CN114388857B - Preparation method of high-durability myricetin chelated cerium ion composite proton exchange membrane - Google Patents
Preparation method of high-durability myricetin chelated cerium ion composite proton exchange membrane Download PDFInfo
- Publication number
- CN114388857B CN114388857B CN202111645581.0A CN202111645581A CN114388857B CN 114388857 B CN114388857 B CN 114388857B CN 202111645581 A CN202111645581 A CN 202111645581A CN 114388857 B CN114388857 B CN 114388857B
- Authority
- CN
- China
- Prior art keywords
- myricetin
- cerium
- proton exchange
- exchange membrane
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a preparation method of a high-durability myricetin chelated cerium ion composite proton exchange membrane, which comprises the following steps: the myricetin cerium complex free radical quencher is introduced into the membrane, and the myricetin and cerium ions play a role in a synergistic manner to quench free radicals (HO) generated in the operation process of the fuel cell, so that the free radicals are inhibited from attacking tertiary carbon and C-S bonds of hydroxyl free radicals to ether groups, main chains of polymer electrolyte membranes and side chains. The method has simple operation steps, and improves the chemical durability of the composite proton exchange membrane on the premise of not losing the proton conductivity of the proton exchange membrane. The invention aims to solve the problem of durability in the field of proton exchange membranes and has better popularization prospect.
Description
Technical Field
The invention belongs to the technical field of proton exchange membrane fuel cells, and particularly relates to a preparation method of a high-durability myricetin chelated cerium ion composite proton exchange membrane.
Background
The proton exchange membrane is one of the core components of the membrane electrode of the proton exchange membrane fuel cell, and plays the roles of conducting protons, insulating electrons and separating cathode and anode gases. Unlike catalysts and the like, failure of such materials can cause irreversible performance degradation and even end-of-life of the MEA. The chemical decay is mainly caused by gas permeation and radical degradation ether groups generated by incomplete two-electron transfer process at the cathode side, tertiary carbon of a main chain and a side chain of the polymer electrolyte membrane, C-S bonds and the like. Therefore, the development of a proton exchange membrane with high durability is urgently needed.
In order to improve the chemical durability of proton exchange membranes, researchers have added inorganic radical scavengers such as metal ions, inorganic nanoparticles, and metal oxides to polymer matrices. In addition, organic antioxidants have also been used to improve the chemical durability of the films. However, they have problems of bleed-off and weak antioxidant effect.
Disclosure of Invention
The invention aims to solve the problems and provide a preparation method of a high-durability myricetin chelated cerium ion composite proton exchange membrane.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a high-durability myricetin chelated cerium ion composite proton exchange membrane comprises the following steps:
(1) Adding perfluorinated sulfonic acid resin into a mixed solvent of water, isopropanol and DMF, and stirring at room temperature to obtain a PFSA ionomer solution;
(2) Mixing myricetin and cerium salt (III) in water-ethanol solution, stirring, centrifuging, filtering, washing, and drying to obtain myricetin cerium complex;
(3) Adding the myricetin cerium complex obtained in the step (2) into a PFSA ionomer solution, stirring to obtain a uniformly dispersed ionomer solution, dispersing the solution by using an ultrasonic cleaner, pouring the casting solution onto flat glass, then carrying out blade coating by using a wire rod, then carrying out drying and annealing treatment, and forming a film to obtain a composite film;
(4) Then the composite membrane in the step (3) is put in H 2 SO 4 Treating in the solution, soaking in deionized water until the cleaning solution is neutral, and drying for later use.
Organic antioxidant and inorganic free radical scavenger are adopted for chelation to fix and synergistically enhance the antioxidant effect and improve the chemical durability of the proton exchange membrane.
Further, in the step (1), the mass ratio of water to isopropanol to DMF in the mixed solvent of water to isopropanol and DMF is 4.5: 72, stirring at room temperature for 24h.
Further, in the step (2), the cerium salt (III) is one or more of cerium (III) nitrate, cerium (III) carbonate, cerium (III) oxalate and cerium (III) chloride.
Further, in the step (2), the molar ratio of myricetin to cerium salt (III) is 1.
Further, in the step (2), the stirring time is 12-24h, and the centrifugal speed is 4000-8000r/min.
Further, in the step (2), the washing solvent is water and ethanol; the drying temperature is 70-90 deg.C, and the drying time is 6-10h.
Further, in step (3), the myricetin cerium complex in step (2) is added to 3g of 28wt% PFSA ionomer solution in an amount of 1wt% of the total mass, and stirred for 24h.
