CN1703793A - Method of manufacturing for electrolyte membrane electrode joint body for fuel cell - Google Patents
Method of manufacturing for electrolyte membrane electrode joint body for fuel cell Download PDFInfo
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- CN1703793A CN1703793A CNA028007077A CN02800707A CN1703793A CN 1703793 A CN1703793 A CN 1703793A CN A028007077 A CNA028007077 A CN A028007077A CN 02800707 A CN02800707 A CN 02800707A CN 1703793 A CN1703793 A CN 1703793A
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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
Abstract
A method for producing an electrolyte membrane electrode assembly for a fuel cell according to this invention comprises the steps of: laminating a hydrogen-ion conductive polymer membrane on one face of a first shape-retaining film; forming a first catalyst layer on the hydrogen-ion conductive polymer membrane; joining a shape-retaining member to the first catalyst layer side of the hydrogen-ion conductive polymer membrane; removing the first shape-retaining film from the hydrogen-ion conductive polymer membrane; and forming a second catalyst layer on a face of the hydrogen-ion conductive polymer membrane exposed by the removal, so that the hydrogen-ion conductive polymer membrane and the catalyst layers are not damaged even when a thin hydrogen-ion conductive polymer membrane is used.
Description
Technical field
The manufacture method of the electrolyte membrane electrode joint body that the present invention relates in fuel cell, use.
Background technology
The thickness of the proton conducting polymer film that uses in existing fuel cell is extremely thin, therefore, directly form very difficulty of catalyst layer on proton conducting polymer film.Say that more specifically the thickness of existing proton conducting polymer film is generally about 20 μ m～50 μ m, and the mechanical strength of film itself is also not enough, therefore be difficult to this film is carried out machining separately.When machining, proton conducting polymer film takes place often, for example, is stretched by the load that is added, simply is cut off by shear stress and casual complications and produce fine fisssure or pin hole.
For fear of these problems, when handling proton conducting polymer film, must pay close attention to, this descends its operability significantly.Also have, proton conducting polymer film has the character that has some swellings at once and will significantly shrink after the solvent evaporates after having adhered to water or organic solvent.For this reason, proton conducting polymer film has been because of having adhered to water or organic solvent, finally causes greatly the contraction to about 5%～10% sometimes.
Usually, catalyst layer is that the catalyst paste that contains dispersants such as water or organic solvent in the middle body coating of proton conducting polymer film forms after drying.At this moment, because above-mentioned character, the middle body that has formed the proton conducting polymer film of catalyst layer obviously shrinks.On the other hand, the peripheral part that does not form catalyst layer does not shrink fully.Big gauffer or lax will take place at the outer peripheral portion of proton conducting polymer film in the result.
The proton conducting polymer film, carbon paper and the packing ring that have formed catalyst layer are being made in the operation of electrolyte membrane electrode joint body this gauffer or relax and to cause following problem with combination such as hot pressing.That is, produce the gap in the joint portion of packing ring and proton conducting polymer film, the part of gauffer is tortuous and be superimposed together proton conducting polymer film generation fine fisssure itself.Used the fuel cell of the electrolyte membrane electrode joint body that such defective is arranged, its air feed leaks, and battery behavior worsens.
Open the spy and to have disclosed the method that forms catalyst layer with so-called transcription technology on the two sides of proton conducting polymer film simultaneously among the flat 10-64574.In the method, 2 supporters that on membranaceous supporter, formed catalyst layer in advance, inwardly proton conducting polymer film is clipped in the middle by catalyst layer, with roller heating and pressurization simultaneously, catalyst layer from supporter one side transcription to the two sides of proton conducting polymer film.Use such method, just can prevent describedly, obtain excellent batch and produce ability because of water or organic solvent make proton conducting polymer film swelling and contraction.
But, in the method, when the single processing, carry this point that very big problem is arranged with roller to the not enough proton conducting polymer film of mechanical strength.That is to say, when carrying, on proton conducting polymer film, be added with tension force, make proton conducting polymer film generation fine fisssure, also can make the proton conducting polymer film fracture in some occasion with roller.Situation for the machining of guide hole of preventing from this situation, had to be provided with the proton delivery conducting polymer film etc.But, because proton conducting polymer film is thin, the breakage that also has the distortion in therefore hole or proton conducting polymer film makes the situation of guide hole disabler.
Furtherly, the method is clamping proton conducting polymer film with warmed-up roller during the transcription catalyst layer, owing to added in the part of proton conducting polymer film and thermal stress to make it that gauffer and lax take place.And then the influence of above-mentioned tension force and heat stretches proton conducting polymer film, causes forming the position deviation of catalyst layer.Also have, when the proton conducting polymer film on the two sides transcription after the catalyst layer is rolled into the roller shape, cracking and abrasion take place in catalyst layer.And then, anode has also taken place contacted, made the mutual pollution problems of both sides' catalyst layer with catalyst layer and catalyst for cathode layer.Because these problems, used fuel cell can not obtain satisfied battery behavior with the electrolyte membrane electrode joint body of said method manufacturing.
Summary of the invention
The objective of the invention is to stablize manufacturing and provide, even in the occasion of using thin proton conducting polymer film the gauffer of proton conducting polymer film and lax and catalyst layer not cracking and abrasion equivalent damage, electrolyte membrane electrode joint body for fuel cell do not take place yet yet.
The essential characteristic of the manufacture method of electrolyte membrane electrode joint body for fuel cell of the present invention is, it is included in the operation (1) that the 1st shape keeps proton conducting polymer film on the one side lamination of film, on the proton conducting polymer film on described the 1st shape maintenance film, form the operation (2) of the 1st catalyst layer in lamination, on the face of described the 1st catalyst layer one side of the described proton conducting polymer film that has formed the 1st catalyst layer in conjunction with the operation (3) of shape maintaining body, described the 1st shape is kept operation (4) that film peels off on described and the proton conducting polymer film that shape maintaining body combines and the proton conducting polymer film that exposed forms the operation (5) of the 2nd catalyst layer having peeled off that described the 1st shape keeps film.
Described operation (1) with, by having disperseed high molecular dispersion liquid of proton-conducting and dry casting process in the laminating technology of proton conducting polymer film heating and pressurization or the coating, the operation that forms described proton conducting polymer film is for preferred.
Described operation (2) or operation (5) with, the catalyst paste printing that contains catalyst and dispersant or dry after being coated on the described proton conducting polymer film, the operation that forms described catalyst layer is for preferred.
Here, to divide into described shape maintaining body substantially be that the 2nd shape keeps film and is the 1st packing ring both of these case to the preferred configuration of the manufacture method of electrolyte membrane electrode joint body for fuel cell of the present invention.
At first, be the occasion that the 2nd shape keeps film at described shape maintaining body, above-mentioned manufacture method is to comprise that the operation of described the 2nd shape maintenance film being peeled off from the proton conducting polymer film that has formed described the 2nd catalyst layer (6) serves as preferred.
And then described manufacture method keeps membrane-bound operation (7) for more preferably with the 3rd shape that keeps film with described the 2nd shape on the face of the 2nd catalyst layer one side that is included in the above-mentioned proton conducting polymer film that has formed the 2nd catalyst layer and can discern.
Especially, above-mentioned operation (3) or (7) with, above-mentioned shape keeps film and through heating and pressurization and the operation of combination is preferred overlapping on the face of catalyst layer one side of described proton conducting polymer film.
