Cross-linked polymer-molecular cluster non-fluorine proton exchange membrane as well as preparation method and application thereof

Abstract

The invention discloses a cross-linked polymer-molecular cluster non-fluorine composite proton exchange membrane and a preparation method and application thereof, the cross-linked polymer-molecular cluster non-fluorine composite proton exchange membrane is mainly prepared from branched polyethyleneimine (PEI), polyvinyl chloride (PVC) and phosphotungstic acid (PW12), quaternized PEI and PVC are subjected to a cross-linking reaction, and then the prepared membrane is immersed in a PW12 solution to prepare the cross-linked polymer-molecular cluster non-fluorine composite proton exchange membrane. Wherein the mass ratio of the PEI to the PVC can be adjusted as required, the mass fraction of the PW12 solution is preferably 5-20%, the proton exchange membrane has good mechanical properties, thermal stability and excellent proton conductivity, and the preparation method is simple, low in cost and environmentally friendly.

Description

Technical Field

[0001] This invention relates to the field of hydrogen fuel cell technology, specifically to a cross-linked polymer-molecular cluster non-fluorinated proton exchange membrane, its preparation method, and its application. Background Technology

[0002] Currently, against the backdrop of global advocacy for energy conservation and emission reduction and China's implementation of the "dual-carbon" policy, the development and utilization of hydrogen energy has entered a phase of rapid growth. Hydrogen fuel cells have attracted widespread attention due to their cleanliness, high energy conversion efficiency, and flexible application scenarios. Proton exchange membrane (PEM) materials are one of their core components. Perfluorosulfonic acid (PFSA) membrane materials, represented by Nafion, are currently the mainstream commercial PEMs. Their chemical structure includes a hydrophobic polytetrafluoroethylene polymer backbone and hydrophilic -SO3H side chains. This unique hydrophobic-philic structure endows PFSA with microphase separation characteristics; in the hydrated state, the hydrophilic -SO3H groups can form continuous nano-transport channels, within which protons can be rapidly conducted. However, because the synthesis of perfluoropolymers and subsequent sulfonation processes require cumbersome synthetic procedures, the manufacturing cost of PFSA remains high, and there is also the potential for environmental and ecological pollution from fluorine-containing substances. Based on these factors, the large-scale application of perfluorosulfonic acid proton exchange membranes in China still faces many challenges. Therefore, developing novel non-fluorinated proton conductor materials with simplified and environmentally friendly preparation processes while ensuring high electrical conductivity is of great significance and application value.

[0003] Non-fluorinated proton exchange membranes (PEMs) have a wide and inexpensive source of materials, and their preparation and processing costs can be well controlled. Furthermore, the segmental structure design and modification of non-fluorinated polymers are relatively easy, and proton conduction in anhydrous environments can be achieved through hybridization modification, enabling stable operation of the PEM under extreme conditions such as high temperature and low humidity. However, current research investment in non-fluorinated PEM materials is limited. Commonly available products include sulfonated aromatic polymer PEMs such as sulfonated polyether ether ketone (SPEEK), sulfonated polysulfone (SPSF), and sulfonated polyether sulfone (SPES), which struggle to balance service stability and proton conductivity, resulting in overall performance improvements. The preparation of non-fluorinated PEM materials remains challenging, requiring a deeper understanding of their service microstructure and structure-property relationships during processing.

[0004] Organic-inorganic composite materials possess the unique functions of both fluorine-free polymer substrates and inorganic fillers, making them suitable for preparing novel non-fluorinated proton exchange membrane materials. Among these, phosphotungstic acid (PW) is a prime example. 12Keggin-type polyoxometalates (POMs), represented by [examples of POMs], are excellent inorganic proton conductors that can effectively enhance the proton conductivity of polymer matrices. Furthermore, as well-defined nano-metal clusters, POMs exhibit good thermal stability and redox activity. Therefore, through a simple non-covalent physical blending method, specific fluorine-free polymer matrices and POMs can be composited to prepare novel nanocomposite proton conductor materials.

