Preparation method of proton exchange membrane water electrolysis hydrogen production membrane electrode

Abstract

The invention discloses a preparation method of a proton exchange membrane water electrolysis hydrogen production membrane electrode, and belongs to the technical field of proton exchange membranes, a catalyst carrier is prepared, S101, a polyimide membrane is inversely fixed in a magnetron sputtering vacuum coating chamber, a cavity cover of the magnetron sputtering vacuum coating chamber is closed, vacuumizing is performed, and a substrate is heated; and S102, argon is introduced into a cavity of the magnetron sputtering vacuum coating chamber, coating is started, the power of the bismuth metal target is set to be 0.2-0.5 kW, and the deposition time is 60-1800 s. In the invention, the physical vapor deposition method is utilized to load the catalyst on the surface of the metal oxide carrier with high specific surface area and ordered nanostructure, so that the exposure of active sites of the catalyst is increased, the dosage of the noble metal catalyst is reduced, and the bonding strength between the catalyst and the carrier is enhanced; the catalyst is not easy to separate from the surface of the carrier, and large-scale slurry agglomeration is avoided.

Description

Technical Field

[0001] The present invention belongs to the technical field of proton exchange membranes, and in particular relates to a method for preparing a membrane electrode for producing hydrogen through electrolysis of water using a proton exchange membrane. Background Art

[0002] The membrane electrode (MEA) is one of the most critical components in a proton exchange membrane (PEM) water electrolysis (H2) system, determining the energy consumption, efficiency, and stability of the system. MEA is typically fabricated using a coating method, where a slurry containing a cathode or anode catalyst is applied to the surface of the PEM and dried to form the cathode or anode catalyst layer. The quality of the catalyst slurry plays a crucial role in MEA performance. Catalyst nanoparticles typically do not exist independently but are attached to a carbon support or metal oxide support. To maximize the exposure of the catalyst's active sites and improve catalytic reaction efficiency, the support's specific surface area should be maximized, the amount of precious metal used should be reduced, and excessive agglomeration and catalyst shedding from the support should be avoided. Currently, catalysts are typically loaded onto supports using ionomers, followed by ultrasonic dispersion and ball milling to improve the uniformity of the slurry. However, commonly used supports have low specific surface areas and are prone to agglomeration, resulting in poor adhesion to the catalyst. Therefore, developing novel high-surface-area supports and corresponding catalyst loading processes to avoid agglomeration, further reduce precious metal loading, and improve MEA performance is of great significance.

[0003] In order to solve the problems of low specific surface area of ​​the catalyst of the traditional proton exchange membrane electrolysis water hydrogen production membrane electrode, easy detachment of the catalyst and easy agglomeration of the slurry, the present invention proposes a method for preparing an ordered high specific surface area proton exchange membrane electrolysis water hydrogen production membrane electrode. The catalyst is loaded on the surface of a metal oxide support with a high specific surface area and an ordered nanostructure by physical vapor deposition. This not only increases the exposure of the catalyst active sites and reduces the amount of precious metal catalyst, but also enhances the bonding strength between the catalyst and the support, making it difficult for the catalyst to detach from the support surface and avoiding large-scale agglomeration of the slurry. The water electrolysis hydrogen production membrane electrode prepared by this process has good process repeatability, high yield, low precious metal catalyst loading, and exhibits low energy consumption and high stability. Summary of the Invention

[0004] The purpose of the present invention is to solve the problems of low specific surface area of ​​traditional proton exchange membrane electrolysis water hydrogen production membrane electrode catalyst, easy catalyst shedding and easy agglomeration of slurry, and propose a preparation method for proton exchange membrane electrolysis water hydrogen production membrane electrode.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] A method for preparing a membrane electrode for hydrogen production by proton exchange membrane water electrolysis comprises the following steps:

[0007] S1. Preparation of catalyst carrier

[0008] S101, fixing the polyimide film upside down in a magnetron sputtering vacuum coating chamber, closing the chamber cover of the magnetron sputtering vacuum coating chamber, drawing vacuum, and heating the substrate;

[0009] S102, introducing argon gas into the cavity of the magnetron sputtering vacuum coating chamber, starting the coating, setting the bismuth metal target power to 0.2-0.5 kW, and the deposition time to 60-1800 s;

[0010] S103, when the substrate is heated to 280-350° C., a mixed gas of oxygen and argon is introduced into the cavity of the magnetron sputtering vacuum coating chamber;

[0011] S104, after the temperature of the magnetron sputtering vacuum coating chamber is lowered to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film with the nanostructure skeleton is taken out, and the polyimide film is used as a catalyst carrier;

[0012] S2. Loading the catalyst on the surface of the polyimide membrane with a nanostructured skeleton

[0013] S201, loading platinum metal as a cathode catalyst on the surface of the polyimide film with a nanostructured skeleton, fixing the polyimide film with a nanostructured skeleton in a magnetron sputtering vacuum coating chamber, closing the chamber cover, evacuating the chamber, and heating the substrate;

[0014] S202, introducing argon gas into the chamber, starting the coating, setting the platinum target power to 0.1-0.4 kW, and the deposition time to 30-180 s, and adjusting the deposition time to control the catalyst loading;

[0015] S203, after the temperature drops to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film loaded with platinum catalyst on the nanostructure skeleton is taken out;

[0016] S204, loading a ruthenium-iridium alloy as an anode catalyst on the surface of the polyimide membrane having a nanostructured skeleton;

[0017] S205, fixing the polyimide film with the nanostructure skeleton in a magnetron sputtering vacuum coating chamber, closing the chamber cover, and drawing the vacuum;

