Proton exchange membrane with semi-interpenetrating polymer network structure and preparation method

Abstract

The invention is applicable to the technical field of fuel cells, and provides a proton exchange membrane with a semi-interpenetrating polymer network structure and a preparation method thereof, and the preparation method comprises the following steps: step (1), synthesizing 4-methyl-N-toluenesulfonyl benzenesulfonamide MBSI; step (2), synthesizing 4, 4 '-[imino bis (sulfonyl)] dibenzoic acid CBSI; (3) performing synthesis amidation reaction to generate a bis (sulfonyl) imidogroup modified silane coupling agent ACA: dissolving CBSI in the step (2) in a proper amount of a mixed solution of Py, TPP and NMP, adding a proper amount of LiCl, adding an amino silane coupling agent after complete dissolution, slowly heating the mixed solution to 120 DEG C, and stirring in nitrogen for 36 hours to generate the bis (sulfonyl) imidogroup modified silane coupling agent ACA; and (4) preparing the proton exchange membrane. The prepared composite membrane has excellent proton conductivity and good mechanical performance, the chemical stability of the membrane is obviously improved, and the performance requirement of the proton exchange membrane of the fuel cell is met.

Description

Technical Field

[0001] This invention relates to the field of fuel cell technology, specifically to a proton exchange membrane with a semi-interpenetrating polymer network structure and its preparation method. Background Technology

[0002] Polybenzimidazole (PBI) polymer is an engineering plastic with excellent thermal stability, good mechanical properties, and superior proton conductivity and chemical stability at high temperatures, making it valuable for applications in fuel cells, aerospace, chemical machinery, protective clothing, and other fields.

[0003] For PBI to be officially applied in fuel cells, it needs to be doped with phosphoric acid (PA). PA-doped PBI membranes (PA-PBI) exhibit excellent proton conductivity and stability under high-temperature, anhydrous conditions. Under anhydrous conditions, proton conduction in the PA-PBI system mainly follows the Grotthuss mechanism, with protons hopping and conducting within the hydrogen bond network of PA-PBI. High levels of phosphoric acid doping (ADL) can achieve even better proton conductivity, but it also introduces two major problems:

[0004] (1) Decreased mechanical properties: A large number of PA molecules enter the polymer chain, which will destroy the original hydrogen bonding and weaken the intermolecular interaction force, resulting in a significant deterioration of mechanical properties;

[0005] (2) PA leaching: During the operation of the fuel cell, PA molecules migrate and are lost under the influence of water molecules. The proton conductivity decreases as PA is lost, which in turn affects the overall performance of the battery.

[0006] Therefore, it is urgent to develop a PBI membrane with high proton conductivity, good mechanical strength and excellent chemical stability to meet the needs of applications such as fuel cells. Summary of the Invention

[0007] The purpose of this invention is to provide a proton exchange membrane with a semi-interpenetrating polymer network structure and its preparation method, so as to provide a proton exchange membrane with excellent proton conductivity and antioxidant properties, good mechanical properties, and which can be used as a proton exchange membrane for fuel cells to block the positive and negative electrodes.

[0008] To achieve the above objectives, the present invention provides the following technical solution: The first aspect of the present invention provides a method for preparing a proton exchange membrane with a semi-interpenetrating polymer network structure, comprising the following steps:

[0009] Step (1), synthesis of 4-methyl-N-toluenesulfonylbenzenesulfonamide MBSI:

[0010] p-Toluenesulfonylamine was added to a two-necked flask, along with an appropriate amount of deionized water and sodium hydroxide. The mixture was heated and stirred until the solution became clear and transparent. Then, p-toluenesulfonyl chloride was added, and the mixture was heated and stirred for several hours. After cooling and filtration, the pH of the filtrate was adjusted to 7 using an appropriate amount of acidic solution. The filtrate residue was collected and dried to obtain the product 4-methyl-N-toluenesulfonylbenzenesulfonamide MBSI.

[0011] Step (2), synthesis of 4,4'-[iminobis(sulfonyl)]bisbenzoic acid CBSI:

[0012] Add MBSI from step (1) to a two-necked flask, add an appropriate amount of deionized water and sodium hydroxide, heat and stir until the solution is clear and transparent, add an appropriate amount of oxidant, filter and collect the filtrate after the reaction is complete, adjust the pH of the filtrate to 7 with an appropriate amount of acidic solution, filter the solution and dry it to obtain the product 4,4'-[iminobis(sulfonyl)]bisbenzoic acid CBSI;

[0013] Step (3): The amidation reaction is used to generate the bis(sulfonyl)imide-modified silane coupling agent ACA.

