Three-dimensional porous graphene composite catalyst layer membrane electrode system and preparation method

Abstract

The invention relates to the technical field of precious metal nano catalytic materials, in particular to a three-dimensional porous graphene composite catalyst layer membrane electrode system and a preparation method thereof.The three-dimensional porous graphene composite catalyst layer membrane electrode system comprises a layer membrane electrode preparation system, and the layer membrane electrode preparation system comprises a platinum-carbon catalyst preparation stage; the platinum-carbon catalyst preparation stage is further provided with a layer membrane electrode slurry preparation stage in a matched mode, the layer membrane electrode slurry preparation stage is further provided with a cathode catalyst layer preparation stage and an anode catalyst layer preparation stage in a matched mode, and the layer membrane electrode preparation method further comprises a membrane electrode treatment stage. The high dispersity and uniformity of the catalyst are realized, the catalytic performance and the stability of the electrode are improved, the electrode structure is optimized, the porosity and the ion conduction performance are improved, and the efficiency and the service life of the battery are remarkably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of precious metal nanocatalytic materials, and in particular to a three-dimensional porous graphene composite catalyst layer membrane electrode system and a preparation method thereof. Background Art

[0002] Hydrogen energy, as a clean, efficient and sustainable new energy, is regarded as the most promising next-generation energy. Proton exchange membrane fuel cells are an ideal form of hydrogen energy with the advantages of high efficiency, cleanliness, low operating temperature and high energy density. They are an ideal clean energy. Membrane electrode is a key component that determines the performance of fuel cells and plays a vital role.

[0003] Membrane Electrode Assembly (MEA) is the core component of the fuel cell and the place where the fuel cell performs redox reactions. It is mainly composed of a gas diffusion layer (GDL), a catalyst layer (CL), a proton exchange membrane (PEM) and a sealing layer. The catalyst layer catalyzes the electrochemical reaction of hydrogen and oxygen, and is divided into a cathode catalyst layer (oxygen reduction reaction) and an anode catalyst layer (hydrogen oxidation reaction). The anode catalyst layer decomposes hydrogen into protons and releases electrons, which reach the cathode through an external circuit. The cathode catalyst layer catalyzes the electrochemical reaction of protons and oxygen to obtain electrons to produce water.

[0004] The catalyst layer has four main functions. The first function is to supply the reaction gas supplied from the gas diffusion layer to the reaction site of the catalyst layer. The second function is to conduct the hydrogen ions required for the reaction on the electrode catalyst or the generated hydrogen ions. The third function is to conduct the electrons required for the reaction or the generated electrons. The fourth function is to accelerate the electrode reaction by using the high catalyst performance and its large reaction area. In short, the catalyst layer needs to have high reaction gas permeability, hydrogen ion conductivity, electron conductivity and catalyst performance.

[0005] The formula of the existing catalyst layer is the same. During the power generation process of a single cell, the reaction conditions at the air inlet and the air outlet are different. The humidity at the air inlet is relatively low, and the hydrogen content is relatively abundant. The humidity near the air outlet is relatively high, and the hydrogen concentration is relatively low. This requires the rear-end catalyst layer to have better drainage and more catalytic active sites. The current catalyst formula is the same and cannot meet the different needs of different regions. Summary of the invention

[0006] In order to solve some of the problems existing in the above-mentioned prior art, the present invention provides a three-dimensional porous graphene composite catalyst layer membrane electrode system and a preparation method to solve the deficiencies existing in the prior art.

[0007] To achieve the above-mentioned purpose, the present invention provides a three-dimensional porous graphene composite catalyst layer membrane electrode system, including a layer membrane electrode preparation system, the layer membrane electrode preparation system includes a platinum-carbon catalyst preparation stage, the platinum-carbon catalyst preparation stage is also equipped with a layer membrane electrode slurry preparation stage, the layer membrane electrode slurry preparation stage is also equipped with a cathode catalyst layer preparation stage and an anode catalyst layer preparation stage, and the layer membrane electrode preparation method also includes a membrane electrode processing stage.

[0008] As a further improvement of the present invention, in order to help form uniform and high-performance catalyst particles and achieve fine preparation and performance optimization of the catalyst, the platinum-carbon catalyst preparation stage includes a unit storage tank, a plurality of groups of material storage units are arranged inside the unit storage tank, a plurality of groups of first raw material storage tanks are arranged on one side of the unit storage tank, the first raw material storage tank is connected to a first mixing bin via a pipeline, the first mixing bin is provided with a flip-type stirring tank, the flip-type stirring tank is provided with a first transition bin, the first transition bin is connected to a first ultrasonic disperser, the first ultrasonic disperser is connected to a hydrothermal reactor via a pipeline, the hydrothermal reactor is provided with a gel cleaning chamber, a deionized water preparation device is separately provided on one side of the gel cleaning chamber, the gel cleaning chamber is connected to a conductivity test box, the conductivity test box is provided with a freeze dryer, a tubular furnace is provided after the freeze dryer, and the tubular furnace is further provided with a weighing sensor.