On the other hand, to the occasion that above-mentioned shape maintaining body of the present invention is the 1st packing ring, above-mentioned operation (3) serves as preferred with the operation of the 1st packing ring on low temperature vacation on the proton conducting polymer film around described the 1st catalyst layer is fixing.
Also have, described manufacture method serves as preferred with the operation (8) that high temperature on the proton conducting polymer film on every side that is included in described the 2nd catalyst layer is melting last the 2nd packing ring.
And then, above-mentioned operation (3) be by 30～100 ℃ down heating and pressurization make the 1st packing ring vacation be fixed on described the 1st catalyst layer around proton conducting polymer film on operation, above-mentioned operation (8) be to melt operation on the proton conducting polymer film around described the 2nd catalyst layer by heating under 100～180 ℃ and adding described the 2nd packing ring of pressure handle, for preferably.
Be that the above-mentioned the 1st and the 2nd shape keeps film preferably to be made of the thermoplastic resin film of thickness 50 μ m～500 μ m again.
The simple declaration of accompanying drawing
Fig. 1 is the longitudinal section of the intermediate in the manufacture process of the electrolyte membrane electrode joint body for fuel cell in the embodiments of the invention.
Fig. 2 is the longitudinal section that has the proton conducting polymer film of the catalyst layer that is combined with the 2nd and the 3rd shape maintenance film in the embodiments of the invention.
Fig. 3 is the longitudinal section of intermediate of the manufacture process of the electrolyte membrane electrode joint body for fuel cell in the another embodiment of the present invention.
Fig. 4 has been to use the longitudinal section of the fuel cell of the electrolyte membrane electrode joint body for fuel cell in the embodiments of the invention.
Embodiment
The inventor etc. are manufactured on proton conducting polymer film and the flawless electrolyte membrane electrode joint body for fuel cell of catalyst layer, the manufacture method below having found for the occasion of using thin proton conducting polymer film in sight is also stable.
The manufacture method of electrolyte membrane electrode joint body for fuel cell of the present invention includes: (1) keeps the operation of proton conducting polymer film on the one side lamination of film in the 1st shape; (2) on keeping proton conducting polymer film on the film, above-mentioned the 1st shape forms the operation of the 1st catalyst layer in lamination; (3) on described the 1st catalyst layer one side of the above-mentioned proton conducting polymer film that has formed the 1st catalyst layer in conjunction with the operation of shape maintaining body; (4) proton conducting polymer film that exposed forms the operation of the 2nd catalyst layer having peeled off that described the 1st shape keeps film above-mentioned the 1st shape to be kept operation that film peels off from the proton conducting polymer film that combines with described shape maintaining body and (5).
Essential characteristic of the present invention is, in the manufacture process of electrolyte membrane electrode joint body, disposes down and the processing proton conducting polymer film in the state that has the 1st shape to keep film or shape maintaining body to keep.Thus, just can solve in the problems referred to above of disposing and being taken place during the combination of the single proton conducting polymer film of processing equipment intensity difference and proton conducting polymer film and catalyst layer.
That is,,, can improve the actual machine intensity of proton conducting polymer film by keep film or shape maintaining body to keep thin proton conducting polymer film with the 1st shape according to the present invention.Thus, even when the proton conducting polymer film that careless disposal approaches, can suppress elongation, warpage, cut-out and the fine fisssure of proton conducting polymer film and the generation of pin hole.Also have,,, can stop gauffer and the lax generation that waits by the blockage effect of proton conducting polymer film having been lowered attached to dispersants such as water in the catalyst paste or organic solvents even on proton conducting polymer film, form in the operation of catalyst layer.
The preferred example of the manufacture method of electrolyte membrane electrode joint body for fuel cell of the present invention is divided into substantially, and it is that (A) the 2nd shape keeps the occasion of film and (B) occasion of the 1st packing ring that aforementioned shapes keeps body.
Be that preface illustrates best example of the present invention with above-mentioned (A) and (B) below.
Example A
This example relates to use the 2nd shape and keeps the electrolyte membrane electrode joint body for fuel cell manufacture method of film as shape maintaining body.
(i) about operation (1)
In operation (1), lamination proton conducting polymer film on the one side of the 1st shape maintenance film.As concrete method, can adopt to keep the 1st shape film and proton conducting polymer film overlapping, both are pressurizeed and the laminating technology of combination with hot plate or warmed-up roller.For example, preferably, the 1st shape is kept film and formed the support membrane of proton conducting polymer film with casting process etc. in advance overlapping, proton conducting polymer film is clipped in the middle of two films, they are pressurizeed down in heated condition.
The proton conducting polymer film that uses this moment be by, for example, the film that proton-conducting polyelectrolytes such as perfluorocarbon sulfonic acid are constituted.As perfluorocarbon sulfonic acid, that enumerate is Nafion112 of du pont company etc.The battery proton conducting polymer film that acts as a fuel, the extremely thin film about the thickness 20 μ m～50 μ m that form on the support membrane goes on the market and has used in advance.Improve for the ionic conductivity that further improves proton conducting polymer film makes battery behavior, proton conducting polymer film from now on will have the more tendency of filming.If filming, above-mentioned problem is just more apparent outstanding, and this also makes importance of the present invention just higher.
Also have, in operation (1), the dispersion liquid that has disperseed the proton-conducting polyelectrolyte is coated on after the 1st shape keeps on the film, drying, the formation proton conducting polymer film also can.This technology generally is referred to as casting process.Described dispersion liquid, be and proton conducting polymer film is dispersed or dissolved in the predetermined solvent with the polyelectrolyte of sample ingredient, volatilize and remove solvent in resulting the filming, obtained proton conducting polymer film.
Keep film as the 1st shape, with the film of thickness 50 μ m～500 μ m of being made of thermoplastic resin, especially the film of thickness 100 μ m～300 μ m is preferred.The shape that thickness is thinner than 50 μ m keeps the mechanical strength of film not enough, therefore, in operations such as aforesaid laminating technology or casting process, keeps the scarce capacity of proton conducting polymer film.On the other hand, when thickness surpasses 500 μ m, make the roller volume become difficult, the property produced in batches decline.
As becoming the thermoplastic resin that shape keeps the material of film,, just have no particular limits so long as when lamination process, there is not the heat-resistant resin of thermal deformation degree.For example, can use PETG, polypropylene, Polyetherimide, polyimides, fluororesin etc.
As required, decision is printed or the precision of the position of coated portion in order to improve, and also can keep being provided with in the film pilot tunnel that the decision position is used or conveying roller is used in shape.Furtherly, keep film as shape, if use thermal stability and the more excellent film of chemical stability, work in-process is injury-free, makes this shape keep film to be reused.
(ii) about operation (2) and operation (5)
In operation (2), on the proton conducting polymer film that remains on the 1st shape maintenance film, form the 1st catalyst layer.The formation method of this 1st catalyst layer be with, keep forming on the proton conducting polymer film on the film the catalyst layer method of formationing in the operation (5) of the 2nd catalyst layer remaining on the 2nd shape, come down to.For this reason, both illustrate simultaneously operation (2) and operation (5) here.
Among the present invention, on the one side of proton conducting polymer film, form the anode catalyst layer, and form the catalyst for cathode layer at another side.That is to say, form the occasion of anode, then use operation (5) to form the catalyst for cathode layer with catalyst layer with operation (2).Otherwise,, then use operation (5) to form the anode catalyst layer in the occasion that forms the catalyst for cathode layer with operation (2).
