CN100454635C - Making method for inorganic proton exchange film fuel cell film pole - Google Patents
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Abstract
The invention relates to an inorganic proton exchange membrane fuel cell membrane electrode preparation method. the preparation method, its characteristic lies in that it includes the following steps: 1) inorganic proton exchange membrane preparation: a) first prepares the heteropolyacid and the inorganic oxide compound forerunner body mix solution; b) the surface active agent solution preparation; c) inorganic proton conduction powder forerunner body preparation; d) inorganic proton exchange membrane preparation: The inorganic proton conduction powder forerunner body which step c) prepares sets in the culture dish, dry, high temperature burning, obtains the inorganic proton conduction powder, joins the thermoplastic resin cementing agent rmo-compression to prepare the inorganic proton exchange membrane; 2) inorganic proton exchange membrane-catalysis layer module preparation; 3) inorganic proton exchange membrane -catalysis layer module seal; 4) inorganic proton exchange membrane fuel cell membrane electrode preparation. The membrane electrode operating temperature of the method preparation is high (may be higher than 200 degree centigrade).
Description
Technical field
The present invention relates to a kind of preparation method of inorganic proton exchange film fuel cell film pole.
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 system 10～20% in battery operation, greatly reduce the performance of battery system and cut down fuel cell relatively and competitiveness (the Fuel Cell Systems Explained 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 the high-temperature fuel cell technology in these unique advantages that promote fuel cell environment adaptability and aspect of performance, at present, becoming focus rapidly about the research of high-temperature fuel cell, one of wherein important direction is exactly the high temperature membrane electrode fabrication.
About traditional direct employing proton conductive resin bonding Catalytic Layer, thereby the patent of preparation membrane electrode is a lot.As U.S. Pat 4896115, US5186877, Chinese patent ZL98108618.7, Japan Patent P2002075382 is directly to adopt proton conductive resin and catalyst modulation slurry, then slurry is transferred on the diffusion layer, obtained the membrane electrode of five in one with proton exchange membrane hot pressing.At high temperature as more than 80 ℃, perhaps not exclusively during humidification, because the Catalytic Layer dehydration is serious, the proton conductivity of proton conductive resin can descend rapidly in the Catalytic Layer, causes battery performance to descend.
The other membrane electrode as Chinese patent 200410013147.0, adopts the method that directly adds inorganic oxide nanoparticles to prepare the water conservation Catalytic Layer.But proton-conducting material is a polymer still, is difficult in more than 100 ℃ and works, and more difficultly is higher than 200 ℃.
In addition, US 20060280982 utilizations have the poly-aryl compound of semi-annular jade pendant acid groups and the high electricity of nitrogen heterocyclic ring aryl polymer preparation is led, resistant to elevated temperatures proton exchange film production membrane electrode assembly, but owing to be proton exchange polymer membrane, temperature of fuel cell operation is below 100 ℃, otherwise there is the film dehydration equally, causes the serious problem that descends of membrane conductivity.
Exploration patent on membrane electrode structure and preparation technology is also more, US20070048594 provides a kind of membrane electrode assembly that is used for fuel cell, it should be this restriction of conduction by near electrode catalyst layer collector body being installed, having been eliminated diffusion layer and supporting layer.Described membrane electrode assembly can comprise nonconducting diffusion layer and supporting layer by near electrode catalyst layer collector body being installed.Select hydrophilic, moisture diffusion layer and support layer material, can improve fuel battery performance.Chinese patent 200610121579.2 has also been reported the membrane electrode assembly of similar fuel cell.But owing to all adopt polymer in these membrane electrodes is that proton-conducting material still is, working temperature can not break through 200 ℃.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of inorganic proton exchange film fuel cell film pole, the membrane electrode working temperature height (can be higher than 200 ℃) of this method preparation.
