CN1794507A - Electrolyte membrane, process for its production and membrane-electrode assembly for polymer electrolyte fuel cells - Google Patents
Electrolyte membrane, process for its production and membrane-electrode assembly for polymer electrolyte fuel cells Download PDFInfo
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- CN1794507A CN1794507A CNA2005101361686A CN200510136168A CN1794507A CN 1794507 A CN1794507 A CN 1794507A CN A2005101361686 A CNA2005101361686 A CN A2005101361686A CN 200510136168 A CN200510136168 A CN 200510136168A CN 1794507 A CN1794507 A CN 1794507A
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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
The invention provides an electrolyte membrane having high strength even if it is thin in the thickness, excellent dimensional stability even upon absorption of water and a low electrical resistance; a process for producing the electrolyte membrane; and a membrane-electrode assembly for polymer electrolyte fuel cells having a high output and excellent durability, having the electrolyte membrane. An electrolyte membrane which is made mainly of an ion exchange resin and reinforced with a non-woven fabric made of continuous fiber of a fluororesin wherein at least some of intersecting points of the continuous fiber are fixed, and which has, as the outermost layer on one side or each side, a layer not reinforced, made of an ion exchange resin which may be the same as or different from the above ion exchange resin.
Description
The present invention relates to a kind of dielectric film enhanced with supatex fabric and its manufacturing method, the membrane-electrode assembly for polymer electrolyte fuel cells with the dielectric film.
In recent years, the research for the polymer electrolyte fuel cells for using the polymer film of proton conductive as electrolyte is being carried out always.Characteristic possessed by such polymer electrolyte fuel cells enables them to operate at low temperature, provides high output density and can minimize, therefore, it is contemplated that they can be used as such as energy source of car.
As the dielectric film for polymer electrolyte fuel cells, usually using the proton conductive amberplex of 20-200 μ m-thick.
The basic performance of the cation-exchange membrane of perfluocarbon polymer (hereinafter referred to as sulfonic perfluorocarbon polymer) composition especially with sulfo group is excellent, therefore is widely studied.
As the method for reducing this cation-exchange membrane resistance, it can be used and increase sulfo group concentration or reduction film thickness.However, film-strength can decline if sulfo group concentration dramatically increases, or film can be easy creep during fuel cell long period of operation, therefore lead to the problem of such as fuel cell durability declines.On the other hand, if the thickness of film reduces, the problem is that the mechanical strength of film reduces, and the case where the film is integrated in gas-diffusion electrode to manufacture membrane-electrode assembly, such processing can relatively difficult or treatment effeciency it is poor.
In addition, the film longitudinal size of dielectric film can become larger, various so as to lead to the problem of after absorbing water.For example, in a fuel cell by membrane-electrode assembly assembling, then operating, which can be such that film size increases by the swelling such as the water of reaction formation or the steam supplied together with fuel gas.When by film and electrode adhesion, electrode would generally follow the change in size of film.Membrane-electrode assembly is usually limited by partition etc., which has flow channel of the groove formed as gas, therefore film size increase causes " fold ".And such fold can be filled in the groove of partition, hinder gas flowing.
A kind of method has been proposed as a method of solving this problem, i.e., impregnates porous media (patent document 1) made of polytetrafluoroethylene (PTFE) (hereinafter referred to as PTFE) with sulfonic perfluorocarbon polymer.However, the porous media of this PTFE is relatively soft due to being PTFE material, humidification is insufficient, not can solve the above problem yet.Furthermore, it is also proposed that excessively a kind of method, porous media (patent document 2) made of spent ion exchange resin filled polyolefin, but its chemical durability is insufficient, thus there are problems in terms of long-time stability.
Further it is proposed that another Enhancement Method, is using fluororesin fiber.There is the method (patent document 4) of a kind of method (patent document 3) of the cation-exchange membrane for preparing and being enhanced with the fluorocarbon polymer reinforcing material of fibrinogen form or the polymer film of preparation fluororesin short fiber reinforced.In these final products, the winding or bonding that reinforcing material itself occurs can not be affirmed, so reinforcing effect is poor, it is necessary to relatively great amount of this kind of reinforcing material be added.In this case, the processing of film tends to be difficult, and is likely to that film resistance increase occurs.
Furthermore, patent document 5 proposes a kind of dielectric film for polymer electrolyte fuel cells, and film fluorination fibre plate enhancing, fluorine fiber therein is discontinuous staple fiber, length is up to 15mm, adhered to one another with binder such as viscose glue, carboxymethyl cellulose or polyvinyl alcohol.This binder is impurity for the dielectric film for fuel cell, and remaining binder can significantly affect the durability of fuel cell.In addition, using the fiber of considerable larger diameter, i.e. fibre diameter is 15 μm, and is to reach well-bonded between fiber, it is desirable that the thickness of amplified medium is times over fibre diameter, therefore, it is considered that being easy to bring increase film resistance in this proposal.Moreover, in the method for handling discontinuous staple fiber according to such as papermaking process, the problem is that thin film is made, therefore with superfine fiber, in this way, actual operation has difficulties.
Patent document 1:JP-B-5-75835 (claims)
Patent document 2:JP-B-7-68377 (claims)
Patent document 3:JP-A-6-231779 (claims)
Patent document 4:WO04/011535 (claims)
Patent document 5:JP-A-2003-297394 (claims, the 0012nd and 0026 section)
Summary of the invention
In such cases, even if it is an object of the present invention to provide still having high-intensitive dielectric film, this dielectric film excellent size stability after absorbing water when one kind thinner thickness, and there is low resistance.Further, it is another object of the present invention to provide a kind of membrane-electrode assembly for polymer electrolyte fuel cells, the sub-assembly is because of with such dielectric film, excellent durability and with high output.
The present invention provides a kind of dielectric film being mainly made of ion exchange resin, the supatex fabric enhancing constituted with the continuous fiber of fluororesin, wherein, at least part crosspoint of continuous fiber is fixed, and the dielectric film or it is per while on have that ion exchange resin is constituted but non-reinforced layer is as outer layer, the ion exchange resin of non-reinforced layer with foregoing ion exchanger resin can be identical or different.
Supatex fabric of the invention is made of continuous fiber, and wherein fiber itself, which is formed, adequately tangles, and can form the quantity very little of the fibre end of dynamic defect.Moreover, at least part crosspoint of continuous fiber is fixed, keep elasticity modulus higher.Therefore, the mechanical strength properties of the dielectric film enhanced by such supatex fabric are excellent.
Dielectric film of the invention or it is per while on have ion exchange resin constitute non-reinforced layer as outer layer, the ion exchange resin of the outer layer can be identical or different with above-mentioned ion exchange resin.There is such outer layer, when dielectric film of the invention is used as the polymer dielectric film of polymer electrolyte fuel cells, the resistance of dielectric film and electrode bound fraction can be reduced.
Furthermore, the present invention provides a kind of methods for manufacturing the dielectric film, this method comprises: spraying the fluororesin of the fusible molding of molten state from a spinning head, fluororesin is stretched by the gas being discharged from the exhaust nozzle being arranged near spinning head and is sprayed into silk, continuous fiber is obtained, continuous fiber is then formed into supatex fabric.
