CN1893157A - Polymer membrane and membrane-electrode assembly for fuel cell and fuel cell system comprising same - Google Patents
Polymer membrane and membrane-electrode assembly for fuel cell and fuel cell system comprising same Download PDFInfo
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- CN1893157A CN1893157A CNA2006101060927A CN200610106092A CN1893157A CN 1893157 A CN1893157 A CN 1893157A CN A2006101060927 A CNA2006101060927 A CN A2006101060927A CN 200610106092 A CN200610106092 A CN 200610106092A CN 1893157 A CN1893157 A CN 1893157A
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- H01M8/1018—Polymeric electrolyte materials
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- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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Abstract
The polymer electrolyte membrane of the present invention includes a proton conductive cation exchange resin, a non-proton-conductive polymer, and an inorganic additive. The inorganic additive is adapted to inhibit a phase separation between the proton conductive cation exchange resin and the non-proton-conductive polymer.
Description
Background of invention
Technical field
The present invention relates to a kind of polymer dielectric film and membrane-electrode assemblies that is used for fuel cell, and the fuel cell system that comprises this polymer dielectric film.More specifically, the present invention relates to a kind of being used to suppresses polymer dielectric film and the membrane-electrode assemblies that hydrocarbon fuel penetrates, and the fuel cell system that comprises this polymer dielectric film.
The description of association area
Fuel cell is a kind of electricity generation system that is used to produce electric energy, it by oxidant and be contained in the alkyl material hydrogen fuel for example the electrochemical redox reaction of methyl alcohol, ethanol or natural gas carry out.
The representative example of fuel cell comprises polymer dielectric film fuel cell (PEMFC) and direct oxidation fuel cell (DOFC).Direct oxidation fuel cell comprises the direct methanol fuel cell of using methyl alcohol to act as a fuel.
Polymer dielectric film fuel cell (PEMFC) has high-energy-density, but need the fuel reforming processor, is used for reforming methane, methyl alcohol, natural gas etc., with the act as a fuel hydrogen-rich gas of gas of generation.
On the contrary, direct oxidation fuel cell (DOFC) has the energy density that is lower than polymer dielectric film fuel cell, but does not need the fuel reforming processor.
Fuel cell comprises the stack of laminations that in fact produces electric power.This stack of laminations comprises the plurality of units battery that piles up in the multilayer mode.Each element cell is made up of membrane-electrode assemblies (MEA) and separator (being also referred to as bipolar sheets).Membrane-electrode assemblies has anode (being called fuel electrode or oxidizing electrode) and the negative electrode (being called air electrode or reducing electrode) that is aggregated the separation of thing dielectric film.
Perfluorinated sulfonic resin (for example, NAFION
) can be as the material that forms polymer dielectric film.The polymer dielectric film that uses perfluorinated sulfonic resin to form has oxygen solubility, electrochemical stability and the durability that is higher than the hydrocarbon polymer film.
Usually, the thicker perfluorinated sulfonic resin film of thickness 50 to 175 μ m provides the perfluorinated sulfonic resin film that relatively approaches with better dimensional stability and mechanical performance, but thicker perfluorinated sulfonic resin film has relatively thinner perfluorinated sulfonic resin film higher film resistance is arranged.On the contrary, thin film has higher proton conductive, but also can allow unreacted fuel gas and liquid to pass its thin polymer film, causes the loss of unreacted fuel gas, thereby reduces fuel cell performance.
Summary of the invention
One aspect of the present invention provides a kind of polymer dielectric film that higher proton conductive and good inhibition hydrocarbon fuel penetrate that has.
Another aspect of the present invention provides a kind of membrane-electrode assemblies, and it comprises above-mentioned polymer dielectric film.
Another aspect of the present invention provides a kind of fuel cell system, and it comprises above-mentioned polymer dielectric film.
According to an embodiment of the invention, provide a kind of polymer dielectric film that comprises proton conductive cation exchange resin, non-proton conducting polymer and inorganic additive.This inorganic additive is suitable for suppressing being separated between proton conductive cation exchange resin and the non-proton conducting polymer.According to another implementation of the invention, provide a kind of polymer dielectric film, the porous carrier that it comprises proton conductive cation exchange resin, non-proton conducting polymer, inorganic additive and has a plurality of holes.This porous carrier supports proton conductive cation exchange resin, non-proton conducting polymer and inorganic additive, and comprises non-proton conducting polymer.Proton conductive cation exchange resin, non-proton conducting polymer and inorganic additive transfer protons, and therefore can be generically and collectively referred to as the proton transport layer.This proton transport layer may reside in hole inside or porous carrier surface.
According to another implementation of the invention, the membrane-electrode assemblies that is used for fuel cell comprises opposed facing anode and negative electrode, and at least one inserts above-mentioned polymer dielectric film wherein.
According to another implementation of the invention, fuel cell system comprises at least one electrogenesis element, fuel supply and oxidant supply.The electrogenesis element comprises membrane-electrode assemblies, the separator that it comprises at least one above-mentioned polymer dielectric film and is fixed on the negative electrode and the anode of polymer dielectric film both sides and is fixed on the membrane-electrode assemblies two sides.Fuel supply provides fuel to the electrogenesis element, and the oxidant supply provides oxidant to the electrogenesis element.
Description of drawings
Fig. 1 is a schematic diagram of showing the direct oxidation fuel cell system configuration according to an embodiment of the invention;
Fig. 2 is a TEM photo of showing the polymer dielectric film surface of the embodiment of the invention 1;
Fig. 3 is a TEM photo of showing the polymer dielectric film surface of the embodiment of the invention 2;
Fig. 4 shows embodiment 1,3,4 and 5 and the diagrammatic sketch at the polymer dielectric film X-ray diffraction peak of Comparative Examples 1;
Fig. 5 shows embodiment 1,3,4 and 5 and the diagrammatic sketch of the methanol permeability of the polymer dielectric film of Comparative Examples 1,3,4,5 and 6; With
Fig. 6 is the diagrammatic sketch of proton conductive of showing the polymer dielectric film of embodiment 1, Comparative Examples 2 and reference example.
