Proton exchange resin with multi-element proton conduction center and preparation method thereof

Abstract

The invention relates to the technical field of proton exchange membrane fuel cells, and provides proton exchange resin with a multi-element proton conduction center and a preparation method of the proton exchange resin. The main chain structure of the proton exchange membrane is a perfluoro skeleton, the side chain contains groups such as sulfonic acid, phosphonic acid and sulfimide, and the formed multiple active centers improve the ion exchange capacity, enhance the proton conductivity and ensure the proton transmission capacity of the proton exchange membrane under low humidity. Meanwhile, the benzene ring structure has relatively large steric hindrance, so that the glass-transition temperature is increased, and the polymer can give consideration to proton conductivity and thermal stability.

Description

Technical Field

[0001] The present invention relates to the technical field of proton exchange membrane fuel cells, and particularly to a proton exchange resin having multiple proton conduction centers and a preparation method thereof. Background Art

[0002] A proton exchange membrane fuel cell (PEMFC) is a device that converts hydrogen into electrical energy, including advantages such as high energy conversion efficiency and fast system reaction, and is an ideal power supply device. The operating stability, reliability, and lifespan of fuel cells are important requirements for vehicle fuel cells. For fuel cells, the proton exchange membrane is one of the main factors determining reliability and lifespan.

[0003] Operating fuel cells at high temperatures can optimize the water and heat management system, improve the tolerance to impurity gases, and thus reduce costs. However, traditional perfluorosulfonic acid proton exchange membranes are limited to operating at relatively low temperatures, about 80 °C. This type of membrane has a low glass transition temperature (<120 °C) and a significant dependence on moisture, and the proton conductivity decreases significantly under low humidity conditions. To increase the conductivity, a common method is to increase the ion exchange capacity of the sulfonic acid resin. By increasing the number of acidic functional groups on the main chain, the goal of increasing the ion conductivity is achieved. However, increasing the ion exchange capacity will lead to a decrease in the mechanical properties of the membrane and a reduction in the glass transition temperature, affecting the thermal stability. Therefore, preparing a proton exchange membrane with high proton conductivity and high thermal stability is of great significance for high-temperature fuel cells. Summary of the Invention

[0004] In view of this, the present invention provides a proton exchange resin having multiple proton conduction centers, a preparation method and applications thereof, to solve the problems of low conductivity at low humidity and poor high-temperature stability of traditional perfluorosulfonic acid proton exchange membranes.

[0005] The technical solution of the present invention is realized as follows: In a first aspect, the present invention provides a proton exchange resin having multiple proton conduction centers, and the structural formula of the proton exchange resin is:

[0006]

[0007] Wherein, x and y are integers between 1 and 100, m and n are integers between 0 and 10, and m and n are not both 0 at the same time. The structure of R is:

[0008]

[0009] Wherein, R 1 , R 2 is -SO 3 H, -PO(OH) 2 , -SO2 -NH-SO 2 -CF 3 one of the following.

[0010] Specifically, the main chain structure of the proton exchange membrane with multiple proton conduction centers is a perfluorinated backbone, and the side chains contain groups such as sulfonic acid, phosphonic acid, and sulfonimide, etc. The formed multiple active centers improve the ion exchange capacity. At the same time, the benzene ring structure has a large steric hindrance, which improves the glass transition temperature, enabling the polymer to balance proton conductivity and thermal stability.

[0011] Based on the above technical solutions, preferably, the structure of R is:

[0012]

[0013] one of the following.

[0014] In a second aspect, the present invention provides a preparation method of a proton exchange resin with multiple proton conduction centers, including the following steps:

[0015] S1, The nucleophilic substitution reaction of the compound PFSF of formula I with liquid ammonia yields the compound PFS-NH of formula II 2 ;

[0016]

[0017] wherein, x and y are integers between 1 and 100, m and n are integers between 0 and 10, and m and n are not both 0 at the same time;

[0018] S2, The amino group on the side chain of PFS-NH 2 undergoes a Hinsberg reaction with the monomer containing benzenesulfonyl chloride to generate a proton exchange resin containing multiple proton conduction centers.

[0019] Based on the above technical solutions, preferably, in step S1, the reaction temperature is -80°C to 30°C, and the reaction time is 24 - 72 h.

[0020] Based on the above technical solutions, preferably, in step S2, the molar ratio of PFS-NH 2 to the monomer containing benzenesulfonyl chloride is 1∶2 - 8.

