Molecular cluster-polymer composite proton exchange membrane as well as preparation method and application thereof
The molecular cluster-polymer proton exchange membrane prepared by the composite of brush polymer and polyoxometalate molecular clusters solves the conductivity and mechanical property problems of existing proton exchange membranes under high temperature conditions, realizes efficient proton transfer, low gas permeability and low-cost fuel cell applications, and is suitable for industrial production.
Patent Information
- Application Number
- CN202510581401.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-07
- Publication Date
- 2025-09-12
AI Technical Summary
Existing proton exchange membranes have problems such as a sudden drop in conductivity under high temperature conditions, poor mechanical properties and flexibility, high gas permeability, high cost and insufficient environmental protection, making it difficult to meet the actual application requirements of fuel cells.
A molecular cluster-polymer composite proton exchange membrane is prepared by combining brush polymers and polyoxometalate molecular clusters through polymerization reaction. The brush polymer provides strong interaction binding sites and the polyoxometalate molecular clusters are evenly dispersed to form an efficient proton transport channel, thereby improving the conductivity, mechanical strength and thermal stability of the membrane.
It achieves stable proton transfer in a high-temperature anhydrous environment, reduces gas permeability, and improves the safety and efficiency of fuel cells. The preparation process is simple, environmentally friendly, and low-cost, making it suitable for large-scale industrial production.
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Figure CN120637549A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of fuel cells, and in particular to a molecular cluster-polymer composite proton exchange membrane and a preparation method and application thereof. Background Art
[0002] A fuel cell is a chemical device that converts the chemical energy of a fuel directly into electrical energy. It represents the fourth generation of power generation technology, following hydropower, thermal power, and nuclear power. The proton exchange membrane (PEM) is a key component of fuel cells and directly impacts their performance, making its development crucial.
[0003] Perfluorosulfonic acid proton exchange membrane (e.g., Nafion membrane) is a relatively common type of proton exchange membrane with advantages such as good chemical stability, high electrical conductivity, and high mechanical strength. However, since it relies on a hydrated environment to achieve high proton conductivity, it will experience a sudden drop in conductivity due to water loss under high temperature conditions (>100°C). In addition, fluorinated materials (e.g., Nafion) also have problems such as complex preparation process, high cost, and the generation of fluorine-containing waste. Phosphoric acid-doped polybenzimidazole (PA-PBI) proton exchange membrane is a high-temperature proton exchange membrane that can be used under high-temperature conditions, but it also has obvious defects, such as: 1) prone to acid leakage and poor stability: phosphoric acid (PA) has weak bonding with the polybenzimidazole (PBI) matrix, and the PA in the proton exchange membrane is prone to seepage during the long-term operation of the fuel cell (the acid loss rate of the PA-PBI proton exchange membrane is >30%), which will cause the performance of the proton exchange membrane to decay significantly; 2) contradiction between mechanical properties and electrical conductivity: PBI has high mechanical strength (Young's modulus E>1000MPa), but poor flexibility (elongation at break <40%), making it difficult to process into a thin layer membrane (thickness>100μm), which will increase the internal resistance of the fuel cell; 3) high gas permeability: the hydrogen permeation current of the PA-PBI proton exchange membrane is >2mA / cm 2 , will trigger fuel cross reaction, which will not only reduce the efficiency of fuel cells, but also pose a safety hazard. In summary, existing proton exchange membranes have obvious defects and are difficult to fully meet the growing requirements of practical applications.
[0004] Therefore, it is of great significance to develop a high-temperature proton exchange membrane with good conductivity, high mechanical strength, excellent thermal stability, low gas permeability, easy processing, low cost, and green environmental protection. Summary of the Invention
[0005] The purpose of the present invention is to provide a molecular cluster-polymer composite proton exchange membrane and a preparation method and application thereof.
[0006] The technical solution adopted by the present invention is:
[0007] A molecular cluster-polymer composite proton exchange membrane comprises a brush polymer and a polyoxometalate molecular cluster; the brush polymer is prepared by polymerization of a polyethylene glycol compound; the polyethylene glycol compound is at least one of poly(ethylene glycol) methacrylate (PEGMA) and poly(ethylene glycol) monomethyl ether acrylate (PEGMEA).