The concrete formation method of the catalyst layer as the 1st and the 2nd is containing the catalyst paste printing of catalyst and decentralized medium (or solvent) or be coated on after the middle body on the proton conducting polymer film, and is dry and form catalyst layer.Catalyst paste, being dispersed or dissolved in the solvent catalyst with the proton-conducting polyelectrolyte of proton conducting polymer film with sample ingredient, the words of modulating are for well.In this catalyst paste, as required, it is good to be mixed into additives such as a spot of surfactant.
The catalyst that is contained in the catalyst layer has played the effect that electrode reaction is carried out smoothly, and it is obtained by the surface that noble metal catalyst is supported on carbon particulate.Usually, be used as the anode catalyst with the surperficial carbon particulate that has supported the Pt-Ru alloy.This Pt-Ru alloy has and prevents that micro CO gas contained in the fuel gas from making the effect of catalyst poisoning.What catalyst for cathode was used is the carbon particulate that the surface has supported Pt.Also have, the proton-conducting polyelectrolyte that in catalyst layer, is contained be clipped between the catalyst particles and proton conducting polymer film and catalyst particles between, have the more smooth effect of carrying out of the electrode reaction of making.
Now, on market handlebar proton-conducting polyelectrolyte be dispersed or dissolved in the predetermined solvent resulting liquid in advance and sold.The solvent of catalyst paste, so long as common coating with or printing with solvent used in sticking with paste just, but wish it is to have than low boiling or low-molecular-weight solvent.Specifically enumerated, primary～tertiary alcohols such as water (hope is ion exchange water or pure water), ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, 2-butanols, the tert-butyl alcohol, their pure radical derivative and ether system, ester system and fluorine are organic solvent etc.They can use separately separately, perhaps can use with the mixed solvent of combination in any.
At this moment, selected solvent is to making not separating out with dispersed decline of proton-conducting polyelectrolyte be necessary.Also have,, be necessary selected the have suitable boiling point and the solvent of vapour pressure in order effectively to form catalyst layer at short notice.In the occasion of low boiling and high-vapor-pressure solvent,, make the continuous printing of catalyst paste and coating become difficulty because evaporation is too fast.On the other hand, the occasion that boiling point height and steam force down, the dried coating film operation after printing or the coating needs long time, in the heating for a long time of this occasion.Also have, in catalyst paste, good with the operability of coating for the dispersed or printing that makes proton-conducting polyelectrolyte and catalyst, as required, additives such as adding surfactant also are possible.
On proton conducting polymer film, form the method for filming of catalyst paste, can adopt print process such as wire mark, photogravure, letterpress and lithographic printing and scraper is coated with, roller coat, casting are coated with, spraying, curtain is coated with and static is coated with etc.
These print processes and rubbing method, both gone for many proton conducting polymer films that shape keeps combining on the film on form the occasion of other catalyst, also go for supply with the mode of roller be combined in shape keep proton conducting polymer film on the film on proton conducting polymer film the occasion of the catalyst layer of formation coiling continuously.
The amount of noble metals such as Pt that adheres on the carbon particulate that is contained in catalyst layer or Pt-Ru alloy is necessary to be controlled at 0.2～0.4mg/cm usually
2Left and right sides scope.If use above-mentioned print process or rubbing method, just can be easy to carry out the control of this adhesion amount.For example, when wire mark, the order number by optimizing galley, the thickness of emulsion, printing added pressure etc. during with scraping roller, printing just can be controlled described adhesion amount.Furtherly, by the particle diameter of optimizing the catalyst in the described catalyst paste, the addition of catalyst and the composition of solvent etc., and the viscosity of adjustment catalyst paste etc., just can come the adhesion amount of control catalyst with higher precision.
In above-mentioned operation of the present invention (2) and (5),, in the operation that forms catalyst layer, can horizontal arrangement has the proton conducting polymer film of smooth surface because shape keeps film or shape maintaining body to keep proton conducting polymer film.Thus, the advantage of these operations (2) and (5) is, even adopting any printing process or the occasion of coating process, and can as easy as rolling off a log formation uniform catalyst layer on proton conducting polymer film.
(iii) about operation (3)
Through operation (3), on the face of the 1st catalyst layer one side of the proton conducting polymer film that has formed the 1st catalyst layer, keep film in conjunction with last the 2nd shape.Concrete method is, can adopt on overlapping on the face of the 1st catalyst layer one side of described proton conducting polymer film the 2nd shape to keep film, both one are reinstated the so-called pressure sintering of hot plate or the heating of warmed-up roller.Here, used the 2nd shape keep film can be with operation (1) in used the 1st shape keep film same film fully.
(iv) about operation (4)
Operation (4) is to keep the 1st shape film to keep the proton conducting polymer film of film to peel off from combining the 2nd shape.Thus, exposed the face that does not also form the proton conducting polymer film of catalyst layer.Then, with the operation (5) of front described in (ii), described expose face except the middle body of outer peripheral portion on form the 2nd catalyst layer.Thus, constituted the intermediate that the proton conducting polymer film that formed catalyst layer on the two sides and the 2nd shape keep the electrolyte membrane electrode joint body that film combines.
Below, press Fig. 1 explanation and the manufacture method of use as the relevant electrolyte membrane electrode joint body for fuel cell of the invention process form A of the 2nd shape maintenance film of shape maintaining body.
At first, by operation (1) proton conducting polymer film 1 on the one side lamination of the 1st shape maintenance film 2, obtained the intermediate 3 shown in Fig. 1 (a).Then, on the proton conducting polymer film 1 of described intermediate 3, form the 1st catalyst layer 4a, obtained the intermediate 5 shown in Fig. 1 (b) by operation (2).
Then,, keep the 2nd shape film 6 to be combined on the face of the 1st catalyst layer 4a one side of proton conducting polymer film 1 of intermediate 5, obtained the intermediate 7 shown in Fig. 1 (c) by operation (3).Next, by operation (4), from the proton conducting polymer film 1 of intermediate 7, keep the 1st shape film 2 to peel off, expose proton conducting polymer film 1, again by operation (5), on the proton conducting polymer film 1 that exposes a side, form the 2nd catalyst layer 4b, obtained the intermediate 8 shown in Fig. 1 (d).
The 2nd shapes in this intermediate 8 keep film 6, in the operation of the manufacturing electrolyte membrane electrode joint body of back, have played preventing inadequate distortion and the damaged effect that has the proton conducting polymer film of catalyst layer of mechanical strength.For example,, the proton conducting polymer film that has catalyst layer of bad mechanical strength be can keep, its distortion and breakage prevented in that the carbon paper of the 2nd catalyst layer 4b one side or packing ring are used for waiting the operation of combination by pressurizeing under the heated condition.Therefore, intermediate 8 is a useful as intermediates in the manufacturing of electrolyte membrane electrode joint body.
As mentioned above, in described operation (2) and (5), owing on the proton conducting polymer film that keeps film to support with shape, formed catalyst layer, even the swelling and the contraction of proton conducting polymer film attached to the occasion on the proton conducting polymer film, almost do not take place in the solvent in catalyst paste yet.Thus, can effectively prevent the damage of the gauffer of the contraction of proton conducting polymer film middle body and outer peripheral portion, lax, pin hole and fine fisssure etc.