[0009] As a further improvement of the present invention, in order to ensure that the components of the slurry are evenly dispersed, which is beneficial to improving the coating quality and catalytic performance of the electrode, the layer electrode slurry preparation stage includes an ultrapure water storage tank, an alloy catalyst storage tank, an ethanol storage tank, an isopropanol storage tank, a n-propanol storage tank, an ethylene glycol storage tank and a perfluorosulfonic acid dispersion storage tank, the ultrapure water storage tank and the alloy catalyst storage tank are connected to a second mixing bin, the ethanol storage tank, the isopropanol storage tank, the n-propanol storage tank, and the ethylene glycol storage tank are connected to a third mixing bin, the perfluorosulfonic acid dispersion storage tank is provided with a fourth mixing bin, the second mixing bin, the third mixing bin and the fourth mixing bin are interconnected by pipelines, the fourth mixing bin is connected to a second ultrasonic disperser and a stirred reactor, and the stirred reactor is connected to a second raw material storage tank by a pipeline.

[0010] As a further improvement of the present invention, in order to ensure the uniform distribution and firm adhesion of the catalyst and improve the catalytic activity and stability of the electrode, the cathode catalyst layer preparation stage includes a medium heating box, the medium heating box is equipped with a process water tank, the process water tank is equipped with a heating platform, the heating platform is equipped with a first multi-roller conveyor belt, and the multi-roller conveyor belt is connected to a first slit coater; the anode catalyst layer preparation stage includes a porous carbon plate dressing platform, the porous carbon plate dressing platform is connected to a second slit coater, and the porous carbon plate dressing platform is equipped with a second multi-roller conveyor belt.

[0011] As a further improvement of the present invention, in order to help optimize the microstructure of the electrode and further improve the catalytic efficiency and battery performance, the membrane electrode processing stage includes a membrane material tensioning area, the membrane material tensioning area is cooperated with a hot press, a cold press is arranged behind the hot press, and a third multi-roller conveyor belt is arranged behind the cold press.

[0012] The present invention provides a three-dimensional porous graphene composite catalyst layer membrane electrode system, the beneficial effects of which are embodied in the following aspects: Improve catalytic performance: Through a carefully designed platinum-carbon catalyst preparation stage, the present invention can prepare a platinum-carbon catalyst with high dispersion and uniformity. This catalyst has more active sites and better catalytic activity, thereby significantly improving the catalytic performance of the electrode. Optimized electrode structure: The meticulous design of the multilayer electrode slurry preparation stage ensures that the slurry composition is uniform and stable. By precisely controlling the proportions and mixing conditions of various raw materials, a slurry with ideal viscosity and fluidity can be prepared. The optimized electrode structure has higher porosity and better ion conductivity, which helps to improve the performance and stability of the battery.

[0013] Enhanced electrode stability: Advanced coating technologies, such as slot coaters, are used during the preparation of the cathode and anode catalyst layers to ensure uniformity and consistency of the catalyst layers. At the same time, the mechanical strength and durability of the electrodes can be further enhanced by precisely controlling the heating and cooling conditions. This enhanced stability enables the electrodes to maintain stable performance during long-term use, extending the battery's service life.

[0014] Improve battery efficiency: The setting of membrane electrode processing stage, including membrane tensioning, hot pressing and cold pressing, helps to optimize the microstructure of the electrode, reduce internal resistance, and improve the power density and efficiency of the battery. These processing steps can also ensure the close bonding between the electrode layers, prevent problems such as delamination or shedding during use, thereby improving the reliability and safety of the battery.