[0008] Preferably, the mass ratio of the brush polymer to the polyoxometalate molecular cluster is 1:0.4-4.
[0009] Preferably, the polyoxometalate molecular cluster is at least one of a Keggin-type polyoxometalate molecular cluster, a Dawson-type polyoxometalate molecular cluster, and a pentavanadate-type polyoxometalate molecular cluster.
[0010] Preferably, the general structural formula of the Keggin-type polyoxometalate molecular cluster is as follows: n [XM 12 O 40 ] n- ·mH2O, wherein X represents the central atom, X is selected from at least one of P, Si, Co, and Al, Y represents the counter ion, Y is selected from at least one of H, Li, Na, and K, M represents the coordinating atom, M is selected from at least one of Nb, W, and Mo, m represents the number of crystallization waters, the number of m depends on the self-bound water and the specific environmental humidity, m is an integer from 0 to 40, and n represents the number of charges carried by the polyanion / the number of counter ions, and n is 3, 4, or 6.
[0011] Further preferably, the Keggin type polyoxometalate molecular cluster is a phosphotungstic acid molecular cluster (X3[PW 12 O 40 ] 3- mH2O), silicotungstic acid molecular clusters (X4[SiW 12 O 40 ] 4- ·mH2O), cobalt tungstate molecular clusters (X6[CoW 12 O 40 ] 6- ·mH2O).
[0012] More preferably, the Keggin-type polyoxometalate molecular cluster is a silicotungstic acid molecular cluster H4[SiW 12 O 40 ] 4- ·mH2O (abbreviated as SiW 12 ), phosphotungstic acid molecular cluster H3[PW 12 O 40 ] 3- mH2O (abbreviated as PW12 ) at least one of.
[0013] Preferably, the general structural formula of the Dawson type polyoxometalate molecular cluster is as follows: n [X2M 18 O 62 ] n- ·mH2O, wherein X represents the central atom, X is selected from at least one of P, Si, Co, and Al, Y represents the counter ion, Y is selected from at least one of H, Li, Na, and K, M represents the coordinating atom, M is selected from at least one of Nb, W, and Mo, m represents the number of crystallization waters, the number of m depends on the self-bound water and the specific environmental humidity, m is an integer from 0 to 60, and n represents the number of charges carried by the polyanion / the number of counter ions, and n is 3, 4, 6, or 8.
[0014] Preferably, the structural formula of the pentavanadate-type polyoxometalate molecular cluster is Li7[V 15 O 36 (CO3)]·39H2O.
[0015] Preferably, the number average molecular weight of the polyethylene glycol compound is 300 g / mol to 2000 g / mol.
[0016] A method for preparing the molecular cluster-polymer composite proton exchange membrane as described above comprises the following steps: dispersing polyethylene glycol compounds, polyoxometalate molecular clusters and an initiator in an organic solvent to prepare a casting solution, injecting the casting solution into a mold for polymerization reaction, and then drying to obtain the molecular cluster-polymer composite proton exchange membrane.
[0017] Preferably, the initiator is at least one of azobisisobutyronitrile, dibenzoyl peroxide, and azobisisoheptylnitrile.
[0018] Preferably, the amount of the initiator is 1% to 5% by weight of the polyethylene glycol compound.
[0019] Preferably, the organic solvent is at least one of N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, and acetic acid.
[0020] Preferably, the mass fraction of the polyoxometalate molecular clusters in the casting solution is 20% to 80%.
[0021] Preferably, the polymerization reaction is carried out at a temperature of 70° C. to 80° C., and the reaction time is 12 h to 18 h.
[0022] Preferably, the drying comprises the following process: first drying at a temperature of 110° C. to 130° C. for 10 to 15 hours, and then vacuum drying at a temperature of 90° C. to 110° C. for 4 to 8 hours.
[0023] A fuel cell comprises the molecular cluster-polymer composite proton exchange membrane.
[0024] Preferably, the fuel cell is a hydrogen proton exchange membrane fuel cell.
[0025] The beneficial effects of the present invention are: the molecular cluster-polymer composite proton exchange membrane of the present invention has the advantages of good conductivity, high mechanical strength, excellent thermal stability, low gas permeability, easy processing, low cost, and green environmental protection, and its preparation method is simple and suitable for large-scale industrial production and application.
