Preparation process of composite enhanced perfluorosulfonic acid proton exchange membrane

Abstract

The invention belongs to the technical field of preparation of perfluorosulfonic acid proton exchange membranes, and particularly relates to a preparation process of a composite enhanced perfluorosulfonic acid proton exchange membrane. The preparation process comprises the following steps: (1) preparing a first polytetrafluoroethylene substrate film; (2) preparing a membrane preparation solution; and (3) coating a glass plate with the membrane-making liquid, flatly covering the membrane-making liquid with a first polytetrafluoroethylene substrate membrane, coating the first polytetrafluoroethylene substrate membrane with the membrane-making liquid again, and finally carrying out heat treatment and post-treatment to prepare the composite enhanced perfluorosulfonic acid proton exchange membrane. According to the preparation process of the composite enhanced perfluorosulfonic acid proton exchange membrane, the first polytetrafluoroethylene substrate membrane and the perfluorosulfonic acid resin membrane preparation liquid have a synergistic effect, and the interfacial compatibility of the first polytetrafluoroethylene substrate membrane and the perfluorosulfonic acid resin membrane preparation liquid is improved; the finally prepared composite enhanced perfluorosulfonic acid proton exchange membrane has excellent mechanical strength, proton conduction effect and capability of inhibiting gas permeation.

Description

Technical Field

[0001] The invention belongs to the technical field of perfluorosulfonic acid proton exchange membrane preparation, and specifically relates to a preparation process of a composite enhanced perfluorosulfonic acid proton exchange membrane. Background Art

[0002] At present, homogeneous proton exchange membranes are difficult to adapt to the complex and multi-functional requirements of fuel cells (such as humidity, temperature, mechanical properties, water transfer within the membrane of electromigration water and reverse diffusion water, etc.), so composite proton exchange membranes are an important research direction. Since the swelling of perfluorosulfonic acid proton exchange membranes in hot water leads to a decrease in its mechanical strength, this is extremely unfavorable for the application of thin proton exchange membranes in fuel cells. In order to improve the mechanical stability of proton exchange membranes, mechanically enhanced proton exchange membranes can be prepared by compounding ionic polymers (proton conductive components) with support components. Based on the PTFE support component, the PTFE used in the enhanced membrane is divided into three categories: (1) expanded and stretched porous PTFE membrane; (2) PTFE woven yarn (embedded in the membrane); (3) PTFE fiber (uniformly dispersed in the membrane). However, due to the basically symmetrical distribution of the CF bonds in the porous polytetrafluoroethylene molecular chain and the relatively regular molecular structure, the microporous PTFE has very low polarity and poor hydrophilicity. The sulfonic acid group in the commonly used proton conductive component sulfonated polymer has good hydrophilicity, and there is an interfacial compatibility problem when the two are compounded.

[0003] Therefore, how to optimize the proton exchange membrane in the fuel cell and improve the proton conductivity of the proton exchange membrane while ensuring the mechanical strength of the prepared proton exchange membrane is a technical problem that needs to be solved urgently. Summary of the invention

[0004] The purpose of the present invention is to provide a process for preparing a composite enhanced perfluorosulfonic acid proton exchange membrane. The proton exchange membrane prepared by the process has excellent mechanical strength and proton conduction performance.

[0005] The preparation process of the composite enhanced perfluorosulfonic acid proton exchange membrane of the present invention comprises the following steps: (1) adding 2-hydroxyethyl methacrylate phosphate to a mixture of anhydrous ethanol and a nonionic fluorocarbon surfactant, then adding α,α-diethoxyacetophenone and stirring evenly to prepare a mixed solution, immersing a polytetrafluoroethylene-based base film in the mixed solution for 30-40 minutes, taking it out and evenly coating the mixed solution on the polytetrafluoroethylene-based base film using a coater, and finally performing ultraviolet light curing to prepare a first polytetrafluoroethylene-based base film; (2) adding the perfluorosulfonic acid resin solution to a mixture of 2-hydroxyethylammonium formate and N-methylpyrrolidone and reacting at 83-85° C. for 48-50 hours to prepare a membrane-forming solution; (3) The membrane-forming liquid prepared in step (2) is coated on a glass plate, and then the first polytetrafluoroethylene-based base film is evenly covered on the membrane-forming liquid, and then the membrane-forming liquid is coated again on the first polytetrafluoroethylene-based base film, and finally heat-treated and post-treated to prepare a composite enhanced perfluorosulfonic acid proton exchange membrane.

