Patterned ordered silicon dioxide proton exchange membrane, preparation method and application

Abstract

The invention relates to the technical field of proton exchange membranes, and discloses a patterned ordered silicon dioxide proton exchange membrane as well as a preparation method and application thereof. The membrane comprises a proton membrane substrate layer and a patterned hollow mesoporous silica deposition region formed by mask spraying. The ordered patterns, such as stripes or dot matrixes, can absorb moisture to retain water by using the silicon dioxide cavity under low humidity, and directionally drain water through the blank area under high humidity, thereby cooperatively solving the problems of water loss and water accumulation of the film under severe environments such as plateau and the like. The invention also discloses a preparation method of the composition. According to the membrane, the performance and durability of the fuel cell in low-humidity and large-temperature-difference environments are remarkably improved.

Description

Technical Field

[0001] This invention belongs to the field of proton exchange membrane technology, specifically relating to a patterned ordered silica proton exchange membrane suitable for high-altitude working conditions, its preparation method, and its application. Background Technology

[0002] The proton exchange membrane (PEM) is a core component of a fuel cell, performing the dual functions of conducting protons and blocking reactant gases. Currently widely used PEMs, such as perfluorosulfonic acid membranes (Nafion) or sulfonated polyether ether ketone (SPEEK) membranes, exhibit proton conductivity highly dependent on the water content within the membrane. Under normal humidity conditions, they demonstrate good performance; however, in low humidity environments, water molecules rapidly escape from the membrane, leading to a sharp decline in proton conductivity and severely impacting the cell's output performance and stability. Therefore, existing technologies typically require complex external humidification systems, which increases the overall size, cost, and operating energy consumption of the fuel cell system.

[0003] The high-altitude environment places more stringent demands on proton exchange membranes. At altitudes of 2000 to 5000 meters, the air pressure is only 0.6 to 0.8 times that of standard atmosphere. This low pressure reduces the diffusion rate of reactant gases and slows the discharge of water generated at the cathode, easily leading to water accumulation and even icing on the membrane electrode surface. Simultaneously, the diurnal temperature range in high-altitude areas can reach as high as 40°C (e.g., -10°C to 30°C), subjecting the membrane to repeated and intense thermal expansion and contraction cycles, accelerating structural aging and mechanical performance degradation. Furthermore, the relative humidity at high altitudes is often below 40%, further exacerbating membrane drying. These factors collectively constitute a triple failure risk of "low humidity membrane drying, low pressure water flooding, and large temperature difference aging," making traditional proton exchange membranes and conventional modification schemes difficult to effectively adapt.

[0004] To improve the water retention performance of membranes, existing technologies mainly focus on modifying the catalyst layer structure or adding hydrophilic materials to the membrane body. For example, patent application CN114094121A discloses a self-humidifying membrane electrode that constructs a hydrophilic-hydrophobic region by template spraying onto a gas diffusion layer. This method focuses on optimizing water management of the catalyst layer, but it does not solve the problem of water loss in the membrane body under low humidity, and the addition of hydrophilic particles may reduce the conductivity of the catalyst layer. Patent application CN115386184B discloses the preparation of a composite membrane by blending mesoporous silica with perfluorosulfonic acid resin, utilizing the high specific surface area of ​​the mesoporous material to adsorb water. However, such blending methods have problems such as easy aggregation of hydrophilic particles and disordered distribution within the membrane, resulting in uneven water retention and potentially affecting the membrane's compactness and mechanical strength.

[0005] Therefore, developing a proton exchange membrane that can actively adapt to the complex working conditions of high-altitude areas, and that combines efficient water retention, directional drainage, and excellent structural stability has become a pressing technical challenge in this field. Summary of the Invention

[0006] To address the shortcomings of existing proton exchange membranes, such as easy water loss in high-altitude, low-humidity environments, easy water accumulation under low air pressure, and easy aging under large temperature differences, the primary objective of this invention is to provide a patterned, ordered silica proton exchange membrane. This membrane, by constructing an ordered, patterned water-retaining structure on a substrate layer, can synergistically achieve efficient water retention and directional drainage, thereby significantly improving its performance and durability under harsh conditions such as high altitudes.