Describe in detail
Usually, thicker perfluorinated sulfonic resin film provides relatively thinner better dimensional stability of perfluorinated sulfonic resin film and mechanical performance, but thicker perfluorinated sulfonic resin film has the relatively thinner higher film resistance of perfluorinated sulfonic resin film.On the contrary, thin film has higher proton conductive, but also can allow unreacted fuel gas and liquid to pass its thin polymer film, causes the loss of unreacted fuel gas, thereby reduces fuel cell performance.
In more detail, hydrocarbon fuel for example methyl alcohol, ethanol or propyl alcohol can transmit by the hydrophilic parts of perfluorinated sulfonic resin, and is oxidized at negative electrode then, and the loss that it causes fuel and redox site makes the fuel battery performance feature obviously worsen.
Separate in order to improve fuel, keep good proton conductive simultaneously, polymer dielectric film can comprise perfluorinated sulfonic resin and not have the compatible polymer blend of the hydrocarbyl polymers of ionic conductivity still have the good separating property of hydrocarbon fuel.This hydrocarbyl polymers can be the polyvinylidene fluoride based polyalcohol, because itself and the chemical resistance of the partial compatibility of perfluorinated sulfonic resin and excellence.Yet because the variable density of polymer mixed solution, poly-vinylidene halide may cause being separated, and therefore can cause obviously changing along the conductivity of polymer dielectric film thickness.
According to an embodiment of the invention, polymer dielectric film provides film seldom a kind of or that be not separated.
According to an embodiment of the invention, polymer dielectric film comprises proton conductive cation exchange resin, non-proton conducting polymer and inorganic additive.
According to an embodiment of the invention, polymer dielectric film may further include porous carrier, it is made of the non-proton conductive supporting polymer that supports proton conductive cation exchange resin, non-proton conducting polymer and inorganic additive, and comprises a plurality of holes.Proton conductive cation exchange resin, non-proton conducting polymer and inorganic additive are to be used to transmit proton, therefore can be generically and collectively referred to as the proton transport layer.The proton transport layer may reside in the hole or porous carrier surperficial.
The non-proton conducting polymer of proton transport layer can improve the mechanical performance of polymer dielectric film and the feature of hydrocarbon fuel separating property (for example Bao polymer dielectric film).The non-limiting example of non-proton conducting polymer comprises polyvinylidene fluoride homopolymers, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol or its composition.
Non-proton conductive supporting polymer can comprise the homopolymers that is selected from polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyimides, poly-benzoxazol, polybenzimidazoles, its composition and its copolymer.
According to an embodiment of the invention, in the proton transport layer of polymer dielectric film, the non-proton conductive supporting polymer that constitutes porous carrier can comprise fluorine-based polymer, for example polytetrafluoroethylene, polyvinylidene fluoride or its copolymer, and in one embodiment, can comprise the polytetrafluoroethylene homopolymers.Here, when porous carrier and proton conductive cation exchange resin all were fluorine-based polymer, then bonding force increased.Porous carrier can have 60% or bigger porosity.According to an execution mode, porous carrier can have 60% to 90% porosity.When porosity less than 60% the time, enough proton transport layers of desired ion conductivity may be provided on the porous carrier surface.
The inorganic additive of proton transport layer can be dispersed in the polymer dielectric film in the nanophase mode.Inorganic additive suppresses being separated between proton conductive cation exchange resin and the non-conductive polymer, and improves hydrocarbon fuel barrier properties and thermal stability.
According to an execution mode, inorganic additive can comprise inorganic silicate.The amount that depends on negative electrical charge, silicate can be divided into pyrophyllite-talcum, montmorillonite (MMT), saponite, fluorine hectorite, kaolinite, vermiculite, LAPONITE (laponites), illite, mica, fragility mica or tetrasilicic acid mica (tetrasilicic micas), and can use any this material in the embodiment of the present invention.
Al in the alumina octahedral sheet in the structure of montmorillonite
3+Ion is by Mg
2+, Fe
2+Or Fe
3+Ion replaces, and Si in the silicate tetrahedral sheet
4+Ion is by Al
3+Ion replaces.In addition, montmorillonite has total negative electrical charge.And, in the montmorillonite, comprise tradable cation and hydrone between the silicate layer, to keep the total charge balance.
In one embodiment, silicate has 1/50 to 1/1000 length-width ratio.In one embodiment, silicate has 1/100 to 1/800 length-width ratio, and in one embodiment, silicate has 1/500 to 1/800 length-width ratio.
When the length-width ratio of silicate greater than 1/50 the time, the silicate of peeling off can not be as the diffusion barrier of gas and liquid, and its barrier properties variation.When the length-width ratio of silicate less than 1/1000 the time, be difficult to cause peeling off because of inserting proton conductive cation exchange resin chain, so do not disperse in the proton conductive cation exchange resin of silicate in polymer dielectric film.
Can handle silicate with organic modifiers.Strong Van der Waals'attractive force makes tabular silicate be difficult to be stripped from and is dispersed in the fluoropolymer resin, still handles with the low-molecular-weight organic modifiers, causes permeating between the plate, promotes the insertion of fluoropolymer resin, thereby is easy to peel off and disperse.
Suitable organic modifiers comprises C
1To C
20Alkylamine, C
1To C
20Alkylene diamine, C
1To C
20Quaternary ammonium salt, aminohexane and nitrogenous heterocyclic compound.The instantiation of alkylamine comprises methylamine hydrochloride, propylamine, butylamine, octylame, decyl amine, dodecyl amine, cetylamine, octadecane amine, N-methyl octadecane amine etc.
