CN110739476A - PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane and preparation method thereof - Google Patents
PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane and preparation method thereof Download PDFInfo
- Publication number
- CN110739476A CN110739476A CN201911004929.0A CN201911004929A CN110739476A CN 110739476 A CN110739476 A CN 110739476A CN 201911004929 A CN201911004929 A CN 201911004929A CN 110739476 A CN110739476 A CN 110739476A
- Authority
- CN
- China
- Prior art keywords
- pbi
- fiber membrane
- proton exchange
- membrane
- temperature
- 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.)
- Granted
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
- H01M8/10—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
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
-
- 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
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
-
- 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
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
-
- 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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Sustainable Development (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Fuel Cell (AREA)
- Conductive Materials (AREA)
Abstract
The invention belongs to the technical field of fuel cells, and particularly relates to a high-temperature-resistant composite proton exchange membrane reinforced by PBI fiber membranes and a preparation method thereof.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to an PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane and a preparation method thereof.
Background
Fuel cells are electric generators for directly converting chemical energy stored in fuel and catalyst into electric energy, and research and development of fuel cells have been greatly progressed so far, and are green energy technologies which are gradually mature, can solve two major problems of energy saving and environmental protection, and are called final new energy forms.
The proton exchange membrane of the traditional PEMFC is formed by perfluorinated sulfonic acid resin, the proton conduction performance of the membrane depends on liquid water seriously, works at 60-90 ℃ as usual, the PEM is dehydrated due to overhigh temperature, the proton conduction rate is reduced sharply, and the performance of the cell is attenuated seriously, therefore, the development of the high-temperature resistant PEMFC is effective to solve the problems of poor environmental tolerance, performance attenuation and the like of the traditional PEMFC such as . in practice, considers that the PEMFC with the working temperature over 100 ℃ can be called as a high-temperature PEMFC, while the high-temperature PEMFC is the core part of the PEMFC and is the key point for realizing high-temperature operation.
Chinese patent application No. 2017113 0.5 discloses high-temperature-resistant composite proton exchange membranes, which are prepared by compounding polybenzimidazole and aromatic polymers with benzyl halogens on side chains to form composite cross-linked membranes and then soaking phosphoric acid, and the prepared composite proton exchange membranes have higher phosphoric acid doping level and good mechanical property.
Disclosure of Invention
The invention aims to solve the technical problems that the defects of the prior art are overcome, kinds of PBI fiber membrane reinforced high-temperature resistant composite proton exchange membranes are provided, the prepared high-temperature resistant composite proton exchange membranes have high mechanical properties and excellent ion conduction properties, and can keep better properties at high temperature, and the invention also provides a preparation method of the high-temperature resistant composite proton exchange membranes.
The invention relates to a PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane which is prepared from a Polybenzimidazole (PBI) porous fiber membrane and perfluorosulfonic acid resin.
Wherein:
the polybenzimidazole porous fiber membrane layer is positioned in the middle of the composite proton exchange membrane, and the perfluorosulfonic acid resin is completely filled in micropores of the polybenzimidazole porous fiber membrane.
The structural formula of the polybenzimidazole is as follows:
the preparation method of the PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane comprises the following steps:
(1) preparation of PBI porous fiber membrane
Adding PBI into a polar solvent to obtain an electrostatic spinning solution, and then preparing the PBI porous fiber membrane by adopting a solution electrostatic spinning process.
(2) Preparation of PBI porous fiber membrane reinforced composite proton exchange membrane
And (3) uniformly spraying the perfluorinated sulfonic acid resin solution on the PBI porous fiber membrane material in a spraying or coating mode, and drying at the temperature of 40-170 ℃ to obtain the PBI enhanced high-temperature resistant composite proton exchange membrane.
Wherein:
the mass concentration of the PBI in the polar solvent in the step (1) is 1-50%.
The thickness of the high-temperature resistant composite proton exchange membrane in the step (2) is 5-100 μm.
Preferably, the preparation method of the PBI porous fiber membrane comprises the following steps:
① preparation of Electrostatic spinning solution
Gradually adding PBI powder into a polar solvent, stirring for 6-12h at 60 ℃ until the PBI powder is completely dissolved, and standing for 8-12h to prepare an electrostatic spinning solution;
② preparation of PBI porous fiber membrane
And (3) placing the PBI solution in an electrostatic spinning propulsion device, setting electrostatic spinning process parameters for electrostatic spinning, and then placing the PBI solution at 50-100 ℃ for vacuum drying to prepare the PBI porous fiber membrane.