For achieving the above object, technical scheme of the present invention is: a kind of preparation method of inorganic proton exchange film fuel cell film pole is characterized in that it comprises the steps:
1) preparation of inorganic proton exchange film:
A) at first prepare heteropoly acid and inorganic oxide precursor body mixed solution: the weight ratio that earlier heteropoly acid is joined water and ethanol is in 1: 3～1: 10 the mixed solvent, wherein the weight ratio of heteropoly acid and water and alcohol mixed solvent is 1: (16～300), stirred 15～30 minutes, added the inorganic oxide precursor body in 10: 1～2: 1 according to inorganic oxide precursor body and heteropoly acid weight ratio then, continue to stir 15～30 minutes, form heteropoly acid and inorganic oxide precursor body mixed solution;
B) preparation of surfactant solution: the weight ratio that surfactant is joined water and ethanol according to inorganic oxide precursor body and surfactant weight ratio 3: 1～1: 1 is in 1: 3～1: 10 mixed solvent, the weight ratio of surfactant and water and alcohol mixed solvent is 1: (30～64), stirred 15～30 minutes, and made surfactant solution;
C) inorganic proton conductive powder presoma preparation: the surfactant solution of step b) preparation slowly is added in the heteropoly acid and inorganic oxide precursor body mixed solution of step a) preparation, stirred under the room temperature 1～2 hour, and made inorganic proton conductive powder presoma;
D) inorganic proton exchange film preparation: the inorganic proton conductive powder presoma of step c) preparation is placed culture dish, 35 ℃～45 ℃ following heat treatment is 7～10 days in drying box, then 350 ℃～400 ℃ following high-temperature calcinations of temperature 1～2 hour, obtain the inorganic proton conductive powder, this inorganic proton conductive powder of milling, add with inorganic proton conductive powder weight ratio be that thermoplastic resin binder's hot pressing of 1: 10～3: 10 is prepared into inorganic proton exchange film;
2) inorganic proton exchange film---the preparation of Catalytic Layer assembly: with catalyst, inorganic proton conductive powder, thermoplastic resin binder, electrically conductive material mix mixture, in mixture, catalyst, inorganic proton conductive powder, thermoplastic resin binder, the shared percentage by weight of electrically conductive material are: catalyst 10～50%, inorganic proton conductive powder 10～40%, electrically conductive material 10～30%, thermoplastic resin binder 10～20%; This mixture spreads upon the centre position of inorganic proton exchange film, and thickness is 5～30 microns (Catalytic Layer), reserves 1～10 millimeter around the inorganic proton exchange film and is used for sealing; Then, N
2The following 200 ℃ of heat treatments of gas shiled 3～10 minutes;
3) inorganic proton exchange film---the sealing of Catalytic Layer assembly: adopt air-tightness polymer or polymer modification material good, that be adapted to work more than 200 ℃ to be used for sealing as encapsulant, in preparation process, encapsulant directly is applied in the position of reserving around the inorganic proton exchange film, and thickness is greater than 2～5 microns of Catalytic Layer;
4) preparation of inorganic proton exchange film fuel cell film pole: at the inorganic proton exchange film of good seal---direct blanket gas diffusion layer promptly obtains inorganic proton exchange film fuel cell film pole on the Catalytic Layer.
Described heteropoly acid is that central atom is P, Si or S, and coordination atom is at least a element among W, Mo and the V.
Described inorganic oxide is SiO
2Or TiO
2, select SiO for use
2The time, then the inorganic oxide precursor body be tetraethoxysilane, tetramethoxy-silicane, tetraethoxysilane any one; Select TiO for use
2The time, then the inorganic oxide precursor body is any one in tetraethyl titanate, isopropyl titanate, the butyl titanate.
Described surfactant is cationic surfactant CTAB (softex kw), or be non-ionic surface active agent F108, F127 (polyoxyethylene/polyoxypropylene polymerization), any one among P123, the P56 (poly-oxireme ether-poly-propylene oxide ether-poly-oxireme ether triblock polymer).
Described thermoplastic resin binder is any in polyether sulfone (PES), polyphenylene oxide ketone (PES), polyphenylene sulfide (PPS), polyamidoimide (PAI), the Kynoar (PVDF).Its flow temperature is higher than 200 ℃.
