A proton exchange membrane and a preparation method and application thereof

Abstract

The application provides a proton exchange membrane and a preparation method and application thereof. The proton exchange membrane comprises perfluorosulfonic acid resin and modified inorganic particles. The modified inorganic particles comprise sulfonic acid modified silicon dioxide / titanium dioxide and sulfonic acid modified zirconium phosphate. In the application, the modified inorganic particles are selected from sulfonic acid modified silicon dioxide / titanium dioxide and sulfonic acid modified zirconium phosphate. The modified inorganic particles have a strong hydrophilic and polar interface layer on the surface, and the matching between the inorganic particles and the perfluorosulfonic acid resin matrix is realized, so that the performance of the proton exchange membrane is improved.

Description

Technical Field

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

[0002] The proton exchange membrane electrolyzer uses electrical energy to decompose water molecules, producing high-purity hydrogen at the cathode and oxygen at the anode. The proton exchange membrane is the core component of the PEM electrolyzer, and its core functions include conducting protons and isolating gases.

[0003] Perfluorosulfonic acid resin molecules contain a large number of polar groups (such as trifluoromethyl and sulfonic acid groups), which leads to poor compatibility when compounded or blended, affecting proton conductivity; the membrane material itself also has problems such as high swelling rate and insufficient long-term hydrolytic stability, which restricts its performance improvement and wide application. Summary of the Invention

[0004] This application is made in view of the above-mentioned problems, and its purpose is to provide a proton exchange membrane with high proton conductivity.

[0005] Specifically, the first aspect of this application provides a proton exchange membrane, comprising a perfluorosulfonic acid resin and modified inorganic particles;

[0006] The modified inorganic particles include sulfonic acid-modified silica / titanium dioxide and sulfonic acid-modified zirconium phosphate.

[0007] According to some embodiments of this application, the raw materials for preparing the sulfonic acid modified silica / titanium dioxide include:

[0008] Silica, titanate, aminosilane and 1,3-propanesulfonate lactone.

[0009] According to some embodiments of this application, the raw materials for preparing the sulfonic acid-modified zirconium phosphate include:

[0010] Zirconium phosphate, allylamine, and styrene sulfonate.

[0011] The second aspect of this application provides a method for preparing the above-mentioned proton exchange membrane, comprising the following steps:

[0012] Modified inorganic particles, perfluorosulfonic acid resin and solvent were mixed and ball-milled to obtain a casting solution;

[0013] The casting solution is cast into a film and then dried.

[0014] According to some embodiments of this application, the mass ratio of the modified inorganic particles to the perfluorosulfonic acid resin is 0.01~0.1:1.

[0015] According to some embodiments of this application, the aminosilane includes at least one of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

[0016] According to some embodiments of this application, the mass ratio of the sulfonic acid modified silica / titanium dioxide to the perfluorosulfonic acid resin is 0.01~0.05:1.

[0017] According to some embodiments of this application, the mass ratio of the sulfonic acid-modified zirconium phosphate to the perfluorosulfonic acid resin is 0.01~0.05:1.

[0018] According to some embodiments of this application, the mass ratio of the sulfonic acid modified silica / titanium dioxide and the sulfonic acid modified zirconium phosphate is 0.5~3:1.

[0019] According to some embodiments of this application, the mass ratio of the sulfonic acid modified silica / titanium dioxide and the sulfonic acid modified zirconium phosphate is 0.5~1.5:1.

[0020] According to some embodiments of this application, the solvent includes ethanol, NMP, and water.

[0021] According to some embodiments of this application, the drying temperature is 100°C to 150°C.

[0022] According to some embodiments of this application, the drying time is 1 hour to 5 hours.

[0023] According to some embodiments of this application, the preparation method of the sulfonic acid modified silica / titanium dioxide includes the following steps:

[0024] S1. A mixture of silica / titanium dioxide, aminosilane, and solvent is mixed and refluxed to obtain a silane-modified mixture;

[0025] S2. The silane-modified mixture, 1,3-propanesulfonic acid lactone, and solvent are mixed and reacted.

[0026] According to some embodiments of this application, the mass-to-volume ratio of the silica / titanium dioxide mixture and aminosilane in step S1 is 1g:1mL~3mL.

