CN112599792B - Preparation method of fuel cell membrane electrode catalyst layer - Google Patents
Preparation method of fuel cell membrane electrode catalyst layer Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8668—Binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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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 belongs to the field of fuel cell membrane electrode preparation, in particular to a fuel cell membrane electrode catalyst layer coating uniformity control method, which comprises the preparation of catalyst slurry and the setting of a coating process, wherein the catalyst slurry comprises solid catalyst particles, a binder, a dispersant and a stabilizer; the method comprises the following steps: mixing solid catalyst particles and a dispersing agent, and adding Na+The formed binder is dispersed by ultrasonic oscillation and high-speed stirring to prepare catalyst slurry; in the coating process, a catalyst layer is prepared by controlling coating thickness, coating speed, coating pressure, coating die head retreat, drying tunnel temperature and other coating processes, and the thickness and uniformity of the catalyst layer are controlled; the catalyst layer prepared by the method disclosed by the invention is excellent in electrochemical performance, thin and uniform, the usage amount of the catalyst is reduced, the cost is saved, and the yield is improved.
Description
Technical Field
The invention relates to a method for controlling the coating uniformity of a catalyst layer of a membrane electrode of a fuel cell, belonging to the field of preparation of membrane electrodes of fuel cells.
Background
A fuel cell is a power generation device that can directly convert chemical energy contained in hydrogen fuel and an oxidant into electric energy and reaction products. Proton exchange membrane fuel cells are receiving attention because of their high stability, no pollution, low noise, and high energy conversion rate.
The key component of the proton exchange membrane fuel cell, namely the electrode part, is the place where the chemical reaction inside the cell occurs, and the preparation mode and the electrode structure of the electrode are the research hotspots in recent years. In the electrode preparation process, the catalyst layer is directly prepared on the gas diffusion layer to form a gas diffusion electrode; or preparing the catalyst layer on the proton exchange membrane directly to form a proton exchange membrane electrode; the uniformity and microstructure of the electrodes directly affect the use of the fuel cell. In the preparation process of the electrode at present, a spraying method is a common preparation method, a prepared catalyst layer is uniform and compact, but the efficiency is low, and a large amount of catalyst is wasted due to spraying airflow; the coating method can effectively solve the defect of low electrode production efficiency, but the prepared electrode often has irreversible damages such as white leakage, cracks, falling and the like on a catalyst layer due to slurry and a process.
In the preparation process of the catalyst layer, the preparation of the catalyst slurry and the dispersion degree liquid directly affect the uniformity and the electrochemical performance of the catalyst layer, people usually adopt a complicated processing mode to prepare the catalyst slurry, for example, a series of additives such as an anti-precipitation agent and a thickening agent are added, the addition of the additives not only makes the dispersion process of the catalyst slurry more difficult, but also leaves the catalyst layer in the preparation process of the catalyst layer, not only affects the electrochemical performance of the catalyst layer, increases the internal resistance of the battery, reduces the transmission efficiency, causes the catalyst layer to have the phenomena of non-uniformity, perforation, cracks and the like, and even possibly has adverse effects on the proton exchange membrane, affects the mechanical strength of the membrane and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a fuel cell membrane electrode catalysis layer, which is used for controlling the uniformity of the catalysis layer from two aspects of catalyst slurry preparation and continuous coating.
In order to realize the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a membrane electrode catalyst layer of a fuel cell, which is characterized by comprising the following steps:
(1) mixing solid catalyst particles and a dispersing agent, and dispersing for 10-30min by ultrasonic oscillation to form a uniform mixed solution; adding stabilizer, dispersing for 10-30min by ultrasonic oscillation and dispersing for 30-60min by high speed stirring to form uniform mixed solution;
(2) adding 1mol/L NaOH solution into the adhesive, wherein the ratio of the molar weight of NaOH to the molar weight of sulfonate in the adhesive is 0.1-2:1, and adding Na into the adhesive+Patterning from H+Form is converted into Na+Molding;
(3) passing the solution obtained in the step (2) through Na+Adding the formed binder into the mixed solution in the step (1), ultrasonically oscillating, and stirring and dispersing at a high speed for 60-100min to prepare catalyst slurry;
the mass ratio of the solid catalyst particles to the binder to the dispersant to the stabilizer is 1-3:7-11:30-50: 20-35;
(4) and (4) coating the catalyst slurry obtained in the step (3) on a proton exchange membrane to obtain the catalyst layer.
