CN101038970A - Method for preparing water-keeping diffusion layer of high temperature proton exchange film fuel cell - Google Patents

Method for preparing water-keeping diffusion layer of high temperature proton exchange film fuel cell Download PDF

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CN101038970A
CN101038970A CNA2007100517554A CN200710051755A CN101038970A CN 101038970 A CN101038970 A CN 101038970A CN A2007100517554 A CNA2007100517554 A CN A2007100517554A CN 200710051755 A CN200710051755 A CN 200710051755A CN 101038970 A CN101038970 A CN 101038970A
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inorganic oxide
diffusion layer
solution
water
fuel cell
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CN100517841C (en
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唐浩林
潘牧
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Wuhan University of Technology WUT
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to method for preparing water-conserving diffusion layer for proton exchange membrane fuel cell. The method for preparing water-conserving diffusion layer for high-temperature proton exchange membrane fuel cell is characterized in that inorganic oxide water-conserving material is prepared earlier than preparation of the diffusion layer, and the surface thereof is coated by PTFE ploymer thereby forming a structure whose core is inorganic oxide water-conserving material and whose shell is hydrophobic PTFE ploymer; the prepared inorganic oxide coated by PTFE and conductive carbon material are mixed together, and then the mixture is paint on the carbon paper, cabon cloth or carbon fiber felt to from the water-conserving diffusion layer for proton exchange membrane fuel cell. The diffusion layer made in this method can conserve water thereby being suitable for high-temperature proton exchange membrane fuel cell.

Description

A kind of preparation method of water-keeping diffusion layer of high temperature proton exchange film fuel cell
Technical field
The present invention relates to a kind of used in proton exchange membrane fuel cell method for preparing water-conserving diffusion layer.
Background technology
Hydrogen is the ubiquitous a kind of element of occurring in nature, is renewable and clean energy resource.Scientists thinks, Hydrogen Energy will remedy and replaces fossil energies such as exhausted day by day coal, oil gradually in 21 century, become the important part of world energy sources general layout.Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cell, be called for short PEMFC) be the important way that Hydrogen Energy is converted to electric energy, its energy conversion efficiency is up to more than 50%, and working temperature is low, noise is low, unique discharging be pure water, can be widely used in vehicles power resources and stationary electric power plant power supply.Therefore, people generally believe, fuel cell be the 21 century first-selection cleaning, efficient power generation technology (the clothing treasured is honest and clean, fuel cell---principle, technology, application, Chemical Industry Press, 2003; Handbook of Fuel Cells, Wiely, V3,2003).In recent years, through various countries scientist and related industry personnel's effort, fuel cell critical material and system integration technology have obtained develop rapidly, and supporting industry also reaches its maturity.Yet, though using, the industry of fuel cell finishes substantially in the technological reserve of battery itself, really move towards industrialization, also must obtain bigger progress in the following aspects.These technology comprise the environmental suitability that improves fuel cell, further reduce the use amount of scarce resource Pt and further reduce the complexity of battery system.
The environmental suitability of fuel cell is that fuel cell moves towards the very important condition that industry is used, studies show that in a large number, the poisoning behavior can take place in fuel cell under CO and sulfide environment, mainly showing as these materials is being difficult to dissociate or desorption (J.Appl.Electrochem.2004 after the absorption on the catalyst, 34,563).This is for fuel cell, and the fuel cell that particularly is applied on the electric automobile is a very big challenge.Even for the fuel cell of common application, because materials such as CO not only can enter by external environment condition, the corrosion of material with carbon element also can cause the generation of CO in the fuel cell operation process, therefore addresses this problem one of prerequisite that remains the industry application.For China, the environmental suitability problem that solves fuel cell seems even more important.Since the reform and opening-up, the manufacturing industry of China has obtained unprecedented development, and these development have improved Chinese national life level, greatly promoted Chinese national power.Yet the manufacturing industry particularly development of heavy industry has also been brought environment damage.Data shows, in the city of China's monitoring in 2004, urban air-quality is inferior to three grades, accounts for 20.2%, air quality is that three grades city accounts for 41.2%, only has 38.6% city to reach National Environmental air quality secondary standard (source: China Environmental State Bulletin in 2004).According to World Resources Institute and China Environmental Monitoring General Station's measuring and calculating, the whole world ten big pollutions in the most serious city, China has just accounted for 7.Though such present situation it is evident that at Continual Improvement this in the near future situation still can continue.Therefore, the environmental suitability problem that solves fuel cell from the angle of technology itself is very important and urgent.
