CN114464856B - Preparation method of multi-metal oxygen cluster hybrid polyelectrolyte semi-interpenetrating network membrane - Google Patents
Preparation method of multi-metal oxygen cluster hybrid polyelectrolyte semi-interpenetrating network membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 84
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 45
- 239000001301 oxygen Substances 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002184 metal Substances 0.000 title claims abstract description 36
- 229920000867 polyelectrolyte Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- 239000013460 polyoxometalate Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011521 glass Substances 0.000 claims abstract description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 229940126062 Compound A Drugs 0.000 claims abstract description 16
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000005266 casting Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 238000009396 hybridization Methods 0.000 claims description 15
- 235000015393 sodium molybdate Nutrition 0.000 claims description 15
- 239000011684 sodium molybdate Substances 0.000 claims description 15
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 claims description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- -1 trihydroxymethoxyaminomethane Chemical compound 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract 2
- 238000000944 Soxhlet extraction Methods 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 239000000446 fuel Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
- 150000003460 sulfonic acids Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000002047 photoemission electron microscopy Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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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
- H01M8/1069—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
-
- 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
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Engineering & Computer Science (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a kind ofThe preparation method of the multi-metal oxygen cluster hybrid polyelectrolyte semi-interpenetrating network membrane comprises the following specific steps: s1, preparing a cross-linking type poly-metal oxygen cluster polymer, namely uniformly mixing a compound A and a compound B in an organic reagent, adding acetic acid to form a uniform mixture, heating the mixture, cooling the mixture to room temperature, and performing suction filtration, washing, soxhlet extraction and drying post-treatment to obtain the cross-linking type poly-metal oxygen cluster polymer; s2: a multi-metal oxygen cluster hybrid polymer electrolyte semi-interpenetrating network membrane: evaporating 25% resin solution to dryness, dissolving in DMF solvent, adding cross-linked polyoxometalate polymer obtained in S1 into resin solution, ultrasound for 30min, standing for 10min, casting on glass plate to form film, drying, removing film, and sequentially placing in 3% H 2 O 2 Solution, 1M H 2 SO 4 And respectively soaking the solution and deionized water for 1h at 80 ℃ to finally obtain the polyoxometalate hybrid polymer electrolyte semi-interpenetrating network membrane.
Description
Technical Field
The invention relates to a preparation method of a multi-metal oxygen cluster hybridization polyelectrolyte semi-interpenetrating network membrane, belonging to the technical field of organic-inorganic hybridization composite membranes.
Background
In the face of global energy shortages and environmental pollution problems caused by burning fossil fuels, the search for an efficient, renewable clean energy has become a trend. Proton Exchange Membrane Fuel Cells (PEMFCs) are regarded as the most potential portable energy conversion devices because of their fast start-up, zero pollution, and high energy density.
The proton exchange membrane serves as one of the core components of the PEMFC, and serves as a proton transfer and fuel barrier. The prior perfluorosulfonic acid resin film PFSA represented by Nafion produced by DuPont in U.S. has serious reduction of proton conductivity and serious mechanical property attenuation under the working condition of high temperature and low humidity, and restricts the development of PEMFC to a certain extent. Therefore, development of a novel high-performance proton exchange membrane has become an important research point of PEMFC.
