CN114006017B - Proton exchange membrane and preparation method and application thereof - Google Patents
Proton exchange membrane and preparation method and application thereof Download PDFInfo
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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Abstract
The invention relates to a proton exchange membrane and a preparation method and application thereof, wherein the preparation method comprises the following steps: step 1, carrying out polymerization reaction on fluorine-containing styrene and derivatives, glycidyl ether and vinyl benzene sulfonic acid sodium salt to obtain a prepolymer; step 2, carrying out grafting reaction and crosslinking on the prepolymer obtained in the step 1 and the amino nitrogen heterocyclic compound to obtain a crosslinked polymer; and step 3, carrying out ion exchange reaction on the crosslinked polymer obtained in the step 2 to obtain the sulfonic acid group crosslinked proton exchange membrane. The method is simple and easy to operate, and the prepared proton exchange membrane has high proton conductivity and is suitable for proton exchange membrane fuel cells.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a proton exchange membrane and a preparation method and application thereof.
Background
Proton exchange membrane fuel cells are a novel power generation device for converting chemical energy of fuel and oxidant into electric energy, and the advantages of high energy density, high energy conversion rate, environmental friendliness and the like make the proton exchange membrane fuel cells considered as one of the most promising clean energy sources at present. As a core component material of the fuel cell, the proton exchange membrane plays a role of blocking fuel gas such as H 2 And oxygen or air, conducting protons, etc., the performance of the proton exchange membrane determines the performance of the fuel cell.
Currently, proton exchange membrane materials are mainly perfluorosulfonic acid (PFSA) proton exchange membranes, such as Nafion membranes manufactured by dupont, which are composed of a fluorocarbon backbone and a branched chain containing sulfonic acid groups, with the sulfonic acid groups being proton conducting units. The proton exchange membrane has the defects of complex preparation process, high cost, high fuel permeability and the like, although the proton exchange membrane has good chemical stability and higher proton conductivity. In addition, the perfluorosulfonic acid proton exchange membrane is severely dependent on water as a transmission medium, has considerable proton conductivity only when the perfluorosulfonic acid proton exchange membrane has sufficient and proper water content at low temperature, and if the working temperature exceeds the boiling point of water, the water is largely evaporated, the quantity of water as a transmission medium is reduced, the proton transmission channel which is communicated is not easy to form, and the proton conductivity of the exchange membrane is sharply reduced.
CN103346341a discloses an acid-base composite high temperature proton exchange membrane and a preparation method thereof, the disclosed acid-base composite high temperature proton exchange membrane is formed by compounding an acidic component and an alkaline component, the acidic component is: polyvinyl phosphonic acid; the basic component is poly (4-vinyl-1H-1, 2, 3-triazole), poly (4- (a-methyl vinyl) -1H-1,2, 3-triazole) or poly (4- (a-methyl vinyl) -1H-1,2, 3-triazole); wherein the molar ratio of the acidic component to the basic component is: 1: (0.1-9). The preparation process disclosed by the method is simple, raw materials are all industrial products, the price is low, and the method is easy to realize large-scale production. The prepared composite membrane has good proton conductivity and can be applied to high-temperature proton exchange membrane fuel cells.
CN104610674a discloses a polystyrene phosphonic acid/polystyrene-1, 2, 3-triazole acid-base composite proton exchange membrane and a preparation method thereof. Wherein the acidic component is: polystyrene phosphonic acid; and the basic component is polystyrene 1,2, 3-triazole. The preparation process disclosed by the method is simple, raw materials are all industrial products, the price is low, and the method is easy to realize large-scale production. The prepared composite membrane has good proton conductivity and can be used for proton exchange membrane fuel cells.
In summary, it is important to develop more processes that are simple in process and that produce proton exchange membranes with excellent proton conductivity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a proton exchange membrane, a preparation method and application thereof, wherein the method is simple and easy to operate, and the prepared proton exchange membrane has high proton conductivity and is suitable for a proton exchange membrane fuel cell.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a proton exchange membrane, the method comprising the steps of:
step 1, carrying out polymerization reaction on fluorine-containing styrene and derivatives, glycidyl ether and vinyl benzene sulfonic acid sodium salt to obtain a prepolymer;
step 2, carrying out grafting reaction and crosslinking on the prepolymer obtained in the step 1 and the amino nitrogen heterocyclic compound to obtain a crosslinked polymer;
and step 3, carrying out ion exchange reaction on the crosslinked polymer obtained in the step 2 to obtain the sulfonic acid group crosslinked proton exchange membrane.