[0027] According to some embodiments of this application, the temperature of the reflux reaction in step S1 is 100°C to 120°C.

[0028] According to some embodiments of this application, the reflux reaction time in step S1 is 20h~30h.

[0029] According to some embodiments of this application, the mass ratio of the silane-modified mixture and 1,3-propanesulfonic acid lactone in step S2 is 1:1~2.

[0030] According to some embodiments of this application, the temperature of the reaction in step S2 is 40°C to 60°C.

[0031] According to some embodiments of this application, the reaction time in step S2 is 20h~30h.

[0032] According to some embodiments of this application, silica and ethanol are mixed to prepare a silica dispersion;

[0033] A titanate dispersion was prepared by mixing titanate, ethanol and acetic acid;

[0034] The titanate dispersion and the silica dispersion were mixed and reacted. After the reaction was completed, the solid phase was collected.

[0035] The solid phase was calcined to obtain a silicon dioxide / titanium dioxide mixture.

[0036] According to some embodiments of this application, the titanate ester includes tetraisopropyl titanate.

[0037] According to some embodiments of this application, the calcination temperature is 400℃~500℃.

[0038] According to some embodiments of this application, the calcination time is 1h to 3h.

[0039] According to some embodiments of this application, the method for preparing the sulfonic acid-modified zirconium phosphate includes the following steps:

[0040] S01. Amine-modified zirconium phosphate is prepared by mixing zirconium phosphate, allylamine and solvent and reacting them.

[0041] S02, amine-modified zirconium phosphate, sodium styrene sulfonate, initiator and solvent are mixed and reacted; after the reaction is completed, acidification is performed.

[0042] According to some embodiments of this application, the mass-to-volume ratio of zirconium phosphate and allylamine is 1g:5mL~10mL.

[0043] According to some embodiments of this application, the temperature of the reaction in step S01 is 20°C to 30°C.

[0044] According to some embodiments of this application, the reaction time in step S01 is 10h to 30h.

[0045] According to some embodiments of this application, the mass ratio of the amine-modified zirconium phosphate and sodium styrene sulfonate is 1:10~20.

[0046] According to some embodiments of this application, the reaction temperature in step S02 is 60°C to 70°C.

[0047] According to some embodiments of this application, the reaction time in step S02 is 10h to 30h.

[0048] According to some embodiments of this application, the zirconium phosphate is plate-shaped zirconium phosphate.

[0049] According to some embodiments of this application, the method for preparing the sheet-like zirconium phosphate includes the following steps:

[0050] The mixture of zirconium salt, phosphoric acid, and water is hydrothermally heated.

[0051] According to some embodiments of this application, the temperature of the hydrothermal system is 160°C to 200°C.

[0052] According to some embodiments of this application, the hydrothermal time is 60h~80h.

[0053] According to some embodiments of this application, the acidification is achieved by adjusting the pH to below 1 using an acid.

[0054] According to some embodiments of this application, the acid includes at least one of hydrogen chloride and sulfuric acid.

[0055] The third aspect of this application provides the application of the aforementioned proton exchange membrane in the preparation of an electrolyzer.

[0056] According to one of the technical solutions in this application, at least the following beneficial effects exist:

[0057] In this application, the modified inorganic particles are selected from sulfonic acid modified silica / titanium dioxide and sulfonic acid modified zirconium phosphate. The surface of the modified inorganic particles has a strongly hydrophilic and strongly polar interface layer, which realizes the matching between the inorganic particles and the perfluorosulfonic acid resin matrix.

[0058] The surface of sulfonic acid modified zirconium phosphate has sulfonic acid groups, which further expand the proton conduction network of perfluorosulfonic acid resin, thereby improving proton conductivity; and zirconium phosphate is in the form of plates, which can provide a fast conduction path for protons, further improving proton conductivity.

[0059] Sulfonic acid-modified silica / titanium dioxide has a certain hydration effect, which binds water molecules and can improve the proton conduction capacity of the interface. At the same time, it can also provide a certain amount of moisture supply to perfluorosulfonic acid resin and sulfonic acid-modified zirconium phosphate, thereby maintaining the stability of the proton conduction network.

