CN111342099B - Preparation method of proton exchange membrane of fiber framework fuel cell - Google Patents
Preparation method of proton exchange membrane of fiber framework fuel cell Download PDFInfo
- Publication number
- CN111342099B CN111342099B CN202010134550.8A CN202010134550A CN111342099B CN 111342099 B CN111342099 B CN 111342099B CN 202010134550 A CN202010134550 A CN 202010134550A CN 111342099 B CN111342099 B CN 111342099B
- Authority
- CN
- China
- Prior art keywords
- fiber
- exchange membrane
- proton exchange
- solution
- mesh cloth
- 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
- 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
- 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
- H01M8/109—After-treatment of the membrane other than by polymerisation thermal other than drying, e.g. sintering
-
- 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
- H01M8/1093—After-treatment of the membrane other than by polymerisation mechanical, e.g. pressing, puncturing
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to the technical field of fuel cells, and particularly provides a preparation method of a proton exchange membrane of a fiber framework fuel cell. The invention forms a mesh fabric by high temperature resistant fiber and sulfonated resin fiber, takes the fiber mesh fabric as a framework, forms aluminum hydroxide bonding coating in situ to form a microporous mesh fabric with high temperature resistance, and coats and permeates Nafion liquid into micropores of the mesh fabric, thereby obtaining a fiber framework fuel cell proton exchange membrane; the silicon dioxide aerogel contained in the proton exchange membrane has certain water retention property under the high-temperature working condition so as to ensure moisture retention, and when the water is retained, the fiber framework contains inorganic fibers, so that the framework is stable and is not easy to swell and damage, and the service life of the proton exchange membrane is effectively prolonged.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to a preparation method of a proton exchange membrane of a fiber framework fuel cell.
Background
A fuel cell is a power generation device that directly converts chemical energy of a fuel and an oxidant into electrical energy through an electrochemical reaction. Mainly comprises a positive electrode, a negative electrode, electrolyte and auxiliary equipment. The fuel cell has the advantages of high efficiency, quick start, small pollution and the like, is considered as a fourth power generation technology which is expected to provide a great amount of electric energy after wind power, water power and solar energy, is a green energy technology, can effectively relieve two problems of 'energy shortage' and 'environmental pollution' in the world at present, and realizes diversification of energy. Proton Exchange Membrane Fuel Cells (PEMFCs) belong to low-temperature Fuel cells, and besides general characteristics of Fuel cells, the Proton Exchange Membrane Fuel cells also have the characteristics of low working temperature, fast start, no electrolyte loss, no corrosion, high energy conversion rate, long service life, light weight, small volume and the like, and are ideal substitute power sources for portable power sources, distributed power stations and future electric vehicles.
Proton Exchange Membranes (PEM) are a critical component of proton exchange membrane fuel cells and directly impact cell performance and life. At present, the commonly used proton exchange membrane is a perfluorosulfonic acid membrane, but is greatly influenced by temperature, and the energy conversion efficiency of the battery is reduced at high temperature. At higher operating temperatures, significant performance degradation can occur due to rapid water evaporation, increased fuel permeation, and environmental pollution of operation.
At present, the hybridization of hygroscopic metal oxide nanoparticles with polymer membranes has been effective in improving the affinity of the membrane for water and maintaining the water in the membrane at high temperatures. However, because the metal oxide nanoparticles are added in the polymer membrane, good micropores are difficult to maintain, and the metal oxide nanoparticles are difficult to connect with the polymer, adverse reactions such as nanoparticle shedding, aggregation and the like often occur during the work of the proton exchange membrane, and the stable water holding is influenced.
The sulfonated resin can better replace the existing perfluorosulfonic acid membrane, for example, sulfonated polyether ether ketone has better alcohol resistance, thermal stability and chemical stability, and proton conductivity is higher, so that better development is achieved, but the defects of membrane swelling, brittleness and the like are still easily caused during high-temperature work, and the service life is influenced.
