhibitors and water-keeping material, the particle size of fine-powdered material is preferably more than the pore-size of the hole that forms in strengthening plate.By such particle size, pulverulent material can advantageously be clipped in the middle in first folding process.
Comprise the method that is used to make composite electrolyte membrane according to the method that is used to make membrane electrode assembly of second aspect present invention according to first aspect, wherein, in described stacked operation, after described duplexer has formed, configuration anode catalyst layer and cathode catalyst layer on the surface of described dielectric substrate; And in described first folding process, described duplexer is folded into makes described anode catalyst layer be configured on the surface of described duplexer, and described cathode catalyst layer is configured on another surface of described duplexer.
By the method that is used to make membrane electrode assembly according to above-mentioned purpose, because anode catalyst layer and cathode catalyst layer are formed in the same surface (wherein having formed dielectric substrate in the duplexer that obtains by stacked operation), so can accurately dispose these catalyst layers.As a result, in keeping first folding process, under the situation of the precision of stacked folded body position, can suppress the distortion of the mutual layout of anode catalyst layer and cathode catalyst layer.In addition, configurable above-mentioned diffusion layer after catalyst layer forms.By adopting the membrane electrode assembly of making in the above described manner, can prevent from when being assembled into membrane electrode assembly in the fuel cell, to produce assembly failure, and the dispersion that is suppressed at fuel battery performance during the generating.
Comprise the method that is used to make composite electrolyte membrane according to the method that is used to make membrane electrode assembly of third aspect present invention according to first aspect, wherein, in described stacked operation, form banded duplexer, and after described duplexer has formed, configuration anode catalyst layer and cathode catalyst layer on the surface of described dielectric substrate make described anode catalyst layer and described cathode catalyst layer form along the horizontal direction of described duplexer; And in described first folding process, described duplexer is folded into along the longitudinal direction makes described anode catalyst layer be configured on the surface of described duplexer, and described cathode catalyst layer is configured on another surface of described duplexer.
In the method that is used for making membrane electrode assembly according to third aspect present invention, in described stacked operation, described anode catalyst layer and described cathode catalyst layer can be arranged such that a plurality of described anode catalyst layers and a plurality of described cathode catalyst layer alternately form along described longitudinal direction.
By the method that is used to make membrane electrode assembly according to above-mentioned aspect, because anode catalyst layer and cathode catalyst layer are formed in the same surface (wherein having formed dielectric substrate in the duplexer that obtains by stacked operation) along horizontal direction, do not have displacement so these catalyst layers can accurately be disposed, so that composite electrolyte membrane is clipped in the middle.The result, in keeping first folding process under the situation of the precision of stacked folded body position, can suppress the distortion of the mutual layout of anode catalyst layer and cathode catalyst layer, can prevent from when being assembled into membrane electrode assembly in the fuel cell to produce assembly failure, and the dispersion that can be suppressed at fuel battery performance during the generating.
In addition, since folding process in that anode catalyst layer and cathode catalyst layer are arranged such that a plurality of anode catalyst layers and a plurality of cathode catalyst layer carry out when alternately forming along the longitudinal direction, so can make a plurality of banded membrane electrode assemblies simultaneously.
Also can be included in behind the described hydrolyzing process described duplexer is folded into along described horizontal direction according to the method that is used to make membrane electrode assembly of third aspect present invention and make described anode catalyst layer and second folding process that on described longitudinal direction, faces with each other in abutting connection with the described cathode catalyst layer of described anode catalyst layer.
According to the present invention, form operation by carrying out second at the banded membrane electrode assembly that produces by above-mentioned manufacture method, can easily obtain not have the single fuel cell that displacement ground forms catalyst layer by a membrane electrode assembly, and need not pile up (stacked) a plurality of membrane electrode assemblies, if dividing plate is configured between the electrode layer of facing.
In addition, because a plurality of anode catalyst layers and a plurality of cathode catalyst layer alternately form along the longitudinal direction and therefore cathode catalyst layer must form in a longitudinal direction in abutting connection with anode catalyst layer, by carrying out second folding process, can form a plurality of anode catalyst layers, and form a plurality of cathode catalyst layers with unidirectional surface opposite with anode catalyst layer with unidirectional surface.As a result, can prevent under the assembly error of anode catalyst layer and cathode catalyst layer in the membrane electrode assembly reliably by the situation of the stacked a plurality of membrane electrode assemblies of typical technical process.
According to the method that is used to make fuel cell of fourth aspect present invention is the method that is used to make fuel cell of method that is used to make membrane electrode assembly that comprises according to the third aspect, and can comprise diffusion layer and dividing plate arrangement step, described diffusion layer and dividing plate arrangement step are disposing diffusion layer behind described second folding process on the surface of the surface of the described anode catalyst layer of described membrane electrode assembly and described cathode catalyst layer, and between described anode catalyst layer with described diffusion layer opposite each other and described cathode catalyst layer, dispose dividing plate, be formed with fuel gas channel and oxygen stream in the described dividing plate, make described fuel gas channel be positioned at described anode catalyst layer side, and described oxygen stream is positioned at described cathode catalyst layer side.
By the method that is used to make fuel cell according to above-mentioned aspect, dividing plate can be configured to behind second folding process to insert towards the flow circuits in a lateral direction of membrane electrode assembly, and can easily obtain single fuel cell.Like this, compare with the typical method that dividing plate is configured between a plurality of membrane electrode assemblies, the quantity of production stage can reduce.In addition, dividing plate can configuration in a continuous manner behind second folding process.Therefore, can be suppressed at sneaking into of pollutant in the process that obtains single fuel cell.
In addition, when configuration diffusion layer and dividing plate, it is preferred disposing the dividing plate that is formed with diffusion layer in its surface in membrane electrode assembly, because diffusion layer and dividing plate can be configured in the membrane electrode assembly simultaneously.But this method is unrestricted, but diffusion layer and dividing plate separate configuration, as long as diffusion layer and dividing plate are configurable in membrane electrode assembly and can produce fuel cell.
In addition, the configuration of catalyst layer can be undertaken by blowing catalyst with spraying, catalyst layer can also be configured on the end liner plate and in heating with add to depress tool using or apply mould catalyst layer is transferred on the dielectric substrate.Using under the situation of catalyst layer ionomer as precursor polymer, can advantageously make membrane electrode assembly, and not have ionomeric thermal degradation when in the follow-up dipping operation.More preferably, the electrolyte that is included in the catalyst layer is fluorine-containing electrolytical precursor.
In addition, can use that normally used gas diffusion layers is not particularly limited as diffusion layer in fuel cell.The example of this gas diffusion layers comprises as comprising carbon fiber plate and the porous, electrically conductive plate of conductive materials as the composition material of main component.For example, the conductive particle of carbon granule is bonded to described plate as binding material for can utilizing hydrophobic resin.In addition, except having the gas flow path that is formed on wherein, dividing plate also can suitably have such structure, and this structure is discharged the water that produces during generating electricity, and makes circulate coolant, so that be suppressed at the heating in the fuel cell during the generating.