Wherein:
the polar solvent used in step ① is or more selected from N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetone, and butanone.
The electrostatic spinning process parameters in the step ② are that the electrostatic spinning voltage is 5-30KV, the injector propulsion speed is 0.01-5mm/min, the spinning distance (the distance between the needle head and the flat plate receiver) is 05-25cm, and the temperature is 20-25 ℃.
The thickness of the PBI porous fiber membrane prepared in the step ② is 6-15 μm.
Compared with the prior art, the invention has the following beneficial effects:
(1) the high-temperature-resistant composite proton exchange membrane reinforced by the PBI fiber membrane is characterized in that the high-strength PBI porous fiber membrane is compounded with a perfluorinated sulfonic acid resin solution, the prepared high-temperature-resistant composite proton exchange membrane not only keeps the high conductivity of the perfluorinated sulfonic acid resin solution, but also can improve the mechanical property of the composite membrane at high temperature by taking the PBI porous fiber membrane as a reinforcing material.
(2) The PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane has the advantages that the PBI porous fiber membrane has high strength and uniform pore diameter, and the prepared high-temperature proton exchange membrane has high mechanical property and excellent ion conduction property and can keep better performance at high temperature.
(3) The PBI porous fiber membrane prepared by the electrostatic spinning process has adjustable pore diameter and fiber diameter, high porosity and good infiltration of perfluorinated sulfonic acid resin solution; the mechanical strength and stability at high temperature are improved, and the conductivity is also improved.
Drawings
FIG. 1 SEM image of PBI fiber membrane of example 1.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
The PBI fiber membrane-reinforced high-temperature resistant composite proton exchange membrane described in this embodiment 1 is prepared from a Polybenzimidazole (PBI) porous fiber membrane and perfluorosulfonic acid resin.
Wherein:
the polybenzimidazole porous fiber membrane layer is positioned in the middle of the composite proton exchange membrane, and the perfluorosulfonic acid resin is completely filled in micropores of the polybenzimidazole porous fiber membrane.
The structural formula of the polybenzimidazole is as follows:
the preparation method of the PBI-enhanced high-temperature resistant composite proton exchange membrane described in this embodiment 1 comprises the following steps:
(1) preparing an electrostatic spinning solution: gradually adding PBI powder into an N, N-dimethylacetamide solvent, stirring for 6 hours at 60 ℃ until the PBI powder is completely dissolved, standing for 8 hours, and preparing into an electrostatic spinning solution with the PBI concentration of 15 wt.%.
(2) Preparing electrostatic spinning: placing the PBI solution in an electrostatic spinning propelling device, setting electrostatic spinning process parameters, wherein the electrostatic spinning voltage is 12kV, the distance between a needle and a flat plate receiver is 10cm, the propelling speed of an injector is 0.03mm/min, carrying out solution electrostatic spinning at normal temperature, the thickness of an electrostatic spinning PBI fiber film is 6 mu m, placing the prepared film at 60 ℃, and carrying out vacuum drying; the porosity can reach 90%, and the modulus can reach 260 MPa.
(3) And (3) uniformly spraying a perfluorinated sulfonic acid resin solution on the surface of the PBI fiber membrane in a spraying mode to prepare composite membrane with a certain thickness, and drying at 120 ℃ to obtain the 10-micron high-temperature-resistant composite proton exchange membrane.
Compared with a perfluorinated proton exchange membrane without an electrostatic spinning PBI fiber membrane, the PBI fiber membrane-reinforced composite membrane has the elastic modulus of 313MPa, the tensile strength of 21MPa, the PBI fiber membrane-free proton membrane elastic modulus of 169MPa, the tensile strength of 11MPa and the mechanical strength of definite improvement, and simultaneously the PBI fiber membrane-reinforced composite membrane has the glass transition temperature of 132 ℃ and the PBI fiber membrane-free proton membrane-reinforced proton membrane glass transition temperature of 110 ℃.
Example 2
The PBI fiber membrane-reinforced high-temperature resistant composite proton exchange membrane described in this embodiment 2 is prepared from a Polybenzimidazole (PBI) fiber membrane and perfluorosulfonic acid resin.
Wherein:
the polybenzimidazole porous fiber membrane layer is positioned in the middle of the composite proton exchange membrane, and the perfluorosulfonic acid resin is completely filled in micropores of the polybenzimidazole porous fiber membrane.