[0018] S206, introducing argon gas into the chamber, starting the film coating, setting the ruthenium target power to 0.2-0.6 kW, and the iridium target power to 0.05-0.15 kW, adjusting the ratio of ruthenium to iridium in the alloy catalyst by controlling the power of the ruthenium target and the iridium target, and adjusting the deposition time to 30-180 s, and controlling the catalyst loading by adjusting the deposition time;

[0019] S207, after the temperature drops to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film loaded with the ruthenium-iridium alloy catalyst on the nanostructure skeleton is taken out;

[0020] S3. Preparation of membrane electrode using transfer method

[0021] S301, aligning and stacking a polyimide membrane with a ruthenium-iridium alloy catalyst loaded on a nanostructure skeleton, an N115 proton exchange membrane, and a polyimide membrane with a platinum catalyst loaded on a nanostructure skeleton, with the catalyst surface in close contact with the proton exchange membrane, and placing them in a hot press;

[0022] S302, tearing off the polyimide membrane, and transferring the nanostructure skeleton loaded with the catalyst to both sides of the proton exchange membrane to obtain a membrane electrode;

[0023] S303, installing the obtained membrane electrode on an electrolyzer to test hydrogen production performance;

[0024] S4. Preparation of membrane electrode using direct coating and spraying methods

[0025] S401, preparing a catalyst slurry, scraping the nanostructured skeleton carrier loaded with the platinum catalyst from the polyimide film using a scraper to obtain a nanostructured skeleton carrier powder loaded with the platinum catalyst;

[0026] S402, mixing water and alcohol (ethanol or n-propanol), and stirring at high speed to obtain a hydroalcohol solution;

[0027] S403, mixing the hydroalcohol solution and the Nafion solution, and stirring at high speed for 300-600 seconds to obtain a dispersion solvent;

[0028] S404, mixing the nanostructured skeleton carrier powder loaded with the platinum catalyst with a dispersing solvent and a thickener to obtain an initial cathode catalyst slurry, wherein the mass ratio of the nanostructured skeleton carrier powder loaded with the platinum catalyst is 10-50%, and the viscosity of the slurry is adjusted by adjusting the amount of the thickener;

[0029] S405, ultrasonically treating the initial catalyst slurry for 30-300 seconds, and then homogenizing it using a high-speed homogenizer for 3-15 minutes to obtain a cathode catalyst slurry. The anode catalyst slurry is prepared in the same manner;

[0030] S5. The cathode catalyst slurry and the anode catalyst slurry prepared in S3-S4 are coated on both sides of the proton exchange membrane by direct coating to prepare a membrane electrode, and the hydrogen production performance is tested;

[0031] S501, placing the N115 proton exchange membrane on a workbench and coating it with cathode catalyst slurry;

[0032] S502, after the cathode catalyst slurry is coated, the cathode catalyst slurry is placed in an oven to obtain a membrane electrode coated with the cathode catalyst slurry;

[0033] S503, placing the membrane electrode coated with the cathode catalyst slurry on a workbench, and coating the other side with the anode catalyst slurry;

[0034] S504. After the cathode catalyst slurry is coated, it is placed in an oven to obtain a complete membrane electrode. The obtained membrane electrode is installed in an electrolyzer to test the hydrogen production performance. The test conditions are a current density of 1A / cm2 and a voltage of 1.6-1.85V;

[0035] S6. Spray-coat the cathode catalyst slurry and the anode catalyst slurry prepared in S3-S4 onto both sides of the proton exchange membrane to prepare a membrane electrode, and test the hydrogen production performance.

[0036] S601, placing the N115 proton exchange membrane on a workbench and spraying the cathode catalyst slurry, and controlling the catalytic coating thickness by controlling the spraying time;

[0037] S602, after the cathode catalyst slurry is sprayed, the cathode catalyst slurry is placed in an oven to obtain a membrane electrode sprayed with the cathode catalyst slurry;

[0038] S603, placing the membrane electrode sprayed with the cathode catalyst slurry on a workbench, and coating the other side with the anode catalyst slurry. The spraying time is 30-120 seconds. The thickness of the catalytic coating can be controlled by controlling the spraying time.

[0039] S604. After spraying the anode catalyst slurry, place it in an oven to obtain a complete membrane electrode, and then install the obtained membrane electrode on the electrolyzer to test the hydrogen production performance.

[0040] As a further description of the above technical solution:

[0041] In the S101, the vacuum is evacuated to below 0.0006P, and the substrate is heated to 50-250°C. In the S102, the argon flow rate is 30-100 sccm, and the gas pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.1-0.5 Pa.

[0042] As a further description of the above technical solution:

[0043] In the above S103, the volume ratio of oxygen is 5-100% by flow rate, and the gas pressure is maintained at 0.05-0.2 Pa for 1-60 minutes.

[0044] As a further description of the above technical solution:

[0045] In the S201, the pressure is evacuated to 0.0005 Pa, the substrate is heated to 50-100° C., and a bias voltage of 0-300 V is applied. In the S202, the argon flow rate is 30-100 sccm, and the pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.1-0.5 Pa.

[0046] As a further description of the above technical solution:

[0047] In the S205, the pressure is evacuated to 0.0005 Pa, heated to 50-100° C., and a bias voltage of 0-300 V is applied. In the S206, the argon flow rate is 30-100 sccm, and the pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.1-0.5 Pa.

[0048] As a further description of the above technical solution:

[0049] In S303, the current density of the electrolytic cell is controlled at 1A / cm2 and the voltage is 1.6-1.85V.

[0050] As a further description of the above technical solution:

[0051] In the step S403 , the stirring rate is controlled at 300-600 s, wherein the mass ratio of water is 40-70%. In the step S405 , the rotation speed of the high-speed homogenizer is 8000-15000 rpm.

