CN112133946A - Carboxyl-containing sulfonated polyaryletherketone sulfone/loaded phosphotungstic acid-ionic liquid metal organic framework composite membrane and preparation method thereof - Google Patents
Carboxyl-containing sulfonated polyaryletherketone sulfone/loaded phosphotungstic acid-ionic liquid metal organic framework composite membrane and preparation method thereof Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 85
- 239000012528 membrane Substances 0.000 title claims abstract description 81
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 80
- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 74
- 150000003457 sulfones Chemical class 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 16
- 229910001338 liquidmetal Inorganic materials 0.000 title abstract description 4
- 150000001450 anions Chemical group 0.000 claims abstract description 54
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 54
- 239000013144 Fe-MIL-100 Substances 0.000 claims abstract description 53
- 239000002131 composite material Substances 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 9
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 30
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 28
- 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 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 24
- 229930185605 Bisphenol Natural products 0.000 claims description 20
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 20
- -1 1-ethyl Chemical group 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- 238000005266 casting Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- IBRQUKZZBXZOBA-UHFFFAOYSA-N 1-chloro-3-(3-chlorophenyl)sulfonylbenzene Chemical class ClC1=CC=CC(S(=O)(=O)C=2C=C(Cl)C=CC=2)=C1 IBRQUKZZBXZOBA-UHFFFAOYSA-N 0.000 claims description 5
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 5
- VSEKSHQBGNBUAW-UHFFFAOYSA-N 4-(2,5-dihydroxyphenyl)benzoic acid Chemical group C1=CC(C(=O)O)=CC=C1C1=CC(O)=CC=C1O VSEKSHQBGNBUAW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004809 Teflon Substances 0.000 claims description 5
- 229920006362 Teflon® Polymers 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 230000007480 spreading Effects 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 3
- 239000013291 MIL-100 Substances 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 3
- 230000004888 barrier function Effects 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000006277 sulfonation reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000001757 thermogravimetry curve 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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- 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
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- 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 Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Composite Materials (AREA)
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Abstract
The invention discloses a carboxyl-containing sulfonated polyaryletherketone sulfone/loaded phosphotungstic acid-ionic liquid metal organic framework composite membrane and a preparation method thereof, belonging to the field of polymer chemistry and proton exchange membrane fuel cells, wherein the mass ratio of MIL-100(Fe) of the carboxyl-containing sulfonated polyaryletherketone sulfone to the loaded heteropoly acid anion group ionic liquid is 1: 0.02-0.08. MIL-100(Fe) loaded with heteropoly acid anion-based ionic liquid has large mesoporous cages and small microporous windows, and heteropoly acid anions are limited in cavities of MIL-100 (Fe). The ionic liquid based on heteropoly acid anions is supported in MIL-100(Fe) without loss by reacting imidazole rings in the ionic liquid with heteropoly acid anions. The supported heteropoly acid anion group ionic liquid in MIL-100(Fe) contains a large number of imidazole ringsBridging oxygen W-O-W bonds and terminal oxygen W ═ O bonds, can facilitate proton transport in the hybrid membrane. MIL-100(Fe) also enhances the mechanical properties, dimensional stability and alcohol barrier ability of the hybrid membrane. The proton conductivity of the composite proton exchange membrane at 80 ℃ is 0.041S cm‑1‑0.123S cm‑1The thickness of the hybrid membrane is 15-25 μm.
Description
Technical Field
The invention belongs to the fields of polymer chemistry and proton exchange membrane fuel cells, and particularly relates to a carboxyl-containing sulfonated polyaryletherketone sulfone/loaded phosphotungstic acid-ionic liquid metal organic framework composite membrane and a preparation method thereof.
Background
Proton Exchange Membranes (PEMs) are the core components of Proton Exchange Membrane Fuel Cells (PEMFCs). Currently, the most commonly used proton exchange membrane is commercial perfluorosulfonic acid resin (Nafion), but the high cost and methanol crossover of Nafion greatly limit its application in proton exchange membrane fuel cells. Therefore, research into alternative polymer electrolyte materials has been developed in the past. Among them, sulfonated poly (arylene ether ketone sulfone), SPAEKS, is the most promising proton exchange membrane material due to its high proton conductivity, good stability, simple preparation method and low cost. However, sulfonated polyaryletherketone sulfones with increasing degrees of sulfonation lead to excessive swelling on water absorption, so that their dimensional stability is reduced. In order to prevent a series of defects brought by high sulfonation degree, the sulfonation degree of the membrane is controlled in the preparation process of the sulfonated polyaryletherketone sulfone, so that the proton conductivity of the proton conducting membrane is low.
In order to increase the proton conductivity of the proton exchange membrane at low sulfonation degrees, the reduction in proton conductivity can be effectively compensated by introducing an additional proton conductor into the membrane. Ionic Liquids (ILs) have good ionic conductivity and chemical stability, and many studies report that ionic liquids are introduced into polymer matrices to prepare proton exchange membranes with high proton conductivity. However, the leaching problem of ionic liquids has not been solved yet, which limits their practical applications.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a carboxyl-containing sulfonated polyaryletherketone sulfone/loaded phosphotungstic acid-ionic liquid metal-organic framework composite membrane and a preparation method thereof, and the composite proton exchange membrane has higher proton conductivity and better dimensional stability by adding MIL-100(Fe) as a carrier, and the preparation process is simple; metal-organic frameworks (MOFs) have attracted much attention as a new crystalline porous material due to their significant advantages of adjustable pore structure, controllable guest molecules, abundant active sites and modifiable functional groups. In particular, the tunable pore structure allows MOFs to be considered as good carriers for encapsulating guest molecules into cavities. Therefore, the leaching problem of the ionic liquid can be effectively solved by selecting the MOFs with the proper cavity size and the ionic liquid, so that the ionic liquid matrix proton exchange membrane is applied, and meanwhile, the introduction of the MOFs can also improve the size stability, the mechanical strength and the chemical stability of the hybrid membrane.
The invention is realized by the following technical scheme:
the invention provides a carboxyl-containing sulfonated polyaryletherketone sulfone/loaded phosphotungstic acid-ionic liquid metal-organic framework composite membrane, which consists of carboxyl-containing sulfonated polyaryletherketone sulfone and MIL-100(Fe) loaded with heteropoly acid anion-based ionic liquid, wherein the mass ratio of the carboxyl-containing sulfonated polyaryletherketone sulfone to the MIL-100(Fe) loaded with heteropoly acid anion-based ionic liquid is 1: 0.02-0.08.
In the scheme, the thickness of the composite proton exchange membrane is 15-25 mu m.
The invention also provides a preparation method of the carboxyl-containing sulfonated polyaryletherketone sulfone/loaded phosphotungstic acid-ionic liquid metal-organic framework composite membrane, which comprises the following steps:
the method comprises the following steps: preparing sulfonated polyaryletherketone sulfone containing carboxyl into a sulfonated polyaryletherketone sulfone solution containing carboxyl;
step two: adding MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid into the sulfonated polyaryletherketone sulfone solution containing carboxyl obtained in the step one to prepare a membrane casting solution;
step three: and D, spreading the membrane casting solution obtained in the step two to obtain the carboxyl-containing sulfonated polyaryletherketone sulfone and the MIL-100(Fe) composite proton exchange membrane loaded with heteropoly acid anion group ionic liquid for the fuel cell.
In the above scheme, the preparation method of the sulfonated polyaryletherketone sulfone solution in the first step comprises:
adding sulfonated polyaryletherketone sulfone containing carboxyl into NMP solvent, and stirring for 24 hours at room temperature to obtain sulfonated polyaryletherketone sulfone solution containing carboxyl; wherein NMP represents N-methyl-2-pyrrolidone, and the mass volume concentration of the sulfonated polyaryletherketone sulfone solution containing carboxyl is 0.05-0.10 g/mL.
In the above scheme, the preparation method of the membrane casting solution in the second step comprises:
adding MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid into a carboxyl-containing sulfonated polyaryletherketone sulfone solution, performing ultrasonic dispersion for 4 hours, and continuously stirring for 2-3 days to obtain a membrane casting solution, wherein the mass ratio of the carboxyl-containing sulfonated polyaryletherketone sulfone to the MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid is 1: 0.02-0.08.
In the above scheme, the third step specifically comprises:
and (3) casting the membrane liquid on a clean glass plate, drying for 48 hours at 80 ℃ for membrane removal, then carrying out acidification treatment for 24 hours, and then washing with deionized water to obtain the MIL-100(Fe) composite proton exchange membrane loaded with the carboxyl-containing sulfonated polyaryletherketone sulfone and the heteropoly acid anion group ionic liquid for the fuel cell.
In the above scheme, the preparation method of the sulfonated polyaryletherketone sulfone containing carboxyl is as follows:
under the protection of nitrogen, adding a mol of a carboxyl-containing bisphenol monomer, b mol of 4,4 '-difluorobenzophenone, c mol of bisphenol monomer and d mol of 4, 4' -sulfonated dichlorodiphenyl sulfone 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, refluxing with water at 110-140 ℃ for 4-6 hours, then discharging the water-carrying agent, raising the temperature to 170-180 ℃, and reacting for 20-30 hours to obtain the carboxyl-containing sulfonated polyaryletherketone sulfone, wherein a + d is b + c.
Preferably, the bisphenol monomer containing carboxyl is 4-carboxyphenyl hydroquinone, the bisphenol monomer is bisphenol A, the salt forming agent is anhydrous potassium carbonate, the water-carrying agent is toluene, and the solvent is sulfolane.
In the scheme, the preparation method of the MIL-100(Fe) loaded with the heteropoly acid anion-based ionic liquid comprises the following steps:
the method comprises the following steps: dissolving ferric trichloride hexahydrate, trimesic acid and phosphotungstic acid in deionized water to obtain a mixed solution, transferring the obtained mixed solution into a stainless steel reactor lined with teflon, reacting for 72 hours at 130 ℃, washing a product obtained by centrifugal separation with deionized water and hot ethanol to remove residual unreacted ferric trichloride hexahydrate, trimesic acid and phosphotungstic acid adsorbed on the surface of the product, and vacuum-drying for 12 hours at 60 ℃ to obtain a brownish red crystal;
step two: and (3) mixing the brownish red crystals obtained in the step one with 1-ethyl, 3-methylimidazole bis-trifluoromethyl sulfonamide amine ionic liquid to obtain MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid.
Preferably, in the preparation method of MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid, in the first step, the molar ratio of ferric trichloride hexahydrate to trimesic acid is 0.5-2: 1, and the molar ratio of phosphotungstic acid to ferric trichloride hexahydrate is 0.1-1: 1;
preferably, in the preparation method of MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid, the mass of the red brown crystals in the second step is 1g, and the volume of the 1-ethyl, 3-methylimidazole bis-trifluoromethyl sulfonamide amine ionic liquid is 0.3-3 mL.
Compared with the prior art, the invention has the following beneficial effects:
the invention firstly provides a fuelThe battery-used MIL-100(Fe) composite proton exchange membrane is prepared from carboxyl-containing sulfonated polyaryletherketone sulfone and heteropoly acid anion-based ionic liquid, wherein the mass ratio of the carboxyl-containing sulfonated polyaryletherketone sulfone to the MIL-100(Fe) loaded heteropoly acid anion-based ionic liquid is 1: 0.02-0.08. The MIL-100(Fe) of the prepared heteropoly acid anion group-loaded ionic liquid has a large mesoporous cage due to the MIL-100(Fe)
And small microporous window
And the size of the heteropoly acid anion (Heteropolyanion) is
The heteropoly acid anions are therefore confined within the cavities of MIL-100 (Fe). The ionic liquid based on heteropoly acid anions is supported in MIL-100(Fe) without loss by reacting imidazole rings in the ionic liquid with heteropoly acid anions. The heteropoly acid anion group ionic liquid loaded in MIL-100(Fe) contains a large number of imidazole rings, bridging oxygen W-O-W bonds and terminal oxygen W ═ O bonds, and can promote proton transmission of the hybrid membrane. Meanwhile, MIL-100(Fe) can also enhance the mechanical properties, dimensional stability and alcohol resistance of the hybrid membrane. The experimental result shows that the proton conductivity of the composite proton exchange membrane is 0.041S cm at 80 DEG C-1-0.123S cm-1The thickness of the hybrid membrane is 15-25 μm.