[0006] in: In step (1), the mass concentration of 2-hydroxyethyl methacrylate phosphate in the mixed solution of anhydrous ethanol and non-ionic fluorocarbon surfactant is 5-7%.

[0007] The mass of the nonionic fluorocarbon surfactant in step (1) accounts for 0.08% of the total mass of anhydrous ethanol and the nonionic fluorocarbon surfactant. The nonionic fluorocarbon surfactant is Capstone-FS-31, and the manufacturer is DuPont China Group Co., Ltd. Shanghai Branch.

[0008] In step (1), the mass of α,α-diethoxyacetophenone accounts for 0.2% of the mass of 2-hydroxyethyl methacrylate phosphate.

[0009] In step (1), the UV curing temperature is room temperature and the UV curing time is 6-8 minutes.

[0010] The polytetrafluoroethylene-based base film in step (1) is manufactured by Shandong Senrong New Materials Co., Ltd., and its model number is SRM001-03.

[0011] The manufacturer of the perfluorosulfonic acid resin solution in step (2) is Chemours Chemical (Shanghai) Co., Ltd., the model is Nafion D2020, and the mass fraction is 20%.

[0012] In step (2), the 2-hydroxyethyl ammonium formate is an aqueous solution of 2-hydroxyethyl ammonium formate, and the mass fraction of the 2-hydroxyethyl ammonium formate solution is 13-15%.

[0013] In step (2), the volume percentage of 2-hydroxyethylammonium formate and N-methylpyrrolidone in the mixed solution of 2-hydroxyethylammonium formate and N-methylpyrrolidone is 0.45:0.55.

[0014] In step (2), the mass ratio of the perfluorosulfonic acid resin solution to the mixed solution of 2-hydroxyethylammonium formate and N-methylpyrrolidone is 1:0.075-0.10.

[0015] In step (3), the heat treatment is first performed at 103-105°C for 1.2-1.3 hours and then at 135-138°C for 15-18 minutes.

[0016] The post-treatment in step (3) is to cool the glass plate to room temperature after the heat treatment is completed, and then peel the film off the glass plate.

[0017] The preparation process of the composite enhanced perfluorosulfonic acid proton exchange membrane of the present invention is as follows: first, the polytetrafluoroethylene-based base membrane is modified to be hydrophilic and to improve the proton conductivity; 2-hydroxyethyl methyl acrylate phosphate is used as a polymerization monomer; α,α-diethoxyacetophenone is used as a photoinitiator; a phosphoric acid group is introduced on the polytetrafluoroethylene-based base membrane through a photocuring reaction to improve the hydrophilicity of the polytetrafluoroethylene-based base membrane; and a nonionic fluorocarbon surfactant Capstone-FS-31 is introduced to provide a channel for proton transfer in the polytetrafluoroethylene-based base membrane. Then, the perfluorosulfonic acid resin solution is modified by a mixed solution of 2-hydroxyethyl ammonium formate and N-methylpyrrolidone; 2-hydroxyethyl ammonium formate is an ionic liquid, which can improve the water retention capacity and transfer site, construct an aqueous phase ion channel to promote proton transfer in the membrane, and improve the interface compatibility and gas permeation resistance of the prepared membrane; and N-methylpyrrolidone can prolong the time of rearrangement and crystallization of the perfluorosulfonic acid resin during the membrane preparation process, improve the mechanical properties of the prepared composite membrane, and reduce the brittleness of the composite membrane.

