CN100559641C - Film electrode composite element and manufacture method thereof and fuel cell - Google Patents

Abstract

Problem of the present invention provides the employing high-fire resistance, high strength, the dielectric film of high tensile modulus of elasticity and low-water-content, also can keep the effect that suppresses fuel crossover, simultaneously can be with the short time, at low temperature, under the low-pressure, and then do not carry out polymerization etc. promptly reduce easily electrode and dielectric film interface resistance use interface resistance reduce the manufacture method of the film electrode composite element of property composition, problem of the present invention can be reached by the manufacture method and the film electrode composite element of film electrode composite element, the manufacture method of film electrode composite element of the present invention, be to make to make dielectric film between between pair of electrodes and the method for the film electrode composite element that forms, it comprises following operation: the operation that at least one side's electrode is reduced property composition and dielectric film applying by the interface resistance that contains plasticizer.Film electrode composite element of the present invention, be to make dielectric film between between pair of electrodes and the film electrode composite element that forms, between at least one side's electrode and dielectric film, has layer (A), when the storage modulus of elasticity that the storage modulus of elasticity of the dielectric film of being measured by the ultra micro hardometer is designated as C, layer (A) was designated as D, storing modulus of elasticity C value was more than the 1GPa.

Description

Film electrode composite element and manufacture method thereof and fuel cell

Technical field

The present invention relates to reach the film electrode composite element and the manufacture method thereof of high-output power density and the fuel cell that uses this film electrode composite element.

Background technology

Fuel cell is the few and energy efficiency height of effluent, the Blast Furnace Top Gas Recovery Turbine Unit (TRT) low to the burden of environment.Therefore, among earth environment protection in recent years improves, be subjected to people once again and pay close attention to.With extensive power generating equipment ratio in the past, the Blast Furnace Top Gas Recovery Turbine Unit (TRT) of Move tools such as more small-scale decentralized power generating equipment, automobile, boats and ships, be the Blast Furnace Top Gas Recovery Turbine Unit (TRT) that also is expected in the future.In addition, power supply as small type mobile devices, portable equipment also receives publicity, substitute as secondary cells such as Ni-MH battery and lithium ion batteries, perhaps as the charger of secondary cell, perhaps by with secondary cell and with (mixing), can expect that lift-launch is on portable equipment such as portable phone and PC etc.

In polymer electrolyte fuel cells (Polymer Electrolyte Fuel Cell), with hydrogen is outside the polymer electrolyte fuel cells in the past (the following PEFC that is recited as sometimes) of fuel, directly supplies with the direct-type fuel cell of fuel such as methyl alcohol and is also just paid close attention to.Direct-type fuel cell is low with PEFC specific output in the past, but because fuel is liquid, does not use modifier, therefore has energy density and increases, and be long advantage the service time of every filling portable equipment once.

Polymer electrolyte fuel cells causes the polyelectrolyte membrane constituting membrane electrode complex (MEA) that becomes the proton conduction body between electrode, anode and the negative electrode of the anode of the reaction of undertaking generating and negative electrode usually, and the monocell that this MEA is formed by the dividing plate clamping (cell) constitutes unit (unit).At this, the Catalytic Layer that by the electrode base material (being also referred to as gas-diffusion electrode or collector body) of the promotion of carrying out gaseous diffusion and collection (giving) electricity, in fact electrode becomes the electrochemical reaction field constitutes.The anode electrode of PEFC for example, fuel such as hydrogen react in the Catalytic Layer of anode electrode, produce proton and electronics, and electrical conductivity is to electrode base material, and proton conducts in polyelectrolyte membrane.Therefore, require gas diffusibility, electronic conductivity, proton-conducting good for anode electrode.On the other hand, at cathode electrode, oxidizing gases such as oxygen and air react with the proton of coming from polyelectrolyte membrane conduction, the electronics of coming from the electrode base material conduction in the Catalytic Layer of cathode electrode, generate water.Therefore, at cathode electrode, also together need to discharge expeditiously the water that generates with gas diffusibility, electronic conductivity, proton-conducting.

In addition, among PEFC, be in the direct-type fuel cell of fuel with methyl alcohol etc., require to have and the different performance of PEFC in the past that with hydrogen is fuel.Promptly, in direct-type fuel cell, in anode, fuel such as methanol aqueous solution react in the Catalytic Layer of anode electrode, produce proton, electronics, carbon dioxide, electrical conductivity is to electrode base material, and proton conduction is to the macromolecule dielectric film, carbon dioxide from electrode base material by outside system, discharging.Therefore, requiring outside the characteristic of the anode electrode of in the past PEFC, also require the permeability of fuel such as methanol aqueous solution, the discharge of carbon dioxide.In addition, at the direct-type fuel cell cathode electrode, with the same reaction of PEFC in the past outside, cause that also fuel such as the methyl alcohol that sees through dielectric film and oxidizing gases such as oxygen or air generate the reaction of carbon dioxide and water in the Catalytic Layer of cathode electrode.Therefore, because the water that generates is more than in the past PEFC, so discharge water more expeditiously.

In the past, as polyelectrolyte membrane, use with Na Off イ オ Application (registered trade mark) (デ ユ Port Application corporate system) was the proton-conducting polymer film as the perfluor of representative always., these perfluors are the proton-conducting polymer film, exist fuel permeability such as methyl alcohol big in direct-type fuel cell, battery output, the inadequate problem of energy efficiency.In addition, perfluor is that the proton-conducting polymer film considers that from the aspect of using fluorine price is also very high.

Once having proposed various is that the different non-perfluor of proton-conducting polymer film is the proton-conducting polymer film with perfluor in the past, for example the fragrant family macromolecule that is to non-fluorine has imported the scheme of the polyelectrolyte membrane of anionic property base (with reference to No. 2002/91225 specification of U.S. Patent Application Publication, No. 5403675 specification of United States Patent (USP), Journal of Membrane Science, Vol.197,231-242 (2002))., these polyelectrolyte membranes easily enter water to inside when increasing the import volume of anionic property base in order to obtain the high conduction degree, have the big shortcomings of fuel crossover such as methyl alcohol.Improvement as this shortcoming, reduce the import volume of anionic property base, reducing countermeasure such as fuel crossover can be inferred easily, but in this countermeasure, the occasion of using as film electrode composite element, not only the ionic conduction degree reduces, and the polyelectrolyte membrane hardening, therefore insufficient with the adhesiveness of electrode, as a result of, ionic conduction degree as film electrode composite element reduces, and the performance of the battery that acts as a fuel becomes insufficient.That is, be the occasion of high-fire resistance, high tensile modulus of elasticity at dielectric film, low fuel intersects and the macroion conductivity even can have concurrently simultaneously, because film is hard, is difficult to soften, therefore easy generation space between the fine surface of Catalytic Layer and dielectric film.This space part accumulates bubbles such as air and carbon dioxide, also constitutes big resistance for ionic conduction, and the performance of the battery that acts as a fuel becomes insufficient.

As its countermeasure, for example once proposed to make between electrolyte and electrode to be situated between in the method (spy opens clear 59-209278 communique, the spy opens flat 4-132168 communique) of material with ionic base.

Open in the clear 59-209278 communique the spy, put down in writing in the inventive embodiments,, use the electrolyte of the hydrocarbon system of polystyrolsulfon acid, polyvinyl sulfonic acid as polymer acid from the method for the polymer acid of Catalytic Layer surface coated paste., the necessary material of the concrete grammar of livering and livering is not open fully.In addition, durability is insufficient sometimes for the service conditions of the material fuel cell of use.

Open in the flat 4-132168 communique the spy, exemplified with perfluor be proton-conducting polymer be coated on the electrode and drying after, through high temperature compacting with the monomer composition solution coat such as six ethylidene glycol dimethylacrylates of electrode and the incorporate method of film, Sodium styrene sulfonate and crosslinking agent after on the electrode, engage with dielectric film, heating and pressurizeing more than 1 hour is with film and the electrode incorporate method of cross-linked polymer by this monomer.

; these methods; the joint of electrode and film needs long-time; need high temperature of about 150 ℃ or the like; therefore it is medium that monomer and solution unnecessarily infiltrate dielectric film; cause bad influence for the effect and the ionic conductivity of the inhibition fuel crossover of dielectric film, can not obtain the fuel cell of high-output power density.And material that these documents are put down in writing system for example is used for using the occasion of the direct-type fuel cell that contains fuel such as methyl alcohol, and the durability of the adhesive layer of electrode and dielectric film is insufficient, therefore can not obtain the fuel cell of high-output power density.

Summary of the invention

The present invention is according to described background technology, the dielectric film that adopts high-fire resistance, high strength, high tensile modulus of elasticity and low-water-content is provided especially, also can keep the effect that suppresses fuel crossover, can reduce simultaneously the manufacture method of film electrode composite element of the resistance at electrode and dielectric film interface with the short time, under low temperature, low-pressure easily, and the fuel cell of high-output power density is provided.In addition, the present invention provide especially the inhibition fuel crossover of the dielectric film that has used high-fire resistance, high strength, high tensile modulus of elasticity and low-water-content the effect height, can obtain the film electrode composite element of high-output power density, the fuel cell of the height output of using this film electrode composite element is provided in addition.

In order to achieve the above object, the present invention adopts following such scheme.Promptly, the present invention is the manufacture method of film electrode composite element, be to make to make dielectric film between between pair of electrodes and the method for the film electrode composite element that forms, it comprises following operation: at least one side's electrode is reduced fit with the dielectric film operation of (following sometimes with the work of applying electrode and dielectric film, as to be included in applying electrode and dielectric film and afterwards their incorporate work to be called " compoundization ") of property composition by the interface resistance that contains macromolecular material with ionic base and plasticizer; And by utilizing solvent extraction, reduce part or all the operation that the property composition is removed plasticizer from above-mentioned interface resistance.

In addition, the present invention is a film electrode composite element, be to make dielectric film between between pair of electrodes and the film electrode composite element that forms, between at least one side's electrode and dielectric film, has layer (A), when the storage modulus of elasticity of the dielectric film of being measured by the ultra micro hardometer was designated as C, storage modulus of elasticity C value was more than the 1GPa.

In addition, the present invention is a film electrode composite element, be to make dielectric film between between pair of electrodes and the film electrode composite element that forms, between at least one side's electrode and dielectric film, has layer (A), this layer (A) pass through scanning probe microscopy to rap the phase difference that (tapping) mode scanning measures different with dielectric film, and dielectric film and layer (A) contain the aromatic hydrocarbon with anionic property base.

In addition, fuel cell of the present invention is characterized by and used this film electrode composite element.

The invention effect

According to the present invention, even use the occasion of the dielectric film of high-fire resistance, high strength, high tensile modulus of elasticity and low-water-content, also can realize the electrode of film electrode composite element and the low interface resistanceization between dielectric film, by using this film electrode composite element, can provide the fuel cell of high-output power density.In addition,, the film electrode composite element of low fuel intercrossing, high-output power density and high-durability can be provided,, the fuel cell of high output can be provided by using this film electrode composite element according to the present invention.

Description of drawings

Fig. 1 is the impedance measuring result's of film electrode composite element circular fit (fit) example.

Fig. 2 has been to use the fuel cell voltage-current characteristics figure of the film electrode composite element of the embodiment of the invention 1 and comparative example 1.

Fig. 3 is that the tensile modulus of elasticity of the dielectric film that uses in the film electrode composite element and the output of having used interface resistance to reduce the fuel cell of property composition in the manufacturing of film electrode composite element do not reduce the figure of relation of ratio of output of the fuel cell of property composition with using interface resistance.

Fig. 4 is the figure that an example of shape fuel cell is piled up in expression.

Fig. 5 is the figure of an example of expression film electrode composite element.

Fig. 6 is the image graph of magnifying electrode/dielectric film part.

Fig. 7 is the sectional view of an example of passive fuel cell.

Fig. 8 is the figure that the interface resistance of expression among the embodiment 2 reduces the temperature dependency that the viscosity of property composition B changes.

Symbol description

1: film electrode composite element

2: liner

3: bipolar separator

4: collector plate

5: the fuel supply mouth

6: trip bolt

7: air flow circuit

8: fuel flow path

9: fuel tank

10: electrode

11: dielectric film (layer)

12: layer (A)

13: Catalytic Layer

14: liner

15: dielectric film

16: fuel supply and generation gas exhaust port

17: anode tap

18: the current collection net

19: Catalytic Layer+layer (A)

20: fuel diffusion layer

21: fuel keeps material

22: cathode leg

23:O shape ring

24: sept

25: cathode leg peristome (temperature measuring is used)

26: air suction inlet

27: framework

28: load

29: wiring

Embodiment

The preferred embodiments of the invention below are described.

The manufacture method of film electrode composite element of the present invention must have: make dielectric film between between pair of electrodes and in the film electrode composite element that forms, at least one side's electrode reduces the operation of property composition and dielectric film applying by the interface resistance that contains plasticizer.

Present inventors find out, even the electrode that uses, the excellent of each member of dielectric film, if big at the occasion electrode and the resistance between dielectric film of compoundization, then as a result of, the performance of film electrode composite element becomes insufficient, thereby has finished the present invention.Particularly in order to suppress the fuel crossover of dielectric film, and in order to improve mechanical strength, preferably can to obtain glass transition point according to Measurement of Dynamic Viscoelasticity and be high-fire resistance, tensile modulus of elasticity more than 120 ℃ be more than the 100MPa, be preferably more than the 500MPa, the more preferably high elastic modulus more than the 1000MPa, high strength and be the molecular structure of the low-water-content below 100% with respect to dielectric film weight, the therefore tendency that exists dielectric film to become firm.That is to say, in order to improve film electrode composite element and to use its fuel cell performance, even find excellent dielectric film, because dielectric film is difficult to distortion, therefore the resistance between above-mentioned electrode and dielectric film becomes big, still has the tendency that can not obtain the film electrode composite element performance expected.

When electrode and compoundization of dielectric film, by making the interface resistance reduction property composition that contains plasticizer between the centre, its at least a portion of fine voids between electrode and dielectric film is full of by this interface resistance reduction property composition, can increase the essence contact area thus, fuel, air and water that takes place and carbon dioxide etc. entered the resistance increase that the space causes when the battery that can prevent to act as a fuel used.In addition, also infiltrate interface resistance reduction property composition in the crackle that produces in the pole catalyze layer, the inside wall of the Catalytic Layer crackle that in the past can not be used to generate electricity also can effectively utilize, and can increase the contact area of electrolyte and catalyst.Its result, film electrode composite element resistance reduces, and it is big that output power density becomes, and can obtain high performance fuel cell.

Further, also can the covering electrodes base material and the projection of Catalytic Layer etc., minute short circuit in the time of can reducing film electrode composite element and make and the minute short circuit in the battery use that acts as a fuel can suppress the film electrode composite element performance and reduce.

In addition,, also can utilize the layer that forms by interface resistance reduction property composition to protect, repair, can realize stable performanceization and raising durability as film electrode composite element even dielectric film has the occasion of pin hole and blemish etc.

In addition, for low interface resistanceization, the area of preferred at least one side's electrode (projected area) reduce property composition and compoundization of dielectric film by interface resistance more than 50%, more preferably more than 75%, more preferably more than 95%.In addition, so more preferably pair of electrodes area separately reduce property composition and compoundization of dielectric film by interface resistance more than 50%, more preferably more than 75%, more preferably more than 95%.

At first, illustrate from interface resistance reduction property composition.What is called interface resistance of the present invention reduces the property composition, preferably satisfies the composition of following condition: ionic conductivity is arranged; At least have flowability or plastically deformable when electrode and compoundization of dielectric film; Excessively landfill electrode internal pore does not hinder the water of fuel and air and generation, the diffusion of carbon dioxide; Good adhesion with dielectric film; Can not give catalytic performance with bad influence; Constitute film electrode composite element, do not flow when generating electricity at least, that is to say, do not have the excessive swelling and the stripping that cause by fuel, be the occasion of fuel for example, have equal or its above anti-methyl alcohol, intensity with the dielectric film that uses with methanol aqueous solution, methyl alcohol; Or the like.Present inventors are satisfactory for satisfying found that of these condition lucubrates composition shown below.

At first, in order to give ionic conductivity, the used interface resistance of the present invention reduces in the property composition must contain the macromolecular material with ionic base.As described ionic base, preferably have the atomic group of negative electrical charge, preferably have the ionic base of proton exchange ability.As such functional group, can preferably adopt sulfonic group (SO ₂(OH)), sulfate (OSO ₂(OH)), sulfimide base (SO ₂NHSO ₂(R represents organic group to R.)), phosphonate group (PO (OH) ₂), phosphate (OPO (OH) ₂), carboxylic acid group (CO (OH)) and their salt etc.These ionic bases can contain in above-mentioned macromolecular material more than 2 kinds, and combination sometimes can be more satisfactory.Combination waits suitable decision according to polymer architecture.Wherein, consider more preferably have any of sulfonic group, sulfimide base, sulfate at least, consider most preferably have sulfonic group at least from the hydrolytic resistance aspect from high proton conductivity aspect.Have sulfonic occasion, this sulfonic group density is from proton-conducting and suppress the aspect that fuel cell intersects and consider preferred 0.1-5.0mmol/g, more preferably 0.5-3.5mmol/g, further preferred 1.0-3.5mmol/g.By making sulfonic group density is more than the 0.1mmol/g, can keep the promptly low interface of proton conduction degree resistance, and by making it to below the 5.0mmol/g, for example be used for liquid fuel such as direct methanol fuel cell directly during the such fuel cell of contact, can prevent that interface resistance from reducing the property layer because of fuel swelling stripping, outflow etc.

