Proton exchange membrane comprising hydrogen barrier coating and preparation method therefor, membrane electrode, and device for hydrogen production via water electrolysis

Abstract

The present application relates to the technical field of hydrogen production via water electrolysis, and specifically relates to a method for preparing a proton exchange membrane comprising a hydrogen barrier coating. The method comprises the following steps: S1, mixing an inorganic filler with a functional resin, adding a solvent, and stirring same to obtain a slurry; S2, coating a surface of a proton exchange membrane with the slurry, the wet thickness of the resulting coating being 10-100 μm, and drying the wet coating to obtain a dried proton exchange membrane; and S3, performing a heat treatment on the dried proton exchange membrane to obtain a proton exchange membrane comprising a hydrogen barrier coating. The present application further relates to a proton exchange membrane comprising a hydrogen barrier coating, a membrane electrode, and a device for hydrogen production via water electrolysis. The hydrogen barrier coating described herein can physically block hydrogen gas from permeating through the proton exchange membrane, thereby improving the efficiency of a water-electrolysis membrane electrode made of the proton exchange membrane, reducing the content of hydrogen in oxygen at an anode side, and further improving the service life and safety of the device for hydrogen production via water electrolysis.

Description

Proton exchange membrane containing hydrogen blocking coating, preparation method thereof, membrane electrode and water electrolysis hydrogen production device TECHNICAL FIELD

[0001] The present application relates to the technical field of water electrolysis hydrogen production, in particular to a proton exchange membrane containing hydrogen blocking coating, a preparation method of the proton exchange membrane containing hydrogen blocking coating and a membrane electrode comprising the proton exchange membrane containing hydrogen blocking coating. BACKGROUND

[0002] Water electrolysis hydrogen production technology based on proton exchange membrane has broad development potential and has begun to enter the demonstration operation stage. Membrane electrode is an important part of PEM (polyelectrolyte membrane) water electrolysis hydrogen production device, which includes proton exchange membrane, anode catalyst layer on the anode side of the proton exchange membrane and cathode catalyst layer on the cathode side of the proton exchange membrane. On the cathode side of the proton exchange membrane, hydrogen protons obtain electrons to generate hydrogen. On the anode side of the proton exchange membrane, water loses electrons to obtain oxygen and protons. The overall reaction is the decomposition of water into hydrogen and oxygen, so that the anode side of the proton exchange membrane has oxygen and the cathode side has hydrogen.

[0003] Commonly used proton exchange membranes include Nafion117, Nafion115 or Nafion212 membranes with thicknesses of 178 μm, 127 μm or 51 μm respectively. Although thinner membranes can reduce voltage loss due to internal resistance of the membrane, thereby reducing electrolytic cell voltage and improving electrolysis efficiency, thinner Nafion membranes increase gas permeability, and in a high-pressure working environment, hydrogen produced in the cathode will penetrate through the membrane to the anode side, resulting in a small amount of hydrogen mixed in the oxygen. Generally, the oxygen purity at the anode outlet of the core of the proton exchange membrane water electrolysis hydrogen production device is between 99% and 99.5% (current density is 1 A / cm 2 , 80℃, normal pressure). However, if the water electrolysis hydrogen production device is operated under pressure, as the pressure of the gas products of the water electrolysis hydrogen production device increases, the gas permeability in the proton exchange membrane will also increase, resulting in further reduction of oxygen product purity and increase of hydrogen content of the water electrolysis hydrogen production device, which may even cause safety problems.

[0004] Currently, methods for reducing hydrogen in oxygen on the anode side of the membrane electrode include adding inorganic proton conductors to ion exchange membranes to block the diffusion and penetration of gas, but this method has a complex preparation process and can damage the structure of the ion exchange membrane. Methods for reducing hydrogen in oxygen on the anode side of the membrane electrode also include synthesizing composite membrane materials from polyether ketone with lower gas permeability and ordinary ion exchange membranes, but the polyether ketone material used has the problem of insufficient chemical stability.

[0005] Therefore, there is a continuous need in the art to develop a proton exchange membrane containing hydrogen blocking coating with high hydrogen blocking efficiency and chemical stability.

