CN100345326C - Unit combined high temperature proton exchange film fuel cell membrane electrode and preparation - Google Patents

Unit combined high temperature proton exchange film fuel cell membrane electrode and preparation Download PDF

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CN100345326C
CN100345326C CNB2004100131485A CN200410013148A CN100345326C CN 100345326 C CN100345326 C CN 100345326C CN B2004100131485 A CNB2004100131485 A CN B2004100131485A CN 200410013148 A CN200410013148 A CN 200410013148A CN 100345326 C CN100345326 C CN 100345326C
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proton exchange
layer
membrane electrode
catalyst
gas diffusion
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CN1581547A (en
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木士春
余军
潘牧
袁润章
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Wuhan University of Technology WUT
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Abstract

The present invention relates to a membrane electrode for high temperature proton exchange membrane fuel batteries and a preparing method of the membrane electrode. The membrane electrode is formed by the combination of a sub cell and a primary unit with a high temperature water retaining function, wherein the sub cell is a gas diffusion layer, and the primary unit is formed by the bonding of the gas diffusion layer, a catalyst layer, an inorganic nanometer particle layer and a proton exchange layer. The present invention has the preparing method that the gas diffusion layer is coated with catalyst slurry to prepare the catalyst layer, proton exchange resin solution is poured to prepare the proton exchange layer, inorganic nanometer particle solution is poured to prepare a high temperature water conserving layer, and the catalyst slurry is coated again to prepare the catalyst layer. The primary unit and the sub cell are contacted at low temperature or pressed through hot pressing to obtain the membrane electrode of the present invention. The preparation of the membrane electrode has the characteristic of high grade integration and is suitable for continuous production. The thickness of the proton exchange layer can be controlled and is free from the limit of the sizes of commercial proton exchange membranes. The bond strength between the diffusion layer and the catalyst layer and between the catalyst layer and the proton exchange layer of the prepared membrane electrode is high, and the contact resistance is low. The membrane electrode of the present invention has a high temperature water retaining property of and can work at high temperature.

Description

A kind of unit-combination type high temperature proton exchange film fuel cell membrane electrode and preparation
Technical field
The present invention relates to a kind of membrane electrode of fuel batter with proton exchange film, particularly by master unit with high-temp water-preserving function and the membrane electrode that combines by the sub-cell that gas diffusion layers is formed.
Background technology
Fuel cell is a kind of cleaning, efficient, the quiet electrochemical engine that moves.People generally believe that it will become a super big industry at mid-21st Century, and the revolution that will bring energy industry.And Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cell PEMFC) has good application prospects in industries such as mobile communication equipment, portable electronics, national defence critical equipment, mechanical transports.
Current, high temperature (＞100 ℃) PEMFC has been subjected to people's common concern, because PEMFC can have the following advantages greater than 100 ℃ of following work: 1) improve the reactivity of catalyst such as platinum black; 2) CO that reduces catalyst poisons, and therefore can select the not really high H of purity 2And methyl alcohol acts as a fuel; 3) improve the electro-chemical activity of fuel such as methyl alcohol, reduce proton exchange membrane (Proton exchange membrane, fuel transmitance PEM); 4) proton conductivity of increase PEM; 5) reduce the requirement of fuel cell water heat management, be highly suitable for the work of high-power PEMFC.Therefore, under hot conditions, help improving the operating efficiency of fuel cell.But the perfluorinated sulfonic acid type PEM that is widely used now only just has proton-conducting under the condition that water exists, when working temperature during greater than 100 ℃, film will dewater, the proton conductivity and the mechanical strength of film are reduced, the transmitance of fuel increases, and is particularly particularly evident for the ultrathin membrane of≤30 μ m.Therefore, the working temperature of PEMFC generally is controlled at below 80 ℃.The main method that improves temperature of fuel cell at present is by perfluoro sulfonic acid membrane being carried out compound or modification, improving the water retention of perfluoro sulfonic acid membrane when high temperature, secondly is to develop not rely on water to carry out the PEM of proton conduction.Obviously, the former is much easier than the latter under existing technical conditions.The former research mainly comprises heteropoly acid and perfluorinated sulfonic acid composite membrane, basic zirconium phosphate and perfluorinated sulfonic acid composite membrane, imidazoles drone salt (pyrazoles drone salt) and perfluorinated sulfonic acid composite membrane, and inorganic oxide is (as SiO 2, ZrO 2Deng)/inorganic-organic hybrid films such as perfluorinated sulfonic acid composite membrane.