The invention patent with application number 201310700094.9 discloses an inorganic/organic composite proton exchange membrane and a preparation method thereof; perfluorosulfonic acid polymers are incorporated and immobilized on SiO by sol-gel methods2In the framework, an inorganic/organic composite proton exchange membrane is thus obtained. Compared with a perfluorosulfonic acid polymer proton exchange membrane (such as a Nafion membrane), the composite proton exchange membrane only contains a small amount of high-cost perfluorosulfonic acid polymer, so that the overall cost is greatly reduced; compared with sulfonated polycyclic aromatic hydrocarbon polymer (such as sulfonated polyether ether ketone), the sulfonated polycyclic aromatic hydrocarbon polymer is fixed on SiO2The introduction of a small amount of perfluorosulfonic acid polymer in the glass skeleton improves the proton conductivity of the composite membrane and improves the durability of the composite membrane. The composite proton exchange membrane prepared by the method not only reduces the cost, but also has high proton conductivity and good durability. However, the invention adopts the perfluorosulfonic acid polymer as the organic matrix, and the perfluorosulfonic acid polymer has higher cost and is greatly influenced by temperature, so that the conductivity of the perfluorosulfonic acid polymer is not high.
Disclosure of Invention
The invention provides a preparation method of a proton exchange membrane of a fiber framework fuel cell, aiming at the defects that the existing proton exchange membrane is easy to evaporate water and difficult to preserve moisture under the high-temperature working condition and is easy to swell and damage during water preservation.
The invention provides a preparation method of a proton exchange membrane of a fiber framework fuel cell, which is characterized by comprising the following steps:
(1) cleaning the high-temperature resistant fiber with a sodium hydroxide solution, and drying;
(2) combing the high-temperature resistant fibers treated in the step (1) with sulfonated resin fibers, and lapping and crossing the fibers into mesh cloth;
(3) spraying a layer of Nafion solution on the mesh cloth obtained in the step (2), then spraying a dispersion solution consisting of an aluminum chloride solution, an ammonia water solution and silicon dioxide aerogel, compacting by a roller, drying, coiling and standing for 1-2 days;
(4) and (4) firstly needling the mesh cloth processed in the step (3), then sending the mesh cloth into a coating machine, spraying a layer of Nafion liquid, drying and coiling to obtain the proton exchange membrane of the fiber framework fuel cell.
Preferably, the high-temperature resistant fiber is an inorganic fiber; further preferably, the high temperature resistant fiber is a continuous glass fiber with a diameter of 20-30 μm.
Preferably, the sodium hydroxide solution in the step (1) has a mass concentration of 3-5%, and the surface of the inorganic fiber is preferably cleaned and activated.
Preferably, the drying temperature in the step (1) is 90-100 ℃.
Preferably, the sulfonated resin fiber in the step (2) is a fiber with the diameter of 10-20 μm obtained by spinning one of sulfonated poly (arylene ether nitrile ketone) and sulfonated poly (ether ketone).
Preferably, the high temperature resistant fibers and the sulfonated resin fibers in the step (2) are mixed and carded in a mass ratio of 1:3-5, and the high temperature resistant fibers and the sulfonated resin fibers are interwoven into a web by carding the web.
Preferably, the Nafion solution in the step (3) is Nafion solution with the mass concentration of 5%, and the spraying amount of the Nafion solution is 10-15% of the total mass of the mesh cloth, and is a commercially available product provided by dupont in the united states. And spraying Nafion liquid to bond the high temperature resistant fiber and the sulfonated resin fiber.
Preferably, the dispersion liquid composed of the aluminum chloride solution, the ammonia water solution and the silica aerogel in the step (3) is formed by dispersing the aluminum chloride solution, the ammonia water solution and the silica aerogel according to the mass ratio of 1:3:3, and the spraying amount is 5-10% of the total mass of the mesh cloth; the aluminum chloride solution and the ammonia water solution are easy to solidify in a Nafion solution slightly acid environment to form aluminum hydroxide, and the silicon dioxide aerogel is adhered and fixed on the surface of the mesh under the adhesion effect of the Nafion solution. Compacting by a roller, and drying to keep the micropores of the silicon dioxide aerogel.
Further preferably, the mass concentration of the aluminum chloride solution is 8%; the mass concentration of the ammonia water solution is 3 percent.
Preferably, the roller compaction in the step (3) is carried out by adopting a compression ratio of 1.5 times. Namely, the roller spacing is set according to the thickness of the coated processing screen cloth and is compacted according to the compression ratio of 1.5. If the thickness of the coated mesh is 0.3mm, the roller interval is set to be 0.2mm for compaction. Too large a compression ratio can result in a reduction in fiber micropores; too low a compression ratio results in a web that is difficult to bond effectively.
Preferably, the needling interval of the needling in the step (4) is 0.1mm, the mesh cloth is effectively penetrated, and the microfilm coated by the aluminum hydroxide bonding is punctured, so that the sprayed Nafion liquid is easily connected with the sulfonated resin fiber in the mesh cloth. The Nafion solution is a Nafion solution with the mass concentration of 5%, and is a commercial product provided by DuPont, and the spraying amount is 5-8% of the total mass of the mesh cloth.