[0014] Dissolve CBSI from step (2) in a suitable amount of a mixed solution of Py, TPP and NMP, and add a suitable amount of LiCl. After complete dissolution, add aminosilane coupling agent, slowly heat the mixed solution to 120°C, and stir under nitrogen for 36 hours. The reactants undergo an amidation reaction to generate bis(sulfonylimide) modified silane coupling agent ACA.

[0015] Step (4), prepare the proton exchange membrane:

[0016] Polyether polybenzimidazole OPBI was dissolved in a polar solvent. After complete dissolution, ACA was added, and the mixture was stirred and coated into a membrane. The membrane was then immersed in an acidic aqueous solution at 100°C to promote the formation of a semi-interpenetrating polymer network. The membrane was then removed, washed with water, and dried to obtain a polybenzimidazole matrix ion exchange membrane with a bis(sulfonylimide) siloxane semi-interpenetrating polymer network structure.

[0017] The mixed mass percentage of OPBI and ACA includes, but is not limited to, 10ACA / 90OPBI, 25ACA / 75OPBI, 40ACA / 60OPBI, and 50ACA / 50OPBI.

[0018] Preferably, the reaction temperature for preparing MBSI in step (1) is 70-95℃, and the reaction time is controlled at 8-12h.

[0019] Preferably, in step (1), the molar ratio of amide to acyl chloride is 2:1.

[0020] Preferably, the oxidant in step (2) includes, but is not limited to, one or more of potassium permanganate, potassium dichromate, potassium chlorate, and hydrogen peroxide.

[0021] Preferably, the aminosilane coupling agent in step (3) includes, but is not limited to, one or more of 3-aminopropyltriethoxysilane, N1-(3-(trimethoxysilyl)propyl)ethane-1,2-diamine, and N-aminoethyl-3-aminopropylmethyldimethoxysilane.

[0022] Preferably, the polar solvent in step (4) includes, but is not limited to, one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

[0023] Preferably, the acidic solution in step (4) includes, but is not limited to, one or more of the following: formic acid aqueous solution, acetic acid aqueous solution, sulfuric acid aqueous solution, sulfurous acid aqueous solution, and hydrochloric acid aqueous solution.

[0024] A second aspect of the present invention provides a proton exchange membrane having a semi-interpenetrating polymer network structure, which is prepared by the method described in the first aspect of the present invention.

[0025] The present invention has at least the following beneficial effects:

[0026] This invention provides a proton exchange membrane with a semi-interpenetrating polymer network structure and a preparation method thereof. The resulting composite membrane has excellent proton conductivity and good mechanical properties, while the chemical stability of the membrane is significantly improved, meeting the performance requirements of proton exchange membranes for fuel cells. Attached Figure Description

[0027] Figure 1 This is a flowchart illustrating the preparation process of OPBI / ACA in Example 1 of the present invention;

[0028] Figure 2 The FT-IR spectrum of ACA in Example 1 of this invention;

[0029] Figure 3 The FTIR spectra of OPBI and OPBI / ACA in Embodiment 1 of the present invention;

[0030] Figure 4 This is a SEM image of OPBI / ACA in Embodiment 1 of the present invention;

[0031] Figure 5 This is a graph showing the conductivity-electrochemical stability-temperature curves of OPBI / ACA after phosphoric acid doping in Example 1 of the present invention.

[0032] Figure 6 This is a graph showing the mechanical properties of OPBI / ACA before phosphoric acid doping in Example 1 of the present invention.

[0033] Figure 7 This is a graph showing the mechanical properties of OPBI / ACA after phosphoric acid doping in Example 1 of the present invention. Detailed Implementation

[0034] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. 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.

[0035] Example 1

[0036] like Figure 1 As shown, this embodiment provides a method for preparing a proton exchange membrane with a semi-interpenetrating polymer network structure, including the following steps:

[0037] (1) Weigh a certain amount of p-toluenesulfonylamine and add it to a two-necked flask. Add an appropriate amount of deionized water and sodium hydroxide. Stir at 70°C until the drug is completely dissolved and the solution is clear and transparent. Add p-toluenesulfonyl chloride and keep the temperature and continue heating and stirring for 12 hours. After the solution cools to room temperature, filter it. Adjust the pH of the filtrate to about 7 with dilute hydrochloric acid solution and then filter the solution. After drying, collect the product 4-methyl-N-toluenesulfonylbenzenesulfonamide (MBSI).

