CN111342096B - Pyridine cross-linked anion exchange membrane for fuel cell and preparation method thereof - Google Patents
Pyridine cross-linked anion exchange membrane for fuel cell and preparation method thereof Download PDFInfo
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Abstract
The invention provides a pyridine cross-linked anion exchange membrane for a fuel cell and a preparation method thereof, belonging to the technical field of polymer chemistry and anion exchange membrane fuel cells. The structural formula of the pyridine cross-linked anion exchange membrane is shown as a formula 1. The pyridine cross-linked anion exchange membrane is prepared by preparing polyether-ether-ketone, preparing brominated polyether-ether-ketone by bromination reaction, and preparing the pyridine cross-linked anion exchange membrane by solution pouring. The 4, 4-bipyridine can improve the anion conduction performance of the membrane, improve the thermal stability of the membrane and simultaneously increase the dimensional stability of the membrane. The maximum proton conductivity of the pyridine cross-linked anion exchange membrane can reach 32.06mS/cm at 80 ℃.
Description
Technical Field
The invention belongs to the field of polymer chemistry and anion exchange membrane fuel cells, and particularly relates to a pyridine cross-linked anion exchange membrane for a fuel cell and a preparation method thereof.
Background
An Anion Exchange Membrane (AEM) is the core part of an Anion Exchange Membrane Fuel Cell (AEMFC), and during operation, the proton exchange membrane plays a role in conducting protons to generate and convert chemical energy into electric energy, and can isolate fuel and oxidant to prevent them from reacting directly. The performance of anion exchange membranes greatly affects the performance of anion exchange membrane fuel cells. The currently marketed proton exchange membrane is a perfluorosulfonic acid type proton exchange membrane (e.g., nafion). The sulfonic acid membrane has the advantages of good proton conductivity, high chemical stability, high thermal stability and the like, but simultaneously has the defects of high price, high methanol permeability, easy water loss at high temperature and the like, so that the further development and application are limited.
In recent years, various polymer membranes have been developed and are expected to be a substitute for Nafion. The functionalized polyether ether ketone has good ionic conductivity, thermal stability and low preparation cost, and is widely concerned by people. Meanwhile, the non-crosslinked polyether-ether-ketone anion exchange membrane has little phase separation between hydrophilic and hydrophobic phases, is easy to absorb water and swell after the quaternary ammoniation degree is improved, and the three-dimensional size of the membrane is greatly changed after dense quaternary amino groups are used as hydrophilic groups to combine with water molecules, so that the mechanical strength is reduced, the quaternary ammoniation degree of the membrane is controlled in the membrane preparation process, and the anion conductivity of the membrane is low. Therefore, the modification of the low-cost polyether-ether-ketone has very important significance in improving the comprehensive performance of the low-cost polyether-ether-ketone.
Disclosure of Invention
The invention aims to provide a pyridine cross-linking anion exchange membrane for a fuel cell and a preparation method thereof, aiming at improving proton conductivity and thermal stability on the basis of different pyridine degrees, keeping better dimensional stability, and simultaneously having simple process and low cost.
The invention firstly provides a pyridine cross-linking type anion exchange membrane for a fuel cell, which has a structural formula shown as a formula 1:
wherein: x is the molar ratio of the nitrogen atoms charged to the bipyridine to the brominated polyetheretherketone repeat units.
The invention also provides a preparation method of the pyridine cross-linked anion exchange membrane for the fuel cell, which comprises the following steps:
the method comprises the following steps: preparing polyether-ether-ketone;
step two: preparation of brominated polyether ether ketones
Putting polyether-ether-ketone into a solvent and stirring, adding a brominating agent N-bromosuccinimide (NBS) and an initiator under the protection of nitrogen, heating an oil bath in a reaction container after completely dissolving, and reacting for 4-6h at 75-85 ℃ to obtain brominated polyether-ether-ketone;
step three: preparation of a pyridine crosslinked anion exchange membrane
Dissolving the brominated polyether-ether-ketone obtained in the second step in water, heating and stirring the solution under the protection of nitrogen, and then adding 4, 4-bipyridyl for reaction to obtain a mixed solution; pouring the mixed liquid on a glass plate, and then carrying out vacuum drying; and (3) carrying out alkalization treatment on the dried membrane, and cleaning the membrane by using deionized water to obtain the pyridine cross-linked anion exchange membrane.