[0006] SUMMARY

[0007] The present application aims to provide a proton exchange membrane with a hydrogen barrier coating layer with high hydrogen barrier efficiency and chemical stability. Specifically, the present application provides a coating structure and preparation method for the hydrogen barrier function of the surface of a proton exchange membrane, which can reduce the hydrogen content in oxygen on the anode side of the proton exchange membrane and improve the hydrogen production efficiency. This hydrogen barrier coating layer can be used on both sides of the proton membrane, which can improve the physical barrier ability of hydrogen while ensuring the overall reaction efficiency of the cathode catalyst layer and the anode catalyst layer.

[0008] The present application also aims to provide a preparation method of a proton exchange membrane with a hydrogen barrier coating layer as described above.

[0009] The present application also aims to provide a membrane electrode comprising a proton exchange membrane with a hydrogen barrier coating layer as described above.

[0010] The present application also aims to provide a water electrolysis hydrogen production device comprising a membrane electrode as described above.

[0011] In order to solve the above technical problems, the present application provides the following technical solutions.

[0012] In a first aspect, the present application provides a preparation method of a proton exchange membrane with a hydrogen barrier coating layer, characterized in that the preparation method comprises the following steps:

[0013] S1: mixing an inorganic filler with a functional resin, adding a solvent and stirring to obtain a slurry;

[0014] S2: coating the slurry on the surface of a proton exchange membrane to obtain a wet coating layer with a wet thickness of 1-100 μm, and drying the wet coating layer at a drying temperature of 50-200 ℃ for a drying time of 10 minutes-4 hours to obtain a dried proton exchange membrane;

[0015] S3: heat treating the dried proton exchange membrane for a heat treatment time of 10 minutes-2 hours at a heat treatment temperature of 120-200 ℃ to obtain the proton exchange membrane with a hydrogen barrier coating layer.

[0016] In an embodiment of the first aspect, the inorganic filler is one or more of graphene, graphite, carbon nanotubes, carbon black, fullerene, boron nitride, and silicon oxide;

[0017] The functional resin is one or more of sulfonated polysulfone, perfluorosulfonic acid resin, perfluorocarboxylic acid resin, and perfluorophosphoric acid resin;

[0018] The solvent is one or more of pure water, ethanol, isopropanol, n-propanol, water, N,N dimethylformamide, N,N dimethylacetamide, and dimethyl sulfoxide.

[0019] In an embodiment of the first aspect, the inorganic filler is one or both of graphene and boron nitride.

[0020] The functional resin is one or both of sulfonated polyether sulfone and perfluorocarboxylic acid resin or a mixture of perfluorosulfonic acid resin.

[0021] In an embodiment of the first aspect, in step S1, the solid content of the slurry is 3-40%, preferably 20-40% by weight.

[0022] In an embodiment of the first aspect, in step S2, the coating method is one or more of spraying, knife coating, slot coating and transfer method, and the coating method is preferably slot coating.

[0023] The wet coating has a wet thickness of 10-100 μm, a drying temperature of 100-200 °C and a drying time of 2-4 hours.

[0024] The proton exchange membrane is a commercial product that can be used for water electrolysis hydrogen production, and has a thickness of 50-130 μm.

[0025] In an embodiment of the first aspect, in step S3, the heat treatment is performed in one of a blast oven, a blast oven, a vacuum oven.

[0026] The heat treatment time is 1-2 hours, and the heat treatment temperature is 180-200 °C.

[0027] In an embodiment of the first aspect, in step S1, the types and amounts of inorganic fillers and functional resins are as follows:

[0028] Graphene 5 parts by weight; sulfonated polyether sulfone 10 parts by weight; perfluorosulfonic acid resin Nafion D2020 20 parts by weight; water 60 parts by weight; slurry solid content 40%.

[0029] In an embodiment of the first aspect, in step S1, the types and amounts of inorganic fillers and functional resins are as follows:

[0030] Boron nitride 5 parts by weight; perfluorocarboxylic acid resin 5 parts by weight; perfluorosulfonic acid resin Nafion D2020 10 parts by weight; water 20 parts by weight; ethanol 60 parts by weight; slurry solid content 20%.

[0031] In a specific embodiment, Nafion D2020 can be weighed according to the calculation, the solid content of Nafion D2020 is 20%, that is, 20 parts by weight, the solvent accounts for 16, and the resin accounts for 4.

[0032] In a second aspect, the present application provides a hydrogen barrier coated proton exchange membrane prepared by the method of the first aspect.