The multi-metal oxygen cluster is a multi-anion cluster compound with definite structure and easy modification and functionalization, has unique optical, electric, magnetic and other characteristics, and has wide application in the fields of energy sources, catalysis, biomedical and the like. The rigid polyanion cluster is used as an ion exchange element, so that the ion conductivity of the membrane is effectively improved, and meanwhile, the hybrid cross-linked network of the membrane improves the mechanical property and the membrane stability, and the membrane is compounded with linear perfluorinated sulfonic acid resin, so that the two components are rigid and flexible, and the comprehensive performance of the membrane is greatly improved. The structural and functional optimization of the perfluorinated sulfonic acid resin is of great significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a multi-metal oxygen cluster hybridization polyelectrolyte semi-interpenetrating network membrane.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the multi-metal oxygen cluster hybrid polyelectrolyte semi-interpenetrating network membrane comprises the following specific steps:
s1. preparation of crosslinked polymetallic oxygen cluster Polymer
Compound a and compound B were combined according to a functional group molar ratio of 3:2, uniformly mixing the mixture in an organic reagent, adding acetic acid to form a uniform mixture, heating the mixture at a certain temperature for a certain time, cooling the mixture to room temperature, filtering, washing, soxhlet extracting, and drying to obtain a cross-linked poly metal oxygen cluster polymer;
s2: multi-metal oxygen cluster hybrid polymer electrolyte semi-interpenetrating network membrane
Evaporating 25% of PFSA resin solution at 60-70 ℃ to dryness, dissolving the solvent in N, N-dimethylformamide DMF solvent, adding the cross-linked polyoxometalate polymer obtained in S1 into the PFSA resin solution, carrying out ultrasonic treatment for 30min, standing for 10min to completely degas the polymer to obtain a membrane solution, casting the membrane on a glass plate to form a membrane, drying at 60 ℃ for 4-6H, heating to 80 ℃ for 12H, drying at 120 ℃ for 4-6H, removing the membrane, sequentially placing the membrane into 3% of H2O2 solution, 1M of H2SO4 solution and deionized water, and respectively soaking the membrane at 80 ℃ for 1H to obtain the polyoxometalate hybrid polymer electrolyte semi-interpenetrating network membrane;
the compound A is [ N (C4H 9) 4]3[ MnMo6O18{ (OCH 2) 3CNH2}2], and the compound B is trimesic aldehyde.
Further, the organic reagent is one or more of acetonitrile, 1, 4-dioxane or mesitylene.
Further, the reaction temperature is 80-120 ℃ and the reaction time is 3-5 days.
Further, the preparation method of the compound A is as follows:
weighing a proper amount of sodium molybdate, dissolving the sodium molybdate in deionized water, adding a proper amount of hydrochloric acid for acidification, and then adding a proper amount of tetrabutylammonium bromide, wherein the molar ratio of the sodium molybdate to the tetrabutylammonium bromide is 2:1, white precipitate is generated, stirring is carried out at room temperature, then, white solid [ N (C4H 9) 4]3[ alpha-Mo 6O26], [ N (C4H 9) 4]3[ alpha-Mo 6O26] is obtained by filtration and collected, mn (Ac) 3 and trihydroxymethoxyaminomethane are mixed and dissolved in acetonitrile, the mol ratio is 1.5:2:5, the mixture is heated to 85 ℃ for reaction, then, the reaction solution is filtered, and is placed in diethyl ether for diffusion for a period of time, thus obtaining the compound A.
Further, in the step S2, the mass ratio of the cross-linked poly metal oxygen cluster polymer to the PFSA resin solution is 0.05 to 0.15:1.
further, the thickness of the polyoxometalate hybridization polyelectrolyte semi-interpenetrating network membrane is 15-22 mu m.
The invention has the beneficial effects that:
(1) The polyoxometalate hybridization polyelectrolyte semi-interpenetrating network membrane prepared by the invention is a polymer semi-interpenetrating network structure formed by interpenetrating linear PFSA resin and cross-linked polyoxometalate polymer, is a transparent film with the film thickness of 15-22 mu m, is insoluble in water, has stable physical and chemical properties, and can be used as a proton exchange membrane of a fuel cell.
(2) In the multi-metal oxygen cluster hybrid polyelectrolyte semi-interpenetrating network membrane formed by the invention, the cross-linked multi-metal oxygen cluster polymer has a rigid framework, so that the mechanical property of the proton exchange membrane is improved, and the good mechanical property and the dimensional stability are maintained when the membrane thickness is reduced; meanwhile, the ion element structure of the multi-metal oxygen cluster is beneficial to constructing a new proton transmission channel and promoting the transmission of protons, thereby improving the proton conductivity.