Drawings
FIG. 1 is an infrared spectrum of pure carboxyl group-containing sulfonated polyaryletherketone sulfones of the present invention, hybrid membranes prepared in example 1, example 2 and example 3;
FIG. 2 is a thermogravimetric plot of pure carboxyl group-containing sulfonated polyaryletherketone sulfones (C-SPAEKS), the hybrid membranes prepared in example 1, example 2 and example 3 of the present invention;
FIG. 3 is a plot of proton conductivity as a function of temperature for pure carboxyl group-containing sulfonated polyaryletherketone sulfones of the present invention, and for hybrid membranes prepared in example 1, example 2 and example 3.
Detailed description of the invention
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of a carboxyl-containing sulfonated polyaryletherketone sulfone and a MIL-100(Fe) composite proton exchange membrane loaded with heteropoly acid anion group ionic liquid for a fuel cell comprises the following specific steps:
(1) adding 0.2mol of a carboxyl-containing bisphenol monomer, 0.8mol of 4,4 '-difluorobenzophenone, 0.8mol of a bisphenol monomer and 0.2mol of 4, 4' -sulfonated dichlorodiphenyl sulfone into a three-neck flask, uniformly mixing, adding anhydrous potassium carbonate, toluene and sulfolane into the three-neck flask, refluxing with water at 110-140 ℃ for 4-6 hours under the protection of nitrogen, discharging the water-carrying agent, raising the temperature to 170-180 ℃, and reacting for 20-30 hours to obtain the carboxyl-containing sulfonated polyaryletherketone sulfone, wherein the carboxyl-containing bisphenol monomer is 4-carboxyphenylhydroquinone, and the bisphenol monomer is bisphenol A.
(2) Dissolving ferric trichloride hexahydrate, trimesic acid and phosphotungstic acid in deionized water to obtain a mixed solution, transferring the obtained mixed solution into a stainless steel reactor lined with Teflon, reacting for 72 hours at 130 ℃, washing a product obtained by centrifugal separation with deionized water and hot ethanol to remove unreacted ferric trichloride hexahydrate, trimesic acid and phosphotungstic acid adsorbed on the surface of the product, and drying in vacuum for 12 hours at 60 ℃ to obtain a brownish red crystal. And mixing the obtained brownish red crystals with 1-ethyl, 3-methylimidazole bistrifluoromethylsulfonamide amine ionic liquid to obtain MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid, wherein the mass of ferric trichloride hexahydrate is 0.38g, the mass of trimesic acid is 0.27g, the molar ratio of phosphotungstic acid to ferric trichloride hexahydrate is 0.1-1: 1, the mass of the brownish red crystals is 1g, 1-ethyl, and the volume of the 3-methylimidazole bistrifluoromethylsulfonamide amine ionic liquid is 3 mL.
(3) 0.5g of sulfonated polyaryletherketone sulfone containing carboxyl is weighed and put into a beaker, 10ml of NMP solvent is added, and the mixture is stirred at room temperature to obtain a uniform solution. Wherein NMP represents N-methyl-2-pyrrolidone.
(4) 0.01g of MIL-100(Fe) supporting the heteropoly acid anion group ionic liquid is weighed and added to the homogeneous solution of the step (3). Ultrasonic dispersion is carried out for 4 hours, and then stirring is continued for 48 hours to obtain film forming liquid. Wherein the mass ratio of MIL-100(Fe) of the heteropoly acid anion group ionic liquid loaded in the film forming liquid to the sulfonated polyaryletherketone sulfone containing carboxyl is 0.02: 1.