Further, in the step (3), the drying temperature is 80 ℃, the time is 12-16h, the annealing temperature is 140-150 ℃, and the time is 4-12h.
Further, in step (4), at 0.5MH 2 SO 4 The treatment time in the solution is 1-3h, and the soaking time in deionized water at 80 ℃ is 2-5h.
Further, the film thickness is prepared to be 8 to 30 μm, preferably 8 to 20 μm.
Compared with the prior art, the invention has the following beneficial effects:
the myricetin cerium complex free radical quencher is introduced into the membrane, myricetin and cerium ions can play a role in a synergistic manner, and free radicals (HO) generated in the operation process of the fuel cell are quenched to inhibit the free radicals from attacking tertiary carbon and C-S bonds of hydroxyl free radicals on ether groups, a main chain of a polymer electrolyte membrane and side chains. The invention improves the chemical durability of the composite proton exchange membrane on the premise of not losing the proton conductivity of the proton exchange membrane. The preparation method of the myricetin cerium complex composite proton exchange membrane is simple, and only the perfluorinated sulfonic acid resin and the myricetin cerium complex are required to be uniformly mixed in a solvent and dried to form a membrane at a certain temperature, so that a solid foundation is laid for large-scale preparation of the composite membrane.
Detailed Description
The present invention is described in detail below with reference to specific examples, but the present invention is not limited thereto in any way.
Example 1
A preparation method of a high-durability myricetin chelated cerium ion composite proton exchange membrane comprises the following steps:
(1) 28g of perfluorosulfonic acid resin was added to 72g of a mixed solvent of water, isopropanol, and DMF in a mass ratio of 4.5.
(2) Mixing 0.0210g of myricetin and 0.0286g of cerous nitrate hexahydrate in 100ml of water-ethanol solution in the mass ratio of 1:1, stirring for 16h, performing centrifugal treatment at the centrifugal speed of 6000r/min, filtering, washing with water and ethanol for six times, and drying for 8h at the temperature of 80 ℃ to obtain the myricetin cerium complex.
(3) The myricetin cerium complex in (2) was added to 3g of a 28wt% PFSA ionomer solution in an amount of 1wt% of the total mass, stirred for 24 hours to obtain a uniformly dispersed ionomer solution, and then the above solution was dispersed for 1 hour using an ultrasonic cleaner. These casting solutions were poured onto a flat glass plate and then drawn down with a wire bar. And then drying at 80 ℃ for 14h and annealing at 140 ℃ for 6h to form a film, wherein the thickness of the composite film is 15 micrometers.
(4) Then 0.5MH of the composite film in the step (3) at 80 DEG C 2 SO 4 Treating the composite membrane in the solution for 1.5h, then soaking the composite membrane in deionized water at the temperature of 80 ℃ for 3h until the cleaning solution is neutral, and then drying the composite membrane for later use.
Example 2
A preparation method of a high-durability myricetin chelated cerium ion composite proton exchange membrane comprises the following steps:
(1) 28g of perfluorosulfonic acid resin was added to 72g of a mixed solvent of water, isopropanol, and DMF in a mass ratio of 4.5.
(2) Mixing 0.0420g of myricetin and 0.0286g of cerous nitrate hexahydrate in 100ml of water-ethanol solution in the mass ratio of 1.
(3) The myricetin cerium complex in (2) was added to 3g of a 28wt% PFSA ionomer solution in an amount of 1wt% of the total mass, stirred for 24 hours to obtain a uniformly dispersed ionomer solution, and then the above solution was dispersed for 1 hour using an ultrasonic cleaner. These casting solutions were poured onto a flat glass plate and then drawn down with a wire bar. And then drying at 80 ℃ for 14h, and annealing at 140 ℃ for 6h to form a film, wherein the thickness of the composite film is 15 micrometers.
(4) Then 0.5MH of the composite film in the step (3) at 80 DEG C 2 SO 4 Treating the composite membrane in the solution for 1.5h, then soaking the composite membrane in deionized water at the temperature of 80 ℃ for 3h until the cleaning solution is neutral, and then drying the composite membrane for later use.
Example 3
A preparation method of a high-durability myricetin chelated cerium ion composite proton exchange membrane comprises the following steps:
(1) 28g of perfluorosulfonic acid resin was added to 72g of a mixed solvent of water, isopropanol, and DMF in a mass ratio of 4.5.
