CN117343290A - Alkali-resistant and oxidation-resistant anion exchange resin and application thereof - Google Patents
Alkali-resistant and oxidation-resistant anion exchange resin and application thereof Download PDFInfo
- Publication number
- CN117343290A CN117343290A CN202311639677.5A CN202311639677A CN117343290A CN 117343290 A CN117343290 A CN 117343290A CN 202311639677 A CN202311639677 A CN 202311639677A CN 117343290 A CN117343290 A CN 117343290A
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- China
- Prior art keywords
- resistant
- anion exchange
- oxidation
- alkali
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000003647 oxidation Effects 0.000 title claims abstract description 46
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 46
- 239000003513 alkali Substances 0.000 title claims abstract description 44
- 239000003957 anion exchange resin Substances 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000000446 fuel Substances 0.000 claims abstract description 21
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000909 electrodialysis Methods 0.000 claims abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 41
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000012528 membrane Substances 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 16
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 16
- 239000012670 alkaline solution Substances 0.000 claims description 14
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- -1 methoxy, ethoxy, propoxy, butoxy, cyclohexyloxy Chemical group 0.000 claims description 9
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 238000005956 quaternization reaction Methods 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000002685 polymerization catalyst Substances 0.000 claims description 5
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 claims description 4
- VRJHQPZVIGNGMX-UHFFFAOYSA-N 4-piperidinone Chemical compound O=C1CCNCC1 VRJHQPZVIGNGMX-UHFFFAOYSA-N 0.000 claims description 4
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 229930184652 p-Terphenyl Natural products 0.000 claims description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005349 anion exchange Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- GKNWQHIXXANPTN-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)F GKNWQHIXXANPTN-UHFFFAOYSA-N 0.000 claims description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 claims 2
- 150000001768 cations Chemical class 0.000 claims 1
- 239000013043 chemical agent Substances 0.000 claims 1
- 229920001002 functional polymer Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 abstract description 4
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical compound CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 abstract description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001450 anions Chemical class 0.000 abstract 1
- 239000002952 polymeric resin Substances 0.000 abstract 1
- 229920003002 synthetic resin Polymers 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 230000008961 swelling Effects 0.000 description 9
- 238000002144 chemical decomposition reaction Methods 0.000 description 8
- 239000005457 ice water Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 230000002238 attenuated effect Effects 0.000 description 4
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- NACWJEQGDKTEKR-UHFFFAOYSA-M 1,1-dimethyl-4-pyridin-1-ium-4-yl-2h-pyridin-1-ium;dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)(C)CC=C1C1=CC=[NH+]C=C1 NACWJEQGDKTEKR-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
-
- 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
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/72—Derivatisation
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Abstract
The invention relates to alkali resistanceAn oxidation resistant anion exchange resin having structural units of the general formula comprising a polymer of an alkaline stable piperidine monomer having a relatively large steric hindrance and an electron donating group with an aromatic monomer, comprising a polymer of a tetramethylpiperidine monomer having an oxidation resistant property with an aromatic monomer; the polymer resin has excellent alkali resistance and oxidation resistance stability, higher anion conductivity and mechanical stability, is a good anion exchange membrane material, and can be widely applied to the fields of water electrolysis hydrogen production, fuel cells, flow batteries, electrodialysis and the like.
Description
Technical Field
The invention belongs to the field of hydroxide anion exchange membranes of fuel cells, electrolytic tanks and flow batteries, and particularly relates to a preparation method and application of an alkali-resistant and oxidation-resistant anion exchange resin membrane.
