CN113113651A - Preparation method of proton exchange membrane material for hydrogen fuel cell - Google Patents
Preparation method of proton exchange membrane material for hydrogen fuel cell Download PDFInfo
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- 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
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- 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
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Abstract
The application relates to the field of fuel cells, and particularly discloses a preparation method of a proton exchange membrane material for a hydrogen fuel cell. The method comprises the following steps: s1: preparing an aminated skeleton compound; s2: dissolving a sulfonated polyaryletherketone substrate with a side group containing carboxyl in dimethyl sulfoxide to form a membrane casting solution, adding organic montmorillonite and an aminated framework compound obtained from S1 into the membrane casting solution, ultrasonically stirring, pouring the mixture on the surface of a smooth and clean glass plate, drying at 55-65 ℃ for 20-30h to form a membrane, drying at 95-110 ℃ for 22-26h, continuously drying the obtained membrane at 170-185 ℃ for 2.5-3h, and putting the composite membrane into a sulfuric acid solution.
Description
Technical Field
The present application relates to the field of fuel cells, and more particularly, to a method for preparing a proton exchange membrane material for a hydrogen fuel cell.
Background
The hydrogen fuel cell has the advantages of good environmental friendliness, high conversion rate and the like, and is considered as an ideal power generation device with good development prospect.
The hydrogen fuel cell basically comprises: the hydrogen is oxidized at the anode to obtain protons, the protons are transferred to the cathode through a proton exchange membrane to react with oxygen (oxidant) in the air, charged ions generated along with the electrochemical reaction are transferred from one electrode to the other electrode under the help of the electrolyte, and finally, an external circuit generates current. The proton exchange membrane, as a core component of the proton exchange membrane fuel cell, not only plays a role in transferring protons, but also avoids direct contact between fuel and oxygen, which directly affects the performance of the fuel cell. The currently widely used commercial proton exchange membrane material is a sulfonic acid type resin material based on a perfluorinated polytetrafluoroethylene structure, but the proton conductivity is very low at a lower water content, and when the material is selected for use at a lower level (applied to a methanol fuel cell), the alcohol permeability is higher, and in order to reduce the alcohol permeability, the sulfonated polymer is widely concerned, wherein the proton conductivity is increased due to the increase of the sulfonation degree, but the water absorption rate and the swelling rate of the membrane are increased.
Disclosure of Invention
In order to improve the proton conductivity of a proton exchange membrane at low water content and inhibit the swelling of the membrane, the application provides a preparation method of the proton exchange membrane material for a hydrogen fuel cell.
The application provides a proton exchange membrane material for a hydrogen fuel cell, which adopts the following technical scheme:
a preparation method of proton exchange membrane material for hydrogen fuel cell is characterized in that: the method comprises the following steps:
s1: preparation of aminated skeleton Compound FeCl3·6H2Dissolving O and amino terephthalic acid in N, N-dimethylformamide, pouring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, naturally cooling the reaction kettle to room temperature at the temperature of 150-175 ℃ for 20-30h, centrifugally collecting a crude product, washing the crude product, drying the crude product at the temperature of 155 ℃ for 22-27h, dispersing the crude product into ethanol, dripping trifluoromethanesulfonate, fully stirring, evaporating the ethanol to dryness, washing the surface of the product with the ethanol, and drying the product at the temperature of 75-85 ℃ to obtain an aminated framework compound;
s2: dissolving a sulfonated polyaryletherketone substrate with a carboxyl group on a side group in dimethyl sulfoxide to form a membrane casting solution, adding organic montmorillonite and an aminated skeleton compound obtained from S1 into the membrane casting solution, ultrasonically stirring, pouring the mixture on the surface of a smooth and clean glass plate, drying the surface of the glass plate at 55-65 ℃ for 20-30h to form a membrane, drying the surface of the glass plate at 95-110 ℃ for 22-26h, continuously drying the obtained membrane at 170-185 ℃ for 2.5-3h, and then putting the composite membrane into a sulfuric acid solution.
