CN113078344B - Method for modifying perfluorinated sulfonic acid proton exchange membrane by gel extrusion casting - Google Patents
Method for modifying perfluorinated sulfonic acid proton exchange membrane by gel extrusion casting Download PDFInfo
- Publication number
- CN113078344B CN113078344B CN202110338643.7A CN202110338643A CN113078344B CN 113078344 B CN113078344 B CN 113078344B CN 202110338643 A CN202110338643 A CN 202110338643A CN 113078344 B CN113078344 B CN 113078344B
- Authority
- CN
- China
- Prior art keywords
- dimensional layered
- sulfonic acid
- exchange membrane
- proton exchange
- perfluorinated sulfonic
- 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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- 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
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
-
- 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
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
-
- 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
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- 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)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Fuel Cell (AREA)
- Conductive Materials (AREA)
Abstract
The invention provides a method for modifying a perfluorosulfonic acid proton exchange membrane by gel extrusion casting, which comprises the following steps: (1) dispersing two-dimensional layered Mxene nanosheet powder in a mixed solution of tetrabutylammonium hydroxide and dopamine hydrochloride, adding a sodium hydroxide solution to adjust the pH value of the solution, centrifugally separating, washing a solid, and then freeze-drying to obtain a tetrabutylammonium and dopamine intercalated two-dimensional layered functionalized Mxene nanosheet; (2) adding two-dimensional layered functionalized Mxene nanosheet into terminal belt-SO3Obtaining gel-like perfluorinated sulfonic acid modified resin in Na perfluorinated sulfonic acid resin solution; (3) adding the gel-like perfluorinated sulfonic acid modified resin into a single-screw extruder for melt extrusion, and forming a film on a forming roller through a tape casting machine head to obtain the two-dimensional layered functionalized Mxene nanosheet modified perfluorinated sulfonic acid proton exchange membrane. The membrane has the advantages of high mechanical strength, high water retention rate, high conductivity, low swelling rate, low air permeability, low methanol transmittance and the like.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to a method for modifying a perfluorosulfonic acid proton exchange membrane by gel extrusion casting.
Background
A fuel cell is a power generation device that directly converts chemical energy stored in hydrogen and oxygen into electrical energy through an electrode chemical reaction. The proton exchange membrane is a core component of the fuel cell, and is a key for determining the performance, life and cost of the fuel cell. An ideal proton exchange membrane must have the characteristics of good proton conductivity, gas permeation resistance, high mechanical strength, good stability and the like.
In view of the above problems, graphene oxide, montmorillonite, carbon nanotubes, etc. are often added to the perfluorosulfonic acid proton exchange homogeneous membrane in the art to improve the performance thereof. Wherein barrier properties and mechanical resistance are one of the focuses of attention, high barrier properties can effectively prevent methanol or hydrogen from directly diffusing from the anode to the cathode through the membrane to generate unnecessary byproducts, and prevent catalyst poisoning; the good mechanical tolerance can ensure that the Membrane Electrode Assembly (MEA) is not easy to generate mechanical damage in the preparation process, thereby improving the electrochemical performance of the fuel cell. Although the current graphene oxide and the like are modified to some extent in the aspect of improving the membrane performance, the graphene oxide and the like are still difficult to process and prepare and have small performance improvement amplitude.
Disclosure of Invention
In view of the problems in the background art, the present invention aims to provide a method for preparing a modified perfluorosulfonic acid proton exchange membrane by gel extrusion casting, wherein the membrane has the advantages of high mechanical strength, high water retention rate, high electrical conductivity, low swelling rate, low air permeability, low methanol permeability and the like.
