CN101942672A - Preparation method of polymer electrolyte membrane electrode - Google Patents
Preparation method of polymer electrolyte membrane electrode Download PDFInfo
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- CN101942672A CN101942672A CN 201010285500 CN201010285500A CN101942672A CN 101942672 A CN101942672 A CN 101942672A CN 201010285500 CN201010285500 CN 201010285500 CN 201010285500 A CN201010285500 A CN 201010285500A CN 101942672 A CN101942672 A CN 101942672A
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Abstract
The invention relates to a preparation method of a polymer electrolyte membrane electrode, which belongs to the technical field of preparation of fuel cells in the electrochemical industry. The preparation method comprises the steps of firstly heating a polymer electrolyte membrane to the glass transition temperature, and leading the polymer electrolyte membrane to achieve the viscous flow state approaching melting; further configuring mixture of a catalytic layer to slurry according to a certain proportion, and preparing a membrane electrode three-in-one component which consists of the catalytic layer/the polymer electrolyte membrane/the catalytic layer and is formed on two sides of the polymer electrolyte membrane; and then heat-pressing a diffusion layer after pretreatment and the three-in-one component to form a five-in-one membrane electrode component with the diffusion layer. The preparation method can overcome the problems of low performances of the membrane electrode, poor stability, short service life and the like caused by swelling of a proton exchange membrane in the traditional preparation of the membrane electrode by adopting the fixed proton exchange membrane formed by the heat-setting method, lead the binding between a catalyst and the proton exchange membrane to be closer, further improve the adhesion and the binding force of the catalyst, further improve the comprehensive performances of the membrane electrode and prolong the service life of the membrane electrode.
Description
Technical field
The present invention relates to a kind of preparation method of electrolyte film-electrode, be suitable for the preparation of the membrane electrode of Proton Exchange Membrane Fuel Cells (PEMFC), direct methanol fuel cell (DMFC), alkaline fuel cell (AFC) and water electrolysis hydrogen production device and regenerative fuel cell electrochemical appliances such as (RFC).
Background technology
Fuel cell is converted into efficient, the eco-friendly power generation assembly of electric energy with chemical energy by the mode of electrochemical reaction as a kind of, has broad application prospects at aspects such as middle-size and small-size power station, power truck and compact powers.The inverse process water electrolysis hydrogen production device of fuel cell can prepare the high-purity hydrogen that does not contain carbon monoxide, sulfide and nitride very expediently from water simultaneously, just is being widely used in civilian industry and national defense industry fields such as space flight, nuclear industry such as chemical industry, the energy, electronics, metallurgy, food, machinery.Fuel cell power generating system and water electrolysis hydrogen production device all need high performance, stable and long-life core component---membrane electrode, for avoiding liquid electrolyte to run off and strong shortcomings such as corrodibility, the polymer dielectric film electrode toggle speed that with the polymer dielectric film is core is fast, good stability, advantages such as the life-span is long have good application prospects.The performance quality key of the power generation assembly of use polymer dielectric or electrolyzer is the microtexture and the composition composition of core component membrane electrode, and the microtexture of membrane electrode and composition composition depend on manufacture craft, and membrane electrode preparation method has determined the performance of membrane electrode largely.At present, mainly concentrate on raising noble metal catalyst utilization ratio, reduce catalyst loading, improve the output power density of membrane electrode and prolong working life about polymer dielectric film electrode preparation method and technology.
