PEM proton exchange membrane with hydrogen barrier layer for electrolyzed water and preparation method of PEM proton exchange membrane
By introducing a hydrogen-resistance layer into the proton exchange membrane for PEM electrolytic water, and spraying the two-dimensional sheet material with Pt particles as slurry, the hydrogen permeability problem is solved, the service life and safety of the membrane are improved, and the production cost is reduced.
Patent Information
- Application Number
- CN202411963565.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-30
- Publication Date
- 2025-03-18
AI Technical Summary
The existing proton exchange membrane for PEM electrolytic water has hydrogen permeability problems, which leads to the intersecting of hydrogen and oxygen, which is high in danger and short in the membrane service life.
The preparation method of proton exchange membrane with a hydrogen-resistance layer is adopted. By spraying the two-dimensional sheet material loaded with Pt particles onto the resin layer of the proton exchange membrane as a slurry, and forming a hydrogen-resistance layer during the heat treatment process, the difficulty of hydrogen permeation is increased.
It effectively solves the problem of hydrogen permeation, improves the service life of the membrane, reduces the risk of inter-sertion between hydrogen and oxygen, and reduces production costs.
Smart Images
Figure CN119640327A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of water electrolysis, and in particular relates to a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis and a preparation method thereof. Background Art
[0002] Unlike alkaline water electrolysis hydrogen production technology, PEM water electrolysis (Proton Exchange Membrane Water Electrolyzers, PEMWE, proton exchange membrane water electrolysis) hydrogen production technology uses proton exchange membrane as a solid electrolyte to replace the diaphragm and liquid electrolyte (30% potassium hydroxide solution or 26% sodium hydroxide solution) used in alkaline electrolyzers, and uses pure water as the raw material for water electrolysis hydrogen production, avoiding potential alkaline solution pollution and corrosion problems. When the PEM electrolyzer is in operation, water molecules undergo oxidation reaction on the anode side, lose electrons, and generate oxygen and protons; then, electrons are transferred to the cathode through an external circuit, and protons are conducted to the cathode through the proton exchange membrane under the action of the electric field, and a reduction reaction occurs on the cathode side to obtain electrons to generate hydrogen. The hydrogen and oxygen after the reaction will be collected and transported through the bipolar plates of the anode and cathode.
[0003] Compared with alkaline water electrolysis hydrogen production technology, PEM water electrolysis hydrogen production technology has the advantages of high current density, high hydrogen purity, and fast response speed. The current density of PEM electrolyzer is usually 10000A / m 2 The purity of hydrogen produced is usually around 99.99%. Since the PEM electrolyzer uses pure water as the electrolysis raw material, the generated hydrogen will not bring in alkaline mist, which is beneficial to improving the quality of hydrogen. In addition, the gas permeability of the proton exchange membrane is low, which helps to avoid the cross-permeation of hydrogen and oxygen. The PEM electrolyzer does not need to strictly control the pressure on both sides of the membrane, has the advantages of fast start-stop and fast power regulation response, and is suitable for the fluctuating input of renewable energy power generation.
[0004] However, since PEM electrolyzers need to operate in a highly acidic and highly oxidizing working environment, the equipment is more dependent on expensive precious metal materials such as iridium, platinum, titanium, etc., resulting in the current PEM water electrolysis hydrogen production technology equipment costs being relatively high. The unit cost of PEM electrolyzers is still much higher than that of alkaline electrolyzers, and their performance and durability also need to be improved.
[0005] Moreover, the perfluorosulfonic acid resin membrane has the problem of hydrogen permeation, which will cause the hydrogen that permeates the membrane to react with oxygen to generate highly oxidizing hydrogen peroxide, which in turn corrodes the proton exchange membrane, causing the service life of the membrane to be seriously reduced, thereby further aggravating the hydrogen permeation problem, and even causing hydrogen and oxygen to cross-link, which is very likely to be dangerous (the explosion limit of hydrogen in air is 4%Vo1). The traditional hydrogen removal method uses an external hydrogen removal device, that is, adding a set of hydrogen removal devices at the oxygen outlet of the electrolyzer of the water electrolysis device, but when the oxygen humidity is high, the hydrogen content is high, and the flow rate is too fast, the hydrogen removal device cannot completely remove the hydrogen, and the external hydrogen removal device is not conducive to system simplification. Summary of the invention
[0006] The embodiment of the present invention provides a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis and a preparation method thereof, aiming to solve the common hydrogen permeation problem of the existing proton exchange membrane for PEM water electrolysis.