In numerous inorganic oxides, SiO 2Deng inorganic nanometer oxide particle water conservation, performance of keeping humidity are preferably arranged, therefore dopen Nano SiO in the Nafion film 2The composite membrane that makes Deng inorganic nanometer oxide particle has water retaining function preferably under 100-130 ℃ of high temperature.The SiO that (2001) such as Mauritzt (1995) and Miyake are synthetic with original position 2Particle is diffused in the Nafion of swelling film and has made composite membrane.This film moisture content in the time of 120 ℃ is higher, and proton conductivity approaches the level of Nafion film, and the methanol permeability of film reduces.But the shortcoming of this composite membrane is the SiO that mixes 2Content exists the phenomenon of successively decreasing to center membrane from the film surface, and most SiO 2Particle can only be deposited on the surface of film, causes SiO 2Particle inhomogeneous inside and outside film.In EP0926754, the nanometer SiO that Arico Antonino and AntonucciVincenzo then will synthesize in advance 2Powder is doped to blend film forming in the proton exchange resins solution.Nanometer SiO in this film 2Decentralization increases, and can also keep higher conductivity in the time of 145 ℃, but nanometer SiO 2Powder is easy to reunite in phase transition behavior takes place, and its particle diameter is difficult to control, and the mechanical strength of film also waits to improve.People such as Masahiro Watanabe (J.Electrochem.Soc, 1996,143,3847-3852) colloid that contains titanium oxide and Nafion resin solution double teeming film forming, made Nafion/TiO 2Composite membrane, but the same problem that has the particle diameter and the decentralization that are difficult to control titanium dioxide in the composite membrane of this method.
In addition, inorganic matter or its oxide particle (particle diameter 0.1～10 μ m) that [CN 1442913A] such as the Mao Zongqiang of Tsing-Hua University will have moisture-keeping functions are coated in the both sides of handing over the matter exchange membrane, make the composite membrane with self-moistening function.Obviously, compare with the nano particle of inorganic matter or its oxide, the moistening effect of the sub-material of micron grade is not best.Therefore, be necessary to be correlated with nano particle moistening effect research.
Current membrane electrode (Membrane Electrode Assembly, MEA) framework mainly contains two kinds of traditional MEA and CCM (catalyst coated membrane), the former be with catalyst coated on gas diffusion layers (gas diffusion layers adopts the porous carbon paper usually), with PEM hot pressing, form the membrane-electrode three-in-one component then.In this structure, catalyst layer electrochemical reaction district and porous carbon paper fuel delivery area are overlapping, because the electrochemical reaction district is different to the character requirement of material with the fuel delivery area, the fuel delivery area requires hydrophobic as the requirement of electrochemical reaction district is hydrophilic, therefore cause taking place mutual interference, limited the performance of battery.Simultaneously greatly waste catalyst material, the potentiality that further reduce the Pt carrying capacity are limited.In addition, because the combination interface of catalyst layer and proton exchange membrane is to form by hot pressing, and catalyst is to be coated on the scraggly porous carbon paper and proton exchange membrane hot pressing again, therefore can not the combination of formation good interface, influence proton transport, limited battery performance.
Therefore, people have developed the fuel cell membrane electrode of CCM framework.It is different from traditional MEA, directly a kind of functional unit of realizing fuel cell electrochemistry overall process that catalyst layer and proton exchange membrane are composited.Adopt the advantage of CCM framework to be: requirement design catalyst layer that 1) can the fuel cell electrochemical reaction, and the interfacial structure between catalyst layer and the proton exchange membrane; 2) catalyst layer can be done very thinly, improves reaction rate to greatest extent and reduces the Pt carrying capacity; 3) help realizing serialization production and the scale manufacturing of CCM, and reduce cost.But in the CCM fuel cell framework, Catalytic Layer is to be coated on the basement membrane with proton exchange function, and the interface of catalyst layer and film is non-excessive layer, has influenced proton transport; In addition, the gas diffusion layers of both sides and CCM generally adopt cold joint to touch, and the contact resistance between them is bigger usually.
