Proton exchange membranes, methods of making and use thereof

Abstract

This invention provides a proton exchange membrane, its preparation method, and its application. The proton exchange membrane has an integrated surface resin layer and an intermediate resin layer, with the surface resin layer located on both sides of the intermediate resin layer. The intermediate resin layer is doped with inorganic particles; wherein the inorganic particles include Pt-based particles, and the weight ratio of Pt-based particles to resin in the proton exchange membrane is (0.1-1):100. The preparation method includes: melting and extruding the resin to obtain a first intermediate product, then blow molding it to form a hollow layer inside the first intermediate product; introducing inorganic particles into the hollow layer to distribute the inorganic particles on the inner wall of the first intermediate product; obtaining a second intermediate product; pressing it to obtain a third intermediate product; and post-processing it to obtain the proton exchange membrane. The proton exchange membrane prepared by this invention helps prevent hydrogen from permeating into the oxygen side of the anode in a PEMWE system, thereby effectively improving the safety of high-pressure operation of the PEMWE system.

Description

Technical Field

[0001] This invention relates to the field of proton exchange membrane technology, and more specifically, to a proton exchange membrane, its preparation method, and its application. Background Technology

[0002] Against the backdrop of climate change and energy transition, proton exchange membrane electrolysis (PEMWE) is considered a crucial method for addressing environmental pollution and energy issues. In a PEMWE system, water entering the anode is decomposed into oxygen, protons, and electrons. Protons pass through the proton exchange membrane to the cathode, while electrons flow out from the anode, through the power circuit, and back to the cathode. At the cathode, the protons and electrons recombine to produce hydrogen. Hydrogen (H2) typically requires high pressure for storage, but the PEMWE system can directly compress and transport hydrogen under high pressure for storage. Compared to using an external compressor for pressurized hydrogen storage, this method of pressurized transport and storage during operation offers higher overall efficiency.

[0003] In proton exchange membrane (PEM) electrolysis of water, the PEM plays a crucial role in conducting protons, isolating electrons, and blocking hydrogen and oxygen. Currently, the most widely used PEMs for water electrolysis are Nafion 117 and Nafion 115, but both are relatively thick. To reduce production costs, it is necessary to produce thinner PEMs.

[0004] However, the PEMWE system needs to operate under pressure, which leads to the proton exchange membrane facing the safety problem of gas permeation. That is, under pressure, hydrogen gas at the cathode can pass through the proton exchange membrane to the oxygen side at the anode, thereby quickly reaching the explosion safety margin of hydrogen and oxygen gas (2% by volume). The thinner proton exchange membrane is more prone to gas permeation, so its safety problem is more significant. Summary of the Invention

[0005] The main objective of this invention is to provide a proton exchange membrane, its preparation method, and its application, in order to solve the problems of easy gas permeation and high safety risks in existing proton exchange membranes.

[0006] To achieve the above objectives, according to one aspect of the present invention, a method for preparing a proton exchange membrane is provided. The proton exchange membrane has an integrated surface resin layer and an intermediate resin layer, with the surface resin layer located on both sides of the intermediate resin layer. The intermediate resin layer is doped with inorganic particles. The inorganic particles include Pt-based particles, and the weight ratio of Pt-based particles to the resin in the proton exchange membrane is (0.1-1):100. The preparation method includes the following steps: Step S1, melting and extruding the resin to obtain a first intermediate product; Step S2, blow molding the first intermediate product to form a hollow layer inside the first intermediate product, and introducing inorganic particles into the hollow layer so that the inorganic particles are distributed on the inner wall of the first intermediate product to obtain a second intermediate product; Step S3, pressing the second intermediate product to obtain a third intermediate product; Step S4, post-processing the third intermediate product to obtain a proton exchange membrane.

[0007] Furthermore, the resin includes one or more of perfluorosulfonyl fluoride resin, sulfonated polyethersulfone resin, sulfonated polybenzimidazole resin, sulfonated polyphenylene sulfide resin, sulfonated polyphosphazene resin, sulfonated polyimide resin, sulfonated polystyrene resin, and sulfonated trifluorostyrene resin.

[0008] Further, the Pt-based particles include Pt particles and / or Pt alloy particles; preferably, the Pt alloy particles include Pt x M y and / or Pt x M y N 1-x-y Wherein, M and N are independently selected from Ru, Pd, Rh, Ir, Os, Fe, Cr, Ni, Co, Mn, Cu, Ti, Sn, V, Ga, or Mo, and M and N are all different, 0.5≤x≤0.95, 0.05≤y≤0.5, 1-xy≤0.45; more preferably, the Pt alloy particles include Pt x Co y Pt x Ni y and Pt x Co y Ni 1-x-y One or more of the following: and / or the particle size of the Pt-based particles is 70–400 nm; and / or the inorganic particles further include CeO2 particles with a particle size of 20–200 nm; preferably, the weight ratio of CeO2 particles to resin in the proton exchange membrane is (0.1–10):100; more preferably, the inorganic particles include one or more of the following: Pt particles, Pt... 0.9 Co 0.1 Particles, and mixtures of Pt particles and CeO2 particles, wherein the mass ratio of Pt particles to CeO2 particles in the mixture is (0.01 to 1):1.

[0009] Furthermore, the thickness of the proton exchange membrane is 20–180 μm, preferably 60–120 μm.

[0010] Further, in step S1, the extrusion temperature is 180–300°C; preferably, the extrusion temperature is 200–280°C.

[0011] Further, in step S2, the blow molding is single-layer blow molding or multi-layer blow molding; preferably, inorganic particles are introduced into the hollow layer by extrusion or air-puff doping; more preferably, the air-puff doping method is atomized air-puff; even more preferably, the atomization method of atomized air-puff is one or more of water atomization, gas atomization, plasma atomization and ultrasonic atomization.

[0012] Further, in step S3, the film blow-up ratio of the third intermediate product is 2.00 to 4.00, and / or the thickness of the third intermediate product is 15 to 160 μm.

[0013] Further, in step S4, the post-processing includes: sequentially washing the third intermediate product with alkali, washing with water, washing with acid, washing with water, and drying to obtain a proton exchange membrane.

[0014] According to another aspect of the present invention, a proton exchange membrane is provided, which is obtained by the preparation method described above.