At present, another technology barrier of Proton Exchange Membrane Fuel Cells industrialization derives from complicated hydro-thermal management system.Though fuel cell has the energy conversion efficiency up to 60%,, other of fuel chemical energy 40% can be because overpotential and ohmic polarization convert heat energy in electrochemical reaction process.Because the Proton Exchange Membrane Fuel Cells general work temperature of present level is less than 80 ℃, more approaching with room temperature, it is very difficult that heat is diffused into environment from the electrochemical reaction zone.Realize the good control to temperature, fuel cell generally can add complicated cooling and heat management system.The complexity of system has not only reduced the reliability of fuel cell, has also reduced the weight power density and the volumetric power density of fuel cell.In addition, what is more important, the power of hydro-thermal management system meeting consuming cells 10-20% of system in battery operation, greatly reduce the performance of battery system and cut down fuel cell relatively and competitiveness (the Fuel Cell SystemsExplained of other energy conversion system, Wiley, 2003).
For the use amount of scarce resource Pt, in recent ten years, some development of technology improve the service efficiency of fuel cell noble metal catalysts greatly.Use in early days nanometer Pt to deceive and be catalyst, the carrying capacity of general catalyst reaches 4mg/cm 2More than could obtain relatively satisfied output performance.Subsequently, the employing of porous dispersed carbon carrier and the three-dimensional of film electrode structure have improved the service efficiency of catalyst greatly, make catalyst consumption reach 1mg/cm 2Below (Prog.Chem., 2004,16,804).Yet, estimate that according to scientist even only repack annual now automobile engine of selling into fuel battery engines, existing P t resource is at state-of-the-art 0.2-0.4mg/cm 2Use amount under still can not meet the demands.Therefore, the service efficiency of Pt catalyst also needs further raising.But, the Pt catalyst will further improve the catalytic efficiency of Pt reaching capacity aspect raising surface area and the decentralization now, has only two possible ways, the first adopts no-Pt catalyst or based on the composite catalyst of Pt, and it two is to improve the electrochemical reaction temperature.For the former, these catalyst at normal temperatures otherwise catalysis speed very slow, or be difficult to improve the electrochemical catalysis total amount of the Pt of unit, therefore, still be difficult at normal temperatures realize what the Pt consumption further reduced.
At the catalyst poisoning that exists in the present fuel cell, hydro-thermal complex management and the not high enough problem of catalyst efficiency, a large amount of scientist in the whole world is actively seeking countermeasure at present.But it is generally acknowledged that the working temperature that improves fuel cell is the effective measures that solve these difficult problems.For catalyst poisoning, studies show that particularly the CO ability to bear of Pt catalyst is index with temperature and rises, in the time of 80 ℃, the CO of 10-20ppm can cause the obvious poisoning and the performance decrease of Pt catalyst, and in the time of 120 ℃, Pt can bring up to about 1000ppm to the tolerance of CO, after temperature is brought up to 200 ℃, Pt is 30, still can operate as normal under the 000ppmCO condition, therefore can not produce CO intoxicating phenomenon (J.Electrochem.Soc.2003 substantially, 150, A1599).Improve working temperature and can reduce the requirement that the battery opposite heat tube is managed system simultaneously, when battery operated temperature is brought up to 120 ℃, the temperature gradient of inside battery and environment can be brought up to about 100 ℃ from present 40 ℃-60 ℃, the heat exchanger effectiveness of battery can improve several times rapidly, and the external heat management system can be simplified rapidly.Concerning with the Pt catalytic efficiency because the raising of temperature, reactant in the absorption of catalyst surface, dissociate and desorption is accelerated greatly, the use amount of Pt catalyst will be expected to descending greatly on the basis at present.
