CN110010942B - Composite proton exchange membrane and preparation method thereof - Google Patents
Composite proton exchange membrane and preparation method thereof Download PDFInfo
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- CN110010942B CN110010942B CN201910197162.1A CN201910197162A CN110010942B CN 110010942 B CN110010942 B CN 110010942B CN 201910197162 A CN201910197162 A CN 201910197162A CN 110010942 B CN110010942 B CN 110010942B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the technical field of proton exchange membrane fuel cells, in particular to a composite proton exchange membrane and a preparation method thereof, which comprises the following steps: s1: preparing a part of fluorosulfonyl fluoride resin; s2: and adding a polytetrafluoroethylene membrane into the low-carbon alcohol solution of the partial fluorosulfonyl fluororesin to prepare the composite proton exchange membrane. The invention can reduce the cost, is convenient for batch production, and simultaneously reduces the thickness of the composite proton exchange membrane, improves the mechanical property and improves the stability.
Description
Technical Field
The invention relates to the technical field of proton exchange membrane fuel cells, in particular to a composite proton exchange membrane and a preparation method thereof.
Background
With the exhaustion of traditional energy sources, new energy sources are more and more concerned in development and utilization, a hydrogen fuel cell automobile is an important direction for the development of new energy vehicles, and the performance of a proton exchange membrane influences the performance of a galvanic pile to a great extent, so that the dynamic economy performance of the whole automobile is influenced.
A Proton Exchange Membrane Fuel Cell (PEMFC) is a device that generates electrical energy by directly performing a chemical reaction on hydrogen and oxygen, has the advantages of high energy conversion rate, short low-temperature start-up time, no electrolyte corrosion, and the like, and can be applied to the fields of aerospace, military, electric vehicles, regional power stations, and the like. The Proton Exchange Membrane (PEM) is one of the core components of the proton exchange membrane fuel cell, the PEM is a membrane which plays a role in transferring protons in the PEM fuel cell, the PEMFC (PEMFC) is provided with two electrodes on two sides of the PEM, the anode is communicated with hydrogen, the cathode is communicated with an oxidant, and H in the hydrogen+Through the proton exchange membrane, electrons can only pass through the wire, and thus, current is formed. The material of the Proton Exchange Membrane (PEM) is generally a perfluoroalkyl sulfonic acid polymer material. This material has good proton conductivity, but the cost of the material is high, which is disadvantageous for commercial large-scale use.
However, in order to reduce the cost of Proton Exchange Membranes (PEM), both partially fluorinated sulfonic acid proton exchange membranes and non-fluorinated proton exchange membranes have been the research direction of researchers. For example, the barad company in canada has developed a polytrifluoroethylene film, which has good thermal stability, chemical stability and relatively high water absorption rate, but the preparation process is too complicated, which affects large-scale industrial application; alternatively, for example, the company is developing a non-fluorinated proton exchange membrane (BaM2G) that has been developed. The membrane is prepared by sulfonating polyphenylquinoxaline and poly-diphenol, the performance of a Membrane Electrode (MEA) prepared by the membrane is better than that of a perfluorosulfonic acid (Nafion)117 membrane, but the service life of the battery is less than 500 hours, so that the development of a partially fluorinated proton exchange membrane by a Brader is forced.
For example, Gore company has developed a novel composite membrane, which is prepared from a polytetrafluoroethylene porous membrane and a perfluorosulfonic acid resin, and defines the commercial model of the composite membrane as Gore-se-lect, and has been applied to Proton Exchange Membrane Fuel Cells (PEMFCs), but Gore company has not published a preparation method of the composite membrane.
A method for preparing a composite proton exchange membrane has also been proposed in chinese patent 01136845, researchers have proposed the preparation of composite membranes from low alcohol solutions of Polytetrafluoroethylene (PTFE) and perfluorosulfonic acid (Nafion) resins, according to the Scanning Electron Microscope (SEM) picture of the composite membrane, the perfluorinated sulfonic acid resin low-alcohol solution is not only immersed into the gaps of the polytetrafluoroethylene, a continuous film was also formed on the surface of the porous membrane, the original Polytetrafluoroethylene (PTFE) film having a thickness of 15 microns, and the composite film having a thickness of 25 microns, and according to the test, the composite membrane prepared by the method is obviously superior to a perfluorosulfonic acid (Nafion) membrane in the aspect of dimensional stability, and simultaneously, the voltammetry characteristic curve of the composite membrane shows that, the performance of the composite membrane is superior to that of a perfluorosulfonic acid (Nafion)115 membrane, and the composite membrane is stable in performance, but the water absorption capacity of the composite membrane is reduced.