Summary of the invention
The purpose of this invention is to provide a kind of high temperature proton exchange film fuel cell membrane electrode and preparation method
High temperature proton exchange film fuel cell membrane electrode of the present invention is the unit-combination type membrane electrode that is combined by sub-cell and the master unit with high-temp water-preserving effect, described sub-cell is a gas diffusion layers, described membrane electrode master unit is the membrane-electrode unit that is formed by gas diffusion layers, catalyst layer, inorganic nano-particle water conservation layer and proton exchange layer bonded together, and its composition or structure are followed successively by gas diffusion layers, catalyst layer, proton exchange layer, inorganic nano-particle water conservation layer, catalyst layer.
Described gas diffusion layers is porous carbon paper or the carbon cloth through hydrophobic treatment, for further strengthening hydrophobic effect, and can be at porous carbon paper or the compound inferior hydrophobic layer of forming by carbon black and polytetrafluoroethylene (PTFE) particle (sublayer) of carbon cloth one side.
The catalyst layer of described master unit mainly carries platinum or platinum alloy carbon-supported catalysts and proton exchange resins by platinum or platinum alloy or carbon to be formed, and the mass ratio of catalyst and proton exchange resins is 10: 2～5.
Described catalyst is meant Pt, Pd, Ru, Rh, Ir, Os noble metal or its carbon loading Pt/C, Pd/C, Ru/C, Rh/C, Ir/C, Os/C, Pt and Pd, Ru, Rh, Ir, the bianry alloy PtPd of Os, PtRu, PtRh, PtIr, PtOs or its carbon loading PtPd/C, PtRu/C, PtRh/C, PtIr/C, PtOs/C, Pt, Pd, Ru, Rh, Ir, Os noble metal and Fe, Cr, Ni, (N is Pt to the bianry alloy NM that Co forms, Pd, Ru, Rh, Ir or Os, M is Fe, Cr, Co or Ni) or its carbon loading NM/C (N, the definition of M is with aforementioned), Pt, Pd, Ru, Rh, Ir, Os noble metal and Fe, Cr, Ni, the ternary alloy three-partalloy NM that Co forms 1M 2(definition of N is with aforementioned, M 1, M 2Be the composition of any two kinds of metallic elements among Fe, Cr, Co and the Ni, as FeCo etc.) or its carbon loading NM 1M 2/ C (N, M 1, M 2Definition with aforementioned).Above-mentioned carrier carbon is generally conductive carbon black or carbon nano-tube, or carbon nano-fiber.
The proton exchange layer of described master unit is made up of the resin with proton exchange function, described proton exchange resins is meant the perfluorinated sulfonic resin with sulfonic acid group, as the Nafion resin or the Nafion solution of du Pont company production, or sulfonation thermal stability polymer, Flemion proton conductor polymer with proton exchange function.
The inorganic nano-particle water conservation layer of described master unit is by nanometer SiO 2, nano-TiO 2Or nanometer Zr (HPO 4) 2Particle and proton exchange resins are formed, and the inorganic nano-particle proportion is 0.1wt%～50wt%.
The preparation process of high temperature proton exchange film fuel cell membrane electrode of the present invention is as follows:
1, catalyst, proton exchange resins are mixed by 10: 2～5: 100～1500 mass ratio is full and uniform with solvent, make catalyst slurry or prepared Chinese ink, described solvent is meant water or organic solvent alcohol, ether, ester, ketone or nitrile, wherein alcohol is methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerol, 1-methoxyl group 2-propyl alcohol (MOP), ether is ether, benzinum, and ester and ketone are ethyl acetate and acetone;
2, the part catalyst slurry is coated to gas diffusion layers one side, vacuumize forms catalyst layer;
3, at proton exchange layer top casting inorganic nano-particle solution, vacuumize forms inorganic nano-particle water conservation layer;
4, remaining catalyst slurry is coated on inorganic nano-particle water conservation layer, vacuumize makes the membrane electrode master unit;
5, the membrane electrode master unit of preparation is close to or hot pressing by contact with the sub-cell of being made up of gas diffusion layers, is made unit-combination type high temperature proton exchange film fuel cell membrane electrode.
Described coating and casting are meant methods such as coating or silk screen printing.
