A high temperature resistant hydrogen fuel cell diaphragm and its preparation method

Abstract

The present invention discloses a high-temperature resistant hydrogen fuel cell diaphragm and a preparation method thereof. Intermediate 1 is obtained by nitration treatment of biphenyl diphenol, and intermediate 1 is reduced with iron powder to obtain intermediate 2. Intermediate 2, phenyl side bisphenol, 4,4'-difluorobenzophenone and 3,3'-sodium disulfonate-4,4'-difluorobenzophenone are subjected to a nucleophilic substitution polymerization reaction to obtain polyaryletherketone. The polyaryletherketone is dissolved in dimethyl methacrylate (DMCA), a modified filler is added, and after ultrasonic homogenization, the mixture is poured into a mold and cured at high temperature to obtain the diaphragm. The modified filler contains imino groups and sulfonic acid groups. At the same time, the polyaryletherketone molecular chain contains a large number of amino groups and sulfonic acid groups, which can form a large number of acid-base pairs, so that protons are transferred between imino groups or amino groups and sulfonic acid groups, thereby increasing proton conductivity. The modified filler contains a large number of hydrogen bond layers, which can build a dense hydrogen bond network. Protons can be transferred in a direction in the orderly channels inside the modified filler, thereby increasing proton conduction.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogen fuel cell preparation, and in particular to a high-temperature resistant hydrogen fuel cell diaphragm and a preparation method thereof. Background Art

[0002] A fuel cell is an energy conversion device that converts the chemical energy in a fuel directly into electrical energy through an electrochemical reaction, without combustion. Unlike traditional energy conversion devices, it does not undergo a thermal process and is therefore not subject to the limitations of the Carnot cycle, resulting in a high theoretical energy conversion rate. The basic components of a fuel cell typically include a cathode, an anode, and an electrolyte. A proton exchange membrane fuel cell (PEMFC) primarily consists of a membrane electrode, a sealing ring, and a bipolar plate. The membrane electrode is the key component, and its performance directly determines the performance of the PEMFC. As the core component of the fuel cell, the PEM isolates the reactant gases at the two electrodes and acts as a channel for hydrogen ions, conducting protons. Its performance directly determines the performance of the fuel cell, making it a hot topic in current fuel cell research. Summary of the Invention

[0003] The purpose of the present invention is to provide a high-temperature resistant hydrogen fuel cell diaphragm and a preparation method thereof, which solves the problem of low proton conductivity of hydrogen fuel cells at this stage.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A method for preparing a high-temperature resistant hydrogen fuel cell membrane comprises the following steps:

[0006] Step S1: mixing biphenol and concentrated sulfuric acid, stirring at a speed of 60-120 r / min and a temperature of 20-25° C., and dropwise adding nitric acid solution. After reacting for 3-5 hours, cooling in an ice-water bath, and filtering and removing the filtrate to obtain intermediate 1;

[0007] Step S2: Intermediate 1, acetic acid, iron powder and DMF are mixed uniformly, and argon is introduced into the mixture for protection. The mixture is reacted at a speed of 120-150 r / min and a temperature of 30-40° C. for 20-25 hours. The filtrate is filtered to remove the solvent, and the solvent is distilled to obtain Intermediate 2.

[0008] Step S3: Intermediate 2, phenyl bisphenol, 4,4'-difluorobenzophenone, 3,3'-sodium disulfonate-4,4'-difluorobenzophenone, potassium carbonate, toluene, and dimethyl sulfoxide are uniformly mixed, and the mixture is reacted at 130-140° C. for 2-4 hours, and then the mixture is heated to 160-170° C. and reacted for 4-6 hours to obtain polyaryletherketone;

[0009] Step S4: dissolving polyaryletherketone in DMAC, adding modified filler, ultrasonically treating at a frequency of 20-30 kHz for 2-3 hours, pouring into a mold, keeping the temperature at 60-65°C for 12-15 hours, heating to 80-85°C for 12-15 hours, heating to 100-105°C for 12-15 hours, heating to 120-125°C for 12-15 hours, and obtaining a high-temperature resistant hydrogen fuel cell membrane.