[0052] As a further description of the above technical solution:

[0053] In S501 and S503, the workbench heating temperature is 35-80°C, the coating rate is 0.5-2m / min, and the coating thickness is 20-50μm. In S502 and S504, the oven temperature is controlled at 60-90°C, and the drying time is controlled at 30-60min.

[0054] As a further description of the above technical solution:

[0055] In the above-mentioned S601 and S603, the workbench heating temperature is 35-80° C., the spraying pressure is 1.5-5 bar, the spraying distance is 15-45 cm, the spraying angle is 30-60°, the spraying time is 30-120 s, and the coating thickness is 10-30 μm.

[0056] As a further description of the above technical solution:

[0057] In S602 and S604, the temperature of the oven is controlled at 60-90°C, and the drying time is controlled at 30-60 minutes. In S604, the test conditions are a current density of 1 A / cm2 and a voltage of 1.6-1.85 V.

[0058] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0059] In the present invention, the catalyst is loaded on the surface of a metal oxide support with a high specific surface area and an ordered nanostructure by physical vapor deposition. This not only increases the exposure of the catalyst's active sites and reduces the amount of precious metal catalyst used, but also enhances the bonding strength between the catalyst and the support, making it difficult for the catalyst to detach from the support surface and avoiding large-scale agglomeration of the slurry. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] Figure 1 This is a schematic diagram of the morphology and structure of bismuth oxide in the method for preparing a membrane electrode for hydrogen production by proton exchange membrane electrolysis of water proposed in the present invention. DETAILED DESCRIPTION

[0061] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0062] See also Figure 1

[0063] Example 1

[0064] The present invention provides a technical solution: a method for preparing a membrane electrode for hydrogen production by proton exchange membrane water electrolysis, characterized in that it specifically comprises the following steps:

[0065] S1. Preparation of catalyst carrier

[0066] S101, fixing the polyimide film upside down in a magnetron sputtering vacuum coating chamber, closing the chamber cover of the magnetron sputtering vacuum coating chamber, drawing vacuum, and heating the substrate;

[0067] In the step S101, the vacuum is evacuated to below 0.0006P, and the substrate is heated to 50°C. In the step S102, the argon flow rate is 30 sccm, and the pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.1 Pa.

[0068] S102, introducing argon gas into the cavity of the magnetron sputtering vacuum coating chamber, starting the coating, setting the bismuth metal target power to 0.2 kW, and the deposition time to 60 s;

[0069] S103, when the substrate is heated to 280° C., a mixed gas of oxygen and argon is introduced into the cavity of the magnetron sputtering vacuum coating chamber;

[0070] In S103, the flow rate is 5% by volume of oxygen, the pressure is maintained at 0.05 Pa, and the maintenance time is 1 minute;

[0071] S104, after the temperature of the magnetron sputtering vacuum coating chamber is lowered to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film with the nanostructure skeleton is taken out, and the polyimide film is used as a catalyst carrier;

[0072] S2. Loading the catalyst on the surface of the polyimide membrane with a nanostructured skeleton

[0073] S201, loading platinum metal as a cathode catalyst on the surface of the polyimide film with a nanostructured skeleton, fixing the polyimide film with a nanostructured skeleton in a magnetron sputtering vacuum coating chamber, closing the chamber cover, evacuating the chamber, and heating the substrate;

[0074] In the step S201 , the vacuum is evacuated to 0.0005 Pa, the substrate is heated to 50° C., and a bias voltage of 0 V is applied. In the step S202 , the argon flow rate is 30 sccm, and the pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.1 Pa.

[0075] S202, introducing argon gas into the chamber, starting the coating, setting the platinum target power to 0.1 kW, and the deposition time to 30 s, and adjusting the deposition time to control the catalyst loading;

[0076] S203, after the temperature drops to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film loaded with platinum catalyst on the nanostructure skeleton is taken out;

[0077] S204, loading a ruthenium-iridium alloy as an anode catalyst on the surface of the polyimide membrane having a nanostructured skeleton;

[0078] S205, fixing the polyimide film with the nanostructure skeleton in a magnetron sputtering vacuum coating chamber, closing the chamber cover, and drawing the vacuum;

[0079] In the step S205 , the vacuum is evacuated to 0.0005 Pa, the chamber is heated to 50° C., and a bias voltage of 0 V is applied. In the step S206 , the argon flow rate is 30 sccm, and the pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.1 Pa.

[0080] S206, introducing argon gas into the chamber, starting the film coating, setting the ruthenium target power to 0.2 kW, and the iridium target power to 0.05 kW, adjusting the ratio of ruthenium to iridium in the alloy catalyst by controlling the power of the ruthenium target and the iridium target, and adjusting the deposition time to 30 s, and controlling the catalyst loading by adjusting the deposition time;

[0081] S207, after the temperature drops to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film loaded with the ruthenium-iridium alloy catalyst on the nanostructure skeleton is taken out;

[0082] S3. Preparation of membrane electrode using transfer method

[0083] S301, aligning and stacking a polyimide membrane with a ruthenium-iridium alloy catalyst loaded on a nanostructure skeleton, an N115 proton exchange membrane, and a polyimide membrane with a platinum catalyst loaded on a nanostructure skeleton, with the catalyst surface in close contact with the proton exchange membrane, and placing them in a hot press;

[0084] S302, tearing off the polyimide membrane, and transferring the nanostructure skeleton loaded with the catalyst to both sides of the proton exchange membrane to obtain a membrane electrode;

[0085] S303, installing the obtained membrane electrode on an electrolyzer to test hydrogen production performance;

[0086] In S303, the current density of the electrolytic cell is controlled at 1A / cm2 and the voltage is 1.6V;

[0087] S4. Preparation of membrane electrode using direct coating and spraying methods

[0088] S401, preparing a catalyst slurry, scraping the nanostructured skeleton carrier loaded with the platinum catalyst from the polyimide film using a scraper to obtain a nanostructured skeleton carrier powder loaded with the platinum catalyst;