By adopting the technical scheme, in the step S1, an aminated metal-organic framework compound (namely a crude product) is obtained in a stainless steel reaction kettle with a polytetrafluoroethylene lining, trifluoromethanesulfonate enters the aminated metal-organic framework compound, and after drying, the trifluoromethanesulfonate is loaded in a nanopore of the aminated metal-organic framework compound to play a good proton transfer role;
in step S2, the amino group in the aminated skeleton compound can react with the side group carboxyl group of the sulfonated polyaryletherketone to form an amide bond, so that the polymer molecule chain segments are stacked more closely, the dimensional stability and the alcohol blocking performance of the composite membrane can be improved significantly, the organic montmorillonite and the sulfonated polyaryletherketone base material have better compatibility, the alcohol blocking performance of the composite membrane is further increased, and the proton conduction performance of the composite membrane formed by the organic montmorillonite, the aminated skeleton compound and the sulfonated polyaryletherketone base material with the side group containing carboxyl group is better at higher temperature and at low water content, and the membrane is not easy to swell.
Optionally, in step S1, FeCl3·6H2The weight ratio of O to the amino terephthalic acid is 1: (0.5-0.7), FeCl3·6H2The ratio of the total weight of O and amino terephthalic acid to the volume of N, N-dimethylformamide added was (13-15) mL/g.
Optionally, in step S1, FeCl3·6H2The weight ratio of O to trifluoromethanesulfonate is 1: (1-1.3).
By adopting the technical scheme, under the proportion, the trifluoromethanesulfonate can better fill the nanochannels of the crude product, so that the conductivity of the nephew of the composite membrane is higher.
Optionally, in step S2, the weight of the aminated skeleton compound is 0.5-0.7% of the weight of the sulfonated polyaryletherketone substrate with the pendant carboxyl group.
By adopting the technical scheme, under the condition of the addition amount of the aminated framework compound, the obtained composite membrane can have higher proton conductivity under the condition of low water content, and can well inhibit the swelling of the membrane.
Optionally, in step S2, the concentration of sulfuric acid is 0.1-0.4 mol/L.
By adopting the technical scheme, the composite membrane can be well activated under the concentration, so that the composite membrane has higher proton conductivity.
Optionally, in step S2, the casting solution is added with the aminated skeleton compound obtained in step S1, and simultaneously added with organic montmorillonite, and ultrasonically stirred for 25-28h, wherein the weight of the organic montmorillonite is 0.1-0.4% of the weight of the sulfonated polyaryletherketone base material with carboxyl groups on the side groups.
By adopting the technical scheme, under the condition of low water content and the addition amount of the organic montmorillonite, the proton conductivity of the obtained composite membrane is further improved, and the swelling of the membrane can be well inhibited.
Optionally, the organic montmorillonite comprises the following preparation steps: adding water into sodium-based montmorillonite, stirring until the sodium-based montmorillonite is completely swelled, preserving heat at 60-65 ℃, then slowly dropwise adding a cetyl trimethyl ammonium bromide solution into the sodium-based montmorillonite, wherein the mass ratio of the sodium-based montmorillonite to the cetyl trimethyl ammonium bromide in the cetyl trimethyl ammonium bromide solution is 1: (0.3-0.5), reacting for 6-7h, filtering, washing, drying, grinding and sieving with a 300-mesh sieve.
By adopting the technical scheme, the hexadecyl trimethyl ammonium bromide can enter the interlayer of the sodium-based montmorillonite, the hydrophobicity of the montmorillonite is enhanced, and the thermal stability of the intercalating agent entering the interlayer is obviously improved; the organic montmorillonite is added into the composite membrane, and the composite membrane can obviously inhibit expansion and improve proton conductivity.