Background
Redox flow batteries are a novel energy conversion device, and charge and discharge can be performed by utilizing the redox reaction of bipolar active substances. There is a great deal of attention for its advantages of high efficiency, cleanliness, safety, etc. In the redox flow battery, an anion exchange membrane separates positive electrode electrolyte from negative electrode electrolyte, so that efficient circulation of battery electrolyte is realized, and the redox flow battery is an important component of the redox flow battery. The ion conductivity of the anion exchange membrane is high, so that the internal resistance of the battery is small, and the battery efficiency is higher; the ion current bearing capacity is high, and the battery has larger current, so that the battery has higher power; the mechanical properties of the membrane stability, etc., all contribute to a significant improvement in fuel cell performance. Therefore, the development and practical application of the flow battery are limited by the alkaline stability, hydroxide ion conductivity, dimensional stability, mechanical properties and the like of the anion exchange membrane. In addition, the anion exchange membrane can be used in a fuel cell and can work with anode and cathode catalysts other than platinum group metals, contributing to lower cell manufacturing costs. In the main chain of the anion exchange membrane, the ether-free carbon chain is more stable; among the organic cations, ammonium cations are commonly used functional groups, wherein the cyclic ammonium cation piperidinium exhibits good alkali resistance, the piperidine monomer and the aromatic monomer polymer have alkaline stability, and the tetramethyl piperidine monomer and the aromatic monomer polymer have antioxidant properties. In addition, the functional groups are bonded with the main chain through chemical bonds, so that the functional groups are not easy to wash off or dissolve in the running process of the battery, and the battery has higher stability. The design of the anion exchange membrane with alkali resistance and oxidation resistance has important significance for the development of batteries.
Disclosure of Invention
In order to solve the problems, the invention discloses an alkali-resistant and oxidation-resistant anion exchange resin and a preparation method thereof, wherein an oxidation-resistant piperidine group is combined with an aromatic monomer, so that the alkali resistance and the oxidation resistance are enhanced.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention provides an alkali-resistant and oxidation-resistant anion exchange resin which is characterized by comprising the following structural units:
wherein Ar is 1 、Ar 2 Independently of one another, selected from the groups of the formula:
，/>，/>，/>，，/>；
R 1 independently hydrogen, hydroxy, oxygen, sulfur, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, isopropyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, N-trimethylpentylamino, methoxy, ethoxy, propoxy, butoxy, cyclohexyloxy;
R 2 independently hydrogen, hydroxy, oxygen, sulfur, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, isopropyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, N-trimethylpentylamino, methoxy, ethoxy, propoxy, butoxy, cyclohexyloxy, or a structural group selected from the group consisting of:、/>；
R 3 independently hydrogen, methyl, ethyl, propyl.
The invention also provides a preparation method of the alkali-resistant and oxidation-resistant anion exchange resin, which comprises the following steps:
(1) Synthesis of the polymer backbone: dissolving piperidone monomer and aromatic monomer in an organic solvent, dropwise adding a polymerization catalyst at the temperature of 0 ℃, and continuously reacting at the temperature for 12-48 hours; slowly pouring the obtained solution into an ethanol water solution; filtering to obtain solid, washing with water, and soaking in alkaline solution at room temperature for 10-24 hr; the product was then filtered, washed with water and dried completely under vacuum at 60 ℃;
(2) Quaternization of the polymer: dissolving the dried polymer obtained in the step (1) in an organic solvent, adding a quaternizing reagent methyl iodide, reacting for 24 hours at 60-80 ℃ to carry out quaternization, washing with diethyl ether, and drying to form a cationic functionalized polymer;
(3) Preparation of anion exchange membrane: dissolving the cationic functionalized polymer obtained in the step (2) in an organic solvent, pouring the solution into a clean polytetrafluoroethylene membrane disc, and drying the solution in a vacuum drying oven at 60 ℃ to form a film; and immersing the prepared membrane into alkaline solution for anion exchange for 12-48 hours, immersing into deionized water for 12-24 hours to remove residual alkaline solution, and finally obtaining the alkali-resistant and oxidation-resistant hydroxide-type exchange membrane.
Further, in the step (1), the piperidone monomer is any two of 2, 6-tetramethyl-4-piperidone, 2, 4-dimethyl-1-piperidone, 1,2, 6-pentamethyl-4-piperidone and N-methyl-1-piperidone; the aromatic monomer is one or more of benzene, biphenyl, p-terphenyl, m-terphenyl, fluorene and 9, 9-dimethylfluorene; the organic solvent is one of ethanol, dichloromethane, chloroform, dichloroethane, tetrachloroethane, carbon tetrachloride, dimethyl sulfoxide and diethyl ether; the polymerization catalyst is one or more of trifluoroacetic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid and heptafluorobutyric acid; the alkaline solution is one of potassium carbonate solution, sodium bicarbonate solution, sodium hydroxide solution, potassium hydroxide solution and ammonia water.