In the above technical solution, further, the coating in the step (4) includes the following steps:
(A) loading the catalyst slurry prepared in the step (1) into a coating die head in continuous coating equipment, and tensioning and placing a proton exchange membrane coil in a conveying mechanism in the continuous coating equipment;
(B) coating the proton exchange membrane coiled material in conveying by the coating die head, stopping feeding every time the coating die head finishes coating, and then retreating along the vertical direction of the proton exchange membrane coiled material;
(C) c, vertically advancing the coating die head in the step B to a position close to the proton exchange membrane coiled material, and then feeding the coating die head to realize the next coating of the proton exchange membrane;
(D) repeating the steps C-D to realize the intermittent coating of the proton exchange membrane and form a proton exchange membrane electrode with a catalyst layer;
(E) and D, drying the proton exchange membrane electrode obtained in the step D.
In the above technical solution, further, the solid catalyst particles are a carbon-supported Pt catalyst or a carbon-supported Pt alloy catalyst, wherein the content of Pt in the carbon-supported Pt catalyst or the carbon-supported Pt alloy catalyst is 20 to 80 wt%.
In the above technical solution, the binder is selected from one or more of 5-20wt% of perfluorinated sulfonic acid resin solution, 1-20wt% of sulfonated polyether ether ketone resin solution, 1-20wt% of sulfonated trifluorostyrene resin solution, and 1-20wt% of polymethylphenylsulfonic acid siloxane resin solution.
In the above technical solution, further, the dispersant is selected from one or more of methanol, ethanol, n-propanol, isopropanol, and butanol; the stabilizer is selected from one or more of propylene glycol, glycerol, ethylene glycol, n-butyl acetate, propylene glycol ethyl ether and 2-ethoxyethanol.
In the above technical solution, further, the viscosity of the catalyst slurry is 100-.
In the above technical solution, further, the uniformity of the catalyst slurry in the step (3) is detected, and the uniformity detection method includes: and (3) dropping the catalyst slurry on a smooth and clean glass surface for natural leveling, then carrying out visual observation, observing the catalyst slurry after drying to have a light transmission phenomenon, and if cracks exist, proving that the catalyst slurry is not uniformly dispersed, and carrying out ultrasonic oscillation and high-speed stirring dispersion on the catalyst slurry again for 30-60 min.
In the above technical solution, further, the retreating distance of the coating die head in the step S2(B) is 100-1000 μm; the coating speed is 1-10m/min, the coating thickness is 50-400 μm, and the coating pressure is 0.01-2 bar.
In the above technical scheme, further, in the step E, gradient drying of the proton exchange membrane electrode is realized by using four-section drying ovens, wherein the temperatures of the four-section drying ovens are respectively set to be 20-60 ℃ at the first section, 30-70 ℃ at the second section, 40-80 ℃ at the third section, and 60-120 ℃ at the fourth section.
Compared with the prior art, the invention has the beneficial effects that:
1. in the preparation process of the catalyst slurry, the catalyst slurry is dispersed more uniformly by changing the binder and adding the stabilizer; first Na to sulfonic acid group of binder+On one hand, the heat stability of the catalyst slurry is greatly increased when the catalyst slurry is coated on the surface of a proton exchange membrane and dried, which is beneficial to the volatilization of a stabilizer, on the other hand, the gas permeability of the prepared catalyst layer is increased, the gas mass transfer resistance is reduced, and the electrochemical performance is improved; secondly, the addition of the stabilizer enables the catalyst slurry to have higher viscosity, the stability of the catalyst slurry is greatly improved, and the catalyst slurry is prevented from settling and layering; finally, in the catalyst slurry dispersing process, the modes of ultrasonic oscillation and high-speed stirring dispersion are selected, so that the dispersing time is shortened, and bubbles in the catalyst slurry can be removed by ultrasonic waves;
2. in the process of coating the catalyst layer by the catalyst slurry, the die head retreating process step is designed, so that the defects of uneven head and tail of the coating and the like in the discontinuous coating process are overcome, in the traditional coating mode, the die head does not retreat in the coating process, so that the tail of the coated tail is trailing, and the coating of the trailing part is thin due to the advanced coating; the catalyst slurry prepared by the invention has good dispersion degree and excellent stability due to the change of the binder and the addition of the stabilizer, and the catalyst layer prepared by the invention has better adhesion with the proton exchange membrane so that the uniformity of the catalyst layer is better; finally, a gradient drying tunnel is selected for drying the catalyst slurry layer, so that on one hand, cracks and falling of the catalyst slurry layer caused by overhigh temperature are avoided when the catalyst slurry layer is dried, on the other hand, the dispersing agent is volatilized from the catalyst slurry layer at low temperature, the temperature is gradually increased, the stabilizing agent with higher boiling point is evaporated, the natural leveling of the coating layer in the drying process is increased, and the catalytic layer is ensured to be stable and uniform;
3. the catalyst layer prepared by the method disclosed by the invention is excellent in electrochemical performance, thin and uniform, the usage amount of the catalyst is reduced, the cost is saved, and the yield is improved.
