CN117567729B - Ion-conducting polymer and preparation method thereof, ion-conducting cross-linked substance and preparation method thereof, anion exchange membrane and application thereof - Google Patents
Ion-conducting polymer and preparation method thereof, ion-conducting cross-linked substance and preparation method thereof, anion exchange membrane and application thereof Download PDFInfo
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- CN117567729B CN117567729B CN202410080544.7A CN202410080544A CN117567729B CN 117567729 B CN117567729 B CN 117567729B CN 202410080544 A CN202410080544 A CN 202410080544A CN 117567729 B CN117567729 B CN 117567729B
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- ion
- exchange membrane
- conducting polymer
- anion exchange
- conducting
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- 239000000126 substance Substances 0.000 title claims description 41
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- 238000004132 cross linking Methods 0.000 claims description 17
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- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- MNHSTWRXCNIKFM-UHFFFAOYSA-N 1,2-diethyl-9h-fluorene Chemical compound C1=CC=C2C3=CC=C(CC)C(CC)=C3CC2=C1 MNHSTWRXCNIKFM-UHFFFAOYSA-N 0.000 claims 1
- CRXBTDWNHVBEIC-UHFFFAOYSA-N 1,2-dimethyl-9h-fluorene Chemical compound C1=CC=C2CC3=C(C)C(C)=CC=C3C2=C1 CRXBTDWNHVBEIC-UHFFFAOYSA-N 0.000 claims 1
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
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- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-O Pyrazolium Chemical compound C1=CN[NH+]=C1 WTKZEGDFNFYCGP-UHFFFAOYSA-O 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- HTMQZWFSTJVJEQ-UHFFFAOYSA-N benzylsulfinylmethylbenzene Chemical compound C=1C=CC=CC=1CS(=O)CC1=CC=CC=C1 HTMQZWFSTJVJEQ-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 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 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-O hydron;pyrimidine Chemical compound C1=CN=C[NH+]=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-O 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- GPRIERYVMZVKTC-UHFFFAOYSA-N p-quaterphenyl Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 GPRIERYVMZVKTC-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
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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
- 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
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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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
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- 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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G2261/122—Copolymers statistical
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- 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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- 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
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Abstract
The application provides an ion-conducting polymer and a preparation method thereof, an ion-conducting cross-linked product and a preparation method thereof, an anion exchange membrane and application thereof, and belongs to the technical field of electrochemistry. According to the application, aryl containing thioether bonds, sulfoxide bonds or/and phosphine bonds is selected as aryl in the main chain of the ion-conducting polymer, and the ion-conducting polymer is used for preparing the anion-exchange membrane, so that the ion conductivity of the anion-exchange membrane can be improved, and the anion-exchange membrane has better electrochemistry; the swelling rate of the anion exchange membrane can be reduced, and the oxidation resistance of the anion exchange membrane can be improved, so that the anion exchange membrane has longer service life, and the application range of the anion exchange membrane is widened to a great extent.
Description
Technical Field
The application relates to the technical field of electrochemistry, in particular to an ion conducting polymer and a preparation method thereof, an ion conducting cross-linked substance and a preparation method thereof, an anion exchange membrane and application thereof.
Background
Anion exchange membranes are a class of polymeric membranes containing basic active groups that are selectively permeable to anions, also known as ion-permselective membranes. Anion exchange membranes play an important role in the electrochemical technical fields of electrolysis, electrodialysis, fuel cells, flow batteries and the like.
The application of the anion exchange membrane is mainly influenced by the electrochemical performance and the service life of the anion exchange membrane; wherein, the service life of the anion exchange membrane is mainly influenced by the swelling rate and oxidation resistance of the anion exchange membrane. However, the existing anion exchange membrane cannot have better electrochemical performance (such as lower ion conductivity and the like), oxidation resistance and lower swelling rate, so that the anion exchange membrane cannot meet the higher requirements of continuous development of technology, and the application of the anion exchange membrane is greatly limited.
Disclosure of Invention
The application aims to provide an ion-conducting polymer and a preparation method thereof, an ion-conducting cross-linked substance and a preparation method thereof, an anion-exchange membrane and application thereof, which aim to improve the electrochemical performance and the service life of the existing anion-exchange membrane, so that the anion-exchange membrane has higher ion conductivity, lower swelling rate and higher oxidation resistance.