Preparation to high temperature proton exchange film fuel cell membrane electrode of the present invention illustrates further below:
The preparation method of nano-particle solution is as follows:
Nanometer SiO 2The preparation of solution.Tetraethoxysilane and absolute ethyl alcohol are mixed, add the mixed solution of absolute ethyl alcohol and 0.3M hydrochloric acid then, and continue down to stir 12-48h, make and contain nanometer SiO at 40～60 ℃ 2The aqueous solution.The volume ratio of above-mentioned additive is: tetraethoxysilane: absolute ethyl alcohol: 0.3M hydrochloric acid=1: 2～30: 0.2～4, wherein 1/2 volume of ethanol is mixed with tetraethoxysilane, in addition 1/2 volume of ethanol and mixed in hydrochloric acid.With nanometer SiO 2The aqueous solution mixes with 5wt%Nafion solution, ultrasonic 0.5-2h.If SiO 2The quality that reaches the Nafion resin is 100%, then SiO 2Proportion is 0.1wt%～50wt%.
Nano-TiO 2The preparation of solution.In butyl titanate, add glacial acetic acid, mix, under vigorous stirring, slowly pour in the distilled water, continue to stir 2-6h, treat hydrolysis fully after, add 70% nitric acid, continue to stir 1-5h after being heated to 60～90 ℃, make nano-TiO 2Colloidal solution.The volume ratio of above-mentioned additive is: butyl titanate: glacial acetic acid: distilled water: 70wt% nitric acid=1: 0.05～0.51～12.Then with nano-TiO 2Colloidal solution mixes with 5wt%Nafion solution, ultrasonic 0.5-2h.If TiO 2The quality that reaches the Nafion resin is 100%, then TiO 2Proportion is 0.1wt%～50wt%.
Nanometer Zr (HPO 4) 2The preparation of solution.Get the basic zirconium chloride (ZrOCl of 1.5M 2) solution and absolute ethyl alcohol mix, and dropwise adds the mixed liquor of absolute ethyl alcohol and 1M phosphoric acid then, continues down to stir 12-24h at 60～90 ℃, obtains containing nanometer Zr (HPO 4) 2The aqueous solution.The volume ratio of above-mentioned additive is: 1.5M basic zirconium chloride: absolute ethyl alcohol: 1M phosphoric acid=1: 3～60: 0.05～1.Wherein 1/2 volume ethanol is mixed with zirconium oxychloride, and 1/2 volume ethanol is mixed with phosphoric acid in addition.To contain nanometer Zr (HPO 4) 2The aqueous solution mix ultrasonic 0.5-2h with 5wt%Nafion solution.If Zr (HPO 4) 2The quality that reaches the Nafion resin is 100%, then Zr (HPO 4) 2Proportion is 0.1wt%～50wt%.
Get the part catalyst slurry, be coated to a side of a gas diffusion layers, vacuumize by coating or method for printing screen.Gas diffusion layers of the present invention is porous carbon paper or the carbon cloth through hydrophobic treatment, for further strengthening hydrophobic effect, and can be at porous carbon paper or the compound inferior hydrophobic layer of forming by carbon black and polytetrafluoroethylene (PTFE) particle of carbon cloth one side.
By the coating or method for printing screen with the proton exchange resins solution-cast to catalyst layer, vacuumize is to film forming.
By coating or method such as silk screen printing with the inorganic nano-particle solution-cast on proton exchange layer, vacuumize forms inorganic nano-particle water conservation layer.
Remaining catalyst slurry is coated on the inorganic nano-particle water conservation layer by coating or method for printing screen,, makes membrane electrode master unit of the present invention through vacuumize.Wherein, catalyst layer is on average thick≤5 μ m, proton exchange bed thickness≤100 μ m, the about 0.1-5 μ of inorganic nano-particle water conservation bed thickness m.
Described sub-cell is a gas diffusion layers.
The membrane electrode master unit and the sub-cell of preparation are close to or hot pressing by contact, are promptly obtained unit-combination type membrane electrode of the present invention.
It is one-sided that the present invention at first is coated in catalyst slurry a gas diffusion layers, catalyst surface casting one deck proton exchange resins solution in coating forms proton exchange layer then, and then the proton exchange layer surface applied one deck inorganic nanometer oxide water conservation layer that is being shaped, coating catalyst slip formed catalyst layer on the water conservation layer at last, promptly make the master unit of fuel cell membrane electrode, and sub-cell only is a gas diffusion layers.With being close to or hot pressing of master unit and sub-cell contact, promptly obtain unit-combination type high temperature membrane electrode of the present invention.Compare with background technology, the present invention has the following advantages:
1) the membrane electrode preparation is highly integrated, is fit to serialization production;
2) proton exchange layer controllable thickness is not subjected to the size restrictions of commercially available proton exchange membrane;
3) diffusion layer and catalyst layer, the bond strength of catalyst layer and proton exchange interlayer is improved, and contact resistance decreases;
4) membrane electrode has the high-temp water-preserving performance, can be 80-120 ℃ of work down.