Described selection of catalysts, comprise Pt catalyst or no-Pt catalyst, for Pt deceives, (X is as catalyst carrier for Pt/X, any in carbon black, carbon nano-tube or the carbon nano-fiber), spinel-type or perofskite type oxide (ABO3, A=Sr, Ce, Pb, La, B=Co, Pd, Ru, Pt), pyrolysis metal phthalocyanine compound MxPc or metal nitrogen oxygen chemicals MO
xN
y(M=Fe, Co, Ni, Cu, Mn), alloy catalyst Pd-Ti, Pd-Co-Au, Pd-Co-Mo, any in them.
Described electrically conductive material is carbon black or graphite.
Described air-tightness is good, be adapted to the polymer of working more than 200 ℃ or polymer modification material is any in poly tetrafluoroethylene, silicon rubber, modified organic silicone resin lacquer W61-55,600# organosilicon heat-resistant lacquer, the 800# organosilicon heat-resistant lacquer.
Described diffusion layer is carbon paper, carbon fiber felt or carbon cloth.
The present invention adopts the fixing heteropoly acid of mesoporous material as proton-conducting material, and the employing vitrification point is higher than 200 ℃ thermal plastic high polymer as binding material, makes proton exchange membrane have the ability of working more than 200 ℃; It is proton-conducting material that Catalytic Layer adopts heteropoly acid, and carbon, non-Pt metal or working temperature are higher than 200 ℃ conducting polymer as electronic material.Therefore, the working temperature of this membrane electrode can be higher than 200 ℃, can select non-Pt material as catalyst simultaneously, does not have the poisoning behavior of CO, has solved the problem that current proton membrane fuel battery exists well.
Compared with prior art, because inorganic proton exchange film fuel cell film pole working temperature provided by the present invention is higher than 200 ℃, therefore have following advantage:
(1) battery temperature is more than 200 ℃, and battery and circumstance of temperature difference have improved (existing battery general work temperature is 60 ℃) more than 140 ℃.Therefore, adopt mea packed battery provided by the invention system, its radiating efficiency is very high, can save water-cooling system substantially.And the water-cooling system of current fuel cell generally will account for more than 10% of battery system cost, and can consume 10～20% system power.
(2) when working more than 200 ℃, if adopt the Pt catalyst, its tolerance to CO can bring up to 30,000ppm
More than, can there be the catalyst poisoning phenomenon.
(3) when working more than 200 ℃, because the dynamics of catalytic reaction speeds up, a lot of no-Pt catalysts can be used for Proton Exchange Membrane Fuel Cells.
Description of drawings
Fig. 1 is a process chart of the present invention
Among the figure: 1-inorganic proton exchange film, 2-inorganic proton exchange film---Catalytic Layer assembly, 3-have the inorganic proton exchange film of sealing strip---Catalytic Layer assembly, 4-inorganic proton exchange film fuel cell film pole.
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: as shown in Figure 1,
1. the preparation of inorganic proton exchange film, carry out according to following steps:
1) take by weighing 20.8 gram HPW (phosphotungstic acid) and 41.6 gram tetraethoxysilanes, be dissolved in the mixed solvent of 50 gram water and 500 gram ethanol compositions, electromagnetic agitation 15 minutes obtains the mixed solution of phosphotungstic acid and tetraethoxysilane.
2) take by weighing 14 gram surfactant P123, be dissolved in the mixed solvent of 50 gram water and 500 gram ethanol compositions, electromagnetic agitation 15 minutes obtains surfactant P123 solution.
3) with step 2) the surfactant P123 solution that makes slowly be added to the step 1) preparation in phosphotungstic acid and tetraethoxysilane mixed solution, stirring is 1 hour under the room temperature, makes inorganic proton conductive powder presoma.
4) the inorganic proton conductive powder presoma with the step 3) preparation places culture dish, place in the vacuum furnace, 45 ℃ of following heat treatments of temperature 10 days, under 400 ℃ of high temperature, calcined 2 hours then, obtain the inorganic proton conductive powder, this inorganic proton conductive powder 20 grams of milling add 6 gram polyether sulfone (PES) binding agent hot pressing and make inorganic proton exchange film.