[0038] (2) Add the product obtained in (1) to a two-necked flask, add deionized water and sodium hydroxide, stir at 70°C, and after the drug is completely dissolved and the solution is clear and transparent, add potassium permanganate as an oxidant. After the solution turns from purple-red to brown, filter and collect the filtrate. Adjust the pH of the filtrate to about 7 with dilute hydrochloric acid solution, filter the solution, dry it and collect the product 4,4'-[iminobis(sulfonyl)]bisbenzoic acid (CBSI).

[0039] (3) CBSI and LiCl were dissolved in a mixed solution of Py, TPP and NMP. Then, the aminosilane coupling agent 3-aminopropyltriethoxysilane (ATPES) was dissolved in 20 ml of NMP and added dropwise to the CBSI solution prepared above. The mixed solution was slowly heated to 120 °C and mechanically stirred under nitrogen for 36 hours to synthesize 4,4-bis(triethoxysilylacetamido)bisbenzenesulfonylimide (ACA) through the amidation reaction of CBSI and ATPES.

[0040] (4) Dissolve polyether polybenzimidazole (OPBI) in the polar solvent N,N-dimethylacetamide (DMAC). After complete dissolution, add ACA, stir and mix evenly, and then coat the mixture into a membrane. Immerse the membrane in a 1 mol / L formic acid solution and place it in a 100℃ oven for 24 h to promote the formation of a semi-interpenetrating polymer network. Dry and remove moisture to obtain a polybenzimidazole matrix quantum exchange membrane with a bis(sulfonyl)imide siloxane type semi-interpenetrating polymer network structure, denoted as OPBI / ACA composite membrane.

[0041] Example 2

[0042] This embodiment provides a method for preparing a proton exchange membrane with a semi-interpenetrating polymer network structure, including the following steps:

[0043] (1) Weigh a certain amount of p-toluenesulfonylamine and add it to a two-necked flask. Add an appropriate amount of deionized water and sodium hydroxide. Stir at 85°C until the drug is completely dissolved and the solution is clear and transparent. Add p-toluenesulfonyl chloride and keep the temperature and continue heating and stirring for 10 hours. After the solution cools to room temperature, filter it. Adjust the pH of the filtrate to about 7 with dilute hydrochloric acid solution and then filter the solution. After drying, collect the product MBSI.

[0044] (2) Add the product obtained in (1) to a two-necked flask, add deionized water and sodium hydroxide, stir at 70°C, and after the drug is completely dissolved and the solution is clear and transparent, add potassium permanganate. After the solution turns from purple-red to brown, filter and collect the filtrate. Adjust the pH of the filtrate to about 7 with dilute hydrochloric acid solution, filter the solution, dry it and collect the product CBSI.

[0045] (3) CBSI and LiCl were dissolved in a mixed solution of Py, TPP and NMP. Then, 3-aminopropyltriethoxysilane (ATPES) was dissolved in 20 ml of NMP and added dropwise to the CBSI solution prepared above. The mixed solution was slowly heated to 120 °C and mechanically stirred under nitrogen for 36 hours to synthesize (NACA) monomer through the amidation reaction of CBSI and N-[3-(trimethoxysilyl)propyl]ethylenediamine.

[0046] (4) Dissolve polyether polybenzimidazole (OPBI) in N,N-dimethylacetamide (DMAC). After complete dissolution, add NACA, stir and mix evenly, and then coat the mixture into a membrane. Immerse the membrane in a 1 mol / L formic acid solution and place it in a 100℃ oven for 24 h to promote the formation of a semi-interpenetrating polymer network. Dry and remove moisture to obtain a polybenzimidazole matrix quantum exchange membrane with a bis(sulfonyl)imide siloxane type semi-interpenetrating polymer network structure, denoted as OPBI / ACA composite membrane.

[0047] Example 3

[0048] This embodiment provides a method for preparing a proton exchange membrane with a semi-interpenetrating polymer network structure, including the following steps:

[0049] (1) Weigh a certain amount of p-toluenesulfonylamine and add it to a two-necked flask. Add an appropriate amount of deionized water and sodium hydroxide. Stir at 95°C until the drug is completely dissolved and the solution is clear and transparent. Add p-toluenesulfonyl chloride and keep the temperature and continue heating and stirring for 8 hours. After the solution cools to room temperature, filter it. Adjust the pH of the filtrate to about 7 with dilute hydrochloric acid solution and then filter the solution. After drying, collect the product MBSI.

