CN115441025B - Colorless proton exchange membrane, preparation method thereof and fuel cell - Google Patents
Colorless proton exchange membrane, preparation method thereof and fuel cell Download PDFInfo
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- CN115441025B CN115441025B CN202211401175.4A CN202211401175A CN115441025B CN 115441025 B CN115441025 B CN 115441025B CN 202211401175 A CN202211401175 A CN 202211401175A CN 115441025 B CN115441025 B CN 115441025B
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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
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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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
- H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
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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
- H01M8/1086—After-treatment of the membrane other than by polymerisation
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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 belongs to the technical field of fuel cells, and particularly relates to a colorless proton exchange membrane, a preparation method thereof and a fuel cell. The invention provides a preparation method of a colorless proton exchange membrane, which comprises the following steps: (1) Adding perfluorosulfonic acid solid resin into a mixed solvent of water and alcohol, and stirring and dissolving to form a dispersion liquid; (2) Adding alcohol amine into the dispersion liquid obtained in the step (1), dropwise adding triton after the alcohol amine is dissolved, and uniformly stirring to obtain a membrane casting liquid; (3) Preparing a primary composite proton exchange membrane from the membrane casting solution obtained in the step (2) and an ePTFE reinforced membrane by a solution casting method; (4) And (4) carrying out acid washing, water washing and drying on the primary composite proton exchange membrane obtained in the step (3) to obtain a colorless proton exchange membrane. The method can solve the problem that the proton exchange membrane turns yellow or even black in the production process, thereby keeping the colorless and transparent state of the proton exchange membrane.
Description
Technical Field
The invention belongs to the technical field of fuel cells, particularly relates to a colorless proton exchange membrane and a preparation method thereof, and further relates to a fuel cell.
Background
The hydrogen as an industrial raw material can be widely applied to the fields of petroleum, chemical industry, metallurgy, electronics, medical treatment and the like, in addition, the hydrogen can be converted into electric energy and heat energy, and the aspects of social production and life can be covered. The traffic transportation field will be scaled up to 31% year by year. Hydrogen fuel cells have attracted increasing social attention in recent years and are in a vigorous development as the most efficient way to utilize hydrogen. As one of the core components of a hydrogen fuel cell, the quality of a proton exchange membrane has a profound influence on the efficiency and stability of the cell.
The proton exchange membrane fuel cell has the advantages of low working temperature, quick start, high specific power, simple structure, convenient operation and the like, and is known as the preferred energy source of electric automobiles, fixed power stations and the like. Inside the fuel cell, the proton exchange membrane provides a channel for the migration and transport of protons, so that the protons pass through the membrane from the anode to the cathode, and form a loop with the electron transfer of an external circuit to provide current to the outside, therefore, the performance of the proton exchange membrane plays a very important role in the performance of the fuel cell, and the performance of the proton exchange membrane directly affects the service life of the cell.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems:
the proton exchange membrane prepared by the tape casting method at the present stage is easy to turn yellow at the high-temperature post-treatment stage, and even blackens under the condition of special high temperature. The reason is that the perfluorosulfonic acid has sharp increase of acidity at high temperature, and acid catalytic reaction is initiated, while ethanol or other alcohols are carbonized under catalytic conditions to form fine carbon particles, and finally, the film body is yellow or even blackened. The non-transparent color of the membrane affects the subsequent processing and manufacturing of the membrane electrode, and on the other hand, the post-treatment temperature of the proton membrane cannot be further increased, and the resin cannot be completely crystallized at low temperature, so that the mechanical property of the proton exchange membrane is reduced.
The present invention is directed to solving, at least in part, one of the technical problems in the related art. Therefore, the embodiment of the invention provides a preparation method of a colorless proton exchange membrane, which can solve the problem that the proton exchange membrane turns yellow or even blackens in the production process, thereby maintaining the colorless and transparent state of the proton exchange membrane.
The preparation method of the colorless proton exchange membrane comprises the following steps:
(1) Adding perfluorosulfonic acid solid resin into a mixed solvent of water and alcohol, and stirring and dissolving to form a dispersion liquid;
(2) Adding alcohol amine into the dispersion liquid obtained in the step (1), dropwise adding triton after the alcohol amine is dissolved, and uniformly stirring to obtain a membrane casting liquid;
(3) Preparing a primary composite proton exchange membrane from the membrane casting solution obtained in the step (2) and an ePTFE reinforced membrane by a solution casting method;
(4) And (4) carrying out acid washing, water washing and drying on the primary composite proton exchange membrane obtained in the step (3) to obtain the colorless proton exchange membrane.