[0015] According to another aspect of the present invention, an application of a proton exchange membrane in the process of water electrolysis is provided.

[0016] The proton exchange membrane using the technical solution of this invention has an integrated surface resin layer and an intermediate resin layer. The surface resin layer is located on both sides of the intermediate resin layer, and the intermediate resin layer is doped with inorganic particles within a specific range. The entire membrane is made by transforming an intermediate product film with a "sandwich" basic structure of surface resin layer-intermediate resin layer-surface resin layer formed by pressing. The inorganic particles are not easily lost and have a wide contact surface with hydrogen. When a small amount of hydrogen permeates into the proton exchange membrane, the Pt-based particles and other inorganic particles uniformly dispersed in the middle of the proton exchange membrane can fully contact the hydrogen and oxidize the hydrogen into protons. The protons then react with the oxygen anions generated by the ionization of water in the electrolyzer to generate water. This helps to prevent hydrogen from permeating into the oxygen side of the anode of the PEMWE system, thereby effectively improving the safety of high-voltage operation of the PEMWE system.

[0017] This invention employs a melt extrusion blow molding process. First, resin is melted, extruded, and blow-molded to obtain a hollow resin layer. Then, inorganic particles are introduced into the hollow resin portion, distributing them along the inner wall of the hollow resin layer. Next, the resin layer and inorganic particles are pressed against the outer surface to ensure close adhesion, resulting in a thin film-like intermediate product of a certain thickness. Finally, post-processing is performed to prepare a proton exchange membrane that effectively prevents hydrogen permeation and reduces safety risks. This melt extrusion blow molding process requires no pre-mixing and does not use solvents during the molding process, making it green, environmentally friendly, safe, and highly efficient. It allows for mass production of membranes with low equipment requirements. The proton exchange membrane prepared by this method has a simple and efficient molding process, simple composition, and low cost. Attached Figure Description

[0018] The accompanying drawings, which form part of this application, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0019] Figure 1 A schematic diagram of a proton exchange membrane fabrication process according to an embodiment of the present invention is shown; and

[0020] Figure 2 A schematic diagram of a proton exchange membrane structure according to an embodiment of the present invention is shown.

[0021] The above figures include the following reference numerals:

[0022] 1. Single-screw extruder; 2. Die; 3. Herringbone plate; 4. Pressure roller;

[0023] A. Resin; B. Inorganic particles; C. Compressed air; D. Third intermediate product; a. First surface resin layer; b. Intermediate layer; c. Second surface resin layer. Detailed Implementation

[0024] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0025] It should be noted that the terms "first," "second," etc., in the specification and claims of this invention are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such data can be used interchangeably where appropriate to describe embodiments of the invention. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion; for example, a process, method, system, product, or apparatus that comprises a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or apparatus.

[0026] Terminology Explanation:

[0027] Film blow-up ratio: The lateral expansion ratio of the film after blow molding compared to before blow molding.

[0028] As described in the background section of this invention, existing proton exchange membranes suffer from problems such as easy gas permeation and high safety risks. To address these issues, a typical embodiment of this invention provides a method for preparing a proton exchange membrane. This proton exchange membrane has an integrated surface resin layer and an intermediate resin layer, with the surface resin layer located on both sides of the intermediate resin layer. The intermediate resin layer is doped with inorganic particles; wherein the inorganic particles include Pt-based particles, and the weight ratio of Pt-based particles to resin in the proton exchange membrane is (0.1-1):100. The method for preparing the proton exchange membrane includes the following steps: Step S1, melting and extruding resin to obtain a first intermediate product; Step S2, blow molding the first intermediate product to form a hollow layer inside the first intermediate product, and introducing inorganic particles into the hollow layer so that the inorganic particles are distributed on the inner wall of the first intermediate product to obtain a second intermediate product; Step S3, pressing the second intermediate product to obtain a third intermediate product; Step S4, post-processing the third intermediate product to obtain the proton exchange membrane.

[0029] In the proton exchange membrane provided by this invention, the proton exchange membrane is obtained by transforming an intermediate product film formed by pressing a "sandwich" basic structure consisting of a surface resin layer, an intermediate resin layer, and a surface resin layer. The inventors unexpectedly discovered during their research that distributing inorganic particles in the middle of the resin layers, rather than on both sides, can effectively reduce the loss of inorganic particles, thereby increasing the contact area between the inorganic particles and hydrogen. When a small amount of hydrogen permeates into the proton exchange membrane, the Pt-based particles and other inorganic particles uniformly dispersed in the middle of the membrane can fully contact the hydrogen and oxidize it into protons, which then react with oxygen anions to generate water. The surface resin on both sides fully encapsulates the inorganic particles, preventing their loss while effectively conducting protons. The synergistic cooperation between the surface resin layer, the intermediate resin layer, and the surface resin layer reduces hydrogen passage, which helps prevent hydrogen from permeating into the oxygen side of the PEMWE system anode, thus effectively avoiding the accumulation of hydrogen and oxygen gases and potential explosion, and effectively improving the safety of the PEMWE system during high-pressure operation.

[0030] Furthermore, the proton exchange membrane of this invention comprises resin and inorganic particles, requiring no pre-mixing and no solvent components to be added during the molding process, resulting in a simple molding process and low cost. The inorganic particles include Pt-based particles, which can effectively catalyze the reaction of hydrogen permeating into the proton exchange membrane to generate water, thus helping to solve the hydrogen permeation problem. The weight ratio of Pt-based particles to resin in the proton exchange membrane is (0.1–1):100. Within this range, the Pt-based particles are less prone to agglomeration, promoting uniform dispersion between resin layers. This effectively prevents hydrogen from entering the oxygen side of the PEMWE system anode through the proton exchange membrane, significantly improving the safety performance of the PEMWE system.

[0031] This invention employs a melt extrusion blow molding process. First, resin is melted, extruded, and blow-molded to obtain a hollow resin layer. Then, inorganic particles are introduced into the hollow resin portion, distributing them along the inner wall of the hollow resin layer. Next, the resin layer and inorganic particles are pressed against the outer surface to ensure close adhesion, resulting in a thin film-like intermediate product of a certain thickness. Finally, post-processing is performed to prepare a proton exchange membrane that effectively prevents hydrogen permeation. This melt extrusion blow molding process requires no pre-mixing and does not use solvents during molding, making it green, environmentally friendly, safe, and highly efficient. It allows for mass production of membranes with low equipment requirements and low cost.