Using method of the invention, composition nonwoven fibres can be made to the fiber of superfine length, and dielectric film can be inhibited due to resistance increase caused by enhancing, so as to form the supatex fabric for the dielectric film reinforcing material for being suitable as fuel cell.
It is preferred that forming supatex fabric in the surface collection continuous fiber with adsorption function (air-suction), the binder solution that subsequent hot pressing or application are made of the fluoropolymer for dissolving in solvent bonds the crosspoint of continuous fiber.
Furthermore, the present invention is provided to the membrane-electrode assemblies of polymer electrolyte fuel cells, it includes cathode and anode respectively with the catalyst layer comprising catalyst and ion exchange resin, and slotting dielectric film between a cathode and an anode, which is constituted by above-mentioned dielectric film.
The supatex fabric enhancing that the continuous fiber of dielectric film fluororesin of the present invention is constituted, makes increase very little of the resistance due to this enhancing, and when film thickness is relatively thin has sufficiently high intensity.In addition, excellent size stability of the dielectric film after absorbing water, even if the polymer electrolyte fuel cells long period of operation with this dielectric film remains to provide constant high output.
Brief Description Of Drawings
Fig. 1 is the sectional view of the spinning head used in the equipment of manufacture meltblown nonwoven fabric.
In Fig. 1, number 1 indicates fluororesin, and 2 be gas, and 3 be the outlet of spinning head, and 4 be the outlet of exhaust nozzle.
Supatex fabric of the present invention is made of the continuous fiber of fluororesin.In the present invention, continuous fiber refers to the fiber that draw ratio is at least 10,000.Fibre length preferably at least 20mm.
Preferably 0.01-13 μm of the fibre diameter of continuous fiber.Due to the fibre diameter very little of continuous fiber, proton transfer can be further smoothly carried out, so as to inhibit resistance to increase since this supatex fabric enhances.In addition, if fibre diameter is small, the quantity of fiber intersection points will increase in same film thickness, so as to improve the intensity of supatex fabric, and improve the dimensional stability of dielectric film.On the other hand, if fibre diameter is too small, the tensile strength of every fiber is lower, is difficult to actually use for processing efficiency angle.Preferably 0.01-5 μm of fibre diameter, preferably 0.01-3 μm.
In the present invention, the fluororesin for constituting supatex fabric is preferably the homopolymer for being based on such as perfluoroolefine such as tetrafluoroethene or hexafluoropropene, chlorotrifluoroethylene or perfluor (alkyl vinyl ether) monomer or the copolymer containing at least one monomeric unit based on these monomers.
Specifically, such as it can be tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer (PFA), Tefzel (ETFE), a tetrafluoroethylene/hexafluoropropylene copolymer (FEP), polytrifluorochloroethylene (PCTFE), ethylene/chlorotrifluoroethylene (ECTFE), gather inclined 1,1- fluoride polymer (PVdF) or polyvinyl fluoride polymer (PVF), the mixture of copolymer or these polymer comprising multiple monomeric units for constituting these polymer.
In these fluororesin, the fluororesin of preferably fusible molding, such as ETFE, PFA, FEP or PVDF, and PFA and ETFE has particularly excellent a mechanical strength and mouldability and it is preferred that.As ETFE, monomeric unit/monomeric unit based on ethylene molar ratio based on tetrafluoroethene (hereinafter referred to as TFE), preferably 70/30 to 30/70, more preferably 65/35 to 40/60.
Above-mentioned ETFE, PFA, FEP or PVDF contain on a small quantity based on the monomeric unit of comonomer.Such comonomer is, for example, the alkene in addition to ethylene, such as vinyl fluoride such as CF2=CFCl；Fluoropropene CF2=CFCF3Or CF2=CHCF3；With C2-12Perfluoroalkyl such as CF3CF2CF2CF2CH=CH2Or CF3CF2CF2CF2CF=CH2Vinyl fluoride；Perfluoroalkyl vinyl ether such as Rf(OCFXCF2)kOCF=CF2(wherein RfIt is C1-6Perfluoroalkyl, X are fluorine atom or trifluoromethyl, and k is the integer of 0-5)；With being easy to be changed into the perfluoroalkyl vinyl ether of carboxyl or sulfo group, such as CH3OC (=O) CF2CF2CF2OCF=CF2Or FSO2CF2CF2OCF(CF3)CF2OCF=CF2；C3Alkene such as propylene；Or C4Alkene such as butylene or isobutene.As the monomer of ETFE, particularly preferred CF3CF2CF2CF2CH=CH2, as the comonomer to PFA, particularly preferred CF3CF2OCF=CF2、CF3CF2CF2OCF=CF2Or CF3CF2CF2OCF(CF3)CF2OCF=CF2。
Containing the monomeric unit situation based on above-mentioned comonomer, the content of these monomeric units is generally at most 30 moles of %, more preferably 0.1-15 moles of %, preferably 0.2-10 moles of % on the basis of the monomeric unit total amount to ETFE, PFA, FEP or PVDF.
The melt flow rate (MFR) (MFR) of fluororesin about fusible molding, to PFA, according to the MFR preferably 40-300g/10min of ASTM D3307.The case where to form very fine fibre, productivity is improved with the reduction of spinning head pressure drop, therefore, more preferably at least 60g/10min.In addition, if MFR is larger, fibre strength obtained can decline, therefore more preferably be at most 150g/10min.In ETFE situation, according to the MFR preferably at least 40g/10min of ASTM D3159.
For supatex fabric of the invention, the processing selected from following at least one type: radiation treatment, corona treatment and the chemical treatment with metallic sodium is preferably carried out.Processing in this way introduces polar group such as-COOH ,-OH or-COF in fiber surface, to improve the adherence on the interface between the ion exchange resin and supatex fabric as matrix, therefore improves humidification.
It is preferred that when using meltblowing method being fluororesin such as PFA or ETFE of fusible molding as fluororesin manufacture supatex fabric method.Fiber is initially formed by resin with the method for another manufacture supatex fabric, the method for then forming supatex fabric is compared, and the productivity of meltblown is high, because the formation of fiber and the formation of fabric can be carried out substantially simultaneously.Furthermore, it is possible to the fiber for constituting supatex fabric is made very elongated, it is suppressed that dielectric film is due to resistance increase caused by enhancing, so as to form the supatex fabric for the dielectric film for being highly suitable for fuel cell.
Fig. 1 is nozzle cross-section figure used in the equipment of meltblown manufacture supatex fabric.In meltblown, the fluororesin 1 of fusible molding is flowed out with molten condition from spinneret exits 3, and fluororesin is stretched to and is sprayed into silk by the gas 2 being discharged from the outlet for the exhaust nozzle being arranged near spinning head 4, obtains continuous fiber.Such continuous fiber is collected on the surface with adsorption function, to form supatex fabric.
Surface with adsorption function refers to, for example, the very fine fibre of dispersion can be made to form the device of form of fabric by the swabbing action of decompression by the air in a kind of film base material one side.What film base material with gas permeability is limited without, but can be such as net, cloth or porous media, when being also not particularly limited to these materials, but forming supatex fabric by fluororesin, the net preferably constituted with metal, because the fusing point of metal is higher.