In order to solve the defects of the proton exchange membrane, improve and improve the prior art, and prepare the proton exchange membrane more suitable for a Proton Exchange Membrane Fuel Cell (PEMFC).
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a composite proton exchange membrane and a preparation method thereof, which can reduce the cost, facilitate mass production, and simultaneously reduce the thickness of the composite proton exchange membrane, improve the mechanical properties, and improve the stability.
In order to solve the above problems, the present invention provides a method for preparing a composite proton exchange membrane, comprising the steps of: s1: preparing a part of fluorosulfonyl fluoride resin; s2: and adding a polytetrafluoroethylene membrane into the low-carbon alcohol solution of the partial fluorosulfonyl fluororesin to prepare the composite proton exchange membrane.
Further, the step S1 further includes: s11: preparing a perfluorosulfonyl ether monomer; s12: carrying out polymerization reaction on the perfluorosulfonyl ether monomer, polytetrafluoroethylene and ethylene to form a part of fluorosulfonyl fluororesin containing sodium ions; s13: and replacing sodium ions in the partial fluorine sulfonyl fluorine resin with hydrogen ions to form partial fluorine sulfonyl fluorine resin.
Further, in step S11, the perfluorosulfonyl ether monomer is formed by a condensation reaction of cyclic sulfone and sodium carbonate, and the cyclic sulfone is formed by a reaction of tetrafluoroethylene and sulfur trioxide.
Further, the step S2 further includes: s21: dissolving part of fluorosulfonyl fluoride resin in a low-carbon alcohol solution to prepare a mixed solution A; s22: soaking a polytetrafluoroethylene membrane into the mixed solution A to prepare a mixed solution B; s23: adding a high-boiling-point solvent into the mixed solution B to prepare a mixed solution C; s24: heating the mixed solution C, and standing the mixed solution C for at least 3 hours.
Further, the low-carbon alcohol solution is one of a methanol solution, an ethanol solution and an isopropanol solution.
Further, the thickness of the polytetrafluoroethylene film is 15um-25 um.
Further, the polytetrafluoroethylene membrane is a porous polytetrafluoroethylene membrane, and the pore diameter of the porous polytetrafluoroethylene membrane is 0.3-0.5 um.
Further, in the step S22, the high boiling point solvent is dimethyl sulfoxide or/and N-dimethylacetamide solvent.
Further, the preparation method also comprises the following steps: s3: placing the composite proton exchange membrane in a vacuum environment at 150-180 ℃, extruding the composite proton exchange membrane to reduce the temperature to below 60 ℃, and spraying a low-carbon alcohol solution of partial fluorosulfonyl fluororesin on the surface of the composite proton exchange membrane; s4: repeating the step S3 for at least three times to restore the temperature threshold of the composite proton exchange membrane.
The invention also provides a composite proton exchange membrane, which is prepared by the preparation method of the composite proton exchange membrane, and comprises partial fluorosulfonyl fluoride resin and a polytetrafluoroethylene membrane, wherein the partial fluorosulfonyl fluoride resin is embedded into interstitial holes of the polytetrafluoroethylene membrane.
Due to the technical scheme, the invention has the following beneficial effects:
1) the composite proton exchange membrane and the preparation method thereof adopt ethylene to replace tetrafluoroethylene, can reduce the manufacturing cost and are convenient for batch production.
2) According to the composite proton exchange membrane and the preparation method thereof, the composite proton exchange membrane is prepared by adopting the porous polytetrafluoroethylene membrane, so that the thickness of the composite proton exchange membrane can be reduced, the mechanical property is improved, and the stability is improved.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the description of the embodiment or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is a flow chart of a method for preparing a composite proton exchange membrane provided in example 1 of the present invention;
fig. 2 is a flowchart of step S1 provided in embodiment 1 of the present invention;
fig. 3 is a flowchart of step S2 provided in embodiment 1 of the present invention;
fig. 4 is a flow chart of a method for preparing a composite proton exchange membrane provided in embodiment 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. In the description of the present invention, it is to be understood that the terms "upper", "lower", "left", "right", "top", "bottom", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. Moreover, the terms "first," "second," and the like are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein.