And then, in described each operation (1)～(5), proton conducting polymer film and the 1st catalyst layer and the 2nd catalyst layer that form thereon, normally direct or indirect keeps film or the 2nd shape to keep film to be kept by the 1st shape.Thus, can prevent the generation of the stretching, pin hole, cracking etc. of each catalyst layer in each operation and proton conducting polymer film.And then, for the conveying between operation or keeping each intermediate being rolled into the occasion of roller shape, proton conducting polymer film necessarily accompanies the 1st shape each other with catalyst layer each other and keeps film or the 2nd shape to keep film.Thus, just can prevent inter process carry and keeping in the catalyst layer that taken place and proton conducting polymer film cracking, peel off and wear away equivalent damage, and contact the catalyst layer pollution each other that causes between the catalyst layer of the catalyst layer that has effectively prevented anode-side and cathode side.
Also have, in the manufacture method relevant with example A of the present invention, after operation (1)～(5) are over, the operation (6) that further enforcement keeps the 2nd shape film to peel off from intermediate 8, shown in Fig. 1 (e), just obtained all having formed the intermediate 9 of catalyst layer on the two sides of proton conducting polymer film.In the occasion of making electrolyte membrane electrode joint bodies with this intermediate 9, can adopt the side separately of the 1st catalyst layer 4a and the 2nd catalyst layer 4b respectively with heat pressing process etc. simultaneously in conjunction with on separately diffusion layer.As diffusion layer, use carbon paper usually.This intermediate 9, institute forms in anode and the independent operation of negative electrode owing to being convenient to, and is useful as intermediates in the manufacture process of electrolyte membrane electrode joint body.
And then, follow operation (1)～(5), be implemented in the operation (7) that keeps film 10 on the face of the 1st catalyst layer 4a one side of intermediate 8 in conjunction with the 3rd shape, as shown in Figure 2, obtained combining respectively the intermediate 11 that catalyst layer and shape keep film on the two sides of proton conducting polymer film.In described operation 7, adopt that the 3rd shape keeps film 10 on overlapping on the face of the 1st catalyst layer 4a of intermediate 8 side, the so-called heat pressing process that they are pressurizeed with hot plate or warmed-up roller is for preferred.
Above-mentioned intermediate 11 keeps film 6 and 10 to protect the surface of proton conducting polymer film 1 and catalyst layer 4a and 4b by the 2nd and the 3rd shape.Therefore, 11 pairs in this intermediate is being preserved for a long time, is being carried and occasion such as pack prevents that the damage of proton conducting polymer film and catalyst layer from being extremely effective to other place.
Furtherly, catalyst layer 4a and catalyst layer 4b, no matter aspect such as its noble metal catalyst kind why not have with, all is almost same black almost in appearance, as a rule, both are with estimating and feel can not be discerned.For this reason, situation about in making the process of fuel cell, getting wrong with regard to the catalyst layer of the catalyst layer of handlebar anode-side and cathode side.In order to get rid of this situation, used the 3rd shape that is used for intermediate 11 to preserve film 10, this is extremely effective to coming to keep film 6 to differentiate with the 2nd shape with range estimation and sense of touch.Specifically, to use, for example, the shape that different shape such as color, thickness or concave-convex surface state keeps film or has a distinguished symbol keeps film for well.At this moment, the 1st shape that is stripped down in the previous operation (4) keeps film 2 just to can be used as the 3rd shape in the operation (7) keeping film 10 and be reused.From these, just make this intermediate 11 become useful as intermediates in the manufacture process of electrolyte membrane electrode joint body.
Example B
Illustrating now to relate to uses the 1st packing ring to be used as the relevant example B of the present invention of manufacture method of the electrolyte membrane electrode joint body for fuel cell of shape maintaining body.
(i) about operation (1) and (2)
Operation (1) and operation (2) can adopt operation (1) and the complete same method of operation (2) with the example A that illustrates previously.
(ii) about operation (3)
Operation (3) is at low temperatures the 1st packing ring vacation as shape maintaining body to be fixed on the proton conducting polymer film that has formed the 1st catalyst layer.
The front was said, in the occasion that forms catalyst layer with aforesaid printing process or coating process, caused the bigger contraction of about 5%～10% degree at the middle body of proton conducting polymer film, consequently, gauffer and lax has taken place at outer peripheral portion.
The present invention is for head it off, in aforementioned operation (1), when the 1st shape keeps forming proton conducting polymer film on the film, by operation (3), the 1st packing ring vacation be fixed in the 1st catalyst layer on the proton conducting polymer film around.Keep film and the 1st packing ring to keep proton conducting polymer film by these the 1st shapes, just can solve the problems referred to above that form the occasion generation of catalyst layer with print process or rubbing method aforementioned.
Here the 1st used packing ring is to make supply gas such as the employed hydrogen of fuel cell, town gas, air or oxygen not to the airtight parts of using of reaction system external leakage.This 1st packing ring can use, for example, and the resin flake about thickness 0.2mm～0.4mm.Specifically, can use, for example, by with the ethylene propylene copolymer being the thin slice that resin constituted of principal component or the resin flake that constitutes superficial layer by ethylene propylene copolymer etc.
In the manufacture method of common electrolyte membrane electrode joint body, 2 packing rings that dispose in the two sides of proton conducting polymer film are melting simultaneously.On the other hand, at first in operation (3), in the pressurization down of 30 ℃～100 ℃ such lower temperatures, vacation is fixed on the proton conducting polymer film the 1st packing ring in the present invention.Then, in the operation of talking about in the back (8), the pressurization under 100 ℃～180 ℃ such higher temperatures of the 2nd packing ring is being melted.At this moment, the 1st packing ring has also been melted simultaneously.Like this, the 1st packing ring and the 2nd packing ring and proton conducting polymer film are melting, and just can prevent that supply gas from leaking from the junction surface of proton conducting polymer film and packing ring.
Here, " false fixing " described in the present invention means the laminate of making suitable peel strength.Also have, described " melting " mean in packing ring and the proton conducting polymer film at least one side's fusion and both being combined into one.
30 ℃～100 ℃ lower temperature in the operation (3) makes the 1st packing ring and proton conducting polymer film melt hardly, and is false fixing with the degree of not being stripped from when the printing process of catalyst paste or painting process operation.On the proton conducting polymer film that the 1st packing ring is fixed by vacation, almost there are not warpage and distortion, maintain its original state and can carry out follow-up operation (4) and (5).
Again, on above-mentioned the 1st shape keeps in film and the 1st packing ring at least one, set in advance for determine to print or the fraising of the hole that uses the necessary position of painting process or conveying roller for well.Employed shape keeps the thickness of film and packing ring, with the handling ease that such hole is set is carried out, suitably is chosen as.
(ii) about operation (4)
Operation (4) keeps the 1st shape film to peel off from the proton conducting polymer film that combines with described the 1st packing ring.Here, the 1st shape keeps film only need be added with mechanism just can being stripped from easily.
(iii) about operation (5)
Middle body on the described proton conducting polymer film that has exposed having peeled off the 1st shape maintenance film is used and the same method of top operation (2), forms the 2nd catalyst layer.
(v) about operation (8)
In example B, do not have operation (6) and (7) of example A, but be carried out at the operation (8) that is melting the 2nd packing ring on every side of the 2nd catalyst layer on the proton conducting polymer film that has formed aforementioned the 2nd catalyst layer under the high temperature.Meanwhile, also having melted with false the 1st fixing packing ring of operation (3).