The preparation method of the colorless proton exchange membrane provided by the embodiment of the invention brings advantages and technical effects, 1, in the embodiment of the invention, the alkalinity of alcohol amine is utilized to inhibit the acid catalytic reaction of sulfonic acid resin at high temperature, thereby avoiding the carbonization reaction of alcohols in a solvent, and finally achieving the colorless and transparent effect; 2. in the embodiment of the invention, the used alcohol amine has a low boiling point, can be volatilized quickly under certain temperature treatment, cannot cause overhigh solvent residue, has a structure and chemical properties similar to those of an alcohol reagent, and cannot generate great influence on the state of a dispersion liquid; 3. in the embodiment of the invention, the triton is dropwise added into the dispersion liquid, so that the infiltration effect of the perfluorinated sulfonic acid resin dispersion liquid on the ePTFE (ePTFE) reinforced layer can be improved, and the strength and the penetrating conductivity of the proton exchange membrane are ensured; 4. in the embodiment of the invention, the ePTFE reinforced membrane is compounded in the initial proton exchange membrane, so that the mechanical strength and the chemical stability of the proton exchange membrane can be further improved; 5. in the embodiment of the invention, the post-treatment temperature of the prepared proton exchange membrane can be greatly increased, which is beneficial to resin crystallization and improves the mechanical property and chemical stability of the proton exchange membrane.
In some embodiments, in step (1), the dispersion has a perfluorosulfonic acid solid resin content of 5 to 25wt%.
In some embodiments, in the step (1), the water and alcohol mixed solvent includes deionized water and an alcohol solvent, and the alcohol solvent includes at least one of ethanol, isopropanol or n-propanol.
In some embodiments, the mass ratio of the deionized water to the alcohol solvent in the water-alcohol mixed solvent is 5.
In some embodiments, in the step (2), the alcohol amine is a small-molecule alcohol amine, and the addition amount of the alcohol amine is 0.5-2.5% of the mass of the dispersion liquid.
In some embodiments, in the step (2), the alcohol amine comprises at least one of ethanolamine, n-propanolamine, isopropanolamine.
In some embodiments, in the step (4), the acid solution used for acid washing is at least one of a sulfuric acid solution, a nitric acid solution, a hydrochloric acid solution, and an oxalic acid solution; the pickling temperature is 30 to 100 ℃, and the pickling time is 0.5 to 5 hours.
In some embodiments, in the step (3), the solution casting method includes at least one of a blade coating, a slit coating, and a slide coating method.
The embodiment of the invention also provides a colorless proton exchange membrane prepared by the preparation method.
The colorless proton exchange membrane prepared by the method has the advantages and technical effects that 1, the colorless proton exchange membrane prepared by the method cannot have the problems of yellowing and even blackening and can be kept in a colorless and transparent state all the time; 2. in the embodiment of the invention, the post-treatment temperature of the colorless proton exchange membrane prepared by the method can be greatly improved, the crystallinity of the perfluorinated sulfonic acid resin can be effectively increased, and the mechanical strength and the chemical stability of the proton exchange membrane are further improved.
The embodiment of the invention also provides a fuel cell, which comprises the colorless proton exchange membrane.
The fuel cell according to the embodiment of the present invention includes the colorless proton exchange membrane according to the embodiment of the present invention, and has all the advantages that the colorless proton exchange membrane according to the embodiment of the present invention can bring, and therefore, the description thereof is omitted here.
Drawings
FIG. 1 is a colorless proton exchange membrane prepared in example 1;
figure 2 is a proton exchange membrane prepared in comparative example 1.
Detailed Description
The following detailed description describes embodiments of the invention, which are exemplary and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The embodiment of the invention provides a preparation method of a colorless proton exchange membrane, which comprises the following steps:
(1) Adding perfluorosulfonic acid solid resin into a mixed solvent of water and alcohol, and stirring and dissolving to form a dispersion liquid;
(2) Adding alcohol amine into the dispersion liquid obtained in the step (1), dropwise adding triton after the alcohol amine is dissolved, and uniformly stirring to obtain a membrane casting liquid;
(3) Preparing a primary composite proton exchange membrane by the casting solution obtained in the step (2) and an ePTFE reinforced membrane through a solution casting method;
(4) And (4) carrying out acid washing, water washing and drying on the primary composite proton exchange membrane obtained in the step (3) to obtain a colorless proton exchange membrane.