[0026] Specifically:
[0027] 1) The molecular cluster-polymer composite proton exchange membrane of the present invention comprises a brush polymer and a polyoxometalate molecular cluster. The brush polymer and the polyoxometalate molecular cluster have good compatibility. The side chain polymer of the brush polymer can provide binding sites that strongly interact with the polyoxometalate molecular cluster. The polyoxometalate molecular cluster is uniformly dispersed in the brush polymer matrix through supramolecular interactions such as hydrogen bonding / electrostatics. At the same time, the main chain of the brush polymer and its entanglement can provide excellent thermal stability and high mechanical strength. The molecular cluster-polymer composite proton exchange membrane has a clear structure and no phase separation occurs. It can stably and efficiently transfer protons in a high-temperature, anhydrous environment. At the same time, the strong binding between the brush polymer and the polyoxometalate molecular cluster can effectively solve the problem of the existing phosphate-based high-temperature proton exchange membrane material that the incorporated small molecule liquid acid is easy to seep out of the polymer matrix, thereby ensuring the stable and efficient transfer of ions in the material, and ultimately making the proton exchange membrane have high gas barrier properties and long life.
[0028] 2) The molecular cluster-polymer composite proton exchange membrane of the present invention comprises a brush polymer and a polyoxometalate molecular cluster. The brush polymer and the polyoxometalate molecular cluster effectively form an efficient proton transport channel through supramolecular interaction, so that the proton exchange membrane has high proton conductivity;
[0029] 3) The molecular cluster-polymer composite proton exchange membrane of the present invention is in a uniform solid flexible film state in a dry state, and has high ion transmission efficiency, good electrical conductivity, high thermal stability (it can still maintain structural stability at temperatures up to 250°C), low gas permeability (reducing the risk of fuel permeation and improving the safety and efficiency of fuel cells), good mechanical properties (high mechanical strength and good flexibility), high safety, and good durability. It is suitable for use in hydrogen proton exchange membrane fuel cells, providing a guarantee for the long-term stable operation of fuel cells;
[0030] 4) The molecular cluster-polymer composite proton exchange membrane of the present invention has a simple preparation process, is green and environmentally friendly (avoids the use of fluorine-containing compounds), and is easy to control product quality. The production cost is significantly reduced compared to commercial high-temperature proton membranes, which is conducive to large-scale industrial production and application. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Figure 1 The figure is a flow chart for preparing the molecular cluster-polymer composite proton exchange membrane of the present invention.
[0032] Figure 2 PEGMA, PW 12 and the infrared spectrum of the molecular cluster-polymer composite proton exchange membrane of Example 1.
[0033] Figure 3 The molecular cluster-polymer composite proton exchange membrane of Example 1, the molecular cluster-polymer composite proton exchange membrane of Example 3 and PW 12 SAXS graph.
[0034] Figure 4 These are stress-strain curves of the molecular cluster-polymer composite proton exchange membranes of Examples 1 to 3.
[0035] Figure 5 The molecular cluster-polymer composite proton exchange membrane of Example 1 and PW 12 TGA curve of .
[0036] Figure 6 This is a graph showing the temperature-dependent conductivity test results of the molecular cluster-polymer composite proton exchange membrane of Example 1.
[0037] Figure 7 This is a graph showing the high-temperature conductivity stability test results of the molecular cluster-polymer composite proton exchange membrane of Example 2.
[0038] Figure 8 This is the polarization curve of the fuel cell assembled with the molecular cluster-polymer composite proton exchange membrane of Example 1.
[0039] Figure 9This is a graph showing the gas barrier test results of the molecular cluster-polymer composite proton exchange membrane of Example 2. DETAILED DESCRIPTION
[0040] The present invention will be further explained and illustrated below with reference to specific embodiments.
