阅读说明：本技术 一种质子交换膜及其制备方法和应用 (Proton exchange membrane and preparation method and application thereof ) 是由 蒋仲杰 黄宏毫 于 2021-06-02 设计创作，主要内容包括：本发明公开了一种质子交换膜及其制备方法和应用。本发明的质子交换膜的组成包括以下质量百分比的组分：磺化聚醚醚酮：93％～99％；磺化炭化铁基MOF：1％～7％。本发明的质子交换膜的制备方法包括以下步骤：将磺化聚醚醚酮和磺化炭化铁基MOF配制成涂膜液,再涂覆在基板上,干燥成膜,即得质子交换膜。本发明的质子交换膜具有低溶胀率、低甲醇渗透率和高质子传导率,且制备方法简单、成本低,适合大面积推广应用。(The invention discloses a proton exchange membrane and a preparation method and application thereof. The proton exchange membrane comprises the following components in percentage by mass: sulfonated polyether ether ketone: 93 to 99 percent; sulfonated carbonized iron-based MOF: 1 to 7 percent. The preparation method of the proton exchange membrane comprises the following steps: preparing a coating solution from sulfonated polyether ether ketone and sulfonated carbonized iron-based MOF, coating the coating solution on a substrate, and drying to form a membrane, thereby obtaining the proton exchange membrane. The proton exchange membrane has the advantages of low swelling rate, low methanol permeability, high proton conductivity, simple preparation method, low cost and suitability for large-area popularization and application.)

1. The proton exchange membrane is characterized by comprising the following components in percentage by mass:

sulfonated polyether ether ketone: 93 to 99 percent;

sulfonated carbonized iron-based MOF: 1 to 7 percent.

2. The proton exchange membrane according to claim 1 wherein: the sulfonation degree of the sulfonated polyether-ether-ketone is 50-80%.

3. The proton exchange membrane according to claim 1 or 2, wherein: the structural formula of the sulfonated polyether ether ketone is as follows:

wherein x is an integer of 10 to 30, and y is an integer of 10 to 30.

4. The proton exchange membrane according to claim 1 or 2, wherein: the sulfonated carbonized iron-based MOF is prepared by the following method:

1) dispersing ferric salt and fumaric acid in a solvent, carrying out coordination reaction, placing the obtained solid product in a protective atmosphere, calcining, immersing the calcined product in an oxalic acid solution, and soaking to obtain carbonized iron-based MOF;

2) dispersing the carbonized iron-based MOF and mercaptosiloxane in a solvent, and carrying out grafting modification to obtain mercaptosiloxane grafted carbonized iron-based MOF;

3) adding the carbonized iron-based MOF grafted by the mercaptosiloxane into a hydrogen peroxide solution, and carrying out oxidation reaction to obtain the sulfonated carbonized iron-based MOF.

5. The proton exchange membrane according to claim 4 wherein: the molar ratio of iron ions to fumaric acid in the iron salt in the step 1) is 3: 25-3: 45.

6. The proton exchange membrane according to claim 4 wherein: the coordination reaction in the step 1) is carried out at the temperature of 80-120 ℃, and the reaction time is 6-15 h; the calcination in the step 1) is carried out at the temperature of 300-500 ℃ for 1-3 h.

7. The proton exchange membrane according to claim 4 wherein: the grafting modification in the step 2) is carried out at the temperature of 80-120 ℃, and the reaction time is 2-24 h.

8. The proton exchange membrane according to claim 4 wherein: and 3) carrying out the oxidation reaction at normal temperature for 1-7 h.

9. The method for preparing a proton exchange membrane according to any one of claims 1 to 8, comprising the steps of: preparing a coating solution from sulfonated polyether ether ketone and sulfonated carbonized iron-based MOF, coating the coating solution on a substrate, and drying to form a membrane, thereby obtaining the proton exchange membrane.

10. Use of a proton exchange membrane according to any one of claims 1 to 8 in the manufacture of a proton exchange membrane fuel cell.

Technical Field

The invention relates to the technical field of fuel cells, in particular to a proton exchange membrane and a preparation method and application thereof.

