阅读说明：本技术 一种燃料电池中交换膜的制备方法 (Preparation method of exchange membrane in fuel cell ) 是由 任小梅 于 2021-11-05 设计创作，主要内容包括：本发明公开了一种燃料电池中交换膜的制备方法,包括将3,6-咔唑二羧酸加入到N,N-二甲基乙酰胺中,加入硝酸铟(In(NO-(3))-(3)·xH-(2)O)和去离子水,在115～130℃下反应100～120h,得到MOF-1；将多巴胺加入到盐酸缓冲液中,然后将MOF-1研磨后加入该缓冲液中,移入静电注射泵,在玻璃板上得到一层复合纤维膜；将聚乙烯醇加入到混合溶剂中,然后加入海藻酸钠和8-羟基芘-1,3,6-三磺酸三钠盐,得到铸膜液；将铸膜液倒入培养皿,刮涂均匀厚度的铸膜液,将复合纤维膜平铺在该培养皿铸膜液上,然后在将铸膜液加入到复合纤维膜上刮涂均匀,将其放置在真空干燥箱中,干燥,从培养皿上剥落得到所述质子交换膜。本发明质子交换膜在低湿度高温环境下具有优异的导电能力。(The invention discloses a preparation method of an exchange membrane In a fuel cell, which comprises the steps of adding 3, 6-carbazole dicarboxylic acid into N, N-dimethylacetamide and adding indium nitrate (In (NO) 3 ) 3 ·xH 2 O) and deionized water, reacting at 115-130 ℃ for 1Obtaining MOF-1 in 00-120 h; adding dopamine into a hydrochloric acid buffer solution, then grinding the MOF-1, adding the ground MOF-1 into the buffer solution, transferring the buffer solution into an electrostatic injection pump, and obtaining a layer of composite fiber membrane on a glass plate; adding polyvinyl alcohol into a mixed solvent, and then adding sodium alginate and 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt to obtain a membrane casting solution; pouring the membrane casting solution into a culture dish, blade-coating the membrane casting solution with uniform thickness, flatly paving the composite fiber membrane on the membrane casting solution of the culture dish, then adding the membrane casting solution on the composite fiber membrane, blade-coating the composite fiber membrane uniformly, placing the composite fiber membrane in a vacuum drying oven, drying, and stripping from the culture dish to obtain the proton exchange membrane. The proton exchange membrane has excellent electric conductivity under the environment of low humidity and high temperature.)

1. A preparation method of an exchange membrane in a fuel cell is characterized by comprising the following steps:

s1: adding 3, 6-carbazole dicarboxylic acid into N, N-dimethylacetamide, ultrasonically stirring to fully dissolve, and adding indium nitrate (In (NO)₃)₃·xH₂O), ultrasonically stirring for 10-25 min, dropwise adding deionized water, ultrasonically stirring, transferring into a high-pressure reaction kettle, reacting for 100-120 h at 115-130 ℃, cooling, washing for 2-4 times by using N, N-dimethylacetamide, and filtering to obtain MOF-1;

s2: adding dopamine into a hydrochloric acid buffer solution, adjusting the pH value of the buffer solution to 10-11, ultrasonically stirring, then grinding the MOF-1 obtained in the step S1, adding the ground MOF-1 into the buffer solution, stirring for 20-30 min, and then moving the buffer solution into an electrostatic injection pump, wherein a layer of composite fiber membrane is obtained on a glass plate under the conditions that the injection voltage is 12-16 kV, the injection distance is 10-14 cm, and the injection rate is 0.45-0.56L/h;

s3: adding polyvinyl alcohol into a mixed solvent, then adding sodium alginate and 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt, stirring at room temperature for 30-45 min, wherein the mass ratio of the polyvinyl alcohol to the sodium alginate to the 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt is (0.69-0.94) g, (0.12-0.23) g, (0.07-0.11) g, and then heating to 70-85 ℃ and stirring for 2-4 h to obtain a casting solution;

s4: pouring the membrane casting solution obtained in the step S3 into a culture dish, blade-coating the membrane casting solution with uniform thickness, naturally cooling for 6-15 min, spreading the composite fiber membrane obtained in the step S2 on the membrane casting solution of the culture dish, blade-coating the membrane casting solution on the composite fiber membrane uniformly, placing the composite fiber membrane in a vacuum drying oven, drying at 60-68 ℃ for 10-18 h, and peeling off the membrane from the culture dish to obtain the exchange membrane.

