CN113249980A - Fiber-reinforced side chain grafted OH-Anion exchange membrane, preparation and application - Google Patents
Fiber-reinforced side chain grafted OH-Anion exchange membrane, preparation and application Download PDFInfo
- Publication number
- CN113249980A CN113249980A CN202110509323.3A CN202110509323A CN113249980A CN 113249980 A CN113249980 A CN 113249980A CN 202110509323 A CN202110509323 A CN 202110509323A CN 113249980 A CN113249980 A CN 113249980A
- Authority
- CN
- China
- Prior art keywords
- fiber
- anion exchange
- membrane
- side chain
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 51
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 39
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 39
- 239000000835 fiber Substances 0.000 claims abstract description 32
- 239000012528 membrane Substances 0.000 claims abstract description 30
- 239000000446 fuel Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000007731 hot pressing Methods 0.000 claims abstract description 12
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940073608 benzyl chloride Drugs 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 52
- 238000009987 spinning Methods 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 238000005266 casting Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000010041 electrostatic spinning Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 210000000170 cell membrane Anatomy 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000008961 swelling Effects 0.000 abstract description 5
- GIKNHHRFLCDOEU-UHFFFAOYSA-N 4-(2-aminopropyl)phenol Chemical compound CC(N)CC1=CC=C(O)C=C1 GIKNHHRFLCDOEU-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000005956 quaternization reaction Methods 0.000 abstract description 3
- 230000002787 reinforcement Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 125000003342 alkenyl group Chemical group 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000034964 establishment of cell polarity Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/047—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with fluoropolymers
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
-
- 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
- H01M8/1088—Chemical modification, e.g. sulfonation
-
- 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)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention provides a fiber-reinforced side chain grafted OH‑A type anion exchange membrane and a preparation method and application thereof, belonging to the field of fuel cells. Mixing polyvinyl benzyl chloride, TMAQA and dispersant, coating on polytetrafluoroethylene membrane, and hot-pressing to obtain quaternized Cl‑Soaking the composite anion exchange membrane in a solution containing hydroxide ions for alkalization to obtain fiber-reinforced side chain grafted OH‑Type anion exchange membranes. The invention takes polytetrafluoroethylene fiber as a reinforcement and polyethyleneQuaternization reaction and alkalization treatment of alkenyl PVBC and TMAQA to obtain the fiber-reinforced side chain grafted OH‑Type anion exchange membranes. The side chain grafting refers to a compound obtained by quaternization reaction of TMAQA and PVBC, compared with PVBC, the side chain grafting enables new groups to be grafted on the PVBC, swelling of the membrane is obviously inhibited, and therefore the size stability of the membrane is improved.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a fiber-reinforced side chain grafted OH-A type anion exchange membrane and a preparation method and application thereof.
Background
In anion exchange membrane fuel cells, the main role of the Anion Exchange Membrane (AEM) is to conduct OH-And the cathode and anode reaction gases are isolated to avoid short circuit of the battery. A good anion exchange membrane should have a high ionic conductivity and good dimensional stability. Due to OH-Mobility of less than H+Therefore, to obtain higher conductivity, anion exchange membranes generally require higher ion exchange capacity, which, however, leads to too high water uptake and reduced mechanical strength of the membrane, which in turn leads to a reduced effective ion concentration in the membrane, which is detrimental to OH-Conduction of (3). Namely, the anion exchange membrane in the prior art has the problem that the conductivity and the mechanical property can not be simultaneously considered.
Disclosure of Invention
In view of the above, the present invention is directed to provide a fiber-reinforced side-chain grafted OH-A type anion exchange membrane and a preparation method and application thereof. The prepared fiber-reinforced side chain grafted OH-The anion exchange membrane realizes the improvement of the conductivity and the mechanical property.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a fiber-reinforced side chain grafted OH-The preparation method of the anion exchange membrane comprises the following steps:
mixing polyvinyl benzyl chloride, dimethylamino-N-ethyl-N, N-dimethyl hexyl-1-amine (TMAQA) and a dispersing agent to obtain a casting solution;
coating the casting film liquid on a polytetrafluoroethylene membrane for hot pressing to form a membrane, and obtaining quaternized Cl-Composite anion exchange membrane；
Quaternizing said Cl-Soaking the type composite anion exchange membrane in a solution containing hydroxide ions for alkalization treatment to obtain the fiber-reinforced side chain grafted OH-Type anion exchange membranes.