At this, so-called sulfonic group density is the sulfonic mole that the per unit dry weight of macromolecular material is imported, and this value is big more, and the expression sulfonation degree is high more.The sulfonic group density of the macromolecular material that uses can be measured by elementary analysis, acid-base titration or nuclear magnetic resonance spectrometry etc.Aspect sulfonic group density measurement easness and precision, the preferred elements analysis adopts this method to analyze usually.But the employing elemental microanalysis methods such as occasion that also contain the sulphur source beyond sulfonic group are difficult to accurately calculate the occasion of sulfonic group density, adopt neutralization titration.In addition, adopting these two kinds of methods all to be difficult to determine the occasion of sulfonic group density, can adopt nuclear magnetic resonance spectrometry.

Concrete example as macromolecular material with ionic base, mechanical strength from interface resistance reduction property layer, the fuel durability, viewpoints such as thermal endurance are considered, the polymer electrolyte material that aromatic rings is arranged on the preferred main chain can be enumerated and contains ionic basic polyphenylene oxide, contain ionic basic polyether-ketone, contain ionic basic polyether-ether-ketone, contain ionic basic polyether sulfone, contain ionic basic polyether ethersulfone, contain ionic basic polyether and phosphine oxide, contain ionic basic polyethers ether phosphine oxide, contain ionic basic polyphenylene sulfide, contain ionic based polyamide, contain ionic basic polyimides, contain ionic based polyetherimide, contain ionic basic polyimidazole, contain ionic Ji Ju oxazole, contain the polyphenylene etc. of ionic base, aromatic hydrocarbon based polymer with ionic base.These have among the macromolecular material of ionic base, the viewpoint of the fuel resistance of the occasion of using methanol aqueous solution from the viewpoint and the fuel of the control easness of ionic basic import volume, the preferred use contains ionic basic polyether-ketone, contains ionic basic polyether-ether-ketone.At this, about ionic base, the face that sees before is described.

About import the method for ionic base to these macromolecular materials, both can import ionic base to polymer, also can carry out polymerization to monomer with ionic base.Introduce sulfonic group to polymer and for example can pass through " Polymer Preprints, Japan ", 51,750 (2002). wait the method for being put down in writing to carry out.Phosphation from the polymer that phosphate for example can be by having hydroxyl to polymer that introduce carries out.Introducing the carboxylic acid group to polymer for example can be undertaken by the polymer with alkyl, hydroxy alkyl is carried out oxidation.Introducing the sulfimide base to polymer for example can be undertaken by having sulfonic polymer with the alkyl sulfonamide processing.Sulfation from the polymer that sulfate for example can be by having hydroxyl to polymer that introduce carries out.Introducing sulfonic group to polymer for example can be undertaken by the method that makes polymer and chlorosulfonic acid, the concentrated sulfuric acid, oleum reaction.These import the method for ionic base, can control the ionic base density that becomes target by the suitable conditions such as processing time, concentration, temperature of selecting.

In addition,, for example can utilize " PolymerPreprints ", the method that 41 (1) (2000) 237. grades are put down in writing to the method that the monomer with ionic base carries out polymerization.Utilizing this method to obtain the occasion of polymer, the degree that ionic base imports can easily be controlled according to the allocating ratio into of the monomer with ionic base.

In addition, the macromolecular material with ionic base of use has the occasion of non-crosslinked structure, and weight average molecular weight is preferred 10,000-5,000,000, and more preferably 30,000-1,000,000.By making weight average molecular weight is more than 10,000, and can obtain as low interface resistive layer can be for practical mechanical strength.On the other hand, be below 5,000,000 by making weight average molecular weight, can obtain the interface resistance reduction property composition of processing ease, can keep good processability.This weight average molecular weight can utilize the GPC method to measure.

In addition, the used interface resistance of the present invention reduces that to contain plasticizer in the property composition be necessary.As plasticizer, what selection can be satisfied previous narration reduces the plasticizer of the condition of property composition as interface resistance.Contain the reason of plasticizer as needs, can enumerate following aspect: below the decomposition temperature of above-mentioned macromolecular material with ionic base and the following interface resistance of temperature that bad influences such as the decomposition of used material and distortion do not take place reduce the property composition and can flow.The occasion that does not contain plasticizer needs to improve temperature to more than the softening point of above-mentioned polyelectrolyte, causes bad influence for other used materials.Therefore become insufficient as the performance of film electrode composite element sometimes.

The said plasticizer of the present invention is to mix with above-mentioned macromolecular material with ionic base, the material that can soften under the low temperature of the softening point more original than this macromolecular material.That is to say, be the material that handling eases such as moulding, system film, coating processing are carried out.In addition, if can reach the condition that above-mentioned interface resistance reduces the property composition, then at normal temperatures no matter liquid still be solid, gas can, but be preferably liquid or solid usually.In addition, no matter being macromolecule or oligomer, is that paste or gel, oily, emulsion form all can be used with its proterties and shape irrelevantly, can simply mix, also can partly react, combine with macromolecular material or absorption securely with ionic base.

Can enumerate isobornyl acrylate particularly; acrylic acid 4-hydroxyl butyl ester; acryloyl morpholine; 12 amino dodecanoic acid; the pi-allyl glycol; alkylphenol; aluminium chelate; M-phthalic acid; diallyl isophthalate; N-isopropylacrylamide; right-the isopropenylbenzene amphyl; itaconic acid; the oxalic acid imino esters; indenes; ethyl cellulose; ethylenimine; n-octyl alcohol; xylenols; the glycidol ethers; crotonic acid; 2-chloroethyl vinyl ethers; to chlorostyrene and derivative thereof; 2-two azos-1-naphthol-5-sulfonic acid sodium; cyanoacetate; diamino-diphenyl ether; N; N-diethyl acrylamide; the diethylene glycol diene propyl carbonate; N; N-two (glycidyl)-ortho-aminotoluene; 1; the 4-cyclohexanedimethanol; bicyclopentadiene; the dihydroxy diphenyl methane; 4; 4 '-dihydroxybiphenyl; methyl diphenylene diisocyanate; DPG; dipentaerythritol six (five) acrylate; N; the N-DMAA; N; dinethylformamide; hydrogenated bisphenol A; shellac; DAAM; dimer diol; thioglycerol; four cyano quino bismethane; the terpenes biphenol; diallyl p phthalate; dodecanedioic acid; three (glycol), two mercaptan; adjacent triazine; adjacent triazine vulcabond; three (glycidyl) chlorinated isocyanurates; three (2-hydroxyethyl) chlorinated isocyanurates; trimethylolethane; trimethylolpropane; trihydroxymethylpropanyltri diglycidyl ether; 2; 6-naphthalene dicarboxylic acids dimethyl ester; naphthalene-1; the 5-vulcabond; neopentyl glycol; the norborene vulcabond; the parazon carboxylic acid; bisgallic acid A2; 1; two (amino methyl) cyclohexanes of 3-; two [4-(1-hydroxyl-oxethyl) phenyl] sulfone; acrylic acid 2-hydroxy methacrylate; the N-vinyl acetamide; sodium vinyl sulfonate; vinyltoluene; the 2-vinylpyridine; 4-vinylpridine; the N-vinyl formamide; the trimethylace tonitric vinyl esters; bis-phenol; phenyl-phosphonic acid and derivative thereof; positive phenyl maleimide; 1; the 3-butanediol; 1; 2; 3; the 4-BTCA; the butyl hemiformal; n-BMA; fumaric acid; furfural; furfuryl alcohol; 1; the 6-hexylene glycol; benzoguanamine; pentaerythrite; PCDL; polytetramethylene ether diol; 1; the 2-polybutadiene; itaconic anhydride; end methylene tetrabydrophthalic anhydride; tetrabydrophthalic anhydride; PMA; m-xylene diamine; glycidyl methacrylate; cyclohexyl methacrylate; benzyl methacrylate; AMS; the 3-methyl isophthalic acid; the 5-pentanediol; alpha-methylene styrene dimer thing; the acetyl group methyl ricinoleate; azelaic acid; isodecyl alcohol; octyl diphenyl phosphate; tricresyl phosphate base diphenyl; azelaic acid two-2-ethylhexyl; decanedioic acid; di-n-octyl sebacate; dibutyl sebacate; triphenyl phosphate; 2; 2; 4-trimethyl-1; the 3-pentanediol diisobutyrate; nonyl alcohol; 1; the 2-butanediol; 1; the 5-pentanediol; trimellitic anhydride; tricresyl phosphate; レ オ Off オ ス (trade name; phosphate is a flame-retardant plasticizer); paraethyl phenol; n-octadecane base-3 (3 '; 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester; distearyl acyl group pentaerythritol diphosphites; phosphorous acid diphenyl isooctyl acrylate; phosphorous acid diphenyl isodecyl ester; myristyl-3; 3 '-thiodipropionate; thio-2 acid; four [methylene-3 (3 '; 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane; three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) chlorinated isocyanurates; three (2, the 4-di-tert-butyl-phenyl) phosphite ester; 1; 1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; triphenyl phosphite; 4,4 '-Ding fork two (3 methy 6 tert butyl phenol); ethyl-2-cyano group-3,3 '-diphenylacrylate ester; 2-(3; 5-di-t-butyl-2-hydroxy phenyl)-the 5-chlorobenzotriazole; チ ヌ PVC Application 318; チ ヌ PVC Application 622LD; two (2; 2,6,6;-tetramethyl-4-piperidines) sebacate; UV-531; 2 (2 '-hydroxyl-the 3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazoles; 2 (2 '-hydroxyl-5 '-aminomethyl phenyl) BTA; the positive methoxy benzophenone of 2-hydroxyl-4-; benzophenone; antimony trioxide; diethyl-N; two (1-hydroxyethyl) the aminomethylphosphonic acid esters of N-; cyclodoecatriene; dibromocresyl glycidyl ether; Guanidine Sulfamate 99; decabrominated dipheny base ether; デ Network ロ ラ Application プ ラ ス (trade name); tetrabromobisphenol A; three (β-chloroethyl) phosphate; three (2, the 3-dibromopropyl) chlorinated isocyanurates; 2,4; the 6-tribromphenol; 1; two (2,4, the 6-tribromophenoxy) ethane of 2-; HBCD; HBB; azo-2-carboxylic acid's acid amides; the 1-aminoethylpiperazine; β-An Jibadousuanzhi; allyl methacrylate; alkenyl succinic anhydrides; imidazoles; methenamine; ethylenebisstearamide; erucyl amide; n-octyl mercaptan; oleamide; peracetic acid; m-xylene diamine; 1; 8-diazabicylo (5; 4,0) endecatylene-7; 1,5-diazabicylo (4; 3; 0) nonene-5; 4,4 '-diaminourea-3,3 '-diethyl diphenyl methane; 3; 3 '-diamino diphenyl sulfone; 4; 4 '-diamino diphenyl sulfone; two (2-ethylhexyl) peroxy dicarbonate; cumyl peroxide; N, N-two (glycidyl) aniline; dichloro diaminourea bismethane; N, the N-dinitropentamethylenetetramine; 9; the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene (ホ ス Off ア Off エ Na Application ス レ Application)-10-oxide; divinylbenzene; the diphenyl disulfide; 2-normal-butyl amino-4; 6-dimercapto-s-triazine; dibenzylidene sorbitol; 3,3 '-dimethyl-4,4 '-diaminodiphenyl-methane; the dimethyl disulfide toluenediamine; stearmide; aluminum stearate; spiroacetal compound; the D-sorbite polyglycidyl ether; dimer acid; ultramicron shape anhydride silica; uncle's lauryl mercaptan; n-dodecyl mercaptan; the isocyanuric acid triallyl ester; triethylamine; 2; 4; 6-three (dimethylaminomethyl) phenol; tripropylene glycol diacrylate; α, α, α-trisbromomethyl phenyl sulfone; three allyl esters of isocyanuric acid; 2; 2; 4-trimethyl-1, the 3-pentanediol mono isobutyrate; trimethylol-propane trimethacrylate; the norbornane diamines; two (two sulphur benzyls) nickel; 2, two (4-the hydroxy phenyl)-HFC-236fa of 2-; two [2-methyl-4-(the positive alkyl sulfide propionyloxy of 3-)-5-tert-butyl-phenyl] thioether; 2-(2 '-hydroxyl-5 '-metacryloxy ethylphenyl-2H-BTA; trimethylace tonitric; phenol aralkyl resin; phenthazine; benzoic acid is to tertiary butyl ester; the 4-tert-butyl catechol; tert butyl peroxy benzoate; N-(n-butoxy methyl) acrylamide; hexamethylene diisocyanate; benzoyl; 1-benzyl-2-ethyl imidazol(e); 1,4-benzoquinone; aluminium borate whisker; the chlorendic acid acid anhydride; chlorendic acid; hexahydrophthalic anhydride; methyl end methylene tetrabydrophthalic anhydride; methyl ethyl ketoxime; N; N '-methylene-bisacrylamide; the di-2-ethylhexylphosphine oxide stearmide; N hydroxymethyl acrylamide; 2 mercapto ethanol; β-Qiu Jibingsuan; the monochloro vinyl-acetic ester; atoleine; N; the N-dimethylacetylamide; N, dinethylformamide; the N-N-methyl-2-2-pyrrolidone N-; dimethyl sulfoxide (DMSO); sulfolane; 1,3-dimethyl-2-imidazolinedione; non-proton property polar solvent classes such as hexamethyl phosphine triamide; gamma-butyrolacton; ester classes such as butyl acetate; ethylene carbonate; carbonates such as propylene carbonate; the glycol monomethyl methyl ether; ethylene glycol monomethyl ether; propylene glycol monomethyl ether; propylene glycol list ethylether; alkylene glycol monoalkyl ethers classes such as ethylene glycol monobutyl ether; perhaps benzyl alcohol; alcohols such as isopropyl alcohol; ethylene glycol; propylene glycol; 1; the 4-butanediol; 1; the 6-hexylene glycol; trimethylene; neopentyl glycol; cyclohexanedimethanol; glycerine; diethylene glycol; pentaerythrite; polyethylene glycol; polypropylene glycol; polyalcohols such as polytetramethylene glycol; acetate; phosphoric acid; sulfuric acid; phthalic acid three monooctyl esters; trioctyl phosphate; decane; decahydronaphthalene; water; acetonitrile; isoquinolin; Permethyl 99A; isopropyl ether; isophorone; o-chloraniline; isopropyl acetate; 1, the 4-diamino-anthraquinone; diisoamyl ether; cyclohexanol; 2-(1-cyclohexenyl group) cyclohexanone; Dichloroethyl ether; 1, the 4-dichloroetane; dibutyl ethers; dimethylacetylamide; dimethyl sulfoxide (DMSO); the sulfo-glycol; oxolane; tetrahydrofurfuryl alcohol; trigly; ethyl lactate; the 2-phenoxetol; hexylene glycol; methyl isopropyl Ketone; 3-methyl-3-methoxybutanol; methoxybutanol; acetate methoxyl group butyl ester; imidazole salts system; pyridiniujm system; the diversified plasticizer such as ionic liquid of quaternary ammonium salt system etc.In these plasticizer, preferably hydrogen bonding is arranged with ionic base of above-mentioned aromatic hydrocarbon based polymer with ionic base etc., according to the transformable plasticizer of temperature different hydro bond number, can give the plasticizer of the interdependence of the viscosity temperature that interface resistance reduces the property composition, and then, preferably make polyalcohols such as spent glycol, propylene glycol, trimethylene, glycerine from masking liquid stability, operation, cost, to the viewpoint of the harmful effect of catalyst low (toxicity the low catalyst).

These plasticizer can use the mixture that also can use more than two kinds separately.Can be according to suitable selections such as the macromolecular material that uses, electrode material, compounding process, conditions with ionic base.In addition, from coating and viewpoints such as system film, storage stability, operating environment, preferably be difficult to the plasticizer that volatilizees.Be the occasion of index with the boiling point for example, can enumerate boiling point and be the plasticizer more than 100 ℃, be preferably more than 150 ℃, more preferably more than 200 ℃.In addition, the compound that does not further preferably under atmospheric pressure have boiling point in fact.

In addition, as described later, from preventing the viewpoint to the influence of electrode catalyst, part or all of preferred plasticizer is removed after applying electrode and dielectric film or after being arranged on the pole catalyze layer at least, at this moment, preferably adopting water or moisture solvent to extract removes.Therefore, preferred especially water miscible plasticizer.Wherein, the intermiscibility excellence that has the macromolecular material with ionic base of aromatic rings on the preferred especially and main chain, provide and at room temperature can keep shape and hot melt also good interface resistance reduction property alcohols composition, that volatility is few, further preferred polyol class.