Monocell assembling and test.Unit-combination type membrane electrode and graphite collector plate, copper facing stainless-steel sheet are assembled into monocell.Effective catalysis area of monocell is 5cm * 5cm, and operating condition is: back pressure P Air=P Hydrogen=0MPa, battery temperature are room temperature-110 ℃, anode 0-100% humidification, and the humidification temperature is 70-100 ℃.Pt carrying capacity≤1mg/cm 2
Description of drawings
Fig. 1 is the composition diagram of membrane electrode of the present invention.
Fig. 2 is the preparation process figure of membrane electrode master unit.
Fig. 3 is SiO 2The transmission electron microscope photo of nano particle (TEM).
Fig. 4 be embodiment 1,2,3 and comparative example 1 in the time of 110 ℃, have the monocell polarization curve of water conservation layer and no water conservation layer membrane electrode.
Number in the figure implication: first-master unit, second-sub-cell, the 1-gas diffusion layers, the 2-catalyst layer, the 3-proton exchange layer, 4-inorganic nano-particle water conservation layer, the 5-catalyst layer, the 6-gas diffusion layers, the a-substrate is a gas diffusion layers, and b-coating catalyst slip in substrate prepares catalyst layer, and c-applies proton exchange resins formulations prepared from solutions proton exchange layer on catalyst layer, d-applies inorganic nano-particle water conservation layer on proton exchange layer, e-coating catalyst slip on inorganic nano-particle water conservation layer prepares catalyst layer.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
The preparation of membrane electrode master unit.At the inferior hydrophobic layer of forming by conductive carbon black and polytetrafluoroethylene (PTFE) particle through the even compound one deck in the carbon paper surface of hydrophobic treatment (sublayer), and under 350 ℃, calcine 20min, make gas diffusion layers.According to carbon supported platinum catalyst: Nafion The portions of resin isopropyl alcohol is that 3: 1: 300 mass ratio prepares catalyst slurry, gets the part slip, is printed onto inferior hydrophobic layer (sublayer) side of gas diffusion layers with silk screen print method, and vacuumize 1-10h makes catalyst layer be hardened in the gaseous diffusion laminar surface.Get 5wt%Nafion  solution, concentrate the volume of half after, be printed onto the catalyst layer surface of sclerosis with silk screen print method, vacuumize 1-10h forms fine and close proton exchange layer on catalyst layer.The tetraethoxysilane of 33ml and the absolute ethyl alcohol of 300ml are mixed, dropwise add the absolute ethyl alcohol of 240ml and the mixed liquor of 0.3M hydrochloric acid 60ml then, under 50 ℃ temperature, continue to stir 12h, obtain containing nanometer SiO 2The aqueous solution.Press SiO 2: the mass ratio of Nafion resin is that 1: 2 relation is with nanometer SiO 2The aqueous solution and 5wt%Nafion solution (Nafion content is 5%) mix, ultrasonic 30min.SiO with preparation 2Be coated on the proton exchange layer of film forming with Nafion solution, form nanometer SiO 2Particle water conservation layer.Remaining catalyst slurry is printed onto with silk screen print method on the water conservation layer of drying, and vacuumize 1-10h makes catalyst layer be hardened in the proton exchange laminar surface.The average thick 2 μ m of the anode catalyst layer (being compounded with a side of water conservation layer) of preparation, the average thick 4 μ m of cathode catalyst layer (being compounded with a side of hydrophobic layer), the about 25 μ m of proton exchange bed thickness, nanometer SiO 2The about 2 μ m of particle water conservation bed thickness, the Pt carrying capacity is 0.6mg/cm 2
Getting a gas diffusion layers identical with master unit is sub-cell, and membrane electrode master unit and sub-cell cold joint are touched, and promptly gets the unit-combination type membrane electrode.The unit-combination type membrane electrode is assembled into monocell with assemblies such as Teflon seal washer, graphite collector plate, copper facing stainless-steel sheets.Effective catalysis area of monocell is 5cm * 5cm.Operating condition is: back pressure P Air=P Hydrogen=0MPa, 110 ℃ of battery temperatures, anode 50% humidification, the humidification temperature is 70 ℃.The polarization curve of monocell is seen accompanying drawing 4.
