CN115566238A - 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 54
- 239000008233 hard water Substances 0.000 title claims abstract description 44
- 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
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 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
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 239000011521 glass Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 11
- -1 phenolic hydroxy compound Chemical class 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 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
- 238000010438 heat treatment Methods 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
- 230000008569 process Effects 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
- 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 35
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000008213 purified water Substances 0.000 abstract description 3
- 238000007790 scraping Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 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
- 238000005516 engineering process Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 4
- 239000013384 organic framework 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
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 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
- 230000000694 effects Effects 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
- 230000008676 import Effects 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
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000008234 soft water Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 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
- 230000009471 action Effects 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
- 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
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 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
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000008403 very hard water Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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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
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
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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
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A composite proton exchange membrane with high hard water resistance, a preparation method and application thereof. The invention belongs to the field of proton exchange membranes. The invention aims to solve the technical problems that the existing proton exchange membrane applied to the field of hydrogen production by electrolyzing water can only be applied to purified water with extremely low hardness, does not have hard water resistance and has narrow hardness range of working water. The preparation method comprises the following steps: step 1: dissolving cyanuric chloride and phenolic hydroxyl compounds 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 and stirring to form a uniform solution; and step 3: and (3) coating the uniform solution on a glass plate by scraping, drying, washing by hydrogen oxide, and then carrying out acid soaking to obtain the composite proton exchange membrane. The proton exchange membrane is used for hydrogen production by electrolysis in hard water. The composite proton exchange membrane has stronger hard water resistance.
Description
Technical Field
The invention belongs to the field of proton exchange membranes, and particularly relates to a composite proton exchange membrane with high hard water resistance, and a preparation method and application thereof.
Background
Among numerous technical schemes for producing hydrogen, the green water electrolysis hydrogen production technology adopting the proton exchange membrane has bright application prospect, and the reason is that firstly, the technology does not need to add alkali liquor like alkaline electrolyzed water, so that pollution is avoided, and secondly, the green water electrolysis hydrogen production technology adopting the proton exchange membrane has 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 the proton exchange membrane. At present, most of proton exchange membranes used in domestic green water electrolysis hydrogen production technology are import membranes of U.S. DuPont and other companies, such as Nafion 117 and the like. The foreign import membrane has the advantages of good chemical stability, but high cost, higher requirement on the water quality of electrolyzed water, and the like, soft water such as deionized water, purified water and the like is required to be used, the hardness of the water is generally divided into 4 grades, the soft water is 0-60ppm, and the slightly hard water is: 60-120ppm, hard water: 120-180ppm, extremely hard water: 181ppm or more, therefore, the existing proton exchange membrane usually needs to perform several stages of filtration and purification on the electrolyzed water during application, while the water purification process increases the cost of producing hydrogen from the electrolyzed water, and if slightly hard water and hard water are directly used, the proton conductivity, stability and service life of the proton exchange membrane are greatly reduced. Therefore, it is important to develop a high-end composite proton exchange membrane with low cost and high proton conductivity and hard water resistance.
Disclosure of Invention
The invention aims to solve the technical problems that the existing proton exchange membrane applied to the field of hydrogen production by electrolyzing water can only be applied to purified water with extremely low hardness, does not have hard water resistance and has narrow working water hardness range, and provides a composite proton exchange membrane with high proton conductivity and high hard water resistance, and a preparation method and application thereof.
One of the purposes of the invention is to provide 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 phenolic hydroxyl compounds 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 perfluorinated sulfonic acid resin powder, and heating and stirring to form a uniform solution;
and step 3: and (3) blade-coating the uniform solution obtained in the step (2) on a glass plate, drying, washing with hydrogen oxide, and acid soaking to obtain the composite proton exchange membrane with high hard water resistance.
Further limiting, the phenolic hydroxyl compound in step 1 is 4,4' -dihydroxydiphenyl sulfone.
Further limiting, in the step 1, the mass ratio of the cyanuric chloride to the phenolic hydroxyl compound is (1.4-2.5): 10.
further limiting, the mass ratio of the cyanuric chloride to the phenolic hydroxyl compound in the step 1 is (1.7-2.1): 10.
further limiting, the mass ratio of the cyanuric chloride to the triethylamine in the step 1 is (0.5-1.2): 4.
further limiting, in the step 1, the organic solvent is one or a mixture of several of methanol, ethanol and isopropanol in any ratio.
Further limiting, the ratio of the mass of the cyanuric chloride to the volume of the organic solvent in step 1 is 1g: (9-28) mL.
Further limiting, the temperature for initiating the polymerization in the step 1 is 35-60 ℃ and the time is 8-48h.
Further limiting, in the step 2, the organic solvent is one or a mixture of several of N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, N-dimethylacetamide and dimethyl sulfoxide according to any ratio.
Further, in step 2, the mass ratio of the nitrogen-rich polymer to the organic solvent is (0.01-22): 100.
More specifically, the mass ratio of the nitrogen-enriched polymer to the organic solvent in the step 2 is (1.5-16): 100.