In addition, as described later, for example easily encroach on dielectric film at plasticizer, the solvent selected, the effect that for example reduces fuel crossover diminishes, intensity reduces to durability and the occasion that the performance to film electrode composite element exerts an influence such as impacts, and the part of preferred plasticizer, solvent are at least after being arranged on interface resistance reduction property composition on the electrode, be removed before fit this electrode and the dielectric film.Preferred employing water or moisture solvent extract to be removed.The ionic base of the macromolecular material with ionic base in the interface resistance reduction property composition is the occasion of the state of slaine, can in extracting solvent, add acid such as hydrochloric acid and sulfuric acid, carry out the part of proton exchange and plasticizer simultaneously, the extraction of solvent is removed, and is industrial because can to omit process number therefore preferred.In addition, from the adhering viewpoint of dielectric film, can in extracting solvent, mix with interface resistance and reduce other plasticizer of plasticizer phase region in the property composition, carry out exchange, the infiltration of plasticizer.Moreover, after being arranged on interface resistance reduction property composition on the electrode, with before this electrode and the dielectric film applying, only the part of plasticizer is removed be because, there is not plasticizer when electrode and dielectric film if fit thereafter, then be arranged on interface resistance reduction property composition and the adhesiveness of dielectric film and the concavo-convex tracing ability reduction of pole catalyze layer on the electrode, can not obtain to improve durability and these effects of the present invention of output of film electrode composite element.

Plasticizer among the present invention from industrial viewpoint, preferably is difficult to volatilize, reduce as interface resistance the good plasticizer of storage stability of property composition as described above when using interface resistance reduction property composition.For example as being suitable for plasticizer of the present invention, preferably can provide plasticizer: the sheet that interface resistance reduction property composition is processed into 100-200 μ m with following each corresponding interface resistance reduction property composition, after 100 ℃ of heated-air dryings 1 hour, the sample that obtains is thus carried out thermogravimetric amount decrement analyze (TG-DTA), (10 ℃/minute of programming rates, N between 100 ℃-300 ℃ ₂Under the atmosphere) thermogravimetric amount reduction rate be 5%～90% scope, perhaps, in any material of hexane, toluene, methyl alcohol, water, flooded 24 hours the scope of weight reduction rate 5%～90% before for dipping in room temperature.If the weight reduction rate in these assay methods is more than 5%, flowability, plastic deformation in the time of then can having dielectric film and compoundization of electrode can obtain the film electrode composite element of excellent properties.In addition, if be below 90%,, can obtain the film electrode composite element of excellent properties then by the possibility step-down of interface resistance reduction property composition landfill electrode internal pore.In addition, also improve and the viewpoint of cost also is preferred from storage stability.More preferably 10%-85%, more preferably 20%-80%.

In addition, from reducing the viewpoint of the interface resistance between dielectric film and interface resistance reduction property composition, preferred adhesiveness is big as far as possible, so interface resistance reduces can contain in the property composition and can dissolve the dielectric film that is used for film electrode composite element or the solvent of swelling.Its content can be from adhesiveness, the viewpoint appropriate experimental of dielectric film Effect on Performance ground is determined.By containing this solvent, often the adhesiveness that reduces between the property composition of dielectric film and interface resistance improves, and can suppress the reduction degree of the ionic conductivity on their interface.On the contrary, when this solvent is too much, just be penetrated into dielectric film inside, have the fuel property cut off that reduces dielectric film, the tendency that film electrode composite element is short-circuited.The occasion that contains this composition is preferably 1 weight %-70 weight % in the interface resistance reduction property composition, more preferably 2 weight %-50 weight %.

Interface resistance reduces the manufacture method of property composition can select generally well-known method, for example can enumerate: macromolecular material and its solvent, the plasticizer that will have ionic base are put in the proper container, mixing method under the temperature that can stir; The macromolecular material and the plasticizer that will have ionic base are put in extruder, the kneader etc., carry out the method for melting mixing etc.In addition, can heat as required this moment.

Only employing has the macromolecular material of ionic base and the occasion that plasticizer can not be made uniform interface resistance reduction property composition, preferably has the macromolecular material of ionic base with dissolution with solvents, the method for adding plasticizer again.This occasion, as selected solvent, the above macromolecular material of solubilized 10 weight % preferably with ionic base, and can with the mixed uniformly solvent of plasticizer.For example preferably use N, N-dimethylacetylamide, N, dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO), sulfolane, 1, pure series solvent such as alkylene glycol monoalkyl ethers such as carbonic ester series solvents such as ester series solvent, ethylene carbonate, propylene carbonate, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol list ethylethers such as non-proton property polar solvent such as 3-dimethyl-2-imidazolinedione, hexamethyl phosphine triamide, gamma-butyrolacton, butyl acetate or isopropyl alcohol.

In interface resistance reduction property composition, except above-mentioned macromolecular material and plasticizer with ionic base, can also be for the intensity and the adhesiveness that improve low interface resistive layer, the purpose of fuel resistance etc., add polyelectrolyte macromolecular material in addition, inorganic material, salt etc., if the function to interface resistance reduction property composition does not have bad influence, then can also add montmorillonite, various inorganic fillers such as glass fibre, carbon fiber, material with carbon elements such as carbon nano-tube, silicon dioxide, aluminium oxide, zirconia, titanium oxide, various finely particulate things such as poly-silsesquioxane.Particularly, macromolecular material and plasticizer shared ratio in interface resistance reduction property composition with ionic base are preferably more than the 10 weight %, more preferably more than the 30 weight %, more preferably more than the 40 weight %.

As making the method for interface resistance of the present invention reduction property composition between between electrode and dielectric film, be not particularly limited.For example interface resistance reduction property composition is arranged on the dielectric film, the dielectric film and the electrode that will be provided with interface resistance reduction property composition are then fitted, the electrode and the dielectric film that perhaps will be provided with interface resistance reduction property composition are fitted, the dielectric film that perhaps will be provided with interface resistance reduction property composition is fitted with the electrode that is provided with interface resistance reduction property composition, thereby makes interface resistance reduce the property composition between between electrode and dielectric film.In addition, can enumerate as an example: the pellicular cascade that will be formed separately by interface resistance reduction property composition is between electrode and dielectric film and the operation of fitting, electrode and dielectric film remain certain interval in advance, inject the operation of interface resistance reduction property composition etc. to its gap.

From the viewpoint that industry such as operation and reproducibility is made, preferably be arranged on interface resistance reduction property composition on the electrode and/or on the dielectric film and the operation of fitting.As be arranged on interface resistance reduction property composition on the electrode, method on the dielectric film, can enumerate: in the method that directly is coated with on the catalytic surface of electrode, on the dielectric film, after being applied to interface resistance reduction property composition on another base material, fitting with electrode electrode, dielectric film and remove the method etc. of base material.

Coating process as interface resistance reduction property composition can use generally well-known method, methods such as applicable spraying, hairbrush brushing, dip-coating, slot die coating, curtain are coated with, flow coat, spin coating, silk screen printing.In addition, the occasion that interface resistance reduction property composition can not be coated with at normal temperatures, the applicable heating and melting that carries out, the heat seeling coating method of cooling off after the coating of employing said method etc.In addition, after being arranged on interface resistance reduction property composition on electrode, the dielectric film, fit in order to fit mutually, but preferably be adjusted to the immobilising viscosity of interface resistance reduction property composition this moment, in addition, in order to make plasticizer, to have the macromolecular material dissolving of ionic base and use the occasion of solvent, can be after the coating interface resistance reduce the property composition, thus be adjusted to them electrode, dielectric film are not caused bad influence the part of the plasticizer in the interface resistance reduction property composition, solvent is dry.Particularly use the occasion of solvent, can determine the degree of drying of solvent by appropriate experimental ground, the interface resistance when adjusting the film electrode composite element making reduces the viscosity of property composition.

The viscosity of the interface resistance reduction property composition that the present invention is used, increase than room temperature along with temperature when preferred pressurization, coating etc. and lowering viscousity takes place, for example, have the macromolecular material of ionic base and state that plasticizer according to circumstances contains solvent use down rotary-type viscosimeter with shear rate 35 (second ^-1) when 30 ℃ of viscosity down measuring were designated as viscosity under the X (Pa), 80 ℃ and are designated as Y (Pa), preferably Y/X was below 0.3.Measure the temperature dependency that the Y/X that obtains represents the viscosity of interface resistance reduction property composition like this, numerical value is more little, represent that the viscosity in the adoptable temperature range changes more greatly in 30 ℃ of-80 ℃ of these manufacturings, if therefore Y/X is below 0.3, then when being room temperature, processing ease under the room temperature during film electrode composite element production process, from the viewpoint of operation for preferably, heating and pressurizing more than room temperature, during heat seeling coating, the flowability rising (viscosity reduction) of interface resistance reduction property composition, can improve the tracing ability of Catalytic Layer, from as the viewpoint of the height outputization of film electrode composite element for preferably.More preferably below 0.2, more preferably below 0.1.

As the viscosity X value under 30 ℃, be preferably more than the 50Pa from the viewpoint of operation, more than the 70Pa, more than the 100Pa, can be the state of measuring difficulty more preferably more preferably.From the viewpoint of Catalytic Layer tracing ability, the viscosity Y value under preferred 80 ℃ is as far as possible little.

Such interface resistance reduces the property composition and can resemble and make following.For example adopt the above macromolecular material of solubilized 10 weight % with ionic base, and can with the mixed uniformly solvent of plasticizer, dissolving has the macromolecular material of ionic base, adds the plasticizer of ormal weight.Usually, plasticizer is the poor solvent that can not dissolve the macromolecular material with ionic base, and the macromolecular material that therefore has ionic base is separated out, and is difficult to obtain uniform interface resistance reduction property composition.; present inventors are according to the combination with macromolecular material and plasticizer of ionic base; discovery has the influence by the functional group of the ionic base of the macromolecular material with ionic base and plasticizer; for room temperature the time, become gel, rubber-like; mobile little, but but by heating the combination that mixes liquidation.This phenomenon is because although containing plasticizer, solvent in a large number when the room temperature, component material hydrogen bonding height has each other suppressed liquidation, but by heating up, the hydrogen bond number reduces, and liquidation takes place.That is if the variation of hydrogen bond number is reversible, then according to the temperature difference liquidation, non-currentization take place reversibly.As the such macromolecular material and the combination of plasticizer with ionic base, the macromolecular material and combination that preferably have the sulfonic group or derivatives thereof with plasticizer of hydroxyl, amide groups, carboxyl etc. as ionic base, wherein, from the viewpoint of storage stability and operation, preferably use polyalcohols such as glycerine as plasticizer.

Y/X preferably determines according to the appropriate experimental ground such as create conditions that interface resistance reduces coating process, the film electrode composite element of property composition, this control can wait according to the addition of the kind of the kind of the macromolecular material with ionic base and ionic base density, plasticizer and addition, solvent to be carried out, and can change the composition that interface resistance reduces the property composition according to the material of selecting and the appropriate experimental ground of creating conditions.The solvent here, in order to mix macromolecular material and plasticizer easily equably with ionic base, in order to adjust Y/X, both can remain in the interface resistance reduction property composition, also can be used as interface resistance and reduce the property composition and before being used to make film electrode composite element, wait and remove, under the condition of removing, also can adjust Y/X by drying.

In addition, even do not use solvent, also can utilize mechanical mixture under the decomposition temperature of plasticizer or the temperature conditions below the boiling point such as mixing roll and kneader to have the macromolecular material and the plasticizer of ionic base, also can adopt the interface resistance that is shaped to sheet to reduce the method that the property composition uses.

The viscosity that interface resistance reduces the property composition changes and had invertibity for well before removing plasticizer, the article that for example coating interface resistance on peeling paper etc. can be reduced the property composition and obtain, on electrode directly the coating interface resistance reduce the property composition and the article that obtain for the time being cool to room temperature preserve the time restriction in the time of can relaxing film electrode composite element and make.

The coating weight of interface resistance reduction property composition is preferably 0.5-30mg/cm as composition ²Be 0.5mg/cm ²When above, but the crackle of space between landfill electrode and dielectric film and Catalytic Layer can be realized low interface resistanceization.If be 30mg/cm ²Below, then the possibility in the necessary space of diffusion of fuel beyond the space between landfill electrode and dielectric film and generation gas reduces, and in addition, the bad influence that interface resistance reduces the contained plasticizer of property composition also reduces.1-10mg/cm more preferably ²

The applicable generally well-known method of compoundization of electrode and dielectric film (" electrochemistry " 1985 for example, 53,269. electroless plating method, " J.Electrochem.Soc. " of record: Electrochemical Scienceand Technology, 1988, the heating and pressurizing bonding method of the gas-diffusion electrode of 135 (9), 2209. records etc.).Preferably pass through heating and pressurizing and incorporate method, but its temperature and pressure gets final product according to suitable selection of dielectric film thickness, moisture rate, Catalytic Layer and electrode base material.In addition, in the present invention, it is compound also can to pressurize under the state of dielectric film dry status or suction.In the method particularly of the present invention, if dielectric film is not a saturation state usually, then can not obtain the dielectric film of the good film electrode composite element of the engagement state of electrode and dielectric film, the electrolyte dry status can be pressurizeed, therefore the essence contact area of dielectric film and Catalytic Layer increases, and the contraction of the dielectric film that causes of the moisture evaporation during heating and pressurizing does not almost have, therefore can obtain the very excellent film electrode composite element of grade, as a result of, can obtain high performance fuel cell.As concrete pressure method, can enumerate the roll-in of having stipulated pressure, gap, stipulate the flat board pressurization of pressure etc., heating-up temperature can suit according to the flowability of interface resistance reduction property composition to select, from industrial productivity with have the viewpoint of thermal decomposition inhibition etc. of the macromolecular material of ionic base, preferably the scope in room temperature～130 ℃ is carried out.Pressurization is preferably as far as possible little from the viewpoint of dielectric film and electrode protection, and the occasion of dull and stereotyped pressurization is preferably the scope of 0.1MPa～10MPa.

In addition, the occasion of interface resistance reduction property composition is set on dielectric film, can on interface resistance reduction property composition, forms the Catalytic Layer of electrode, thereby make film electrode composite element.In addition, the occasion of interface resistance reduction property composition is set on electrode, even do not prepare dielectric film again, reduce property composition electrode dielectric film, that interface resistance reduces the property composition of holding concurrently as interface resistance and fit each other being provided with, also can be made into film electrode composite element.This occasion, the coating weight per unit area of interface resistance reduction property composition is preferably the degree that thickens to not short circuit, and preferably the electrode area the earth than at least one side is coated with interface resistance reduction property composition.

In addition, when the film electrode composite element of compoundization is acted as a fuel cell power generation, the occasion of generating electricity for a long time, it is current indeterminate that plasticizer with what kind of state exists in film electrode composite element, it is indeterminate that the existence of plasticizer gives the influence of fuel cell, so preferred plasticizer is removed to limit as far as possible.As the method for removing, must solvent wash (extraction).Remove plasticizer by solvent extraction, for example with the situation ratio of removing plasticizer by heated drying, can prevent to the Catalytic Layer of dielectric film and electrode that heat load caused was aging, tendency with output raising of the fuel cell that has used film electrode composite element of the present invention, in addition, the contraction of the occasion that the plasticizer of filming that is formed by interface resistance reduction property composition removes is little, electrode, dielectric film and to reduce the interfacial adhesion of filming that the property composition forms by interface resistance good, these aspects are excellence all.Particularly from operation, environmental problem, prevent from the viewpoint of catalyst poisoning etc. from preferably to adopt the washing (extraction) of water or pure water to remove.Therefore, industrial preferred plasticizer also is water-soluble.

As the concrete operation of removing, be to make the good solvent of the film electrode composite element that reduces compoundization of property composition by interface resistance and plasticizer and do not have the solvent of bad influence to contact, thereby plasticizer is removed in extraction to materials useds such as dielectric film and catalyst.For example can enumerate, use the occasion of water-soluble plasticizer, with film electrode composite element at water, alcohol, or the method for flooding certain hour in the alcohol solution equal solvent, the method of removing with extractions such as steam, after film electrode composite element being placed in the cell of fuel cell, circulation water such as from the fuel supply position on one side, alcohol, or alcohol solution equal solvent or steam, the method that plasticizer is removed on one side, perhaps, with the methanol aqueous solution is the occasion of fuel, double as initial stage aging process ground, and one side of anode utilizes methanol aqueous solution to remove when generating, the method that the water that one side utilization of negative electrode generates is removed, or the like.

