CN110444793B - Durable proton exchange membrane, preparation method and application thereof - Google Patents
Durable proton exchange membrane, preparation method and application thereof Download PDFInfo
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- CN110444793B CN110444793B CN201910757749.3A CN201910757749A CN110444793B CN 110444793 B CN110444793 B CN 110444793B CN 201910757749 A CN201910757749 A CN 201910757749A CN 110444793 B CN110444793 B CN 110444793B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a durable proton exchange membrane, a preparation method and application thereof, wherein the durable proton exchange membrane is composed of an ionic polymer and a Schiff base phenolic amine compound, the mass percent of the ionic polymer is 90-99.8%, and the mass percent of the Schiff base phenolic amine compound is 0.2-10%. Schiff base phenolic amine substances in the durable proton exchange membrane are organic substances, can donate active hydrogen as a free radical remover so as to quench free radicals (HO) generated in the operation process of a fuel cell, inhibit the active hydrogen from attacking defect end groups of an ionic polymer macromolecular chain and ether bonds of a main chain and a sulfonate side chain in the proton exchange membrane, improve the durability of the proton exchange membrane, and are easy to mix and disperse with the ionic polymer so as to prepare the homogeneous proton exchange membrane.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a durable proton exchange membrane, a preparation method and application thereof.
Background
The proton exchange membrane fuel cell has the advantages of high conversion efficiency, high specific energy, wide power range and the like, can provide clean, efficient and reliable electric energy for devices needing electric power, is mainly applied to the fields of portable and fixed power generation, automobiles and the like, and is an energy solution with the widest application range.
The aging of the proton exchange membrane can lead to a sharp increase in the permeation of the cathode and anode reactant gases, resulting in severe mixed polarization and ultimately complete cell failure.
Therefore, it is necessary to prepare a proton exchange membrane material having high durability.
Disclosure of Invention
The invention aims to provide a proton exchange membrane, a preparation method and application thereof, which overcome the defects of poor performance of the proton exchange membrane caused by poor durability and easy aging of the conventional proton exchange membrane.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a durable proton exchange membrane which is composed of an ionic polymer and Schiff base phenolic amine compounds; the mass percent of the ionic polymer is 90-99.8%, and the mass percent of the Schiff base phenolic amine compound is 0.2-10%.
The invention also provides a preparation method of the durable proton exchange membrane, which comprises the following steps: the ion polymer and the Schiff base phenolic amine compound are uniformly mixed in the solvent, and the durable ion exchange membrane is prepared after drying and annealing treatment.
The invention also provides an application of the durable proton exchange membrane in a fuel cell membrane.
The invention has the beneficial effects that:
the invention provides a durable proton exchange membrane, a preparation method and application thereof, wherein the durable proton exchange membrane is composed of an ionic polymer and Schiff base phenolic amine compounds, wherein the Schiff base phenolic amine compounds are used for bridging hindered phenol and diphenylamine in one molecule through Schiff base to form special Schiff base phenolic amine compounds, and can inhibit free radicals from attacking defect end groups of a macromolecular chain, so that quenching attenuation caused by the free radicals is reduced, the quenching attenuation capacity of the quenching attenuation is higher than that of a single phenolic structure or amine structure, and the prepared proton exchange membrane has a durable function.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 shows the results of the oxidation resistance tests performed on different materials;
FIG. 2 is a graph showing the results of durability tests of the proton exchange membranes prepared in examples 1 to 4 of the present invention and the membrane in comparative example 1;
FIG. 3 is a schematic diagram of the mechanism by which SPD1 scavenges free radicals in examples 1-2;
FIG. 4 is a schematic representation of the mechanism by which SPD2 scavenges free radicals in examples 3-4.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The durable proton exchange membrane, the preparation method and the application thereof provided by the embodiment of the invention are specifically described below.