[0018] Compared with the prior art, the present invention has the following beneficial effects: (1) In the preparation process of the composite enhanced perfluorosulfonic acid proton exchange membrane described in the present invention, the first polytetrafluoroethylene-based base membrane and the perfluorosulfonic acid resin membrane-making liquid work synergistically to improve the interface compatibility between the two, so that the finally prepared composite enhanced perfluorosulfonic acid proton exchange membrane has excellent mechanical strength, proton conduction effect and ability to inhibit gas permeation.

[0019] (2) The preparation process of the composite enhanced perfluorosulfonic acid proton exchange membrane described in the present invention is simple, the parameters are easy to control, and the various steps work synergistically with each other to prepare a composite enhanced perfluorosulfonic acid proton exchange membrane with stable performance. DETAILED DESCRIPTION

[0020] The present invention is further described below with reference to the embodiments.

[0021] Example 1 The preparation process of the composite enhanced perfluorosulfonic acid proton exchange membrane described in this embodiment 1 comprises the following steps: (1) adding 2-hydroxyethyl methacrylate phosphate to a mixture of anhydrous ethanol and a nonionic fluorocarbon surfactant, then adding α,α-diethoxyacetophenone and stirring evenly to prepare a mixed solution, immersing a polytetrafluoroethylene-based base film in the mixed solution for 35 minutes, taking it out and evenly coating the mixed solution on the polytetrafluoroethylene-based base film using a coater, and finally performing ultraviolet light curing to prepare a first polytetrafluoroethylene-based base film; (2) adding the perfluorosulfonic acid resin solution to a mixture of 2-hydroxyethylammonium formate and N-methylpyrrolidone and reacting the mixture at 84° C. for 49 hours to prepare a membrane-forming solution; (3) The membrane-forming liquid prepared in step (2) is coated on a glass plate, and then the first polytetrafluoroethylene-based base film is evenly covered on the membrane-forming liquid, and then the membrane-forming liquid is coated again on the first polytetrafluoroethylene-based base film, and finally heat-treated and post-treated to prepare a composite enhanced perfluorosulfonic acid proton exchange membrane.

[0022] in: In step (1), the mass concentration of 2-hydroxyethyl methacrylate phosphate in the mixed solution of anhydrous ethanol and non-ionic fluorocarbon surfactant is 6%.

[0023] The mass of the nonionic fluorocarbon surfactant in step (1) accounts for 0.08% of the total mass of anhydrous ethanol and the nonionic fluorocarbon surfactant. The nonionic fluorocarbon surfactant is Capstone-FS-31, and the manufacturer is DuPont China Group Co., Ltd. Shanghai Branch.

[0024] In step (1), the mass of α,α-diethoxyacetophenone accounts for 0.2% of the mass of 2-hydroxyethyl methacrylate phosphate.

[0025] In step (1), the UV curing temperature is room temperature and the UV curing time is 7 minutes.

[0026] The polytetrafluoroethylene-based base film in step (1) is manufactured by Shandong Senrong New Materials Co., Ltd., and its model number is SRM001-03.

[0027] The manufacturer of the perfluorosulfonic acid resin solution in step (2) is Chemours Chemical (Shanghai) Co., Ltd., the model is Nafion D2020, and the mass fraction is 20%.

[0028] In step (2), the 2-hydroxyethyl ammonium formate is an aqueous solution of 2-hydroxyethyl ammonium formate, and the mass fraction of the 2-hydroxyethyl ammonium formate solution is 14%.

[0029] In step (2), the volume percentage of 2-hydroxyethylammonium formate and N-methylpyrrolidone in the mixed solution of 2-hydroxyethylammonium formate and N-methylpyrrolidone is 0.45:0.55.

[0030] In step (2), the mass ratio of the perfluorosulfonic acid resin solution to the mixed solution of 2-hydroxyethylammonium formate and N-methylpyrrolidone is 1:0.088.