Composite electrolyte membrane according to fifth aspect present invention has dielectric substrate at least and strengthens plate, described dielectric substrate comprises electrolyte, porous polymer material is impregnated with described electrolyte in described reinforcement plate, described composite electrolyte membrane comprises at least: add layer, in described interpolation layer, with hydrogen peroxide decomposes Cheng Shui and oxygen and suppress free radical inhibitors that hydroxy radical produces and in the water-keeping material at least one is added to described electrolyte; Form the described layer described reinforced layer that is clipped in the middle that add; With the lip-deep described dielectric substrate that is formed on each described reinforced layer.
Composite electrolyte membrane according to sixth aspect present invention has dielectric substrate and reinforced layer at least, described dielectric substrate comprises electrolyte, porous polymer material is impregnated with described electrolyte in described reinforced layer, and described composite electrolyte membrane comprises at least: as first dielectric substrate of described dielectric substrate; Form the interpolation layer that described first dielectric substrate is clipped in the middle, in described interpolation layer, with hydrogen peroxide decomposes Cheng Shui and oxygen and suppress free radical inhibitors that hydroxy radical produces and in the water-keeping material at least one is added to described electrolyte; Be formed on the described lip-deep described reinforced layer that adds layer; With as described dielectric substrate and be formed on lip-deep second dielectric substrate of described reinforced layer.
By composite electrolyte membrane according to above-mentioned aspect, be added with the interpolation layer that is selected from least a additive among free radical inhibitors and the water-keeping material by forming as mentioned above, can be suppressed at during the fuel cell power generation moving and flow losses of when water moves these materials.
Composite electrolyte membrane according to seventh aspect present invention comprises a pair of anode catalyst layer and cathode catalyst layer at least, described anode catalyst layer and cathode catalyst layer are configured on two surfaces of composite electrolyte membrane, so that described anode catalyst layer and described cathode catalyst layer are clipped in the middle described composite electrolyte membrane, in described composite electrolyte membrane, the reinforcement plate that comprises porous polymer material is impregnated with and comprises electrolytical electrolyte plate, wherein, described membrane electrode assembly is banded membrane electrode assembly, and a plurality of described anode catalyst layer and the alternately formation along the longitudinal direction on the surface of described membrane electrode assembly of a plurality of described cathode catalyst layer.
Composite electrolyte membrane according to eighth aspect present invention has a pair of anode catalyst layer and cathode catalyst layer at least, described anode catalyst layer and cathode catalyst layer are configured on two surfaces according to the composite electrolyte membrane of the 5th aspect, so that described composite electrolyte membrane is clipped in the middle, wherein, described membrane electrode assembly is banded membrane electrode assembly, and described anode catalyst layer and the alternately formation along the longitudinal direction on the surface of described membrane electrode assembly of described cathode catalyst layer.
Composite electrolyte membrane according to ninth aspect present invention has a pair of anode catalyst layer and cathode catalyst layer at least, described anode catalyst layer and cathode catalyst layer are configured on two surfaces according to the composite electrolyte membrane of the 6th aspect, so that described composite electrolyte membrane is clipped in the middle, wherein, described membrane electrode assembly is banded membrane electrode assembly, and described anode catalyst layer and the alternately formation along the longitudinal direction on the surface of described membrane electrode assembly of described cathode catalyst layer.
Membrane electrode assembly by above-mentioned aspect, because a plurality of anode catalyst layers and a plurality of cathode catalyst layer are formed on the surface of membrane electrode assembly along the longitudinal direction,, membrane electrode assembly make described anode catalyst layer and described cathode catalyst layer on described longitudinal direction face with each other in abutting connection with described anode catalyst layer so can being folded into along horizontal direction.Zhe Die membrane electrode assembly is formed with a plurality of anode catalyst layer and a plurality of cathode catalyst layers with unidirectional surface opposite with the direction of anode catalyst layer with unidirectional surface therein in the above described manner.
Can be folded into along horizontal direction according to the membrane electrode assembly of the 7th to the 9th aspect and to make described anode catalyst layer and described cathode catalyst layer on described longitudinal direction face with each other in abutting connection with described anode catalyst layer.
Membrane electrode assembly according to above-mentioned aspect has such structure, and this structure is formed with a plurality of anode catalyst layer and a plurality of cathode catalyst layers with unidirectional surface opposite with the direction of anode catalyst layer with unidirectional surface therein.Therefore, by configuration diffusion layer and dividing plate in the folded part of membrane electrode assembly, can easily make fuel cell and not have the correlation technique assembly failure of the membrane electrode assembly of existence usually.
Comprise membrane electrode assembly according to the 9th aspect according to the fuel cell of tenth aspect present invention, this fuel cell comprises: described membrane electrode assembly; Diffusion layer, described diffusion layer are configured on the surface of the surface of described anode catalyst layer of described membrane electrode assembly and described cathode catalyst layer; And dividing plate, at least be formed with fuel gas channel that is positioned at described anode catalyst layer side and the oxygen stream that is positioned at described cathode catalyst layer side in the described dividing plate, and described dividing plate is configured between the described anode catalyst layer and described cathode catalyst layer with described diffusion layer opposite each other.According to this aspect, can be by cutting off the fuel cell that obtains desired amt along the longitudinal direction folded portions (part of each single fuel cell of connection of dielectric film) of membrane electrode assembly.
According to the present invention, can obtain a kind of composite electrolyte membrane with stable dimensions precision, wherein the homogeneity of the electrolyte characteristic in the film improves.In addition, can obtain a kind of like this membrane electrode assembly, wherein anode catalyst layer and cathode catalyst layer are formed does not have displacement ground formation composite electrolyte membrane.In addition, can easily obtain the fuel cell of the desired amt of contamination-free.
Description of drawings
From can being more clearly visible above-mentioned and/or other purpose, feature and advantage of the present invention the description of a preferred embodiment with reference to the accompanying drawings, similar in the accompanying drawings Reference numeral is used to represent similar element, and wherein:
Fig. 1 is the schematic diagram of method that is used to make composite electrolyte membrane that first embodiment of the invention is shown;
Fig. 2 is the schematic diagram that is used to implement the manufacturing equipment of manufacture method shown in Figure 1;
Fig. 3 is the schematic diagram of method that is used to make composite electrolyte membrane that second embodiment of the invention is shown;
Fig. 4 is the schematic diagram of method that is used to make composite electrolyte membrane that third embodiment of the invention is shown;
Fig. 5 is the schematic diagram of method that is used to make composite electrolyte membrane that fourth embodiment of the invention is shown;
Fig. 6 is the schematic diagram that is used to implement the manufacturing equipment of manufacture method shown in Figure 5;
Fig. 7 is the schematic diagram of method that is used to make composite electrolyte membrane that fifth embodiment of the invention is shown;
Fig. 8 is the schematic diagram of method that is used to make composite electrolyte membrane that sixth embodiment of the invention is shown;
Fig. 9 is the schematic diagram of method that is used to make membrane electrode assembly that one embodiment of the invention is shown;
Figure 10 illustrates second of membrane electrode assembly shown in Figure 9 and folds;
Figure 11 illustrates the method that is used for making from membrane electrode assembly shown in Figure 10 fuel cell;
Figure 12 illustrates the method for fuel cell that is used for having from the fuel cell manufacturing by method manufacturing shown in Figure 11 the element cell of desired amt;
Figure 13 A is illustrated in the method that is used for making by casting films formation method composite electrolyte membrane according to the method that is used for making composite electrolyte membrane of correlation technique;
Figure 13 B is illustrated in the method that is used for forming on composite electrolyte membrane by transfering process catalyst layer according to the method that is used for making composite electrolyte membrane of correlation technique; And
Figure 14 is the schematic diagram that the example of the solid polymer type fuel battery (single battery) according to correlation technique is shown.