Optionally, the sulfonated polyaryletherketone substrate with the side group containing carboxyl comprises the following componentsThe preparation method comprises the following steps: adding phenolphthalein, tetramethyl biphenol, difluorobenzophenone, sulfonated difluorobenzophenone and K in sequence2CO3Then adding dimethyl sulfoxide and toluene, stirring until solid substances are dissolved, heating the system to 135-145 ℃ under the conditions of continuous stirring and nitrogen introduction, refluxing the toluene for 3-5h, removing generated water, removing the toluene, heating to 185 ℃ under 170-2.5 h, pouring the obtained viscous polymer solution into a beaker filled with deionized water, precipitating, filtering, crushing, washing and drying the polymer solid.
By adopting the technical scheme, phenolphthalein, difluorobenzophenone, tetramethylbiphenol and sulfonated difluorobenzophenone are polymerized together, phenolphthalein provides carboxyl of a side group, and sulfonated difluorobenzophenone provides a sulfonic group, so that sulfonated polyaryletherketone with the carboxyl side group is obtained.
Optionally, the phenolphthalein, tetramethylbiphenol, difluorobenzophenone, sulfonated difluorobenzophenone, and K2CO3The weight ratio of (1): (0.7-0.8): (0.65-0.7): (1.30-1.35): (1.0-1.2).
Optionally, the volume ratio of dimethyl sulfoxide to toluene is 1: (0.35-0.38), phenolphthalein, tetramethylbiphenol, difluorobenzophenone, sulfonated difluorobenzophenone and K2CO3The ratio of the total weight of (A) to the total volume of dimethyl sulfoxide and toluene is 1 g: (2.5-2.6) mL.
By adopting the technical scheme, the sulfonated polyaryletherketone base material with the side group containing carboxyl can be prepared with high yield.
In summary, the present application has the following beneficial effects:
the amination framework compound loaded with the trifluoromethanesulfonate, the organic montmorillonite and the sulfonated polyaryletherketone with the carboxyl side group are compounded together to form the composite membrane, the amination framework compound can be connected with the sulfonated polyaryletherketone, and the organic montmorillonite is well dispersed in the sulfonated polyaryletherketone, so that the proton conductivity of the composite membrane is increased under the combined action of the amination framework compound, the membrane expansion is effectively inhibited, and the alcohol resistance performance is better.
Detailed Description
The present application is further described in detail with reference to the following contents and examples.
Amino terephthalic acid, purity 99%, manufacturer wuhan woxuan biotechnology limited;
n, N-dimethylformamide with the purity of 99.9 percent, wherein the manufacturer is Jinan Yuanxiang chemical industry;
trifluoromethane sulfonate, cat # 2926-30-9, manufactured by Shanghai Banghong chemical industry Co., Ltd;
na-montmorillonite, cat # B0023, a manufacturer, Shijiazhuangkun mineral products Limited;
cetyl trimethyl ammonium bromide, technical grade, manufactured by Jinan Hui Chuan chemical Co., Ltd;
phenolphthalein, purity 99%, manufacturer Hubei Xinkang pharmaceutical chemical Co., Ltd;
the purity of the tetramethyl biphenyl diphenol is 99 percent, and the manufacturer is Hubei Yuancheng Sai Chu technology company;
difluorobenzophenone with the content of 98 percent, wherein the manufacturer is Wuhanxin Confucian chemical Co., Ltd;
the purity of the sulfonated difluorobenzophenone is 99 percent, and the Tianjin inkstone technology of a manufacturer.
Preparation example
Preparation example 1
The sulfonated polyaryletherketone base material with the side group containing carboxyl comprises the following preparation steps:
1g of phenolphthalein, 0.7g of tetramethylbiphenol, 0.7g of difluorobenzophenone, 1.30g of sulfonated difluorobenzophenone and 1.2g K were added in this order2CO3Then adding 9.07mL of dimethyl sulfoxide and 3.18mL of toluene, stirring until solid substances are dissolved, continuously stirring, introducing nitrogen, heating the system to 135 ℃, refluxing the toluene for 5h, removing generated water, removing the toluene, heating to 170 ℃, keeping for 2.5h, adding 5mL of 1mol/L sulfuric acid, stirring, pouring the obtained viscous polymer solution into a beaker filled with deionized water, precipitating, filtering, crushing, washing and drying the polymer solid.