Pressure sintering is adopted in early stage membrane electrode preparation usually, being about to two uses polytetrafluoroethylene (PTFE) to be positioned over the proton exchange membrane both sides as the porous gas diffusive electrode of binding agent, hot pressing forms hydrophobic film electrode five in one assembly in 130～150 ℃ of temperature ranges, perhaps two porous gas diffusive electrode and proton exchange membrane hot pressings of adopting perfluorinated sulfonic resin to substitute the PTFE binding agent is got the hydrophilic film electrode.After the nineties in 20th century, many scholars begin to attempt to prepare the three in one membreane electrode assembly of being made up of Catalytic Layer/proton exchange membrane/Catalytic Layer based on proton exchange membrane, it is CCM (catalyst coated membrane) method, mainly can be summarized as two general orientation: the one, the slurry that preparation earlier is made up of catalyzer, resin solution and dispersion agent, be uniformly dispersed the back preparation on the transfer medium surface, and then transfer on the proton exchange membrane surface, be called indirect method usually, also be transfer method.People such as Wilson have proposed indirect CCM method than earlier,, peel off the PTFE film and make CCM with proton exchange membrane hot pressing by two PTFE films that have Catalytic Layer; Other method is for avoiding the troublesome operation of indirect CCM multiple operation, enhance productivity, further develop under the background of reduction precious metal carrying capacity, after soon the slurry of being made up of catalyzer, resin solution and dispersion agent was uniformly dispersed, directly preparation (sputter, spraying, printing, roll extrusion etc.) was to proton exchange membrane two surfaces.Introduced a kind of preparation method of three-in-one membrane electrode assembly as patent documentation CN1269428A, it adopts the powder direct heat of a certain proportion of catalyzer and proton conductor polymkeric substance to be pressed in and forms three-in-one component on the proton exchange membrane; U.S. Pat 5415888 has been introduced a kind of preparation method of membrane-membrane electrode for fuel cell, and it will consist of catalyzer, proton conductor polymers soln, alcohol organic solvent and be made into the brushing of ink shape solution by a certain percentage and form three in one membreane electrode on polymer dielectric film; U.S. Pat 6720106 adopts the preparation method who directly the catalysis slip is sprayed on the proton exchange membrane, and the current density of prepared monocell when 0.5V is 1A/cm
2The tiling of proton exchange membrane is technological difficulties in this direct CCM method making processes, and the proton exchange membrane that how to tile is the key of direct CCM method technology.Usually adopt modes such as vacuum pad and framework to fix the tiling proton exchange membrane in practice, but actual effect is all undesirable, it is insufficient with contacting of granules of catalyst that the swelling of proton exchange membrane can cause, and catalyst distribution is inhomogeneous, and performance is lower.Problems such as Catalytic Layer and proton exchange membrane combination stability difference and vacuum are inhaled and frame fixation also may produce physical damage to proton exchange membrane, have caused the membrane electrode over-all properties lower, and the life-span is short.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of new polymer dielectric film electrode, to overcome in the prior art because the proton exchange membrane swelling causes the membrane electrode performance to reduce, problems such as poor stability and work-ing life are short, make the prepared polymer dielectric film electrode that goes out of this method can not cause the phenomenon of proton exchange membrane generation swelling crumple, and granules of catalyst is fully contacted with proton exchange membrane, thereby increase the sticking power and the bonding force of catalyzer, improve the utilization ratio of catalyzer, and then the over-all properties of raising membrane electrode, and prolong its use long lifetime.
Technical scheme of the present invention is as follows:
A kind of preparation method of polymer dielectric film electrode is characterized in that this method prepares as follows:
1) polymer dielectric film pre-treatment: polymer dielectric film is tiled on the substrate, and is heated to second-order transition temperature, polymer dielectric film is reached near fused viscosity flow state;
2) preparation catalyst mixture: with catalyzer, polymer electrolyte and dispersant, after sonic oscillation disperses, form homodisperse catalyst mixture, wherein, catalyzer: polymer electrolyte: the mass ratio of dispersion agent=1: 0.1～10: 2～500;
3) catalyst mixture for preparing is prepared equably the both sides of pretreated polymer dielectric film in step 1), form the three in one membreane electrode assembly that both sides are loaded with Catalytic Layer;
4) preparation diffusion layer: carbon paper, carbon cloth or carbon felt after ptfe emulsion soaks, dries, at 200-500 ℃ of sintering, are prepared the thin layer that contains tetrafluoroethylene and toner mixture then on a side surface, form diffusion layer at 200-500 ℃ of sintering again; Or directly adopting metal polyporous material as diffusion layer, described metal polyporous material is stainless (steel) wire, titanium net or nickel screen;
5) diffusion layer for preparing in the step 4) is placed on the both sides of the three in one membreane electrode for preparing in the step 3), at 80 ℃-650 ℃, 0-500kg/cm
2Condition under hot pressing 0-60 minute, form five in one polymer dielectric film electrode.
In the technique scheme, in the polymer dielectric film preprocessing process described in the step 1), polymer dielectric film is heated in the scope of second-order transition temperature ± 20 degree.Preparation process in the described step 3) comprises curtain coating, printing or spraying.