Embodiment 2
The preparation method of membrane electrode master unit and monocell assembling are identical with embodiment 1 with test condition, and the inorganic nano-particle that different is in the water conservation layer is TiO 2The preparation method is as follows: add the glacial acetic acid of 25ml in the butyl titanate of 100ml, and mix, slowly pour under vigorous stirring in the 600ml water, continue to stir 3h, after the hydrolysis fully, add the nitric acid of 10ml 70wt%, continue after being heated to 80 ℃ to stir 2h, make nano-TiO 2Colloidal solution.Press TiO 2: the Nafion resin is that 1: 2 mass ratio is with nano-TiO 2The aqueous solution mixes with 5wt%Nafion solution, ultrasonic 30min.The average thick 2 μ m of the anode catalyst layer (being compounded with a side of water conservation layer) of preparation, the average thick 4 μ m of cathode catalyst layer (being compounded with a side of hydrophobic layer), the about 25 μ m of proton exchange bed thickness, nano-TiO 2The about 2 μ m of particle water conservation bed thickness, the Pt carrying capacity is 0.6mg/cm 2The polarization curve of monocell is seen accompanying drawing 4.
Embodiment 3
The preparation method of membrane electrode master unit and monocell assembling are identical with embodiment 1 with test condition, and different is that the water conservation layer is mainly by nanometer Zr (HPO 4) 2Form with the Nafion resin.Its preparation method is as follows: the basic zirconium chloride (ZrOCl that gets 1.5M 2) solution 100ml evenly mixes with the absolute ethyl alcohol of 400ml, dropwise adds the absolute ethyl alcohol of 400ml and the mixed liquor of 1M phosphoric acid 20ml then, continues to stir 24h under 80 ℃ temperature, obtains containing nanometer Zr (HPO 4) 2The aqueous solution.Press Zr (HPO 4) 2With the mass ratio of Nafion resin be that 1: 2 relation is with nanometer Zr (HPO 4) 2The aqueous solution and 5wt%Nafion solution mix, ultrasonic 10min.The average thick 2 μ m of the anode catalyst layer (being compounded with a side of water conservation layer) of preparation, the average thick 4 μ m of cathode catalyst layer (being compounded with a side of hydrophobic layer), the about 25 μ m of proton exchange bed thickness, nanometer Zr (HPO 4) 2The about 2 μ m of particle water conservation bed thickness, the Pt carrying capacity is 0.6mg/cm 2The polarization curve of monocell is seen accompanying drawing 4.
Comparative example 1
The preparation method of membrane electrode master unit, sub-cell material and monocell assembling are identical with embodiment 1 with test condition, but do not contain inorganic nano-particle water conservation layer in the membrane electrode master unit.The polarization curve of monocell is seen accompanying drawing 4.
As can be seen from Figure 4, do not contain the membrane electrode of inorganic nano water conservation layer, electrical property descends very obvious under hot conditions.And under the equal conditions, the membrane electrode with inorganic nano water conservation layer has shown electric preferably output performance.In addition, be not difficult to find out nanometer SiO 2The electric output performance of particle water conservation layer membrane electrode is better than and has nano-TiO 2Particle and nanometer Zr (HPO 4) 2Particle water conservation layer membrane electrode.

Claims (6)

1, a kind of membrane electrode of fuel batter with proton exchange film, it is characterized in that membrane electrode is the unit-combination type membrane electrode that is combined by sub-cell and the master unit with high-temp water-preserving function, described membrane electrode sub-cell is a gas diffusion layers, described membrane electrode master unit is the membrane-electrode unit that is formed by gas diffusion layers, catalyst layer, inorganic nano-particle water conservation layer and proton exchange layer bonded together, and its composition or structure are followed successively by gas diffusion layers, catalyst layer, proton exchange layer, inorganic nano-particle water conservation layer, catalyst layer; The preparation process of described membrane electrode is as follows:
1) catalyst, proton exchange resins are mixed by 10: 2～5: 100～1500 mass ratio is full and uniform with solvent, make catalyst slurry or prepared Chinese ink, described solvent is meant water or alcohol, ether, ester, ketone or nitrile, wherein alcohol is methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerol, 1-methoxyl group 2-propyl alcohol, ether is ether, benzinum, and ester and ketone are ethyl acetate and acetone;
2) the part catalyst slurry is coated to gas diffusion layers one side, vacuumize forms catalyst layer;
3) with the proton exchange resins solution-cast on catalyst layer, vacuumize forms proton exchange layer;
4) at proton exchange layer top casting inorganic nano-particle solution, vacuumize forms inorganic nano-particle water conservation layer;
5) remaining catalyst slurry is coated on the inorganic nano-particle water conservation layer, vacuumize makes the membrane electrode master unit;
6) the membrane electrode master unit of preparation is close to or hot pressing by contact with the sub-cell of being made up of gas diffusion layers, is made the unit-combination type membrane electrode of fuel batter with proton exchange film;
Wherein the described inorganic nano-particle solution of step 4 is: nanometer SiO 2Or nano-TiO 2Or nanometer Zr (HPO 4) 2The aqueous solution or colloidal solution and 5wt%Nafion The mixed liquor of solution.