The non-limiting example of alkylene diamine comprises 1,6-hexamethylene diamine and 1,12-dodecane diamines.The non-limiting example of quaternary ammonium salt comprises dimethyl quaternary ammonium, benzyl quaternary ammonium, 2-ethylhexyl quaternary ammonium, two 2-ethoxy quaternary ammonium, methyl quaternary ammonium etc.The non-limiting example of alkylammonium salt comprises tetramethyl ammonium chloride, octadecyl trimethylammonium bromide, DTAB, two octadecyl dimethyl ammonium bromide and two (2-ethoxy) methyl octadecyl ammonium chloride etc.The non-limiting example of aminohexane comprises 6-aminohexane and 12-aminohexane.The non-limiting example of nitrogenous heterocyclic compound comprises the 1-pyrisept.
As mentioned above, can use with the inorganic silicate after the organic modifiers processing.Perhaps, can use commercially available organically-modified inorganic silicate.Suitable organically-modified inorganic silicate comprises Cloisite6A, Cloisite10A, and Cloisite15A, Cloisite20A, Cloisite25A and Cloisite30B are produced by Southern Clay Products Inc..In one embodiment, use Cloisite10A.
The proton conductive cation exchange resin provides the composite membrane with ionic conductivity.The proton conductive cation exchange resin can be any fluoropolymer resin that has the cation exchange base at its side chain.The cation exchange base is selected from sulfonic group, carboxylic acid group, phosphonate group and its derivative.According to an embodiment of the invention, the ion exchange ratio of proton conductive cation exchange resin is 3 to 33, and its equivalent weight (EW) is 700 to 2,000.
Also can determine the ion exchange ratio of ion exchange resin by the quantity of carbon number in the main polymer chain and cation exchange base.
The non-limiting example of proton conductive cation exchange resin comprises at least a proton conductive polymer, and it is selected from fluorine-based polymer, benzimidazole-based polymer, polyimides based polyalcohol, polyetherimide amine based polymer, polyphenylene sulfide based polyalcohol, polysulfones based polyalcohol, polyether sulfone based polyalcohol, polyether-ketone based polyalcohol, polyethers-ether ketone group polymer and polyphenylene quinoxalinyl polymer.
The instantiation of fluorine-based polymer comprises poly-(perfluorinated sulfonic acid) (NAFION , the E.I.Dupont de Nemours Company) by following general formula 1 representative; Aciplex by following general formula 2 representatives
TM(Asahi kasei Chemical), Flemion
TM(Asahi Glass), and Fumion
TMThe fluorine carbon vinethene of (commodity turn to fumatech); With vinethene fluoride by following general formula 3 representatives.Also can use to be disclosed in U.S. Patent number 4,330,654,4,358,545,4,417,969,4,610,762,4,433,082,5,094,995,5,596,676 and 4,940,525 polymer, its full content is hereby incorporated by.
Here, in the above-mentioned general formula 1, X is H, Li, Na, K, Cs, 4-butyl amine or NR1R2R3R4.R1, R2, R3 and R4 are selected from H, CH respectively
3And C
2H
5M is 1 at least; N is 2 at least; X is about 3.5 to 5; Y is 1,000 at least.
MSO
2CFRfCF
2O[CFYCF
2O]
nCF＝CF
2?(2)
Here, in the above-mentioned general formula 2, Rf is fluorine or C
1To C
10Perfluoroalkyl; Y is fluorine or trifluoromethyl; N is 1 to 3; M be selected from fluorine, hydroxyl, amino and-OMe, wherein Me is alkali metal base or quaternary ammonium group.
Here, in the above-mentioned general formula 3, k is 0 or 1,1 to be 3 to 5 integer.
Above-mentioned poly-(perfluorinated sulfonic acid) (NAFION
TM) the sulfonic acid end group be hydration to form micellar structure, it provides the proton translocation path, and its effect is similar to typical acidic aqueous solution.In one embodiment of the invention, as poly-(perfluorinated sulfonic acid) (NAFION
) when the cation exchange resin, can for example hydrogen ion, sodium ion, potassium ion, cesium ion or 4-butyl amine (TBA) replace the ion-exchange group (SO of side chain terminal with monovalent ion
3X) X in.
Poly-(ether ether ketone) that the instantiation of benzimidazole-based polymer, polyimides based polyalcohol, polyetherimide amine based polymer, polyphenylene sulfide based polyalcohol, polysulfones based polyalcohol, polyether sulfone based polyalcohol, polyether-ketone based polyalcohol, polyethers-ether ketone group polymer and polyphenylene quinoxalinyl polymer comprises polybenzimidazoles, polyimides, polysulfones, polysulfones derivative, sulfonation (s-PEEK), polyphenylene oxide, polyphenylene sulfide and polyphosphazene (polyphosphazane).
Perhaps, can use a kind of dielectric film, wherein the polystyrolsulfon acid polymer is to be grafted on polyethylene, polyacrylic polymer, fluoroethylene polymer or the ethylene/tetrafluoroethylene polymer.
In polymer dielectric film, proton conductive cation exchange resin and non-proton conducting polymer can exist to 50 weight ratio with 50 to 90: 10.According to an execution mode, proton conductive cation exchange resin and non-proton conducting polymer existed to 30 weight ratio with 70 to 80: 20.Based on the total amount of 100 weight portion proton conductive cation exchange resins and non-proton conducting polymer, the inorganic additive use amount can be 1 to 10 weight portion, and is 1 to 5 weight portion in one embodiment.When non-proton conducting polymer and inorganic additive amount surpass above-mentioned scope, or the proton conductive cation exchange resin is during less than above-mentioned scope, and film conductivity reduces.On the contrary, when non-proton conducting polymer and inorganic additive amount are lower than above-mentioned scope, hydrocarbon fuel barrier properties possible deviation.