[0041] Example 1:
[0042] A molecular cluster-polymer composite proton exchange membrane, and its preparation method (preparation flow chart as shown in Figure 1 As shown) are as follows:
[0043] 1g of poly (ethylene glycol) methacrylate (PEGMA; number average molecular weight 360g / mol), 1g of phosphotungstic acid molecular cluster H3 [PW 12 O 40 ] 3- ·mH2O(PW 12 ) and 30 mg of azobisisobutyronitrile were added to 10 mL of N, N-dimethylformamide (DMF), and then stirred at 55 ° C until the solution was uniform and transparent to obtain a casting solution, and then the casting solution was injected into the mold, sealed, and then reacted at 70 ° C for 12 h, and then the film was taken out from the mold, and then dried at a temperature of 120 ° C for 12 h, and then vacuum dried at a temperature of 100 ° C for 8 h to obtain a molecular cluster-polymer composite proton exchange membrane (PEGMA, PW 12 The mass ratio is 1:1).
[0044] Example 2:
[0045] A molecular cluster-polymer composite proton exchange membrane, the preparation method of which is as follows (preparation flow chart as shown in Figure 1 shown):
[0046] 1g of poly (ethylene glycol) methacrylate (PEGMA; number average molecular weight 360g / mol), 1.5g of silicotungstic acid molecular cluster H4[SiW 12 O 40 ] 4- ·mH2O(SiW 12 ) and 30 mg of azobisisoheptane nitrile were added to 10 mL of tetrahydrofuran (THF), and stirred at 55 ° C until the solution was uniform and transparent to obtain a casting solution, and then the casting solution was injected into the mold, sealed, and reacted at 70 ° C for 12 h. The film was then taken out from the mold, dried at a temperature of 120 ° C for 12 h, and then vacuum dried at a temperature of 100 ° C for 8 h to obtain a molecular cluster-polymer composite proton exchange membrane (PEGMA, SiW 12 The mass ratio is 2:3).
[0047] Example 3:
[0048] A molecular cluster-polymer composite proton exchange membrane, the preparation method of which is as follows (preparation flow chart as shown in Figure 1 shown):
[0049] 1g of poly (ethylene glycol) monomethyl ether acrylate (PEGMEA; number average molecular weight 960g / mol), 1g of phosphotungstic acid molecular cluster H3 [PW 12 O 40 ] 3- ·mH2O(PW 12 ) and 30 mg of azobisisobutyronitrile were added to 10 mL of tetrahydrofuran (THF), and stirred at 55 ° C until the solution was uniform and transparent to obtain a casting solution, and then the casting solution was injected into the mold, sealed, and reacted at 70 ° C for 12 h. The film was taken out from the mold and dried at a temperature of 120 ° C for 12 h, and then vacuum dried at a temperature of 100 ° C for 8 h to obtain a molecular cluster-polymer composite proton exchange membrane (PEGMEA, PW 12 The mass ratio is 1:1). Comparative Example:
[0050] A proton exchange membrane, the preparation method of which is as follows:
[0051] 3g of phosphotungstic acid molecular cluster H3[PW 12 O 40 ] 3- ·mH2O(PW 12 ) was dissolved in 7 g of linear polyethylene glycol (PEG; number average molecular weight 400 g / mol) at 65 ° C with stirring, and then vacuum dried at 60 ° C for 12 h, and then pressed into a membrane by hot pressing process (70 ° C, pressure holding 1 h) to obtain a proton exchange membrane (PEG, PW 12 The mass ratio is 7:3).
[0052] Performance testing:
[0053] 1) Poly (ethylene glycol) methacrylate (PEGMA) in Example 1, phosphotungstic acid molecular cluster H3 [PW 12 O 40 ] 3- ·mH2O(PW 12 ) and the infrared spectra of the molecular cluster-polymer composite proton exchange membrane of Example 1 are as follows Figure 2 shown.
[0054] Depend on Figure 2 It can be seen that there is no stretching vibration peak of C=C double bond in the infrared spectrum of molecular cluster-polymer composite proton exchange membrane, indicating that the C=C double bond in PEGMA reacts completely during the polymerization process, forming a brush-like polymer with CC bond connection in the main chain and polyethylene glycol in the side chain. In addition, by comparing PEGMA and PW12 The infrared spectrum of PEGMA and PW 12 The structure remains intact.
[0055] 2) The molecular cluster-polymer composite proton exchange membrane of Example 1, the molecular cluster-polymer composite proton exchange membrane of Example 3 and the phosphotungstic acid molecular cluster H3[PW 12 O 40 ] 3- ·mH2O(PW 12 ) small angle X-ray scattering (SAXS) pattern as shown in Figure 3 shown.