The sulfonic acid group copolymerization crosslinking type proton exchange membrane prepared by the method is different from a perfluorosulfonic acid type proton exchange membrane, and the internal structure of the perfluorosulfonic acid type proton exchange membrane does not contain an N-heterocyclic group. The structure of the invention has acidic partial sulfonic acid groups as proton donors and basic N-heterocyclic groups, the N-heterocyclic groups are used as cross-linking agents and proton acceptors, and the two are in a polymer network to promote the continuous exchange of protons between the acidic and the basic groups so as to form hydrogen bond jump type transmission sites, thereby being beneficial to proton conduction and improving proton conductivity and being suitable for proton exchange membrane fuel cells. In addition, the preparation method of the invention has simple preparation process, easily obtained raw materials and easy industrialization. The cross-linked proton exchange membrane has the advantages compared with the direct mixing of the alkaline component and the acidic component that: the acidic part and the alkaline part are in the same polymer network, so that the problem of phase separation possibly caused by direct mixing of the alkaline component and the acidic component is avoided, and meanwhile, the cross-linked integral structure can keep better mechanical properties such as mechanics and the like.
Preferably, in the step 1, the mass ratio of the fluorine-containing styrene and the derivative thereof, the glycidyl ether and the vinylbenzenesulfonic acid sodium salt is 1 (0.1-5): (0.1-5), wherein 0.1-5 may be 1,2,3, 4, etc., and the mass of the glycidyl ether and the vinyl benzenesulfonic acid sodium salt may be the same or different.
The mass ratio of the fluorine-containing styrene to the derivative thereof, the glycidyl ether and the vinylbenzenesulfonic acid sodium salt is 1 (0.1-5): (0.1-5), the content of glycidyl ether is reduced by the amount of acid groups, functional sites for conducting protons are reduced, and conductivity is lowered; the content of glycidyl ether is too low, the cross-linking sites are reduced, the grafting of cross-linked basic groups to a polymer network is reduced, the basic sites for receiving proton jump are fewer, and the conductivity is reduced to a certain extent.
Preferably, the fluorostyrene comprises 2.3.4.5.6-pentafluorostyrene.
Preferably, the glycidyl ether is allyl glycidyl ether and/or 4-vinylbenzyl glycidyl ether.
Preferably, the initiator of the polymerization reaction includes any one or a combination of at least two of Azobisisobutyronitrile (AIBN), azobisisoheptonitrile, or dimethyl azobisisobutyrate.
Preferably, the initiator is present in a mass percentage of 1.5% to 2.5%, for example 1.6%, 1.8%, 2%, 2.2%, 2.4%, etc., based on 100% of the total mass of the fluorostyrene and its derivatives, glycidyl ether and vinylbenzenesulfonic acid sodium salt.
Preferably, the polymerization reaction temperature is 70-80 ℃, e.g., 72 ℃, 74 ℃, 76 ℃, 78 ℃, etc.
Preferably, the polymerization reaction time is 18 to 24 hours, for example 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, etc.
Preferably, in the step 2, the mass ratio of the prepolymer to the amino nitrogen containing heterocyclic compound is 1 (0.1-3), wherein 0.1-3 may be 0.5, 1, 1.5, 2, 2.5, etc.
Preferably, the amino nitrogen-containing heterocyclic compound comprises any one or a combination of at least two of amino imidazole compounds, amino benzimidazole compounds, amino piperazine compounds, amino piperidine compounds, amino pyrrole compounds, amino triazole compounds or melamine.
Preferably, the amino-nitrogen containing heterocyclic compound comprises any one or a combination of at least two of 2-aminoimidazole, 4-aminoimidazole, 1- (3-aminopropyl) imidazole, 2-aminobenzimidazole, 1-aminopiperazine, 2-aminopiperazine, aminoethylpiperazine, 3-amino-1, 2, 4-triazole, 2-aminopiperidine, 3-aminopiperidine, 4-aminopiperidine, 3-aminopyrrole or melamine.
Preferably, in step 2, the grafting reaction is carried out at a temperature of 90-100℃such as 92℃94℃96℃98℃and the like.