Preparation example 2
The difference from preparation example 1 is that: 1g of phenolphthalein, 0.75g of tetramethylbiphenol, 0.68g of difluorobenzophenone, 1.32g of sulfonated difluorobenzophenone and 1.1g K were added in this order2CO3Then adding 9.09mL of dimethyl sulfoxide and 4.28mL of toluene, stirring until solid substances are dissolved, continuously stirring, introducing nitrogen, heating the system to 145 ℃ to reflux the toluene for 3-5h, removing the generated water, removing the toluene, heating to 185 ℃ to 170 ℃ and keeping for 1.5-2.5h, adding 5mL of 1mol/L sulfuric acid, stirring, pouring the obtained viscous polymer solution into a beaker filled with deionized water to precipitate, filtering, crushing, washing and drying the polymer solid.
Preparation example 3
The difference from preparation example 1 is that: 1g of phenolphthalein, 0.8g of tetramethylbiphenol, 0.65g of difluorobenzophenone, 1.35g of sulfonated difluorobenzophenone and 1.0g K were added in this order2CO3Then adding 9.04mL of dimethyl sulfoxide and 3.44mL of toluene, stirring until solid substances are dissolved, continuously stirring, introducing nitrogen, heating the system to 145 ℃, refluxing the toluene for 3h, removing generated water, removing the toluene, heating to 185 ℃ and keeping the temperature for 1.55h, adding 5mL of 1mol/L sulfuric acid, stirring, pouring the obtained viscous polymer solution into a beaker filled with deionized water, precipitating, filtering, crushing, washing and drying the polymer solid.
Preparation example 4
The organic montmorillonite comprises the following preparation steps:
adding 18mL of water into 1g of sodium-based montmorillonite, stirring until the sodium-based montmorillonite is completely swelled, keeping the temperature at 65 ℃, dissolving 0.3g of hexadecyl trimethyl ammonium bromide in 7.5mL of water to obtain a hexadecyl trimethyl ammonium bromide solution, slowly dropwise adding the hexadecyl trimethyl ammonium bromide solution into the sodium-based montmorillonite, reacting for 6 hours, and filtering, washing, drying, grinding and sieving the obtained precipitate with a 300-mesh sieve.
Preparation example 5
The difference from preparation example 4 is that: adding 21mL of water into 1g of sodium-based montmorillonite, stirring until the sodium-based montmorillonite is completely swelled, keeping the temperature at 63 ℃, dissolving 0.4g of hexadecyl trimethyl ammonium bromide into 10mL of water to obtain a hexadecyl trimethyl ammonium bromide solution, slowly dripping the hexadecyl trimethyl ammonium bromide solution into the sodium-based montmorillonite, reacting for 6.5 hours, and filtering, washing, drying, grinding and sieving the obtained precipitate with a 300-mesh sieve.
Preparation example 6
The difference from preparation example 4 is that: adding 24mL of water into 1g of sodium-based montmorillonite, stirring until the sodium-based montmorillonite is completely swelled, keeping the temperature at 60 ℃, dissolving 0.5g of hexadecyl trimethyl ammonium bromide in 12.5mL of water to obtain a hexadecyl trimethyl ammonium bromide solution, slowly dropwise adding the hexadecyl trimethyl ammonium bromide solution into the sodium-based montmorillonite, reacting for 7 hours, and filtering, washing, drying, grinding and sieving the obtained precipitate with a 300-mesh sieve.