In order to achieve the above object, the present invention provides a method for gel extrusion casting of a modified perfluorosulfonic acid proton exchange membrane, comprising the steps of: (1) preparing a two-dimensional layered functionalized Mxene nanosheet: dispersing two-dimensional layered Mxene nanosheet powder in a mixed solution of tetrabutylammonium hydroxide and dopamine hydrochloride with the mass concentration of 20-30%, stirring at 50-80 ℃ for 5-8h, cooling to room temperature, adding a sodium hydroxide solution under the condition of continuous stirring to adjust the pH of the solution to 6.8-7.2, centrifugally separating, washing a solid, and freeze-drying for 10-20h to obtain a two-dimensional layered functional Mxene nanosheet with the tetrabutylammonium and dopamine intercalation; the weight-volume ratio of the two-dimensional layered Mxene nanosheet powder to the mixed solution is 0.01-0.2 g/mL; (2) preparing perfluorosulfonic acid modified resin: adding the two-dimensional layered functionalized Mxene nanosheet in the step (1) into a perfluorinated sulfonic acid resin solution with the mass concentration of 20-30% and the terminal zone of-SO 3Na, uniformly stirring, introducing an inert gas into an autoclave, maintaining the temperature at 120-; the solvent of the perfluorinated sulfonic acid resin solution consists of water, ethanol and N, N-dimethylformamide in a mass ratio of 20:10 (10-15); (3) extrusion casting film forming: adding the gel-like perfluorinated sulfonic acid modified resin obtained in the step (2) into a single-screw extruder for melt extrusion, and forming a film on a forming roller through a tape casting machine head to obtain a two-dimensional layered functionalized Mxene nanosheet modified perfluorinated sulfonic acid proton exchange membrane; setting temperature of each zone of the extruder: 140 ℃ in the first zone, 160 ℃ in the second zone, 180 ℃ in the third zone, 185 ℃ in the fourth zone and 175 ℃ in the head.
Optionally, the two-dimensional layered Mxene nanosheet is Ti3C2，Ti2One or a combination of C, Ti4C3, V3C2 and V2C, preferably Ti3C2。
Optionally, the mass ratio of tetrabutylammonium hydroxide to dopamine hydrochloride in the step (1) is 1 (1-3).
Optionally, the washing in the step (1) is washing with deionized water for 1-2 times and washing with anhydrous ethanol for 1-2 times in sequence.
Optionally, the freeze-drying environment in step (1) is protected by inert gas, and the inert gas is one of nitrogen and argon.
The invention has the following beneficial effects:
(1) according to the invention, tetrabutylammonium hydroxide and dopamine hydrochloride are utilized to carry out ion intercalation treatment on the Mxene nanosheet, the obtained two-dimensional layered functionalized Mxene nanosheet can be uniformly dispersed in the perfluorosulfonic acid proton exchange membrane, and performance tests show that the mechanical strength, durability, swelling rate and methanol permeability of the two-dimensional layered functionalized Mxene nanosheet modified perfluorosulfonic acid proton exchange membrane, water retention rate and conductivity and the like are greatly improved, especially in the aspect of air permeability. The reason is that the interlayer spacing of the Mxene nano-sheets is greatly increased, the specific surface area is increased, the dispersity and the compatibility of the nano-sheets in the perfluorosulfonic acid resin are improved through the synergistic treatment of the intercalator tetrabutylammonium hydroxide and the dopamine hydrochloride, the intercalator has active groups such as hydroxyl or amino and the like, and is easy to be chemically bonded with functional groups such as F, OH, O and the like on the Mxene nano-sheets, and the interfacial bonding force of the modified nano-sheets and the perfluorosulfonic acid resin is also found to be better, so that the mechanical strength of the membrane is remarkably improved.