[0007] In order to solve the above technical problems, the embodiment of the present invention first provides a method for preparing a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis, comprising the following steps:
[0008] S01, laying the expanded porous film on the first resin, heating to 40°C to 60°C after the expanded porous film is completely soaked, continuing to heat at 40°C to 60°C for 30min to 40min, and then drying to obtain a composite film containing a resin layer;
[0009] S02, spraying the slurry on the resin layer of the composite film containing the resin layer to obtain a sprayed composite film containing a hydrogen barrier layer (i.e., a slurry layer), the spraying time being 2 min to 10 min;
[0010] S03. Coat the third resin on the hydrogen barrier layer of the spray-coated composite membrane containing the hydrogen barrier layer to obtain a coated composite membrane with a coating thickness of 60 μm to 840 μm; dry the coated composite membrane at 60°C to 80°C for 1 h to 5 h, and then heat-treat it at 130°C to 180°C for 10 min to 60 min to obtain a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis.
[0011] As a preferred embodiment, in step S01,
[0012] The expanded porous film is preferably one or a mixture of at least two of expanded porous polytetrafluoroethylene, expanded porous polybenzimidazole, expanded porous polyethylene, expanded porous polystyrene and artificial graphite or expanded porous polyethyleneimine.
[0013] The thickness of the first resin is 60 micrometers to 840 micrometers, preferably 400 micrometers.
[0014] The first resin is preferably one or a mixture of at least two of phenolic resin, epoxy resin, polyimide, polyvinylidene fluoride, short side branched perfluorosulfonic acid, polyvinylidene fluoride, phenolic resin, benzoxazine, liquid crystal resin, asphalt, polyphenylene sulfide, polyetheretherketone, epoxy resin and polyethersulfone.
[0015] The heating temperature is preferably 50° C. to 60° C. The first resin is completely cured by heating.
[0016] The drying is preferably carried out in a blast drying oven; the drying temperature is 60°C to 80°C, preferably 70°C to 80°C; the drying time is 1h to 4h, preferably 2h to 3h. Through drying, the solvent of the first resin is dried and evaporated.
[0017] As a preferred embodiment, in step S02,
[0018] The slurry is prepared by the following method:
[0019] S021, mixing the first solvent, chloroplatinic acid, a reducing agent and a two-dimensional sheet material in a mass ratio of 1000:1:5:(40-80), reacting at 100° C. to 200° C. for 2 h to 8 h to obtain a two-dimensional sheet material loaded with Pt particles;
[0020] S022. The second resin, the second solvent and the two-dimensional sheet material loaded with Pt particles in step S021 are stirred and mixed at a mass ratio of 20:100:(5-50) for 2h-8h and then ultrasonically mixed for 1h-4h to obtain a slurry.
[0021] In step S021,
[0022] The first solvent is preferably one or a mixture of at least two of methanol, ethanol, toluene, acetone, n-propane and isopropane.
[0023] The reducing agent is preferably one or a mixture of at least two of ethylene glycol, hydrazine hydrate and NaHB.
[0024] The two-dimensional sheet material is preferably one or a mixture of at least two of manganese dioxide two-dimensional sheet material, silicon dioxide two-dimensional sheet material, titanium dioxide two-dimensional sheet material, graphene sheet material, clay sheet material and selenium disulfide two-dimensional sheet material.
[0025] The reaction is preferably carried out at 120° C. to 180° C. for 3 h to 7 h.
[0026] In step S022,
[0027] The second resin is one or a mixture of at least two of phenolic resin, epoxy resin, polyimide, polyvinylidene fluoride, short side-branched perfluorosulfonic acid, polyvinylidene fluoride, benzoxazine, liquid crystal resin, asphalt, polyphenylene sulfide, polyetheretherketone or polyethersulfone.