Thus, obtained the intermediate of electrolyte membrane electrode joint body that the 1st packing ring, the 1st catalyst layer, proton conducting polymer film, the 2nd catalyst layer and the 2nd packing ring are combined.
Here, at first use aforementioned the 3rd operation, false fixing at following the 1st packing ring of 30 ℃～100 ℃ low temperature, make proton conducting polymer film and the 1st packing ring maintain the state that does not almost have warpage and distortion.Under 100 ℃～180 ℃ high temperature, the while is being melted the 1st packing ring and the 2nd packing ring, can almost not had the intermediate of warpage and distortion on the two sides of the proton conducting polymer film after this false fixedly operation.
Be the false fixed temperature in operation of saying (3) and the operation (8) and melting temperature and can wait with heat treatment time and pressure and do suitable change more here.But, when changing false fixed temperature respectively and melting temperature, preferably in above-mentioned temperature range, carry out.
Also have, by the above-mentioned intermediate of resulting electrolyte membrane electrode joint body of the present invention later on of having done like that, keep film or packing ring because of around catalyst layer, necessarily having shape, in coiling operation or keeping operation, just can prevent very effectively catalyst layer fine fisssure, peel off and abrasion etc.So manufacture method of the present invention is even also be favourable the intermediate long preservation of electrolyte membrane electrode joint body the time.
And then in each operation of using laminating technology or casting process, aforementioned the 1st shape is preserved film does not have variation heat, chemistry fully with aging.Therefore, can in manufacture method of the present invention, reuse.So, from reducing production costs and protecting the countermeasure of environment to consider that the relevant manufacture method of the present invention also is favourable.
Next, illustrate by Fig. 3 and use the manufacture method of the 1st packing ring as the relevant electrolyte membrane electrode joint body for fuel cell of the example B of the present invention of shape maintaining body.
At first, use the same operation (1) of the manufacture method relevant with example A, proton conducting polymer film 1 on the one side lamination of the 1st shape maintenance film 2 obtains the intermediate 3 shown in Fig. 3 (a).Then, use the same operation (2) of the manufacture method relevant, on the proton conducting polymer film 1 of intermediate, form the 1st catalyst layer 4a, obtained the intermediate 5 shown in Fig. 3 (b) thus with example A.Then, by operation (3), false fixing the 1st packing ring 20a on the aforementioned proton conducting polymer film 1 of intermediate 5 as shape maintaining body.Thus, obtained intermediate 21 shown in Fig. 3 (c).Next, keep the 1st shape film 2 to strip down, expose proton conducting polymer film 1 from the proton conducting polymer film 1 of intermediate 21 by operation (4).Use operation (5) on the proton conducting polymer film 1 that exposes a side, to form the 2nd catalyst layer 4b then, obtained the intermediate 22 shown in Fig. 3 (d).Be that the tool 23 of accepting among relevant Fig. 3 (d) is talked in the back more again.
Then, in operation (8), last the 2nd packing ring 20b in the peripheral part fractional melting of the proton conducting polymer film 1 of the 2nd catalyst layer 4b one side that has formed intermediate 22.Meanwhile, the 1st packing ring 20a that has fixed by aforementioned operation (3) vacation at the peripheral part fractional melting of the proton conducting polymer film 1 that forms the 1st catalyst layer 4a one side.Thus, obtained the intermediate 24 of electrolyte membrane electrode joint body.
Come more specific description the present invention with embodiment below, but, it is described that the present invention is not limited in these embodiment.
Embodiment 1
Press the order of Fig. 1 (a)～(e), the two sides that is produced on proton conducting polymer film 1 has formed the intermediate 9 of the electrolyte membrane electrode joint body of catalyst layer 4a and 4b respectively, makes fuel cell with it.At first 1st shape of proton conducting polymer film 1 lamination of thickness 30 μ m in the PETG film formation of thickness 190 μ m kept making the intermediate 3 shown in Fig. 1 (a) on the film 2.Proton conducting polymer film 1 usefulness be the material that the perfluorocarbon sulfonic acid with following formula (x=5 in the formula～13.5, y ≈ 1000, m=1, n=2) expression constitutes.
The so-called reprint method lamination of above-mentioned proton conducting polymer film 1 usefulness keeps on the film 2 in the 1st shape.Specifically, at first, keep the proton conducting polymer film 1 and the 1st shape that form on support membrane with casting process in advance film 2 to overlap.Then, it is used between 2 warmed-up rollers that have been coated with silicon rubber after the pressurization, peels off support membrane, the pressure that the surface temperature of roller is 110 ℃, the about 10mm/s of transporting velocity, add is about 1MPa.
In intermediate 3, almost there are not warpage or distortion, even proton conducting polymer film 1 itself does not observe fine fisssure or pin hole equivalent damage yet.Also have, proton conducting polymer film 1 keeps the appropriate driving fit of film 2 with the 1st shape, even so the warpage that intermediate 3 is made curvature radius (R) 50mm degree peeled off to get off yet.
Then, use anode the catalyst paste wire mark on proton conducting polymer film 1, place in room temperature and make solvent evaporates.Thus, form the 1st catalyst layer 4a (anode side catalyst layer), made the intermediate 5 shown in Fig. 1 (b).The amount of the Pt-Ru alloy that adheres on the carbon particulate in catalyst layer 4a is 0.3mg/cm
2, the about 10 μ m of the thickness of catalyst layer 4a.Anode is that the Pt-Ru alloy of average grain diameter 2nm～3nm is supported on the carbon black of average grain diameter 50nm～60nm with 50 weight % with what use in the catalyst.The anode catalyst paste is to be used in the 5g catalyst to add the 15g ion exchange water, after mixing, add alcohol dispersion liquid and 10g isopropyl alcohol that 30g contains the perfluorocarbon sulfonic acid of 91 weight %, and the limit edged mixes with ultrasonic vibration and is modulated into.The 200 purpose versions and the polyurethane scraping roller of stainless steel have been used in the wire mark.
Next, keep intermediate 5 and the 2nd shape film 6 overlapping, it is inserted between two warmed-up rollers that have been coated with silicon rubber, the intermediate 7 shown in Fig. 1 (c) has been made in pressurization.What the 2nd shape kept film 6 usefulness is the PETG film that its thickness that has simultaneously carried out roughened is 190 μ m.Keep this 2nd shape the one side of not making roughened of film 6 to combine with proton conducting polymer film 1 and catalyst layer 4a.The surface temperature of roller is that 110 ℃, intermediate 5 and the 2nd shape keep the about 10mm/s of film 6 transporting velocities, the pressure that adds is about 1MPa.
Almost there are not warpage or distortion in the intermediate 7, even proton conducting polymer film 1 itself does not observe fine fisssure or pin hole equivalent damage yet.Also have, proton conducting polymer film 1 keeps the appropriate driving fit of film 2 and 6 with the 1st and the 2nd shape, even so the warpage that intermediate 7 is made curvature radius (R) 50mm degree do not stripped down yet.
Next, keep the 1st shape film 2 to peel off from intermediate 7.Printing the catalyst for cathode paste with wire mark, be positioned over room temperature and make solvent evaporates owing to peeling off on the proton conducting polymer film 1 that exposes.Thus, formed the 2nd catalyst layer 4b (cathode-side catalytic layer), made intermediate 8 as Fig. 1 (d).