The invention forms the mesh cloth by the high temperature resistant fiber and the sulfonated resin fiber, takes the fiber mesh cloth as the framework, forms the microporous mesh cloth with high temperature resistance by forming aluminum hydroxide in situ for bonding and coating, and coats and permeates Nafion liquid into the micropores of the mesh cloth, thereby obtaining the proton exchange membrane of the fiber framework fuel cell.
Compared with the prior art, the preparation method of the proton exchange membrane of the fiber framework fuel cell has the outstanding characteristics and beneficial effects that:
(1) the proton exchange membrane obtained by using the inorganic fiber and the sulfonated resin fiber as frameworks has excellent high-temperature stability.
(2) The silica aerogel is adhered to the fiber by utilizing the formation of aluminum hydroxide, and the micropores of the silica aerogel obviously improve the water retention at high temperature.
(3) The invention contains inorganic fiber, can overcome swelling at high temperature, prolongs the service life of the membrane and improves the high-temperature working stability. The preparation method is simple, the raw materials are easy to obtain, and the method can be widely applied to proton exchange membrane fuel cells.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Cleaning continuous glass fiber with diameter of 20-30 μm with 3% sodium hydroxide solution to clean and activate inorganic fiber surface, and drying at 100 deg.C;
(2) carding the glass fiber treated in the step (1) and sulfonated poly (arylene ether nitrile ketone) fiber with the diameter of 10-20 mu m by a conventional fiber carding machine according to the mass ratio of 1:3, and lapping and crossing to form mesh cloth;
(3) spraying a layer of Nafion solution with the mass concentration of 5% on the mesh cloth obtained in the step (2), wherein the spraying amount is 10% of the total mass of the mesh cloth, so that the Nafion solution fully permeates the mesh cloth, then spraying a dispersion solution consisting of an aluminum chloride solution, an ammonia water solution and silicon dioxide aerogel, wherein the dispersion solution is formed by dispersing the aluminum chloride solution with the mass concentration of 8%, the ammonia water solution with the mass concentration of 3% and the silicon dioxide aerogel according to the mass ratio of 1:3:3, and the spraying amount is 10% of the total mass of the mesh cloth; the aluminum chloride solution and the ammonia water solution are easily solidified in a Nafion solution slightly acid environment to form aluminum hydroxide, the silicon dioxide aerogel is adhered and fixed on the surface of the mesh under the adhesion action of the Nafion solution, the thickness of the sprayed mesh is 0.3mm, the mesh is compacted and adjusted by a roller to be 0.2mm, and then the mesh is dried by the roller at 100 ℃, coiled and aged for 1 day;
(4) and (3) firstly needling the mesh cloth processed in the step (3), wherein the needling distance is 0.1mm, the mesh cloth is effectively penetrated, and a microfilm coated by aluminum hydroxide bonding is punctured, so that the sprayed Nafion solution is easily connected with the sulfonated resin fiber in the mesh cloth, then the mesh cloth is sent into a coating machine, and a layer of Nafion solution is sprayed, wherein the Nafion solution is a Nafion solution with the mass concentration of 5%, the Nafion solution is a commercial product provided by DuPont in the United states, and the spraying amount is 8% of the total mass of the mesh cloth. And then drying the membrane by a roller at 100 ℃ and reeling the membrane to obtain the proton exchange membrane of the fiber framework fuel cell.