[0015] A method for preparing a three-dimensional porous graphene composite catalyst layer membrane electrode system, the preparation method comprising the following steps: Step 1: prepare a graphite oxide solution to prepare a graphite oxide suspension solution of a certain concentration, transport the graphite oxide solution to several groups of storage units in a unit storage tank, first mix ultrapure water and the graphite oxide solution in a first mixing bin, and perform concentration detection on the mixed solution; Step 2: Mix the mixed liquid obtained in step 1 with the hydrogen fuel electrocatalyst in another group of first mixing chambers, add a small amount of NiCl·HO solution, and mix again to obtain a mixed liquid; Step 3: transporting the mixed solution obtained in step 2 into a flip-type agitator for stirring and mixing, sending the mixed solution into a transition bin for mixed solution concentration detection, and after the detection is completed, sending the mixed solution into a first ultrasonic disperser for ultrasonic stirring at room temperature; Step 4: Transfer the mixed solution to a hydrothermal reactor for hydrothermal reaction, wait for the reactor to cool to room temperature, transfer the gel obtained by the reaction to a gel cleaning chamber for cleaning, and replenish water in time through a deionized water preparation device; Step 5: The washed product enters a conductivity test box, and the purity and ion content of the product are tested by a conductivity test. The product after the conductivity test is transported to a freeze dryer, and in the freeze dryer, the product is subjected to low-temperature freezing and vacuum drying to remove moisture and solvent from the product, thereby obtaining a dry platinum-carbon complex; Step 6: The dried platinum-carbon composite enters a tube furnace for heat treatment. Heat treatment can further improve the structure and performance of the platinum-carbon composite. A weighing sensor is arranged behind the tube furnace to accurately weigh the product after heat treatment. Step 7: Ensure that there is sufficient raw material in each of the ultrapure water storage tank, alloy catalyst storage tank, ethanol storage tank, isopropanol storage tank, n-propanol storage tank, ethylene glycol storage tank and perfluorosulfonic acid dispersion storage tank; Step 8: transporting ultrapure water from the ultrapure water storage tank to the second mixing chamber through a pipeline, and transporting the alloy catalyst from the alloy catalyst storage tank to the second mixing chamber through a pipeline; in the second mixing chamber, the ultrapure water and the alloy catalyst are preliminarily mixed; Step nine: transporting the raw materials in the ethanol storage tank, the isopropanol storage tank, the n-propanol storage tank and the ethylene glycol storage tank to the third mixing bin through a pipeline, wherein the four alcohol raw materials are preliminarily mixed in the third mixing bin and mixed with the mixed liquid in step eight; Step 10: transporting the perfluorosulfonic acid dispersion from the perfluorosulfonic acid dispersion storage tank to the fourth mixing chamber through a pipeline, and mixing the mixed solution obtained in step 8 with the perfluorosulfonic acid dispersion in the fourth mixing chamber; Step 11: The final mixed solution obtained in step 10 is transferred to a second ultrasonic disperser. After the dispersion is completed, the mixed solution is sent to a stirred reactor for stirring and mixing and carbon black is added. After the stirring is completed, the mixed slurry is transported to a second raw material storage tank through a pipeline for storage; Step 12: Preheat the medium heating box to reach the required temperature range to provide a stable heat source for subsequent process steps. Fill the process water tank with an appropriate amount of process water, which will be heated by the heating table to reach the temperature conditions required for coating; Step 13: The heating table is started to heat the process water in the process water tank to a predetermined temperature. The heated process water or other coating medium is transported to the first multi-roller conveyor belt through a pipeline. The multi-roller conveyor belt runs at a stable speed to ensure that the coating medium is evenly distributed on the conveyor belt. Step 14: After the coating medium is evenly distributed on the first multi-roller conveyor belt, the first slit coater starts to work, and the slit coater evenly coats the coating medium on the conveyor belt, such as the proton exchange membrane, through a precisely controlled slit to form a precursor of the cathode catalyst layer; Step 15: After coating, the substrate material is dried by a hot air device, and the dried cathode catalyst layer precursor enters the next process step; Step 16: On the porous carbon plate dressing platform, the required porous carbon plate and coating medium are prepared, and the second slit coater evenly coats the coating medium on the porous carbon plate through a precisely controlled slit. After coating, the porous carbon plate is conveyed by the second multi-roller conveyor belt; Step 17: hot air drying is performed during the transportation process. After the coating is completed and the catalyst layer is completely dried, the anode catalyst layer is prepared and the processed anode catalyst layer is transferred to the next process for assembly; Step 18: Send the film material into the tensioning area, where the film material will be tightened by the tensioning device. After being tightened, the film material enters the hot press area, where the hot press applies high temperature and pressure to heat press the film material. Step 19: After the hot pressing treatment, the film material enters the cold press area, and the cold press further processes the film material by applying pressure and at a lower temperature. After the cold pressing treatment, the film material enters the third multi-roller conveyor belt area, where the film material is rolled by multiple rollers to be further flattened and compacted; Step 20: The cooling device on the conveyor belt quickly cools the membrane material to room temperature, and the cold-pressed membrane electrode is sealed and stored.

[0016] The present invention provides a method for preparing a three-dimensional porous graphene composite catalyst layer membrane electrode system. The beneficial effects of the preparation method are embodied in the following aspects: Precise concentration control and mixing: In the early stage of preparation, the concentration of graphite oxide solution is accurately detected and mixed with hydrogen fuel electrocatalyst, NiCl·HO solution, etc. to ensure the accurate ratio of reactants, thereby improving the quality and performance of the final product. The setting of multiple mixing chambers and detection links makes the entire mixing process more controllable and reduces the problem of unstable product performance caused by concentration fluctuations.

[0017] Effective dispersion and reaction: The use of ultrasonic dispersers and flip stirrers to disperse and stir the mixed liquid effectively improves the dispersion uniformity of the reactants, allowing the catalyst to be more evenly distributed on the graphene surface, improving the catalytic efficiency. The use of a hydrothermal reactor provides a high-temperature and high-pressure reaction environment for the mixed liquid, which helps the catalyst and graphene to be closely combined, forming a stable three-dimensional porous structure.

[0018] Strict purity and conductivity control: The purity and ion content of the product are tested by the conductivity test box to ensure that the conductivity of the product meets the requirements, which is crucial for improving the conductivity and catalytic performance of the electrode. The introduction of the cleaning and deionized water preparation device effectively removes impurities and residual solvents in the product and improves the purity of the product.

[0019] Heat treatment and accurate weighing: The heat treatment step in the tube furnace further improves the structure and performance of the platinum-carbon composite, giving it better catalytic activity and stability. The setting of the weighing sensor ensures the accurate weighing of the product after heat treatment, providing accurate data support for subsequent processes.

[0020] Multi-component mixing and coating process: Through the coordinated use of multiple storage tanks and mixing bins, the precise proportioning and mixing of multiple raw materials is achieved, providing a guarantee for the preparation of high-performance composite catalysts. The use of slit coaters ensures the uniform coating of the coating medium, making the catalyst layer more evenly distributed on the substrate material, and improving the performance and stability of the electrode.

[0021] Perfect post-processing technology: The tensioning, hot pressing and cold pressing of the membrane material effectively removes bubbles and defects in the membrane material, and improves the flatness and tightness of the membrane electrode. The setting of the cooling device ensures that the membrane material will not deform or crack due to temperature changes during the cooling process, thus ensuring the quality of the membrane electrode.