Background

Proton Exchange Membrane Fuel Cells (PEMFCs) can convert chemical energy in fuel (e.g., hydrogen, methanol, etc.) and oxygen into electrical energy in an electrochemical reaction directly without combustion. The fuel is oxidized at the anode, the generated protons are transmitted to the cathode through the proton exchange membrane, the lost electrons reach the cathode through an external circuit, and the oxygen obtains the electrons at the cathode and is combined with the protons to generate water. The energy conversion of the fuel cell is not limited by Carnot cycle, the fuel utilization rate is very high, and the fuel cell is a high-efficiency and environment-friendly power generation device. The proton exchange membrane is one of the most critical components in the PEMFC, and plays roles of conducting protons and blocking fuel permeation (preventing fuel from diffusing from the anode to the cathode to cause catalyst poisoning of the cathode) in the fuel cell, and the superiority and inferiority of the performance thereof directly affect the overall performance of the PEMFC.

Currently, the most commonly used proton exchange membrane is a perfluorosulfonic acid membrane (e.g., Nafion membrane), which has high proton conductivity and chemical stability, but has the problems of high cost and high fuel permeability, which seriously hinders the practical application of PEMFCs. Sulfonated polyether ether ketone (SPEEK) has a hydrophobic main chain and a sulfonate group, has a structure similar to that of perfluorosulfonic acid, has high proton conductivity and methanol permeability lower than that of a perfluorosulfonic acid membrane when used as a proton exchange membrane, has the characteristics of low cost and high mechanical strength, and has better application prospect. However, the proton conductivity of the SPEEK membrane depends on the degree of sulfonation, the SPEEK membrane with low sulfonation degree has good dimensional stability, but the sulfonate groups for conducting protons are few, so the proton conductivity is low, and the requirement of the SPEEK membrane as a proton exchange membrane cannot be met, and the high sulfonation degree can cause the SPEEK membrane to excessively swell in water, the membrane structure is damaged, and the requirement of the SPEEK membrane as a proton exchange membrane cannot be met. In conclusion, most of the existing proton exchange membranes have obvious defects and cannot completely meet the requirements of practical application.

Therefore, there is a need to develop a proton exchange membrane with low cost, low swelling ratio, low methanol permeability, and high proton conductivity.

Disclosure of Invention

The invention aims to provide a proton exchange membrane and a preparation method and application thereof.

The technical scheme adopted by the invention is as follows:

a proton exchange membrane comprises the following components in percentage by mass:

sulfonated polyether ether ketone: 93 to 99 percent;

sulfonated carbonized iron-based MOF: 1 to 7 percent.

Preferably, the sulfonation degree of the sulfonated polyether ether ketone is 50-80%. The sulfonation Degree (DS) refers to the degree of replacement of hydrogen on a polyether-ether-ketone structural unit by a sulfonate group, and the theoretical value of the DS can be calculated by an Ion Exchange Capacity (IEC) value, and the calculation formula is as follows:where IEC is the amount of exchangeable ion species per gram and the exchange ion of the sulfonated polyetheretherketone is the hydrogen on the sulfonic acid group.

Preferably, the sulfonated polyether ether ketone has a structural formula:

wherein x is an integer of 10 to 30, and y is an integer of 10 to 30.

Preferably, the sulfonated carbonized iron-based MOF is prepared by the following method:

1) dispersing ferric salt and fumaric acid in a solvent, carrying out coordination reaction, placing the obtained solid product in a protective atmosphere, calcining, immersing the calcined product in an oxalic acid solution, and soaking to obtain carbonized iron-based MOF;

2) dispersing the carbonized iron-based MOF and mercaptosiloxane in a solvent, and carrying out grafting modification to obtain mercaptosiloxane grafted carbonized iron-based MOF;

3) adding the carbonized iron-based MOF grafted by the mercaptosiloxane into a hydrogen peroxide solution, and carrying out oxidation reaction to obtain the sulfonated carbonized iron-based MOF.

Preferably, the ferric salt in step 1) is at least one of ferric nitrate, ferric acetate, ferric trichloride and ferric sulfate.