[0021] Based on the above technical solutions, preferably, PFS-NH 2 is added to an organic solvent and heated to 120°C, stirred for 6 - 12 h to completely dissolve it, then cooled to 0°C, and the monomer containing benzenesulfonyl chloride and an acid-binding agent are added for the Hinsberg reaction. After the reaction is completed, acid (1M H 2 SO4 )Precipitate, then recrystallize and purify in a mixed solution of ethanol and water, and finally dry in a vacuum oven at 80 °C for 24 h to obtain a solid proton exchange resin.

[0022] Based on the above technical solutions, preferably, in step S2, the reaction time is 12 - 72 h, and the molar ratio of PFS-NH 2 to the acid-binding agent is 1∶2 - 10.

[0023] Based on the above technical solutions, preferably, the organic solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, ethyl acetate, hexafluorobenzene, and dioxane; the acid-binding agent is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, cesium carbonate, lithium hydride, sodium hydride, triethylamine, and ethylenediamine.

[0024] Thirdly, the present invention provides an application of a proton exchange resin with multiple proton conduction centers in the preparation of a proton exchange membrane. Dissolve the proton exchange resin in an alcohol solution to form a solution with a solid content of 10 wt%, and then use the casting method to remove the solvent at 80 °C to form a film, obtaining a proton exchange membrane.

[0025] The mass ratio of the proton exchange resin to the alcohol solution is (1 - 5):20, the mass ratio of water to alcohol in the alcohol solution is 1:0.5 - 2, and the alcohol is at least one of methanol, ethanol, isopropanol, ethylene glycol, or n-propanol.

[0026] Fourthly, the present invention provides an application of the proton exchange membrane in fuel cells and electrolyzers.

[0027] The proton exchange resin with multiple proton conduction centers, its preparation method and application of the present invention have the following beneficial effects:

[0028] (1) The main chain structure of the proton exchange membrane of the present invention is a perfluorinated backbone, and the side chains contain groups such as sulfonic acid, phosphonic acid, and sulfonimide, forming multiple active centers that improve the ion exchange capacity, enhance the proton conductivity, and ensure the proton transport ability of the proton exchange membrane under low humidity. At the same time, the benzene ring structure has a large steric hindrance, which increases the glass transition temperature, enabling the polymer to balance proton conductivity and thermal stability.

[0029] (2) The rigid groups of the proton exchange membrane of the present invention reduce the flexibility of the side chains, increase the steric hindrance, and increase the glass transition temperature (>120 °C), thereby ensuring that the proton exchange membrane works at a higher temperature.

[0030] (3) While maintaining the crystallinity of the main chain unchanged, multiple acidic groups are introduced into the side chain of the proton exchange membrane of the present invention, which has broad application prospects in the field of high-temperature and low-humidity fuel cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0032] Figure 1 It is a comparison chart of the fuel cell performance of the example and the perfluorosulfonic acid proton exchange membrane at 120 °C and 40% RH;

[0033] Figure 2 It is a comparison chart of the water electrolysis performance of the example and the perfluorosulfonic acid proton exchange membrane at 90 °C. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0034] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0035] As analyzed in the background art of this application, increasing the number of acidic functional groups on the main chain can achieve the goal of improving the ionic conductivity. However, increasing the ion exchange capacity will lead to a decrease in the mechanical properties of the membrane and a decrease in the glass transition temperature, affecting the thermal stability. Therefore, preparing a proton exchange membrane with high proton conductivity and high thermal stability is of great significance for high-temperature fuel cells. To solve this problem, this application provides a proton exchange resin with multiple proton conduction centers, its preparation method and application.

[0036] The following further illustrates the present invention with specific experimental steps. The following examples are intended to illustrate the present invention rather than further limit the present invention.

[0037] Example 1

[0038] This example provides a proton exchange membrane prepared from a proton exchange resin with multiple proton conduction centers, and its preparation method includes the following steps:

[0039] (1) Add 10 mmol of Compound PFSF of Formula I to a single-necked flask, place it in a low-temperature bath, and maintain at -78 °C. Subsequently, continuously introduce 800 mL of NH 3 , stir and react for 72 h. After the reaction is completed, heat to 80 °C, and add 200 mL of 1 mol / L sulfuric acid solution to neutralize the excess NH 3 , then wash until neutral to obtain the final product PFS-NH 2 .