Between 5～500 microns of the thickness of the polymer dielectric film described in the present invention.Polymer electrolyte is perfluorinated sulfonic acid polymer electrolyte or sour doping polybenzimidazole polymer electrolyte.Described catalyzer is Pt, Ru, Ir, Au, Ni, Co, Zn, Ag or their alloy and oxide compound.
The present invention compares with documents, has the following advantages and the high-lighting effect: make dielectric film show viscosity flow character
The present invention is in preparation process, by polymer dielectric film is heated to second-order transition temperature, polymer dielectric film is reached near fused viscosity flow state, this kind state can be caught catalyzer well, thereby improved the bonding force between polymer dielectric film and the catalyzer, simultaneously can reach catalyst loading and the gradient of necessarily successively decreasing be arranged along the polymer dielectric film direction, and polymer electrolyte has certain incremental gradient, can expand the electrochemistry three-dimensional structure of membrane electrode like this, help reducing ion, electronics, the resistance to mass transfer of reactive material and product, increase the best electrochemical reaction district between Catalytic Layer and the polymer dielectric film effectively, improved the utilization ratio of catalyzer.By the prepared polymer dielectric film electrode of this method the multi phase interface of reactive fuel, oxygenant, water, catalyzer and electronics is strengthened, thereby catch more electronics and active ion, improved the electrical property of unit electrode activity area, in conjunction with fine and close Catalytic Layer and polyelectrolyte floor electrolytical fuel transmitance is reduced greatly simultaneously, the service efficiency (generating) or the productive rate (electrolysis) of fuel have been improved, simultaneously also help promoting battery operated open circuit voltage, or increase electrolytic current efficiency.The polymer dielectric film electrode that method of the present invention is prepared, effectively overcome in the prior art owing to proton exchange membrane swelling caused contacts insufficient, the low defective of the inhomogeneous performance that causes of catalyst distribution with granules of catalyst, make between catalyzer and the dielectric film and can produce firm bonding force, thereby have advantages such as advantages of excellent stability and long lifetime.
Description of drawings
The electrical property figure of the polymer dielectric film electrode of the present invention that Fig. 1 uses for fuel cell.
Fig. 2 is the electrical property figure of direct sodium borohydride fuel cell with polymer dielectric film electrode of the present invention.
Fig. 3 for the SPE water electrolysis hydrogen production with polymer dielectric film electrode electrical property figure of the present invention.
Embodiment
The preparation method of polymer dielectric film electrode provided by the invention, adopt " heat setting type method " fixedly proton exchange membrane, soon proton exchange membrane is tiled in and is heated to second-order transition temperature on the substrate, generally polymer dielectric film is heated in the scope of second-order transition temperature ± 20 degree; Proton exchange membrane is near fused viscosity flow state, carries out curtain coating, printing or the spraying of catalyst pulp again.Solvent in the catalyst pulp is the moment volatilization at high temperature; can not cause proton exchange membrane generation swelling to become the phenomenon of fold; and; granules of catalyst can fully contact with the proton exchange membrane near molten state; can make catalyzer and proton exchange membrane in conjunction with more tight; increase the bonding strength of membrane electrode assembly, improve the sticking power and the bonding force of catalyzer, electrode structure is more optimized.Concrete processing step of the present invention is as follows:
1) polymer dielectric film is tiled in carries out heat pre-treatment on the substrate, Heating temperature reaches in the scope of polymer dielectric film second-order transition temperature ± 20 degree; The thickness of polymer dielectric film is generally between 5-500 μ m.
2) preparation catalyst mixture: with catalyzer, polymer electrolyte and dispersant, after sonic oscillation disperses, form homodisperse catalyst mixture, wherein, catalyzer: polymer electrolyte: the mass ratio of dispersion agent=1: (0.1-10): (2-500); Catalyzer of the present invention is Pt, Ru, Ir, Au, Ni, Co, Zn, Ag or their alloy and oxide compound.Described polymer electrolyte is perfluorinated sulfonic acid polymer electrolyte or sour doping polybenzimidazole polymer electrolyte.
3) catalyst mixture for preparing is prepared equably on the surface of the hot polymer dielectric film described in the step 1), form the three in one membreane electrode assembly that both sides are loaded with Catalytic Layer; Wherein method can not adopt curtain coating, printing or spraying.