[0010] Furthermore, the usage ratio of biphenol, concentrated sulfuric acid and nitric acid solution in step S1 is 0.02 mol:50 mL:15 mL, the mass fraction of concentrated sulfuric acid is 98%, and the mass fraction of nitric acid solution is 56%.

[0011] Furthermore, the usage ratio of the intermediate 1, acetic acid and iron powder in step S2 is 0.02 mol:30 mL:5.23 g.

[0012] Furthermore, the usage ratio of the intermediate 2, phenyl side bisphenol, 4,4'-difluorobenzophenone, 3,3'-sodium disulfonate-4,4'-difluorobenzophenone, potassium carbonate, toluene and dimethyl sulfoxide in step S3 is 3 mmol:7 mmol:5 mmol:5 mmol:5 mL:50 mL.

[0013] Furthermore, the amount of the modified filler in step S4 is 0.5-3% of the mass of the polyaryletherketone.

[0014] Furthermore, the modified filler is prepared by the following steps:

[0015] Step A1: Aluminum chloride is dissolved in deionized water to prepare an aluminum chloride solution, ammonia water is added dropwise, and the mixture is stirred at a speed of 200-300 r / min and a temperature of 20-25° C. for 20-30 minutes. Graphene oxide is added and stirred for 1-2 hours. The pH is adjusted to 5-5.5, the temperature is raised to 240-250° C., the reaction is carried out for 20-25 hours, the mixture is cooled to room temperature, and the filtrate is removed by filtration. The substrate is dispersed in deionized water, 4-anilinesulfonic acid and 1-hydroxybenzotriazole are added, the mixture is reacted at a speed of 150-200 r / min and a temperature of 40-50° C. for 3-5 hours, and the filtrate is removed by filtration to prepare a pretreated base material;

[0016] Step A2: Pyrrole, 4-formylbenzoic acid, and propionic acid are mixed uniformly, and the mixture is refluxed at a speed of 150-200 r / min and a temperature of 145-150°C for 2-3 hours. The mixture is then cooled to room temperature, and glacial methanol is added. The mixture is stirred at 0°C for 30-40 minutes. The filtrate is filtered to remove the filtrate. The substrate, ferric chloride hexahydrate, and DMF are mixed uniformly, and the mixture is refluxed at a speed of 200-300 r / min and a temperature of 155-160°C for 4-6 hours to prepare a metal organic framework.

[0017] Step A3: The metal organic framework is dispersed in DMF, KH550 and 1-hydroxybenzotriazole are added, and the reaction is carried out at a speed of 300-500 r / min and a temperature of 40-50°C for 5-7 hours, and the filtrate is removed by filtering. The substrate, pretreated base material and deionized water are mixed, and the mixture is stirred at a speed of 150-200 r / min and a temperature of 20-25°C for 3-5 hours. Tris-HCl buffer is added to an alkaline pH value, dopamine is added, and ultrasonic treatment is carried out at a frequency of 30-40 kHz for 1-1.5 hours. The filtrate is removed by filtering to obtain a modified filler.

[0018] Furthermore, the amount ratio of the aluminum chloride solution, ammonia water and graphene oxide described in step A1 is 10 mL: 10 mL: 0.3 g, the concentration of the aluminum chloride solution is 0.1 mol / L, the concentration of ammonia water is 0.3 mol / L, the amount of 4-anilinesulfonic acid is 5-8% of the mass of graphene oxide, and the molar ratio of 4-anilinesulfonic acid and 1-hydroxybenzotriazole is 1:1.1.

[0019] Furthermore, the usage ratio of pyrrole, 4-formylbenzoic acid, propionic acid and glacial methanol in step A2 is 4 mol:4 mol:15 mL:20 mL, and the usage ratio of substrate, ferric chloride hexahydrate and DMF is 0.35 mmol:2 mmol:15 mL.

[0020] Furthermore, the amount of KH550 used in step A3 is 8-10% of the mass of the metal organic framework, the molar ratio of KH550 to 1-hydroxybenzotriazole is 1:1.1, and the mass ratio of the substrate, pretreatment base material and dopamine is 1.8-2.5:1:7.