[0060] In sulfonic acid-modified silica / titanium dioxide and sulfonic acid-modified zirconium phosphate, the rigid silica / titanium dioxide particles act as physical crosslinking points, effectively limiting polymer chain slippage and creep. The lamellar zirconium phosphate, as a two-dimensional reinforcing phase, binds tightly to the polymer chains, further enhancing the stability of the proton exchange membrane. Detailed Implementation

[0061] To make the objectives, technical solutions, and advantages of this application clearer, the following description and illustration are provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application. All other embodiments obtained by those skilled in the art based on the embodiments provided in this application without inventive effort are within the scope of protection of this application.

[0062] Obviously, the following description is merely some examples or embodiments of this application. Those skilled in the art can apply this application to other similar scenarios without any inventive effort. Furthermore, it is understood that although the effort involved in such development may be complex and lengthy, for those skilled in the art related to the content disclosed in this application, any changes to design, manufacturing, or production based on the technical content disclosed in this application are merely conventional technical means and should not be construed as insufficient disclosure of the content of this application.

[0063] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0064] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0065] The method for preparing silicon dioxide / titanium dioxide in the embodiments of this application consists of the following steps:

[0066] S1. A silica dispersion was prepared by ultrasonically dispersing a mixture of silica (D50 of 100 nm) and ethanol (mass-volume ratio of silica to ethanol of 1 g: 100 mL) for 30 min.

[0067] Tetraisopropyl titanate and ethanol (volume ratio of tetraisopropyl titanate to ethanol is 1:10) were mixed and then acetic acid (volume ratio of acetic acid to ethanol is 1:25) was added. The mixture was stirred for 5 minutes to obtain a titanate dispersion.

[0068] S2. Add the titanate dispersion dropwise to the silica dispersion (dropping rate is 2 mL / min). Stir (800 rpm) and use nitrogen protection during the dropwise addition. After the dropwise addition is completed, react at 25°C for 6 h. After the reaction is completed, collect the solid phase, wash and dry it, and then calcine it. After calcine, cool it to 25°C.

[0069] The calcination heating rate was 2℃ / min, the calcination holding temperature was 450℃, and the calcination holding time was 2h.

[0070] The method for preparing zirconium phosphate in this application embodiment consists of the following steps:

[0071] Zirconium oxychloride (ZrOCl2·8H2O) was mixed with water to prepare a 0.1 mol / L zirconium oxychloride solution.

[0072] Zirconium oxychloride solution was added dropwise to concentrated phosphoric acid (mass fraction of 85%, molar ratio of phosphoric acid to zirconium of 10:1), and after the addition was completed, the mixture was subjected to hydrothermal reaction at 180℃ for 72 h.

[0073] After the reaction is complete, the solid and liquid phases are separated, the solid phase is collected, washed, and dried.

[0074] Example 1

[0075] This embodiment describes a method for preparing a proton exchange membrane, comprising the following steps:

[0076] S1. The perfluorosulfonic acid resin dispersion (Aquivion D79-25BS, 25wt%) was mixed with ethanol and stirred for 6 hours to obtain a perfluorosulfonic acid resin dispersion (mass fraction of 5%).

[0077] Sulfonic acid modified silica / titanium dioxide dispersion was prepared by ultrasonic dispersion after mixing sulfonic acid modified silica / titanium dioxide (the mass ratio of perfluorosulfonic acid resin and sulfonic acid modified silica / titanium dioxide is 100:3) and NMP for 30 min.

[0078] Sulfonic acid-modified zirconium phosphate (the mass ratio of perfluorosulfonic acid resin to sulfonic acid-modified zirconium phosphate is 100:2) and NMP were mixed and ultrasonically dispersed for 30 min to obtain a sulfonic acid-modified zirconium phosphate dispersion.

[0079] S2, sulfonic acid modified silica / titanium dioxide dispersion and sulfonic acid modified zirconium phosphate dispersion were mixed and sonicated for 15 min to obtain filler dispersion;

[0080] The filler dispersion and the perfluorosulfonic acid resin dispersion were mixed and ball-milled (300 rpm) for 4 hours. After ball milling, the mixture was allowed to stand to remove bubbles, and the casting solution was obtained.