Preferably, the first step specifically includes: under the protection of nitrogen, methyl hydroquinone, 4-difluorobenzophenone and a salt forming agent K are respectively added into a flask 2 CO 3 NMP as solvent and toluene as water-carrying agent; slowly heating to 120 ℃, refluxing for 4h at constant temperature, then heating to 165 ℃ and reacting for 3-6h; introducing the obtained viscous polymer into clear water, cooling the polymer into filaments, and crushing the obtained filaments into powder by using a dry powder crusher; boiling the powder in boiling water for 10 min for 10 times; the powder obtained after filtration was dried in an oven at 80 ℃ for 24h to obtain polyetheretherketone, named PEEK.
Preferably, the mass ratio of the methyl hydroquinone to the 4, 4-difluorobenzophenone to the salt forming agent is 2.483:4.364:3.306.
preferably, the mass ratio of the polyether-ether-ketone to the brominating agent to the initiator is 1:1.18:0.08.
preferably, the solvent is 1, 2-tetrachloroethane.
Preferably, the reaction temperature of the second step is 80 ℃, and the reaction time is 4h.
Preferably, the initiator is Benzoyl Peroxide (BPO).
Preferably, the mass ratio of the brominated polyether-ether-ketone to the 4, 4-bipyridine is preferably 0.4: (0.0082-0.041).
Preferably, the heating temperature of the second step is 80 ℃, and the time is 4h.
The invention has the advantages of
The invention provides a pyridine cross-linking anion exchange membrane for a fuel cell and a preparation method thereof, wherein the structural formula of the pyridine cross-linking anion exchange membrane is shown as a formula 1. The pyridine cross-linked anion exchange membrane is prepared by preparing polyether-ether-ketone, preparing brominated polyether-ether-ketone by bromination reaction, and preparing the pyridine cross-linked anion exchange membrane by a solution pouring method. The main chain of the polyether-ether-ketone has benzyl methyl groups, and the polyether-ether-ketone can be subjected to bromination reaction with N-bromosuccinimide (NBS) and further subjected to quaternary ammoniation with 4, 4-bipyridine to obtain the ion conductivity capacity, and the pyridine cross-linked anion exchange membrane can control the grafting degree and the cross-linking degree by adjusting and controlling the feeding ratio of the 4, 4-bipyridine, so that AEM with different 4, 4-bipyridine group contents is prepared: biPyBPEEK-x (x is the molar ratio of nitrogen atoms input into the bipyridyl to the repeating units of the polymer), and the 4, 4-bipyridyl can improve the anion conduction performance of the membrane, improve the thermal stability of the membrane and simultaneously increase the dimensional stability of the membrane. The maximum proton conductivity of the pyridine cross-linked anion exchange membrane can reach 32.06mS/cm at 80 ℃.
The preparation method of the pyridine cross-linked anion exchange membrane is simple, the production period is short, the raw materials are easy to obtain, the cost of the pyridine cross-linked anion exchange membrane is lower than that of a perfluorosulfonic acid membrane, and the pyridine cross-linked anion exchange membrane is expected to be applied to the field of fuel cells.
Drawings
FIG. 1 is an infrared spectrum of BiPyBPEEK-10%, biPyBPEEK-30%, biPyBPEEK-50% and BPEEK obtained in example 1-3, respectively.
FIG. 2 is an SEM photograph of BiPyBPEEK-10%, biPyBPEEK-30% and BiPyBPEEK-50% of the exchange membranes obtained in examples 1-3, respectively.
FIG. 3 is a TGA plot of BiPyBPEEK-10%, biPyBPEEK-30%, and BiPyBPEEK-50% exchange membrane samples obtained in examples 1-3, respectively.
FIG. 4 is a graph of conductivity versus temperature for BiPyBPEEK-10%, biPyBPEEK-30%, and BiPyBPEEK-50% exchange membrane samples obtained in examples 1-3, respectively.
FIG. 5 is a graph showing the alkali resistance stability of the BiPyBPEEK-10%, biPyBPEEK-30% and BiPyBPEEK-50% exchange membrane samples obtained in examples 1-3, respectively.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention firstly provides a pyridine cross-linking anion exchange membrane for a fuel cell, which has a structural formula shown as a formula 1:
wherein: x is the molar ratio of the nitrogen atoms charged to the bipyridine to the polymeric brominated polyetheretherketone repeat units.
The invention also provides a preparation method of the pyridine cross-linked anion exchange membrane for the fuel cell, which comprises the following steps:
the method comprises the following steps: preparing polyether-ether-ketone;
under the protection of nitrogen, methyl hydroquinone, 4-difluorobenzophenone and a salt forming agent K are respectively added into a flask 2 CO 3 NMP as solvent and toluene as water-carrying agent; slowly heating to 120 ℃, refluxing for 4 hours at constant temperature, then heating to 165 ℃, and reacting for 3-6 hours; introducing the obtained viscous polymer into clear water, cooling the polymer into filaments, and crushing the obtained filaments into powder by using a dry powder crusher; boiling the powder in boiling water for 10 min for 10 times; the powder obtained after filtration was dried in an oven at 80 ℃ for 24h. The mass ratio of the methyl hydroquinone, the 4, 4-difluorobenzophenone and the salt forming agent is preferably 2.483:4.364:3.306. the number average molecular weight of the polyether-ether-ketone polymer is preferably 50000-80000.
The reaction formula is as follows:
step two: preparation of brominated polyether ether ketones
In a reaction vessel, adding polyether-ether-ketone into a solvent and stirring, wherein the solvent is preferably 1, 2-tetrachloroethane, adding a brominating agent N-bromosuccinimide (NBS) and an initiator under the protection of nitrogen, wherein the initiator is preferably BPO, heating an oil bath in the reaction vessel after completely dissolving, and reacting for 4-6h at 75-85 ℃, preferably 80 ℃ and preferably for 4h; and (3) after the mixed solution is yellow and transparent, turning off and heating the mixed solution to naturally cool the mixed solution to room temperature, pouring the solution into absolute ethyl alcohol to separate out yellow flocculent precipitated polymer, washing the flocculent precipitated polymer for a plurality of times by using the absolute ethyl alcohol, and then drying the flocculent yellow product in vacuum to obtain the brominated polyether-ether-ketone. The mass ratio of the polyether-ether-ketone to the brominating agent to the initiator is preferably 1:1.18:0.08.
the reaction formula is as follows:
step three: preparation of a pyridylated crosslinked anion exchange membrane
Dissolving the brominated polyether-ether-ketone obtained in the second step in water, heating and stirring under the protection of nitrogen, wherein the heating temperature is preferably 60 ℃, and then adding 4, 4-bipyridyl for reaction, wherein the reaction time is preferably 24h, so as to obtain a mixed solution; pouring the mixed liquid on a glass plate, and then carrying out vacuum drying; the drying temperature is preferably 70-90 ℃, the time is preferably 24-36h, the membrane obtained after drying is subjected to alkalization treatment, and the membrane is washed by deionized water to obtain the pyridine cross-linked anion exchange membrane. The mass ratio of the brominated polyether-ether-ketone to the 4, 4-bipyridine is preferably 0.4: (0.0082-0.041), more preferably 0.4:0.041. the reaction process is as follows:
wherein: x is the molar ratio of the nitrogen atoms charged to the bipyridine to the polymer repeat units.
The present invention is described in further detail below with reference to specific examples, in which the starting materials are all commercially available.
Example 1
(1) Under the protection of nitrogen, 2.483g of methyl hydroquinone, 4.364g of 4,4-difluorobenzophenone and 3.306 salt forming agent K are respectively added into a flask 2 CO 3 17mL of solvent NMP and 15mL of water-carrying agent toluene; slowly heating to 120 ℃, refluxing for 4 hours at constant temperature, then heating to 165 ℃, and reacting for 4 hours; the resulting viscous polymer was introduced into clear water to cool the polymer into filaments. Crushing the obtained filamentous solid polymer into powder by using a dry powder crusher; boiling the powder in boiling water for 10 min for 10 times; drying the filtered powder in an oven at 80 ℃ for 24 hours to obtain polyether-ether-ketone;
(2) Adding 1g of the polyether-ether-ketone into a three-neck flask, stirring by using 1, 2-tetrachloroethane as a solvent, adding 1.18g of brominating agent NBS and 0.08g of initiator BPO after the polyether-ether-ketone is completely dissolved under the protection of nitrogen, heating the three-neck flask in an oil bath after the brominating agent NBS and the initiator BPO are completely dissolved, slowly heating to 80 ℃, and continuously reacting for 4 hours. And (3) stopping heating until the mixed solution is yellow and transparent, naturally cooling to room temperature, pouring the solution into absolute ethyl alcohol, and separating out yellow flocculent precipitated polymer. Washing with absolute ethyl alcohol for many times, and then drying in vacuum to obtain a yellow flocculent product brominated polyether-ether-ketone.
