Low-hydrogen-permeability proton exchange membrane, and preparation method therefor and use thereof

Abstract

The present invention relates to the technical field of the electrolysis of water, and specifically relates to a low-hydrogen-permeability proton exchange membrane, and a preparation method therefor and the use thereof. The proton exchange membrane comprises a Pt-containing additive layer and a matrix membrane, wherein the Pt-containing additive layer is composed of a Pt additive and a fluorine-containing proton exchange resin, the Pt-containing additive layer comprises an array layer and a flattening layer, the thickness ratio and the active-component ratio of the array layer to the flattening layer are respectively within the ranges of 1:(0.5-30) and 1:(1-50), and the array layer is composed of arrays arranged in order and an array layer resin coating the arrays. In the low-hydrogen-permeability proton exchange membrane provided by the present invention, by providing the Pt-containing additive layer consisting of the array layer and the flattening layer, the specific surface area of the Pt-containing additive layer is effectively increased by means of the arrays in the array layer, thereby achieving the efficient utilization of an additive; moreover, the hydrogen permeability improvement effect is further improved by controlling the thickness ratio and the active-component ratio of the array layer to the flattening layer and the parameters of the arrays.

Description

A low-hydrogen-permeability proton exchange membrane, its preparation method and application Technical Field

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

[0002] As a clean, zero-carbon future energy source, hydrogen energy is experiencing unprecedented development opportunities and is triggering an energy revolution globally. Currently, major economies have successively launched hydrogen energy development strategies, plans, policies, and major projects. Hydrogen energy uses hydrogen gas as its energy carrier. While there are numerous methods for hydrogen production, the electrolysis of water using renewable energy is the most promising method, expected to account for 70% of all hydrogen production technologies by 2050. Among these, PEM (proton exchange membrane) water electrolysis technology has a very broad market prospect and commercial value due to its advantages such as high current density, fast response speed, small cell size, flexible operation, ease of rapid load changes, and good compatibility with wind and solar power. However, the production cost of PEM hydrogen production is still 2-3 times higher than that of hydrogen production from steam methane. To further reduce production costs, it is necessary to improve hydrogen conversion efficiency. Currently, using thin films (approximately 50 μm thick) is one possibility for reducing proton exchange membrane costs and improving its hydrogen conversion efficiency. However, a thinner membrane leads to higher gas permeability, allowing more hydrogen gas to pass through the membrane from the cathode side to the anode side. Under standard conditions, the lower explosive limit of hydrogen in oxygen is 4 vol%. For safety reasons, the proportion of hydrogen in oxygen should not exceed 2 vol%.

[0003] Currently, several methods exist for suppressing hydrogen content in oxygen. One typical approach is the use of hydrocarbon-based alternative membranes, which exhibit better gas barrier performance, but these membranes generally have lower stability and higher water expansion rates. Another possibility for suppressing gas cross-contamination is the introduction of a recombination catalyst. Researchers have demonstrated that Pt is a suitable catalyst for recombinating hydrogen and oxygen to form water. It can be incorporated into different components on the anode side: in an external gas recombination device, a porous anode transport layer (PTL), an anode catalyst layer, or a proton exchange membrane. However, introducing an external gas recombination device requires pre-drying of the gas, which does not address the overall anode circuit safety issue. Introducing a porous anode transport layer or catalyst layer exposes Pt to a high potential >1.23V, leading to catalyst dissolution or passivation due to oxide formation, which is detrimental to long-term stability. Therefore, directly incorporating Pt-like nanoparticles into the membrane is one of the most promising strategies for suppressing hydrogen content in oxygen while reducing membrane thickness and improving system efficiency.

[0004] Takenaka and Fedkiw et al. first described the integration of a Pt catalyst into a membrane for use in a polymer electrolyte fuel cell (PEFC). To do this, the polymer membrane was first inserted into a solution containing platinum ions in a first step, and then reduced by a chemical reducing agent in a second step, thereby creating a platinum layer at the membrane edge. Johnson Matthey was the first to apply a recombined catalyst in a PEM membrane, achieving significant improvements compared to a reference membrane. Under conditions of 60°C and 1 bar anolyte pressure, the hydrogen cross-linking was reduced by a factor of 3, while other properties remained similar. Furthermore, in US patents US4959132A, US5342494A, US5472799A, US5800938A, US5766787A, and US20050175886A1, in-situ reduction (such as NaBH4, hydrogen, hydrazine, etc.) of metal salts (such as chloroplatinic acid) or platinum-amine complexes (such as [Pt(NH3)4] were employed. 2+ Pt-containing proton exchange membranes have been prepared using methods described in patents CN1464580A, CN1881667A, CN113416982A, CN113594521A, and CN101170181A. These methods involve filling ultrasonically dispersed Pt particles into one or both sides of a porous reinforced membrane or resin layer using methods such as scraping, spin coating, spraying, impregnation, casting, or casting to prepare composite proton exchange membranes. However, the membrane structures obtained by these prior art techniques only contain a single layer of flat additives, resulting in limited additive utilization. Therefore, a novel composite proton exchange membrane containing Pt additives is urgently needed to solve the aforementioned technical problems. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a low-hydrogen-permeation proton exchange membrane, its preparation method and application. By setting an array of Pt-containing additive layers in the proton exchange membrane, the hydrogen permeation inhibition effect is effectively improved.

[0006] To achieve the above-mentioned technical effects, the present invention adopts the following technical solution:

[0007] A low-hydrogen-permeability proton exchange membrane includes a Pt-containing additive layer and a substrate membrane, wherein the Pt-containing additive layer is located on one or both sides of the substrate membrane; the total thickness of the low-hydrogen-permeability proton exchange membrane is 5μm-220μm, preferably 5μm-150μm, and more preferably 5μm-120μm.

[0008] The Pt-containing additive layer is composed of Pt-containing additives and fluorine-containing proton exchange resin, wherein the mass of the active component in the Pt-containing additives is 0.01wt%-40.0wt% of the mass of the fluorine-containing proton exchange resin;

[0009] The Pt-containing additive layer comprises an array layer and a flattening layer, with a thickness ratio of 1:(0.5-30) and a molar ratio of active components in the array layer and flattening layer of 1:(1-50). The array layer has a thickness of 0.1 μm-15 μm and consists of an ordered array and an array layer resin encapsulating the array, with an array density of 1.0 × 10⁻⁶. 7 pcs / cm 2 -1.0×10 9 pcs / cm 2 The height of a single array is 1.0 to 17.0 times its width; the array layer as a whole is rectangular.

[0010] The substrate membrane is a fluorine-containing proton exchange membrane;

[0011] The low hydrogen permeation proton exchange membrane provided by this invention further improves the hydrogen permeation reduction effect by setting a Pt-containing additive layer composed of an array layer and a flat layer, and by controlling the thickness of the array layer and the flat layer, the ratio of active components and the array parameters.

[0012] Preferably, the shapes of each array in the array layer include, but are not limited to, cylindrical, prismatic, and conical shapes, with conical shapes being more preferred; the array density is 1.0 × 10⁻⁶. 8 pcs / cm 2 -8.0×10 8 pcs / cm 2 The height of a single array is 1.0 to 5.0 times its width; preferably, the array density is 2.0 × 10⁻⁶. 8 pcs / cm 2 -6.0×10 8 pcs / cm 2 The height of a single array is 1.0 to 3.0 times its width; the protrusions of each array are oriented toward and / or away from the substrate membrane.

[0013] Preferably, when the array layer is far from the substrate membrane, an array protective layer is also provided on the side of the array layer that is far from the substrate membrane; the array protective layer is made of fluorinated proton exchange resin and the thickness of the array protective layer is in the range of 1μm-10μm; more preferably, the thickness of the array protective layer is in the range of 2μm-5μm.

[0014] Preferably, the fluorinated proton exchange resin is selected from at least one of fluorosulfonic acid resin, fluorocarboxylic acid resin, or fluorophosphate resin with long or short branches, and the number average molecular weight of the fluorinated proton exchange resin is in the range of 150,000 to 600,000, and the exchange capacity is in the range of 0.8 mmol / g to 1.6 mmol / g; more preferably, the number average molecular weight of the fluorinated proton exchange resin is in the range of 200,000 to 400,000, and the exchange capacity is in the range of 1.0 mmol / g to 1.2 mmol / g.

[0015] Preferably, the active component in the Pt-type additive is 0.2wt%-5.0wt% of the mass of the fluorinated proton exchange resin; more preferably, the active component in the Pt-type additive is 0.4wt%-1.0wt% of the mass of the fluorinated proton exchange resin.

[0016] Preferably, the morphology of the Pt-type additive is sphere, rod, wire, sheet, tube, or core-shell. The Pt-type additive of the present invention is a single metal, alloy, supported single metal, or supported alloy containing a catalytically active component. The catalytically active component of the Pt-type additive is selected from Pt, Au, Pd, Ru, Rh, Ir, Co, Ni, Fe, Mo, W, Cu, or Ag, preferably Pt, Co, and Pt / Co alloys. The support for the supported single metal or supported alloy is one or more composites of carbon, silicon dioxide, alumina, titanium dioxide, and molecular sieves, preferably carbon support, silicon dioxide support, and titanium dioxide support.