About air-swabbing action, it is desirable that have the suction capactity that can sufficiently aspirate and the continuous fiber sprayed is kept to become form of fabric.Therefore, the surface with adsorption function is compared with fortunately away from having at least wind speed of 0.1m/sec in the 1cm of surface.In addition, if the Kong Tai great on the surface with adsorption function, fiber itself can be drawn into net and be difficult to separate, or be likely to lose flatness.Therefore, the hole of net is preferably up to 2mm, is more preferably up to 0.15mm, is preferably up to 0.06mm, is particularly preferably up to 0.03mm.
Have a case that flexibility in the film base material with gettering ability, which can be placed on to the conveyer belt of an energy continuous rotation, and is used as the transmission material that there is gettering ability can collect.For example, a kind of method can be used, by film base material continuous spreading of the volume on a roller, and supatex fabric is formed at a surface thereof, then separate and is rolled, to simplify manufacturing method.
The bulk density of obtainable supatex fabric is influenced by the hardness or thermal property of resin used.Using meltblown, by using the resin of low viscosity, the supatex fabric of some crosspoint weldings with fiber usually can be obtained.In addition, in some cases, such welding may not occur, it then can first obtain the cotton shape precursor for supatex fabric, they can be collected by the conveyer belt for collection with getter action, then carried out pressurization combination, obtained the supatex fabric of predetermined bulk density.
In the method for above-mentioned formation supatex fabric, as the crosspoint of fruit fiber is not fixed, such as the operation processing of winding can be more difficult.When at least partly crosspoint of fiber is fixed, the elasticity modulus and intensity as supatex fabric base substance can get.As a result, the self-supporting property of supatex fabric itself has been obtained, to improve treatment effeciency, and manufacturing, there is the dielectric film of this supatex fabric will also become easy.At least part crosspoint of fiber is fixed, as described above, have following manner: (1) collecting when continuous fiber forms supatex fabric makes fiber welding, (2) by hot pressing supatex fabric come welding fiber therein, (3) solution for the adhesive being made of coating the fluoropolymer for dissolving in solvent bonds the crosspoint of wherein fiber.
Hot pressing in the mode (2), welding deformation does not occur for fiber but is provided under melting-cementing property temperature range to carry out more fortunately.Although this depends on the thermal property for constituting the fluororesin of fiber the case where crystallizing fluororesin, hot pressing is more preferably being carried out from (- 20 DEG C of fusing point) to melting range more fortunately from (- 50 DEG C of fusing point) to the temperature range of fusing point.In noncrystalline fluororesin situation, preferably from (- 50 DEG C of glass transition temperature) to the range of glass transition temperature, hot pressing more preferably is carried out in the range from (- 20 DEG C of glass transition temperature) to glass transition temperature.In addition, pressure when hot pressing is although dependent on above-mentioned temperature range used, but generally it can be carried out welding in this way in 0.5-10MPa range, and apparent fibre deformation will not be generated.
In aforesaid way (3), refer to and can be dissolved with solvent for the fluoropolymer for dissolving in solvent in binding fiber crosspoint, and room temperature can be with fluoropolymer existing for at least solution form of 0.1 concentration.Here, the solution in this specification includes the liquid that macroscopic observation is solution, but microcosmic fluoropolymer therein exists with dispersity or solvent swelling state.
Above-mentioned adhesive is made of fluoropolymer, therefore in the environment for actually using the fuel cell, chemical durability is excellent.Preferred polymer is that the hydrogen atom being wherein connected on carbon atom is all replaced by fluorine atoms.In addition, the fluoropolymer-containing elasticity modulus for dissolving in solvent should be higher, to improve the intensity of the supatex fabric with this adhesives.Fluoropolymer room temperture elastic modulus preferably at least 105Pa, preferably at least 108Pa.This means that fluoropolymer-containing glass transition temperature is at least room temperature in terms of glass transition temperature angle, it is preferably at least 40 DEG C (this temperature is considered within the scope of industrial room temperature).
Polymer (i) described below is to (iii) as the fluoropolymer-containing preferred example for dissolving in solvent for constituting adhesive.
(i) fluoropolymer in molecule containing ion-exchange group or its precursor group.
Ion-exchange group can be such as sulfo group (- SO3) or sulfimide base (- SO H2NHSO2Rf, wherein RfIt is perfluoroalkyl).In addition, the precursor group of such ion-exchange group can be such as-SO2F base.Particularly preferably with the fluoropolymer of ion-exchange group, because it can become electrolyte, the open area ratio (open area ratio) of supatex fabric will not be reduced, and not will lead to the increase of dielectric film resistance.Fluoropolymer with ion-exchange group can be identical or different with the ion exchange resin of composition dielectric film.
As having ion-exchange group or its precursor in molecule, and main chain is the example of the fluorocarbon polymer of aliphatic structure, preferably comprising based on by CF2=CF- (OCF2CFX)m-Op-(CF2)n-SO2F is (wherein, X is fluorine atom or trifluoromethyl, m is the integer of 0-3, n is the integer of 0-12, p is 0 or 1, as long as working as n=0, p=0 when m=1-3) copolymer of the repetitive unit of perfluorochemical that indicates, or such copolymer is hydrolyzed for sour form (- SO therein2F base is changed into-SO3H yl) obtain polymer.It is known that having-SO2The fluoropolymer of F base can be dissolved in the flon solvent such as ASAHIKLIN AK-225 (being prepared by Asahi Glass Co., Ltd) of a kind of substitution, it is generally known that have-SO3The fluoropolymer energy solvent of H base is in ethanol.
(ii) it is substantially free of ion-exchange group and has the fluoropolymer of alicyclic structure in main chain.
This fluoropolymer is distorted as caused by its molecular structure and is difficult to crystallize, and energy solvent is in fluorocarbon solvents.Main chain has the fluoropolymer-containing example of alicyclic structure, there is the polymer containing following structural formula (a), (b) and the repetitive unit of any expression in (c).This quasi polymer can be dissolved in such as perfluor benzene, trifluoroethane, perfluor (2- butyl tetrahydrofuran) or Fluorinert FC-77 (manufacture of 3M company).
(iii) it is substantially free of the fluoroolefin type fluoropolymer of ion-exchange group.
This fluoropolymer can be such as tetrafluoroethylene/hexafluoropropylene/1,1- fluoride copolymers, or comprising based on selected from tetrafluoroethene, hexafluoropropene, vinylidene fluoride and chlorotrifluoroethylene at least one repetitive unit and based on selected from vinyl ethers, vinyl esters, the copolymer of at least one repetitive unit of allyl ether, allyl ester, isopropenyl ethers, isopropenyl ester, metering system ether, methacrylate, acrylate and methacrylate.
This fluoropolymer can be dissolved in ketone, esters, chloric ethane, benzene derivative etc..