Preferably, the grafting reaction is carried out for a period of time ranging from 18 to 24 hours, for example 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, etc.
Preferably, the grafting reaction is carried out in an anhydrous solvent.
Preferably, in step 3, the ion exchange reaction is performed in a hydrochloric acid solution.
Illustratively, the reaction process of the preparation method of the present invention is as follows:
in the reaction formula, R refers to a ring of imidazole, benzimidazole, piperazine, piperidine, pyrrole, triazole or melamine.
In a second aspect, the present invention provides a proton exchange membrane prepared by the method of the first aspect.
In a third aspect, the present invention provides a fuel cell comprising the proton exchange membrane of the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method has simple preparation process and easily obtained raw materials, and the proton conductivity of the formed proton exchange membrane is more than 7.9mS/cm, thereby being beneficial to proton conduction and being applicable to proton exchange membrane fuel cells.
(2) The mass ratio of the 2.3.4.5.6-pentafluorostyrene, the glycidyl ether and the sodium p-vinylbenzenesulfonate is 1 (0.1-5), the formed proton exchange membrane has better performance, and the proton conductivity is more than 8.6 mS/cm.
Drawings
FIG. 1 is an infrared plot of the proton exchange membranes described in examples 1-5.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a proton exchange membrane, which is prepared by the following method, and the method comprises the following steps:
step 1, polymerization reaction: under the protection of nitrogen, 1.94g of 2.3.4.5.6-pentafluorostyrene, 1.14g of allyl glycidyl ether and 4.12g of sodium p-vinylbenzenesulfonate are dissolved in 30mL of absolute ethyl alcohol, 2wt% of initiator AIBN is added, magnetic stirring is carried out, reflux reaction is carried out for 24 hours at 70 ℃, cooling is carried out, the reaction mixture is poured into diethyl ether to separate out polymer, ethanol is redissolved, unreacted residues are removed repeatedly for 3 times, and the copolymer is obtained after drying treatment;
step 2, dissolving 7.1g of the polymer obtained in the step 1 and 0.83g of 2-aminoimidazole containing amino nitrogen heterocyclic compound in anhydrous DMSO, magnetically stirring for 0.5h, pouring into a clean glass plate, heating at 90 ℃ in an oven for 24h to complete grafting reaction, crosslinking, evaporating to remove all solvents, and stripping by a blade to obtain a crosslinked network polymer;
and step 3, cutting the crosslinked polymer in the step 2 into small pieces, immersing the small pieces in 0.1M HCl solution for 30 hours to finish sodium ion conversion of acidic protons, taking out the small pieces, and washing the small pieces with deionized water for multiple times to remove residual HCl, thereby obtaining the sulfonic acid-based crosslinked proton exchange membrane.
Example 2
The embodiment provides a proton exchange membrane, which is prepared by the following method, and the method comprises the following steps:
step 1, polymerization reaction: under the protection of nitrogen, 1.94g of 2.3.4.5.6-pentafluorostyrene, 1.14g of allyl glycidyl ether and 4.12g of sodium p-vinylbenzenesulfonate are dissolved in 30mL of absolute ethyl alcohol, 2wt% of initiator AIBN is added, magnetic stirring is carried out, reflux reaction is carried out for 24 hours at 70 ℃, cooling is carried out, the reaction mixture is poured into diethyl ether to separate out polymer, ethanol is redissolved, unreacted residues are removed repeatedly for 3 times, and the copolymer is obtained after drying treatment;
step 2, dissolving 7.1g of the polymer obtained in the step 1 and 1.33g of 2-aminobenzimidazole containing an amino nitrogen heterocyclic compound in anhydrous DMSO, magnetically stirring for 0.5h, pouring into a clean glass plate, heating at 90 ℃ in an oven for 24h to complete a grafting reaction, crosslinking, evaporating to remove all solvents, and stripping by a blade to obtain a crosslinked network polymer;
and step 3, cutting the crosslinked polymer in the step 2 into small pieces, immersing the small pieces in 0.1M HCl solution for 24 hours to finish sodium ion conversion of acidic protons, taking out the small pieces, and washing the small pieces with deionized water for multiple times to remove residual HCl, thereby obtaining the sulfonic acid-based crosslinked proton exchange membrane.