[0032] It is understood that the proton exchange membrane of the present invention, based on the basic "sandwich" structure of surface resin layer - intermediate resin layer - surface resin layer, can have a multi-layer structure according to actual needs, as long as the resin layers are located on both sides of the intermediate resin layer.

[0033] This application does not specifically limit the type of resin; commonly used resins in the art can be applied to this application. In order to give the proton exchange membrane better proton conduction and mechanical properties, in a preferred embodiment, the resin includes one or more of perfluorosulfonyl fluoride resin, sulfonated polyethersulfone resin, sulfonated polybenzimidazole resin, sulfonated polyphenylene sulfide resin, sulfonated polyphosphazene resin, sulfonated polyimide resin, sulfonated polystyrene resin, and sulfonated trifluorostyrene resin; preferably, the resin is a perfluorosulfonyl fluoride resin.

[0034] To further reduce the amount of Pt used and lower costs, while improving the catalytic efficiency of Pt-based particles to more fully catalytically convert hydrogen permeating into the proton exchange membrane, in a preferred embodiment, the Pt-based particles include Pt particles and / or Pt alloy particles; preferably, the Pt alloy particles include Pt... x M y and / or Pt x M y N 1-x-y Wherein, M and N are independently selected from Ru, Pd, Rh, Ir, Os, Fe, Cr, Ni, Co, Mn, Cu, Ti, Sn, V, Ga, or Mo, and M and N are all different, 0.5≤x≤0.95, 0.05≤y≤0.5, 1-xy≤0.45; more preferably, the Pt alloy particles include Pt x Co y Pt x Ni y and Pt x Co y Ni 1-x-y One or more of the following; and / or, the particle size of the Pt-based particles is 70–400 nm. Under the above conditions, the formation of alloys between Pt and other metals can better control the adsorption / desorption performance between the catalyst and hydrogen / oxygen, more effectively reduce the activation energy of the catalytic reaction, increase the catalytic reaction rate, and thus further reduce the hydrogen permeation of the proton exchange membrane.

[0035] To further improve the durability of the membrane and thus extend its service life, in a preferred embodiment, the inorganic particles further include CeO2 particles with a particle size of 20–200 nm; preferably, the weight ratio of CeO2 particles to resin in the proton exchange membrane is (0.1–10):100. More preferably, the inorganic particles include one or more of the following: Pt particles, Pt... 0.9 Co 0.1 The mixture contains Pt particles and a mixture of Pt and CeO2 particles, wherein the mass ratio of Pt particles to CeO2 particles in the mixture is (0.01–1):1. Under the above conditions, the proton exchange membrane prepared exhibits superior durability and gas permeation resistance.

[0036] In a preferred embodiment, the thickness of the proton exchange membrane obtained by the preparation method is 20–180 μm, preferably 60–120 μm. Under these thickness conditions, the proton exchange membrane can not only more effectively block hydrogen and oxygen, but also better conduct protons, further reducing production costs.

[0037] To ensure more thorough melting and mixing of the resin and further improve the uniformity of the resin layer, in a preferred embodiment, the extrusion temperature in step S1 is 180–300°C, preferably 200–280°C. Regarding the resin extrusion speed in the preparation method provided by this invention, those skilled in the art can adapt and conventionally adjust it according to the specifications and dimensions of existing extruders and the total amount of resin extruded, such as an extrusion speed of 0.5–1.2 kg / h.

[0038] To further improve the effect of the resin layer in blocking hydrogen permeation, in a preferred embodiment, in step S2, the blow molding is either single-layer blow molding or multi-layer blow molding. The third intermediate product obtained from single-layer blow molding is directly pressed from the blow-molded resin on both sides and the inorganic particles in the middle. The third intermediate product obtained from multi-layer blow molding can be pressed from multiple layers of resin and the inorganic particles in the very center, or it can be pressed by introducing inorganic particles into the porous layers of each resin layer. To ensure a more uniform distribution of inorganic particles in the hollow portion of the resin layer, thereby further improving the conversion efficiency of the inorganic particles for hydrogen and reducing hydrogen permeation, it is preferable to introduce inorganic particles into the hollow layer by extrusion or pneumatic doping. The rate of introduction of inorganic particles can be maintained at an appropriate ratio between the proportion of inorganic particle doping and the resin extrusion rate, such as an inorganic particle introduction rate of 1–35 g / h. The aforementioned rate of inorganic particle introduction is understandable to those skilled in the art and will not be elaborated further here. To achieve more uniform dispersion of inorganic particles and more thorough contact between them and hydrogen, thereby consuming more hydrogen that has permeated into the proton exchange membrane and further reducing the amount of hydrogen entering the anode to improve safety performance, more preferably, the doping method is atomized atomization; more preferably, the atomization method of atomized atomization is one or more of water atomization, gas atomization, plasma atomization, and ultrasonic atomization. Under the above conditions, inorganic particles can be more uniformly dispersed in the resin layer.

[0039] To further improve the physical and mechanical properties of the proton exchange membrane, in a preferred embodiment, in step S3, the film blow-up ratio of the third intermediate product is 2.00 to 4.00, that is, the transverse width of the film obtained after blow molding and pressing is increased by 2.00 to 4.00 times compared with that before blow molding; and / or, the thickness of the third intermediate product is 15 to 160 μm. Under the above conditions, the physical and mechanical properties of the film can be further improved while meeting the basic performance requirements of the film, and the production cost can be reduced.

[0040] To further improve the performance of the proton exchange membrane and to more fully transform the groups in the resin, in a preferred embodiment, step S4 includes post-treatment comprising: sequentially subjecting the third intermediate product to alkali washing, a first water washing, acid washing, a second water washing, and drying to obtain the proton exchange membrane. Under the above conditions, the formation of sulfonic acid groups is more favorable, resulting in a proton exchange membrane with superior proton conduction capabilities, making it more suitable for use in PEMWE systems.

[0041] In another typical embodiment of the present invention, a proton exchange membrane is also provided, obtained by the above-described preparation method. The proton exchange membrane obtained by the preparation method of the present invention has a uniform and controllable thickness, uniform distribution of inorganic particles, no other solvents incorporated, a simple composition, and low cost. Applying this proton exchange membrane can more fully catalyze the permeated hydrogen gas, and more effectively reduce the safety risks caused by gas permeation in the PEMWE system.