[0081] S3. After the casting solution is coated, a wet film with a thickness of 350 μm is obtained. The wet film is then treated at 25℃ for 12 h, 35℃ for 6 h and 45℃ for 4 h in sequence to obtain a dry film.

[0082] S4. Heat-treat the dry film, and then cool it to room temperature to obtain a heat-treated dry film.

[0083] The heat treatment process is as follows:

[0084] Increase the temperature to 120℃ at a rate of 1℃ / min and maintain it at 120℃ for 1 hour;

[0085] Then increase the temperature to 140℃ at a rate of 0.5℃ / min and maintain it at 140℃ for 2 hours;

[0086] S5. Immerse the heat-treated dry film in a 1 mol / L sulfuric acid solution and keep it at 80℃ for 1 hour. Then wash and air dry naturally.

[0087] The preparation method of sulfonic acid modified silica / titanium dioxide in this embodiment is as follows:

[0088] S1. After mixing silica / titanium dioxide and toluene (mass-volume ratio of 1g:100mL), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (volume ratio of toluene of 1:50) was added, and the mixture was refluxed at 110℃ for 24h. After the reaction was completed, the solid phase was collected, washed and dried to obtain the silane-modified mixture.

[0089] S2. Mix the silane-modified mixture and acetonitrile (mass-volume ratio of 1 g: 100 mL), add 1,3-propanesulfonate lactone (mass ratio of 1.2:1 to the silane-modified mixture), and react at 50 °C for 24 h under nitrogen protection. After the reaction is complete, collect the solid phase, wash and dry it.

[0090] The preparation method of sulfonic acid modified zirconium phosphate in this embodiment is as follows:

[0091] S1. Zirconium phosphate and water (mass-volume ratio of 1g:100mL) are mixed and sonicated for 1 hour to obtain a zirconium phosphate dispersion.

[0092] Under ice-water bath conditions, allylamine was added to a zirconium phosphate dispersion (the mass-to-volume ratio of zirconium phosphate and allylamine was 1 g: 10 mL). After the addition was completed, the mixture was stirred at 25 °C for 20 h, and the solid phase was collected by centrifugation.

[0093] A amine-modified zirconium phosphate dispersion was prepared by mixing the solid phase and water (the mass-volume ratio of the solid phase and water was 1 g: 100 mL).

[0094] S2. Under a nitrogen atmosphere, sodium styrene sulfonate dispersion (1 g / mL) was added dropwise to allylamine-modified zirconium phosphate dispersion (the mass ratio of amine-modified zirconium phosphate to sodium styrene sulfonate was 1:15). After the addition was complete, the temperature was raised to 65°C, and potassium persulfate dispersion (the mass ratio of potassium persulfate to sodium styrene sulfonate was 1:100) was added. After the addition was complete, the reaction was carried out at 65°C for 20 h. After the reaction was complete, hydrochloric acid was added to adjust the pH to 1. The solid phase was collected, washed, and dried (at 60°C).

[0095] Example 2

[0096] This embodiment describes a method for preparing a proton exchange membrane, which differs from Embodiment 1 in that:

[0097] The mass-to-volume ratio of the silica / titanium dioxide mixture and aminosilane is 1 g: 3 mL;

[0098] The mass-to-volume ratio of zirconium phosphate to allylamine is 1 g: 5 mL;

[0099] The mass ratio of sulfonic acid modified silica / titanium dioxide to perfluorosulfonic acid resin is 1:100.

[0100] Example 3

[0101] This embodiment describes a method for preparing a proton exchange membrane, which differs from Embodiment 1 in that:

[0102] The mass-to-volume ratio of the silica / titanium dioxide mixture and aminosilane is 1 g: 1 mL;

[0103] The mass-to-volume ratio of zirconium phosphate to allylamine is 1 g: 10 mL.

[0104] Example 4

[0105] This embodiment describes a method for preparing a proton exchange membrane, which differs from Embodiment 1 in that:

[0106] Replace N-(2-aminoethyl)-3-aminopropyltrimethoxysilane with 3-aminopropyltriethoxysilane (in equal amounts).

[0107] Example 5

[0108] This embodiment describes a method for preparing a proton exchange membrane, which differs from Embodiment 1 in that:

[0109] The mass-to-volume ratio of the silica / titanium dioxide mixture and aminosilane is 1 g: 2.4 mL;

[0110] The mass-to-volume ratio of zirconium phosphate to allylamine is 1 g: 8 mL;

[0111] The mass ratio of sulfonic acid modified silica / titanium dioxide to perfluorosulfonic acid resin is 5:100.

[0112] Comparative Example 1

[0113] This comparative example illustrates a method for preparing a proton exchange membrane, comprising the following steps:

[0114] S1. Mix the perfluorosulfonic acid resin dispersion (Aquivion D79-25BS, 25wt%) with ethanol and stir for 6 hours to obtain a perfluorosulfonic acid resin dispersion (mass fraction of 5%). Let it stand to remove bubbles and obtain a casting solution.

[0115] S2. After the casting solution is coated, a wet film with a thickness of 350 μm is obtained. The wet film is then treated at 25℃ for 12 h, 35℃ for 6 h and 45℃ for 4 h in sequence to obtain a dry film.

[0116] S3. Heat-treat the dry film, and then cool it to room temperature to obtain a heat-treated dry film.

[0117] The heat treatment process is as follows:

[0118] Increase the temperature to 120℃ at a rate of 1℃ / min and maintain it at 120℃ for 1 hour;

[0119] Then increase the temperature to 140℃ at a rate of 0.5℃ / min and maintain it at 140℃ for 2 hours;

[0120] S4. Immerse the heat-treated dry film in a 1 mol / L sulfuric acid solution and keep it at 80℃ for 1 hour. Then wash and air dry naturally.

[0121] Comparative Example 2

[0122] This comparative example describes a method for preparing a proton exchange membrane, which differs from Example 4 in that:

[0123] Replace the sulfonic acid modified silica / titanium dioxide with silica / titanium dioxide.

[0124] Comparative Example 3

[0125] This comparative example is a method for preparing a proton exchange membrane, consisting of the following steps: The difference from Example 4 is that:

[0126] Sulfonic acid-modified zirconium phosphate was replaced with zirconium phosphate.

[0127] Comparative Example 4

[0128] This comparative example is a method for preparing a proton exchange membrane, consisting of the following steps: The difference from Example 4 is that:

[0129] Replace sulfonic acid modified silica / titanium dioxide with silica / titanium dioxide;

[0130] Sulfonic acid-modified zirconium phosphate was replaced with zirconium phosphate.

[0131] Comparative Example 5

[0132] This comparative example is a method for preparing a proton exchange membrane, consisting of the following steps: The difference from Example 4 is that sulfonic acid-modified zirconium phosphate is not added.

[0133] Comparative Example 6

[0134] This comparative example is a method for preparing a proton exchange membrane, consisting of the following steps: The difference from Example 4 is that sulfonic acid-modified silica / titanium dioxide is not added.

[0135] The proton exchange membrane (mass m0) was soaked in deionized water at 80℃ for 72h. The soaked membrane was then dried at 80℃ for 8h (mass m1). Hydrolytic stability = (m1-m0) / m0×100%.

[0136] Proton conductivity test: The test was conducted at a temperature of 25℃ and a humidity of 100% RH. The test results are shown in Table 1.

[0137]

[0138] In Comparative Example 1, no inorganic filler was used for modification, resulting in limited water retention capacity. In particular, the water evaporated easily under low humidity, leading to rapid degradation of the proton conduction network and low proton conductivity.

[0139] In Comparative Example 2, only zirconium phosphate was modified. The unmodified silica / titanium dioxide readily agglomerated in the casting solution and also agglomerated with the modified zirconium phosphate, resulting in a discontinuous proton conduction network formed by the perfluorosulfonic acid resin dispersion, thus affecting the proton conductivity.

[0140] In Comparative Example 3, only silica / titanium dioxide was modified without the addition of modified zirconium phosphate, which resulted in the formation of inert insulating particles in the film, leading to a decrease in proton conductivity.

[0141] In Comparative Example 4, both unmodified fillers were incompatible with the polymer matrix, resulting in severe multiphase separation and filler agglomeration during the composite process. The agglomerated inorganic particles severely disrupted the continuous phase for proton conduction, leading to a significant decrease in electrical conductivity.