[0028] The second solvent is preferably one or a mixture of at least two of methanol, water, ethanol, DMAc, DMF, DMSO, toluene, acetone, n-propane and isopropane.
[0029] The stirring and mixing time is preferably 4 h to 6 h; the ultrasonic mixing time is preferably 2 h to 3 h.
[0030] The spraying is preferably carried out using an ultrasonic sprayer.
[0031] The spraying time is preferably 4 to 6 minutes.
[0032] As a preferred embodiment, in step S03,
[0033] The third resin is preferably one or a mixture of at least two of phenolic resin, epoxy resin, polyimide, polyvinylidene fluoride, short side-branched perfluorosulfonic acid, polyvinylidene fluoride, benzoxazine, liquid crystal resin, asphalt, polyphenylene sulfide, polyetheretherketone, epoxy resin and polyethersulfone.
[0034] The coating thickness is preferably 400 microns.
[0035] The drying temperature is preferably 65° C. to 75° C.; the drying time is preferably 2 h to 3 h.
[0036] The heat treatment is preferably performed at 140° C. to 170° C. for 15 min to 45 min.
[0037] On the other hand, an embodiment of the present invention also provides a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis prepared by the above preparation method.
[0038] Compared with the prior art, the technical solution of the embodiment of the present invention has the following beneficial effects: the present application uses slurry (a two-dimensional sheet material loaded with Pt particles) as a hydrogen barrier layer, which is sprayed onto the resin layer (resin layer as a supporting layer) inside the proton exchange membrane, and can effectively solve the hydrogen permeation problem existing in the proton exchange membrane for PEM electrolysis of water. Pt is deposited in situ on the two-dimensional sheet material, which can not only improve the utilization rate of the Pt precious metal, but also has a strong stability, which can effectively avoid the loss of Pt in the membrane electrode during long-term operation. The Pt particles in the hydrogen barrier layer can effectively catalyze hydrogen to generate protons, which is conducive to proton transmission. In addition, using two-dimensional sheets as carriers of Pt particles can also make the permeation path of hydrogen more tortuous, increasing the difficulty of hydrogen permeation. Therefore, under the dual effects of Pt catalysis and the steric hindrance effect of the two-dimensional sheet, the transmembrane permeation of hydrogen is further prevented. The preparation method of the present application is simple, the production cost is low, the production efficiency is high, and it is easy to batch or large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS
[0039] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying creative work.
[0040] Figure 1 This is a schematic diagram of the working principle of the hydrogen barrier layer of the proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis according to an embodiment of the present invention.
[0041] The realization of the purpose, functional features and advantages of the present invention will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION
[0042] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. 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 creative work are within the scope of protection of the present invention.
[0043] In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the fact that ordinary technicians in the field can implement it. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the scope of protection required by the present invention.
[0044] In the embodiments of the present application, the selection and dosage ratio of each raw material component can be selected and combined according to actual needs, and the solution of the present application can be implemented as long as the requirements of the present application are met.
[0045] The present application discloses a method for preparing a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis, comprising the following steps:
[0046] S01, laying the expanded porous film on the first resin, after the expanded porous film is completely infiltrated, heating to 40°C-60°C (depending on actual needs, it can be 40°C, or 45°C, or 50°C, or 60°C, etc.), continuing heating at 40°C-60°C (depending on actual needs, it can be 40°C, or 45°C, or 50°C, or 60°C, etc.) for 30min-40min (depending on actual needs, it can be 30min, or 33min, or 37min, or 40min, etc.), and then drying to obtain a composite film containing a resin layer;
[0047] S02, spraying the slurry on the resin layer of the composite film containing the resin layer to obtain a sprayed composite film containing a hydrogen barrier layer (i.e., a slurry layer), the spraying time being 2 min to 10 min (depending on actual needs, it can be 2 min, or 3 min, or 6 min, or 10 min, etc.);
[0048] S03, coating the third resin on the hydrogen barrier layer of the spray-coated composite film containing the hydrogen barrier layer to obtain a coated composite film, the coating thickness of which is 60 microns to 840 microns (depending on actual needs, it can be 60 microns, or 250 microns, or 500 microns, or 840 microns, etc.); drying the coated composite film at 60°C to 80°C (depending on actual needs, it can be 60°C, or 65°C, or 70°C, or 80°C, etc.) for 1h to 5h (depending on actual needs, it can be 60°C, or 65°C, or 70°C, or 80°C, etc.) According to actual needs, it can be 1h, or 2h, or 3h, or 5h, etc.), and then heat-treated at 130℃~180℃ (according to actual needs, it can be 130℃, or 135℃, or 150℃, or 180℃, etc.) for 10min~60min (according to actual needs, it can be 10min, or 25min, or 45min, or 60min, etc.) to obtain a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis.