Embodiment
Below with reference to accompanying drawings specific embodiments of the invention are described.
Fig. 1 is the schematic diagram of method that is used to make composite electrolyte membrane (dielectric film) that first embodiment is shown, and Fig. 2 is the schematic diagram that is used to implement the manufacturing equipment of manufacture method shown in Figure 1.
As depicted in figs. 1 and 2, at first, prepare the plate (electrolyte plate) 11 that constitutes by banded electrolyte and, and carry out stacked operation by the band shape reinforcement plate 12 that constitutes for the polytetrafluoroethylene (PTFE) of porous polymer material.More specifically, in stacked operation, electrolyte plate 11 and strengthen plate 12 and be heated with stacked and produce duplexer 10A, wherein the electrolyte plate is as dielectric substrate 11a, and strengthens plate 12 as reinforced layer 12a.
Be used to make two stacked methods of plate to implement by pasting or flooding.More specifically, as shown in Figure 2, for example, by between a pair of roller 31a, 31b to electrolyte plate 11 with strengthen plate 12 and heat together and pressurize, the part of electrolyte plate can be impregnated in the surface of reinforcement plate 12.The temperature of the heating of carrying out in this operation is preferably in 100 to 280 ℃ scope.As a result, can make electrolyte plate 11 and reinforcement plate 12 integrated.Can use the electrolyte that dissolves to replace electrolyte plate 11.
Then, the duplexer 10A that produces in stacked operation is folded.More specifically, at the folding duplexer 10A of central portion, make the part of the front surface in reinforced layer 12a one side (reinforced layer surface) of duplexer 10A be positioned on another part of this front surface, produce duplexer 10B thus along the centre line L of duplexer 10A.
More specifically, as shown in Figure 2, protuberance that can be by having V-arrangement and recess and along roller 32a, the 32b of direction of transfer (MD direction) rotation of duplexer 10A at the folded duplexer 10A of the central folding in a lateral direction of duplexer 10A.Then, utilize duplexer 10A that roller 33a, 33b be deformed into the V-arrangement shape further to be folded into and make the part of reinforced layer 12a of duplexer 10A be positioned on another part, and by make the surface engagement of reinforced layer 12a with roller 33a, 33b heating and pressurization.The temperature of heating duplexer 10A is preferably in 100 to 280 ℃ scope in this operation.
Then, the duplexer 10B that produces in folding process turns over 90 ° by roller 34a, 34b, and duplexer 10B is impregnated.More specifically, duplexer 10B heating and pressurization are dissolved up to electrolyte, and with electrolyte-impregnated in reinforced layer 12a, to make duplexer 10C.
More specifically, as shown in Figure 2, the electrolyte of the lip-deep dielectric substrate 11a of duplexer 10B can be impregnated in the hole of porous reinforced layer 12a, and can utilize the heating and impression roller 35a, the 35b that rotate along the direction of transfer of duplexer 10B to obtain to be impregnated with electrolytical reinforced layer 12b.The temperature of heating duplexer 10B is preferably in 200 to 280 ℃ scope in this operation.
The duplexer 10C that produces in the dipping operation is hydrolyzed, can gives duplexer 10C with ion exchanging function, and can obtain composite electrolyte membrane 100A.As shown in Figure 2, behind hydrolyzing process, can make composite electrolyte membrane 100A drying, and can utilize the composite electrolyte membrane 100A of coiler device (not shown) coiling en plaque.
Thus obtained composite electrolyte membrane 100A is only formed by two plate manufacturings: electrolyte plate 11 and reinforcement plate 12.Therefore, the described plate of can easily arranging, and the quality of dielectric film is stablized.In addition, duplexer 10A can be folded and the electrolyte of an electrolyte plate 11 can be impregnated.As a result, the homogeneous electrolyte that constitutes same electrolyte plate 11 is configured on two surfaces of composite electrolyte membrane 100A, and the thickness of dielectric film is also stablized.Like this, can improve the homogeneity of electrolyte characteristic in the dielectric film, obtain high-precision dielectric film, and the performance of steady fuel battery.
In addition, folding process is carried out to a part that makes on the surface (reinforced layer surface) of reinforced layer 12a one side and is positioned on another part, and becomes the front surface of duplexer 10B on the surface of dielectric substrate 11a one side (bath surface).Therefore, in the dipping operation, dielectric substrate 11a is formed in the superficial layer on the thickness direction, and the position of reinforced layer 12a is stablized.As a result, in the fuel cell that is equipped with dielectric film 100A, the dispersion that water moves in the surface of dielectric film 100A during generating electricity is suppressed by the dielectric substrate 11a of superficial layer.In addition, can improve the adhesion of dielectric film 100A and catalyst layer (not shown), and fuel battery performance can be stablized.
In addition, making by manufacture method shown in Figure 2 under the situation of composite electrolyte membrane 100A, can be only by making two member engages carry out stacked operation, and the operation from stacked operation to hydrolyzing process can be embodied as continuous program.Therefore, can simplify working process, help quality control, and can boost productivity.
Fig. 3 illustrates second embodiment that is used to make the method for composite electrolyte membrane according to of the present invention.The difference of this embodiment and first embodiment shown in Figure 1 is to dispose catalyst layer 13a, 13b.Fig. 3 shows the operation before the catalyst layer that forms membrane electrode assembly (MEA) 50A.The manufacture method of second embodiment comprises above-mentioned stacked operation, folding process, dipping operation and hydrolyzing process, and these operations adopt identical Reference numeral and omit its detailed description.
As shown in Figure 3, in stacked operation, electrolyte plate 11 is engaged with stacked with strengthening plate 12, and produce the duplexer 10A that constitutes by dielectric substrate 11a and reinforced layer 12a.Then, after duplexer 10A has formed, anode catalyst layer 13a and cathode catalyst layer 13b are configured on the surface of dielectric substrate 11a, and produce the duplexer 10D that is formed with catalyst layer 13a, 13b on it.