In a first aspect, the present application provides an ion conducting polymer having the expression formula: ax-Bm-Cn-Dp, the ion conducting polymer has the following structural formula:
; wherein x is more than or equal to 0, m is more than or equal to 0, n is more than 0, and p is more than 0; r 1 and R 3 are each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl; r 2 and R 4 are each a group containing a fluorine atom; ar 1、Ar2、Ar3 and Ar 4 are each independently selected from the group consisting of a first aryl group or a second aryl group; the ion conducting polymer contains a first aryl group; the first aryl group contains at least one of a thioether bond, a sulfoxide bond and a phosphine bond, and the second aryl group does not contain a thioether bond, a sulfoxide bond and a phosphine bond; the structural formulae of R a and R b are each independently as follows: Or/> ; R 5 and R 6 are each independently selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a group containing a salt unit, and a hydrogen atom; x 1 - and X 2 - are both anions; y is a natural number of 1 to 6.
According to the application, aryl containing thioether bonds, sulfoxide bonds or/and phosphine bonds is selected as aryl in the main chain of the ion-conducting polymer, and the ion-conducting polymer is used for preparing the anion-exchange membrane, so that the ion conductivity of the anion-exchange membrane can be improved, and the anion-exchange membrane has better electrochemistry; the swelling rate of the anion exchange membrane can be reduced, and the oxidation resistance of the anion exchange membrane can be improved, so that the anion exchange membrane has longer service life, and the application range of the anion exchange membrane is widened to a great extent.
In a second aspect, the present application provides a method for preparing an ion-conducting polymer, the method comprising: copolymerizing the first component and the second component in the presence of a catalyst; then adding a third component into the system after the copolymerization reaction to carry out salt forming reaction; the catalyst comprises at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, concentrated sulfuric acid, p-toluenesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, perfluoropropionic acid, heptafluorobutyric acid and phosphotungstic acid; the first component comprises a first monomer, or the first component comprises the first monomer and a second monomer; the second component comprises a third monomer and a sixth monomer, or the second component comprises a third monomer and a sixth monomer, and the second component further comprises at least one of a fourth monomer and a fifth monomer; the first monomer is a substituted or unsubstituted first aromatic compound, and the first aromatic compound contains at least one of thioether bonds, sulfoxide bonds and phosphine bonds; the second monomer is a substituted or unsubstituted second aromatic compound, and the second aromatic compound does not contain thioether bonds, sulfoxide bonds and phosphine bonds; the structural formula of the third monomer is as follows: ; the structural formula of the fourth monomer is as follows: /(I) ; The structural formula of the fifth monomer is as follows: /(I); The structural formula of the sixth monomer is as follows: /(I); Wherein R 1 and R 3 are each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl; r 2 and R 4 are each a group containing a fluorine atom; the structural formulae of R a1 and R b1 are each independently as follows: /(I)Or; R 5 is selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, a group containing a salt unit, a hydrogen atom; the third component comprises a first substance or/and a second substance; the structural formula of the first substance is R 6-R13, and the structural formula of the second substance isWherein R 6 is selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, R 13、R7 and R 8 are each independently selected from halogen atom, carbonate group or sulfate group, and y is a natural number of 1 to 6.
In a third aspect, the present application provides a method of preparing an ion-conducting cross-link, the method comprising: the ion-conducting polymer provided in the first aspect is subjected to a crosslinking reaction in the presence of a crosslinking agent.
In a fourth aspect, the present application provides an ion-conducting crosslinked material prepared by the method for preparing an ion-conducting crosslinked material according to the third aspect.
In a fifth aspect, the present application provides an anion exchange membrane, the anion exchange membrane comprising an ion conducting system; or, the anion exchange membrane comprises a porous supporting layer and a filler filled in the pores of the porous supporting layer, wherein the filler comprises inorganic hydrophilic particles and an ion conduction system; or, the anion exchange membrane comprises a porous support layer and a filler filled in the pores of the porous support layer, wherein the filler comprises an ion conduction system; alternatively, the anion exchange membrane comprises inorganic hydrophilic particles and an ion conducting system. Wherein the ion conducting system comprises: ion-conducting polymers or/and ion-conducting crosslinks; the ion-conducting polymer is the ion-conducting polymer provided in any one of the above first aspects, or the ion-conducting polymer is an ion-conducting polymer produced by the production method of the ion-conducting polymer provided in the above second aspect; the ion-conducting crosslinked material is an ion-conducting crosslinked material produced by the method for producing an ion-conducting crosslinked material according to the third aspect, or the ion-conducting crosslinked material is an ion-conducting crosslinked material according to the fourth aspect.