The aging of the proton exchange membrane can lead to a sharp increase in the permeation of the cathode and anode reactant gases, resulting in severe mixed polarization and ultimately complete cell failure. The long-term observation of relevant researchers has revealed that the main reasons for proton exchange membrane failure are: the hydroxyl free radical attacks the defective terminal group of the polymer chain, and the carboxyl group is reduced into carbon dioxide and F ions to cause the decompression type decomposition of the resin polymer; in addition, the ether bond connecting the main chain and the sulfonate side chain is also decomposed by the hydroxyl radical.
In order to prevent chemical attenuation caused by free radicals in the electrochemical reaction process, the addition of the free radical quenching agent is an effective solution, and can decompose and eliminate the free radicals in the reaction process on line, thereby prolonging the service life of the membrane. Oxide nanoparticles with variable valence metals such as cerium oxide, manganese oxide and titanium oxide are often adopted in the proton exchange membrane of the fuel cell as a radical quencher, but because the compatibility of the oxide and ionic polymer is poor, the risk of reducing the mechanical strength and ionic conductivity of the proton exchange membrane exists, and the preparation process is complex. Organic antioxidants such as vitamins, phenols, and amines have a certain radical scavenging ability, but their own scavenging ability is inferior to that of the valence-variable metal oxides.
Therefore, the embodiment of the invention provides a durable proton exchange membrane which is composed of an ionic polymer and Schiff base phenolic amine compounds; the mass percent of the ionic polymer is 90-99.8%, and the mass percent of the Schiff base phenolic amine compound is 0.2-10%.
Further, the ionic polymer comprises one or more of perfluorosulfonic acid ionic polymer, polyarylether ionic polymer and polyolefin ionic polymer.
Further, the Schiff base phenolic amine compound is selected from:
The preparation process of the Schiff Base Phenolic amine compound provided in the embodiment of the invention can be found in the literature ("Schiff Base bridge Phenolic diamines for high alcohol efficiency and Superior thermoplastic lube inhibitors", Shasha Yu, etc., Ind.Eng.Chem.Res, 3.27.2017).
Therefore, the durable proton exchange membrane provided by the embodiment of the invention is composed of an ionic polymer and a schiff base phenolic amine compound, and the schiff base phenolic amine compound is doped in the membrane and used as a free radical scavenger, so that the chemical attenuation caused by free radicals is prevented in the following way: meanwhile, the Schiff base phenolic amine compound in the embodiment of the invention can realize good compatibility with an ionic polymer in a solvent, so that the prepared proton exchange membrane has good mechanical strength and ionic conductivity, and overcomes the defects of the traditional metal oxide radical quencher.
Specifically, the method comprises the following steps: the Schiff base phenolic amine compound bridges hindered phenol and diphenylamine in one molecule through Schiff base, can donate active hydrogen as a free radical remover so as to quench free radicals (HO) generated in the operation process of a fuel cell, inhibit the free radicals from attacking defect end groups of an ionic polymer macromolecular chain and ether bonds of a main chain and a sulfonate side chain in a proton exchange membrane, and improve the durability of the proton exchange membrane.
Further, the thickness of the proton exchange membrane is 5 μm to 200 μm, and preferably, the thickness of the proton exchange membrane is 5 μm to 50 μm.
The embodiment of the invention also provides a preparation method of the proton exchange membrane, which comprises the following steps: the ion polymer and the Schiff base phenolic amine compound are uniformly mixed in the solvent, and the durable ion exchange membrane is prepared after drying and annealing treatment.
The embodiment of the invention also provides a preparation method of the proton exchange membrane, which comprises the following steps: uniformly mixing the ionic polymer, the Schiff base phenolic amine compound and the solvent in proportion to form a mixed solution, drying the mixed solution to form a primary membrane, and annealing the primary membrane to obtain the proton exchange membrane. The Schiff base phenolic amine compound and the ionic polymer have good compatibility in the solvent, so that a uniform mixed solution can be formed, and the proton exchange membrane can be obtained after drying and annealing treatment. Preferably, the proton exchange membrane in the embodiment of the present invention can also be prepared by using a conventional method such as a calendering method, a casting method, a blowing method, and a stretching method.