[0007] Another objective of this invention is to provide a method for preparing the aforementioned proton exchange membrane and its application. This method offers controllable processes and enables precise and orderly deposition of silica microspheres on the membrane surface. When applied to fuel cells, this membrane makes the fuel cells suitable for low-humidity, high-temperature environments.

[0008] To solve the above-mentioned technical problems, the present invention is implemented as follows: The present invention also provides a patterned ordered silica proton exchange membrane, characterized in that it comprises a proton membrane substrate layer and a patterned hollow mesoporous silica deposition region; The proton membrane substrate is made of perfluorosulfonic acid resin or sulfonated polyether ether ketone, with a total thickness of 30-40 μm. The patterned hollow mesoporous silica deposition region is formed by mask spraying hollow mesoporous silica microspheres onto a specific area of ​​the proton membrane substrate layer. The hollow mesoporous silica microspheres have a particle size of 100-1000 nm and a mesoporous pore size of 2-10 nm. The ordered pattern of the patterned hollow mesoporous silica deposition region is selected from one or more combinations of parallel stripe patterns, serpentine stripe patterns, and global dot matrix patterns, wherein: The width of the parallel stripe pattern is 1-2 mm and the spacing between the stripes is 1-2 mm. The serpentine stripe pattern has a stripe width of 1-2 mm and a stripe spacing of 1-2 mm; The shape of the dots in the global dot matrix pattern is one or more combinations of circles, rectangles, triangles or trapezoids, the diameter of the dots is 0.3-0.8mm, and the spacing between the dots is 1-1.5mm; Patterned ordered structures are used to retain water in low-humidity environments by absorbing moisture through silica regions, and to drain water in high-humidity environments by using silica-free blank regions.

[0009] Furthermore, the ordered pattern of the patterned hollow mesoporous silica deposition region is a parallel stripe pattern, which is used to form directional drainage channels on the film surface.

[0010] The present invention also provides a method for preparing the patterned ordered silica proton exchange membrane, comprising the following steps: Step S1, preparing hollow mesoporous silica dispersion: Hollow mesoporous silica microspheres are dispersed in a solvent, wherein the solvent is selected from one or more of methanol, ethanol, isopropanol, n-propanol and dimethyl sulfoxide, and the mass percentage of the solvent is 98%-99.5%. Then a dispersant is added, wherein the dispersant is selected from one or two of Tween 80 and KH-550, and the mass percentage of the dispersant is 0.1%-0.5%. The dispersion is ultrasonically dispersed at a low temperature of 0-5℃ for 30-60 minutes to obtain hollow mesoporous silica dispersion. Step S2, coating the bottom film: Mix the perfluorosulfonic acid resin solution with isopropanol, wherein the concentration of the perfluorosulfonic acid resin solution is 15-25 wt%, stir at 600 r / min for 30 minutes to form a uniform resin solution, pour the resin solution onto the PTFE substrate, and coat it uniformly with a scraper to form a continuous, bubble-free wet film, and dry the wet film in stages: first dry at 55-65℃ for 2-2.5 hours, then raise the temperature to 75-85℃ for 1.5-2 hours, and finally raise the temperature to 95-105℃ for 1-1.5 hours to obtain the bottom film; Step S3, patterned silica spraying: Place the bottom film obtained in step S2 on the vacuum adsorption stage of the ultrasonic spraying machine, cover the surface of the bottom film with a patterned PET flexible mask, spray the hollow mesoporous silica dispersion obtained in step S1 onto the hollow area of ​​the mask, remove the mask after spraying, and place the film in a 60°C oven to dry for 1 hour. Step S4, coating and curing of the top layer film: The same resin solution as in step S2 is coated on the surface of the bottom layer film containing patterned silica to form a top wet film. The top wet film is dried in stages: first, it is dried at 55-65°C for 2-2.5 hours, then heated to 75-85°C for 1.5-2 hours, and finally heated to 115-125°C for annealing for 1-1.5 hours. After cooling to room temperature, it is peeled off from the PTFE substrate to obtain the final post-processed film. Step S5, post-membrane treatment: The post-treated membrane is sequentially immersed in 5% H2O2 solution at 80°C for 1 hour, deionized water at 80°C for 1 hour, 0.5mol / L H2SO4 solution at 80°C for 1 hour, and deionized water at 80°C for 1 hour, and finally vacuum dried at 60°C for 2 hours to obtain the patterned ordered silica proton exchange membrane.