Preferably, the molar ratio of the iron ions in the iron salt in the step 1) to the fumaric acid is 3: 25-3: 45.

Preferably, the coordination reaction in the step 1) is carried out at 80-120 ℃, and the reaction time is 6-15 h.

Preferably, the protective atmosphere in step 1) is a nitrogen atmosphere.

Preferably, the calcination in the step 1) is carried out at 300-500 ℃, and the calcination time is 1-3 h.

Preferably, the mercaptosiloxane in step 2) is at least one of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and mercaptopropylmethyldimethoxysilane.

Preferably, the solvent in step 2) is at least one of toluene, n-butanol, xylene, ethanol, hexane and carbon tetrachloride.

Preferably, the grafting modification in the step 2) is carried out at the temperature of 80-120 ℃, and the reaction time is 2-24 h.

Preferably, the oxidation reaction in the step 3) is carried out at normal temperature (10-30 ℃) for 1-7 hours.

The preparation method of the proton exchange membrane comprises the following steps: preparing a coating solution from sulfonated polyether ether ketone and sulfonated carbonized iron-based MOF, coating the coating solution on a substrate, and drying to form a membrane, thereby obtaining the proton exchange membrane.

Preferably, the preparation method of the proton exchange membrane comprises the following steps: preparing a coating solution from sulfonated polyether ether ketone and sulfonated carbonized iron-based MOF, coating the coating solution on a substrate, drying for 6-24 h at 60-80 ℃, and drying for 6-24 h at 90-150 ℃ to obtain the proton exchange membrane.

Preferably, the solvent in the coating solution is at least one of N, N-dimethylacetamide, N-dimethylformamide, N-dimethylpyrrolidone and dimethyl sulfoxide.

The invention has the beneficial effects that: the proton exchange membrane has the advantages of low swelling rate, low methanol permeability, high proton conductivity, simple preparation method, low cost and suitability for large-area popularization and application.

Specifically, the method comprises the following steps:

1) the invention takes the sulfonated polyether ether ketone as the matrix of the proton exchange membrane, has the advantages of low cost and simple synthesis, and the prepared proton exchange membrane has low cost and good performance;

2) the iron-based MOF has uniform particle size, the particle size is controllable, the carbonized iron-based MOF prepared from the iron-based MOF has the advantages of uniform particle size, large specific surface area, easiness in functionalization and the like, the problem of instability of the carbonized iron-based MOF in an acidic environment is solved by carbonizing the iron-based MOF, and the carbonized iron-based MOF is suitable for preparing a proton exchange membrane;

3) the carbonized iron-based MOF is functionalized by sulfonic acid and then used as a filler of the SPEEK proton exchange membrane, so that more functional groups can be provided for proton conduction, the proton conductivity of the proton exchange membrane is greatly improved, and the swelling and methanol permeability of the proton exchange membrane are reduced due to the strong interaction between the carbonized iron-based MOF and a membrane substrate;

4) the proton exchange membrane has simple preparation steps and low cost, and is suitable for large-area popularization and application.

Drawings

FIG. 1 is a flow chart of the preparation of sulfonated carbonized iron-based MOFs in the present invention.

FIG. 2 is an SEM image of the surface of the proton exchange membrane of example 2.

FIG. 3 is an SEM image of a cross-section of a proton exchange membrane of example 2.

Detailed Description

The invention will be further explained and illustrated with reference to specific examples.

Example 1:

a proton exchange membrane is prepared by the following steps:

1) putting polyether ether ketone (PEEK) with the number average molecular weight of 6200 g/mol-15800 g/mol into a vacuum oven, drying for 24 hours at 80 ℃, adding 5g of dried PEEK into 100mL of concentrated sulfuric acid with the mass fraction of 98% while stirring, violently stirring for 3 hours at 50 ℃, slowly adding the reaction mixture into a large amount of ice-water mixed liquid while stirring, drawing the mixture into threads, washing the threads to be neutral by using pure water for multiple times, filtering, putting the filtered solid into the oven, and drying for 24 hours at 60 ℃ to obtain sulfonated polyether ether ketone;