The manufacture method of film electrode composite element of the present invention, perfluor applicable to Na Off イ オ Application (registered trade mark) (デ ユ Port Application corporate system) representative is whole dielectric films such as dielectric film and hydrocarbon system dielectric film, is particularly suitable for the manufacturing of the film electrode composite element of the above-mentioned dielectric film that has used high-fire resistance, high strength, high tensile modulus of elasticity and low-water-content.Can enumerate glass transition temperature particularly more than 130 ℃, more than the tensile modulus of elasticity 100MPa, moisture content 40 weight % are with inferior film, can enumerate to contain ionic basic polyphenylene oxide, contain ionic basic polyether-ketone, contain ionic basic polyether-ether-ketone, contain ionic basic polyether sulfone, contain ionic basic polyether ethersulfone, contain ionic basic polyether and phosphine oxide, contain ionic basic polyethers ether phosphine oxide, contain ionic basic polyphenylene sulfide, contain ionic based polyamide, contain ionic basic polyimides, contain ionic based polyetherimide, contain ionic basic polyimidazole, contain ionic Ji Ju oxazole, contain ionic basic polyphenylene, contain ionic basic poly methylene imine, contain ionic basic polyimides azomethine, styrene-the maleimide that contains ionic base polystyrene and contain ionic base is a cross-linked copolymer etc., contain ionic basic polyolefin macromolecule with and the aromatic series hydrocarbon system macromolecule with ionic base of crosslinked body etc.These macromolecular materials can use separately or and with more than two kinds.Can be used as polymer blend, polymer alloy and the stack membrane more than two layers uses.In addition, about the scope of the introduction method of the ionic base here and ionic base, synthetic method, molecular weight, same as described above.Particularly, as described above, most preferably have sulfonic macromolecular material, have an example of sulfonic macromolecular material, can enumerate: will contain-SO as use as ionic base ₃The polymer of M base (M is a metal) removes in high-temperature heat treatment then and desolvates from solution state system film, carries out the method that proton exchange forms film.If above-mentioned metal M is for getting final product with the metal that sulfonic acid forms salt, but consider from the aspect of price and environmental pressure, preferred Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Cr, Mo, W etc., wherein, more preferably Li, Na, K, Ca, Sr, Ba, further preferred Li, Na, K.By under their state of slaine, making film, at high temperature be heat-treated to be possible, this method is suitable for obtaining the macromolecular material system of high glass transition point, low water absorption.

As above-mentioned heat treated temperature, from the absorptive aspect of resulting film, preferred 100 ℃-500 ℃, more preferably 200 ℃-450 ℃, further preferred 250 ℃-400 ℃.Be preferably more than 100 ℃ from obtaining the low water absorption aspect.On the other hand, by being defined as below 500 ℃, can prevent that macromolecular material from decomposing.

In addition,, consider preferred 10 seconds-24 hours from the productivity ratio aspect as heat treatment time, more preferably 30 seconds-1 hour, further preferred 45 seconds-30 minutes.By making heat treatment time is more than 10 seconds, can fully remove and desolvate, and can obtain the effect of enough inhibition fuel crossover.In addition, by being defined as below 24 hours, polymer unwinds can not caused and keep proton-conducting that productivity ratio also increases.

As the manufacture method of dielectric film, can exemplify: with suitable rubbing method coated polymeric solution, remove and desolvate, carry out acid-treated method after at high temperature handling.

As coating process, methods such as applicable spraying, hairbrush brushing, dip-coating, slot die coating, curtain are coated with, flow coat, spin coating, silk screen printing.

In the rubbing method that uses solvent, can utilize heat that solvent is carried out drying, solvent with dissolve polymer not adopts system films such as wet type freezing method, when solvent-free, the applicable method that makes it to solidify by light, heat, moisture etc., the polymer heating and melting is made the method for membranaceous back cooling etc.

As the solvent that is used to make film, for example preferably use N, N-dimethylacetylamide, N, dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO), sulfolane, 1, pure series solvent such as alkylene glycol monoalkyl ethers such as carbonic ester series solvents such as ester series solvent, ethylene carbonate, propylene carbonate, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol list ethylethers such as non-proton property polar solvent class such as 3-dimethyl-2-imidazolinedione, hexamethyl phosphine triamide, gamma-butyrolacton, butyl acetate or isopropyl alcohol.

As the thickness of the dielectric film that uses, preferred usually use 3-2000 μ m's.For obtain can anti-practicality film-strength, preferably thick than 3 μ m, promptly improve power generation performance in order to reduce film resistance, preferably thin than 2000 μ m.The more preferably scope of thickness is 5-1000 μ m, and further preferred range is 10-500 μ m.

Thickness can adopt the whole bag of tricks control.For example use the occasion of solvent cast legal system film, can control, in addition, for example adopt the occasion of cast polymerization legal system film, can adjust by the spacer thickness between plate by solution concentration or the coating thickness on substrate.

In addition, dielectric film of the present invention and have the macromolecular material of ionic base also can utilize method such as radiation exposure to make macromolecular structure whole or a part is crosslinked as required.By making it crosslinked, can expect to obtain further to suppress fuel crossover and to the effect of the swelling of fuel, mechanical strength improves, and is often better.As the kind of radiation exposure, for example can enumerate electron beam irradiation and radiation gamma.By having cross-linked structure, can suppress with respect to the expansion between the macromolecular chain of the infiltration of moisture and fuel.Water absorption can be suppressed in addition, also can suppress swelling, so the result can reduce fuel crossover with respect to fuel for lower.In addition, owing to can restrain macromolecular chain, therefore also can give thermal endurance and rigidity.Here no matter crosslinked be that chemical crosslinking or physical crosslinking can.This cross-linked structure can adopt generally well-known method to form, and for example can shine by copolymerization, the electron beam of polyfunctional monomer to form.Particularly the crosslinked viewpoint from economy of polyfunctional monomer is for preferably, can enumerate monofunctional vinyl monomer and polyfunctional monomer copolymer, adopt polyfunctional monomer to have vinyl, allylic macromolecule carries out crosslinked and material that form.The cross-linked structure here means and does not have in fact at the state of the flowability of heat or the state insoluble in fact to solvent.

In addition, in the dielectric film of the present invention, in the scope of the effect of not damaging ionic conductivity and inhibition fuel crossover, for improve mechanical strength, improve ionic base thermal stability, improve purpose such as processability, can contain filler, inorganic fine particles, both can make it to form network, the particulate that is formed by polymer, metal oxide, also can be the film that is penetrated in supporter etc.

Then explanation is suitable for the example of the electrode of film electrode composite element of the present invention.This electrode is formed by Catalytic Layer and electrode base material.Here said Catalytic Layer is the layer that comprises the catalyst that promotes electrode reaction, electrical conductivity body, ion-conducting material etc.As catalyst contained in such Catalytic Layer, for example preferably use noble metal catalysts such as platinum, palladium, ruthenium, rhodium, iridium, gold.Both can use a kind in them separately, also two or more kinds may be used and use alloy, mixture etc.

In addition, use the occasion of electrical conductivity body (conduction material) in the Catalytic Layer,, preferably use inorganic conductive material from electronic conductivity and chemical stability aspect.Wherein, can enumerate the material with carbon element of noncrystalline, crystalline.For example, preferably use carbon blacks such as channel black, thermals, furnace black, acetylene black from electronic conductivity and specific surface area size.As furnace black, can enumerate the バ Le カ Application XC-72R (registered trade mark) of キ ヤ ボ Star ト corporate system, バ Le カ Application P (registered trade mark), Block ラ Star Network パ one Le ズ 880 (registered trade mark), Block ラ Star Network パ one Le ズ 1100 (registered trade mark), Block ラ Star Network パ one Le ズ 1300 (registered trade mark), Block ラ Star Network パ one Le ズ 2000 (registered trade mark), リ one ガ Le 400 (registered trade mark), the ケ Star チ エ Application Block ラ Star Network EC (registered trade mark) of ケ Star チ エ Application Block ラ Star Network イ Application one Na シ ヨ Na Le corporate system, EC600JD, the #3150 of Mitsubishi Chemical Ind's system, #3250 etc., in addition, except carbon black, also can use native graphite, pitch, coke, by polyacrylonitrile, Delanium that organic compounds such as phenol resin obtain and carbon etc.As the form of these material with carbon elements, except unsetting particle shape, also can use the material with carbon element of fibrous, flakey, tubulose, coniform, loudspeaker shape.In addition, also can use the material that these material with carbon elements has been carried out reprocessing processing and obtained.

In addition, use the occasion of electrical conductivity body, preferred and catalyst particle evenly disperses from the electrode performance aspect.For this reason, preferred catalyst particle and electrical conductivity body are made masking liquid in advance and are disperseed well.In addition, as Catalytic Layer, be the embodiment of also preferably using incorporate catalyst-loaded carbon of catalyst and electrical conductivity body etc.By using this catalyst-loaded carbon, the utilization ratio of catalyst improves, and helps battery performance to improve and cost degradation.Here, in Catalytic Layer, use the occasion of catalyst-loaded carbon,, also can add conductive agent in order further to improve electronic conductivity.As such conductive agent, preferably use above-mentioned carbon black.

As the material with ionic conductivity (ion-conducting material) used in the Catalytic Layer, usually various organic and inorganic materials are known, but be used for the occasion of fuel cell, the preferred polymer (ionic conductivity polymer) that improves ionic conductivity that uses with sulfonic group, carboxylic acid group, phosphate isoiony base.Wherein, consider preferred polymer with ionic conductivity or the polymer electrolyte material of the present invention that constitutes by fluoroalkyl ether side chain and fluoroalkyl main chain that use from the viewpoint of the stability of ionic base.As perfluor is the ionic conductivity polymer, for example preferably uses the Na Off イ オ Application (registered trade mark) of デ ユ Port Application corporate system, the Aciplex (registered trade mark) of Asahi Chemical Industry's corporate system, the Off レ ミ オ Application (registered trade mark) of Asahi Glass corporate system etc.These ionic conductivity polymer are arranged in the Catalytic Layer with the state of solution or dispersion liquid.At this moment, be used to dissolve or the solvent of dispersed polymeres is not particularly limited, but consider, preferred polar solvent from the deliquescent aspect of ionic conductivity polymer.In addition, as above-mentioned dielectric film and preferred hydrocarbon system macromolecular material also can be used for the material (ion-conducting material) that Catalytic Layer has ionic conductivity very suitably.Be the occasion of the fuel cell of fuel particularly, consider that from the viewpoint of anti-methyl alcohol above-mentioned hydrocarbon system macromolecular material is often effective at aspects such as durability with methanol aqueous solution, methyl alcohol.

Above-mentioned catalyst and electrical conductivity body class are generally powder, so ion-conducting material is undertaken the task of fixing them usually.It is in the masking liquid of main composition material that ion-conducting material adds to catalyst particle and electrical conductivity body when making Catalytic Layer in advance, and coating is preferred from considering aspect the electrode performance under homodisperse state.The amount of contained ion-conducting material in the Catalytic Layer, should determine according to the conductivity of desired electrode characteristic and used ion-conducting material etc. is suitable, be not particularly limited, but by weight, be preferably the scope of 1-80%, more preferably the scope of 5-50%.The occasion that ion-conducting material is very few, the ionic conduction degree is low, too much occasion infringement permeability, arbitrary situation often all reduces electrode performance.

In such Catalytic Layer, except above-mentioned catalyst, electrical conductivity body, ion-conducting material, can also contain various materials.Particularly, can contain above-mentioned ionic conductivity polymer polymer in addition in order to improve the caking property of material contained in the Catalytic Layer.As such polymer, for example can use the copolymer of other monomers such as polymer, their copolymer, the monomeric unit that constitutes these polymer and ethene, styrene of polyvinyl fluoride (PVF), Kynoar (PVDF), polyhexafluoropropylene (FEP), polytetrafluoroethylene, poly-perfluoroalkyl vinyl ether contain fluorine atoms such as (PFA) or mixed polymer etc.The content of these polymer in Catalytic Layer is preferably the scope of 5-40% by weight.The occasion that polymer content is too much, electronics and ion drag force increase, the tendency that exists electrode performance to reduce.

In addition, be the occasion of liquid, gas at fuel, the preferred catalytic layer has the structure that this liquid, gas see through easily, is preferably the structure that the by-product material that also promotes to accompany with electrode reaction is discharged.

In addition, as electrode base material, can use resistance low, can carry out current collection or give the base material of electricity.In addition, above-mentioned Catalytic Layer is also used as the occasion of collector body, can not use electrode base material especially.As the constituent material of electrode base material, for example can enumerate carbonaceous, conductivity inorganic substances, for example can exemplify material with carbon element, stainless steel, molybdenum, titaniums etc. such as the sintered body that derives from polyacrylonitrile, the sintered body that derives from pitch, graphite and expanded graphite.Their form does not limit especially, for example can use with fibrous or particle shape, but from the aspect of fuel permeability, fibrous conductive materials (conducting fibre) such as preferred carbon fiber.As the electrode base material that has used conducting fibre, also can use and weave cotton cloth or arbitrary structure of nonwoven fabrics.For example can use carbon paper TGP series, the SO series of eastern beautiful corporate system, carbon cloth (カ one ボ Application Network ロ ス) of E-TEK corporate system etc.As such weaving cotton cloth, can use without particular limitation that plain weave, twill-weave, satin weave, line are knitted, pattern fabric etc.In addition, as nonwoven fabrics, can use nonwoven fabrics that obtains by paper process, needle point method, spun-bond process, water acupuncture manipulation, meltblown etc. without particular limitation.In addition, can also be braid.In these cloth and silks, particularly use the occasion of carbon fiber, preferred use will be used the flat fabric carbonization of anti-combustion weaving silk or graphitization and weaving cotton cloth of obtaining, anti-combustion silk utilized needle point method and water acupuncture manipulation etc. to be processed into to carry out after the nonwoven fabrics carbonization or graphitization and the nonwoven fabrics that obtains, use anti-fire thread or carbonization silk or graphitization silk utilize nonwoven fabrics that paper process obtains etc.Particularly there is the aspect of the cloth and silk of intensity to consider, preferably uses nonwoven fabrics, fabric (cloth) from obtaining thin.

As the used carbon fiber of such electrode base material, can enumerate polyacrylonitrile (PAN) based carbon fiber, phenol based carbon fiber, pitch-based carbon fiber, artificial silk based carbon fiber etc.

In addition, for the kind electrode base material, the part on the discharge road that also can be used to prevent hydrophobic treatment that the gaseous diffusion permeability that caused by hydropexis reduces, is used to form water is hydrophobic, hydrophilic treated, be used to reduce the carbon dust interpolation of resistance etc.In addition, between electrode base material and Catalytic Layer, also the conductive intermediate layer that contains inorganic conductive material and hydrophobic polymer at least can be set.Particularly electrode base material is the occasion of the big carbon fibre fabric of porosity, nonwoven fabrics, by conductive intermediate layer is set, can suppresses Catalytic Layer and infiltrate the performance reduction that electrode base material caused.

The interface resistance of film electrode composite element of the present invention can be with Rr as its index.About Rr, in following " assay method " the 6th etc., be described in detail.

Fuel as the fuel cell that has used the film electrode composite element of making by the inventive method, can enumerate mixture of the organic compound of carbon number 1-6 such as oxygen, hydrogen and methane, ethane, propane, butane, methyl alcohol, isopropyl alcohol, acetone, glycerine, ethylene glycol, formic acid, acetate, dimethyl ether, quinhydrones, cyclohexane and they and water etc., can be the mixture more than a kind or 2 kinds.Particularly from the viewpoint of generating efficiency, cell integrated system simplification, the preferred fuel that uses the organic compound that comprises hydrogen, carbon number 1-6 from the generating efficiency aspect, particularly preferably is hydrogen and methanol aqueous solution.Use the occasion of methanol aqueous solution,, select according to the fuel cell system that uses is suitable, but consider to be preferably high as far as possible concentration from the viewpoint of long-time driving as the concentration of methyl alcohol.For example, active type fuel cell with subsidiary engines such as the necessary systems, cooling fan, fuel dilution system, product recovery system that medium is delivered to film electrode composite element of generatings such as liquid-feeding pump and Air Blast fan, preferably be that fuel more than the 30-100% utilizes fuel tank or fuel cassette to inject with methanol concentration, be diluted to about 0.5-20%, deliver to film electrode composite element, the passive fuel cell that does not have subsidiary engine, particular methanol concentration are the fuel of 10-100% scope.

Another embodiment preferred of the present invention below is described.

Film electrode composite element of the present invention, be to make dielectric film between between pair of electrodes and the film electrode composite element that forms, between at least one side's electrode and dielectric film, has layer (A), when the storage modulus of elasticity that the storage modulus of elasticity of the dielectric film of being measured by the ultra micro hardometer is designated as C, layer (A) was designated as D, storing modulus of elasticity C value was more than the 1GPa.

The layer here (A) can use with above-mentioned interface resistance and reduce the identical materials in fact of the macromolecular material with ionic base in the property composition.Here, so-called and interface resistance reduce in the property composition the macromolecular material with ionic base in fact identical materials be meant the principal component identical materials.The principal component identical materials here is meant that the 50 weight % of material of formation are above and is identical materials.At this moment, even interface resistance reduces density, the kind difference of the ionic base of the macromolecular material with ionic base contained in the property composition,, then can be used as identical materials and treat if the main chain backbone of this macromolecular material is identical.In addition, if for example polyether-ether-ketone is identical in conjunction with the kind of the base of aromatic rings with polyether-ketone etc., then can be used as identical materials.

In addition, film electrode composite element of the present invention, the material of formation dielectric film and layer (A) is identical in fact to be preferred from the interfacial adhesion aspect.At this, dielectric film with layer (A) even in be mixed with respectively different additive, macromolecular material, even have different substituting group or derivatives thereofs, even copolymerization has different compositions, if 50 weight % of the material of formation dielectric film and layer (A) are above to be identical materials, then also can be judged as identical materials in fact.Moreover, according to above-mentioned, even it is different with density, the kind of the ionic base of the macromolecular material with ionic base of layer (A) to constitute dielectric film, if the main chain backbone of this macromolecular material is identical, then can be used as identical materials treats, if for example polyether-ether-ketone is identical in conjunction with the kind of the base of aromatic rings with polyether-ketone etc., then can be used as identical materials.