[0005] Patent application number 202210657846.7 discloses a method for preparing a proton exchange membrane for a fuel cell, comprising: crosslinking a polyvinyl alcohol aqueous solution with a polyvinylimide aqueous solution of different mass fractions to form a membrane, immersing it in a heteropoly acid aqueous solution of different concentrations and then drying it; then quaternizing the crosslinked membrane; finally immersing the quaternized crosslinked membrane in a heteropoly acid aqueous solution of different concentrations and then drying it to obtain a proton exchange membrane. This invention improves the proton conductivity and its stability of the proton conductivity of the proton exchange membrane, reduces the process cost, and is suitable for large-scale production. However, excessive polyvinyl alcohol content can lead to excessive swelling of the material and cause mechanical failure. Summary of the Invention

[0006] The purpose of this invention is to provide a cross-linked polymer-molecular cluster non-fluorine composite proton exchange membrane, its preparation method and application. This proton exchange membrane has good mechanical properties, thermal stability and excellent proton conductivity, and the preparation method is simple, low-cost and environmentally friendly.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing a cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane, using branched polyethyleneimine (PEI), polyvinyl chloride (PVC), and phosphotungstic acid (PW) 12 The membrane is prepared by crosslinking quaternized branched polyethyleneimine and polyvinyl chloride, followed by immersion in a phosphotungstic acid solution. The crosslinked polymer-molecular cluster non-fluorinated composite proton exchange membrane has the following structural formula: Preferably, the PW 12 The mass fraction of the solution is 5%-20%.

[0008] PW is preferred. 12 The mass fraction of the solution can be any value within the range of 5%-20%, such as 5%, 8%, 10%, 12%, 15%, 18%, or 20%.

[0009] Preferably, the method for preparing a cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane includes the following steps: (1) Quaternization of branched polyethyleneimine: First, branched polyethyleneimine (PEI) is dissolved in dimethylformamide (DMF) solution to obtain a dilute solution with a mass fraction of 4%-6%. Bromopropane (BP) is added, and the molar ratio of bromopropane and amine groups in PEI is controlled. After reflux reaction, a bright yellow transparent QPEI solution is obtained. (2) Crosslinking reaction: Take QPEI and polyvinyl chloride (PVC) prepared in step (1) in different mass ratios and add them to the organic solvent dimethylformamide (DMF) solution. Heat and stir until the polyvinyl chloride (PVC) is completely dissolved. Continue stirring to obtain a light yellow PEI-PVC mixed solution. Remove the organic solvent from the QPEI-PVC mixed solution to obtain a uniform amber transparent crosslinked polymer film. (3) Finally, the prepared QPEI-PVC composite membrane is coated with phosphotungstic acid (PW) 12 After soaking in the aqueous solution, remove and wipe off the surface moisture, then place in a sealed bag and store at room temperature to obtain QPEI-PVC-PW. 12 Composite membrane.

[0010] In any of the above schemes, the preferred method is that in step (1), the molar ratio of amino groups in bromopropane (BP) and branched polyethyleneimine (PEI) is 1:1-3, and a bright yellow transparent QPEI solution is obtained by reflux reaction at 75℃-85℃ for 24 hours.

[0011] Specifically, the molar ratio of amino groups in BP and PEI can be any value in the range of 1:1-3, such as 1:1, 1:2, or 1:3.

[0012] In any of the above schemes, it is preferred that in step (2), polyvinyl chloride (PVC) is added to the QPEI solution so that the mass ratio of QPEI to PVC is 1:1-3, and the PVC has a K-value of 72-71.

[0013] Specifically, the mass ratio of QPEI to PVC can be any value within the range of 1:1 to 3, such as 1:1, 1:2, or 1:3.

[0014] In any of the above schemes, it is preferred that in step (2), QPEI and polyvinyl chloride (PVC) are added to the organic solvent DMF solution, the polymer (here the polymer represents the total mass fraction of QPEI+PVC) mass fraction in the solution is controlled to be below 10%, the solution is heated to 75℃-85℃ and stirred until the PVC is completely dissolved, and then the reaction is continued at 75℃-85℃ for 6 hours.