2. The method as claimed in claim 1, wherein the mass ratio of 3, 6-carbazole dicarboxylic acid, trimesic acid and indium nitrate is (0.2-0.3): (0.038-0.046): (0.19-0.28).

3. The method as claimed in claim 1, wherein the volume ratio of N, N-dimethylacetamide to deionized water is (4.5-8): (1-2.2).

4. The method for preparing an exchange membrane in a fuel cell according to claim 1, wherein the mass ratio of the dopamine to the MOF-1 in the step S2 is (4.6-6.9): (1.02-1.96).

5. The method as set forth in claim 1, wherein the mixed solvent in step S3 is N, N-dimethylformamide and deionized water in a volume ratio of (5-10) - (3.5-7).

Technical Field

The invention belongs to the technical field of fuel cells, and particularly relates to a preparation method of an exchange membrane in a fuel cell.

Background

Proton exchange membrane fuel cells have received much attention because of their high energy density, high energy conversion efficiency, ease of operation, and environmental friendliness. Proton Exchange Membranes (PEMs) are the core components of fuel cells, which are carriers of conductive ions and play a role in transferring protons; meanwhile, the membrane is a membrane material for blocking fuel and oxidant, is a proton selective permeable membrane, and the performance of the membrane directly influences the performance of the fuel cell. The proton exchange membrane, which is an important component of the fuel cell, must be able to ensure the operation of the fuel cell in the presence of a certain amount of moisture, and therefore, the proton exchange membrane must have a certain moisture retention capacity.

Currently, the commonly adopted moisturizing methods can be divided into two types of external moisturizing and internal moisturizing according to the integration compactness of the moisturizing methods and the galvanic pile: the external humidification is to separate the humidification subsystem from the battery and humidify the reaction gas before the reaction gas enters the battery; the internal humidification is to integrate the humidification subsystem with the battery, and the humidification is carried out after the reaction gas enters the battery. However, in the existing proton exchange membrane, under a low-humidity high-temperature environment, the conductivity of the proton exchange membrane is reduced sharply due to the fact that water molecules in the membrane are easy to lose.

Disclosure of Invention

Aiming at the defect that the conductivity of the proton exchange membrane is sharply reduced due to the fact that water molecules in the proton exchange membrane are easy to lose under the environment with lower humidity and high temperature in the prior art, the invention aims to provide a preparation method of the exchange membrane in a fuel cell, which comprises the following steps:

s1: adding 3, 6-carbazole dicarboxylic acid into N, N-dimethylacetamide, ultrasonically stirring to fully dissolve, and adding indium nitrate (In (NO)₃)₃·xH₂O), ultrasonically stirring for 10-25 min, dropwise adding deionized water, ultrasonically stirring, transferring into a high-pressure reaction kettle, reacting for 100-120 h at 115-130 ℃, cooling, washing for 2-4 times with N, N-dimethylacetamide, and filtering to obtain the MOF-1.

S2: adding dopamine into a hydrochloric acid buffer solution, adjusting the pH value of the buffer solution to 10-11, ultrasonically stirring, then grinding the MOF-1 obtained in the step S1, adding the ground MOF-1 into the buffer solution, stirring for 20-30 min, and then moving the buffer solution into an electrostatic injection pump, wherein a layer of composite fiber membrane is obtained on a glass plate under the conditions that the injection voltage is 12-16 kV, the injection distance is 10-14 cm, and the injection speed is 0.45-0.56L/h.