[0011] Furthermore, in step S2, the volume ratio of the perfluorosulfonic acid resin solution to isopropanol is 1:1.

[0012] Furthermore, in step S2, the gap between the scrapers is 100-400 μm.

[0013] Furthermore, in step S3, the spraying parameters include: nozzle height 30mm, spraying pressure 0.02MPa, carrier air flow rate 1500ml / min, and air supply flow rate 0.1ml / min.

[0014] The present invention also provides an application of the patterned ordered silica proton exchange membrane described above in a fuel cell, wherein the fuel cell is a high-altitude fuel cell or a fuel cell for arid regions.

[0015] Compared with the prior art, the advantages of this invention are as follows: (1) Collaborative water management: Through the patterned design of "hollow mesoporous SiO2 ordered deposition zone" and "SiO2-free blank zone", the functional regionalization is realized. The silica zone uses its cavities and mesopores to strongly adsorb and lock in water under low humidity, increasing the water absorption rate of the membrane by more than 30%-50%; the blank zone serves as an efficient gas channel and drainage channel, avoiding the risk of water accumulation and freezing on the membrane surface under high humidity or low pressure.

[0016] (2) Excellent environmental adaptability: The structure is designed specifically for the complex working conditions of "low humidity, low pressure and large temperature difference" on the plateau, effectively solving the triple failure challenge faced by traditional membranes.

[0017] (3) Enhanced structural stability: The physical cross-linking points formed between the silica microspheres and the resin matrix can restrict the thermal movement of the polymer chains in the hot and cold cycle, slow down the thermal aging process of the film, and improve the dimensional stability and mechanical strength.

[0018] (4) Balanced performance: This invention avoids the problems of decreased conductivity, particle agglomeration, and uneven water retention caused by simply blending hydrophilic particles into the catalyst layer or membrane body, and achieves a balance between high proton conductivity, good water retention and excellent mechanical properties. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort, wherein: Figure 1 A flowchart illustrating the method for preparing a patterned, ordered silica proton exchange membrane provided by this invention. Detailed Implementation

[0020] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] The terms "first," "second," etc., used in the specification and claims of this invention are used to distinguish similar objects and not to describe a specific order or sequence. It should be understood that such data can be interchanged where appropriate so that embodiments of the invention can be implemented in orders other than those illustrated or described herein, and the objects distinguished by "first," "second," etc., are generally of the same class and the number of objects is not limited; for example, a first object can be one or more. Furthermore, in the specification and claims, "and / or" indicates at least one of the connected objects, and the character " / " generally indicates that the preceding and following objects are in an "or" relationship.