(2) The invention utilizes the addition of the modified two-dimensional layered nanosheets, which is beneficial to the realization of extrusion processing, can improve the performance of the membrane, and can make full use of the existing equipment in the field and realize the full appearance, uniform thickness and no blank breaking of the perfluorinated sulfonic acid proton exchange membrane, thereby realizing the thickness range of the perfluorinated sulfonic acid proton exchange membrane of 1-1.8 microns and meeting the requirements of the performance.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
The method for modifying the perfluorinated sulfonic acid proton exchange membrane by gel extrusion casting comprises the following steps: (1) preparing a two-dimensional layered functionalized Mxene nanosheet: dispersing two-dimensional layered Mxene nanosheet powder in a mixed solution of tetrabutylammonium hydroxide and dopamine hydrochloride with the mass concentration of 20-30%, stirring at 50-80 ℃ for 5-8h, cooling to room temperature, adding a sodium hydroxide solution under the condition of continuous stirring to adjust the pH of the solution to 6.8-7.2, centrifugally separating, washing a solid, and freeze-drying for 10-20h to obtain a two-dimensional layered functional Mxene nanosheet with the tetrabutylammonium and dopamine intercalation; the weight-volume ratio of the two-dimensional layered Mxene nanosheet powder to the mixed solution is 0.01-0.2 g/mL; (2) preparing perfluorosulfonic acid modified resin: adding 20-30% of terminal band-SO into the two-dimensional layered functionalized Mxene nanosheet in the step (1)3Na perfluorosulfonic acid resin solution is evenly stirred,keeping the temperature at 120-150 ℃ after introducing inert gas into the autoclave, preserving the heat for 2-10h, discharging and taking out, keeping the stirring speed at 200-500r/min and the heating temperature at 100-120 ℃ and drying to obtain the gel-like perfluorinated sulfonic acid modified resin; the solvent of the perfluorinated sulfonic acid resin solution consists of water, ethanol and N, N-dimethylformamide in a mass ratio of 20:10 (10-15); (3) extrusion casting film forming: adding the gel-like perfluorinated sulfonic acid modified resin obtained in the step (2) into a single-screw extruder for melt extrusion, and forming a film on a forming roller through a tape casting machine head to obtain a two-dimensional layered functionalized Mxene nanosheet modified perfluorinated sulfonic acid proton exchange membrane; setting temperature of each zone of the extruder: 140 ℃ in the first zone, 160 ℃ in the second zone, 180 ℃ in the third zone, 185 ℃ in the fourth zone and 175 ℃ in the head. The two-dimensional layered Mxene nanosheet is Ti3C2，Ti2C，Ti4C3，V3C2And V2One or a combination of C, preferably Ti3C2. The mass ratio of tetrabutylammonium hydroxide to dopamine hydrochloride in the step (1) is 1 (1-3). The washing in the step (1) is sequentially washing with deionized water for 1-2 times and washing with absolute ethyl alcohol for 1-2 times. The freeze drying environment in the step (1) is protected by inert gas, and the inert gas is one of nitrogen or argon.
The invention also discloses the two-dimensional layered functionalized Mxene nanosheet modified perfluorosulfonic acid proton exchange membrane prepared by the preparation method.
The two-dimensional layered functionalized Mxene nanosheet modified perfluorinated sulfonic acid proton exchange membrane prepared by the preparation method can be applied to fuel cells and chlor-alkali industry.
The following will specifically describe the method of gel extrusion casting modified perfluorosulfonic acid proton exchange membrane according to the present invention with reference to specific examples.
Example 1
(1) Preparing a two-dimensional layered functionalized Mxene nanosheet: two-dimensional layered Mxene nanosheet Ti2Dispersing powder C in mixed solution of tetrabutylammonium hydroxide and dopamine hydrochloride with mass concentration of 20%, stirring at 50 deg.C for 5 hr, cooling to room temperature, adding sodium hydroxide solution under stirring to adjust pH to 6.8, centrifuging, sequentially removingWashing the solid with ionized water for 1 time and absolute ethyl alcohol for 1 time, and freeze-drying the solid for 10 hours under the protection of nitrogen gas to obtain a tetrabutylammonium and dopamine intercalated two-dimensional layered functionalized Mxene nanosheet; the weight-volume ratio of the two-dimensional layered Mxene nanosheet powder to the mixed solution is 0.01 g/mL; the mass ratio of tetrabutylammonium hydroxide to dopamine hydrochloride is 1: 1;
(2) preparing perfluorosulfonic acid modified resin: adding 20 mass percent of terminal band-SO into the two-dimensional layered functionalized Mxene nanosheet in the step (1)3Uniformly stirring in a Na perfluorinated sulfonic acid resin solution, introducing inert gas into an autoclave, maintaining the temperature at 120 ℃, preserving the heat for 10 hours, discharging and taking out, and maintaining the stirring speed at 200r/min and the heating temperature at 100 ℃ for drying to obtain gel perfluorinated sulfonic acid modified resin; the solvent of the perfluorinated sulfonic acid resin solution consists of water, ethanol and N, N-dimethylformamide in a mass ratio of 20:10 (10-15);
(3) extrusion casting film forming: adding the gel-like perfluorinated sulfonic acid modified resin obtained in the step (2) into a single-screw extruder for melt extrusion, and forming a film on a forming roller through a tape casting machine head to obtain a two-dimensional layered functionalized Mxene nanosheet modified perfluorinated sulfonic acid proton exchange membrane; setting temperature of each zone of the extruder: 140 ℃ in the first zone, 160 ℃ in the second zone, 180 ℃ in the third zone, 185 ℃ in the fourth zone and 175 ℃ in the head.