2) 32mmol of fumaric acid were dissolved in 40mL of N, N-dimethylformamide, and 3mmol of Fe (NO) were added with stirring₃)₃Continuously stirring until the solid is completely dissolved, adding the reaction solution into a high-pressure hydrothermal reaction kettle with the volume of 100mL, and placing the reaction kettle in a blast oven for heatingReacting at 100 ℃ for 10 hours, pouring out reaction liquid after the reaction kettle is cooled, centrifuging at the rotating speed of 8000r/min, alternately cleaning the solid obtained by centrifuging with absolute ethyl alcohol and N, N-dimethylformamide, centrifuging after each cleaning, at the rotating speed of 8000r/min, adding the solid obtained by the last centrifuging into an oven, drying at 60 ℃ for 12 hours, adding the dried product into a tubular furnace, continuously introducing nitrogen into the tubular furnace, raising the temperature in the tubular furnace to 400 ℃, keeping for 2 hours, naturally cooling, taking out the product, placing the product into an oxalic acid solution with the mass fraction of 13.4%, stirring at room temperature for 24 hours, filtering, washing the filtered solid with water for multiple times, placing into the oven, and drying at 60 ℃ for 24 hours to obtain the carbonized iron-based MOF;

3) adding 0.2g of carbonized iron-based MOF and 3mL of 3-mercaptopropyltrimethoxysilane into 15mL of toluene, performing ultrasonic dispersion, adding the dispersion into a condensation reflux reaction device, heating to 80 ℃, refluxing for 4H, filtering, washing the filtered solid with absolute ethyl alcohol for 3 times, and performing ultrasonic dispersion on the solid product in H with the mass fraction of 30%₂O₂Stirring the solution for 5h at normal temperature, filtering, washing the filtered solid with ethanol and water for multiple times, and drying in an oven to obtain sulfonated carbonized iron-based MOF (the preparation flow chart is shown in figure 1);

4) dispersing 1g of sulfonated polyether ether ketone in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of sulfonated polyether ether ketone, dispersing 100mg of sulfonated carbonized iron-based MOF in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of sulfonated carbonized iron-based MOF, mixing the N, N-dimethylacetamide solution of sulfonated polyether ether ketone and the MOF N, N-dimethylacetamide solution of sulfonated iron-based carbonized iron-based MOF according to a volume ratio of 99:10, performing ultrasonic treatment to prepare a coating solution, casting the coating solution onto a glass plate, placing the glass plate in a vacuum oven, drying the glass plate for 12 hours at 80 ℃, and drying the glass plate for 12 hours at 100 ℃ to obtain a proton exchange membrane (the thickness is 80 mu m, and the mass percentage content of the sulfonated carbonized iron-based MOF is 1%).

Example 2:

a proton exchange membrane is prepared by the following steps:

dispersing 1g of sulfonated polyether ether ketone in example 1 in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of sulfonated polyether ether ketone, dispersing 100mg of sulfonated carbonized iron-based MOF in example 1 in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of sulfonated carbonized iron-based MOF, mixing the N, N-dimethylacetamide solution of sulfonated polyether ether ketone and the N, N-dimethylacetamide solution of sulfonated carbonized iron-based MOF according to a volume ratio of 97:30, performing ultrasound to prepare a coating solution, casting the coating solution onto a glass plate, placing the glass plate into a vacuum oven, drying the glass plate at 80 ℃ for 12h, and drying the glass plate at 100 ℃ for 12h to obtain a proton exchange membrane (the thickness is 80 μm, and the mass percentage content of the sulfonated carbonized iron-based MOF is 3%).

A Scanning Electron Microscope (SEM) image of the surface of the proton exchange membrane prepared in this example is shown in fig. 2, and a SEM image of the cross section is shown in fig. 3.

As can be seen from fig. 2: the surface of the proton exchange membrane is uniform and smooth, the structure is compact, and no pinholes exist on the surface, which shows that the sulfonated carbonized iron-based MOF and the sulfonated polyether ether ketone are uniformly mixed, and the sulfonated carbonized iron-based MOF is not gathered on the surface of the membrane but is coated inside the membrane structure by the sulfonated polyether ether ketone.