[0042] In another typical embodiment of the present invention, the application of the above-mentioned proton exchange membrane in the process of water electrolysis is also provided.

[0043] Typical, but not limiting, weight ratios of Pt-based particles to resin in the proton exchange membrane are 0.1:100, 0.15:100, 0.2:100, 0.25:100, 0.3:100, 0.35:100, 0.4:100, 0.45:100, 0.5:100, 0.55:100, 0.6:100, 0.65:100, 0.7:100, and 0.75:100. The particle size of the Pt-based particles is 70nm, 80nm, 90nm, 100nm, 150nm, 170nm, 200nm, 210nm, 250nm, 300nm, 350nm, 400nm, or any two of these values;

[0044] Typically, but not limitingly, when the inorganic particles also include CeO2 particles, the particle size of the CeO2 particles is 20 nm, 40 nm, 60 nm, 80 nm, 100 nm, 120 nm, 140 nm, 160 nm, 180 nm, 200 nm, or any two of these values; the weight ratio of CeO2 particles to the resin in the proton exchange membrane is 0.1:100, 0.2:100, 0.3:100, 0.4:100, 0.5:100, 0.6:100, 0.7:100, 0.8:100, 0.9:100, 1:100, 2:100, 3:100, 4:100, 5:100, 6:100, 7:100, 8:100, 9:100, 10:100, or any two of these values.

[0045] Typically, but not limitingly, when the inorganic particles comprise a mixture of Pt particles and CeO2 particles, the mass ratio of Pt particles to CeO2 particles in the mixture is 0.01:1, 0.02:1, 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, or any two of these values ​​within a range.

[0046] Typical, but not limiting, proton exchange membrane thicknesses are 20 μm, 40 μm, 60 μm, 80 μm, 100 μm, 120 μm, 140 μm, 160 μm, 180 μm or any two of these values.

[0047] Typically, but not limitingly, in step S1, the extrusion temperature is 180°C, 200°C, 220°C, 240°C, 260°C, 280°C, 300°C, or a range of any two of these values.

[0048] Typically, but not limitingly, in step S3, the film blow-up ratio of the third intermediate product is 2.00, 2.20, 2.40, 2.60, 2.80, 3.00, 3.20, 3.40, 3.50, 3.60, 3.71, 3.75, 3.80, 4.00, or any two of these values; the thickness of the third intermediate product is 15 μm, 20 μm, 40 μm, 60 μm, 80 μm, 100 μm, 120 μm, 140 μm, 160 μm, or any two of these values.

[0049] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0050] Example 1

[0051] A schematic diagram of the proton exchange membrane preparation process is shown below. Figure 1 A schematic diagram of the proton exchange membrane structure can be found in [link to diagram]. Figure 2 In this embodiment, resin A is a perfluorosulfonyl fluoride resin with a weight-average molecular weight of 84,000, and inorganic particles B are Pt particles;

[0052] In step S1, the screw speed of the single-screw extruder 1 is 30 rpm and the die outlet temperature is 260°C. 5 kg of perfluorosulfonyl fluoride resin granules are added to the die of the single-screw extruder 1. Under the action of temperature and screw, the molten resin is extruded from the die at a rate of 1 kg / h. The single-screw extruder 1 is equipped with an annular die 2 with a diameter of 3 cm and a gap of 1 mm. After the molten resin is extruded from the die, it passes through the die 2 to obtain the first intermediate product.

[0053] Step S2: Compressed air C is introduced into die 2 to blow-mold the first intermediate product. The first intermediate product is in the form of a film with a hollow layer inside. Next, 15g of Pt particles with a particle size of 170nm are added to the die head of the single screw extruder 1 at a rate of 3g / h. After being extruded from the die head, the Pt particles pass through die 2 and enter the hollow layer of the first intermediate product to obtain the second intermediate product.

[0054] Step S3: The second intermediate product is pressed by the herringbone plate 3 and the pressure roller 4 to obtain a third intermediate product D with an intermediate resin layer containing Pt belt, a resin blow-up ratio of 3.71, and a thickness of 100μm.

[0055] Step S4: The third intermediate product D is hydrolyzed in a 20% potassium hydroxide solution at 80°C, washed with water, acidified in a 0.5M sulfuric acid solution at 80°C, washed with water again, and dried to obtain a proton exchange membrane with a thickness of 120 μm. The membrane has an integrated first surface resin layer a, an intermediate resin layer b, and a second surface resin layer c. The first and second surface resin layers are located on both sides of the intermediate resin layer, and the intermediate resin layer is doped with inorganic particles.

[0056] Example 2

[0057] The only difference from Example 1 is that the inorganic particles are introduced into the hollow layer of the first intermediate product by ultrasonic atomization pneumatic doping, specifically:

[0058] In step S2, compressed air C is introduced into the die 2 to blow-mold the first intermediate product. The first intermediate product is film-shaped with a hollow layer inside. Next, 15g of Pt particles with a particle size of 170nm are melted and fed into the surface of the tool head of the ultrasonic transducer to form a thin liquid layer. Under the action of ultrasonic vibration, the thin liquid layer excites surface tension waves. When the amplitude of the liquid droplets on the surface exceeds the amplitude of the tool head, the droplets will fly out and be atomized into small droplets. The atomized Pt particles are mixed with the air at a speed of 3g / h and enter the hollow layer of the first intermediate product to obtain the second intermediate product.

[0059] Example 3

[0060] The only difference from Example 1 is that the inorganic particles B are a mixture of Pt particles and CeO2 particles, with a CeO2 particle to resin weight ratio of 3:100, and the infeed rate of inorganic particles B is 33 g / h. Specifically:

[0061] Step S2: Compressed air C is introduced into die 2 to blow-mold the first intermediate product. The first intermediate product is film-shaped and has a hollow layer inside. Next, 15g of Pt particles with a particle size of 170nm and 150g of CeO2 particles with a particle size of 100nm are mixed to obtain inorganic particles B. Inorganic particles B are added to the die head of a single screw extruder 1 at a rate of 33g / h. After the mixture is extruded through the die head, it passes through die 2 and enters the hollow layer of the first intermediate product to obtain the second intermediate product.