Example 2
(1) Preparing a two-dimensional layered functionalized Mxene nanosheet: two-dimensional layered Mxene nanosheet V3C2Dispersing the powder in a mixed solution of tetrabutylammonium hydroxide and dopamine hydrochloride with the mass concentration of 30%, stirring for 8 hours at 80 ℃, cooling to room temperature, adding a sodium hydroxide solution under the condition of continuous stirring to adjust the pH value of the solution to 7.2, performing centrifugal separation, washing the solution with deionized water for 2 times and absolute ethyl alcohol for 2 times in sequence to wash the solid, and freeze-drying the solid for 20 hours under the protection of nitrogen to obtain a tetrabutylammonium and dopamine intercalated two-dimensional layered functionalized Mxene nanosheet; the weight-volume ratio of the two-dimensional layered Mxene nanosheet powder to the mixed solution is 0.02 g/mL; the mass ratio of tetrabutylammonium hydroxide to dopamine hydrochloride is 1: 3;
(2) preparing perfluorosulfonic acid modified resin: the two-dimensional layer of step (1)Adding 30% of terminal band-SO into the functionalized Mxene nanosheet3Uniformly stirring in a Na perfluorinated sulfonic acid resin solution, introducing inert gas into an autoclave, maintaining the temperature at 150 ℃, preserving the heat for 2 hours, discharging and taking out, and maintaining the stirring speed at 500r/min and the heating temperature at 110 ℃ for drying to obtain gel perfluorinated sulfonic acid modified resin; the solvent of the perfluorinated sulfonic acid resin solution consists of water, ethanol and N, N-dimethylformamide in a mass ratio of 20:10: 15;
(3) extrusion casting film forming: adding the gel-like perfluorinated sulfonic acid modified resin obtained in the step (2) into a single-screw extruder for melt extrusion, and forming a film on a forming roller through a tape casting machine head to obtain a two-dimensional layered functionalized Mxene nanosheet modified perfluorinated sulfonic acid proton exchange membrane; setting temperature of each zone of the extruder: 140 ℃ in the first zone, 160 ℃ in the second zone, 180 ℃ in the third zone, 185 ℃ in the fourth zone and 175 ℃ in the head.
Example 3
(1) Preparing a two-dimensional layered functionalized Mxene nanosheet: two-dimensional layered Mxene nanosheet Ti3C2Dispersing the powder in a mixed solution of tetrabutylammonium hydroxide and dopamine hydrochloride with the mass concentration of 25%, stirring for 6.5h at 65 ℃, cooling to room temperature, adding a sodium hydroxide solution under the condition of continuous stirring to adjust the pH value of the solution to 7, performing centrifugal separation, washing the solution with deionized water for 2 times and absolute ethyl alcohol for 1 time in sequence to wash the solid, and freeze-drying the solid for 10h under the protection of argon to obtain a tetrabutylammonium and dopamine intercalated two-dimensional layered functionalized Mxene nanosheet; the weight-volume ratio of the two-dimensional layered Mxene nanosheet powder to the mixed solution is 0.1 g/mL; the mass ratio of tetrabutylammonium hydroxide to dopamine hydrochloride is 1: 2;
(2) preparing perfluorosulfonic acid modified resin: adding terminal band-SO with the mass concentration of 25% into the two-dimensional layered functionalized Mxene nanosheet in the step (1)3Uniformly stirring in a Na perfluorinated sulfonic acid resin solution, introducing inert gas into an autoclave, maintaining the temperature at 130 ℃, preserving the heat for 8 hours, discharging and taking out, and maintaining the stirring speed at 300r/min and the heating temperature at 120 ℃ for drying to obtain gel perfluorinated sulfonic acid modified resin; the solvent of the perfluorinated sulfonic acid resin solution consists of water, ethanol and N, N-dimethylformamide in a mass ratio of 20:10: 12;
(3) extrusion casting film forming: adding the gel-like perfluorinated sulfonic acid modified resin obtained in the step (2) into a single-screw extruder for melt extrusion, and forming a film on a forming roller through a tape casting machine head to obtain a two-dimensional layered functionalized Mxene nanosheet modified perfluorinated sulfonic acid proton exchange membrane; setting temperature of each zone of the extruder: 140 ℃ in the first zone, 160 ℃ in the second zone, 180 ℃ in the third zone, 185 ℃ in the fourth zone and 175 ℃ in the head.