The polymer dielectric film of embodiment of the present invention is the film of thickness 10 to 50 μ m.This film has good hydrocarbon fuel separating property, thereby can improve the power output density when being used as the polymer dielectric film of fuel cell.
Polymer dielectric film that can manufacturing embodiment of the present invention as described below.At first, dissolving has the ion exchange resin of cation exchange base in organic solvent, with preparation cation exchange resin solution.The use amount of cation exchange resin can be for 0.5 to 30wt%.
Organic solvent can be a for example dimethyl acetate of hydrophobic organic solvent.Should not use for example ethanol of hydrophilic organic solvent.Reason is, cation exchange resin possess hydrophilic property and inorganic additive has hydrophobicity, and when using hydrophilic solvent for example ethanol is as organic solvent, inorganic additive may precipitate.The non-limiting example of hydrophobic organic solvent comprises dimethyl acetate, dimethylacetylamide, dimethyl formamide, N-methyl-2-pyrrolidine-diones and its composition.
Commercially available the gathering that is dissolved in water and the 2-propyl alcohol mixed solvent is used for cation exchange resin after (perfluorinated sulfonic acid) can at room temperature evaporate mixed solvent, and the product that obtains is dissolved in hydrophobic solvent for example in the dimethyl acetate again, thereby the preparation concentration range is 0.5 to 30wt% cation exchange resin solution.
Cation exchange resin solution to obtaining adds non-proton conductive polymer solution, with preparation cation exchange resin-polymer solution.It is 5 to 30wt% non-proton conducting polymer that non-proton conductive polymer solution comprises concentration.Solvent can comprise dimethylacetylamide, dimethyl formamide etc., and non-proton conducting polymer is same as described above.Mixed-cation exchanger resin solution and non-proton conductive polymer solution, make can be with 50 to 90: 10 to 50 weight ratio mixed-cation exchanger resin and non-proton conducting polymer; And in one embodiment, this weight ratio be 70 to 80: 20 to 30.
Subsequently, inorganic additive is added to mixing then in cation exchange resin-polymer solution.Under machinery or ultrasonic agitation condition, carry out mixed process at 50 to 120 ℃.When temperature was lower than 50 ℃, mixing needed the cost long time.On the contrary, when temperature during, then can evaporate multi-solvent, so that be difficult to controlled concentration greater than 120 ℃.
Based on the total amount of 100 weight portion proton conductive cation exchange resins and non-proton conducting polymer, the inorganic additive addition can be 1 to 10 weight portion.When the amount of inorganic additive is lower than 1 weight portion, can not effectively implement the barrier that fuel is penetrated.On the contrary, when it was higher than 10 weight portions, the film that obtains may be a fragility.
Then the solution that obtains is formed film, to produce polymer dielectric film.
Perhaps, can be to the porous carrier that constitutes by above-mentioned non-proton conductive supporting polymer with the solution coat that obtains, dry under 100 to 120 ℃ of temperature then, with the preparation polymer dielectric film.For example this coating process is carried out in roller coat, dip-coating, spraying or slit die formula (slof-die) coating can to use common wet coating method.
Above-mentioned preparation method is relatively easily, and can be used for large-scale production.
In one embodiment, the membrane-electrode assemblies with above-mentioned polymer dielectric film comprises opposed facing anode and negative electrode, and the polymer dielectric film that inserts therebetween.
Anode and negative electrode comprise catalyst layer and electrode base material.
Catalyst layer comprises at least a catalyst, and it is selected from platinum, ruthenium, osmium, platinum-ruthenium alloys, platinum osmium alloy, platinum-nickel alloys, platinum-M alloy and its composition, and wherein M is a transition elements, is selected from Ga, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Mo, W, Rh, Ru and its composition.In the present invention, anode can comprise identical catalyst material with negative electrode.Perhaps, in direct oxidation fuel cell, plant platinum-ruthenium alloys by one or more and form anode, it can be stood the CO that is produced during the catalyst reaction and poison.Platinum-ruthenium alloys can comprise at least a material, and it is selected from Pt, Pt/Ru, Pt/W, Pt/Ni, Pt/Sn, Pt/Mo, Pt/Pd, Pt/Fe, Pt/Cr, Pt/Co, Pt/Ru/W, Pt/Ru/Mo, Pt/Ru/V, Pt/Fe/Co, Pt/Ru/Rh/Ni, Pt/Ru/Sn/W and its composition.
Metallic catalyst can carrier band in carrier or not with carbon black (black) type carrier band.Suitable carriers comprises material with carbon element, for example acetylene carbon black, step on card (denka) carbon black, activated carbon, Ke Tejin (ketjen) carbon black, graphite, carbon nano-tube, carbon nano-fiber, carbon nanocoils, Nano carbon balls etc., or inorganic material particle, for example aluminium oxide, silicon dioxide, zirconia and titanium dioxide.
Catalyst layer may further include adhesive resin, to improve its adhesiveness and proton transfer performance.
Adhesive resin can be the fluoropolymer resin that has the cation exchange base at its side chain.The cation exchange base can be selected from sulfonic group, carboxylic acid group, phosphate, phosphonate group and its derivative.The non-limiting example of fluoropolymer resin comprises at least a proton conductive polymer, and it is selected from perfluor based polyalcohol, benzimidazole-based polymer, polyimides based polyalcohol, polyetherimide amine based polymer, polyphenylene sulfide based polyalcohol, polysulfones based polyalcohol, polyether sulfone based polyalcohol, polyether-ketone based polyalcohol, polyethers-ether ketone group polymer and polyphenylene quinoxalinyl polymer.In the embodiment, proton conductive polymer comprises at least a material, it is selected from poly-(perfluorinated sulfonic acid), poly-(perfluorocarboxylic acid), tetrafluoroethene and has the polyether-ketone sulfide of the copolymer of sulfonic fluorovinyl ether, defluorinate, aryl ketones, poly-(2,2 '-(metaphenylene)-5,5 '-bisbenzimidazole) and poly-(2, the 5-benzimidazole).