In a sixth aspect, the present application provides the use of an anion exchange membrane provided in the fifth aspect above for the preparation of an electrolyzed water device, an electrodialysis device, a fuel cell or an electrochemical energy storage device; the electrochemical energy storage device comprises a flow battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance spectrum of an ion-conducting polymer prepared in the step (2) of example 1 of the present application.
FIG. 2 is a nuclear magnetic resonance spectrum of the ion-conducting polymer prepared in the step (2) of example 2 of the present application.
FIG. 3 is a nuclear magnetic resonance spectrum of the ion-conducting polymer prepared in the step (2) of example 3 of the present application.
FIG. 4 is a nuclear magnetic resonance spectrum of the ion-conducting polymer prepared in the step (2) of example 4 of the present application.
FIG. 5 is a nuclear magnetic resonance spectrum of an ion-conducting polymer prepared in the step (2) of example 7 of the present application.
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of the ion-conducting polymer obtained in the step (2) of the comparative example of the present application.
Detailed Description
For the anion exchange membrane, under the electrochemical use scene, one side of the anion exchange membrane, which is subjected to oxidation reaction, is attacked by free radicals with high oxidability, so that the stability of the anion exchange membrane is reduced, and the service life of the anion exchange membrane is further reduced.
The ideal anion exchange membrane should have high ion conductivity, low swelling rate and high oxidation resistance, and in order to enable the anion exchange membrane to have high ion conductivity, low swelling rate and high oxidation resistance, the application provides an ion conducting polymer, and the expression general formula of the ion conducting polymer is as follows: ax-Bm-Cn-Dp, the ion conducting polymer has the following structural formula:
。
Wherein x is greater than or equal to 0, m is greater than or equal to 0, n is greater than 0, and p is greater than 0.
R 1 and R 3 are each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl.
R 2 and R 4 are each a group containing a fluorine atom.
Ar 1、Ar2、Ar3 and Ar 4 are each independently selected from the group consisting of a first aryl group or a second aryl group; the ion conducting polymer contains a first aryl group; the first aryl group contains at least one of a thioether bond, a sulfoxide bond, and a phosphine bond, and the second aryl group does not contain a thioether bond, a sulfoxide bond, and a phosphine bond.
The structural formulae of R a and R b are each independently as follows:
Or/> 。
R 5 and R 6 are each independently selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a group containing a salt unit, and a hydrogen atom.
X 1 - and X 2 - are anions.
Y is a natural number of 1 to 6.
In the present application, the expression of "ion-conducting polymer" is as follows: ax-Bm-Cn-Dp' is not limited to the order of connection of the four copolymerized units A, B, C and D in the ion-conducting polymer, as long as the four copolymerized units A, B, C and D are contained in the ion-conducting polymer.
In the present application, the four copolymerized units corresponding to A, B, C and D are not necessarily copolymerized units of one structure, but copolymerized units formed by copolymerized subunits of a plurality of different structures; for example, the structural formula of the A copolymerized unit is: the A copolymerized unit may be a copolymerized unit of only one structure, or the A copolymerized unit may be a unit of the formula/> 、AndA copolymer unit formed of a plurality of copolymer subunits, wherein Ar 1a、Ar1b, ar 1c, etc. may be the same or different, R 1a、R1b, R 1c, etc. may be the same or different, R 2a、R2b, R 2c, etc. may be the same or different; B. the three copolymerization units C and D are the same and are not described in detail herein.
The present application is not limited to the "connection sites on Ar 1、Ar2、Ar3 and Ar 4".
In the present application, the phrase "the ion conductive polymer contains a first aryl group" means that: the ion-conducting polymer may contain only a first aryl group; for example, when "p and n in the above structural formula of the ion-conducting polymer are both > 0, and x and m are both 0", the ion-conducting polymer may contain only Ar 3 and Ar 4,Ar3 and Ar 4, and only one of them is a first aryl group, and may be Ar 3 and Ar 4 are both first aryl groups, or may be Ar 3 and Ar 4, and one of them is a first aryl group and the other is a second aryl group.