Further, the total mass of the ionic polymer and the Schiff base phenolic amine compound accounts for 1-30% of the mass of the solvent, and preferably, the total mass of the ionic polymer and the Schiff base phenolic amine compound accounts for 5-20% of the mass of the solvent.
Further, the solvent is composed of a low boiling point polar solvent and a high boiling point polar solvent;
preferably, the low-boiling polar solvent comprises one or more of ethanol, ethyl acetate, water, methanol and isopropanol, and the high-boiling polar solvent comprises one or more of ethylene glycol, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone. The polar solvent can make the ionic polymer and the Schiff base phenolic amine compound easily dissolved in the solvent to generate uniform mixed solution, and agglomeration phenomenon does not occur in the solution, so that the prepared proton exchange membrane has uniform and stable properties, and the defect of performance reduction caused by poor compatibility of the traditional free radical quencher and the ionic polymer is overcome.
Further, the drying comprises the following steps: and (3) placing the solution in ultrasound to remove bubbles, heating for the first time to volatilize the low-boiling-point solvent in the ionic polymer, then coating the solution on a substrate by a blade, and heating for the second time to volatilize the high-boiling-point polar solvent in the solution to obtain the initial film.
Further, the annealing comprises the following steps: annealing the primary membrane at the temperature of 150-160 ℃ to form a durable proton exchange membrane;
preferably, the primary film is annealed in a high-temperature vacuum dry environment.
The embodiment of the invention also provides an application of the durable proton exchange membrane in a fuel cell membrane.
In the embodiment of the invention, the durable proton exchange membrane is applied to the fuel cell membrane, and as can be seen from the above content, the schiff base phenolic amine substances doped in the proton exchange membrane are organic substances, and can donate active hydrogen as a free radical scavenger so as to quench free radicals (HO ·) generated in the operation process of the fuel cell, inhibit the free radicals from attacking the defect end groups of the ionic polymer macromolecular chains in the proton exchange membrane and ether bonds of the main chain and the sulfonate side chain, improve the durability of the proton exchange membrane, and delay the aging speed of the fuel cell and prolong the service life of the cell by using the proton exchange membrane as the membrane in the fuel cell.
The features and properties of the present invention are described in further detail below with reference to examples.
The Schiff base phenolic amine compounds referred to in the examples of the present invention are illustrated below:
2, 6-di-tert-butyl-4-methylphenol, abbreviated as BHT;
diphenylamine, abbreviated DPA.
Example 1
The preparation method of the proton exchange membrane comprises the following steps:
(1) preparation of solutions
Mixing an ionic polymer resin solution: solvent: the Schiff base phenolic amine compound is prepared from the following components in a mass ratio of 1000: 300: 1, taking 100g of 5% Nafion resin solution, adding 30g of high boiling point polar solvent N, N-dimethylformamide, uniformly mixing, adding 0.1g of Schiff base phenolic amine organic matter SPD1, and dispersing and uniformly mixing to obtain a solution.
(2) Preparation of Primary film
And putting the solution into a beaker, uniformly heating the solution for 1h at a heating plate of 50 ℃ to remove the low-boiling-point solvent in the nafion resin solution, uniformly spreading the solution on a glass plate substrate by adopting a blade coating method, and drying the solution at 120 ℃ for 0.5h to volatilize the high-boiling-point solvent N, N-dimethylformamide to obtain the initial membrane.
(3) Preparation of proton exchange membranes
And (3) placing the primary membrane in a vacuum drying oven to carry out annealing treatment for 20min at 150 ℃ to obtain the composite proton exchange membrane with the thickness of about 200 microns.
Example 2
The preparation method of the proton exchange membrane comprises the following steps:
(1) preparation of solutions
Mixing an ionic polymer resin solution: solvent: the Schiff base phenolic amine compound is prepared from the following components in a mass ratio of 1000: 300: 2. taking 100g of 5% Nafion resin solution, adding 30g of high boiling point polar solvent N, N-dimethylformamide, uniformly mixing, adding 0.2g of Schiff base phenolic amine organic matter SPD1, and dispersing and uniformly mixing to obtain a solution.