The preparation method of the colorless proton exchange membrane provided by the embodiment of the invention has the advantages and technical effects that the alkalinity of the alcohol amine is utilized to inhibit the acid catalytic reaction of the sulfonic acid resin at high temperature, so that the carbonization reaction of alcohols in a solvent is avoided, and the colorless and transparent effect is finally achieved; in the embodiment of the invention, the used alcohol amine has a low boiling point, can be volatilized quickly under certain temperature treatment, cannot cause overhigh solvent residue, has a structure and chemical properties similar to those of an alcohol reagent, and cannot generate great influence on the state of a dispersion liquid; in the embodiment of the invention, the triton is dropwise added into the dispersion liquid, so that the infiltration effect of the perfluorinated sulfonic acid resin dispersion liquid on the ePTFE (ePTFE) reinforced layer can be improved, and the strength and the penetrating conductivity of the proton exchange membrane are ensured; in the embodiment of the invention, the ePTFE reinforced membrane is compounded in the initial proton exchange membrane, so that the mechanical strength and the chemical stability of the proton exchange membrane can be further improved; in the embodiment of the invention, the post-treatment temperature of the prepared proton exchange membrane can be greatly increased, which is beneficial to resin crystallization and improves the mechanical property and chemical stability of the proton exchange membrane.
In some embodiments, preferably, in the step (1), the content of the perfluorosulfonic acid solid resin in the dispersion is 5 to 25wt%. Further preferably, the stirring and dissolving is performed at 20 to 250 ℃ and 0.1 to 30MPa for 2 to 12 hours.
In the embodiment of the invention, the content of the perfluorosulfonic acid solid resin and the stirring and dissolving conditions are optimized, so that the perfluorosulfonic acid solid resin is rapidly dissolved to form uniform dispersion liquid, and the production efficiency is improved.
In some embodiments, preferably, in the step (1), the mixed solvent of water and alcohol comprises deionized water and an alcohol solvent, and the alcohol solvent comprises at least one of ethanol, isopropanol or n-propanol. Further preferably, the mass ratio of the deionized water to the alcohol solvent in the water-alcohol mixed solvent is 5.
In the embodiment of the present invention, the kind and the ratio of the water and alcohol mixed solvent are preferably selected to facilitate the dissolution of the perfluorosulfonic acid solid resin to form a uniform dispersion liquid.
In some embodiments, preferably, in the step (2), the alcohol amine is a small molecule alcohol amine, and the amount of the alcohol amine added is 0.5-2.5% of the mass of the dispersion liquid. Further preferably, the alcohol amine comprises at least one of ethanolamine, n-propanolamine, and isopropanolamine.
In the embodiment of the invention, the type and the dosage of the alcohol amine are further optimized, and a proper amount of the alcohol amine can effectively inhibit the acid catalytic reaction at high temperature and can be effectively removed in the subsequent treatment process, so that the adverse effect on the proton exchange membrane is avoided.
In some embodiments, in the step (2), the addition amount of the triton is 0.5 to 4% of the mass of the dispersion, and the stirring time is 2 to 12h.
In the embodiment of the invention, the addition amount of the triton in the dispersion liquid is optimized, the proper addition amount is more favorable for the infiltration of the triton to the ePTFE reinforced membrane, the cost can be reasonably controlled, and the prepared colorless proton exchange membrane has better performance.
In some embodiments, preferably, in the step (4), the acid solution used for acid washing is at least one of a sulfuric acid solution, a nitric acid solution, a hydrochloric acid solution, and an oxalic acid solution; the pickling temperature is 30-100 ℃, the pickling time is 0.5-5 h, and the concentration of the acidic solution is 5-40wt%.
In the embodiment of the invention, the acid washing treatment is carried out, so that hydrogen ion replacement can be carried out, and the conductivity of the proton exchange membrane is improved.
In some embodiments, preferably, in the step (3), the solution casting method includes at least one of a blade coating method, a slit coating method, and a slide coating method.
In some embodiments, preferably, in the step (3), the primary composite proton exchange membrane is prepared as follows: a. coating a first layer of casting solution with the thickness of 100-1000 mu m; b. covering an ePTFE reinforced membrane with the thickness of 3-15 mu m and the porosity of 30-90% on the surface of the first layer of membrane casting solution; c. coating a second layer of casting solution with the thickness of 100-1000 mu m on the surface of the ePTFE reinforced membrane; d. and c, conveying the sample obtained in the step c into a 60-120 ℃ air-blast drying oven to be heated for 5-30min, and then raising the temperature to 160-300 ℃ to continue heating for 5-30min.
The embodiment of the invention also provides a colorless proton exchange membrane prepared by the preparation method.