Further, the molar ratio of the piperidone monomer to the aromatic monomer in the step (1) is 1:1-5, wherein the molar ratio of the 1-piperidone to the 4-piperidone is 1: 1-2; the volume ratio of the organic solvent to the polymerization catalyst is 2-3: 2-4% of 1, 1-piperidone monomer and organic solvent, 7-29% of aromatic monomer and organic solvent, wherein the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1:12-20; the concentration of the alkaline solution is 1-2M; the alkaline solution is K 2 CO 3 A solution.
Further, in the step (2), the mass-volume ratio of the dried polymer obtained in the step (1) to methyl iodide is 1:1-3; the mass volume percentage of the dried polymer obtained in the step (1) and the organic solvent is 5% -10%; the organic solvent is one or more of dichloromethane, chloroform, dichloroethane, tetrachloroethane, carbon tetrachloride, dimethyl sulfoxide and diethyl ether.
Further, in the step (3), the mass volume percentage of the cationic functionalized polymer obtained in the step (2) to the organic solvent is 5% -10%; the organic solvent is one or more of dichloromethane, chloroform, dichloroethane, tetrachloroethane, carbon tetrachloride, dimethyl sulfoxide and diethyl ether; the alkaline solution is KOH solution.
The invention also provides an application of the alkali-resistant and oxidation-resistant anion exchange resin in a fuel cell, wherein the fuel cell comprises an alkaline fuel cell; such applications include hydrogen production by electrolysis of water, fuel cells, flow batteries, electrodialysis.
The invention also provides application of the alkali-resistant and oxidation-resistant anion exchange resin in a flow battery, wherein the flow battery comprises an all-vanadium flow battery, an organic flow battery, an iron-chromium flow battery and a zinc-bromine flow battery.
The invention also provides application of the alkali-resistant and oxidation-resistant anion exchange resin prepared by the preparation method in a fuel cell, wherein the fuel cell comprises an alkaline fuel cell; such applications include hydrogen production by electrolysis of water, fuel cells, flow batteries, electrodialysis.
The invention also provides application of the alkali-resistant and oxidation-resistant anion exchange resin prepared by the preparation method in a flow battery, wherein the flow battery comprises an all-vanadium flow battery, an organic flow battery, an iron-chromium flow battery and a zinc-bromine flow battery.
The beneficial effects of the invention are as follows:
the oxidation-resistant piperidine group is combined with the aromatic monomer, so that the enhancement of alkali resistance and oxidation resistance is realized. The prepared anion exchange membrane has various selected component configurations and sizes, and is suitable for various application scenes: fuel cells, electrolytic cells, electrodialysers, solar hydrogen generators, flow batteries, sensors, water purifiers, wastewater treatment systems, ion exchangers, and the like.
Drawings
FIG. 1 is a chart of coulombic efficiency, voltage efficiency, energy efficiency and cycle number of charge-discharge cycle tests of an alkali-resistant and oxidation-resistant anion exchange membrane prepared in example 9 of the present invention in a water-based organic flow battery;
fig. 2 is a chart of coulombic efficiency, voltage efficiency, energy efficiency and cycle number of charge-discharge cycle tests of the alkali-resistant and oxidation-resistant anion-exchange membrane prepared in example 6 of the present invention in an all-vanadium redox flow battery.
Detailed Description
The present invention is further illustrated in the following drawings and detailed description, which are to be understood as being merely illustrative of the invention and not limiting the scope of the invention.
Example 1
(1) 2, 6-tetramethyl-4-piperidone (0.782 g,5 mmol), 2, 4-dimethyl-1-piperidone (0.705 g,5 mmol) and biphenyl (1.540 g,10 mmol) were added to a 100mL three-necked flask containing 20mL of methylene chloride, and trifluoroacetic acid (TFA) (0.5 mL) and trifluoromethanesulfonic acid (TFSA) (10 mL) were added dropwise under an ice-water bath at 0℃and the reaction was continued at that temperature for 24 hours. The resulting solution was slowly poured into an aqueous ethanol solution. Filtration gave a solid which was washed with water and at room temperature at 1M K 2 CO 3 Soaking for about 10 hours. The product was then filtered, washed with water and dried completely under vacuum at 60 ℃.
(2) The polymer (1 g) obtained above was dissolved in 20mL of dimethyl sulfoxide, 1mL of methyl iodide was rapidly added, the quaternization reaction was carried out at 60℃for 24 hours, and the resulting viscous yellow solution was added dropwise to diethyl ether. The yellow solid was filtered, washed with diethyl ether and then dried under vacuum at 60 ℃.