In the present application, the salt unit means: having a structure formed by "a first anionic unit covalently linked to an ion-conducting polymer" and "a first cationic unit electrostatically bound to the first anionic unit"; or, the salt unit means: has a structure formed by "a second cationic unit covalently linked to an ion-conducting polymer" and "a second anionic unit electrostatically bound to the second cationic unit".
As an example, y may be 1,2, 3,4, 5, 6.
According to the application, aryl containing thioether bonds, sulfoxide bonds or/and phosphine bonds is selected as aryl in the main chain of the ion conducting polymer, the thioether bonds, the sulfoxide bonds or/and the phosphine bonds can be used as sacrificial units, and the aryl is oxidized by attack of highly oxidative free radicals in an oxidative atmosphere of an electrochemical use scene, so that the main chain framework of the ion conducting polymer is not broken by oxidation; therefore, the ion conductivity of the anion exchange membrane prepared by adopting the ion conducting polymer can be improved, so that the anion exchange membrane has better electrochemistry; the swelling rate of the anion exchange membrane can be reduced, and the oxidation resistance of the anion exchange membrane can be improved, so that the anion exchange membrane has longer service life, and the application range of the anion exchange membrane is widened to a great extent.
In some alternative embodiments of the application, the first aryl group has the formula:
、、、 Or/> ; Wherein, t and q are both more than or equal to 0; ar 5 and Ar 6 are substituted or unsubstituted aryl groups, and Ar 5 and Ar 6 can be used as the connecting site of the first aryl group; r 9 and R 10 are both substituted or unsubstituted alkyl groups; r 11 is selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl.
The structural formula of the first aryl is shown as the above, so that the anion exchange membrane prepared by adopting the ion conducting polymer has higher ion conductivity, lower swelling rate and higher oxidation resistance, and the application range of the anion exchange membrane is further widened.
In the present application, "Ar 5 and Ar 6 in the first aryl group can be used as the linking site of the first aryl group" means that: when only Ar 5 is included in the first aryl group, any two sites on Ar 5 serve as attachment sites to other units on the backbone of the ion conducting polymer; when the first aryl group contains only Ar 5 and Ar 6, any two sites on Ar 5 may be used as the bonding sites with other units on the main chain of the ion-conducting polymer, any two sites on Ar 6 may be used as the bonding sites with other units on the main chain of the ion-conducting polymer, or any one site of Ar 5 and any one site of Ar 6 may be used as the bonding sites with other units on the main chain of the ion-conducting polymer.
Further, in some alternative embodiments of the application, ar 5 and Ar 6 are each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted p-terphenyl, substituted or unsubstituted m-terphenyl, substituted or unsubstituted o-terphenyl, substituted or unsubstituted p-tetraphenyl, substituted or unsubstituted m-tetrabiphenyl, substituted or unsubstituted pentabiphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diethylfluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, and substituted or unsubstituted naphthyl.
In other possible embodiments of the present application, ar 5 and Ar 6 are not limited to the above groups, and may be substituted or unsubstituted aryl groups.
In some alternative embodiments of the application, R 9 and R 10 are each independently selected from the group consisting of substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted cyclohexyl.
In other possible embodiments of the present application, R 9 and R 10 are not limited to the above groups, and may be substituted or unsubstituted alkyl groups.
In some alternative embodiments of the application, R 11 is selected from substituted or unsubstituted C 1~C6 alkyl, substituted or unsubstituted C 3~C7 cycloalkyl, substituted or unsubstituted phenyl; is beneficial to further improving the oxidation resistance of the anion exchange membrane and further widening the application range of the anion exchange membrane.
In some alternative embodiments of the application, t and q are both 0, which is advantageous for further increasing the ion conductivity of the anion exchange membrane.
In some alternative embodiments of the application, the first aryl group has the formula:
、 Or (b) ; Wherein, t and q are both more than or equal to 0; ar 5 and Ar 6 are substituted or unsubstituted aryl groups, and Ar 5 and Ar 6 can be used as the connecting site of the first aryl group; r 11 is selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl; further, t and q are both 0. The structural formula of the first aryl is shown as above, which is favorable for further improving the oxidation resistance of the anion exchange membrane and further widening the application range of the anion exchange membrane.