[0021] Beneficial effects of the present invention: A high-temperature resistant hydrogen fuel cell membrane prepared by the present invention comprises the following steps: nitroating biphenol to graft a nitro group onto a benzene ring to obtain an intermediate 1; reducing the intermediate 1 with iron powder to convert the nitro group into an amino group to obtain an intermediate 2; subjecting the intermediate 2, phenyl side-group bisphenol, 4,4'-difluorobenzophenone, and 3,3'-sodium disulfonate-4,4'-difluorobenzophenone to a nucleophilic substitution polymerization reaction to obtain a polyaryletherketone; dissolving the polyaryletherketone in DMAC, adding a modified filler, ultrasonically homogenizing the mixture, pouring the mixture into a mold, and curing the mixture at high temperature to obtain the membrane; wherein the modified filler comprises aluminum chloride as a raw material, adding ammonia water, reacting the aluminum chloride with the ammonia water to produce an aluminum hydroxide sol, adding graphene oxide, and subjecting the mixture to high-temperature treatment to form boehmite in the interlayer gaps of the graphene oxide; and then adding 4-anilinesulfonic acid to cause dehydration condensation between the amino groups on the 4-anilinesulfonic acid and the carboxyl groups on the graphene oxide. , so that sulfonic acid groups are grafted on the surface of graphene to prepare a pretreated base material, pyrrole and 4-formylbenzoic acid are reacted to prepare tetracarboxylporphyrin, which is then reacted with ferric chloride hexahydrate to form a metal organic framework, and the metal organic framework is reacted with KH550, so that the carboxyl groups on the metal organic framework and the amino groups on KH550 are dehydrated and condensed, and then mixed with water in the pretreated base material, so that the siloxane is hydrolyzed and coated on the surface of the pretreated base material, and then polydopamine is coated on the surface to prepare a modified filler. The modified filler contains imino and sulfonic acid groups. At the same time, the polyaryletherketone molecular chain contains a large number of amino and sulfonic acid groups that can form a large number of acid-base pairs, so that protons are transferred between the imino or amino groups and the sulfonic acid groups, thereby increasing the proton conductivity. The modified filler contains a large number of hydrogen bond layers, which can construct a dense hydrogen bond network, and protons can be directed in the orderly channels inside it, thereby increasing the conduction of protons. DETAILED DESCRIPTION

[0022] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0023] Example 1

[0024] A method for preparing a high-temperature resistant hydrogen fuel cell membrane, comprising the following steps

[0025] Step S1: mixing biphenol and concentrated sulfuric acid, stirring at a speed of 60 r / min and a temperature of 20° C., and dropwise adding a nitric acid solution. After reacting for 3 h, cooling in an ice-water bath, filtering and removing the filtrate to obtain an intermediate 1;

[0026] Step S2: Intermediate 1, acetic acid, iron powder and DMF were mixed uniformly, and argon was introduced into the mixture. The mixture was reacted at a speed of 120 r / min and a temperature of 30° C. for 20 h. The filtrate was filtered and the solvent was removed by distillation to obtain Intermediate 2.

[0027] Step S3: Intermediate 2, phenyl bisphenol, 4,4'-difluorobenzophenone, 3,3'-sodium disulfonate-4,4'-difluorobenzophenone, potassium carbonate, toluene, and dimethyl sulfoxide are uniformly mixed, and the mixture is reacted at 130° C. for 2 h, and then heated to 160° C. for 4 h to obtain polyaryletherketone;

[0028] Step S4: dissolving polyaryletherketone in DMAC, adding modified filler, ultrasonically treating at a frequency of 20 kHz for 2 hours, pouring into a mold, keeping the temperature at 60°C for 12 hours, heating to 80°C for 12 hours, heating to 100°C for 12 hours, heating to 120°C, and heating for 12 hours to obtain a high-temperature resistant hydrogen fuel cell membrane.