Example one
The embodiment provides a preparation method of a composite proton exchange membrane, as shown in fig. 1, including the following steps:
s1: preparing a part of fluorosulfonyl fluoride resin.
Specifically, a product formed by replacing a part of polytetrafluoroethylene with ethylene in the production process of perfluorosulfonyl fluororesin is a part of fluorosulfonyl fluororesin.
Specifically, as shown in fig. 2, the step S1 further includes: s11: preparing a perfluorosulfonyl ether monomer; s12: carrying out polymerization reaction on the perfluorosulfonyl ether monomer, polytetrafluoroethylene and ethylene to form a part of fluorosulfonyl fluororesin containing sodium ions; s13: and replacing sodium ions in the partial fluorine sulfonyl fluorine resin with hydrogen ions to form partial fluorine sulfonyl fluorine resin.
Specifically, in step S11, the perfluorosulfonyl ether monomer is formed by a condensation reaction between cyclic sulfone and sodium carbonate, and the cyclic sulfone is formed by a reaction between tetrafluoroethylene and sulfur trioxide.
Further, the chemical formula of the partial fluorosulfonyl fluoride resin is shown in the specification, wherein x is 3-6, y is 1, z is 3-4, and m is 1.
Specifically, the membrane formed by the partial fluorosulfonyl fluoride resin can realize the principle of proton exchange: the microstructure of the film formed of the partial fluorosulfonyl fluoride resin is an ion cluster structure in which, in the microstructure, the fluorocarbon of the partial fluorine sulfonyl fluorine resin and the hydrocarbon main chain of the partial fluorine sulfonyl fluorine resin form a crystal phase region, the fluorocarbon has hydrophobic property, part of ether branched chains of the partial fluorosulfonyl fluororesin and part of fluorocarbon chains of the partial fluorosulfonyl fluororesin form an intermediate phase, the sulfonate of the partial fluorine sulfonyl fluorine resin and water ions absorbed by the partial fluorine sulfonyl fluorine resin form a water nuclear ion cluster, the water nuclear ion clusters are distributed in the crystal phase region, the water nuclear ion clusters are 4nm, the distance between every two adjacent water nuclear ion clusters is 5nm, the adjacent water nuclear ion clusters are connected through a tubule, the width of the tubule phase is 1nm, and water or ions can exchange protons through the tubule phase region.
S2: and adding a polytetrafluoroethylene membrane into the low-carbon alcohol solution of the partial fluorosulfonyl fluororesin to prepare the composite proton exchange membrane.
Specifically, as shown in fig. 3, the step S2 further includes: s21: dissolving part of fluorosulfonyl fluoride resin in a low-carbon alcohol solution to prepare a mixed solution A; s22: dissolving a polytetrafluoroethylene membrane into the mixed solution A to prepare a mixed solution B; s23: adding a high-boiling-point solvent into the mixed solution B to prepare a mixed solution C; s24: heating the mixed solution C, and standing the mixed solution C for at least 3 hours.
Specifically, the low-carbon alcohol solution is one of a methanol solution, an ethanol solution and an isopropanol solution.
In some embodiments, the lower alcohol solution can also be selected from aqueous solutions of other lower alcohol compounds.
Specifically, in the step S21, the thickness of the polytetrafluoroethylene film is 15um to 25 um.
Further, the polytetrafluoroethylene membrane is a porous polytetrafluoroethylene membrane, and the pore diameter of the porous polytetrafluoroethylene membrane is 0.3-0.5 um.
Further, the step S21 is capable of removing organic impurities in the partial fluorosulfonyl fluoride resin and appropriately swelling the partial fluorosulfonyl fluoride resin.
Specifically, in step S22, the high boiling point solvent is dimethyl sulfoxide or/and N-dimethylacetamide, and the high boiling point solvent can improve the flexibility and compactness of the composite membrane.
Further, the step S23 enables the partial fluorosulfonyl fluoride resin to be dissolved into the porous polytetrafluoroethylene membrane, enabling the thickness of the composite proton exchange membrane to be reduced.