(3) Preparation of anion exchange membrane: the polymer (1 g) obtained in the step (2) is dissolved in 20mL of dimethyl sulfoxide, fully dissolved into uniform transparent solution, poured into a clean polytetrafluoroethylene membrane disc, and dried in a vacuum drying oven at 60 ℃ to form a membrane. The resulting membrane was immersed in 1M KOH for 24 hours of anion exchange, washed under argon and immersed in deionized water for about 24 hours to remove residual KOH, and finally an alkali-resistant, oxidation-resistant, hydroxide-form exchange membrane was obtained.
The prepared anion exchange membrane has high mechanical property (tensile strength: 32.1 MPa, elongation at break: 36%) and OH in 5M KOH at 80 DEG C - The conductivity is 84.5mS/cm, and the swelling degree is 6.84%. The material is soaked in 80 ℃ high-concentration alkaline aqueous solution (10M NaOH), no obvious chemical degradation exists within 60 days, and the conductivity is attenuated by 12.25%.
Example 2
(1) 2, 6-tetramethyl-4-piperidone (0.938 g,6 mmol), 2, 4-dimethyl-1-piperidone (0.564 g,4 mmol) and biphenyl (3.084 g,20mmol) into a 100mL three-necked flask containing 20mL of methylene chloride, trifluoroacetic acid (TFA) (0.8 mL) and trifluoromethanesulfonic acid (TFSA) (10 mL) were added dropwise under an ice-water bath at 0℃and the reaction was continued at that temperature for 24 hours. The resulting solution was slowly poured into an aqueous ethanol solution. Filtration gave a solid which was washed with water and at room temperature at 1M K 2 CO 3 Soaking for about 10 hours. The product was then filtered, washed with water and dried completely under vacuum at 60 ℃.
(2) Similar to step (2) of example 1, except that the amount of polymer added was 1.5g and methyl iodide was 2.5mL.
(3) Preparation of anion exchange membrane: similar to step (3) of example 1, except that the amount of the polymer added was 1.5g, an alkali-resistant, oxidation-resistant hydroxide form of the exchange membrane was finally obtained.
The prepared anion exchange membrane has high mechanical property (tensile strength: 36.7 MPa, elongation at break: 32%) and OH in 5M KOH at 80 DEG C - The conductivity is 87.2mS/cm, and the swelling degree is 7.26%. Immersed in 80 ℃ high-concentration alkaline aqueous solution (10M NaOH) there was no significant chemical degradation within 60 days, but the conductivity was attenuated by 10.61%.
Example 3
(1) 2, 6-tetramethyl-4-piperidone (0.938 g,6 mmol), 2, 4-dimethyl-1-piperidone (0.423 g,3 mmol) and biphenyl (7.712 g,50 mmol) were added to a 100mL three-necked flask containing 20mL dichloromethane, and trifluoroacetic acid (TFA) (0.4 mL) and trifluoromethanesulfonic acid (TFSA) (6 mL) were added dropwise under an ice-water bath at 0℃and the reaction was continued at that temperature for 24 hours. The resulting solution was slowly poured into an aqueous ethanol solution. Filtration gave a solid which was washed with water and at room temperature at 1M K 2 CO 3 Soaking for about 10 hours. The product was then filtered, washed with water and dried completely under vacuum at 60 ℃.
(2) Similar to step (2) of example 1, except that the amount of the polymer added was 2g and methyl iodide was 6mL.
(3) Preparation of anion exchange membrane: similar to step (3) of example 1, except that the amount of the polymer added was 2g, an alkali-resistant, oxidation-resistant hydroxide form of the exchange membrane was finally obtained.
The prepared anion exchange membrane has high mechanical property (tensile strength: 35.3 MPa, elongation at break: 33%), OH in 5M KOH at 80 DEG C - The conductivity is 86.3mS/cm, and the swelling degree is 7.11%. Immersed in 80 ℃ high-concentration alkaline aqueous solution (10M NaOH) there was no significant chemical degradation for 60 days, but the conductivity decayed by 11.59%.