[0050] (2) Add the product obtained in (1) to a two-necked flask, add deionized water and sodium hydroxide, stir at 70°C, and after the drug is completely dissolved and the solution is clear and transparent, add potassium permanganate. After the solution turns from purple-red to brown, filter and collect the filtrate. Adjust the pH of the filtrate to about 7 with dilute hydrochloric acid solution, filter the solution, dry it and collect the product CBSI.

[0051] (3) CBSI and LiCl were dissolved in a mixed solution of Py, TPP and NMP. Then, 3-aminopropyltriethoxysilane (ATPES) was dissolved in 20 ml of NMP and added dropwise to the CBSI solution prepared above. The mixed solution was slowly heated to 120 °C and mechanically stirred under nitrogen for 36 hours to synthesize (NCA) monomer through the amidation reaction of CBSI and N-aminoethyl-3-aminopropylmethyldimethoxysilane.

[0052] (4) Dissolve polyether polybenzimidazole (OPBI) in N,N-dimethylacetamide (DMAC). After complete dissolution, add NACA, stir and mix evenly, and then coat the mixture into a membrane. Immerse the membrane in a 1 mol / L formic acid solution and place it in a 100℃ oven for 24 h to promote the formation of a semi-interpenetrating polymer network. Dry and remove moisture to obtain a polybenzimidazole matrix quantum exchange membrane with a bis(sulfonyl)imide siloxane type semi-interpenetrating polymer network structure, denoted as OPBI / ACA composite membrane.

[0053] Example 4

[0054] This embodiment provides a method for preparing a proton exchange membrane with a semi-interpenetrating polymer network structure, which is the same as in Embodiment 1, except that:

[0055] (2) The oxidant is potassium dichromate; (3) The aminosilane coupling agent is N1-(3-(trimethoxysilyl)propyl)ethane-1,2-diamine; (4) The polar solvent is N,N-dimethylformamide; (4) The formic acid aqueous solution is replaced by the acetic acid aqueous solution.

[0056] Example 5

[0057] This embodiment provides a method for preparing a proton exchange membrane with a semi-interpenetrating polymer network structure, which is the same as in Embodiment 1, except that:

[0058] (2) The oxidant is potassium chlorate; (3) The aminosilane coupling agent is N-aminoethyl-3-aminopropylmethyldimethoxysilane; (4) The polar solvent is dimethyl sulfoxide; (4) The formic acid aqueous solution is replaced by sulfuric acid aqueous solution.

[0059] Example 6

[0060] This embodiment provides a method for preparing a proton exchange membrane with a semi-interpenetrating polymer network structure, which is the same as in Embodiment 1, except that:

[0061] (2) The oxidant is hydrogen peroxide; (3) The aminosilane coupling agent is N-aminoethyl-3-aminopropylmethyldimethoxysilane; (4) The polar solvent is N-methylpyrrolidone; (4) The formic acid aqueous solution is replaced by a mixture of sulfurous acid aqueous solution and hydrochloric acid aqueous solution, with a mixing volume ratio of 1:2.

[0062] The MBSI yield in Examples 1-6 above was 60-85%. A series of related performance tests were performed on the product prepared in Example 1 above, and the results are as follows:

[0063] 1. Structural characterization of ACA:

[0064] The structure of ACA was characterized by FT-IR spectroscopy, and the test results are as follows: Figure 2 As shown, the characteristic peak of the stretching vibration of the NH bond is at 3329 cm⁻¹. -1 The characteristic peak of the elastic vibration of the NH bond is visible at 1538 cm⁻¹. -1 It appears at 844cm. -1 The characteristic peak is the methylene (-CH) in the ACA molecule. 2- The vibrational peaks of the infrared spectrum indicate that ACA was successfully prepared.