Further, in the step 2, the mass ratio of the perfluorosulfonic acid resin powder to the organic solvent is (2-35): 100.
Further, in the step 2, the mass ratio of the perfluorosulfonic acid resin powder to the organic solvent is (8-30): 100.
The second purpose of the invention is to provide a composite proton exchange membrane with high hard water resistance prepared by the preparation method.
The invention also aims to provide the application of the composite proton exchange membrane with high hard water resistance prepared by the preparation method in the electrolysis of hard water to prepare hydrogen.
Further limiting, the hardness of the hard water is more than or equal to 80ppm.
Compared with the prior art, the invention has the remarkable effects that:
the invention 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 invention synthesizes a novel nitrogen-rich polymer, and nitrogen-rich functional groups in the novel nitrogen-rich polymer can form an additional hydrogen bond network with sulfonate groups in perfluorinated sulfonic acid resin, thereby obviously improving the density of the hydrogen bond network in the proton exchange membrane and further providing an additional large number of proton transfer channels. In addition, the synthesized novel nitrogen-rich polymer has functional groups with larger steric hindrance, can effectively protect the formed hydrogen bond network, and simultaneously hinders the exchange effect of impurity ions on protons in hard water.
2) The compact hydrogen bond skeleton structure has stronger capability of complexing protons, can resist the ion exchange action of metal ions and the like in hard water, widens the range of the hardness value of the water quality of the electrolyzed water for hydrogen production by electrolyzing water, and can normally work even if being applied to the hard water (80 ppm) with certain hardness (namely the concentration of common impurity ions such as calcium ions, magnesium ions, aluminum ions and the like in the water).
3) The method effectively improves the proton conductivity of the perfluorosulfonic acid composite membrane, has better membrane forming uniformity, simple and quick preparation process and low price of raw materials, and the obtained composite proton exchange membrane is more uniform.
4) The composite proton exchange membrane with high hard water resistance has good interface compatibility, can improve the structural density of the composite membrane, and effectively reduces the hydrogen permeability.
Drawings
FIG. 1 is a scanning electron micrograph of a nitrogen-rich polymer obtained in example 1;
FIG. 2 is a scanning electron microscope image of the composite PEM obtained in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional in the art and are commercially available to those skilled in the art.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, process, 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, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or range defined 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 a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise specified, the range is intended to include the endpoints thereof, and all integers and fractions within the range. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
Example 1: the preparation method of the composite proton exchange membrane with high hard water resistance provided by the embodiment comprises the following steps:
step 1: dissolving 0.225g of cyanuric chloride and 0.9g of 4,4' -dihydroxy diphenyl sulfone in 4.5mL of methanol, then adding 1.35g of triethylamine to initiate polymerization at 40 ℃, centrifuging after polymerizing for 8h to obtain precipitate, washing the precipitate for 3 times by using the methanol, and then drying in vacuum at 60 ℃ for 12h to obtain a nitrogen-enriched polymer;
the scanning electron micrograph of the obtained nitrogen-enriched polymer is shown in FIG. 1, and it can be seen from FIG. 1 that the nitrogen-enriched polymer is in the form of rod and particle of micron scale.
Step 2: ultrasonically dispersing 1.5g of nitrogen-rich polymer into 100g of N-methyl pyrrolidone, then adding 30g of perfluorosulfonic acid resin powder, and heating and stirring at 80 ℃ to form a uniform solution;
and 3, step 3: and (3) blade-coating the emulsion obtained in the step (2) on a glass plate, firstly drying for 10h by blowing at 80 ℃, then drying for 4h in vacuum at 120 ℃, washing for 1h by using 3wt% of hydrogen peroxide, then washing with deionized water, then soaking for 1h by using 0.5M sulfuric acid at 80 ℃, washing for 3 times by using the deionized water, and controlling the blade-coating thickness to obtain the composite proton exchange membrane with the thickness of 180 mu M and high hard water resistance.
The scanning electron micrograph of the composite proton exchange membrane obtained in this example 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 good compatibility of the novel nitrogen-rich polymer and the perfluorosulfonic acid resin.
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' -dihydroxy diphenyl sulfone in 4.5mL of methanol, then adding 1.35g of triethylamine to initiate polymerization at 40 ℃, centrifuging after polymerizing for 8h to obtain precipitate, washing the precipitate for 3 times by using the methanol, and then drying in vacuum at 60 ℃ for 12h to obtain a nitrogen-enriched polymer;
and 2, step: ultrasonically dispersing 1.2g of nitrogen-rich polymer into 100g of N-methyl pyrrolidone, then adding 30g of perfluorosulfonic acid resin powder, and heating and stirring at 80 ℃ to form a uniform solution;
and step 3: and (3) blade-coating the emulsion obtained in the step (2) on a glass plate, firstly drying for 10h by blowing at 80 ℃, then drying for 4h in vacuum at 120 ℃, washing for 1h by using 3wt% of hydrogen peroxide, then washing with deionized water, then soaking for 1h by using 0.5M sulfuric acid at 80 ℃, washing for 3 times by using the deionized water, and controlling the blade-coating thickness to obtain the composite proton exchange membrane with the thickness of 180 mu M and high hard water resistance.