Hydrogen in the ion-exchange group of the side chain terminal of proton conductive polymer (H) can be replaced by Na, K, Li, Cs or tetrabutylammonium.When the H in the terminal ion-exchange group of the side chain of proton conductive polymer is replaced by Na or tetrabutylammonium, during the preparation carbon monoxide-olefin polymeric, can use NaOH or tetrabutylammonium hydroxide respectively.When H is replaced by K, Li or Cs, can use any compound that is suitable for replacing.
Adhesive resin can use separately or be used in combination with other adhesive resin.Adhesive resin can use with non-conductive polymer, with the adhesion of improvement with polymer dielectric film.Can use non-conductive polymer with controlled quentity controlled variable, to adapt to its purpose.
The non-limiting example of non-conductive polymer comprises polytetrafluoroethylene (PTFE), tetrafluoraoethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene/tetrafluoroethylene (ETFE), chlorotrifluoroethylene-ethylene copolymer (ECTFE), polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP), DBSA, sorbierite and its composition.
Electrode base sheet can be used for support electrode, and also can be used for fuel and oxidant are dispersed on the catalyst layer, to help the reaction of they and catalyst layer.Electrode base sheet is a conductive substrate.The non-limiting example of this conductive substrate comprises carbon paper, carbon cloth, carbon felt (felt) and hardware cloth (perforated membrane that for example has hardware cloth fiber or metal-coating of polymeric fibres).
Can handle this electrode base sheet with the fluoro resin of waterproof, reduce because of the water that produces during the fuel cell-driven makes the reactant diffuser efficiency to reduce or to prevent.Fluoro resin may comprise; but be not limited to, polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyhexafluoropropylene, poly-perfluoroalkyl vinyl ether, poly-perfluor sulfonyl base fluoride, alkoxy vinyl ethers, the ethylene, propylene of fluoridizing, polytrifluorochloroethylene, fluorinated ethylene polymer and its copolymer.
Can between electrode base sheet and catalyst layer, add microporous layers (MPL), to increase the diffusion effect of reactant.Microporous layers can include, but are not limited to, small size conductive powder, for example carbon dust, carbon black, acetylene black, activated carbon, carbon fiber, fullerene, nano-sized carbon or its composition.Nano-sized carbon can comprise, such as the material of carbon nano-tube, carbon nano-fiber, carbon nanocoils, carbon nanohorn, carbon nano ring or its composition.By on electrode base sheet, coating comprises the composition of conductive powder, adhesive resin and solvent, and forms microporous layers.Adhesive resin can comprise; but be not limited to poly-polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyhexafluoropropylene, poly-perfluoroalkyl vinyl ether, poly-perfluor sulfonyl base fluoride, alkoxy vinyl ethers, polyvinyl alcohol, cellulose acetate or its copolymer.Solvent can include, but are not limited to, alcohols, for example ethanol, isopropyl alcohol, ethanol, normal propyl alcohol or butanols; Water; Dimethylacetylamide (DMA); Dimethyl formamide; Methyl-sulfoxide (DMSO); The N-methyl pyrrolidone; Or oxolane.
The viscosity that depends on composition, coating process can include, but are not limited to, screen printing, spraying, doctor blade method, intaglio plate coating, dip-coating, silk screen printing, brushing etc.
According to one embodiment of the invention, comprise that the fuel cell system of membrane-electrode assemblies comprises at least one electrogenesis element, fuel supply and oxidant supply.
The electrogenesis element comprises membrane-electrode assemblies, and it comprises polymer dielectric film and the negative electrode of placing on the polymer dielectric film two sides and anode and the separator of placing on the membrane-electrode assemblies two sides (being also referred to as bipolar plates).Electricity is to produce by oxygenated fuel and reduction-oxidation agent.
Fuel supply provides the fuel that comprises hydrogen to the electrogenesis element, and the oxidant supply provides oxidant to the electrogenesis element.Fuel comprises liquid or Gaseous Hydrogen fuel, or hydrocarbon-based fuel for example methyl alcohol, ethanol, propyl alcohol, butanols or natural gas.Oxidant comprises oxygen or air.According to an embodiment of the invention, fuel cell system can be to use the direct oxidation fuel cell system of hydrocarbon fuel.
Illustrate the schematic construction according to the fuel cell system 1 of an embodiment of the invention among Fig. 1, it just illustrates in many fuel cell system embodiments one.Some fuel cell systems use pumps providing fuel and/or oxidant to the electrogenesis element, and other provide fuel and/or oxidant and do not use pump with diffusion way.
With reference to figure 1, fuel cell system 1 comprises at least one electrogenesis element 3, with the fuel that provides by fuel supply 5 by oxidation and also the oxidant that provides of reason oxidant supply 7 produce electric energy.
In addition, fuel supply 5 is furnished with the storage tank 9 of storage of fuels, with the pump 11 that is connected storage tank 9.The fuel that petrolift 11 will be stored in the storage tank 9 provides to stack of laminations 15.
Provide the oxidant supply 7 of oxidant to be furnished with at least one pump 13 to electrogenesis element 3, be used to provide oxidant to stack of laminations.
Following examples illustrate in greater detail the present invention.Yet, be appreciated that to the invention is not restricted to these
Embodiment.
Embodiment 1
At room temperature evaporate 5wt%NAFION/H
2(SolutionTechnology Inc EW=1100), joins in the dimethylacetylamide (DMA) with concentration 5wt% the perfluor sulfoacid resin solution of O/2-propyl alcohol then.Then, the product that obtains 100 ℃ of stirrings 24 hours is with preparation cation exchange resin solution.