The structural formula of the polybenzimidazole is as follows:
the preparation method of the PBI-enhanced high-temperature resistant composite proton exchange membrane described in this embodiment 2 comprises the following steps:
(1) preparing an electrostatic spinning solution: gradually adding PBI powder into N, N-dimethylacetamide solvent, stirring at 60 ℃ for 8h until the PBI powder is completely dissolved, standing for 12h, and preparing PBI with the concentration of 20 wt.%.
(2) Preparing electrostatic spinning: placing the PBI solution in an electrostatic spinning propelling device, setting electrostatic spinning process parameters, wherein the electrostatic spinning voltage is 15kV, the distance between a needle and a flat plate receiver is 20cm, the propelling speed of an injector is 0.03mm/min, carrying out solution electrostatic spinning at normal temperature, the thickness of an electrostatic spinning PBI fiber film is 8 mu m, placing the prepared film at 60 ℃, and carrying out vacuum drying; the porosity can reach 92%, and the modulus can reach 240 MPa.
(3) And (3) uniformly spraying a perfluorinated sulfonic acid resin solution on the surface of the PBI fiber membrane in a blade coating mode to prepare composite membrane with a certain thickness, and drying at 120 ℃ to obtain the 15-micron high-temperature-resistant composite proton exchange membrane.
Compared with a perfluorinated proton exchange membrane without an electrostatic spinning PBI fiber membrane, the elastic modulus of the composite membrane reinforced by the PBI fiber membrane reaches 324MPa, the tensile strength is 23MPa, the elastic modulus of the proton membrane without the PBI fiber membrane is only 169MPa, the tensile strength is 11MPa, the mechanical strength is improved by degrees, the glass transition temperature of the composite membrane reinforced by the PBI fiber membrane is 135 ℃, and the glass transition temperature of the proton membrane reinforced by the PBI fiber membrane is 110 ℃.
Example 3
The PBI fiber membrane-reinforced high-temperature resistant composite proton exchange membrane described in this embodiment 3 is prepared from a Polybenzimidazole (PBI) fiber membrane and perfluorosulfonic acid resin.
Wherein:
the polybenzimidazole porous fiber membrane layer is positioned in the middle of the composite proton exchange membrane, and the perfluorosulfonic acid resin is completely filled in micropores of the polybenzimidazole porous fiber membrane.
The structural formula of the polybenzimidazole is as follows:
the preparation method of the PBI-enhanced high-temperature resistant composite proton exchange membrane described in this embodiment 3 comprises the following steps:
(1) preparing an electrostatic spinning solution: gradually adding PBI powder into N, N-dimethylacetamide solvent, stirring at 60 ℃ for 12h until the PBI powder is completely dissolved, standing for 12h, and preparing PBI with the concentration of 20 wt.%.
(2) Preparing electrostatic spinning: placing the PBI solution in an electrostatic spinning propelling device, setting electrostatic spinning process parameters, electrostatic spinning voltage of 15kV, distance between a needle and a flat plate receiver of 15cm, propelling speed of an injector of 0.03mm/min, carrying out solution electrostatic spinning at normal temperature, wherein the thickness of an electrostatic spinning PBI fiber film is 12 microns, placing the prepared film at 60 ℃, and carrying out vacuum drying; the porosity can reach 95%, and the modulus can reach 230 Mpa.
(3) And (3) uniformly spraying a perfluorinated sulfonic acid resin solution on the surface of the PBI fiber membrane in a spraying mode to prepare composite membrane with a certain thickness, and drying at 120 ℃ to obtain the 18-micron high-temperature-resistant composite proton exchange membrane.
Compared with a perfluorinated proton exchange membrane without an electrostatic spinning PBI fiber membrane, the PBI fiber membrane-reinforced composite membrane has the elastic modulus of 336MPa, the tensile strength of 26MPa, the PBI fiber membrane-free proton membrane elastic modulus of only 169MPa, the tensile strength of 11MPa, and the mechanical strength of definite improvement, and meanwhile, the PBI fiber membrane-reinforced composite membrane has the glass transition temperature of 138 ℃ and the PBI fiber membrane-reinforced proton membrane-free glass transition temperature of 110 ℃.
Example 4
The PBI fiber membrane-reinforced high-temperature-resistant composite proton exchange membrane described in this embodiment 4 is prepared from a Polybenzimidazole (PBI) fiber membrane and perfluorosulfonic acid resin.