Detailed Description
The invention is further illustrated, but is not in any way limited, by the following specific examples.
Example 1
The preparation of the fuel cell membrane electrode catalysis layer comprises the following steps:
(1) weighing 10g of 20wt% Pt/C catalyst and 300g of isopropanol, and mixing the Pt/C catalyst and the isopropanol, and performing ultrasonic oscillation for 10 min; then 200g of n-butyl acetate is added, and ultrasonic oscillation is continuously used for 10 min;
(2) weighing 70g of 5 wt% perfluorosulfonic acid resin solution, placing into a glass container, adding 10mL of 1mol/L NaOH aqueous solution, and stirring at 25 ℃ for 4h to obtain Na+Shaped perfluoroSulfonic acid resin solution;
(3) na in (2)+Adding the molded perfluorinated sulfonic acid resin liquid into the mixture obtained in the step (1), performing ultrasonic oscillation for 30min, and performing high-speed stirring and dispersion for 60min to obtain catalyst slurry, detecting the uniformity of the catalyst slurry through a smooth glass surface, namely dropping the catalyst slurry on the smooth and clean glass surface to naturally level, observing after drying, and performing uniform dispersion if no light transmission, no crack, no granular sensation and no flocculence exist, or performing ultrasonic oscillation and high-speed stirring and dispersion on the catalyst slurry again for 30-60 min;
(4) and (4) intermittently coating the catalyst slurry in the step (3) on the proton exchange membrane at a coating speed of 1m/min and a coating thickness of 50 micrometers, with a die head retreating to a distance of 100 micrometers from the surface of the proton exchange membrane after the coating is finished and a feeding pressure of 0.01bar, and passing through drying tunnels with the temperatures of 20 ℃, 30 ℃, 40 ℃ and 60 ℃ respectively to obtain a uniform catalyst layer.
Example 2:
the preparation of the membrane electrode catalyst layer of the fuel cell comprises the following steps:
(1) weighing 20g of 80wt% Pt/C catalyst and 333g of ethanol, mixing, and performing ultrasonic oscillation for 30 min; then 233g of propylene glycol is added, and ultrasonic oscillation is continuously used for 30 min;
(2) 73g of 5 wt% perfluorosulfonic acid resin solution was weighed into a glass container, 12mL of 1mol/L NaOH aqueous solution was added thereto, and the mixture was stirred at 25 ℃ for 4 hours to obtain Na+A molded perfluorosulfonic acid resin liquid;
(3) na in (2)+Adding the molded perfluorinated sulfonic acid resin liquid into the mixture obtained in the step (1), ultrasonically oscillating for 60min, stirring at a high speed for dispersing for 100min to obtain catalyst slurry, and detecting the uniformity of the catalyst slurry through a smooth glass surface;
(4) and (4) intermittently coating the catalyst slurry in the step (3) on the proton exchange membrane at a coating speed of 10m/min and a coating thickness of 100 micrometers, with a die head retreating to a distance of 200 micrometers from the surface of the proton exchange membrane after the coating is finished and a feeding pressure of 2bar, and drying the catalyst slurry through drying tunnels at 60 ℃, 70 ℃, 80 ℃ and 120 ℃ respectively to obtain a uniform catalyst layer.
Example 3:
the preparation of the membrane electrode catalyst layer of the fuel cell comprises the following steps:
(1) weighing 15g of 40 wt% Pt/C catalyst and 400g of ethanol, mixing, and performing ultrasonic oscillation for 20 min; then 187g of glycerol is added, and the ultrasonic oscillation is continuously used for 20 min;
(2) 60g of 5 wt% perfluorosulfonic acid resin solution is weighed and put into a glass container, 8mL of 1mol/L NaOH aqueous solution is added, and the mixture is stirred for 4 hours at 25 ℃ to obtain Na+A molded perfluorosulfonic acid resin liquid;
(3) na in (2)+Adding the molded perfluorinated sulfonic acid resin liquid into the mixture obtained in the step (1), ultrasonically oscillating for 60min, stirring at a high speed for dispersing for 100min to obtain catalyst slurry, and detecting the uniformity of the catalyst slurry through a smooth glass surface;
(4) and (3) intermittently coating the catalyst slurry on the proton exchange membrane at a coating speed of 10m/min and a coating thickness of 100 microns, with a die head retreating to a distance of 200 microns from the surface of the proton exchange membrane after the coating is finished and a feeding pressure of 2bar, and passing through drying tunnels at 50 ℃, 60 ℃, 80 ℃ and 100 ℃ respectively to obtain a uniform catalytic layer.