(2) Mixing 0.0630g of myricetin and 0.0286g of cerous nitrate hexahydrate in 100ml of water-ethanol solution in a mass ratio of 1:1, stirring for 16h, performing centrifugal treatment at a centrifugal speed of 6000r/min, then filtering, washing for six times by using water and ethanol, and drying for 8h at the temperature of 80 ℃ to obtain the myricetin cerium complex.
(3) The myricetin cerium complex in (2) was added to 3g of a 28wt% PFSA ionomer solution in an amount of 1wt% of the total mass, stirred for 24 hours to obtain a uniformly dispersed ionomer solution, and then the above solution was dispersed for 1 hour using an ultrasonic cleaner. These casting solutions were poured onto a flat glass plate and then drawn down with a wire bar. And then drying at 80 ℃ for 14h, and annealing at 140 ℃ for 6h to form a film, wherein the thickness of the composite film is 15 micrometers.
(4) Then 0.5MH of the composite film in the step (3) at 80 DEG C 2 SO 4 Treating the composite membrane in the solution for 1.5h, then soaking the composite membrane in deionized water at the temperature of 80 ℃ for 3h until the cleaning solution is neutral, and then drying the composite membrane for later use.
Example 4:
a preparation method of a high-durability myricetin chelated cerium ion composite proton exchange membrane comprises the following steps:
(1) Adding 28g of perfluorosulfonic acid resin to 72g of a mixed solvent of water, isopropanol, DMF in a mass ratio of 4.5;
(2) Mixing 0.0840g of myricetin and 0.0286g of cerous nitrate hexahydrate in 100ml of water-ethanol solution in the mass ratio of 1.
(3) The myricetin cerium complex in (2) was added to 3g of a 28wt% PFSA ionomer solution in an amount of 1wt% of the total mass, stirred for 24 hours to obtain a uniformly dispersed ionomer solution, and then the above solution was dispersed for 1 hour using an ultrasonic cleaner. These casting solutions were poured onto a flat glass plate and then drawn down with a wire bar. And then drying at 80 ℃ for 14h, and annealing at 140 ℃ for 6h to form a film, wherein the thickness of the composite film is 15 micrometers.
(4) Then 0.5MH of the composite film in the step (3) at 80 DEG C 2 SO 4 Treating the composite membrane in the solution for 1.5h, then soaking the composite membrane in deionized water at the temperature of 80 ℃ for 3h until the cleaning solution is neutral, and then drying the composite membrane for later use.
Comparative example 1
A PFSA homogeneous film was used as comparative example 1, and the preparation method of the PFSA homogeneous film was the same as that of example 1 except that no myricetin cerium complex was doped.
Performance test
1. Proton conductivity
The preparation methods of examples 1-4 and comparative example 1 are respectively adopted to prepare the proton exchange membrane, and GB/T20042.3-2009 proton exchange membrane fuel cell part 3 is adopted: the proton exchange membrane test method respectively detects the proton conductivity of the proton exchange membranes prepared in examples 6-10 and comparative example 1; temperature 80 ℃ C., 100% RH.
2. Tensile strength
The preparation methods of examples 1-4 and comparative example 1 were respectively adopted to prepare proton exchange membranes, and part 3 of a GB/T20042.32009 proton exchange membrane fuel cell was adopted: proton exchange membrane test methods the tensile strength of the proton exchange membranes prepared in examples 6-10 and comparative example 1, respectively, was tested.
3. Water absorption rate
The preparation methods of examples 1-4 and comparative example 1 are respectively adopted to prepare the proton exchange membrane, and GB/T20042.3-2009 proton exchange membrane fuel cell part 3 is adopted: the proton exchange membrane test method respectively detects the water absorption of the proton exchange membranes prepared in the examples 6-10 and the comparative example 1; the temperature was 80 ℃.
4. Durability test
The preparation methods of example 2 and comparative example 1 were respectively adopted to prepare proton exchange membranes, and 8ppm Fe 2+ (0.00732 g of ferrous sulfate heptahydrate) was added to 30wt% of 200ml of H 2 O 2 Preparing a Fenton reagent. Thereafter, 4cm by 4cm of the film (dry weight m has been weighed) are placed in a water bath at 80 ℃ f ) And immersing the membrane into a Fenton reagent, and testing the corrosion degree of the membrane after 6 hours of treatment, thereby judging the chemical stability of the membrane. And (3) washing the membrane treated by the Fenton reagent in deionized water at 80 ℃ for 4h, drying the membrane at 80 ℃ for 12h, and weighing the membrane. The fenton mass loss rate of the membrane was calculated as follows:
in the formula:
m i wet weight of membrane, mg;
m f -dry weight of membrane, mg.