[0049] In the present application, the prepared proton exchange membrane with hydrogen barrier layer for PEM water electrolysis is applied in the field of PEM water electrolysis. In this field, since it is a hydrogen production device, the cathode hydrogen concentration and pressure are much higher than the environment of the fuel cell, and the requirements for the membrane's ability to block hydrogen permeation are higher. The proton exchange membrane used in fuel cells is difficult to meet the use needs in this field. The present application sets the hydrogen barrier layer at the weakest part of the entire proton exchange membrane (because it is not dense enough and becomes the place where hydrogen is most easily permeable), that is, close to the resin layer (equivalent to the support layer), which can more accurately eliminate the hydrogen molecules that have penetrated.
[0050] As a preferred embodiment, in step S01,
[0051] The expanded porous film is preferably one or a mixture of at least two of expanded porous polytetrafluoroethylene, expanded porous polybenzimidazole, expanded porous polyethylene, expanded porous polystyrene and artificial graphite or expanded porous polyethyleneimine.
[0052] The thickness of the first resin is 60 microns to 840 microns (depending on actual needs, it can be 60 microns, or 250 microns, or 500 microns, or 840 microns, etc.), preferably 400 microns. By controlling the thickness and composition of the first resin, while ensuring that it meets the support strength requirements, it can be well adapted to the hydrogen barrier layer, effectively catalyze hydrogen to generate protons, and facilitate proton transport. The first resin is preferably a mixture of one or at least two of phenolic resin, epoxy resin, polyimide, polyvinylidene fluoride, short side branched perfluorosulfonic acid, polyvinylidene fluoride, phenolic resin, benzoxazine, liquid crystal resin, asphalt, polyphenylene sulfide, polyetheretherketone, epoxy resin and polyethersulfone.
[0053] The heating temperature is preferably 50° C. to 60° C. (depending on actual needs, it can be 50° C., or 52° C., or 55° C., or 60° C., etc.) The first resin is completely cured by heating.
[0054] The drying is preferably carried out in a blast drying oven; the drying temperature is 60°C to 80°C (depending on actual needs, it can be 60°C, or 65°C, or 70°C, or 80°C, etc.), preferably 70°C to 80°C (depending on actual needs, it can be 70°C, or 75°C, or 78°C, or 80°C, etc.); the drying time is 1h to 4h (depending on actual needs, it can be 1h, or 2h, or 2.5h, or 3h, or 4h, etc.), preferably 2h to 3h. By drying, the solvent of the first resin is dried and evaporated.
[0055] As a preferred embodiment, in step S02,
[0056] The slurry is prepared by the following method:
[0057] S021. The first solvent, chloroplatinic acid, a reducing agent and a two-dimensional sheet material are uniformly mixed in a mass ratio of 1000:1:5:(40-80) (depending on actual needs, it can be 1000:1:5:40, or 1000:1:5:50, or 1000:1:5:55, or 1000:1:5:60, or 1000:1:5:80, etc.), and reacted at 100°C to 200°C (depending on actual needs, it can be 100°C, or 120°C, or 150°C, or 200°C, etc.) for 2h to 8h (depending on actual needs, it can be 2h, or 3h, or 5h, or 6h, or 8h, etc.) to obtain a two-dimensional sheet material loaded with Pt particles;
[0058] S022. The second resin, the second solvent and the two-dimensional sheet material loaded with Pt particles in step S021 are stirred and mixed in a mass ratio of 20:100:(5-50) (depending on actual needs, it can be 20:100:5, or 20:100:15, or 20:100:25, or 20:100:35, or 20:100:50, etc.), and then ultrasonically mixed for 1h-4h (depending on actual needs, it can be 1h, or 2h, or 2.5h, or 3h, or 4h, etc.) to obtain a slurry.