In view of high-temperature fuel cell technology these unique advantages at lifting fuel cell environment adaptability and aspect of performance, at present, research about high-temperature fuel cell is becoming focus rapidly, wherein, keep the moisture in the membrane electrode effectively, the loss speed of moisture in the membrane electrode is reduced be the aspect in wherein wanting.(Gas Diffusion Layer GDL) has the moisture that certain moisture-retaining capacity helps keeping membrane electrode to diffusion layer in the membrane electrode.And the difficult point that improves the water holding capacity of diffusion layer is not reduce the hydrophobic ability of diffusion layer.This be because, though fuel cell is at hot operation, as be higher than 120 ℃, most of water will exist with the form of gas, but when reaching capacity vapour pressure, the water in the diffusion layer can separate out with liquid form, make gas not pass through diffusion layer smoothly, cause the battery antipole, reduce output performance even destroy the entire cell unit.
At present, Chinese patent CN200480027044.8, CN200510018882.5, CN200410097890.9 relate to the preparation method of diffusion layer, but these diffusion layers do not have water holding capacity, therefore are not suitable for high-temperature fuel cell.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of water-keeping diffusion layer of high temperature proton exchange film fuel cell, the diffusion layer of this method preparation has water holding capacity, is suitable for high temperature proton exchange film fuel cell and uses.
To achieve these goals, technical scheme of the present invention is: a kind of preparation method of water-keeping diffusion layer of high temperature proton exchange film fuel cell is characterized in that it comprises the steps:
1) preparation inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid particle:
(a) be that the ionomer solution of 1.2%-10% is regulated the pH value to 6.5-7.5 with NaOH with weight concentration, be transferred in the anhydrous organic solvent then, get solution A, make ionomer content in solution A reach 1-9wt.%, then distill this solution 4-6 hour to remove the moisture in the solution, obtain the ionomer precursor solution;
(b) according to inorganic oxide and ionomer weight ratio 0.01: 1-0.1: 1, the inorganic oxide precursor body of this inorganic oxide is joined in the ionomer precursor solution of step (a) preparation and stirred 20-30 minute, make the inorganic oxide precursor liquid solution;
(c) according to the inorganic oxide precursor body hydrolysis water requirement 1-10 of institute ratio doubly, with HCl content is that 37wt.%, water content are that the dense HCl solution of 63wt% joins in the inorganic oxide precursor liquid solution of step (b) preparation, fully mix, obtain the inorganic oxide nanoparticles dispersion liquid that ionomer is modified;
(d) the inorganic oxide nanoparticles dispersion liquid that ionomer is modified and weight concentration are that the polytetrafluoroethylene (PTFE) emulsion of 10%-60% is mixed, and make the weight ratio of inorganic oxide and polytetrafluoroethylene reach 1: 20-1: 5; Stirred 1 hour under 1000-5000 rev/min mixing speed then, obtain inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system, wherein inorganic oxide is nuclear, and the PTFE polymer is a shell;
2) preparation of water-keeping diffusion layer:
(a) inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system is mixed with conductive carbon material, the part by weight of conductive carbon material and polytetrafluoroethylene (PTFE) is 2.5: 1-3.5: 1, add entry or anhydrous organic solvent then, make that solid content is 20%-80% in the mixed solution; Under 1000-5000 rev/min mixing speed, stirred 10-24 hour, obtain the diffusion layer slip;
(b) with the silk screen printing of diffusion layer slip, casting, be coated with or be sprayed on carbon paper, carbon cloth or the carbon fiber felt, segmentation heat treatment in heat-treatment furnace, wherein temperature was handled 10 minutes for 100 ℃, handled 10 minutes for 350 ℃ subsequently, form water-keeping diffusion layer (being water-keeping diffusion layer of high temperature proton exchange film fuel cell).
Described ionomer is selected the sulfonic acid type anionic polymer for use, and this polymer has the side chain that has sulfonate group, is in perfluorinated sulfonic resin, sulfonation trifluorostyrene, sulfonated polyether-ether-ketone, the hydrocarbon alkyl resin of sulfonation any one.
Described anhydrous organic solvent is selected, be any one or any mixing that (contains two kinds) more than two kinds in N-methyl pyrrolidone, fourth-two eyeball, acetate, glycol-ether, the ethylene glycol-methyl ether, any is any proportioning when (containing two kinds) more than two kinds and mixing.