Wherein:
the polybenzimidazole porous fiber membrane layer is positioned in the middle of the composite proton exchange membrane, and the perfluorosulfonic acid resin is completely filled in micropores of the polybenzimidazole porous fiber membrane.
The structural formula of the polybenzimidazole is as follows:
the preparation method of the PBI-enhanced high-temperature resistant composite proton exchange membrane described in this embodiment 4 comprises the following steps:
(1) preparing an electrostatic spinning solution: gradually adding PBI powder into N, N-dimethylacetamide solvent, stirring at 60 ℃ for 12h until the PBI powder is completely dissolved, standing for 12h, and preparing PBI with the concentration of 25 wt.%.
(2) Preparing electrostatic spinning: placing the PBI solution in an electrostatic spinning propelling device, setting electrostatic spinning process parameters, electrostatic spinning voltage of 18kV, distance between a needle and a flat plate receiver of 15cm, propelling speed of an injector of 0.03mm/min, carrying out solution electrostatic spinning at normal temperature, wherein the thickness of an electrostatic spinning PBI fiber film is 15 microns, placing the prepared film at 60 ℃, and carrying out vacuum drying.
(3) And (3) uniformly spraying a perfluorinated sulfonic acid resin solution on the surface of the PBI fiber membrane in a spraying mode to prepare composite membrane with a certain thickness, and drying at 120 ℃ to obtain the high-temperature-resistant composite proton exchange membrane with the thickness of 20 microns.
Compared with a perfluorinated proton exchange membrane without an electrostatic spinning PBI fiber membrane, the PBI fiber membrane-reinforced composite membrane has the elastic modulus of 351MPa, the tensile strength of 28MPa, the PBI fiber membrane-free proton membrane elastic modulus of only 169MPa, the tensile strength of 11MPa and the mechanical strength of definite improvement, and meanwhile, the PBI fiber membrane-reinforced composite membrane has the glass transition temperature of 140 ℃ and the PBI fiber membrane-reinforced proton membrane-free glass transition temperature of 110 ℃.
Claims (10)
- The high temperature resistant composite proton exchange membrane reinforced by kinds of PBI fiber membrane is characterized in that the membrane is prepared by polybenzimidazole porous fiber membrane and perfluorosulfonic acid resin.
- 2. The PBI fiber membrane-reinforced high temperature resistant composite proton exchange membrane of claim 1, wherein: the structural formula of polybenzimidazole is:
- 3. the PBI fiber membrane-reinforced high temperature resistant composite proton exchange membrane of claim 1, wherein: the polybenzimidazole porous fiber membrane layer is positioned in the middle of the composite proton exchange membrane, and the perfluorosulfonic acid resin is completely filled in micropores of the polybenzimidazole porous fiber membrane.
- 4, A preparation method of the PBI fiber membrane reinforced high temperature resistant composite proton exchange membrane of claim 1, which is characterized by comprising the following steps:(1) preparation of PBI porous fiber membraneAdding PBI into a polar solvent to obtain an electrostatic spinning solution, and then preparing a PBI porous fiber membrane by adopting a solution electrostatic spinning process;(2) preparation of PBI porous fiber membrane reinforced composite proton exchange membraneAnd (3) uniformly spraying the perfluorinated sulfonic acid resin solution on the PBI porous fiber membrane material in a spraying or coating mode, and drying at the temperature of 40-170 ℃ to obtain the PBI enhanced high-temperature resistant composite proton exchange membrane.
- 5. The preparation method of the PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane according to claim 4, which is characterized in that: the mass concentration of the PBI in the polar solvent in the step (1) is 1-50%.
- 6. The preparation method of the PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane according to claim 4, which is characterized in that: the thickness of the high-temperature resistant composite proton exchange membrane in the step (2) is 5-100 μm.
- 7. The preparation method of the PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane according to claim 4, which is characterized in that: the preparation method of the PBI porous fiber membrane comprises the following steps:① preparation of Electrostatic spinning solutionGradually adding PBI powder into a polar solvent, stirring for 6-12h at 60 ℃ until the PBI powder is completely dissolved, and standing for 8-12h to prepare an electrostatic spinning solution;② preparation of PBI porous fiber membraneAnd (3) placing the PBI solution in an electrostatic spinning propulsion device, setting electrostatic spinning process parameters for electrostatic spinning, and then carrying out vacuum drying at 50-100 ℃ to prepare the PBI porous fiber membrane.