Examples
Example 1
A preparation method of proton exchange membrane material for hydrogen fuel cell is characterized in that: the method comprises the following steps:
s1: preparation of aminated skeleton Compound 1g FeCl3·6H2Dissolving O and 0.5g of amino terephthalic acid in 22.5mL of N, N-dimethylformamide, pouring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, naturally cooling the reaction kettle to room temperature for 30h at 150 ℃, centrifugally collecting a crude product, washing the crude product, drying the crude product for 27h at 145 ℃, dispersing the crude product into 5.25mL of ethanol, dripping 1g of trifluoromethanesulfonate, fully stirring, evaporating the ethanol to dryness, washing the surface of the product with the ethanol, and drying the product at 85 ℃ to obtain an aminated framework compound;
s2: dissolving 10g of sulfonated polyaryletherketone base material with side groups containing carboxyl in 25mL of dimethyl sulfoxide to form membrane casting solution, adding 0.01g of organic montmorillonite and 0.07g of aminated skeleton compound into the membrane casting solution, ultrasonically stirring for 25h, pouring the mixture on the surface of a smooth and clean glass plate, drying at 65 ℃ for 20h to form a membrane, drying at 110 ℃ for 22h, continuously drying the obtained membrane at 185 ℃ for 3h, and then putting the composite membrane into 0.4mol/L sulfuric acid solution.
The organo montmorillonite was obtained from preparation 1 and the aminated backbone compound was obtained from preparation 6.
Example 2
The difference from example 1 is that:
s1: preparation of aminated skeleton Compound 1g FeCl3·6H2Dissolving O and 0.6g of amino terephthalic acid in 22.4mL of N, N-dimethylformamide, pouring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, naturally cooling the reaction kettle to room temperature for 24h at 165 ℃, centrifugally collecting a crude product, washing the crude product, drying the crude product for 24h at 150 ℃, dispersing the crude product into 5.6mL of ethanol, dripping 1.2g of trifluoromethanesulfonate, fully stirring, evaporating the ethanol to dryness, washing the surface of the product with the ethanol, and drying the product at 80 ℃ to obtain an aminated framework compound;
s2: adding organic montmorillonite and aminated skeleton compound into the membrane casting solution, ultrasonically stirring for 26h, pouring the mixture on the surface of a smooth and clean glass plate, drying at 60 ℃ for 24h to form a membrane, drying at 100 ℃ for 24h, continuously drying the obtained membrane at 175 ℃ for 2.63h, and then putting the composite membrane into a 0.2mol/L sulfuric acid solution.
Example 3
The difference from example 1 is that:
s1: preparation of aminated skeleton Compound 1g FeCl3·6H2Dissolving O and 0.7g of amino terephthalic acid in 22.1mL of N, N-dimethylformamide, pouring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, naturally cooling the reaction kettle to room temperature for 20h at 175 ℃, centrifugally collecting a crude product, washing the crude product, drying the crude product for 22h at 155 ℃, dispersing the crude product into 6mL of ethanol, dripping 1.3g of trifluoromethanesulfonate into the ethanol, fully stirring, evaporating the ethanol to dryness, washing the surface of the product with the ethanol, and drying the product at 75 ℃ to obtain an aminated skeleton compound;
s2: adding organic montmorillonite and aminated skeleton compound into the membrane casting solution, ultrasonically stirring for 28h, pouring the mixture onto the surface of a smooth and clean glass plate, drying at 55 ℃ for 30h to form a membrane, drying at 95 ℃ for 26h, continuously drying the obtained membrane at 170 ℃ for 3h, and then putting the composite membrane into a 0.1mol/L sulfuric acid solution.
Example 4
The difference from example 2 is that: the organo montmorillonite was obtained from preparation 2 and the aminated backbone compound was obtained from preparation 5.
Example 5
The difference from example 2 is that: the organo montmorillonite was obtained from preparation 3 and the aminated backbone compound was obtained from preparation 4.
Example 6
The difference from example 4 is that: 0.06g of aminated skeleton compound and 0.03g of organic montmorillonite.
Example 7
The difference from example 4 is that: 0.05g of aminated skeleton compound and 0.04g of organic montmorillonite.
Comparative example
Comparative example 1
Commercially available N117 membranes, brand dupont, were purchased from shanghai hesen electric limited.
Comparative example 2
The difference from example 6 is that: the aminated skeleton compound is replaced by organic montmorillonite with equal weight.
Comparative example 3
The difference from example 6 is that: the organic montmorillonite is replaced by aminated skeleton compound with the same weight.