[0015] Specifically, the polymer mass fraction of the solution is controlled to be ≤10%, which can be 10%, 8%, 6%, 4%, or 2%; the heating temperature and stirring temperature can be any value within the range of 75℃-85℃, such as 75℃, 78℃, 80℃, 82℃, or 85℃.

[0016] In any of the above schemes, it is preferred that in step (2), the QPEI-PVC mixed solution is poured into a clean glass dish and vacuum dried at 75℃-85℃ for 24 hours to completely remove the organic solvent, thereby obtaining a uniform amber-colored transparent cross-linked polymer film. The vacuum drying temperature is any value within the range of 75℃-85℃, such as 75℃, 78℃, 80℃, 82℃, or 85℃.

[0017] In any of the above schemes, it is preferred that, in step (3), the prepared QPEI-PVC composite film is placed in a PW solution with a mass fraction of 5 wt%-20 wt%. 12 Soak in aqueous solution for 10-14 hours. PW 12 The aqueous solution has any mass fraction in the range of 5 wt% to 20 wt%, such as 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%.

[0018] The present invention also discloses a cross-linked polymer-molecular cluster non-fluorine composite proton exchange membrane, which is prepared by any of the preparation methods described above.

[0019] The present invention also discloses that the cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane prepared by the above method can be used in the preparation of hydrogen fuel cells. Beneficial effects

[0020] (1) This invention provides a cross-linked polymer-molecular cluster non-fluorine composite proton exchange membrane, its preparation method and application. The proton exchange membrane has good mechanical properties, thermal stability and excellent proton conductivity. The preparation method is simple, low cost and environmentally friendly.

[0021] (2) The non-fluorinated proton exchange membrane of the present invention uses PEI and PVC as substrates, and forms a stable bicontinuous polymer network structure through cross-linking reaction, and effectively reloads negatively charged PW through quaternary ammonium groups. 12 After molecular clustering, not only is the proton conductivity improved, but it also has good mechanical properties and thermal stability, which can meet the stable operation requirements of hydrogen fuel cells under extreme conditions such as high temperature and low humidity.

[0022] (3) The preparation method is simple and easy to implement, without the need for complex synthesis processes and expensive equipment. It is low in cost and the whole preparation process is green and environmentally friendly, avoiding the use of fluorine-containing compounds, which is conducive to large-scale industrial production and application.

[0023] (4) QPEI is obtained by quaternizing PEI, and then crosslinked with PVC to form QPEI-PVC film. The quaternary ammonium groups can effectively complex PW. 12 Molecular clusters further optimize the mechanical and electrical properties of the composite membrane, enabling it to exhibit higher electrical conductivity under hydration conditions, thus providing a strong guarantee for the efficient operation of hydrogen fuel cells. Attached Figure Description

[0024] Figure 1 This describes the synthetic route for QPEI-PVC crosslinked polymers. Figure 2 FT-IR spectra of PEI, QPEI, PVC, and cross-linked QPEI-PVC polymer films; Figure 3 The diagram shows the SAXS curve of the polymer membrane and the microphase separation structure of the composite membrane. Yellow represents the hydrophobic PVC component, and blue represents the hydrophilic PEI / QPEI component. Figure 4 TGA curves for PEI, PVC, and the polymer film of Example 2; Figure 5 The tensile curve of the composite membrane; Figure 6 The electrochemical impedance spectroscopy of the polymer film in Example 3 is shown. Detailed Implementation

[0025] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Example

[0026] A method for preparing a cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane, the preparation flow chart is shown below. Figure 1 As shown, the specific steps include: (1) Quaternization of PEI: 2g of PEI (Mw ~70K Da) was dissolved in 40 mL of dimethylformamide (DMF) to obtain a dilute solution with a PEI mass fraction of 5%. BP (GC, >99.0%) was added, and the molar ratio of BP to amino groups in PEI was controlled to be 1:2. The solution was refluxed at 80℃ for 24 hours to obtain a bright yellow transparent QPEI solution.