[0022] When the present invention is working, first, in a unit storage tank, a graphite oxide solution and ultrapure water are mixed in a first mixing chamber; then, a hydrogen fuel electrocatalyst and a NiCl·HO solution are added for secondary mixing to form a uniform mixed solution; the mixed solution is sent to a flip-type stirring tank for full stirring to ensure that each component is evenly dispersed; then, the mixed solution enters a first ultrasonic disperser and is ultrasonically stirred at room temperature to further promote the uniformity of the mixed solution; the ultrasonically dispersed mixed solution is transferred to a hydrothermal reactor for hydrothermal reaction; after the reaction is completed, the obtained gel is sent to a gel cleaning chamber for cleaning to remove impurities; during the cleaning process, a deionized water preparation device provides a continuous deionized water supply to the cleaning chamber; the cleaned gel enters a conductivity test box for detection to ensure that the purity and ion content of the product meet the requirements; then, the product is sent to a freeze dryer for low-temperature freezing and vacuum drying to remove moisture and solvent; the dried platinum-carbon composite enters a tubular furnace for heat treatment to further improve its structure and performance; a weighing sensor arranged behind the tubular furnace is used to accurately measure the weight of the product after heat treatment.

[0023] Raw materials are taken out from the ultrapure water storage tank, the alloy catalyst storage tank and various alcohol storage tanks, and preliminarily mixed in the second mixing chamber and the third mixing chamber respectively; then the perfluorosulfonic acid dispersion is taken out from the perfluorosulfonic acid dispersion storage tank, and finally mixed with the previous mixed liquid in the fourth mixing chamber; the final mixed liquid is sent to the second ultrasonic disperser for ultrasonic dispersion treatment to ensure that the components are evenly dispersed; then the mixed liquid enters the stirred reactor for stirring and mixing to form a uniform layer membrane electrode slurry; after the stirring is completed, the slurry is sent to the second raw material storage tank for storage and standby.

[0024] The medium heating box and the process water tank are preheated to the required temperature; the heated process water or other coating medium is transported to the first multi-roller conveyor belt; the first slit coater evenly coats the coating medium on the proton exchange membrane through a precisely controlled slit to form a precursor of the cathode catalyst layer; after coating, the precursor is cured into the cathode catalyst layer by hot air drying; the porous carbon plate and the coating medium are prepared on the porous carbon plate dressing platform; the second slit coater evenly coats the coating medium on the porous carbon plate through a precisely controlled slit to form a precursor of the anode catalyst layer; after coating, hot air drying is also performed to cure the anode catalyst layer.

[0025] The prepared film material is sent to the tensioning area for tensioning treatment to ensure its flatness; then the film material enters the hot press area for hot pressing treatment under high temperature and high pressure to enhance its structure and performance; the hot-pressed film material enters the cold press area for further treatment at a lower temperature to enhance its stability; then the film material is flattened and compacted on the third multi-roller conveyor belt to ensure its surface flatness and internal structure tightness; finally, a cooling device is used to quickly cool the film material to room temperature and seal it for storage. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to facilitate understanding by those skilled in the art, the present invention is further described below with reference to the accompanying drawings: Figure 1 It is a structural diagram of the platinum-carbon catalyst preparation stage of the present invention.

[0027] Figure 2 It is a structural diagram of the layer membrane electrode slurry preparation stage of the present invention.

[0028] Figure 3 It is a structural diagram of the cathode catalyst layer preparation stage of the present invention.

[0029] Figure 4 It is a structural diagram of the anode catalyst layer preparation stage of the present invention.

[0030] Figure 5 It is a structural diagram of the membrane electrode processing stage of the present invention.

[0031] Among them, 1 platinum-carbon catalyst preparation stage, 2 membrane electrode slurry preparation stage, 3 cathode catalyst layer preparation stage, 4 anode catalyst layer preparation stage, 5 membrane electrode processing stage, 6 unit storage tank, 7 first raw material storage tank, 8 first mixing bin, 9 flip stirring tank, 10 first transition bin, 11 first ultrasonic disperser, 12 hydrothermal reactor, 13 gel cleaning chamber, 14 deionized water preparation device, 15 conductivity test box, 16 freeze dryer, 17 tubular furnace, 18 weighing sensor, 19 ultrapure water storage tank, 20 alloy catalyst storage tank, 21 ethanol storage tank, 22 Isopropyl alcohol storage tank, 23 n-propyl alcohol storage tank, 24 ethylene glycol storage tank, 25 perfluorosulfonic acid dispersion storage tank, 26 second mixing bin, 27 third mixing bin, 28 fourth mixing bin, 29 second ultrasonic disperser, 30 stirred reactor, 31 second raw material storage tank, 32 medium heating box, 33 process water tank, 34 heating table, 35 first multi-roller conveyor belt, 36 first slit coater, 37 porous carbon plate dressing platform, 38 second slit coater, 39 second multi-roller conveyor belt, 40 film material tensioning area, 41 hot press, 42 cold press, 43 third multi-roller conveyor belt. DETAILED DESCRIPTION

[0032] In order to enable those skilled in the art to better understand the technical solution in this application, Figure 1-5 The present invention is further described. The following examples are only used to more clearly illustrate the technical solution of the present invention, and are not intended to limit the protection scope of the present invention.

[0033] like Figure 1-5A three-dimensional porous graphene composite catalyst membrane electrode system is shown, including a membrane electrode preparation system, the membrane electrode preparation system includes a platinum-carbon catalyst preparation stage 1, the platinum-carbon catalyst preparation stage 1 is also provided with a membrane electrode slurry preparation stage 2, the membrane electrode slurry preparation stage 2 is also provided with a cathode catalyst layer preparation stage 3 and an anode catalyst layer preparation stage 4, and the membrane electrode preparation method also includes a membrane electrode processing stage 5.