[0089] S402, mixing water and alcohol (ethanol or n-propanol), and stirring at high speed to obtain a hydroalcohol solution;

[0090] S403, mixing the hydroalcohol solution and the Nafion solution, and stirring at high speed for 300 seconds to obtain a dispersion solvent;

[0091] In said S403, the stirring rate is controlled at 300s, wherein the mass ratio of water is 40%, and in said S405, the speed of the high-speed homogenizer is 8000 rpm;

[0092] S404, mixing the nanostructured skeleton carrier powder loaded with the platinum catalyst with a dispersing solvent and a thickener to obtain an initial cathode catalyst slurry, wherein the mass ratio of the nanostructured skeleton carrier powder loaded with the platinum catalyst is 10%, and the viscosity of the slurry is adjusted by adjusting the amount of the thickener;

[0093] S405, ultrasonically treating the initial catalyst slurry for 30 seconds, and then homogenizing it using a high-speed homogenizer for 3 minutes to obtain a cathode catalyst slurry. The anode catalyst slurry is prepared in the same way;

[0094] S5. The cathode catalyst slurry and the anode catalyst slurry prepared in S3-S4 are coated on both sides of the proton exchange membrane by direct coating to prepare a membrane electrode, and the hydrogen production performance is tested;

[0095] S501, placing the N115 proton exchange membrane on a workbench and coating it with cathode catalyst slurry;

[0096] S502, after the cathode catalyst slurry is coated, the cathode catalyst slurry is placed in an oven to obtain a membrane electrode coated with the cathode catalyst slurry;

[0097] S503, placing the membrane electrode coated with the cathode catalyst slurry on a workbench, and coating the other side with the anode catalyst slurry;

[0098] In S501 and S503, the workbench heating temperature is 35°C, the coating rate is 0.5 m / min, and the coating thickness is 20 μm. In S502 and S504, the oven temperature is controlled at 60°C and the drying time is controlled at 30 min.

[0099] S504, after coating the cathode catalyst slurry, place it in an oven to obtain a complete membrane electrode, and install the obtained membrane electrode on an electrolyzer to test the hydrogen production performance. The test conditions are a current density of 1A / cm2 and a voltage of 1.6V;

[0100] S6. Spray-coat the cathode catalyst slurry and the anode catalyst slurry prepared in S3-S4 onto both sides of the proton exchange membrane to prepare a membrane electrode, and test the hydrogen production performance.

[0101] S601, placing the N115 proton exchange membrane on a workbench and spraying the cathode catalyst slurry, and controlling the catalytic coating thickness by controlling the spraying time;

[0102] S602, after the cathode catalyst slurry is sprayed, the cathode catalyst slurry is placed in an oven to obtain a membrane electrode sprayed with the cathode catalyst slurry;

[0103] S603, placing the membrane electrode sprayed with the cathode catalyst slurry on a workbench, and coating the other side with the anode catalyst slurry. The spraying time is 30-120 seconds. The thickness of the catalytic coating can be controlled by controlling the spraying time.

[0104] In S601 and S603, the workbench heating temperature is 35°C, the spraying pressure is 1.5 bar, the spraying distance is 15 cm, the spraying angle is 30°, the spraying time is 30 s, and the coating thickness is 10 μm;

[0105] S604, after spraying the anode catalyst slurry, place it in an oven to obtain a complete membrane electrode, and install the obtained membrane electrode on an electrolyzer to test the hydrogen production performance;

[0106] In S602 and S604, the temperature of the oven is controlled at 60° C., and the drying time is controlled at 30 min. In S604, the test conditions are a current density of 1 A / cm 2 and a voltage of 1.6 V.

[0107] Example 2

[0108] The present invention provides a technical solution: a method for preparing a membrane electrode for hydrogen production by proton exchange membrane water electrolysis, characterized in that it specifically comprises the following steps:

[0109] S1. Preparation of catalyst carrier

[0110] S101, fixing the polyimide film upside down in a magnetron sputtering vacuum coating chamber, closing the chamber cover of the magnetron sputtering vacuum coating chamber, drawing vacuum, and heating the substrate;

[0111] In the step S101, the vacuum is evacuated to below 0.0006P, and the substrate is heated to 150° C. In the step S102, the argon flow rate is 70 sccm, and the pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.3 Pa.

[0112] S102, introducing argon gas into the cavity of the magnetron sputtering vacuum coating chamber, starting the coating, setting the bismuth metal target power to 0.35 kW, and the deposition time to 900 s;

[0113] S103, when the substrate is heated to 320° C., a mixed gas of oxygen and argon is introduced into the cavity of the magnetron sputtering vacuum coating chamber;

[0114] In S103, the flow rate is 50% by volume of oxygen, the pressure is maintained at 0.1 Pa, and the duration is 30 minutes;

[0115] S104, after the temperature of the magnetron sputtering vacuum coating chamber is lowered to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film with the nanostructure skeleton is taken out, and the polyimide film is used as a catalyst carrier;

[0116] S2. Loading the catalyst on the surface of the polyimide membrane with a nanostructured skeleton

[0117] S201, loading platinum metal as a cathode catalyst on the surface of the polyimide film with a nanostructured skeleton, fixing the polyimide film with a nanostructured skeleton in a magnetron sputtering vacuum coating chamber, closing the chamber cover, evacuating the chamber, and heating the substrate;

[0118] In the step S201 , the vacuum is evacuated to 0.0005 Pa, the substrate is heated to 75° C., and a bias voltage of 150 V is applied. In the step S202 , the argon flow rate is 70 sccm, and the pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.3 Pa.