- 8. The method of claim 7, wherein the polar solvent used in step ① is selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetone, and butanone .
- 9. The method for preparing the PBI fiber membrane-reinforced high-temperature-resistant composite proton exchange membrane according to claim 7, wherein the electrostatic spinning process parameters in the step ② are that the electrostatic spinning voltage is 5-30KV, the injector propulsion speed is 0.01-5mm/min, the spinning distance is 05-25cm, and the temperature is 20-25 ℃.
- 10. The method for preparing the PBI fiber membrane-reinforced high-temperature-resistant composite proton exchange membrane according to claim 7, wherein the thickness of the PBI porous fiber membrane prepared in the step ② is 6-15 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911004929.0A CN110739476B (en) | 2019-10-22 | 2019-10-22 | PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911004929.0A CN110739476B (en) | 2019-10-22 | 2019-10-22 | PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110739476A true CN110739476A (en) | 2020-01-31 |
| CN110739476B CN110739476B (en) | 2020-09-22 |
Family
ID=69270769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911004929.0A Active CN110739476B (en) | 2019-10-22 | 2019-10-22 | PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110739476B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111395008A (en) * | 2020-03-26 | 2020-07-10 | 中国科学院金属研究所 | Perfluorosulfonic acid resin/polyvinylidene fluoride composite electrospun membrane and preparation method thereof |
| CN117913331A (en) * | 2024-03-14 | 2024-04-19 | 中海储能科技(北京)有限公司 | Proton exchange membrane modification method for iron-chromium flow battery and perfluorinated sulfonic acid composite membrane |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030235737A1 (en) * | 2002-06-19 | 2003-12-25 | Yoocharn Jeon | Metal-coated polymer electrolyte and method of manufacturing thereof |
| CN101367903A (en) * | 2008-08-07 | 2009-02-18 | 同济大学 | Enhancement type composite proton exchanging film based on semi-interpenetrating network |
| CN104629081A (en) * | 2015-01-28 | 2015-05-20 | 同济大学 | Preparation method of pore-filing type proton exchange membrane taking double ether crosslinked porous polybenzimidazole imide as base |
| CN104893228A (en) * | 2015-06-29 | 2015-09-09 | 蔡恩扬 | High-strength and high-hardness PA (polyamide)/ABS (acrylonitrile butadiene styrene)/PBI (polybenzimidazole) plastic alloy and method for manufacturing same |
| CN105355949A (en) * | 2015-10-16 | 2016-02-24 | 同济大学 | Preparation method of nanofiber composite proton exchange membrane |
| US20160204459A1 (en) * | 2015-01-13 | 2016-07-14 | Korea Institute Of Science And Technology | Porous nafion membrane and method for preparing the same |
| CN106941145A (en) * | 2017-02-21 | 2017-07-11 | 上海奥威科技开发有限公司 | With high temperature resistant, the barrier film of flame-retarding characteristic and preparation method |
| CN107221693A (en) * | 2016-09-27 | 2017-09-29 | 黄河科技学院 | A kind of high temperature proton exchange film of polybenzimidazoles/ionic liquid MULTILAYER COMPOSITE and preparation method thereof |
-
2019
- 2019-10-22 CN CN201911004929.0A patent/CN110739476B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030235737A1 (en) * | 2002-06-19 | 2003-12-25 | Yoocharn Jeon | Metal-coated polymer electrolyte and method of manufacturing thereof |
| CN101367903A (en) * | 2008-08-07 | 2009-02-18 | 同济大学 | Enhancement type composite proton exchanging film based on semi-interpenetrating network |
| US20160204459A1 (en) * | 2015-01-13 | 2016-07-14 | Korea Institute Of Science And Technology | Porous nafion membrane and method for preparing the same |
| CN104629081A (en) * | 2015-01-28 | 2015-05-20 | 同济大学 | Preparation method of pore-filing type proton exchange membrane taking double ether crosslinked porous polybenzimidazole imide as base |
| CN104893228A (en) * | 2015-06-29 | 2015-09-09 | 蔡恩扬 | High-strength and high-hardness PA (polyamide)/ABS (acrylonitrile butadiene styrene)/PBI (polybenzimidazole) plastic alloy and method for manufacturing same |
| CN105355949A (en) * | 2015-10-16 | 2016-02-24 | 同济大学 | Preparation method of nanofiber composite proton exchange membrane |
| CN107221693A (en) * | 2016-09-27 | 2017-09-29 | 黄河科技学院 | A kind of high temperature proton exchange film of polybenzimidazoles/ionic liquid MULTILAYER COMPOSITE and preparation method thereof |
