CN112778558A - Polyether bond-free anion exchange membrane of polyarylpiperidine for fuel cell and preparation method thereof - Google Patents
Polyether bond-free anion exchange membrane of polyarylpiperidine for fuel cell and preparation method thereof Download PDFInfo
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- CN112778558A CN112778558A CN202110160218.3A CN202110160218A CN112778558A CN 112778558 A CN112778558 A CN 112778558A CN 202110160218 A CN202110160218 A CN 202110160218A CN 112778558 A CN112778558 A CN 112778558A
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- exchange membrane
- anion exchange
- polyarylpiperidine
- fuel cell
- bromoethanol
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- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 68
- 239000000446 fuel Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 title description 3
- 229920000570 polyether Polymers 0.000 title description 3
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims abstract description 20
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 claims abstract description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000004305 biphenyl Substances 0.000 claims description 9
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- HDAQULSMVCCKSS-UHFFFAOYSA-N dichloromethanesulfonic acid Chemical compound OS(=O)(=O)C(Cl)Cl HDAQULSMVCCKSS-UHFFFAOYSA-N 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000002791 soaking Methods 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical class [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
-
- 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
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
-
- 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
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
-
- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/72—Derivatisation
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- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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- 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
Abstract
The non-ether bond anion exchange membrane of the polyarylpiperidine for the fuel cell and the preparation method thereof are characterized in that the anion exchange membrane is prepared according to different molar ratios of grafted n-butyl bromide to bromoethanol: wherein the molar ratio of the grafted n-butyl bromide to the bromoethanol is as follows: a: b, a and b are even numbers of 2-8, a + b =10, the main chain of the anion exchange membrane is polybiphenyl piperidine without ether bonds, the alkaline stability is improved, the alkaline resistance is improved, and meanwhile, the microphase separation structure of the anion exchange membrane is changed by grafting bromoethanol and n-butyl bromide with different proportions on the side chain so as to solve the problems of alkaline resistance and conductivity balance of the anion exchange membrane, and the experimental result shows that: the anion exchange membrane of the polyarylpiperidine has ion conductivity of 0.47-0.61S/cm at 80 ℃, and the thickness of the anion exchange membrane is 22-26 mu m.
Description
Technical Field
The invention relates to a polymer chemistry and anion exchange membrane fuel cell, in particular to an ether bond-free anion exchange membrane of polyarylpiperidine for a fuel cell and a preparation method thereof.
Background
In recent years, in order to pursue rapid economic development, fossil energy has been excessively used, and problems such as energy depletion and environmental pollution have been caused. At present, most of research focuses on the field of proton exchange membrane fuel cells, but because the catalysts of the proton exchange membrane fuel cells need to adopt rare noble metals, the popularization and the development of the proton exchange membrane fuel cells are greatly limited. In contrast, the anion exchange membrane fuel cell has the advantages of fast fuel oxidation rate, low liquid alcohol fuel permeability, capability of using non-noble metal catalysts and the like, and has a wide application prospect, so that research on the anion exchange membrane fuel cell is widely concerned by researchers.
The performance of an anion exchange membrane as a core component of an anion exchange membrane fuel cell directly determines the performance of the anion exchange membrane fuel cell. The types of anion exchange membrane materials researched at present are quite various, and polyether sulfone, polyether ketone, polyvinyl alcohol, polyphenyl ether and the like can be used as the anion exchange membrane matrix materials. The anion exchange membrane also has a plurality of advantages, the catalyst with low price can be selected to replace the noble metal catalyst, the use cost of the fuel cell is greatly reduced, the application in a large range can not depend on the existing resource reserves, the popularization and the application in a large area are facilitated, and the anion exchange membrane is undoubtedly a great breakthrough for promoting the rapid development of the fuel cell.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention provides the polyether bond-free anion exchange membrane of the polyarylpiperidine for the fuel cell and the preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme: the anion exchange membrane is prepared according to different molar ratios of grafted n-butyl bromide to bromoethanol:
wherein the molar ratio of the grafted n-butyl bromide to the bromoethanol is as follows: a: b, a and b are both even numbers of 2-8, and a + b = 10;
the structural formula is shown as formula I:
the invention provides a preparation method of an ether bond-free anion exchange membrane of polyarylpiperidine for a fuel cell, which comprises the following steps:
the method comprises the following steps: uniformly mixing biphenyl and N-methyl-4-piperidone in dichloromethane under the condition of ice-water bath; slowly dropwise adding trichloroacetic acid and dichloromethane sulfonic acid, reacting for 4 hours, discharging in a potassium carbonate solution, and obtaining a white solid, namely a main chain of the polyarylpiperidine;
step two: dissolving the white solid obtained in the step one in NMP to obtain a polymer solution;
step three: adding n-butyl bromide and bromoethanol in different molar ratios, wherein the molar ratio of the n-butyl bromide to the bromoethanol is as follows: a: b, a and b are both even numbers of 2-8, and a + b = 10;
step four: and D, performing casting film forming on the film forming solution obtained in the step three by adopting a tape casting method to obtain the polyarylpiperidine anion exchange membrane.