Preferably, the polytetrafluoroethylene-based membrane has a porosity greater than 90%.
Preferably, the thickness of the polytetrafluoroethylene fiber base film is 5-20 μm.
Preferably, the molar ratio of the polyvinyl benzyl chloride to the dimethylamino-N-ethyl-N, N-dimethyl hexyl-1-amine is 1: 1-1: 4.
Preferably, the hydroxide ion-containing solution is an aqueous KOH solution or an aqueous NaOH solution.
Preferably, the concentration of the hydroxide ions in the solution containing the hydroxide ions is 0.1-2 mol.L-1。
Preferably, the pressure of the hot-pressing film forming is 0.5-1.5 MPa, the temperature is 80-120 ℃, and the time is 0.5-1 h.
Preferably, the polytetrafluoroethylene-based membrane is prepared by a method comprising the steps of:
mixing a spinning carrier and a polytetrafluoroethylene aqueous solution to obtain a spinning solution;
carrying out electrostatic spinning on the spinning solution to obtain spinning fibers;
and carrying out heat treatment on the spinning fiber in a protective atmosphere to obtain the polytetrafluoroethylene fiber base film.
The invention also provides the fiber-reinforced side chain grafted OH prepared by the preparation method of the technical scheme-Type anion exchange membranes.
The invention also provides the OH grafted by the fiber reinforced side chain in the technical scheme-The use of a type anion exchange membrane as a fuel cell membrane.
The invention provides a fiber-reinforced side chain grafted OH-The preparation method of the anion exchange membrane comprises the following steps:
mixing polyvinyl benzyl chloride and dimethylamino-N-ethylMixing the base-N, N-dimethyl hexyl-1-amine (TMAQA) and a dispersing agent to obtain a casting solution; coating the casting film liquid on a polytetrafluoroethylene membrane for hot pressing to form a membrane, and obtaining quaternized Cl-Type composite anion exchange membranes; quaternizing said Cl-Soaking the type composite anion exchange membrane in a solution containing hydroxide ions for alkalization treatment to obtain the fiber-reinforced side chain grafted OH-Type anion exchange membranes.
Compared with the prior art, the invention has the following beneficial effects:
the invention takes polytetrafluoroethylene fiber as a reinforcement, and obtains the fiber-reinforced side chain grafted OH through quaternization reaction and alkalization treatment of polyvinyl benzyl chloride (PVBC) and dimethylamino-N-ethyl-N, N-dimethyl hexyl-1-amine (TMAQA)-Type anion exchange membranes. The side chain grafting refers to a compound obtained by quaternization reaction of dimethylamino-N-ethyl-N, N-dimethylhex-1-amine (TMAQA) and polyvinyl benzyl chloride (PVBC), compared with the PVBC, the side chain grafting enables the PVBC to be grafted with new groups, and swelling of the membrane is obviously inhibited, so that the size stability of the membrane is improved, and the integral performance of the anion exchange membrane is improved.
In addition, the invention has the advantages of grafting reaction and amination reaction in the hot-pressing film forming process, environmental protection and no use of toxic raw materials.
Furthermore, the invention adopts the electrostatic spinning process to prepare the polytetrafluoroethylene-based membrane, so that the base membrane has good specific surface area and porosity.
Drawings
FIG. 1 is a diagram of dimethylamino-N-ethyl-N, N-dimethylhex-1-amine1HNMR spectrogram;
FIG. 2 is a cell polarization curve for a cell made with the fiber reinforced side-chain grafted OH-type anion exchange membrane made in example 1.