[0034] The platinum-carbon catalyst preparation stage 1 includes a unit storage tank 6, wherein several groups of material storage units are arranged inside the unit storage tank 6, and several groups of first raw material storage tanks 7 are arranged on one side of the unit storage tank 6. The first raw material storage tank 7 is connected with a first mixing bin 8 through a pipeline, and the first mixing bin 8 is provided with a flip-type stirring tank 9, and the flip-type stirring tank 9 is provided with a first transition bin 10, and the first transition bin 10 is connected with a first ultrasonic disperser 11, and the first ultrasonic disperser 11 is connected with a hydrothermal reactor 12 through a pipeline, and the hydrothermal reactor 12 is provided with a gel cleaning chamber 13, and a deionized water preparation device 14 is separately provided on one side of the gel cleaning chamber 13, and the gel cleaning chamber 13 is connected with a conductivity test box 15, and the conductivity test box 15 is provided with a freeze dryer 16, and a tubular furnace 17 is provided after the freeze dryer 16, and the tubular furnace 17 is provided with a weighing sensor 18.

[0035] The membrane electrode slurry preparation stage 2 includes an ultrapure water storage tank 19, an alloy catalyst storage tank 20, an ethanol storage tank 21, an isopropanol storage tank 22, a n-propanol storage tank 23, an ethylene glycol storage tank 24 and a perfluorosulfonic acid dispersion storage tank 25. The ultrapure water storage tank 19 and the alloy catalyst storage tank 20 are connected with a second mixing bin 26, the ethanol storage tank 21, the isopropanol storage tank 22, the n-propanol storage tank 23, and the ethylene glycol storage tank 24 are connected with a third mixing bin 27, and the perfluorosulfonic acid dispersion storage tank 25 is provided with a fourth mixing bin 28. The second mixing bin 26, the third mixing bin 27 and the fourth mixing bin 28 are interconnected by pipelines, and the fourth mixing bin 28 is connected with a second ultrasonic disperser 29 and a stirred reactor 30, and the stirred reactor 30 is connected with a second raw material storage tank 31 by a pipeline.

[0036] The cathode catalyst layer preparation stage 3 includes a medium heating box 32, the medium heating box 32 is equipped with a process water tank 33, the process water tank 33 is equipped with a heating platform 34, the heating platform 34 is equipped with a first multi-roller conveyor belt 35, and the multi-roller conveyor belt is connected to a first slit coater 36; the anode catalyst layer preparation stage 4 includes a porous carbon plate dressing platform 37, the porous carbon plate dressing platform 37 is connected to a second slit coater 38, and the porous carbon plate dressing platform 37 is equipped with a second multi-roller conveyor belt 39.

[0037] The membrane electrode processing stage 5 includes a membrane material tensioning area 40 , and the membrane material tensioning area 40 is provided with a hot press 41 , a cold press 42 is provided behind the hot press 41 , and a third multi-roller conveyor belt 43 is provided behind the cold press 42 .