2. inorganic proton exchange film---the preparation of Catalytic Layer assembly: (Johnson Matthey company produces to take by weighing 3 gram Pt/C catalyst, the average grain diameter of formed by catalytic active particles Pt is 3nm, the Pt carrying capacity is 40wt%), 1g inorganic proton conductive powder, 2.3 the gram carbon blacks, 1 the gram polyether sulfone (PES), evenly mix, stirred 1 hour for 3000 rev/mins with refiner, spread upon 1-4) centre position of inorganic proton exchange film of preparation, thickness is 15 microns, reserves 5 millimeters around the film and is used for sealing.Then, N
2The following 200 ℃ of heat treatments of gas shiled 10 minutes obtain inorganic proton exchange film---the Catalytic Layer assembly.
3. inorganic proton exchange film---the sealing of Catalytic Layer assembly: adopt modified organic silicone resin lacquer W61-55, modified organic silicone resin is coated with lacquer W61-55 is applied in 1-4) 5 millimeters positions reserving around the inorganic proton exchange film of preparation, 18 microns of thickness, 300 ℃, 1.3Mpa hot pressing 2 minutes.
4. the preparation of inorganic proton exchange film fuel cell film pole: at the inorganic proton exchange film that sealing strip is arranged of step 3 preparation---directly cover carbon paper on the Catalytic Layer and obtain inorganic proton exchange film fuel cell film pole.Membrane electrode is at 240 ℃, and the output performance of 25RH% is 0.51V@600mA cm
-2
Embodiment 2:
1. the preparation of inorganic proton exchange film, process is carried out according to following steps:
1) take by weighing 4 gram HPMo (phosphomolybdic acid) and 8 gram tetraethoxysilanes, be dissolved in the mixed solvent of 50 gram water and 150 gram ethanol compositions, electromagnetic agitation 20 minutes obtains the mixed solution of phosphomolybdic acid and tetraethoxysilane.
2) take by weighing 4 gram surfactant PMAA, be dissolved in the mixed solvent of 50 gram water and 150 gram ethanol compositions, electromagnetic agitation 20 minutes obtains surfactant PMAA solution.
3) with step 2) in the surfactant PMAA solution that the makes phosphomolybdic acid that slowly is added to the step 1) preparation and the tetraethoxysilane mixed solution, stirring is 1 hour under the room temperature, makes inorganic proton conductive powder presoma.
4) the inorganic proton conductive powder presoma with the step 3) preparation places culture dish, place in the vacuum furnace, 35 ℃ of following heat treatments of temperature 10 days, under 350 ℃ of high temperature, calcined 2 hours then, obtain the inorganic proton conductive powder, this inorganic proton conductive powder 10 grams of milling add 1 gram polyphenylene oxide ketone (PES) binding agent hot pressing and make inorganic proton exchange film.
2. inorganic proton exchange film---the preparation of Catalytic Layer assembly: take by weighing 4 gram PdCoO3,1 gram inorganic proton conductive powder, 2 gram graphite, 1 gram polyphenylene oxide ketone (PES), evenly mix, stirred 1.5 hours for 3000 rev/mins with refiner, spread upon step 1-4) centre position of inorganic proton exchange film of preparation, thickness is 22 microns, reserves 4.5 millimeters around the film and is used for sealing.Then, N
2The following 200 ℃ of heat treatments of gas shiled 10 minutes obtain inorganic proton exchange film---the Catalytic Layer assembly.
3. inorganic proton exchange film---the sealing of Catalytic Layer assembly: employing silicon rubber is encapsulant, and silicon rubber directly is applied in 1-4) 4.5 millimeters positions reserving around the inorganic proton exchange film of preparation, 25 microns of thickness.
4. the preparation of inorganic proton exchange film fuel cell film pole: at the inorganic proton exchange film that sealing strip is arranged of step 3 preparation---directly cover carbon paper on the Catalytic Layer and obtain inorganic proton exchange film fuel cell film pole.Membrane electrode is at 320 ℃, and the output performance of 10RH% is 0.32V@600mA cm
-2
Embodiment 3:
1. the preparation of inorganic proton exchange film, process is carried out according to following steps:
1) take by weighing 1 gram HSiW (silico-tungstic acid) and 10 gram tetraethyl titanates, be dissolved in the mixed solvent of 50 gram water and 250 gram ethanol compositions, electromagnetic agitation 30 minutes obtains silico-tungstic acid and tetraethyl titanate mixed solution.