The 200 purpose versions and the polyurethane scraping roller of stainless steel have been used in the wire mark.The amount of the Pt that adheres on the carbon particulate in the 2nd catalyst layer 4b is 0.3mg/cm
2, the about 10 μ m of thickness.What use in the catalyst for cathode is that the Pt of average grain diameter 3nm is supported on the carbon black of average grain diameter 50nm～60nm with 50 weight %.It is to be used in to add the 15g ion exchange water in the 5g catalyst that catalyst for cathode is stuck with paste, after mixing, add 30g contain 91 weight % perfluorocarbon sulfonic acid alcohol dispersion liquid and as the 10g isopropyl alcohol of solvent, the limit edged mixes with ultrasonic vibration and is modulated into.
Then, keep the 2nd shape film 6 to peel off, make the proton conducting polymer film 1 (intermediate 9) that the two sides has formed catalyst layer 4a and 4b from intermediate 8.Then, make fuel cell with this intermediate 9.
Fig. 4 is the longitudinal section of the fuel cell that makes.In the catalyst layer 4a of intermediate 9 and the outside of 4b, engage with diffusion layer 13b with diffusion layer 13a and negative electrode with anode separately for ventilative and leachy carbon paper system.Thus, anode 14a and negative electrode 14b have been formed.And then, melting upper gasket 20a and 20b on the two sides of the outer peripheral portion of proton conducting polymer film 1, formed electrolyte membrane electrode joint body.In the outside separately of diffusion layer 13a and 13b, have the anode side conductive dividing plate 17a and the cathode side conducting diaphragm 17b that gas passage 16b is arranged of gas passage 16a in the configuration.In the outside separately of conducting diaphragm 17a and 17b, the coldplate 19 of cooling-water duct 18 is arranged in the configuration.
Battery temperature by the fuel cell of making is like this remained in 75 ℃, carry out its discharge test.In anode one side, supply with humidification, the hydrogen of heating of 75 ℃ of dew points, and negative electrode one side supply with 65 ℃ of dew points humidification, add warm air.Discharging condition is hydrogen utilization ratio 70%, air utilization ratio 40%, current density 0.7A/cm
2The result is to have obtained the good like this output voltage of 0.68V.
Embodiment 2
Press the order of Fig. 1 (a)～(e), the two sides that is produced on proton conducting polymer film 1 has formed the intermediate 9 of the electrolyte membrane electrode joint body of catalyst layer 4a and 4b respectively, makes fuel cell with it.
At first, contain with embodiment 1 in the alcohol dispersion liquid of the same perfluorocarbon sulfonic acid 91 weight % that use be coated on the 1st shape that the polypropylene screen by thickness 50 μ m constitutes and keep on the film 2 drying.Carry the 1st shape to keep the speed of film to be taken as 0.7m/min.Coating process is knife height 0.16mm, overcoating 3 times.This room temperature of filming is placed drying, keep having formed on the film 2 proton conducting polymer film 1 of thickness 30 μ m in the 1st shape.Made the intermediate 3 shown in Fig. 1 (a) with said method.
Almost there are not warpage or distortion in the intermediate 3, even proton conducting polymer film 1 itself does not observe fine fisssure or pin hole equivalent damage yet.Also have, proton conducting polymer film 1 keeps the appropriate driving fit of film 2 with the 1st shape, even so the warpage that intermediate 3 is made curvature radius (R) 50mm degree do not stripped down yet.
Then, on the proton conducting polymer film 1 of intermediate 3, form the catalyst layer 4a of anode-side, made the intermediate 5 shown in Fig. 1 (b).Catalyst layer 4a is except using the solvent of catalyst paste as anode with normal propyl alcohol replacement isopropyl alcohol, to form similarly to Example 1.The amount of the Pt-Ru alloy that has adhered on the carbon particulate among the formed catalyst layer 4a is 0.3mg/cm
2, the about 10 μ m of the thickness of catalyst layer 4a.
Next, use the polyimide film of thickness 100 μ m to keep film 6,, form the intermediate 7 of Fig. 1 (c) expression with method similarly to Example 1 except 130 ℃ of hot plate temperatures, plus-pressure are about 5MPa as the 2nd shape.
Almost there are not warpage or distortion in the intermediate 7, even proton conducting polymer film 1 itself does not observe fine fisssure or pin hole equivalent damage yet.Also have, proton conducting polymer film 1 keeps the appropriate driving fit of film 2 with the 1st and the 2nd shape, even so the warpage that intermediate 7 is made curvature radius (R) 50mm degree do not stripped down yet.
Next, keep the 1st shape film 2 to peel off, expose proton conducting polymer film 1 from intermediate 7.On the proton conducting polymer film 1 that exposes, form the 2nd catalyst layer 4b (cathode-side catalytic layer).The 2nd catalyst layer 4b forms the solvent of isopropyl alcohol as the catalyst for cathode paste similarly to Example 1 except replacing with normal propyl alcohol.Thus, made intermediate 8 as Fig. 1 (d).The Pt amount of adhering on the carbon particulate among the 2nd catalyst layer 4b that forms is 0.3mg/cm
2Also have the about 10 μ m of the thickness of the 2nd catalyst layer 4b.
Then, keep the 2nd shape film 6 to peel off, make intermediate shown in Figure 29 from intermediate 8.These intermediate 9 usefulness method is similarly to Example 1 made fuel cell.With similarly to Example 1 method to the use of discharging of this fuel cell.The result is to have obtained the good like this output voltage of 0.68V.
Press the order of Fig. 3 (a)～(e), formed catalyst layer 4a and 4b respectively,, further make fuel cell with it by its intermediate 24 that combines the electrolyte membrane electrode joint body that constitutes with packing ring 20a and 20b on the two sides of proton conducting polymer film 1.
At first, use with the same fully method of embodiment 1 and make with the intermediate 3 shown in Fig. 3 (a).Almost there are not warpage or distortion in the intermediate 3, even it is proton conducting polymer film 1 itself does not observe fine fisssure or pin hole equivalent damage yet, in good condition.Also have, the proton conducting polymer film 1 of this intermediate 3 and the appropriate driving fit of maintenance film 2 are peeled off to be got off even therefore make the warpage of curvature radius (R) 50mm degree yet.Then, use with the same fully method of embodiment 1 and make the intermediate 5 shown in Fig. 3 (b).
Next, the outer peripheral portion at the catalyst layer 4a that does not form proton conducting polymer film 1 of intermediate 5 disposes the 1st packing ring 20a, and they are inserted between 2 rollers of heating, and the 1st packing ring 20a vacation is fixed on the proton conducting polymer film 1.Thus, obtained intermediate 21 shown in Fig. 3 (c).What described roller was used is to scribble silicon rubber from the teeth outwards.
This 1st packing ring 20a makes the resin flake that is made of ethylene propylene copolymer with the perforating of Thomson type.Also have, the condition that roller uses is, 90 ℃ of surface temperatures, and transporting velocity 10mm/s and the pressure that adds are 1MPa.
Almost there are not warpage or distortion in this intermediate 21, even it is proton conducting polymer film 1 and catalyst layer 4a itself do not observe fine fisssure or pin hole equivalent damage yet, in good condition.Also have, the proton conducting polymer film 1 of this intermediate 21, shape keep the appropriate driving fit of respectively controlling oneself of film 2 and the 1st packing ring 6, even therefore the warpage that intermediate 21 is made curvature radius (R) 50mm degree is peeled off to be got off yet.