[0017] Preferably, the total thickness of the Pt-based additive layer ranges from 2μm to 30μm, more preferably from 2μm to 20μm, and even more preferably from 2μm to 10μm; the thickness ratio of the array layer to the planar layer is 1:(0.5-30), more preferably 1:(1-15), and even more preferably 1:(1-3); the molar ratio of the active components in the array layer to the planar layer is 1:(1-50), more preferably 1:(1-15), and even more preferably 1:(1-3).

[0018] Specifically, the fluorinated proton exchange membrane is either a fluorinated proton exchange resin-reinforced membrane or a fluorinated proton exchange resin-unreinforced membrane. Further, the fluorinated proton exchange resin-unreinforced membrane is a homogeneous membrane made from fluorinated proton exchange resin.

[0019] Preferably, the fluorinated proton exchange resin reinforced membrane comprises a resin layer and a reinforcing layer. The number of reinforcing layers is 1-10, preferably 1-5, and more preferably 1-3. The number of resin layers is one more than the number of reinforcing layers, and the reinforcing layer is located between two adjacent resin layers. The total thickness of the fluorinated proton exchange resin reinforced membrane is 3μm-218μm, preferably 3μm-148μm, and more preferably 3μm-118μm. The thickness of the resin layer is 1μm-30μm, preferably 1μm-20μm. The thickness of the reinforcing layer is 1μm-30μm, preferably 1μm-10μm.

[0020] Preferably, the thickness of the fluorinated proton exchange resin unreinforced membrane is 3μm-218μm, more preferably 3μm-148μm, and even more preferably 3μm-118μm.

[0021] The present invention also provides a method for preparing the above-mentioned low-permeability proton exchange membrane, comprising the following steps:

[0022] S1. Disperse Pt additives in a solvent by ultrasonication to obtain dispersion A. Add fluorine proton exchange resin to the solvent and stir to obtain dispersion B. Take dispersion A and dispersion B and stir to mix them to obtain dispersion C.

[0023] S2. Take the surface-modified silicon-based template, fill the array channels of the silicon-based template with dispersion C, treat with negative pressure, continue to add dispersion C to reach the preset thickness of the flat layer, dry and cure, peel off the silicon-based template to obtain an integrally formed flat layer and an orderly array, wrap dispersion B around the array to obtain a layer containing Pt additives.

[0024] S3. Prepare a substrate membrane on the Pt-containing additive layer obtained in step S2 to obtain a low-hydrogen-permeability proton exchange membrane.

[0025] Preferably, in step S1, the solvent is selected from at least one of water, ethanol, n-propanol, isopropanol, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), or N-methylpyrrolidone (NMP); the ultrasonic dispersion power is 180W-630W, the ultrasonic dispersion time is 0.5h-6h, the stirring speed is 200rpm-800rpm, and the stirring time is 24h-72h; more preferably, the ultrasonic dispersion power is 180W-450W, the ultrasonic dispersion time is 1h-4h, the stirring speed is 200rpm-600rpm, and the stirring time is 48h-72h.

[0026] Preferably, in step S1, the mass ratio of dispersion A to dispersion B in dispersion C is in the range of (0.2-1):1; more preferably, the mass ratio of dispersion A to dispersion B is in the range of (0.5-0.7):1.

[0027] Preferably, in step S2, the silicon-based template undergoes vacuum-programmed temperature vapor phase surface modification. Specifically, the surface modifying agent is selected from octadecyltrichlorosilane, octyltrimethoxysilane, (3-aminopropyl)trimethoxysilane, (3-mercaptopropyl)trimethoxysilane, or octadecyltrimethoxysilane, preferably octyltrimethoxysilane; the surface modification temperature is a programmed temperature rise of (50-70℃)-(80-100℃)-(120-200℃), with the three temperature segments lasting for 8h, 3h, and 1h respectively, preferably (60-70℃)-(80-90℃)-(120-180℃), and further preferably (65-70℃)-(85-90℃)-(150-160℃); the surface modification vacuum degree is -0.20MPa to -0.10MPa, preferably -0.15MPa to -0.10MPa, and further preferably -0.12MPa to -0.10MPa.

[0028] Preferably, in step S2, the vacuum degree during negative pressure treatment is -0.20MPa to -0.10MPa, more preferably -0.15MPa to -0.10MPa.

[0029] Preferably, in step S3, the method for preparing the substrate membrane includes spraying, spin coating, blade coating, impregnation, casting, screen printing, etc. The process of preparing the substrate membrane is to prepare a non-reinforced membrane containing fluorinated proton exchange resin using dispersion B, or the process of preparing the substrate membrane is to prepare a reinforced membrane containing fluorinated proton exchange resin using dispersion B and reinforcing material; preferably, the reinforcing material can be selected from one or more of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene (PVF), polypropylene (PP), polyvinyl chloride (PVC), ethylene-tetrafluoroethylene copolymer (ETFE), polyphenylene sulfide (PPS) nonwoven fabric, polyether ether ketone (PEEK), polyimide (PI), fluorinated polyimide (FPI), polysulfone (PSF), perfluoroethylene propylene fiber (FEP), or perfluoroalkoxy vinyl ether copolymer fiber (PFA), preferably polytetrafluoroethylene (PTFE), polyphenylene sulfide (PPS) nonwoven fabric, polyether ether ketone (PEEK), and polysulfone (PSF).

[0030] Preferably, step S3 further includes, after the substrate film is prepared, if the array layer is far from the substrate film, using dispersion B to prepare an array protective layer on the side of the array layer far from the substrate film, coating dispersion B on the side of the array layer far from the substrate film, and then drying to form the final product.

[0031] The present invention also provides the application of the above-mentioned low-hydrogen permeation proton exchange membrane or the low-hydrogen permeation proton exchange membrane prepared by the above-mentioned preparation method in membrane electrodes.

[0032] Preferably, in a low-hydrogen-permeability proton exchange membrane, for a proton exchange membrane containing a Pt-type additive layer on one side, the additive layer is located at the anode of the water electrolysis or the negative electrode of the fuel cell.

[0033] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0034] 1. The low-hydrogen-permeability proton exchange membrane provided by this invention, by setting a Pt-containing additive layer composed of an array layer and a flat layer, effectively increases the specific surface area of ​​the Pt-containing additive layer by utilizing the array in the array layer, realizing the efficient utilization of the additive. Furthermore, by controlling the thickness of the array layer and the flat layer, the ratio of active components, and the array parameters, the hydrogen permeation improvement effect is further enhanced. When this low-hydrogen-permeability proton exchange membrane is prepared as a membrane electrode for use in water electrolysis to produce hydrogen, the hydrogen content in oxygen is significantly reduced, reaching or falling below 0.1 vol%, with a minimum of 0.017 vol%, effectively solving safety issues and providing new materials and methods for the development of PEM water electrolysis hydrogen production technology.

[0035] 2. The low-hydrogen-permeability proton exchange membrane provided by this invention, when used to prepare a membrane electrode for fuel cell power generation, exhibits a significantly higher initial voltage, reaching 0.98V, and higher performance under low humidity conditions, providing new materials and methods for the development of fuel cell technology.

[0036] 3. In the preparation method provided by the present invention, by modifying the surface of the silicon-based template, the obtained Pt-containing additive layer can be quickly peeled off from the silicon-based template, which not only helps to maintain the array shape, but also allows for repeated use and effectively controls economic costs. Attached Figure Description

[0037] Figure 1 is a schematic diagram of the structure of the low-hydrogen-permeable proton exchange membrane provided in Embodiments 1-6, 9 and 13 of the present invention;

[0038] Figure 2 is a schematic diagram of the structure of the low-hydrogen-permeable proton exchange membrane provided in Embodiments 7 and 11 of the present invention;

[0039] Figure 3 is a schematic diagram of the structure of the low-hydrogen-permeable proton exchange membrane provided in Embodiment 8 of the present invention;

[0040] Figure 4 is a schematic diagram of the structure of the low hydrogen permeation proton exchange membrane provided in Comparative Examples 6 and 13 of the present invention.

[0041] Figure 5 is a schematic diagram of the low hydrogen permeation proton exchange membrane provided in Comparative Example 7 of the present invention.

[0042] Figure 6 is a schematic diagram of the structure of the low-hydrogen-permeable proton exchange membrane provided in Embodiments 10 and 12 of the present invention;

[0043] Figure 7 is a schematic diagram of the membrane electrode provided in Embodiment 14 of the present invention;

[0044] Figure 8 is a schematic diagram of the membrane electrode provided in Embodiment 15 of the present invention;

[0045] Figure 9 shows the battery polarization curves of the proton exchange membrane in the application of water electrolysis for hydrogen production based on typical embodiments and comparative examples.

[0046] Figure 10 shows the cell polarization curves of the proton exchange membrane in fuel cell power generation applications based on typical embodiments and comparative examples.