[0038] A method for preparing a three-dimensional porous graphene composite catalyst layer membrane electrode system, the preparation method comprising the following steps: Step 1: prepare a graphite oxide solution to prepare a graphite oxide suspension solution of a certain concentration, transport the graphite oxide solution to several groups of storage units in the unit storage tank 6, first mix ultrapure water and the graphite oxide solution in the first mixing chamber 8, and perform concentration detection on the mixed solution; Step 2: Mix the mixed liquid obtained in step 1 with the hydrogen fuel electrocatalyst in another group of first mixing chambers 8, add a small amount of NiCl2·6H2O solution, and mix again to obtain a mixed liquid; Step 3: transport the mixed solution obtained in step 2 into a flip-type agitator for stirring and mixing, and send the mixed solution into a transition bin for mixed solution concentration detection. After the detection is completed, send the mixed solution into a first ultrasonic disperser 11 for ultrasonic stirring at room temperature; Step 4: Transfer the mixed solution to the hydrothermal reactor 12 for hydrothermal reaction, wait for the reactor temperature to cool to room temperature, transfer the gel obtained by the reaction to the gel cleaning chamber 13 for cleaning, and replenish water in time through the deionized water preparation device 14; Step 5: The washed product enters the conductivity test box 15, and the purity and ion content of the product are tested by the conductivity test. The product after the conductivity test is transported to the freeze dryer 16, and the moisture and solvent in the product are removed by low-temperature freezing and vacuum drying in the freeze dryer 16 to obtain a dry platinum-carbon complex; Step 6: The dried platinum-carbon composite enters the tube furnace 17 for heat treatment. The heat treatment can further improve the structure and performance of the platinum-carbon composite. A weighing sensor 18 is arranged behind the tube furnace 17 to accurately weigh the product after the heat treatment. Step 7: Ensure that sufficient raw materials are stored in the ultrapure water storage tank 19, the alloy catalyst storage tank 20, the ethanol storage tank 21, the isopropanol storage tank 22, the n-propanol storage tank 23, the ethylene glycol storage tank 24 and the perfluorosulfonic acid dispersion storage tank 25; Step 8: transporting ultrapure water from the ultrapure water storage tank 19 to the second mixing chamber 26 through a pipeline, and transporting the alloy catalyst from the alloy catalyst storage tank 20 to the second mixing chamber 26 through a pipeline; in the second mixing chamber 26, the ultrapure water and the alloy catalyst are preliminarily mixed; Step nine: transporting the raw materials in the ethanol storage tank 21, the isopropanol storage tank 22, the n-propanol storage tank 23 and the ethylene glycol storage tank 24 to the third mixing bin 27 through a pipeline, wherein the four alcohol raw materials are preliminarily mixed in the third mixing bin 27 and mixed with the mixed liquid in step eight; Step 10: transporting the perfluorosulfonic acid dispersion from the perfluorosulfonic acid dispersion storage tank 25 to the fourth mixing chamber 28 through a pipeline, and mixing the mixed solution obtained in step 8 with the perfluorosulfonic acid dispersion in the fourth mixing chamber 28; Step 11: The final mixed solution obtained in step 10 is transferred to the second ultrasonic disperser 29. After the dispersion is completed, the mixed solution is sent to the stirred reactor 30 for stirring and mixing and adding carbon black. After the stirring is completed, the mixed slurry is transported to the second raw material storage tank 31 through a pipeline for storage; Step 12: Preheat the medium heating box 32 to reach the required temperature range to provide a stable heat source for the subsequent process steps. Fill the process water tank 33 with an appropriate amount of process water, which will be heated by the heating table 34 to reach the temperature conditions required for coating; Step 13: The heating table 34 is started to heat the process water in the process water tank 33 to a predetermined temperature. The heated process water or other coating medium is transported to the first multi-roller conveyor belt 35 through a pipeline. The multi-roller conveyor belt runs at a stable speed to ensure that the coating medium is evenly distributed on the conveyor belt. Step 14: After the coating medium is evenly distributed on the first multi-roller conveyor belt 35, the first slit coater 36 starts to work. The slit coater evenly coats the coating medium on the conveyor belt, such as the proton exchange membrane, through a precisely controlled slit to form a precursor for the cathode catalyst layer; Step 15: After coating, the substrate material is dried by a hot air device, and the dried cathode catalyst layer precursor enters the next process step; Step 16: On the porous carbon plate dressing platform 37, the required porous carbon plate and coating medium are prepared, and the second slit coater 38 evenly coats the coating medium on the porous carbon plate through a precisely controlled slit. After coating, the porous carbon plate is transported by the second multi-roller conveyor belt 39; Step 17: hot air drying is performed during the transportation process. After the coating is completed and the catalyst layer is completely dried, the anode catalyst layer is prepared and the processed anode catalyst layer is transferred to the next process for assembly; Step 18: Send the film material to the tensioning area, where the film material will be tightened by the tensioning device. After being tightened, the film material enters the hot press 41 area, where the hot press 41 applies high temperature and pressure to perform hot pressing treatment on the film material; Step 19: After the hot pressing treatment, the film material enters the cold press 42 area, and the cold press 42 further processes the film material by applying pressure and at a lower temperature. After the cold pressing treatment, the film material enters the third multi-roller conveyor belt 43 area, and on the third multi-roller conveyor belt 43, the film material is subjected to the rolling action of multiple rollers, so as to be further flattened and compacted; Step 20: The cooling device on the conveyor belt quickly cools the membrane material to room temperature, and the cold-pressed membrane electrode is sealed and stored.

[0039] When the present invention is working, first, in the unit storage tank 6, the graphite oxide solution and the ultrapure water are mixed in the first mixing chamber 8; then, the hydrogen fuel electrocatalyst and the NiCl2·6H2O solution are added for secondary mixing to form a uniform mixed solution; the mixed solution is sent to the flip stirring tank 9 for full stirring to ensure that the components are evenly dispersed; then the mixed solution enters the first ultrasonic disperser 11 and is ultrasonically stirred at room temperature to further promote the uniformity of the mixed solution; the ultrasonically dispersed mixed solution is transferred to the hydrothermal reactor 12 for hydrothermal reaction; after the reaction is completed, the obtained gel is sent to the first ultrasonic disperser 11 for ultrasonic stirring at room temperature to further promote the uniformity of the mixed solution; The gel enters the gel cleaning chamber 13 for cleaning to remove impurities; during the cleaning process, the deionized water preparation device 14 provides a continuous supply of deionized water to the cleaning chamber; the cleaned gel enters the conductivity test box 15 for testing to ensure that the purity and ion content of the product meet the requirements; the product is then sent to the freeze dryer 16 for low-temperature freezing and vacuum drying to remove moisture and solvent; the dried platinum-carbon composite enters the tubular furnace 17 for heat treatment to further improve its structure and performance; the weighing sensor 18 arranged after the tubular furnace 17 is used to accurately measure the weight of the product after heat treatment.

[0040] Raw materials are taken out from the ultrapure water storage tank 19, the alloy catalyst storage tank 20 and various alcohol storage tanks, and preliminarily mixed in the second mixing chamber 26 and the third mixing chamber 27 respectively; then the perfluorosulfonic acid dispersion is taken out from the perfluorosulfonic acid dispersion storage tank 25, and finally mixed with the previous mixed liquid in the fourth mixing chamber 28; the final mixed liquid is sent to the second ultrasonic disperser 29 for ultrasonic dispersion treatment to ensure that the components are evenly dispersed; then the mixed liquid enters the stirred reactor 30 for stirring and mixing to form a uniform layer membrane electrode slurry; after the stirring is completed, the slurry is sent to the second raw material storage tank 31 for storage and standby.