2) take by weighing 10 gram Surfactant PEG, be dissolved in the mixed solvent of 50 gram water and 250 gram ethanol compositions, electromagnetic agitation 30 minutes obtains Surfactant PEG solution.
3) with step 2) in the Surfactant PEG solution that the makes silico-tungstic acid that slowly is added to the step 1) preparation and the tetraethyl titanate mixed solution, stirring is 2 hours under the room temperature, makes inorganic proton conductive powder presoma.
4) the inorganic proton conductive powder presoma with the step 3) preparation places culture dish, place in the vacuum furnace, 35 ℃ of following heat treatments of temperature 7 days, under 400 ℃ of high temperature, calcined 2 hours then, obtain the inorganic proton conductive powder, this inorganic proton conductive powder 2 grams of milling, inorganic proton exchange film is made in polyphenylene sulfide (PPS) the binding agent hot pressing that adds 0.2 gram.
2. inorganic proton exchange film---the preparation of Catalytic Layer assembly: take by weighing 4 gram Pd-Co-Mo, 1 gram inorganic proton conductive powder, 2 gram carbon nano-tube, 1 gram polyphenylene sulfide (PPS), evenly mix, stirred 1.5 hours for 3000 rev/mins with refiner, spread upon step 1-4) centre position of inorganic proton exchange film of preparation, thickness is 25 microns, reserves 5 millimeters around the film and is used for sealing.Then, N
2The following 200 ℃ of heat treatments of gas shiled 10 minutes obtain inorganic proton exchange film---the Catalytic Layer assembly.
3. inorganic proton exchange film---the sealing of Catalytic Layer assembly: adopting the 600# organosilicon heat-resistant lacquer is encapsulant, and the 600# organosilicon heat-resistant lacquer directly is applied in 1-4) 5 millimeters positions reserving around the inorganic proton exchange film of preparation, 28 microns of thickness.
4. the preparation of inorganic proton exchange film fuel cell film pole: at the inorganic proton exchange film that sealing strip is arranged of step 3 preparation---direct coated carbon fibrofelt obtains inorganic proton exchange film fuel cell film pole on the Catalytic Layer, membrane electrode is at 280 ℃, and the output performance of 15RH% is 0.43V@600mA cm
-2
Embodiment 4:
1. the preparation of inorganic proton exchange film, carry out according to following steps:
1) take by weighing 20.8 gram HPW (phosphotungstic acid) and 41.6 gram tetramethoxy-silicanes, be dissolved in the mixed solvent of 50 gram water and 500 gram ethanol compositions, electromagnetic agitation 15 minutes obtains phosphotungstic acid and tetramethoxy-silicane mixed solution.
2) take by weighing 14 gram cationic surfactant CTAB, be dissolved in the mixed solvent of 50 gram water and 500 gram ethanol compositions, electromagnetic agitation 15 minutes obtains cationic surfactant CTAB solution.
3) with step 2) the cationic surfactant CTAB solution that makes slowly be added to the step 1) preparation in phosphotungstic acid and tetramethoxy-silicane mixed solution, stirring is 1 hour under the room temperature, makes inorganic proton conductive powder presoma.
4) the inorganic proton conductive powder presoma with the step 3) preparation places culture dish, place in the vacuum furnace, 45 ℃ of following heat treatments of temperature 10 days, under 400 ℃ of high temperature, calcined 2 hours then, obtain the inorganic proton conductive powder, this inorganic proton conductive powder 20 grams of milling add 6 gram Kynoar (PVDF) binding agent hot pressing and make inorganic proton exchange film.