Comparative example 1:
(1) weighing 10g of 20wt% Pt/C catalyst and 300g of isopropanol, and mixing the Pt/C catalyst and the isopropanol, and performing ultrasonic oscillation for 10 min; adding 70g of 5 wt% perfluorosulfonic acid resin solution, carrying out ultrasonic oscillation for 30min, and carrying out high-speed stirring and dispersion for 60min to obtain catalyst slurry;
(2) and (2) intermittently coating the catalyst slurry in the step (1) on a proton exchange membrane at a coating speed of 1m/min and a coating thickness of 50 microns, and passing through drying tunnels with the temperatures of 60 ℃ respectively to obtain the catalyst layer.
Comparative example 2:
(1) weighing 20g of 80wt% Pt/C catalyst and 333g of ethanol, mixing, and performing ultrasonic oscillation for 30 min; then 233g of propylene glycol is added, and ultrasonic oscillation is continuously used for 30 min; adding 73g of 5 wt% perfluorosulfonic acid resin solution, ultrasonically oscillating for 60min, and stirring at a high speed for dispersing for 100min to obtain catalyst slurry;
(2) and (2) intermittently coating the catalyst slurry in the step (1) on a proton exchange membrane by selecting a process with the coating speed of 10m/min, the coating thickness of 100 mu m and the pressure of 2bar, and drying the proton exchange membrane by a drying tunnel at the temperature of 120 ℃ to obtain the catalyst layer.
The embodiment and the comparative example show that in the preparation process of the catalyst slurry, the stability of the catalyst slurry is greatly improved after the stabilizer is added, and the viscosity of the catalyst can be controlled within a proper range; the binder is processed by Na+After the forming treatment, the ion bonding force of the catalyst layer slurry layer is stronger in the drying process, so that the defects such as cracks and the like can not occur, and the uniformity of the prepared catalyst layer is better; and Na+After the forming treatment, the gas transmission resistance of the catalyst layer is reduced, and the battery performance is excellent. In the intermittent coating process, the die head is additionally retreated and a gradient drying channel is adopted, the thicknesses of the head part and the tail part of the coating are uniform, and the die head retreats to overcome the defects of uneven head part and tail part of the coating and the like in the intermittent coating process.
The stability of the catalyst slurry prepared according to the present invention was tested by the following method: and (3) placing the catalyst slurry in a glass container for 48h, dividing the catalyst slurry into an upper layer, a middle layer and a lower layer according to the scale marks on the glass container, respectively testing the viscosity of the three layers of slurry, and analyzing whether the slurry is settled or not through the viscosity change. The results are shown in table 1, as measured by an electronic digital viscometer. The viscosity of the catalyst slurry prepared by the invention is stable after 48 hours, and the phenomena of sedimentation and delamination do not occur. And no sediment and agglomeration occurred.
The test results are shown in table 1:
| examples | 1 | 2 | 3 | Comparison of1 | Comparative example 2 |
| Upper layer viscosity/cp | 168 | 179 | 171 | 112 | 132 |
| Middle layer viscosity/cp | 170 | 184 | 181 | 150 | 186 |
| Lower layer viscosity/cp | 180 | 192 | 188 | 187 | 221 |
The porosity of the catalytic layer prepared by the invention is tested by a mercury intrusion method, the model of the mercury intrusion instrument is Poremaster GT60(Quantachrome), and the pressure range is 1.38 multiplied by 103-4.13×107Pa(0.2-0.4×104psi), the contact angle of mercury is 140 deg.. The porosity obtained is shown in Table 2. As can be seen from the table, the porosity of the catalytic layer prepared by the present invention is significantly higher than that of the catalytic layer without the binder treatment.