Comparative example 1
Nanosheet removing Ti3C2The procedure is as in example 3 except that the powder is not functionalized.
Comparative example 2
The procedure is as in example 3 except that only tetrabutylammonium hydroxide is used as the intercalating agent.
Comparative example 3
The procedure was as in example 3 except that the intercalating agent used was dopamine hydrochloride alone.
Comparative example 4
Except replacing nano-sheet Ti with montmorillonite3C2The procedure of example 3 was repeated except for the powder.
Performance testing
Tensile strength (23 ℃, 50% RH), according to test standard astm d 882;
conductivity, measured at 25 ℃ by the method of zawood zinski;
linear expansion (23 ℃, 50% RH to immersion in water), according to test standard ASTM756, test conditions: at 23 ℃, the relative humidity is 50% to be completely immersed in water;
hydrogen transmission rate lsv (line sweep voltametry) was tested using an electrochemical workstation (PGSTAT 30.Eco chemie b.v): the gas flow rate is 300sccm/min, the scanning speed is 2mV/s, and the scanning range is 0-0.7 v.
Methanol permeability is tested by adopting an IM6e type electrochemical workstation of Zahner company of Germany to carry out open-circuit potential test, an auxiliary electrode is a Pt sheet electrode, a reference electrode is a KCl saturated Ag/AgCl electrode, a Pt/C gas diffusion electrode is used as a working electrode, and pure O is used in the test process2Continuously through the solution near the working electrode.
Water retention rate: water content/% (100 ℃, 1h), referenced to test standard astm d 570;
the results of the performance tests of the products obtained in the above examples and comparative examples are shown in Table 1 below.
Table 1 results of performance testing
As can be seen from Table 1, the two-dimensional layered functionalized Mxene nanosheet modified perfluorosulfonic acid proton exchange membrane prepared by the preparation method provided by the invention has the advantages of good mechanical strength, low swelling rate, low methanol permeability and low hydrogen permeability, relatively high conductivity and relatively good water retention rate, and the membrane is better in durability and suitable for fuel cells.
Although some specific embodiments of the present invention have been described in detail by way of illustration, it should be understood by those skilled in the art that the above illustration is only for the purpose of illustration and is not intended to limit the scope of the invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.