2. inorganic proton exchange film---the preparation of Catalytic Layer assembly: (Johnson Matthey company produces to take by weighing 3 gram Pt/C catalyst, the average grain diameter of formed by catalytic active particles Pt is 3nm, the Pt carrying capacity is 40wt%), 1 gram inorganic proton conductive powder, 2.3 gram carbon nano-fibers, 1 gram Kynoar (PVDF), evenly mix, stirred 1 hour for 3000 rev/mins with refiner, spread upon 1-4) centre position of inorganic proton exchange film of preparation, thickness is 15 microns, reserves 5 millimeters around the film and is used for sealing.Then, N
2The following 200 ℃ of heat treatments of gas shiled 10 minutes obtain inorganic proton exchange film---the Catalytic Layer assembly.
3. inorganic proton exchange film---the sealing of Catalytic Layer assembly: adopt the 600# organosilicon heat-resistant lacquer, the 600# organosilicon heat-resistant lacquer is applied in 1-4) 5 millimeters positions reserving around the inorganic proton exchange film of preparation, 18 microns of thickness, 300 ℃, 1.3Mpa hot pressing 2 minutes.
4. the preparation of inorganic proton exchange film fuel cell film pole: at the inorganic proton exchange film that sealing strip is arranged of step 3 preparation---directly cover carbon cloth on the Catalytic Layer and obtain inorganic proton exchange film fuel cell film pole.Membrane electrode is at 240 ℃, and the output performance of 25RH% is 0.51V@600mA cm
-2
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 heteropoly acid, inorganic oxide precursor body, surfactant, thermoplastic resin binder, catalyst, electrically conductive material, encapsulant concrete raw material separately can both realize the present invention, do not enumerate embodiment one by one at this.
Claims (6)
1. the preparation method of an inorganic proton exchange film fuel cell film pole is characterized in that it comprises the steps:
1) preparation of inorganic proton exchange film:
A) at first prepare heteropoly acid and inorganic oxide precursor body mixed solution: the weight ratio that earlier heteropoly acid is joined water and ethanol is in 1: 3～1: 10 the mixed solvent, wherein the weight ratio of heteropoly acid and water and alcohol mixed solvent is 1: (16～300), stirred 15～30 minutes, added the inorganic oxide precursor body in 10: 1～2: 1 according to inorganic oxide precursor body and heteropoly acid weight ratio then, continue to stir 15～30 minutes, form heteropoly acid and inorganic oxide precursor body mixed solution;
Described inorganic oxide is SiO
2Or TiO
2, select SiO for use
2The time, then the inorganic oxide precursor body be tetraethoxysilane, tetramethoxy-silicane, tetraethoxysilane any one; Select TiO for use
2The time, then the inorganic oxide precursor body is any one in tetraethyl titanate, isopropyl titanate, the butyl titanate;
B) preparation of surfactant solution: the weight ratio that surfactant is joined water and ethanol according to inorganic oxide precursor body and surfactant weight ratio 3: 1～1: 1 is in 1: 3～1: 10 mixed solvent, the weight ratio of surfactant and water and alcohol mixed solvent is 1: (30～64), stirred 15～30 minutes, and made surfactant solution;
C) inorganic proton conductive powder presoma preparation: the surfactant solution of step b) preparation slowly is added in the heteropoly acid and inorganic oxide precursor body mixed solution of step a) preparation, stirred under the room temperature 1～2 hour, and made inorganic proton conductive powder presoma;
D) inorganic proton exchange film preparation: the inorganic proton conductive powder presoma of step c) preparation is placed culture dish, 35 ℃～45 ℃ following heat treatment is 7～10 days in drying box, then 350 ℃～400 ℃ following high-temperature calcinations of temperature 1～2 hour, obtain the inorganic proton conductive powder, this inorganic proton conductive powder of milling, add with inorganic proton conductive powder weight ratio be that thermoplastic resin binder's hot pressing of 1: 10～3: 10 is prepared into inorganic proton exchange film;
2) inorganic proton exchange film---the preparation of Catalytic Layer assembly: with catalyst, inorganic proton conductive powder, thermoplastic resin binder, electrically conductive material mix mixture, in mixture, catalyst, inorganic proton conductive powder, thermoplastic resin binder, the shared percentage by weight of electrically conductive material are: catalyst 10～50%, inorganic proton conductive powder 10～40%, electrically conductive material 10～30%, thermoplastic resin binder 10～20%; Mixture spreads upon the centre position of inorganic proton exchange film, and thickness is 5～30 microns, reserves 1～10 millimeter around the inorganic proton exchange film and is used for sealing; Then, N
2The following 200 ℃ of heat treatments of gas shiled 3～10 minutes;
3) inorganic proton exchange film---the sealing of Catalytic Layer assembly: adopt air-tightness polymer or polymer modification material good, that be adapted to work more than 200 ℃ to be used for sealing as encapsulant, in preparation process, encapsulant directly is applied in the position of reserving around the inorganic proton exchange film;
Described air-tightness is good, be adapted to the polymer of working more than 200 ℃ or polymer modification material is any in poly tetrafluoroethylene, silicon rubber, modified organic silicone resin lacquer W61-55,600# organosilicon heat-resistant lacquer, the 800# organosilicon heat-resistant lacquer;
4) preparation of inorganic proton exchange film fuel cell film pole: at the inorganic proton exchange film of good seal---direct blanket gas diffusion layer promptly obtains inorganic proton exchange film fuel cell film pole on the Catalytic Layer.