[0040] (2) Add 5 mmol of PFS-NH 2 resin and 20 mL of N,N-dimethylformamide to a single-necked flask, heat it to 120 °C, stir for 12 h to completely dissolve it. Then cool to 0 °C, add 10 mmol of 1,4-benzenedisulfonyl chloride, and then add 10 mmol of solid sodium hydroxide. After maintaining the reaction at 0 °C for 36 h, pour it into 1 M H 2 SO 4 solution to precipitate. Then wash with water until neutral, at this time the sulfonyl chloride is hydrolyzed into the sulfonic acid form. Subsequently, recrystallize and purify in a mixed solution of ethanol and water with a mass ratio of 1:1. Finally, dry in a vacuum oven at 80 °C for 24 h to obtain a white solid product.

[0041] (3) Dissolve the above polymer (2 g) in 20 mL of a water-alcohol solution (water:ethanol mass ratio = 1:1). Pour the polymer solution onto a clean glass plate, then dry in an oven at 80 °C for 24 h and anneal at 140 °C for 5 h; Peel the film from the glass plate and soak it in 1 M H 2 SO 4 solution, soak at 80 °C for 12 h, then wash 3 times with deionized water, and dry to obtain the final proton exchange membrane containing sulfonimide and sulfonic acid groups, with the structural formula as follows:

[0042]

[0043] where x = 5, y = 1, m = 1, n = 1.

[0044] Example 2

[0045] This example provides a proton exchange membrane prepared from a proton exchange resin with multiple proton conduction centers, and its preparation method includes the following steps:

[0046] (1) Add 5 mmol of Compound PFSF of Formula I to a single-necked flask, place it in a low-temperature bath, and maintain at -78 °C. Subsequently, continuously introduce 500 ml of NH 3 , stir and react for 72 h. After the reaction is completed, heat to 80 °C, and add 100 ml of 1 mol / L sulfuric acid solution to neutralize the excess NH 3, and then wash it to neutrality to obtain the final product PFS-NH 2 .

[0047] (2) Add 5 mmol of PFS-NH 2 resin and 20 mL of N,N-dimethylformamide into a single-necked flask, heat it to 120 °C, stir for 12 h to completely dissolve it. Then cool it down to 0 °C, add 5.1 mmol of 1,4-benzenedisulfonyl chloride, and then add 20 mmol of solid sodium hydroxide. Keep the reaction at 0 °C for 12 h. Then add another monomer, 5.1 mmol of trifluoromethanesulfonamide, and continue the reaction for 24 h. Pour it into 1 M H 2 SO 4 solution to precipitate. Then wash it with water to neutrality. Subsequently, recrystallize and purify it in a mixed solution of ethanol and water with a mass ratio of 1:1. Finally, dry it in a vacuum oven at 80 °C for 24 h to obtain a white solid product.

[0048] (3) Dissolve the above polymer (2 g) in 20 mL of a water-alcohol solution (mass ratio of water:ethanol = 1:1). Cast the polymer solution on a clean glass plate, then dry it in an oven at 80 °C for 24 h and anneal it at 140 °C for 5 h; Peel the film from the glass plate and soak it in 1 M H 2 SO 4 solution and soak it at 80 °C for 12 h, then wash it 3 times with deionized water, and dry it to obtain the final proton exchange membrane containing disulfonimide groups, with the structural formula as follows:.

[0049]

[0050] where x = 4, y = 1, m = 1, n = 1.

[0051] Example 3

[0052] This example provides a proton exchange membrane prepared from a proton exchange resin with multiple proton conduction centers, and its preparation method includes the following steps:

[0053] (1) Add 5 mmol of Compound PFSF of Formula I into a single-necked flask, place it in a low-temperature bath, keep it at -80 °C, and then continuously introduce 500 ml of NH 3 , stir and react for 72 h. After the reaction is completed, heat it to 60 °C, and add 100 ml of 1 mol / L sulfuric acid solution to neutralize the excess NH 3 , and then wash it to neutrality to obtain the final product PFS-NH 2 .

[0054] (2) Add 5 mmol of PFS-NH 2Resin and 20 mL of N,N-dimethylformamide were added to a single-necked flask, and the mixture was heated to 120 °C and stirred for 12 h to completely dissolve it. Then, the temperature was lowered to 0 °C, 10 mmol of 4-bromobenzenesulfonyl chloride was added, and 30 mmol of solid sodium hydroxide was added. After reacting at 0 °C for 36 h, it was poured into 1 M H 2 SO 4 solution, and a precipitate was formed. Then it was washed with water until neutral. Subsequently, it was recrystallized and purified in a mixed solution of ethanol and water with a mass ratio of 1:1. Finally, it was dried in a vacuum oven at 80 °C for 24 h to obtain a white solid product.

