CN111370723B - Preparation method of perfluorosulfonic acid membrane with adjustable and controllable microstructure - Google Patents
Preparation method of perfluorosulfonic acid membrane with adjustable and controllable microstructure Download PDFInfo
- Publication number
- CN111370723B CN111370723B CN202010197944.8A CN202010197944A CN111370723B CN 111370723 B CN111370723 B CN 111370723B CN 202010197944 A CN202010197944 A CN 202010197944A CN 111370723 B CN111370723 B CN 111370723B
- Authority
- CN
- China
- Prior art keywords
- perfluorosulfonic acid
- temperature
- membrane
- solvent
- acid resin
- 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
Images
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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0221—Organic resins; Organic polymers
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0226—Composites in the form of mixtures
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to the field of preparation of a perfluorosulfonic acid membrane with an adjustable microstructure, in particular to a preparation method of a perfluorosulfonic acid membrane with an adjustable microstructure. Mixing solvents with different high and low boiling points to be used as solvents to dissolve the perfluorosulfonic acid resin, preparing the membrane at different temperatures, mixing the solvents with modified particles to prepare the composite membrane, and regulating and controlling a microscopic mechanism of the membrane by adopting a super-strong gradient magnetic field to improve the conductivity of the perfluorosulfonic acid membrane and control ion permeation. The perfluorosulfonic acid membrane prepared by the invention has the advantages of controllable microstructure, good chemical and thermal stability and good dimensional stability, and can be applied to flow batteries of different systems.
Description
Technical Field
The invention relates to the field of preparation of a perfluorosulfonic acid membrane with an adjustable microstructure, in particular to a preparation method of a perfluorosulfonic acid membrane with an adjustable microstructure.
Background
Renewable energy sources such as solar energy and wind energy are one of the most popular subjects in the modern times. Compared with coal, natural gas, petroleum and nuclear energy, the renewable energy is cheaper, reliable and environment-friendly, and conforms to the strategy of sustainable development. Storage of energy, particularly of large-scale renewable resources, may be critical to implementing this strategy. Due to the characteristics of long service life, effective heat management, mutual independence of power and energy storage, easiness in maintenance and the like, the flow battery can be applied to large-scale electric energy storage.
The separator is one of the key components of a flow battery. At present, diaphragm materials for vanadium batteries reported at home and abroad are mainly ion exchange membranes, wherein a perfluorosulfonic acid membrane is one of commercial proton conducting membranes with excellent comprehensive performance.
The method for preparing the perfluorinated ion exchange membrane by the solution casting method is firstly reported by Moore and the like, the solution film forming firstly requires to prepare corresponding solution, an ionic polymer is dissolved by selecting a proper solvent at a higher temperature and pressure and then is cast and scraped on a flat template, then the solvent is volatilized at a certain temperature, the ionic polymer is formed into a film, and the finished film can be obtained by cutting and finishing after heat treatment.
The properties and performances of the perfluorosulfonic acid ion exchange membrane prepared by adopting the solution membrane forming method greatly depend on the properties of a perfluorosulfonic acid solution, a plurality of scholars also make corresponding researches on the properties of solutions of perfluorosulfonic acid resin in different solvents, and a structural model is also provided for the forms of perfluorosulfonic acid resin molecules in the solutions. After studying the resin molecular morphology in the diluted perfluorosulfonic acid ionomer/water/methanol solution by using a dynamic light scattering method, in the extremely diluted solution, sulfonic acid groups are fully dissociated and face the outer end of a rod-shaped structure, the rod-shaped structure is fully extended, the effective charge density of the ionic groups is lower along with the increase of the concentration, disordered chain segments at the outer end of the rod-shaped aggregate are more, a molecular chain can be inserted into a plurality of rod-shaped aggregates, and the rod-shaped aggregates can be self-assembled through the superposition of the disordered chain segments. Therefore, solution casting film formation is subject to a phase inversion process from solution to film, wherein the change process of solution properties and the control process of film formation have important influence on the structure and performance of final film formation.