[0022] The present invention also provides a patterned ordered silica proton exchange membrane, comprising a proton membrane substrate layer and a patterned hollow mesoporous silica deposition region; The proton membrane substrate is made of perfluorosulfonic acid resin or sulfonated polyether ether ketone, with a total thickness of 30-40 μm. The mass ratio of hollow mesoporous silica to matrix resin is 1:5 to 1:20; The patterned hollow mesoporous silica deposition region is formed by mask spraying hollow mesoporous silica microspheres onto a specific area of ​​the proton membrane substrate layer. The hollow mesoporous silica microspheres have a particle size of 100-1000 nm and a mesoporous pore size of 2-10 nm. The ordered pattern of the patterned hollow mesoporous silica deposition region is selected from one or more combinations of parallel stripe patterns, serpentine stripe patterns, and global dot matrix patterns. The parallel stripe pattern has a stripe width of 1-2 mm and a stripe spacing of 1-2 mm. The serpentine stripe pattern has a stripe width of 1-2 mm and a stripe spacing of 1-2 mm. The global dot matrix pattern has dots in the shape of one or more combinations of circles, rectangles, triangles, or trapezoids, with a dot diameter of 0.3-0.8 mm and a dot spacing of 1-1.5 mm. The spray loading of the patterned hollow mesoporous silica deposition zone is 2-10 mg / cm². Patterned ordered structures are used to retain water in low humidity environments and to drain water in a directional manner in high humidity environments.

[0023] Furthermore, the ordered pattern of the patterned hollow mesoporous silica deposition region is a parallel stripe pattern, used to form directional drainage channels on the film surface. Please see Figure 1 As shown, the present invention also provides a method for preparing the patterned ordered silica proton exchange membrane, comprising the following steps: Step S1, preparing hollow mesoporous silica dispersion: Hollow mesoporous silica microspheres are dispersed in a solvent, wherein the solvent is selected from one or more of methanol, ethanol, isopropanol, n-propanol and dimethyl sulfoxide, and the mass percentage of the solvent is 98%-99.5%. Then a dispersant is added, wherein the dispersant is selected from one or two of Tween 80 and KH-550, and the mass percentage of the dispersant is 0.1%-0.5%. The dispersion is ultrasonically dispersed at a low temperature of 0-5℃ for 30-60 minutes to obtain hollow mesoporous silica dispersion. Step S2, coating the bottom film: Mix the perfluorosulfonic acid resin solution with isopropanol, wherein the concentration of the perfluorosulfonic acid resin solution is 15-25 wt%, stir at 600 r / min for 30 minutes to form a uniform resin solution, pour the resin solution onto the PTFE substrate, and coat it uniformly with a scraper to form a continuous, bubble-free wet film, and dry the wet film in stages: first dry at 55-65℃ for 2-2.5 hours, then raise the temperature to 75-85℃ for 1.5-2 hours, and finally raise the temperature to 95-105℃ for 1-1.5 hours to obtain the bottom film; Step S3, patterned silica spraying: Place the bottom film obtained in step S2 on the vacuum adsorption stage of the ultrasonic spraying machine, cover the surface of the bottom film with a patterned PET flexible mask, spray the hollow mesoporous silica dispersion obtained in step S1 onto the hollow area of ​​the mask, remove the mask after spraying, and place the film in a 60°C oven to dry for 1 hour. Step S4, coating and curing of the top layer film: The same resin solution as in step S2 is coated on the surface of the bottom layer film containing patterned silica to form a top wet film. The top wet film is dried in stages: first, it is dried at 55-65°C for 2-2.5 hours, then heated to 75-85°C for 1.5-2 hours, and finally heated to 115-125°C for annealing for 1-1.5 hours. After cooling to room temperature, it is peeled off from the PTFE substrate to obtain the final post-processed film. Step S5, post-membrane treatment: The post-treated membrane is sequentially immersed in 5% H2O2 solution at 80°C for 1 hour, deionized water at 80°C for 1 hour, 0.5mol / L H2SO4 solution at 80°C for 1 hour, and deionized water at 80°C for 1 hour, and finally vacuum dried at 60°C for 2 hours to obtain the patterned ordered silica proton exchange membrane.

[0024] In step S2, the volume ratio of the perfluorosulfonic acid resin solution to isopropanol is 1:1.