[0055] (3) 5 mmol of the above polymer and 20 mL of N,N-dimethylformamide were added to a single-necked flask, and 10 mmol of triethyl phosphite was added. The mixture was heated to 170 °C and refluxed for 24 h. After the reaction was completed, it was poured into 1 M HCl solution, and a precipitate was formed. Then it was acidified with 1 M HCl at 80 °C for 24 h, and then washed with water until neutral. Subsequently, it was recrystallized and purified in a mixed solution of ethanol and water with a mass ratio of 1:1. Finally, it was dried in a vacuum oven at 80 °C for 24 h to obtain a white solid product.

[0056] (4) The above polymer (2 g) was dissolved in 20 mL of an aqueous alcohol solution (mass ratio of water:ethanol = 1:1). The polymer solution was cast on a clean glass plate, then dried in an oven at 80 °C for 24 h and annealed at 140 °C for 5 h; the film was peeled off from the glass plate and soaked in 1 M H 2 SO 4 solution and soaked at 80 °C for 12 h, then washed 3 times with deionized water, and finally dried to obtain a final proton exchange membrane containing sulfonimide and phosphonic acid groups, with the structural formula as follows:

[0057]

[0058] where x = 5, y = 1, m = 1, n = 1.

[0059] Example 4

[0060] This example provides a proton exchange membrane prepared from a proton exchange resin with multiple proton conduction centers, and its preparation method includes the following steps:

[0061] (1) 10 mmol of the compound PFSF of formula I was added to a single-necked flask and placed in a low-temperature bath, maintaining -50 °C. Subsequently, 800 ml of NH 3 was continuously introduced, and the mixture was stirred and reacted for 72 h. After the reaction was completed, it was heated to 50 °C, and 300 ml of 1 mol / L sulfuric acid solution was added to neutralize the excess NH 3 , and then washed until neutral to obtain the final product PFS-NH 2 .

[0062] (2) Add 5 mmol of PFS-NH 2 resin and 20 mL of N,N-dimethylformamide into a single-necked flask, heat it to 120 °C, stir for 12 h to completely dissolve it. Then cool it down to 0 °C, add 10 mmol of 1,3-benzenedisulfonyl chloride, and then add 15 mmol of solid sodium hydroxide. Keep reacting at 0 °C for 36 h, and then pour it into 1 M H 2 SO 4 solution to precipitate. Then wash it with water until neutral, at this time the sulfonyl chloride is hydrolyzed into the sulfonic acid form. Subsequently, recrystallize and purify it in a mixed solution of ethanol and water with a mass ratio of 1:1. Finally, dry it in a vacuum oven at 80 °C for 24 h to obtain a white solid product.

[0063] (3) Dissolve the above polymer (2 g) in 20 mL of a water-alcohol solution (water:ethanol mass ratio = 1:1). Pour the polymer solution onto a clean glass plate, then dry it in an oven at 80 °C for 24 h and anneal it at 140 °C for 5 h; Peel the membrane from the glass plate and soak it in 1 M H 2 SO 4 solution, soak it at 80 °C for 12 h, then wash it 3 times with deionized water, and dry it to obtain a final proton exchange membrane containing sulfonimide and sulfonic acid groups, with the structural formula as follows:

[0064]

[0065] where x = 4, y = 1, m = 1, n = 1.

[0066] Example 5

[0067] This example provides a proton exchange membrane prepared from a proton exchange resin with multiple proton conduction centers, and its preparation method includes the following steps:

[0068] (1) Add 5 mmol of Compound PFSF of Formula I into a single-necked flask, place it in a low-temperature bath, keep it at -78 °C, and then continuously introduce 500 ml of NH 3 , stir and react for 72 h. After the reaction is completed, heat it to 80 °C, and add 100 ml of 1 mol / L sulfuric acid solution to neutralize the excess NH 3 , and then wash it until neutral to obtain the final product PFS-NH 2 .