The invention content is as follows:
the invention aims to provide a preparation method of a perfluorosulfonic acid membrane with an adjustable microstructure, which is characterized in that perfluorosulfonic acid resin is dissolved by a mixed solvent, modified particles are mixed, the temperature gradient in the membrane forming process is controlled, and meanwhile, the microstructure of the membrane is adjusted in a super-strong gradient magnetic field environment, so that the perfluorosulfonic acid membrane with the controllable microstructure is obtained.
The technical scheme of the invention is as follows:
a preparation method of a perfluorosulfonic acid membrane with an adjustable microstructure comprises the steps of mixing solvents with high boiling points and low boiling points in different modes and different dissolving concentrations to serve as a dissolving resin solvent, and dissolving perfluorosulfonic acid resin in the mixed solvent at 180-220 ℃ to form a perfluorosulfonic acid resin solution; adding the modified ionic substance into a perfluorinated sulfonic acid resin solution, stirring for 20-30 h, carrying out vacuum defoaming on the mixed solution, drying under different temperature control systems, and simultaneously adopting a gradient magnetic field to carry out treatment to form a film.
The preparation method of the perfluorosulfonic acid membrane with the adjustable and controllable microstructure comprises the step of using one or more than two of acetone, 1-dichloroethane, chloroform, methanol, tetrahydrofuran, ethanol and ethyl acetate as low-boiling-point solvents.
The preparation method of the microstructure-adjustable perfluorosulfonic acid membrane comprises the step of preparing a high-boiling-point solvent from one or more than two of N, N-dimethylformamide, cyclohexanone, N-dimethylacetamide, N-methylformamide, dimethyl sulfoxide, ethylene glycol and N-methylpyrrolidone.
The preparation method of the perfluorosulfonic acid membrane with the adjustable microstructure comprises the following steps of: one way is that the high boiling point solvent and the low boiling point solvent are mixed before the perfluorosulfonic acid resin is dissolved, and then the mixture is dissolved to prepare the perfluorosulfonic acid resin solution; and the other mode is that the perfluorinated sulfonic acid resin is dissolved by adopting a high-boiling-point solvent, then the low-boiling-point solvent is added under stirring, and the mixture is stirred for 20-30 hours to obtain a perfluorinated sulfonic acid resin solution.
The preparation method of the perfluorosulfonic acid membrane with the adjustable microstructure comprises the following steps of mixing a high-boiling-point solvent and a low-boiling-point solvent, wherein the high-boiling-point solvent accounts for more than or equal to 40% and A is less than 100%, and the low-boiling-point solvent accounts for more than 0% and less than 40% by mass percentage.
According to the preparation method of the perfluorosulfonic acid membrane with the adjustable microstructure, in a perfluorosulfonic acid resin solution, different dissolving concentrations of perfluorosulfonic acid resin are 2-40 wt%.
The preparation method of the perfluorosulfonic acid membrane with the adjustable microstructure comprises the following steps of: the first method is that the temperature is controlled for 2-5 h at the low temperature of 50-90 ℃, and then the temperature is controlled for 2-5 h in a high temperature region when the temperature is increased to 140-180 ℃; the other method is that the temperature is directly increased to 140-180 ℃ of the high temperature region, the temperature is controlled for 2-5 h in the high temperature region, and then the temperature is reduced to 50-90 ℃ of the low temperature region, and the temperature is controlled for 12-24 h.
According to the preparation method of the perfluorosulfonic acid membrane with the adjustable and controllable microstructure, the modified ionic substance is lanthanum oxide, cerium oxide, yttrium oxide or cobalt oxide.
According to the preparation method of the perfluorosulfonic acid membrane with the adjustable microstructure, the gradient magnetic field is processed into a membrane in a two-stage gradient high-intensity magnetic field environment of 3-8T, 8-15T and no 8T.
The design idea of the invention is as follows:
the invention mainly improves the performance of the membrane by regulating and controlling the microstructure of the membrane, and changes the structure of the membrane by changing the property of the solution and utilizing the action of an external super-strong gradient magnetic field. Mixing solvents with different high and low boiling points to be used as solvents to dissolve the perfluorosulfonic acid resin, preparing the membrane at different temperatures, mixing the solvents with modified particles to prepare the composite membrane, and regulating and controlling a microscopic mechanism of the membrane by adopting a super-strong gradient magnetic field to improve the conductivity of the perfluorosulfonic acid membrane and control ion permeation.
The invention has the following advantages and beneficial effects:
the membrane prepared by the method has a controllable structure, improves the conductivity and ion selectivity of the perfluorosulfonic acid membrane, prepares membranes with different structures by changing the performance of the solution and regulating and controlling the preparation process, has good chemical and thermal stability and good dimensional stability, and is suitable for flow batteries of different systems.
Drawings
FIG. 1 is a schematic diagram of the film formation in a magnetic field environment according to the method of the present invention.
Detailed Description
The technical means of the present invention will be described in more detail below with reference to examples and drawings.
Example 1
In this embodiment, the preparation method of the perfluorosulfonic acid membrane with an adjustable microstructure includes the following specific steps:
(1) dissolving 5g of perfluorosulfonic acid resin in 30ml of ethanol, 20ml of water and 50ml of N, N-dimethylacetamide, and heating and dissolving the mixture in a high-pressure reaction kettle at the temperature of 220 ℃. The modified ionic substance (0.2g of lanthanum oxide) was added to the perfluorosulfonic acid resin solution and stirred for 24 h.
(2) And (2) carrying out vacuum ultrasonic treatment on the solution obtained in the step (1) for 1h to remove bubbles and impurities.
(3) And (3) casting the solution in the step (2) on a glass plate by adopting a solution casting method, preserving heat for 12h at the temperature of 60 ℃, and then heating to 130 ℃ for drying for 4h to volatilize into a film.
The relevant performance data for this example is as follows:
the conductive performance and ion selectivity of the separator obtained in this example were tested: the conductivity was 0.053s cm-1Permeability of tetravalent vanadium ion is 6.78X 10-7cm2·min-1。
Example 2
In this embodiment, the preparation method of the perfluorosulfonic acid membrane with an adjustable microstructure includes the following specific steps:
(1) dissolving 5g of perfluorosulfonic acid resin in 30ml of ethanol, 20ml of water and 50ml of N, N-dimethylacetamide, and heating and dissolving the mixture in a high-pressure reaction kettle at the temperature of 220 ℃. The modified ionic substance (0.2g of cerium oxide) was added to the perfluorosulfonic acid resin solution and stirred for 24 hours.
(2) And (2) carrying out vacuum ultrasonic treatment on the solution obtained in the step (1) for 1h to remove bubbles and impurities.
(3) Casting the solution obtained in the step (2) on a glass plate by adopting a solution casting method, preserving the temperature for 12 hours at the temperature of 60 ℃, and simultaneously adding a 5T magnetic field; then the temperature is raised to 130 ℃ and dried for 4 hours, and simultaneously 10T of strong magnetic field is added to volatilize and form a film.
The relevant performance data for this example is as follows:
the conductive performance and ion selectivity of the separator obtained in this example were tested: the conductivity was 0.059 s-cm-1Permeability of tetravalent vanadium ion is 6.4X 10-7cm2·min-1。
Example 3
In this embodiment, the preparation method of the perfluorosulfonic acid membrane with an adjustable microstructure includes the following specific steps:
(1) dissolving 5g of perfluorosulfonic acid resin in 30ml of ethanol, 20ml of water and 50ml of N, N-dimethylacetamide, and heating and dissolving the mixture in a high-pressure reaction kettle at the temperature of 220 ℃. Modified ionic substance (0.2g yttrium oxide) was added to the perfluorosulfonic acid resin solution and stirred for 24 h.