Detailed Description
The invention provides a preparation method of a fiber-reinforced side chain grafted OH-type anion exchange membrane, which comprises the following steps:
mixing polyvinyl benzyl chloride, dimethylamino-N-ethyl-N, N-dimethyl hexyl-1-amine (TMAQA) and a dispersing agent to obtain a casting solution;
coating the casting film liquid on a polytetrafluoroethylene membrane for hot pressing to form a membrane, and obtaining quaternized Cl-Type composite anion exchange membranes;
quaternizing said Cl-Soaking the type composite anion exchange membrane in a solution containing hydroxide ions for alkalization treatment to obtain the fiber-reinforced side chain grafted OH-Type anion exchange membranes.
The source of the raw material used in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used.
The invention mixes polyvinyl benzyl chloride, dimethylamino-N-ethyl-N, N-dimethyl hexyl-1-amine and dispersant to obtain casting film liquid.
In the invention, the molar ratio of the polyvinyl benzyl chloride to the dimethylamino-N-ethyl-N, N-dimethyl hexyl-1-amine is preferably 1: 1-1: 4.
In the present invention, the dimethylamino-N-ethyl-N, N-dimethylhex-1-amine (TMAQA) is preferably obtained by reacting N, N', -tetramethyl-1, 6-hexanediamine (TMHDA) with ethyl bromide, and the specific steps are preferably as follows:
dissolving 6mLN, N, N ', N', -tetramethyl-1, 6-hexanediamine (TMHDA) in 75mL of ethanol at room temperature, dropwise adding 2.1mL of bromoethane under the argon atmosphere, reacting for 48 hours, then, performing rotary evaporation to remove ethanol solvent, washing residual solids for a plurality of times with diethyl ether, filtering, placing filter cakes in acetone, fully dissolving, filtering, and performing rotary evaporation on filtrate to obtain a white solid product, namely the dimethylamino-N-ethyl-N, N-dimethyl hexan-1-amine (TMAQA).
In the present invention, the dimethylamino-N-ethyl-N, N-dimethylhex-1-amine (TMAQA) is prepared according to the following formula:
in the present invention, the dispersant preferably includes one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and chloroform, and when the dispersant is preferably a mixture of a plurality of dispersants, the present invention is not particularly limited with respect to the kind and the amount ratio of each substance in the mixture, and the mixture may be used in any ratio. The dosage of the dispersant is not specially limited, and the polyvinyl benzyl chloride and the dimethylamino-N-ethyl-N, N-dimethyl hexyl-1-amine can be completely dissolved.
After obtaining the membrane casting solution, coating the membrane casting solution on a polytetrafluoroethylene membrane for hot-pressing membrane forming to obtain quaternized Cl-A composite anion exchange membrane.
The present invention is not particularly limited to the specific manner of coating, and may be carried out by a method known to those skilled in the art.
In the present invention, the porosity of the polytetrafluoroethylene-based film is preferably greater than 90%.
In the invention, the thickness of the polytetrafluoroethylene fiber base film is preferably 5-20 μm.
In the present invention, the polytetrafluoroethylene-based film is preferably produced by a method comprising the steps of:
mixing a spinning carrier and a polytetrafluoroethylene aqueous solution to obtain a spinning solution;
carrying out electrostatic spinning on the spinning solution to obtain spinning fibers;
and carrying out heat treatment on the spinning fiber in a protective atmosphere to obtain the polytetrafluoroethylene fiber base film.
The invention mixes spinning carrier and water solution of polytetrafluoroethylene to obtain spinning solution.
In the present invention, the spinning carrier is preferably polyvinylpyrrolidone, polyoxyethylene, polyvinyl alcohol, polyacrylonitrile or polyaniline.
In the invention, the mass ratio of the polytetrafluoroethylene to the spinning carrier in the aqueous solution of polytetrafluoroethylene is preferably 30: 1-80: 1, and more preferably 50: 1. In the invention, the mass percentage of the polytetrafluoroethylene in the aqueous solution of polytetrafluoroethylene is preferably 5-60%.