[0027] (2) Add 2g of PVC (K-value 72-71) to the QPEI solution to make the mass ratio of QPEI to PVCP 1:1. Dissolve the PVC in DMF solvent, keeping the total mass fraction of the polymer in the solution below 10%. Heat to 80 °C and stir until the PVC is completely dissolved. Continue stirring at 80 °C for 6 hours to obtain a pale yellow PEI-PVC mixed solution. Pour the QPEI-PVC mixed solution into a clean glass dish and vacuum dry at 80 °C for 24 hours to completely remove the organic solvent, obtaining a uniform amber transparent crosslinked polymer QPEI-PVC composite film.

[0028] (3) The QPEI-PVC composite film was placed in a 5 wt% PW solution. 12 After soaking in an aqueous solution for 12 hours, remove and wipe off the surface moisture, then store in a sealed bag at room temperature to obtain QPEI-PVC-PW. 12 5wt% composite membrane. Example

[0029] A method for preparing a cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane is similar to that in Example 1, except that it includes the following steps: (1) Dissolve 2g PEI (Mw ~70K Da) in dimethylformamide (DMF) to obtain a 5% dilute solution. Add BP (GC, >99.0%) and control the molar ratio of amino groups in BP and PEI to be 1:2. After refluxing at 80℃ for 24 hours, a bright yellow transparent QPEI solution is obtained.

[0030] (2) Add 2g of PVC (K-value 72-71) to the QPEI solution to make the mass ratio of QPEI to PVC 1:1. Dissolve the PVC in DMF solvent, keeping the total polymer mass fraction below 10%. Heat to 80℃ and stir until the PVC is completely dissolved. Continue stirring at 80℃ for 6 hours to obtain a pale yellow PEI-PVC mixed solution. Pour the QPEI-PVC mixed solution into a clean glass dish and vacuum dry at 80℃ for 24 hours to completely remove the organic solvent, obtaining a uniform amber transparent crosslinked polymer QPEI-PVC composite film.

[0031] (3) The QPEI-PVC composite film was placed in a PW solution with a mass fraction of 10 wt%. 12 Soak in aqueous solution for 12 hours, remove and wipe off the surface moisture, put into a sealed bag and store at room temperature to obtain QPEI-PVC 10wt% composite film.

[0032] A method for preparing a cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane includes the following steps: After drying 2g of PEI (Mw ~70K Da) under vacuum at 60℃ for 24h, 2g of PEI and 2g of PVC were added to an appropriate amount of DMF solvent, controlling the total polymer mass fraction of the solution to be 8%. The mixture was heated to 80℃ and stirred until the PVC (K-value 72-71) was completely dissolved. The reaction was then continued at 80℃ for 6 hours to obtain a pale yellow PEI-PVC mixed solution. This mixed solution was poured into a glass dish and dried under vacuum at 80℃ for 24 hours to obtain a PEI-PVC crosslinked polymer film. The PEI-PVC composite film was then subjected to a reaction in a solution containing 10 wt% PW... 12 Soak in an aqueous solution for 12 hours, remove and wipe off the surface moisture, place in a sealed bag and store at room temperature to obtain PEI-PVC-PW. 12 Composite membrane.

[0033] (1) Infrared spectra of PEI, QPEI, PVC and cross-linked QPEI-PVC polymer films are shown below. Figure 2 As shown.

[0034] Depend on Figure 2 It can be seen that, compared with the original PEI, the QPEI-PVC polymer membrane prepared by this invention can be clearly observed to retain the original absorption signal, and at 3400 cm⁻¹, the QPEI obtained can also significantly improve absorption. -1 and 1650 cm -1 R4N appeared + The characteristic absorption peak of quaternary ammonium salts, R4N + The retention of quaternary ammonium salts can effectively adsorb negatively charged PW through electrostatic interactions. 12 Molecular clusters. Simultaneously at 2912 cm⁻¹ -1 A strong absorption peak originating from bromopropane (-CH3) was observed at 696 cm⁻¹, confirming the successful preparation of QPEI. In the QPEI-PVC composite membrane, a strong absorption peak at 696 cm⁻¹ was observed. -1 The absorption peak signal of C-Cl from PVC was significantly weakened at 1238 cm⁻¹. -1 The appearance of a new absorption peak, which originates from the CN stretching vibration in the secondary amine group, indicates that a new covalent bond has been formed between QPEI and PVC, meaning that a cross-linking reaction has been successfully carried out.