[0062] Step S3: The second intermediate product is pressed by the herringbone plate 3 and the pressure roller 4 to obtain the third intermediate product D, which is an intermediate resin layer containing a mixture of Pt particles and CeO2 particles.

[0063] Example 4

[0064] The only difference from Example 1 is that the inorganic particle B is Pt. 0.9 Co 0.1 Alloy, specifically:

[0065] Step S2: Compressed air C is introduced into die 2 to blow-mold the first intermediate product. The first intermediate product is in the form of a film with a hollow internal layer. Next, 15g of Pt with a particle size of 200nm is added. 0.9 Co 0.1 The alloy, Pt, is added to the die of a single-screw extruder at a rate of 3 g / h. 0.5 Co 0.5 After being extruded through the die, the alloy passes through die 2 and enters the hollow layer of the first intermediate product to obtain the second intermediate product.

[0066] Step S3: The second intermediate product is pressed by the herringbone plate 3 and the pressure roller 4 to obtain an intermediate layer containing Pt.0.9 Co 0.1 The third intermediate product D of the alloy intermediate resin layer.

[0067] Example 5

[0068] The only differences from Example 1 are that the resin extrusion rate is 0.7 kg / h, the inorganic particles B are Pt particles, the feed rate is 2.1 g / h, the thickness of the third intermediate product is 60 μm, and the thickness of the proton exchange membrane is 80 μm. Specifically:

[0069] In step S1, the screw speed of the single-screw extruder 1 is 30 rpm and the die outlet temperature is 280℃. 5 kg of perfluorosulfonyl fluoride resin granules are added to the die of the single-screw extruder 1. Under the action of temperature and screw, the molten resin is extruded from the die at a rate of 0.7 kg / h. The single-screw extruder 1 is equipped with an annular die 2 with a diameter of 3 cm and a gap of 1 mm. After the molten resin is extruded from the die, it passes through the die 2 to obtain the first intermediate product.

[0070] In step S2, compressed air C is introduced into die 2 to blow-mold the first intermediate product. The first intermediate product is in the form of a film with a hollow layer inside. Next, 15g of Pt particles with a particle size of 170nm are added to the die of a single screw extruder 1 at a rate of 2.1g / h. After being extruded from the die, the Pt particles pass through die 2 and enter the hollow layer of the first intermediate product to obtain the second intermediate product.

[0071] Step S3: The second intermediate product is pressed by the herringbone plate 3 and the pressure roller 4 to obtain a third intermediate product D with an intermediate resin layer containing Pt belt, a resin blow-up ratio of 3.71, and a thickness of 60 μm.

[0072] Step S4: The third intermediate product D is hydrolyzed in a 20% potassium hydroxide solution at 80°C, washed with water, acidified in a 0.5M sulfuric acid solution at 80°C, washed with water again, and dried to obtain a proton exchange membrane with a thickness of 80 μm. The membrane has an integrated first surface resin layer, an intermediate resin layer, and a second surface resin layer. The first surface resin layer and the second surface resin layer are located on both sides of the intermediate resin layer. The intermediate resin layer is doped with inorganic particles.

[0073] Example 6

[0074] A schematic diagram of the proton exchange membrane preparation process is shown below. Figure 1 A schematic diagram of the proton exchange membrane structure can be found in [link to diagram]. Figure 2 In this embodiment, resin A is a sulfonated polyethersulfone resin with a weight-average molecular weight of 135,000, and inorganic particles B are Pt. 0.7 Co 0.15 Ni 0.15 alloy;

[0075] In step S1, the screw speed of the single-screw extruder 1 is 30 rpm and the die outlet temperature is 240℃. 5 kg of sulfonated polyethersulfone resin granules are added to the die of the single-screw extruder 1. Under the action of temperature and screw, the molten resin is extruded from the die at a rate of 0.85 kg / h. The single-screw extruder is equipped with an annular die 2 with a diameter of 3 cm and a gap of 1 mm. After the molten resin is extruded from the die, it passes through the die 2 to obtain the first intermediate product.

[0076] Step S2: Compressed air C is introduced into die 2 to blow-mold the first intermediate product. The first intermediate product is in the form of a film with a hollow interior. Next, 25g of Pt with a particle size of 210nm is added. 0.7 Co 0.15 Ni 0.15 Pt is added to the die head of a single-screw extruder at a rate of 4.25 g / h. 0.7 M 0.15 N 0.15 After being extruded through the die head, it passes through die 2 and enters the hollow layer of the first intermediate product to obtain the second intermediate product;

[0077] Step S3: The second intermediate product is pressed by the herringbone plate 3 and the pressure roller 4 to obtain an intermediate layer containing Pt. 0.7 Co 0.15 Ni 0.15 The alloy's intermediate resin layer, the third intermediate product D with a resin blow-up ratio of 3 and a thickness of 100 μm;

[0078] Step S4: The third intermediate product D is hydrolyzed in a 20% potassium hydroxide solution at 80°C, washed with water, acidified in a 0.5M sulfuric acid solution at 80°C, washed with water again, and dried to obtain a proton exchange membrane with a thickness of 120 μm. The membrane has an integrated first surface resin layer, an intermediate resin layer, and a second surface resin layer. The first surface resin layer and the second surface resin layer are located on both sides of the intermediate resin layer. The intermediate resin layer is doped with inorganic particles.

[0079] Example 7

[0080] A schematic diagram of the proton exchange membrane preparation process is shown below. Figure 1 A schematic diagram of the proton exchange membrane structure can be found in [link to diagram]. Figure 2 In this embodiment, resin A is sulfonated polybenzimidazole resin with a weight average molecular weight of 149,000 and sulfonated polyphenylene sulfide resin with a weight average molecular weight of 121,000, and inorganic particles B is a mixture of Pt particles and CeO2 particles.

[0081] In step S1, the screw speed of the single-screw extruder 1 is 30 rpm and the die outlet temperature is 300℃. 4 kg of sulfonated polybenzimidazole resin granules are added to the die of the single-screw extruder 1. Under the action of temperature and screw, the molten resin is extruded from the die at a rate of 1.2 kg / h. The single-screw extruder is equipped with an annular die 2 with a diameter of 3 cm and a gap of 1 mm. After the molten resin is extruded from the die, it passes through the die to obtain the first intermediate product.