Storage modulus of elasticity among the present invention is represented the rigidity of material, has found out that rigidity is high more, promptly stores the big more material of modulus of elasticity numerical value, and is high more to the patience of fuel, in addition, the tendency that also exists thermal endurance to improve, thus the present invention finished.Promptly, in order to suppress fuel crossover, the swelling that suppresses with respect to fuel is important, and this inhibition swelling effect and storage modulus of elasticity have correlation, if particularly the storage modulus of elasticity C of the dielectric film of constituting membrane electrode complex is more than the 1GPa, then suppress the effect height of fuel crossover.The storage modulus of elasticity C of dielectric film is preferably more than the 2GPa, more preferably more than the 3GPa.And then if the storage modulus of elasticity D of layer (A) also is more than the 1GPa, the effect that then can further improve the inhibition fuel crossover is therefore preferred, and more preferably storing modulus of elasticity D is more than the 2GPa, and further preferably storing modulus of elasticity D is more than the 3GPa.

Particularly can think, the most surperficial viscoplasticity rerum natura of the material of dielectric film that employing ultra micro hardometer is measured and layer (A) etc., with the correlation height of the quality of fuel crossover be because, the cause that the absorption of fuel begins from material surface, therefore present inventors are conceived to the most surperficial viscoplasticity rerum natura, thereby have finished the present invention.

The storage Determination of Modulus can be used ultra micro hardometer (TriboIndenter of Hysitron corporate system) to obtain modulus reflection picture [storage modulus of elasticity (E ') as loss elastic modulus (E ") as] and carry out.

For example, with Electronic Speculum with epoxy resin (day new EM corporate system Quetol812) embedding film electrode composite element and after making it to solidify, make the ultra-thin section in the cross section of film electrode composite element of ultra micro slicing machine (ラ イ カ corporate system Ultracut S), as working sample, measure under the following conditions, use a hertz contact theory to calculate modulus of elasticity.

Determinator: the Tribo Indenter of Hysitron corporate system

Use pressure head: the Cubecorner pressure head (radius of curvature 50nm) of ダ イ ヤ モ Application De corporate system

Measure the visual field: about 30mm is square

Measure frequency: 200Hz

Measure atmosphere: in the atmosphere at room temperature

Contact load: 0.3 μ N

The scleroscopic measuring principle of ultra micro below is described.

Rigidity (K) when people know axial symmetry pressure head pressing in sample, that measure system is represented by formula (1).

$K=\frac{2}{\sqrt{\mathrm{\π}}}\sqrt{A}{E}^{*}---\left(1\right)$

Wherein, A is sample contacts the impression that forms with pressure head a projected area, E ^*Complex elastic-modulus for pressure head system and sample system.

On the other hand, when pressure head contacts with sample is the most surperficial, regard the pressure head tip as sphere, can think applicable about the spherical hertz contact theory that contacts with semi-infinite slab.In the hertz contact theory, the radius a on the impression perspective plane when pressure head contacts with sample is represented by formula (2).

$a={\left(\frac{3\mathrm{PR}}{{4E}^{*}}\right)}^{\frac{1}{3}}---\left(2\right)$

Wherein, P is a load, and R is the radius of curvature at pressure head tip.

Therefore, sample contact with pressure head and the projected area A of the impression that forms by formula (3) expression, E can be calculated in use formula (1)-(3) ^*

$A={\mathrm{\πa}}^2=\mathrm{\π}{\left(\frac{3\mathrm{PR}}{{4E}^{*}}\right)}^{\frac{2}{3}}---\left(3\right)$

So-called modulus reflection, be based on above-mentioned hertz of contact theory, make pressure head contact sample the most surperficial, pressure head is vibrated minutely, to obtain as the function of time at response amplitude, the phase difference of vibration, thereby obtain the method for K (mensuration is rigidity) and D (sample decay).

When this vibration during for simple harmonious oscillator, summation (the detecting the load composition) F (t) of power that pressure head is invaded the direction of sample is represented by formula (4).

$F\left(t\right)=m\frac{d^2\mathrm{<figure-callout\; id="2"\; label="h\; dt"\; filenames="C20058004208000561.png,C20058004208000563.png"\; state="\{\{state\}\}">h</figure-callout>}}{{\mathrm{dt}}^{}}+D\left(\frac{\mathrm{dh}}{\mathrm{dt}}\right)+\mathrm{Kh}---\left(4\right)$

Wherein, the 1st expression of formula (4) derives from the power of ram shaft (m: the quality of ram shaft), the 2nd expression of formula (4) derives from the power of the viscosity composition of sample, the rigidity of the 3rd of formula (4) expression sample system, t express time.The F (t) of formula (4) exists with ... the time, therefore represents an accepted way of doing sth (5).

F(t)＝F ₀exp(iωt)(5)

Wherein, F ₀Be constant, ω is the angular oscillation frequency.With formula (5) substitution formula (4), the formula that substitution is separated especially as ordinary differential equation (6) solves an equation, and can obtain the relational expression of formula (7)-(10).

h＝h ₀exp{i(ωt-φ)}(6)

$\left|\frac{F_0}{{\mathrm{<figure-callout\; id="0"\; label="h"\; filenames="C20058004208000562.png,C20058004208000563.png"\; state="\{\{state\}\}">h</figure-callout>}}_0}\right|=\sqrt{{(K-m{\mathrm{\&omega;}}^2)}^2+\left({\mathrm{D\&omega;}}^2\right)}---\left(7\right)$

$\tan \mathrm{\&phi;}=\frac{\mathrm{D\&omega;}}{K-{\mathrm{m\&omega;}}^2}---\left(8\right)$

$K=\frac{F_0}{{\mathrm{<figure-callout\; id="0"\; label="h"\; filenames="C20058004208000562.png,C20058004208000563.png"\; state="\{\{state\}\}">h</figure-callout>}}_0}\cos \mathrm{\&phi;}+m{\mathrm{\&omega;}}^2---\left(9\right)$

$D=\frac{F_0}{{\mathrm{<figure-callout\; id="0"\; label="h"\; filenames="C20058004208000562.png,C20058004208000563.png"\; state="\{\{state\}\}">h</figure-callout>}}_0\mathrm{\&omega;}}\sin \mathrm{\&phi;}---\left(10\right)$

Wherein, Φ is a phase difference.M is known when mensuration, passes through the vibration amplitude (h of instrumentation displacement when therefore measuring for the examination body ₀), phase difference (Φ) and excited vibration amplitude (F ₀), can calculate K and D by (7)-(10) formula.

With E ^*Regard storage modulus of elasticity (E ') as, conclusion formula (1)-Shi (10), mensuration is among the rigidity, uses the Ks (=K-m ω that derives from sample ²) calculate the storage modulus of elasticity by formula (11).

$E^{*}=\frac{K_s\sqrt{\mathrm{\&pi;}}}{2\sqrt{A}}---\left(11\right)$

In addition, film electrode composite element of the present invention, with the loss elastic modulus of dielectric film be designated as E, when the loss elastic modulus of layer (A) is designated as F, wantonly 1 value among preferred loss elastic modulus E and the F is more than the 0.1GPa.

Loss elastic modulus is represented the viscosity of material, and the strong more survivable tendency of the big more viscosity of value is arranged.If be more than the 0.1GPa, then the mechanical endurance of material improves, and uses the durability of the fuel cell of film electrode composite element of the present invention also to improve.This value is preferably more than the 0.2GPa, more preferably more than the 0.3GPa.And then, if the loss elastic modulus F of the loss elastic modulus E of dielectric film, layer (A) is more than the 0.1GPa, then can further improve the durability of the fuel cell that uses film electrode composite element of the present invention, therefore preferred, more preferably loss elastic modulus E, F are more than the 0.2GPa, and further preferred loss elastic modulus E, F are more than the 0.3GPa.

Loss elastic modulus also can similarly be measured with above-mentioned storage Determination of Modulus among the present invention, and the mensuration in the above-mentioned formula (8) is among the rigidity, uses the Ks derive from sample to calculate loss elastic modulus by the formula of concluding in the lump with formula (11) (12).

$E^{\&prime;\&prime;}=\frac{\mathrm{\&omega;D}\sqrt{\mathrm{\&pi;}}}{2\sqrt{A}}---\left(12\right)$

In addition, film electrode composite element of the present invention, any of preferred C/D at least or E/F is 0.5-1.5.C/D and E/F are the ratios of the most surperficial viscoplasticity rerum natura of dielectric film and layer (A), the index of the deformation extent of each layer on the interface that expression is fitted, if be 0.5-1.5, then film electrode composite element of the present invention is made the occasion of fuel cell, the deformation extent of dielectric film and layer (A) is same under various fuel cell operation environment, therefore can reduce and peel off and distortion etc., durability can improve.More preferably 0.7-1.4, more preferably 0.8-1.3.In addition, if C/D, E/F are 0.5-1.5, then more can reduce and peel off and distortion etc., durability further improves, and is therefore preferred.More preferably C/D, E/F are 0.7-1.4, and further preferred C/D, E/F are 0.8-1.3.

Another preferred embodiment of the present invention below is described.

Film electrode composite element of the present invention makes dielectric film between between pair of electrodes and form, between at least one side's electrode and dielectric film, has layer (A), the phase difference and the dielectric film that mode scanning measures that rap that passes through scanning probe microscopy of this layer (A) is different in essence, and dielectric film and layer (A) contain the aromatic hydrocarbon with anionic property base.

Phase difference among the present invention is the index of pliability, can adopt following method to measure.For example with Electronic Speculum with epoxy resin (day new EM corporate system Quetol812) embedding film electrode composite element and after making it to solidify, with the cross section that ultra micro slicing machine (ラ イ カ corporate system Ultracut S) is made film electrode composite element, can measure by the mode scanning of rapping of scanning probe microscopy.

The pattern of rapping among so-called the present invention, be as " scanning probe microscopy that is used for nanometer technology " (2002), Japan's Surface Science can be compiled, ball kind Co., Ltd. distribution and Characterizationand optimization of scan speed for tapping-mode atomic force microscopy; Rev.Sci.Instrum., Vol.73.No.8, pp2928-2936 (2002); American Institute ofPhysics probe that put down in writing, that make vibration is approaching from the sample top, contacts sample gently, obtains AFM picture, the alike method in position of sample.The title of this pattern also is sometimes referred to as interrupted contact mode (Intermittent contact mode), circulation contact mode (cyclic contact mode) or power microscope (dynamic force microscope), but the present invention is referred to as the pattern of rapping.

The mensuration of phase difference can use u s company's system scanning type probe microscope (NanoscopeIIIa, Dimension3000) and phase-detection (PHASE-D01 type) to carry out.Particularly, sweep limits is defined as for example 12.5 μ m * 25 μ m, makes with resonance frequency and measure probe vibration, scanned sample surface (rapping mode scanning) simultaneously.At this moment, the radius of curvature of probe tip is 5-20nm, and rapping frequency is 150-450kHz.Utilize such condition to rap mode scanning, measure with respect to for make AC signal that the probe vibration imports, rap the phase difference (hysteresis) of the AC signal that mode scanning exports.By measuring the phase difference of each scanning element respectively, the phase difference in the exportable sweep limits distributes, and at the surf zone big with the interaction force of probe, phase difference is big, in the little zone of interaction force, detects thereby phase difference is little.That is, part phase difference soft relatively in the sample is big, and hard part phase difference is little, so phase difference becomes the index of presentation surface pliability.

In addition, film electrode composite element of the present invention has the layer (A) that phase difference and dielectric film are different in essence, and dielectric film and the layer (A) contain the aromatic hydrocarbon that has the anionic property base on the main chain.Here, so-called phase difference is different in essence and is meant, behind the decimal point of the absolute value of phase difference when measuring down, each layer (dielectric film and layer (A)) in the same visual field of dielectric film and layer (A) the 1st different.In addition, the ultrathin section sample, in the cross section of film electrode composite element utilizes the occasion of transmission electron microscope observing, can be observed line between dielectric film and electrode as some borders, have significantly occasion of layer (A), be meant behind the decimal point of absolute value of phase difference of each layer (dielectric film and layer (A)) the 2nd different.

Moreover, identical materials constitutes even dielectric film and layer (A) adopt in fact, because the higher order structure of the polymer that manufacturing process's difference causes is not equal, obtain the occasion of the different film electrode composite element of phase difference on the result, can think that the film electrode composite element that replenishes the said determination result is included in the scope of the present invention.

Here, illustrate to make to have the layer (A) that phase difference and dielectric film are different in essence, and dielectric film and layer (A) contain the reason that the film electrode composite element of the aromatic hydrocarbon that has the anionic property base on the main chain gets final product.Present inventors find out, even the excellent of the electrode that uses, each member of dielectric film, if occasion electrode and the resistance between dielectric film in compoundization are big, then as a result of the performance of film electrode composite element becomes insufficient, thereby has finished the present invention.Particularly for the fuel crossover that suppresses dielectric film, improve high temperature useful life longevity, mechanical strength, preferably the glass transition point that obtains according to dynamic viscoelastic be more than 120 ℃ high-fire resistance, more than the tensile modulus of elasticity 100MPa, preferably can obtain more than the 500MPa, the above high elastic modulus of further preferred 1000MPa, high strength and be the molecular structure of the low-water-content 100% below with respect to dielectric film weight, so the dielectric film existence becomes firm tendency.Therefore, from having the viewpoint of above-mentioned performance, productivity ratio and processability, the aromatic hydrocarbon with anionic property base is that the use of the dielectric film of principal component is necessary.

; in order to improve film electrode composite element and to use its fuel cell performance, even find excellent dielectric film, because dielectric film is difficult to distortion; therefore it is big that above-mentioned electrode and the resistance between dielectric film become, and existence can not obtain the tendency of the performance of the film electrode composite element expected.

So, among the present invention, be filled being provided with at least a portion that can suppress fuel crossover, keep the fine space between mechanical strength and electrode and dielectric film between dielectric film and electrode, improved the tracing ability that brings by electrolyte of catalyst surface shape, can increase the layer of the contact area of electrode and dielectric film substantially, that is, phase difference and dielectric film are different in essence, contain the layer of the macromolecular material of the aromatic hydrocarbon that has the anionic property base on main chain.

Particularly the high temperature more than 40 ℃, use the occasion of the high concentration methanol aqueous solution of 20 weight %-99.9 weight %, to utilize common adhesive, perfluor be proton-conducting polymer etc. to electrode and dielectric film when fitting, existence can be seen the tendency that durability that the deterioration by the membrane electrode interface causes reduces, but among the present invention, the layer that dielectric film and phase difference and dielectric film are different in essence (A), form by the macromolecular material that contains the aromatic hydrocarbon that has the anionic property base on the main chain, therefore can realize the film electrode composite element of high strength, high-durability.Here, the aromatic hydrocarbon that has the anionic property base on the so-called main chain is meant the unit that directly combines the anionic property base on the aromatic rings.The effect that the main chain that makes above-mentioned anionic property base be present in aromatic hydrocarbon suppresses fuel crossover is big.

Promptly, when making above-mentioned anionic property base be present in the main chain of aromatic hydrocarbon, aromatic hydrocarbon be positioned at macromolecular material on the main chain firm, be difficult to move, aromatic hydrocarbon by its main chain is directly in conjunction with the anionic property base, even for example methanol aqueous solution is invaded in the polymer, part with anionic property base can not move freely, and the result can suppress fuel can invade ratio in the polymer, can reduce fuel crossover.

In film electrode composite element of the present invention, the phase difference (I) of the layer (A) that phase difference of dielectric film (M) and phase difference and dielectric film are different in essence, no matter which side is big or little, all there is not special problem, in the manufacturing process of film electrode composite element, in order to increase the contact area with electrode, the flexibility of (A) that phase difference and dielectric film are different in essence can change.

The ratio (M/I) of the phase difference (I) of the layer (A) that phase difference of dielectric film (M) and phase difference and dielectric film are different in essence is preferably 0.1-10, more preferably 0.5-2 (wherein except the M/I=1).

Particularly the high temperature more than 40 ℃, use the occasion of the high concentration methanol aqueous solution of 20 weight %-99.9 weight %, film electrode composite element of the present invention, particularly about dielectric film, the preferred dielectric film of selecting to use the effect height, high-fire resistance, high strength, high tensile modulus of elasticity and the low-water-content that suppress fuel crossover, but the layer (A) about dielectric film and phase difference and dielectric film are different in essence is also preferably formed by the electrolytic polymer with same performance.For this reason, the principal component of the material of the layer (A) that the dielectric film that constitutes film electrode composite element of the present invention and phase difference and dielectric film are different in essence is preferably identical in fact, in addition, the fusible viewpoint at the interface of the layer (A) that is different in essence from dielectric film and phase difference and dielectric film, as described above, being meant that the 50 weight % of material of formation are above is identical materials.

At this moment, even density, the kind difference of the anionic property base of the macromolecular material that contains the aromatic hydrocarbon that has the anionic property base on the main chain that uses if main chain backbone is identical, then can be treated by the essence identical materials.In addition, if for example polyether-ether-ketone is identical in conjunction with the kind of the base of aromatic rings with polyether-ketone etc., then can be used as identical materials.

In addition, dielectric film with layer (A) even in be mixed with respectively different additive, macromolecular material, even have different substituting group or derivatives thereofs, even copolymerization has different compositions, if 50 weight % of the material of formation dielectric film and layer (A) are above to be identical materials, then also can be judged as identical materials in fact.Moreover, according to above-mentioned, even it is different with density, the kind of the anionic property base of the macromolecular material that contains the aromatic hydrocarbon that has the anionic property base on the main chain of layer (A) to constitute dielectric film, if the main chain backbone of this macromolecular material is identical, then can be used as identical materials treats, if for example polyether-ether-ketone is identical in conjunction with the kind of the base of aromatic rings with polyether-ketone etc., then can be used as identical materials.

Then, illustrate that containing among the present invention has the macromolecular material of the aromatic hydrocarbon of anionic property base.As the anionic property base, preferably has the proton exchange ability.As such functional group, can preferably adopt sulfonic group (SO ₂(OH)), sulfate (OSO ₂(OH)), sulfimide base (SO ₂NHSO ₂(R represents organic group to R.)), phosphonate group (PO (OH) ₂), phosphate (OPO (OH) ₂), carboxylic acid group (CO (OH)) and their salt etc.These anionic property bases can contain in above-mentioned macromolecular material more than 2 kinds, and combination sometimes can be more satisfactory.Combination waits suitable decision according to polymer architecture.Wherein, consider more preferably have any of sulfonic group, sulfimide base, sulfate at least, consider most preferably have sulfonic group at least from the hydrolytic resistance aspect from high proton conductivity aspect.Have sulfonic occasion, this sulfonic group density is from proton-conducting and suppress the aspect that fuel cell intersects and consider preferred 0.1-5.0mmol/g, more preferably 0.5-3.5mmol/g, further preferred 1.0-3.5mmol/g.By making sulfonic group density is more than the 0.1mmol/g, can obtain high-output power density, and by making it to below the 5.0mmol/g, for example be used for liquid fuel such as direct methanol fuel cell directly during the such fuel cell of contact, can prevent that interface resistance from reducing the property layer because of excessively swelling stripping of fuel, outflow etc.

At this, so-called sulfonic group density is according to foregoing such definition.

Concrete example as the aromatic hydrocarbon that has the anionic property base on the main chain, viewpoints such as the mechanical strength of the layer (A) that is different in essence from dielectric film and phase difference and dielectric film, fuel durability, thermal endurance are considered, can enumerate aromatic hydrocarbon based polymer polyphenylene oxide, polyether-ketone, polyether-ether-ketone, polyether sulfone, polyether ethersulfone, polyether and phosphine oxide, polyethers ether phosphine oxide, polyphenylene sulfide, polyamide, polyimides, Polyetherimide, polyimidazole, Ju oxazole, polyphenylene etc., introduced the anionic property base on the aromatic rings of main chain.These macromolecular materials can use separately, perhaps and with more than 2 kinds, also can make polymer blend, polymer alloy uses.

Wherein, the high temperature more than 40 ℃ particularly, the occasion of using the high concentration methanol aqueous solution of 20 weight %-99.9 weight % to act as a fuel, inhibition from fuel crossover, mechanical strength, the fuel durability, stable on heating viewpoint is set out, particularly preferably be, the material that constitutes dielectric film and layer (A) is selected to contain and derives from 9, the polyether-ether-ketone of the composition of two (4-hydroxy phenyl) fluorenes of 9-, contain and derive from 4, the polyether-ether-ketone of the composition of 4 '-dihydroxy tetraphenylmethane, contain and derive from 4, the polyether-ether-ketone of the composition of 4 '-dihydroxy benaophenonel, derive from 4 with containing, the polyether-ketone of the composition of 4 '-dihydroxy benaophenonel.These materials can use separately, perhaps and with more than 2 kinds, can form polymer blend, polymer alloy uses.

About import the method for anionic property base to these macromolecular materials, described with the front.

Film electrode composite element of the present invention can pile up shape with multi-disc to be used, and electrode can also be connected to wait under the state of arranging on the dielectric film and use.Fig. 4 illustrates an example of the fuel cell that piles up shape.By a plurality of film electrode composite elements are installed, and make to adopt and to have both the dividing plate that conductive materials such as the material with carbon element of fuel flow path and air flow circuit or metal form by the surface and the back side and sandwich, series connection (wherein, the outermost dividing plate has only the either party's of fuel or air stream on its single face), make fuel cell.Liquid fuel can utilize various pumps from supplies such as fuel tanks, felt, nonwoven fabrics etc. also can be set on fuel flow path utilize capillarity to supply with.Air can utilize supplies forcibly such as fan, also can utilize the air that exists naturally in air flow circuit.

The occasion of electrode being connected under the state of arranging on the dielectric film and using as the example of Fig. 5, can be used the compound film electrode composite element of changing a plurality of electrodes on dielectric film.

The film electrode composite element of the present invention that these fuel cells are used shown in the interface enlarged drawing of the electrode 10 of Fig. 6 and dielectric film 11, is being fitted with the state of concavo-convex layer (A) 12 by having followed Catalytic Layer 4.

In addition, Fig. 7 illustrates an example of the passive fuel cell that does not use subsidiary engine etc.

In addition, fuel cell can be built in the used equipment, also can be used as plug-in element and uses.In addition, from the viewpoint of safeguarding, the formation that also preferably can take off and install film electrode composite element from cell of fuel cell.

Fuel battery performance of the present invention, according to the equipment difference that drives, the shape of the supply method of fuel and air, the shape of battery, stream, current collection method, design of electronic circuits etc. are also different, thus the size of film electrode composite element, quantity, series connection and/or quantity in parallel etc. according to device design suitable be chosen as suitable.

The performance of film electrode composite element of the present invention changes according to selection, the temperature of use, the fuel concentration of dielectric film, layer (A), electrode etc., but monocell " EFC05-01SP " (the electrode area 5cm of the エ レ Network ト ロ ケ system corporate system that can pack into commercially available ²Use monocell) estimate.

In addition, fuel as the fuel cell that has used film electrode composite element of the present invention, according to mixture of the above-mentioned organic compound that can enumerate carbon number 1-6 such as oxygen, hydrogen and methane, ethane, propane, butane, methyl alcohol, isopropyl alcohol, acetone, glycerine, ethylene glycol, formic acid, acetate, dimethyl ether, quinhydrones, cyclohexane like that and they and water etc., can select mixture more than a kind or 2 kinds etc. according to purposes, but be mainly used in the occasion preferred liquid supply-type of portable equipment.So-called liquid supply-type is that liquid such as methanol aqueous solution, preferred anode side feed fluid are supplied with in expression at least one side's electrode.By feed fluid, the range of choice of fail safe and fuel supply enlarges, and the simplification of system becomes possibility, can realize the miniaturization of fuel cell, is useful as the power supply of mobile electronic apparatus etc.

Resistance about the film electrode composite element made can be positioned on it in cell of fuel cell, uses the rate response resolver 1255B of Solartron corporate system and potentiostat SI1287 to measure.As the example of condition determination, to film electrode composite element impressed current I (mA), amplitude I/10 (mA), measure with the frequency range of 50kHz～10mHz, measure impedance.The impedance of measuring is plotted complex number plane figure, and the size of the arc of resulting circular arc or its shape out of shape is as resistance R r (right-hand member-left end of Rr=X coordinate (real number coordinate) section).The right-hand member of the X coordinate that obtains at this moment, section and left end for semicircle and the intersection point X coordinate that obtains by complex number plane figure, right-hand member and left end separately.Do not constitute the occasion of semicircle, by Nyquist diagram from " Zview Electrochemical ImpedanceSoftware " (Scribner Associates, Inc. circular fit (fit) system) is inferred semicircle, uses the right-hand member and the left end (with reference to Fig. 1) of this X coordinate section.

Moreover, resistance R r exists with ... current value and the amplitude that adds greatly, therefore among the present invention, the long-pending I (mA) of the current density value during maximum output when measuring voltage-current characteristic according to adding like that of record among following [assay method] (6) and the electrode area of evaluation is decided to be its 1/10 with amplitude.The Rr that obtains like this exists with ... interface resistance greatly, so Rr becomes the index that the effect of interface resistance of the present invention reduction property composition is used in expression.We can say that promptly then the interface resistance value becomes big if the Rr value becomes big, the interface resistance value diminishes if the Rr value diminishes.And, owing to exist the Rr value more little, obtain the tendency of high output more, therefore the Rr of film electrode composite element of the present invention is preferably 1.5 Ω cm ²Below, 1.2 Ω cm more preferably ²Below, 1.0 Ω cm more preferably ²Below.Membrane electrode composite membrane of the present invention, the Rr when particularly using 60 ℃ of methanol aqueous solution, the battery temperatures of 3 weight % is preferably 1.5 Ω cm ²Below, 1.2 Ω cm more preferably ²Below, 1.0 Ω cm more preferably ²Below.By possessing such important document, internal resistance of fuel cell reduces, and makes the voltage drop of the occasion that the electric current obtained increases little, can realize high output, and the range of choice of the unit of lift-launch enlarges.

As power output, for example battery temperature is that 60 ℃, anode side are supplied with 3% methanol aqueous solution with the speed that 0.5ml/ divides, and the peak power output density of the air fed occasion of speed of dividing with 50ml/ to cathode side is preferably 40mW/cm ²More than, if be 40mW/cm ²More than, then can reduce the area of film electrode composite element, the range of choice of drivable equipment enlarges, thereby is useful.50mW/cm more preferably ²More than, 60mW/cm more preferably ²More than.

In addition, with 100mA/cm ²The voltage retention that above current density is carried out after 100 hours the generating is preferably more than 50%, more preferably more than 60%, more preferably more than 70%.Therefore the range of choice of carrying equipment enlarged preferably when current density was higher, more preferably 150mA/cm ²More than, 250mA/cm more preferably ²Membrane electrode composite membrane of the present invention, particularly use the methanol aqueous solution of 20 weight %, at 50 ℃ with 250mA/cm ²Constant current operation (the following evaluation that will carry out under the condition of constant current value roughly is called " constant current evaluation ".) voltage retention after 100 hours, be preferably more than 50%, more preferably more than 60%, more preferably more than 70%.By possessing such important document, the occasion of battery-mounting in the equipment that act as a fuel, this equipment can use for a long time.Certainly preferably, even less than 100mA/cm ², also have preferred more than 50%, more preferably more than 60%, further preferred voltage retention more than 70%.Moreover above-mentioned output power density for example also can use the evaluating apparatus of Dongyang テ Network ニ Network corporate system, potentiostat to measure as solartron system 1255B as solartron system 1470, rate response resolver.

In addition, to use the bag to gas trapping from the gas trapping that negative electrode is discharged before the impressed current, this two side's of carbon dioxide that methyl alcohol in the gas chromatograph for determination sample gas of use system band and oxidation generate concentration, the methyl alcohol penetrate amount of the film electrode composite element of calculating is used the methanol aqueous solution of 3 weight %, is that 60 ℃ occasion is preferably 10 μ mol/cm at battery temperature ²/ minute below.If be 10 μ mol/cm ²/ minute below, then fuel crossover is little to the influence that output reduces, the driving time of carrying equipment prolongs, and also is useful from this point consideration.8 μ mol/cm more preferably ²/ minute below, 5 μ mol/cm more preferably ²/ minute below.

In addition, anode, negative electrode do not carry out fuel supply initiatively, the occasion of temperature controlled passive occasion, output power density when 30 weight % methanol aqueous solution fuel, by can design the area of film electrode composite element lessly, the range of choice of drivable equipment enlarges, and is preferably 15mW/cm ²More than, 20mW/cm more preferably ²More than, 40mW/cm more preferably ²More than.

As fuel cell applications of the present invention, the electric power supply source of moving body preferably.Particularly be preferably used as and be portable phone, PC, PDA, video camera (camcorder), digital camera, the hand-held terminal machine, the RFID reader, portable equipments such as various display classes, electric razor, household electrical appliances such as sweeper, electric tool, home-use electric power is supplied with machine, passenger car, automobile such as bus and truck, motorcycle, electric assisted bicycle, robot, motor-driven carrier (Eco-Kart), electric wheelchair, the electric power supply source of the Move tool of boats and ships and railway etc.The particularly portable equipment of using, not only as the electric power supply source, the charging purposes that also is used to carry the secondary cell on portable equipment, and can be used as hybrid power supply source with secondary cell, solar cell and usefulness suitably.

Embodiment

Be described in more detail the present invention by the following examples, but these examples are in order to understand example of the present invention better, the present invention is not limited by them.

[assay method]

(1) sulfonic group density

After agitator treating in 25 ℃ of pure water is more than 24 hours, refining after 24 hours 100 ℃ of vacuumizes, and dried polymer, measure by elementary analysis.The analysis of C, H, N adopts full-automatic Atomic Absorption SpectrophotometerICP varioEL to implement, and the analysis of S is implemented by the titration of flask combustion method barium acetate, about the analysis of P, adopts flask combustion method phosphovanadomolybdic acid colorimetric method to implement.Calculate the sulfonic group density (mmol/g) of per unit gram by the ratio of components of each polymer.

(2) weight average molecular weight

Measure the weight average molecular weight of polymer by GPC.Integral apparatus as UV-detector and differential refractometer, use the HLC-8022GPC of Japanese TOSOH corporate system, in addition, as the GPC post, use 2 of the TSK gel SuperHM-H (internal diameter 6.0mm, length 15cm) of Japanese TOSOH corporate system, adopt N-N-methyl-2-2-pyrrolidone N-solvent (the N-N-methyl-2-2-pyrrolidone N-solvent that contains the lithium bromide of 10mmol/L), divide mensuration with flow 0.2mL/, convert by polystyrene standard and obtain weight average molecular weight.

(3) thickness

Use is installed in the ID-C112 type of the ミ Star ト ヨ system on the granite comparator testing stand BSG-20 of ミ Star ト ヨ (Mitutoyo) system and measures.

(4) tensile modulus of elasticity

Use " テ Application シ ロ Application " (Tensilon of the オ リ エ of Co., Ltd. Application テ Star Network corporate system, universal testing machine), at the modulus of elasticity of measuring stretch mode between force cell 5N, stroke (range) 40%, chuck under apart from the condition of 3cm, crosshead speed 100mm/ branch, n=5.Test piece is that the polymer that will make film like flooded 24 hours in 25 ℃ of water, is cut into the rectangle of the about 5cm of length, width 2mm and makes.

(5) analysis of the plasticizer in the film composite cleaning solution

The hydromining that will be used to wash is analyzed with the gas chromatograph " 5890series II " of Hewlett Packard corporate system.Condition determination is as follows.

Implantation temperature (Injection temp): 250 ℃

Press (Column head press): 20psi before the post

Carrier gas (Carrier gas): He

Injection way (Injection mode): split sampling (Split) [linear flow (Line flow) 40ml/ branch]

Barrier film cleans (Septum purge): He 3.0ml/ branch

Injection capacity (Injection volume): 2.0 μ l

Detector temperature (Detector temp): 250 ℃

Detector gas (Detector gas): H ₂40ml/ branch, air (Air) 400ml/ branch, assist gas (Aux) (N ₂) the 40ml/ branch

Post baking oven initial temperature (Column oven temp Initial): 50 ℃

Finally (Final): 250 ℃

Speed (Rate): 20 ℃/minute

(6) resistance of film electrode composite element

The film electrode composite element of making is installed in the cell of fuel cell (monocell " EFC05-01SP " of エ レ Network ト ロ ケ system corporate system), use the rate response resolver 1255B of Solartron corporate system and potentiostat SI1287 to measure.As condition determination, for example, measure with the frequency range of 50kHz～10mHz to film electrode composite element impressed current I (mA), amplitude I/10 (mA), measure impedance.The impedance of measuring is plotted complex number plane figure, and the size of resulting circular arc or its arc out of shape is as resistance R r (right-hand member-left end of Rr=X coordinate section).The right-hand member of the X coordinate that obtains at this moment, section and left end for semicircle and the intersection point X coordinate that obtains by complex number plane figure, right-hand member and left end separately.Do not constitute the occasion of semicircle, infer semicircle from the circular fit (fit) of " Zview ElectrochemicalImpedance Software " (Scribner Associates, Inc. system), use the right-hand member and the left end of this X coordinate section by Nyquist diagram.Fig. 1 illustrates the impedance measuring result's of film electrode composite element example.Moreover, resistance R r exists with ... current value and the amplitude that adds greatly, therefore in assay method of the present invention, anode side divides supply 3 weight % methyl alcohol (MeOH) aqueous solution with 0.5ml/, divide ventilating air to cathode side with 50ml/, making battery temperature is 60 ℃, and the long-pending I (mA) of the current density value when adding the maximum output when measuring voltage-current characteristic and the electrode area of evaluation is decided to be its 1/10 with amplitude.Because Rr exists with ... interface resistance greatly, so Rr becomes expression and uses interface resistance of the present invention to reduce the index of the effect of property composition, and it is little of well.

(7) mensuration of storage modulus of elasticity, loss elastic modulus

A. the affirmation in film electrode composite element cross section

To cut with cutting machine at 24 hours film electrode composite element of 60 ℃ of drying under reduced pressure, with Electronic Speculum epoxy resin (day new EM corporate system Quetol812) embedding, after in 60 ℃ of baking ovens, making this epoxy resin cure, make the ultra-thin section of the about 100nm of thickness of ultra micro slicing machine (ラ イ カ corporate system Ultracut S) with 48 hours.