Table 1 shows the results of proton conductivity, water absorption, tensile strength, and fenton mass loss test for the proton exchange membranes prepared in examples 1-4 of the present invention and the proton exchange membrane prepared in comparative example 1.
TABLE 1
Combining examples 1-4 and comparative example 1 with table 1, it can be seen that the addition of different molar ratios of myricetin cerium complex to the raw materials of examples 1-4, compared to comparative example 1, the proton conductivity of the proton exchange membranes prepared in examples 1-4 is not much different from that of the proton exchange membrane prepared in comparative example 1, as is the water absorption tendency. The addition of the myricetin cerium complex can not obviously influence the proton conductivity of the proton exchange membrane. In addition, the proton exchange membranes prepared in examples 1-4 also did not differ significantly in tensile strength from the proton exchange membrane in comparative example 1. For chemical durability, the addition of myricetin cerium complex in examples 1-4 significantly reduced the mass loss of the membrane in terms of the fenton mass loss rate of the membrane. The mass loss rate is less than that of the proton exchange membrane in the comparative example 1 (2.1%).
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a high-durability myricetin chelated cerium ion composite proton exchange membrane is characterized by comprising the following steps:
(1) Adding perfluorosulfonic acid resin into a mixed solvent of water, isopropanol and DMF, and stirring at room temperature to obtain a PFSA ionomer solution;
(2) Mixing myricetin and +3 cerium salt in water-ethanol solution, stirring, centrifuging, filtering, washing, and drying to obtain myricetin cerium complex;
(3) Adding the myricetin cerium complex obtained in the step (2) into a PFSA ionomer solution, stirring to obtain an evenly dispersed ionomer solution, dispersing the solution by using an ultrasonic cleaner, pouring the casting solution onto plate glass, carrying out blade coating by using a wire rod, drying, annealing, and forming a film to obtain a composite film;
(4) Then the composite membrane in the step (3) is put in H 2 SO 4 Treating in the solution, soaking in deionized water until the cleaning solution is neutral, and drying for later use.
2. The preparation method of the highly durable myricetin chelated cerium ion composite proton exchange membrane as claimed in claim 1, wherein the mass ratio of water, isopropanol and DMF in the mixed solvent of water, isopropanol and DMF in step (1) is 4.5: 72, stirring at room temperature for 24h.
3. The method as claimed in claim 1, wherein in the step (2), the +3 cerium salt is one or more of cerium nitrate, cerium carbonate, cerium oxalate and cerium chloride.
4. The method for preparing a highly durable myricetin-cerium ion composite proton exchange membrane according to claim 1, wherein in the step (2), the molar ratio of the myricetin to the +3 cerium salt is 1.
5. The method for preparing a highly durable myricetin-cerium ion composite proton exchange membrane according to claim 1, wherein in the step (2), the stirring time is 12-24 hours, and the centrifugal speed is 4000-8000r/min.
6. The method for preparing a highly durable myricetin chelated cerium ion composite proton exchange membrane as claimed in claim 1, wherein in the step (2), the washing solvent is water and ethanol; the drying temperature is 70-90 deg.C, and the drying time is 6-10h.
7. The method of claim 1, wherein in step (3), the myricetin cerium complex in step (2) is added to 3g of 28wt% PFSA ionomer solution by 1wt% of the total mass, and stirred for 24h.
8. The method for preparing a highly durable myricetin chelated cerium ion composite proton exchange membrane as claimed in claim 1, wherein in step (3), the drying temperature is 80 ℃ and the time is 12-16h, the annealing temperature is 140-150 ℃ and the time is 4-12h.
9. The method for preparing a highly durable myricetin-cerium ion composite proton exchange membrane according to claim 1, wherein in the step (4), MH is performed at 0.5MH 2 SO 4 The solution is treated for 1-3h, and soaked in deionized water at 80 ℃ for 2-5h.