2. the preparation method of a kind of inorganic proton exchange film fuel cell film pole according to claim 1, it is characterized in that: described heteropoly acid is that central atom is P, Si or S, and coordination atom is at least a element among W, Mo and the V.
3. the preparation method of a kind of inorganic proton exchange film fuel cell film pole according to claim 1, it is characterized in that: described surfactant is cationic surfactant CTAB, or is among non-ionic surface active agent F108, F127, P123, the P56 any one.
4. the preparation method of a kind of inorganic proton exchange film fuel cell film pole according to claim 1 is characterized in that: described thermoplastic resin binder any in polyether sulfone, polyphenylene oxide ketone, polyphenylene sulfide, polyamidoimide, the Kynoar.
5. the preparation method of a kind of inorganic proton exchange film fuel cell film pole according to claim 1, it is characterized in that: described electrically conductive material is carbon black or graphite.
6. the preparation method of a kind of inorganic proton exchange film fuel cell film pole according to claim 1, it is characterized in that: described diffusion layer is carbon paper, carbon fiber felt or carbon cloth.
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| CN105655610B (en) * | 2014-12-01 | 2018-02-06 | 中国科学院大连化学物理研究所 | The ultra-thin Catalytic Layer adhered on a kind of anion-exchange membrane and its preparation and application |
| CN111063924B (en) * | 2019-12-27 | 2022-10-14 | 先进储能材料国家工程研究中心有限责任公司 | Transition layer slurry for membrane electrode, preparation method of transition layer slurry, membrane electrode and preparation method of membrane electrode |
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| CN1461070A (en) * | 2003-05-19 | 2003-12-10 | 清华大学 | Method for preparing heat-resisting proton exchange film |
| WO2005045976A1 (en) * | 2003-11-06 | 2005-05-19 | Renault S.A.S | Ion-conducting composite membranes |
| CN1901263A (en) * | 2005-07-12 | 2007-01-24 | 三星Sdi株式会社 | Ion conductive composite membrane using inorganic conductor and method of manufacturing the same |
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| CN1461070A (en) * | 2003-05-19 | 2003-12-10 | 清华大学 | Method for preparing heat-resisting proton exchange film |
| WO2005045976A1 (en) * | 2003-11-06 | 2005-05-19 | Renault S.A.S | Ion-conducting composite membranes |
| CN1901263A (en) * | 2005-07-12 | 2007-01-24 | 三星Sdi株式会社 | Ion conductive composite membrane using inorganic conductor and method of manufacturing the same |
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| 杂多酸掺杂聚酰亚胺/二氧化硅复合质子交换膜的制备和性能研究. 浦鸿汀，侯继斅，杨正龙.功能材料，第36卷第12期. 2005 |
| 杂多酸掺杂聚酰亚胺/二氧化硅复合质子交换膜的制备和性能研究. 浦鸿汀，侯继斅，杨正龙.功能材料，第36卷第12期. 2005 * |
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