[0029] The amount ratio of biphenol, concentrated sulfuric acid and nitric acid solution described in step S1 is 0.02 mol:50 mL:15 mL, the mass fraction of concentrated sulfuric acid is 98%, and the mass fraction of nitric acid solution is 56%.

[0030] The usage ratio of the intermediate 1, acetic acid and iron powder in step S2 is 0.02 mol:30 mL:5.23 g.

[0031] The amount ratio of the intermediate 2, phenyl side bisphenol, 4,4'-difluorobenzophenone, 3,3'-sodium disulfonate-4,4'-difluorobenzophenone, potassium carbonate, toluene and dimethyl sulfoxide described in step S3 is 3 mmol:7 mmol:5 mmol:5 mmol:5 mL:50 mL.

[0032] The amount of the modified filler described in step S4 is 0.5% of the mass of the polyaryletherketone.

[0033] The modified filler is prepared by the following steps:

[0034] Step A1: Aluminum chloride is dissolved in deionized water to prepare an aluminum chloride solution, ammonia water is added dropwise, and the mixture is stirred at a speed of 200 r / min and a temperature of 20° C. for 20 minutes. Graphene oxide is added and stirred for 1 hour. The pH is adjusted to 5, the temperature is raised to 240° C., and the reaction is carried out for 20 hours. The mixture is cooled to room temperature, and the filtrate is removed by filtration. The substrate is dispersed in deionized water, 4-anilinesulfonic acid and 1-hydroxybenzotriazole are added, and the mixture is reacted at a speed of 150 r / min and a temperature of 40° C. for 3 hours. The filtrate is then removed by filtration to prepare a pretreated base material;

[0035] Step A2: Pyrrole, 4-formylbenzoic acid, and propionic acid were mixed uniformly, refluxed at a speed of 150 r / min and a temperature of 145°C for 2 hours, cooled to room temperature, added with glacial methanol, stirred at a temperature of 0°C for 30 minutes, filtered and removed the filtrate, and the substrate, ferric chloride hexahydrate, and DMF were mixed uniformly, and refluxed at a speed of 200 r / min and a temperature of 155°C for 4 hours to prepare a metal-organic framework;

[0036] Step A3: The metal organic framework is dispersed in DMF, KH550 and 1-hydroxybenzotriazole are added, and the reaction is carried out at a speed of 300 r / min and a temperature of 40°C for 5 hours. The filtrate is filtered out, and the substrate, pretreated base material and deionized water are mixed. The mixture is stirred at a speed of 150 r / min and a temperature of 20°C for 3 hours. Tris-HCl buffer is added to an alkaline pH value, dopamine is added, and ultrasonic treatment is carried out at a frequency of 30 kHz for 1 hour. The filtrate is filtered out to obtain a modified filler.

[0037] The amount ratio of the aluminum chloride solution, ammonia water and graphene oxide described in step A1 is 10 mL: 10 mL: 0.3 g, the concentration of the aluminum chloride solution is 0.1 mol / L, the concentration of ammonia water is 0.3 mol / L, the amount of 4-anilinesulfonic acid is 5% of the mass of graphene oxide, and the molar ratio of 4-anilinesulfonic acid and 1-hydroxybenzotriazole is 1:1.1.

[0038] The amount ratio of pyrrole, 4-formylbenzoic acid, propionic acid and glacial methanol described in step A2 is 4 mol:4 mol:15 mL:20 mL, and the amount ratio of substrate, ferric chloride hexahydrate and DMF is 0.35 mmol:2 mmol:15 mL.

[0039] The amount of KH550 used in step A3 is 8% of the mass of the metal-organic framework, the molar ratio of KH550 to 1-hydroxybenzotriazole is 1:1.1, and the mass ratio of the substrate, pretreated base material and dopamine is 1.8-2.5:1:7.