After the spinning solution is obtained, the spinning solution is subjected to electrostatic spinning to obtain the spinning fiber.
In the present invention, the parameters of the electrospinning preferably include: the voltage is 8-25 kV, preferably 21kV, the distance from the needle head to the receiving plate is 5-20 cm, the relative humidity is 10-30%, the flow rate of the spinning solution is 0.2-1 mL/h, and the spinning time is 0.5-5 h, more preferably 1 h.
After the spinning fiber is obtained, the spinning fiber is subjected to heat treatment in a protective atmosphere to obtain the polytetrafluoroethylene fiber base film.
In the invention, the heat treatment is preferably carried out in a nitrogen atmosphere, the temperature of the heat treatment is preferably 150-390 ℃, more preferably 300-370 ℃, the time is preferably 0.5-5 h, more preferably 1-3 h, and the heat treatment is used for removing spinning carriers in spinning fibers to obtain the polytetrafluoroethylene fiber base film with high porosity.
In the invention, the pressure of the hot-pressing film forming is preferably 0.5-1.5 MPa, more preferably 1MPa, the temperature is preferably 80-120 ℃, more preferably 100 ℃, and the time is preferably 0.5-1 h.
To give quaternized Cl-After forming the composite anion exchange membrane, the invention quaternizes the Cl-Soaking the type composite anion exchange membrane in a solution containing hydroxide ions for alkalization treatment to obtain the fiber-reinforced side chain grafted OH-Type anion exchange membranes.
In the present invention, the hydroxide ion-containing solution is preferably an aqueous KOH solution or an aqueous NaOH solution.
In the present invention, the concentration of hydroxide ions in the hydroxide ion-containing solution is preferably 0.1 to 2 mol.L-1。
In the invention, the soaking is preferably carried out for 24-48 h, more preferably 36h under the condition of room temperature, and the soaking is used for carrying out ion exchange to exchange chloride ions into hydroxide ions.
In the present invention, the washing is preferably water washing, which has the effect of washing the surface with residual KOH solution or NaOH solution.
The invention also provides the fiber-reinforced side chain grafted OH prepared by the preparation method of the technical scheme-Type anion exchange membranes.
The invention also provides the OH grafted by the fiber reinforced side chain in the technical scheme-The use of a type anion exchange membrane as a fuel cell membrane. The invention is not particularly limited to the specific manner of use described, as such may be readily adapted by those skilled in the art.
To further illustrate the invention, the following examples are given to provide fiber-reinforced pendant-grafted OH-The anion exchange membranes of the type and the methods for their preparation and use are described in detail but they are not to be understood as limiting the scope of the invention.
Example 1
Uniformly mixing polyvinylpyrrolidone, a polytetrafluoroethylene aqueous solution (the mass fraction is 60%) and deionized water, wherein the mass ratio of polytetrafluoroethylene to polyvinylpyrrolidone is 50:1, carrying out electrostatic spinning (the voltage is 21kV, the advancing speed of a spinning solution is 0.2mL/h, and the spinning time is 1h), collecting spinning fibers, and sintering in a nitrogen-filled oven at 370 ℃ for 30 minutes to obtain a polytetrafluoroethylene fiber base film, wherein the porosity is 92%, and the thickness is 5 microns.
dimethylamino-N-ethyl-N, N-dimethylhex-1-amine (TMAQA) was prepared as follows:
dissolving 6mLN, N, N ', N', -tetramethyl-1, 6-hexanediamine (TMHDA) in 75mL of ethanol at room temperature, dropwise adding 2.1mL of bromoethane under the argon atmosphere, reacting for 48 hours, then, performing rotary evaporation to remove ethanol solvent, washing residual solids for a plurality of times with diethyl ether, filtering, placing filter cakes in acetone, fully dissolving, filtering, and performing rotary evaporation on filtrate to obtain a white solid product, namely the dimethylamino-N-ethyl-N, N-dimethyl hexan-1-amine (TMAQA).