More specifically, in the catalyst arrangement step, can dispose catalyst layer 13a, 13b by utilizing injector to blow catalyst, perhaps catalyst layer can be configured on the end liner plate, can catalyst layer be transferred on the dielectric substrate by utilizing instrument or the heating of coating mould and pressurization then.Utilize the catalyst layer ionomer to be to prevent the ionomer thermal degradation when of ionomer in follow-up dipping operation as the advantage of precursor polymer.
Then, in folding process, duplexer 10D is folded into makes anode catalyst layer 13a be configured on the surface of duplexer 10E, and cathode catalyst layer 13b is configured on another surface of duplexer 10E.In follow-up dipping operation, make electrolyte-impregnated in reinforced layer 12a, and produce duplexer 10F.In hydrolyzing process, the electrolyte of giving duplexer 10F is with ion exchanging function, and can obtain to comprise the membrane electrode assembly 50A of composite electrolyte membrane 100B.
Make the method for composite electrolyte membrane 100B and membrane electrode assembly 50A by above-mentioned being used to, anode catalyst layer 13a and cathode catalyst layer 13b are formed in the same surface that has formed dielectric substrate 11a of the duplexer 10A that obtains in stacked operation.Therefore, catalyst layer 13a, 13b can accurately locate.As a result, under the situation that can keep the precision of the folding position of duplexer 10D in the folding process, can suppress the displacement of anode catalyst layer 13a and cathode catalyst layer 13b.
By in fuel cell, adopting the membrane electrode assembly 50A comprise the dielectric film 100B that makes in the above described manner, can prevent from when film being assembled into the element cell of fuel cell, to produce assembly failure, and the dispersion that suppresses fuel battery performance during the generating.Especially, since the dielectric substrate 11a of superficial layer with good stable formation, so can improve the adhesion of dielectric substrate 11a and catalyst layer 13a, 13b.
Fig. 4 illustrates the 3rd embodiment that is used to make the method for composite electrolyte membrane according to of the present invention.The difference of the manufacture method of the 3rd embodiment and first embodiment shown in Figure 1 is folding direction difference in folding process.The manufacture method of the 3rd embodiment comprises above-mentioned stacked operation, dipping operation and hydrolyzing process, and these operations adopt identical Reference numeral and omit its detailed description.
As shown in Figure 4, in stacked operation, electrolyte plate 11 is engaged with stacked with strengthening plate 12, and produce the duplexer 10A that constitutes by dielectric substrate 11a and reinforced layer 12a.Then, the duplexer 10A that produces is carried out folding process in stacked operation.More specifically, duplexer 10A is folded at central portion along the centre line L of duplexer 10A and makes the part of the front surface in dielectric substrate 11a one side (dielectric substrate surface) of duplexer 10A be positioned on another part of this front surface, produce duplexer 10G thus.
Then, in the dipping operation, make electrolyte-impregnated in reinforced layer 12a and produce duplexer 10H.In hydrolyzing process, the electrolyte of giving duplexer 10H is with ion exchanging function, and can obtain composite electrolyte membrane 100C.
Make the method for composite electrolyte membrane 100C by above-mentioned being used to, be folded in the duplexer 10A operation below and make the part on surface of dielectric substrate 11a be positioned on another part, and reinforced layer 12a becomes the surface of dielectric film.Therefore, dielectric substrate 11b is formed on the center on the thickness direction of composite electrolyte membrane 100C, and it is configurable in the surface layer part near the surface on the thickness direction of dielectric film to be impregnated with electrolytical reinforced layer 12b.As a result, can improve the croop property of dielectric film 100C in the operation of fuel cells process.
Fig. 5 illustrates the 4th embodiment that is used to make the method for composite electrolyte membrane according to of the present invention.Fig. 6 is the schematic diagram that is used to implement the manufacturing equipment of manufacture method shown in Figure 5.The difference of the manufacture method of the 4th embodiment and first embodiment is, disposes water-keeping material after stacked operation.The manufacture method of the 4th embodiment comprises above-mentioned stacked operation, dipping operation and hydrolyzing process, and these operations adopt identical Reference numeral and omit its detailed description.
As shown in Figure 5, in stacked operation, electrolyte plate 11 is engaged with stacked with strengthening plate 12, and produce the duplexer 10A that constitutes by dielectric substrate 11a and reinforced layer 12a.In water-keeping material arrangement step subsequently, after duplexer 10A has formed, water-keeping material 14 is configured on the surface of reinforced layer 12a.More specifically, as shown in Figure 6, apply or spray or water-keeping material 14 is coated on the surface of reinforced layer 12a, make water-keeping material dispose thereon equably by sputter by coating processes such as pattern.Like this, because water-keeping material is sandwiched between the reinforced layer in following folding process, be preferred so water-keeping material adheres to prevent that it breaks away from during folding securely.When the material that uses fine-powdered during, because in the middle of it was sandwiched in, so as mentioned above, during folding, the particle size of water-keeping material was preferred greater than the diameter of the hole that forms in strengthening plate as water-keeping material.
Then, in folding process, water-keeping material 14 is sandwiched between the reinforced layer 12a, thereby the part on the surface of reinforced layer side is positioned on another part, and duplexer 10I is folded, and produces duplexer 10J.In the dipping operation, the electrolyte-impregnated that makes dielectric substrate 11a and produces duplexer 10K in water-keeping material 14 and reinforced layer 12a.In hydrolyzing process, the electrolyte hydrolysis that makes duplexer 10K to be giving its ion exchanging function, and obtains composite electrolyte membrane 100D.
Like this, as shown in Figure 5, can obtain composite electrolyte membrane 100D, it comprises that at least wherein water-keeping material 14 is added to an electrolytical interpolation layer 14b, forms and will add the lip-deep dielectric substrate 11a that layer 14b is clipped in the middle and is impregnated with electrolytical reinforced layer 12b and is formed on reinforced layer 12b as additive, and aforementioned layers is piled up along the thickness direction of film.
In the composite electrolyte membrane 100D that makes in the above described manner, in the middle of water-keeping material 14 is sandwiched in as additive during folding, water-keeping material can be fixed on the center on the thickness direction of dielectric film 100D thus.As a result, can prevent that water-keeping material 14 from moving under the effect that water moves, and can be suppressed at the flow losses during the fuel cell power generation.As a result, can guarantee stable proton-conducting.
Fig. 7 illustrates the 5th embodiment that is used to make the method for composite electrolyte membrane according to of the present invention.The difference of the manufacture method of the 5th embodiment and the 4th embodiment is, has catalyst layer in stacked operation.The manufacture method of the 5th embodiment comprises above-mentioned dipping operation, folding process and hydrolyzing process, and these operations adopt identical Reference numeral and omit its detailed description.
As shown in Figure 7, in stacked operation, electrolyte plate 11 is engaged with stacked with reinforcement plate 12.Simultaneously, anode catalyst layer 13a and the cathode catalyst layer 13b that is configured on the end liner plate 81 is configured and produces duplexer 10L from the surface that is positioned at electrolyte plate 11 opposite sides.