The catalyst slurry prepared by the method is prepared into a membrane electrode to be assembled into a battery, and then the battery performance under the hydrogen-oxygen condition is evaluated. And (3) testing conditions are as follows: battery operating temperature: the test results are shown in Table 2 at 60 ℃, H2/O2100 RH%, flow rate 40/100mL/min and air inlet all at normal pressure. From the battery test results, the preparation method of the catalyst slurry and the preparation and treatment process of the catalyst layer are adopted, so that the power generation performance of the battery is obviously excellent.
The test results are shown in table 2:
| examples | Porosity/% | 0.6V | 0.7V | 0.8V |
| 1 | 82 | 0.79 | 0.65 | 0.42 |
| 2 | 79 | 0.82 | 0.68 | 0.44 |
| 3 | 81 | 0.78 | 0.59 | 0.47 |
| Comparative example 1 | 63 | 0.63 | 0.41 | 0.21 |
| Comparative example 2 | 71 | 0.61 | 0.39 | 0.19 |
It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (6)
1. A preparation method of a membrane electrode catalyst layer of a fuel cell is characterized by comprising the following steps:
(1) mixing solid catalyst particles and a dispersing agent, and dispersing for 10-30min by ultrasonic oscillation to form a uniform mixed solution; adding stabilizer, dispersing for 10-30min by ultrasonic oscillation and dispersing for 30-60min by high speed stirring to form uniform mixed solution;
(2) adding 1mol/L NaOH solution into the adhesive, wherein the ratio of the molar weight of the sodium hydroxide to the molar weight of the sulfonate in the adhesive is 0.1-2:1, and adding the adhesive Na+Patterning from H+Form is converted into Na+Molding;
(3) passing the solution obtained in the step (2) through Na+Adding the formed binder into the mixed solution in the step (1), ultrasonically oscillating, and stirring and dispersing at a high speed for 60-100min to prepare catalyst slurry;
the mass ratio of the solid catalyst particles to the binder to the dispersant to the stabilizer is 1-3:7-11:30-50: 20-35;
(4) coating the catalyst slurry obtained in the step (3) on a proton exchange membrane to obtain a catalyst layer;
the coating in the step (4) comprises the following steps:
(A) loading the catalyst slurry prepared in the step (1) into a coating die head in continuous coating equipment, and tensioning and placing a proton exchange membrane coil in a conveying mechanism in the continuous coating equipment;
(B) coating the proton exchange membrane coiled material in conveying by the coating die head, stopping feeding every time the coating die head finishes coating, and then retreating along the vertical direction of the proton exchange membrane coiled material;
(C) c, vertically advancing the coating die head which finishes the step B to a position close to the proton exchange membrane coiled material, and then feeding the coating die head to realize the next coating of the proton exchange membrane;
(D) repeating the steps B-C to realize the intermittent coating of the proton exchange membrane and form a proton exchange membrane electrode with a catalyst layer;
(E) drying the proton exchange membrane electrode obtained in the step D;
the retreat distance of the coating die head in the step (B) is 100-; the coating speed is 1-10m/min, the coating thickness is 50-400 μm, and the coating pressure is 0.01-2 bar;
in the step (E), the gradient drying of the proton exchange membrane electrode is realized by adopting four sections of drying ovens, wherein the temperatures of the four sections of drying ovens are respectively set as follows: the temperature of the first section is 20-60 ℃, the temperature of the second section is 30-70 ℃, the temperature of the third section is 40-80 ℃, and the temperature of the fourth section is 60-120 ℃.
2. The method of claim 1, wherein: the solid catalyst particles are carbon-supported Pt catalysts or carbon-supported Pt alloy catalysts, wherein the Pt content in the carbon-supported Pt catalysts or the carbon-supported Pt alloy catalysts is 20-80 wt%.
3. The method of claim 1, wherein: the binder is selected from one or more of 5-20wt% of perfluorinated sulfonic acid resin liquid, 1-20wt% of sulfonated polyether ether ketone resin liquid, 1-20wt% of sulfonated trifluorostyrene resin liquid and 1-20wt% of polymethylphenylsulfonic acid siloxane resin liquid.
4. The method of claim 1, wherein: the dispersing agent is selected from one or more of methanol, ethanol, n-propanol, isopropanol and butanol; the stabilizer is selected from one or more of propylene glycol, glycerol, ethylene glycol, n-butyl acetate, propylene glycol ethyl ether and 2-ethoxyethanol.