As can be seen from fig. 3: the sulfonated carbonized iron-based MOF is uniformly dispersed in the sulfonated polyether ether ketone, and the sulfonated carbonized iron-based MOF does not have an agglomeration phenomenon, which is important for improving the proton conductivity of the proton exchange membrane.

Example 3:

a proton exchange membrane is prepared by the following steps:

dispersing 1g of sulfonated polyether ether ketone in example 1 in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of sulfonated polyether ether ketone, dispersing 100mg of sulfonated carbonized iron-based MOF in example 1 in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of sulfonated carbonized iron-based MOF, mixing the N, N-dimethylacetamide solution of sulfonated polyether ether ketone and the N, N-dimethylacetamide solution of sulfonated carbonized iron-based MOF according to a volume ratio of 95:50, performing ultrasound to prepare a coating solution, casting the coating solution onto a glass plate, placing the glass plate into a vacuum oven, drying the glass plate at 80 ℃ for 12h, and drying the glass plate at 100 ℃ for 12h to obtain a proton exchange membrane (the thickness is 80 μm, and the mass percentage content of the sulfonated carbonized iron-based MOF is 5%).

Example 4:

a proton exchange membrane is prepared by the following steps:

dispersing 1g of sulfonated polyether ether ketone in example 1 in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of sulfonated polyether ether ketone, dispersing 100mg of sulfonated carbonized iron-based MOF in example 1 in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of sulfonated carbonized iron-based MOF, mixing the N, N-dimethylacetamide solution of sulfonated polyether ether ketone and the N, N-dimethylacetamide solution of sulfonated carbonized iron-based MOF according to a volume ratio of 93:70, performing ultrasound to prepare a coating solution, casting the coating solution onto a glass plate, placing the glass plate into a vacuum oven, drying the glass plate at 80 ℃ for 12h, and drying the glass plate at 100 ℃ for 12h to obtain a proton exchange membrane (the thickness is 80 μm, and the mass percentage content of the sulfonated carbonized iron-based MOF is 7%). Comparative example 1:

a proton exchange membrane is prepared by the following steps:

dispersing 1g of sulfonated polyether ether ketone obtained in example 1 in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of sulfonated polyether ether ketone, casting the N, N-dimethylacetamide solution of sulfonated polyether ether ketone on a glass plate, placing the glass plate in a vacuum oven, drying at 80 ℃ for 12h, and drying at 100 ℃ for 12h to obtain the proton exchange membrane (the thickness is 80 μm). Comparative example 2:

a proton exchange membrane is prepared by the following steps:

dispersing 1g of sulfonated polyether ether ketone in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of sulfonated polyether ether ketone, dispersing 100mg of the carbonized iron-based MOF in 1 in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of carbonized iron-based MOF, mixing the N, N-dimethylacetamide solution of sulfonated polyether ether ketone and the N, N-dimethylacetamide solution of carbonized iron-based MOF according to a volume ratio of 99:10, performing ultrasonic treatment to prepare a coating solution, casting the coating solution onto a glass plate, placing the glass plate in a vacuum oven, drying at 80 ℃ for 12h, and drying at 100 ℃ for 12h to obtain the proton exchange membrane (the thickness is 80 μm, and the mass percentage content of the carbonized iron-based MOF is 1%).

Comparative example 3:

a proton exchange membrane is prepared by the following steps:

dispersing 1g of sulfonated polyether ether ketone in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of sulfonated polyether ether ketone, dispersing 100mg of the carbonized iron-based MOF in 1 in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of carbonized iron-based MOF, mixing the N, N-dimethylacetamide solution of sulfonated polyether ether ketone and the N, N-dimethylacetamide solution of carbonized iron-based MOF according to a volume ratio of 97:30, performing ultrasonic treatment to prepare a coating solution, casting the coating solution onto a glass plate, placing the glass plate in a vacuum oven, drying at 80 ℃ for 12h, and drying at 100 ℃ for 12h to obtain a proton exchange membrane (the thickness is 80 μm, and the mass percentage content of the carbonized iron-based MOF is 3%).