[0056] Depend on Figure 3 It can be seen that the phosphotungstic acid molecular clusters in the molecular cluster-polymer composite proton exchange membranes of Example 1 and Example 3 are in a uniformly dispersed state.
[0057] 3) The molecular cluster-polymer composite proton exchange membranes of Examples 1 to 3 were subjected to tensile testing, and the obtained stress-strain curves were as follows: Figure 4 The Young's modulus and elongation at break test results (measured by tensile testing at a rate of 10 mm / min) are shown in the following table:
[0058] Table 1 Test results of Young's modulus and elongation at break of molecular cluster-polymer composite proton exchange membrane
[0059] Test items Young's modulus (MPa) Elongation at break (%) Example 1 150 140 Example 2 220 210 Example 3 25 230
[0060] Depend on Figure 4 As shown in Table 1, the molecular cluster-polymer composite proton exchange membranes of Examples 1 to 3 have relatively high breaking strength and breaking elongation, indicating that the molecular cluster-polymer composite proton exchange membrane of the present invention has high mechanical strength.
[0061] 4) The molecular cluster-polymer composite proton exchange membrane of Example 1 and the phosphotungstic acid molecular cluster H3[PW 12 O 40 ] 3- ·mH2O(PW 12 )’s thermogravimetric (TGA) curve is as follows Figure 5 shown.
[0062] Depend on Figure 5 It can be seen that the extrapolated decomposition starting temperatures of the molecular cluster-polymer composite proton exchange membrane and the phosphotungstic acid molecular cluster of Example 1 are both above 250°C, and both have relatively high decomposition temperatures (>250°C), indicating that the molecular cluster-polymer composite proton exchange membrane of the present invention has excellent thermal stability.
[0063] 5) The test results of the temperature-dependent conductivity (i.e., temperature-dependent ionic conductivity) of the molecular cluster-polymer composite proton exchange membrane of Example 1 are as follows: Figure 6 (Apply a small-amplitude AC potential wave with different frequencies to the electrochemical system, measure the change of the ratio of the AC potential to the current signal with the sine wave frequency ω, or the change of the phase angle Φ of the impedance with ω, and then calculate the ionic conductivity σ of the film sample; the ionic conductivity calculation formula is: σ = d / SR, where d is the thickness of the molecular cluster-polymer composite proton exchange membrane in cm, and S is the electrode area in cm 2 , R is the resistance obtained by the AC impedance method, in Ω; the temperature-variable conductivity test is carried out in the temperature range of 80°C to 200°C, and the equilibrium time at each temperature is 30 min) as shown in the following figure. The high-temperature conductivity stability test results of the molecular cluster-polymer composite proton exchange membrane of Example 2 are as follows: Figure 7 As shown, the high temperature conductivity test results of the molecular cluster-polymer composite proton exchange membranes of Examples 1 to 3 are shown in the following table:
[0064] Table 2 High temperature conductivity test results of molecular cluster-polymer composite proton exchange membrane
[0065] Test items Conductivity / 180℃(mS / cm) Example 1 1.3 Example 2 1.5 Example 3 1.6
[0066] Depend on Figure 6 、 Figure 7 As shown in Table 2, the molecular cluster-polymer composite proton exchange membranes of Examples 1 to 3 have high ionic conductivity in a high temperature, anhydrous environment, can efficiently transfer protons, and the molecular cluster-polymer composite proton exchange membranes have high electrochemical stability in a high temperature environment.
[0067] 6) The molecular cluster-polymer composite proton exchange membrane of Example 1 and two gas diffusion electrodes were assembled into a sandwich membrane electrode assembly by hot pressing, and then installed in a fuel cell experimental device for testing. The polarization curves obtained are shown in FIG. Figure 8 shown.
[0068] Depend on Figure 8 It can be seen that the power density of the fuel cell assembled with the molecular cluster-polymer composite proton exchange membrane of Example 1 is 218 mW / cm at a temperature of 180°C. 2 (The open circuit potential is 0.99 V), indicating that the molecular cluster-polymer composite proton exchange membrane of the present invention is suitable for use in high-temperature fuel cells.