(2) Preparation of Primary film
And putting the solution into a beaker, uniformly heating the solution for 1h at a heating plate of 50 ℃ to remove the low-boiling-point solvent in the nafion resin solution, uniformly spreading the solution on a glass plate substrate by adopting a blade coating method, and drying the solution at 120 ℃ for 0.5h to volatilize the high-boiling-point solvent N, N-dimethylformamide to obtain the initial membrane.
(3) Preparation of proton exchange membranes
And (3) placing the primary membrane in a vacuum drying oven to carry out annealing treatment for 20min at 150 ℃ to obtain the composite proton exchange membrane with the thickness of about 200 microns.
Example 3
The preparation method of the proton exchange membrane comprises the following steps:
(1) preparation of solutions
Mixing an ionic polymer resin solution: solvent: the Schiff base phenolic amine compound is prepared from the following components in a mass ratio of 1000: 300: 1. taking 100g of 5% Nafion resin solution, adding 30g of high boiling point polar solvent N, N-dimethylformamide, uniformly mixing, adding 0.1g of Schiff base phenolic amine organic matter SPD2, and dispersing and uniformly mixing to obtain a solution.
(2) Preparation of Primary film
And putting the solution into a beaker, uniformly heating the solution for 1h at a heating plate of 50 ℃ to remove the low-boiling-point solvent in the nafion resin solution, uniformly spreading the solution on a glass plate substrate by adopting a blade coating method, and drying the solution at 120 ℃ for 0.5h to volatilize the high-boiling-point solvent N, N-dimethylformamide to obtain the initial membrane.
(3) Preparation of proton exchange membranes
And (3) placing the primary membrane in a vacuum drying oven to carry out annealing treatment for 20min at 150 ℃ to obtain the composite proton exchange membrane with the thickness of about 200 microns.
Example 4
The preparation method of the proton exchange membrane comprises the following steps:
(1) preparation of solutions
Mixing an ionic polymer resin solution: solvent: the Schiff base phenolic amine compound is prepared from the following components in a mass ratio of 1000: 300: 2. taking 100g of 5% Nafion resin solution, adding 30g of high boiling point polar solvent N, N-dimethylformamide, uniformly mixing, adding 0.2g of Schiff base phenolic amine organic matter SPD1, and dispersing and uniformly mixing to obtain a solution.
(2) Preparation of Primary film
And putting the solution into a beaker, uniformly heating the solution for 1h at a heating plate of 50 ℃ to remove the low-boiling-point solvent in the nafion resin solution, uniformly spreading the solution on a glass plate substrate by adopting a blade coating method, and drying the solution at 120 ℃ for 0.5h to volatilize the high-boiling-point solvent N, N-dimethylformamide to obtain the initial membrane.
(3) Preparation of proton exchange membranes
And (3) placing the primary membrane in a vacuum drying oven to carry out annealing treatment for 20min at 150 ℃ to obtain the composite proton exchange membrane with the thickness of about 200 microns.
Comparative example 1
The film of comparative example 1 was Nafion 211, manufactured by dupont, usa.
Test results
The antioxidant properties of BHT, DPA, SPD1 and SPD2, which comprise the Antioxidants of 5 μmol/g, were tested and the results are shown in fig. 1 (see literature ("Schiff Base bridge Phenolic diamines for high efficiency and Superior thermoplastic Antioxidants", shashasha Yu et al, in.eng.chem.res, 2017, 3 months 27 days)), from fig. 1 it can be seen that the Antioxidants SPD1 and SPD2 used in the examples of the present invention have an oxidation resistance much higher than the oxidation resistance of conventional BHT and DPA, indicating that: the oxidation resistance of the compounds formed by combining the structures of phenols and amines of the SPD1 and SPD2 in the embodiment of the present invention is significantly higher than that of the compounds with phenol or amine structures alone, which may be because the phenol and amine structures in the SPD1 and SPD2 compounds are synergistic with each other, so that the oxidation resistance is enhanced, and because the SPD1 and SPD2 compounds in the preparation process are only used as one additive without the structure being changed, it can be basically predicted that: the durable proton exchange membrane prepared by the SPD1 and SPD2 compounds in the embodiment of the invention has the advantages of unchanged oxidation resistance and good quenching capability of free radicals.