4) preparation diffusion layer: adopt carbon paper, carbon cloth or carbon felt, soak through ptfe emulsion, strengthen hydrophobicity at 200-500 ℃ of sintering again, on the one side surface, prepare the thin layer that one deck contains tetrafluoroethylene and toner mixture again, form diffusion layer at 200-500 ℃ of sintering then; Or directly adopting metal polyporous material as diffusion layer, described metal polyporous material is stainless (steel) wire, titanium net or nickel screen;
5) diffusion layer for preparing in the step 4) is placed on the both sides of the three in one membreane electrode for preparing in the step 3), at 80 ℃-650 ℃, 0-500kg/cm
2Condition under hot pressing 0-60 minute, form five in one polymer dielectric film electrode.
Below by several specific embodiments method of the present invention is described further.
Embodiment 1:
Select the perfluorinated sulfonic resin film of 50 micron thickness for use, be fixed on the porous stainless steel plate and be heated to 120 and spend (second-order transition temperature is 135 degree), and keep slowly heating, keep the viscosity flow state.The Pt/C that takes by weighing (40%) catalyzer, 5% perfluorinated sulfonic resin and Virahol, make the Pt/C catalyzer: perfluorinated sulfonic resin: the mass ratio of Virahol is 1: 10: 500, sonic oscillation formed catalyst solution to be sprayed in 8 minutes, got this solution of 1.000g with 500ml.min
-1.cm
-2The speed curtain coating on above-mentioned polymer dielectric film, meanwhile, the commercialization carbon paper is immersed in 30% the PTFE emulsion 1 minute, formed hydrophobic carbon paper in 90 minutes with being placed on 340 ℃ of retort furnace sintering, the carbon dust paste that will contain 10%PTFE is coated on the good carbon paper of hydrophobic treatment, and coating carbon dust carrying capacity is 1.0mg/cm
2, will scribble the gas diffusion layers of carbon-coating at last and be sprayed with the proton exchange membrane of Catalytic Layer at 80 ℃ and 200kg/cm
2Pressure under hot pressing 60 minutes form membrane electrode, membrane electrode is placed between two carbon plates that are carved with serpentine flow path, adopting two duralumin anchor clamps to be assembled into monocell, is 160 ℃ at battery temperature, and gaseous tension is to carry out the test of battery polarization curve under the non-pressurized condition.Battery performance is seen Fig. 1.
Embodiment 2:
Select the acid doping polybenzimidazole membrane of 60 micron thickness for use, be fixed on the porous stainless steel plate and be heated to 420 and spend (second-order transition temperature is 430 degree), and keep slowly heating, keep the viscosity flow state.The Pt/C that takes by weighing (40%) catalyzer, 5% polybenzimidazole film resin and Virahol, make the Pt/C catalyzer: sour doping polybenzimidazole resin: the mass ratio of Virahol is 1: 10: 500, sonic oscillation formed catalyst solution to be sprayed in 8 minutes, got this solution of 1.000g with 100ml.min
-1.cm
-2The speed curtain coating on above-mentioned sour doping polybenzimidazole membrane, meanwhile, the commercialization carbon paper is immersed in 30% the PTFE emulsion 1 minute, formed hydrophobic carbon paper in 90 minutes with being placed on 340 ℃ of retort furnace sintering, the carbon dust paste that will contain 10%PTFE is coated on the good carbon paper of hydrophobic treatment, and coating carbon dust carrying capacity is 1.0mg/cm
2, will scribble the gas diffusion layers of carbon-coating at last and be sprayed with the proton exchange membrane of Catalytic Layer at 80 ℃ and 200kg/cm
2Pressure under hot pressing 60 minutes form membrane electrode, membrane electrode being placed between two carbon plates that are carved with serpentine flow path, adopt two duralumin anchor clamps to be assembled into monocell, is 160 ℃ at battery temperature, and gaseous tension is to test under the non-pressurized condition, and maximum power density can reach 300mW/cm
2
Embodiment 3:
Select 25 microns perfluorinated sulfonic acid proton exchange membrane for use, be fixed on the porous stainless steel plate and to be heated to 115 degree (second-order transition temperature be 135 degree) standby.Take by weighing Pt/C (the containing 40%Pt) catalyzer of 0.500g, 5% perfluorinated sulfonic resin of 1.000g and the aqueous isopropanol of 1.000g, make the Pt/C catalyzer: perfluorinated sulfonic resin: the mass ratio of Virahol is 1: 0.1: 2.Formed the watery material of catalyst ink to be sprayed in ultrasonic 8 minutes, the employing airbrush is that the air of 0.1MPa is carrier gas with the relative pressure, with 0.02ml.min
-1.cm
-2Speed be painted on the above-mentioned proton exchange membrane.Meanwhile, the commercialization carbon paper is immersed in 20% the PTFE emulsion 5 minutes, formed hydrophobic carbon paper in 60 minutes with being placed on 340 ℃ of retort furnace sintering, the carbon dust paste that will contain 20%PTFE is coated on the good carbon paper of hydrophobic treatment, and coating carbon dust carrying capacity is 1.0mg/cm
2The proton exchange membrane that will scribble the gas diffusion layers of carbon dust at last and be sprayed with perfluorinated sulfonic resin layer and Catalytic Layer hot pressing under the pressure of 140 ℃ and 5MPa formed membrane electrode in 2 minutes, membrane electrode is placed between two carbon plates that are carved with serpentine flow path, adopt two duralumin anchor clamps to be assembled into monocell, at battery temperature is 60 ℃, and hydrogen and air moistening temperature are that 40 ℃ and gaseous tension are to carry out the test of battery polarization curve under the non-pressurized condition.The maximum power density of battery can reach 400mW/cm
2
Embodiment 4:
Select 5.0cm for use
2Thickness is 500 microns proton exchange membrane, and being heated to its second-order transition temperature is that 135 degree are standby.Adopt the one-level balance to take by weighing 5% perfluor sulfoacid resin solution 0.040g, add the ethanol of 2.000g afterwards, thorough mixing evenly becomes perfluorinated sulfonic resin layer solution to be painted, and the air of getting this solution 0.250g and with the relative pressure be 1MPa is carrier gas, with 0.1ml.min
-1.cm
-2Speed be sprayed on the above-mentioned proton exchange membrane.Take by weighing Pt black catalyzer, 5% perfluorinated sulfonic resin of 1.650g and the aqueous isopropanol of 20.000g of 0.300g, in the ultrasonic cleaning instrument, formed cathod catalyst ink shape material to be sprayed in ultrasonic 8 minutes, get this miscellany of 1.000g with 0.1ml.min
-1.cm
-2Speed be sprayed on both sides and be loaded with on the side surface of proton exchange membrane of perfluorinated sulfonic resin layer; Then, take by weighing Pt-Ru/C black catalyzer, 5% perfluorinated sulfonic resin of 1.650g and the aqueous isopropanol of 20.000g of 0.300g, ultrasonic 8 minutes formation anode catalyst ink shape materials to be sprayed in the ultrasonic cleaning instrument, the helium of getting this miscellany of 1.000g and with the relative pressure be 1MPa is carrier gas, with 0.02ml.min
-1.cm
-2Speed be sprayed on both sides and be loaded with on the opposite side surface of proton exchange membrane of perfluorinated sulfonic resin layer.Meanwhile, the commercialization carbon paper is immersed in 40% the PTFE emulsion 5 minutes, formed hydrophobic carbon paper in 50 minutes with being placed on 340 ℃ of retort furnace sintering, the carbon dust paste that will contain 25%PTFE is coated on the good carbon paper of hydrophobic treatment, and coating carbon dust carrying capacity is 1.5mg/cm
2, will scribble the gas diffusion layers of carbon-coating at last and be sprayed with the proton exchange membrane of perfluorinated sulfonic resin layer and Catalytic Layer at 150 ℃ and 500kg/cm
2Pressure under hot pressing 2 minutes form the five in one membrane electrode.Membrane electrode being placed between two carbon plates that are carved with serpentine flow path, adopt two duralumin anchor clamps to be assembled into monocell, is 60 ℃ at battery temperature, is that fuel and atmospheric air are to carry out the test of battery polarization curve under the condition of oxygenant with methyl alcohol.Maximum power density can reach 100mW/cm
2
Embodiment 5:
Select 5.0cm for use