[0031] In step (3), the heat treatment is first performed at 104°C for 1.25 h and then at 137°C for 16 min.

[0032] The post-treatment in step (3) is to cool the glass plate to room temperature after the heat treatment is completed, and then peel the film off the glass plate.

[0033] Example 2 The preparation process of the composite enhanced perfluorosulfonic acid proton exchange membrane described in Example 2 is composed of the following steps: (1) adding 2-hydroxyethyl methacrylate phosphate to a mixture of anhydrous ethanol and a nonionic fluorocarbon surfactant, then adding α,α-diethoxyacetophenone and stirring evenly to prepare a mixed solution, immersing a polytetrafluoroethylene-based base film in the mixed solution for 30 minutes, taking it out and evenly coating the mixed solution on the polytetrafluoroethylene-based base film using a coater, and finally performing ultraviolet light curing to prepare a first polytetrafluoroethylene-based base film; (2) adding the perfluorosulfonic acid resin solution to a mixture of 2-hydroxyethylammonium formate and N-methylpyrrolidone and reacting the mixture at 83° C. for 48 hours to prepare a membrane-forming solution; (3) The membrane-forming liquid prepared in step (2) is coated on a glass plate, and then the first polytetrafluoroethylene-based base film is evenly covered on the membrane-forming liquid, and then the membrane-forming liquid is coated again on the first polytetrafluoroethylene-based base film, and finally heat-treated and post-treated to prepare a composite enhanced perfluorosulfonic acid proton exchange membrane.

[0034] in: In step (1), the mass concentration of 2-hydroxyethyl methacrylate phosphate in the mixed solution of anhydrous ethanol and non-ionic fluorocarbon surfactant is 5%.

[0035] The mass of the nonionic fluorocarbon surfactant in step (1) accounts for 0.08% of the total mass of anhydrous ethanol and the nonionic fluorocarbon surfactant. The nonionic fluorocarbon surfactant is Capstone-FS-31, and the manufacturer is DuPont China Group Co., Ltd. Shanghai Branch.

[0036] In step (1), the mass of α,α-diethoxyacetophenone accounts for 0.2% of the mass of 2-hydroxyethyl methacrylate phosphate.

[0037] In step (1), the UV curing temperature is room temperature and the UV curing time is 6 minutes.

[0038] The polytetrafluoroethylene-based base film in step (1) is manufactured by Shandong Senrong New Materials Co., Ltd., and its model number is SRM001-03.

[0039] The manufacturer of the perfluorosulfonic acid resin solution in step (2) is Chemours Chemical (Shanghai) Co., Ltd., the model is Nafion D2020, and the mass fraction is 20%.

[0040] In step (2), the 2-hydroxyethyl ammonium formate is an aqueous solution of 2-hydroxyethyl ammonium formate, and the mass fraction of the 2-hydroxyethyl ammonium formate solution is 13%.

[0041] In step (2), the volume percentage of 2-hydroxyethylammonium formate and N-methylpyrrolidone in the mixed solution of 2-hydroxyethylammonium formate and N-methylpyrrolidone is 0.45:0.55.

[0042] In step (2), the mass ratio of the perfluorosulfonic acid resin solution to the mixed solution of 2-hydroxyethylammonium formate and N-methylpyrrolidone is 1:0.075.

[0043] The heat treatment in step (3) is first performed at 103°C for 1.2 h and then at 135°C for 15 min.

[0044] The post-treatment in step (3) is to cool the glass plate to room temperature after the heat treatment is completed, and then peel the film off the glass plate.