Example 4
(1) 2, 6-tetramethyl-4-piperidone (0.938 g,6 mmol), 2, 4-dimethyl-1-piperidone (0.564 g,4 mmol) and biphenyl (1.542 g,10 mmol) were added to a 100mL three-necked flask containing 20mL dichloromethane, and trifluoroacetic acid (TFA) (0.5 mL) and trifluoromethanesulfonic acid (TFSA) (10 mL) were added dropwise under an ice-water bath at 0℃and the reaction was continued at that temperature for 24 hours. The resulting solution was slowly poured into an aqueous ethanol solution. Filtration gave a solid which was washed with water and at room temperature at 1M K 2 CO 3 Soaking for about 10 hours. The product was then filtered, washed with water and dried completely under vacuum at 60 ℃.
(2) (3) in the same manner as in the step (2) and (3) of example 1, an alkali-resistant and oxidation-resistant hydroxide-form exchange membrane was finally obtained.
The prepared anion exchange membrane has high mechanical property (tensile strength: 44.5 MPa, elongation at break: 51%) and high OH in 5M KOH at 80 DEG C - The conductivity (134.7 mS/cm) has higher dimensional stability (swelling degree is only 4.71%). No significant chemical degradation was observed within 60 days when immersed in 80 ℃ high-concentration alkaline aqueous solution (10M NaOH), and the conductivity decay was only 9.74%.
Example 5
(1) 2, 6-tetramethyl-4-piperidone (0.782 g,5 mmol), 2, 4-dimethyl-1-piperidone (0.705 g,5 mmol) and p-terphenyl (2.303 g,10 mmol) were added to a 100mL three-necked flask containing 20mL methylene chloride, 0.5 mL TFA and 10 mL TFSA were added dropwise under an ice water bath at 0deg.C, and the reaction was continued at that temperature for 24 hours. The resulting solution was slowly poured into an aqueous ethanol solution. Filtration gave a solid which was washed with water and at room temperature at 1M K 2 CO 3 Soaking for about 10 hours. The product was then filtered, washed with water and dried completely under vacuum at 60 ℃.
(2) (3) in the same manner as in the step (2) and (3) of example 1, an alkali-resistant and oxidation-resistant hydroxide-form exchange membrane was finally obtained.
The prepared anion exchange membrane has high mechanical property (tensile strength: 30.8 MPa, elongation at break: 34%) and swelling degree of 6.25%. OH in 5M KOH at 80 DEG C - The conductivity is 89.2mS/cm, the material is soaked in 80 ℃ high-concentration alkaline aqueous solution (10M NaOH), no obvious chemical degradation exists within 60 days, and the conductivity is attenuated by 13.11%.
Example 6
(1) 2, 6-tetramethyl-4-piperidone (0.938 g,6 mmol), 2, 4-dimethyl-1-piperidone (0.564 g,4 mmol) and p-terphenyl (4.602 g,20 mmol) were added to a 100mL three-necked flask containing 20mL dichloromethane, and 0.5 mL TFA and 10 mL TFSA were added dropwise under an ice water bath at 0deg.C, and the reaction was continued at that temperature for 24 hours. The resulting solution was slowly poured into an aqueous ethanol solution. Filtration gave a solid which was washed with water and at room temperature at 1M K 2 CO 3 Soaking for about 10 hours. The product was then filtered, washed with water and dried completely under vacuum at 60 ℃.
(2) (3) in the same manner as in the step (2) and (3) of example 1, an alkali-resistant and oxidation-resistant hydroxide-form exchange membrane was finally obtained.
The prepared anion exchange membrane has high mechanical property (tensile strength: 40.8 MPa, elongation at break: 47%) and higher dimensional stability (swelling degree is only 4.31%). Has a high OH content in 5M KOH at 80 DEG C - The conductivity (133.2 mS/cm) is not obviously degraded chemically within 60 days when the material is soaked in 80 ℃ high-concentration alkaline aqueous solution (10M NaOH), and the conductivity decay is only 9.66%.
Example 7
(1) The same as in step (1) of example 2.
(2) The polymer (1.5 g) obtained in the step (1) was dissolved in 20mL of dimethyl sulfoxide, 1mL of methyl iodide was rapidly added, the quaternization reaction was carried out at 60℃for 24 hours, and the resulting viscous yellow solution was added dropwise to diethyl ether. The yellow solid was filtered, washed with diethyl ether and then dried under vacuum at 60 ℃.