2Thickness is 175 microns sodium ion-exchange membrane, is heated to second-order transition temperature 150 and spends standby.Adopt the one-level balance to take by weighing 5% perfluor sulfoacid resin solution 0.500g and the sodium hydroxide solution 0.5000g of 0.05M, the Virahol that adds 4.000g afterwards, full and uniformly be mixed into sodium perfluor sulfoacid resin solution to be sprayed, get this solution of 0.500g with 0.1ml.min
-1.cm
-2Speed be sprayed on the above-mentioned sodium ion exchange membrane, take by weighing 5% perfluor sulfoacid resin solution of 0.180g, sodium hydroxide solution and the Virahol of 4.000g and the Co catalyst preparation anode catalyst slurry of 0.030g of 0.05M; Take by weighing 5% perfluor sulfoacid resin solution of 0.180g, sodium hydroxide solution and the Virahol of 4.000g and the MnO of 0.030g of 0.05M
2Preparation of Catalyst cathod catalyst slurry formed the watery material of catalyst ink to be sprayed in ultrasonic 8 minutes, respectively with 0.02ml.min in the ultrasonic cleaning instrument
-1.cm
-2Speed be sprayed on the sodium ion exchange membrane both sides that both sides are loaded with sodium type perfluorinated sulfonic resin layer.Shear carbon paper simultaneously with the area Catalytic Layer, hot pressing formed membrane electrode in 8 minutes under the pressure of 135 ℃ and 5MPa, membrane electrode is placed between two carbon plates that are carved with serpentine flow path, adopt two stainless steel anchor clamps to be assembled into monocell, anode fuel adopts the NaBH of 0.5M
4Alkali (NaOH concentration is 2.0M) solution is as anodolyte solution, and negative electrode adopts the H of 6.0M
2O
2As oxygenant, be 60 ℃ at battery temperature and carry out the performance test of direct sodium borohydride fuel cell membrane electrode that performance is seen Fig. 2.
Embodiment 6:
Select 5.0cm for use
2Thickness is 175 microns sodium ion-exchange membrane, is heated to second-order transition temperature 150 and spends standby.Take by weighing 5% perfluor sulfoacid resin solution of 0.180g, sodium hydroxide solution and the Virahol of 4.000g and the Au catalyst preparation anode catalyst slurry of 0.030g of 0.05M; Take by weighing 5% perfluor sulfoacid resin solution of 0.180g, sodium hydroxide solution and the Virahol of 4.000g and the Ag catalyst preparation cathod catalyst slurry of 0.030g of 0.05M, in the ultrasonic cleaning instrument, formed the watery material of catalyst ink in ultrasonic 8 minutes, be printed on respectively on the above-mentioned ion-exchange membrane surface.Shear carbon paper simultaneously with the area Catalytic Layer, hot pressing formed membrane electrode in 10 minutes under the pressure of 145 ℃ and 10MPa, membrane electrode is placed between two carbon plates that are carved with parallel fluid channels, adopt two stainless steel anchor clamps to be assembled into monocell, anode fuel adopts the NaBH of 0.5M
4Alkali (NaOH concentration is 2.0M) solution is as anodolyte solution, and negative electrode adopts the H of 6.0M
2O
2As oxygenant, be 60 ℃ at battery temperature and carry out the performance test of direct sodium borohydride fuel cell membrane electrode that maximum power density can reach 110mW/cm
2
Embodiment 7.
Select 5.0cm for use
2Thickness is 175 microns sodium ion-exchange membrane, is heated to second-order transition temperature 150 and spends standby.The mixture of 0.180g5% perfluorinated sulfonic resin, 0.05MNaOH solution and 4.000g Virahol is joined black anode catalyst of Pt and the 0.030g IrO of the 0.030g that has taken by weighing respectively
2In the cathod catalyst, in the ultrasonic cleaning instrument, formed the watery material of catalyst ink to be sprayed in ultrasonic 8 minutes, with 0.1ml.min
-1.cm
-2Speed be sprayed on respectively on the above-mentioned ion-exchange membrane surface, afterwards membrane electrode is placed 80 ℃ 0.5M H
2SO
4Carry out protonated processing 120 minutes in the solution, shear titanium net simultaneously, directly overlay above-mentioned membrane electrode two sides, form SPE electrolyzer membrane electrode with the area Catalytic Layer.Mea is dressed up the water electrolysis hydrogen production device, by micropump supply deionized water, carry out the performance test experiment at 80 ℃, performance is seen Fig. 3.
Embodiment 8.