(KYNAR761) non-proton conducting polymer joins among the DMA with concentration 5wt% for PVdF, Elf Atochem, stirs at 100 ℃ then and dissolves in 24 hours with polyvinylidene fluoride.Mix 70g NAFION/DMA solution and 30g PVdF/DMA solution, stirred 24 hours at 100 ℃ then, mix compatible cation exchange resin-polymer solution with preparation.(Cloisite10A, Southern Clay Products Inc) is added in cation exchange resin-polymer solution at 100 ℃ with the montmorillonite inorganic additive particle of length-width ratio 1/200 to 1/800.Mechanical agitation mixture then, and apply ultrasonic wave with even dispersion inorganic material composition, thus preparation proton transport layer composition.Based on the total amount of 100 weight portion proton conductive cation exchange resins and non-proton conducting polymer, add 1 weight portion montmorillonite inorganic additive.
The proton transport layer composition is coated on the polyvinylidene fluoride polymer carrier with 60% above porosity, then 100 ℃ of dryings, to prepare the polymer dielectric film that fuel cell is used.The polymer dielectric film that obtains is that 30 μ m are thick, has with the nanometer state to be dispersed in inorganic additive in the polymer dielectric film.In the polymer dielectric film that obtains, the weight ratio of cation exchange resin, non-proton conducting polymer and inorganic additive is 70: 30: 1.
Except total amount based on 100 weight portion proton conductive cation exchange resins and non-proton conducting polymer, add beyond the 10 weight portion montmorillonite inorganic additives, use the method substantially the same to prepare polymer dielectric film with embodiment 1.
The TEM photo on embodiment 1 and 2 polymer dielectric film surfaces is shown in Fig. 2 and 3.Among Fig. 2 and 3, dark part represents that the mixture of montmorillonite and polyvinylidene fluoride, the particularly Long Lines Department in the circle of Fig. 2 divide expression MMT.
Except total amount based on 100 weight portion proton conductive cation exchange resins and non-proton conducting polymer, add beyond the 3 weight portion montmorillonite inorganic additives, use the method substantially the same to prepare polymer dielectric film with embodiment 1.
Embodiment 4
Except total amount based on 100 weight portion proton conductive cation exchange resins and non-proton conducting polymer, add beyond the 5 weight portion montmorillonite inorganic additives, use the method substantially the same to prepare polymer dielectric film with embodiment 1.
Except total amount based on 100 weight portion proton conductive cation exchange resins and non-proton conducting polymer, add beyond the 7 weight portion montmorillonite inorganic additives, use the method substantially the same to prepare polymer dielectric film with example I.
Comparative Examples 1
Use NAFION117 as polymer dielectric film.
Comparative Examples 2
Use NAFION115 as polymer dielectric film.
Comparative Examples 3
(Cloisite10A, Southern Clay Products Inc.) are added in the cation exchange resin-polymer solution of 100 weight portions by embodiment 1 preparation with the montmorillonite inorganic additive particle of 1 weight portion length-width ratio 1/200 to 1/800.The mixture that use obtains is produced polymer dielectric film by film production process.
Comparative Examples 4
Except based on cation exchange resin-polymer solution according to embodiment 1 preparation, use beyond the 3 weight portion montmorillonite inorganic additive particles, produce polymer dielectric film with identical with Comparative Examples 3 basically method.
Comparative Examples 5
Except based on cation exchange resin-polymer solution according to embodiment 1 preparation, use beyond the 5 weight portion montmorillonite inorganic additive particles, produce polymer dielectric film with identical with Comparative Examples 3 basically method.
Comparative Examples 6
Except based on cation exchange resin-polymer solution according to embodiment 1 preparation, use beyond the 7 weight portion montmorillonite inorganic additive particles, produce polymer dielectric film with identical with Comparative Examples 3 basically method.
The X-ray diffraction peak of polymer dielectric film
Use has the X-ray diffraction measuring equipment measured X ray diffraction peaks of the X-ray diffractometer (Phillips, X ' pert ProX-ray) of CuKa ray (λ=1.5406 ).Among Fig. 4, the part of representing with arrow is corresponding to the characteristic peak of MMT.In the polymer dielectric film, NAFION, MMT and PVdF are miscible mutually, therefore do not demonstrate the characteristic peak of MMT.Do not consider that MMT all demonstrates similar X-ray diffraction peak, and its addition shows that the crystallinity of polymer dielectric film is not influenced by MMT.
Methanol permeability
As shown in Figure 5, embodiment 1,3,4 and 5 film methanol permeability with Comparative Examples of being starkly lower than 1. Embodiment 1,3,4 and 5 film also have relatively low in the Comparative Examples 3,4,5 of using the montmorillonite inorganic additive and 6 methanol permeability.The inorganic additive of these presentation of results in the polymer dielectric film of each embodiment suppressed the passage of methyl alcohol effectively.When using with non-proton conducting polymer, this inhibition effect has great synergy.
Proton conductive
Measure the proton conductive of the polymer dielectric film of embodiment 1 and Comparative Examples 2, the results are shown in Fig. 6.Be used for comparison, shown that also the weight ratio that comprises as reference example is 6: 4 the NAFION and the film proton conductive of polyvinylidene fluoride.
As shown in Figure 6, demonstrate suitable proton conductive in the operating temperature of methyl alcohol direct oxidation fuel cell, this fuel cell can at room temperature be operated, no matter whether use MMT and polyvinylidene fluoride among the embodiment 1.
With regard to this point, according to an embodiment of the invention, polymer dielectric film can be thinner relatively, and also improve ionic conductivity and mechanical performance, and improve the hydrocarbon fuel barrier characteristics.Therefore, this film can be used for direct oxidation fuel cell.
Though describe the present invention in conjunction with exemplary embodiment, those skilled in the art are to be understood that the present invention is not limited to disclosed embodiment, and on the contrary, it covers the interior various variations of spirit and scope of claims and its equivalent.
