CN116826124A - Composite perfluorosulfonic acid proton exchange membrane and preparation method and application thereof - Google Patents
Composite perfluorosulfonic acid proton exchange membrane and preparation method and application thereof Download PDFInfo
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- CN116826124A CN116826124A CN202310879114.7A CN202310879114A CN116826124A CN 116826124 A CN116826124 A CN 116826124A CN 202310879114 A CN202310879114 A CN 202310879114A CN 116826124 A CN116826124 A CN 116826124A
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- exchange membrane
- proton exchange
- perfluorosulfonic acid
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- 239000012528 membrane Substances 0.000 title claims abstract description 87
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 49
- 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 abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 14
- 150000000703 Cerium Chemical class 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000003460 sulfonic acids Chemical class 0.000 claims description 14
- 239000000446 fuel Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229960001759 cerium oxalate Drugs 0.000 claims description 3
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 3
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 6
- 230000006872 improvement Effects 0.000 abstract description 5
- 238000002144 chemical decomposition reaction Methods 0.000 abstract description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 7
- 239000000805 composite resin Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- -1 hydroxyl radicals Chemical class 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010345 tape casting Methods 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 239000012028 Fenton's reagent Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229940123457 Free radical scavenger Drugs 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000012556 adjustment buffer 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
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000007760 free radical scavenging Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Dispersion Chemistry (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to a perfluorosulfonic acid proton exchange membrane, in particular to a composite perfluorosulfonic acid proton exchange membrane and a preparation method and application thereof, comprising the following steps: s1: preparation of Ce-TMA MOFs: adding cerium salt and trimesic acid into a water-ethanol mixed solvent, filtering and drying after the reaction to obtain Ce-TMA MOFs; s2: preparing a composite perfluorosulfonic acid proton exchange membrane: and (3) mixing the Ce-TMA MOFs obtained in the step (S1) with the perfluorosulfonic acid resin solution, stirring, carrying out ultrasonic treatment, and then coating, and carrying out heat treatment to obtain the composite perfluorosulfonic acid proton exchange membrane. Compared with the prior art, the invention solves the problem that the proton exchange membrane in the prior art is failed due to chemical degradation of hydrogen peroxide and hydroxyl radical (HO), realizes the improvement of the chemical stability of the proton exchange membrane, and shows excellent proton conductivity.
Description
Technical Field
The invention relates to a perfluorosulfonic acid proton exchange membrane, in particular to a composite perfluorosulfonic acid proton exchange membrane and a preparation method and application thereof.
Background
Along with the rapid development of society, the demand of people for energy is also increasing, and the traditional fossil fuels can pollute the environment and destroy ecology in the use process, so that sustainable clean energy is widely concerned. Proton Exchange Membrane Fuel Cells (PEMFCs) have been recently considered to have a wide application prospect in the scenes of electric vehicles, power generation, portable devices, and the like because of their high working efficiency, zero pollution, and renewable energy source-hydrogen as a raw material.
The fuel cell membrane electrode is a key component of PEMFCs, and the Proton Exchange Membrane (PEM) is a core of the membrane electrode, so that the proton conducting effect is achieved, and the gas between the anode and the cathode can be separated, so that safety accidents are avoided. The perfluorosulfonic acid proton exchange membrane which has been commercialized today shows better proton conductivity, chemical stability and mechanical properties at high humidity and low temperature. However, during operation of the fuel cell, the electrodes generate large amounts of hydrogen peroxide and hydroxyl radicals (ho·) which cause severe chemical degradation of the membrane and even direct failure of the proton exchange membrane.
Chinese patent CN114373971B discloses a method for preparing proton exchange membrane by blending perfluorinated sulfonic acid resin and Ce-MOF, and by adding metal organic framework Ce-MOF additive, a composite proton exchange membrane with good proton conductivity and chemical durability is prepared. However, the MOF material in this patent only plays a role in supporting and fixing cerium ions, and does not have the effect of scavenging free radicals.
In view of the foregoing, there remains a need for improvements in proton exchange membranes to achieve better free radical scavenging.
Disclosure of Invention
The invention aims to solve at least one of the problems and provide a composite perfluorosulfonic acid proton exchange membrane, a preparation method and application thereof, so as to solve the problem that the proton exchange membrane in the prior art is invalid due to chemical degradation of hydrogen peroxide and hydroxyl radicals (HO), realize the improvement of the chemical stability of the proton exchange membrane and show excellent proton conductivity.