The ultra-thin section of making carried 100 purpose Cu are online in the thing corporate system of should consulting and deliberating, use the system transmission electron microscope H-7100FA of Hitachi to carry out tem observation, carry out the observation of membrane electrode compound cross-section, confirmed the place of dielectric film and layer (A) with accelerating voltage 100kV.

B. the mensuration of utilizing the ultra micro hardometer to carry out

As sample, use ultra micro hardometer (TriboIndenter of Hysitron corporate system) to obtain the modulus reflection picture of dielectric film part and layer (A) part above-mentioned ultra-thin section, calculate storage modulus of elasticity, loss elastic modulus.Obtain dielectric film storage modulus of elasticity C, layer (A) storage modulus of elasticity D value and than the value of the loss elastic modulus F of the loss elastic modulus E of C/D and dielectric film, layer (A) and compare E/F

Condition determination illustrates below.

Determinator: the Tribo Indenter of Hysitron corporate system

Use pressure head: the Cubecorner pressure head (radius of curvature 50nm) of ダ イ ヤ モ Application De corporate system

Measure the visual field: about 30mm is square

Measure frequency: 200Hz

Measure atmosphere: in the atmosphere at room temperature

Contact load: 0.3 μ N

(8) mensuration of phase difference

A. the affirmation in film electrode composite element cross section

To cut with cutting machine at 24 hours film electrode composite element of 60 ℃ of drying under reduced pressure, with Electronic Speculum epoxy resin (day new EM corporate system Quetol812) embedding, after in 60 ℃ of baking ovens, making this epoxy resin cure, make the ultra-thin section of the about 100nm of thickness of ultra micro slicing machine (ラ イ カ corporate system Ultracut S) with 48 hours.

The ultra-thin section of making carried 100 purpose Cu are online in the thing corporate system of should consulting and deliberating, use the system transmission electron microscope H-7100FA of Hitachi to carry out tem observation with accelerating voltage 100kV, carry out the observation of membrane electrode compound cross-section, confirmed the place of the layer (A) that dielectric film is different with phase difference.

B. the mensuration of utilizing scanning type probe microscope to carry out

To in ethanol, carry out ultrasonic washing with the cross section of microtome cutting, with reference to the mensuration position of tem observation picture decision dielectric film and layer (A), use U.S.'s PVC one デ ジ of コ company Le イ Application ス Star Le メ Application Star system scanning type probe microscope (NanoscopeIIIa, Dimension3000) and phase-detection エ Network ス テ Application ダ one モ ジ ユ, one Le (PHASE-D01 type) to measure respectively.Sweep limits is defined as 12.5 μ m * 25 μ m, makes with resonance frequency and measures probe vibration, scanned sample surface (rapping mode scanning) simultaneously.At this moment, the radius of curvature of probe tip is 5-20nm, raps frequency and adopts 150-450kHz.

Utilize above-mentioned condition to rap mode scanning, mensuration is with respect to for making AC signal that probe vibration imports, rap the phase difference (hysteresis) of the AC signal that mode scanning exports, measure the phase difference (hysteresis) of each scanning element respectively, the ratio of phase difference, the brightest part of the part in observing sample except the film electrode composite element constituent, the epoxy resin cured product that uses when promptly making the ultra-thin section sample of film electrode composite element is made as 0, the numerical value that obtains after the phase difference standardization with the layer of part near dielectric film part and the electrode is designated as M respectively, I represents with M/I.

(9) performance evaluation of film electrode composite element

A. voltage retention

The film electrode composite element group is gone into monocell " EFC05-01SP " (the electrode area 5cm of エ レ Network ト ロ ケ system corporate system ²Use monocell), battery temperature is defined as 50 ℃, anode side is supplied with 20 weight % methanol aqueous solutions with the speed that 0.5ml/ divides, supply with synthesis of air to cathode side with the speed that 50ml/ divides, use evaluating apparatus, the potentiostat of Dongyang テ Network ニ Network corporate system to measure voltage-current characteristic as solartron system 1255B, read current density 250mA/cm as solartron system 1470, rate response resolver ²Voltage, later on every 1 hour pattern of generation outage in 5 hours, with 250mA/cm ²Constant current lead to the operation of calculating 100 hours.Constant current is read current density 250mA/cm by current-voltage curve after estimating ²Voltage, calculate from the conservation rate that begins for the first time.

B. the mensuration of fuel (methyl alcohol) transit dose (below be sometimes referred to as " MCO ")

To trap gas trapping before the impressed current from the synthesis of air that negative electrode is discharged with the bag, use the gas chromatograph " MicroGC CP4900 " of ジ one エ Le サ イ エ Application ス system band Autosampler, this two side's of carbon dioxide that methyl alcohol in the working sample gas and oxidation generate concentration and calculating.The carbon dioxide here is assumed to the carbon dioxide that derives from all methyl alcohol that see through and produce.The air mass flow of negative electrode is designated as L (ml/ branch), be designated as Z (volume %) and added up to volume to be designated as V (ml) by the methyl alcohol of gas chromatograph for determination and the total concentration of carbon dioxide, aperture area (the methanol aqueous solution fuel in the film electrode composite element is the area of contact directly) is designated as A (cm ²), calculate by following formula.

MCO (mol/cm ²/ minute)=(L+V) * (Z/100)/22400/A

C. passive evaluation

Under the state that accumulates 30 weight % methanol aqueous solutions on the anode, use the evaluating apparatus of Dongyang テ Network ニ Network corporate system, potentiostat to measure as solartron system 1255B as solartron system 1470, rate response resolver.Current scanning speed is the 10mV/ branch, is measured to voltage 30mV.The electric current of current-voltage curve and voltage are long-pending to reach the highest point divided by the resulting value of electrode area, as output power density.

(10) viscosimetric analysis of interface resistance reduction property composition

Use rotary-type viscosimeter (レ オ テ Star Network corporate system レ オ メ one RC20 type) shear rate 35 (second ^-1) condition under measure viscosity between 20 ℃-100 ℃ of temperature.

Geometry (filling the annex of sample) uses the taper flat board, adopts the value that obtains according to RHEO2000 software.

In evaluation method of the present invention, the temperature dependency that the ratio Y/X of the value Y (Pa) of 30 ℃ value X (Pa) and 80 ℃ changes as viscosity.

[synthesis example] with macromolecular material of ionic base

(1) synthesis example 1

Make 4,4 '-difluoro benzophenone 109.1g is at oleum (50%SO ₃) among the 150mL 100 ℃ of reactions 10 hours.Then, drop into slightly in the water of volume at every turn, add salt 200g with among the NaOH and back and make the synthetic precipitation.The precipitation that filtration obtains with ethanol water crystallization again, obtains 3,3 '-disulfonate-4,4 '-difluoro benzophenone disodium (ジ ソ ジ ウ system).(harvest yield 181g, yield rate 86%).Use potash 6.9g, 4,4 '-(9H-fluorenes-9-subunit (イ リ デ Application)) bis-phenol 14g and 4,4 '-difluoro benzophenone 2.6g and above-mentioned 3,3 '-disulfonate-4,4 '-difluoro benzophenone disodium 12g carries out polymerization at 190 ℃ in the N-N-methyl-2-2-pyrrolidone N-.Precipitate again by the water that adopts volume and to make with extra care, obtain polymer A.The sulfonic group density of the proton displacement film of the polymer A that obtains is 2.4mmol/g by elementary analysis, and weight average molecular weight is 240,000.

(2) synthesis example 2

Use potash 6.9g, 4,4 '-dihydroxy tetraphenylmethane 14g and 4,3 of 4 '-difluoro benzophenone 7g and above-mentioned synthesis example 1,3 '-disulfonate-4,4 '-difluoro benzophenone disodium 5g carries out polymerization at 190 ℃ in the N-N-methyl-2-2-pyrrolidone N-.Precipitate again by the water that adopts volume and to make with extra care, obtain polymer B.The sulfonic group density of the proton displacement film of the polymer B that obtains is 1.8mmol/g by elementary analysis, and weight average molecular weight is 180,000.

[the making example of dielectric film]

Above-mentioned polymer A is dissolved in N, and the N-dimethylacetylamide is made the masking liquid of solid constituent 25%.This masking liquid curtain coating is applied on the glass plate,, obtains the film of 72 μ m 70 ℃ of dryings 30 minutes and then 100 ℃ of dryings 1 hour.And then, under nitrogen atmosphere, be warmed up to 200-300 ℃ with 1 hour, after heat-treating in 10 minutes condition of 300 ℃ of heating, natural cooling, dipping carries out more than 12 hours after the proton displacement in 1N hydrochloric acid, dipping fully washing more than 1 day obtains dielectric film A in the pure water of big excess quantity.The tensile modulus of elasticity of film is 1300MPa.

In addition, make film too, obtain dielectric film B about polymer B.The tensile modulus of elasticity of dielectric film is 1310MPa.

[electrode is made example]

(1) with the methanol aqueous solution is the film electrode composite element electrode of fuel

U.S. イ one テ Star Network (E-TEK) the corporate system carbon cloth of being made by carbon fibre fabric is carried out 20%PTFE to be handled.Particularly, in the aqueous dispersions of the polytetrafluoroethylene that contains 20 weight % (being designated hereinafter simply as PTFE), flood carbon cloth, mention the back drying, burn till.Coating contains the carbon black dispersion liquid of 20 weight %PTFE on its one side, burns till, and produces electrode base material.Coating is by Johson﹠amp on this electrode base material; The C catalyst that supports Pt-Ru " HiSPEC " (registered trade mark) 7000 of Matthey corporate system and " HiSPEC " (registered trade mark) 6000, DuPont corporate system 20% " Na Off イ オ Application " be the anode catalyst masking liquid that forms of (registered trade mark) solution and normal propyl alcohol (Nafion), drying is produced electrode A.Being coated on the face that has been coated with carbon black dispersion liquid of anode catalyst masking liquid carried out.In addition, the same cathod catalyst masking liquid that coating is formed by the C catalyst TEC10V50E that supports Pt and " Na Off イ オ Application " (" Nafion " (registered trade mark)) solution of Tanaka's noble metal industrial group system on above-mentioned electrode base material, drying has been made electrode B.

(2) with hydrogen be the film electrode composite element electrode of fuel

50 weight %) and make that the weight ratio of platinum and " Na Off イ オ Application " (registered trade mark) is 1: 0.5 in Aldrich corporate system " Na Off イ オ Application " (registered trade mark) solution, add catalyst-loaded carbon (catalyst: Pt, carbon: Cabot corporate system ValcanXC-72, platinum loading:, stir well, prepared the catalyst-polymer composition.This catalyst-polymer composition is coated on the electrode base material (east beautiful (strain) system carbon paper TGP-H-060) that has carried out hydrophobic treatment (PTFE of the 20 weight % that infiltrate also burns till) in advance, dry immediately, made electrode C.

[embodiment 1]

Will as the macromolecular material with ionic base, polymer A 10g, pack in the container as N-N-methyl-2-2-pyrrolidone N-60g, the glycerine 40g of plasticizer, stir till becoming evenly, made interface resistance and reduced property composition A.The Y/X of the temperature dependency that the viscosity of expression interface resistance reduction property composition A changes is 0.08.This interface resistance reduction property composition A is applied on above-mentioned electrode A, the electrode B and makes is 3mg/cm ², 100 ℃ of heat treatments 1 minute.It is 5cm that these electrode cutting are become electrode area ²

Then, these electrodes that have interface resistance reduction property composition A are stacked, and make interface resistance reduction property composition A become dielectric film A side, and carried out heating and pressurizing 1 minute at 100 ℃ of pressure with 5MPa, obtain film electrode composite element.Film electrode composite element after the compacting was flooded 30 minutes in the 50ml pure water, extract and wash the plasticizer that remains among the interface resistance reduction property composition A, the generating of packing into is made fuel cell with in the unit.In addition, flood the glycerine in the water of this film electrode composite element with the GC quantitative analysis, detecting is 60 μ g/cm ², can confirm in membrane electrode compounded chemical preface in interface resistance reduction property composition, containing glycerine state as plasticizer.

Anode side divides supply 3 weight % methyl alcohol (MeOH) aqueous solution with 0.5ml/, divides ventilating air to cathode side with 50ml/, the evaluation of generating electricity.In addition, battery temperature is adjusted into 60 ℃.The constant current of in film electrode composite element, circulating during evaluation, the voltage when measuring this.Increase electric current in turn, measure till voltage becomes below the 10mV.The long-pending of the electric current of each measuring point and voltage is power output.This fuel cell voltage-current characteristics is shown in Fig. 2.In addition, the Rr value is 0.9 Ω cm ²

Storage modulus of elasticity, loss elastic modulus and the phase difference in the cross section of this film electrode composite element have been measured, can confirm the layer (A) that the dielectric film part is different with phase difference, the ratio M/I of phase difference is 0.95, the storage modulus of elasticity C of dielectric film part is 9.2GPa, loss elastic modulus E is 1.4GPa, the storage modulus of elasticity D of layer (A) part is 9.2GPa, and loss elastic modulus F is 1.7GPa, C/D=1, E/F=0.82.

The voltage retention of film electrode composite element, first voltage are 0.25V, and the constant current generating voltage after 100 hours is 0.24V, demonstrate the durability of 96% excellence.

In addition, the methyl alcohol penetrate amount of this film electrode composite element is 4.5 μ mol/cm ²/ minute.In addition, the output in passive evaluation demonstrates 40mW/cm ²

[comparative example 1]

The mode of clamping is stacked not use interface resistance reduction property composition with electrode A, electrode B and dielectric film A, carries out heating and pressurizing 8 minutes at 100 ℃ of pressure with 5MPa, obtains film electrode composite element.Fig. 2 illustrates the fuel cell voltage-current characteristics that has used this film electrode composite element.In addition, the Rr value is 2.5 Ω cm ²Know clearly that by Fig. 2 embodiment 1 one sides demonstrate the voltage-current characteristic than comparative example 1 excellence.Try to measure storage modulus of elasticity, loss elastic modulus and the phase difference in the cross section of this film electrode composite element, can only observe the dielectric film part.The methyl alcohol penetrate amount of this film electrode composite element is 4 μ mol/cm ²/ minute, but can't carry out the voltage retention evaluation.This film electrode composite element is output as 5mW/cm in passive evaluation ²

[embodiment 2]

Will as the macromolecular material with ionic base, polymer A 10g, pack in the container as N-N-methyl-2-2-pyrrolidone N-40g, the glycerine 40g of plasticizer, stir till becoming evenly, made interface resistance and reduced property composition B.Fig. 8 illustrates the temperature dependency of the viscosity of interface resistance reduction property composition B.The Y/X of the temperature dependency that the viscosity of expression interface resistance reduction property composition B changes is 0.05.This interface resistance reduction property composition B is applied to peel off also make to be 3mg/cm on the base material ²,, made the stripping film that has interface resistance reduction property composition 100 ℃ of heat treatments 1 minute.This stripping film that has interface resistance reduction property composition is overlapped on electrode A, the electrode B, carried out heating and pressurizing 1 minute, peel peeling paper off, obtain having the electrode of interface resistance reduction property composition at 100 ℃ of pressure with 2MPa.It is 5cm that these electrodes are cut into electrode area ², obtain film electrode composite element similarly to Example 1.Make and estimate the fuel cell that uses this film electrode composite element similarly to Example 1, voltage-current characteristic roughly overlaps with embodiment 1 as a result, and peak power output is 102mW/cm ²In addition, the Rr value is 0.8 Ω cm ²Storage modulus of elasticity, loss elastic modulus and the phase difference in the cross section of this film electrode composite element have been measured, can confirm the layer (A) that the dielectric film part is different with phase difference, the ratio M/I of phase difference is 0.74, the storage modulus of elasticity C of dielectric film part is 9.2GPa, loss elastic modulus E is 1.47GPa, the storage modulus of elasticity D of layer (A) part is 8.8GPa, and loss elastic modulus F is 1.8GPa, C/D=1.04, E/F=0.82.

The voltage retention of film electrode composite element, first voltage are 0.26V, and the constant current generating voltage after 100 hours is 0.25V, demonstrate the durability of 96% excellence.

In addition, the methyl alcohol penetrate amount of this film electrode composite element is 4.0 μ mol/cm ²/ minute.In addition, the output in passive evaluation demonstrates 39mW/cm ²

[embodiment 3]

Made the stripping film that has interface resistance reduction property composition B of embodiment 2.It is square that this stripping film that has interface resistance reduction property composition B is cut into 2.4cm, interface resistance reduction property composition B contacts with dielectric film A, pastes on the two sides in the face of ground mutually, carry out heating and pressurizing after 1 minute at 60 ℃ of pressure, peel off base material with 1MPa.Be 5cm then with electrode area ²Electrode A, electrode B overlap and be arranged on reducing on the layer that the property composition forms of dielectric film two sides by interface resistance, carried out heating and pressurizing 1 minute at 100 ℃ of pressure with 2MPa, obtain having the electrode of interface resistance reduction property composition.Make similarly to Example 1 and estimate and use this to have the fuel cell of the electrode of interface resistance reduction property composition, voltage-current characteristic roughly overlaps with embodiment 1 as a result, and peak power output is 99mW/cm ²In addition, the Rr value is 0.85 Ω cm ²Storage modulus of elasticity, loss elastic modulus and the phase difference in the cross section of this film electrode composite element have been measured, can confirm the layer (A) that the dielectric film part is different with phase difference, the ratio M/I of phase difference is 1.11, the storage modulus of elasticity C of dielectric film part is 7.5GPa, loss elastic modulus E is 1.8GPa, the storage modulus of elasticity D of layer (A) part is 8.8GPa, and loss elastic modulus F is 1.7GPa, C/D=0.85, E/F=1.05.