The prepared TMAQA is subjected to1HNMR characterization, the spectrogram is shown in figure 1.
PVBC was dissolved in NMP at a concentration of 0.1g/mL in the PVBC solution. After the solution was stirred and dissolved, 2mL of PVBC solution was added to TMAQA and stirred at room temperature for 20 seconds to obtain a casting solution. Wherein the PVBC: TMHDA ═1:2 (molar ratio). Spreading the casting film liquid on a polytetrafluoroethylene membrane, and carrying out hot pressing for 1h by using an oil press (the pressure is 1MPa, the temperature is 100 ℃) to form the membrane. Then the membrane is soaked in 1 mol.L under the condition of vacuum pumping-1The KOH solution is added for 36 hours, and the residual KOH solution on the surface is washed by deionized water to obtain the fiber reinforced side chain grafted OH-Type anion exchange membranes.
The resulting fiber-reinforced side-chain grafted OH-The anion exchange membrane has good dimensional stability and mechanical strength, the swelling rate is 2.1 percent, the mechanical strength is 150.5MPa, and the prepared fiber reinforced side chain grafted OH-The type anion exchange membrane is used as a fuel cell diaphragm to be assembled into a hydrogen-oxygen fuel cell, the performance of the cell is good, and the room-temperature conductivity is 30mS cm-1A conductivity at 80 ℃ of 65mS · cm-1。
FIG. 2 shows side-chain grafted OH with fiber reinforcement made in example 1-The cell polarization curve of the cell prepared by the anion exchange membrane is shown. The performance test of the cell is that under the condition of full humidification at 60 ℃, hydrogen and oxygen are heated and humidified in a humidification tank and then are introduced into the cell, and the flow rates of the hydrogen and the oxygen are respectively fixed at 100 and 200 mL/min-1And the back pressure on both sides is 0.2MPa, thus the fiber reinforced side chain grafted OH provided by the invention-The anion exchange membrane is suitable for use in an anion exchange membrane fuel cell.
Example 2
Uniformly mixing polyvinylpyrrolidone, a polytetrafluoroethylene aqueous solution (the mass fraction is 60%) and deionized water, wherein the mass ratio of polytetrafluoroethylene to polyvinylpyrrolidone is 30:1, carrying out electrostatic spinning (the voltage is 25kV, the advancing speed of a spinning solution is 1mL/h, and the spinning time is 5h), collecting spinning fibers, and sintering in a nitrogen-filled oven at 390 ℃ for 5h to obtain a polytetrafluoroethylene fiber base film, wherein the porosity is 91%, and the thickness is 20 microns.
TMAQA was prepared as in example 1.
PVBC was dissolved in chloroform at a concentration of 0.1g/mL in the PVBC solution. After the solution was stirred and dissolved, 2mL of PVBC solution was added to TMAQA and stirred at room temperature for 20 seconds to obtain a casting solution. Wherein the PVBC: TMHDA is 1:4 (molar ratio). Casting filmSpreading the solution on a polytetrafluoroethylene membrane, and hot-pressing for 1h to form the membrane by using an oil press (the pressure is 1.5MPa, the temperature is 80 ℃). Then the membrane is soaked in 2 mol.L under the condition of vacuum pumping-1And (4) adding the KOH solution for 36h, and washing the residual KOH solution on the surface by using deionized water to obtain the fiber-reinforced side chain type anion exchange membrane.
