CN113078341A - Polyether-ether-ketone/cationic metal-organic framework crosslinked film and preparation method thereof - Google Patents
Polyether-ether-ketone/cationic metal-organic framework crosslinked film and preparation method thereof Download PDFInfo
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 85
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 85
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 53
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 14
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000012528 membrane Substances 0.000 claims abstract description 47
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 17
- 239000000446 fuel Substances 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 50
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 44
- 238000005266 casting Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 13
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical group CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 6
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N CHCl3 Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- HKCNCNXZAZPKDZ-UHFFFAOYSA-N (4,4-difluorocyclohexa-1,5-dien-1-yl)-phenylmethanone Chemical compound C1=CC(F)(F)CC=C1C(=O)C1=CC=CC=C1 HKCNCNXZAZPKDZ-UHFFFAOYSA-N 0.000 claims description 3
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- 230000007480 spreading Effects 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims 4
- 229930185605 Bisphenol Natural products 0.000 claims 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- SUNVJLYYDZCIIK-UHFFFAOYSA-N durohydroquinone Chemical compound CC1=C(C)C(O)=C(C)C(C)=C1O SUNVJLYYDZCIIK-UHFFFAOYSA-N 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 9
- 150000001768 cations Chemical group 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000012456 homogeneous solution Substances 0.000 description 8
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000002047 photoemission electron microscopy Methods 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/08—Fuel cells with aqueous electrolytes
- H01M8/083—Alkaline fuel cells
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Fuel Cell (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a polyether-ether-ketone/cationic metal-organic framework crosslinked membrane for a fuel cell, namely imidazole functionalized polyether-ether-ketone and cationic D-UiO-66-NH2The mass ratio is 1: 0.005-0.02. The imidazole monomer used in the prepared imidazole functionalized polyether ether ketone contains double bonds, can enable the membrane to inhibit the excessive swelling of the membrane through crosslinking, and the prepared cationic D-UiO-66-NH2The cation group on the anion exchange membrane can help to construct an ion transmission channel and further improve the ion conductivity, and experimental results show that the ion conductivity of the anion exchange membrane is 0.026-0.073S cm at 80 DEG C‑1The thickness of the anion exchange membrane is 16-31 μm.
Description
Technical Field
The invention belongs to the field of polymer chemistry and alkaline fuel cells, and particularly relates to a polyether-ether-ketone/cationic metal-organic framework crosslinked membrane and a preparation method thereof.
Background
Fuel cells are electrochemical devices that convert chemical energy into electrical energy. Fuel cells can be divided into Proton Exchange Membrane Fuel Cells (PEMFCs) and Anion Exchange Membrane Fuel Cells (AEMFCs). Commercial PEMs (such as Nafion) are known for high ionic conductivity and excellent physicochemical properties (dimensional stability and mechanical properties). However, expensive catalysts, high fuel permeability and the manufacturing cost of Nafion have been obstacles to the large-scale spread of PEMFCs. AEMFCs are becoming the focus of much attention for many advantages, including improved oxygen reduction kinetics, reduced corrosive oxidation in alkaline media, and the use of non-noble metal catalysts. As a core component of the AEMFC; the important role of Anion Exchange Membranes (AEMs) is to block fuel and oxidant between the anode and the cathode and to simultaneously transport OH through the membrane-Ions;
currently, the main research direction for AEMs is still to be developed for the aspects of ion conductivity, dimensional stability and alkali resistance stability of the membrane. Polyether ether ketone (PEEK) has excellent thermal stability, good mechanical properties, chemical stability and the like, and is a polymer commonly used in AEMs; conjugated pi bonds exist in an N heterocyclic ring structure in imidazole groups, so that the imidazole grafted membrane has high ionic conductivity, the chemical stability in an alkaline environment is superior to that of other cationic groups, and meanwhile, imidazole also has good thermal stability, but the cationic groups have hydrophilicity and can directly influence the dimensional stability of the membrane after being introduced too much. 1-vinyl imidazole is selected as a functional group, the molecule not only contains imidazole cations, but also contains a double-bond structure, and the effect of inhibiting the swelling of the membrane can be achieved through double-bond crosslinking. Metal-organic frameworks (MOFs) are used as porous crystal materials, and have high mechanical stability and thermal stability, designable pore size and large specific surface area. To further improve the ionic conductivity of the membrane, we introduced into the membrane cationic MOFs, which can help transport OH as cationic groups-Can effectively compensate the influence of crosslinking on the ionic conductivityAnd (6) sounding.