Then, can obtain to comprise the membrane electrode assembly 50B of composite electrolyte membrane 100E by water-keeping material arrangement step, folding process, dipping operation and hydrolyzing process.In this case, end liner plate 81 is removed from duplexer 10K after the operation at dipping, the electrolyte of giving duplexer 10K behind hydrolyzing process is with ion exchanging function, and can obtain to comprise the membrane electrode assembly 50B of composite electrolyte membrane 100E.
Like this, similar with second embodiment, can suppress the displacement of anode catalyst layer 13a and cathode catalyst layer 13b, can prevent the assembly failure of the element cell of fuel cell, and the dispersion of fuel battery performance during can suppressing to generate electricity.In the composite electrolyte membrane 100E that makes in the above described manner, water-keeping material is fixed on the center on the thickness direction of dielectric film 100E.As a result, can prevent that water-keeping material 14 from moving under the effect that water moves, and can suppress the flow losses during the fuel cell power generation.As a result, can guarantee stable proton-conducting.
Fig. 8 illustrates the 6th embodiment that is used to make the method for composite electrolyte membrane according to of the present invention.The difference of the manufacture method of the 6th embodiment and the 4th embodiment is, disposes water-keeping material before stacked operation.The manufacture method of the 6th embodiment comprises above-mentioned dipping operation, folding process and hydrolyzing process, and these operations adopt identical Reference numeral and omit its detailed description.
As shown in Figure 8, in stacked operation, at first, configuration water-keeping material 14.Collocation method is same as the previously described embodiments.Then, in stacked operation, electrolyte plate 11 and reinforcement plate 12 are arranged such that water-keeping material 14 is configured between electrolyte plate 11 and the reinforcement plate 12.Owing to engage is to flood from a side of strengthening plate 12 by the electrolyte that makes electrolyte plate 11 to carry out, and water-keeping material 14 is added to electrolytical interpolation layer 14b as additive so form wherein after engaging in duplexer 10P between dielectric substrate 11a and reinforced layer 12a.Then, obtain composite electrolyte membrane 100F by folding process, dipping operation and hydrolyzing process.
Like this, as shown in Figure 8, can obtain composite electrolyte membrane 100F, it comprises the first electrolyte layers 11a as dielectric substrate at least, wherein water-keeping material is added to electrolyte and the interpolation layer 14b that the first dielectric substrate 11a is clipped in the middle, forms and will add the lip-deep second dielectric substrate 11b that layer 14b is clipped in the middle and is impregnated with electrolytical reinforced layer 12b and is formed on reinforced layer 12b as additive, and aforementioned layers is piled up along the thickness direction of film.
In the composite electrolyte membrane 100F that obtains in the above described manner, duplexer 10A is folded into and makes the part on surface of dielectric substrate 11a be positioned on another part, and reinforced layer 12a becomes the surface of dielectric film.Therefore, dielectric substrate 11a is formed on the center on the thickness direction of composite electrolyte membrane 100F, be impregnated with electrolytical reinforced layer 12b and be configured in the surface layer part near the surface on the thickness direction of dielectric film, and it is in its vicinity configurable to add layer.As a result, not only can improve the croop property of dielectric film 100F in the operation of fuel cells process, and can further improve the water holding capacity of dielectric film 100F.
Fig. 9 is the schematic diagram of method that is used to make membrane electrode assembly that one embodiment of the invention is shown, and this figure is used to illustrate second folding process that is applied to membrane electrode assembly shown in Figure 9.As shown in Figure 9, prepare the plate (electrolyte plate) 11 that constitutes by banded electrolyte and by the band shape reinforcement plate 12 that constitutes for the polytetrafluoroethylene (PTFE) of porous polymer material.Then, in stacked operation, to electrolyte plate 11 with strengthen that plate 12 heats, pressurization and stacked, and produce duplexer 10A, wherein the electrolyte plate is as dielectric substrate 11a, and strengthens plate 12 as reinforced layer 12a.
Then, after duplexer 10A has formed, anode catalyst layer 13a and cathode catalyst layer 13b are configured on the surface of dielectric substrate 11a, and produce duplexer 10D with formation catalyst layer 13a, 13b thereon.
More specifically, in the catalyst arrangement step, formed the back at duplexer 10A and formed two row anode catalyst layer 13a and cathode catalyst layer 13b at the horizontal direction S of the surperficial upper edge duplexer 10A of dielectric substrate 11a.In addition, anode catalyst layer 13a and cathode catalyst layer 13b (direction of transfer) L also along the longitudinal direction are arranged such that (in other words a plurality of anode catalyst layer 13a and a plurality of cathode catalyst layer 13b alternately form, make two row anode catalyst layer 13a and cathode catalyst layer 13b form diagonally), and by pressurization and being equal to or less than heating fixes these layers under 170 ℃ the temperature.
With with second embodiment in identical mode, configuration to catalyst layer 13a, 13b can blow, carry out by employing end liner plate or by utilizing instrument or coating mould to shift by utilizing injector, and collocation method is not particularly limited, as long as a plurality of catalyst layer 13a, 13b can be configured on the expectation surface of dielectric substrate 11a with above-mentioned layout.
Then, in folding process, with with above-mentioned several embodiment in identical mode at the central portion of the duplexer 10D folding duplexer 10D of L along the longitudinal direction, make anode catalyst layer 13a be configured on the surface of duplexer 10E, and cathode catalyst layer 13b is configured in duplexer 10E another surperficial upward (anode catalyst layer 13a and cathode catalyst layer 13b are configured to duplexer 10E (composite electrolyte membrane) is clipped in the middle).Then, in the dipping operation, make electrolyte-impregnated in reinforced layer 12a, and produce duplexer 10F.In hydrolyzing process, the electrolyte of giving duplexer 10F is with ion exchanging function, and can obtain to comprise the membrane electrode assembly 50C of composite electrolyte membrane 100B.
Because anode catalyst layer 13a and cathode catalyst layer 13b are formed in the same surface (having formed the dielectric substrate 11a of duplexer in this surface after stacked operation) along horizontal direction S,, these catalyst layers 13a, 13b accurately be not configured to composite electrolyte membrane 100B is clipped in the middle so can having displacement ground.The result, in keeping folding process under the situation of the folding position precision of duplexer 10E, can suppress the displacement of the mutual layout of anode catalyst layer 13a and cathode catalyst layer 13b, can prevent from the following assembling of fuel cell 1, to produce assembly failure, and the performance that can be suppressed at during fuel cell 1 generating is disperseed.
So, membrane electrode assembly 50C is carried out second folds.More specifically, as shown in figure 10, in second folding process that behind hydrolyzing process, carries out, along horizontal direction S (along the C1-C1 among the figure, C2-C2 ...) folded membrane electrode assemblie 50C, make anode catalyst layer 13a with on longitudinal direction L the cathode catalyst layer 13b in abutting connection with anode catalyst layer 13a face with each other.