[0040] Example 2

[0041] A method for preparing a high-temperature resistant hydrogen fuel cell membrane, comprising the following steps

[0042] Step S1: mixing biphenol and concentrated sulfuric acid, stirring at a speed of 60 r / min and a temperature of 25° C., and dropwise adding a nitric acid solution. After reacting for 4 hours, cooling in an ice-water bath, and filtering and removing the filtrate to obtain an intermediate 1;

[0043] Step S2: Intermediate 1, acetic acid, iron powder and DMF were mixed uniformly, and argon was introduced into the mixture. The mixture was reacted at a speed of 120 r / min and a temperature of 35° C. for 25 h. The filtrate was filtered and the solvent was removed by distillation to obtain Intermediate 2.

[0044] Step S3: Intermediate 2, phenyl bisphenol, 4,4'-difluorobenzophenone, 3,3'-sodium disulfonate-4,4'-difluorobenzophenone, potassium carbonate, toluene, and dimethyl sulfoxide are uniformly mixed, and the mixture is reacted at 135° C. for 3 h, and then the mixture is heated to 165° C. and reacted for 5 h to obtain polyaryletherketone;

[0045] Step S4: dissolving polyaryletherketone in DMAC, adding modified filler, ultrasonically treating at a frequency of 25 kHz for 2 hours, pouring into a mold, keeping the temperature at 65°C for 13 hours, raising the temperature to 80°C, keeping the temperature for 15 hours, raising the temperature to 105°C, keeping the temperature for 12 hours, raising the temperature to 120°C, and keeping the temperature for 15 hours to obtain a high-temperature resistant hydrogen fuel cell membrane.

[0046] The amount ratio of biphenol, concentrated sulfuric acid and nitric acid solution described in step S1 is 0.02 mol:50 mL:15 mL, the mass fraction of concentrated sulfuric acid is 98%, and the mass fraction of nitric acid solution is 56%.

[0047] The usage ratio of the intermediate 1, acetic acid and iron powder in step S2 is 0.02 mol:30 mL:5.23 g.

[0048] The amount ratio of the intermediate 2, phenyl side bisphenol, 4,4'-difluorobenzophenone, 3,3'-sodium disulfonate-4,4'-difluorobenzophenone, potassium carbonate, toluene and dimethyl sulfoxide described in step S3 is 3 mmol:7 mmol:5 mmol:5 mmol:5 mL:50 mL.

[0049] The amount of the modified filler described in step S4 is 1.5% of the mass of the polyaryletherketone.

[0050] The modified filler is prepared by the following steps:

[0051] Step A1: Aluminum chloride is dissolved in deionized water to prepare an aluminum chloride solution, ammonia water is added dropwise, and the mixture is stirred at a speed of 300 r / min and a temperature of 25° C. for 30 minutes. Graphene oxide is added and stirred for 2 hours. The pH is adjusted to 5.5, the temperature is raised to 250° C., and the reaction is carried out for 25 hours. The mixture is cooled to room temperature, and the filtrate is filtered to remove the filtrate. The substrate is dispersed in deionized water, 4-anilinesulfonic acid and 1-hydroxybenzotriazole are added, and the mixture is reacted at a speed of 200 r / min and a temperature of 50° C. for 5 hours. The filtrate is filtered to prepare a pretreated base material;

[0052] Step A2: Pyrrole, 4-formylbenzoic acid, and propionic acid were mixed uniformly, refluxed at 200 r / min and 145°C for 3 h, cooled to room temperature, added with glacial methanol, stirred at 0°C for 35 min, filtered and removed the filtrate, and the substrate, ferric chloride hexahydrate, and DMF were mixed uniformly, refluxed at 200 r / min and 160°C for 5 h to prepare a metal-organic framework;

[0053] Step A3: The metal organic framework is dispersed in DMF, KH550 and 1-hydroxybenzotriazole are added, and the reaction is carried out at a speed of 300 r / min and a temperature of 45°C for 6 hours. The filtrate is filtered out, and the substrate, pretreated base material and deionized water are mixed. The mixture is stirred at a speed of 180 r / min and a temperature of 25°C for 4 hours. Tris-HCl buffer is added to an alkaline pH value, dopamine is added, and ultrasonic treatment is carried out at a frequency of 35 kHz for 1.5 hours. The filtrate is filtered out to obtain a modified filler.