[0059] By controlling the preparation conditions of the slurry, it can be well matched with the resin layer by layer, which can not only improve the utilization rate of Pt precious metal, effectively catalyze hydrogen to generate protons, and facilitate proton transmission; it can also make the hydrogen permeation path more tortuous, increase the difficulty of hydrogen permeation, and further prevent hydrogen from penetrating across the membrane.
[0060] In step S021,
[0061] The first solvent is preferably one or a mixture of at least two of methanol, ethanol, toluene, acetone, n-propane and isopropane.
[0062] The reducing agent is preferably one or a mixture of at least two of ethylene glycol, hydrazine hydrate and NaHB.
[0063] The two-dimensional sheet material is preferably one or a mixture of at least two of manganese dioxide two-dimensional sheet material, silicon dioxide two-dimensional sheet material, titanium dioxide two-dimensional sheet material, graphene sheet material, clay sheet material and selenium disulfide two-dimensional sheet material.
[0064] The reaction is preferably carried out at 120°C to 180°C (depending on actual needs, it can be 120°C, 130°C, 150°C, 180°C, etc.) for 3h to 7h (depending on actual needs, it can be 3h, 4h, 5h, 6h, 7h, etc.).
[0065] In step S022,
[0066] The second resin is one or a mixture of at least two of phenolic resin, epoxy resin, polyimide, polyvinylidene fluoride, short side-branched perfluorosulfonic acid, polyvinylidene fluoride, benzoxazine, liquid crystal resin, asphalt, polyphenylene sulfide, polyetheretherketone or polyethersulfone.
[0067] The second solvent is preferably one or a mixture of at least two of methanol, water, ethanol, DMAc, DMF, DMSO, toluene, acetone, n-propane and isopropane.
[0068] The stirring and mixing time is preferably 4h to 6h (depending on actual needs, it can be 4h, or 4.5h, or 5h, or 6h, etc.); the ultrasonic mixing time is preferably 2h to 3h (depending on actual needs, it can be 2h, or 2.5h, or 3h, etc.).
[0069] The spraying is preferably carried out using an ultrasonic sprayer.
[0070] The spraying time is preferably 4 to 6 minutes (depending on actual needs, it can be 4 minutes, 5 minutes, 6 minutes, etc.).
[0071] As a preferred implementation, in step S03,
[0072] The third resin is preferably one or a mixture of at least two of phenolic resin, epoxy resin, polyimide, polyvinylidene fluoride, short side-branched perfluorosulfonic acid, polyvinylidene fluoride, benzoxazine, liquid crystal resin, asphalt, polyphenylene sulfide, polyetheretherketone, epoxy resin and polyethersulfone.
[0073] Generally, in the embodiments of the present application, the first resin, the second resin and the third resin use the same components, so that they can be well adapted to the slurry layer, which can not only improve the utilization rate of the Pt precious metal, but also effectively catalyze hydrogen to generate protons, thereby facilitating proton transport.
[0074] In one embodiment, a method for preparing a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis is provided, comprising the following steps:
[0075] S01, laying the expanded porous film on the first resin, heating to 50° C. after the expanded porous film is completely soaked, continuing to heat at 50° C. for 30 min, and then drying to obtain a composite film containing a resin layer;
[0076] S02, spraying the slurry on the resin layer of the composite film containing the resin layer to obtain a sprayed composite film containing a hydrogen barrier layer, the spraying time being 8 minutes;
[0077] S03. Coat the third resin on the hydrogen barrier layer of the sprayed composite membrane containing the hydrogen barrier layer to obtain a coated composite membrane with a coating thickness of 400 microns; dry the coated composite membrane at 70°C for 3 hours, and then heat treat it at 150°C for 30 minutes to obtain a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis.