[0065] 2. Structural characterization of proton exchange membranes:

[0066] 2.1 The structure of the OPBI / ACA composite membrane was characterized by FT-IR, and the test results are as follows: Figure 3 As shown. By comparing the FT-IR spectra of OPBI, it was found that the composite film spectrum is at 1073 cm⁻¹. -1 The appearance of a new characteristic vibration peak at 2844 cm⁻¹ indicates the formation of a Si-O-Si cross-linked structure within the composite membrane. -1 The methylene group (-CH) from the ACA molecule appeared at [location]. 2- The vibrational peaks of ACA were observed. FT-IR results indicate that ACA successfully hydrolyzed and self-crosslinked in the composite membrane to form a Si-O-Si structure.

[0067] 2.2 Surface morphology image of the proton exchange membrane as shown below Figure 4 As shown, the surface of the proton exchange membrane is rough because of the poor compatibility between the silicon-based inorganic phase and the organic polymer OPBI.

[0068] 3. Proton conductivity of OPBI / ACA:

[0069] like Figure 5 As shown, the resistance of five groups of films was tested in the temperature range of 100-200℃ under similar acid doping rates. The test results show that in the 100-160℃ temperature range, the proton conductivity of all films increases due to the accelerated migration rate of phosphate ions with increasing temperature. However, in the 160-200℃ temperature range, the proton conductivity of the film decreases due to the polymerization reaction between phosphate molecules to form oligomers. Under similar phosphate doping rates, the conductivity of four composite films is significantly improved compared to pure OPBI films in all temperature ranges, with the 50ACA / 50OPBI composite film exhibiting the highest proton conductivity. The self-crosslinked bis(sulfonyl)imide-based siloxane proton conductor provides additional protons within the OPBI / ACA composite film while enhancing the hydrogen bond network, which facilitates proton conduction within the composite film through hydrogen bond breaking and recombination.

[0070] 4. Mechanical properties of OPBI / ACA:

[0071] like Figure 6 , Figure 7 As shown, the mechanical properties of the OPBI / ACA composite film before and after phosphoric acid doping were tested.

[0072] Before acid doping, the elongation at break of the composite membrane initially increased and then decreased with the deepening of ACA self-crosslinking. This indicates that within a certain range, the semi-interpenetrating crosslinked network structure formed by the self-crosslinking of bissulfimide siloxane and OPBI polymer possesses good molecular chain flexibility, allowing it to withstand greater deformation without fracture under external force. The tensile strength of all composite membranes decreased because of the poor compatibility between the silicon-based inorganic phase and the OPBI polymer organic phase, resulting in structural defects in the composite membrane as a whole, which became more pronounced with increasing ACA content.

[0073] After doping, due to the plasticizing effect of phosphoric acid on the polymer, the elongation at break of all films significantly increased, while the tensile strength significantly decreased. The semi-interpenetrating cross-linked network structure enhanced the molecular chain flexibility of the acid-doped composite film, resulting in a higher elongation at break compared to the pure OPBI film. Under a certain degree of ACA self-crosslinking, the acid-doped composite film exhibited higher tensile strength than the OPBI film. This is because the tight semi-interpenetrating cross-linked network structure limited the dimensional changes of the film after phosphoric acid doping. Simultaneously, the presence of the silicon-based inorganic phase limited the plasticizing effect of phosphoric acid on the film to some extent, enhancing the resistance of the OPBI / ACA composite film to external forces, which possesses excellent dimensional stability. However, with increasing ACA content, the compatibility between the organic and inorganic phases within the composite film gradually deteriorated, leading to a decrease in the overall compatibility. Figure 4 SEM images showed a significantly deepened inorganic phase aggregation on the membrane surface, even exhibiting structural damage. Consequently, the mechanical properties of the membrane significantly decreased after phosphate doping. Overall, the semi-interpenetrating network structure formed by the in-situ self-crosslinking of a certain amount of bis(sulfonyl)imide-based siloxane and the OPBI polymer can enhance the mechanical properties of the composite membrane, meeting the HTPEM mechanical property requirements.

[0074] In summary, this invention synthesizes CBSI and prepares bissulfimide-modified silane coupling agents with different structures through an amidation reaction with an amino-type silane coupling agent. These modified silane coupling agents are then blended with polybenzimidazole to form a membrane, which is then subjected to an acidic environment to promote the formation of a semi-interpenetrating polymer network. Finally, after washing and drying, a polybenzimidazole-based proton exchange membrane with a bissulfimide-siloxane semi-interpenetrating polymer network structure is obtained. Compared with existing polybenzimidazole proton exchange membranes, the composite membrane of this invention exhibits excellent proton conductivity and good mechanical properties, while significantly improving the membrane's chemical stability, thus meeting the performance requirements of fuel cell proton exchange membranes.