[0054] The amount ratio of the aluminum chloride solution, ammonia water and graphene oxide described in step A1 is 10 mL: 10 mL: 0.3 g, the concentration of the aluminum chloride solution is 0.1 mol / L, the concentration of ammonia water is 0.3 mol / L, the amount of 4-anilinesulfonic acid is 5-8% of the mass of graphene oxide, and the molar ratio of 4-anilinesulfonic acid and 1-hydroxybenzotriazole is 1:1.1.

[0055] The amount ratio of pyrrole, 4-formylbenzoic acid, propionic acid and glacial methanol described in step A2 is 4 mol:4 mol:15 mL:20 mL, and the amount ratio of substrate, ferric chloride hexahydrate and DMF is 0.35 mmol:2 mmol:15 mL.

[0056] The amount of KH550 used in step A3 is 9% of the mass of the metal-organic framework, the molar ratio of KH550 to 1-hydroxybenzotriazole is 1:1.1, and the mass ratio of the substrate, pretreated base material and dopamine is 2.3:1:7.

[0057] Example 3

[0058] A method for preparing a high-temperature resistant hydrogen fuel cell membrane, comprising the following steps

[0059] Step S1: mixing biphenol and concentrated sulfuric acid, stirring at a speed of 120 r / min and a temperature of 25° C., and dropwise adding a nitric acid solution. After reacting for 5 h, cooling in an ice-water bath, and filtering and removing the filtrate to obtain an intermediate 1;

[0060] Step S2: Intermediate 1, acetic acid, iron powder and DMF were mixed uniformly, and argon was introduced into the mixture. The mixture was reacted at a speed of 150 r / min and a temperature of 40° C. for 25 h. The filtrate was filtered and the solvent was removed by distillation to obtain Intermediate 2.

[0061] Step S3: Intermediate 2, phenyl bisphenol, 4,4'-difluorobenzophenone, 3,3'-sodium disulfonate-4,4'-difluorobenzophenone, potassium carbonate, toluene, and dimethyl sulfoxide are uniformly mixed, and the mixture is reacted at 140° C. for 4 hours, and then the mixture is heated to 170° C. and reacted for 6 hours to obtain polyaryletherketone;

[0062] Step S4: dissolving polyaryletherketone in DMAC, adding modified filler, ultrasonically treating at a frequency of 30 kHz for 3 hours, pouring into a mold at a temperature of 65°C, keeping warm for 15 hours, heating to 85°C, keeping warm for 15 hours, heating to 105°C, keeping warm for 15 hours, heating to 125°C, and keeping warm for 15 hours to obtain a high-temperature resistant hydrogen fuel cell membrane.

[0063] The amount ratio of biphenol, concentrated sulfuric acid and nitric acid solution described in step S1 is 0.02 mol:50 mL:15 mL, the mass fraction of concentrated sulfuric acid is 98%, and the mass fraction of nitric acid solution is 56%.

[0064] The usage ratio of the intermediate 1, acetic acid and iron powder in step S2 is 0.02 mol:30 mL:5.23 g.

[0065] The amount ratio of the intermediate 2, phenyl side bisphenol, 4,4'-difluorobenzophenone, 3,3'-sodium disulfonate-4,4'-difluorobenzophenone, potassium carbonate, toluene and dimethyl sulfoxide described in step S3 is 3 mmol:7 mmol:5 mmol:5 mmol:5 mL:50 mL.

[0066] The amount of the modified filler described in step S4 is 3% of the mass of the polyaryletherketone.