In some alternative embodiments of the application, the first aryl group is selected from diphenyl sulfide @) Diphenyl sulfoxide (/ >)) Dibenzyl thioether radical [ ]) Dibenzyl sulfoxide (/ >)) 2-Methyldiphenyl sulfide group (/ >)) At least one of (a) and (b); is beneficial to further improving the oxidation resistance of the anion exchange membrane and further widening the application range of the anion exchange membrane.
Further, in some alternative embodiments of the present application, the first aryl group is selected from at least one of a diphenyl sulfide group and a diphenyl sulfoxide group; is beneficial to further improving the oxidation resistance of the anion exchange membrane and further widening the application range of the anion exchange membrane.
In some alternative embodiments of the application, the second aryl group is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted p-terphenyl, substituted or unsubstituted m-terphenyl, substituted or unsubstituted o-terphenyl, substituted or unsubstituted p-tetrabiphenyl, substituted or unsubstituted m-tetrabiphenyl, substituted or unsubstituted pentabiphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diethylfluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, and substituted or unsubstituted naphthyl.
Further, the structural formula of the second aryl group is as follows:
、 Or/> . The second aryl group is selected from the structures shown above, which is advantageous for further improving the ion conductivity of the anion exchange membrane.
In other possible embodiments of the present application, the second aryl group is not limited to the above groups, and may be any "substituted or unsubstituted aryl group, and the aryl group does not contain a thioether bond, a sulfoxide bond, or a phosphine bond".
In some alternative embodiments of the application, the ratio of the molar amount of the first aryl group to the molar amount of the second aryl group in the ion-conducting polymer is less than or equal to 0.3; is beneficial to further improving the ion conductivity of the anion exchange membrane.
As an example, the ratio of the molar amount of the first aryl group to the molar amount of the second aryl group in the ion conducting polymer may be any one point value or a range value between any two of 0.001, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, and 0.3.
In some alternative embodiments of the present application, the ion conducting polymer contains both a first aryl group and a second aryl group; the anion exchange membrane prepared by the ion conducting polymer has higher ion conductivity, and further widens the application range of the anion exchange membrane.
In some alternative embodiments of the application, for the case where "R 5 or/and R 6 is a group containing a salt unit", the structural formula of the group containing a salt unit is as follows: Wherein z is more than or equal to 0, R 12 + is ammonium group with positive charge, and X 3 - is anion.
In the present application, the positively charged ammonium group means: the N atom in the primary, tertiary, quaternary or cyclic amine groups is positively charged by protonation.
Further, z is a natural number of 1 to 3. As an example, z may be 1, 2 or 3.
In some alternative embodiments of the application, R 12 + is selected from a positively charged cyclic amine group or a positively charged quaternary ammonium group; the anion exchange membrane prepared by crosslinking the ion conducting polymer has higher ion conductivity, lower swelling rate and higher oxidation resistance, and further widens the application range of the anion exchange membrane.
Still further, the positively charged cyclic amine group includes at least one of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium; is beneficial to further improving the ion conductivity of the anion exchange membrane.
In some alternative embodiments of the application, R 12 + is selected from the group consisting of tetramethylimidazolium, N-methylpiperidinium, andAt least one of (a) and (b); is beneficial to further improving the ion conductivity of the anion exchange membrane.
In other possible embodiments of the present application, R 12 + may be other positively charged ammonium ions, for example, R 12 + may be a positively charged primary amino cation, a positively charged secondary amino cation, or a positively charged tertiary amino cation; r 12 + may be other positively charged cyclic amine groups, and the application is not limited.
In some alternative embodiments of the application, X 3 - is selected from at least one of a halide, a triflate anion, and a p-toluenesulfonate anion. As an example, X 3 - may be Cl -、I- or Br -, or the like.
In other possible embodiments of the present application, X 3 - may be at least one selected from the group consisting of bicarbonate ion, hydroxide ion, p-trifluorobenzenesulfonic acid anion, phosphorus hexafluoride anion, and boron tetrafluoride anion.
In some alternative embodiments of the application, R 5 and R 6 are both substituted or unsubstituted C 1~C3 alkyl; illustratively, R 5 and R 6 are both methyl.
In some alternative embodiments of the application, each of X 1 - and X 2 - is independently selected from at least one of a halide ion, a p-toluenesulfonic acid anion, and a trifluoromethanesulfonic acid anion. As an example, each of X 1 - and X 2 - independently may be Cl -、I- or Br - or the like.