[0119] S202, introducing argon gas into the chamber, starting the coating, setting the platinum target power to 0.25 kW, and the deposition time to 100 s, and adjusting the deposition time to control the catalyst loading;

[0120] S203, after the temperature drops to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film loaded with platinum catalyst on the nanostructure skeleton is taken out;

[0121] S204, loading a ruthenium-iridium alloy as an anode catalyst on the surface of the polyimide membrane having a nanostructured skeleton;

[0122] S205, fixing the polyimide film with the nanostructure skeleton in a magnetron sputtering vacuum coating chamber, closing the chamber cover, and drawing the vacuum;

[0123] In the step S205 , the vacuum is evacuated to 0.0005 Pa, the chamber is heated to 75° C., and a bias voltage of 150 V is applied. In the step S206 , the argon flow rate is 75 sccm, and the pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.3 Pa.

[0124] S206, introducing argon gas into the chamber, starting the film coating, setting the ruthenium target power to 0.4 kW, and the iridium target power to 0.8 kW, adjusting the ratio of ruthenium to iridium in the alloy catalyst by controlling the power of the ruthenium target and the iridium target, and adjusting the deposition time to 100 s, and controlling the catalyst loading by adjusting the deposition time;

[0125] S207, after the temperature drops to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film loaded with the ruthenium-iridium alloy catalyst on the nanostructure skeleton is taken out;

[0126] S3. Preparation of membrane electrode using transfer method

[0127] S301, aligning and stacking a polyimide membrane with a ruthenium-iridium alloy catalyst loaded on a nanostructure skeleton, an N115 proton exchange membrane, and a polyimide membrane with a platinum catalyst loaded on a nanostructure skeleton, with the catalyst surface in close contact with the proton exchange membrane, and placing them in a hot press;

[0128] S302, tearing off the polyimide membrane, and transferring the nanostructure skeleton loaded with the catalyst to both sides of the proton exchange membrane to obtain a membrane electrode;

[0129] S303, installing the obtained membrane electrode on an electrolyzer to test hydrogen production performance;

[0130] In S303, the current density of the electrolytic cell is controlled at 1A / cm2 and the voltage is 1.7V;

[0131] S4. Preparation of membrane electrode using direct coating and spraying methods

[0132] S401, preparing a catalyst slurry, scraping the nanostructured skeleton carrier loaded with the platinum catalyst from the polyimide film using a scraper to obtain a nanostructured skeleton carrier powder loaded with the platinum catalyst;

[0133] S402, mixing water and alcohol (ethanol or n-propanol), and stirring at high speed to obtain a hydroalcohol solution;

[0134] S403, mixing the hydroalcohol solution and the Nafion solution, and stirring at high speed for 450 seconds to obtain a dispersion solvent;

[0135] In said S403, the stirring rate is controlled at 450s, wherein the mass ratio of water is 65%, and in said S405, the speed of the high-speed homogenizer is 12000 rpm;

[0136] S404, mixing the nanostructured skeleton carrier powder loaded with the platinum catalyst with a dispersing solvent and a thickener to obtain an initial cathode catalyst slurry, wherein the mass ratio of the nanostructured skeleton carrier powder loaded with the platinum catalyst is 30%, and the viscosity of the slurry is adjusted by adjusting the amount of the thickener;

[0137] S405, ultrasonically treating the initial catalyst slurry for 150 seconds, and then homogenizing it using a high-speed homogenizer for 9 minutes to obtain a cathode catalyst slurry. The anode catalyst slurry is prepared in the same way;

[0138] S5. The cathode catalyst slurry and the anode catalyst slurry prepared in S3-S4 are coated on both sides of the proton exchange membrane by direct coating to prepare a membrane electrode, and the hydrogen production performance is tested;

[0139] S501, placing the N115 proton exchange membrane on a workbench and coating it with cathode catalyst slurry;

[0140] S502, after the cathode catalyst slurry is coated, the cathode catalyst slurry is placed in an oven to obtain a membrane electrode coated with the cathode catalyst slurry;

[0141] S503, placing the membrane electrode coated with the cathode catalyst slurry on a workbench, and coating the other side with the anode catalyst slurry;

[0142] In S501 and S503, the workbench heating temperature is 65°C, the coating rate is 0.1 m / min, and the coating thickness is 35 μm. In S502 and S504, the oven temperature is controlled at 75°C and the drying time is controlled at 45 min.

[0143] S504, after coating the cathode catalyst slurry, place it in an oven to obtain a complete membrane electrode, and install the obtained membrane electrode on an electrolyzer to test the hydrogen production performance. The test conditions are a current density of 1A / cm2 and a voltage of 1.7V;

[0144] S6. Spray-coat the cathode catalyst slurry and the anode catalyst slurry prepared in S3-S4 onto both sides of the proton exchange membrane to prepare a membrane electrode, and test the hydrogen production performance.

[0145] S601, placing the N115 proton exchange membrane on a workbench and spraying the cathode catalyst slurry, and controlling the catalytic coating thickness by controlling the spraying time;

[0146] S602, after the cathode catalyst slurry is sprayed, the cathode catalyst slurry is placed in an oven to obtain a membrane electrode sprayed with the cathode catalyst slurry;

[0147] S603, placing the membrane electrode sprayed with the cathode catalyst slurry on a workbench, and coating the other side with the anode catalyst slurry. The spraying time is 80 seconds, and the thickness of the catalytic coating is controlled by controlling the spraying time;

[0148] In S601 and S603, the workbench heating temperature is 65°C, the spraying pressure is 3.5 bar, the spraying distance is 30 cm, the spraying angle is 45°, the spraying time is 75 s, and the coating thickness is 20 μm;

[0149] S604, after spraying the anode catalyst slurry, place it in an oven to obtain a complete membrane electrode, and install the obtained membrane electrode on an electrolyzer to test the hydrogen production performance;

[0150] In S602 and S604, the temperature of the oven is controlled at 75° C., and the drying time is controlled at 45 min. In S604, the test conditions are a current density of 1 A / cm 2 and a voltage of 1.7 V.