[0067] The modified filler is prepared by the following steps:

[0068] Step A1: Aluminum chloride is dissolved in deionized water to prepare an aluminum chloride solution, ammonia water is added dropwise, and the mixture is stirred at a speed of 300 r / min and a temperature of 25° C. for 30 minutes. Graphene oxide is added and stirred for 2 hours. The pH is adjusted to 5.5, the temperature is raised to 250° C., and the reaction is carried out for 25 hours. The mixture is cooled to room temperature, and the filtrate is filtered to remove the filtrate. The substrate is dispersed in deionized water, 4-anilinesulfonic acid and 1-hydroxybenzotriazole are added, and the mixture is reacted at a speed of 200 r / min and a temperature of 50° C. for 5 hours. The filtrate is filtered to prepare a pretreated base material;

[0069] Step A2: Pyrrole, 4-formylbenzoic acid, and propionic acid were mixed uniformly, and the mixture was refluxed at a speed of 200 r / min and a temperature of 150°C for 3 hours. After cooling to room temperature, glacial methanol was added, and the mixture was stirred at a temperature of 0°C for 40 minutes. The filtrate was filtered and removed. The substrate, ferric chloride hexahydrate, and DMF were mixed uniformly, and the mixture was refluxed at a speed of 300 r / min and a temperature of 160°C for 6 hours to prepare a metal organic framework.

[0070] Step A3: The metal organic framework is dispersed in DMF, KH550 and 1-hydroxybenzotriazole are added, and the reaction is carried out at a speed of 500 r / min and a temperature of 50°C for 7 hours. The filtrate is filtered out, and the substrate, pretreated base material and deionized water are mixed. The mixture is stirred at a speed of 200 r / min and a temperature of 25°C for 5 hours. Tris-HCl buffer is added to an alkaline pH value, dopamine is added, and ultrasonic treatment is carried out at a frequency of 40 kHz for 1.5 hours. The filtrate is filtered out to obtain a modified filler.

[0071] The amount ratio of the aluminum chloride solution, ammonia water and graphene oxide described in step A1 is 10 mL: 10 mL: 0.3 g, the concentration of the aluminum chloride solution is 0.1 mol / L, the concentration of ammonia water is 0.3 mol / L, the amount of 4-anilinesulfonic acid is 8% of the mass of graphene oxide, and the molar ratio of 4-anilinesulfonic acid and 1-hydroxybenzotriazole is 1:1.1.

[0072] The amount ratio of pyrrole, 4-formylbenzoic acid, propionic acid and glacial methanol described in step A2 is 4 mol:4 mol:15 mL:20 mL, and the amount ratio of substrate, ferric chloride hexahydrate and DMF is 0.35 mmol:2 mmol:15 mL.

[0073] The amount of KH550 used in step A3 is 10% of the mass of the metal-organic framework, the molar ratio of KH550 to 1-hydroxybenzotriazole is 1:1.1, and the mass ratio of the substrate, pretreated base material and dopamine is 2.5:1:7.

[0074] Comparative Example 1

[0075] Compared with Example 1, this comparative example uses nano-silica instead of the modified filler, and the remaining steps are the same.

[0076] Comparative Example 2

[0077] Compared with Example 1, this comparative example uses the metal organic framework prepared in step A2 to replace the modified filler, and the remaining steps are the same.

[0078] Comparative Example 3

[0079] Compared with Example 1, this comparative example uses the pretreated base material prepared in step A1 instead of the modified filler, and the remaining steps are the same.

[0080] Examples 1-3 and Comparative Examples 1-3 were fabricated into 100 μm thick separators and cut into 1 cm × 4 cm specimens. Proton conductivity was measured using a four-electrode method at 100°C in anhydrous conditions. The calculation formula is σ = L / RA, where L represents the distance between the electrodes, R represents the impedance of the specimen, and A represents the cross-sectional area of the specimen. The results are shown in the following table.

[0081] .

[0082] It can be seen from the above table that the proton conductivity of the high temperature resistant hydrogen fuel cell membranes prepared in Examples 1-3 is 0.2801-0.2833 S / cm, indicating that the present invention has very good proton conductivity.