[0045] Example 3 The preparation process of the composite enhanced perfluorosulfonic acid proton exchange membrane described in this embodiment 3 comprises the following steps: (1) adding 2-hydroxyethyl methacrylate phosphate to a mixture of anhydrous ethanol and a nonionic fluorocarbon surfactant, then adding α,α-diethoxyacetophenone and stirring evenly to prepare a mixed solution, immersing a polytetrafluoroethylene-based base film in the mixed solution for 40 minutes, taking it out and evenly coating the mixed solution on the polytetrafluoroethylene-based base film using a coater, and finally performing ultraviolet light curing to prepare a first polytetrafluoroethylene-based base film; (2) adding the perfluorosulfonic acid resin solution to a mixture of 2-hydroxyethylammonium formate and N-methylpyrrolidone and reacting the mixture at 85° C. for 50 hours to prepare a membrane-forming solution; (3) The membrane-forming liquid prepared in step (2) is coated on a glass plate, and then the first polytetrafluoroethylene-based base film is evenly covered on the membrane-forming liquid, and then the membrane-forming liquid is coated again on the first polytetrafluoroethylene-based base film, and finally heat-treated and post-treated to prepare a composite enhanced perfluorosulfonic acid proton exchange membrane.

[0046] in: In step (1), the mass concentration of 2-hydroxyethyl methacrylate phosphate in the mixed solution of anhydrous ethanol and non-ionic fluorocarbon surfactant is 7%.

[0047] The mass of the nonionic fluorocarbon surfactant in step (1) accounts for 0.08% of the total mass of anhydrous ethanol and the nonionic fluorocarbon surfactant. The nonionic fluorocarbon surfactant is Capstone-FS-31, and the manufacturer is DuPont China Group Co., Ltd. Shanghai Branch.

[0048] In step (1), the mass of α,α-diethoxyacetophenone accounts for 0.2% of the mass of 2-hydroxyethyl methacrylate phosphate.

[0049] In step (1), the UV curing temperature is room temperature and the UV curing time is 8 minutes.

[0050] The polytetrafluoroethylene-based base film in step (1) is manufactured by Shandong Senrong New Materials Co., Ltd., and its model number is SRM001-03.

[0051] The manufacturer of the perfluorosulfonic acid resin solution in step (2) is Chemours Chemical (Shanghai) Co., Ltd., the model is Nafion D2020, and the mass fraction is 20%.

[0052] In step (2), the 2-hydroxyethyl ammonium formate is an aqueous solution of 2-hydroxyethyl ammonium formate, and the mass fraction of the 2-hydroxyethyl ammonium formate solution is 15%.

[0053] In step (2), the volume percentage of 2-hydroxyethylammonium formate and N-methylpyrrolidone in the mixed solution of 2-hydroxyethylammonium formate and N-methylpyrrolidone is 0.45:0.55.

[0054] In step (2), the mass ratio of the perfluorosulfonic acid resin solution to the mixed solution of 2-hydroxyethylammonium formate and N-methylpyrrolidone is 1:0.10.

[0055] In step (3), the heat treatment is first performed at 105°C for 1.3 h and then at 138°C for 18 min.

[0056] The post-treatment in step (3) is to cool the glass plate to room temperature after the heat treatment is completed, and then peel the film off the glass plate.

[0057] Comparative Example 1 The preparation process of the composite enhanced perfluorosulfonic acid proton exchange membrane described in this comparative example 1 consists of the following steps: (1) 2-hydroxyethyl methacrylate phosphate is added to anhydrous ethanol, and then α, α-diethoxyacetophenone is added and stirred evenly to prepare a mixed solution, a polytetrafluoroethylene-based base film is immersed in the mixed solution for 35 minutes, and after taking out, the mixed solution is evenly coated on the polytetrafluoroethylene-based base film using a coater, and finally ultraviolet light curing is performed to prepare a first polytetrafluoroethylene-based base film; (2) adding the perfluorosulfonic acid resin solution to a mixture of 2-hydroxyethylammonium formate and N-methylpyrrolidone and reacting the mixture at 84° C. for 49 hours to prepare a membrane-forming solution; (3) The membrane-forming liquid prepared in step (2) is coated on a glass plate, and then the first polytetrafluoroethylene-based base film is evenly covered on the membrane-forming liquid, and then the membrane-forming liquid is coated again on the first polytetrafluoroethylene-based base film, and finally heat-treated and post-treated to prepare a composite enhanced perfluorosulfonic acid proton exchange membrane.