The proton exchange membranes obtained in examples 1 to 4 and comparative example 1 were used to prepare membrane electrodes of fuel cells, and the open circuit voltage of the membrane electrodes was measured according to the accelerated test execution standard of the U.S. department of energy, wherein hydrogen was introduced into the anode, air was introduced into the cathode, the cathode and anode outlet pressures were 150KPa (absolute pressure), the cell temperature was 90 ℃, the cathode and anode relative humidity was 30%, the gas flow rate was 10-fold excess and was 0.2A/cm2The test time was 100 hours. The following table 1 shows the durability test of the proton exchange membranes obtained in examples 1 to 4 and comparative example 1 to prepare the membrane electrode for fuel cells.
TABLE 1
| Initial voltage/mV | End voltage/mV | Voltage drop/mV | |
| Example 1 | 1021 | 852 | 169 |
| Example 2 | 1030 | 869 | 161 |
| Example 3 | 1024 | 899 | 125 |
| Example 4 | 1022 | 907 | 115 |
| Comparative example 1 | 1035 | 781 | 254 |
As can be seen from table 1 above, the durable proton exchange membranes prepared in examples 1 to 4 of the present invention have a voltage drop value significantly lower than that of Nafion 211 in comparative example 1.
Meanwhile, as can be seen from the test result of fig. 2, the voltage drop (115-169mV) of the membrane electrode prepared by the proton exchange membrane added with the schiff base phenolic amine radical quencher is obviously lower than that of the Nafion proton exchange membrane (254mV), and the membrane electrode has better durability. The Schiff base phenolic amine free radical quencher is characterized in that a diphenylamine molecule and a sterically hindered phenol molecule are bridged through Schiff base, active hydrogen exists on the diphenylamine molecule and the sterically hindered phenol molecule, and when free radicals appear in a proton exchange membrane, the active hydrogen on the Schiff base phenolic amine can capture the free radicals to prevent the self-existing radicals from attacking the proton exchange membrane, so that the oxidation resistance and the durability are improved.
As for the free radical quencher SPD1, as shown in FIG. 3, hydrogen on diphenylamine N-H is relatively active to directly capture free radicals in the proton exchange membrane, while hydrogen on hindered phenol O-H forms hydrogen bonds with nearby nitrogen atoms to be relatively stable.
As for the free radical quencher SPD2, as shown in figure 4, hydrogen on diphenylamine N-H and hydrogen on hindered phenol O-H are very active, diphenylamine N-H is more active than hindered phenol O-H relatively, so diphenylamine free radical is firstly generated in the solution, hindered phenol free radical is more stable, previously generated diphenylamine free radical can rapidly take the active hydrogen on hindered phenol to generate phenol free radical, through the process, diphenylamine with higher activity in SPD2 is continuously regenerated, and thus the capability of capturing free radical is better than that of SPD 1.