Claims (6)
1. A method for modifying a perfluorosulfonic acid proton exchange membrane by gel extrusion casting is characterized by comprising the following steps:
(1) preparing a two-dimensional layered functionalized Mxene nanosheet: dispersing two-dimensional layered Mxene nanosheet powder in a mixed solution of tetrabutylammonium hydroxide and dopamine hydrochloride with the mass concentration of 20-30%, stirring at 50-80 ℃ for 5-8h, cooling to room temperature, adding a sodium hydroxide solution under the condition of continuous stirring to adjust the pH of the solution to 6.8-7.2, centrifugally separating, washing a solid, and freeze-drying for 10-20h to obtain a two-dimensional layered functional Mxene nanosheet with the intercalation of tetrabutylammonium ions and dopamine; the weight-volume ratio of the two-dimensional layered Mxene nanosheet powder to the mixed solution is 0.01-0.2 g/mL;
(2) preparing perfluorosulfonic acid modified resin: the two-dimensional layer of step (1)Adding 20-30% of terminal band-SO into the functionalized Mxene nanosheet3Uniformly stirring in a Na perfluorinated sulfonic acid resin solution, introducing inert gas into an autoclave, maintaining the temperature of 120-; the solvent of the perfluorinated sulfonic acid resin solution consists of water, ethanol and N, N-dimethylformamide in a mass ratio of 20:10 (10-15);
(3) extrusion casting film forming: adding the gel-like perfluorinated sulfonic acid modified resin obtained in the step (2) into a single-screw extruder for melt extrusion, and forming a film on a forming roller through a tape casting machine head to obtain a two-dimensional layered functionalized Mxene nanosheet modified perfluorinated sulfonic acid proton exchange membrane; setting temperature of each zone of the extruder: 140 ℃ in the first zone, 160 ℃ in the second zone, 180 ℃ in the third zone, 185 ℃ in the fourth zone and 175 ℃ in the head.
2. The method of gel extrusion casting a modified perfluorosulfonic proton exchange membrane according to claim 1, wherein said two-dimensional layered Mxene nanosheet is Ti3C2，Ti2C，Ti4C3，V3C2And V2C, one or a combination thereof.
3. The method of gel extrusion casting a modified perfluorosulfonic proton exchange membrane according to claim 1, wherein said two-dimensional layered Mxene nanosheet is Ti3C2。
4. The method of gel extrusion casting a modified perfluorosulfonic proton exchange membrane according to claim 1, wherein the mass ratio of tetrabutylammonium hydroxide and dopamine hydrochloride in the step (1) is 1 (1-3).
5. The method of gel extrusion casting a modified perfluorosulfonic acid proton exchange membrane according to claim 1, wherein the washing of the step (1) is sequentially washing 1-2 times with deionized water and 1-2 times with anhydrous ethanol.
6. The method of gel extrusion casting a modified perfluorosulfonic acid proton exchange membrane according to claim 1, wherein the freeze drying environment of step (1) is one of nitrogen or argon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110338643.7A CN113078344B (en) | 2021-03-30 | 2021-03-30 | Method for modifying perfluorinated sulfonic acid proton exchange membrane by gel extrusion casting |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110338643.7A CN113078344B (en) | 2021-03-30 | 2021-03-30 | Method for modifying perfluorinated sulfonic acid proton exchange membrane by gel extrusion casting |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113078344A CN113078344A (en) | 2021-07-06 |
| CN113078344B true CN113078344B (en) | 2022-04-01 |
Family
ID=76611368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110338643.7A Active CN113078344B (en) | 2021-03-30 | 2021-03-30 | Method for modifying perfluorinated sulfonic acid proton exchange membrane by gel extrusion casting |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113078344B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114843567B (en) * | 2022-05-17 | 2024-01-26 | 江苏科润膜材料有限公司 | High-temperature-resistant sulfonated polyimide proton exchange membrane and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1990527A (en) * | 2005-12-26 | 2007-07-04 | 北京化工大学 | Method for preparing perfluorinated sulfonic acid ionic membrane by gel extruding and flow-flattening film |
| CN103715438A (en) * | 2013-12-27 | 2014-04-09 | 郑州大学 | Nano-composite proton exchange membrane as well as preparation method and application thereof |
| CN105576267A (en) * | 2015-12-25 | 2016-05-11 | 郑州大学 | Organic-inorganic hybrid proton exchange membrane and preparation method and application thereof |
| CN108298541A (en) * | 2018-02-05 | 2018-07-20 | 中国科学院电工研究所 | A kind of preparation method of two-dimensional layer MXene nanometer sheets |