According to the technical scheme: the first step is specifically as follows: adding 0.02mol of biphenyl and 0.024mol of N-methyl-4-piperidone into a reaction vessel, adding a solvent, dissolving and mixing uniformly, cooling to 0 ℃, adding 1.5mL of trichloroacetic acid, slowly adding 14.4mL of trifluoromethanesulfonic acid, reacting for 4 hours, adding a saturated potassium carbonate solution, shearing, boiling, and washing to obtain the main chain of the polyarylpiperidine.
According to the technical scheme: the solvent is dichloromethane.
Has the advantages that: the invention firstly provides an ether bond-free anion exchange membrane of polyarylpiperidine for a fuel cell, the main chain of the anion exchange membrane is polyether-biphenyl piperidine without ether bond, so that the alkaline stability is improved, the alkali resistance is improved, and simultaneously, the microphase separation structure of the anion exchange membrane is changed by grafting bromoethanol and n-butyl bromide with different proportions on the side chain, so as to solve the problems of alkali resistance and conductivity balance of the anion exchange membrane, and the experimental result shows that: the anion exchange membrane of the polyarylpiperidine has ion conductivity of 0.47-0.61S/cm at 80 ℃, and the thickness of the anion exchange membrane is 22-26 mu m.
The invention also provides a preparation method of the polyarylamide ether bond-free anion exchange membrane for the fuel cell, which is used for preparing the polyarylamide ether bond-free anion exchange membrane by utilizing nucleophilic polycondensation.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a nuclear magnetic spectrum of a pure polymer of polyarylate piperidine prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic spectrum of a polyarylpiperidine grafted bromoethanol prepared in example 1 of the present invention;
FIG. 3 shows the NMR spectra of polyarylpiperidine grafted n-butyl bromide prepared in example 1 of the present invention.
Detailed Description
The following describes in further detail embodiments of the present invention with reference to fig. 1-3.
Example one, given by FIGS. 1-3, the present invention provides an ether bond free anion exchange membrane of a polyarylpiperidine for a fuel cell, prepared with a different molar ratio of grafted n-butyl bromide to bromoethanol:
wherein the molar ratio of the grafted n-butyl bromide to the bromoethanol is as follows: a: b, a and b are both even numbers of 2-8, and a + b = 10;
the structural formula is shown as formula I:
examples, given by way of example in fig. 1-3, the present invention provides a method for preparing an ether bond-free anion exchange membrane of a polyarylamide for a fuel cell, comprising the steps of:
the method comprises the following steps: adding 0.02mol (3.084g) of biphenyl, 0.024mol (2.715g) of N-methyl-4-piperidone and 6mL of dichloromethane into a three-necked bottle connected with a mechanical stirrer and 100mL under the condition of ice-water bath, dissolving and uniformly mixing, adding 0.75mL of trifluoroacetic acid and 15mL of trifluoromethanesulfonic acid, reacting for 4 hours, discharging into a saturated potassium carbonate aqueous solution, shearing, boiling for 3 times with distilled water, and drying in an oven at 60 ℃ for 24 hours to obtain the polyarylalpiperidine pure polymer;
step two: dissolving 0.2g of polyarylpiperidine polymer in 8ml of N-methylpyrrolidone (NMP), adding bromoethanol after uniform dissolution, and stirring the mixed solution at 80 ℃ for 24 hours to obtain a film-forming solution;
step three: casting the film-forming solution obtained in the step two on a smooth flat glass plate to form a film, and then drying the film in a 60 ℃ oven for 24 hours to obtain the polyarylpiperidine anion exchange membrane;
step four: the fuel cell was soaked with the polyarylpiperidine anion exchange membrane in saturated NaHCO3 solution for 24 hours, then soaking the membrane in deionized water for 24 hours, changing water for washing for many times during the period to wash off inorganic salts remained on the surface of the membrane, soaking the treated polyarylpiperidine anion exchange membrane in deionized water for standby, the ion conductivity of the polyarylpiperidyl anion exchange membrane at 80 ℃ is 0.054mS/cm, the membrane thickness is 22 μm, tested at 30 ℃, the ionic conductivity of the polyarylpiperidine anion exchange membrane is 0.016 mS/cm, 720 hours after the sodium silicate is soaked, the ion conductivity is still kept about 0.051S/cm at 80 ℃, good alkali-resistant stability is reflected, the nuclear magnetic spectrum of the poly-arylpiperidinyl anion-exchange membrane obtained in the example 1 is shown in figure 2, and as can be seen from figure 2, the poly-arylpiperidinyl anion-exchange membrane is successfully synthesized in the example.