The embodiment provides a preparation method of a composite proton exchange membrane, which can adopt ethylene to replace tetrafluoroethylene, can reduce the manufacturing cost, and is convenient for batch production.
Example two
The second embodiment provides a preparation method of a composite proton exchange membrane, as shown in fig. 4, including the following steps:
s1: preparing a part of fluorosulfonyl fluoride resin.
Specifically, a product formed by replacing a part of polytetrafluoroethylene with ethylene in the production process of perfluorosulfonyl fluororesin is a part of fluorosulfonyl fluororesin.
Specifically, the step S1 further includes: s11: preparing a perfluorosulfonyl ether monomer; s12: carrying out polymerization reaction on the perfluorosulfonyl ether monomer, polytetrafluoroethylene and ethylene to form a part of fluorosulfonyl fluororesin containing sodium ions; s13: and replacing sodium ions in the partial fluorine sulfonyl fluorine resin with hydrogen ions to form partial fluorine sulfonyl fluorine resin.
Specifically, in step S11, the perfluorosulfonyl ether monomer is formed by a condensation reaction between cyclic sulfone and sodium carbonate, and the cyclic sulfone is formed by a reaction between tetrafluoroethylene and sulfur trioxide under certain conditions.
Further, the chemical formula of the partial fluorosulfonyl fluoride resin is shown in the specification, wherein x is 3-6, y is 1, z is 3-4, and m is 1.
Specifically, the membrane formed by the partial fluorosulfonyl fluoride resin can realize the principle of proton exchange: the microstructure of the film formed of the partial fluorosulfonyl fluoride resin is an ion cluster structure in which, in the microstructure, the fluorocarbon of the partial fluorine sulfonyl fluorine resin and the hydrocarbon main chain of the partial fluorine sulfonyl fluorine resin form a crystal phase region, the fluorocarbon has hydrophobic property, part of ether branched chains of the partial fluorosulfonyl fluororesin and part of fluorocarbon chains of the partial fluorosulfonyl fluororesin form an intermediate phase, the sulfonate of the partial fluorine sulfonyl fluorine resin and water ions absorbed by the partial fluorine sulfonyl fluorine resin form a water nuclear ion cluster, the water nuclear ion clusters are distributed in the crystal phase region, the water nuclear ion clusters are 4nm, the distance between every two adjacent water nuclear ion clusters is 5nm, the adjacent water nuclear ion clusters are connected through a tubule, the width of the tubule phase is 1nm, and water or ions can exchange protons through the tubule phase region.
S2: and adding a polytetrafluoroethylene membrane into the low-carbon alcohol solution of the partial fluorosulfonyl fluororesin to prepare the composite proton exchange membrane.
Specifically, the step S2 further includes: s21: dissolving part of fluorosulfonyl fluoride resin in a low-carbon alcohol solution to prepare a mixed solution A; s22: dissolving a polytetrafluoroethylene membrane into the mixed solution A to prepare a mixed solution B; s23: adding a high-boiling-point solvent into the mixed solution B to prepare a mixed solution C; s24: heating the mixed solution C, and standing the mixed solution C for at least 3 hours.
Specifically, the low-carbon alcohol solution is one of a methanol solution, an ethanol solution and an isopropanol solution.
In some embodiments, the lower alcohol solution can also be selected from aqueous solutions of other lower alcohol compounds.
Specifically, the thickness of the polytetrafluoroethylene film is 15um-25 um.
Further, the polytetrafluoroethylene membrane is a porous polytetrafluoroethylene membrane, and the pore diameter of the porous polytetrafluoroethylene membrane is 0.3-0.5 um.
Further, the step S21 is capable of removing organic impurities in the partial fluorosulfonyl fluoride resin and appropriately swelling the partial fluorosulfonyl fluoride resin.
Specifically, in step S22, the high boiling point solvent is dimethyl sulfoxide or/and N-dimethylacetamide, and the high boiling point solvent can improve the flexibility and compactness of the composite membrane.
Further, the step S23 enables the partial fluorosulfonyl fluoride resin to be dissolved into the porous polytetrafluoroethylene membrane, enabling the thickness of the composite proton exchange membrane to be reduced.