[0078] In step S01,
[0079] The expanded porous film is expanded porous polytetrafluoroethylene.
[0080] The thickness of the first resin is 400 μm.
[0081] The first resin is short-side branched perfluorosulfonic acid.
[0082] The drying is carried out in a blast drying oven; the drying temperature is 65° C.; and the drying time is 2 hours.
[0083] In step S02,
[0084] The slurry is prepared by the following method:
[0085] S021, mixing the first solvent, chloroplatinic acid, a reducing agent and a two-dimensional sheet material in a mass ratio of 1000:1:5:50, reacting at 180° C. for 6 hours to obtain a two-dimensional sheet material loaded with Pt particles;
[0086] S022. The second resin, the second solvent and the two-dimensional sheet material loaded with Pt particles in step S021 are stirred and mixed at a mass ratio of 20:100:20 for 4 hours and then ultrasonically mixed for 2 hours to obtain a slurry.
[0087] In step S021, the first solvent is methanol, the reducing agent is ethylene glycol, and the two-dimensional sheet material is a manganese dioxide two-dimensional sheet material.
[0088] In step S022,
[0089] The second resin is a short-side branched perfluorosulfonic acid.
[0090] The second solvent is n-propane.
[0091] The spraying is carried out by using an ultrasonic sprayer.
[0092] In step S03,
[0093] The third resin is short-side branched perfluorosulfonic acid.
[0094] The thickness of the prepared PEM water electrolysis proton exchange membrane with hydrogen barrier layer is 55 microns; the tensile strength is 42MPa; the elongation at break is 125%; the proton conductivity is 288mS / cm at 80°C and 100% relative humidity; the hydrogen permeability is 0.002mL / min·cm 2 ·atm. Tested in a PEM electrolyzer, with deionized water flowing in at 80°C, maintaining 2A / cm 2 The current density only requires an electrolysis voltage of 1.69 V. It can be seen that the prepared proton exchange membrane meets the relevant requirements of proton exchange membranes for PEM electrolyzers.
[0095] Comparative Example 1
[0096] A method for preparing a proton exchange membrane for a PEM electrolyzer comprises the following steps:
[0097] S01, drop 4 ml of short side branched perfluorosulfonic acid resin solution onto the glass plate, and control the coating height to be 400 μm for coating;
[0098] S02, laying the expanded porous polytetrafluoroethylene film on the resin solution of step S01, and after it is completely soaked, controlling the temperature of the coating table to 50° C., heating the resin solution to completely evaporate and solidify;
[0099] S03, dripping 4 ml of the short side-branched perfluorosulfonic acid resin solution onto the expanded porous film of step S02, and controlling the coating height to be 400 μm for coating;
[0100] S04, transferring the semi-finished product in step S03 to a blast drying oven, controlling the temperature to 65° C. for 2 hours, and further drying the solvent for later use.
[0101] S05. Transfer the composite membrane obtained in S07 to a forced air drying oven, control the temperature to 70° C., dry for 3 hours, and heat treat at 150° C. for 30 minutes to obtain a proton exchange membrane for a PEM electrolyzer.
[0102] The thickness of the prepared proton exchange membrane for PEM electrolyzer is 51 microns; the tensile strength is 39 MPa; the elongation at break is 112%; the proton conductivity is 233 mS / cm at 80°C and 100% relative humidity; the hydrogen permeability is 0.012 mL / min·cm 2 ·atm. Tested in a PEM electrolyzer, with deionized water introduced at 80°C and maintained at 2A / cm2 A current density of 1.80 V is required for electrolysis.
[0103] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.
Claims
1. A method for preparing a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis, characterized in that: The steps include: S01, laying the expanded porous film on the first resin, heating to 40°C to 60°C after the expanded porous film is completely soaked, continuing to heat at 40°C to 60°C for 30min to 40min, and then drying to obtain a composite film containing a resin layer; S02, spraying the slurry on the resin layer of the composite film containing the resin layer to obtain a sprayed composite film containing a hydrogen barrier layer, the spraying time being 2 min to 10 min; S03. Coat the third resin on the hydrogen barrier layer of the spray-coated composite membrane containing the hydrogen barrier layer to obtain a coated composite membrane with a coating thickness of 60 μm to 840 μm; dry the coated composite membrane at 60°C to 80°C for 1 h to 5 h, and then heat-treat it at 130°C to 180°C for 10 min to 60 min to obtain a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis.