5. The method of claim 1, wherein: the viscosity of the catalyst slurry was 100-.
6. The production method according to claim 1, characterized in that: the uniformity detection is carried out on the catalyst slurry obtained in the step (3), and the uniformity detection method comprises the following steps: and (3) dropping the catalyst slurry on a smooth and clean glass surface, naturally leveling, observing by naked eyes, drying the catalyst slurry, observing that the catalyst slurry has a light transmission phenomenon and cracks, and then performing ultrasonic oscillation and high-speed stirring and dispersing on the catalyst slurry for 30-60 min.
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| CN114243033A (en) * | 2021-12-09 | 2022-03-25 | 同济大学 | Flaw-free catalyst directly coated proton exchange membrane and preparation method and application thereof |
| CN114243034B (en) * | 2021-12-15 | 2023-11-14 | 中国科学院大连化学物理研究所 | Anti-precipitation catalyst slurry and preparation method thereof |
| CN114210532B (en) * | 2021-12-15 | 2023-02-03 | 中国科学院大连化学物理研究所 | CCM continuous coating process for fuel cell membrane electrode |
| CN115275225A (en) * | 2022-08-30 | 2022-11-01 | 中汽创智科技有限公司 | Preparation method of membrane electrode catalyst coating |
| CN115537068A (en) * | 2022-09-06 | 2022-12-30 | 中国科学院大连化学物理研究所 | Membrane electrode catalysis layer ink-jet printing ink and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1457521A (en) * | 2001-03-08 | 2003-11-19 | 松下电器产业株式会社 | Gas diffusion electrode and fuel cell using this |
| CN1477724A (en) * | 2003-07-02 | 2004-02-25 | 中山大学 | Preparation method of membrane electrode commponent of proton exchange membrane fuel cell |
| CN1838456A (en) * | 2006-04-28 | 2006-09-27 | 华南理工大学 | Direct spraying method for preparing fuel cell membrane electrode |
| CN101714635A (en) * | 2008-10-06 | 2010-05-26 | 现代自动车株式会社 | Electrode for polymer electrolyte membrane fuel cell, membrane-electrode assembly, and methods for manufacturing the same |
| CN108780877A (en) * | 2016-03-11 | 2018-11-09 | Nec能源元器件株式会社 | The manufacturing method of electrochemical appliance and electrode for electrochemical device |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN204320598U (en) * | 2014-12-01 | 2015-05-13 | 深圳市旭合盛科技有限公司 | A kind of apparatus for coating of adjustable coating spacing |
| CN205436215U (en) * | 2016-03-22 | 2016-08-10 | 南京国轩电池有限公司 | Unusual automatic device of retreating of die head of response battery level piece coating |
| KR20190072580A (en) * | 2016-10-20 | 2019-06-25 | 바스프 에스이 | A process for producing a catalyst containing an intermetallic compound and a catalyst prepared by the process |
| CN208052533U (en) * | 2017-12-25 | 2018-11-06 | 浙江精诚模具机械有限公司 | A kind of die lip combined type lamination die head |
| CN111261876B (en) * | 2018-11-30 | 2021-05-04 | 中国科学院大连化学物理研究所 | Application of sodium sulfonated polyether ether ketone as binder in zinc-nickel flow battery electrode |
| CN111261879A (en) * | 2020-01-23 | 2020-06-09 | 同济大学 | Catalyst slurry containing dispersing aid, catalyst layer prepared from catalyst slurry and fuel cell electrode |
| CN111477923A (en) * | 2020-03-24 | 2020-07-31 | 武汉惠强新能源材料科技有限公司 | Three-layer co-extrusion composite proton exchange membrane and preparation method thereof |
-
2020
- 2020-12-14 CN CN202011475544.5A patent/CN112599792B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1457521A (en) * | 2001-03-08 | 2003-11-19 | 松下电器产业株式会社 | Gas diffusion electrode and fuel cell using this |
| CN1477724A (en) * | 2003-07-02 | 2004-02-25 | 中山大学 | Preparation method of membrane electrode commponent of proton exchange membrane fuel cell |
| CN1838456A (en) * | 2006-04-28 | 2006-09-27 | 华南理工大学 | Direct spraying method for preparing fuel cell membrane electrode |
| CN101714635A (en) * | 2008-10-06 | 2010-05-26 | 现代自动车株式会社 | Electrode for polymer electrolyte membrane fuel cell, membrane-electrode assembly, and methods for manufacturing the same |
| CN108780877A (en) * | 2016-03-11 | 2018-11-09 | Nec能源元器件株式会社 | The manufacturing method of electrochemical appliance and electrode for electrochemical device |
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