S3: adding polyvinyl alcohol into a mixed solvent, then adding sodium alginate and 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt, stirring at room temperature for 30-45 min, wherein the mass ratio of the polyvinyl alcohol to the sodium alginate to the 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt is (0.69-0.94) g, (0.12-0.23) g, (0.07-0.11) g, and then heating to 70-85 ℃ and stirring for 2-4 h to obtain a casting solution.

S4: pouring the membrane casting solution obtained in the step S3 into a culture dish, blade-coating the membrane casting solution with uniform thickness, naturally cooling for 6-15 min, spreading the composite fiber membrane obtained in the step S2 on the membrane casting solution of the culture dish, blade-coating the membrane casting solution on the composite fiber membrane uniformly, placing the composite fiber membrane in a vacuum drying oven, drying at 60-68 ℃ for 10-18 h, and peeling off the membrane from the culture dish to obtain the exchange membrane.

Preferably, the mass ratio of the 3, 6-carbazole dicarboxylic acid, the trimesic acid and the indium nitrate is (0.2-0.3): (0.038-0.046): 0.19-0.28).

Preferably, the volume ratio of the N, N-dimethylacetamide to the deionized water is (4.5-8) to (1-2.2).

Preferably, the mass ratio of the dopamine to the MOF-1 in the step S2 is (4.6-6.9): (1.02-1.96).

Preferably, the mixed solvent in the step S3 is N, N-dimethylformamide and deionized water in a volume ratio of (5-10) - (3.5-7).

Compared with the prior art, the invention has the following beneficial effects:

according to the proton exchange membrane and the preparation method thereof, a metal organic framework material MOF-1 with high proton conductivity is utilized, then the metal organic framework is coated under an acidic condition through dopamine modification, a fiber membrane is obtained through an electrostatic spinning technology, and a polyvinyl alcohol, sodium alginate and 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt casting membrane liquid is further used for coating the fiber membrane with a casting membrane to obtain the proton exchange membrane, wherein sulfonate groups in the polyvinyl alcohol and the 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt have hydrophilicity, so that the proton exchange membrane has good water absorption performance, and a three-dimensional network structure is formed after sodium alginate is compounded, so that the proton exchange membrane has good water retention performance, and even in a high-temperature low-humidity environment, the proton exchange membrane can be guaranteed to have good conductivity.

Detailed Description

The following embodiments of the present invention are described in detail, and the embodiments are implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Example 1

A preparation method of an exchange membrane in a fuel cell specifically comprises the following steps:

s1: adding 3, 6-carbazole dicarboxylic acid into N, N-dimethylacetamide, ultrasonically stirring to fully dissolve, and adding indium nitrate (In (NO)₃)₃·xH₂O), ultrasonically stirring for 10min, dropwise adding deionized water, ultrasonically stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 100h at 115 ℃, cooling, washing for 2 times by using N, N-dimethylacetamide, and filtering to obtain the MOF-1, wherein the mass ratio of the 3, 6-carbazole dicarboxylic acid to the trimesic acid to the indium nitrate is 0.2:0.038: 0.19.

S2: adding dopamine into a hydrochloric acid buffer solution, adjusting the pH value of the buffer solution to 10, carrying out ultrasonic stirring, then grinding the MOF-1 in the step S1, adding the ground MOF-1 into the buffer solution, wherein the mass ratio of dopamine to MOF-1 is 4.6:1.02, stirring for 20min, then moving the mixture into an electrostatic injection pump, and obtaining a layer of composite fiber membrane on a glass plate under the conditions that the injection voltage is 12kV, the injection distance is 10cm, and the injection rate is 0.45L/h.

S3: adding polyvinyl alcohol into a mixed solvent of N, N-dimethylformamide and deionized water in a volume ratio of 5:3.5, then adding sodium alginate and 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt, stirring at room temperature for 30min, wherein the mass ratio of the polyvinyl alcohol to the sodium alginate to the 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt is 0.69g:0.12g:0.07g, and then heating to 70 ℃ and stirring for 2h to obtain a casting solution.