In summary, the embodiment of the invention provides a durable proton exchange membrane, a preparation method and an application thereof, wherein the durable proton exchange membrane is composed of an ionic polymer and a Schiff base phenolic amine compound; the mass percent of the ionic polymer is 90-99.8%, and the mass percent of the Schiff base amine compound is 0.2-10%. Schiff base phenolic amine substances in the durable proton exchange membrane are organic substances, can donate active hydrogen as a free radical remover so as to quench free radicals (HO) generated in the operation process of a fuel cell, inhibit the active hydrogen from attacking defect end groups of an ionic polymer macromolecular chain and ether bonds of a main chain and a sulfonate side chain in the proton exchange membrane, improve the durability of the proton exchange membrane, and are easy to mix and disperse with the ionic polymer so as to prepare the homogeneous proton exchange membrane.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (12)
1. A durable proton exchange membrane comprised of an ionic polymer and a schiff base phenolic amine compound; the mass percent of the ionic polymer is 90-99.8%, and the mass percent of the Schiff base phenolic amine compound is 0.2-10%;
the Schiff base phenolic amine compound is selected from:
2. The durable proton exchange membrane according to claim 1, wherein the ionic polymer comprises one or more of perfluorosulfonic acid ionic polymer, polyarylether ionic polymer and polyolefin ionic polymer.
3. The durable proton exchange membrane of claim 1 wherein the proton exchange membrane has a thickness of 5 μ ι η to 200 μ ι η.
4. The durable proton exchange membrane of claim 3 wherein the proton exchange membrane has a thickness of 5 μm to 50 μm.
5. A method for preparing a durable proton exchange membrane according to any one of claims 1 to 4, wherein the ionic polymer and the Schiff base phenolic amine compound are uniformly mixed in a solvent, and the durable proton exchange membrane is prepared through drying and annealing treatment.
6. The method according to claim 5, wherein the total mass of the ionic polymer and the Schiff base phenolic amine compound is 1-30% of the mass of the solvent.
7. The method according to claim 6, wherein the total mass of the ionic polymer and the Schiff base phenolic amine compound is 5-20% of the mass of the solvent.
8. The production method according to claim 5, wherein the solvent is composed of a low-boiling polar solvent and a high-boiling polar solvent,
the low-boiling-point polar solvent comprises one or more of ethanol, ethyl acetate, water, methanol and isopropanol, and the high-boiling-point polar solvent comprises one or more of ethylene glycol, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.
9. The method for preparing according to claim 5, wherein the drying comprises the steps of:
and (3) placing the uniformly mixed solution in ultrasound to remove bubbles, heating for the first time to volatilize the low-boiling-point polar solvent in the ionic polymer, then coating the solution on a substrate in a blade mode, and heating for the second time to volatilize the high-boiling-point polar solvent in the solution to obtain the primary film.
10. The method of manufacturing according to claim 9, wherein the annealing treatment includes the steps of: and carrying out annealing treatment on the primary film in a high-temperature vacuum environment.
11. The method as claimed in claim 10, wherein the primary membrane is annealed in a vacuum environment of 150-160 ℃.
12. Use of the durable proton exchange membrane according to any one of claims 1 to 4 or the durable proton exchange membrane prepared by the preparation method according to any one of claims 5 to 11 in a fuel cell membrane.
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| CN112259770B (en) * | 2020-10-21 | 2022-03-22 | 贵州梅岭电源有限公司 | Anti-degradation enhanced proton exchange membrane and preparation method thereof |
| CN112436170B (en) * | 2020-11-30 | 2022-03-04 | 山东东岳未来氢能材料股份有限公司 | High-tolerance perfluorinated proton membrane and preparation method thereof |
| CN114221003B (en) * | 2021-11-23 | 2024-03-01 | 佛山仙湖实验室 | Proton exchange membrane for proton exchange membrane fuel cell and preparation method thereof |
| CN114276573B (en) * | 2021-12-30 | 2023-05-30 | 上海应用技术大学 | High-durability organic antioxidant chelated cerium ion composite proton exchange membrane, and preparation method and application thereof |
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| 4种水杨醛类席夫碱的绿色合成、表征及其光致、热致变色性能研究;赵永等;《化学试剂》;20160731;第38卷(第7期);1-10 * |
| Schiff Base Bridged Phenolic Diphenylamines for Highly Efficient and Superior Therostable Lubricant Antioxidants;Shasha Yu 等;《Ind.Eng.Chem.Res》;20170327;第56卷;1-10 * |
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