For the solvent containing binder solution preferably can on the surface with adsorption function drying and curing, therefore preferably a kind of boiling point is up to 150 DEG C of solvent, and more preferable boiling point is at least a kind of 100 DEG C of solvent.To guarantee to be easy the fiber intersection points of bonded nonwoven fabric, the content of the solvent with above-mentioned boiling point is at least the 75% of solvent gross mass, preferably at least 95%, preferably at least 98%.
Solution containing adhesive preferably uses spraying method to apply.When using spraying method, the solution containing adhesive is set to form sprayable state, supatex fabric contains binder solution by spray regime, when the solution is sucked into the surface with adsorption function, adhesive can be selectively applied on fiber, the hole without blocking supatex fabric.
The characteristics of spray coating method is from small hole while to spray carrier gas and the solution to be applied, and spray regime is influenced by solution viscosity is applied.In the paint finishing of common air-jetting type, it is known that by the shear stress in spray nozzle front end pneumatically, solution forms fine drop, and solution viscosity is lower, and the drop of formation is smaller.In addition, being by the way that in spray nozzle front end, since the shear stress that the injection of solution itself generates generates fine drop, viscosity is lower at this time, and effect is better in the airless spraying system without using ejection medium such as air.If drop is larger, adhesive can block the hole of supatex fabric.Therefore, the viscosity of the solution containing adhesive is preferably at most 10Pas, more preferably at most 1Pas, particularly up to 0.1Pas.
In the present invention, the ion exchange resin of the main component as dielectric film can be cation exchange resin, and the cation exchange resin being made of hydrocarbon polymer or partially fluorinated hydrocarbon polymer can be used for example.Be used for fuel cell the case where, preferably excellent durability sulfonic perfluorocarbon polymer constitute cation exchange resin.Ion exchange resin in dielectric film can be a kind of ion exchange resin composition, be also possible to the ion exchange resin of two or more mixing.
Common polymer can be used as sulfonic perfluoro carbon polymer.For example, sulfonic perfluoro carbon polymer can be by that will have SO2The precursor that the resin of F end group is constituted, which is hydrolyzed, becomes sour form to obtain.Here, in the present specification, perfluocarbon polymer can contain such as ether oxygen atom.
By with SO2Precursor made of the resin of F end group preferably includes based on by CF=CF- (OCF2CFX)m-Op-(CF2)n-SO2F is (wherein, X is fluorine atom or trifluoromethyl, m is the integer of 0-3, n is the integer of 0-12, p is 0 or 1, as long as working as n=0, when p=0, m=1-3) monomeric unit of perfluorochemical that indicates and the monomeric unit based on perfluoroolefine such as tetrafluoroethene or hexafluoropropene, chlorotrifluoroethylene or perfluor (alkyl vinyl ether) copolymer.It particularly preferably include the monomeric unit based on above-mentioned perfluorochemical and the copolymer based on tetrafluoroethylene monomer unit.
As the preferred example of above-mentioned perfluorochemical, the compound for thering is any of following chemical formula to indicate.Below in chemical formula, q is the integer of 1-8, and r is the integer of 1-8, and s is the integer of 1-8, and t is the integer of 1-5.
CF2=CFO (CF2)qSO2F
CF2=CFOCF2CF(CF3)O(CF2)rSO2F
CF2=CF (CF2)sSO2F
CF2=CF (OCF2CF(CF3))tO(CF2)2SO2F
In addition, the cation exchange resin of the polymer in addition to perfluocarbon polymer, can be the copolymer for example comprising the monomeric unit and the monomeric unit indicated by following structural formula (2) that are indicated by following structural formula (1).Here, P1It is phenyl trityl (triyl), xenyl trityl, naphthalene trityl, phenanthryl trityl or anthracene trityl, P2It is phenylene, biphenylene, naphthylene, phenanthrylene or anthrylene, A1It is-SO3M2Base (wherein, M2Be hydrogen atom or alkali metal atom, be below also such) ,-COOM2Base or the group that this group can be changed by hydrolyzing, B1And B2It is oxygen atom, sulphur atom, sulfonyl or isopropylidene each independently.To P1Or P2Constitutional isomer be not particularly limited.P1Or P2In at least one hydrogen atom can be by fluorine atom, chlorine atom, bromine atom or C1-3Alkyl replaces.
-P2-B2- (2)
The case where being used as the polymer dielectric film of fuel cell, the ion exchange capacity of ion exchange resin of the invention is preferably 0.5-2.0meq/g dried resin, particularly preferred 0.7-1.6meq/g dried resin.If ion exchange capacity is too small, resistance can be larger.On the other hand, if ion exchange capacity is too big, the affinity with water can be too strong, and dielectric film is likely to dissolve during power generation.
If dielectric film is too thick, the resistance of film can be larger.In addition, the thinner effect of film thickness is better, because counter diffusion may occur for the water formed on the cathode side in the polymer dielectric film situation for being used as fuel cell.On the other hand, the problem of dielectric film is too thin, can be extremely difficult to enough mechanical strengths, and may bring such as gas leakage.Therefore, the thickness of dielectric film of the invention, the upper limit are preferably up to 100 μm, more preferable 50 μm maximum, preferably 30 μm maximum, and preferably at least 5 μm of lower limit, preferably at least 20 μm.
In addition, the thickness of supatex fabric is preferably up to 50 μm from the point of view of the thickness of above-mentioned dielectric film, and it is more preferable 30 μm maximum, it is preferably 20 μm maximum.At this point, considering from reaching humidification and reducing film resistance, the Unit Weight of supatex fabric preferably 5-50g/m2(2.5-25c/m2)。
Manufacture is mainly made of ion exchange resin and the method for the dielectric film with supatex fabric enhancing, can be the method below for example: (1) casting method: the solution of supatex fabric spent ion exchange resin or dispersion liquid are coated or impregnated at this time, it is subsequently dried to form film, or a kind of (2) method, wherein, in a heated condition, the ion exchange resin material for being pre-formed form membrane is laminated on supatex fabric and is integrally formed.The composite membrane of such supatex fabric and ion exchange resin can be enhanced by stretching etc..
Dielectric film its or it is per while on have that ion exchange resin is constituted but non-reinforced layer is as outer layer, this ion exchange resin can be identical or different with the above-mentioned ion exchange resin by supatex fabric enhancing.Resistance in the adhesive segment of dielectric film and electrode can be reduced when dielectric film of the invention is used as the polymer dielectric film of polymer electrolyte fuel cells using such structure.There is such situation, when forming the composite membrane of supatex fabric and ion exchange resin as described above, will be made of ion exchange resin but the layer not reinforced is formed as outer layer.Furthermore it is possible to the solution of ion exchange resin or dispersion liquid are applied in the surface of composite membrane, or an ion exchange resin membrane is laminated on the surface of the composite membrane after forming such composite membrane, layer be made of ion exchange resin but non-reinforced is formed.It is preferred that outer layer of the non-reinforced layer as every one side.Layer be made of ion exchange resin but non-reinforced can contain the component other than reinforcing material without increasing resistance.