[0035] (2) Small-angle X-ray scattering (SAXS) technology can be used to reflect the density difference of electron clouds in the scattering material and the surrounding medium, and to obtain the electron density fluctuations in the range of 1 to 100 nm, thereby revealing the submicron-scale structural information inside the material. The small-angle X-ray scattering (SAXS) images of the molecular cluster-polymer composite proton exchange membrane in Example 2 and the comparative molecular cluster-polymer composite proton exchange membrane are shown below. Figure 3 As shown.

[0036] Depend on Figure 3 It can be seen that in the low q region, the cross-linked polymer composite films of Example 2 and the comparative example showed scattering peaks of different intensities. Õ This demonstrates that the material structure exhibits microphase separation behavior. Therefore, it can be inferred that in the PEI-PVC crosslinked polymer composite membrane, due to the difference in hydrophilic and hydrophobic structures between the PEI and PVC components, a microphase separation structure of hydrophilic PEI and hydrophobic PVC occurs after crosslinking. Meanwhile, the composite membrane of Example 2 at 0.015 Å... -1 A more pronounced scattering signal peak q appears at this location. Õ Furthermore, the position of its scattering peak shifts further towards the lower q region, indicating that the QPEI obtained after the quaternization reaction can form a larger-scale microphase separation structure after crosslinking with PVC. The continuous hydrophilic channels of QPEI are beneficial for constructing a more efficient proton transfer pathway.

[0037] (3) The thermogravimetric analysis (TGA) curves of PEI, PVC and the molecular cluster-polymer composite proton exchange membrane of Example 2 are shown below. Figure 4 As shown.

[0038] Depend on Figure 4 It can be seen that the extrapolated decomposition initiation temperature of the molecular cluster-polymer composite proton exchange membrane and the phosphotungstic acid molecular cluster in Example 2 are both above 200℃, and both have a high decomposition temperature (>200℃), indicating that the molecular cluster-polymer composite proton exchange membrane of the present invention has excellent thermal stability.

[0039] (4) Tensile tests were performed on the molecular cluster-polymer composite proton exchange membranes of Examples 1-2 and Comparative Example 1, and the stress-strain relationship curves obtained are as follows: Figure 5 As shown, the test results of Young's modulus and elongation at break (measured by tensile testing at a tensile rate of 10 mm / min) are shown in Table 1 below: Table 1. Tensile fracture and elongation at break test results of molecular cluster-polymer composite proton exchange membranes Depend on Figure 5As shown in Table 1, the molecular cluster-polymer composite proton exchange membranes of Examples 1-2 and Comparative Example 1 have higher tensile strength and elongation at break. The composite membranes after quaternization have stronger electrostatic interactions, which increases the mechanical strength of the composite membranes.

[0040] (5) The electrochemical impedance spectroscopy results of the molecular cluster-polymer composite proton exchange membrane in Example 2 are as follows: Figure 6 As shown, (an AC potential wave with a small amplitude and different frequency is applied to the electrochemical system, and the ratio of AC potential to current signal is measured as a function of the sinusoidal wave frequency ω, or the phase angle Φ of the impedance is measured as a function of ω, and then the ionic conductivity σ of the thin film sample is calculated; the formula for calculating ionic conductivity is: σ = d / SR, where d is the thickness of the molecular cluster-polymer composite proton exchange membrane in cm, S is the electrode area in cm2, and R is the resistance obtained by AC impedance method in Ω; the conductivity test results of the molecular cluster-polymer composite proton exchange membranes of Examples 1-2 and Comparative Example 1 at 80℃ are shown in Table 2 below: Table 2 Proton conductivity of composite membranes (80℃, hydrated state) As shown in Table 2, the molecular cluster-polymer composite proton exchange membranes of Examples 1-2 and Comparative Example 1 have high electrical conductivity. The composite proton exchange membrane after PEI quaternization has a stronger adsorption capacity for PW12 molecular clusters. At the same time, the material provides a richer hydrogen bond network and proton jumping sites, thus making the material have higher electrical conductivity. The composite membrane can be used as a proton exchange membrane in fuel cells. Example