S4: pouring the membrane casting solution obtained in the step S3 into a culture dish, blade-coating the membrane casting solution with uniform thickness, naturally cooling for 6min, spreading the composite fiber membrane obtained in the step S2 on the membrane casting solution of the culture dish, blade-coating the membrane casting solution on the composite fiber membrane uniformly, placing the composite fiber membrane in a vacuum drying oven, drying for 10h at 60 ℃, and stripping off the culture dish to obtain the exchange membrane.

Example 2

A preparation method of an exchange membrane in a fuel cell specifically comprises the following steps:

s1: adding 3, 6-carbazole dicarboxylic acid into N, N-dimethylacetamide, ultrasonically stirring to fully dissolve, and adding indium nitrate (In (NO)₃)₃·xH₂O), ultrasonically stirring for 25min, dropwise adding deionized water, ultrasonically stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 120h at 130 ℃, cooling, washing for 4 times by using N, N-dimethylacetamide, and filtering to obtain the MOF-1, wherein the mass ratio of the 3, 6-carbazole dicarboxylic acid to the trimesic acid to the indium nitrate is 0.3:0.046: 0.28.

S2: adding dopamine into a hydrochloric acid buffer solution, adjusting the pH value of the buffer solution to 11, carrying out ultrasonic stirring, then grinding the MOF-1 in the step S1, adding the ground MOF-1 into the buffer solution, wherein the mass ratio of dopamine to MOF-1 is 6.9:1.96, stirring for 30min, then moving the mixture into an electrostatic injection pump, and obtaining a layer of composite fiber membrane on a glass plate under the conditions that the injection voltage is 16kV, the injection distance is 14cm, and the injection rate is 0.56L/h.

S3: adding polyvinyl alcohol into a mixed solvent of N, N-dimethylformamide and deionized water in a volume ratio of 10:7, then adding sodium alginate and 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt, stirring for 45min at room temperature, wherein the mass ratio of the polyvinyl alcohol to the sodium alginate to the 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt is 0.94g to 0.23g to 0.11g, and then heating to 85 ℃ and stirring for 4h to obtain a casting solution.

S4: pouring the membrane casting solution obtained in the step S3 into a culture dish, blade-coating the membrane casting solution with uniform thickness, naturally cooling for 15min, spreading the composite fiber membrane obtained in the step S2 on the membrane casting solution of the culture dish, blade-coating the membrane casting solution on the composite fiber membrane uniformly, placing the composite fiber membrane in a vacuum drying oven, drying at 68 ℃ for 18h, and peeling off the membrane from the culture dish to obtain the exchange membrane.

Example 3

A preparation method of an exchange membrane in a fuel cell specifically comprises the following steps:

s1: adding 3, 6-carbazole dicarboxylic acid into N, N-dimethylacetamide, ultrasonically stirring to fully dissolve, and adding indium nitrate (In (NO)₃)₃·xH₂O), ultrasonically stirring for 15min, dropwise adding deionized water, ultrasonically stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 110h at 120 ℃, cooling, washing for 3 times by using N, N-dimethylacetamide, and filtering to obtain the MOF-1, wherein the mass ratio of the 3, 6-carbazole dicarboxylic acid to the trimesic acid to the indium nitrate is 0.23:0.042: 0.21.

S2: adding dopamine into a hydrochloric acid buffer solution, adjusting the pH value of the buffer solution to 10.4, carrying out ultrasonic stirring, then grinding the MOF-1 in the step S1, adding the ground MOF-1 into the buffer solution, wherein the mass ratio of dopamine to MOF-1 is 5.7:1.24, stirring for 25min, then moving the mixture into an electrostatic injection pump, and obtaining a layer of composite fiber membrane on a glass plate under the conditions that the injection voltage is 14kV, the injection distance is 12cm, and the injection speed is 0.48L/h.

S3: adding polyvinyl alcohol into a mixed solvent of N, N-dimethylformamide and deionized water in a volume ratio of 7:5, then adding sodium alginate and 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt, stirring at room temperature for 35min, wherein the mass ratio of the polyvinyl alcohol to the sodium alginate to the 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt is 0.77g to 0.18g to 0.085g, and then heating to 75 ℃ and stirring for 3h to obtain a casting solution.