Example 3
The embodiment provides a proton exchange membrane, which is prepared by the following method, and the method comprises the following steps:
step 1, polymerization reaction: under the protection of nitrogen, 1.94g of 2.3.4.5.6-pentafluorostyrene, 1.14g of allyl glycidyl ether and 4.12g of sodium p-vinylbenzenesulfonate are dissolved in 30mL of absolute ethyl alcohol, 2wt% of initiator AIBN is added, magnetic stirring is carried out, reflux reaction is carried out for 24 hours at 70 ℃, cooling is carried out, the reaction mixture is poured into diethyl ether to separate out polymer, ethanol is redissolved, unreacted residues are removed repeatedly for 3 times, and the copolymer is obtained after drying treatment;
step 2, dissolving 7.1g of the polymer obtained in the step 1 and 1.03g of 1-aminopiperazine containing an amino nitrogen heterocyclic compound in anhydrous DMSO, magnetically stirring for 0.5h, pouring into a clean glass plate, heating at 90 ℃ in an oven for 24h to complete a grafting reaction, crosslinking, evaporating to remove all solvents, and stripping by a blade to obtain a crosslinked network polymer;
and step 3, cutting the crosslinked polymer in the step 2 into small pieces, immersing the small pieces in 0.1M HCl solution for 24 hours to finish sodium ion conversion of acidic protons, taking out the small pieces, and washing the small pieces with deionized water for multiple times to remove residual HCl, thereby obtaining the sulfonic acid-based crosslinked proton exchange membrane.
Example 4
The embodiment provides a proton exchange membrane, which is prepared by the following method, and the method comprises the following steps:
step 1, polymerization reaction: under the protection of nitrogen, 1.94g of 2.3.4.5.6-pentafluorostyrene, 1.14g of allyl glycidyl ether and 4.12g of sodium p-vinylbenzenesulfonate are dissolved in 30mL of absolute ethyl alcohol, 2wt% of initiator AIBN is added, magnetic stirring is carried out, reflux reaction is carried out for 18 hours at 80 ℃, cooling is carried out, the reaction mixture is poured into diethyl ether to separate out polymer, ethanol is redissolved, unreacted residues are removed repeatedly for 3 times, and the copolymer is obtained after drying treatment;
step 2, dissolving the polymer obtained in the step 1 and 3-amino-1, 2, 4-triazole containing amino nitrogen heterocyclic compound in anhydrous DMSO according to the molar ratio of 1:0.1, magnetically stirring for 0.5h, pouring into a clean glass disc, putting into a baking oven at 100 ℃ for heating for 18h to complete grafting reaction, crosslinking, evaporating to remove all solvents, and stripping by a blade to obtain a crosslinked network polymer;
and step 3, cutting the crosslinked polymer in the step 2 into small pieces, immersing the small pieces in 0.1M HCl solution for 24 hours to finish sodium ion conversion of acidic protons, taking out the small pieces, and washing the small pieces with deionized water for multiple times to remove residual HCl, thereby obtaining the sulfonic acid-based crosslinked proton exchange membrane.
Example 5
The embodiment provides a proton exchange membrane, which is prepared by the following method, and the method comprises the following steps:
step 1, polymerization reaction: under the protection of nitrogen, 1.94g of 2.3.4.5.6-pentafluorostyrene, 1.14g of allyl glycidyl ether and 4.12g of sodium p-vinylbenzenesulfonate are dissolved in 30mL of absolute ethyl alcohol, 2wt% of initiator AIBN is added, magnetic stirring is carried out, reflux reaction is carried out for 20 hours at 75 ℃, cooling is carried out, the reaction mixture is poured into diethyl ether to separate out polymer, ethanol is redissolved, unreacted residues are removed repeatedly for 3 times, and the copolymer is obtained after drying treatment;
step 2, dissolving the polymer obtained in the step 1 and melamine containing amino nitrogen heterocyclic compound in anhydrous DMSO according to a molar ratio of 1:3, magnetically stirring for 0.5h, pouring into a clean glass disc, placing into an oven, heating at 95 ℃ for 20h, completing grafting reaction, crosslinking, evaporating to remove all solvents, and stripping by a blade to obtain a crosslinked network polymer;
and step 3, cutting the crosslinked polymer in the step 2 into small pieces, immersing the small pieces in 0.1M HCl solution for 24 hours to finish sodium ion conversion of acidic protons, taking out the small pieces, and washing the small pieces with deionized water for multiple times to remove residual HCl, thereby obtaining the sulfonic acid-based crosslinked proton exchange membrane.