Example 2
(1) Cleaning continuous glass fiber with diameter of 20-30 μm with 3% sodium hydroxide solution to clean and activate inorganic fiber surface, and drying at 100 deg.C;
(2) carding the glass fiber treated in the step (1) and sulfonated polyether ether ketone fiber with the diameter of 10-20 mu m by a conventional fiber carding machine according to the mass ratio of 1:4, and lapping and crossing to form mesh cloth;
(3) spraying a layer of Nafion solution with the mass concentration of 5% on the mesh cloth obtained in the step (2), wherein the spraying amount is 15% of the total mass of the mesh cloth, so that the Nafion solution fully permeates the mesh cloth, then spraying a dispersion solution consisting of an aluminum chloride solution, an ammonia water solution and silicon dioxide aerogel, wherein the dispersion solution is formed by dispersing the aluminum chloride solution with the mass concentration of 8%, the ammonia water solution with the mass concentration of 3% and the silicon dioxide aerogel according to the mass ratio of 1:3:3, and the spraying amount is 5% of the total mass of the mesh cloth; the aluminum chloride solution and the ammonia water solution are easy to solidify in a Nafion liquid slightly acid environment to form aluminum hydroxide, the silicon dioxide aerogel is adhered and fixed on the surface of the mesh under the adhesion effect of the Nafion liquid, the thickness of the sprayed mesh is 0.3mm, the mesh is compacted and adjusted by a roller to be 0.2mm, and then the mesh is dried by the roller at 100 ℃, coiled and aged for 2 days;
(4) and (3) firstly needling the mesh cloth processed in the step (3), wherein the needling distance is 0.1mm, the mesh cloth is effectively penetrated, and a microfilm coated by aluminum hydroxide bonding is punctured, so that the sprayed Nafion solution is easily connected with the sulfonated resin fiber in the mesh cloth, then the mesh cloth is sent into a coating machine, and a layer of Nafion solution is sprayed, wherein the Nafion solution is a Nafion solution with the mass concentration of 5%, the Nafion solution is a product sold in the market by DuPont in America, and the spraying amount is 5% of the total mass of the mesh cloth. And then drying the membrane by a roller at 100 ℃ and reeling the membrane to obtain the proton exchange membrane of the fiber framework fuel cell.
Example 3
(1) Cleaning continuous glass fiber with diameter of 20-30 μm with 5% sodium hydroxide solution to clean and activate inorganic fiber surface, and drying at 100 deg.C;
(2) mixing the glass fiber treated in the step (1) and sulfonated poly (arylene ether nitrile ketone) fiber with the diameter of 10-20 mu m in a mass ratio of 1:3, carding and carding by adopting conventional fibers, lapping and crossing to form screen cloth;
(3) spraying a layer of Nafion solution with the mass concentration of 5% on the mesh cloth obtained in the step (2), wherein the spraying amount is 15% of the total mass of the mesh cloth, so that the Nafion solution fully permeates the mesh cloth, then spraying a dispersion solution consisting of an aluminum chloride solution, an ammonia water solution and silicon dioxide aerogel, wherein the dispersion solution is formed by dispersing the aluminum chloride solution with the mass concentration of 8%, the ammonia water solution with the mass concentration of 3% and the silicon dioxide aerogel according to the mass ratio of 1:3:3, and the spraying amount is 8% of the total mass of the mesh cloth; the aluminum chloride solution and the ammonia water solution are easily solidified in a Nafion solution slightly acid environment to form aluminum hydroxide, the silicon dioxide aerogel is adhered and fixed on the surface of the mesh under the adhesion action of the Nafion solution, the thickness of the sprayed mesh is 0.3mm, the mesh is compacted and adjusted by a roller to be 0.2mm, and then the mesh is dried by the roller at 100 ℃, coiled and aged for 1 day;
(4) and (3) firstly needling the mesh cloth processed in the step (3), wherein the needling distance is 0.1mm, the mesh cloth is effectively penetrated, and a microfilm coated by aluminum hydroxide bonding is punctured, so that the sprayed Nafion solution is easily connected with the sulfonated resin fiber in the mesh cloth, then the mesh cloth is sent into a coating machine, and a layer of Nafion solution is sprayed, wherein the Nafion solution is a Nafion solution with the mass concentration of 5%, the Nafion solution is a commercial product provided by DuPont in the United states, and the spraying amount is 8% of the total mass of the mesh cloth. And then drying the membrane by a roller at 100 ℃ and reeling the membrane to obtain the proton exchange membrane of the fiber framework fuel cell.
Comparative example 1
(1) Cleaning continuous glass fiber with diameter of 20-30 μm with 3% sodium hydroxide solution to clean and activate inorganic fiber surface, and drying at 100 deg.C;
(2) carding the glass fiber treated in the step (1) and sulfonated poly (arylene ether nitrile ketone) fiber with the diameter of 10-20 mu m by a conventional fiber carding machine according to the mass ratio of 1:3, and lapping and crossing to form mesh cloth;
(3) spraying a layer of Nafion solution with the mass concentration of 5% on the mesh cloth obtained in the step (2), wherein the spraying amount is 10% of the total mass of the mesh cloth, so that the Nafion solution fully permeates the mesh cloth, the thickness of the sprayed mesh cloth is 0.3mm, the mesh cloth is compacted and adjusted by a roller to be 0.2mm, and then the mesh cloth is dried by the roller with the temperature of 100 ℃, rolled and stored for 1 day;
(4) and (3) firstly needling the mesh cloth processed in the step (3), wherein the needling distance is 0.1mm, the mesh cloth is effectively penetrated, then the mesh cloth is sent into a coating machine, and a layer of Nafion liquid is sprayed, wherein the Nafion liquid is Nafion solution with the mass concentration of 5%, and the Nafion liquid is a product sold in the market by DuPont company in America, and the spraying amount is 8% of the total mass of the mesh cloth. And then drying the membrane by a roller at 100 ℃ and reeling the membrane to obtain the proton exchange membrane of the fiber framework fuel cell.