Described inorganic oxide is selected, and selects SiO for use 2, SiO then 2Presoma can be selected any one in tetraethoxysilane, the tetramethoxy-silicane; Select TiO for use 2, TiO then 2Presoma can be selected any one in metatitanic acid second fat, metatitanic acid isopropyl ester, the metatitanic acid fourth fat.
Diffusion layer of the present invention comprises conductive carbon material, hydrophobic material and three kinds of components of inorganic oxide water-keeping material.Hydrophobic material is the polytetrafluoroethylene (PTFE) polymer, and the inorganic oxide water-keeping material is any in nano silicon, the nano titanium oxide.The inorganic oxide water-keeping material prepares prior to diffusion layer, and its surface is PTFE polymer parcel, forms the inorganic oxide water-keeping material and is nuclear, and hydrophobic PTFE polymer is the structure of shell.The PTFE parcel inorganic oxide for preparing mixes with conductive carbon material, and brushing forms the used in proton exchange membrane fuel cell water-keeping diffusion layer on carbon paper, carbon cloth or carbon fiber felt.Because inorganic oxide is wrapped up by hydrophobic PTFE polymer, therefore the adding of water-keeping material can't change the hydrophobicity of whole diffusion layer, but distinctive surface hydroxyl of inorganic oxide and double electrical layers can keep the water content of diffusion layer, when fuel cell high temperature and low humidity work, can reduce the moist gradient from the proton exchange membrane to the diffusion layer in the whole membrane electrode, thereby reduce the loss of moisture, water holding capacity is strong, helps the hot operation of battery.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
1) gets the Nafion of 5wt% (weight concentration) (Du Pont company produces solution, and 5wt% is Nafion Resin, 95wt% are low-boiling point alcohol compositions such as water and ethanol, isopropyl alcohol) 500 grams, regulate pH value to 7.5 with NaOH, be transferred to 500 then and restrain in the N-methyl pyrrolidones, electromagnetic agitation 30min fully is dissolved in the N-methyl pyrrolidone perfluorinated sulfonic resin.Distill this solution 5 hours removing the moisture in the solution, reach 203 ℃ to solution temperature, obtain perfluorinated sulfonic resin/N-methyl pyrrolidone solution.
2) take by weighing the 4g tetraethoxysilane, be dissolved in the perfluorinated sulfonic resin/N-methyl pyrrolidone solution of step 1) preparation electromagnetic agitation 30min.Add the HCl solution (HCl content is that 37wt.%, water content are 63wt%) that is in excess in 4 times of tetraethoxysilane hydrolysis, electromagnetic agitation 8h obtains the SiO that perfluorinated sulfonic resin (Nafion DE 520 solution) is modified 2Nanoparticle dispersion liquid.
3) SiO that above-mentioned perfluorinated sulfonic resin (Nafion DE 520 solution) is modified 2Nanoparticle dispersion liquid and 76g weight concentration are that 30% polytetrafluoroethylene (PTFE) emulsion is mixed and (made inorganic oxide SiO 2Reach 1 with the weight ratio of polytetrafluoroethylene: 20-1: 5).Under 1000-5000 rev/min mixing speed, stirred 1 hour then, obtain SiO 2/ hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system.
4) with SiO 2/ hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system is mixed with the 75g conductive carbon material, adds 50mL water, stirs 20 hours under 1000-5000 rev/min mixing speed, obtains the diffusion layer slip.
5) the diffusion layer slip is screen-printed to carbon paper, segmentation heat treatment in heat-treatment furnace, wherein temperature was handled 10 minutes for 100 ℃, handled 10 minutes for 350 ℃ subsequently, formed water-keeping diffusion layer.
Technology as a setting, directly the employing weight concentration is 30% polytetrafluoroethylene (PTFE) emulsion preparation Catalytic Layer, other process is consistent with present embodiment 1, its process is to be 30% polytetrafluoroethylene (PTFE) emulsion with the 76g weight concentration, mix with the 75g conductive carbon material, add 50mL water, under 1000-5000 rev/min mixing speed, stirred 20 hours, obtain the diffusion layer slip.The diffusion layer slip is screen-printed to carbon paper, segmentation heat treatment in heat-treatment furnace, wherein temperature was handled 10 minutes for 100 ℃, handled 10 minutes for 350 ℃ subsequently.Obtain the diffusion layer of technology as a setting.