[0025] In step S2, the gap between the scrapers is 100-400 μm.

[0026] In step S3, the spraying parameters include: nozzle height 30mm, spraying pressure 0.02MPa, carrier air flow rate 1500ml / min, and air supply flow rate 0.1ml / min.

[0027] The present invention also provides an application of the patterned ordered silica proton exchange membrane described above in a fuel cell, wherein the fuel cell is a high-altitude fuel cell or a fuel cell for arid regions. The application environment of the high-altitude fuel cell is an altitude of 2000-5000m, relative humidity ≤40%, air pressure 0.6-0.8atm, and diurnal temperature range of -10℃ to 30℃.

[0028] The present invention will be further described in detail below with reference to specific embodiments and comparative examples. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0029] Example 1 Raw materials and specifications: Perfluorosulfonic acid resin solution: Type D2020, solid content 20wt%; Hollow mesoporous silica microspheres: pore size 2nm, particle size 200nm, specific surface area 2400m² / g; Solvent: Isopropanol (analytical grade); Dispersant: Tween 80; step: Step 1, Preparation of silica dispersion: Weigh 1.0g of hollow mesoporous silica microspheres, add 99g of isopropanol and 0.5g of Tween 80, and ultrasonically disperse at 350W power for 45 minutes at a low temperature of 3℃ to obtain a uniform and stable silica dispersion.

[0030] Step 2, base film coating: A 20wt% Nafion solution was mixed with isopropanol at a volume ratio of 1:1 and mechanically stirred at 600 rpm for 30 minutes to form a homogeneous resin solution. Using a 100 μm gap scraper, the resin solution was uniformly coated onto a PTFE substrate to form a continuous, bubble-free wet film. Subsequently, staged drying was performed: first at 60°C for 2 hours, then at 80°C for 1.8 hours, and finally at 100°C for 1.2 hours, yielding a bottom film with a thickness of approximately 12 μm.

[0031] Step 3, SiO2 patterned spraying: The aforementioned base film was flattened and fixed onto the vacuum adsorption stage of an ultrasonic spraying machine (vacuum degree 0.2 MPa). A striped flexible PET mask (stripes 1 mm wide, 1 mm spacing) was then placed on its surface. Spraying parameters were set as follows: nozzle height 30 mm, spraying pressure 0.02 MPa, carrier gas (N2) flow rate 1500 ml / min, and liquid supply flow rate 0.1 ml / min. The silica dispersion prepared in step 1 was sprayed onto the cutout areas of the mask. After spraying, the mask was carefully removed, and the film was placed in a 60°C forced-air drying oven for 1 hour. Weighing using an electronic balance, the film weight increased by 125 mg (film area 25 cm²). 2 The calculated silica loading was 5 mg / cm³. 2 .

[0032] Step 4, Top film coating and curing: On the surface of the patterned silica base film, a top film was coated using the same resin solution and a 200 μm gap doctor blade. This was followed by staged drying and heat treatment: first, drying at 60°C for 2 hours, then at 80°C for 1.8 hours, and finally annealing at 120°C for 1.5 hours. After cooling to room temperature, the film was slowly peeled off from the PTFE substrate to obtain the final treated film.

[0033] Step 5, Post-membrane treatment: The final treatment membrane was sequentially immersed in the following solutions: 5% H2O2 aqueous solution, 80℃, 1 hour; Deionized water, 80℃, 1 hour; 0.5 mol / L H2SO4 solution, 80℃, 1 hour; Deionized water, 80℃, 1 hour.

[0034] After processing, the membrane was placed in a vacuum drying oven at 60°C for 2 hours to obtain the final patterned ordered silica proton exchange membrane (total thickness approximately 35 μm).

[0035] Example 2 The difference between this embodiment and Embodiment 1 is that it aims to demonstrate the feasibility of different patterns and parameters.