Claims (36)
1. polymer dielectric film that is used for fuel cell, it comprises:
The proton conductive cation exchange resin;
Non-proton conducting polymer; With
Be suitable for suppressing the inorganic additive that is separated between proton conductive cation exchange resin and the non-proton conducting polymer.
2. the polymer dielectric film of claim 1, wherein the proton conductive cation exchange resin is included in the fluoropolymer resin that its side chain has the cation exchange base, and wherein the cation exchange base is selected from sulfonic group, carboxylic acid group, phosphate, phosphonate group and its derivative.
3. the polymer dielectric film of claim 1, wherein the ion exchange ratio of proton conductive cation exchange resin is about 3 to 33, and wherein the equivalent weight of proton conductive cation exchange resin (EW) is about 700 to 2,000.
4. the polymer dielectric film of claim 2, wherein the proton conductive cation exchange resin comprises at least a proton conductive polymer, it is selected from fluorine-based polymer, benzimidazole-based polymer, polyimides based polyalcohol, polyetherimide amine based polymer, polyphenylene sulfide based polyalcohol, polysulfones based polyalcohol, polyether sulfone based polyalcohol, polyether-ketone based polyalcohol, polyethers-ether ketone group polymer, polyphenylene quinoxalinyl polymer and its composition.
5. the polymer dielectric film of claim 4, wherein fluoropolymer resin is fluorine-based polymer.
6. the polymer dielectric film of claim 1, it further comprises porous carrier, this porous carrier is made up of the non-proton conductive supporting polymer that is suitable for supporting proton conductive cation exchange resin, non-proton conducting polymer and inorganic additive, and wherein porous carrier comprises a plurality of pores.
7. the polymer dielectric film of claim 6, wherein non-proton conductive supporting polymer comprises at least a homopolymers, and this homopolymers is selected from polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyimides, poly-benzoxazol, polybenzimidazoles, its composition and its copolymer.
8. the polymer dielectric film of claim 6, wherein non-proton conductive supporting polymer comprises at least a material that is selected from polytetrafluoroethylene, polyvinylidene fluoride, its copolymer and its composition.
9. the polymer dielectric film of claim 8, wherein non-proton conductive supporting polymer comprises polytetrafluoroethylene.
10. the polymer dielectric film of claim 1, wherein non-proton conducting polymer comprises at least a material that is selected from polyvinylidene fluoride homopolymers, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol and its composition.
11. the polymer dielectric film of claim 1, wherein proton conductive cation exchange resin and non-proton conducting polymer are to exist to 50 mixing ratio with 50 to 90: 10.
12. the polymer dielectric film of claim 11, wherein proton conductive cation exchange resin and non-proton conducting polymer are to exist to 30 mixing ratio with 70 to 80: 20.
13. the polymer dielectric film of claim 1, wherein the use amount of inorganic additive is about 1 to 10 weight portion based on the total amount of 100 weight portion proton conductive cation exchange resins and non-proton conducting polymer.
14. the polymer dielectric film of claim 13, wherein the use amount of inorganic additive is 1 to 5 weight portion based on the total amount of 100 weight portion proton conductive cation exchange resins and non-proton conducting polymer.
15. the polymer dielectric film of claim 1, wherein inorganic additive comprises at least a material that is selected from pyrophyllite-talcum, montmorillonite (MMT), saponite, fluorine hectorite, kaolinite, vermiculite, LAPONITE, illite, mica, fragility mica, tetrasilicic acid mica and its composition.
16. the polymer dielectric film of claim 1, wherein inorganic additive is to disperse with the nanometer state.
17. the polymer dielectric film of claim 6, wherein porous carrier has and is no less than 60% porosity.
18. a membrane-electrode assemblies that is used for fuel cell comprises:
Opposed facing anode and negative electrode and
Be inserted in the polymer dielectric film between anode and the negative electrode,
Wherein polymer dielectric film comprises:
The proton conductive cation exchange resin;
Non-proton conducting polymer; With
Be suitable for suppressing the inorganic additive that is separated between proton conductive cation exchange resin and the non-proton conducting polymer.
19. the membrane-electrode assemblies of claim 18, wherein the proton conductive cation exchange resin is included in the fluoropolymer resin that its side chain has the cation exchange base, and wherein the cation exchange base is selected from sulfonic group, carboxylic acid group, phosphate, phosphonate group and its derivative.
20. the membrane-electrode assemblies of claim 18, wherein the ion exchange ratio of proton conductive cation exchange resin is about 3 to 33, and wherein the equivalent weight of proton conductive cation exchange resin (EW) is about 700 to 2,000.
21. the membrane-electrode assemblies of claim 20, wherein the proton conductive cation exchange resin comprises at least a proton conductive polymer, it is selected from fluorine-based polymer, benzimidazole-based polymer, polyimides based polyalcohol, polyetherimide amine based polymer, polyphenylene sulfide based polyalcohol, polysulfones based polyalcohol, polyether sulfone based polyalcohol, polyether-ketone based polyalcohol, polyethers-ether ketone group polymer, polyphenylene quinoxalinyl polymer and its composition.
22. the membrane-electrode assemblies of claim 18, wherein polymer dielectric film further comprises porous carrier, this porous carrier is made up of the non-proton conductive supporting polymer that is suitable for supporting proton conductive cation exchange resin, non-proton conducting polymer and inorganic additive, and wherein porous carrier comprises a plurality of pores.
23. the membrane-electrode assemblies of claim 22, wherein non-proton conductive supporting polymer comprises at least a homopolymers, and this homopolymers is selected from polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyimides, poly-benzoxazol, polybenzimidazoles, its composition and its copolymer.
24. the membrane-electrode assemblies of claim 18, wherein non-proton conducting polymer comprises at least a material that is selected from polyvinylidene fluoride homopolymers, polyvinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol and its composition.