S4: pouring the membrane casting solution obtained in the step S3 into a culture dish, blade-coating the membrane casting solution with uniform thickness, naturally cooling for 10min, spreading the composite fiber membrane obtained in the step S2 on the membrane casting solution of the culture dish, blade-coating the membrane casting solution on the composite fiber membrane uniformly, placing the composite fiber membrane in a vacuum drying oven, drying for 14h at 63 ℃, and stripping from the culture dish to obtain the exchange membrane.

Example 4

A preparation method of an exchange membrane in a fuel cell specifically comprises the following steps:

s1: adding 3, 6-carbazole dicarboxylic acid into N, N-dimethylacetamide, ultrasonically stirring to fully dissolve, and adding indium nitrate (In (NO)₃)₃·xH₂O), ultrasonically stirring for 20min, dropwise adding deionized water, ultrasonically stirring, transferring the mixture into a high-pressure reaction kettle, reacting for 115h at 125 ℃, cooling, washing for 4 times by using N, N-dimethylacetamide, and filtering to obtain the MOF-1, wherein the mass ratio of the 3, 6-carbazole dicarboxylic acid to the trimesic acid to the indium nitrate is 0.28:0.044: 0.26.

S2: adding dopamine into a hydrochloric acid buffer solution, adjusting the pH value of the hydrochloric acid buffer solution to 10.8, carrying out ultrasonic stirring, then grinding the MOF-1 in the step S1, adding the ground MOF-1 into the buffer solution, wherein the mass ratio of dopamine to MOF-1 is 6.6:1.92, stirring for 28min, then moving the mixture into an electrostatic injection pump, and obtaining a layer of composite fiber membrane on a glass plate under the conditions that the injection voltage is 15kV, the injection distance is 13cm, and the injection speed is 0.54L/h.

S3: adding polyvinyl alcohol into a mixed solvent of N, N-dimethylformamide and deionized water in a volume ratio of 9:6.5, then adding sodium alginate and 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt, stirring at room temperature for 40min, wherein the mass ratio of the polyvinyl alcohol to the sodium alginate to the 8-hydroxypyrene-1, 3, 6-trisulfonic acid trisodium salt is 0.92g:0.21g:0.1g, and then heating to 80 ℃ and stirring for 4h to obtain a casting solution.

S4: pouring the membrane casting solution obtained in the step S3 into a culture dish, carrying out blade coating on the membrane casting solution with uniform thickness, naturally cooling for 14min, spreading the composite fiber membrane obtained in the step S2 on the membrane casting solution of the culture dish, adding the membrane casting solution into the composite fiber membrane, carrying out blade coating on the composite fiber membrane uniformly, placing the composite fiber membrane in a vacuum drying oven, drying the composite fiber membrane for 16h at 66 ℃, and stripping the composite fiber membrane from the culture dish to obtain the exchange membrane.

Experimental example:

the proton exchange membranes prepared in the examples 1 to 4 are cut into a size of 1cm multiplied by 1cm, and then clamped in a device with a hollow structure of 1cm multiplied by 1cm to test the proton conductivity, the test output voltage is 1000mV, the frequency is 100Hz to 1MHz, the proton conductivity is respectively tested under the conditions of 50 percent, 80 percent and 95 percent of humidity at 50 to 90 ℃,

the proton conductivity equation is:

wherein l is the sample length (cm); s is the effective membrane area (cm)²) (ii) a R is a resistance value (omega), the test results are shown in Table 1,

table 1. test results:

as can be seen from Table 1 above, the proton exchange membranes prepared in examples 1-4 of the present invention have conductivities of 2.6 × 10 at 90 ℃ under 95% humidity conditions^-1mS/cm²While the conductivity at 90 ℃ under 50% humidity was 3X 10^-2mS/cm²As described above, the proton exchange membrane of the present invention has good conductivity even in a low humidity and high temperature environment.