(5) And (3) casting the film forming liquid obtained in the step (2) onto a clean glass plate, drying for 48 hours at the temperature of 80 ℃, naturally cooling to room temperature, then demoulding in water, carrying out acidification treatment for 24 hours, and then repeatedly washing in deionized water to remove residual hydrochloric acid, thus obtaining the MIL-100(Fe) composite proton exchange membrane of the carboxyl-containing sulfonated polyaryletherketone sulfone and the supported heteropoly acid anion group ionic liquid.
The obtained carboxyl-containing sulfonated polyaryletherketone sulfone and MIL-100(Fe) composite proton exchange membrane loaded with heteropoly acid anion group ionic liquid are tested at 80 ℃, and the conductivity of the proton exchange composite membrane is 0.063S cm-1Film thickness 15 μm, conductivity 0.025S cm, measured at 30 ℃-1。
Example 2
Adding 0.2mol of bisphenol monomer containing carboxyl, 0.8mol of 4,4 '-difluorobenzophenone, 0.8mol of bisphenol monomer and 0.2mol of 4, 4' -sulfonated dichlorodiphenyl sulfone into a three-neck flask, uniformly mixing, adding anhydrous potassium carbonate, toluene and sulfolane into the three-neck flask, refluxing with water at 110-140 ℃ for 4-6 hours under the protection of nitrogen, discharging the water-carrying agent, raising the temperature to 170-180 ℃, and reacting for 20-30 hours to obtain sulfonated polyaryletherketone sulfone containing carboxyl, wherein the bisphenol monomer containing carboxyl is 4-carboxyphenylhydroquinone and the bisphenol monomer is bisphenol A.
(2) Dissolving ferric trichloride hexahydrate, trimesic acid and phosphotungstic acid in deionized water to obtain a mixed solution, transferring the obtained mixed solution into a stainless steel reactor lined with Teflon, reacting for 72 hours at 130 ℃, washing a product obtained by centrifugal separation with deionized water and hot ethanol to remove unreacted ferric trichloride hexahydrate, trimesic acid and phosphotungstic acid adsorbed on the surface of the product, and drying in vacuum for 12 hours at 60 ℃ to obtain a brownish red crystal. And mixing the obtained brownish red crystals with 1-ethyl, 3-methylimidazole bistrifluoromethylsulfonamide amine ionic liquid to obtain MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid, wherein the mass of ferric trichloride hexahydrate is 0.38g, the mass of trimesic acid is 0.27g, the molar ratio of phosphotungstic acid to ferric trichloride hexahydrate is 0.1-1: 1, the mass of the brownish red crystals is 1g, 1-ethyl, and the volume of the 3-methylimidazole bistrifluoromethylsulfonamide amine ionic liquid is 3 mL.
(3) 0.5g of sulfonated polyaryletherketone sulfone containing carboxyl is weighed and put into a beaker, 10ml of NMP solvent is added, and the mixture is stirred at room temperature to obtain a uniform solution. Wherein NMP represents N-methyl-2-pyrrolidone.
(4) 0.02g of MIL-100(Fe) supporting the heteropoly acid anion group ionic liquid is weighed and added into the homogeneous solution in the step (2). Ultrasonic dispersion is carried out for 4 hours, and then stirring is continued for 48 hours to obtain film forming liquid. Wherein the mass ratio of MIL-100(Fe) of the heteropoly acid anion group ionic liquid loaded in the film forming liquid to the sulfonated polyaryletherketone sulfone containing carboxyl is 0.04: 1.
(5) And (3) casting the film forming liquid obtained in the step (2) onto a clean glass plate, drying for 48 hours at the temperature of 80 ℃, naturally cooling to room temperature, then demoulding in water, carrying out acidification treatment for 24 hours, and then repeatedly washing in deionized water to remove residual hydrochloric acid, thus obtaining the MIL-100(Fe) composite proton exchange membrane of the carboxyl-containing sulfonated polyaryletherketone sulfone and the supported heteropoly acid anion group ionic liquid.