[0151] Example 3

[0152] The present invention provides a technical solution: a method for preparing a membrane electrode for hydrogen production by proton exchange membrane water electrolysis, characterized in that it specifically comprises the following steps:

[0153] S1. Preparation of catalyst carrier

[0154] S101, fixing the polyimide film upside down in a magnetron sputtering vacuum coating chamber, closing the chamber cover of the magnetron sputtering vacuum coating chamber, drawing vacuum, and heating the substrate;

[0155] In the step S101, the pressure is evacuated to below 0.0006P, and the substrate is heated to 250° C. In the step S102, the argon flow rate is 100 sccm, and the pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.5 Pa.

[0156] S102, introducing argon gas into the cavity of the magnetron sputtering vacuum coating chamber, starting the coating, setting the bismuth metal target power to 0.5 kW, and the deposition time to 1800 s;

[0157] S103, when the substrate is heated to 350° C., a mixed gas of oxygen and argon is introduced into the cavity of the magnetron sputtering vacuum coating chamber;

[0158] In the step S103, the volume ratio of oxygen is 100%, and the pressure is maintained at 0.2 Pa for 60 minutes;

[0159] S104, after the temperature of the magnetron sputtering vacuum coating chamber is lowered to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film with the nanostructure skeleton is taken out, and the polyimide film is used as a catalyst carrier;

[0160] S2. Loading the catalyst on the surface of the polyimide membrane with a nanostructured skeleton

[0161] S201, loading platinum metal as a cathode catalyst on the surface of the polyimide film with a nanostructured skeleton, fixing the polyimide film with a nanostructured skeleton in a magnetron sputtering vacuum coating chamber, closing the chamber cover, evacuating the chamber, and heating the substrate;

[0162] In the step S201 , the pressure is evacuated to 0.0005 Pa, the substrate is heated to 50-100° C., and a bias voltage of 300 V is applied. In the step S202 , the argon flow rate is 100 sccm, and the pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.5 Pa.

[0163] S202, introducing argon gas into the chamber, starting the coating, setting the platinum target power to 0.4 kW, and the deposition time to 30-180 s, adjusting the deposition time to control the catalyst loading;

[0164] S203, after the temperature drops to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film loaded with platinum catalyst on the nanostructure skeleton is taken out;

[0165] S204, loading a ruthenium-iridium alloy as an anode catalyst on the surface of the polyimide membrane having a nanostructured skeleton;

[0166] S205, fixing the polyimide film with the nanostructure skeleton in a magnetron sputtering vacuum coating chamber, closing the chamber cover, and drawing the vacuum;

[0167] In the step S205 , the pressure is evacuated to 0.0005 Pa, the chamber is heated to 100° C., and a bias voltage of 300 V is applied. In the step S206 , the argon flow rate is 100 sccm, and the pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.5 Pa.

[0168] S206, introducing argon gas into the chamber, starting the film coating, setting the ruthenium target power to 0.6 kW, and the iridium target power to 0.15 kW, adjusting the ratio of ruthenium to iridium in the alloy catalyst by controlling the power of the ruthenium target and the iridium target, and adjusting the deposition time to 180 s, and controlling the catalyst loading by adjusting the deposition time;

[0169] S207, after the temperature drops to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film loaded with the ruthenium-iridium alloy catalyst on the nanostructure skeleton is taken out;

[0170] S3. Preparation of membrane electrode using transfer method

[0171] S301, aligning and stacking a polyimide membrane with a ruthenium-iridium alloy catalyst loaded on a nanostructure skeleton, an N115 proton exchange membrane, and a polyimide membrane with a platinum catalyst loaded on a nanostructure skeleton, with the catalyst surface in close contact with the proton exchange membrane, and placing them in a hot press;

[0172] S302, tearing off the polyimide membrane, and transferring the nanostructure skeleton loaded with the catalyst to both sides of the proton exchange membrane to obtain a membrane electrode;

[0173] S303, installing the obtained membrane electrode on an electrolyzer to test hydrogen production performance;

[0174] In S303, the current density of the electrolytic cell is controlled at 1A / cm2 and the voltage is 1.85V;

[0175] S4. Preparation of membrane electrode using direct coating and spraying methods

[0176] S401, preparing a catalyst slurry, scraping the nanostructured skeleton carrier loaded with the platinum catalyst from the polyimide film using a scraper to obtain a nanostructured skeleton carrier powder loaded with the platinum catalyst;

[0177] S402, mixing water and alcohol (ethanol or n-propanol), and stirring at high speed to obtain a hydroalcohol solution;

[0178] S403, mixing the hydroalcohol solution and the Nafion solution, and stirring at high speed for 300-600 seconds to obtain a dispersion solvent;

[0179] In said S403, the stirring rate is controlled at 600s, wherein the mass ratio of water is 70%, and in said S405, the speed of the high-speed homogenizer is 15000 rpm;

[0180] S404, mixing the nanostructured skeleton carrier powder loaded with the platinum catalyst with a dispersing solvent and a thickener to obtain an initial cathode catalyst slurry, wherein the mass ratio of the nanostructured skeleton carrier powder loaded with the platinum catalyst is 10-50%, and the viscosity of the slurry is adjusted by adjusting the amount of the thickener;

[0181] S405, ultrasonically treating the initial catalyst slurry for 300 seconds, and then homogenizing it using a high-speed homogenizer for 15 minutes to obtain a cathode catalyst slurry. The anode catalyst slurry is prepared in the same manner;

[0182] S5. The cathode catalyst slurry and the anode catalyst slurry prepared in S3-S4 are coated on both sides of the proton exchange membrane by direct coating to prepare a membrane electrode, and the hydrogen production performance is tested;

[0183] S501, placing the N115 proton exchange membrane on a workbench and coating it with cathode catalyst slurry;

[0184] S502, after the cathode catalyst slurry is coated, the cathode catalyst slurry is placed in an oven to obtain a membrane electrode coated with the cathode catalyst slurry;

[0185] S503, placing the membrane electrode coated with the cathode catalyst slurry on a workbench, and coating the other side with the anode catalyst slurry;

[0186] In S501 and S503, the workbench heating temperature is 80°C, the coating rate is 2m / min, and the coating thickness is 50μm. In S502 and S504, the oven temperature is controlled at 90°C and the drying time is controlled at 60min.