This folding can for example have the Foldable tool of the thickness that makes that following dividing plate can import, push the end of Foldable tool and fold along horizontal direction S and carry out by preparation, but method for folding is not particularly limited, as long as folding can carrying out to making that catalyst layer 13a, the 13b of adjacency faces with each other on longitudinal direction L.
Under the situation that second folding process carries out in the above described manner, if following dividing plate etc. is configured between these relative catalyst layer 13a, 13b, then can easily produce the single battery of the fuel cell that does not wherein have displacement ground formation catalyst layer 13a, 13b, and need not to make a plurality of membrane electrode assemblies stacked from a continuous membrane electrode assembly 50C.
In addition, because a plurality of anode catalyst layer 13a and a plurality of cathode catalyst layer 13b L along the longitudinal direction alternately form, and cathode catalyst layer 13b always is formed on longitudinal direction L in the layer of anode catalyst layer 13a, so second folding process forms a plurality of anode catalyst layer 13a with unidirectional surface (surface that contacts with diffusion layer 15), and form a plurality of cathode catalyst layer 13b with the unidirectional surface opposite (surface that contacts with diffusion layer 15) with aforementioned direction.As a result, can prevent the anode catalyst layer of issuable membrane electrode assembly with the stacked a plurality of membrane electrode assembly of usual way time the and the assembly error of cathode catalyst layer.
To describe membrane electrode assembly that a kind of utilization makes in the above described manner below and make the method for fuel cell.Figure 11 illustrates the method that is used for making from membrane electrode assembly 50C shown in Figure 10 fuel cell.
In the present embodiment, configuration diffusion layer 15 on anode catalyst layer 13a that the method that is used to make fuel cell is included in behind second folding process at membrane electrode assembly 50C and the surface of cathode catalyst layer 13b, have the operation of configuration dividing plate 60 between the anode catalyst layer 13a of diffusion layer opposite each other and the cathode catalyst layer 13b then, be formed with fuel gas channel 61 and oxygen stream 62 in the described dividing plate 60.
More specifically, prepare to be formed with therein the dividing plate 60 of fuel gas channel 61 and oxygen stream 62.Then, on two surfaces of dividing plate 60, dispose the lip-deep diffusion layer 15 that is used to be configured in anode catalyst layer 13a and cathode catalyst layer 13b.Then, can diaphragm seal electrode assemblie 50C and member 63 adhered thereto be attached to two ends on the longitudinal direction of dividing plate 60.
To have diffusion layer 15 and be attached with of the folded part insertion of the dividing plate 60 of sealant 63, and make diffusion layer 15 be positioned on the anode catalyst layer 13a and cathode catalyst layer 13b of membrane electrode assembly 50C towards membrane electrode assembly 50C.The result, form stacked electrode on the upper surface of relative catalyst layer 13a, 13b by diffusion layer 15 and dividing plate 60 being clipped in membrane electrode assembly 50C, and follow-up heating and produce along the pressurization of thickness direction and wherein to pile up the fuel cell 1 that a plurality of element cells are arranged.
Pass through said method, compare with the usual way of configuration dividing plate between a plurality of membrane electrode assemblies, can reduce the quantity of operation work step, and owing to can behind second folding process, dispose dividing plate in a continuous manner, sneak into pollutant so can be suppressed in the process of the element cell that forms fuel cell 1.
Figure 12 illustrates the method for fuel cell that is used for comprising from the fuel cell manufacturing by manufacture method manufacturing shown in Figure 11 the element cell of desired amt.As shown in figure 12, in the fuel cell of being made by manufacture method shown in Figure 11 1, the fuel cell that is made of a plurality of element cells connects by dielectric film under state of insulation.Therefore, as shown in figure 11, can be by the dielectric film that cuts off the coupling part obtain fuel cell 1A, the 1b that the element cell by essential quantity constitutes down, and the assembly error aspect the mutual layout that is orientated (orientation on anode/cathode surface) that during battery stack, produces in assembled state (element cell) from the plurality of units battery to hundreds of.
Described according to the embodiment of composite electrolyte membrane of the present invention, membrane electrode assembly and fuel cell hereinbefore and be used to make their method, but, the invention is not restricted to these embodiment, but can under the situation that does not deviate from the essence of in claims, describing of the present invention, make various design variant.
For example, in the 4th to the 6th embodiment, use water-keeping material as additive, but the free radical inhibitors that also can use the oxide by transition metal such as cerium to constitute is with the hydrogen peroxide decomposes Cheng Shui and oxygen that will produce as accessory substance during fuel cell power generation and the generation that suppresses hydroxy radical.
In addition, in the composite electrolyte membrane of in first to the 6th embodiment, making, can be with excisions such as cutters as the folded end of the folding surplus that in folding process, forms.
In second to the 5th embodiment, catalyst layer is additionally disposed, but obviously, can be by additionally disposing diffusion layer shown in Figure 14 at catalyst layer and dividing plate obtains fuel cell.
In addition, in the embodiment shown in fig. 11, when configuration diffusion layer and dividing plate, have be formed on its lip-deep diffusion layer dividing plate by being configured in the membrane electrode assembly in the folded part that is inserted into membrane electrode assembly, but this method is unrestricted, but diffusion layer and dividing plate be separate configuration also, as long as diffusion layer and dividing plate are configurable in membrane electrode assembly and can produce fuel cell.In addition, in the present embodiment, after stacked operation, dispose catalyst layer, but anode catalyst layer and cathode catalyst layer also can further be disposed on the diffusion layer that is configured on the dividing plate, and need not catalyst layer is configured on the dielectric film, as long as can accurately dispose anode catalyst layer and cathode catalyst layer.
In addition, in the embodiment shown in Fig. 9 to 12, for example the additive for water-loss reducer and free radical inhibitors is not configured in the composite electrolyte membrane, but, for example be that the additive of water-loss reducer and free radical inhibitors is configurable in composite electrolyte membrane for the method for in the 4th to the 6th embodiment shown in Fig. 5,7 and 8, describing.
Although described the present invention with reference to exemplary embodiment of the present invention, should be appreciated that to the invention is not restricted to described exemplary embodiment or configuration.On the contrary, the invention is intended to contain various modification and equivalent arrangements.In addition, though the various key elements that show exemplary embodiment with various combinations and configuration as example comprise other combination more, still less or only single key element and configuration also within the spirit and scope of the present invention.
Claims (19)
1. method that is used to make composite electrolyte membrane comprises:
Duplexer be folded into make the part on surface of described duplexer be positioned at first folding process on this surperficial another part, described duplexer be by make as comprising of dielectric substrate electrolytical electrolyte plate with integrated acquisition of stiffener lamella superimposition that comprises porous polymer material as reinforced layer;
The dipping operation of the described electrolyte-impregnated that makes the described duplexer that is folded in the described reinforced layer; With
Make the hydrolyzing process of the described electrolyte hydrolysis of flooding in the described duplexer.