The water-keeping diffusion layer that the present invention is prepared is assembled into monocell with Nafion211 film (the Pt/C catalyst of 0.3g/cm-2, catalyst Pt content 60% are respectively coated in the film both sides), at 120 ℃, and 50RH% air inlet humidification, 600mAcm -2Under the condition, 200 minutes, output voltage 0.53-0.62V, fall was less than 0.5mV/ minute.Under the same conditions, the diffusion layer output voltage 0.39-0.62V of technology has descended 1.6mV/ minute as a setting.
Embodiment 2:
1) get sulfonation trifluorostyrene solution 400 gram of 8wt%, regulate pH value to 6.5 with NaOH, be transferred to then in 600 Ke Ding-two eyeball, electromagnetic agitation 30min fully is dissolved in fourth-two eyeball sulfonation trifluorostyrene.Distill this solution removing the moisture in the solution, reach 267 ℃ to solution temperature, obtain sulfonation trifluorostyrene/fourth-two eyeball solution.
2) measure 13.6g metatitanic acid fourth fat, be dissolved in sulfonation trifluorostyrene/fourth-two eyeball solution of step 1) preparation electromagnetic agitation 30min.Add the HCl solution (HCl content is that 37wt.%, water content are 63wt%) that is in excess in 1 times of hydrolysis, electromagnetic agitation 8h obtains the TiO that the sulfonation trifluorostyrene is modified 2Nanoparticle dispersion liquid.
3) TiO that sulfonation trifluorostyrene is modified 2Nanoparticle dispersion liquid and 53g weight concentration are that 60% polytetrafluoroethylene (PTFE) emulsion is mixed and (made inorganic oxide TiO 2Reach 1 with the weight ratio of polytetrafluoroethylene: 20-1: 5).Under 1000-5000 rev/min mixing speed, stirred 1 hour then, obtain TiO 2/ hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system.
4) with TiO 2/ hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system is mixed with the 56g conductive carbon material, adds 200mL fourth-two eyeball, stirs 10 hours under 1000-5000 rev/min mixing speed, obtains the diffusion layer slip.
5) the diffusion layer slip is sprayed on the carbon fiber felt, segmentation heat treatment in heat-treatment furnace, wherein temperature was handled 10 minutes for 100 ℃, handled 10 minutes for 350 ℃ subsequently, handled 10 minutes for 350 ℃ subsequently, formed water-keeping diffusion layer.
Prepared water-keeping diffusion layer is assembled into monocell with Nafion211 film (the Pt/C catalyst of 0.3g/cm-2, catalyst Pt content 60% are respectively coated in the film both sides), at 120 ℃, and 50RH% air inlet humidification, 600mAcm -2Under the condition, 100 minutes, output voltage 0.58-0.62V, fall was less than 0.4mV/ minute.
Embodiment 3:
1) get sulfonated polyether-ether-ketone solution 400 gram of 10wt%, regulate pH value to 6.5 with NaOH, be transferred to 3000 then and restrain in ethylene glycol-methyl ethers, electromagnetic agitation 30min fully is dissolved in ethylene glycol-methyl ether sulfonated polyether-ether-ketone.Distill this solution removing the moisture in the solution, reach 125 ℃ to solution temperature, obtain the ethylene glycol-methyl ether solution of sulfonated polyether-ether-ketone.
2) measure the 51g tetramethoxy-silicane, be dissolved in the ethylene glycol-methyl ether solution of sulfonated polyether-ether-ketone of step 1) preparation electromagnetic agitation 30min.Add the HCl solution (HCl content is that 37wt.%, water content are 63wt%) that is in excess in 10 times of hydrolysis, electromagnetic agitation 8h obtains the SiO that sulfonated polyether-ether-ketone is modified 2Nanoparticulate dispersion.