[0083] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A method for preparing a high-temperature resistant hydrogen fuel cell membrane, characterized in that: The specific steps include the following Step S1: mixing biphenol and concentrated sulfuric acid, stirring, and adding nitric acid solution dropwise. After reaction, cooling in an ice-water bath, filtering and removing the filtrate, to obtain intermediate 1; Step S2: Intermediate 1, acetic acid, iron powder and DMF are mixed and reacted to obtain Intermediate 2; Step S3: Mixing the intermediate 2, phenyl bisphenol, 4,4'-difluorobenzophenone, 3,3'-sodium disulfonate-4,4'-difluorobenzophenone, potassium carbonate, toluene and dimethyl sulfoxide to produce a polyaryletherketone; Step S4: dissolving polyaryletherketone in DMAC, adding modified filler, ultrasonically treating, pouring into a mold, and then keeping the mold at high temperature to prepare a high-temperature resistant hydrogen fuel cell membrane; The modified filler is prepared by the following steps: Step A1: dissolving aluminum chloride in deionized water to prepare an aluminum chloride solution, adding ammonia water dropwise, stirring, adding graphene oxide, stirring, heating to react, cooling to room temperature, filtering to remove the filtrate, dispersing the substrate in deionized water, adding 4-anilinesulfonic acid and 1-hydroxybenzotriazole, reacting, and filtering to remove the filtrate to prepare a pretreated base material; Step A2: Pyrrole, 4-formylbenzoic acid, and propionic acid are mixed and refluxed for reaction, then cooled to room temperature, glacial methanol is added, stirred, and the filtrate is removed by filtration. The substrate, ferric chloride hexahydrate, and DMF are mixed and refluxed for reaction to prepare a metal organic framework; Step A3: The metal organic framework is dispersed in DMF, KH550 and 1-hydroxybenzotriazole are added, and after reaction, the filtrate is filtered to remove the filtrate, the substrate, the pretreated base material and deionized water are mixed and stirred, Tris-HCl buffer and dopamine are added, and ultrasonic treatment is performed to obtain a modified filler.

2. The method for preparing a high-temperature resistant hydrogen fuel cell membrane according to claim 1, characterized in that: The usage ratio of biphenol, concentrated sulfuric acid and nitric acid solution in step S1 is 0.02 mol:50 mL:15 mL.

3. The method for preparing a high-temperature resistant hydrogen fuel cell membrane according to claim 1, characterized in that: The usage ratio of the intermediate 1, acetic acid and iron powder in step S2 is 0.02 mol:30 mL:5.23 g.

4. The method for preparing a high-temperature resistant hydrogen fuel cell membrane according to claim 1, characterized in that: The amount ratio of the intermediate 2, phenyl side bisphenol, 4,4'-difluorobenzophenone, 3,3'-sodium disulfonate-4,4'-difluorobenzophenone, potassium carbonate, toluene and dimethyl sulfoxide described in step S3 is 3 mmol:7 mmol:5 mmol:5 mmol:5 mL:50 mL.

5. The method for preparing a high-temperature resistant hydrogen fuel cell membrane according to claim 1, characterized in that: The amount of the modified filler in step S4 is 0.5-3% of the mass of the polyaryletherketone.

6. The method for preparing a high-temperature resistant hydrogen fuel cell membrane according to claim 1, characterized in that: The amount ratio of the aluminum chloride solution, ammonia water and graphene oxide described in step A1 is 10 mL:10 mL:0.3 g, the amount of 4-anilinesulfonic acid is 5-8% of the mass of graphene oxide, and the molar ratio of 4-anilinesulfonic acid and 1-hydroxybenzotriazole is 1:1.

1.

7. The method for preparing a high-temperature resistant hydrogen fuel cell membrane according to claim 1, characterized in that: The amount ratio of pyrrole, 4-formylbenzoic acid, propionic acid and glacial methanol described in step A2 is 4 mol:4 mol:15 mL:20 mL, and the amount ratio of substrate, ferric chloride hexahydrate and DMF is 0.35 mmol:2 mmol:15 mL.

8. The method for preparing a high-temperature resistant hydrogen fuel cell membrane according to claim 1, characterized in that: The amount of KH550 used in step A3 is 8-10% of the mass of the metal organic framework, the molar ratio of KH550 to 1-hydroxybenzotriazole is 1:1.1, and the mass ratio of the substrate, pretreated base material and dopamine is 1.8-2.5:1:

7.

9. A high-temperature resistant hydrogen fuel cell membrane, characterized in that: Prepared according to any one of the preparation methods of claims 1-8.