[0036] Pattern change: Replace the mask with a global dot matrix mask, with circular dots, a dot diameter of 0.5mm, and a dot spacing of 1.2mm.

[0037] Silica parameters: Hollow mesoporous silica microspheres with a particle size of 500nm and a mesopore size of 5nm are used.

[0038] Load control: By adjusting the number of spray coats, the spray load of silica is controlled at 8 mg / cm³. 2 .

[0039] Matrix material: The proton exchange membrane matrix layer uses sulfonated polyether ether ketone (SPEEK) resin solution.

[0040] The remaining steps and parameters are basically the same as in Example 1, and a proton exchange membrane with a dot matrix pattern is finally obtained.

[0041] Example 3 The difference between this embodiment and Embodiment 1 is that it demonstrates the feasibility of different preparation parameters.

[0042] Dispersion solvent: The solvent was changed to a mixture of ethanol and dimethyl sulfoxide (mass ratio 1:1).

[0043] Dispersant: KH-550 silane coupling agent is used as the dispersant.

[0044] Drying parameters: The bottom layer and top layer films are dried at 55℃ for 2.5 hours, then heated to 75℃ for 2 hours, and finally treated at 95℃ (bottom layer film) / 115℃ (top layer film annealing) for 1.5 hours.

[0045] The remaining steps are similar to those in Example 1, and a patterned proton exchange membrane with good performance was successfully prepared.

[0046] Comparative Example To verify the effectiveness of the present invention, a comparative example was set up. This comparative example used hollow mesoporous silica microspheres of the same mass as in Example 1, but instead of patterned mask spraying, the silica dispersion was directly physically mixed with Nafion resin solution, and then a composite film with uniformly dispersed silica was prepared by a casting method. The mass ratio of silica to resin in this composite film was also controlled at approximately 1:10.

[0047] Effect verification: The membranes obtained in Examples 1-3 and the comparative membranes were subjected to performance tests, and the results are shown in the table below: Test results show that, compared with traditional blended modified membranes, the patterned ordered silica proton exchange membrane provided by this invention exhibits significant advantages in water retention, dimensional stability, proton conductivity, mechanical strength, and durability, and is particularly suitable for harsh environments such as high altitudes.

[0048] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Unless otherwise specified, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes that element.

[0049] Furthermore, it should be noted that the scope of the methods and systems in the embodiments of the present invention is not limited to performing functions in the order shown or discussed, but may also include performing functions substantially simultaneously or in the reverse order, depending on the functions involved. For example, the described methods may be performed in a different order than described, and various steps may be added, omitted, or combined. In addition, features described with reference to certain examples may be combined in other examples.

[0050] The embodiments of the present invention have been described above with reference to the accompanying drawings. However, the present invention is not limited to the specific embodiments described above. The specific embodiments described above are merely illustrative and not restrictive. Those skilled in the art can make many other forms under the guidance of the present invention without departing from the spirit and scope of the claims, and all of these forms are within the protection scope of the present invention.

Claims

1. A patterned, ordered silica proton exchange membrane, characterized in that, Includes a proton exchange membrane substrate layer and a patterned hollow mesoporous silica deposition region; The proton membrane substrate is made of perfluorosulfonic acid resin or sulfonated polyether ether ketone, with a total thickness of 30-40 μm. The patterned hollow mesoporous silica deposition region is formed by mask spraying hollow mesoporous silica microspheres onto a specific area of ​​the proton membrane substrate layer. The hollow mesoporous silica microspheres have a particle size of 100-1000 nm and a mesoporous pore size of 2-10 nm. The ordered pattern of the patterned hollow mesoporous silica deposition region is selected from one or more combinations of parallel stripe patterns, serpentine stripe patterns, and global dot matrix patterns, wherein: The width of the parallel stripe pattern is 1-2 mm and the spacing between the stripes is 1-2 mm. The serpentine stripe pattern has a stripe width of 1-2 mm and a stripe spacing of 1-2 mm; The shape of the dots in the global dot matrix pattern is one or more combinations of circles, rectangles, triangles or trapezoids, the diameter of the dots is 0.3-0.8mm, and the spacing between the dots is 1-1.5mm; Patterned ordered structures are used to retain water in low-humidity environments by absorbing moisture through silica regions, and to drain water in high-humidity environments by using silica-free blank regions.