2. the method that is used to make composite electrolyte membrane according to claim 1 also comprises the stacked operation that forms duplexer by heating and stacked described electrolyte plate and described reinforcement plate.
3. the method that is used to make composite electrolyte membrane according to claim 1 and 2, wherein, in described dipping operation, the described duplexer that is folded of heating is up to described electrolyte dissolution, and makes described electrolyte-impregnated in described reinforced layer.
4. according to each described method that is used to make composite electrolyte membrane in the claim 1 to 3, wherein, in described first folding process, described duplexer is folded into a part that makes in the described duplexer on the surface of described dielectric substrate side is positioned on this surperficial another part.
5. according to each described method that is used to make composite electrolyte membrane in the claim 1 to 3, wherein, in described first folding process, described duplexer is folded into a part that makes in the described duplexer on the surface of described reinforced layer side is positioned on this surperficial another part.
6. the method that is used to make composite electrolyte membrane according to claim 5, wherein, in described stacked operation, after described duplexer had formed, configuration was with hydrogen peroxide decomposes Cheng Shui and oxygen and suppress free radical inhibitors that hydroxy radical produces and in the water-keeping material at least one on the surface of described reinforced layer.
7. according to each described method that is used to make composite electrolyte membrane in the claim 1 to 5, wherein, in described stacked operation, configuration is with hydrogen peroxide decomposes Cheng Shui and oxygen and suppress free radical inhibitors that hydroxy radical produces and in the water-keeping material at least one between described electrolyte plate and described reinforcement plate.
8. a method that is used to make membrane electrode assembly comprises according to each described method that is used to make composite electrolyte membrane in the claim 5 to 7, it is characterized in that:
In described stacked operation, after described duplexer has formed, configuration anode catalyst layer and cathode catalyst layer on the surface of described dielectric substrate; And
In described first folding process, described duplexer is folded into makes described anode catalyst layer be configured on the surface of described duplexer, and described cathode catalyst layer is configured on another surface of described duplexer.
9. a method that is used to make membrane electrode assembly comprises according to each described method that is used to make composite electrolyte membrane in the claim 5 to 7, it is characterized in that:
In described stacked operation, form banded duplexer, and after described duplexer had formed, configuration anode catalyst layer and cathode catalyst layer on the surface of described dielectric substrate made described anode catalyst layer and described cathode catalyst layer form along the horizontal direction of described duplexer; And
In described first folding process, described duplexer is folded into along the longitudinal direction makes described anode catalyst layer be configured on the surface of described duplexer, and described cathode catalyst layer is configured on another surface of described duplexer.
10. the method that is used to make membrane electrode assembly according to claim 9, wherein, in described stacked operation, described anode catalyst layer and described cathode catalyst layer are arranged such that a plurality of described anode catalyst layers and a plurality of described cathode catalyst layer alternately form along described longitudinal direction.
11. the method that is used to make membrane electrode assembly according to claim 10, it is characterized in that, also be included in behind the described hydrolyzing process described duplexer is folded into along described horizontal direction and make described anode catalyst layer and second folding process that on described longitudinal direction, faces with each other in abutting connection with the described cathode catalyst layer of described anode catalyst layer.
12. method that is used to make fuel cell, comprise the method that is used to make membrane electrode assembly according to claim 11, it is characterized in that also comprising diffusion layer and dividing plate arrangement step, described diffusion layer and dividing plate arrangement step are disposing diffusion layer behind described second folding process on the surface of the surface of the described anode catalyst layer of described membrane electrode assembly and described cathode catalyst layer, and between described anode catalyst layer with described diffusion layer opposite each other and described cathode catalyst layer, dispose dividing plate, be formed with fuel gas channel and oxygen stream in the described dividing plate, make described fuel gas channel be positioned at described anode catalyst layer side, and described oxygen stream is positioned at described cathode catalyst layer side.
13. a composite electrolyte membrane that has dielectric substrate and reinforced layer at least, described dielectric substrate comprises electrolyte, and porous polymer material is impregnated with described electrolyte in described reinforced layer,
Described composite electrolyte membrane is characterised in that and comprises:
Add layer, in described interpolations layer, with hydrogen peroxide decomposes Cheng Shui and oxygen and suppress the free radical inhibitors of hydroxy radical generation and in the water-keeping material at least one is added to described electrolyte;
Form the described layer described reinforced layer that is clipped in the middle that add; With
Be formed on the lip-deep described dielectric substrate of each described reinforced layer.
14. a composite electrolyte membrane that has dielectric substrate and reinforced layer at least, described dielectric substrate comprises electrolyte, and porous polymer material is impregnated with described electrolyte in described reinforced layer,
Described composite electrolyte membrane is characterised in that and comprises:
First dielectric substrate as described dielectric substrate;
Form the interpolation layer that described first dielectric substrate is clipped in the middle, in described interpolation layer, with hydrogen peroxide decomposes Cheng Shui and oxygen and suppress free radical inhibitors that hydroxy radical produces and in the water-keeping material at least one is added to described electrolyte;
Be formed on the described lip-deep described reinforced layer that adds layer; With
As described dielectric substrate and be formed on lip-deep second dielectric substrate of described reinforced layer.
15. membrane electrode assembly, at least have a pair of anode catalyst layer and cathode catalyst layer, described anode catalyst layer and cathode catalyst layer are configured on two surfaces of composite electrolyte membrane, so that described anode catalyst layer and described cathode catalyst layer are clipped in the middle described composite electrolyte membrane, in described composite electrolyte membrane, the reinforcement plate that comprises porous polymer material is impregnated with and comprises electrolytical electrolyte plate
Described membrane electrode assembly is characterised in that
Described membrane electrode assembly is banded membrane electrode assembly, and described anode catalyst layer and the alternately formation along the longitudinal direction on the surface of described membrane electrode assembly of described cathode catalyst layer.
16. membrane electrode assembly, at least comprise a pair of anode catalyst layer and cathode catalyst layer, described anode catalyst layer and cathode catalyst layer are configured on two surfaces of composite electrolyte membrane according to claim 13, so that described composite electrolyte membrane is clipped in the middle, described membrane electrode assembly is characterised in that
Described membrane electrode assembly is banded membrane electrode assembly, and described anode catalyst layer and the alternately formation along the longitudinal direction on the surface of described membrane electrode assembly of described cathode catalyst layer.
17. membrane electrode assembly, at least comprise a pair of anode catalyst layer and cathode catalyst layer, described anode catalyst layer and cathode catalyst layer are configured on two surfaces of composite electrolyte membrane according to claim 14, so that described composite electrolyte membrane is clipped in the middle, described membrane electrode assembly is characterised in that
Described membrane electrode assembly is banded membrane electrode assembly, and described anode catalyst layer and the alternately formation along the longitudinal direction on the surface of described membrane electrode assembly of described cathode catalyst layer.