Performance test
Detection method/test method
According to the third part of the national standard GB/T20042.3-2009 proton exchange membrane fuel cell: proton exchange membrane test method the proton exchange membranes of examples 1 to 8 and comparative examples 1 to 3 were tested for proton conductivity (S/cm), swelling ratio (%); and (3) detecting the methanol permeability by the following method: the methanol permeability of the composite membrane was tested in the assembled cell using linear voltammetry. The anode of the cell was charged with 2M methanol solution while the cathode of the cell was protected with pre-humidified nitrogen. Under these experimental conditions, the cathode acts asThe working electrode and the anode are used as reference electrodes, when methanol solution permeates from the cathode to the anode, electrochemical oxidation is generated in an anode catalytic layer, the generated electrochemical oxidation current is related to the permeability of the methanol solution, the higher the methanol permeability is, the larger the generated electrochemical current is, and the P ═ is (L multiplied by CD)max)/(6F×k×Cfuel) Wherein, P (cm)2(S) represents the methanol permeability of the proton exchange membrane, L (cm) is the thickness of the membrane, CDmax(mA cm-2) Is the limit oxidation current density measured by the LSV method, F is the Faraday constant, Cfuel(M) actual concentration of methanol fuel, k is a correction factor at different methanol fuel concentrations, and k is 0.739 when the methanol concentration is 2M.
The results are reported in Table 1.
TABLE 1 test results Table
With reference to table 1, it can be seen from examples 1-7 and comparative example 1 that the proton conductivity, swelling ratio and methanol permeability of the membrane prepared in examples 1-8 are significantly better than those of comparative example 1, so that the performance of the proton exchange membrane prepared by the scheme of the present application is significantly better.
In examples 1 to 3, the process conditions of the steps for preparing the proton exchange membrane were different, and the proton exchange membrane obtained in example 2 had higher proton conductivity and lower methanol permeability, so the process conditions of example 2 were better.
In examples 2 and 4 to 5, the preparation conditions of the organic montmorillonite and the aminated framework compound are different, wherein the proton conductivity and the methanol permeability of the proton exchange membrane obtained in example 4 are better, so that the proton exchange membrane with better performance is more favorably obtained under the conditions of example 4.
In examples 4 and 6 to 7, the addition ratio of the organic montmorillonite to the aminated skeleton compound was different, and the proton exchange membrane obtained in example 6 was superior in proton conductivity and methanol permeability, so the addition ratio of the organic montmorillonite to the aminated skeleton compound in example 6 was superior. In example 6 and comparative examples 2 to 3, a certain proportion of organic montmorillonite and aminated framework compound, only organic montmorillonite and only aminated framework compound are respectively added, wherein the proton conductivity and methanol permeability of the proton exchange membrane obtained in example 6 are greatly superior to those of the proton exchange membranes obtained in comparative examples 2 to 3, so the adding proportion of the organic montmorillonite and the aminated framework compound in example 6 is better.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A preparation method of proton exchange membrane material for hydrogen fuel cell is characterized in that: the method comprises the following steps:
s1: preparation of aminated skeleton Compound FeCl3·6H2Dissolving O and amino terephthalic acid in N, N-dimethylformamide, pouring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, naturally cooling the reaction kettle to room temperature at the temperature of 150-175 ℃ for 20-30h, centrifugally collecting a crude product, washing the crude product, drying the crude product at the temperature of 155 ℃ for 22-27h, dispersing the crude product into ethanol, dripping trifluoromethanesulfonate, fully stirring, evaporating the ethanol to dryness, washing the surface of the product with the ethanol, and drying the product at the temperature of 75-85 ℃ to obtain an aminated framework compound;
s2: dissolving a sulfonated polyaryletherketone substrate with a carboxyl group on a side group in dimethyl sulfoxide to form a membrane casting solution, adding organic montmorillonite and an aminated skeleton compound obtained from S1 into the membrane casting solution, ultrasonically stirring, pouring the mixture on the surface of a smooth and clean glass plate, drying the surface of the glass plate at 55-65 ℃ for 20-30h to form a membrane, drying the surface of the glass plate at 95-110 ℃ for 22-26h, continuously drying the obtained membrane at 170-185 ℃ for 2.5-3h, and then putting the composite membrane into a sulfuric acid solution.