Comparative example 1 compared to example 1, no coating treatment was performed with a dispersion consisting of an aluminum chloride solution, an ammonia aqueous solution, and a silica aerogel, and thus a good microporous water-retaining structure was not formed, affecting water retention at high temperature.
Comparative example 2
(1) Combing the sulfonated polyether-ether-ketone fibers with the diameter of 10-20 mu m by a conventional fiber carding machine, and lapping and crossing to form mesh cloth;
(2) spraying a layer of Nafion solution with the mass concentration of 5% on the mesh cloth obtained in the step (1), wherein the spraying amount is 15% of the total mass of the mesh cloth, so that the Nafion solution fully permeates the mesh cloth, then spraying a dispersion solution consisting of an aluminum chloride solution, an ammonia water solution and silicon dioxide aerogel, wherein the dispersion solution is formed by dispersing the aluminum chloride solution with the mass concentration of 8%, the ammonia water solution with the mass concentration of 3% and the silicon dioxide aerogel according to the mass ratio of 1:3:3, and the spraying amount is 5% of the total mass of the mesh cloth; the aluminum chloride solution and the ammonia water solution are easy to solidify in a Nafion liquid slightly acid environment to form aluminum hydroxide, the silicon dioxide aerogel is adhered and fixed on the surface of the mesh under the adhesion effect of the Nafion liquid, the thickness of the sprayed mesh is 0.3mm, the mesh is compacted and adjusted by a roller to be 0.2mm, and then the mesh is dried by the roller at 100 ℃, coiled and aged for 2 days;
(3) and (3) firstly needling the mesh cloth processed in the step (2), wherein the needling distance is 0.1mm, the mesh cloth is effectively penetrated, and a microfilm coated by aluminum hydroxide bonding is punctured, so that the sprayed Nafion solution is easily connected with the sulfonated resin fiber in the mesh cloth, then the mesh cloth is sent into a coating machine, and a layer of Nafion solution is sprayed, wherein the Nafion solution is a Nafion solution with the mass concentration of 5%, the Nafion solution is a product sold in the market by DuPont in America, and the spraying amount is 5% of the total mass of the mesh cloth. And then drying the membrane by a roller at 100 ℃ and reeling the membrane to obtain the proton exchange membrane of the fiber framework fuel cell.
Comparative example 2 compared to example 2, the use of inorganic fibers did not affect the high temperature stability and the tendency to swell affected the lifetime of the proton exchange membrane.
Comparative example 3
(1) Cleaning continuous glass fiber with diameter of 20-30 μm with 3% sodium hydroxide solution to clean and activate inorganic fiber surface, and drying at 100 deg.C;
(2) carding the glass fiber treated in the step (1) and sulfonated poly (arylene ether nitrile ketone) fiber with the diameter of 10-20 mu m by a conventional fiber carding machine according to the mass ratio of 1:3, and lapping and crossing to form mesh cloth;
(3) spraying a layer of Nafion solution with the mass concentration of 5% on the mesh cloth obtained in the step (2), wherein the spraying amount is 15% of the total mass of the mesh cloth, so that the Nafion solution fully permeates the mesh cloth, then spraying a dispersion solution consisting of an aluminum chloride solution, an ammonia water solution and silicon dioxide aerogel, wherein the dispersion solution is formed by dispersing the aluminum chloride solution with the mass concentration of 8%, the ammonia water solution with the mass concentration of 3% and the silicon dioxide aerogel according to the mass ratio of 1:3:3, and the spraying amount is 8% of the total mass of the mesh cloth; the aluminum chloride solution and the ammonia water solution are easily solidified in a Nafion solution slightly acid environment to form aluminum hydroxide, the silicon dioxide aerogel is adhered and fixed on the surface of the mesh under the adhesion action of the Nafion solution, the thickness of the sprayed mesh is 0.3mm, the mesh is compacted and adjusted by a roller to be 0.1mm, and then the mesh is dried by the roller at 100 ℃, coiled and aged for 1 day;
(4) and (3) firstly needling the mesh cloth processed in the step (3), wherein the needling distance is 0.1mm, the mesh cloth is effectively penetrated, and a microfilm coated by aluminum hydroxide bonding is punctured, so that the sprayed Nafion solution is easily connected with the sulfonated resin fiber in the mesh cloth, then the mesh cloth is sent into a coating machine, and a layer of Nafion solution is sprayed, wherein the Nafion solution is a Nafion solution with the mass concentration of 5%, the Nafion solution is a commercial product provided by DuPont in the United states, and the spraying amount is 8% of the total mass of the mesh cloth. And then drying the membrane by a roller at 100 ℃ and reeling the membrane to obtain the proton exchange membrane of the fiber framework fuel cell.