[0041] The medium heating box 32 and the process water tank 33 are preheated to the required temperature; the heated process water or other coating medium is transported to the first multi-roller conveyor belt 35; the first slit coater 36 evenly coats the coating medium on the proton exchange membrane through a precisely controlled slit to form a precursor of the cathode catalyst layer; after coating, the precursor is cured into a cathode catalyst layer by hot air drying; a porous carbon plate and a coating medium are prepared on a porous carbon plate dressing platform 37; the second slit coater 38 evenly coats the coating medium on the porous carbon plate through a precisely controlled slit to form a precursor of the anode catalyst layer; after coating, hot air drying is also performed to cure the anode catalyst layer.

[0042] The prepared film material is sent to the tensioning area for tensioning treatment to ensure its flatness; then the film material enters the hot press area 41 for hot pressing treatment under high temperature and high pressure to enhance its structure and performance; the hot-pressed film material enters the cold press area 42 for further treatment at a lower temperature to enhance its stability; then the film material is leveled and compacted on the third multi-roller conveyor belt 43 to ensure its surface flatness and internal structure tightness; finally, a cooling device is used to quickly cool the film material to room temperature and seal it for storage.

[0043] The present invention is not limited to the above-mentioned embodiments. On the basis of the technical solution disclosed in the present invention, technicians in this field can make some substitutions and deformations to some technical features therein according to the disclosed technical content without creative labor, and these substitutions and deformations are all within the protection scope of the present invention.

Claims

1. A three-dimensional porous graphene composite catalyst layer membrane electrode system, including a layer membrane electrode preparation system, characterized in that: The membrane electrode preparation system comprises a platinum-carbon catalyst preparation stage (1), the platinum-carbon catalyst preparation stage (1) is also provided with a membrane electrode slurry preparation stage (2), the membrane electrode slurry preparation stage (2) is also provided with a cathode catalyst layer preparation stage (3) and an anode catalyst layer preparation stage (4), and the membrane electrode preparation method also comprises a membrane electrode processing stage (5).

2. A three-dimensional porous graphene composite catalyst layer membrane electrode system according to claim 1, characterized in that: The platinum-carbon catalyst preparation stage (1) comprises a unit storage tank (6), wherein a plurality of groups of material storage units are arranged inside the unit storage tank (6), and a plurality of groups of first raw material storage tanks (7) are arranged on one side of the unit storage tank (6), and the first raw material storage tank (7) is connected to a first mixing bin (8) via a pipeline, and the first mixing bin (8) is provided with a flip-type stirring tank (9), and the flip-type stirring tank (9) is provided with a first transition bin (10), and the first transition bin (10) is connected to a first ultrasonic disperser (11), and the The first ultrasonic disperser (11) is connected to a hydrothermal reactor (12) via a pipeline, the hydrothermal reactor (12) is provided with a gel cleaning chamber (13), a deionized water preparation device (14) is separately provided on one side of the gel cleaning chamber (13), the gel cleaning chamber (13) is connected to a conductivity test box (15), the conductivity test box (15) is provided with a freeze dryer (16), a tubular furnace (17) is provided behind the freeze dryer (16), and the tubular furnace (17) is further provided with a weighing sensor (18).

3. The three-dimensional porous graphene composite catalyst layer membrane electrode system according to claim 1, characterized in that: The membrane electrode slurry preparation stage (2) comprises an ultrapure water storage tank (19), an alloy catalyst storage tank (20), an ethanol storage tank (21), an isopropanol storage tank (22), an n-propanol storage tank (23), an ethylene glycol storage tank (24) and a perfluorosulfonic acid dispersion storage tank (25); the ultrapure water storage tank (19) and the alloy catalyst storage tank (20) are connected to a second mixing tank (26); the ethanol storage tank (21), the isopropanol storage tank (22), the n-propanol storage tank (23) , the ethylene glycol storage tank (24) is connected to a third mixing chamber (27), the perfluorosulfonic acid dispersion storage tank (25) is provided with a fourth mixing chamber (28), the second mixing chamber (26), the third mixing chamber (27) and the fourth mixing chamber (28) are interconnected via pipelines, the fourth mixing chamber (28) is connected to a second ultrasonic disperser (29) and a stirred reactor (30), and the stirred reactor (30) is connected to a second raw material storage tank (31) via a pipeline.

4. The three-dimensional porous graphene composite catalyst layer membrane electrode system according to claim 1, characterized in that: The cathode catalyst layer preparation stage (3) includes a medium heating box (32), the medium heating box (32) is provided with a process water tank (33), the process water tank (33) is provided with a heating platform (34), the heating platform (34) is provided with a first multi-roller conveyor belt (35), and the multi-roller conveyor belt is connected to a first slit coater (36); the anode catalyst layer preparation stage (4) includes a porous carbon plate coating platform (37), the porous carbon plate coating platform (37) is connected to a second slit coater (38), and the porous carbon plate coating platform (37) is provided with a second multi-roller conveyor belt (39).

5. The three-dimensional porous graphene composite catalyst layer membrane electrode system according to claim 1, characterized in that: The membrane electrode processing stage (5) comprises a membrane material tensioning area (40), the membrane material tensioning area (40) is provided with a hot press (41), a cold press (42) is provided behind the hot press (41), and a third multi-roller conveyor belt (43) is provided behind the cold press (42).