[0082] In step S2, compressed air C is introduced into die 2 to blow-mold the first intermediate product. The first intermediate product is film-shaped and has a hollow interior. Next, 4 kg of sulfonated polyphenylene sulfide resin granules are added to the die of a single-screw extruder. Under the action of temperature and screw, the molten resin is extruded through the die at a rate of 1.2 kg / h and passes through die 2 into the interior of the first intermediate product. Compressed air C is continued to be introduced into die 2 for blow molding, so that the sulfonated polyphenylene sulfide resin is located inside the first intermediate product and is film-shaped, while the interior of the sulfonated polyphenylene sulfide resin is a hollow interior. 8 g of Pt particles with a particle size of 70 nm and 800 g of CeO2 particles with a particle size of 200 nm are mixed. The mixture of Pt particles and CeO2 particles is added to the die of a single-screw extruder at a rate of 119 g / h. The Pt particles are extruded through the die and pass through die 2 into the hollow interior of the sulfonated polyphenylene sulfide resin to obtain the second intermediate product.

[0083] Step S3: The second intermediate product is pressed by the herringbone plate 3 and the pressure roller 4 to obtain a third intermediate product D with an intermediate resin layer containing a mixture of Pt particles and CeO2 particles, a resin blow-up ratio of 2.00, and a thickness of 160 μm.

[0084] Step S4: The third intermediate product D is hydrolyzed in a 20% potassium hydroxide solution at 80°C, washed with water, acidified in a 0.5M sulfuric acid solution at 80°C, washed with water again, and dried to obtain a proton exchange membrane with a thickness of 180 μm. The membrane has an integrated first surface resin layer, an intermediate resin layer, and a second surface resin layer. The first surface resin layer and the second surface resin layer are located on both sides of the intermediate resin layer. The intermediate resin layer is doped with inorganic particles.

[0085] Example 8

[0086] A schematic diagram of the proton exchange membrane preparation process is shown below. Figure 1 A schematic diagram of the proton exchange membrane structure can be found in [link to diagram]. Figure 2 In this embodiment, resin A is a sulfonated polyphosphazene resin with a weight-average molecular weight of 105,000, and inorganic particles B are Pt. 0.5 Co 0.5 alloy;

[0087] In step S1, the screw speed of the single-screw extruder 1 is 30 rpm and the die outlet temperature is 200℃. 5 kg of sulfonated polyphosphazene resin granules are added to the die of the single-screw extruder 1. Under the action of temperature and screw, the molten resin is extruded from the die at a rate of 0.5 kg / h. The single-screw extruder 1 is equipped with an annular die 2 with a diameter of 3 cm and a gap of 1 mm. After the molten resin is extruded from the die, it passes through the die 2 to obtain the first intermediate product.

[0088] Step S2: Compressed air C is introduced into die 2 to blow-mold the first intermediate product. The first intermediate product is in the form of a film with a hollow interior. Next, 50g of Pt with a particle size of 175nm is added. 0.5 Co 0.5 Pt is added to the die head of a single-screw extruder at a rate of 5 g / h. 0.5 Co 0.5 After being extruded through the die head, it passes through die 2 and enters the hollow layer of the first intermediate product to obtain the second intermediate product;

[0089] Step S3: The second intermediate product is pressed by the herringbone plate 3 and the pressure roller 4 to obtain an intermediate layer containing Pt. 0.5 Co 0.5 The alloy's intermediate resin layer, the third intermediate product D with a resin blow-up ratio of 4 and a thickness of 15 μm;

[0090] Step S4: The third intermediate product D is hydrolyzed in a 20% potassium hydroxide solution at 80°C, washed with water, acidified in a 0.5M sulfuric acid solution at 80°C, washed with water again, and dried to obtain a proton exchange membrane with a thickness of 20 μm. The membrane has an integrated first surface resin layer, an intermediate resin layer, and a second surface resin layer. The first and second surface resin layers are located on both sides of the intermediate resin layer, and the intermediate resin layer is doped with inorganic particles.

[0091] Example 9

[0092] A schematic diagram of the proton exchange membrane preparation process is shown below. Figure 1 A schematic diagram of the proton exchange membrane structure can be found in [link to diagram]. Figure 2 In this embodiment, resin A is a sulfonated polyimide resin with a weight-average molecular weight of 98,000, and inorganic particles B are a mixture of Pt particles and CeO2 particles;

[0093] In step S1, the screw speed of the single-screw extruder 1 is 30 rpm and the die outlet temperature is 220°C. 5 kg of sulfonated polyimide resin granules are added to the die of the single-screw extruder 1. Under the action of temperature and screw, the molten resin is extruded from the die at a rate of 1.2 kg / h. The single-screw extruder 1 is equipped with an annular die 2 with a diameter of 3 cm and a gap of 1 mm. After the molten resin is extruded from the die, it passes through the die to obtain the first intermediate product.

[0094] Step S2: Compressed air C is introduced into the die to blow-mold the first intermediate product, which is in the form of a film with a hollow layer inside. 50g of Pt particles with a particle size of 400nm and 50g of CeO2 particles with a particle size of 20nm are mixed. The mixture of Pt particles and CeO2 particles is added to the die of a single screw extruder 1 at a rate of 24g / h. After being extruded from the die, the Pt particles pass through the die 2 and enter the hollow layer inside the sulfonated polyphenylene sulfide resin to obtain the second intermediate product.

[0095] Step S3: The second intermediate product is pressed by the herringbone plate 3 and the pressure roller 4 to obtain a third intermediate product D with an intermediate resin layer containing a mixture of Pt particles and CeO2 particles, a resin blow-up ratio of 2, and a thickness of 140 μm.

[0096] Step S4: The third intermediate product D is hydrolyzed in a 20% potassium hydroxide solution at 80°C, washed with water, acidified in a 0.5M sulfuric acid solution at 80°C, washed with water again, and dried to obtain a proton exchange membrane with a thickness of 160 μm. The membrane has an integrated first surface resin layer, an intermediate resin layer, and a second surface resin layer. The first surface resin layer and the second surface resin layer are located on both sides of the intermediate resin layer. The intermediate resin layer is doped with inorganic particles.