[0069] (2) Add 5 mmol of PFS-NH 2The resin and 20 mL of N,N-dimethylformamide were added to a single-necked flask, which was heated to 120 °C and stirred for 12 h to completely dissolve it. Then the temperature was lowered to 0 °C, 5.1 mmol of 1,3-benzenedisulfonyl chloride was added, and then 20 mmol of solid sodium hydroxide was added. After reacting at 0 °C for 12 h. Another monomer, 5.1 mmol of trifluoromethanesulfonamide, was added, and the reaction was continued for 24 h. It was poured into 1 M H 2 SO 4 solution, and a precipitate was formed. Then it was washed with water until neutral. Subsequently, it was recrystallized and purified in a mixed solution of ethanol and water with a mass ratio of 1:1. Finally, it was dried in a vacuum oven at 80 °C for 24 h to obtain a white solid product.

[0070] (3) Dissolve the above polymer (2 g) in 20 mL of a water-alcohol solution (water:ethanol mass ratio = 1:1). The polymer solution was cast on a clean glass plate, then dried in an oven at 80 °C for 24 h and annealed at 140 °C for 5 h; the film was peeled off from the glass plate and soaked in 1 M H 2 SO 4 solution, soaked at 80 °C for 12 h, then washed 3 times with deionized water, and dried to obtain the final proton exchange membrane containing disulfonimide groups, with the structural formula as follows:

[0071]

[0072] where x = 5, y = 1, m = 1, n = 1.

[0073] Example 6

[0074] This example provides a proton exchange membrane prepared from a proton exchange resin with multiple proton conduction centers, and its preparation method includes the following steps:

[0075] (1) Add 10 mmol of Compound PFSF of Formula I to a single-necked flask, place it in a low-temperature bath, keep it at -50 °C, and then continuously introduce 800 ml of NH 3 , stir and react for 72 h. After the reaction is completed, heat it to 50 °C, and add 300 ml of 1 mol / L sulfuric acid solution to neutralize the excess NH 3 , and then wash it until neutral to obtain the final product PFS-NH 2 .

[0076] (2) Add 5 mmol of PFS-NH 2 resin and 20 mL of N,N-dimethylformamide to a single-necked flask, heat it to 120 °C, stir for 12 h to completely dissolve it. Then lower the temperature to 0 °C, add 10 mmol of 3-bromobenzenesulfonyl chloride, and then add 40 mmol of solid sodium hydroxide. After reacting at 0 °C for 36 h. Pour it into 1 M H 2SO 4 In the solution, a precipitate was formed. Then it was washed with water until neutral. Subsequently, it was recrystallized and purified in a mixed solution of ethanol and water with a mass ratio of 1:1. Finally, it was dried in a vacuum oven at 80 °C for 24 h to obtain a white solid product.

[0077] (3) Add 5 mmol of the above polymer and 20 mL of N,N-dimethylformamide to a single-necked flask, then add 10 mmol of triethyl phosphite, heat it to 170 °C, and reflux for 24 h. After the reaction was completed, it was poured into 1 M HCl solution, and a precipitate was formed. Then it was acidified with 1 M HCl at 80 °C for 24 h, and then washed with water until neutral. Subsequently, it was recrystallized and purified in a mixed solution of ethanol and water with a mass ratio of 1:1. Finally, it was dried in a vacuum oven at 80 °C for 24 h to obtain a white solid product.

[0078] (4) Dissolve the above polymer (2 g) in 20 mL of a water-alcohol solution (mass ratio of water:ethanol = 1:1). The polymer solution was cast on a clean glass plate, then dried in an oven at 80 °C for 24 h and annealed at 140 °C for 5 h; the film was peeled off from the glass plate and immersed in 1 M H 2 SO 4 solution, immersed at 80 °C for 12 h, then washed 3 times with deionized water, and after drying, a final proton exchange membrane containing sulfonimide and phosphonic acid groups was obtained. The structural formula is as follows:

[0079]

[0080] where x = 6, y = 1, m = 1, n = 1.