Comparative example 3 roll compaction used a compression ratio of 3 relative to example 1, resulting in a reduction in micropores, affecting on the one hand the water retention and on the other hand the permeability of the post-applied Nafion liquid.
Comparative example 4
(1) Cleaning continuous glass fiber with diameter of 20-30 μm with 3% sodium hydroxide solution to clean and activate inorganic fiber surface, and drying at 100 deg.C;
(2) carding the glass fiber treated in the step (1) and sulfonated poly (arylene ether nitrile ketone) fiber with the diameter of 10-20 mu m by a conventional fiber carding machine according to the mass ratio of 1:3, and lapping and crossing to form mesh cloth;
(3) spraying a layer of Nafion solution with the mass concentration of 5% on the mesh cloth obtained in the step (2), wherein the spraying amount is 15% of the total mass of the mesh cloth, so that the Nafion solution fully permeates the mesh cloth, then spraying a dispersion solution consisting of an aluminum chloride solution, an ammonia water solution and silicon dioxide aerogel, wherein the dispersion solution is formed by dispersing the aluminum chloride solution with the mass concentration of 8%, the ammonia water solution with the mass concentration of 3% and the silicon dioxide aerogel according to the mass ratio of 1:3:3, and the spraying amount is 8% of the total mass of the mesh cloth; the aluminum chloride solution and the ammonia water solution are easily solidified in a Nafion solution slightly acid environment to form aluminum hydroxide, the silicon dioxide aerogel is adhered and fixed on the surface of the mesh under the adhesion action of the Nafion solution, the thickness of the sprayed mesh is 0.3mm, the mesh is compacted and adjusted by a roller to be 0.2mm, and then the mesh is dried by the roller at 100 ℃, coiled and aged for 1 day;
(4) and (3) conveying the mesh cloth processed in the step (3) into a coating machine, and spraying a layer of Nafion solution, wherein the Nafion solution is a Nafion solution with the mass concentration of 5%, and the Nafion solution is a product sold in the market by DuPont in the United states, and the spraying amount is 8% of the total mass of the mesh cloth. And then drying the membrane by a roller at 100 ℃ and reeling the membrane to obtain the proton exchange membrane of the fiber framework fuel cell.
Comparative example 4 compared to example 3, no needle punching was used, so that the film formed by the aluminum hydroxide bonding could not be punched, and it was difficult to connect the sprayed Nafion liquid with the sulfonated resin fibers in the mesh, thereby affecting the proton conductivity.
The proton exchange membranes obtained in examples 1 to 3 and comparative examples 1 to 4 were cut into the same large pieces, and the initial proton conductivity at room temperature and 95% relative humidity was measured; then the sample is placed for 96 hours under the conditions of 95 percent of relative humidity and 85 ℃, the proton conductivity is tested again, and the stability and the water retention swelling damage condition under the high-temperature working condition are measured by the attenuation change of the proton conductivity. The results are shown in Table 1.