S3: and (2) placing the composite proton exchange membrane in a vacuum environment at 150-180 ℃, extruding the composite proton exchange membrane to reduce the temperature to below 60 ℃, and spraying a low-carbon alcohol solution of part of the fluorosulfonyl fluororesin on the surface of the composite proton exchange membrane.
S4: repeating the step S3 for at least three times to restore the temperature threshold of the composite proton exchange membrane.
In particular, the temperature threshold is 23 ℃.
Specifically, the steps S3 and S4 can adjust flexibility, mechanical strength, and insolubility in a high-temperature solvent of the composite proton exchange membrane.
The second embodiment provides a preparation method of a composite proton exchange membrane, which can replace tetrafluoroethylene with ethylene, reduce the manufacturing cost, and facilitate mass production, and meanwhile, the composite proton exchange membrane prepared by using a porous polytetrafluoroethylene membrane can reduce the thickness of the composite proton exchange membrane, improve the mechanical properties, and improve the stability.
The foregoing description has disclosed fully preferred embodiments of the present invention. It should be noted that those skilled in the art can make modifications to the embodiments of the present invention without departing from the scope of the appended claims. Accordingly, the scope of the appended claims is not to be limited to the specific embodiments described above.
Claims (9)
1. A preparation method of a composite proton exchange membrane is characterized by comprising the following steps:
s1: preparing a part of fluorosulfonyl fluoride resin; the step S1 further includes: s11: preparing a perfluorosulfonyl ether monomer; s12: carrying out polymerization reaction on the perfluorosulfonyl ether monomer, polytetrafluoroethylene and ethylene to form a part of fluorosulfonyl fluororesin containing sodium ions; s13: replacing sodium ions in the partial fluorosulfonyl fluoride resin with hydrogen ions to form a partial fluorosulfonyl fluoride resin;
s2: and adding a polytetrafluoroethylene membrane into the low-carbon alcohol solution of the partial fluorosulfonyl fluororesin to prepare the composite proton exchange membrane.
2. The method according to claim 1, wherein in step S11, the perfluorosulfonyl ether monomer is formed by a condensation reaction between cyclic sulfone and sodium carbonate, and the cyclic sulfone is formed by a reaction between tetrafluoroethylene and sulfur trioxide.
3. The method according to claim 1, wherein the step S2 further comprises:
s21: dissolving part of fluorosulfonyl fluoride resin in a low-carbon alcohol solution to prepare a mixed solution A;
s22: soaking a polytetrafluoroethylene membrane into the mixed solution A to prepare a mixed solution B;
s23: adding a high-boiling-point solvent into the mixed solution B to prepare a mixed solution C;
s24: heating the mixed solution C, and standing the mixed solution C for at least 3 hours.
4. The method for preparing a composite proton exchange membrane according to claim 3, wherein the low carbon alcohol solution is one of a methanol solution, an ethanol solution and an isopropanol solution.
5. The method for preparing a composite proton exchange membrane according to claim 3, wherein the thickness of the polytetrafluoroethylene membrane is 15um to 25 um.
6. The method for preparing a composite proton exchange membrane according to claim 5, wherein the polytetrafluoroethylene membrane is a porous polytetrafluoroethylene membrane, and the pore diameter of the porous polytetrafluoroethylene membrane is 0.3um to 0.5 um.
7. The method according to claim 3, wherein in step S23, the high-boiling-point solvent is dimethyl sulfoxide or/and N-dimethylacetamide.
8. A method for preparing a composite proton exchange membrane according to claim 1, wherein the method further comprises the steps of:
s3: placing the composite proton exchange membrane in a vacuum environment at 150-180 ℃, extruding the composite proton exchange membrane to reduce the temperature to below 60 ℃, and spraying a low-carbon alcohol solution of partial fluorosulfonyl fluororesin on the surface of the composite proton exchange membrane;
s4: repeating the step S3 for at least three times to restore the temperature threshold of the composite proton exchange membrane.
9. A composite proton exchange membrane, characterized in that the composite proton exchange membrane is prepared by the preparation method of the composite proton exchange membrane according to any one of claims 1 to 8, and the composite proton exchange membrane comprises a part of fluorosulfonyl fluoride resin and a polytetrafluoroethylene membrane, and the part of fluorosulfonyl fluoride resin is embedded in interstitial pores of the polytetrafluoroethylene membrane.
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