[0187] S504, after coating the cathode catalyst slurry, placing it in an oven to obtain a complete membrane electrode, and installing the obtained membrane electrode on an electrolyzer to test the hydrogen production performance. The test conditions are a current density of 1A / cm2 and a voltage of 1.85V;

[0188] S6. Spray-coat the cathode catalyst slurry and the anode catalyst slurry prepared in S3-S4 onto both sides of the proton exchange membrane to prepare a membrane electrode, and test the hydrogen production performance.

[0189] S601, placing the N115 proton exchange membrane on a workbench and spraying the cathode catalyst slurry, and controlling the catalytic coating thickness by controlling the spraying time;

[0190] S602, after the cathode catalyst slurry is sprayed, the cathode catalyst slurry is placed in an oven to obtain a membrane electrode sprayed with the cathode catalyst slurry;

[0191] S603, placing the membrane electrode sprayed with the cathode catalyst slurry on a workbench, and coating the other side with the anode catalyst slurry. The spraying time is 120 seconds, and the thickness of the catalytic coating is controlled by controlling the spraying time;

[0192] In S601 and S603, the workbench heating temperature is 80°C, the spraying pressure is 5 bar, the spraying distance is 45 cm, the spraying angle is 60°, the spraying time is 120 s, and the coating thickness is 30 μm;

[0193] S604, after spraying the anode catalyst slurry, place it in an oven to obtain a complete membrane electrode, and install the obtained membrane electrode on an electrolyzer to test the hydrogen production performance;

[0194] In S602 and S604, the temperature of the oven is controlled at 90° C. and the drying time is controlled at 60 min. In S604, the test conditions are a current density of 1 A / cm 2 and a voltage of 1.85 V.

[0195] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A method for preparing a membrane electrode for hydrogen production by proton exchange membrane water electrolysis, characterized in that: The specific steps include: S1. Preparation of catalyst carrier S101, fixing the polyimide film upside down in a magnetron sputtering vacuum coating chamber, closing the chamber cover of the magnetron sputtering vacuum coating chamber, drawing vacuum, and heating the substrate; S102, introducing argon gas into the cavity of the magnetron sputtering vacuum coating chamber, starting the coating, setting the bismuth metal target power to 0.2-0.5 kW, and the deposition time to 60-1800 s; S103, when the substrate is heated to 280-350° C., a mixed gas of oxygen and argon is introduced into the cavity of the magnetron sputtering vacuum coating chamber; S104, after the temperature of the magnetron sputtering vacuum coating chamber is lowered to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film with the nanostructure skeleton is taken out, and the polyimide film is used as a catalyst carrier; S2. Loading the catalyst on the surface of the polyimide membrane with a nanostructured skeleton S201, loading platinum metal as a cathode catalyst on the surface of the polyimide film with a nanostructured skeleton, fixing the polyimide film with a nanostructured skeleton in a magnetron sputtering vacuum coating chamber, closing the chamber cover, evacuating the chamber, and heating the substrate; S202, introducing argon gas into the chamber, starting the coating, setting the platinum target power to 0.1-0.4 kW, and the deposition time to 30-180 s, and adjusting the deposition time to control the catalyst loading; S203, after the temperature drops to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film loaded with platinum catalyst on the nanostructure skeleton is taken out; S204, loading a ruthenium-iridium alloy as an anode catalyst on the surface of the polyimide membrane having a nanostructured skeleton; S205, fixing the polyimide film with the nanostructure skeleton in a magnetron sputtering vacuum coating chamber, closing the chamber cover, and drawing the vacuum; S206, introducing argon gas into the chamber, starting the film coating, setting the ruthenium target power to 0.2-0.6 kW, and the iridium target power to 0.05-0.15 kW, adjusting the ratio of ruthenium to iridium in the alloy catalyst by controlling the power of the ruthenium target and the iridium target, and adjusting the deposition time to 30-180 s, and controlling the catalyst loading by adjusting the deposition time; S207, after the temperature drops to room temperature, nitrogen is introduced into the chamber to break the vacuum, the chamber cover is opened, and the polyimide film loaded with the ruthenium-iridium alloy catalyst on the nanostructure skeleton is taken out; S3. Preparation of membrane electrode using transfer method S301, aligning and stacking a polyimide membrane with a ruthenium-iridium alloy catalyst loaded on a nanostructure skeleton, an N115 proton exchange membrane, and a polyimide membrane with a platinum catalyst loaded on a nanostructure skeleton, with the catalyst surface in close contact with the proton exchange membrane, and placing them in a hot press; S302, tearing off the polyimide membrane, and transferring the nanostructure skeleton loaded with the catalyst to both sides of the proton exchange membrane to obtain a membrane electrode; S303, installing the obtained membrane electrode on an electrolyzer to test hydrogen production performance; S4. Preparation of membrane electrode using direct coating and spraying methods S401, preparing a catalyst slurry, scraping the nanostructured skeleton carrier loaded with the platinum catalyst from the polyimide film using a scraper to obtain a nanostructured skeleton carrier powder loaded with the platinum catalyst; S402, mixing water and alcohol (ethanol or n-propanol), and stirring at high speed to obtain a hydroalcohol solution; S403, mixing the hydroalcohol solution and the Nafion solution, and stirring at high speed for 300-600 seconds to obtain a dispersion solvent; S404, mixing the nanostructured skeleton carrier powder loaded with the platinum catalyst with a dispersing solvent and a thickener to obtain an initial cathode catalyst slurry, wherein the mass ratio of the nanostructured skeleton carrier powder loaded with the platinum catalyst is 10-50%, and the viscosity of the slurry is adjusted by adjusting the amount of the thickener; S405, ultrasonically treating the initial catalyst slurry for 30-300 seconds, and then homogenizing it using a high-speed homogenizer for 3-15 minutes to obtain a cathode catalyst slurry. The anode catalyst slurry is prepared in the same manner; S5. The cathode catalyst slurry and the anode catalyst slurry prepared in S3-S4 are coated on both sides of the proton exchange membrane by direct coating to prepare a membrane electrode, and the hydrogen production performance is tested; S501, placing the N115 proton exchange membrane on a workbench and coating it with cathode catalyst slurry; S502, after the cathode catalyst slurry is coated, the cathode catalyst slurry is placed in an oven to obtain a membrane electrode coated with the cathode catalyst slurry; S503, placing the membrane electrode coated with the cathode catalyst slurry on a workbench, and coating the other side with the anode catalyst slurry; S504. After the cathode catalyst slurry is coated, it is placed in an oven to obtain a complete membrane electrode. The obtained membrane electrode is installed in an electrolyzer to test the hydrogen production performance. The test conditions are a current density of 1A / cm2 and a voltage of 1.6-1.85V; S6. Spray-coat the cathode catalyst slurry and the anode catalyst slurry prepared in S3-S4 onto both sides of the proton exchange membrane to prepare a membrane electrode, and test the hydrogen production performance. S601, placing the N115 proton exchange membrane on a workbench and spraying the cathode catalyst slurry, and controlling the catalytic coating thickness by controlling the spraying time; S602, after the cathode catalyst slurry is sprayed, the cathode catalyst slurry is placed in an oven to obtain a membrane electrode sprayed with the cathode catalyst slurry; S603, placing the membrane electrode sprayed with the cathode catalyst slurry on a workbench, and coating the other side with the anode catalyst slurry. The spraying time is 30-120 seconds. The thickness of the catalytic coating can be controlled by controlling the spraying time. S604. After spraying the anode catalyst slurry, place it in an oven to obtain a complete membrane electrode, and then install the obtained membrane electrode on the electrolyzer to test the hydrogen production performance.