[0058] in: In step (1), the mass concentration of 2-hydroxyethyl methacrylate phosphate in anhydrous ethanol is 6%.

[0059] In step (1), the mass of α,α-diethoxyacetophenone accounts for 0.2% of the mass of 2-hydroxyethyl methacrylate phosphate.

[0060] In step (1), the UV curing temperature is room temperature and the UV curing time is 7 minutes.

[0061] The polytetrafluoroethylene-based base film in step (1) is manufactured by Shandong Senrong New Materials Co., Ltd., and its model number is SRM001-03.

[0062] The manufacturer of the perfluorosulfonic acid resin solution in step (2) is Chemours Chemical (Shanghai) Co., Ltd., the model is Nafion D2020, and the mass fraction is 20%.

[0063] In step (2), the 2-hydroxyethyl ammonium formate is an aqueous solution of 2-hydroxyethyl ammonium formate, and the mass fraction of the 2-hydroxyethyl ammonium formate solution is 14%.

[0064] In step (2), the volume percentage of 2-hydroxyethylammonium formate and N-methylpyrrolidone in the mixed solution of 2-hydroxyethylammonium formate and N-methylpyrrolidone is 0.45:0.55.

[0065] In step (2), the mass ratio of the perfluorosulfonic acid resin solution to the mixed solution of 2-hydroxyethylammonium formate and N-methylpyrrolidone is 1:0.088.

[0066] In step (3), the heat treatment is first performed at 104°C for 1.25 h and then at 137°C for 16 min.

[0067] The post-treatment in step (3) is to cool the glass plate to room temperature after the heat treatment is completed, and then peel the film off the glass plate.

[0068] Comparative Example 2 The preparation process of the composite enhanced perfluorosulfonic acid proton exchange membrane described in this comparative example 2 consists of the following steps: (1) adding 2-hydroxyethyl methacrylate phosphate to a mixture of anhydrous ethanol and a nonionic fluorocarbon surfactant, then adding α,α-diethoxyacetophenone and stirring evenly to prepare a mixed solution, immersing a polytetrafluoroethylene-based base film in the mixed solution for 35 minutes, taking it out and evenly coating the mixed solution on the polytetrafluoroethylene-based base film using a coater, and finally performing ultraviolet light curing to prepare a first polytetrafluoroethylene-based base film; (2) adding the perfluorosulfonic acid resin solution to 2-hydroxyethylammonium formate and reacting at 84° C. for 49 hours to prepare a membrane-forming solution; (3) The membrane-forming liquid prepared in step (2) is coated on a glass plate, and then the first polytetrafluoroethylene-based base film is evenly covered on the membrane-forming liquid, and then the membrane-forming liquid is coated again on the first polytetrafluoroethylene-based base film, and finally heat-treated and post-treated to prepare a composite enhanced perfluorosulfonic acid proton exchange membrane.

[0069] in: In step (1), the mass concentration of 2-hydroxyethyl methacrylate phosphate in the mixed solution of anhydrous ethanol and non-ionic fluorocarbon surfactant is 6%.

[0070] The mass of the nonionic fluorocarbon surfactant in step (1) accounts for 0.08% of the total mass of anhydrous ethanol and the nonionic fluorocarbon surfactant. The nonionic fluorocarbon surfactant is Capstone-FS-31, and the manufacturer is DuPont China Group Co., Ltd. Shanghai Branch.

[0071] In step (1), the mass of α,α-diethoxyacetophenone accounts for 0.2% of the mass of 2-hydroxyethyl methacrylate phosphate.

[0072] In step (1), the UV curing temperature is room temperature and the UV curing time is 7 minutes.

[0073] The polytetrafluoroethylene-based base film in step (1) is manufactured by Shandong Senrong New Materials Co., Ltd., and its model number is SRM001-03.