[0097] Example 10

[0098] The only difference from Example 1 is that the inorganic particles are introduced into the hollow layer of the first intermediate product by water atomization and pneumatic doping, specifically:

[0099] In step S2, compressed air C is introduced into the die 2 to blow-mold the first intermediate product. The first intermediate product is in the form of a film with a hollow layer inside. Next, 15g of Pt particles with a particle size of 170nm are melted into a liquid metal and sprayed into atomized particles by a high-speed airflow. The atomized Pt particles are mixed with the air at a speed of 3g / h and enter the hollow layer of the first intermediate product to obtain the second intermediate product.

[0100] Example 11

[0101] The only difference from Example 1 is that the inorganic particles are introduced into the hollow layer of the first intermediate product by gas atomization pneumatic doping, specifically:

[0102] In step S2, compressed air C is introduced into the die 2 to blow-mold the first intermediate product. The first intermediate product is in the form of a film with a hollow layer inside. Next, 15g of Pt particles with a particle size of 170nm are melted into a liquid metal. During free fall, the particles are broken and atomized by gas shearing and extrusion. The atomized Pt particles are mixed with the air at a rate of 3g / h and enter the hollow layer of the first intermediate product to obtain the second intermediate product.

[0103] Example 12

[0104] The only difference from Example 1 is that the inorganic particles are introduced into the hollow layer of the first intermediate product by plasma atomization pneumatic doping, specifically:

[0105] In step S2, compressed air C is introduced into the die 2 to blow-mold the first intermediate product. The first intermediate product is in the form of a film with a hollow layer inside. Next, 15g of Pt particles with a particle size of 170nm are melted into a liquid film on the end face of a high-speed rotating electrode rod in a high-temperature plasma gun. The liquid film is broken into droplets under the action of high-speed centrifugal force and is physicochemically atomized. The atomized Pt particles are mixed with air at a rate of 3g / h and enter the hollow layer of the first intermediate product to obtain the second intermediate product.

[0106] Comparative Example 1

[0107] The difference between Comparative Example 1 and Example 1 is that inorganic particles were not introduced during the preparation of the proton exchange membrane.

[0108] Comparative Example 2

[0109] Example 1 using the patent with publication number CN101246966A, entitled "Proton Exchange Membrane with Reverse Gas Permeation Layer and Humidification Function and its Preparation Method Thereof":

[0110] Preparation of reverse osmosis membrane layer based on porous perfluorosulfonic acid membrane:

[0111] 1. Add 1 ml of 5 wt% perfluorosulfonic acid resin solution ( A solution (produced by DuPont) was prepared by dispersing 5 grams of Pt / C (10 wt%) catalyst in 100 ml of 10% isopropanol aqueous solution and stirring at high speed (10,000 rpm) for 10 minutes under vacuum to obtain a catalyst slurry.

[0112] 2. Preparation of perfluorosulfonic acid porous membrane: 400 mL of a 5% perfluorosulfonic acid resin solution (solvents: 30% ethanol, 70% isopropanol) was poured into a glass container with dimensions of 10 cm (length), 10 cm (width), and 5 cm (height). The container was then vacuum-dried at 80°C for 18 hours to obtain a cast membrane. The cast membrane was peeled off the glass surface and hot-pressed at 120±10°C and 2 MPa. The hot-pressed membrane was cut into 5 cm wide strips, which were then longitudinally stretched at 120–130°C and allowed to cool naturally to room temperature. Finally, the longitudinally stretched membrane was transversely stretched at 120±10°C at a stretching speed of 5 m / s and a stretching ratio of 10 times. The resulting microporous membrane was heat-set at 120±10°C for 5 minutes to obtain a perfluorosulfonic acid hydrophilic porous membrane.

[0113] 3. Take a perfluorosulfonic acid porous membrane with a thickness of 5 μm, a porosity greater than 80%, and an average pore size of 0.7 μm. Immerse the perfluorosulfonic acid porous membrane in a catalyst slurry under vacuum for 5 minutes, then remove and vacuum dry. Repeat the above immersion and drying process once. Boil the membrane in 0.5 M H2SO4 solution for 1 hour, then thoroughly soak, wash, and vacuum dry it with deionized water. Finally, hot-press the filled porous proton exchange membrane at a temperature of 140±10℃, a pressure of 2 MPa, and a time of 60 seconds to prepare a porous perfluorosulfonic acid reverse osmosis membrane (layer). The Pt loading of the membrane is 0.004 mg / cm³. 2 .

[0114] Preparation of proton exchange membranes:

[0115] The reverse gas osmosis membrane prepared above and the SiO2 nanoparticle-doped porous polytetrafluoroethylene (PTFE) matrix proton exchange membrane prepared by Wuhan University of Technology (ZL200510018749.X) were cut into modules of the same specifications. Then, the SiO2 nanoparticle-doped porous PTFE matrix proton exchange membrane (11 μm thickness), the reverse gas osmosis membrane (4 μm), and the SiO2 nanoparticle-doped porous PTFE matrix proton exchange membrane (11 μm) were stacked neatly in the order of top to bottom. A polytetrafluoroethylene film of the same size was placed at the bottom and top of each module to obtain a five-in-one stack. The five-in-one stack was hot-pressed at a pressure of 2.5 MPa and a temperature of 140 ± 10 °C for 2 minutes. After that, the stack was removed and the surface polytetrafluoroethylene film was peeled off to obtain the proton exchange membrane.

[0116] The hydrogen permeation, proton conductivity, and water electrolysis performance of the proton exchange membranes in the above examples and comparative examples were measured, and the test results are shown in Table 1.

[0117] Test method:

[0118] Hydrogen permeation of proton exchange membrane: An electrochemical method was used, specifically as follows: the proton exchange membrane was made into a membrane electrode and then assembled into a single-cell electrolyzer. The single-cell electrolyzer was activated for 2 hours at a gradient point current density and an activation temperature of 80℃. Anode water inlet mode was used with a water flow rate of 200 mL / min. When the voltage fluctuation range was less than 2%, it was considered to be fully activated. The activated single cell was then tested at a certain current density and cathode back pressure. The volume fraction of hydrogen in the anode oxygen was measured at a certain current density and cathode back pressure.

[0119] Proton conductivity: The four-electrode proton compensation method was used. The specific steps were as follows: the membrane was assembled in the conductivity test fixture and immersed in water at 80°C for 3 hours. According to the four-electrode method, the electrochemical workstation was connected to the platinum wire of the fixture and the test was carried out.