(3) 0.4g of brominated polyetheretherketone was dissolved in 6ml of NMP solvent, heated to 60 ℃ with stirring under nitrogen, 8.2mg of 4, 4-bipyridine was added, and reacted for twenty-four hours. Pouring the obtained solution on a preheated glass plate, placing the glass plate in a constant-temperature oven to react and dry at the temperature of 80 ℃ for twenty-four hours, taking off the film on the glass plate, soaking the glass plate in 2M KOH solution for twenty-four hours, and then washing the glass plate with deionized water for many times to remove residual KOH on the surface of the film to obtain the pyridine functionalized polyether ether ketone, which is recorded as BiPyBPEEK-10%.
Example 2
(1) Under the protection of nitrogen, 2.483g of methyl hydroquinone, 4.364g of 4,4-difluorobenzophenone and 3.306 of salt forming agent K are respectively added into a flask 2 CO 3 17mL of solvent NMP and 15mL of water-carrying agent toluene; slowly heating to 120 ℃, refluxing for 4h at constant temperature, then heating to 165 ℃ and reacting for 4h; will be provided withThe resulting viscous polymer was introduced into clear water to cool the polymer into filaments. Crushing the obtained filiform solid polymer into powder by using a dry powder crusher; boiling the powder in boiling water for 10 min for 10 times; drying the powder obtained after filtering in an oven at 80 ℃ for 24h to obtain polyether-ether-ketone;
(2) Adding 1g of the polyether-ether-ketone into a three-neck flask, stirring by using 1, 2-tetrachloroethane as a solvent, adding 1.18g of brominating agent NBS and 0.08g of initiator BPO after the polyether-ether-ketone is completely dissolved under the protection of nitrogen, heating the three-neck flask in an oil bath after the brominating agent NBS and the initiator BPO are completely dissolved, slowly heating to 80 ℃, and continuously reacting for 4 hours. And (3) stopping heating until the mixed solution is yellow and transparent, naturally cooling to room temperature, pouring the solution into absolute ethyl alcohol, and separating out yellow flocculent precipitated polymer. Washing with absolute ethyl alcohol for many times, and then drying in vacuum to obtain a yellow flocculent product brominated polyether-ether-ketone.
(3) 0.4g of brominated polyetheretherketone was dissolved in 6ml of NMP solvent, heated to 60 ℃ with stirring under nitrogen, 24.6mg of 4, 4-bipyridine were added and reacted for twenty-four hours. Pouring the obtained solution on a preheated glass plate, placing the glass plate in a constant-temperature oven to react and dry at the temperature of 80 ℃ for twenty-four hours, removing the film on the glass plate, soaking the glass plate in 2M KOH solution for twenty-four hours, and then washing the glass plate with deionized water for many times to remove residual KOH on the surface of the film to obtain the pyridine functionalized polyether ether ketone, which is recorded as BiPyBPEEK-30%.
Example 3
(1) Under the protection of nitrogen, 2.483g of methyl hydroquinone, 4.364g of 4,4-difluorobenzophenone and 3.306 of salt forming agent K are respectively added into a flask 2 CO 3 17mL of solvent NMP and 15mL of water-carrying agent toluene; slowly heating to 120 ℃, refluxing for 4h at constant temperature, then heating to 165 ℃ and reacting for 4h; the resulting viscous polymer was introduced into clear water to cool the polymer into filaments. Crushing the obtained filamentous solid polymer into powder by using a dry powder crusher; boiling the powder in boiling water for 10 min for 10 times; drying the filtered powder in an oven at 80 ℃ for 24 hours to obtain polyether-ether-ketone;
(2) Adding 1g of the polyether-ether-ketone into a three-neck flask, stirring by using 1, 2-tetrachloroethane as a solvent, adding 1.18g of brominating agent NBS and 0.08g of initiator BPO after the polyether-ether-ketone is completely dissolved under the protection of nitrogen, heating the three-neck flask in an oil bath after the brominating agent NBS and the initiator BPO are completely dissolved, slowly heating to 80 ℃, and continuously reacting for 4 hours. And (3) after the mixed solution is yellow and transparent, closing and heating the mixed solution to naturally cool the mixed solution to room temperature, pouring the solution into absolute ethyl alcohol, and separating out yellow flocculent precipitated polymer. Washing with absolute ethyl alcohol for many times, and then drying in vacuum to obtain a yellow flocculent product brominated polyether-ether-ketone.