TABLE 1
Claims (8)
1. A preparation method of a proton exchange membrane of a fiber framework fuel cell is characterized by comprising the following steps:
(1) cleaning the high-temperature resistant fiber with a sodium hydroxide solution, and drying;
(2) combing the high-temperature resistant fibers treated in the step (1) with sulfonated resin fibers, and lapping and crossing the fibers into mesh cloth;
(3) spraying a layer of Nafion solution on the mesh cloth obtained in the step (2), then spraying a dispersion solution consisting of an aluminum chloride solution, an ammonia water solution and silicon dioxide aerogel, compacting by a roller, drying, coiling and standing for 1-2 days; the dispersion liquid composed of the aluminum chloride solution, the ammonia water solution and the silicon dioxide aerogel is formed by dispersing the aluminum chloride solution, the ammonia water solution and the silicon dioxide aerogel according to the mass ratio of 1:3:3, and the spraying amount is 5-10% of the total mass of the mesh cloth; the mass concentration of the aluminum chloride solution is 8%; the mass concentration of the ammonia solution is 3 percent;
(4) and (4) firstly needling the mesh cloth processed in the step (3), then sending the mesh cloth into a coating machine, spraying a layer of Nafion liquid, drying and coiling to obtain the proton exchange membrane of the fiber framework fuel cell.
2. The preparation method of the proton exchange membrane of the fiber framework fuel cell according to claim 1, which is characterized in that: the high-temperature resistant fiber is one of continuous glass fiber, brucite fiber and sepiolite fiber with the diameter of 20-30 mu m.
3. The preparation method of the proton exchange membrane of the fiber framework fuel cell according to claim 1, which is characterized in that: the mass concentration of the sodium hydroxide solution in the step (1) is 3-5%.
4. The preparation method of the proton exchange membrane of the fiber framework fuel cell according to claim 1, which is characterized in that: the drying temperature in the step (1) is 90-100 ℃.
5. The preparation method of the proton exchange membrane of the fiber framework fuel cell according to claim 1, which is characterized in that: the sulfonated resin fiber in the step (2) is a fiber with the diameter of 10-20 mu m, which is obtained by spinning one of sulfonated poly (arylene ether nitrile ketone) and sulfonated poly (ether ketone).
6. The preparation method of the proton exchange membrane of the fiber framework fuel cell according to claim 1, which is characterized in that: mixing and carding the high-temperature resistant fibers and the sulfonated resin fibers in a mass ratio of 1: 3-5; the Nafion solution is 5% in mass concentration, and the spraying amount is 10-15% of the total mass of the mesh cloth.
7. The preparation method of the proton exchange membrane of the fiber framework fuel cell according to claim 1, which is characterized in that: and (4) compacting by using the roller in the step (3) by adopting a compression ratio of 1.5 times.
8. The preparation method of the proton exchange membrane of the fiber framework fuel cell according to claim 1, which is characterized in that: the needling distance of the needling in the step (4) is 0.1 mm; the mass concentration of the Nafion liquid is 5 percent; the spraying amount is 5-8% of the total mass of the mesh cloth.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010134550.8A CN111342099B (en) | 2020-03-02 | 2020-03-02 | Preparation method of proton exchange membrane of fiber framework fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010134550.8A CN111342099B (en) | 2020-03-02 | 2020-03-02 | Preparation method of proton exchange membrane of fiber framework fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111342099A CN111342099A (en) | 2020-06-26 |
| CN111342099B true CN111342099B (en) | 2020-11-17 |
Family
ID=71187849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010134550.8A Active CN111342099B (en) | 2020-03-02 | 2020-03-02 | Preparation method of proton exchange membrane of fiber framework fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111342099B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112271301B (en) * | 2020-10-16 | 2021-11-23 | 山东汉德自动化控制设备有限公司 | Method for preparing fuel cell membrane electrode by inorganic in-situ adhesion |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101087028A (en) * | 2007-06-06 | 2007-12-12 | 武汉理工大学 | Fuel battery proton exchange film keeping humidity via mineral fiber and its making method |
| CN101562251A (en) * | 2009-05-26 | 2009-10-21 | 华南理工大学 | Proton exchange membrane used for direct methanol fuel cell and preparation method thereof |
| CN103296297A (en) * | 2013-06-07 | 2013-09-11 | 湖北工程学院 | Preparation method of organic-inorganic composite proton exchange membrane for fuel cell |