(3) As in step (3) of example 1, an alkali-resistant, oxidation-resistant, hydroxide-form exchange membrane was finally obtained.
The prepared anion exchange membrane has high mechanical property (tensile strength: 38.3 MPa, elongation at break: 34%) and high dimensional stability (swelling degree: 7.14%). Has a high OH content in 5M KOH at 80 DEG C - Conductivity (83.4 mS/cm), no obvious chemical degradation in 60 days, but 14.66% reduction in conductivity, when immersed in 80 ℃ high-concentration alkaline aqueous solution (10M NaOH).
Example 8
(1) 2, 6-tetramethyl-4-piperidone (0.782 g,5 mmol), 2, 4-dimethyl-1-piperidone (0.705 g,5 mmol) and 9, 9-dimethylfluorene (1.943 g,10 mmol) were added to a 100mL three-necked flask containing 20mL dichloromethane, and 0.5 mL TFA and 10 mL TFSA were added dropwise under an ice-water bath at 0deg.C, and the reaction was continued at that temperature for 24 hours. The resulting solution was slowly poured into an aqueous ethanol solution. Filtration gave a solid which was washed with water and at room temperature at 1M K 2 CO 3 Soaking for about 10 hours. The product was then filtered, washed with water and dried completely under vacuum at 60 ℃.
(2) (3) in the same manner as in the step (2) and (3) of example 1, an alkali-resistant and oxidation-resistant hydroxide-form exchange membrane was finally obtained.
The prepared anion exchange membrane has high mechanical property (tensile strength: 30.1 MPa, elongation at break: 29%), swelling degree of 7.8%, and OH in 5M KOH at 80 DEG C - The conductivity is 79.4mS/cm. The material is soaked in 80 ℃ high-concentration alkaline aqueous solution (10M NaOH), no obvious chemical degradation exists within 60 days, and the conductivity is attenuated by 14.35%.
Example 9
(1) 2, 6-tetramethyl-4-piperidineKetone (0.938 g,6 mmol), 2, 4-dimethyl-1-piperidone (0.564 g,4 mmol) and 9, 9-dimethylfluorene (5.8238 g,30 mmol) were added to a 100mL three-necked flask containing 20mL dichloromethane, and 0.8 mL TFA and 10 mL TFSA were added dropwise under an ice water bath at 0 ℃ and the reaction was continued at that temperature for 24 hours. The resulting solution was slowly poured into an aqueous ethanol solution. Filtration gave a solid which was washed with water and at room temperature at 1M K 2 CO 3 Soaking for about 10 hours. The product was then filtered, washed with water and dried completely under vacuum at 60 ℃.
(2) (3) in the same manner as in the step (2) and (3) of example 1, an alkali-resistant and oxidation-resistant hydroxide-form exchange membrane was finally obtained.
The prepared anion exchange membrane has high mechanical property (tensile strength: 46.1 MPa, elongation at break: 44%), high dimensional stability (swelling degree is only 4.66%), and high OH in 5M KOH at 80 DEG C - Conductivity (. About.131.4 mS/cm). No obvious chemical degradation occurs within 60 days when the material is immersed in 80 ℃ high-concentration alkaline aqueous solution (10M NaOH), and the conductivity decay is only 10.23%.
Example 10
The alkali-resistant and oxidation-resistant anion exchange membranes prepared in the above examples 4, 6, 7 and 9 were assembled in an aqueous flow battery as electrolyte membranes, the active material of the positive electrolyte was TEMPO-ammonium chloride, the active material of the negative electrolyte was 1, 1-dimethyl-4, 4' -bipyridinium chloride, the supporting electrolyte was sodium chloride, and the assembled flow battery was subjected to charge-discharge cycle test at 18-28℃with a current density of 80mA/cm 2 The results of the alkali-resistant and oxidation-resistant anion-exchange membrane prepared in example 9 are shown in the following figure 1, and it can be seen that there is no significant attenuation of the membrane within 200 cycles of charge-discharge cycles.