Preferably 1-20 μm on each face of the thickness of non-reinforced layer, because there can be good barrier action to the fuel gas of fuel cell in this way, and film resistance can be inhibited.This non-reinforced preferably 2-15 μm of thickness degree, best 2-10 μm.Here, in the present specification, the thickness of non-reinforced layer can observe its section with such as optical microscopy, laser microscope or SEM to measure.The thickness of non-reinforced layer refers to shortest distance between dielectric film surface and nonwoven fibres.
When dielectric film of the present invention is used as the polymer dielectric film of polymer electrolyte fuel cells, proton transfer is covered by the fiber of supatex fabric.If the thickness of non-reinforced layer is too thin, electric current is that the path length avoiding fiber and detour is larger, therefore causes the unnecessary increase of resistance.Especially when the thickness of non-reinforced layer is less than the half of fibre diameter, resistance is significantly increased.When the case where non-reinforced thickness degree corresponding at least to the fiber radius of continuous fiber, the path length that detours of electric current may be smaller, therefore, can avoid unnecessary resistance and increases, this is to need in this way.
Dielectric film of the invention may be used as the polymer dielectric film of the membrane-electrode assembly of polymer electrolyte fuel cells.Membrane-electrode assembly for polymer electrolyte fuel cells includes the cathode and anode of each own catalyst layer comprising catalyst and ion exchange resin, and inserts polymer dielectric film between a cathode and an anode.
Conventionally, it can be made using for example following method for the membrane-electrode assembly of polymer electrolyte fuel cells.First, obtain a homogeneous dispersion, the dispersion includes the fine grain conductive carbon black powder loaded platinum catalyst or platinum alloy catalyst above it and the liquid composition containing electrolyte, and forms gas-diffusion electrode using following any method, obtains membrane-electrode assembly together.
First method is: above-mentioned dispersion is applied on the two sides of dielectric film, it is dry, and then two panels carbon paper or carbon film are bonded on this two sides.Second method is: above-mentioned dispersion is coated on two panels carbon paper or carbon film, it is dry, and then dielectric film is clipped between the two panels carbon paper or carbon film, is bonded on dielectric film on one side so that being coated with dispersion.The third method is: above-mentioned dispersion being coated on a piece of base material film in addition prepared, drying forms catalyst layer, then, which is transferred to the two sides of dielectric film respectively, then two panels carbon paper or carbon film are bonded on this two sides.Here, carbon paper or carbon film have the function of passing through the uniform diffusion gas of the layer containing catalyst as current-collector and gas diffusion layers.
Membrane-electrode assembly obtained is clipped between two partitions, the groove for constituting the channel of fuel gas or oxidizing gas is formed respectively on partition to be had, the anode surface of membrane-electrode assembly is supplied hydrogen to, oxygen or air supply cathode plane, to constitute polymer electrolyte fuel cells.
Embodiment
In the following, referring to some embodiments and comparative example, present invention be described in more detail, it should be understood that the present invention is not limited by these embodiments and comparative example.
Embodiment 1
Use a kind of equipment (being manufactured by NIPPON NOZZLE Co., Ltd) and PFA (trade name: Fluon PFA P-61XP for manufacturing meltblown nonwoven fabric, it is manufactured by Asahi Glass Co., Ltd, MFR=40g/10min.), it is 330 DEG C in spinneret temperature, under conditions of hot air temperature for stretching is 360 DEG C, supatex fabric is formed on the conveyer belt with suction capactity.Constitute supatex fabric is fluororesin continuous fiber, and draw ratio is at least 10,000.With the micro- region sem observation supatex fabric 2.6cm × 2.6cm, because not observing that fibre length is not more than the fiber of 13mm at this time.Then, which passes through (290 DEG C, 10MPa) of hot pressing densifications.Wherein the diameter of fiber is 10 μm, supatex fabric with a thickness of 20 μm, the Unit Weight of supatex fabric is 10g/m2(5cc/m2)。
Then, the edge of taut firmly supatex fabric in a certain way, supatex fabric is immersed in ion exchange resin in the solution (solids level concentration: 5 mass %) of ethyl alcohol (as solvent) using this state, the ion exchange resin (hereinafter referred to as ion exchange resin (A)) is by CF2=CF2With CF2=CF-OC2FCF(CF3)-OCF2CF2SO3The copolymer of H is constituted, and ion exchange capacity is 1.1meq/g dried resin, and pulls the supatex fabric with 100mm/min. speed, so that above-mentioned ion exchange resin (A) is impregnated into supatex fabric.This immersion/drawing operation in triplicate, then still it is taut live state under, 55 DEG C drying 1 hour, acquisition composite membrane.
On the other hand, the solution by above-mentioned ion exchange resin (A) in alcohol solvent, is applied on a piece of PET film with die coating method, 1 hour dry at 140 DEG C, obtain be made of above-mentioned ion exchange resin (A) with a thickness of 10 μm of monofilm 1.
Above-mentioned monofilm 1 is respectively placed in every one side of above-mentioned composite membrane, is carried out hot pressing (160 DEG C, 5Pa, 15 minutes), dielectric film is obtained.It to this dielectric film, is tested using following method, test result is listed in table 1.In addition, with its section of laser capture microdissection sem observation, obtain non-reinforced layer with a thickness of 10 μm.
Measure tear strength
Firstly, cutting the square sample of wide 100mm, long 100mm from dielectric film, it is used for ionization meter.The cutting line of a 50mm is marked from sample one end to sample centre with pocket knife.Then, it is torn to make to cut line front end, with the fixture up and down of cupping machine, two ends is separated up and down, and with the tearing of the speed of 500mm/min.Relative to the vertical and horizontal of film, the value that power needed for measurement tearing is obtained divided by Electrolyte film thickness is averaged as tear strength.
Change in size after measurement water suction
Dielectric film is cut into 200mm × 200mm square, 25 DEG C is exposed to, 16 hours in the environment of 50% humidity, measures the vertical and horizontal length of sample.Then, sample is immersed in 25 DEG C of deionized waters 1 hour, then measures vertical and horizontal length in the same way.The average value that sample is extended in vertical and horizontal is obtained, as change in size.
It prepares fuel cell and is tested
Fuel cell is assembled as follows.Firstly, ion exchange resin (A) is put into the mixed solvent (1: 1 mass ratio) of second alcohol and water, and in the flask with reflux unit, 60 DEG C of stirrings are dissolved for 16 hours, obtain the polymer solution that solid content is 9%.Then, the carbon dust, water and ethyl alcohol for having loaded platinum are added in order, obtains the catalyst dispersion (solid content: 9 mass %) being dispersed in the mixed dispersant of second alcohol and water (1: 1 mass ratio).Then, the polymer solution and catalyst dispersion are mixed with 11: 3 mass ratio, obtains coating solution.Then, using die coating method, this coating solution is applied in every one side of dielectric film, forms the catalyst layer of 10 μ m-thicks after dry in every one side of film, platinum load capacity is 0.5mg/cm2.Again in the outside of every one side, carbon cloth is placed as gas diffusion layers, membrane-electrode assembly is made.In the outside of the every one side of the membrane-electrode assembly, the partition made of carbon plate is placed, the narrow groove that zigzag is formd on the partition is used as gas passage, and heater is placed outside partition, to assemble polymer electrolyte fuel cells, effective membrane area is 25cm2。
Fuel cell is maintained at 80 DEG C, supplies air to cathode respectively under 0.15MPa pressure, hydrogen supplies anode.It is 0.1A/cm in current density2And 1A/cm2When, cell voltage is measured respectively.As a result it is listed in table 1.