[0081] Comparative Example

[0082] Perfluorosulfonic acid was used as the comparative example, and the model of perfluorosulfonic acid was Nafion TM 211, produced by DuPont Company in the United States. The structural formula of perfluorosulfonic acid is:

[0083]

[0084] In order to evaluate the specific technical effects of the multi-proton conduction center resin and its proton exchange membrane described in the present invention, specific performance tests were carried out on Examples 1-6 in terms of ion exchange capacity and proton conductivity, etc. Among them, the ion exchange capacity was tested by acid-base titration; the proton conductivity was measured by a two-electrode alternating current impedance method on an electrochemical workstation (Solartron-1287). The specific test data are shown in Table 1:

[0085] Table 1 Performance Test of Proton Exchange Membrane

[0086]

[0087] As can be seen from Table 1, the ion exchange capacity of the proton exchange membrane prepared by the present invention is higher than 1.30 mmol g -1 . The proton conductivity is not less than 50 mS cm at 120 °C and 40% RH -1 , and can reach up to 63 mS cm -1 or so, which is at least 50% higher than that of perfluorosulfonic acid (Comparative Example 1) (see Figure 1 ). At 80 °C and 100% RH, it can reach up to 268 mS cm -1 or so, which is at least 0.65 times higher than that of perfluorosulfonic acid (Comparative Example 1). Among Examples 1-6, the proton exchange membrane containing sulfonimide and sulfonic acid groups (Example 1) has the highest ion exchange capacity and proton conductivity, followed by the proton exchange membrane containing bis-sulfonimide groups (Example 5). Because the sulfonimide group and the sulfonic acid group are more acidic, and the structure with a sulfonimide group at the end makes it more difficult for protons to leave compared to the sulfonic acid group, the combined performance of the sulfonimide and sulfonic acid groups is better.

[0088] Therefore, the proton exchange membrane prepared by the present invention has a high ion conductivity because it contains multiple proton conduction centers, increasing the ion exchange capacity. In addition, the performance of the fuel cell and electrolyzed water assembled using the proton exchange membrane of the present invention is significantly better than that of the perfluorosulfonic acid membrane (see Figure 2 ).

[0089] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A proton exchange resin having multiple proton conduction centers, characterized in that: The structural formula of the proton exchange resin is: Wherein, x and y are integers between 1 and 100, m and n are integers between 0 and 10, and m and n are not 0 at the same time, and the structure of R is: Among them, R1, R2 are one of -SO3H, -PO(OH)2, and -SO2-NH-SO2-CF3.

2. A proton exchange resin having multiple proton conducting centers as claimed in claim 1, characterized in that: The structure of R is: One of them.

3. The method for preparing a proton exchange resin having multiple proton conduction centers according to claim 1 or 2, characterized in that: The following steps are involved: S1, the compound PFSF of formula I undergoes nucleophilic substitution reaction with liquid ammonia to obtain the compound PFS-NH2 of formula II; Wherein, x and y are integers between 1 and 100, m and n are integers between 0 and 10, and m and n are not 0 at the same time; S2, the amino group on the side chain of PFS-NH2 undergoes Hinsberg reaction with monomers containing benzenesulfonyl chloride to generate a proton exchange resin containing multiple proton conduction centers.

4. The method for preparing a proton exchange resin having multiple proton conduction centers according to claim 3, characterized in that: In step S1, the reaction temperature is -80°C to 30°C, and the reaction time is 24-72h.

5. The method for preparing a proton exchange resin having multiple proton conduction centers according to claim 3, characterized in that: In step S2, the molar ratio of PFS-NH2 to the monomer containing benzenesulfonyl chloride is 1:2-8.

6. The method for preparing a proton exchange resin having multiple proton conduction centers according to claim 3, characterized in that: In step S2, PFS-NH2 is added to an organic solvent and heated to dissolve, then the temperature is lowered to 0°C, a monomer containing benzenesulfonyl chloride and an acid binding agent are added to carry out a Hinsberg reaction, and after the reaction is completed, an acid is added to precipitate, which is purified and dried to obtain a proton exchange resin.

7. The method for preparing a proton exchange resin having multiple proton conduction centers according to claim 6, characterized in that: In step S2, the reaction time is 12-72 hours, and the molar ratio of PFS-NH2 to the acid binding agent is 1:2-10.

8. The method for preparing a proton exchange resin having multiple proton conduction centers according to claim 6, characterized in that: The organic solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, ethyl acetate, hexafluorobenzene and dioxane; the acid binding agent is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, cesium carbonate, lithium hydride, sodium hydride, triethylamine and ethylenediamine.

9. Use of a proton exchange resin having multiple proton conduction centers as claimed in any one of claims 1 to 8 in the preparation of a proton exchange membrane, characterized in that: The proton exchange resin is dissolved in an alcohol solution, and then a film is prepared by a tape casting method to obtain a proton exchange membrane.

10. Use of the proton exchange membrane as claimed in claim 9 in fuel cells and water electrolyzers.

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