[0033] In a third aspect, the present application provides a membrane electrode comprising the hydrogen barrier coated proton exchange membrane of the second aspect.

[0034] In a fourth aspect, the present application provides a water electrolysis hydrogen generation device comprising the membrane electrode of the third aspect.

[0035] Compared with the prior art, the positive effects of the present application are that the hydrogen barrier coating of the present application is made of two-dimensional inorganic fillers and functional resin, the inorganic fillers increase the path of hydrogen diffusion and reduce the diffusion ability of hydrogen. In addition, the functional resin has a certain hydrophobicity, which optimizes the transfer of water in the proton exchange membrane and reduces the dissolution of hydrogen in water. In summary, the hydrogen barrier coating described herein improves the efficiency of the water electrolysis membrane electrode made of the proton exchange membrane, reduces the hydrogen content in the oxygen on the anode side, and further improves the service life and safety of the water electrolysis hydrogen generation device. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 shows the dissolution-diffusion mechanism of hydrogen permeating the proton exchange membrane.

[0037] Figure 2 shows scanning electron microscope images of a commercially available proton exchange membrane Nafion 212 and a hydrogen barrier coated proton exchange membrane according to an embodiment of the present application.

[0038] Figure 3 shows a scanning electron microscope image of the cross-section of a hydrogen barrier coated proton exchange membrane according to Example 1.

[0039] Figure 4 shows the hydrogen in oxygen test results of a hydrogen barrier coated proton exchange membrane according to Example 1.

[0040] Figure 5 shows a scanning electron microscope image of the cross-section of a hydrogen barrier coated proton exchange membrane according to Example 2. DETAILED DESCRIPTION

[0041] Unless otherwise indicated, all parts and percentages in the present application are based on weight, and the test and characterization methods used are those in synchronization with the filing date of the present application. In applicable cases, the contents of any patent, patent application or publication referred to in the present application are incorporated herein by reference in their entirety, and equivalent homologous patents are also introduced by reference, especially the definitions disclosed in these documents regarding the synthesis technology, product and processing design, polymer, comonomer, initiator or catalyst, etc. in the art. If the definition of a specific term disclosed in the prior art is inconsistent with any definition provided in the present application, the definition of the term provided in the present application shall prevail.

[0042] Numerical ranges are approximations, and thus the term "comprises between approximately the recited numerical limits, unless otherwise expressly specified. A numerical range includes all values from and including the lower and to and including the upper range limits. For ranges containing values that are less than one or containing fractional numbers more precise than 0.0001, 0.001, 0.01 or 0.1, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. For ranges containing single digit numbers less than one or fractional numbers more precise than 0.1, one unit is alternatively considered to be 0.1. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest and highest values interpreted as the minimum and maximum allowed function are to be considered to be expressly stated. The use of the term "about" means that a value can vary from the stated value by as much as 10% of the value. The terms "first," "second," and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another.

[0043] With respect to chemical compounds, the singular forms "a," "an," and "the" include all isomeric forms, unless the specific forms are explicitly described. Additionally, the terms "a", "an", and "the" preceding elements or any of the combinations of elements do not preclude the presence of more than one of the referred elements in the compositions.

[0044] The terms "comprising", "including", "containing", and variations thereof do not exclude the presence of other components, steps or processes, and are used herein to mean that additional components, steps or processes can be added. Thus, use of the term "comprising" or "including" in the claims has the same effect as "consisting of" or "consisting essentially of" in the claims. The term "consisting essentially of" does not exclude the presence of additional components, steps or processes so long as they do not affect the basic and novel characteristics of the composition or method. The term "consisting of" excludes any component, step or process not specifically recited. The term "or", in the context of using "and / or", means that the listed members are individually useful, and the conjunction "or" should be interpreted in the inclusive sense.

[0045] In one embodiment, the present application provides a method for preparing a proton exchange membrane with hydrogen barrier coating, the method comprising the steps of:

[0046] S1: mixing the inorganic filler with the functional resin, adding a solvent and stirring to obtain a slurry;

[0047] S2: coating the slurry on the surface of the proton exchange membrane, the wet thickness of the obtained coating layer is 1-100 μm, and the wet coating layer is dried, the drying temperature is 50-200 ℃, the drying time is 10 minutes-4 hours, to obtain the dried proton exchange membrane;

[0048] S3: heat treating the dried proton exchange membrane, the heat treating time is 10 minutes-2 hours, the heat treating temperature is 120-200 ℃, to obtain the proton exchange membrane containing the hydrogen blocking coating.