Secondly, operation keeps the 1st shape film 2 to peel off from intermediate 21 by hand.On the one side of the proton conducting polymer film 1 that exposes by peeling off, use method similarly to Example 1 to form the 2nd catalyst layer 4b (cathode-side catalytic layer).Thus, obtained the intermediate 22 shown in Fig. 3 (d).
Since the formation of the proton conducting polymer film 1 of this moment the thickness of part of thickness and formation the 1st packing ring 20a of part of the 1st catalyst layer 4a be different, the tool 23 of accepting that is represented by dotted lines with the bottom of Fig. 3 (e) carries out the printing of catalyst paste.This accepts tool 23 can be used for determining simultaneously the position.
Formation the 1st catalyst layer 4a here and the operation of the 2nd catalyst layer 4b owing to almost do not have gauffer and distortion on proton conducting polymer film, the flat configuration of this film water, just can not wanted the printing that special device and technology are carried out catalyst paste.The result is to form the catalyst layer of stay in grade.
Next, in the formation of described intermediate 22 the 2nd catalyst layer 4b part around the 2nd packing ring 20b in the configuration, they are inserted in warmed-up 2 rollers chien shih, and it is melting, and has made the intermediate 24 shown in Fig. 3 (e).What above-mentioned roller was used also is that the surface scribbles silicon rubber.
This 2nd packing ring 20b makes the resin flake that is made of ethylene propylene copolymer with the perforating of Thomson type.Also have, the condition that roller uses is, 150 ℃ of surface temperatures, and transporting velocity 5mm/s and the pressure that adds are 1MPa.
Almost there are not warpage or distortion in this intermediate 24, even it is proton conducting polymer film 1 and catalyst layer itself do not observe fine fisssure or pin hole equivalent damage yet, in good condition.Also have, the proton conducting polymer film 1 of this intermediate 24 and the 1st packing ring 20a and the 2nd packing ring 20b respectively control oneself and are melting fully, even the warpage that intermediate 24 is made curvature radius (R) 50mm degree does not strip down yet.
Use the intermediate 24 of this electrolyte membrane electrode joint body make shown in Figure 4, with embodiment 1 in fuel cell with the fuel cell of spline structure.At first, in the catalyst layer 4a of intermediate 24 and the outside of 4b, form with the anode that constitutes by carbon paper with diffusion layer 13a and negative electrode with anode 14a and negative electrode 14b that diffusion layer 13b engages, constituted electrolyte membrane electrode joint body.
In the outside separately of the diffusion layer 13a and the 13b of this electrolyte membrane electrode joint body, the anode side conductive dividing plate 17a of gas passage 16a is arranged in the configuration and the cathode side conducting diaphragm 17b of gas passage 16b is arranged.In the outside separately of conducting diaphragm 17a and 17b, dispose the coldplate 19 of cooling-water duct 18.To the use of discharging of such fuel cell that constitutes, the result is to have obtained the good like this output voltage of 0.68V with similarly to Example 1 condition.
Embodiment 4
Press the order of Fig. 3 (a)～(e), after the two sides of proton conducting polymer film 1 has formed catalyst layer 4a and 4b respectively, combine the intermediate 24 that constitutes electrolyte membrane electrode joint body with packing ring 20a and 20b, further make fuel cell with it by it.
At first, the same with embodiment 2, on keeping film 2, shape formed the proton conducting polymer film 1 of thickness 30 μ m, obtained the intermediate 3 shown in Fig. 3 (a).Almost there are not warpage or distortion in the intermediate 3, even it is proton conducting polymer film 1 itself does not observe fine fisssure or pin hole equivalent damage yet, in good condition.Also have, the proton conducting polymer film 1 of intermediate 3 keeps the appropriate driving fit of film 2 with the 1st shape, even so the warpage that this intermediate 3 is made curvature radius (R) 50mm degree do not stripped down yet.
Then, on the proton conducting polymer film 1 of intermediate 3, use the method identical, form the catalyst layer 4a of anode-side, obtained the intermediate 5 shown in Fig. 3 (b) with embodiment 2.
Next, replace obtaining the intermediate 21 shown in Fig. 3 (c) similarly to Example 3 around the roller except 2 blocks of hot plates that scribble silicon rubber with the surface.80 ℃ of the surface temperatures of above-mentioned hot plate, plus-pressure are about 1MPa.Almost there are not warpage or distortion in this intermediate 21.And the proton conducting polymer film 1 of intermediate 21 and catalyst layer itself do not observe fine fisssure or pin hole equivalent damage yet, and be in good condition.Also have, the proton conducting polymer film 1 of this intermediate 21, shape keep film 2 and the appropriate each other driving fit of the 1st packing ring 20a, intermediate 21 are made the warpage of curvature radius (R) 50mm degree and are also peeled off to get off.
Then,, form the 2nd catalyst layer 4b similarly to Example 3, obtained the intermediate 22 shown in Fig. 3 (d) except being the organic solvent with normal propyl alcohol.
Then, replace obtaining the intermediate 24 shown in Fig. 3 (e) similarly to Example 3 around the roller except 2 blocks of hot plates that scribble silicon rubber with the surface.135 ℃ of the surface temperatures of above-mentioned hot plate, plus-pressure are about 1MPa.
Almost there are not warpage or distortion in this electrolyte membrane electrode joint body intermediate 24.And proton conducting polymer film and catalyst layer itself do not observe fine fisssure or pin hole equivalent damage yet, and be in good condition.Also have, the appropriate each other driving fit of the proton conducting polymer film 1 of this intermediate 24 and the 1st packing ring 20a and the 2nd packing ring 20b is made intermediate 24 warpage of curvature radius (R) 50mm degree and is also peeled off to get off.
Use the fuel cell of this intermediate 24 by similarly to Example 3 method manufacturing structure as shown in Figure 4.With similarly to Example 1 method to the use of discharging of this fuel cell.The result is to have obtained the good like this output voltage of 0.68V.
Be again, when printed catalyst was stuck with paste in embodiment 3 and embodiment 4, the 1st shape kept the periphery that does not dispose catalyst layer of film the 2, the 1st packing ring 20a and the 2nd packing ring 20b, had set in advance and had determined hole that the position is used or the fraising that send roller to use.Thus, can on relatively-stationary position, form catalyst layer 4a and catalyst layer 4b easily.
Furtherly, in embodiment 3 and embodiment 4, be black, and be dark brown, used the material of band look respectively at the 2nd packing ring 20b of the 2nd catalyst layer one side at the 1st packing ring 20a of the 1st catalyst layer 4a one side.Thus, can discern the 1st catalyst layer 4a and the 2nd catalyst layer easily.In addition, for example, glassy surface processing has been carried out on surface at the 1st packing ring 20a that has the 1st catalyst layer 4a one side, and what have that the surface of the 2nd packing ring 20b of the 2nd catalyst layer 4b one side does is frosted face processing etc., with estimating or feel just can effectively be discerned 2 kinds of used packing rings.
By the present invention, even when using thin proton conducting polymer film, also can be manufactured on the electrolyte membrane electrode joint body for fuel cell that does not have warpage in the proton conducting polymer film, not have cracking, abrasion, pollution equivalent damage in lax, fine fisssure, pin hole equivalent damage and the catalyst layer with good operability.Use this electrolyte membrane electrode joint body that the fuel cell of excellent just can be provided.