Example two, given by figures 1-3, the present invention provides an ether bond free anion exchange membrane of a polyarylpiperidine for a fuel cell, prepared with a different molar ratio of grafted n-butyl bromide to bromoethanol:
wherein the molar ratio of the grafted n-butyl bromide to the bromoethanol is as follows: a: b, a and b are both even numbers of 2-8, and a + b = 10;
the structural formula is shown as formula I:
examples, given by way of example in fig. 1-3, the present invention provides a method for preparing an ether bond-free anion exchange membrane of a polyarylamide for a fuel cell, comprising the steps of:
the method comprises the following steps: adding 0.02mol (3.084g) of biphenyl, 0.024mol (2.715g) of N-methyl-4-piperidone and 6mL of dichloromethane into a 100mL three-necked bottle connected with a mechanical stirrer under the condition of ice-water bath, dissolving and uniformly mixing, adding 0.063mol (0.75 mL) of trifluoroacetic acid and 15mL of trifluoromethanesulfonic acid, reacting for 4 hours, discharging into a potassium carbonate aqueous solution, shearing, boiling for 3 times with distilled water, and drying in a vacuum oven at 60 ℃ for 24 hours; obtaining a polyarylpiperidine polymer;
step two: dissolving 0.2g of polyarylpiperidine polymer in 8ml of N-methylpyrrolidone (NMP), adding N-butyl bromide after uniform dissolution, and stirring the solution at 80 ℃ for 12 hours to obtain a film forming solution;
step three: casting the film-forming solution obtained in the step two on a glass culture dish to form a film, and then drying the film for 24 hours at room temperature to obtain the polyarylpiperidine anion exchange membrane;
step four: the fuel cell was soaked with the polyarylpiperidine anion exchange membrane in saturated NaHCO3 solution for 24 hours, then soaking the membrane in deionized water for 24 hours, changing water for washing for many times during the period to wash off inorganic salt remained on the surface of the membrane, soaking the pretreated polyarylpiperidine anion exchange membrane in deionized water for standby, testing at 80 ℃, the ion conductivity of the polyarylpiperidyl anion-exchange membrane was 0.43m S/cm, the membrane thickness was 32 μm, as measured at 30 ℃, the ionic conductivity of the polyarylpiperidine anion exchange membrane is 0.011S/cm, 720 hours after the sodium silicate is soaked, the ion conductivity is still kept at 0.038S/cm at 80 ℃, good alkali-resistant stability is reflected, the infrared spectrogram of the poly-arylpiperidinyl anion-exchange membrane obtained in example 1 is shown in figure 2, and as can be seen from figure 3, the poly-arylpiperidinyl anion-exchange membrane is successfully synthesized in the example.
Comparative example 1
The method comprises the following steps: adding 0.02mol (3.084g) of biphenyl, 0.024mol (2.715g) of N-methyl-4-piperidone and 6mL of dichloromethane into a 100mL three-necked bottle connected with a mechanical stirrer under the condition of ice-water bath, dissolving and uniformly mixing, adding 0.063mol (0.75 g) of trifluoroacetic acid and 15mL of trifluoromethanesulfonic acid, reacting for 4 hours, discharging into a potassium carbonate aqueous solution, shearing, boiling for 3 times with distilled water, and drying in a vacuum oven at 60 ℃ for 24 hours; to obtain the polyarylpiperidine polymer.