2. The method for preparing a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis according to claim 1, characterized in that: In step S01, The expanded porous film is one or a mixture of at least two of expanded porous polytetrafluoroethylene, expanded porous polybenzimidazole, expanded porous polyethylene, expanded porous polystyrene and artificial graphite or expanded porous polyethyleneimine; The thickness of the first resin is 60 micrometers to 840 micrometers.
3. The method for preparing a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis according to claim 1, characterized in that: In step S01, The first resin is one or a mixture of at least two of phenolic resin, epoxy resin, polyimide, polyvinylidene fluoride, short side branched perfluorosulfonic acid, polyvinylidene fluoride, phenolic resin, benzoxazine, liquid crystal resin, asphalt, polyphenylene sulfide, polyetheretherketone, epoxy resin and polyethersulfone; The drying is carried out in a blast drying oven; the drying temperature is 60° C. to 80° C.; and the drying time is 1 h to 4 h.
4. The method for preparing a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis according to claim 1, characterized in that: In step S02, the slurry is prepared by the following method: S021, mixing the first solvent, chloroplatinic acid, a reducing agent and a two-dimensional sheet material in a mass ratio of 1000:1:5:(40-80), reacting at 100° C. to 200° C. for 2 h to 8 h to obtain a two-dimensional sheet material loaded with Pt particles; S022. The second resin, the second solvent and the two-dimensional sheet material loaded with Pt particles in step S021 are stirred and mixed at a mass ratio of 20:100:(5-50) for 2h-8h and then ultrasonically mixed for 1h-4h to obtain a slurry.
5. The method for preparing a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis according to claim 4, characterized in that: In step S021, The first solvent is one or a mixture of at least two of methanol, ethanol, toluene, acetone, n-propane and isopropane; The reducing agent is one or a mixture of at least two of ethylene glycol, hydrazine hydrate and NaHB.
6. The method for preparing a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis according to claim 4, characterized in that: In step S021, The two-dimensional sheet material is one or a mixture of at least two of a manganese dioxide two-dimensional sheet material, a silicon dioxide two-dimensional sheet material, a titanium dioxide two-dimensional sheet material, a graphene sheet material, a clay sheet material and a selenium disulfide two-dimensional sheet material; The reaction is carried out at 120° C. to 180° C. for 3 h to 7 h.
7. The method for preparing a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis according to claim 4, characterized in that: In step S022, The second resin is one or a mixture of at least two of phenolic resin, epoxy resin, polyimide, polyvinylidene fluoride, short side-branched perfluorosulfonic acid, polyvinylidene fluoride, benzoxazine, liquid crystal resin, asphalt, polyphenylene sulfide, polyetheretherketone or polyethersulfone; The second solvent is one or a mixture of at least two of methanol, water, ethanol, DMAc, DMF, DMSO, toluene, acetone, n-propane and isopropane.
8. The method for preparing a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis according to claim 4, characterized in that: In step S022, The stirring and mixing time is 4h to 6h; the ultrasonic mixing time is 2h to 3h; The spraying is carried out by using an ultrasonic spraying machine; The spraying time is 4 to 6 minutes.
9. The method for preparing a proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis according to claim 1, characterized in that: In step S03, The third resin is one or a mixture of at least two of phenolic resin, epoxy resin, polyimide, polyvinylidene fluoride, short side branched perfluorosulfonic acid, polyvinylidene fluoride, benzoxazine, liquid crystal resin, asphalt, polyphenylene sulfide, polyetheretherketone, epoxy resin and polyethersulfone; The drying temperature is 65°C to 75°C; the drying time is 2h to 3h; The heat treatment is performed at 140° C. to 170° C. for 15 min to 45 min.
10. A proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis, characterized in that: The proton exchange membrane with a hydrogen barrier layer for PEM water electrolysis is prepared by the preparation method according to any one of claims 1 to 9.