[0074] The manufacturer of the perfluorosulfonic acid resin solution in step (2) is Chemours Chemical (Shanghai) Co., Ltd., the model is Nafion D2020, and the mass fraction is 20%.

[0075] In step (2), the 2-hydroxyethyl ammonium formate is an aqueous solution of 2-hydroxyethyl ammonium formate, and the mass fraction of the 2-hydroxyethyl ammonium formate solution is 14%.

[0076] In step (2), the mass ratio of the perfluorosulfonic acid resin solution to 2-hydroxyethylammonium formate is 1:0.088.

[0077] In step (3), the heat treatment is first performed at 104°C for 1.25 h and then at 137°C for 16 min.

[0078] The post-treatment in step (3) is to cool the glass plate to room temperature after the heat treatment is completed, and then peel the film off the glass plate.

[0079] Comparative Example 3 The preparation process of the composite enhanced perfluorosulfonic acid proton exchange membrane described in this comparative example 3 consists of the following steps: (1) adding 2-hydroxyethyl methacrylate phosphate to a mixture of anhydrous ethanol and a nonionic fluorocarbon surfactant, then adding α,α-diethoxyacetophenone and stirring evenly to prepare a mixed solution, immersing a polytetrafluoroethylene-based base film in the mixed solution for 35 minutes, taking it out and evenly coating the mixed solution on the polytetrafluoroethylene-based base film using a coater, and finally performing ultraviolet light curing to prepare a first polytetrafluoroethylene-based base film; (2) adding the perfluorosulfonic acid resin solution into N-methylpyrrolidone and reacting at 84° C. for 49 hours to prepare a membrane-forming solution; (3) The membrane-forming liquid prepared in step (2) is coated on a glass plate, and then the first polytetrafluoroethylene-based base film is evenly covered on the membrane-forming liquid, and then the membrane-forming liquid is coated again on the first polytetrafluoroethylene-based base film, and finally heat-treated and post-treated to prepare a composite enhanced perfluorosulfonic acid proton exchange membrane.

[0080] in: In step (1), the mass concentration of 2-hydroxyethyl methacrylate phosphate in the mixed solution of anhydrous ethanol and non-ionic fluorocarbon surfactant is 6%.

[0081] The mass of the nonionic fluorocarbon surfactant in step (1) accounts for 0.08% of the total mass of anhydrous ethanol and the nonionic fluorocarbon surfactant. The nonionic fluorocarbon surfactant is Capstone-FS-31, and the manufacturer is DuPont China Group Co., Ltd. Shanghai Branch.

[0082] In step (1), the mass of α,α-diethoxyacetophenone accounts for 0.2% of the mass of 2-hydroxyethyl methacrylate phosphate.

[0083] In step (1), the UV curing temperature is room temperature and the UV curing time is 7 minutes.

[0084] The polytetrafluoroethylene-based base film in step (1) is manufactured by Shandong Senrong New Materials Co., Ltd., and its model number is SRM001-03.

[0085] The manufacturer of the perfluorosulfonic acid resin solution in step (2) is Chemours Chemical (Shanghai) Co., Ltd., the model is Nafion D2020, and the mass fraction is 20%.

[0086] In step (2), the mass ratio of the perfluorosulfonic acid resin solution to N-methylpyrrolidone is 1:0.088.

[0087] In step (3), the heat treatment is first performed at 104°C for 1.25 h and then at 137°C for 16 min.

[0088] The post-treatment in step (3) is to cool the glass plate to room temperature after the heat treatment is completed, and then peel the film off the glass plate.