(2) And (2) carrying out vacuum ultrasonic treatment on the solution obtained in the step (1) for 1h to remove bubbles and impurities.
(3) And (3) mixing 0.01g of lanthanum oxide into the solution in the step (2), and stirring for 24 hours.
(4) Casting the solution obtained in the step (3) on a glass plate by adopting a solution casting method, preserving the temperature for 12 hours at the temperature of 60 ℃, and simultaneously adding a 5T magnetic field; then the temperature is raised to 130 ℃ and dried for 4 hours, and simultaneously 10T of strong magnetic field is added to volatilize and form a film.
The relevant performance data for this example is as follows:
the conductive performance and ion selectivity of the separator obtained in this example were tested: the conductivity is 0.064 s-cm-1Permeability of tetravalent vanadium ion is 5.53X 10-7cm2·min-1。
Example 4
In this embodiment, the preparation method of the perfluorosulfonic acid membrane with an adjustable microstructure includes the following specific steps:
(1) 5g of perfluorosulfonic acid resin was dissolved in 30ml of ethanol, 20ml of water and 50ml of ethylene glycol, and the solution was heated and dissolved in a high-pressure reaction vessel at a temperature of 220 ℃. Modified ionic substance (0.2g cobalt oxide) was added to the perfluorosulfonic acid resin solution and stirred for 24 h.
(2) And (2) carrying out vacuum ultrasonic treatment on the solution obtained in the step (1) for 1h to remove bubbles and impurities.
(3) And (3) casting the solution in the step (2) on a glass plate by adopting a solution casting method, preserving heat for 12h at the temperature of 60 ℃, and then heating to 170 ℃ for drying for 4h to volatilize into a film.
The relevant performance data for this example is as follows:
the conductive performance and ion selectivity of the separator obtained in this example were tested: the conductivity was 0.042 s-cm-1Permeability of tetravalent vanadium ion is 5.98X 10-7cm2·min-1。
Example 5
In this embodiment, the preparation method of the perfluorosulfonic acid membrane with an adjustable microstructure includes the following specific steps:
(1) 5g of perfluorosulfonic acid resin was dissolved in 30ml of ethanol, 20ml of water and 50ml of ethylene glycol, and the solution was heated and dissolved in a high-pressure reaction vessel at a temperature of 220 ℃. Modified ionic substance (0.05g of lanthanum oxide) was added to the perfluorosulfonic acid resin solution and stirred for 24 h.
(2) And (2) carrying out vacuum ultrasonic treatment on the solution obtained in the step (1) for 1h to remove bubbles and impurities.
(3) And (3) casting the solution in the step (2) on a glass plate by adopting a solution casting method, preserving heat for 12h at the temperature of 60 ℃, then heating to 170 ℃, drying for 4h, and simultaneously adding a 5T magnetic field and a 10T strong magnetic field to volatilize and form a film.
The relevant performance data for this example is as follows:
the conductive performance and ion selectivity of the separator obtained in this example were tested: the conductivity was 0.045 s-cm-1Permeability of tetravalent vanadium ion is 5.98X 10-7cm2·min-1。
Example 6
In this embodiment, the preparation method of the perfluorosulfonic acid membrane with an adjustable microstructure includes the following specific steps:
(1) 5g of perfluorosulfonic acid resin was dissolved in 30ml of ethanol, 20ml of water and 50ml of ethylene glycol, and the solution was heated and dissolved in a high-pressure reaction vessel at a temperature of 220 ℃. Modified ionic substance (0.05g of cerium oxide) was added to the perfluorosulfonic acid resin solution and stirred for 24 hours.
(2) And (2) carrying out vacuum ultrasonic treatment on the solution obtained in the step (1) for 1h to remove bubbles and impurities.
(3) And (3) mixing 0.01g of lanthanum oxide into the solution in the step (2), and stirring for 24 hours.