3) SiO that sulfonation trifluorostyrene is modified 2Nanoparticulate dispersion and 1330g weight concentration are that 30% polytetrafluoroethylene (PTFE) emulsion is mixed and (made inorganic oxide SiO 2Reach 1 with the weight ratio of polytetrafluoroethylene: 20-1: 5).Under 1000-5000 rev/min mixing speed, stirred 1 hour then, obtain SiO 2/ hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system.
4) with SiO 2/ hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system is mixed with 100 gram conductive carbon materials, adds 150mL water, stirs 10-24 hour under 1000-5000 rev/min mixing speed, obtains the diffusion layer slip.
5) the diffusion layer slip is applied on the carbon cloth, segmentation heat treatment in heat-treatment furnace, wherein temperature was handled 10 minutes for 100 ℃, handled 10 minutes for 350 ℃ subsequently, handled 10 minutes for 350 ℃ subsequently, formed water-keeping diffusion layer.
Prepared water-keeping diffusion layer is assembled into monocell with Nafion211 film (the Pt/C catalyst of 0.3g/cm-2, catalyst Pt content 60% are respectively coated in the film both sides), at 120 ℃, and 50RH% air inlet humidification, 600mAcm -2Under the condition, 200 minutes, output voltage 0.50-0.62V, fall was less than 0.6mV/ minute.
Embodiment 4:
A kind of preparation method of water-keeping diffusion layer of high temperature proton exchange film fuel cell, it comprises the steps:
1) preparation inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid particle:
(a) be that 1.2% ionomer solution is regulated pH value to 6.5 with NaOH with weight concentration, be transferred in the anhydrous organic solvent then, get solution A, make ionomer content in solution A reach 1wt.%, then distill this solution 6 hours to remove the moisture in the solution, obtain the ionomer precursor solution; Described ionomer is the hydrocarbon alkyl resin of sulfonation, and described anhydrous organic solvent is an acetate;
(b) according to inorganic oxide SiO 2With ionomer (the hydrocarbon alkyl resin of sulfonation) weight ratio 0.01: 1, with this inorganic oxide SiO 2Inorganic oxide precursor body (tetramethoxy-silicane) join in the ionomer precursor solution of step (a) preparation and stirred 20 minutes, make the inorganic oxide precursor liquid solution;
(c) according to the ratio of 1 times of inorganic oxide precursor body (tetramethoxy-silicane) hydrolysis institute water requirement, with HCl content is that 37wt.%, water content are that the dense HCl solution of 63wt% joins in the inorganic oxide precursor liquid solution of step (b) preparation, fully mix, obtain the inorganic oxide nanoparticles dispersion liquid that ionomer is modified;
(d) the inorganic oxide nanoparticles dispersion liquid that ionomer is modified and weight concentration are that 10% polytetrafluoroethylene (PTFE) emulsion is mixed, and make inorganic oxide (or title inorganic oxide nanoparticles) SiO 2Reach 1: 20 with the weight ratio of polytetrafluoroethylene; Stirred 1 hour under 1000 rev/mins mixing speed then, obtain inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system, wherein inorganic oxide is nuclear, and the PTFE polymer is a shell;
2) preparation of water-keeping diffusion layer:
(a) inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system is mixed with conductive carbon material, the part by weight of conductive carbon material and polytetrafluoroethylene (PTFE) is 2.5: 1, add anhydrous organic solvent then, described anhydrous organic solvent is an acetate, makes that solid content is 20%-80% in the mixed solution; Under 1000 rev/mins mixing speed, stirred 24 hours, obtain the diffusion layer slip;
(b) the diffusion layer slip is sprayed on the carbon cloth, segmentation heat treatment in heat-treatment furnace, wherein temperature was handled 10 minutes for 100 ℃, handled 10 minutes for 350 ℃ subsequently, formed water-keeping diffusion layer (being water-keeping diffusion layer of high temperature proton exchange film fuel cell).