[0089] The performance of the composite enhanced perfluorosulfonic acid proton exchange membrane prepared in Examples 1-3 and Comparative Examples 1-3 was tested, and the results are shown in Table 1 below: Table 1 Performance test results of composite enhanced perfluorosulfonic acid proton exchange membrane

Claims

1. A process for preparing a composite enhanced perfluorosulfonic acid proton exchange membrane, characterized in that: It consists of the following steps: (1) adding 2-hydroxyethyl methacrylate phosphate to a mixture of anhydrous ethanol and a nonionic fluorocarbon surfactant, then adding α,α-diethoxyacetophenone and stirring evenly to prepare a mixed solution, immersing a polytetrafluoroethylene-based base film in the mixed solution for 30-40 minutes, taking it out and evenly coating the mixed solution on the polytetrafluoroethylene-based base film using a coater, and finally performing ultraviolet light curing to prepare a first polytetrafluoroethylene-based base film; (2) adding the perfluorosulfonic acid resin solution to a mixture of 2-hydroxyethylammonium formate and N-methylpyrrolidone and reacting at 83-85° C. for 48-50 hours to prepare a membrane-forming solution; (3) The membrane-forming liquid prepared in step (2) is coated on a glass plate, and then the first polytetrafluoroethylene-based base film is evenly covered on the membrane-forming liquid, and then the membrane-forming liquid is coated again on the first polytetrafluoroethylene-based base film, and finally heat-treated and post-treated to prepare a composite enhanced perfluorosulfonic acid proton exchange membrane.

2. The process for preparing the composite enhanced perfluorosulfonic acid proton exchange membrane according to claim 1, characterized in that: In step (1), the mass concentration of 2-hydroxyethyl methacrylate phosphate in the mixed solution of anhydrous ethanol and non-ionic fluorocarbon surfactant is 5-7%.

3. The process for preparing the composite enhanced perfluorosulfonic acid proton exchange membrane according to claim 1, characterized in that: In step (1), the mass of the nonionic fluorocarbon surfactant accounts for 0.08% of the total mass of anhydrous ethanol and the nonionic fluorocarbon surfactant, and the nonionic fluorocarbon surfactant is Capstone-FS-31.

4. The process for preparing the composite enhanced perfluorosulfonic acid proton exchange membrane according to claim 1, characterized in that: In step (1), the mass of α,α-diethoxyacetophenone accounts for 0.2% of the mass of 2-hydroxyethyl methacrylate phosphate.

5. The process for preparing the composite enhanced perfluorosulfonic acid proton exchange membrane according to claim 1, characterized in that: In step (1), the UV curing temperature is room temperature and the UV curing time is 6-8 minutes.

6. The process for preparing the composite enhanced perfluorosulfonic acid proton exchange membrane according to claim 1, characterized in that: The manufacturer of the perfluorosulfonic acid resin solution in step (2) is Chemours Chemical (Shanghai) Co., Ltd., the model is Nafion D2020, and the mass fraction is 20%.

7. The process for preparing the composite enhanced perfluorosulfonic acid proton exchange membrane according to claim 1, characterized in that: In step (2), the 2-hydroxyethyl ammonium formate is an aqueous solution of 2-hydroxyethyl ammonium formate, and the mass fraction of the 2-hydroxyethyl ammonium formate solution is 13-15%.

8. The process for preparing the composite enhanced perfluorosulfonic acid proton exchange membrane according to claim 1, characterized in that: In step (2), the volume percentage of 2-hydroxyethylammonium formate and N-methylpyrrolidone in the mixed solution of 2-hydroxyethylammonium formate and N-methylpyrrolidone is 0.45:0.

55.

9. The process for preparing the composite enhanced perfluorosulfonic acid proton exchange membrane according to claim 1, characterized in that: In step (2), the mass ratio of the perfluorosulfonic acid resin solution to the mixed solution of 2-hydroxyethylammonium formate and N-methylpyrrolidone is 1:0.075-0.

10.

10. The process for preparing the composite enhanced perfluorosulfonic acid proton exchange membrane according to claim 1, characterized in that: In step (3), the heat treatment is first performed at 103-105° C. for 1.2-1.3 h, and then at 135-138° C. for 15-18 min; The post-treatment in step (3) is to cool the glass plate to room temperature after the heat treatment is completed, and then peel the film off the glass plate.

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