(4) Casting the solution obtained in the step (3) on a glass plate by adopting a solution casting method, preserving the temperature for 12 hours at the temperature of 60 ℃, and simultaneously adding a 5T magnetic field; then the temperature is increased to 170 ℃ and the mixture is dried for 4 hours, and simultaneously 10T of strong magnetic field is added to volatilize the mixture into a film.
The relevant performance data for this example is as follows:
the conductive performance and ion selectivity of the separator obtained in this example were tested: the conductivity is 0.068 s-cm-1Permeability of tetravalent vanadium ion is 4.57X 10-7cm2·min-1。
Example 7
In this embodiment, the preparation method of the perfluorosulfonic acid membrane with an adjustable microstructure includes the following specific steps:
(1) 5g of perfluorosulfonic acid resin was dissolved in 30ml of ethanol, 20ml of water and 50ml of ethylene glycol, and the solution was heated and dissolved in a high-pressure reaction vessel at a temperature of 220 ℃. Modified ionic substance (0.05g of yttrium oxide) was added to the perfluorosulfonic acid resin solution and stirred for 24 hours.
(2) And (2) carrying out vacuum ultrasonic treatment on the solution obtained in the step (1) for 1h to remove bubbles and impurities.
(3) And (3) mixing 0.01g of yttrium oxide into the solution in the step (2), and stirring for 24 hours.
(4) Casting the solution obtained in the step (3) on a glass plate by adopting a solution casting method, preserving the temperature for 12 hours at the temperature of 60 ℃, and simultaneously adding a 5T magnetic field; then the temperature is increased to 170 ℃ and the mixture is dried for 4 hours, and simultaneously 10T of strong magnetic field is added to volatilize the mixture into a film.
The relevant performance data for this example is as follows:
the conductive performance and ion selectivity of the separator obtained in this example were tested: the conductivity was 0.082s cm-1Permeability of tetravalent vanadium ion is 4.23X 10-7cm2·min-1。
As shown in FIG. 1, the method of the present invention is schematically illustrated in the formation of a film in a magnetic field environment. The embodiment result shows that the perfluorosulfonic acid membrane prepared by the invention has the advantages of controllable microstructure, good chemical and thermal stability and good dimensional stability, and can be applied to flow batteries of different systems.
Claims (5)
1. A preparation method of a perfluorosulfonic acid membrane with an adjustable microstructure is characterized in that a solvent of the perfluorosulfonic acid membrane is a solvent which is prepared by mixing high-boiling point solvents and low-boiling point solvents in different modes and different dissolving concentrations to serve as a dissolving resin solvent, and perfluorosulfonic acid resin is dissolved at 180-220 ℃ in the mixed solvent to form a perfluorosulfonic acid resin solution; adding the modified ionic substance into a perfluorinated sulfonic acid resin solution, stirring for 20-30 h, carrying out vacuum defoaming on the mixed solution, drying under different temperature control systems, and simultaneously adopting a gradient magnetic field to process to form a film;
in different ways: one way is that the high boiling point solvent and the low boiling point solvent are mixed before the perfluorosulfonic acid resin is dissolved, and then the mixture is dissolved to prepare the perfluorosulfonic acid resin solution; dissolving the perfluorinated sulfonic acid resin by using a high-boiling-point solvent, adding a low-boiling-point solvent while stirring, and stirring for 20-30 hours to obtain a perfluorinated sulfonic acid resin solution;
different temperature control systems: the first method is that the temperature is controlled for 2-5 h at the low temperature of 50-90 ℃, and then the temperature is controlled for 2-5 h in a high temperature region when the temperature is increased to 140-180 ℃; the other way is that the temperature is directly increased to 140-180 ℃ of the high temperature region, the temperature is controlled for 2-5 h in the high temperature region, and then the temperature is reduced to 50-90 ℃ of the low temperature region, and the temperature is controlled for 12-24 h;
the modified ionic substance is lanthanum oxide, cerium oxide, yttrium oxide or cobalt oxide;
the gradient magnetic field is processed into a film in a two-stage gradient high-intensity magnetic field environment of 3-8T, 8-15T and no 8T.