Disclosure of Invention
The invention aims to provide a polyether-ether-ketone/cationic metal-organic framework cross-linked membrane and a preparation method thereof, and aims to improve the ionic conductivity while maintaining good stability of the membrane. According to the invention, cationic MOFs are doped into the polyether-ether-ketone polymer, so that the cross-linked membrane can keep good dimensional stability and high ionic conductivity.
The invention is realized by the following technical scheme:
the invention provides a preparation method of a polyether-ether-ketone/cationic metal-organic framework cross-linked membrane, wherein the cross-linked membrane is prepared from polyether-ether-ketone functionalized by imidazole and cationic MOF (D-UiO-66-NH)2) The composition is characterized in that the addition content of the cationic MOF is 0.5-2% of the mass of the polymer.
The invention firstly provides a preparation method of a polyether-ether-ketone/cationic metal-organic framework cross-linked membrane, which comprises the following steps:
A. preparing imidazole functionalized polyether-ether-ketone into imidazole functionalized polyether-ether-ketone solution;
B. cationic MOF (D-UiO-66-NH)2) Adding the solution obtained in the step A to prepare a membrane casting solution;
C. b, spreading the membrane casting solution obtained in the step B to obtain a cross-linked polyether-ether-ketone/cationic metal-organic framework cross-linked membrane for the fuel cell;
in the above scheme, the preparation method of the imidazole-functionalized polyetheretherketone solution in step a comprises:
adding imidazole functionalized polyether-ether-ketone into an NMP solvent, and stirring for several hours at room temperature to obtain an imidazole functionalized polyether-ether-ketone solution, wherein NMP represents N-methyl-2-pyrrolidone, and the mass volume concentration of the solution is 0.05 g/mL;
the preparation method of the casting solution obtained in the step B in the scheme comprises the following steps:
cationic MOF (D-UiO-66-NH)2) Adding into imidazole functionalized polyether ether ketone solution, ultrasonically dispersing for several hours, continuously stirring for several days, adding BPO (benzoyl peroxide) and cationic MOF (metal organic framework) to stir and dissolve to obtain a membrane casting solutionThe adding content is 0.5-2% of the mass of the polymer;
the specific implementation method of the step C in the scheme comprises the following steps:
and casting the casting solution on a clean glass plate, drying for several hours in a constant-temperature oven, demoulding, performing alkalization treatment, and washing with deionized water to obtain the cross-linked polyether-ether-ketone/metal organic framework cross-linked membrane.
In the above scheme, the preparation method of the imidazole functionalized polyether ether ketone comprises the following steps:
D. synthesizing polyether-ether-ketone;
E. synthesizing brominated polyether-ether-ketone;
F. and (3) synthesizing imidazole functionalized polyether ether ketone.
In the scheme, the synthesis method of the polyether-ether-ketone in the step D comprises the following steps:
the methyl hydroquinone and the 4, 4-difluorobenzophenone are added into a three-neck flask and uniformly mixed, then a salt forming agent, a water-carrying agent and a solvent are added into the three-neck flask, the water-carrying agent is discharged after the water-carrying agent is refluxed, and the polyether-ether-ketone is obtained by heating reaction. The salt forming agent is anhydrous potassium carbonate, the water carrying agent is toluene, and the solvent is NMP;
in the scheme, the synthesis method of the brominated polyether-ether-ketone in the step E comprises the following steps:
d, adding the polyether-ether-ketone obtained in the step D into a three-neck flask, adding 1,1,2, 2-tetrachloroethane as a solvent, dissolving under the protection of nitrogen, then adding a brominating agent and an initiator, heating for reaction after complete dissolution, pouring the obtained solution into ethanol, and washing to obtain brominated polyether-ether-ketone;
in the above scheme, the synthesis method of imidazole-functionalized polyether ether ketone in step F comprises:
adding brominated polyether-ether-ketone and a solvent NMP into a three-neck flask, uniformly mixing, adding excessive 1-vinyl imidazole, heating under the protection of nitrogen for reaction for several hours, cooling to room temperature, pouring the obtained solution into ethanol for washing, and drying to obtain the imidazole functionalized polyether-ether-ketone.
In the above scheme, the cationic MOF (D-UiO-66-NH)2) The preparation method comprises the following steps:
G、D-UiO-66-NH2synthesizing;
H、D-UiO-66-NH2the cation of (1) is converted into cation.
D-UiO-66-NH in step G in the scheme2The synthesis method comprises the following steps:
adding amino terephthalic acid, 2, 5-pyridinedicarboxylic acid and zirconium tetrachloride into DMF (N, N-dimethylformamide), adding acetic acid as a mineralizer, stirring at room temperature, transferring into a reaction kettle with a polytetrafluoroethylene lining, heating for reaction, cooling the reaction kettle to room temperature, and centrifugally washing the obtained solution to obtain a light yellow solid;
cationized D-UiO-66-NH described in step H of the above scheme2The synthesis method comprises the following steps:
DMF and CHCl were used before synthesis3The resulting MOF was subjected to guest-exchange activation, followed by soaking the crystals in DMF and CHCl3Medium and regular replacement of fresh CHCl3Activated D-UiO-66-NH2Immersion in CH3Adding the mixture into a mixed solution of I/DMF, finally heating in vacuum, washing with DMF, and drying in vacuum to obtain the cationic D-UiO-66-NH2。
The invention has the following beneficial effects:
the invention firstly provides a polyether-ether-ketone/cationic metal-organic framework crosslinked membrane, wherein the mass ratio of imidazole functionalized polyether-ether-ketone to cationic MOF is 1:0.5% -2%. Prepared cationic UiO-66-NH2The imidazole group on the ionic liquid can help to construct a rigid auxiliary ion transmission channel, and further improve the ionic conductivity. The experimental result shows that the ion conductivity of the anion exchange membrane is 0.025S cm at 80 DEG C-1-0.073 S cm-1The thickness of the anion exchange membrane is 16-31 μm.
Drawings
FIG. 1 is a nuclear magnetic spectrum of pure polyetheretherketone, brominated polyetheretherketone, imidazole functionalized polyetheretherketone in the present invention;
fig. 2 is a curve of ion conductivity with temperature variation of the imidazole functionalized polyether ether ketone membrane and the membrane with different addition content of cationic MOF in the invention.
Detailed description of the invention
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of examples, but it is to be understood that the description is intended to illustrate further features and advantages of the invention, and not to limit the scope of the claims which follow;
a preparation method of a polyether-ether-ketone/cationic metal organic framework anion exchange membrane for a fuel cell comprises the following specific steps:
(1) 4.364 g of 4, 4-difluorobenzophenone, 2.483 g of methylhydroquinone and 3.306 g of salt former K2CO3Adding NMP solvent and toluene as water-carrying agent into a reaction container, respectively, uniformly mixing, heating the obtained mixture under the protection of nitrogen, and heating to 110 deg.C oCThen slowly raising the temperature, observing the turbidity of the toluene in the water carrying device, and continuing stirring for 4h at the temperature (the temperature of the carried water is generally 124- oCIn between) this operation is mainly intended to remove the water from the mixture. And after the water is brought, raising the temperature of the solution to 165 ℃, continuing to react for 3-6 h, pouring the solution into water when the viscosity of the solution is remarkably increased, washing the formed gray polymer for about 3 times by deionized water, and drying to obtain a gray product of polyether-ether-ketone. Wherein NMP is N-methyl pyrrolidone;
(2) adding 1 g of the polyether-ether-ketone obtained in the step into a three-neck bottle, adding 1,1,2, 2-tetrachloroethane as a solvent, stirring and dissolving a polymer under the protection of nitrogen, adding 1.19 g of brominating agent NBS and 0.08 g of BPO as initiators after the polymer is completely dissolved, continuously dissolving, heating the mixed solution after the polymer is completely dissolved, slowly heating the mixed solution to 80 ℃ from normal temperature oCAnd reacting for 5h under the condition. And (3) cooling the mixed solution to room temperature, and then pouring the solution into ethanol for washing for 3 times to obtain a yellow precipitate, namely brominated polyether-ether-ketone. Wherein NBS is N-bromosuccinimide, BPO is benzoyl peroxide;
(3) adding 5 g of brominated polyether ether ketone and 50 ml of NMP solvent into a 100 ml three-neck bottle, after uniformly dissolving, dripping 5.2 ml of excessive 1-vinyl imidazole into a reaction container, and raising the temperature of the mixed solution from normal temperature to 45 ℃ under the nitrogen atmosphere oCAnd then reacted for 12 h. After the reaction is finished, cooling the solution to room temperature, pouring the solution into absolute ethyl alcohol for washing for multiple times, and then drying to obtain a brown solid, namely the 1-vinyl imidazole graft polymer;
(4) 0.1413 g of aminoterephthalic acid, 0.0430 g of 2, 5-pyridinedicarboxylic acid and 0.2396 g of zirconium tetrachloride were added to 30mL of DMF (N, N-dimethylformamide), 0.663 g of acetic acid was added as a mineralizer, the mixture was stirred at room temperature for 10min and transferred to a 50 mL polytetrafluoroethylene-lined reaction vessel, 120 g of which was stirred at room temperature oCHeating for 24 h, cooling the reaction kettle to room temperature, centrifuging the obtained solution for 10min, repeatedly washing and filtering with N, N-dimethylformamide, and drying under vacuum to obtain light yellow solid product UiO-66-NH2；
(5) DMF and CHCl were used before synthesis3The resulting MOF is subjected to guest-exchange activation, followed by crystallization at 80 oCDMF and CHCl3Soaking for three days, adding fresh CHCl every 24 h3Activated D-UiO-66-NH2Immersion in CH3Adding I/DMF (1:10) mixed solution for five days, finally heating under vacuum at 358K, washing the obtained solution with DMF, and drying under vacuum to obtain cationic D-UiO-66-NH2。
Example 1
(1) 0.5 g of imidazole-functionalized polyether ether ketone was weighed into a beaker, 10 mL of NMP solvent was added, and the mixture was stirred at room temperature to obtain a homogeneous solution. Wherein NMP represents N-methyl-2-pyrrolidone;
(2) casting the deposition solution obtained in step (1) onto a clean glass plate at 80 deg.CoDrying for 48 hours, naturally cooling to room temperature, then demoulding in water, treating for 24 hours by using sodium hydroxide, and then repeatedly washing in deionized water to remove residual NaOH, thus obtaining the cross-linked polyether-ether-ketone/cationic metal-organic framework cross-linked membrane;
the resulting crosslinked film was processed at 30 oCThe ionic conductivity of the material is 0.021S cm-1The ionic conductivity of the conductive polymer is 0.048S cm when the conductive polymer is tested at 80 DEG C-1The film thickness was 23 μm.
Example 2
(1) 0.5 g of imidazole-functionalized polyether ether ketone was weighed into a beaker, 10 mL of NMP solvent was added, and the mixture was stirred at room temperature to obtain a homogeneous solution. Wherein NMP represents N-methyl-2-pyrrolidone;
(2) weighing 0.0025 g of cationic D-UiO-66-NH2And (2) adding the mixture into the uniform solution obtained in the step (1). Ultrasonically dispersing for 4 hours, then continuously stirring for 48 hours, adding BPO and stirring for two hours to obtain film forming liquid. Wherein the mass ratio of the CMOF to the imidazole functionalized polyether ether ketone in the obtained casting solution is 0.5%;
(3) casting the deposition solution obtained in step (2) onto a clean glass plate at 80 deg.CoDrying for 48 hours, naturally cooling to room temperature, then demoulding in water, treating for 24 hours by using sodium hydroxide, and then repeatedly washing in deionized water to remove residual NaOH, thus obtaining the cross-linked polyether-ether-ketone/cationic metal-organic framework cross-linked membrane;
the resulting crosslinked film was processed at 30 oCThe ionic conductivity of the material is 0.011S cm-1At 80 oCThe ionic conductivity of the sample is 0.037S cm-1The film thickness was 26.5. mu.m.
Example 3
(1) 0.5 g of imidazole-functionalized polyether ether ketone was weighed into a beaker, 10 mL of NMP solvent was added, and the mixture was stirred at room temperature to obtain a homogeneous solution. Wherein NMP represents N-methyl-2-pyrrolidone;
(2) 0.005 g of cationic D-UiO-66-NH2 was weighed and added to the homogeneous solution of step (1). Ultrasonically dispersing for 4 hours, then continuously stirring for 48 hours, adding BPO and stirring for two hours to obtain film forming liquid. Wherein the mass ratio of the CMOF to the imidazole functionalized polyether ether ketone in the obtained casting solution is 1 percent;
(3) casting the deposition solution obtained in step (2) onto a clean glass plate at 80 deg.C oCDrying for 48 hours, naturally cooling to room temperature, then demoulding in water, treating for 24 hours by soda soaking, and then repeatedly washing in deionized water to remove residual NaOH, thus obtaining the cross-linked polyether-ether-ketone/cationic metal organic framework anion exchange membrane;
the obtained anion exchange membrane is at 30 oCThe ionic conductivity of the sample is 0.025S cm-1In a80 oCThe ionic conductivity of the sample is 0.073S cm-1The film thickness was 16 μm.
Example 4
(1) 0.5 g of imidazole-functionalized polyether ether ketone was weighed into a beaker, 10 mL of NMP solvent was added, and the mixture was stirred at room temperature to obtain a homogeneous solution. Wherein NMP represents N-methyl-2-pyrrolidone;
(2) 0.0075 g of cationic D-UiO-66-NH2 was weighed and added to the homogeneous solution of step (1). Ultrasonically dispersing for 4 hours, then continuously stirring for 48 hours, adding BPO and stirring for two hours to obtain film forming liquid. Wherein the mass ratio of the CMOF to the imidazole functionalized polyether ether ketone in the obtained casting solution is 1.5%;
(3) casting the deposition solution obtained in step (2) onto a clean glass plate at 80 deg.CoDrying for 48 hours, naturally cooling to room temperature, then demoulding in water, treating for 24 hours by using sodium hydroxide, and then repeatedly washing in deionized water to remove residual NaOH, thus obtaining the cross-linked polyether-ether-ketone/cationic metal-organic framework cross-linked membrane;
the obtained anion exchange membrane is at 30 oCThe ionic conductivity of the polymer is 0.018S cm-1At 80 oCThe ionic conductivity of the sample is 0.055S cm-1 The film thickness was 18 μm.
Example 5
(1) 0.5 g of imidazole-functionalized polyether ether ketone was weighed into a beaker, 10 mL of NMP solvent was added, and the mixture was stirred at room temperature to obtain a homogeneous solution. Wherein NMP represents N-methyl-2-pyrrolidone;
(2) 0.01 g of cationic D-UiO-66-NH2 was weighed and added to the homogeneous solution of step (1). Ultrasonically dispersing for 4 hours, then continuously stirring for 48 hours, adding BPO and stirring for two hours to obtain film forming liquid. Wherein the mass ratio of the CMOF to the imidazole functionalized polyether ether ketone in the obtained casting solution is 2 percent;
(3) casting the deposition solution obtained in step (2) onto a clean glass plate at 80 deg.CoDrying for 48 hours under C, naturally cooling to room temperature, removing the membrane in water, treating for 24 hours with sodium hydroxide, and repeatedly washing in deionized water to remove residual NaOH, thus obtaining the productA cross-linked polyether-ether-ketone/cationic metal organic framework anion exchange membrane;
the obtained anion exchange membrane is at 30 oCThe ionic conductivity of the sample is 0.026S cm-1At 80 oCThe ionic conductivity of the sample is 0.014S cm-1The film thickness was 31 μm.
FIG. I is a nuclear magnetic spectrum of pure polyetheretherketone, brominated polyetheretherketone, and imidazole-functionalized polyetheretherketone in the present invention. It can be seen as a proton peak on the benzyl group at 2.35 ppm; a new peak appears at 4.52 ppm after bromination, which indicates that bromination is successful; the successful grafting of imidazole is indicated by the appearance of a new peak at 9.46 ppm after the grafting of imidazole.
FIG. two is a graph showing the ion conductivity of the imidazole-functionalized polyetheretherketone membrane of the present invention and the CMOF membrane at different addition levels as a function of temperature. The ion conductivity of the polyether-ether-ketone/cationic metal-organic framework crosslinked membrane with the addition ratio of 1% is highest.
The above description of the embodiments is only for the purpose of assisting understanding of the method of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall into the protection scope of the claims of the present invention.
Claims (8)
1. The polyether-ether-ketone/cationic metal-organic framework crosslinked membrane for the fuel cell is characterized in that the anion exchange membrane is prepared from imidazole functionalized polyether-ether-ketone and cationic D-UiO-66-NH2Wherein, imidazole functionalized polyether ether ketone and cationic D-UiO-66-NH2The mass ratio of (1): 0.005-0.02.
2. The membrane of claim 1, wherein the imidazole functionalized polyether ether ketone is prepared by the following steps:
step one, adding a bisphenol monomer and 4, 4-difluorobenzophenone into a three-neck flask, uniformly mixing, then adding a salt forming agent, a water-carrying agent and a solvent into the three-neck flask, uniformly stirring, heating for reaction, refluxing with water for 4-6 hours, then discharging the water-carrying agent, and continuing heating for reaction to obtain polyether-ether-ketone;
step two, adding the obtained polyether-ether-ketone into a three-neck flask, adding 1,1,2, 2-tetrachloroethane as a solvent, dissolving under the protection of nitrogen, then adding a brominating agent NBS and an initiator BPO, heating for reaction after complete dissolution, pouring the obtained solution into ethanol, and washing to obtain brominated polyether-ether-ketone;
and step three, adding brominated polyether ether ketone and a solvent NMP into a three-neck flask, uniformly mixing, adding excessive 1-vinyl imidazole, heating under the protection of nitrogen, reacting for several hours, cooling to room temperature, pouring the obtained solution into ethanol, washing, and drying to obtain the imidazole functionalized polyether ether ketone.
3. The membrane of claim 2, wherein in the first step, the bisphenol monomer is methyl hydroquinone, trimethyl hydroquinone, or tetramethyl hydroquinone, the salt former is anhydrous potassium carbonate, the water-carrying agent is toluene, and the solvent is one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, or sulfolane.
4. The PEEK/cationic crosslinked membrane of claim 1, wherein the cationic D-UiO-66-NH is selected from the group consisting of2The preparation method comprises the following steps:
adding amino terephthalic acid, 2, 5-pyridinedicarboxylic acid and zirconium tetrachloride into DMF (N, N-dimethylformamide), adding acetic acid as a mineralizer, stirring at room temperature, transferring into a reaction kettle with a polytetrafluoroethylene lining, heating for reaction, cooling the reaction kettle to room temperature, and centrifuging and washing the obtained solution to obtain a light yellow solid;
step two, DMF and CHCl are used before synthesis3The resulting MOF was subjected to guest-exchange activation, followed by soaking the crystals in DMF and CHCl3In and regularly change freshnessCHCl (2)3Activated D-UiO-66-NH2Immersion in CH3Adding the mixture into a mixed solution of I/DMF, finally heating in vacuum, washing with DMF, and drying in vacuum to obtain the cationic D-UiO-66-NH2。
5. The method for preparing the polyetheretherketone/cationic metal-organic framework crosslinked membrane for a fuel cell according to claim 1, comprising the steps of:
step one, preparing imidazole functionalized polyether-ether-ketone into imidazole functionalized polyether-ether-ketone solution;
step two, adding cationic metal organic framework (D-UiO-66-NH)2) Adding the solution obtained in the step one to prepare a membrane casting solution;
and step three, spreading the membrane casting solution obtained in the step two to obtain the cross-linked polyether-ether-ketone/cationic metal-organic framework cross-linked membrane for the fuel cell.
6. The method for preparing the PEEK/cationic metal-organic framework crosslinked membrane for the fuel cell according to claim 5, wherein the preparation method of the imidazole-functionalized PEEK solution in the first step comprises: adding imidazole functionalized polyether-ether-ketone into a solvent, and stirring for several hours at room temperature to obtain an imidazole functionalized polyether-ether-ketone solution, wherein the solvent is one of N-methyl-2-pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
7. The method for preparing the polyetheretherketone/cationic metal-organic framework crosslinked membrane for a fuel cell according to claim 5, wherein the method for preparing the membrane casting solution in the second step comprises: cationic metal organic framework (D-UiO-66-NH)2) Adding the mixture into imidazole functionalized polyether-ether-ketone solution, performing ultrasonic dispersion for 4 hours, continuing stirring for 3 days, adding BPO, stirring and dissolving to obtain a casting solution, wherein the BPO is benzoyl peroxide, and the addition content of the cationic metal organic framework is 0.5-2% of the mass of the polymer.
8. The preparation method of the PEEK/cationic metal-organic framework crosslinked membrane for the fuel cell according to claim 5, wherein the specific method in the third step is as follows: and (3) casting the membrane casting solution onto a clean glass plate, drying at 80 ℃ for 48 hours for membrane removal, then carrying out soda treatment for 24 hours, and then washing with deionized water to obtain the polyether-ether-ketone/cationic metal organic framework cross-linked membrane for the fuel cell.
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