The obtained fiber-reinforced side chain type anion-exchange membrane shows good dimensional stability and mechanical strength, the swelling ratio is 2.4%, the mechanical strength is 148.6MPa, and the assembled hydrogen-oxygen fuel cell has good performance. OH grafted with the prepared fiber-reinforced side chain-The type anion exchange membrane is used as a fuel cell diaphragm to be assembled into a hydrogen-oxygen fuel cell, the performance of the cell is good, and the room-temperature conductivity is 24mS cm-1And a conductivity of 57mS · cm at 80 DEG C-1。
Example 3
As in example 2, the only difference is PVBC: TMHDA ═ 1:1 (molar ratio)
The obtained fiber-reinforced side chain type anion exchange membrane shows good dimensional stability and mechanical strength, the swelling ratio is 2.7%, the mechanical strength is 147.4MPa, and the assembled hydrogen-oxygen fuel cell has good performance. OH grafted with the prepared fiber-reinforced side chain-The type anion exchange membrane is used as a fuel cell diaphragm to be assembled into a hydrogen-oxygen fuel cell, the performance of the cell is good, and the room-temperature conductivity is 20mS cm-1Conductivity at 80 ℃ of 54mS · cm-1。
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. Fiber-reinforced side chain grafted OH-The preparation method of the anion exchange membrane is characterized by comprising the following steps:
mixing polyvinyl benzyl chloride, dimethylamino-N-ethyl-N, N-dimethyl hexyl-1-amine and a dispersing agent to obtain a casting solution;
coating the casting film liquid on a polytetrafluoroethylene membrane for hot pressing to form a membrane, and obtaining quaternized Cl-Type composite anion exchange membranes;
quaternizing said Cl-Soaking the type composite anion exchange membrane in a solution containing hydroxide ions for alkalization treatment to obtain the fiber-reinforced side chain grafted OH-Type anion exchange membranes.
2. The method of claim 1, wherein the polytetrafluoroethylene-based membrane has a porosity greater than 90%.
3. The method according to claim 1 or 2, wherein the polytetrafluoroethylene fiber-based film has a thickness of 5 to 20 μm.
4. The method according to claim 1, wherein the molar ratio of the polyvinylbenzyl chloride to dimethylamino-N-ethyl-N, N-dimethylhex-1-amine is 1:1 to 1: 4.
5. The method according to claim 1, wherein the hydroxide ion-containing solution is an aqueous KOH solution or an aqueous NaOH solution.
6. The method according to claim 1 or 5, wherein the concentration of hydroxide ions in the hydroxide ion-containing solution is 0.1 to 2 mol-L-1。
7. The preparation method according to claim 1, wherein the hot-pressing film forming pressure is 0.5-1.5 MPa, the temperature is 80-120 ℃, and the time is 0.5-1 h.
8. The production method according to claim 1, wherein the polytetrafluoroethylene-based film is produced by a method comprising the steps of:
mixing a spinning carrier and a polytetrafluoroethylene aqueous solution to obtain a spinning solution;
carrying out electrostatic spinning on the spinning solution to obtain spinning fibers;
and carrying out heat treatment on the spinning fiber in a protective atmosphere to obtain the polytetrafluoroethylene fiber base film.
9. The preparation method of any one of claims 1 to 8, wherein the prepared fiber-reinforced side chain grafted OH-Type anion exchange membranes.
10. The fiber reinforced side-chain grafted OH of claim 9-The use of a type anion exchange membrane as a fuel cell membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110509323.3A CN113249980A (en) | 2021-05-11 | 2021-05-11 | Fiber-reinforced side chain grafted OH-Anion exchange membrane, preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110509323.3A CN113249980A (en) | 2021-05-11 | 2021-05-11 | Fiber-reinforced side chain grafted OH-Anion exchange membrane, preparation and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113249980A true CN113249980A (en) | 2021-08-13 |
Family
ID=77222582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110509323.3A Pending CN113249980A (en) | 2021-05-11 | 2021-05-11 | Fiber-reinforced side chain grafted OH-Anion exchange membrane, preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113249980A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159974A (en) * | 2011-12-19 | 2013-06-19 | 中国科学院大连化学物理研究所 | Preparation method of crosslinking type polymer anion exchange membrane |