2. The method for preparing a proton exchange membrane water electrolysis hydrogen production membrane electrode according to claim 1, characterized in that: In the S101, the vacuum is evacuated to below 0.0006P, and the substrate is heated to 50-250°C. In the S102, the argon flow rate is 30-100 sccm, and the gas pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.1-0.5 Pa.

3. The method for preparing a proton exchange membrane water electrolysis hydrogen production membrane electrode according to claim 2, characterized in that: In the above S103, the volume ratio of oxygen is 5-100% by flow rate, and the gas pressure is maintained at 0.05-0.2 Pa for 1-60 minutes.

4. The method for preparing a proton exchange membrane water electrolysis hydrogen production membrane electrode according to claim 1, characterized in that: In the S201, the pressure is evacuated to 0.0005 Pa, the substrate is heated to 50-100° C., and a bias voltage of 0-300 V is applied. In the S202, the argon flow rate is 30-100 sccm, and the pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.1-0.5 Pa.

5. The method for preparing a proton exchange membrane water electrolysis hydrogen production membrane electrode according to claim 4, characterized in that: In the S205, the pressure is evacuated to 0.0005 Pa, heated to 50-100° C., and a bias voltage of 0-300 V is applied. In the S206, the argon flow rate is 30-100 sccm, and the pressure in the magnetron sputtering vacuum coating chamber is maintained at 0.1-0.5 Pa.

6. The method for preparing a proton exchange membrane water electrolysis hydrogen production membrane electrode according to claim 1, characterized in that: In S303, the current density of the electrolytic cell is controlled at 1A / cm2 and the voltage is 1.6-1.85V.

7. The method for preparing a proton exchange membrane water electrolysis hydrogen production membrane electrode according to claim 1, characterized in that: In the step S403 , the stirring rate is controlled at 300-600 s, wherein the mass ratio of water is 40-70%. In the step S405 , the rotation speed of the high-speed homogenizer is 8000-15000 rpm.

8. The method for preparing a proton exchange membrane water electrolysis hydrogen production membrane electrode according to claim 1, characterized in that: In S501 and S503, the workbench heating temperature is 35-80°C, the coating rate is 0.5-2m / min, and the coating thickness is 20-50μm. In S502 and S504, the oven temperature is controlled at 60-90°C, and the drying time is controlled at 30-60min.

9. The method for preparing a proton exchange membrane water electrolysis hydrogen production membrane electrode according to claim 1, characterized in that: In the above-mentioned S601 and S603, the workbench heating temperature is 35-80° C., the spraying pressure is 1.5-5 bar, the spraying distance is 15-45 cm, the spraying angle is 30-60°, the spraying time is 30-120 s, and the coating thickness is 10-30 μm.

10. The method for preparing a membrane electrode for hydrogen production by proton exchange membrane water electrolysis according to claim 9, characterized in that: In S602 and S604, the temperature of the oven is controlled at 60-90°C, and the drying time is controlled at 30-60 minutes. In S604, the test conditions are a current density of 1 A / cm2 and a voltage of 1.6-1.85 V.

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