The voltage retention of film electrode composite element, first voltage are 0.26V, and the constant current generating voltage after 100 hours is 0.25V, demonstrate the durability of 96% excellence.

In addition, the methyl alcohol penetrate amount of this film electrode composite element is 5.4 μ mol/cm ²/ minute.In addition, the output in passive evaluation demonstrates 42mW/cm ²

[embodiment 4]

Made the stripping film that has interface resistance reduction property composition B similarly to Example 2.This stripping film that has interface resistance reduction property composition B is overlapped onto on electrode A, the electrode B, carried out heating and pressurizing 1 minute, peel peeling paper off, obtain having the electrode of interface resistance reduction property composition B at 100 ℃ of pressure with 2MPa.It is 5cm that these electrodes are cut into electrode area ², dipping with the pure water washing, extracted plasticizer and the solvent removed among the interface resistance reduction property composition B after 5 hours in 20% methanol aqueous solution.Then, so that clamp dielectric film A, carried out heating and pressurizing 1 minute, obtain film electrode composite element at 130 ℃ of pressure with 5MPa with these electrode clampings.Make and estimate the fuel cell that uses this film electrode composite element similarly to Example 1, voltage-current characteristic roughly overlaps with embodiment 1 as a result, and peak power output is 105mW/cm ²In addition, the Rr value is 0.79 Ω cm ²Storage modulus of elasticity, loss elastic modulus and the phase difference in the cross section of this film electrode composite element have been measured, can confirm the layer (A) that the dielectric film part is different with phase difference, the ratio M/I of phase difference is 0.95, the storage modulus of elasticity C of dielectric film part is 9.2GPa, loss elastic modulus E is 1.47GPa, the storage modulus of elasticity D of layer (A) part is 8.8GPa, and loss elastic modulus F is 1.8GPa, C/D=1.04, E/F=0.82.

The voltage retention of film electrode composite element, first voltage are 0.27V, and the constant current generating voltage after 100 hours is 0.25V, demonstrate the durability of 93% excellence.

In addition, the methyl alcohol penetrate amount of this film electrode composite element is 4.0 μ mol/cm ²/ minute.In addition, the output in passive evaluation demonstrates 43mW/cm ²

[comparative example 2]

On electrode A, electrode B, be coated with commercially available " Na Off イ オ Application " (registered trade mark) solution (ア Le De リ Star チ corporate system reagent),, had the electrode of " Na Off イ オ Application " (registered trade mark) tunicle 100 ℃ of dryings.The Y/X of the temperature dependency that the viscosity of expression " Na Off イ オ Application " (registered trade mark) solution changes is 0.5, infiltrates " Na Off イ オ Application " (registered trade mark) solution etc. in the electrode, and coating is bad.Use デ ユ Port Application corporate system " Na Off イ オ Application 117 " (registered trade mark) as dielectric film, adopt above-mentioned electrode, do not use interface resistance reduction property composition just to carry out the stacked and feasible dielectric film of clamping, carried out heating and pressurizing 30 minutes at 100 ℃ of pressure, obtain film electrode composite element with 5MPa.

This film electrode composite element, Rr value are 0.8 Ω cm ²Storage modulus of elasticity, loss elastic modulus and the phase difference in the cross section of this film electrode composite element have been measured, can confirm the layer (A) that the dielectric film part is different with phase difference, the ratio M/I of phase difference is 0.99, the storage modulus of elasticity C of dielectric film part is 0.8GPa, loss elastic modulus E is 0.06GPa, the storage modulus of elasticity D of layer (A) part is 0.7GPa, and loss elastic modulus F is 0.05GPa, C/D=1.14, E/F=1.2., dielectric film and layer (A) are the macromolecular materials that does not contain the aromatic hydrocarbon that has the anionic property base on the main chain, so the methyl alcohol penetrate amount of film electrode composite element is big, is 13.0 μ mol/cm ²/ minute, about voltage retention, first voltage is 0.21V, and the voltage of constant current generating after 100 hours is 0.1V, and voltage retention is 48%, poor durability.In addition, in passive evaluation, be output as 10mW/cm ², be low output.Evaluation battery after these are estimated disintegrates, and takes out film electrode composite element, visualization, and what the result took place at the interface of electrode and dielectric film that the swelling of methanol aqueous solution causes peels off, and the part of catalyst is destroyed and is flowed out.

[comparative example 3]

Will as the macromolecular material with ionic base, polymer A 10g, pack in the container as N-N-methyl-2-2-pyrrolidone N-60g, the glycerine 40g of plasticizer, stir till becoming evenly, made interface resistance and reduced property composition A.This interface resistance reduction property composition A is applied on above-mentioned electrode A, the electrode B and makes is 3mg/cm ², 100 ℃ of heat treatments 1 minute.It is 5cm that these electrode cutting are become electrode area ²

Then, use デ ユ Port Application corporate system " Na Off イ オ Application 117 " (registered trade mark) as dielectric film, these electrodes that have interface resistance reduction property composition A are stacked, and make interface resistance reduction property composition A become the dielectric film side, carried out heating and pressurizing 5 minutes at 100 ℃ of pressure, obtain film electrode composite element with 5MPa.Film electrode composite element after the compacting was flooded 30 minutes in the 50ml pure water, extract and wash the plasticizer that remains among the interface resistance reduction property composition A, the generating of packing into is made fuel cell with in the unit.The Rr value of this film electrode composite element is 0.9 Ω cm ²In addition, storage modulus of elasticity, loss elastic modulus and the phase difference in the cross section of this film electrode composite element have been measured, can confirm the layer (A) that the dielectric film part is different with phase difference, the ratio M/I of phase difference is 12.8, the storage modulus of elasticity C of dielectric film part is 0.8GPa, and loss elastic modulus E is 0.06GPa, and the storage modulus of elasticity D of layer (A) part is 9.2GPa, loss elastic modulus F is 1.7GPa, C/D=0.09, E/F=0.04.This film electrode composite element, the storage modulus of elasticity C of dielectric film is less than 4Gpa, so the penetration of methanol aqueous solution fuel is big, and the methyl alcohol penetrate amount is 14 μ mol/cm ²/ minute, the effect that suppresses methyl alcohol is little.The voltage retention of film electrode composite element, first voltage are 0.17V, and the voltage of constant current generating after 100 hours is 0.08V, and voltage retention is 47%, poor durability.In addition, in passive evaluation, be output as 8mW/cm ², be low output.Evaluation battery after these are estimated disintegrates, take out film electrode composite element, visualization, the result has taken place to peel off at the interface of electrode and dielectric film, can think that reason is the change in size difference that the swelling because of methanol aqueous solution of constituent material separately causes.

[embodiment 5]

As electrode, use 2 above-mentioned electrode C, in addition, obtain film electrode composite element similarly to Example 1.After this film electrode composite element extracted washing similarly to Example 1, install in the battery, made cell of fuel cell.At battery temperature: 60 ℃, fuel gas: hydrogen, oxidizing gas: air, gas effciency: anode 70%/negative electrode 40% time, this cell of fuel cell is carried out current-voltage (I-V) measure, maximum is output as 600mW/cm as a result ², limiting current density is 1500mA/cm ²

Moreover, describe about limiting current density, usually electrode reaction comprise that absorption, disassociation, the electric charge of reactant of the position of this reaction moves, nearby reactant of this position, product a lot of continuous processes such as move, but the speed of each process, the degree (being called non-equilibrium degree later on) that departs from from the poised state (electric current is 0 state) of this process is big more, just fast more, the relation of the degree of this non-equilibrium degree and the size of speed is different and different according to each process.In electric current stable state when circulation ground,, the speed of all processes is identical, and therefore the non-equilibrium degree of the process of carrying out easily is very little, and it is big to be not easy the non-equilibrium degree of the process of carrying out.Here, if increase current density, i.e. electrode reaction speed, the non-equilibrium degree that then particularly is not easy the process of carrying out is very big, always reaches physics limit.That is, can not obtain that above current density, but this current density is the limiting current density here.

[comparative example 4]

With 2 plate electrode C, do not use interface resistance reduction property composition ground to carry out the stacked and feasible dielectric film A that clamps, carried out heating and pressurizing 8 minutes at 100 ℃ of pressure with 5MPa, obtain film electrode composite element.This film electrode composite element is installed in the battery, carry out the evaluation of fuel cell similarly to Example 4.

Maximum is output as 200mW/cm ², limiting current density is 700mA/cm ²,, be the performance of difference with embodiment 4 ratios.

[embodiment 6]

Use have ionic base macromolecular material, synthesis example 4,4 '-(9H-fluorenes-9-subunit (イ リ デ Application)) bis-phenol and 4,4 '-difluoro benzophenone and 3,3 '-disulfonate-4,4 '-difluoro benzophenone disodium, change their cooperation ratio, make dielectric film and reach various tensiles modulus of elasticity.The system film makes that thickness is 75 ± 3 μ m, adopts method similarly to Example 2 to reduce property composition B and electrode A, compoundization of B by interface resistance, has made film electrode composite element.Also make the film electrode composite element that does not use interface resistance reduction property composition B simultaneously, make fuel cell and estimate similarly to Example 1, Fig. 3 has concluded the ratio (having used interface resistance to reduce the ratio of power output that the power output of the fuel cell of property composition/do not use interface resistance reduces the fuel cell of property composition) of peak power output separately and the relation of tensile modulus of elasticity.

Find out clearly that by Fig. 3 it is big to reduce its peak power output of film electrode composite element that the property composition makes in the scope of all tensiles modulus of elasticity by interface resistance, particularly tensile modulus of elasticity reach 100MPa when above its effect become remarkable.

[embodiment 7]

The dielectric film A of embodiment 3 is changed to dielectric film B, made film electrode composite element in addition similarly to Example 3.

Storage modulus of elasticity, loss elastic modulus and the phase difference in the cross section of this film electrode composite element have been measured, can confirm the layer (A) that the dielectric film part is different with phase difference, the ratio M/I of phase difference is 1.31, the storage modulus of elasticity C of dielectric film part is 9.5GPa, loss elastic modulus E is 1.8GPa, the storage modulus of elasticity D of layer (A) part is 8.8GPa, and loss elastic modulus F is 1.7GPa, C/D=1.08, E/F=1.06.

The voltage retention of film electrode composite element, first voltage are 0.26V, and the constant current generating voltage after 100 hours is 0.25V, demonstrate the durability of 96% excellence.

In addition, the methyl alcohol penetrate amount of this film electrode composite element is 5.4 μ mol/cm ²/ minute.In addition, the output in passive evaluation demonstrates 42mW/cm ²In addition, the methyl alcohol penetrate amount of this film electrode composite element is 3.8 μ mol/cm ²/ minute.In addition, the output in passive evaluation demonstrates 35mW/cm ²

[embodiment 8]

Will as the macromolecular material with aromatic hydrocarbon that ionic base is arranged, polymer B 10g, pack in the container as N-N-methyl-2-2-pyrrolidone N-50g, the glycerine 40g of plasticizer, stirring has been made interface resistance reduction property composition till becoming evenly.Be applied to said composition on above-mentioned electrode A, the electrode B and make and be 4mg/cm ², 100 ℃ of heat treatments 1 minute.It is 5cm that these electrode cutting are become electrode area ²

Then, these electrodes that have interface resistance reduction property composition are stacked, and make interface resistance reduction property composition become dielectric film B side, carried out heating and pressurizing 1 minute at 100 ℃ of pressure with 5MPa, after the compacting film electrode composite element was flooded 30 minutes in the 50ml pure water, extract and wash the plasticizer that remains in the interface resistance reduction property composition, made film electrode composite element.

Storage modulus of elasticity, loss elastic modulus and the phase difference in the cross section of this film electrode composite element have been measured, can confirm the layer (A) that the dielectric film part is different with phase difference, the ratio M/I of phase difference is 0.95, the storage modulus of elasticity C of dielectric film part is 9.5GPa, loss elastic modulus E is 1.9GPa, the storage modulus of elasticity D of layer (A) part is 8.8GPa, and loss elastic modulus F is 1.7GPa, C/D=1.07, E/F=1.12.

The voltage retention of film electrode composite element, first voltage are 0.23V, and the constant current generating voltage after 100 hours is 0.22V, demonstrate the durability of 96% excellence.

In addition, the methyl alcohol penetrate amount of this film electrode composite element is 5.9 μ mol/cm ²/ minute.In addition, the output in passive evaluation demonstrates 37mW/cm ²

[embodiment 9]

Will as the macromolecular material with aromatic hydrocarbon that ionic base is arranged, polymer A 10g, pack in the container as N-N-methyl-2-2-pyrrolidone N-50g, the glycerine 40g of plasticizer, stirring has been made interface resistance reduction property composition till becoming evenly.Be applied to said composition on above-mentioned electrode A, the electrode B and make and be 3mg/cm ², 100 ℃ of heat treatments 1 minute.It is 5cm that these electrode cutting are become electrode area ²

Then, these electrodes that have interface resistance reduction property composition are stacked, and make interface resistance reduction property composition become dielectric film A side, and carried out heating and pressurizing 1 minute at 100 ℃ of pressure with 5MPa, obtain film electrode composite element.After the compacting film electrode composite element was flooded 30 minutes in the 50ml pure water, extract and wash the plasticizer that remains in the interface resistance reduction property composition, made film electrode composite element.

Storage modulus of elasticity, loss elastic modulus and the phase difference in the cross section of this film electrode composite element have been measured, can confirm the layer (A) that the dielectric film part is different with phase difference, the ratio M/I of phase difference is 0.95, the storage modulus of elasticity C of dielectric film part is 9.5GPa, loss elastic modulus E is 1.9GPa, the storage modulus of elasticity D of layer (A) part is 8.8GPa, and loss elastic modulus F is 1.7GPa, C/D=1.07, E/F=1.12.

The voltage retention of film electrode composite element, first voltage are 0.25V, and the constant current generating voltage after 100 hours is 0.24V, demonstrate the durability of 96% excellence.

In addition, the methyl alcohol penetrate amount of this film electrode composite element is 5.0 μ mol/cm ²/ minute.In addition, the output in passive evaluation demonstrates 42mW/cm ²

Utilizability on the industry

The manufacture method of film electrode composite element of the present invention is applicable to various electrochemical appliance (examples Such as fuel cell, apparatus for electrolyzing, chloric alkali electrolysis device etc.) the manufacturing of film electrode composite element. Among these devices, be very suitable for fuel cell usefulness, particularly be very suitable for hydrogen or methanol-water Solution is the fuel cell of fuel.

In addition, film electrode composite element of the present invention is applicable to (for example combustion of various electrochemical appliances Material battery, apparatus for electrolyzing, chloric alkali electrolysis device etc.) film electrode composite element. Install it at these In, be very suitable for fuel cell usefulness, particularly be very suitable for take hydrogen or methanol aqueous solution to fuel Fuel cell.

As the purposes of fuel cell of the present invention, do not limit especially, can be preferably used as into portable phone, PC, PDA, video camera, digital camera, Portable TV, digital audio-frequency player, hard Household electrical appliances, toys, the electric bicycles, electronic such as the portable equipments such as disk player, battery type sweeper The movement of the vehicles such as wheelchair, two-wheel motorcycle, automobile, bus, truck, boats and ships, railway etc. The electric power supply source of instrument, robot, biochemical cyborg, seat formula generator etc., existing once electricity The substitute of pond, secondary cell or with them, the AC-battery power source of solar cell or charging use.

Among the present invention the expression number range " more than ", " following " comprise given figure.

Claims (5)

1. film electrode composite element, be to make dielectric film between pair of electrodes and the film electrode composite element that forms, between at least one side's electrode and dielectric film, have a layer A, phase difference and the dielectric film that mode scanning measures that rap that passes through scanning probe microscopy of this layer A is different in essence, and, dielectric film and layer A contain the aromatic hydrocarbon that has the anionic property base on the main chain, when the storage modulus of elasticity of the dielectric film of being measured by the ultra micro hardometer is designated as C, storage modulus of elasticity C value is more than the 1GPa, the loss elastic modulus of dielectric film is designated as E, when the loss elastic modulus of layer A was designated as F, the value of any of loss elastic modulus E and F was more than the 0.1GPa.

2. film electrode composite element as claimed in claim 1, when the storage modulus of elasticity of layer A was designated as D, any among C/D or the E/F was 0.5～1.5 at least.

3. film electrode composite element as claimed in claim 1, the material that constitutes above-mentioned dielectric film or layer A comprises polyether-ether-ketone or polyether-ketone.

4. film electrode composite element as claimed in claim 1, it is identical in fact with the material of layer A to constitute dielectric film.

5. a fuel cell has used the described film electrode composite element of claim 1.

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