Claims (13)
1. the manufacture method of an electrolyte membrane electrode joint body for fuel cell, it includes: (1) keeps the operation of lamination proton conducting polymer film on the one side of film in the 1st shape; (2) on keeping proton conducting polymer film on the film, described the 1st shape forms the operation of the 1st catalyst layer in above-mentioned lamination; (3) on the face of described the 1st catalyst layer one side of the proton conducting polymer film that has formed described the 1st catalyst layer in conjunction with the operation of shape maintaining body; (4) proton conducting polymer film that exposed forms the operation of the 2nd catalyst layer having peeled off that described the 1st shape keeps film described the 1st shape to be kept operation that film peels off and (5) from the proton conducting polymer film that combines described shape maintaining body.
2. the manufacture method of claim item 1 described electrolyte membrane electrode joint body for fuel cell, wherein said operation (1) are the operations that forms described proton conducting polymer film by the casting process of dispersion liquid coating that disperses the laminating technology of proton conducting polymer film heating and pressurization lamination or the proton-conducting macromolecule and drying.
3. the manufacture method of claim item 1 described electrolyte membrane electrode joint body for fuel cell, wherein said operation (2) or (5) are dry after containing the catalyst paste printing of catalyst and dispersant or being coated on the described proton conducting polymer film and form the operation of described catalyst layer.
4. the manufacture method of claim item 1 described electrolyte membrane electrode joint body for fuel cell, wherein said shape maintaining body are that the 2nd shape keeps film.
5. the manufacture method of claim item 4 described electrolyte membrane electrode joint body for fuel cell, it has further comprised the operation that (6) keep film to peel off from the proton conducting polymer film that has formed described the 2nd catalyst layer to described the 2nd shape.
6. the manufacture method of claim item 4 described electrolyte membrane electrode joint body for fuel cell, its further comprised (7) on the face of the 2nd catalyst layer one side of the proton conducting polymer film that has formed described the 2nd catalyst layer in conjunction with on can keep the 3rd shape of film identification to keep the operation of film with described the 2nd shape.
7. the manufacture method of claim item 4 described electrolyte membrane electrode joint body for fuel cell, wherein said operation (3) or (7) are to keep described shape film to overlap on the face of catalyst layer one side of described proton conducting polymer film and through heating and pressurization and the operation of combination.
8. it is that thermoplastic resin film by thickness 50 μ m～500 μ m is constituted that the manufacture method of claim item 4 described electrolyte membrane electrode joint body for fuel cell, the wherein said the 1st and the 2nd shape keep film.
9. the manufacture method of claim item 1 described electrolyte membrane electrode joint body for fuel cell, wherein said shape maintaining body is the 1st packing ring.
10. the manufacture method of claim item 9 described electrolyte membrane electrode joint body for fuel cell, wherein said operation (3) be the 1st packing ring false at low temperatures be fixed on described the 1st catalyst layer around proton conducting polymer film on operation.
11. the manufacture method of claim item 9 described electrolyte membrane electrode joint body for fuel cell, it has comprised that further (8) at high temperature melting operation on the proton conducting polymer film around described the 2nd catalyst layer to the 2nd packing ring.
12. the manufacture method of claim item 11 described electrolyte membrane electrode joint body for fuel cell, wherein said operation (3) be 30 ℃～100 ℃ following heating and pressurizing the 1st packing ring vacation is fixed on described the 1st catalyst layer around proton conducting polymer film on operation, described operation (8) is the 2nd packing ring to be melted operation on the proton conducting polymer film on every side at described the 2nd catalyst layer in heating and pressurizing under 100 ℃～180 ℃ the high temperature.
13. it is that thermoplastic resin film by thickness 50 μ m～500 μ m is constituted that the manufacture method of claim item 9 described electrolyte membrane electrode joint body for fuel cell, wherein said the 1st shape keep film.
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| JP073999/2001 | 2001-03-15 | ||
| JP2001073999A JP2002280012A (en) | 2001-03-15 | 2001-03-15 | Method of manufacturing for electrolyte membrane electrode joint body for fuel cell |
| JP088676/2001 | 2001-03-26 |
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| CN1703793A true CN1703793A (en) | 2005-11-30 |
| CN1310362C CN1310362C (en) | 2007-04-11 |
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| CN (1) | CN1310362C (en) |
Cited By (2)
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|---|---|---|---|---|
| CN101887975A (en) * | 2010-04-09 | 2010-11-17 | 新源动力股份有限公司 | Integrated preparation method for membrane-membrane electrode for fuel cell |
| CN102414888A (en) * | 2010-02-10 | 2012-04-11 | 松下电器产业株式会社 | Catalyst-coated membrane assembly manufacturing method and device |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3898707B2 (en) * | 2004-05-10 | 2007-03-28 | 行政院原子能委員會核能研究所 | Manufacturing method of fuel cell membrane electrode assembly manufactured by printing process |
| JP2006059661A (en) * | 2004-08-19 | 2006-03-02 | Toyota Motor Corp | Solid polymer fuel cell |
| CN1949568B (en) | 2005-10-13 | 2010-09-29 | 比亚迪股份有限公司 | Method for preparing membrane electrode of fuel cell |
| JP2008108468A (en) * | 2006-10-23 | 2008-05-08 | Aisin Seiki Co Ltd | Fuel cell film, membrane electrode assembly, and fuel cell |
| JP6136419B2 (en) * | 2013-03-21 | 2017-05-31 | 凸版印刷株式会社 | Membrane electrode assembly and fuel cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5547551A (en) * | 1995-03-15 | 1996-08-20 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
| DE19548421B4 (en) * | 1995-12-22 | 2004-06-03 | Celanese Ventures Gmbh | Process for the continuous production of membrane electrode assemblies |
| JPH1064574A (en) * | 1996-08-26 | 1998-03-06 | Fuji Electric Co Ltd | Manufacture of solid high polymer electrolyte type fuel cell |
| JP3805495B2 (en) * | 1996-09-24 | 2006-08-02 | 松下電器産業株式会社 | Polymer electrolyte fuel cell |
| JPH1116586A (en) * | 1997-06-20 | 1999-01-22 | Japan Storage Battery Co Ltd | Manufacture of high polymer electrolyte film-gas diffusion electrode body |
| US5879828A (en) * | 1997-10-10 | 1999-03-09 | Minnesota Mining And Manufacturing Company | Membrane electrode assembly |
| US6042959A (en) * | 1997-10-10 | 2000-03-28 | 3M Innovative Properties Company | Membrane electrode assembly and method of its manufacture |
| JP2000285932A (en) * | 1999-03-31 | 2000-10-13 | Asahi Glass Co Ltd | Manufacture of electrode/film junction for solid polymer fuel cell |
-
2001
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102414888A (en) * | 2010-02-10 | 2012-04-11 | 松下电器产业株式会社 | Catalyst-coated membrane assembly manufacturing method and device |
| CN101887975A (en) * | 2010-04-09 | 2010-11-17 | 新源动力股份有限公司 | Integrated preparation method for membrane-membrane electrode for fuel cell |
| CN101887975B (en) * | 2010-04-09 | 2012-07-18 | 新源动力股份有限公司 | Integrated preparation method for membrane-membrane electrode for fuel cell |
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| JP2002280012A (en) | 2002-09-27 |
| CN1310362C (en) | 2007-04-11 |
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