Step two: 0.2g of polyarylpiperidine polymer is dissolved in 8ml of N-methylpyrrolidone (NMP), N-butyl bromide and bromoethanol are added after uniform dissolution, and the mixed solution is stirred for 12 hours at the temperature of 80 ℃ to obtain a film-forming solution.
Step three: and casting the film-forming solution obtained in the step two on a glass culture dish to form a film, and drying the film for 24 hours at room temperature to obtain the polyarylpiperidine anion exchange membrane.
Step four: soaking the polyarylpiperidine anion exchange membrane for the fuel cell in a saturated NaHO3 solution for 24 hours, then soaking the membrane in ionic water for 24 hours, changing water for washing for many times during the soaking process to wash out inorganic salts remained on the surface of the membrane, soaking the pretreated polyarylpiperidine anion exchange membrane in deionized water for later use, testing at 80 ℃, wherein the ionic conductivity of the polyarylpiperidine anion exchange membrane is 0.54S/cm, the membrane thickness is 27 mu m, testing at 30 ℃, the ionic conductivity of the polyarylpiperidine anion exchange membrane is 0.016S/cm, and after soaking in alkali for 720 hours, the ionic conductivity still maintains 0.052S/cm at 80 ℃, thereby embodying good alkali-resistant stability
Has the advantages that: the invention firstly provides an ether bond-free anion exchange membrane of polyarylpiperidine for a fuel cell, the main chain of the anion exchange membrane is polyether-biphenyl piperidine without ether bond, so that the alkaline stability is improved, the alkali resistance is improved, and simultaneously, the microphase separation structure of the anion exchange membrane is changed by grafting bromoethanol and n-butyl bromide with different proportions on the side chain, so as to solve the problems of alkali resistance and conductivity balance of the anion exchange membrane, and the experimental result shows that: the anion exchange membrane of the polyarylpiperidine has ion conductivity of 0.47-0.61S/cm at 80 ℃, and the thickness of the anion exchange membrane is 22-26 mu m.
The invention also provides a preparation method of the polyarylamide ether bond-free anion exchange membrane for the fuel cell, which is used for preparing the polyarylamide ether bond-free anion exchange membrane by utilizing nucleophilic polycondensation.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The polyether-bond-free anion exchange membrane of the polyarylpiperidine for the fuel cell is characterized in that the anion exchange membrane is prepared according to different molar ratios of grafted n-butyl bromide to bromoethanol:
wherein the molar ratio of the grafted n-butyl bromide to the bromoethanol is as follows: a: b, a and b are both even numbers of 2-8, and a + b = 10;
the structural formula is shown as formula I:
2. the preparation method of the ether bond-free anion exchange membrane of the polyarylpiperidine for the fuel cell is characterized by comprising the following steps:
the method comprises the following steps: uniformly mixing biphenyl and N-methyl-4-piperidone in dichloromethane under the condition of ice-water bath; slowly dropwise adding trichloroacetic acid and dichloromethane sulfonic acid, reacting for 4 hours, discharging in a potassium carbonate solution, and obtaining a white solid, namely a main chain of the polyarylpiperidine;
step two: dissolving the white solid obtained in the step one in NMP to obtain a polymer solution;
step three: adding n-butyl bromide and bromoethanol in different molar ratios, wherein the molar ratio of the n-butyl bromide to the bromoethanol is as follows: a: b, a and b are both even numbers of 2-8, and a + b = 10;
step four: and D, performing casting film forming on the film forming solution obtained in the step three by adopting a tape casting method to obtain the polyarylpiperidine anion exchange membrane.
3. The method for preparing an ether linkage-free anion exchange membrane of a polyarylamide for a fuel cell according to claim 2, wherein the first step is specifically: adding 0.02mol of biphenyl and 0.024mol of N-methyl-4-piperidone into a reaction vessel, adding a solvent, dissolving and mixing uniformly, cooling to 0 ℃, adding 1.5mL of trichloroacetic acid, slowly adding 14.4mL of trifluoromethanesulfonic acid, reacting for 4 hours, adding a saturated potassium carbonate solution, shearing, boiling, and washing to obtain the main chain of the polyarylpiperidine.
4. The method of claim 2, wherein the solvent is dichloromethane.
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| CN114524912A (en) * | 2022-03-15 | 2022-05-24 | 北京化工大学 | Side-chain piperidine cation grafted polybiphenyl alkaline membrane and preparation method thereof |
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