[0049] In one specific embodiment, the inorganic filler is one or more of graphene, graphite, carbon nanotube, carbon black, fullerene, boron nitride and silicon oxide. In one specific embodiment, the functional resin is one or more of sulfonated polysulfone, perfluorosulfonic acid resin, perfluorocarboxylic acid resin, perfluorophosphonic acid resin. In one specific embodiment, the solvent is one or more of pure water, ethanol, isopropanol, n-propanol, water, N,N dimethylformamide, N,N dimethylacetamide, dimethyl sulfoxide.

[0050] In one specific embodiment, the perfluorocarboxylic acid resin has the following structural formula:

[0051] wherein m=100-200, n=10-50.

[0052] In one preferred embodiment, the inorganic filler is one or both of graphene and boron nitride, the functional resin is one or both of sulfonated polyether sulfone and perfluorocarboxylic acid resin, and the mixture of perfluorocarboxylic acid resin.

[0053] Referring to FIG. 1, the hydrogen blocking principle of the present application will be described in detail. As shown in FIG. 1, the penetration of gas adopts a dissolution-diffusion mechanism. Specifically, the hydrogen gas penetrates the proton exchange membrane mainly in the following two ways: (1) dissolution and (2) diffusion. In the case of dissolution, part of the hydrogen gas dissolves in the water of the hydrogen blocking coating on the one side interface of the hydrogen blocking coating, and the water dissolving the hydrogen gas is transported in the hydrogen blocking coating due to the different pressures on both sides of the hydrogen blocking coating and the different hydrophilic and hydrophobic properties of the polymers in different regions of the hydrogen blocking coating. When the water dissolving the hydrogen gas passes through the hydrogen blocking coating and reaches the other side interface of the hydrogen blocking coating, the dissolved hydrogen gas is released when the external conditions change. In the case of diffusion, the hydrogen gas is adsorbed on the one side interface of the hydrogen blocking coating, then diffuses in the polymer layer of the hydrogen blocking coating, reaches the other side interface of the hydrogen blocking coating, and desorbs when the external conditions change, thereby completing the penetration of hydrogen gas.

[0054] The hydrogen blocking technology of the present application simultaneously considers two permeation modes of hydrogen and makes targeted blocking respectively. First, high molecular materials with different functional groups (such as perfluorocarboxylic acid resin, sulfonated polyether sulfone, etc.) are used to prepare the coating, so that the hydrogen blocking coating has a certain hydrophobicity, the transfer of water in the membrane is optimized, the dissolution of hydrogen in water is reduced, and the diffusion of dissolved hydrogen in water in the hydrogen blocking coating is reduced. Second, inorganic two-dimensional materials (such as boron nitride, graphene, etc.) are used to increase the diffusion path of hydrogen in the hydrogen blocking coating, thereby reducing the diffusion ability of hydrogen.

[0055] It needs to be particularly pointed out that, compared with the thickness of the proton exchange membrane, the thickness of the hydrogen blocking coating of the present application after drying is less than or equal to 10 microns, preferably less than or equal to 5 microns, without destroying the original structure of the proton exchange membrane, and without adversely affecting the permeability of the proton exchange membrane.

[0056] In one specific embodiment, in step S1, the solid content of the slurry is 3-40%, preferably 20-40%.

[0057] In one specific embodiment, in step S2, the coating method is one or more of spraying, knife coating, slot coating and transfer printing method, and the coating method is preferably slot coating.

[0058] The wet thickness of the wet coating is 10-100 μm, the drying temperature is 100-200 °C, and the drying time is 2-4 hours.

[0059] The proton exchange membrane is a commercial product that can be used for water electrolysis hydrogen production, and the thickness is 50-130 microns.

[0060] In one specific embodiment, in step S3, the heat treatment is carried out in one of a blast oven, a blast oven, a vacuum oven.

[0061] The heat treatment time is 0.5-2 hours, and the heat treatment temperature is 180-200 °C.

[0062] In another embodiment, the present application provides a proton exchange membrane containing a hydrogen blocking coating, which is prepared by the preparation method as described above.

[0063] In another embodiment, the present application provides a membrane electrode comprising a proton exchange membrane containing a hydrogen blocking coating as described above.