2, membrane electrode according to claim 1 is characterized in that the gas diffusion layers of described sub-cell and master unit is porous carbon paper or carbon cloth through hydrophobic treatment.
3, membrane electrode according to claim 2, it is characterized in that described sub-cell and master unit gas diffusion layers through the porous carbon paper of hydrophobic treatment or the compound more inferior hydrophobic layer of forming by carbon black and polytetrafluoroethylgranule granule of a side of carbon cloth.
4, membrane electrode according to claim 1, the catalyst layer that it is characterized in that described master unit mainly carries platinum or platinum alloy carbon-supported catalysts and proton exchange resins by platinum or platinum alloy or carbon to be formed, and the mass ratio of catalyst and proton exchange resins is 10: 2～5.
5, membrane electrode according to claim 1, the proton exchange layer that it is characterized in that described master unit is made up of the resin with proton exchange function, described proton exchange resins is meant the perfluorinated sulfonic resin with sulfonic acid group, or has sulfonation thermal stability polymer, the Flemion proton conductor polymer of proton exchange function.
6, membrane electrode according to claim 1 is characterized in that the inorganic nano-particle of inorganic nano-particle water conservation layer of described master unit and the quality of proton exchange resins are 100%, and the inorganic nano-particle proportion is 0.1wt%～50wt%.
CNB2004100131485A 2004-05-14 2004-05-14 Unit combined high temperature proton exchange film fuel cell membrane electrode and preparation Expired - Fee Related CN100345326C (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0926754A1 (en) * 1997-12-10 1999-06-30 De Nora S.P.A. Polymeric membrane electrochemical cell operating at temperatures above 100 C
CN1276633A (en) * 2000-07-27 2000-12-13 钟家轮 Fuel cell with more membrane electrodes on one membrane and its preparing process
EP1213780A2 (en) * 2000-12-11 2002-06-12 Toyota Jidosha Kabushiki Kaisha Fuel cell stack with polymer electrolyte
WO2003063280A2 (en) * 2002-01-22 2003-07-31 E.I. Du Pont De Nemours And Company Unitized membrane electrode assembly and process for its preparation
CN1442913A (en) * 2002-03-29 2003-09-17 清华大学 Humidity preservation composite film used for proton exchange film fuel battery and its preparation method
CN1487610A (en) * 2003-08-13 2004-04-07 中国科学院长春应用化学研究所 Prepn of electrode for proton exchange film fuel cell
CN1492530A (en) * 2002-10-24 2004-04-28 江苏隆源双登电源有限公司 Process for producing fuel cell film electrode

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0926754A1 (en) * 1997-12-10 1999-06-30 De Nora S.P.A. Polymeric membrane electrochemical cell operating at temperatures above 100 C
CN1276633A (en) * 2000-07-27 2000-12-13 钟家轮 Fuel cell with more membrane electrodes on one membrane and its preparing process
EP1213780A2 (en) * 2000-12-11 2002-06-12 Toyota Jidosha Kabushiki Kaisha Fuel cell stack with polymer electrolyte
WO2003063280A2 (en) * 2002-01-22 2003-07-31 E.I. Du Pont De Nemours And Company Unitized membrane electrode assembly and process for its preparation
CN1442913A (en) * 2002-03-29 2003-09-17 清华大学 Humidity preservation composite film used for proton exchange film fuel battery and its preparation method
CN1492530A (en) * 2002-10-24 2004-04-28 江苏隆源双登电源有限公司 Process for producing fuel cell film electrode
CN1487610A (en) * 2003-08-13 2004-04-07 中国科学院长春应用化学研究所 Prepn of electrode for proton exchange film fuel cell

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