2. The method for preparing a proton exchange membrane material for a hydrogen fuel cell according to claim 1The method is characterized in that: in step S1, FeCl3·6H2The weight ratio of O to the amino terephthalic acid is 1: (0.5-0.7), FeCl3·6H2The ratio of the total weight of O and amino terephthalic acid to the volume of N, N-dimethylformamide added was (13-15) mL/g.
3. The method of producing a proton exchange membrane material for a hydrogen fuel cell according to claim 1, characterized in that: in step S1, FeCl3·6H2The weight ratio of O to trifluoromethanesulfonate is 1: (1-1.3).
4. The method of producing a proton exchange membrane material for a hydrogen fuel cell according to claim 1, characterized in that: in step S2, the weight of the aminated skeleton compound is 0.5-0.7% of the weight of the sulfonated polyaryletherketone base material with the side group containing carboxyl.
5. The method of producing a proton exchange membrane material for a hydrogen fuel cell according to claim 1, characterized in that: in step S2, the concentration of sulfuric acid is 0.1-0.4 mol/L.
6. The method of producing a proton exchange membrane material for a hydrogen fuel cell according to claim 1, characterized in that: in step S2, adding the aminated skeleton compound obtained in step S1 into the casting solution, adding organic montmorillonite, and ultrasonically stirring for 25-28h, wherein the weight of the organic montmorillonite is 0.1-0.4% of that of the sulfonated polyaryletherketone base material with carboxyl on the side group.
7. The method of producing a proton exchange membrane material for a hydrogen fuel cell according to claim 1, characterized in that: the organic montmorillonite comprises the following preparation steps: adding water into sodium-based montmorillonite, stirring until the sodium-based montmorillonite is completely swelled, preserving heat at 60-65 ℃, then slowly dropwise adding a cetyl trimethyl ammonium bromide solution into the sodium-based montmorillonite, wherein the mass ratio of the sodium-based montmorillonite to the cetyl trimethyl ammonium bromide in the cetyl trimethyl ammonium bromide solution is 1: (0.3-0.5), reacting for 6-7h, filtering, washing, drying, grinding and sieving with a 300-mesh sieve.
8. The method of producing a proton exchange membrane material for a hydrogen fuel cell according to claim 1, characterized in that: the sulfonated polyaryletherketone base material with the side group containing carboxyl comprises the following preparation steps: adding phenolphthalein, tetramethyl biphenol, difluorobenzophenone, sulfonated difluorobenzophenone and K in sequence2CO3Then adding dimethyl sulfoxide and toluene, stirring until solid substances are dissolved, heating the system to 135-145 ℃ under the conditions of continuous stirring and nitrogen introduction, refluxing the toluene for 3-5h, removing generated water, removing the toluene, heating to 185 ℃ under 170-2.5 h, pouring the obtained viscous polymer solution into a beaker filled with deionized water, precipitating, filtering, crushing, washing and drying the polymer solid.
9. The method of producing a proton exchange membrane material for a hydrogen fuel cell according to claim 8, characterized in that: the phenolphthalein, tetramethylbiphenol, difluorobenzophenone, sulfonated difluorobenzophenone and K2CO3The weight ratio of (1): (0.7-0.8): (0.65-0.7): (1.30-1.35): (1.0-1.2).
10. The method of producing a proton exchange membrane material for a hydrogen fuel cell according to claim 8, characterized in that: the volume ratio of the dimethyl sulfoxide to the toluene is 1: (0.35-0.38), phenolphthalein, tetramethylbiphenol, difluorobenzophenone, sulfonated difluorobenzophenone and K2CO3The ratio of the total weight of (A) to the total volume of dimethyl sulfoxide and toluene is 1 g: (2.5-2.6) mL.
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