| CN106630930A (en) * | 2016-09-28 | 2017-05-10 | 成都新柯力化工科技有限公司 | Method for continuously preparing aerogel heat-insulating felt |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150162611A1 (en) * | 2012-07-31 | 2015-06-11 | Sharp Kabushiki Kaisha | Cathode active material for non-aqueous electrolyte secondary battery |
| KR101703055B1 (en) * | 2015-04-20 | 2017-02-06 | 한국과학기술연구원 | 5-(2,6-dioxy-phenyl)tetrazole containing polymer, membrane, electrochemical device including the same and method for preparing the same |
| CN108649240B (en) * | 2018-05-15 | 2021-06-22 | 常州大学 | Fuel cell |
-
2020
- 2020-03-02 CN CN202010134550.8A patent/CN111342099B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101087028A (en) * | 2007-06-06 | 2007-12-12 | 武汉理工大学 | Fuel battery proton exchange film keeping humidity via mineral fiber and its making method |
| CN101562251A (en) * | 2009-05-26 | 2009-10-21 | 华南理工大学 | Proton exchange membrane used for direct methanol fuel cell and preparation method thereof |
| CN103296297A (en) * | 2013-06-07 | 2013-09-11 | 湖北工程学院 | Preparation method of organic-inorganic composite proton exchange membrane for fuel cell |
| CN106630930A (en) * | 2016-09-28 | 2017-05-10 | 成都新柯力化工科技有限公司 | Method for continuously preparing aerogel heat-insulating felt |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111342099A (en) | 2020-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101800321B (en) | Method for preparing membrane electrode for hydrophilicity and hydrophobicity-adjustable proton exchange membrane fuel battery on the basis of catalyst/membrane technology | |
| KR101376362B1 (en) | Polymer Electrolyte Membrane for Fuel Cell and Method of manufacturing the same | |
| Choudhury et al. | High performance and eco-friendly chitosan hydrogel membrane electrolytes for direct borohydride fuel cells | |
| JP2013503436A (en) | POLYMER ELECTROLYTE MEMBRANE FOR FUEL CELL AND METHOD FOR PRODUCING THE SAME | |
| KR101292214B1 (en) | Preparation and characterization of sulfonated polyetheretherketone(SPEEK) nanofibrous membrane for proton exchange membrane fuel cell by electrospinning | |
| CN103515640B (en) | A kind of carbon nanofiber-reinforcedproton proton exchange membrane and preparation method thereof | |
| CN101246966B (en) | Proton exchanging film with inverse gas filter layer and humidification function and method for producing the same | |
| CN108232085A (en) | Poly ion liquid coated bacteria cellulose membrane and preparation method thereof | |
| CN101237055A (en) | A fiber enhanced inorganic adulterated full fluorin proton exchange film | |
| CN100505395C (en) | Self-humidifying proton exchange film fuel cell membrane electrode preparation method | |
| CN106784942B (en) | A kind of high-intensitive, high temperature proton conductive composite membrane of high proton conductivity and its application in high-temperature fuel cell | |
| CN111342099B (en) | Preparation method of proton exchange membrane of fiber framework fuel cell | |
| CN110676495A (en) | Preparation method of nanofiber reinforced proton/alkaline membrane | |
| CN101350415B (en) | Microporous-film-reinforced fluorine-containing cross-linking doping ion-exchange membrane and preparation method thereof | |
| CN100483814C (en) | Method for preparation of membrane electrode of water-keeping proton exchange film fuel cells | |
| CN111129557B (en) | Phosphoric acid modified polybenzimidazole proton exchange membrane and preparation method thereof | |
| CN112323510A (en) | Method for preparing gas diffusion layer carbon paper by continuous coating at low cost | |
| CN101745321B (en) | Micro-porous membrane reinforced perfluorinated cross-linking ion exchange membrane and preparation method thereof | |
| CN100452501C (en) | Modified alcohol-barrier proton exchange film based on hydrophilic area surface and its production | |
| CN113889636B (en) | Nanofiber composite membrane for flow battery and preparation method and application thereof | |
| CN101733019B (en) | Microporous membrane reinforced fluorine-containing crosslinked and doped ion exchange membrane and preparation method thereof | |
| CN108306037B (en) | Diaphragm for zinc-bromine flow battery, preparation method and application thereof | |
| CN114204089A (en) | Proton exchange composite membrane and continuous preparation method thereof | |
| CN101757863B (en) | Fluorine-containing crosslinking ionic membrane reinforced by fibre and preparation method thereof | |
| CN103665417A (en) | Reverse osmosis membranes made with pfsa ionomer and eptfe |
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 |
Effective date of registration: 20220513 Address after: Room 501, unit 2, floor 4, building 10, No. 67, Chaoyang Road, Chaoyang District, Beijing 100020 Patentee after: Zhongshengxin Holding Co.,Ltd. Address before: 610091, Sichuan, Chengdu province Qingyang dragon industrial port, East Sea 4 Patentee before: CHENDU NEW KELI CHEMICAL SCIENCE Co.,Ltd. CHINA |
|
| TR01 | Transfer of patent right |