Comparative example 1: the present 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 of the comparative example comprises the following steps:
step 1: dissolving 7g of hexachlorocyclotriphosphazene and 10.5g of melamine in 120mLN and N-dimethylformamide, then adding 32g of triethylamine and 0.19g of tetrabutylammonium hydrogen sulfate, carrying out reflux reaction for 70 hours at 80 ℃, centrifuging, washing with water after the reaction is finished, and carrying out vacuum drying for 12 hours at 80 ℃ to obtain a conjugated organic framework material;
step 2: ultrasonically dispersing 2g of the conjugated organic framework material obtained in the step 1 into 133mL of azomethyl pyrrolidone to obtain a dispersion liquid, adding 20g of perfluorosulfonic acid resin powder into the dispersion liquid, and magnetically stirring to form a uniform emulsion;
and 3, step 3: and (3) blade-coating the emulsion obtained in the step (2) on a glass plate, firstly carrying out air blowing drying at 80 ℃ for 10h, then carrying out vacuum drying at 120 ℃ for 4h, washing for 1h by using 3wt% of hydrogen peroxide, then washing with deionized water, then carrying out acid soaking for 1h at 80 ℃ by using 1M sulfuric acid, washing with deionized water for 3 times, and controlling the blade-coating thickness to obtain the conjugated organic framework/perfluorosulfonic acid resin composite proton exchange membrane with the thickness of 180 mu M.
Detection test
Detection conditions are as follows: the proton conductivity measurements were carried out at 80 ℃ and 100% relative humidity (soaking in water).
As a result: initial proton conductivity, proton conductivity after 90 days of soaking in slightly hard water (80 ppm) at 70 c, and proton conductivity retention of the proton exchange membranes of examples 1-2 and comparative examples 1-3 are shown in table 1, and the data show that the proton exchange membranes of examples have stronger hard water resistance than the proton exchange membranes of comparative examples of the present invention, and the proton conductivity of 0.213S/cm is maintained even after 90 days of soaking in slightly hard water at 70 c, and the proton conductivity retention is as high as 90.6%. The comparative example, however, is not suitable for hydrogen production by electrolysis of water because of a serious decrease in proton conductivity.
Initial proton conductivity, proton conductivity after boiling in ultra hard water (237 ppm) at 70 ℃ for 10 hours, and proton conductivity retention of the proton exchange membranes of examples 1-2 and comparative examples 1-3 are shown in table 2, and the results show that the examples of the present invention have stronger hard water resistance than the comparative examples, and 46.8% of proton conductivity is maintained after boiling in ultra hard water having a hardness value as high as 237ppm for 10 hours. The composite proton exchange membrane has strong potential in widening the range of the use hardness value of the water quality of the electrolyzed water for hydrogen production by electrolyzing water.
Table 1: comparison of proton conductivity of different proton exchange membranes in slightly hard water
Table 2: comparison of proton conductivity of different proton exchange membranes in very hard water
The above description is only a preferred embodiment of the present invention, and these embodiments are based on different implementations of the present invention, and the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of a composite proton exchange membrane with high hard water resistance is characterized by comprising the following steps:
step 1: dissolving cyanuric chloride and phenolic hydroxyl compounds 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 perfluorinated sulfonic acid resin powder, and heating and stirring to form a uniform solution;
and 3, step 3: and (3) blade-coating the uniform solution obtained in the step (2) on a glass plate, drying, washing with hydrogen oxide, and acid soaking to obtain the composite proton exchange membrane with high hard water resistance.
2. The method of claim 1, wherein the phenolic hydroxy compound in step 1 is 4,4' -dihydroxydiphenyl sulfone.
3. The method according to claim 1, wherein the mass ratio of cyanuric chloride to phenolic hydroxyl compound in step 1 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 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.
4. The method according to claim 3, wherein the mass ratio of cyanuric chloride to phenolic hydroxyl compound in step 1 is (1.7-2.1): 10.
5. the process according to claim 1, wherein the polymerization is initiated in step 1 at a temperature of 35 to 60 ℃ for a time of 8 to 48 hours.
6. The method according to claim 1, wherein the organic solvent in step 2 is one or more of N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, N-dimethylacetamide and dimethyl sulfoxide, 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.
7. The method of claim 6 wherein the mass ratio of nitrogen-rich polymer to organic solvent in step 2 is (1.5-16): 100 and the mass ratio of perfluorosulfonic acid resin powder to organic solvent is (8-30): 100.
8. A composite proton exchange membrane having high hard water resistance prepared by the method of claims 1-7.
9. The composite proton exchange membrane with high hard water resistance prepared by the method of claims 1-7 is used for preparing hydrogen by electrolysis in hard water.
10. Use according to claim 9, characterized in that the hardness of hard water is > 80ppm.
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