-
2021
- 2021-03-30 CN CN202110338643.7A patent/CN113078344B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1990527A (en) * | 2005-12-26 | 2007-07-04 | 北京化工大学 | Method for preparing perfluorinated sulfonic acid ionic membrane by gel extruding and flow-flattening film |
| CN103715438A (en) * | 2013-12-27 | 2014-04-09 | 郑州大学 | Nano-composite proton exchange membrane as well as preparation method and application thereof |
| CN105576267A (en) * | 2015-12-25 | 2016-05-11 | 郑州大学 | Organic-inorganic hybrid proton exchange membrane and preparation method and application thereof |
| CN108298541A (en) * | 2018-02-05 | 2018-07-20 | 中国科学院电工研究所 | A kind of preparation method of two-dimensional layer MXene nanometer sheets |
Non-Patent Citations (1)
| Title |
|---|
| Quaternary Ti3C2Tx enhanced ionic conduction in quaternized polysulfone membrane for alkaline anion exchange membrane fuel cells;Xiaole Zhang 等;《Journal of Membrane Science》;20100628;第563卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113078344A (en) | 2021-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kim et al. | Enhanced electrochemical performance and long-term durability of composite membranes through a binary interface with sulfonated unzipped graphite nanofibers for polymer electrolyte fuel cells operating under low relative humidity | |
| Yu et al. | CNT@ polydopamine embedded mixed matrix membranes for high-rate and long-life vanadium flow batteries | |
| CN102544542B (en) | Organic-inorganic hybrid composite proton exchange membrane with low penetration rate | |
| CN110256913B (en) | Preparation method of antioxidant, water-retaining agent, mixture and modified fuel cell membrane electrode | |
| Devrim et al. | Composite membrane by incorporating sulfonated graphene oxide in polybenzimidazole for high temperature proton exchange membrane fuel cells | |
| EP1429403B1 (en) | Membrane-electrode structure and polymer electrolyte fuel cell using the same | |
| EP2061110B1 (en) | Reinforced electrolyte membrane for fuel cell, method for production thereof, membrane-electrode assembly for fuel cell, and solid polymer-type fuel cell having the assembly | |
| CN102838863B (en) | Novel polymer proton exchange membrane and preparation method thereof | |
| CN110444793B (en) | Durable proton exchange membrane, preparation method and application thereof | |
| JP2018116935A (en) | Formation of active layer with improved performance | |
| WO2009125636A1 (en) | Proton conductive polymer electrolyte membrane, process for producing the proton conductive polymer electrolyte membrane, and membrane-electrode assembly and polymer electrolyte fuel cell using the proton conductive polymer electrolyte membrane | |
| Liu et al. | Enhanced mechanical durability of perfluorosulfonic acid proton-exchange membrane based on a double-layer ePTFE reinforcement strategy | |
| CN113078344B (en) | Method for modifying perfluorinated sulfonic acid proton exchange membrane by gel extrusion casting | |
| JP2002298867A (en) | Solid polymer fuel cell | |
| US20040097603A1 (en) | Ion-exchange fluororesin membrane | |
| Ma et al. | The research status of Nafion ternary composite membrane | |
| JPH1079257A (en) | Ion exchange membrane | |
| CN113078345B (en) | Method for preparing modified perfluorinated sulfonic acid proton exchange membrane by steel band tape casting method | |
| CN111925544B (en) | High-strength water-retention perfluorinated sulfonic acid proton exchange membrane, preparation method and application | |
| KR20110114992A (en) | A catalyst slurry composition, a method for preparing a membrane-electrode assembly for fuel cell using the same and the membrane-electrode assembly for fuel cell prepared therefrom | |
| Gil-Castell et al. | Functionalised poly (vinyl alcohol)/graphene oxide as polymer composite electrolyte membranes | |
| JP2009187803A (en) | Membrane electrode composite and fuel cell | |
| CN111193054B (en) | Preparation method of proton exchange membrane | |
| CN111969232A (en) | Preparation method of fuel cell diaphragm material | |
| CN112421085A (en) | Perfluorosulfonic acid resin proton membrane for hydrogen fuel cell and preparation method 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 | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 211616 No. 116, Guandong Road, Jinhu Economic Development Zone, Huai'an City, Jiangsu Province Patentee after: JIANGSU KERUN MEMBRANE MATERIAL CO.,LTD. Address before: 211600 Jinbei Town Industrial Concentration Zone No. 8, Jinhu County, Huaian City, Jiangsu Province Patentee before: JIANGSU KERUN MEMBRANE MATERIAL CO.,LTD. |