2. The method for preparing a perfluorosulfonic acid membrane having a controllable microstructure according to claim 1, wherein the low-boiling solvent is one or more of acetone, 1-dichloroethane, chloroform, methanol, tetrahydrofuran, ethanol, and ethyl acetate.
3. The method for producing a microstructure-controllable perfluorosulfonic acid membrane according to claim 1, wherein the high-boiling solvent is one or more of N, N-dimethylformamide, cyclohexanone, N-dimethylacetamide, N-methylformamide, dimethyl sulfoxide, ethylene glycol, and N-methylpyrrolidone.
4. The method of claim 1, wherein the mixed solvent of high and low boiling point solvents comprises 40% to 100% of high boiling point solvent and 0% to 40% of low boiling point solvent.
5. The method for producing a perfluorosulfonic acid membrane having a controllable microstructure according to claim 1, wherein the perfluorosulfonic acid resin solution has a different dissolved concentration of the perfluorosulfonic acid resin of 2 to 40 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010197944.8A CN111370723B (en) | 2020-03-19 | 2020-03-19 | Preparation method of perfluorosulfonic acid membrane with adjustable and controllable microstructure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010197944.8A CN111370723B (en) | 2020-03-19 | 2020-03-19 | Preparation method of perfluorosulfonic acid membrane with adjustable and controllable microstructure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111370723A CN111370723A (en) | 2020-07-03 |
| CN111370723B true CN111370723B (en) | 2021-04-09 |
Family
ID=71206772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010197944.8A Active CN111370723B (en) | 2020-03-19 | 2020-03-19 | Preparation method of perfluorosulfonic acid membrane with adjustable and controllable microstructure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111370723B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115224439A (en) * | 2022-08-11 | 2022-10-21 | 长园泽晖新能源材料研究院(珠海)有限公司 | High-performance lithium ion battery diaphragm and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1845363A (en) * | 2005-04-08 | 2006-10-11 | 中国科学院大连化学物理研究所 | Composite proton exchange membrane synthesizing method for fuel cell |
| CN101192675A (en) * | 2006-10-16 | 2008-06-04 | 通用汽车环球科技运作公司 | Additive for fuel battery layer |
| CN103044698A (en) * | 2012-12-18 | 2013-04-17 | 中国科学院金属研究所 | Preparation method for perfluoro-sulfonate ion exchange membrane |
| WO2019054759A1 (en) * | 2017-09-18 | 2019-03-21 | 롯데케미칼 주식회사 | Separation film complex and redox flow battery |
| CN110112447A (en) * | 2019-05-09 | 2019-08-09 | 朝阳华鼎储能技术有限公司 | Multilayer composite proton exchange membrane and preparation method thereof containing perfluorinated sulfonic resin |
| CN110148770A (en) * | 2019-05-09 | 2019-08-20 | 朝阳华鼎储能技术有限公司 | A kind of structure regulating method of perfluorosulfonic acid proton exchange film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101546816B1 (en) * | 2012-11-09 | 2015-08-25 | 한국화학연구원 | Ion conducting polymer comprising partially branched multiblock copolymer and use thereof |
-
2020
- 2020-03-19 CN CN202010197944.8A patent/CN111370723B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1845363A (en) * | 2005-04-08 | 2006-10-11 | 中国科学院大连化学物理研究所 | Composite proton exchange membrane synthesizing method for fuel cell |
| CN101192675A (en) * | 2006-10-16 | 2008-06-04 | 通用汽车环球科技运作公司 | Additive for fuel battery layer |
| CN103044698A (en) * | 2012-12-18 | 2013-04-17 | 中国科学院金属研究所 | Preparation method for perfluoro-sulfonate ion exchange membrane |
| WO2019054759A1 (en) * | 2017-09-18 | 2019-03-21 | 롯데케미칼 주식회사 | Separation film complex and redox flow battery |
| CN110112447A (en) * | 2019-05-09 | 2019-08-09 | 朝阳华鼎储能技术有限公司 | Multilayer composite proton exchange membrane and preparation method thereof containing perfluorinated sulfonic resin |