Examples 6 to 9
Examples 6 to 9 differ from example 1 in the mass ratios of 2.3.4.5.6-pentafluorostyrene, allyl glycidyl ether and p-vinylbenzenesulfonic acid sodium salt, respectively, being: 1:0.1:2.12 (example 6), 1:5:2.12 (example 7), 1:0.02:2.12 (example 8) and 1:6:2.12 (example 9), the mass of 2.3.4.5.6-pentafluorostyrene and p-vinylbenzenesulfonic acid sodium salt being 1.94g and 4.12g, respectively, the remainder being identical to example 1.
Comparative example 1
This comparative example differs from example 1 in that the allyl glycidyl ether is not grafted to the amino nitrogen containing heterocyclic compound and the two are directly mixed.
The preparation method of the proton exchange membrane of the comparative example comprises the following steps:
step 1, polymerization reaction: under the protection of nitrogen, 1.94g of 2.3.4.5.6-pentafluorostyrene, 1.14g of allyl glycidyl ether and 4.12g of sodium p-vinylbenzenesulfonate are dissolved in 30mL of absolute ethyl alcohol, 2wt% of initiator AIBN is added, magnetic stirring is carried out, reflux reaction is carried out for 24 hours at 70 ℃, cooling is carried out, the reaction mixture is poured into diethyl ether to separate out polymer, ethanol is redissolved, unreacted residues are removed repeatedly for 3 times, and the copolymer is obtained after drying treatment;
step 2, dissolving 7.1g of the polymer obtained in the step 1 and 0.83g of 2-aminoimidazole containing amino nitrogen heterocyclic compound in anhydrous DMSO, magnetically stirring for 0.5h, pouring into a clean glass disc, evaporating to remove all solvents, and stripping by a blade to obtain a polymer mixture;
and step 3, cutting the polymer mixture in the step 2 into small pieces, immersing the small pieces in 0.1M HCl solution for 30 hours to finish sodium ion conversion of acidic protons, taking out the small pieces, and washing the small pieces with deionized water for multiple times to remove residual HCl, thus obtaining the sulfonic acid matrix proton exchange membrane.
Performance testing
The proton exchange membranes described in examples 1-9 and comparative example 1 were tested as follows:
(1) Infrared testing: the structure of the polymer film samples before and after sulfonation was analyzed by a Nicolet Magna 370 infrared spectrometer from Nicolet corporation, and infrared test directly utilized the polymer film samples.
(2) Proton conductivity: the proton conductivity of the proton exchange membrane is measured indirectly by an AC impedance method through an electrochemical workstation and a four-electrode method, the proton conductivity of the proton exchange membrane is measured indirectly by an AC impedance method, the proton exchange membrane is dried at 100 ℃, then is cut into square and placed on a platinum electrode, and the proton conductivity can be calculated by obtaining a button-deficit-Style curve under each test condition after the test is completed.
The test results are summarized in table 1 and fig. 1.
In FIG. 1, 1150cm -1 Is C-F vibration characteristic peak, 1010cm -1 is-SO 3 - As can be seen from FIG. 1, the method of the present invention can prepare a sulfonic acid group cross-linked proton exchange membrane.
TABLE 1
| Proton conductivity (mS/cm) | |
| Example 1 | 12.6 |
| Example 2 | 11.5 |
| Example 3 | 12.3 |
| Example 4 | 9.2 |
| Example 5 | 12.8 |
| Example 6 | 9.7 |
| Example 7 | 8.6 |
| Example 8 | 8.1 |
| Example 9 | 7.9 |
| Comparative example 1 | 7.4 |
As can be seen from the data in Table 1, the preparation process of the method is simple, the raw materials are easy to obtain, the proton conductivity of the formed proton exchange membrane is more than 7.9mS/cm, the proton conduction is facilitated, and the method is suitable for proton exchange membrane fuel cells.
The mass ratio of the 2.3.4.5.6-pentafluorostyrene, the glycidyl ether and the sodium p-vinylbenzenesulfonate is 1 (0.1-5), the formed proton exchange membrane has better performance, and the proton conductivity is more than 8.6 mS/cm.