Embodiment 2
Using the equipment and PFA of manufacture meltblown nonwoven fabric identical with embodiment 1, it is 350 DEG C in spinneret temperature, under conditions of the hot air temperature for stretching is 380 DEG C, forms supatex fabric on the conveyer belt with suction capactity.Then, by hot pressing (290 DEG C, 10MPa), densify the supatex fabric.Wherein the diameter of fiber is 5 μm, and for supatex fabric with a thickness of 20 μm, the Unit Weight of supatex fabric is 10g/m2(5cc/m2).Then, dielectric film is manufactured according to the same manner as in Example 1, and is similarly tested, and test result is listed in table 1.
Embodiment 3
Using the equipment and PFA of manufacture meltblown nonwoven fabric identical with embodiment 1, it is 380 DEG C in spinneret temperature, under conditions of the hot air temperature for stretching is 400 DEG C, forms supatex fabric on the conveyer belt with suction capactity.Then, by hot pressing (290 DEG C, 10MPa), densify the supatex fabric.Wherein the diameter of fiber is 0.5 μm, and for supatex fabric with a thickness of 20 μm, the Unit Weight of supatex fabric is 10g/m2(5cc/m2).Then, dielectric film is manufactured according to the same manner as in Example 1, and is similarly tested, and test result is listed in table 1.
Embodiment 4
Using the equipment and PFA of manufacture meltblown nonwoven fabric identical with embodiment 1, it is 330 DEG C in spinneret temperature, under conditions of the hot air temperature for stretching is 360 DEG C, forms supatex fabric on the conveyer belt with suction capactity.Then, by hot pressing (290 DEG C, 10MPa), densify the supatex fabric.Wherein the diameter of fiber is 0.5 μm, and for supatex fabric with a thickness of 200 μm, the Unit Weight of supatex fabric is 100g/m2(5cc/m2)。
According to the same manner as in Example 1, the supatex fabric is entered by having the solution of above-mentioned ion exchange resin (A) to be impregnated with, then with certain area ratio biaxial tension 10 times, prepare composite membrane, its fibre diameter is 0.05 μm, with a thickness of 20 μm, supatex fabric Unit Weight is 10g/m2(5cc/m2).Then, dielectric film is manufactured according to the same manner as in Example 1, and is similarly tested, and test result is listed in table 1.
Embodiment 5
Using the equipment and PFA of manufacture meltblown nonwoven fabric identical with embodiment 1, it is 330 DEG C in spinneret temperature, under conditions of the hot air temperature for stretching is 330 DEG C, forms supatex fabric on the conveyer belt with suction capactity.Then, by hot pressing (302 DEG C, 5MPa), densify the supatex fabric.Wherein the diameter of fiber is 15 μm, and for supatex fabric with a thickness of 20 μm, the Unit Weight of supatex fabric is 10g/m2(5cc/m2).Then, dielectric film is manufactured according to the same manner as in Example 1, and is similarly tested, and test result is listed in table 1.
Embodiment 6
Using the equipment and PFA of manufacture meltblown nonwoven fabric identical with embodiment 1, it is 330 DEG C in spinneret temperature, under conditions of the hot air temperature for stretching is 260 DEG C, forms supatex fabric on the conveyer belt with suction capactity.Then, by hot pressing (302 DEG C, 5MPa), densify the supatex fabric.Wherein the diameter of fiber is 10 μm, and for supatex fabric with a thickness of 20 μm, the Unit Weight of supatex fabric is 10g/m2(5cc/m2).Then, dielectric film is manufactured according to the same manner as in Example 1, is a difference in that the monofilm 2 using 5 μm of thickness made of ion exchange resin (A).It is similarly tested, test result is listed in table 1.
Embodiment 7
Using the equipment and PFA of manufacture meltblown nonwoven fabric identical with embodiment 1, it is 330 DEG C in spinneret temperature, under conditions of the hot air temperature for stretching is 260 DEG C, forms supatex fabric on the conveyer belt with suction capactity.Then, by hot pressing (302 DEG C, 5MPa), densify the supatex fabric.Wherein the diameter of fiber is 10 μm, and for supatex fabric with a thickness of 20 μm, the Unit Weight of supatex fabric is 10g/m2(5cc/m2)。
On the other hand, with die coating method, solution of the above-mentioned ion exchange resin (A) in alcohol solvent is applied on a piece of PEF film, and 1 hour dry at 140 DEG C, obtain above-mentioned ion exchange resin (A) with a thickness of 15 μm of monofilm 3.
Above-mentioned monofilm 3 is placed respectively in every one side of above-mentioned supatex fabric, and carries out hot pressing (165 DEG C, 5MPa, 5 minutes), obtains dielectric film.It is similarly tested, test result is listed in table 1.
Comparative example 1
The die head of monofilament is fixed on a general-purpose extruder, and uses a general FRP rebar machine, will be stretched with the identical PFA melting extrusion of embodiment 1 at 380 DEG C, is obtained PFA fiber (diameter of section: 15 μm).This PFA fiber is cut into 1mm length with scissors, and is mixed with solution (solids level concentration: 9 mass %s) of the ion exchange resin (A) in etoh solvent, the solution for being wherein dispersed with staple fiber is obtained.Then, which is applied on a substrate, obtains composite membrane after dry, it is dry after with a thickness of 20 μm.Then, dielectric film is manufactured according to the same manner as in Example 1, and is similarly tested, and test result is listed in table 2.
Comparative example 2
Composite membrane is manufactured according to the same manner as in Example 1, is not laminated non-reinforced layer above it at this time, manufactures dielectric film.It is similarly tested, test result is listed in table 2.
Comparative example 3
With die coating method, solution of the above-mentioned ion exchange resin (A) in etoh solvent is applied on a pet film, it is 1 hour dry at 140 DEG C, obtain 50 μm of thickness made of above-mentioned ion exchange resin of monofilm 4.It is similarly tested, test result is listed in table 2.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| Fibers form | Continuously | Continuously | Continuously | Continuously | Continuously | Continuously | Continuously |
| Fibre diameter (μm) | 10 | 5 | 0.5 | 0.05 | 15 | 10 | 10 |
| Supatex fabric thickness (μm) | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Non-reinforced thickness degree (μm) | 10 | 10 | 10 | 10 | 10 | 5 | 5 |
| Tear strength (N/mm) | 6 | 6 | 5 | 5 | 3.5 | 6 | 6 |
| Change in size (%) | 3.8 | 3.2 | 2.5 | 2 | 4.8 | 3.2 | 3.2 |
| 0.1A/cm2When cell voltage (V) | 0.75 | 0.76 | 0.77 | 0.77 | 0.75 | 0.75 | 0.75 |
| 1A/cm2When cell voltage (V) | 0.55 | 0.58 | 0.60 | 0.62 | 0.53 | 0.53 | 0.53 |
Table 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Fibers form | Staple fiber | Continuously | - |
| Fibre diameter (μm) | 15 | 10 | - |
| Supatex fabric thickness (μm) | 20 | 20 | - |
| Non-reinforced thickness degree (μm) | 10 | 0 | 50 |
| Tear strength (N/mm) | 3 | 6 | 0.5 |
| Change in size (%) | 6 | 3 | 15 |
| 0.1A/cm2When cell voltage (V) | 0.73 | 0.63 | 0.72 |
| 1A/cm2When cell voltage (V) | 0.51 | < 0.4 | 0.64 |
In following embodiment 8-10 and comparative example 4, according to the physical property of following method measurement adhesive and the physical property of supatex fabric.