[0142] In Comparative Example 5, the absence of sulfonic acid-modified zirconium phosphate resulted in a smaller proton conduction network, leading to a decrease in proton conductivity.

[0143] In Comparative Example 6, no sulfonic acid-modified silica / titanium dioxide was added, and the water-retaining network provided by sulfonic acid-modified silica / titanium dioxide was absent, resulting in a decrease in proton conductivity.

[0144] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A proton exchange membrane, characterized in that, Including perfluorosulfonic acid resins and modified inorganic particles; The modified inorganic particles include sulfonic acid modified silica / titanium dioxide and sulfonic acid modified zirconium phosphate; The raw materials for preparing the sulfonic acid modified silica / titanium dioxide include: Silica, titanate, aminosilane and 1,3-propanesulfonate lactone; The raw materials for preparing the sulfonic acid-modified zirconium phosphate include: Zirconium phosphate, allylamine, and styrene sulfonate; The mass ratio of the modified inorganic particles to the perfluorosulfonic acid resin is 0.01~0.1:1; The mass ratio of the sulfonic acid-modified silica / titanium dioxide to the perfluorosulfonic acid resin is 0.01~0.05:1; The mass ratio of the sulfonic acid-modified zirconium phosphate to the perfluorosulfonic acid resin is 0.01~0.05:1; The mass ratio of sulfonic acid modified silica / titanium dioxide to sulfonic acid modified zirconium phosphate is 0.5~3:1; The method for preparing the sulfonic acid modified silica / titanium dioxide includes the following steps: S1. A mixture of silica / titanium dioxide, aminosilane, and solvent is mixed and refluxed to obtain a silane-modified mixture; S2. The silane-modified mixture, 1,3-propanesulfonic acid lactone, and solvent are mixed and reacted. The method for preparing the sulfonic acid-modified zirconium phosphate includes the following steps: S01. Amine-modified zirconium phosphate is prepared by mixing zirconium phosphate, allylamine and solvent and reacting them. S02, amine-modified zirconium phosphate, sodium styrene sulfonate, initiator and solvent are mixed and reacted; after the reaction is completed, acidification is performed.

2. A method for preparing a proton exchange membrane as described in claim 1, comprising the following steps: Modified inorganic particles, perfluorosulfonic acid resin and solvent were mixed and ball-milled to obtain a casting solution; The casting solution is cast into a film and then dried.

3. The preparation method according to claim 2, characterized in that, The solvents include ethanol, NMP, and water; The drying temperature is 100℃~150℃; The drying time is 1 hour to 5 hours.

4. The preparation method according to claim 2, characterized in that, In step S1, the mass-to-volume ratio of the silica / titanium dioxide mixture and aminosilane is 1 g: 1 mL to 3 mL; The reflux reaction temperature in step S1 is 100℃~120℃; The reflux reaction time in step S1 is 20h~30h; The mass ratio of the silane-modified mixture and 1,3-propanesulfonic acid lactone in step S2 is 1:1~2; The reaction temperature in step S2 is 40℃~60℃; The reaction time in step S2 is 20h~30h.

5. The preparation method according to claim 4, characterized in that, A silica dispersion was prepared by mixing silica and ethanol. A titanate dispersion was prepared by mixing titanate, ethanol and acetic acid; The titanate dispersion and the silica dispersion were mixed and reacted. After the reaction was completed, the solid phase was collected. The solid phase was calcined to obtain a silicon dioxide / titanium dioxide mixture; The calcination temperature is 400℃~500℃; The calcination time is 1 hour to 3 hours.

6. The preparation method according to claim 2, characterized in that, The mass-to-volume ratio of zirconium phosphate to allylamine is 1g:5mL~10mL; The reaction temperature in step S01 is 20℃~30℃; The reaction time in step S01 is 10h~30h; The zirconium phosphate is plate-shaped zirconium phosphate.

7. The preparation method according to claim 6, characterized in that, The mass ratio of the amine-modified zirconium phosphate to sodium styrene sulfonate is 1:10~20; The reaction temperature in step S02 is 60℃~70℃; The reaction time in step S02 is 10h to 30h.

8. The application of the proton exchange membrane as described in claim 1 in the preparation of an electrolyzer.

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