The colorless proton exchange membrane prepared by the method has the advantages and technical effects that the problem of yellowing and even blackening does not occur, and the colorless proton exchange membrane can be kept in a colorless and transparent state all the time; in the embodiment of the invention, the post-treatment temperature of the colorless proton exchange membrane prepared by the method can be greatly improved, the crystallinity of the perfluorinated sulfonic acid resin can be effectively increased, and the mechanical strength and the chemical stability of the proton exchange membrane are further improved.
The embodiment of the invention also provides a fuel cell, which comprises the colorless proton exchange membrane.
The fuel cell in the embodiment of the present invention includes the colorless proton exchange membrane in the embodiment of the present invention, and the fuel cell in the embodiment of the present invention has all the advantages that the colorless proton exchange membrane in the embodiment of the present invention can bring, and is not described herein again.
The technical solution of the present invention is described below with reference to specific examples.
Example 1
1. Weighing 20g of perfluorosulfonic acid resin solid, adding the perfluorosulfonic acid resin solid into a mixed solvent of 78g of water and ethanol, wherein the ratio of water to alcohol is 1.
2. And opening a switch of the scraper coater, setting the length of the scraped film to be 300mm, adjusting the height of the scraper to be 300 mu m, starting scraping after feeding, and covering an ePTFE reinforced film on the surface of the liquid after finishing the feeding, wherein the film thickness is 11 mu m.
3. Standing for 5min after the film covering is finished, adjusting the height of a scraper to be 250 mu m, and continuously scraping and coating a second layer of film casting liquid on the surface of the reinforced film.
4. After the scraping coating is finished, the sample is sent into a 60 ℃ air-blast drying oven to be heated for 10min, and then the temperature is increased to 220 ℃ to be continuously heated for 20min.
5. After the proton membrane is prepared, fixing the proton membrane by using a mold, keeping the membrane surface flat, and soaking the proton membrane in a 20wt% sulfuric acid solution for 3 hours at an acid solution temperature of 60 ℃.
6. And after the acid washing is finished, soaking the membrane in deionized water at the temperature of 80 ℃ for 1 hour, repeatedly cleaning, and then air-drying to be tested.
The proton exchange membrane prepared in this example is shown in fig. 1, and it can be seen from fig. 1 that the proton exchange membrane does not change color after being treated at the post-treatment temperature of 220 ℃, and is still a transparent membrane.
Example 2
1. Weighing 10g of perfluorosulfonic acid resin solid, adding the perfluorosulfonic acid resin solid into a mixed solvent of 89g of water and isopropanol, wherein the water-alcohol ratio is 1.
2. And opening a switch of the scraper coater, setting the length of the scraped film to 300mm, adjusting the height of the scraper to 100 mu m, starting scraping after feeding, and covering an ePTFE reinforced film on the surface of the liquid after finishing the feeding, wherein the film thickness is 3 mu m.
3. Standing for 5min after finishing the film coating, adjusting the height of a scraper to 70 mu m, and continuously scraping a second layer of film casting liquid on the surface of the reinforced film.
4. After the scraping coating is finished, the sample is sent into a 60 ℃ air-blast drying oven to be heated for 10min, and then the temperature is increased to 220 ℃ to be continuously heated for 10min.
5. After the proton membrane is prepared, fixing the proton membrane by using a mold, keeping the membrane surface smooth, and soaking the proton membrane in 15wt% sulfuric acid solution for 2 hours at the acid solution temperature of 60 ℃.
6. And after the acid washing is finished, soaking the membrane in deionized water at the temperature of 80 ℃ for 1 hour, repeatedly cleaning, and then air-drying to be tested.
Example 3
This example is the same as example 1 except that the isopropanolamine added in step (1) is replaced with 2g of ethanolamine to prepare a proton exchange membrane.
Example 4
This example is the same as example 1 except that isopropanolamine added in step (1) is replaced with 2g of n-propanolamine.
Comparative example 1
This example is the same as example 1 except that no isopropanolamine is added in step (1) and the sample in step (4) is heated in a 60 ℃ forced air drying oven for 10min, and then heated to 160 ℃ for 20min.
The proton exchange membrane prepared by the comparative example is shown in fig. 2, and it can be seen that the proton exchange membrane prepared by the comparative example turns yellow and black after being treated at the post-treatment temperature of 160 ℃.
Comparative example 2
This example is the same as example 1 except that no triton was added.
In this comparative example, without triton, the perfluorosulfonic acid resin dispersion could not wet the reinforcing layer and could not form a film.
The proton exchange membranes prepared in examples 1 to 4 and comparative example 1 were subjected to swelling degree test and tensile test, and the conductivity of the membranes was measured by a four-electrode probe method, and the results are shown in tables 1 to 5.