Adhesive elasticity modulus, glass transition temperature
The fluoropolymer for dissolving in solvent for constituting adhesive is subjected to hot pressing (temperature: 200 DEG C, pressure: 5MPa), prepares about 200 μm of thickness of film sample.Then, it cuts out the sample of 5mm × 35mm from the film sample, and with general measurement of dynamic viscoelasticity device DVA-200 (ITK Co., Ltd manufactures), temperature is scanned with 2 DEG C/min. under 1Hz frequency, it is measured with stretch mode, the complex elastic modulus of -50 DEG C to 150 DEG C of measurement.Obtain 25 DEG C of complex elastic modulus value.In addition, being more than 10 by complex elastic modulus8The temperature range of Pa and drop to 10 since temperature raises7Temperature between the temperature range of Pa when loss modulus maximum is taken as glass transition temperature (Tg).
Supatex fabric Unit Weight, supatex fabric open area when diameter
The PET film for being coated with adhesive is pressed on supatex fabric, the supatex fabric is shifted, increases the Unit Weight of measurement supatex fabric by the area and weight that shift.In addition, measuring supatex fabric thickness and fibre diameter by microscope cross-sections.Open area ratio is calculated by following formula.
Open area ratio (%)=100-A × 100/ (B × C)
A: constitute supatex fabric each material but not be electrolyte material made of nonwoven fabric portions Unit Weight (g/m2)
B: by constitute supatex fabric material but not be electrolyte each material density (g/m3)
C: supatex fabric thickness (m)
The tensile strength of supatex fabric
In 1 hour after its formation, the supatex fabric of bonding is cut into the sample of loose 10mm and long 70mm, with 50mm/min. tensile speed, distance is 50mm between fixture, carries out tension test, measures tensile strength.
Embodiment 8
Using manufacture meltblown nonwoven fabric equipment, and using and the identical PFA of embodiment 1, spinneret temperature be 390 DEG C, for stretching hot air temperature be 480 DEG C under conditions of, supatex fabric is formed on the conveyer belt with suction capactity.Transmission for collecting has the hole 1mm with a for band shape SUS type net, and is being 1m/sec. away from the wind speed in net surface 1cm.To the supatex fabric before anchoring fiber crosspoint, measurement open area ratio is 70%.
Then, with Fluorinert FC-77, (3M company is manufactured, boiling point: 100 DEG C) dilution CYTOP (trade name: CTL-109S, the manufacture of Asahi Glass Co., Ltd) solution to 0.5% concentration and viscosity be 0.003Pas (25 DEG C), the solution of acquisition, which is used as, contains binder solution.With commercially available manual spray device, the solution is sprayed on the supatex fabric several times, stands 1 minute in air, solvent dries out.Then, the suction for stopping conveyer belt peeling and is formed in the online supatex fabric, obtains the supatex fabric of self-supporting.The physical property with the supatex fabric of fixed fiber intersection points is measured, table 3 is as a result listed in.
In such a state, four sides of the taut firmly supatex fabric of the quadrangle framing mask made of PTFE, supatex fabric is immersed in ion exchange resin (A) in the solution (solids level concentration: 5 mass %) of etoh solvent, with 100mm/min. speed drawing, it is impregnated into above-mentioned ion exchange resin (A) in supatex fabric.This immersion/drawing operation in triplicate, then still it is taut live state under, 55 DEG C drying 1 hour, acquisition composite membrane.
It places 5 μm of thickness of the monofilm 2 used such as embodiment 6 respectively in every one side of the composite membrane, carries out hot pressing (160 DEG C, 5Pa, 15 minutes), obtain dielectric film.
Manufacture fuel cell is simultaneously tested
Ion exchange resin (A) is added in the mixed solvent (1: 1 mass ratio) of second alcohol and water, and in the flask for having reflux unit, 60 DEG C of stirrings are dissolved for 16 hours, obtain the polymer solution that solid content is 9%.Then, water and ethyl alcohol is added in order in the carbon dust for having loaded platinum, obtains the catalyst dispersion (solid content: 9 mass %) being dispersed in the mixed dispersant of second alcohol and water (1: 1 mass ratio).Then, the polymer solution and catalyst dispersion are mixed with 11: 3 mass ratio, obtains coating solution.Then, using die coating method, this coating solution is applied in every one side of dielectric film, forms the catalyst layer of 10 μ m-thicks after dry in every one side of film, platinum load capacity is 0.5mg/cm2.In addition, placing carbon cloth in the outside of every one side as gas diffusion layers, membrane-electrode assembly being made.In the every one side of the membrane-electrode assembly, the partition made of carbon plate is placed, the narrow groove that zigzag is formed on the carbon plate is used as gas passage, heater is placed outside partition, to be assembled into polymer electrolyte fuel cells, effective membrane area is 25cm2。
Fuel cell is maintained at 80 DEG C, supplies air to cathode respectively under 0.15MPa pressure, hydrogen supplies anode.It is 0.1A/cm in current density2And 1A/cm2When, cell voltage is measured respectively.As a result it is listed in table 3.
Embodiment 9
Supatex fabric is prepared according to the same manner as in Example 8, as different from Example 8, is heated 16 hours using at 58 DEG C, by CF2=CF2With CF2=CF-OC2FCF(CF3)-OCF2CF2SO2The copolymer of F (is converted into-SO3Ion exchange capacity when H-type: 1.1meq/g dried resin) it is dissolved in ASAHKLIN AK-225 (Asahi Glass Co., Ltd manufacture, mode: 58 DEG C) in the solution (solid content: 0.5%, viscosity: 0.01Pas (25 DEG C)) that obtains as containing binder solution.Progress and the identical test of embodiment 8, are as a result listed in table 3.
In addition, according to the same manner as in Example 8, manufacturing dielectric film and fuel cell, and measure cell voltage.As a result it is listed in table 3.
Embodiment 10
Supatex fabric is prepared according to the same manner as in Example 8, as different from Example 8, dilutes CF using ethyl alcohol (boiling point: 78 DEG C)2=CF2With CF2=CF-OC2FCF(CF3)-OCF2CF2SO3H copolymer (ProductName: FSS-1, AsahiGlass Co., Ltd manufacture) solution is used as to the solution of 0.5% concentration and 0.01Pas (25 DEG C) viscosity and contains binder solution.Progress and the identical test of embodiment 8, are as a result listed in table 3.
In addition, according to the same manner as in Example 8, manufacturing dielectric film and fuel cell, and measure cell voltage.As a result it is listed in table 3.