18. according to each described membrane electrode assembly in the claim 15 to 17, wherein, described membrane electrode assembly is folded into along horizontal direction and makes described anode catalyst layer and the described cathode catalyst layer in abutting connection with described anode catalyst layer on described longitudinal direction face with each other.
19. a fuel cell that comprises membrane electrode assembly according to claim 17 is characterized in that comprising:
Described membrane electrode assembly;
Diffusion layer, described diffusion layer are configured on the surface of the surface of described anode catalyst layer of described membrane electrode assembly and described cathode catalyst layer; With
Dividing plate, at least be formed with fuel gas channel that is positioned at described anode catalyst layer side and the oxygen stream that is positioned at described cathode catalyst layer side in the described dividing plate, and described dividing plate is configured between the described anode catalyst layer and described cathode catalyst layer with described diffusion layer opposite each other.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| JP304748/2007 | 2007-11-26 | ||
| JP2007304748 | 2007-11-26 | ||
| JP079471/2008 | 2008-03-26 | ||
| JP2008079471A JP4600500B2 (en) | 2007-11-26 | 2008-03-26 | Manufacturing method of fuel cell |
| PCT/IB2008/003027 WO2009068949A2 (en) | 2007-11-26 | 2008-11-11 | Composite electrolyte membrane, membrane-electrode assembly, fuel cell, and methods for manufacturing same |
Publications (2)
| Publication Number | Publication Date |
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| CN101874322A true CN101874322A (en) | 2010-10-27 |
| CN101874322B CN101874322B (en) | 2013-08-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008801178470A Expired - Fee Related CN101874322B (en) | 2007-11-26 | 2008-11-11 | Composite electrolyte membrane, membrane-electrode assembly, fuel cell, and methods for manufacturing same |
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| JP (1) | JP4600500B2 (en) |
| CN (1) | CN101874322B (en) |
| DE (1) | DE112008003166B8 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109494389A (en) * | 2017-09-13 | 2019-03-19 | 丰田自动车株式会社 | The method for manufacturing membrane electrode assembly |
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|---|---|---|---|---|
| JP5423595B2 (en) * | 2010-06-23 | 2014-02-19 | トヨタ自動車株式会社 | Membrane electrode diffusion layer assembly and manufacturing method thereof |
| JP5429137B2 (en) | 2010-11-04 | 2014-02-26 | トヨタ自動車株式会社 | Fuel cell and fuel cell manufacturing method |
| JP2013073856A (en) * | 2011-09-28 | 2013-04-22 | Sekisui Chem Co Ltd | Manufacturing method of electric module and electric module |
| WO2014027441A1 (en) * | 2012-08-14 | 2014-02-20 | トヨタ自動車株式会社 | Electrolyte membrane for fuel cells and method for producing same |
| JP6090122B2 (en) * | 2013-11-12 | 2017-03-08 | トヨタ自動車株式会社 | Method for manufacturing electrolyte membrane structure |
| JP6451489B2 (en) * | 2015-05-14 | 2019-01-16 | トヨタ自動車株式会社 | Method for producing reinforced electrolyte membrane |
| JP2017045707A (en) * | 2015-08-25 | 2017-03-02 | トヨタ自動車株式会社 | Production method for reinforced electrolyte membrane |
| CN106602082B (en) * | 2016-12-27 | 2023-11-28 | 南京大学昆山创新研究院 | Method and device for preparing fuel cell membrane electrode roller-to-roller |
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| JP3271801B2 (en) * | 1992-09-22 | 2002-04-08 | 田中貴金属工業株式会社 | Polymer solid electrolyte fuel cell, humidifying method of the fuel cell, and manufacturing method |
| JP3498321B2 (en) * | 1992-09-25 | 2004-02-16 | 田中貴金属工業株式会社 | Polymer solid oxide fuel cell |
| JPH08259710A (en) * | 1995-03-28 | 1996-10-08 | Sumitomo Electric Ind Ltd | Ion-exchange membrane |
| JP3925764B2 (en) * | 1999-10-19 | 2007-06-06 | 株式会社豊田中央研究所 | High durability solid polymer electrolyte |
| EP1139472B1 (en) * | 2000-03-31 | 2006-07-05 | Asahi Glass Company Ltd. | Electrolyte membrane for solid polymer type fuel cell and producing method thereof |
| JP2003003078A (en) * | 2000-09-19 | 2003-01-08 | Nisshinbo Ind Inc | Ion-conductive composition, gel elecrolyte, and non- aqueous electrolytic cell and electric double layer capacitor |
| JP3891820B2 (en) * | 2001-10-29 | 2007-03-14 | 株式会社トクヤマ | Ion exchange resin membrane |
| JP2003331860A (en) * | 2002-05-16 | 2003-11-21 | Nec Corp | Unit cell structure, fuel cell, and its manufacturing method |
| JP4538683B2 (en) * | 2002-11-08 | 2010-09-08 | 大日本印刷株式会社 | Catalyst layer forming sheet for fuel cell, method for producing the sheet, and method for producing catalyst layer-electrolyte membrane laminate |
| JP2006049002A (en) * | 2004-08-02 | 2006-02-16 | Toyota Motor Corp | Manufacturing method of solid polyelectrolyte, solid polyelectrolyte film, and fuel cell |
| JP4967226B2 (en) * | 2004-11-17 | 2012-07-04 | トヨタ自動車株式会社 | Membrane-electrode assembly manufacturing method, membrane-electrode assembly, and fuel cell |
| JP2007026915A (en) * | 2005-07-19 | 2007-02-01 | Dainippon Printing Co Ltd | Manufacturing method of catalyst layer-electrolyte membrane assembly of polymer electrolyte fuel cell, and catalyst layer-electrolyte membrane assembly |
| JP2007250265A (en) * | 2006-03-14 | 2007-09-27 | Toyota Motor Corp | Reinforced type electrolyte film for fuel cell, its manufacturing method, membrane-electrode assembly for fuel cell, and solid polymer fuel cell equipped with it |
| JP5023570B2 (en) * | 2006-06-21 | 2012-09-12 | トヨタ自動車株式会社 | Reinforcing electrolyte membrane and method for producing membrane electrode assembly |
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2008
- 2008-03-26 JP JP2008079471A patent/JP4600500B2/en not_active Expired - Fee Related
- 2008-11-11 CN CN2008801178470A patent/CN101874322B/en not_active Expired - Fee Related
- 2008-11-11 DE DE112008003166.5T patent/DE112008003166B8/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109494389A (en) * | 2017-09-13 | 2019-03-19 | 丰田自动车株式会社 | The method for manufacturing membrane electrode assembly |
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| Publication number | Publication date |
|---|---|
| JP2009152166A (en) | 2009-07-09 |
| DE112008003166T5 (en) | 2010-10-14 |
| DE112008003166B8 (en) | 2014-04-03 |
| JP4600500B2 (en) | 2010-12-15 |
| DE112008003166B4 (en) | 2014-01-09 |
| CN101874322B (en) | 2013-08-28 |
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