[0075] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or basic characteristics. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0076] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for producing a proton exchange membrane having a semi-interpenetrating polymer network structure, characterized by, Comprising the following steps: Step (1), synthesis of 4-methyl-N-tosylbenzenesulfonamide MBSI: The p-toluenesulfonamide is added to a two-necked flask, and an appropriate amount of deionized water and sodium hydroxide is added. After the solution is clear and transparent, p-toluenesulfonamide is added, and the mixture is continuously heated and stirred for several hours, then cooled and filtered. The filtrate is adjusted to pH 7 using an appropriate amount of acidic solution, and the filtrate is collected and dried to obtain the product 4-methyl-N-tosylbenzenesulfonamide MBSI. Step (2), synthesis of 4,4'-[imino bis(sulfonyl)] dibenzoic acid CBSI: The MBSI from step (1) is added to a two-necked flask, and an appropriate amount of deionized water and sodium hydroxide is added. After the solution is clear and transparent, an appropriate amount of oxidizing agent is added, and the mixture is filtered after the reaction is complete. The filtrate is adjusted to pH 7 using an appropriate amount of acidic solution, and the solution is filtered and dried to obtain the product 4,4'-[imino bis(sulfonyl)] dibenzoic acid CBSI. Step (3), synthesis of amide reaction to generate bis-sulfonimidoyl modified silane coupling agent ACA: The CBSI from step (2) is dissolved in a mixture of appropriate amounts of Py, TPP, and NMP, and an appropriate amount of LiCl is added. After complete dissolution, amino silane coupling agent is added, and the mixture is slowly heated to 120°C under nitrogen atmosphere and stirred for 36 hours. The reactants undergo amide reaction to generate bis-sulfonimidoyl modified silane coupling agent ACA. Step (4), preparation of proton exchange membrane: The polyether polybenzimidazole OPBI is dissolved in a polar solvent, and ACA is added after complete dissolution. The mixture is stirred and mixed uniformly, then coated into a film. The film is immersed in an acidic aqueous solution, and the semi-interpenetrating polymer network is generated at 100°C. The film is taken out, washed with water, and dried to obtain a polybenzimidazole-based proton exchange membrane with a semi-interpenetrating polymer network structure of bis-sulfonimidoyl siloxane. The mixing mass percentage of OPBI and ACA includes but is not limited to 10ACA / 90OPBI, 25ACA / 75OPBI, 40ACA / 60OPBI, 50ACA / 50OPBI.

2. The method of claim 1, wherein the semi-IPN proton exchange membrane is prepared by the steps of: The preparation reaction temperature of MBSI in step (1) is 70-95°C, and the reaction time is controlled at 8-12h.

3. The method of claim 1, wherein the semi-interpenetrating polymer network structure is formed by the steps of: (a) dissolving the polymer in a solvent; (b) adding the inorganic material to the polymer solution; (c) removing the solvent; and (d) drying the resulting mixture. The molar ratio of amide to acyl chloride in step (1) is 2:

1.

4. The method for preparing a proton exchange membrane with a semi-interpenetrating polymer network structure according to claim 1, characterized in that: The oxidizing agent in step (2) includes but is not limited to one or more of potassium permanganate, potassium dichromate, potassium chlorate, and hydrogen peroxide.

5. The method for preparing a proton exchange membrane with a semi-interpenetrating polymer network structure according to claim 1, characterized in that: The amino silane coupling agent in step (3) includes but is not limited to one or more of 3-aminopropyltriethoxysilane, N1-(3-(trimethoxysilyl)propyl)ethane-1,2-diamine, and N-aminoethyl-3-aminopropylmethyldimethoxysilane.

6. The method for preparing a proton exchange membrane with a semi-interpenetrating polymer network structure according to claim 1, characterized in that: The polar solvent in step (4) includes but is not limited to one or more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methyl pyrrolidone.

7. The method for preparing a proton exchange membrane with a semi-interpenetrating polymer network structure according to claim 1, characterized in that: The acidic solution in step (4) includes but is not limited to one or more of formic acid aqueous solution, acetic acid aqueous solution, sulfuric acid aqueous solution, sulfurous acid aqueous solution, and hydrochloric acid aqueous solution.

8. A proton exchange membrane having a semi-interpenetrating polymer network structure, characterized by: The proton exchange membrane is prepared by the method of any one of claims 1 to 7.

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