[0041] A method for preparing a cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane is similar to that in Example 1, except that the molar ratio of amine groups in BP and PEI is 1:1. Example

[0042] A method for preparing a cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane is similar to that in Example 1, except that the molar ratio of amine groups in BP and PEI is 1:3. Example

[0043] A method for preparing a cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane is similar to that in Example 1, except that the mass ratio of QPEI to PVC is 1:2. Example

[0044] A method for preparing a cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane is similar to that in Example 1, except that the mass ratio of QPEI to PVC is 1:3. Example

[0045] A method for preparing a cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane is similar to that in Example 1, except that PW 12 The aqueous solution has a mass fraction of 15 wt%. Example

[0046] A method for preparing a cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane is similar to that in Example 1, except that PW 12 The aqueous solution has a mass fraction of 20 wt%.

[0047] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing a cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane, characterized in that, The membrane is prepared using branched polyethyleneimine, polyvinyl chloride, and phosphotungstic acid. It is obtained by crosslinking quaternized branched polyethyleneimine and polyvinyl chloride, followed by immersing the prepared membrane in a phosphotungstic acid solution. The crosslinked polymer-molecular cluster non-fluorinated composite proton exchange membrane structure is described. The formula is as follows.

2. The method for preparing the cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane according to claim 1, characterized in that, Includes the following steps: (1) Quaternization of branched polyethyleneimine: First, the branched polyethyleneimine is dissolved in dimethylformamide solution to obtain a dilute solution with a mass fraction of 4%-6%. Bromopropane is added, and the molar ratio of bromopropane to amino groups in the branched polyethyleneimine is controlled. After reflux reaction, a bright yellow transparent QPEI solution is obtained. (2) Crosslinking reaction: Take the QPEI solution and polyvinyl chloride prepared in step (1) with different mass ratios and add them to the organic solvent dimethylformamide solution. Heat and stir until the polyvinyl chloride is completely dissolved. Continue stirring to obtain a light yellow PEI-PVC mixed solution. Remove the organic solvent from the QPEI-PVC mixed solution to obtain a uniform amber transparent crosslinked polymer film. (3) Finally, the prepared QPEI-PVC composite film was immersed in phosphotungstic acid aqueous solution, then removed, the surface moisture was wiped off, and it was placed in a sealed bag and stored at room temperature to obtain QPEI-PVC-PW. 12 Composite membrane.

3. The method for preparing the cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane as described in claim 2, characterized in that, In step (1), the molar ratio of amino groups in bromopropane and branched polyethyleneimine is 1:1-3. After reflux reaction at 75℃-85℃ for 24 hours, a bright yellow transparent QPEI solution is obtained.

4. The preparation method for rapid detection of outer membrane permeability of Gram-negative bacteria as described in claim 2, characterized in that, In step (2), polyvinyl chloride is added to the QPEI solution so that the mass ratio of QPEI to polyvinyl chloride is 1:1-3, and the PVC has a K-value of 72-71.

5. The method for preparing the cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane as described in claim 2, characterized in that, In step (2), QPEI and polyvinyl chloride are added to the organic solvent dimethylformamide solution, and the polymer mass fraction of the solution is controlled to be below 10%. The mixture is heated to 75℃-85℃ and stirred until the PVC is completely dissolved. The mixture is then stirred and reacted at 75℃-85℃ for 6 hours.

6. The method for preparing the cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane as described in claim 2, characterized in that, In step (2), the QPEI-PVC mixed solution is poured into a clean glass dish and vacuum dried at 75℃-85℃ for 24 hours to completely remove the organic solvent, resulting in a uniform amber transparent cross-linked polymer film.

7. The method for preparing the cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane as described in claim 2, characterized in that, In step (3), the prepared QPEI-PVC composite film is placed in a PW film with a mass fraction of 5 wt%-20 wt%. 12 Soak in an aqueous solution for 10-14 hours.

8. A cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane, prepared by the preparation method described in any one of claims 1-7.

9. The cross-linked polymer-molecular cluster non-fluorinated composite proton exchange membrane prepared by the preparation method according to any one of claims 1-7 is used in the preparation of hydrogen fuel cells.

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