[0120] Electrolysis performance: The proton exchange membrane is fabricated as a membrane electrode with an active area of ​​25 cm². 2 The cathode platinum loading is 0.1 mg / cm³. 2 The iridium loading at the anodized oxide level is 0.3 mg / cm³. 2 Then, they were assembled into a single-cell electrolyzer, and the water electrolysis performance of the proton exchange membrane was tested under the operating temperature of 80℃.

[0121] Table 1

[0122]

[0123]

[0124] As can be seen from the above, compared with the comparative examples, the proton exchange membranes of the various embodiments of the present invention have lower hydrogen permeation and better water electrolysis performance. In addition, the proton conductivity is not significantly adversely affected. Using the preparation method of the present invention, the proton exchange membrane has an integrated surface resin layer and an intermediate resin layer, with the surface resin layer located on both sides of the intermediate resin layer. The intermediate resin layer is doped with inorganic particles within a specific range. The proton exchange membrane is obtained by transforming an intermediate product film formed by pressing a "sandwich" basic structure of surface resin layer-intermediate resin layer-surface resin layer. The inorganic particles are not easily lost and have a wide contact surface with hydrogen. When a small amount of hydrogen permeates into the proton exchange membrane, the Pt-based particles and other inorganic particles uniformly dispersed in the middle of the proton exchange membrane can fully contact the hydrogen and oxidize the hydrogen into protons, which then react with oxygen anions to generate water. This helps to prevent hydrogen from permeating into the oxygen side of the anode of the PEMWE system, thereby effectively improving the safety of high-voltage operation of the PEMWE system. The preparation process of this invention does not require pre-mixing and does not require the use of solvents in the molding process. It is green, environmentally friendly, safe, has high production efficiency, can produce membranes in large quantities, has low equipment requirements, and low cost.

[0125] Furthermore, it can be seen that when all process parameters are within the preferred range of the present invention, the hydrogen permeation of the proton exchange membrane is less, and the safety performance of the PEMWE system is higher when operating at high pressure.

[0126] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a proton exchange membrane, characterized in that, The proton exchange membrane has an integrated surface resin layer and an intermediate resin layer, with the surface resin layer located on both sides of the intermediate resin layer. The intermediate resin layer is doped with inorganic particles; wherein, the inorganic particles include Pt-based particles, and the weight ratio of the Pt-based particles to the resin in the proton exchange membrane is (0.1~1):

100. The preparation method includes the following steps: Step S1: Melt and extrude the resin to obtain the first intermediate product; Step S2: Blow-molding the first intermediate product to form a hollow layer inside the first intermediate product, and introducing the inorganic particles into the hollow layer so that the inorganic particles are distributed on the inner wall of the first intermediate product to obtain the second intermediate product. Step S3: Press the second intermediate product to obtain the third intermediate product; Step S4: The third intermediate product is post-processed to obtain the proton exchange membrane.

2. The preparation method according to claim 1, characterized in that, The resin includes one or more of perfluorosulfonyl fluoride resin, sulfonated polyethersulfone resin, sulfonated polybenzimidazole resin, sulfonated polyphenylene sulfide resin, sulfonated polyphosphazene resin, sulfonated polyimide resin, sulfonated polystyrene resin, and sulfonated trifluorostyrene resin.

3. The preparation method according to claim 1 or 2, characterized in that, The Pt-based particles include Pt particles and / or Pt alloy particles; and / or The Pt-based particles have a particle size of 70~400 nm; and / or The inorganic particles also include CeO2 particles with a particle size of 20~200 nm.

4. The preparation method according to claim 3, characterized in that, The Pt alloy particles include Pt x M y and / or Pt x M y N 1-x-y Wherein, M and N are independently selected from Ru, Pd, Rh, Ir, Os, Fe, Cr, Ni, Co, Mn, Cu, Ti, Sn, V, Ga, or Mo, and M and N are distinct, with 0.5 ≤ x ≤ 0.95, 0.05 ≤ y ≤ 0.5, and 1 - xy ≤ 0.45; and / or The weight ratio of the CeO2 particles to the resin in the proton exchange membrane is (0.1~10):

100.

5. The preparation method according to claim 4, characterized in that, The Pt alloy particles include Pt x Co y Pt x Ni y and Pt x Co y Ni 1-x-y One or more; and / or The inorganic particles include one or more of the following: Pt particles, Pt 0.9 Co 0.1 Particles, and a mixture of the Pt particles and the CeO2 particles, wherein the mass ratio of the Pt particles to the CeO2 particles in the mixture is (0.01~1):

1.

6. The preparation method according to any one of claims 1 to 5, characterized in that, The thickness of the proton exchange membrane is 20~180 μm.

7. The preparation method according to claim 6, characterized in that, The thickness of the proton exchange membrane is 60~120 μm.

8. The preparation method according to any one of claims 1 to 7, characterized in that, In step S1, the extrusion temperature is 180~300℃.

9. The preparation method according to claim 8, characterized in that, In step S1, the extrusion temperature is 200~280℃.

10. The preparation method according to any one of claims 1 to 9, characterized in that, In step S2, the blow molding is either single-layer blow molding or multi-layer blow molding.

11. The preparation method according to claim 10, characterized in that, In step S2, the inorganic particles are introduced into the hollow layer by extrusion or air-puff doping.

12. The preparation method according to claim 11, characterized in that, In step S2, the method of air delivery doping is atomized air delivery.

13. The preparation method according to claim 12, characterized in that, In step S2, the atomization method of the atomizing air delivery is one or more of water atomization, air atomization, plasma atomization and ultrasonic atomization.

14. The preparation method according to any one of claims 1 to 13, characterized in that, In step S3 The film blow-up ratio of the third intermediate product is 2.00 to 4.00, and / or the thickness of the third intermediate product is 15 to 160 μm.

15. The preparation method according to any one of claims 1 to 14, characterized in that, In step S4 The post-processing includes: sequentially subjecting the third intermediate product to alkaline washing, first water washing, acid washing, second water washing, and drying to obtain the proton exchange membrane.

16. A proton exchange membrane, characterized in that, It is obtained by the preparation method according to any one of claims 1 to 15.

17. The application of the proton exchange membrane according to claim 16 in the process of water electrolysis.

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