25. the membrane-electrode assemblies of claim 18, wherein proton conductive cation exchange resin and non-proton conducting polymer is to exist to 50 mixing ratio with 50 to 90: 10.
26. the membrane-electrode assemblies of claim 18, wherein the use amount of inorganic additive is about 1 to 10 weight portion based on the total amount of 100 weight portion proton conductive cation exchange resins and non-proton conducting polymer.
27. the membrane-electrode assemblies of claim 18, wherein inorganic additive comprises at least a material that is selected from pyrophyllite-talcum, montmorillonite (MMT), saponite, fluorine hectorite, kaolinite, vermiculite, LAPONITE, illite, mica, fragility mica, tetrasilicic acid mica and its composition.
28. the membrane-electrode assemblies of claim 18, wherein inorganic additive is to disperse with the nanometer state.
29. the membrane-electrode assemblies of claim 22, wherein porous polymer carrier has and is no less than 60% porosity.
30. the membrane-electrode assemblies of claim 18, wherein polymer dielectric film is used for direct oxidation fuel cell.
31. a fuel cell system comprises:
At least a electrogenesis element, it comprises
Opposed facing anode and negative electrode and
Be inserted in the polymer dielectric film between anode and the negative electrode, and comprise:
The proton conductive cation exchange resin;
Non-proton conducting polymer; With
Be suitable for suppressing the inorganic additive that is separated between proton conductive cation exchange resin and the non-proton conducting polymer;
Be suitable for providing the fuel supply of fuel to the electrogenesis element; With
Be suitable for providing the oxidant supply of oxidant to the electrogenesis element.
32. the fuel cell system of claim 31, wherein the proton conductive cation exchange resin is included in the fluoropolymer resin that its side chain has the cation exchange base, and wherein the cation exchange base is selected from sulfonic group, carboxylic acid group, phosphate, phosphonate group and its derivative.
33. the fuel cell system of claim 31, wherein polymer dielectric film further comprises porous carrier, this porous carrier is made up of the non-proton conductive supporting polymer that is suitable for supporting proton conductive cation exchange resin, non-proton conducting polymer and inorganic additive, and wherein porous carrier comprises a plurality of pores.
34. the fuel cell system of claim 33, wherein non-proton conductive supporting polymer comprises at least a homopolymers, and this homopolymers is selected from polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyimides, poly-benzoxazol, polybenzimidazoles, its composition and its copolymer.
35. the fuel cell system of claim 31, wherein inorganic additive comprises at least a material that is selected from pyrophyllite-talcum, montmorillonite (MMT), saponite, fluorine hectorite, kaolinite, vermiculite, LAPONITE, illite, mica, fragility mica, tetrasilicic acid mica and its composition.
36. the fuel cell system of claim 31, wherein fuel cell system is the direct oxidation fuel cell system.
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| KR20050056245 | 2005-06-28 | ||
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| KR (1) | KR100778502B1 (en) |
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| EP2443195A1 (en) * | 2009-06-15 | 2012-04-25 | Arkema, Inc. | Organic/inorganic composite blend membrane compositions of polyelectrolye blends with nanoparticles |
| CN102623734A (en) * | 2012-04-16 | 2012-08-01 | 上海锦众信息科技有限公司 | Preparation method of high-performance composite proton exchange membrane of fuel cell |
| CN102668207A (en) * | 2009-12-18 | 2012-09-12 | Lg化学株式会社 | Macromolecular electrolyte membrane for a fuel cell, and a membrane electrode binder material and a fuel cell comprising the same |
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| KR20150097024A (en) * | 2014-02-17 | 2015-08-26 | 삼성에스디아이 주식회사 | Polymer electrolyte membrane, membrane electrode assembly and fuel cell including the same |
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| EP0815606B1 (en) | 1995-03-20 | 2000-06-07 | E.I. Du Pont De Nemours And Company | Membranes containing inorganic fillers for fuel cells |
| GB9619133D0 (en) | 1996-09-13 | 1996-10-23 | Secr Defence | An electrolyte |
| NL1014403C1 (en) | 2000-02-17 | 2001-08-20 | Nedstack Holding B V | Method for manufacturing a plate-shaped semi-finished product that is suitable for use in, among others, Polymer Electrolyte Fuel Cells. |
| KR100403754B1 (en) * | 2001-06-19 | 2003-10-30 | 송민규 | Composite Polymeric Electrolyte Membrane, Preparation Method Thereof and Fuel Cell Containing the Same |
| US20040058227A1 (en) * | 2002-07-09 | 2004-03-25 | Matsushita Electric Industrial Co., Ltd. | Electrolyte membrane-electrode assembly for a fuel cell, fuel cell using the same and method of making the same |
| KR100486728B1 (en) * | 2002-12-12 | 2005-05-03 | 삼성에스디아이 주식회사 | Nanocomposite electrolyte membrane and fuel cell employing the same |
| KR100528345B1 (en) * | 2003-08-29 | 2005-11-15 | 삼성에스디아이 주식회사 | Polymer Nano-Composite membrane and fuel cell adopting the same |
| KR100684730B1 (en) * | 2004-10-14 | 2007-02-20 | 삼성에스디아이 주식회사 | Polymer electrolyte for direct oxidation fuel cell, method of preparing same and direct oxidation fuel cell comprising same |
-
2006
- 2006-06-28 DE DE602006008536T patent/DE602006008536D1/en active Active
- 2006-06-28 CN CNB2006101060927A patent/CN100405648C/en not_active Expired - Fee Related
- 2006-06-28 KR KR1020060058453A patent/KR100778502B1/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| KR100778502B1 (en) | 2007-11-29 |
| CN100405648C (en) | 2008-07-23 |
| DE602006008536D1 (en) | 2009-10-01 |
| KR20070001011A (en) | 2007-01-03 |
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