| CN106941145A (en) * | 2017-02-21 | 2017-07-11 | 上海奥威科技开发有限公司 | With high temperature resistant, the barrier film of flame-retarding characteristic and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| SU MIN AHN ET AL: "Polybenzimidazole/Nafion hybrid membrane with improved chemical stability for vanadium redox flow battery application", 《RSC ADVANCES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111395008A (en) * | 2020-03-26 | 2020-07-10 | 中国科学院金属研究所 | Perfluorosulfonic acid resin/polyvinylidene fluoride composite electrospun membrane and preparation method thereof |
| CN111395008B (en) * | 2020-03-26 | 2021-10-08 | 中国科学院金属研究所 | Perfluorosulfonic acid resin/polyvinylidene fluoride composite electrospun membrane and preparation method thereof |
| CN117913331A (en) * | 2024-03-14 | 2024-04-19 | 中海储能科技(北京)有限公司 | Proton exchange membrane modification method for iron-chromium flow battery and perfluorinated sulfonic acid composite membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110739476B (en) | 2020-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9136034B2 (en) | Polymer electrolyte membrane for a fuel cell, and method for preparing same | |
| KR101376362B1 (en) | Polymer Electrolyte Membrane for Fuel Cell and Method of manufacturing the same | |
| KR20110021217A (en) | Polymer electrolyte membrane for fuel cell and method of manufacturing the same | |
| CN109608794B (en) | PTFE microporous membrane and preparation method thereof and composite proton exchange membrane | |
| CN103515640B (en) | A kind of carbon nanofiber-reinforcedproton proton exchange membrane and preparation method thereof | |
| CN104701560B (en) | A kind of fuel battery proton exchange film and preparation method thereof | |
| US20220238959A1 (en) | Functional coating material for lithium ion battery separator and preparation method therefor | |
| CN101320818B (en) | Fibre reinforced multi-layer fluorine-contained ionic exchange film | |
| CN108285643A (en) | Cellulose nano-fibrous/the Sulfonated Polyethersulfone Proton Exchange Membrane of one kind and preparation method | |
| CN101320817B (en) | Fibre reinforced multi-layer fluorine-contained cross-linking doping ionic membrane and preparation method thereof | |
| CN110739476B (en) | PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane and preparation method thereof | |
| CN110364757A (en) | The preparation method of the phosphate-doped anhydrous proton exchange membrane with fibre structure | |
| CN116525900A (en) | Proton exchange membrane of fuel cell and preparation method thereof | |
| CN110676495A (en) | Preparation method of nanofiber reinforced proton/alkaline membrane | |
| CN109411769B (en) | Preparation method of long-life carbon fiber paper for fuel cell | |
| CN101348574B (en) | Fiber reinforced inorganic doping cross-linking fluorinion-containing exchange film | |
| CN101350413B (en) | Fiber-reinforced multilayer fluorine-containing cross-linking ionic membrane and preparation method thereof | |
| CN111900312A (en) | High-performance lithium battery diaphragm and preparation method thereof | |
| CN101764232B (en) | Fluorinated proton exchange membrane with cross-linked network structure and preparation thereof | |
| CN107623138B (en) | Composite proton exchange membrane and preparation method thereof | |
| CN101350419B (en) | Fiber-reinforced fluorine-containing cross-linking ionic membrane and preparation method thereof | |
| CN105826585A (en) | Preparing method for high-temperature composite proton exchange membrane for fuel cell | |
| CN110838568A (en) | Lithium ion battery composite diaphragm and preparation method thereof | |
| CN109346751A (en) | A kind of preparation method of composite proton exchange membrane for fuel cell | |
| CN104681833B (en) | Nano ceramic fiber tube fuel battery proton exchange membrane and preparation method |
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 | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 256401 Dongyue fluorosilicone Material Industrial Park, Tangshan Town, Huantai, Zibo, Shandong Patentee after: Shandong Dongyue future hydrogen energy materials Co., Ltd Address before: 256401 Dongyue fluorosilicone Material Industrial Park, Tangshan Town, Huantai, Zibo, Shandong Patentee before: Shandong Dongyue future hydrogen energy materials Co.,Ltd. |