The aim of the invention is achieved by the following technical scheme:
the invention discloses a preparation method of a composite perfluorosulfonic acid proton exchange membrane, which comprises the following steps:
s1: preparation of Ce-TMA MOFs: adding cerium salt and trimesic acid into a water-ethanol mixed solvent, filtering and drying after the reaction to obtain Ce-TMA MOFs;
s2: preparing a composite perfluorosulfonic acid proton exchange membrane: and (3) mixing the Ce-TMA MOFs obtained in the step (S1) with the perfluorosulfonic acid resin solution, stirring, carrying out ultrasonic treatment, and then coating, and carrying out heat treatment to obtain the composite perfluorosulfonic acid proton exchange membrane.
Preferably, in step S1, the molar ratio of cerium salt to trimesic acid is 1:1-3:1, the mass ratio of water to ethanol is 1:1-4:1, 1mmol of cerium salt and 1mmol of trimesic acid are dissolved in each 100mL of water-ethanol mixed solvent.
Preferably, the cerium salt is selected from one or more of cerium nitrate hexahydrate, cerium oxalate and cerium carbonate.
Preferably, in the step S1, the reaction temperature is 20-50 ℃ and the reaction time is 3-12h; the drying temperature is 60-110 deg.C and the drying time is 0.5-2h.
Preferably, in step S2, after the Ce-TMA MOFs are mixed with the perfluorosulfonic acid resin solution, the mass percentage of the Ce-TMA MOFs is 0.2 to 10%.
Preferably, in step S2, the perfluorosulfonic acid resin solution is prepared by the steps of:
and adding the perfluorosulfonic acid resin into the water-isopropanol mixed solvent, and stirring to obtain the perfluorosulfonic acid resin solution.
Preferably, the mass ratio of water to isopropanol is 1:1-1:3, the mass concentration of the perfluorinated sulfonic acid resin in the perfluorinated sulfonic acid resin solution is 10-30wt%.
Preferably, in step S2, the stirring time is 24-48 hours; the ultrasonic time is 0.5-2h; the heat treatment temperature is 80-120 ℃ and the heat treatment time is 4-12h.
The second aspect of the invention discloses a composite perfluorosulfonic acid proton exchange membrane, which is prepared by any one of the methods.
The invention in a third aspect discloses application of the composite perfluorosulfonic acid proton exchange membrane in the fields of fuel cells, water electrolysis hydrogen production and flow batteries.
The working principle of the invention is as follows:
TMA MOFs are a common and typical metal organic framework, have water absorption, exist in proton membranes for a long time, and form a hydrogen bond network connecting water molecules and hydroxyl groups, facilitating proton conduction. The large specific surface area of the MOF material provides the opportunity to accommodate more proton carriers while also creating the opportunity to enhance the proton conductivity of the composite membrane. Meanwhile, in Ce-TMA MOFs, ce-O bond and oxygen vacancy formation increases Ce 3+ /Ce 4+ Thereby significantly improving the capability of the Ce-TMA MOFs for eliminating hydroxyl free radicals.
Compared with the prior art, the invention has the following beneficial effects:
1. the MOF material selected by the invention has the following advantages:
(1) Compared with the conventional free radical scavenger, the free radical scavenger is not easy to migrate out of the membrane;
(2) Improving proton transmission path and enhancing tight connection with water molecules;
(3) The hydrogen bond network existing in the MOF material has excellent proton conductivity;
(4) The MOF material has low cost and large-scale application production potential.
2. According to the invention, the Ce-TMA MOFs is added into the perfluorinated sulfonic acid resin solution, so that the prepared composite proton membrane has excellent proton conductivity while maintaining high chemical durability, meets the application requirements of a fuel cell, and has important application value.
Drawings
FIG. 1 is a graph showing the change in proton conductivity with temperature of the composite perfluorosulfonic acid proton exchange membrane prepared in examples 1-5 and comparative example 1;
FIG. 2 is a graph showing the release amount of Fenton-explained fluoride ions for the composite perfluorosulfonic acid proton exchange membrane prepared in examples 1-5 and comparative example 1.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
In the examples below, unless otherwise specified, the reagents used may be conventional commercial products and the methods employed may be means well known in the art.
The preparation method of the cerium-containing metal organic framework compound and perfluorinated sulfonic acid resin composite proton exchange membrane mainly comprises the following steps:
(1) Adding perfluorosulfonic acid resin powder into a mixed solvent of water and isopropanol in a mass ratio of 1:1-1:3, and stirring for 12 hours at room temperature to obtain 10-30wt% of perfluorosulfonic acid solution;
(2) Adding cerium salt and trimesic acid into a mixed solvent of water and ethanol in a mass ratio of 1:1-4:1 according to a molar ratio of 1:1-3:1, stirring, filtering and drying to obtain Ce-TMA MOFs;
wherein the cerium salt is one or more of cerium nitrate hexahydrate, cerium oxalate and cerium carbonate, the stirring temperature is 20-50 ℃, the reaction time is 3-12h, the drying temperature is 60-110 ℃, and the drying time is 0.5-2h;
(3) Adding Ce-TMA MOFs into a perfluorinated sulfonic acid resin solution according to a certain mass ratio for mixing, stirring, carrying out ultrasonic treatment, casting the uniformly dispersed mixed solution through a coating machine, carrying out heat treatment for a certain time in an oven at a certain temperature, and standing and cooling to room temperature to obtain the Ce-TMA MOFs and perfluorinated sulfonic acid resin composite proton exchange membrane.
Wherein the addition amount of Ce-TMA MOFs is 0.2-10% of the ratio of the Ce-TMA MOFs to the perfluorosulfonic acid resin solution, the stirring time is 24-48h, the ultrasonic time is 0.5-2h, the heat treatment temperature is 80-120 ℃ and the time is 4-12h.
The following examples are given under the premise of the technical method of the present invention, and the detailed operation method and the specific experimental procedure are listed, but the scope of the present invention is not limited to the following examples.
Example 1
The preparation method of the cerium-containing metal organic framework compound and perfluorinated sulfonic acid resin composite proton exchange membrane comprises the following steps:
(1) Adding 3g of perfluorosulfonic acid resin into 8.54g of mixed solvent with the mass ratio of water to isopropanol being 1:1, and stirring for 48 hours at room temperature to obtain a uniform 26wt% perfluorosulfonic acid solution;
(2) 1mmol of trimesic acid is added into 70mL of water-ethanol solution, heating and stirring are carried out, and heating is stopped after all the solution is dissolved;
(3) Adding 1mmol of cerium nitrate hexahydrate into 30mL of deionized water, stirring at room temperature until the cerium nitrate hexahydrate is fully dissolved, slowly dripping the cerium nitrate hexahydrate into the cooled solution obtained in the step (2) by using a dropper, and continuously stirring at 30 ℃ for reaction for 12 hours;
filtering the solution, and drying the filtered product in an oven for 1h to obtain Ce-TMA MOFs;
(4) Ce-TMA MOFs were added in an amount of 0.5wt% to 3g of a 26wt% perfluorosulfonic acid resin solution, stirred for 48 hours to give a uniform dispersion, and then sonicated for 0.5 hours to uniformly disperse the additives and remove bubbles.
And (3) carrying out tape casting coating on the uniformly dispersed mixed solution by a coating machine, drying for 8 hours in an oven at 80 ℃, and standing and cooling to room temperature to obtain the composite proton exchange membrane.
Example 2
A Ce-containing metal organic framework compound and perfluorinated sulfonic acid resin composite proton exchange membrane and a preparation method thereof comprise the following steps:
(1) Adding 3g of perfluorosulfonic acid resin into 8.54g of mixed solvent with the mass ratio of water to isopropanol being 1:1, and stirring for 48 hours at room temperature to obtain a uniform 26wt% perfluorosulfonic acid solution;
(2) 1mmol of trimesic acid is added into 70mL of aqueous ethanol solution, heating and stirring are carried out, and heating is stopped after all the trimesic acid is dissolved;
(3) Adding 1mmol of cerium nitrate hexahydrate into 30mL of deionized water, stirring at room temperature until the cerium nitrate hexahydrate is fully dissolved, slowly dripping the cerium nitrate hexahydrate into the cooled solution obtained in the step (2) by using a dropper, and continuously stirring at 30 ℃ for reaction for 12 hours;
filtering the solution, and drying the filtered product in an oven for 1h to obtain Ce-TMA MOFs;
(4) Ce-TMA MOFs were added in an amount of 0.8wt% to 3g of a 26wt% perfluorosulfonic acid resin solution, stirred for 48 hours to give a uniform dispersion, and then sonicated for 0.5 hours to uniformly disperse the additives and remove bubbles.
And (3) carrying out tape casting coating on the uniformly dispersed mixed solution by a coating machine, drying for 4 hours at 120 ℃, and standing and cooling to room temperature to obtain the composite proton exchange membrane.
Example 3
A Ce-containing metal organic framework compound and perfluorinated sulfonic acid resin composite proton exchange membrane and a preparation method thereof comprise the following steps:
(1) Adding 3g of perfluorosulfonic acid resin into 8.54g of mixed solvent with the mass ratio of water to isopropanol being 1:1, and stirring for 48 hours at room temperature to obtain a uniform 26wt% perfluorosulfonic acid solution;
(2) 1mmol of trimesic acid is added into 70mL of aqueous ethanol solution, heating and stirring are carried out, and heating is stopped after all the trimesic acid is dissolved;
(3) Adding 1mmol of cerium nitrate hexahydrate into 30mL of deionized water, stirring at room temperature until the cerium nitrate hexahydrate is fully dissolved, slowly dripping the cerium nitrate hexahydrate into the cooled solution obtained in the step (2) by using a dropper, and continuously stirring at 30 ℃ for reaction for 12 hours;
filtering the solution, and drying the filtered product in an oven for 1h to obtain Ce-TMA MOFs;
(4) Ce-TMA MOFs were added in an amount of 1wt% to 3g of a 26wt% perfluorosulfonic acid resin solution and stirred for 48 hours to give a uniform dispersion, followed by ultrasonic treatment for 0.5 hour to uniformly disperse the additives and remove bubbles.
And (3) carrying out tape casting coating on the uniformly dispersed mixed solution by a coating machine, drying for 6 hours at 90 ℃, and standing and cooling to room temperature to obtain the composite proton exchange membrane.
Example 4
A Ce-containing metal organic framework compound and perfluorinated sulfonic acid resin composite proton exchange membrane and a preparation method thereof comprise the following steps:
(1) Adding 3g of perfluorosulfonic acid resin into 8.54g of mixed solvent with the mass ratio of water to isopropanol being 1:1, and stirring for 48 hours at room temperature to obtain a uniform 26wt% perfluorosulfonic acid solution;
(2) 1mmol of trimesic acid is added into 70mL of aqueous ethanol solution, heating and stirring are carried out, and heating is stopped after all the trimesic acid is dissolved;
(3) Adding 1mmol of cerium nitrate hexahydrate into 30mL of deionized water, stirring at room temperature until the cerium nitrate hexahydrate is fully dissolved, slowly dripping the cerium nitrate hexahydrate into the cooled solution obtained in the step (2) by using a dropper, and continuously stirring at 30 ℃ for reaction for 12 hours;
filtering the solution, and drying the filtered product in an oven for 1h to obtain Ce-TMA MOFs;
(4) Ce-TMA MOFs were added in an amount of 1.5wt% to 3g of a 26wt% perfluorosulfonic acid resin solution and stirred for 48 hours to give a uniform dispersion, followed by ultrasonic treatment for 0.5h to uniformly disperse the additives and remove bubbles.
And (3) carrying out tape casting coating on the uniformly dispersed mixed solution by a coating machine, drying for 6 hours at 90 ℃, and standing and cooling to room temperature to obtain the composite proton exchange membrane.
Example 5
A Ce-containing metal organic framework compound and perfluorinated sulfonic acid resin composite proton exchange membrane and a preparation method thereof comprise the following steps:
(1) Adding 3g of perfluorosulfonic acid resin into 8.54g of mixed solvent with the mass ratio of water to isopropanol being 1:1, and stirring for 48 hours at room temperature to obtain a uniform 26wt% perfluorosulfonic acid solution;
(2) 1mmol of trimesic acid is added into 70mL of aqueous ethanol solution, heating and stirring are carried out, and heating is stopped after all the trimesic acid is dissolved;
(3) Adding 1mmol of cerium nitrate hexahydrate into 30mL of deionized water, stirring at room temperature until the cerium nitrate hexahydrate is fully dissolved, slowly dripping the cerium nitrate hexahydrate into the cooled solution obtained in the step (2) by using a dropper, and continuously stirring at 30 ℃ for reaction for 12 hours;
filtering the solution, and drying the filtered product in an oven for 1h to obtain Ce-TMA MOFs;
(4) Ce-TMA MOFs were added in an amount of 2wt% to 3g of a 26wt% perfluorosulfonic acid resin solution and stirred for 48 hours to give a uniform dispersion, followed by ultrasonic treatment for 0.5 hour to uniformly disperse the additives and remove bubbles.
And (3) carrying out tape casting coating on the uniformly dispersed mixed solution by a coating machine, drying for 6 hours at 90 ℃, and standing and cooling to room temperature to obtain the composite proton exchange membrane.
Comparative example 1
The main difference between the preparation method of this comparative example and the above example is that no Ce-TMA MOFs were added and the rest of the procedure was the same as in example one.
The prepared composite proton membrane is subjected to the following performance detection:
1. proton conductivity
The preparation methods of examples 1-5 and comparative example 1 were used to prepare composite proton exchange membranes, respectively, using the proton exchange membrane fuel cell section 3 of GB/T20042.3-2009: proton exchange Membrane test method proton conductivities of the proton exchange membranes prepared in examples 1 to 3 and comparative example 1 were examined, respectively.
2. Chemical stability test
Proton exchange membranes were prepared by the preparation methods of examples 1 to 5 and comparative example 1, respectively, using 4ppm Fe 2+ (0.00366 g of ferrous sulfate heptahydrate) 30wt% of 50mL H was added 2 O 2 And 150mL of deionized water to prepare the Fenton reagent. Thereafter, a 4cm film (dry weight m has been weighed) was subjected to a water bath at 80℃ dry ) Immersing in Fenton reagent, treating for 4h,the degree of corrosion of the film was tested to determine the chemical durability of the film. After Fenton experiments the membranes were rinsed in deionized water at 80℃for 2h. The residual liquid collected after the Fenton experiment was measured for the content of fluoride ions released into the Fenton solution by a fluorimeter. Mainly comprises the following steps, firstly, measuring the volume of the residual solution after the reaction and recording as V solution 10mL was added to a 100mL volumetric flask, followed by 10mL Total Ionic Strength Adjustment Buffer (TISAB) to provide constant ionic strength, and finally deionized water was used to scale the line. The fluoride ion release (mmol/g) of the membrane is calculated from the following formula:
in the formula, [ F ] - ]In terms of the release amount (mmol/g) of fluorine ions, V solution Residual volume (mL) of Fenton reagent, M F Is the molar mass of fluorine (19.0 g/mol), m dry Is the starting dry weight (mg) of the film sample.
3. Water absorption rate
Proton exchange membranes were prepared by the preparation methods of examples 1 to 5 and comparative example 1, respectively, the prepared membranes were cut into 2 cm. Times.2 cm membranes, dried in an oven at 80℃for 4 hours, and taken out to weigh m immediately 1 . Then placing the sample membrane into deionized water with different temperatures, taking out the membrane after completely immersing the membrane into deionized water, each temperature gradient being 25min, taking out the membrane, absorbing surface water with filter paper, and weighing and recording m 2 . The water absorption of the prepared film samples was calculated from the following formula:
m is in 1 And m 2 The mass of the dry film forming sample and the mass of the wet film forming sample are respectively.
4. Tensile Strength and elongation at break
Proton exchange membranes were prepared by the preparation methods of examples 1 to 5 and comparative example 1, respectively, using the third part of the proton exchange membrane fuel cell of GB/T20042.3-2009: proton exchange membrane fuel cell test methods tensile strength and elongation at break were measured for examples 1-5 and comparative example 1, respectively.
As can be seen from FIG. 1 in combination with examples 1-5 and comparative example 1, the proton conductivities of examples 1-3 are all higher than that of comparative example 1, while the proton conductivities of examples 4-5 are only slightly lower than that of comparative example 1 at 30-80 ℃. It can be seen that an appropriate amount of the additive contributes to an improvement in proton conductivity, and the tendency of proton conductivity shows a decrease with an increase in the additive, which may be mainly because an excessive amount of the additive blocks a proton conducting channel, resulting in a decrease in its conducting efficiency.
As can be seen from fig. 2 in combination with examples 1 to 5 and comparative example 1, the proton membranes of examples 1 to 5 each have a lower fluoride ion release than that of the proton membrane of comparative example 1, indicating that the composite proton exchange membrane prepared in the present invention exhibits excellent chemical durability.
As can be seen from Table 1 in combination with examples 1-5 and comparative example 1, the water absorption of the proton membranes of examples 2-5 is higher than that of the proton membrane of comparative example 1, and the water absorption of the proton membrane of example 1 is substantially the same as that of comparative example 1. The proton membranes prepared in examples 2-5 exhibited a tendency to absorb water as a whole, mainly depending on the overall water absorption of the proton membranes prepared.
Table 1 water absorption test results
| Comparative example 1 | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| 30℃ | 11.62％ | 11.58％ | 12.58％ | 12.98％ | 13.69％ | 17.36％ |
| 40℃ | 14.20％ | 14.16％ | 15.16％ | 15.87％ | 16.66％ | 21.60％ |
| 50℃ | 15.30％ | 16.21％ | 18.21％ | 18.90％ | 19.09％ | 24.29％ |
| 60℃ | 18.01％ | 19.85％ | 20.85％ | 23.65％ | 24.04％ | 27.12％ |
| 70℃ | 20.01％ | 20.51％ | 24.51％ | 25.90％ | 26.61％ | 31.49％ |
| 80℃ | 21.76％ | 22.14％ | 27.74％ | 28.56％ | 29.05％ | 33.72％ |
As can be seen from table 2 in combination with examples 1-5 and comparative example 1, the tensile strength of the proton membranes of examples 1-5 is higher than that of the proton membrane of comparative example 1, which indicates that Ce-MOF plays a supporting role in the proton exchange membrane, further improving the strength of the proton exchange membrane.
TABLE 2 chemical stability, tensile Strength and elongation at break test results
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the composite perfluorosulfonic acid proton exchange membrane is characterized by comprising the following steps:
s1: preparation of Ce-TMA MOFs: adding cerium salt and trimesic acid into a water-ethanol mixed solvent, filtering and drying after the reaction to obtain Ce-TMA MOFs;
s2: preparing a composite perfluorosulfonic acid proton exchange membrane: and (3) mixing the Ce-TMA MOFs obtained in the step (S1) with the perfluorosulfonic acid resin solution, stirring, carrying out ultrasonic treatment, and then coating, and carrying out heat treatment to obtain the composite perfluorosulfonic acid proton exchange membrane.
2. The method for preparing a composite perfluorosulfonic acid proton exchange membrane according to claim 1, wherein in step S1, the molar ratio of cerium salt to trimesic acid is 1:1-3:1, the mass ratio of water to ethanol is 1:1-4: 1-3mmol cerium salt and 1mmol trimesic acid are dissolved in each 100mL water-ethanol mixed solvent.
3. The method for preparing a composite perfluorosulfonic acid proton exchange membrane according to claim 2, wherein the cerium salt is one or more selected from the group consisting of cerium nitrate hexahydrate, cerium oxalate and cerium carbonate.
4. The method for preparing a composite perfluorosulfonic acid proton exchange membrane according to claim 1, wherein in the step S1, the reaction temperature is 20-50 ℃ and the reaction time is 3-12h; the drying temperature is 60-110 deg.C and the drying time is 0.5-2h.
5. The method for preparing a composite perfluorosulfonic acid proton exchange membrane according to claim 1, wherein in step S2, after Ce-TMA MOFs are mixed with perfluorosulfonic acid resin solution, the mass percentage of Ce-TMA MOFs is 0.2-10%.
6. The method for preparing a composite perfluorosulfonic acid proton exchange membrane according to claim 1, wherein in step S2, the perfluorosulfonic acid resin solution is prepared by the steps of:
and adding the perfluorosulfonic acid resin into the water-isopropanol mixed solvent, and stirring to obtain the perfluorosulfonic acid resin solution.
7. The method for preparing the composite perfluorosulfonic acid proton exchange membrane according to claim 6, wherein the mass ratio of water to isopropanol is 1:1-1:3, the mass concentration of the perfluorinated sulfonic acid resin in the perfluorinated sulfonic acid resin solution is 10-30wt%.
8. The method for preparing a composite perfluorosulfonic acid proton exchange membrane according to claim 1, wherein in step S2, the stirring time is 24-48 hours; the ultrasonic time is 0.5-2h; the heat treatment temperature is 80-120 ℃ and the heat treatment time is 4-12h.
9. A composite perfluorosulfonic acid proton exchange membrane prepared by the method of any one of claims 1-8.
10. Use of the composite perfluorosulfonic acid proton exchange membrane of claim 9 in the fields of fuel cells, water electrolysis hydrogen production and flow batteries.
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| CN117127214B (en) * | 2023-10-26 | 2024-08-16 | 内蒙古工业大学 | Preparation method and application of Ce-MOF-CNT/PVA membrane electrode |
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