Embodiment 5:
A kind of preparation method of water-keeping diffusion layer of high temperature proton exchange film fuel cell, it comprises the steps:
1) preparation inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid particle:
(a) be that 9% ionomer solution is regulated pH value to 7.0 with NaOH with weight concentration, be transferred in the anhydrous organic solvent then, get solution A, make ionomer content in solution A reach 7wt.%, then distill this solution 5 hours to remove the moisture in the solution, obtain the ionomer precursor solution; Described ionomer is a perfluorinated sulfonic resin, and described anhydrous organic solvent is the N-methyl pyrrolidone;
(b) according to inorganic oxide SiO 2With ionomer (perfluorinated sulfonic resin) weight ratio 0.05: 1, with this inorganic oxide SiO 2Inorganic oxide precursor body (tetraethoxysilane) join in the ionomer precursor solution of step (a) preparation and stirred 25 minutes, make the inorganic oxide precursor liquid solution;
(c) according to the ratio of 5 times of inorganic oxide precursor body (tetraethoxysilane) hydrolysis institute water requirements, with HCl content is that 37wt.%, water content are that the dense HCl solution of 63wt% joins in the inorganic oxide precursor liquid solution of step (b) preparation, fully mix, obtain the inorganic oxide nanoparticles dispersion liquid that ionomer is modified;
(d) the inorganic oxide nanoparticles dispersion liquid that ionomer is modified and weight concentration are that 40% polytetrafluoroethylene (PTFE) emulsion is mixed, and make the weight ratio of inorganic oxide and polytetrafluoroethylene reach 1: 10; Stirred 1 hour under 3000 rev/mins mixing speed then, obtain inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system, wherein inorganic oxide is nuclear, and the PTFE polymer is a shell;
2) preparation of water-keeping diffusion layer:
(a) inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system is mixed with conductive carbon material, the part by weight of conductive carbon material and polytetrafluoroethylene (PTFE) is 3: 1, adds entry then, makes that solid content is 20%-80% in the mixed solution; Under 3000 rev/mins mixing speed, stirred 20 hours, obtain the diffusion layer slip;
(b) the diffusion layer slip is sprayed on the carbon fiber felt, segmentation heat treatment in heat-treatment furnace, wherein temperature was handled 10 minutes for 100 ℃, handled 10 minutes for 350 ℃ subsequently, formed water-keeping diffusion layer (being water-keeping diffusion layer of high temperature proton exchange film fuel cell).
Embodiment 6:
A kind of preparation method of water-keeping diffusion layer of high temperature proton exchange film fuel cell, it comprises the steps:
1) preparation inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid particle:
(a) be that 10% ionomer solution is regulated pH value to 7.5 with NaOH with weight concentration, be transferred in the anhydrous organic solvent then, get solution A, make ionomer content in solution A reach 9wt.%, then distill this solution 4 hours to remove the moisture in the solution, obtain the ionomer precursor solution; Described ionomer is the sulfonation trifluorostyrene, and described anhydrous organic solvent is a glycol-ether;
(b) according to inorganic oxide TiO 2With ionomer (sulfonation trifluorostyrene) weight ratio 0.1: 1, with this inorganic oxide TiO 2Inorganic oxide precursor body (metatitanic acid isopropyl ester) join in the ionomer precursor solution of step (a) preparation and stirred 30 minutes, make the inorganic oxide precursor liquid solution;
(c) according to the ratio of 10 times of inorganic oxide precursor body (metatitanic acid isopropyl ester) hydrolysis institute water requirements, with HCl content is that 37wt.%, water content are that the dense HCl solution of 63wt% joins in the inorganic oxide precursor liquid solution of step (b) preparation, fully mix, obtain the inorganic oxide nanoparticles dispersion liquid that ionomer is modified;
(d) the inorganic oxide nanoparticles dispersion liquid that ionomer is modified and weight concentration are that 60% polytetrafluoroethylene (PTFE) emulsion is mixed, and make the weight ratio of inorganic oxide and polytetrafluoroethylene reach 1: 5; Stirred 1 hour under 5000 rev/mins mixing speed then, obtain inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system, wherein inorganic oxide is nuclear, and the PTFE polymer is a shell;
2) preparation of water-keeping diffusion layer:
(a) inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system is mixed with conductive carbon material, the part by weight of conductive carbon material and polytetrafluoroethylene (PTFE) is 3.5: 1, add anhydrous organic solvent then, described anhydrous organic solvent is a glycol-ether, makes that solid content is 80% in the mixed solution; Under 5000 rev/mins mixing speed, stirred 10 hours, obtain the diffusion layer slip;
(b) the diffusion layer slip is cast on the carbon paper, segmentation heat treatment in heat-treatment furnace, wherein temperature was handled 10 minutes for 100 ℃, handled 10 minutes for 350 ℃ subsequently, formed water-keeping diffusion layer (being water-keeping diffusion layer of high temperature proton exchange film fuel cell).