Comparative example 4:

a proton exchange membrane is prepared by the following steps:

dispersing 1g of sulfonated polyether ether ketone in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of sulfonated polyether ether ketone, dispersing 100mg of the carbonized iron-based MOF in 1 in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of carbonized iron-based MOF, mixing the N, N-dimethylacetamide solution of sulfonated polyether ether ketone and the N, N-dimethylacetamide solution of carbonized iron-based MOF according to a volume ratio of 95:50, performing ultrasonic treatment to prepare a coating solution, casting the coating solution onto a glass plate, placing the glass plate in a vacuum oven, drying at 80 ℃ for 12h, and drying at 100 ℃ for 12h to obtain a proton exchange membrane (the thickness is 80 μm, and the mass percentage content of the carbonized iron-based MOF is 5%).

Comparative example 5:

a proton exchange membrane is prepared by the following steps:

dispersing 1g of sulfonated polyether ether ketone in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of sulfonated polyether ether ketone, dispersing 100mg of the carbonized iron-based MOF in 1 in 10mL of N, N-dimethylacetamide to prepare an N, N-dimethylacetamide solution of carbonized iron-based MOF, mixing the N, N-dimethylacetamide solution of sulfonated polyether ether ketone and the N, N-dimethylacetamide solution of carbonized iron-based MOF according to a volume ratio of 93:70, performing ultrasound to prepare a coating solution, casting the coating solution onto a glass plate, placing the glass plate in a vacuum oven, drying at 80 ℃ for 12h, and drying at 100 ℃ for 12h to obtain a proton exchange membrane (the thickness is 80 μm, and the mass percentage content of the carbonized iron-based MOF is 7%).

And (3) performance testing:

1) the ion exchange capacity, water absorption and swelling ratio of the proton exchange membranes of examples 1 to 4 and comparative examples 1 to 5 were measured, and the results are shown in the following table:

TABLE 1 ion exchange Capacity, Water absorption, and swelling Rate test results for proton exchange membranes

As can be seen from Table 1:

a) the addition of the sulfonated carbonized iron-based MOF can maintain the ion exchange capacity of the proton exchange membrane, particularly the ion exchange capacity of the proton exchange membrane in the examples 1 and 2 is very close to that of a pure sulfonated polyether ether ketone membrane (comparative example 1), while the addition of the carbonized iron-based MOF can cause the decrease of the ion exchange capacity of the proton exchange membrane, and the decrease degree of the ion exchange capacity is more obvious along with the increase of the addition amount of the carbonized iron-based MOF (the ion exchange capacities of the proton exchange membranes in the comparative examples 2-5 are all decreased, and the decrease of the comparative example 5 is most obvious);

b) the water absorption rate and the expansion rate of the proton exchange membrane can be reduced by adding the sulfonated carbonized iron-based MOF and the carbonized iron-based MOF, and the water absorption rate and the expansion rate of the proton exchange membrane can be reduced more and more along with the increase of the added amount of the sulfonated carbonized iron-based MOF or the carbonized iron-based MOF (the change trend is more obvious at 80 ℃).

2) The proton conductivity and methanol permeability of examples 1 to 4 and comparative examples 1 to 5 were measured, and the results are shown in the following table:

TABLE 2 proton conductivity and methanol permeability test results for proton exchange membranes

As can be seen from Table 2:

a) the addition of the sulfonated carbonized iron-based MOF can obviously improve the proton conductivity of the proton exchange membrane at different temperatures, but the higher the addition amount of the sulfonated carbonized iron-based MOF is, the higher the proton conductivity is, the addition of the sulfonated carbonized iron-based MOF can also cause the reduction of the methanol permeability, but the methanol permeability can also start to rise after the amount of the sulfonated carbonized iron-based MOF exceeds a certain value;

b) the proton conductivity of the proton exchange membrane can be properly improved when the addition amount of the carbonized iron-based MOF is less, but the effect is not as obvious as that of the sulfonated carbonized iron-based MOF, and the proton conductivity of the proton exchange membrane can be reduced when the addition amount of the carbonized iron-based MOF reaches a certain value.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.