Select 5.0cm for use
2Thickness is the proton exchange membrane of 175 μ m, and it is standby to be heated to 130 degree (second-order transition temperature be 135 degree).The mixture of 0.180g 5% perfluorinated sulfonic resin and 4.000g Virahol is joined black anode catalyst of Pt and the 0.030g IrO of the 0.030g that has taken by weighing respectively
2+ RuO
2In the cathod catalyst, in the ultrasonic cleaning instrument, formed the watery material of catalyst ink to be sprayed in ultrasonic 8 minutes, with 0.1ml.min
-1.cm
-2Speed be sprayed on respectively on the above-mentioned proton exchange membrane both side surface, shear stainless (steel) wire simultaneously with the area Catalytic Layer, directly overlay above-mentioned membrane electrode two sides, form SPE electrolyzer membrane electrode.Mea is dressed up the water electrolysis hydrogen production device,, carry out the performance test experiment at 80 ℃ by micropump supply deionized water.At electrolytic current density is 1A/cm
2Condition under, electrolysis voltage is 1.78V.
Claims (6)
1. the preparation method of a polymer dielectric film electrode is characterized in that this method prepares as follows:
1) polymer dielectric film pre-treatment: polymer dielectric film is tiled on the substrate, and is heated to second-order transition temperature, polymer dielectric film is reached near fused viscosity flow state;
2) preparation catalyst mixture: with catalyzer, polymer electrolyte and dispersant, after sonic oscillation disperses, form homodisperse catalyst mixture, wherein, catalyzer: polymer electrolyte: the mass ratio of dispersion agent=1: 0.1～10: 2～500;
3) catalyst mixture for preparing is prepared equably the both sides of pretreated polymer dielectric film in step 1), form the three in one membreane electrode assembly that both sides are loaded with Catalytic Layer;
4) preparation diffusion layer: carbon paper, carbon cloth or carbon felt after ptfe emulsion soaks, dries, at 200-500 ℃ of sintering, are prepared the thin layer that contains tetrafluoroethylene and toner mixture then on a side surface, form diffusion layer at 200-500 ℃ of sintering again; Or directly adopting metal polyporous material as diffusion layer, described metal polyporous material is stainless (steel) wire, titanium net or nickel screen;
5) diffusion layer for preparing in the step 4) is placed on the both sides of the three in one membreane electrode for preparing in the step 3), at 80 ℃-650 ℃, 0-500kg/cm
2Condition under hot pressing 0-60 minute, form five in one polymer dielectric film electrode.
2. according to the preparation method of the described polymer dielectric film electrode of claim 1, it is characterized in that: in the polymer dielectric film preprocessing process described in the step 1), polymer dielectric film is heated in the scope of second-order transition temperature ± 20 degree.
3. according to the preparation method of the described polymer dielectric film electrode of claim 1, it is characterized in that: the preparation process in the step 3) comprises curtain coating, printing or spraying.
4. according to the preparation method of the described polymer dielectric film electrode of claim 1, it is characterized in that: the thickness of described polymer dielectric film is between 5～500 microns.
5. according to the preparation method of the described polymer dielectric film electrode of claim 1, it is characterized in that: described polymer electrolyte is perfluorinated sulfonic acid polymer electrolyte or sour doping polybenzimidazole polymer electrolyte.
6. according to the preparation method of the described polymer dielectric film electrode of claim 1, it is characterized in that: described catalyzer is Pt, Ru, Ir, Au, Ni, Co, Zn, Ag or their alloy and oxide compound.
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| CN107881528A (en) * | 2016-09-29 | 2018-04-06 | 中国科学院大连化学物理研究所 | The preparation and membrane electrode and application of a kind of electrolytic cell membrane electrode |
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| CN110797539A (en) * | 2019-09-24 | 2020-02-14 | 东莞市魔方新能源科技有限公司 | Preparation method of hydrogen fuel cell membrane electrode and hydrogen fuel cell membrane electrode |
| CN111204851A (en) * | 2020-01-17 | 2020-05-29 | 陕西科技大学 | Graphite felt/porous carbon rolled electrode material, preparation method thereof and application thereof in jet reactor |
| CN112813460A (en) * | 2020-12-28 | 2021-05-18 | 同济大学 | Membrane electrode activation method for SPE electrolytic cell, application and electrolytic cell structure |
| CN112877724A (en) * | 2021-01-12 | 2021-06-01 | 万华化学集团股份有限公司 | Preparation method of polymer electrolyte membrane electrode and method for preparing dimethyl sebacate through electrolysis |
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