[0069] 7) The molecular cluster-polymer composite proton exchange membrane of Example 2 is placed between the two chambers of the test chamber, sealed, and then the lower chamber is evacuated, while the upper chamber is kept at a certain pressure of the test gas. As the gas molecules pass through the molecular cluster-polymer composite proton exchange membrane, the pressure in the lower chamber will gradually increase. This change is monitored by a high-precision pressure sensor, and the gas permeation per unit area per unit time is calculated. The obtained gas barrier test results are as follows: Figure 9 shown.
[0070] Depend on Figure 9 It can be seen that the molecular cluster-polymer composite proton exchange membrane of Example 2 has extremely strong gas barrier properties, and the gas barrier coefficients of hydrogen and oxygen are small (<10 -14 cm 2 ·s·Pa), which can effectively prevent the fuel crossover phenomenon in fuel cell equipment and ensure the stable application of molecular cluster-polymer composite proton exchange membrane in fuel cells.
[0071] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.
Claims
1. A molecular cluster-polymer composite proton exchange membrane, characterized in that: The composition includes a brush polymer and a polyoxometalate molecular cluster; the brush polymer is prepared by polymerization reaction of a polyethylene glycol compound; the polyethylene glycol compound is at least one of poly(ethylene glycol) methacrylate and poly(ethylene glycol) monomethyl ether acrylate.
2. The molecular cluster-polymer composite proton exchange membrane according to claim 1, characterized in that: The mass ratio of the brush polymer to the polyoxometalate molecular cluster is 1:0.4-4.
3. The molecular cluster-polymer composite proton exchange membrane according to claim 1 or 2, characterized in that: The polyoxometalate molecular cluster is at least one of a Keggin-type polyoxometalate molecular cluster, a Dawson-type polyoxometalate molecular cluster, and a pentavanadate-type polyoxometalate molecular cluster.
4. The molecular cluster-polymer composite proton exchange membrane according to claim 3, characterized in that: The general structural formula of the Keggin-type polyoxometalate molecular cluster is as follows: n [XM 12 O 40 ] n- ·mH2O, wherein X represents the central atom, X is selected from at least one of P, Si, Co, and Al, Y represents the counter ion, Y is selected from at least one of H, Li, Na, and K, M represents the coordinating atom, M is selected from at least one of Nb, W, and Mo, m represents the number of crystal waters, the number of m depends on the self-bound water and the specific environmental humidity, m is an integer from 0 to 40, and n represents the number of charges carried by the polyanion / the number of counter ions, and n is 3, 4, or 6.
5. The molecular cluster-polymer composite proton exchange membrane according to claim 3, characterized in that: The general structural formula of the Dawson type polyoxometalate molecular cluster is as follows: n [X2M 18 O 62 ] n- ·mH2O, wherein X represents the central atom, X is selected from at least one of P, Si, Co, and Al, Y represents the counter ion, Y is selected from at least one of H, Li, Na, and K, M represents the coordinating atom, M is selected from at least one of Nb, W, and Mo, m represents the number of crystallization waters, the number of m depends on the self-bound water and the specific environmental humidity, m is an integer from 0 to 60, and n represents the number of charges carried by the polyanion / the number of counter ions, and n is 3, 4, 6, or 8.
6. The molecular cluster-polymer composite proton exchange membrane according to claim 3, characterized in that: The structural formula of the pentavanadate-type polyoxometalate molecular cluster is Li7[V 15 O 36 (CO3)]·39H2O.
7. The molecular cluster-polymer composite proton exchange membrane according to claim 1 or 2, characterized in that: The number average molecular weight of the polyethylene glycol compound is 300 g / mol to 2000 g / mol.
8. A method for preparing a molecular cluster-polymer composite proton exchange membrane according to any one of claims 1 to 7, characterized in that: The following steps are involved: Polyethylene glycol compounds, polyoxometalate molecular clusters and initiators are dispersed in an organic solvent to prepare a casting solution, which is then injected into a mold for polymerization reaction and then dried to obtain a molecular cluster-polymer composite proton exchange membrane.
9. The preparation method according to claim 8, characterized in that: The polymerization reaction is carried out at a temperature of 70° C. to 80° C., and the reaction time is 12 h to 18 h.
10. A fuel cell, characterized in that: A molecular cluster-polymer composite proton exchange membrane comprising the molecular cluster-polymer composite proton exchange membrane according to any one of claims 1 to 7.