(3) 0.4g of brominated polyetheretherketone was dissolved in 6ml of NMP solvent, heated to 60 ℃ with stirring under nitrogen, 41mg of 4, 4-bipyridine was added, and reacted for twenty-four hours. Pouring the obtained solution on a preheated glass plate, placing the glass plate in a constant-temperature oven to react and dry for twenty-four hours at the temperature of 80 ℃, removing the film on the glass plate, soaking the glass plate in 2M KOH solution for twenty-four hours, and then washing the glass plate for multiple times by using deionized water to remove the KOH remaining on the surface of the film to obtain the pyridine functionalized polyether ether ketone, which is recorded as BiPyBPEEK-50%.
Based on the method, the invention provides a pyridine cross-linked anion exchange membrane which is prepared by adopting the preparation method. The pyridine cross-linked anion exchange membrane has excellent performances of good ion conductivity, good size stability and the like.
The properties of BiPyBPEEK-10%, biPyBPEEK-30% and BiPyBPEEK-50% of examples 1-3 were compared.
(1) Infrared characterization of films
FIG. 1 shows the IR spectra of BiPyBPEEK-x and pure BPEEK obtained in examples 1-3, where the C-N bond between the N atom of the bipyridine and the C atom of the bromomethyl group is also 1185cm compared to the pure membrane -1 A new stretching vibration peak appears, which indicates that C-N bonds in BiPyBPEEK-x are formed in a large amount, and 4, 4-bipyridyl successfully reacts with bromomethyl. Meanwhile, gelation occurring in the grafting reaction process indicates that two sections of 4, 4-bipyridyl successfully react with bromomethyl, so that a cross-linked structure appears in the film.
(2) Microscopic morphology of the film
FIG. 2 is a scanning electron micrograph of the surface of BiPyBPEEK-x obtained in example 1-3, wherein the graph a represents BiPyBPEEK-10%, the graph b represents BiPyBPEEK-30%, and the graph c represents BiPyBPEEK-50%, from which it can be seen that pores and gaps gradually appear on the surface of the film with the increase of 4,4-bipyridine, probably because of the phase separation phenomenon therein due to the introduction of the cross-linked structure.
(3) Characterization of Heat resistance stability of the film
Figure 3 is a graph of the thermal weight loss curves of bipy BPEEK-x and pure BPEEK obtained in examples 1-3, from which it can be seen that all membranes have one slight weight loss plateau and two major weight loss plateaus. The first slight weight loss plateau before 200 ℃ is due to the elimination of residual small molecules inside the membrane, including water, solvents or BPO, etc. The second weight loss plateau before 350 ℃ was due to the shedding of the polymer side chains. While the last weight loss occurred above 400 c due to polymer backbone degradation. On top of that, an increase in the content of 4, 4-bipyridine would shift the weight loss plateau of each membrane material towards high temperatures, probably because the cross-linked structure provides more stable thermal stability.
(4) Ionic conductivity of membrane
FIG. 4 is a line graph showing the change of ion conductivity with temperature of BiPyBPEEK-x obtained in examples 1-3, and it can be seen that the ion conductivity of all three membranes is at a lower level at low temperature, and as the temperature rises, the ion conductivity rises rapidly, and the content of bipyridyl salt increases, so that the conductivity is improved. OH in AEM - The content of (b) increases with the increase of quaternary ammonium groups, and the transmission channel of ions becomes wider, thus leading to the increase of ion conductivity.
(5) Alkali-resistant stability of membranes
FIG. 5 is a graph showing the alkali resistance curves of BiPyBPEEK-x obtained in examples 1-3, where the membrane material decreased with increasing time in the alkaline solution, but slowly enough, and the presence of the cross-linked structure well protected the functional groups from the strong nucleophile OH - Attack and the apparent morphology of the membrane material is not significantly changed.
(6) Mechanical Property characterization of the films
Table 1 is a characterization of the mechanical properties of BiPyBPEEK-x obtained in examples 1-3, from which it can be seen that the addition of bipyridine, i.e., the presence of a cross-linked structure, greatly increased the Young's modulus and the maximum stress of the film, but decreased the elongation at break. The following test data results all meet the use requirements of the fuel cell.