The alkali-resistant and oxidation-resistant anion exchange membrane cell performance comparisons obtained in examples 4, 6, 7, 9 are shown in table 1 below,
table 1 comparison of the Properties of alkali-resistant and Oxidation-resistant anion exchange membranes prepared in examples 4, 6, 7 and 9
Example 11
The alkali-resistant and oxidation-resistant anion exchange membrane prepared in the embodiment 6 is used as an electrolyte membrane to be assembled in an all-vanadium redox flow battery, and the active material of positive electrolyte is VOSO 4 The active material of the negative electrode electrolyte is V 2 (SO 4 ) 3 Sulfuric acid is used as supporting electrolyte, and the assembled all-vanadium redox flow battery is subjected to charge-discharge cycle test at 25 ℃ with current density of 80mA/cm 2 The test results are shown in the following figure 2, the coulomb efficiency is 99.66%, the energy efficiency is 72.40%, the voltage efficiency is 72.65%, and the film has no obvious attenuation in 50 circles of charge-discharge cycles.
It should be noted that the foregoing merely illustrates the technical idea of the present invention and is not intended to limit the scope of the present invention, and that a person skilled in the art may make several improvements and modifications without departing from the principles of the present invention, which fall within the scope of the claims of the present invention.
Claims (10)
1. An alkali-resistant and oxidation-resistant anion exchange resin is characterized in that the structural formula of the anion exchange resin is shown as formula 1:
formula 1;
wherein m, n are polymerization degree, are integers and are not 0;
Ar 1 、Ar 2 independently of one another, selected from the groups of the formula:
，/>，/>，/>，，/>；
R 1 independently is one of hydrogen, hydroxy, oxygen, sulfur, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, isopropyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, N-trimethylpentylamino, methoxy, ethoxy, propoxy, butoxy, cyclohexyloxy;
R 2 independently hydrogen, hydroxy, oxygen, sulfur, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, isopropyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, N, N, N-trimethylpentylamino, methoxy, ethoxy, propoxy, butoxy, cyclohexyloxy,、/>one of the following;
R 3 independently is one of hydrogen, methyl, ethyl and propyl.
2. A process for preparing an alkali-resistant, oxidation-resistant anion exchange resin as claimed in claim 1, comprising the steps of:
(1) Synthesis of the polymer backbone: dissolving piperidone monomer and aromatic monomer in an organic solvent, dropwise adding a polymerization catalyst at the temperature of 0 ℃, and continuously reacting at the temperature for 12-48 hours; slowly pouring the obtained solution into an ethanol water solution; filtering to obtain solid, washing with water, and soaking in alkaline solution at room temperature for 10-24 hr; the product was then filtered, washed with water and dried completely under vacuum at 60 ℃;
(2) Quaternization of the polymer: dissolving the dried polymer obtained in the step (1) in an organic solvent, adding a quaternizing reagent methyl iodide, reacting for 24 hours at 60-80 ℃ to carry out quaternization, washing with diethyl ether, and drying to form a cationic functional polymer;
(3) Preparation of anion exchange membrane: dissolving the cationic functionalized polymer obtained in the step (2) in an organic solvent, pouring the solution into a clean polytetrafluoroethylene membrane disc, and drying the solution in a vacuum drying oven at 60 ℃ to form a film; and immersing the prepared membrane into alkaline solution for anion exchange for 12-48 hours, immersing into deionized water for 12-24 hours to remove residual alkaline solution, and finally obtaining the alkali-resistant and oxidation-resistant hydroxide-type exchange membrane.
3. The method for preparing alkali-resistant and oxidation-resistant anion exchange resin according to claim 2, wherein in the step (1), the piperidone monomer is any two of 2, 6-tetramethyl-4-piperidone, 2, 4-dimethyl-1-piperidone, 1,2, 6-pentamethyl-4-piperidone and N-methyl-1-piperidone; the aromatic monomer is one or more of benzene, biphenyl, p-terphenyl, m-terphenyl, fluorene and 9, 9-dimethylfluorene; the organic solvent is one of ethanol, dichloromethane, chloroform, dichloroethane, tetrachloroethane, carbon tetrachloride, dimethyl sulfoxide and diethyl ether; the polymerization catalyst is one or more of trifluoroacetic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid and heptafluorobutyric acid; the alkaline solution is one of potassium carbonate solution, sodium bicarbonate solution, sodium hydroxide solution, potassium hydroxide solution and ammonia water.