(3) The preparation method has the advantages that the required materials are cheap and easy to obtain, the preparation process is simple and controllable, the rigid skeleton and the ion element of the polyoxometalate are fully utilized, and the mechanical properties of the hybrid film formed by the polyoxometalate and the PFSA resin are greatly improved. A new proton transmission channel is constructed in the hybrid membrane, so that proton transmission is promoted, and the proton conductivity of the membrane is improved; the cross-linked poly metal oxygen cluster polymer has good compatibility with PFSA resin solution, can be used as a proton exchange membrane of a proton exchange membrane fuel cell, and has the proton conductivity of 0.079S/cm-0.106S/cm in a room temperature all-wet state, and is improved by 172% -266% compared with a recast PFSA membrane. The conductivity of the hybrid film is 0.131S/cm-0.257S/cm at 80 ℃ and 100% RH, and 4.5-8.9 times of that of the recast PFSA film.
Drawings
FIG. 1 is an infrared spectrum of PFSA recast films and PFSA/Anderson polyoxometalate hybrid polyelectrolyte network films containing different mass fractions of crosslinked polyacid polymers.
FIG. 2 is a scanning electron microscope image of the membrane surface and cross section of a PFSA/Anderson polyoxometalate hybrid polyelectrolyte network membrane of the invention.
FIG. 3 is a thermogravimetric analysis of a PFSA/Anderson polyoxometalate hybrid polyelectrolyte network membrane of the invention.
FIG. 4 is a graph of conductivity versus temperature for PFSA recast membranes and PFSA/Anderson polyoxometalate hybrid polyelectrolyte semi-interpenetrating network membranes comprising different mass fractions of crosslinked polyacid polymers.
FIG. 5 is an open circuit voltage, power density and EIS spectra at different current densities for PFSA recast films and PFSA/Anderson polyoxometalate hybrid polyelectrolyte network films containing different mass fractions of crosslinked polyacid polymers.
Detailed Description
The invention is illustrated below by means of specific examples, without however limiting the invention.
Example 1
The preparation method of the multi-metal oxygen cluster hybrid polyelectrolyte semi-interpenetrating network membrane comprises the following specific steps:
s1. preparation of crosslinked polymetallic oxygen cluster Polymer
Compound a and compound B were combined according to a functional group molar ratio of 3:2, uniformly mixing the mixture in an organic reagent, adding acetic acid to form a uniform mixture, heating the mixture at 80-120 ℃ for 3-5 days, cooling the mixture to room temperature, filtering, washing, soxhlet extracting, and drying to obtain the cross-linked poly-metal oxygen cluster polymer;
wherein the compound A is [ N (C4H 9) 4]3[ MnMo6O18{ (OCH 2) 3CNH2}2], and the compound B is trimesoyl aldehyde; the organic reagent is one or more of acetonitrile, 1, 4-dioxane or mesitylene.
The preparation method of the compound A comprises the following steps:
weighing a proper amount of sodium molybdate, dissolving the sodium molybdate in deionized water, adding a proper amount of hydrochloric acid for acidification, and then adding a proper amount of tetrabutylammonium bromide, wherein the molar ratio of the sodium molybdate to the tetrabutylammonium bromide is 2:1, white precipitate is generated, stirring is carried out at room temperature, then, white solid [ N (C4H 9) 4]3[ alpha-Mo 6O26], [ N (C4H 9) 4]3[ alpha-Mo 6O26] is obtained by filtration and collected, mn (Ac) 3 and trihydroxymethoxyaminomethane are mixed and dissolved in acetonitrile, the mol ratio is 1.5:2:5, the mixture is heated to 85 ℃ for reaction, then, the reaction solution is filtered, and is placed in diethyl ether for diffusion for a period of time, thus obtaining the compound A.
S2: multi-metal oxygen cluster hybrid polymer electrolyte semi-interpenetrating network membrane
1.2g of 25% PFSA resin solution is weighed, the solvent is evaporated in a forced air drying oven at 60-70 ℃, then the solvent is dissolved in 16ml of N, N-dimethylformamide DMF solvent, then the cross-linked polyoxometalate polymer obtained in 15.79mg S1 is weighed and added into the PFSA resin solution, the cross-linked polyoxometalate polymer is fully dissolved by ultrasonic treatment for 30min, and the solution is left stand for 10min to completely degas, so that a film solution with 2wt% of solid content is obtained;
and casting the film on a glass plate with the thickness of 9cm multiplied by 9cm, placing the glass plate in a vacuum oven, drying the glass plate at 60 ℃ for 4 hours, heating the glass plate to 80 ℃ for 12 hours, drying the glass plate at 120 ℃ for 4 hours, removing the film, sequentially placing the glass plate in a 3% H2O2 solution, a 1M H2SO4 solution and deionized water, and respectively soaking the glass plate in 80 ℃ for 1 hour to finally obtain the semi-interpenetrating network film containing 5 weight percent of the polyoxometalate hybrid polymer electrolyte.
The mass ratio of the cross-linked poly metal oxygen cluster polymer to the PFSA resin solution in the step S2 is 0.05-0.15: 1.
the thickness of the polyoxometalate hybridization polyelectrolyte semi-interpenetrating network membrane is 15-22 mu m.
Example 2
The preparation method of the multi-metal oxygen cluster hybrid polyelectrolyte semi-interpenetrating network membrane comprises the following specific steps:
s1. preparation of crosslinked polymetallic oxygen cluster Polymer
Compound a and compound B were combined according to a functional group molar ratio of 3:2, uniformly mixing the mixture in an organic reagent, adding acetic acid to form a uniform mixture, heating the mixture at 80-120 ℃ for 3-5 days, cooling the mixture to room temperature, filtering, washing, soxhlet extracting, and drying to obtain the cross-linked poly-metal oxygen cluster polymer;
wherein the compound A is [ N (C4H 9) 4]3[ MnMo6O18{ (OCH 2) 3CNH2}2], and the compound B is trimesoyl aldehyde; the organic reagent is one or more of acetonitrile, 1, 4-dioxane or mesitylene.
The preparation method of the compound A comprises the following steps:
weighing a proper amount of sodium molybdate, dissolving the sodium molybdate in deionized water, adding a proper amount of hydrochloric acid for acidification, and then adding a proper amount of tetrabutylammonium bromide, wherein the molar ratio of the sodium molybdate to the tetrabutylammonium bromide is 2:1, white precipitate is generated, stirring is carried out at room temperature, then, white solid [ N (C4H 9) 4]3[ alpha-Mo 6O26], [ N (C4H 9) 4]3[ alpha-Mo 6O26] is obtained by filtration and collection, mn (Ac) 3 and trihydroxymethoxyaminomethane are mixed and dissolved in acetonitrile, the mol ratio is 1.5:2:5, the mixture is heated to 85 ℃ for reaction, then, the reaction solution is filtered, and is placed in diethyl ether for diffusion for a period of time, thus obtaining the compound A.
S2: multi-metal oxygen cluster hybrid polymer electrolyte semi-interpenetrating network membrane
1.132g of 25% PFSA resin solution is weighed, the solvent is evaporated in a forced air drying oven at 60-70 ℃, then the solvent is dissolved in 16ml of N, N-dimethylformamide DMF solvent, then 31.58mg of the cross-linked polyoxometalate polymer obtained in S1 is weighed and added into the PFSA resin solution, the cross-linked polyoxometalate polymer is fully dissolved by ultrasonic treatment for 30min, and the solution is left stand for 10min to completely degas, so that a film solution with 2wt% of solid content is obtained;
and casting the film on a glass plate with the thickness of 9cm multiplied by 9cm, placing the glass plate in a vacuum oven, drying the glass plate at 60 ℃ for 5 hours, heating the glass plate to 80 ℃ for 12 hours, drying the glass plate at 120 ℃ for 5 hours, removing the film, sequentially placing the glass plate in a 3% H2O2 solution, a 1M H2SO4 solution and deionized water, and respectively soaking the glass plate in 80 ℃ for 1 hour to finally obtain the 10wt% polyoxometalate hybrid polymer electrolyte semi-interpenetrating network film.
The mass ratio of the cross-linked poly metal oxygen cluster polymer to the PFSA resin solution in the step S2 is 0.05-0.15: 1.
the thickness of the polyoxometalate hybridization polyelectrolyte semi-interpenetrating network membrane is 15-22 mu m.
Example 3
The preparation method of the multi-metal oxygen cluster hybrid polyelectrolyte semi-interpenetrating network membrane comprises the following specific steps:
s1. preparation of crosslinked polymetallic oxygen cluster Polymer
Compound a and compound B were combined according to a functional group molar ratio of 3:2, uniformly mixing the mixture in an organic reagent, adding acetic acid to form a uniform mixture, heating the mixture at 80-120 ℃ for 3-5 days, cooling the mixture to room temperature, filtering, washing, soxhlet extracting, and drying to obtain the cross-linked poly-metal oxygen cluster polymer;
wherein the compound A is [ N (C4H 9) 4]3[ MnMo6O18{ (OCH 2) 3CNH2}2], and the compound B is trimesoyl aldehyde; the organic reagent is one or more of acetonitrile, 1, 4-dioxane or mesitylene.
The preparation method of the compound A comprises the following steps:
weighing a proper amount of sodium molybdate, dissolving the sodium molybdate in deionized water, adding a proper amount of hydrochloric acid for acidification, and then adding a proper amount of tetrabutylammonium bromide, wherein the molar ratio of the sodium molybdate to the tetrabutylammonium bromide is 2:1, white precipitate is generated, stirring is carried out at room temperature, then, white solid [ N (C4H 9) 4]3[ alpha-Mo 6O26], [ N (C4H 9) 4]3[ alpha-Mo 6O26] is obtained by filtration and collected, mn (Ac) 3 and trihydroxymethoxyaminomethane are mixed and dissolved in acetonitrile, the mol ratio is 1.5:2:5, the mixture is heated to 85 ℃ for reaction, then, the reaction solution is filtered, and is placed in diethyl ether for diffusion for a period of time, thus obtaining the compound A.
S2: multi-metal oxygen cluster hybrid polymer electrolyte semi-interpenetrating network membrane
1.052g of 25% PFSA resin solution is weighed, the solvent is evaporated in a forced air drying oven at 60-70 ℃, then the solvent is dissolved in 16ml of N, N-dimethylformamide DMF solvent, then 31.58mg of the cross-linked polyoxometalate polymer obtained in S1 is weighed and added into the PFSA resin solution, the cross-linked polyoxometalate polymer is fully dissolved by ultrasonic treatment for 30min, and the solution is left for 10min to completely degas, so that a film solution with 2wt% of solid content is obtained;
and casting the film on a glass plate with the thickness of 9cm multiplied by 9cm, placing the glass plate in a vacuum oven, drying the glass plate at 60 ℃ for 6 hours, heating the glass plate to 80 ℃ for 12 hours, drying the glass plate at 120 ℃ for 6 hours, removing the film, sequentially placing the glass plate in a 3% H2O2 solution, a 1M H2SO4 solution and deionized water, and respectively soaking the glass plate in 80 ℃ for 1 hour to finally obtain the semi-interpenetrating network film containing 15wt% of the polyoxometalate hybrid polymer electrolyte.
The mass ratio of the cross-linked poly metal oxygen cluster polymer to the PFSA resin solution in the step S2 is 0.05-0.15: 1.
the thickness of the polyoxometalate hybridization polyelectrolyte semi-interpenetrating network membrane is 15-22 mu m.
Comparative example
1.28g of 25% PFSA resin solution is weighed, the solvent is evaporated in a forced air drying oven at 60-70 ℃, then the solvent is dissolved in 16ml of N, N-dimethylformamide DMF solvent, then the solution is cast into a film on a 9cm multiplied by 9cm glass plate, and the film is placed in a vacuum oven, dried for 8 hours at 80 ℃ and then dried for 12 hours at 120 ℃ after the temperature is raised to obtain the recast resin film.
FIG. 1 shows an infrared spectrum of recast PFSA films and hybrid films of various examples containing different mass fractions of cross-linked multi-metallic oxygen cluster polymers.
By comparison of the individual hybrid films and recast PFSA films in infrared characterization, the characteristic peaks at 2817cm "1, 1053 cm" 1 were attributed to stretching vibrations of O-H and o=s=o, and the peaks of all hybrid sipn films at 2817cm "1 were significantly weaker due to hydrogen bonding formed between mo=o bonds and SO3H, which is consistent with the attenuation of the characteristic peaks at 814, 917 and 938 cm" 1 for mo=o; the above results indicate that the driving force for the construction of hybrid polyelectrolyte semi-interpenetrating network membrane hybrid sipn is induced by hydrogen bonding.
FIG. 2 shows scanning electron microscopy images of recast PFSA films and hybrid films of various examples containing different mass fractions of cross-linked multi-metallic oxygen cluster polymers.
From the figure, it can be seen that the surfaces of all the hybrid sipn films exhibited a dense and flat state. The section also has no obvious folds, and the compatibility of the perfluorinated sulfonic acid resin and the cross-linked polyoxometalate polymer is better, so that a good film forming state is achieved. The thickness of the film is between 15 μm and 22 μm.
FIG. 3 shows a thermogravimetric analysis of PFSA/Anderson polymetallic oxygen cluster hybrid polyelectrolyte network membranes. It can be seen from the figure that the thermal stability of the hybrid film is improved due to the introduction of the polyoxometalate hybrid polymer.
Table 1 below sets forth a table of tensile strength and elongation at break for PFSA/Anderson polyoxometalate hybrid polyelectrolyte semi-interpenetrating network membranes. The tensile strength of the recast PFSA is 14.5Mpa, the elongation at break is 42.5%, and when the cross-linked multi-metal oxygen cluster polymer is added to construct a hybrid semi-interpenetrating polymer network, the tensile strength of the hybrid polyelectrolyte semi-interpenetrating polymer network film hybrid SIPN is 18.2-28.6 Mpa, and the mechanical property is improved.
TABLE 1
| Membranes | TensileStrength(Mpa) | Elongationatbreak(%) |
| RecastPFSA | 14.5 | 42.5 |
| HybridSIPN-5% | 28.6 | 38.3 |
| HybridSIPN-10% | 20 | 30.9 |
| HybridSIPN-15% | 18.2 | 23.2 |
Proton conductivity is one of the important parameters for evaluating PEMs performance. We studied the change in proton conductivity with temperature for recast PFSA membranes and hybrid sipn membranes as shown in figure 4. As the temperature increases, the proton conductivity of all membranes increases significantly. The highest proton conductivity of the hybrid SIPN-10% is 0.106S/cm-0.259S/cm in the range of 20-80 ℃. At 80℃the proton conductivity of the hybrid SIPN-10% membrane was 3.2 times that of the recast PFSA (0.082S/cm).
The quality of the PFSA/Anderson polyoxometalate hybrid polyelectrolyte semi-interpenetrating network membranes was evaluated by fuel cell testing. FIG. 5 is an open circuit voltage, power density at different current densities for recast PFSA films, NC700 films, and polymer electrolyte network films containing different mass fractions of multi-metal oxygen cluster hybrid polymers.
The polarization curves measured in FIG. 5 show that the recast PFSA film and the hybrid SIPN film have an open circuit voltage of 0.9V or more, indicating low hydrogen permeability. In addition, we can see that the slope of the hybrid sipn membrane in the medium current density region is lower, indicating that the internal resistance of the fuel cell is smaller and the addition of the cross-linked multi-metallic oxygen cluster polymer promotes proton transport within the membrane. The highest current density and power density of the recast PFSA were 1552mA/cm2 and 706mW/cm2, respectively. In contrast, the highest power density of hybrid sipn-10% was increased by 40.4%, which is mainly due to the reduced transmission resistance in the membrane caused by the increase in proton conductivity, which can also be verified by EIS data of MEA at different current densities, as can be seen from fig. 5b-d, the ohmic resistance of all hybrid sipn membranes is lower than commercial NC700, indicating that hybrid sipn membranes have higher conductivity and good membrane electrode interface compatibility.
The results prove that the proton conductivity and the battery performance of the hybrid membrane can be improved to a certain extent by introducing the cross-linked poly-metal oxygen cluster polymer, and the cross-linked polymer is entangled with the perfluorinated sulfonic acid resin, so that the compactness of the membrane is enhanced, and pinholes in the operation process of the membrane are reduced, thereby improving the battery performance of the membrane.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention and not for limiting the technical solution of the present invention, and although the present invention has been described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that the present invention may be modified or equivalently replaced without departing from the spirit and scope of the present invention, and any modification or partial replacement thereof should be included in the scope of the claims of the present invention.
Claims (6)
1. The preparation method of the multi-metal oxygen cluster hybridization polyelectrolyte semi-interpenetrating network membrane is characterized by comprising the following specific steps of:
s1: preparation of crosslinked polymetallic oxygen cluster polymers
Compound a and compound B were combined according to a functional group molar ratio of 3:2, uniformly mixing the mixture in an organic reagent, adding acetic acid to form a uniform mixture, heating the mixture at a certain temperature for a certain time, cooling the mixture to room temperature, filtering, washing, soxhlet extracting, and drying to obtain a cross-linked poly metal oxygen cluster polymer;
s2: multi-metal oxygen cluster hybrid polymer electrolyte semi-interpenetrating network membrane
Evaporating 25% of PFSA resin solution at 60-70 ℃ to dryness, dissolving the solvent in N, N-dimethylformamide DMF solvent, adding the cross-linked polyoxometalate polymer obtained in S1 into the PFSA resin solution, carrying out ultrasonic treatment for 30min, standing for 10min to completely degas the polymer to obtain a membrane solution, casting the membrane on a glass plate to form a membrane, drying at 60 ℃ for 4-6H, heating to 80 ℃ for 12H, drying at 120 ℃ for 4-6H, removing the membrane, sequentially placing the membrane into 3% of H2O2 solution, 1M of H2SO4 solution and deionized water, and respectively soaking the membrane at 80 ℃ for 1H to obtain the polyoxometalate hybrid polymer electrolyte semi-interpenetrating network membrane;
the compound A is [ N (C4H 9) 4]3[ MnMo6O18{ (OCH 2) 3CNH2}2], and the compound B is trimesic aldehyde.
2. The method for preparing the polyoxometalate hybridization polyelectrolyte semi-interpenetrating network membrane according to claim 1, wherein the organic reagent is one or more of acetonitrile, 1, 4-dioxane or mesitylene.
3. The method for preparing the polyoxometalate hybridization polyelectrolyte semi-interpenetrating network membrane according to claim 1, wherein the reaction temperature is 80-120 ℃ and the reaction time is 3-5 days.
4. The preparation method of the polyoxometalate hybridization polyelectrolyte semi-interpenetrating network membrane according to claim 1, wherein the preparation method of the compound A is as follows:
weighing a proper amount of sodium molybdate, dissolving the sodium molybdate in deionized water, adding a proper amount of hydrochloric acid for acidification, and then adding a proper amount of tetrabutylammonium bromide, wherein the molar ratio of the sodium molybdate to the tetrabutylammonium bromide is 2:1, white precipitate is generated, stirring is carried out at room temperature, then, white solid [ N (C4H 9) 4]3[ alpha-Mo 6O26], [ N (C4H 9) 4]3[ alpha-Mo 6O26] is obtained by filtration and collected, mn (Ac) 3 and trihydroxymethoxyaminomethane are mixed and dissolved in acetonitrile, the mol ratio is 1.5:2:5, the mixture is heated to 85 ℃ for reaction, then, the reaction solution is filtered, and is placed in diethyl ether for diffusion for a period of time, thus obtaining the compound A.
5. The method for preparing the polyoxometalate hybridization polyelectrolyte semi-interpenetrating network membrane according to claim 1, wherein the method comprises the following steps of,
the mass ratio of the cross-linked poly metal oxygen cluster polymer to the PFSA resin solution in the step S2 is 0.05-0.15: 1.
6. the method for preparing the polyoxometalate hybridization polyelectrolyte semi-interpenetrating network membrane according to claim 5, wherein the thickness of the polyoxometalate hybridization polyelectrolyte semi-interpenetrating network membrane is 15-22 μm.
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