The upper limit of each raw material proportioning, lower limit and interval value can both be realized the present invention in the preparation process of the present invention, and ionomer, anhydrous organic solvent, inorganic oxide precursor body concrete raw material separately can both realize the present invention, do not enumerate embodiment one by one at this.

Claims (4)

1. the preparation method of a water-keeping diffusion layer of high temperature proton exchange film fuel cell is characterized in that it comprises the steps:
1) preparation inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid particle:
(a) be that the ionomer solution of 1.2%-10% is regulated the pH value to 6.5-7.5 with NaOH with weight concentration, be transferred in the anhydrous organic solvent then, get solution A, make ionomer content in solution A reach 1-9wt.%, then distill this solution 4-6 hour to remove the moisture in the solution, obtain the ionomer precursor solution;
(b) according to inorganic oxide and ionomer weight ratio 0.01: 1-0.1: 1, the inorganic oxide precursor body of this inorganic oxide is joined in the ionomer precursor solution of step (a) preparation and stirred 20-30 minute, make the inorganic oxide precursor liquid solution;
(c) according to the inorganic oxide precursor body hydrolysis water requirement 1-10 of institute ratio doubly, with HCl content is that 37wt.%, water content are that the dense HCl solution of 63wt% joins in the inorganic oxide precursor liquid solution of step (b) preparation, fully mix, obtain the inorganic oxide nanoparticles dispersion liquid that ionomer is modified;
(d) the inorganic oxide nanoparticles dispersion liquid that ionomer is modified and weight concentration are that the ptfe emulsion of 10%-60% mixes, and the weight ratio that makes inorganic oxide and polytetrafluoroethylene is 1: 20-1: 5; Under 1000-5000 rev/min mixing speed, stirred 1 hour then, obtain inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system;
2) preparation of water-keeping diffusion layer:
(a) inorganic oxide/hydrophobic PTFE polyalcohol nucleocapsid Dispersion of Particles system is mixed with conductive carbon material, the part by weight of conductive carbon material and polytetrafluoroethylene is 2.5: 1-3.5: 1, add entry or anhydrous organic solvent then, make that solid content is 20%-80% in the mixed solution; Under 1000-5000 rev/min mixing speed, stirred 10-24 hour, obtain the diffusion layer slip;
(b) with the silk screen printing of diffusion layer slip, casting, be coated with or be sprayed on carbon paper, carbon cloth or the carbon fiber felt, segmentation heat treatment in heat-treatment furnace, wherein 100 ℃ of temperature were handled 10 minutes, handled 10 minutes for 350 ℃ subsequently, formed water-keeping diffusion layer.
2. the preparation method of a kind of water-keeping diffusion layer of high temperature proton exchange film fuel cell according to claim 1, it is characterized in that: described ionomer is any one in perfluorinated sulfonic resin, sulfonation trifluorostyrene, sulfonated polyether-ether-ketone, the hydrocarbon alkyl resin of sulfonation.
3. the preparation method of a kind of water-keeping diffusion layer of high temperature proton exchange film fuel cell according to claim 1, it is characterized in that: described anhydrous organic solvent is any one or any mixing more than two kinds in N-methyl pyrrolidone, fourth-two eyeball, acetate, glycol-ether, the ethylene glycol-methyl ether, and any is any proportioning when mixing more than two kinds.
4. the preparation method of a kind of water-keeping diffusion layer of high temperature proton exchange film fuel cell according to claim 1, it is characterized in that: described inorganic oxide is SiO 2Or TiO 2, select SiO for use 2, SiO then 2Presoma is any one in tetraethoxysilane, the tetramethoxy-silicane; Select TiO for use 2, TiO then 2Presoma is any one in metatitanic acid second fat, metatitanic acid isopropyl ester, the metatitanic acid fourth fat.
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