TABLE 1 mechanical Properties of BiPyBPEEK-x and pure films
In summary, the invention provides a pyridine cross-linked anion exchange membrane and a preparation method thereof, the preparation method comprises the steps of firstly preparing polyether ether ketone of a polymer main chain of the membrane, and then, brominating and grafting 4, 4-bipyridine into the brominated polyether ether ketone. And finally, preparing the pyridine cross-linked anion exchange membrane by a solution pouring method. The 4, 4-bipyridine can improve the anion conductivity of the membrane, improve the thermal stability of the membrane and simultaneously increase the dimensional stability of the membrane, but the excessive 4, 4-bipyridine can reduce the elongation at break of the membrane material, and when the content of bipyridine in BiPyBPEEK-x is 50%, the highest ion conductivity can be realized under the condition of meeting the use requirement of a fuel cell.
The above description of the embodiments is only for the purpose of helping understanding the method of the present invention and the core idea thereof, and it should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (10)
1. A pyridine cross-linking anion exchange membrane for a fuel cell is characterized in that the structural formula is shown as formula 1:
wherein: x is the molar ratio of the nitrogen atoms charged to the bipyridine to the brominated polyetheretherketone repeat units.
2. The method for preparing the pyridine cross-linked anion exchange membrane for the fuel cell according to claim 1, wherein the method comprises the following steps:
the method comprises the following steps: preparing polyether-ether-ketone;
step two: preparation of brominated polyether ether ketones
Putting polyether-ether-ketone into a solvent in a reaction container, stirring, adding a brominating agent N-bromosuccinimide and an initiator under the protection of nitrogen, heating in an oil bath in the reaction container after completely dissolving, and reacting at 75-85 ℃ for 4-6h to obtain brominated polyether-ether-ketone;
step three: preparation of a pyridine crosslinked anion exchange membrane
Dissolving the brominated polyether-ether-ketone obtained in the step two in a solvent, heating and stirring under the protection of nitrogen, and then adding 4, 4-bipyridyl for reaction to obtain a mixed solution; pouring the mixed liquid on a glass plate, and then carrying out vacuum drying; and (3) carrying out alkalization treatment on the dried membrane, and cleaning the membrane by using deionized water to obtain the pyridine cross-linked anion exchange membrane.
3. The method for preparing the cross-linked pyridine anion-exchange membrane for the fuel cell according to claim 2, wherein the first step specifically comprises: under the protection of nitrogen, methyl hydroquinone, 4-difluorobenzophenone and a salt forming agent K are respectively added into a flask 2 CO 3 NMP as solvent and toluene as water-carrying agent; slowly heating to 120 ℃, refluxing for 4h at constant temperature, then heating to 165 ℃ and reacting for 3-6h; introducing the obtained viscous polymer into clear water, cooling the polymer into filaments, and crushing the obtained filaments into powder by using a dry powder crusher; boiling the powder in boiling water for 10 min for 10 times; the powder obtained after filtration was dried in an oven at 80 ℃ for 24h to obtain polyetheretherketone, named PEEK.
4. The method of claim 3, wherein the mass ratio of the methylhydroquinone to the 4, 4-difluorobenzophenone and the salt forming agent is 2.483:4.364:3.306.
5. the preparation method of the pyridine cross-linked anion-exchange membrane for the fuel cell according to claim 2, wherein the mass ratio of the polyether-ether-ketone to the brominating agent to the initiator is 1:1.18:0.08.
6. the method of claim 2, wherein the solvent is 1, 2-tetrachloroethane.
7. The method for preparing the pyridine cross-linked anion-exchange membrane for the fuel cell according to claim 2, wherein the reaction temperature in the second step is 80 ℃ and the reaction time is 4h.
8. The method of claim 2, wherein the initiator is benzoyl peroxide.
9. The method for preparing the pyridine cross-linked anion-exchange membrane for the fuel cell according to claim 2, wherein the mass ratio of the brominated polyetheretherketone to the 4, 4-bipyridine is preferably 0.4: (0.0082-0.041).
10. The method for preparing a pyridine cross-linked anion-exchange membrane for a fuel cell according to claim 2, wherein the heating temperature in the second step is 80 ℃ and the heating time is 4h.
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