10. The method for preparing a highly durable myricetin chelated cerium ion composite proton exchange membrane as claimed in claim 1, wherein the prepared membrane has a thickness of 8-30 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111645581.0A CN114388857B (en) | 2021-12-30 | 2021-12-30 | Preparation method of high-durability myricetin chelated cerium ion composite proton exchange membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111645581.0A CN114388857B (en) | 2021-12-30 | 2021-12-30 | Preparation method of high-durability myricetin chelated cerium ion composite proton exchange membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114388857A CN114388857A (en) | 2022-04-22 |
| CN114388857B true CN114388857B (en) | 2022-11-15 |
Family
ID=81199898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111645581.0A Active CN114388857B (en) | 2021-12-30 | 2021-12-30 | Preparation method of high-durability myricetin chelated cerium ion composite proton exchange membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114388857B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113193218A (en) * | 2021-04-29 | 2021-07-30 | 深圳氢时代新能源科技有限公司 | Proton exchange membrane applied to fuel cell and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101777659A (en) * | 2009-12-07 | 2010-07-14 | 山东东岳神舟新材料有限公司 | Perfluorosulfonic composite proton exchange membrane for fuel cell |
| CN108878993A (en) * | 2017-05-12 | 2018-11-23 | 中国科学院大连化学物理研究所 | A method of slowing down proton exchange membrane electrochemical degradation |
| CN107200748B (en) * | 2017-07-02 | 2019-05-03 | 石家庄学院 | Fluorine-containing dihydromyricetin derivative and its preparation method and application |
| KR102396985B1 (en) * | 2018-11-02 | 2022-05-12 | 주식회사 엘지에너지솔루션 | Crosslinked polyolefin separator having inorganic layer and high power secondary battery comprising the same |
-
2021
- 2021-12-30 CN CN202111645581.0A patent/CN114388857B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113193218A (en) * | 2021-04-29 | 2021-07-30 | 深圳氢时代新能源科技有限公司 | Proton exchange membrane applied to fuel cell and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114388857A (en) | 2022-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110336052B (en) | Mixed matrix type cation exchange membrane and preparation method thereof | |
| CN102522576B (en) | Fuel cell membrane with high tolerance and its preparation method | |
| CN104134813B (en) | A kind of long-life polyelectrolyte film and preparation method thereof | |
| CN102945972A (en) | Preparation method of composite proton exchange membrane for all vanadium redox flow battery | |
| CN102504310A (en) | Preparation method of sulfonated polyimide/chitosan composite proton conducting film | |
| CN114388857B (en) | Preparation method of high-durability myricetin chelated cerium ion composite proton exchange membrane | |
| CN109888344A (en) | The method for preparing sulfonated polyether-ether-ketone load non-platinum catalyst proton exchange membrane using method of electrostatic spinning | |
| CN116826124A (en) | Composite perfluorosulfonic acid proton exchange membrane and preparation method and application thereof | |
| Zheng et al. | Durability improvement of proton exchange membrane fuel cells by doping silica‒ferrocyanide antioxidant | |
| CN114373971B (en) | Preparation method of proton exchange membrane blended by perfluorinated sulfonic acid resin and Ce-MOF | |
| CN111342095B (en) | High-temperature fuel cell proton exchange membrane and preparation method thereof | |
| CN116613362A (en) | Composite amphoteric ion exchange membrane for vanadium battery and preparation method thereof | |
| CN111342094B (en) | Preparation method of rare earth doped perfluorosulfonic acid membrane | |
| CN114276573B (en) | High-durability organic antioxidant chelated cerium ion composite proton exchange membrane, and preparation method and application thereof | |
| CN114349365B (en) | Preparation method of high-durability 3, 4-dihydroxyphenylalanine chelated cerium ion composite proton exchange membrane | |
| CN114836767A (en) | Preparation method of catalyst slurry for hydrogen production by PEM (proton exchange membrane) electrolysis of water and preparation method of membrane electrode of catalyst slurry | |
| CN109411796B (en) | Cross-linking type proton exchange membrane for vanadium battery and preparation method | |
| CN115084608B (en) | Antioxidant proton exchange membrane, preparation method thereof and proton exchange membrane fuel cell | |
| CN114373970B (en) | Proton exchange membrane with high proton conductivity and high durability as well as preparation method and application thereof | |
| CN117254079A (en) | Proton exchange membrane containing Mn metal complex and preparation method and application thereof | |
| CN117543035B (en) | Nafion-C/CeO2Pt composite membrane and preparation method and application thereof | |
| CN117254081B (en) | Anti-aging proton exchange membrane, preparation method thereof and membrane electrode assembly | |
| CN117393819B (en) | Preparation and application of modified perfluorosulfonic acid proton exchange membrane | |
| CN112436169B (en) | Long-life perfluorinated proton membrane and preparation method thereof | |
| CN112552545A (en) | In-situ molecular level hybridization membrane preparation method, product and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |