CN115566238B - Composite proton exchange membrane with high hard water resistance and preparation method and application thereof - Google Patents
Composite proton exchange membrane with high hard water resistance and preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 55
- 239000008233 hard water Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 48
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- -1 phenolic hydroxyl compound Chemical class 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 3
- 238000007790 scraping Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 34
- 238000005868 electrolysis reaction Methods 0.000 abstract description 12
- 150000003460 sulfonic acids Chemical class 0.000 abstract description 7
- 239000008213 purified water Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000003892 spreading Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000007664 blowing Methods 0.000 description 3
- 239000000306 component Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000008234 soft water Substances 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying 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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- 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
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
-
- 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
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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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- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
A composite proton exchange membrane with high hard water resistance, a preparation method and application thereof. The application belongs to the field of proton exchange membranes. The application aims to solve the technical problems that the existing proton exchange membrane applied to the field of hydrogen production by water electrolysis can only be applied to purified water with extremely low hardness, and has no capability of resisting hard water and a narrow hardness range of working water quality. The preparation method comprises the following steps: step 1: dissolving cyanuric chloride and a phenolic hydroxyl compound in an organic solvent, and then adding triethylamine to initiate polymerization to obtain a nitrogen-rich polymer; step 2: ultrasonically dispersing a nitrogen-rich polymer in an organic solvent, and then adding perfluorinated sulfonic acid resin powder to stir until a uniform solution is formed; step 3: and (3) scraping the uniform solution on a glass plate, drying, washing with hydrogen peroxide, and soaking with acid to obtain the composite proton exchange membrane. The proton exchange membrane is used for producing hydrogen by electrolysis in hard water. The composite proton exchange membrane has stronger hard water resistance.
Description
Technical Field
The application belongs to the field of proton exchange membranes, and particularly relates to a composite proton exchange membrane with high hard water resistance, a preparation method and application thereof.
Background
In a plurality of technical schemes for producing hydrogen, the proton exchange membrane green water electrolysis hydrogen production technology has bright application prospect, and firstly, the technology does not need to add alkali liquor like alkaline water electrolysis, so pollution is avoided, and secondly, the proton exchange membrane green water electrolysis hydrogen production technology has extremely strong strategic value in the aspect of national energy safety.
The core component of the proton exchange membrane green water electrolysis hydrogen production technology is a proton exchange membrane. At present, most of proton exchange membranes used in domestic proton exchange membrane green water electrolysis hydrogen production technology are imported membranes of companies such as DuPont and the like in the United states, such as Nafion 117 and the like. The foreign imported membrane has the advantages of good chemical stability, but high cost, high requirement on the quality of the electrolyzed water, and needs to use soft water such as deionized water, purified water and the like, wherein the hardness of the water is generally divided into 4 grades, and the soft water comprises 0-60ppm of slightly hard water: 60-120ppm, hard water: 120-180ppm, extremely hard water: 181ppm or more, therefore, the existing proton exchange membrane generally needs to carry out several levels of filtration and purification on the electrolysis water when in use, and the water purification process can increase the cost of hydrogen production by the whole electrolysis water, if the water is directly used with slightly hard water, the proton conductivity, the stability and the service life of the proton exchange membrane can be greatly reduced. Therefore, it is important to develop a high-end composite proton exchange membrane with low cost and high proton conductivity and high hard water resistance.
Disclosure of Invention
The application aims to solve the technical problems that the existing proton exchange membrane applied to the field of hydrogen production by water electrolysis can only be applied to purified water with extremely low hardness, does not have the capability of resisting hard water and has a narrower hardness range of working water quality, and provides a composite proton exchange membrane with high proton conductivity and high capability of resisting hard water, and a preparation method and application thereof.
The application aims at providing a preparation method of a composite proton exchange membrane with high hard water resistance, which comprises the following steps:
step 1: dissolving cyanuric chloride and a phenolic hydroxyl compound in an organic solvent, and then adding triethylamine to initiate polymerization to obtain a nitrogen-rich polymer;
step 2: ultrasonically dispersing a nitrogen-rich polymer in an organic solvent, then adding perfluorosulfonic acid resin powder, heating and stirring until a uniform solution is formed;
step 3: and (3) scraping the uniform solution obtained in the step (2) on a glass plate, drying, washing with hydrogen peroxide, and soaking with acid to obtain the composite proton exchange membrane with high hard water resistance.
Further defined, the phenolic hydroxyl compound in step 1 is 4,4' -dihydroxydiphenyl sulfone.
Further defined, the mass ratio of cyanuric chloride to phenolic hydroxyl compound in step 1 is (1.4-2.5): 10.
further defined, the mass ratio of cyanuric chloride to phenolic hydroxyl compound in step 1 is (1.7-2.1): 10.
further defined, the mass ratio of cyanuric chloride to triethylamine in the step 1 is (0.5-1.2): 4.
further limited, the organic solvent in the step 1 is one or a mixture of several of methanol, ethanol and isopropanol according to any ratio.
Further defined, the ratio of the mass of cyanuric chloride to the volume of the organic solvent in step 1 is 1g: (9-28) mL.
Further defined, the temperature at which the polymerization is initiated in step 1 is from 35 to 60℃for a period of from 8 to 48 hours.
The organic solvent in the step 2 is one or a mixture of a plurality of N-methyl pyrrolidone, N-dimethylformamide, tetrahydrofuran, N-dimethylacetamide and dimethyl sulfoxide according to any ratio.
Further defined, the mass ratio of the nitrogen-rich polymer to the organic solvent in step 2 is (0.01-22): 100.
Further defined, the mass ratio of the nitrogen-rich polymer to the organic solvent in step 2 is (1.5-16): 100.
Further, the mass ratio of the perfluorosulfonic acid resin powder to the organic solvent in step 2 is (2-35): 100.
Further, the mass ratio of the perfluorosulfonic acid resin powder to the organic solvent in step 2 is (8-30): 100.
The second object of the present application is to provide a composite proton exchange membrane with high hard water resistance prepared by the preparation method.
The application further aims to provide an application of the composite proton exchange membrane with high hard water resistance prepared by the preparation method in preparing hydrogen by electrolysis in hard water.
Further defined, the hardness of the hard water is more than or equal to 80ppm.
Compared with the prior art, the application has the remarkable effects that:
the application synthesizes a novel nitrogen-rich polymer, and the composite proton exchange membrane prepared by compounding the novel nitrogen-rich polymer and perfluorinated sulfonic acid resin has stronger hard water resistance and has the following specific advantages:
1) The novel nitrogen-rich polymer is synthesized, and the nitrogen-rich functional groups in the novel nitrogen-rich polymer can form an additional hydrogen bond network with the sulfonate in the perfluorinated sulfonic acid resin, so that the density of the hydrogen bond network in the proton exchange membrane is remarkably improved, and an additional large number of proton transfer channels are provided. In addition, the synthesized novel nitrogen-rich polymer has a functional group with larger steric hindrance, can effectively protect the formed hydrogen bond network, and simultaneously prevents the exchange effect of impurity ions in hard water on protons.
2) The compact hydrogen bond skeleton structure has stronger capability of complexing protons, can resist the ion exchange effect of metal plasma in hard water, widens the use hardness value range of the quality of electrolytic water used for producing hydrogen by the electrolytic water, and can normally work even if the compact hydrogen bond skeleton structure is applied to hard water (80 ppm) with certain hardness (namely the concentration of common calcium ions, magnesium ions, aluminum ions and other impurity ions in water).
3) The method effectively improves the proton conductivity of the perfluorinated sulfonic acid composite membrane, has better membrane forming uniformity, simple and quick preparation process and low raw material price, and the obtained composite proton exchange membrane is more uniform.
4) The composite proton exchange membrane with high hard water resistance has good interfacial compatibility, can improve the structural density of the composite membrane, and effectively reduces the hydrogen permeability.
Drawings
FIG. 1 is a scanning electron microscope image of the nitrogen-rich polymer obtained in example 1;
FIG. 2 is a scanning electron microscope image of the composite proton exchange membrane obtained in example 1.
Detailed Description
The present application will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range. In the description and claims of the application, the range limitations may be combined and/or interchanged, if not otherwise specified, including all the sub-ranges subsumed therein.
The indefinite articles "a" and "an" preceding an element or component of the application are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
Example 1: the preparation method of the composite proton exchange membrane with high hard water resistance of the embodiment comprises the following steps:
step 1: dissolving 0.225g of cyanuric chloride and 0.9g of 4,4' -dihydroxydiphenyl sulfone in 4.5mL of methanol, adding 1.35g of triethylamine to initiate polymerization at 40 ℃, centrifuging after 8h of polymerization to obtain a precipitate, washing the precipitate with methanol for 3 times, and then drying in vacuum at 60 ℃ for 12h to obtain a nitrogen-rich polymer;
the scanning electron microscope photograph of the obtained nitrogen-rich polymer is shown in fig. 1, and as can be seen from fig. 1, the nitrogen-rich polymer is in the shape of rods and particles with the micron level.
Step 2: 1.5g of nitrogen-rich polymer is ultrasonically dispersed in 100g N-methyl pyrrolidone, 30g of perfluorosulfonic acid resin powder is added, and the mixture is heated and stirred at 80 ℃ to form a uniform solution;
step 3: and (3) spreading the emulsion obtained in the step (2) on a glass plate, firstly drying by blowing at 80 ℃ for 10 hours, then drying in vacuum at 120 ℃ for 4 hours, washing with 3wt% hydrogen peroxide for 1 hour, then washing with deionized water, soaking with 0.5M sulfuric acid at 80 ℃ for 1 hour, washing with deionized water for 3 times, and controlling the spreading thickness to obtain the composite proton exchange membrane with the high hard water resistance and 180 mu M thickness.
The scanning electron microscope photograph of the composite proton exchange membrane obtained in the embodiment is shown in fig. 2, and it can be seen from fig. 2 that the composite proton exchange membrane with high hard water resistance has a flat and smooth surface, a compact structure, and the compatibility of the novel nitrogen-rich polymer and the perfluorinated sulfonic acid resin is good.
Example 2: the preparation method of the composite proton exchange membrane with high hard water resistance of the embodiment comprises the following steps:
step 1: dissolving 0.225g of cyanuric chloride and 0.9g of 4,4' -dihydroxydiphenyl sulfone in 4.5mL of methanol, adding 1.35g of triethylamine to initiate polymerization at 40 ℃, centrifuging after 8h of polymerization to obtain a precipitate, washing the precipitate with methanol for 3 times, and then drying in vacuum at 60 ℃ for 12h to obtain a nitrogen-rich polymer;
step 2: 1.2g of nitrogen-rich polymer is ultrasonically dispersed in 100g N-methyl pyrrolidone, 30g of perfluorosulfonic acid resin powder is added, and the mixture is heated and stirred at 80 ℃ to form a uniform solution;
step 3: and (3) spreading the emulsion obtained in the step (2) on a glass plate, firstly drying by blowing at 80 ℃ for 10 hours, then drying in vacuum at 120 ℃ for 4 hours, washing with 3wt% hydrogen peroxide for 1 hour, then washing with deionized water, soaking with 0.5M sulfuric acid at 80 ℃ for 1 hour, washing with deionized water for 3 times, and controlling the spreading thickness to obtain the composite proton exchange membrane with the high hard water resistance and 180 mu M thickness.
Comparative example 1: this comparative example provides a pure perfluorosulfonic acid resin proton exchange membrane.
Comparative example 2: this comparative example provides a commercial proton exchange membrane Nafion 117.
Comparative example 3: the preparation method of the conjugated organic framework/perfluorinated sulfonic acid resin composite proton exchange membrane in the comparative example comprises the following steps:
step 1: dissolving 7g of hexachlorocyclotriphosphazene and 10.5g of melamine in 120mLN, N-dimethylformamide, adding 32g of triethylamine and 0.19g of tetrabutylammonium bisulfate, carrying out reflux reaction at 80 ℃ for 70 hours, centrifuging after the reaction, washing with water, and vacuum drying at 80 ℃ for 12 hours to obtain a conjugated organic frame material;
step 2: 2g of the conjugated organic framework material obtained in the step 1 is ultrasonically dispersed in 133mL of nitrogen methyl pyrrolidone to obtain a dispersion liquid, 20g of perfluorosulfonic acid resin powder is added into the dispersion liquid, and magnetic stirring is carried out until a uniform emulsion is formed;
step 3: and (3) spreading the emulsion obtained in the step (2) on a glass plate, firstly drying by blowing at 80 ℃ for 10 hours, then drying in vacuum at 120 ℃ for 4 hours, washing with 3wt% hydrogen peroxide for 1 hour, then washing with deionized water, soaking with 1M sulfuric acid at 80 ℃ for 1 hour, washing with deionized water for 3 times, and controlling the spreading thickness to obtain the conjugated organic frame/perfluorinated sulfonic acid resin composite proton exchange membrane with the thickness of 180 mu M.
Detection test
Detection conditions: proton conductivity was measured at 80℃and 100% relative humidity (immersion in water).
Results: the initial proton conductivities of the proton exchange membranes of examples 1-2 and comparative examples 1-3, proton conductivities after soaking in 70 ℃ slightly hard water (80 ppm) for 90 days, and proton conductivity retentions are shown in table 1, and the data indicate that the proton conductivities of the examples have stronger resistance to hard water than the proton exchange membranes of the present application, and that the proton conductivity retentions are as high as 90.6% even after soaking in 70 ℃ slightly hard water for 90 days. The proton conductivity of the comparative example was severely reduced, and was not suitable for hydrogen production by water electrolysis.
The initial proton conductivities of the proton exchange membranes of examples 1-2 and comparative examples 1-3, proton conductivities after boiling in extremely hard water (237 ppm) at 70 ℃ for 10 hours, and proton conductivity retentions are shown in table 2, and the results indicate that the examples of the present application have stronger resistance to hard water than the comparative examples, and still maintain 46.8% proton conductivities after boiling in extremely hard water with hardness values up to 237ppm for 10 hours. The composite proton exchange membrane has strong potential in widening the use hardness value range of the electrolytic water quality used for producing hydrogen by the electrolytic water.
Table 1: proton conductivity contrast for different proton exchange membranes in slightly harder water
Table 2: proton conductivity contrast of different proton exchange membranes in extremely hard water
In the foregoing, the present application is merely preferred embodiments, which are based on different implementations of the overall concept of the application, and the protection scope of the application is not limited thereto, and any changes or substitutions easily come within the technical scope of the present application as those skilled in the art should not fall within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (7)
1. The preparation method of the composite proton exchange membrane with high hard water resistance is characterized by comprising the following steps:
step 1: dissolving cyanuric chloride and a phenolic hydroxyl compound in an organic solvent, and then adding triethylamine to initiate polymerization to obtain a nitrogen-rich polymer; the phenolic hydroxyl compound is 4,4' -dihydroxydiphenyl sulfone, and the mass ratio of cyanuric chloride to the phenolic hydroxyl compound is (1.4-2.5): 10, the mass ratio of cyanuric chloride to triethylamine is (0.5-1.2): 4, the organic solvent is one or a mixture of a plurality of methanol, ethanol and isopropanol, and the ratio of the mass of the cyanuric chloride to the volume of the organic solvent is 1g: (9-28) mL;
step 2: ultrasonically dispersing a nitrogen-rich polymer in an organic solvent, then adding perfluorosulfonic acid resin powder, heating and stirring until a uniform solution is formed; the mass ratio of the nitrogen-rich polymer to the organic solvent is (1.5-16) 100, and the mass ratio of the perfluorosulfonic acid resin powder to the organic solvent is (8-30) 100;
step 3: and (3) scraping the uniform solution obtained in the step (2) on a glass plate, drying, washing with hydrogen peroxide, and soaking with acid to obtain the composite proton exchange membrane with high hard water resistance.
2. The method according to claim 1, wherein the mass ratio of cyanuric chloride to phenolic hydroxyl compound in step 1 is (1.7-2.1): 10.
3. the process according to claim 1, wherein the polymerization is initiated in step 1 at a temperature of 35-60℃for a period of 8-48h.
4. The method according to claim 1, wherein the organic solvent in the step 2 is one or a mixture of several of N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, N-dimethylacetamide and dimethylsulfoxide, the mass ratio of the nitrogen-rich polymer to the organic solvent is (0.01-22): 100, and the mass ratio of the perfluorosulfonic acid resin powder to the organic solvent is (2-35): 100.
5. The composite proton exchange membrane with high hard water resistance prepared by the method of claims 1-4.
6. The composite proton exchange membrane with high hard water resistance prepared by the method of claims 1-4 is used for electrolytic hydrogen production in hard water.
7. The process according to claim 6, wherein the hardness of the hard water is 80ppm or more.
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