The obtained carboxyl-containing sulfonated polyaryletherketone sulfone and MIL-100(Fe) composite proton exchange membrane loaded with heteropoly acid anion group ionic liquid are tested at 80 ℃, and the conductivity of the proton exchange composite membrane is 0.123S cm-1Film thickness 21 μm, conductivity 0.058S cm measured at 30 ℃-1。
Example 3
(1) Adding 0.2mol of a carboxyl-containing bisphenol monomer, 0.8mol of 4,4 '-difluorobenzophenone, 0.8mol of a bisphenol monomer and 0.2mol of 4, 4' -sulfonated dichlorodiphenyl sulfone into a three-neck flask, uniformly mixing, adding anhydrous potassium carbonate, toluene and sulfolane into the three-neck flask, refluxing with water at 110-140 ℃ for 4-6 hours under the protection of nitrogen, discharging the water-carrying agent, raising the temperature to 170-180 ℃, and reacting for 20-30 hours to obtain the carboxyl-containing sulfonated polyaryletherketone sulfone, wherein the carboxyl-containing bisphenol monomer is 4-carboxyphenylhydroquinone, and the bisphenol monomer is bisphenol A.
(2) Dissolving ferric trichloride hexahydrate, trimesic acid and phosphotungstic acid in deionized water to obtain a mixed solution, transferring the obtained mixed solution into a stainless steel reactor lined with Teflon, reacting for 72 hours at 130 ℃, washing a product obtained by centrifugal separation with deionized water and hot ethanol to remove unreacted ferric trichloride hexahydrate, trimesic acid and phosphotungstic acid adsorbed on the surface of the product, and drying in vacuum for 12 hours at 60 ℃ to obtain a brownish red crystal. And mixing the obtained brownish red crystals with 1-ethyl, 3-methylimidazole bistrifluoromethylsulfonamide amine ionic liquid to obtain MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid, wherein the mass of ferric trichloride hexahydrate is 0.38g, the mass of trimesic acid is 0.27g, the molar ratio of phosphotungstic acid to ferric trichloride hexahydrate is 0.1-1: 1, the mass of the brownish red crystals is 1g, 1-ethyl, and the volume of the 3-methylimidazole bistrifluoromethylsulfonamide amine ionic liquid is 3 mL.
(3) 0.5g of sulfonated polyaryletherketone sulfone containing carboxyl is weighed and put into a beaker, 10ml of NMP solvent is added, and the mixture is stirred at room temperature to obtain a uniform solution. Wherein NMP represents N-methyl-2-pyrrolidone.
(4) 0.03g of MIL-100(Fe) supporting the heteropoly acid anion group ionic liquid is weighed and added into the uniform solution in the step (2). Ultrasonic dispersion is carried out for 4 hours, and then stirring is continued for 48 hours to obtain film forming liquid. Wherein the mass ratio of MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid in the film forming liquid to sulfonated polyaryletherketone sulfone containing carboxyl is 0.06: 1.
(5) And (3) casting the film forming liquid obtained in the step (2) onto a clean glass plate, drying for 48 hours at the temperature of 80 ℃, naturally cooling to room temperature, then demoulding in water, carrying out acidification treatment for 24 hours, and then repeatedly washing in deionized water to remove residual hydrochloric acid, thus obtaining the MIL-100(Fe) composite proton exchange membrane of the carboxyl-containing sulfonated polyaryletherketone sulfone and the supported heteropoly acid anion group ionic liquid.
The obtained carboxyl-containing sulfonated polyaryletherketone sulfone and MIL-100(Fe) composite proton exchange membrane loaded with heteropoly acid anion group ionic liquid are tested at 80 ℃, and the conductivity of the proton exchange composite membrane prepared in example 3 is 0.090S cm-1Film thickness 25 μm, conductivity 0.046S cm measured at 30 ℃-1。
The swelling rates of the pure carboxyl-containing sulfonated polyaryletherketone sulfone and the hybrid membranes prepared in the examples 1, 2 and 3 are respectively 6.3%, 6%, 5.5% and 5.2% when tested at 90 ℃, and it can be seen that the change of the swelling rates is small, which indicates that the composite proton exchange membrane has good dimensional stability.
FIG. 1 is an IR spectrum of pure carboxyl group-containing sulfonated polyaryletherketone sulfones of the present invention, and hybrid membranes prepared in example 1, example 2 and example 3. It can be seen from the figure that the characteristic peaks of the sulfonic acid group are 1276.58 and 1154.22cm, respectively-1. No distinct peaks characteristic of MOFs were found in the ir spectrum of the hybrid film, probably due to the fact that MOFs are masked by the polymer.
FIG. 2 is the thermogravimetric curves of pure carboxyl group-containing sulfonated polyaryletherketone sulfones (C-SPAEKS), the hybrid membranes prepared in example 1, example 2 and example 3 in the present invention. The thermal stability of the hybrid membrane is greatly affected by MIL-100(Fe) loaded with heteropoly acid anion-based ionic liquid. There are three decomposition stages in the TGA curve of the hybrid membrane. Wherein below 200 ℃ is the first stage due to the evaporation of absorbed water, residual solvent and bound water. The second stage starts at 275 ℃ and the sulfonic and hydroxyl groups in the C-SPAEKS start to decompose, which leads to a decrease in proton conductivity of the hybrid membrane. The hybrid membrane of MIL-100(Fe) incorporating the heteropoly acid anion based ionic liquid has a more significant loss in the second weight loss stage and increases with the increase in the MIL-100(Fe) content of the heteropoly acid anion based ionic liquid, which is due to the weight loss caused by the decomposition of the ionic liquid in the MIL-100(Fe) supporting heteropoly acid anion based ionic liquid. Finally, the stem of C-SPAEKS was destroyed above 450 ℃.
FIG. 3 is a plot of proton conductivity as a function of temperature for pure carboxyl group-containing sulfonated polyaryletherketone sulfones of the present invention, and for hybrid membranes prepared in example 1, example 2 and example 3. All hybrid membranes showed higher proton conductivity than pure C-SPAEKS.
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 (10)
1. The composite proton exchange membrane is characterized by being composed of sulfonated polyaryletherketone sulfone containing carboxyl and MIL-100(Fe) loaded with heteropoly acid anion-based ionic liquid, wherein the mass ratio of the sulfonated polyaryletherketone sulfone containing carboxyl to the MIL-100(Fe) loaded with heteropoly acid anion-based ionic liquid is 1: 0.02-0.08.
2. The carboxyl-containing sulfonated polyaryletherketone sulfone/supported phosphotungstic acid-ionic liquid metal-organic framework composite membrane as claimed in claim 1, wherein the preparation method of the carboxyl-containing sulfonated polyaryletherketone sulfone comprises the following steps:
under the protection of nitrogen, adding a mol of a carboxyl-containing bisphenol monomer, b mol of 4,4 '-difluorobenzophenone, c mol of bisphenol monomer and d mol of 4, 4' -sulfonated dichlorodiphenyl sulfone 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, refluxing with water at 110-140 ℃ for 4-6 hours, then discharging the water-carrying agent, raising the temperature to 170-180 ℃, and reacting for 20-30 hours to obtain the carboxyl-containing sulfonated polyaryletherketone sulfone, wherein a + d is b + c.
3. The carboxyl-containing sulfonated polyaryletherketone sulfone/supported phosphotungstic acid-ionic liquid metal-organic framework composite membrane as claimed in claim 2, wherein the carboxyl-containing bisphenol monomer is 4-carboxyphenylhydroquinone, the bisphenol monomer is bisphenol A, the salt forming agent is anhydrous potassium carbonate, the water carrying agent is toluene, and the solvent is sulfolane.
4. The carboxyl-containing sulfonated polyaryletherketone sulfone/supported phosphotungstic acid-ionic liquid metal-organic framework composite membrane as claimed in claim 1, wherein the preparation method of MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid is as follows:
the method comprises the following steps: dissolving ferric trichloride hexahydrate, trimesic acid and phosphotungstic acid in deionized water to obtain a mixed solution, transferring the obtained mixed solution into a stainless steel reactor lined with teflon, reacting for 72 hours at 130 ℃, washing a product obtained by centrifugal separation with deionized water and hot ethanol to remove residual unreacted ferric trichloride hexahydrate, trimesic acid and phosphotungstic acid adsorbed on the surface of the product, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain a brownish red crystal;
step two: and (3) mixing the brownish red crystals obtained in the step one with 1-ethyl, 3-methylimidazole bis (trifluoromethyl) sulfonyl imide ionic liquid to obtain MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid.
5. The carboxyl-containing sulfonated polyaryletherketone sulfone/supported phosphotungstic acid-ionic liquid metal-organic framework composite membrane as claimed in claim 4, wherein in the first step, the molar ratio of ferric trichloride hexahydrate to trimesic acid is 0.5-2: 1, and the molar ratio of phosphotungstic acid to ferric trichloride hexahydrate is 0.1-1: 1.
6. The carboxyl-containing sulfonated polyaryletherketone sulfone/supported phosphotungstic acid-ionic liquid metal-organic framework composite membrane as claimed in claim 4, wherein in the second step, the mass of the brownish red crystal is 1g, and the volume of the 1-ethyl, 3-methylimidazole bis (trifluoromethyl) sulfonyl imide ionic liquid is 0.3-3 mL.
7. The preparation method of the carboxyl-containing sulfonated polyaryletherketone sulfone/supported phosphotungstic acid-ionic liquid metal-organic framework composite membrane as claimed in claim 1, characterized by comprising the following steps:
the method comprises the following steps: preparing sulfonated polyaryletherketone sulfone containing carboxyl into a sulfonated polyaryletherketone sulfone solution containing carboxyl;
step two: adding MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid into the sulfonated polyaryletherketone sulfone solution containing carboxyl obtained in the step one to prepare a membrane casting solution;
step three: and D, spreading the membrane casting solution obtained in the step two to obtain the carboxyl-containing sulfonated polyaryletherketone sulfone and the MIL-100(Fe) composite proton exchange membrane loaded with heteropoly acid anion group ionic liquid for the fuel cell.
8. The preparation method of the carboxyl-containing sulfonated polyaryletherketone sulfone/supported phosphotungstic acid-ionic liquid metal-organic framework composite membrane as claimed in claim 7, wherein the preparation method of the sulfonated polyaryletherketone sulfone solution in the first step is as follows:
adding sulfonated polyaryletherketone sulfone containing carboxyl into NMP solvent, and stirring for 24 hours at room temperature to obtain sulfonated polyaryletherketone sulfone solution containing carboxyl; wherein NMP represents N-methyl-2-pyrrolidone, and the mass volume fraction of the sulfonated polyaryletherketone sulfone solution containing carboxyl is 0.05-0.10 g/mL.
9. The preparation method of the carboxyl-containing sulfonated polyaryletherketone sulfone/supported phosphotungstic acid-ionic liquid metal-organic framework composite membrane according to claim 7, wherein the preparation method of the membrane casting solution in the second step is as follows:
adding MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid into a carboxyl-containing sulfonated polyaryletherketone sulfone solution, performing ultrasonic dispersion for 4 hours, and continuously stirring for 2-3 days to obtain a membrane casting solution, wherein the mass ratio of the carboxyl-containing sulfonated polyaryletherketone sulfone to the MIL-100(Fe) loaded with heteropoly acid anion group ionic liquid is 1: 0.02-0.08.
10. The preparation method of the carboxyl-containing sulfonated polyaryletherketone sulfone/supported phosphotungstic acid-ionic liquid metal-organic framework composite membrane according to claim 7, wherein the third step is specifically as follows:
and (3) casting the membrane liquid on a clean glass plate, drying for 48 hours at 80 ℃ for membrane removal, then carrying out acidification treatment for 24 hours, and then washing with deionized water to obtain the MIL-100(Fe) composite proton exchange membrane loaded with the carboxyl-containing sulfonated polyaryletherketone sulfone and the heteropoly acid anion group ionic liquid for the fuel cell.
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