6. The method for preparing a three-dimensional porous graphene composite catalyst layer membrane electrode system according to claim 1, characterized in that: The preparation method comprises the following steps: Step 1: preparing a graphite oxide solution to prepare a graphite oxide suspension solution of a certain concentration, transporting the graphite oxide solution to a plurality of storage units in a unit storage tank (6), first mixing ultrapure water and the graphite oxide solution in a first mixing chamber (8), and performing a concentration test on the mixed solution; Step 2: Mix the mixed liquid obtained in step 1 with the hydrogen fuel electrocatalyst in another group of first mixing chambers (8), add a small amount of NiCl2·6H2O solution, and mix again to obtain a mixed liquid; Step 3: transporting the mixed solution obtained in step 2 into a flip-type agitator for stirring and mixing, sending the mixed solution into a transition bin for mixed solution concentration detection, and after the detection is completed, sending the mixed solution into a first ultrasonic disperser (11) for ultrasonic stirring at room temperature; Step 4: transferring the mixed solution to a hydrothermal reactor (12) for hydrothermal reaction, waiting for the reactor to cool to room temperature, transferring the gel obtained by the reaction to a gel cleaning chamber (13) for cleaning, and replenishing water in a timely manner through a deionized water preparation device (14); Step 5: The washed product enters a conductivity test box (15) to detect the purity and ion content of the product through a conductivity test. The product that has passed the conductivity test is transported to a freeze dryer (16). In the freeze dryer (16), water and solvent in the product are removed through low-temperature freezing and vacuum drying to obtain a dry platinum-carbon complex. Step 6: The dried platinum-carbon composite enters a tubular furnace (17) for heat treatment. The heat treatment can further improve the structure and performance of the platinum-carbon composite. A weighing sensor (18) is arranged behind the tubular furnace (17) for accurately weighing the product after the heat treatment. Step 7: Ensure that sufficient raw materials are stored in the ultrapure water storage tank (19), the alloy catalyst storage tank (20), the ethanol storage tank (21), the isopropanol storage tank (22), the n-propanol storage tank (23), the ethylene glycol storage tank (24) and the perfluorosulfonic acid dispersion storage tank (25); Step 8: transporting ultrapure water from the ultrapure water storage tank (19) to the second mixing chamber (26) through a pipeline, and transporting the alloy catalyst from the alloy catalyst storage tank (20) to the second mixing chamber (26) through a pipeline; in the second mixing chamber (26), the ultrapure water and the alloy catalyst are preliminarily mixed; Step nine: transporting the raw materials in the ethanol storage tank (21), the isopropanol storage tank (22), the n-propanol storage tank (23) and the ethylene glycol storage tank (24) to the third mixing bin (27) through a pipeline. In the third mixing bin (27), the above four alcohol raw materials are preliminarily mixed and then mixed with the mixed liquid in step eight; Step 10: transporting the perfluorosulfonic acid dispersion from the perfluorosulfonic acid dispersion storage tank (25) to the fourth mixing chamber (28) through a pipeline, and mixing the mixed liquid obtained in step 8 with the perfluorosulfonic acid dispersion in the fourth mixing chamber (28); Step 11: The final mixed solution obtained in step 10 is transferred to a second ultrasonic disperser (29). After the dispersion is completed, the mixed solution is sent to a stirred reactor (30) for stirring and mixing and carbon black is added. After the stirring is completed, the mixed slurry is transported to a second raw material storage tank (31) through a pipeline for storage; Step 12: preheating the medium heating box (32) to reach the required temperature range to provide a stable heat source for the subsequent process steps, and filling the process water tank (33) with a proper amount of process water, which will be heated by the heating table (34) to reach the temperature conditions required for coating; Step 13: The heating table (34) is started to heat the process water in the process water tank (33) to a predetermined temperature. The heated process water or other coating medium is transported to the first multi-roller conveyor belt (35) through a pipeline. The multi-roller conveyor belt runs at a stable speed to ensure that the coating medium is evenly distributed on the conveyor belt. Step 14: After the coating medium is evenly distributed on the first multi-roller conveyor belt (35), the first slit coater (36) starts to work, and the slit coater evenly coats the coating medium on the conveyor belt, such as the proton exchange membrane, through a precisely controlled slit, to form a precursor of the cathode catalyst layer; Step 15: After coating, the substrate material is dried by a hot air device, and the dried cathode catalyst layer precursor enters the next process step; Step 16: On the porous carbon plate dressing platform (37), the required porous carbon plate and coating medium are prepared, and the second slit coater (38) coats the coating medium evenly on the porous carbon plate through a precisely controlled slit. After coating, the porous carbon plate is transported by a second multi-roller conveyor belt (39); Step 17: hot air drying is performed during the transportation process. After the coating is completed and the catalyst layer is completely dried, the anode catalyst layer is prepared and the processed anode catalyst layer is transferred to the next process for assembly; Step 18: Send the film material into the tensioning area, where the film material will be tensioned by the tensioning device. After being tensioned, the film material enters the hot press (41) area, where the hot press (41) applies high temperature and pressure to perform hot pressing treatment on the film material; Step 19: After the hot pressing treatment, the film material enters the cold pressing machine (42) area. The cold pressing machine (42) further processes the film material by applying pressure and at a lower temperature. After the cold pressing treatment, the film material enters the third multi-roller conveyor belt (43) area. On the third multi-roller conveyor belt (43), the film material is subjected to the rolling action of multiple rollers, thereby being further flattened and compacted. Step 20: The cooling device on the conveyor belt quickly cools the membrane material to room temperature, and the cold-pressed membrane electrode is sealed and stored.

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