| CN109384944A (en) * | 2017-08-02 | 2019-02-26 | 中国科学院大连化学物理研究所 | Cross-linking type block polymer anion-exchange membrane and its preparation and application |
| CN111244512A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Ultrathin cross-linked composite enhanced polymer anion exchange membrane and preparation method and application thereof |
| CN112160039A (en) * | 2020-08-19 | 2021-01-01 | 浙江理工大学 | Preparation method of polytetrafluoroethylene fiber with porous structure |
-
2021
- 2021-05-11 CN CN202110509323.3A patent/CN113249980A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159974A (en) * | 2011-12-19 | 2013-06-19 | 中国科学院大连化学物理研究所 | Preparation method of crosslinking type polymer anion exchange membrane |
| CN109384944A (en) * | 2017-08-02 | 2019-02-26 | 中国科学院大连化学物理研究所 | Cross-linking type block polymer anion-exchange membrane and its preparation and application |
| CN111244512A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Ultrathin cross-linked composite enhanced polymer anion exchange membrane and preparation method and application thereof |
| CN112160039A (en) * | 2020-08-19 | 2021-01-01 | 浙江理工大学 | Preparation method of polytetrafluoroethylene fiber with porous structure |
Non-Patent Citations (1)
| Title |
|---|
| 张建军: "阴离子交换膜制备及碱性燃料电池", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109390617B (en) | Cross-linked polybenzimidazole basic anion exchange membrane and preparation and application thereof | |
| CN109638326B (en) | Preparation method of polybenzimidazole anion exchange membrane | |
| CN104466063B (en) | Poly-dopamine surface modification polyether sulfone nanofiber composite diaphragm, preparation method and application | |
| CN111525185A (en) | Flexible zinc ion battery polymer electrolyte and preparation and application thereof | |
| CN113667161B (en) | Preparation method of modified poly (vinylidene fluoride-co-hexafluoropropylene) -grafted vinyl imidazole anion exchange membrane | |
| CN108084302A (en) | A kind of preparation method of alkalescence anion-exchange resin | |
| CN102532572B (en) | Preparation method of quaternized chitosan anion hybrid membrane doped with positive polystyrene latex | |
| CN115414791B (en) | Surface quaternization modified nanofiltration membrane, preparation and application of surface quaternization modified nanofiltration membrane in separation of magnesium and lithium in salt lake | |
| CN101949047B (en) | Preparation method for bipolar membrane modified by solid polymer electrolyte | |
| Zhou et al. | Application of a novel PUB enhanced semi‐interpenetrating chitosan‐based anion exchange membrane | |
| CN113402725B (en) | Preparation method and application of heteropoly acid modified metal organic framework compound | |
| CN113235300B (en) | Preparation method of high-temperature-resistant lithium ion battery composite diaphragm | |
| CN107666004B (en) | Simple and green cross-linked composite anion exchange membrane and preparation method thereof | |
| CN108461792B (en) | Composite alkaline polymer electrolyte membrane and preparation method and application thereof | |
| CN113249980A (en) | Fiber-reinforced side chain grafted OH-Anion exchange membrane, preparation and application | |
| CN112201858A (en) | Three-dimensional porous alginic acid fiber membrane skeleton reinforced composite polymer solid electrolyte membrane and preparation method and application thereof | |
| CN108823983B (en) | Preparation method of quaternized polyvinyl alcohol/chitosan electrostatic spinning solid electrolyte film | |
| CN114696035B (en) | Cellulose-based composite diaphragm for lithium ion battery and preparation method thereof | |
| JP2013229325A (en) | Polymer electrolyte membrane, membrane electrode assembly and fuel cell | |
| CN111342095A (en) | High-temperature fuel cell proton exchange membrane and preparation method thereof | |
| CN115763961A (en) | Epoxy resin-based gel electrolyte and preparation method and application thereof | |
| CN113527725A (en) | Preparation method of modified polyvinyl alcohol-based gel electrolyte membrane for lithium-sulfur battery | |
| CN109428036B (en) | Preparation method of lithium-oxygen battery diaphragm | |
| CN112751067A (en) | Cross-linked anion exchange membrane and preparation method and application thereof | |
| CN108598535B (en) | Polyacrylonitrile and ionic liquid composite anion exchange membrane for 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210813 |