2. The patterned ordered silica proton exchange membrane according to claim 1, characterized in that, The ordered pattern of the patterned hollow mesoporous silica deposition region is a parallel stripe pattern, which is used to form directional drainage channels on the film surface.

3. A method for preparing a patterned ordered silica proton exchange membrane as described in claim 1 or 2, characterized in that, Includes the following steps: Step S1, preparing hollow mesoporous silica dispersion: Hollow mesoporous silica microspheres are dispersed in a solvent, wherein the solvent is selected from one or more of methanol, ethanol, isopropanol, n-propanol and dimethyl sulfoxide, and the mass percentage of the solvent is 98%-99.5%. Then a dispersant is added, wherein the dispersant is selected from one or two of Tween 80 and KH-550, and the mass percentage of the dispersant is 0.1%-0.5%. The dispersion is ultrasonically dispersed at a low temperature of 0-5℃ for 30-60 minutes to obtain hollow mesoporous silica dispersion. Step S2, coating the bottom film: Mix the perfluorosulfonic acid resin solution with isopropanol, wherein the concentration of the perfluorosulfonic acid resin solution is 15-25 wt%, stir at 600 r / min for 30 minutes to form a uniform resin solution, pour the resin solution onto the PTFE substrate, and coat it uniformly with a scraper to form a continuous, bubble-free wet film, and dry the wet film in stages: first dry at 55-65℃ for 2-2.5 hours, then raise the temperature to 75-85℃ for 1.5-2 hours, and finally raise the temperature to 95-105℃ for 1-1.5 hours to obtain the bottom film; Step S3, patterned silica spraying: Place the bottom film obtained in step S2 on the vacuum adsorption stage of the ultrasonic spraying machine, cover the surface of the bottom film with a patterned PET flexible mask, spray the hollow mesoporous silica dispersion obtained in step S1 onto the hollow area of ​​the mask, remove the mask after spraying, and place the film in a 60°C oven to dry for 1 hour. Step S4, coating and curing of the top layer film: The same resin solution as in step S2 is coated on the surface of the bottom layer film containing patterned silica to form a top wet film. The top wet film is dried in stages: first, it is dried at 55-65°C for 2-2.5 hours, then heated to 75-85°C for 1.5-2 hours, and finally heated to 115-125°C for annealing for 1-1.5 hours. After cooling to room temperature, it is peeled off from the PTFE substrate to obtain the final post-processed film. Step S5, post-membrane treatment: The post-treated membrane is sequentially immersed in 5% H2O2 solution at 80°C for 1 hour, deionized water at 80°C for 1 hour, 0.5mol / L H2SO4 solution at 80°C for 1 hour, and deionized water at 80°C for 1 hour, and finally vacuum dried at 60°C for 2 hours to obtain the patterned ordered silica proton exchange membrane.

4. The preparation method according to claim 3, characterized in that, In step S2, the volume ratio of the perfluorosulfonic acid resin solution to isopropanol is 1:

1.

5. The preparation method according to claim 3, characterized in that, In step S2, the gap between the scrapers is 100-400 μm.

6. The preparation method according to claim 3, characterized in that, In step S3, the spraying parameters include: nozzle height 30mm, spraying pressure 0.02MPa, carrier air flow rate 1500ml / min, and air supply flow rate 0.1ml / min.

7. The application of a patterned ordered silica proton exchange membrane as described in claim 1 or 2 in a fuel cell, characterized in that, The fuel cell is a high-altitude fuel cell or a fuel cell for arid regions.

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