4. The method for preparing alkali-resistant and oxidation-resistant anion exchange resin according to claim 2, wherein the molar ratio of the piperidone monomer to the aromatic monomer in the step (1) is 1:1-5, and the molar ratio of 1-piperidone to 4-piperidone is 1: 1-2; the organic solvent and the polymerization catalystThe volume ratio of the chemical agent is 2-3: 2-4% of 1, 1-piperidone monomer and organic solvent, 7-29% of aromatic monomer and organic solvent, wherein the volume ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1:12-20; the concentration of the alkaline solution is 1-2M; the alkaline solution is K 2 CO 3 A solution.
5. The method for preparing alkali-resistant and oxidation-resistant anion exchange resin according to claim 2, wherein in the step (2), the mass-volume ratio of the dried polymer obtained in the step (1) to methyl iodide is 1:1-3; the mass volume percentage of the dried polymer obtained in the step (1) and the organic solvent is 5% -10%; the organic solvent is one or more of dichloromethane, chloroform, dichloroethane, tetrachloroethane, carbon tetrachloride, dimethyl sulfoxide and diethyl ether.
6. The method for preparing alkali-resistant and oxidation-resistant anion exchange resin according to claim 2, wherein in the step (3), the mass volume percentage of the cation functionalized polymer obtained in the step (2) to the organic solvent is 5% -10%; the organic solvent is one or more of dichloromethane, chloroform, dichloroethane, tetrachloroethane, carbon tetrachloride, dimethyl sulfoxide and diethyl ether; the alkaline solution is KOH solution.
7. Use of the alkali-resistant, oxidation-resistant anion exchange resin of claim 1 in a fuel cell, wherein said fuel cell comprises an alkaline fuel cell; such applications include hydrogen production by electrolysis of water, fuel cells, flow batteries, electrodialysis.
8. The use of the alkali-resistant and oxidation-resistant anion exchange resin according to claim 1 in a flow battery, wherein the flow battery comprises an all-vanadium flow battery, an organic flow battery, an iron-chromium flow battery, and a zinc-bromine flow battery.
9. Use of the alkali-resistant, oxidation-resistant anion exchange resin prepared by the preparation method according to any one of claims 2-6 in a fuel cell, wherein the fuel cell comprises an alkaline fuel cell; such applications include hydrogen production by electrolysis of water, fuel cells, flow batteries, electrodialysis.
10. The application of the alkali-resistant and oxidation-resistant anion exchange resin prepared by the preparation method according to any one of claims 2-6 in a flow battery, wherein the flow battery comprises an all-vanadium flow battery, an organic flow battery, an iron-chromium flow battery and a zinc-bromine flow battery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311639677.5A CN117343290A (en) | 2023-12-04 | 2023-12-04 | Alkali-resistant and oxidation-resistant anion exchange resin and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112175170A (en) * | 2020-09-01 | 2021-01-05 | 中国科学院山西煤炭化学研究所 | Flexible-chain-segment-containing anion exchange membrane based on piperidone and aromatic polymerization, and preparation method and application thereof |
| CN113372596A (en) * | 2021-05-28 | 2021-09-10 | 西安交通大学 | Alkaline anion exchange membrane based on chemical crosslinking and preparation method thereof |
| CN113851683A (en) * | 2021-08-27 | 2021-12-28 | 重庆大学 | Preparation method of carbazole polyaromatic hydrocarbon piperidine anion exchange membrane |
| WO2022170022A1 (en) * | 2021-02-04 | 2022-08-11 | University Of Delaware | Oxidation resistant polymers for use as anion exchange membranes and ionomers |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175170A (en) * | 2020-09-01 | 2021-01-05 | 中国科学院山西煤炭化学研究所 | Flexible-chain-segment-containing anion exchange membrane based on piperidone and aromatic polymerization, and preparation method and application thereof |
| WO2022170022A1 (en) * | 2021-02-04 | 2022-08-11 | University Of Delaware | Oxidation resistant polymers for use as anion exchange membranes and ionomers |
| CN113372596A (en) * | 2021-05-28 | 2021-09-10 | 西安交通大学 | Alkaline anion exchange membrane based on chemical crosslinking and preparation method thereof |
| CN113851683A (en) * | 2021-08-27 | 2021-12-28 | 重庆大学 | Preparation method of carbazole polyaromatic hydrocarbon piperidine anion exchange membrane |
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