| CN110148770A (en) * | 2019-05-09 | 2019-08-20 | 朝阳华鼎储能技术有限公司 | A kind of structure regulating method of perfluorosulfonic acid proton exchange film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111370723A (en) | 2020-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110336052B (en) | Mixed matrix type cation exchange membrane and preparation method thereof | |
| CN102945972A (en) | Preparation method of composite proton exchange membrane for all vanadium redox flow battery | |
| CN108878993A (en) | A method of slowing down proton exchange membrane electrochemical degradation | |
| CN106046404B (en) | NafionTMModifiedTwo-dimensional layered material nanosheet-polymer hybrid proton exchange membrane and preparation method thereof | |
| CN104332576B (en) | A kind of preparation method of battery asymmetry SPEEK/PP/FCB composite diaphragm | |
| CN110041552B (en) | Composite high-temperature proton exchange membrane based on sulfonated aryl ether type polybenzimidazole and sulfonated polysilsesquioxane and preparation method thereof | |
| CN110350223B (en) | Nano intercalation internal selection SPEEK/GO/TiO2Preparation method of composite ion selective membrane | |
| WO2016124052A1 (en) | Proton exchange membrane for fuel cells and preparation method therefor | |
| CN110364757A (en) | The preparation method of the phosphate-doped anhydrous proton exchange membrane with fibre structure | |
| CN102544541B (en) | Preparation method of asymmetric PSFA (polysilicate ferric aluminum)/PP (polypropylene)/SPEEK (sulfonated polyetheretherketone) composite membrane | |
| WO2021043009A1 (en) | Crystalline sulfonated polyimide block copolymer proton exchange membrane, preparation method therefor, and use thereof | |
| CN108428837B (en) | Side chain type sulfonated polyimide/perfluorosulfonic acid composite membrane and preparation method and application thereof | |
| CN111370723B (en) | Preparation method of perfluorosulfonic acid membrane with adjustable and controllable microstructure | |
| CN101562251A (en) | Proton exchange membrane used for direct methanol fuel cell and preparation method thereof | |
| CN108878933A (en) | A kind of preparation method of Nafion/lignin compound proton exchange membrane | |
| CN110112447B (en) | Multi-layer composite proton exchange membrane containing perfluorinated sulfonic acid resin and preparation method thereof | |
| CN104124463A (en) | Ionic liquid-polymer composite membrane for hydrogen chloride fuel cell and preparation and application thereof | |
| CN110444794A (en) | The method of sulfonation organic polymer doped sulfonated inorganic matter preparation high-performance proton exchange membrane based on microorganism electrochemical technology | |
| CN111525167B (en) | Preparation method of perfluorosulfonic acid resin/modified lignin composite ion exchange membrane | |
| CN112029126A (en) | Sulfonated polyether sulfone proton exchange membrane with Co-MOF @ phosphotungstic acid/PVDF framework and preparation method thereof | |
| CN108878937A (en) | A kind of preparation method of Nafion/FCB composite diaphragm | |
| CN111342094B (en) | Preparation method of rare earth doped perfluorosulfonic acid membrane | |
| CN1305155C (en) | High-temperature resistant proton exchange membrane and its production | |
| CN103490085A (en) | Preparation method of konjac glucomannan/heteropoly acid composite proton conductive film | |
| CN101240077B (en) | Chitosan and acroleic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer mixing film, preparation method 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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210728 Address after: 110172 doors 1, 2 and 3, No. 189-28, JINZI street, Shenfu demonstration zone, Shenyang City, Liaoning Province Patentee after: Liaoning kejing New Material Co.,Ltd. Address before: 112700 Jianye Road, North Industrial Park, Diaobingshan City, Tieling City, Liaoning Province Patentee before: Liaoning kejing New Material Technology Co.,Ltd. |