[0047] Among them, 1. flattening layer; 2. array layer; 3. resin layer; 4. reinforcement layer; 5. array protection layer; 6. non-reinforced membrane; 11. anode plate; 12. anode diffusion layer; 13. anode catalyst; 14. proton exchange membrane; 15. cathode catalyst; 16. cathode diffusion layer; 17. cathode plate. Detailed Implementation

[0048] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0049] The reagents used in each example and comparative example are all commonly available commercial reagents, and their sources will not be repeated here.

[0050] Example 1:

[0051] A low-hydrogen-permeability proton exchange membrane, as shown in Figure 1, is prepared by the following steps:

[0052] S1. Pt nanorod particles were ultrasonically dispersed (450W, 2h) in a mixed solvent of water and n-propanol (volume ratio 1:1) to form dispersion A. Long-branched perfluorosulfonic acid resin (PFSA) with an exchange capacity of 1.2 mmol / g and a number-average molecular weight of 240,000 was added to a mixed solvent of water and n-propanol (volume ratio 1:1) and stirred (300 rpm, 72h) to dissolve into a 30 wt% resin dispersion B. Dispersions A and B were mixed evenly at a mass ratio of 3:5 to obtain dispersion C, wherein the mass of Pt nanoparticles was 0.4 wt% of the mass of PFSA.

[0053] S2. The silicon-based template was vapor-modified with octyltrimethoxysilane under vacuum programmed temperature. Octyltrimethoxysilane and the silicon-based template were placed in two separate petri dishes, then placed in a vacuum drying oven. The temperature was programmed at 65℃-85℃-150℃ for 8 hours, 3 hours, and 1 hour respectively, with a vacuum degree of -0.10 MPa. The template was then removed and ultrasonically cleaned sequentially with chloroform, n-hexane, and isopropanol for 10 minutes each. The template was then immersed in dispersion C and treated under vacuum (-0.1 MPa) for 2 hours to ensure that dispersion C uniformly filled the template pores, forming an ordered array. A certain amount of dispersion C was then slowly added dropwise to achieve a specific thickness, and the mixture was dried and cured to form a smooth layer 1. Finally, the template was directly peeled off from the film, and dispersion B was wrapped around the array to form a Pt-containing additive layer with a conical array structure and an array density of 2.3 × 10⁻⁶. 8 pcs / cm 2 The height of a single array is 1.1 times its width; in addition, the total thickness of the Pt-based additive layer is 5 μm, of which the thickness of the planarization layer 1 is 3 μm and the thickness of the array layer 2 is 2 μm; the thickness ratio of the planarization layer 1 to the array layer 2 is 3:2; the molar ratio of the active components in the Pt-based additives in the planarization layer 1 and the array layer 2 is 1:1.

[0054] S3. Continue spraying resin dispersion B onto the Pt-containing additive layer, and use PTFE as the reinforcing layer 4 to prepare a single-reinforced fluorine-containing proton-reinforced membrane. As shown in Figure 1, the exchange membrane consists of resin layer 3 (20 μm), reinforcing layer 4 (10 μm), resin layer 3 (20 μm), array layer 2 (2 μm), and flattening layer 1 (3 μm) from top to bottom. There are two resin layers 3, and the reinforcing layer 4 is located between the two resin layers 3. The total thickness of the membrane is 55 μm.

[0055] Example 2:

[0056] A low-hydrogen-permeability proton exchange membrane, as shown in Figure 1, is prepared by the following steps:

[0057] S1. Pt nanorod particles were ultrasonically dispersed (240W, 3h) in a mixed solvent of ethanol and n-propanol (volume ratio 3:1) to form dispersion A. Long-branched perfluorocarboxylic acid resin with an exchange capacity of 1.2 mmol / g and a number-average molecular weight of 400,000 was added to a mixed solvent of ethanol and n-propanol (volume ratio 3:1) and stirred (600 rpm, 48h) to dissolve into a 30wt% resin dispersion B. Dispersions A and B were mixed evenly at a mass ratio of 3:5 to obtain dispersion C, wherein the mass of Pt nanoparticles was 0.4wt% of the mass of perfluorocarboxylic acid resin.

[0058] S2. The template was vapor-modified with octadecyltrimethoxysilane under vacuum and programmed temperature. The octadecyltrimethoxysilane and the silicon-based template were placed in two separate petri dishes, then placed in a vacuum drying oven. The temperature was programmed to rise from 67℃ to 88℃ to 155℃, with three temperature stages lasting 8 hours, 3 hours, and 1 hour respectively, under a vacuum of -0.10 MPa. The template was then removed and ultrasonically cleaned sequentially with chloroform, n-hexane, and isopropanol for 10 minutes each. The template was then immersed in dispersion C and treated under vacuum (-0.15 MPa) for 2 hours to ensure that dispersion C uniformly filled the template pores, forming an ordered array. A certain amount of dispersion C was then slowly added dropwise to achieve a specific thickness, and the mixture was dried and cured to form a smooth layer 1. Finally, the template was directly peeled off from the film, and dispersion B was wrapped around the array to form a Pt-containing additive layer with a conical array structure and an array density of 2.3 × 10⁻⁶. 8 pcs / cm 2 The height of a single array is 1.1 times its width; in addition, the total thickness of the Pt-based additive layer is 10 μm, of which the thickness of the planarization layer 1 is 7 μm and the thickness of the array layer 2 is 3 μm; the thickness ratio of the planarization layer 1 to the array layer 2 is 7:3; the mass of the active component of the Pt-based additive in both the planarization layer 1 and the array layer 2 accounts for 0.4 wt% of the mass of the resin powder; the molar ratio of the active component of the Pt-based additive in the planarization layer 1 and the array layer 2 is 1:1.

[0059] S3. Continue spraying resin dispersion B onto the Pt-containing additive layer, and use PPS as the reinforcing layer 4 to prepare a single-reinforced fluorine-containing proton-reinforced membrane. As shown in Figure 1, the exchange membrane consists of resin layer 3 (20 μm), reinforcing layer 4 (5 μm), resin layer 3 (20 μm), array layer 2 (3 μm), and flattening layer 1 (7 μm) from top to bottom. There are two resin layers 3, and the reinforcing layer 4 is located between the two resin layers 3. The total thickness of the membrane is 55 μm.

[0060] Example 3:

[0061] A low-hydrogen-permeability proton exchange membrane, as shown in Figure 1, is prepared by the following steps:

[0062] S1. Pt nanospheres were ultrasonically dispersed in DMF solvent (450W, 2h) to form dispersion A. Long-branched perfluorosulfonic acid resin (PFSA) with an exchange capacity of 1.2 mmol / g and a number-average molecular weight of 240,000 was added to DMF solvent and stirred (200 rpm, 72h) to dissolve into a 30 wt% resin dispersion B. Dispersions A and B were mixed evenly in a mass ratio of 3:5 to obtain dispersion C, wherein the mass ratio of Pt to resin powder was 0.4 wt%.

[0063] S2. The template was modified in the gas phase using (3-aminopropyl)trimethoxysilane under vacuum temperature program. The (3-aminopropyl)trimethoxysilane and the silicon-based template were placed in two separate petri dishes, then placed in a vacuum drying oven. The temperature was programmed to rise from 70℃ to 90℃ to 160℃, with three temperature stages lasting 8 hours, 3 hours, and 1 hour respectively, under a vacuum of -0.13 MPa. The template was then removed and ultrasonically cleaned sequentially with chloroform, n-hexane, and isopropanol for 10 minutes each. The template was then immersed in dispersion C and treated under vacuum (-0.1 MPa) for 2 hours to ensure that dispersion C uniformly filled the template pores, forming an ordered array. A certain amount of dispersion C was then slowly added dropwise to achieve a specific thickness, and the mixture was dried and cured to form a smooth layer 1. Finally, the template was directly peeled off from the film, and dispersion B was wrapped around the array to form a Pt-containing additive layer with a conical array structure and an array density of 5.7 × 10⁻⁶. 8 pcs / cm 2 The height of a single array is 5.0 times its width; in addition, the total thickness of the Pt-based additive layer is 5 μm, of which the thickness of the planarization layer 1 is 3 μm and the thickness of the array layer 2 is 2 μm; the thickness ratio of the planarization layer 1 to the array layer 2 is 3:2; the mass of the active component of the Pt-based additive in both the planarization layer 1 and the array layer 2 accounts for 0.4 wt% of the mass of the resin powder; the molar ratio of the active component of the Pt-based additive in the planarization layer 1 and the array layer 2 is 1:1.

[0064] S3. Continue spraying resin dispersion B onto the Pt-containing additive layer, and use PEEK as the reinforcing layer 4 to prepare a single-reinforced fluorine-containing proton-reinforced membrane. As shown in Figure 1, the exchange membrane consists of resin layer 3 (20 μm), reinforcing layer 4 (10 μm), resin layer 3 (20 μm), array layer 2 (2 μm), and flattening layer 1 (3 μm) from top to bottom. There are two resin layers 3, and the reinforcing layer 4 is located between the two resin layers 3. The total thickness of the membrane is 55 μm.

[0065] Example 4:

[0066] A low-hydrogen-permeability proton exchange membrane, as shown in Figure 1, is prepared by the following steps:

[0067] S1. Pt nanospheres were ultrasonically dispersed in water and n-propanol (volume ratio 1:1) for 2 hours to form dispersion A. Long-branched perfluorosulfonic acid resin (PFSA) with an exchange capacity of 1.0 mmol / g and a number-average molecular weight of 260,000 was dissolved in water and n-propanol (volume ratio 1:1) by stirring (400 rpm, 60 hours) to form a 30 wt% resin dispersion B. Dispersions A and B (mass ratio 3:5) were mixed thoroughly to obtain dispersion C, where the mass ratio of Pt to resin powder was 0.8 wt%.

[0068] S2. The template was modified in the vapor phase using octyltrimethoxysilane under vacuum with programmed temperature rise. Octyltrimethoxysilane and the silicon-based template were placed in two separate petri dishes, then placed in a vacuum drying oven. The temperature was programmed to rise from 65℃ to 85℃ to 150℃, with three temperature stages lasting 8 hours, 3 hours, and 1 hour respectively, under a vacuum of -0.10 MPa. The template was then removed and ultrasonically cleaned sequentially with chloroform, n-hexane, and isopropanol for 10 minutes each. The template was then immersed in dispersion C and treated under vacuum (-0.1 MPa) for 2 hours to ensure that dispersion C uniformly filled the template pores, forming an ordered array. A certain amount of dispersion C was then slowly added dropwise to achieve a specific thickness, and the mixture was dried and cured to form a smooth layer 1. Finally, the template was directly peeled off from the film, and dispersion B was wrapped around the array to form a Pt-containing additive layer with a conical array structure and an array density of 5.7 × 10⁻⁶. 8 pcs / cm 2 The height of a single array is 5.0 times its width; in addition, the total thickness of the Pt-based additive layer is 10 μm, of which the thickness of the planarization layer 1 is 7 μm and the thickness of the array layer 2 is 3 μm; the thickness ratio of the planarization layer 1 to the array layer 2 is 7:3; the mass of the active component of the Pt-based additive in both the planarization layer 1 and the array layer 2 accounts for 0.8 wt% of the mass of the resin powder; the molar ratio of the active component of the Pt-based additive in the planarization layer 1 and the array layer 2 is 1:1;

[0069] S3. Continue spraying resin dispersion B onto the Pt-containing additive layer, and use PSF as the reinforcing layer 4 to prepare a single-reinforced fluorine-containing proton-reinforced membrane. As shown in Figure 1, the exchange membrane consists of resin layer 3 (20 μm), reinforcing layer 4 (5 μm), resin layer 3 (20 μm), array layer 2 (3 μm), and flattening layer 1 (7 μm) from top to bottom. There are two resin layers 3, and the reinforcing layer 4 is located between the two resin layers 3. The total thickness of the membrane is 55 μm.

[0070] Example 5:

[0071] A low-hydrogen-permeability proton exchange membrane, as shown in Figure 1, is prepared by the following steps:

[0072] S1. Pt nanospheres were ultrasonically dispersed (450W, 2h) in a mixed solvent of water and n-propanol (volume ratio 1:1) to form dispersion A. Long-branched perfluorosulfonic acid resin (PFSA) with an exchange capacity of 1.0 mmol / g and a number-average molecular weight of 260,000 was dissolved in a mixed solvent of water and n-propanol (volume ratio 1:1) by stirring (400 rpm, 48h) to form a 30 wt% resin dispersion B. Dispersions A and B (mass ratio 3:5) were mixed thoroughly to obtain dispersion C, where the mass ratio of Pt to resin powder was 0.4 wt%. Pt nanoparticles were ultrasonically dispersed (450W, 2h) in a mixed solvent of water and n-propanol (volume ratio 1:1) to form dispersion D. Dispersions D and B (mass ratio 3:5) were mixed thoroughly to obtain dispersion E, where the mass ratio of Pt to resin powder was 0.12 wt%.

[0073] S2. The template was modified in the gas phase using octyltrimethoxysilane under vacuum with programmed temperature rise. Octyltrimethoxysilane and the silicon-based template were placed in two separate petri dishes, then placed in a vacuum drying oven. The temperature was programmed to rise from 65℃ to 85℃ to 150℃, with three temperature stages lasting 8 hours, 3 hours, and 1 hour respectively, under a vacuum of -0.10 MPa. The template was then removed and ultrasonically cleaned sequentially with chloroform, n-hexane, and isopropanol for 10 minutes each. The template was then immersed in dispersion C and treated under vacuum (-0.1 MPa) for 2 hours, allowing dispersion C to uniformly fill the template pores and form an ordered array. A certain amount of dispersion E was then slowly added to achieve a specific thickness, and the mixture was dried and cured to form a smooth layer 1. Finally, the template was directly peeled off from the film, and dispersion B was wrapped around the array to form a Pt-containing additive layer with a conical array structure and an array density of 5.7 × 10⁻⁶. 8 pcs / cm 2The height of a single array is 2.6 times its width; in addition, the total thickness of the Pt-based additive layer is 10 μm, of which the thickness of the planarization layer 1 is 5 μm and the thickness of the array layer 2 is 5 μm; the thickness ratio of the planarization layer 1 to the array layer 2 is 1:1; the mass of the active component of the Pt-based additive in the Pt-based additive layer accounts for 0.8 wt% of the mass of the resin powder; the molar ratio of the active component of the Pt-based additive in the planarization layer 1 and the array layer 2 is 3:1.

[0074] S3. Continue spraying resin dispersion B onto the Pt-containing additive layer, and use PTFE as the reinforcing layer 4 to prepare a single-reinforced fluorine-containing proton-reinforced membrane. As shown in Figure 1, the exchange membrane consists of resin layer 3 (20 μm), reinforcing layer 4 (5 μm), resin layer 3 (20 μm), array layer 2 (5 μm), and flattening layer 1 (5 μm) from top to bottom. There are two resin layers 3, and the reinforcing layer 4 is located between the two resin layers 3. The total thickness of the membrane is 55 μm.

[0075] Example 6:

[0076] A low-permeability proton exchange membrane is prepared according to the following steps, as shown in Figure 1:

[0077] S1. Pt nanospheres were ultrasonically dispersed (450W, 2h) in a mixed solvent of water and n-propanol (volume ratio 1:1) to form dispersion A. Long-branched perfluorosulfonic acid resin (PFSA) with an exchange capacity of 1.0 mmol / g and a number-average molecular weight of 260,000 was added to a mixed solvent of water and n-propanol (volume ratio 1:1) and stirred (400 rpm, 48h) to dissolve into a 30 wt% resin dispersion B. Dispersions A and B were mixed evenly at a mass ratio of 3:5 to obtain dispersion C, wherein the mass ratio of Pt to resin powder was 0.8 wt%.

[0078] S2. The template was modified in the vapor phase using octyltrimethoxysilane under vacuum with programmed temperature rise. Octyltrimethoxysilane and the silicon-based template were placed in two separate petri dishes, then placed in a vacuum drying oven. The temperature was programmed to rise from 65℃ to 85℃ to 150℃, with three temperature stages lasting 8 hours, 3 hours, and 1 hour respectively, under a vacuum of -0.10 MPa. The template was then removed and ultrasonically cleaned sequentially with chloroform, n-hexane, and isopropanol for 10 minutes each. The template was then immersed in dispersion C and treated under vacuum (-0.1 MPa) for 2 hours to ensure that dispersion C uniformly filled the template pores, forming an ordered array. A certain amount of dispersion C was then slowly added dropwise to achieve a specific thickness, and the mixture was dried and cured to form a smooth layer 1. Finally, the template was directly peeled off from the film, and dispersion B was wrapped around the array to form a Pt-containing additive layer with a conical array structure and an array density of 5.7 × 10⁻⁶. 8 pcs / cm 2The height of a single array is 2.6 times its width; in addition, the total thickness of the Pt-based additive layer is 10 μm, of which the thickness of the planarization layer 1 is 5 μm and the thickness of the array layer 2 is 5 μm; the thickness ratio of the planarization layer 1 to the array layer 2 is 1:1; the mass of the active component of the Pt-based additive in both the planarization layer 1 and the array layer 2 accounts for 0.8 wt% of the mass of the resin powder; the molar ratio of the active component of the Pt-based additive in the planarization layer 1 and the array layer 2 is 1:1.

[0079] S3. Continue spraying resin dispersion B onto the Pt-containing additive layer, and use PTFE as the reinforcing layer 4 to prepare a single-reinforced fluorine-containing proton-reinforced membrane. As shown in Figure 1, the exchange membrane consists of resin layer 3 (20 μm), reinforcing layer 4 (5 μm), resin layer 3 (20 μm), array layer 2 (5 μm), and flattening layer 1 (5 μm) from top to bottom. There are two resin layers 3, and the reinforcing layer 4 is located between the two resin layers 3. The total thickness of the membrane is 55 μm.

[0080] Example 7:

[0081] A low-hydrogen-permeability proton exchange membrane, as shown in Figure 2, is prepared by the following steps:

[0082] S1. Pt / C nanoparticles were ultrasonically dispersed (180W, 2h) in a mixed solvent of water and n-propanol (volume ratio 1:1) to form dispersion A. Short-branched perfluorophosphate resin with an exchange capacity of 1.1 mmol / g and a number-average molecular weight of 250,000 was added to a mixed solvent of water and n-propanol (volume ratio 1:1) and stirred (300 rpm, 24h) to dissolve it into a 30 wt% resin dispersion B. Dispersions A and B were mixed evenly at a mass ratio of 3:5 to obtain dispersion C, wherein the mass ratio of Pt to resin powder was 0.6 wt%.

[0083] S2. The template was modified in the vapor phase using octyltrimethoxysilane under vacuum with programmed temperature rise. Octyltrimethoxysilane and the silicon-based template were placed in two separate petri dishes, then placed in a vacuum drying oven. The temperature was programmed to rise from 65℃ to 85℃ to 150℃, with three temperature stages lasting 8 hours, 3 hours, and 1 hour respectively, under a vacuum of -0.10 MPa. The template was then removed and ultrasonically cleaned sequentially with chloroform, n-hexane, and isopropanol for 10 minutes each. The template was then immersed in dispersion C and treated under vacuum (-0.1 MPa) for 2 hours to ensure that dispersion C uniformly filled the template pores, forming an ordered array. A certain amount of dispersion C was then slowly added dropwise to achieve a specific thickness, and the mixture was dried and cured to form a smooth layer 1. Finally, the template was directly peeled off from the film, and dispersion B was wrapped around the array to form a Pt-containing additive layer with a conical array structure and an array density of 5.7 × 10⁻⁶. 8 pcs / cm 2The height of a single array is 4.2 times its width; in addition, the total thickness of the Pt-based additive layer is 10 μm, of which the thickness of the planarization layer 1 is 7 μm and the thickness of the array layer 2 is 3 μm; the thickness ratio of the planarization layer 1 to the array layer 2 is 7:3; the mass of the active component of the Pt-based additive in both the planarization layer 1 and the array layer 2 accounts for 0.6 wt% of the mass of the resin powder; the molar ratio of the active component of the Pt-based additive in the planarization layer 1 and the array layer 2 is 1:1.

[0084] S3. On the Pt-containing additive layer, the resin dispersion B is sprayed onto the array to form a protective layer 5 with a thickness of 3 μm.

[0085] S4. A single-reinforced fluorine-containing proton-reinforced membrane was prepared by using PTFE as the reinforcing layer 4 and coating it with resin dispersion B. The resin layer 3 had a thickness of 18.5 μm, the reinforcing layer 4 had a thickness of 5 μm, and the membrane thickness was 42 μm.

[0086] S5. The membrane with array structure and array protective layer 5 prepared in step (3) and the single-reinforced proton membrane prepared in step (4) are combined by hot pressing (160℃, 2.5MPa, 5min) to form a proton exchange membrane with array structure on top, and the total membrane thickness is 55μm. As shown in Figure 2, the exchange membrane consists of array protective layer 5 (3μm), array layer 2 (3μm), planarization layer 1 (7μm), resin layer 3 (18.5μm), reinforcement layer 4 (5μm) and resin layer 3 (18.5μm) from top to bottom. There are two resin layers 3. The reinforcement layer 4 is located between the two resin layers 3. The total membrane thickness is 55μm.

[0087] Example 8:

[0088] A low-permeability proton exchange membrane, as shown in Figure 3, is prepared by the following steps:

[0089] S1. Pt nanospheres were ultrasonically dispersed (450 W, 2 h) in DMAC solvent to form dispersion A. Long-branched perfluorosulfonic acid resin (PFSA) with an exchange capacity of 1.2 mmol / g and a number-average molecular weight of 240,000 was added to DMAC solvent and stirred (300 rpm, 24 h) to dissolve into a 30 wt% resin dispersion B. Appropriate amounts of additive dispersion A and resin dispersion B were mixed thoroughly to obtain dispersion C, wherein the mass ratio of Pt to PFSA was 0.4 wt%.

[0090] S2. The template was modified in the vapor phase using octyltrimethoxysilane under vacuum with programmed temperature rise. Octyltrimethoxysilane and the silicon-based template were placed in two separate petri dishes, then placed in a vacuum drying oven. The temperature was programmed to rise from 65℃ to 85℃ to 150℃, with three temperature stages lasting 8 hours, 3 hours, and 1 hour respectively, under a vacuum of -0.10 MPa. The template was then removed and ultrasonically cleaned sequentially with chloroform, n-hexane, and isopropanol for 10 minutes each. The template was then immersed in dispersion C and treated under vacuum (-0.1 MPa) for 2 hours to ensure that dispersion C uniformly filled the template pores, forming an ordered array. A certain amount of dispersion C was then slowly added dropwise to achieve a specific thickness, and the mixture was dried and cured to form a smooth layer 1. Finally, the template was directly peeled off from the film, and dispersion B was wrapped around the array to form a Pt-containing additive layer with a conical array structure and an array density of 5.7 × 10⁻⁶. 8 pcs / cm 2 The height of a single array is 4.2 times its width; in addition, the total thickness of the Pt-based additive layer is 5 μm, of which the thickness of the planarization layer 1 is 3 μm and the thickness of the array layer 2 is 2 μm; the thickness ratio of the planarization layer 1 to the array layer 2 is 3:2; the mass of the active component of the Pt-based additive in both the planarization layer 1 and the array layer 2 accounts for 0.4 wt% of the mass of the resin powder; the molar ratio of the active component of the Pt-based additive in the planarization layer 1 and the array layer 2 is 1:1.

[0091] S3. Resin dispersion B is sprayed onto the Pt-containing additive layer, and PEEK is used as the reinforcing layer 4 to prepare a single-reinforced fluorine-containing proton-reinforced membrane. The resin layer 3 has a thickness of 19 μm, the reinforcing layer 4 has a thickness of 5 μm, and the total membrane thickness is 48 μm.

[0092] S4. Repeat steps (1)-(2) to prepare the Pt-containing additive layer. Then, the resin dispersion B is sprayed onto the array to form an array protective layer 5 with a thickness of 2 μm.

[0093] S5. The membrane with array structure and array protective layer 5 prepared in step (4) and the single-reinforced proton membrane with array structure prepared in step (3) are prepared by hot pressing (160℃, 2.5MPa, 5min) to form a proton exchange membrane with array structure on both sides, with a total membrane thickness of 55μm. As shown in Figure 3, the exchange membrane is arranged from top to bottom as array protective layer 5 (2μm), array layer 2 (2μm), planarization layer 1 (3μm), resin layer 3 (19μm), reinforcement layer 4 (5μm), resin layer 3 (19μm), array layer 2 (2μm) and planarization layer 1 (3μm). There are two resin layers 3. The reinforcement layer 4 is located between the two resin layers 3. The total membrane thickness is 55μm.

[0094] Example 9:

[0095] A low-hydrogen-permeability proton exchange membrane, as shown in Figure 1, is prepared by the following steps:

[0096] S1. Co@Pt nano-alloy particles with Pt as the shell were ultrasonically dispersed (450W, 2h) in a mixed solvent of water and n-propanol (volume ratio 1:1) to form dispersion A. Long-branched perfluorosulfonic acid resin (PFSA) with an exchange capacity of 1.0 mmol / g and a number-average molecular weight of 260,000 was added to a mixed solvent of water and n-propanol (volume ratio 1:1) and stirred (400rpm, 48h) to dissolve into a 30wt% resin dispersion B. Dispersions A and B were mixed evenly at a mass ratio of 3:5 to obtain dispersion C, wherein the mass ratio of Pt to resin powder was 0.8wt%.

[0097] S2. The template was modified in the vapor phase using octyltrimethoxysilane under vacuum with programmed temperature rise. Octyltrimethoxysilane and the silicon-based template were placed in two separate petri dishes, then placed in a vacuum drying oven. The temperature was programmed to rise from 65℃ to 85℃ to 150℃, with three temperature stages lasting 8 hours, 3 hours, and 1 hour respectively, under a vacuum of -0.10 MPa. The template was then removed and ultrasonically cleaned sequentially with chloroform, n-hexane, and isopropanol for 10 minutes each. The template was then immersed in dispersion C and treated under vacuum (-0.1 MPa) for 2 hours to ensure that dispersion C uniformly filled the template pores, forming an ordered array. A certain amount of dispersion C was then slowly added dropwise to achieve a specific thickness, and the mixture was dried and cured to form a smooth layer 1. Finally, the template was directly peeled off from the film, and dispersion B was wrapped around the array to form a Pt-containing additive layer with a conical array structure and an array density of 5.7 × 10⁻⁶. 8 pcs / cm 2 The height of a single array is 2.6 times its width; in addition, the total thickness of the Pt-based additive layer is 10 μm, of which the thickness of the planarization layer 1 is 5 μm and the thickness of the array layer 2 is 5 μm; the thickness ratio of the planarization layer 1 to the array layer 2 is 1:1; the mass of the active component of the Pt-based additive in both the planarization layer 1 and the array layer 2 accounts for 0.8 wt% of the mass of the resin powder; the molar ratio of the active component of the Pt-based additive in the planarization layer 1 and the array layer 2 is 1:1.

[0098] S3. Continue spraying resin dispersion B onto the Pt-containing additive layer, and use PTFE as the reinforcing layer 4 to prepare a single-reinforced fluorine-containing proton-reinforced membrane. As shown in Figure 1, the exchange membrane consists of resin layer 3 (20 μm), reinforcing layer 4 (5 μm), resin layer 3 (20 μm), array layer 2 (5 μm), and flattening layer 1 (5 μm) from top to bottom. There are two resin layers 3, and the reinforcing layer 4 is located between the two resin layers 3. The total thickness of the membrane is 55 μm.

[0099] Example 10:

[0100] A low-permeability proton exchange membrane, as shown in Figure 6, differs from the preparation steps in Example 1 in that step S3 is as follows:

[0101] Resin dispersion B was sprayed onto the Pt-containing additive layer to prepare a non-reinforced fluorine-containing proton exchange resin membrane 6, ultimately forming a proton exchange membrane with an array structure at the bottom layer. Steps (1)-(2) were repeated to prepare the Pt-containing additive layer. Then, resin dispersion B was sprayed onto the Pt-containing additive layer to form an array protective layer 5 with a thickness of 2 μm. The prepared membrane with the array structure and array protective layer 5 and the prepared proton exchange membrane with the array structure at the bottom layer were then hot-pressed (160℃, 2.5MPa, 5min) to prepare a proton exchange membrane with an array structure on both sides. As shown in Figure 6, the exchange membrane consists of array protective layer 5 (2 μm), array layer 2 (2 μm), flat layer 1 (3 μm), non-reinforced membrane 6 (208 μm), array layer 2 (2 μm), and flat layer 1 (3 μm) from top to bottom, with a total membrane thickness of 220 μm. Other preparation steps were the same as in Example 1.

[0102] Example 11:

[0103] A proton exchange membrane, as shown in Figure 2, differs from Example 7 in that the thickness of the array protective layer 5 is 10 μm and the thickness of the resin layer 3 is 15 μm, while other conditions are the same as in Example 7. As shown in Figure 2, the exchange membrane consists of, from top to bottom, an array protective layer 5 (10 μm), an array layer 2 (3 μm), a planarization layer 1 (7 μm), a resin layer 3 (15 μm), a reinforcing layer 4 (5 μm), and another resin layer 3 (15 μm). There are two resin layers 3, and the reinforcing layer 4 is located between the two resin layers 3. The total thickness of the membrane is 55 μm.

[0104] Example 12:

[0105] A proton exchange membrane, as shown in Figure 6, differs from Example 1 in that the thickness of the prepared proton exchange membrane is 120 μm, the thickness of the additive layer is 30 μm, the thickness of the reinforcing layer 4 is 30 μm, the thickness of the resin layer 3 is 30 μm, and the height of a single array is 17.0 times its width. All other conditions are the same as in Example 1. As shown in Figure 1, the exchange membrane, from top to bottom, consists of resin layer 3 (30 μm), reinforcing layer 4 (30 μm), resin layer 3 (30 μm), array layer 2 (12 μm), and flattening layer 1 (18 μm). There are two resin layers 3, and the reinforcing layer 4 is located between the two resin layers 3. The total membrane thickness is 120 μm.

[0106] Example 13:

[0107] A low-hydrogen-permeability proton exchange membrane, as shown in Figure 4, is prepared by the following steps:

[0108] S1. Pt / C nanoparticles were ultrasonically dispersed (450W, 2h) in a mixed solvent of water and n-propanol (volume ratio 1:1) to form dispersion A. Long-branched perfluorosulfonic acid resin (PFSA) with an exchange capacity of 1.0 mmol / g and a number-average molecular weight of 260,000 was added to a mixed solvent of water and n-propanol (volume ratio 1:1) and stirred (400rpm, 48h) to dissolve into a 30 wt% resin dispersion B. Dispersions A and B were mixed evenly at a mass ratio of 3:5 to obtain dispersion C, wherein the mass ratio of Pt to resin powder was 0.8 wt%.

[0109] S2. The template was modified in the vapor phase using octyltrimethoxysilane under vacuum with programmed temperature rise. Octyltrimethoxysilane and the silicon-based template were placed in two separate petri dishes, then placed in a vacuum drying oven. The temperature was programmed to rise from 65℃ to 85℃ to 150℃, with three temperature stages lasting 8 hours, 3 hours, and 1 hour respectively, under a vacuum of -0.10 MPa. The template was then removed and ultrasonically cleaned sequentially with chloroform, n-hexane, and isopropanol for 10 minutes each. The template was then immersed in dispersion C and treated under vacuum (-0.1 MPa) for 2 hours to ensure that dispersion C uniformly filled the template pores, forming an ordered array. A certain amount of dispersion C was then slowly added dropwise to achieve a specific thickness, and the mixture was dried and cured to form a smooth layer 1. Finally, the template was directly peeled off from the film, and dispersion B was wrapped around the array to form a Pt-containing additive layer with a conical array structure and an array density of 5.7 × 10⁻⁶. 8 pcs / cm 2 The height of a single array is 2.6 times its width; in addition, the total thickness of the Pt-based additive layer is 3 μm, of which the thickness of the planarization layer 1 is 1 μm and the thickness of the array layer 2 is 2 μm; the thickness ratio of the planarization layer 1 to the array layer 2 is 1:2; the mass of the active component of the Pt-based additive in both the planarization layer 1 and the array layer 2 accounts for 0.8 wt% of the mass of the resin powder; the molar ratio of the active component of the Pt-based additive in the planarization layer 1 and the array layer 2 is 1:1.

[0110] S3. Continue spraying resin dispersion B onto the Pt-containing additive layer, and use PTFE as the reinforcing layer 4 to prepare a single-reinforced fluorine-containing proton-reinforced membrane. As shown in Figure 1, the exchange membrane consists of resin layer 3 (6 μm), reinforcing layer 4 (3 μm), resin layer 3 (3 μm), array layer 2 (2 μm), and flattening layer 1 (1 μm) from top to bottom. There are two resin layers 3, and the reinforcing layer 4 is located between the two resin layers 3. The total thickness of the membrane is 15 μm.

[0111] Example 14:

[0112] A membrane electrode, as shown in Figure 7, includes the proton exchange membrane prepared in Example 1, and from left to right, it consists of an anode plate 11, an anode diffusion layer 12, an anode catalyst 13, a proton exchange membrane 14, a cathode catalyst 15, a cathode diffusion layer 16, and a cathode plate 17.

[0113] Example 15:

[0114] A membrane electrode, as shown in Figure 8, includes the proton exchange membrane prepared in Example 8, and from left to right are an anode plate 11, an anode diffusion layer 12, an anode catalyst 13, a proton exchange membrane 14, a cathode catalyst 15, a cathode diffusion layer 16, and a cathode plate 17.

[0115] Comparative Example 1:

[0116] A proton exchange membrane is prepared according to the following steps:

[0117] A long-branched perfluorosulfonic acid resin (PFSA) with an exchange capacity of 1.0 mmol / g and a number-average molecular weight of 260,000 was dissolved in a mixed solvent of water and n-propanol (volume ratio 1:1) by stirring (300 rpm, 24 h) to form a 30 wt% resin dispersion. A film was formed by coating with PTFE as a reinforcing layer (5 μm). After heating, the solvent was evaporated to obtain a 55 μm single-reinforced proton exchange membrane.

[0118] Comparative Example 2:

[0119] A proton exchange membrane is prepared according to the following steps:

[0120] S1. Pt nanospheres were ultrasonically dispersed (450W, 2h) in a mixed solvent of water and n-propanol (volume ratio 1:1) to form dispersion A. Long-branched perfluorosulfonic acid resin (PFSA) with an exchange capacity of 1.0 mmol / g and a number-average molecular weight of 260,000 was added to a mixed solvent of water and n-propanol (volume ratio 1:1) and stirred (300rpm, 24h) to dissolve into a 30wt% resin dispersion B. Dispersions A and B were mixed evenly at a mass ratio of 3:5 to obtain dispersion C. An additive film was prepared by a scraping method and dried to form the desired shape. The mass ratio of Pt to resin powder was 0.8wt%, and the thickness of the additive layer was 10μm.

[0121] S2. Continue to spray resin dispersion B onto the Pt-containing additive layer, and use PTFE as the reinforcing layer to prepare a single-reinforced fluorine-containing proton-reinforced membrane. From top to bottom, the membrane consists of a resin layer (20 μm), a reinforcing layer (5 μm), a resin layer (20 μm), and a Pt-containing additive layer (10 μm). There are two resin layers, and the reinforcing layer is located between the two resin layers. The total membrane thickness is 55 μm.

[0122] Comparative Example 3:

[0123] A proton exchange membrane is prepared according to the following steps:

[0124] S1. Co@Pt nano-alloy particles with Pt as the shell were ultrasonically dispersed (450W, 2h) in a mixed solvent of water and n-propanol (volume ratio 1:1) to form dispersion A. Long-branched perfluorosulfonic acid resin (PFSA) with an exchange capacity of 1.0 mmol / g and a number-average molecular weight of 260,000 was added to a mixed solvent of water and n-propanol (volume ratio 1:1) and stirred (300rpm, 24h) to dissolve into a 30wt% resin dispersion B. Dispersion A and dispersion B were mixed evenly at a mass ratio of 3:5 to obtain dispersion C. An additive film was prepared by a scraping method and dried to form the desired shape. The mass ratio of Pt to resin powder was 0.8wt%, and the thickness of the additive layer was 10μm.

[0125] S2. Continue to spray resin dispersion B onto the Pt-containing additive layer, and use PTFE as the reinforcing layer to prepare a single-reinforced fluorine-containing proton-reinforced membrane. From top to bottom, the membrane consists of a resin layer (20 μm), a reinforcing layer (5 μm), a resin layer (20 μm), and a Pt-containing additive layer (10 μm). There are two resin layers, and the reinforcing layer is located between the two resin layers. The total membrane thickness is 55 μm.

[0126] Comparative Example 4:

[0127] A proton exchange membrane is prepared according to the following steps:

[0128] S1. Pt nanorod particles were ultrasonically dispersed (450W, 2h) in a mixed solvent of water and n-propanol (volume ratio 1:1) to form dispersion A. Long-branched perfluorosulfonic acid resin (PFSA) with an exchange capacity of 1.2 mmol / g and a number-average molecular weight of 240,000 was added to a mixed solvent of water and n-propanol (volume ratio 1:1) and stirred (300 rpm, 24h) to dissolve into a 30 wt% resin dispersion B. Dispersions A and B were mixed evenly at a mass ratio of 3:5 to obtain dispersion C. An additive film was prepared by a scraping method and dried to form the desired shape. The mass ratio of Pt to resin powder was 0.4 wt%, and the thickness of the additive layer was 5 μm.

[0129] S2. Continue to spray resin dispersion B onto the Pt-containing additive layer, and use PTFE as the reinforcing layer to prepare a single-reinforced fluorine-containing proton-reinforced membrane. From top to bottom, the membrane consists of a resin layer (17.5 μm), a reinforcing layer (10 μm), a resin layer (17.5 μm), and a Pt-containing additive layer (10 μm). There are two resin layers, and the reinforcing layer is located between the two resin layers. The total membrane thickness is 55 μm.

[0130] Comparative Example 5:

[0131] A proton exchange membrane is prepared according to the following steps:

[0132] S1. Pt / C nanoparticles were ultrasonically dispersed (180W, 2h) in a mixed solvent of water and n-propanol (volume ratio 1:1) to form dispersion A. Long-branched perfluorosulfonic acid resin (PFSA) with an exchange capacity of 1.1 mmol / g and a number-average molecular weight of 250,000 was added to a mixed solvent of water and n-propanol (volume ratio 1:1) and stirred (300 rpm, 24h) to dissolve into a 30 wt% resin dispersion B. Dispersion A and dispersion B were mixed evenly at a mass ratio of 3:5 to obtain dispersion C. An additive film was prepared by a scraping method and dried to form the desired shape. The mass ratio of Pt to resin powder was 0.6 wt%, and the thickness of the additive layer was 10 μm.

[0133] S2. Continue to spray resin dispersion B onto the Pt-containing additive layer, and use PTFE as the reinforcing layer to prepare a single-reinforced fluorine-containing proton-reinforced membrane. From top to bottom, the membrane consists of a resin layer (20 μm), a reinforcing layer (5 μm), a resin layer (20 μm), and a Pt-containing additive layer (10 μm). There are two resin layers, and the reinforcing layer is located between the two resin layers. The total membrane thickness is 55 μm.

[0134] Comparative Example 6:

[0135] A low-hydrogen-permeability proton exchange membrane is prepared in a manner that differs from that in Example 1, except that step S3 is as follows:

[0136] Resin dispersion B was sprayed onto the Pt-containing additive layer to prepare a fluorinated proton exchange resin unreinforced membrane, ultimately forming a proton exchange membrane with an array structure at the bottom. As shown in Figure 4, the exchange membrane consists of an unreinforced membrane (50 μm), an array layer (2 μm), and a flat layer (3 μm) from top to bottom, with a total membrane thickness of 55 μm. All other preparation steps were the same as in Example 1.

[0137] Comparative Example 7:

[0138] A low-hydrogen-permeability proton exchange membrane is prepared in a manner that differs from that in Example 1, except that step S3 is as follows:

[0139] Resin dispersion B was sprayed onto the array layer to form an array protective layer 55 with a thickness of 2 μm. Resin dispersion B was then coated onto the array to prepare a fluorinated proton exchange resin unreinforced membrane with a thickness of 13 μm. The prepared membrane with the array structure and array protective layer 55, along with the prepared fluorinated proton exchange resin unreinforced membrane, were then hot-pressed (160℃, 2.5 MPa, 5 min) to prepare a proton exchange membrane with the array structure on top. As shown in Figure 5, the exchange membrane, from top to bottom, consists of the array protective layer 55 (2 μm), the array layer (2 μm), the flat layer (3 μm), and the unreinforced membrane (13 μm), with a total membrane thickness of 20 μm. All other preparation steps were the same as in Example 1.

[0140] Comparative Example 8:

[0141] A proton exchange membrane differs from Example 1 in that the thickness of the planarization layer in the prepared proton exchange membrane is 30 times that of the array layer, while all other conditions are the same as in Example 1.

[0142] Comparative Example 9:

[0143] A proton exchange membrane differs from Example 1 in that the active component of the planar layer in the prepared proton exchange membrane is 50 times that of the array layer, while all other conditions are the same as in Example 1.

[0144] Comparative Example 10:

[0145] A proton exchange membrane, differing from Example 1, has an array density of 2.0 × 10⁻⁶. 7 pcs / cm 2 All other conditions are the same as in Example 1.

[0146] Comparative Example 11:

[0147] A proton exchange membrane differs from Example 1 in that the height of a single array in the proton exchange membrane is 8.0 times its width, while all other conditions are the same as in Example 1.

[0148] Comparative Example 12:

[0149] A proton exchange membrane differs from that of Example 1 in that the active component in the prepared proton exchange membrane is 10.0 wt% of the fluorinated proton exchange resin in terms of the mass of the Pt-based additive, and the array density is 1.0 × 10⁻⁶. 7 pcs / cm 2 All other conditions are the same as in Example 1.

[0150] Comparative Example 13:

[0151] A proton exchange membrane, differing from Comparative Example 6, has a thickness of 5 μm, an additive layer thickness of 2 μm, an active component in the Pt-based additive comprising 10.0 wt% of the fluorinated proton exchange resin, a planarization layer to array layer thickness ratio of 1:1, and an array density of 1.0 × 10⁻⁶. 9 pcs / cm 2 All other conditions are the same as those in Comparative Example 6.

[0152] Comparative Example 14:

[0153] A proton exchange membrane differs from Example 1 in that the thickness of the proton exchange membrane is 5 μm, the thickness of the reinforcing layer is 1 μm, the thickness of the additive layer is 2 μm, and the mass of the active component in the Pt-type additive is 40.0 wt% of the mass of the fluorinated proton exchange resin. All other conditions are the same as in Example 1.

[0154] Comparative Example 15:

[0155] A proton exchange membrane differs from Example 1 in that the proton exchange membrane has a thickness of 220 μm, a reinforcing layer thickness of 15.7 μm, a total of 10 layers, an additive thickness of 30 μm, and the active component in the Pt-type additive has a mass of 0.01 wt% of the mass of the fluorinated proton exchange resin. All other conditions are the same as in Example 1.

[0156] Comparative Example 16:

[0157] A proton exchange membrane differs from Comparative Example 1 in that the proton exchange membrane has a thickness of 15 μm, the reinforcing layer has a thickness of 3 μm, and the resin layer has a thickness of 6 μm. All other conditions are the same as those in Comparative Example 1.

[0158] Performance testing

[0159] The membrane electrode core component prepared using the low-hydrogen-permeability proton exchange membrane provided by this invention can be used in fuel cells, electrolyzers, or other electrochemical reaction devices. Examples of hydrogen production via water electrolysis and fuel cell power generation are given below:

[0160] The proton exchange membrane prepared above was used to fabricate a membrane electrode assembly for hydrogen production via water electrolysis. The anode catalyst layer had an Ir loading of approximately 1.7 mg / cm³. 2 The cathode catalyst layer has a Pt loading of approximately 0.5 mg / cm³. 2 To evaluate performance, an electrolyzer for hydrogen production from water electrolysis was assembled using each of the membrane electrode samples described above. The test conditions were 70℃ and 3.0 A / cm². 2 At ambient pressure (5 μm and 15 μm proton exchange membranes in the examples and comparative examples); 70 °C, 3.0 A / cm 25 bar pressure difference (55 μm, 120 μm and 220 μm proton membranes in the examples and comparative examples).

[0161] The results showed that at the same current density (3.0 A / cm²), 2 Compared with the proton exchange membrane provided in the comparative example, the hydrogen content in the oxygen content of the membrane prepared in this example is significantly reduced (all ≤0.10%) at the same membrane thickness, as shown in Table 1 for specific data; in addition, the electrochemical performance is significantly improved (voltage decreases by 0.03V-0.8V), as shown in Table 2 and Figure 9 for specific data.

[0162] Table 1. Parameters of the proton exchange membrane and hydrogen content in oxygen in the examples and comparative examples.

[0163]

[0164] In each embodiment, Examples 6 and 9 achieved relatively better hydrogen permeation suppression effects because they had optimal additive content, additive layer thickness, array density, array aspect ratio, ratio of active components between the flat layer and the array layer, and ratio of the thickness of the flat layer and the array layer. This indicates that by reasonably controlling the ratio of active components, thickness ratio, and array parameters of the array layer and the flat layer, the hydrogen permeation improvement effect can be further enhanced. In addition, compared with Example 6, Example 9 had a better hydrogen permeation suppression effect, which may be due to the fact that Co@Pt nano-alloy particles with Pt as the shell can effectively improve the utilization efficiency of the noble metal Pt. At the same time, due to the special surface electronic structure and the special interaction between the core and the shell, the Pt-based core-shell structure catalyst exhibits higher catalytic activity and stability.

[0165] Table 2 shows the battery polarization curve data of the proton exchange membrane in the application of water electrolysis for hydrogen production, based on typical embodiments and comparative examples.

[0166]

[0167] As shown in Table 2 and Figure 9, among the embodiments, Examples 6 and 9 achieved the best voltage performance. This is because they had the optimal additive content, additive layer thickness, array density, array aspect ratio, ratio of active components between the planar layer and the array layer, and ratio of the thickness of the planar layer and the array layer. This demonstrates that by reasonably controlling the ratio of active components, thickness ratio, and array parameters of the array layer and the planar layer, the electrical performance can be further improved. In addition, compared with Example 6, Example 9 had better voltage performance, which may be due to the fact that the Co@Pt nano-alloy particles with Pt as the shell can effectively improve the utilization efficiency of the noble metal Pt. At the same time, due to the special surface electronic structure and the special interaction between the core and the shell, the Pt-based core-shell structure catalyst exhibited higher catalytic activity and stability. Among the embodiments, Example 1 had the worst voltage performance because its additive content and array density were the lowest, which was not conducive to the effective utilization of the catalyst.

[0168] Table 3 shows the cell polarization curve data of proton exchange membrane in fuel cell power generation based on typical embodiments and comparative examples.

[0169]

[0170] The proton exchange membranes prepared in Examples 13, 14, and 16 were assembled into membrane electrode assemblies for fuel cell performance testing. The platinum loading of the catalyst layer was 0.5 mg / cm³. 2 The test conditions were 75°C, 40%RH, and a hydrogen-air atmosphere. As shown in Table 3 and Figure 10, Examples 13 and 14 exhibited better voltage performance compared to Comparative Example 16 because they contained Pt-based additives, which reduce hydrogen permeation. This demonstrates that this type of proton exchange membrane can effectively improve the performance of fuel cells.

[0171] The embodiments described above provide a detailed explanation of the technical solutions and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, additions, and equivalent substitutions made within the scope of the principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A low-hydrogen-permeability proton exchange membrane, characterized in that, It includes a Pt-containing additive layer and a substrate membrane, with the Pt-containing additive layer located on one or both sides of the substrate membrane; the total thickness of the low-hydrogen-permeable proton exchange membrane is 5μm-220μm; The Pt-containing additive layer is composed of Pt-based additives and fluorinated proton exchange resin. The Pt-based additives are selected from Pt nanoparticles, Pt / C nanoparticles, or Co@Pt nanoalloy particles. The mass of the active component in the Pt-based additives is 0.4wt%-1.0wt% of the mass of the fluorinated proton exchange resin. The Pt-containing additive layer includes an array layer and a planarization layer, with a thickness ratio of 1:(1-3) and a molar ratio of active components in the array layer and planarization layer of 1:(1-3). The array layer has a thickness of 0.1 μm-15 μm and consists of an ordered array and an array layer resin encapsulating the array, with an array density of 1.0 × 10⁻⁶. 7 pcs / cm 2 -1.0×10 9 pcs / cm 2 The height of a single array is 1.0 to 17.0 times its width; The substrate membrane is a fluorine-containing proton exchange membrane.

2. The low-hydrogen-permeability proton exchange membrane as described in claim 1, characterized in that, The arrays in the array layer are cylindrical, prismatic, or conical in shape, and the array density is 1.0 × 10⁻⁶. 8 pcs / cm 2 -8.0×10 8 pcs / cm 2 The height of a single array is 1.0 to 5.0 times its width.

3. The low-hydrogen-permeability proton exchange membrane as described in claim 1, characterized in that, An array protective layer is also provided on the side of the array layer away from the substrate membrane; the array protective layer is made of fluorinated proton exchange resin and has a thickness of 1μm-10μm.

4. The low-hydrogen-permeability proton exchange membrane as described in claim 1, characterized in that, The total thickness of the Pt-based additive layer ranges from 2 μm to 30 μm.

5. The low-hydrogen-permeability proton exchange membrane as described in claim 1, characterized in that, The fluorinated proton exchange membrane is a fluorinated proton exchange resin reinforced membrane or a fluorinated proton exchange resin unreinforced membrane; The fluorinated proton exchange resin reinforced membrane comprises a resin layer and a reinforcing layer. The number of reinforcing layers ranges from 1 to 10, with one more resin layer than reinforcing layer, and the reinforcing layer is located between two adjacent resin layers. The total thickness of the fluorinated proton exchange resin reinforced membrane is 3 μm to 218 μm, the thickness of a single resin layer is 1 μm to 30 μm, and the thickness of a single reinforcing layer is 1 μm to 30 μm. Fluorine-containing proton exchange resin unreinforced membranes consist only of a resin layer with a thickness of 3μm-218μm.

6. The method for preparing a low-hydrogen-permeability proton exchange membrane according to any one of claims 1-5, characterized in that, Includes the following steps: S1. Disperse Pt additives in a solvent by ultrasonication to obtain dispersion A, disperse fluorine proton exchange resin in a solvent to obtain dispersion B, and stir and mix dispersion A and dispersion B to obtain dispersion C. S2. Take the surface-modified silicon-based template, fill the array channels of the silicon-based template with dispersion C, treat with negative pressure, continue to add dispersion C to reach the preset thickness of the flat layer, dry and cure, peel off the silicon-based template to obtain an integrally formed flat layer and an orderly array, wrap dispersion B around the array to obtain a layer containing Pt additives. S3. Prepare a substrate membrane on the Pt-containing additive layer obtained in step S2 to obtain a low-hydrogen-permeability proton exchange membrane.

7. The preparation method according to claim 6, characterized in that, In step S1, the solvent is selected from at least one of water, ethanol, n-propanol, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, or N-methylpyrrolidone; the ultrasonic dispersion power is 180W-630W, the ultrasonic dispersion time is 0.5h-6h, the stirring speed is 200rpm-800rpm, and the stirring time is 24h-72h. In step S1, the mass ratio of dispersion A to dispersion B in dispersion C is (0.2-1):

1.

8. The preparation method according to claim 6, characterized in that, In step S2, the silicon-based template undergoes vacuum-programmed temperature vapor-phase surface modification. The surface modification reagents selected are octadecyltrichlorosilane, octyltrimethoxysilane, (3-aminopropyl)trimethoxysilane, (3-mercaptopropyl)trimethoxysilane, or octadecyltrimethoxysilane and octyltrimethoxysilane. The surface modification temperature is programmed at (50-70℃)-(80-100℃)-(120-200℃). The surface modification vacuum degree is -0.20MPa to -0.10MPa. In step S2, the vacuum degree during negative pressure treatment is -0.20MPa to -0.10MPa.

9. The preparation method according to claim 6, characterized in that, In step S3, the process of preparing the matrix membrane is to prepare a non-reinforced membrane containing fluorine proton exchange resin using dispersion B, or the process of preparing the matrix membrane is to prepare a reinforced membrane containing fluorine proton exchange resin using dispersion B and reinforcing material. The reinforcing material is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyvinyl chloride, ethylene-tetrafluoroethylene copolymer, polyphenylene sulfide nonwoven fabric, polyether ether ketone, polyimide, fluorinated polyimide, polysulfone, perfluoroethylene propylene fiber or perfluoroalkoxy vinyl ether copolymer fiber; Step S3 also includes preparing an array protective layer on the side of the array layer away from the matrix membrane after the matrix membrane is prepared.

10. The application of the low-hydrogen-permeability proton exchange membrane according to any one of claims 1-5 or the low-hydrogen-permeability proton exchange membrane prepared by the preparation method according to any one of claims 6-9 in water electrolysis or fuel cell membrane electrode assembly.

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