[0064] Examples

[0065] The technical solutions of the present application will be clearly and completely described below in combination with the embodiments of the present application. Unless otherwise specified, the reagents and raw materials used can be purchased through commercial channels. The experimental methods in the following examples are not specified, and are selected according to conventional methods and conditions, or according to the product instructions.

[0066] Raw materials and tests

[0067] In the following examples and comparative examples, the specifications of raw materials and processing parameters are shown in Table 1.

[0068] Table 1 Specifications of raw materials and processing parameters

[0069] In the perfluorocarboxylic acid resin used in Example 2, m = 100, n = 10.

[0070] In the following examples and comparative examples, the samples for performance characterization and test conditions are described as follows.

[0071] Scanning electron microscope test

[0072] In the present application, the scanning electron microscope test is performed on a scanning electron microscope of Hitachi flex1000.

[0073] In the present application, the sample preparation method for cross section is described as follows:

[0074] Put the sample of appropriate size into liquid nitrogen and get brittle fracture.

[0075] Hydrogen production efficiency test

[0076] The membrane electrode is prepared on the treated membrane by means of slit coating, and the effective area of the membrane electrode is 5*5 cm 2 , the effective noble metal loading (anode: iridium: 1 mg / cm 2 ; cathode: platinum: 0.4 mg / cm 2 ). After the finished membrane electrode is loaded into a single cell test device, the test is performed.

[0077] Online testing is adopted, hydrogen gas on the cathode side is collected, and the difference between the actual hydrogen production and the theoretical value is calculated.

[0078] Oxygen hydrogen test

[0079] After collecting oxygen gas on the anode side by online testing, gas chromatography is used for component analysis.

[0080] Example 1

[0081] The present embodiment relates to a proton exchange membrane containing a hydrogen barrier coating and a preparation method thereof, as well as a membrane electrode and a water electrolysis hydrogen production device comprising the proton exchange membrane containing the hydrogen barrier coating.

[0082] Specifically, the preparation method of the hydrogen barrier coating containing proton exchange membrane of the embodiment comprises: mixing inorganic fillers with functional resin, adding a solvent and stirring to obtain a slurry. The slurry is coated on one surface of a proton exchange membrane Nafion 212 to obtain a wet coating layer, and the wet coating layer is dried to obtain a dried proton exchange membrane. The dried proton exchange membrane is subjected to heat treatment to obtain the hydrogen barrier coating containing proton exchange membrane.

[0083] The raw material usage, drying conditions and heat treatment conditions of the hydrogen barrier coating containing proton exchange membrane of Example 1 are shown in Table 2.

[0084] Table 2 Raw material usage, drying conditions and heat treatment conditions of Examples 1 and 2

[0085] Then, the hydrogen barrier coating containing proton exchange membrane is characterized, the morphology and thickness thereof are photographed by a scanning electron microscope, and the oxygen hydrogen concentration of the anode side of the hydrogen barrier coating containing proton exchange membrane over time is tested by an oxygen hydrogen test.

[0086] Referring to FIGS. 2 and 3, in FIG. 2, FIG. 2(a) shows the surface morphology of the purchased proton exchange membrane Nafion 212, FIG. 2(d) shows the surface morphology of the hydrogen barrier coating containing proton exchange membrane according to Example 1, and FIG. 2(e) shows the surface morphology of the hydrogen barrier coating containing proton exchange membrane according to Example 1. As can be seen from the figures, the hydrogen barrier coating containing proton exchange membranes according to Examples 1 and 2 have a dense structure.

[0087] Table 3 Hydrogen barrier performance test results of Examples 1 and 2

[0088] Referring to FIG. 4 and Table 3, the oxygen hydrogen concentration of the anode side of the hydrogen barrier coating containing proton exchange membranes according to Examples 1 and 2 is 0, i.e., the purity of oxygen is 100%, in the 120 hours of testing, indicating that the hydrogen barrier coating containing proton exchange membrane of the embodiment has stable and excellent hydrogen barrier performance.

[0089] In addition, in order to verify that the hydrogen barrier coating of the embodiment does not destroy the original structure of the proton exchange membrane Nafion 212, the hydrogen production efficiency of the proton exchange membrane Nafion 212 and the hydrogen barrier coating containing proton exchange membrane of Example 1 under different current densities is also tested, and the results are shown in Table 4. As can be seen from Table 4, after the drying and heat treatment of the proton exchange membrane Nafion 212 of the embodiment, the hydrogen production efficiency is slightly improved under the same current density, indicating that the original performance of the proton exchange membrane Nafion 212 is not adversely affected.