Table 1 example 1 colorless proton exchange membrane performance report
Table 2 example 2 colorless proton exchange membrane performance report
Table 3 example 3 colorless proton exchange membrane performance report
Table 4 example 4 colorless proton exchange membrane performance report
Table 5 comparative example 1 colorless proton exchange membrane performance report
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although the above embodiments have been shown and described, it should be understood that they are exemplary and should not be construed as limiting the present invention, and that many changes, modifications, substitutions and alterations to the above embodiments may be made by those of ordinary skill in the art without departing from the scope of the present invention.
Claims (8)
1. A preparation method of a colorless proton exchange membrane is characterized by comprising the following steps:
(1) Adding perfluorosulfonic acid solid resin into a mixed solvent of water and alcohol, and stirring and dissolving to form a dispersion liquid;
(2) Adding alcohol amine into the dispersion liquid obtained in the step (1), dropwise adding triton after the alcohol amine is dissolved, and uniformly stirring to obtain a membrane casting liquid; the alcohol amine comprises at least one of ethanolamine, n-propanol amine and isopropanol amine; the addition amount of the alcohol amine is 0.5-2.5% of the mass of the dispersion liquid; the addition amount of the triton is 0.5 to 4 percent of the mass of the dispersion liquid;
(3) Preparing a primary composite proton exchange membrane by the casting solution obtained in the step (2) and an ePTFE reinforced membrane through a solution casting method;
(4) And (4) carrying out acid washing, water washing and drying on the primary composite proton exchange membrane obtained in the step (3) to obtain the colorless proton exchange membrane.
2. The method for preparing a colorless proton exchange membrane according to claim 1, wherein in the step (1), the content of the perfluorosulfonic solid resin in the dispersion is 5-25wt%.
3. The method for preparing the colorless proton exchange membrane according to claim 1 or 2, wherein in the step (1), the mixed solvent of water and alcohol comprises deionized water and an alcohol solvent, and the alcohol solvent comprises at least one of ethanol, isopropanol or n-propanol.
4. The method for preparing the colorless proton exchange membrane according to claim 3, wherein the mass ratio of the deionized water to the alcohol solvent in the water and alcohol mixed solvent is 5.
5. The method for preparing the colorless proton exchange membrane according to claim 1, wherein in the step (4), the acidic solution used for the acid washing is at least one of a sulfuric acid solution, a nitric acid solution, a hydrochloric acid solution and an oxalic acid solution; the pickling temperature is 30 to 100 ℃, and the pickling time is 0.5 to 5 hours.
6. The method for preparing the colorless proton exchange membrane according to claim 1, wherein in the step (3), the solution casting method comprises at least one of blade coating, slit coating and slide coating.
7. A colorless proton exchange membrane, which is characterized by being prepared by the preparation method of any one of claims 1 to 6.
8. A fuel cell comprising the colorless proton exchange membrane of claim 7.
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| KR20110048948A (en) * | 2009-11-04 | 2011-05-12 | 한국과학기술원 | Heat controllable visualization apparatus for transparent pemfc |
| CN106046403A (en) * | 2016-05-31 | 2016-10-26 | 江苏师范大学 | Preparation method of composite proton exchange membrane based on hydrophilic porous supporting body |
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| CN1725536A (en) * | 2005-06-08 | 2006-01-25 | 广州市培源燃料电池有限公司 | Self-moist proton exchange film and its preparation method |
| KR100766896B1 (en) * | 2005-11-29 | 2007-10-15 | 삼성에스디아이 주식회사 | Polymer electrolyte for fuel cell and fuel cell system comprising same |
| CN101170181B (en) * | 2006-10-25 | 2010-08-11 | 新源动力股份有限公司 | A compound proton exchange film for self-humidity increase fuel battery and its making method |
| CN103296297B (en) * | 2013-06-07 | 2015-02-11 | 湖北工程学院 | Preparation method of organic-inorganic composite proton exchange membrane for fuel cell |
| CN112599825A (en) * | 2020-12-21 | 2021-04-02 | 武汉理工大学 | Pt-doped composite proton exchange membrane and preparation method thereof |
| CN113462015A (en) * | 2021-06-30 | 2021-10-01 | 江苏师范大学 | Method for preparing perfluorosulfonic acid resin solution based on waste Nafion membrane |
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| KR20110048948A (en) * | 2009-11-04 | 2011-05-12 | 한국과학기술원 | Heat controllable visualization apparatus for transparent pemfc |
| CN106046403A (en) * | 2016-05-31 | 2016-10-26 | 江苏师范大学 | Preparation method of composite proton exchange membrane based on hydrophilic porous supporting body |
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