Analysis of comparative example 1 and example 1 shows that comparative example 1 has less performance than example 1, demonstrating better performance after crosslinking of the acidic and basic components in the proton exchange membrane.
As can be seen from analysis examples 6-9, the properties of examples 8-9 are inferior to those of examples 6-7, and it is demonstrated that the proton exchange membrane formed by the process of preparing a proton exchange membrane, wherein the mass ratio of the polymer to the substance containing an amino nitrogen heterocyclic compound in the step 2 is 1 (0.1-3), and the mass ratio of the glycidyl ether in the step 1 is within a certain range, namely, the mass ratio of the 2.3.4.5.6-pentafluorostyrene, the glycidyl ether and the sodium p-vinylbenzenesulfonate is 1 (0.1-5): (0.1-5).
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (16)
1. A method for preparing a proton exchange membrane, which is characterized by comprising the following steps:
step 1, carrying out polymerization reaction on fluorine-containing styrene, glycidyl ether and vinyl benzene sulfonic acid sodium salt to obtain a prepolymer;
step 2, carrying out grafting reaction and crosslinking on the prepolymer obtained in the step 1 and the amino nitrogen heterocyclic compound to obtain a crosslinked polymer;
step 3, carrying out ion exchange reaction on the crosslinked polymer obtained in the step 2 to obtain a sulfonic group crosslinked proton exchange membrane;
in step 3, the ion exchange reaction is performed in a hydrochloric acid solution.
2. The preparation method according to claim 1, wherein in the step 1, the mass ratio of the fluorine-containing styrene, the glycidyl ether and the vinylbenzenesulfonic acid sodium salt is 1 (0.1-5): (0.1-5).
3. The method of claim 1, wherein the fluorinated styrene comprises 2.3.4.5.6-pentafluorostyrene.
4. The method of preparation according to claim 1, wherein the glycidyl ether comprises allyl glycidyl ether and/or 4-vinylbenzyl glycidyl ether.
5. The method according to claim 1, wherein the initiator of the polymerization reaction comprises any one or a combination of at least two of azobisisobutyronitrile, azobisisoheptonitrile, and dimethyl azobisisobutyrate.
6. The method according to claim 5, wherein the mass percentage of the initiator is 1.5% to 2.5% based on 100% of the total mass of the fluorine-containing styrene, the glycidyl ether and the vinylbenzenesulfonic acid sodium salt.
7. The process according to claim 1, wherein the polymerization reaction temperature is 70-80 ℃.
8. The method of claim 1, wherein the polymerization time is 18 to 24 hours.
9. The method according to claim 1, wherein in the step 2, the mass ratio of the prepolymer to the amino nitrogen containing heterocyclic compound is 1 (0.1-3).
10. The method according to claim 1, wherein the amino nitrogen-containing heterocyclic compound comprises any one or a combination of at least two of an aminoimidazole compound, an aminobenzimidazole compound, an aminopiperazine compound, an aminopiperidine compound, an aminopyrrole compound, an aminotriazole compound, and melamine.
11. The method according to claim 10, wherein the amino nitrogen-containing heterocyclic compound comprises any one or a combination of at least two of 2-aminoimidazole, 4-aminoimidazole, 1- (3-aminopropyl) imidazole, 2-aminobenzimidazole, 1-aminopiperazine, 2-aminopiperazine, aminoethylpiperazine, 3-amino-1, 2, 4-triazole, 2-aminopiperidine, 3-aminopiperidine, 4-aminopiperidine, 3-aminopyrrole, and melamine.
12. The process according to claim 1, wherein in step 2, the grafting reaction is carried out at a temperature of 90-100 ℃.
13. The method according to claim 1, wherein the grafting reaction is carried out for 18 to 24 hours.
14. The process according to claim 1, wherein the grafting reaction is carried out in an anhydrous solvent.
15. A proton exchange membrane prepared by the method of any one of claims 1-14.
16. A fuel cell comprising the proton exchange membrane of claim 15.
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| CN112366341A (en) * | 2020-11-26 | 2021-02-12 | 江苏宝林商务信息咨询有限公司 | Cross-linking type solid electrolyte ion exchange membrane for fuel cell and preparation method thereof |
| CN112635804A (en) * | 2021-01-15 | 2021-04-09 | 安徽知凸凸科技服务有限公司 | Alkaline anion exchange membrane for fuel cell and preparation method thereof |
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