[0090] Table 4 Hydrogen production efficiency of Nafion 212 and the hydrogen barrier coating containing proton exchange membrane of Example 1

[0091] As can be seen from the data shown in Table 4, the hydrogen production efficiency of the hydrogen barrier coating-containing proton exchange membrane according to Example 1 did not decrease, but slightly increased, compared to the commercially available proton exchange membrane Nafion 212.

[0092] The above description of the embodiments is to assist those of ordinary skill in the art to understand and apply the present application. Those skilled in the art can easily make various modifications to the embodiments and apply the general principles described herein to other embodiments without having to make creative efforts. Therefore, the present application is not limited to the embodiments described herein, and improvements and modifications made by those skilled in the art based on the disclosure of the present application without departing from the scope and spirit of the present application are within the scope of the present application.

Claims

1. A method for producing a proton exchange membrane comprising a hydrogen barrier coating, characterized by, The preparation method comprises the following steps: S1: mixing inorganic filler and functional resin, adding solvent and stirring to obtain slurry; S2: coating the slurry on the surface of the proton exchange membrane to obtain a wet coating layer with a wet thickness of 1-100 μm, and drying the wet coating layer at a drying temperature of 50-200 ℃ for 10 minutes to 4 hours to obtain a dried proton exchange membrane; S3: heat treating the dried proton exchange membrane for 10 minutes to 2 hours at a heat treatment temperature of 120-200 ℃ to obtain the proton exchange membrane containing hydrogen barrier coating.

2. The production method according to claim 1, wherein The inorganic filler is one or more of graphene, graphite, carbon nanotube, carbon black, fullerene, boron nitride and silicon oxide; The functional resin is one or more of sulfonated polysulfone, perfluorosulfonic acid resin, perfluorocarboxylic acid resin and perfluorophosphoric acid resin; The solvent is one or more of pure water, ethanol, isopropanol, n-propanol, water, N,N dimethylformamide, N,N dimethylacetamide and dimethyl sulfoxide.

3. The production method according to claim 2, wherein The inorganic filler is one or both of graphene and boron nitride; The functional resin is one or both of sulfonated polyether sulfone and perfluorocarboxylic acid resin and a mixture of perfluorosulfonic acid resin.

4. The production method according to any one of claims 1 to 3, wherein In step S1, the solid content of the slurry is 3-40%, preferably 20%-40% by weight.

5. The production method according to any one of claims 1 to 3, wherein In step S2, the coating method is one or more of spraying, doctor blade coating, slot coating and transfer method, and the coating method is preferably slot coating; The wet thickness of the wet coating layer is 10-100 μm, the drying temperature is 100-200 ℃, and the drying time is 2 hours to 4 hours; The proton exchange membrane is a commercial product that can be used for water electrolysis hydrogen production, and the thickness is 50-130 microns.

6. The production method according to any one of claims 1 to 3, wherein In step S3, the heat treatment is carried out in one of the blast oven, the blast oven, the vacuum oven; The heat treatment time is 1 hour to 2 hours, and the heat treatment temperature is 180-200 ℃.

7. The production method according to any one of claims 1 to 3, wherein In step S1, the types and amounts of inorganic fillers and functional resins are as follows: Graphene 5 parts by weight; sulfonated polyether sulfone, 10 parts by weight; perfluorosulfonic acid resin Nafion D2020 20 parts by weight; water 60 parts by weight; the solid content of the slurry is 40%.

8. The production method according to any one of claims 1 to 3, wherein In step S1, the types and amounts of inorganic fillers and functional resins are as follows: Boron nitride 5 parts by weight; perfluorocarboxylic acid resin, 5 parts by weight; perfluorosulfonic acid resin Nafion D2020 10 parts by weight; water 20 parts by weight; ethanol 60 parts by weight; the solid content of the slurry is 20%.

9. A proton exchange membrane containing hydrogen barrier coating prepared by the preparation method of any one of claims 1-8.

10. A membrane electrode comprising the proton exchange membrane containing hydrogen barrier coating of claim 9.

11. An electrolytic water hydrogen production device comprising the membrane electrode of claim 10.

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