Comparative example 4
According to the same manner as in Example 8, supatex fabric is formed on the conveyer belt for collection, is not fixed the crosspoint of fiber, stops suction, is handled a part of fiber release therein when the supatex fabric, that is, is failed the supatex fabric for obtaining self-supporting.Tension test is carried out according to the same manner as in Example 8, and gained intensity is less than 10N/m.
Table 3
| Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 4 | ||
| Adhesive | Complex elastic modulus (Pa) | 1×109 | 6×106 | 3×108 | - |
| Tg(℃) | 108 | 0 | 78 | - | |
| Solution viscosity (Pas) | 0.003 | 0.01 | 0.01 | - | |
| Supatex fabric | Fibre diameter (μm) | 10 | 10 | 10 | 10 |
| Supatex fabric Unit Weight (g/m2) | 10 | 10 | 10 | 10 | |
| Thickness (μm) | 16.6 | 16.6 | 16.6 | 16.6 | |
| Open area ratio (before fixed) (%) | 70.0 | 70.0 | 70.0 | 70.0 | |
| Open area ratio (after fixed) (%) | 69.5 | 69.5 | 70.0 | - | |
| Tensile strength (N/m) | 120 | 120 | 120 | < 10 | |
| Battery testing | 0.1A/cm2When cell voltage (V) | 0.82- 0.86 | 0.82- 0.86 | 0.82- 0.86 | - |
| 1A/cm2When cell voltage (V) | 0.55- 0.65 | 0.55- 0.65 | 0.55- 0.65 | - |
In accordance with the invention it is possible to effectively manufacture is used to the supatex fabric that enhances, even and if can obtain film thickness it is relatively thin when still there is the dielectric film of high mechanical strength, the excellent size stability of the dielectric film after absorbing water, and with low resistance.Using the treatment effeciency and excellent in stability of membrane-electrode assembly made of this dielectric film, the polymer electrolyte fuel cells with high-durability energy can be obtained.
The Japanese patent application No.2005-170890 that the Japanese patent application No.2004-371367 and on June 10th, 2005 that on December 22nd, 2004 submits are submitted, the full content including specification, claims, drawings and abstract are incorporated herein by reference.
Claims (15)
1. a kind of dielectric film, mainly it is made of ion exchange resin, and enhanced with the supatex fabric that the continuous fiber of fluororesin is constituted, wherein at least part crosspoint of continuous fiber is fixed, and the dielectric film or it is per while on there is ion exchange resin to be made but the layer that does not reinforce is as outer layer, the ion exchange resin for not reinforcing layer with foregoing ion exchanger resin can be identical or different.
2. dielectric film as described in claim 1, it is characterized in that, fluororesin is selected from least one of tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer, Tefzel, tetrafluoroethylene/hexafluoropropylene copolymer and polyvinylidene fluoride polymer.
3. dielectric film as claimed in claim 1 or 2, which is characterized in that the fibre diameter of continuous fiber is 0.01-13 μm.
4. dielectric film as claimed in any one of claims 1-3, which is characterized in that the thickness value of non-reinforced layer is at least the fiber radius value of continuous fiber.
5. such as dielectric film of any of claims 1-4, which is characterized in that the crosspoint of continuous fiber is fixed by the welding between fiber.
6. such as dielectric film of any of claims 1-4, which is characterized in that the crosspoint of continuous fiber is fixed with the adhesive that the fluoropolymer for dissolving in solvent is constituted.
7. the method for dielectric film described in a kind of any one of manufacturing claims 1-6, this method comprises: the fluororesin of the fusible molding of molten state is sprayed from a spinning head, pass through the gas being discharged from the exhaust nozzle being arranged near spinning head, fluororesin is stretched and is spun into silk, continuous fiber is obtained, and continuous fiber is formed into supatex fabric.
8. the method for manufacture dielectric film as claimed in claim 7, which is characterized in that collect continuous fiber on the surface with adsorption function and form supatex fabric, carry out hot pressing then with the crosspoint of welding continuous fiber.
9. the method for manufacture dielectric film as claimed in claim 7, it is characterized in that, continuous fiber is collected on the surface with adsorption function forms supatex fabric, the solution for the adhesive that then coating is constituted containing the fluoropolymer for dissolving in solvent, to bond the crosspoint of continuous fiber.
10. the method for manufacture dielectric film as claimed in claim 9, which is characterized in that elasticity modulus when dissolving in the fluoropolymer room temperature of solvent is at least 105Pa.
11. the method for the manufacture dielectric film as described in claim 9 or 10, which is characterized in that the fluoropolymer for dissolving in solvent has ion-exchange group.
12. the method for the manufacture dielectric film as described in any one of claim 9-11, which is characterized in that the solution by spray application containing adhesive.
13. the method for the manufacture dielectric film as described in any one of claim 9-12, which is characterized in that the surface with adsorption function is the net that aperture is up to 2mm.
14. the method for the manufacture dielectric film as described in any one of claim 9-13, which is characterized in that the wind speed away from the surface with adsorption function in 1cm is at least 0.1m/sec.
15. a kind of membrane-electrode assembly for polymer electrolyte fuel cells, it includes cathode and anode respectively with the catalyst layer comprising catalyst and ion exchange resin, and slotting polymer dielectric film between a cathode and an anode, wherein polymer dielectric film is made of dielectric film of any of claims 1-6.
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| JP2004371367 | 2004-12-22 | ||
| JP2004371367 | 2004-12-22 | ||
| JP2005170890 | 2005-06-10 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105845445A (en) * | 2016-04-01 | 2016-08-10 | 中国航空工业集团公司北京航空材料研究院 | Composite structural member capable of storing/releasing charge and preparing method and application thereof |
| CN109962273A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | A kind of MEA component preparation method |
| CN110787653A (en) * | 2018-08-01 | 2020-02-14 | 孝感市思远新材料科技有限公司 | Composite membrane containing covalent organic framework material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3075580B2 (en) * | 1991-04-05 | 2000-08-14 | 旭硝子株式会社 | Fluorine-containing cation exchange membrane for electrolysis |
| JP3342726B2 (en) * | 1993-01-29 | 2002-11-11 | 旭硝子株式会社 | Solid polymer electrolyte fuel cell and method of manufacturing the same |
| JP3668478B2 (en) * | 2000-07-06 | 2005-07-06 | 松下電器産業株式会社 | Method for producing membrane electrode assembly and method for producing polymer electrolyte fuel cell |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105845445A (en) * | 2016-04-01 | 2016-08-10 | 中国航空工业集团公司北京航空材料研究院 | Composite structural member capable of storing/releasing charge and preparing method and application thereof |
| CN105845445B (en) * | 2016-04-01 | 2018-06-29 | 中国航空工业集团公司北京航空材料研究院 | Composite material structural member of energy storage/release charge and its preparation method and application |
| CN109962273A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | A kind of MEA component preparation method |
| CN110787653A (en) * | 2018-08-01 | 2020-02-14 | 孝感市思远新材料科技有限公司 | Composite membrane containing covalent organic framework material and preparation method thereof |
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