In other possible embodiments of the present application, X 1 - and X 2 - may be at least one selected from the group consisting of bicarbonate ion, hydroxide ion, p-trifluorobenzenesulfonic acid anion, phosphorus hexafluoride anion, and boron tetrafluoride anion.
In some alternative embodiments of the application, R a and R b are both of the formula; R 5 and R 6 are each independently selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a group containing a salt unit, and a hydrogen atom; x 1 - is an anion.
In some alternative embodiments of the application, R 1 and R 3 are each independently selected from halogen substituted or unsubstituted alkyl, halogen substituted or unsubstituted aryl; further, R 1 and R 3 are both phenyl.
In some alternative embodiments of the application, R 2 and R 4 are each independently selected from halogen substituted or unsubstituted alkyl, halogen substituted or unsubstituted aryl; further, R 2 and R 4 are each independently selected from the group consisting of fluorine atom substituted alkyl groups of C 1~C3 or fluorine atom substituted aryl groups.
Still further, R 2 and R 4 are both trifluoromethyl; is beneficial to increasing the hydrophilicity of the ion conducting polymer.
In some alternative embodiments of the application, the ion conducting polymer has the formula:
、、、 Or (b) ; Wherein, M 2 and M 4 are p-terphenyl groups, and M 1 and M 3 are diphenyl sulfide groups. The structural formula of the ion-conducting polymer is shown in the specification, so that the anion-exchange membrane prepared by adopting the ion-conducting polymer has higher ion conductivity, lower swelling rate and higher oxidation resistance, and the application range of the anion-exchange membrane is further widened.
In some alternative embodiments of the application, 30% or more (x+m)/(x+m+n+p) or more 0, 100% or more (n+p)/(x+m+n+p) or more 70%.
In some alternative embodiments of the application, the ion-conducting polymer has a number average molecular weight of 10000Da to 1000000Da. If the number average molecular weight of the ion conducting polymer is larger, the mechanical strength of the anion exchange membrane is not improved; if the number average molecular weight of the ion conducting polymer is smaller, the viscosity of the ion conducting polymer is larger, which is not beneficial to further improving the film forming effect of the anion exchange membrane.
The application provides a preparation method of an ion-conducting polymer, which comprises the following steps: copolymerizing the first component and the second component in the presence of a catalyst; and then adding a third component into the system after the copolymerization reaction to carry out salt forming reaction.
The catalyst comprises at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, concentrated sulfuric acid, p-toluenesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, perfluoropropionic acid, heptafluorobutyric acid and phosphotungstic acid.
The first component includes a first monomer, or, the first component includes a first monomer and a second monomer.
The second component comprises a third monomer and a sixth monomer; or, the second component includes a third monomer and a sixth monomer, and the second component further includes at least one of a fourth monomer and a fifth monomer.
The first monomer is a substituted or unsubstituted first aromatic compound, and the first aromatic compound contains at least one of thioether bond, sulfoxide bond and phosphine bond.
The second monomer is a substituted or unsubstituted second aromatic compound, and the second aromatic compound does not contain thioether bonds, sulfoxide bonds and phosphine bonds.
The structural formula of the third monomer is as follows: ; the structural formula of the fourth monomer is as follows: /(I) ; The structural formula of the fifth monomer is as follows: /(I); The structural formula of the sixth monomer is as follows: /(I); Wherein R 1 and R 3 are each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl; r 2 and R 4 are each a group containing a fluorine atom; the structural formulae of R a1 and R b1 are each independently as follows: /(I)Or; R 5 is selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, a group containing a salt unit, and a hydrogen atom.
The third component comprises a first substance or/and a second substance; the structural formula of the first substance is R 6-R13, and the structural formula of the second substance isWherein R 6 is selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, R 13、R7 and R 8 are each independently selected from halogen atom, carbonate group or sulfate group, and y is a natural number of 1 to 6.
It is understood that R 1、R2、R3、R4、R5、R6 and y in the third monomer, fourth monomer, fifth monomer, sixth monomer, first substance, and second substance are consistent with R 1、R2、R3、R4、R5、R6 and y, respectively, in the ion conducting polymer provided above, and are not described herein.
It will be appreciated that the first monomer in the first component is correspondingly selected according to the first aryl group in the ion-conducting polymer described above, for example, when the "first aryl group of the ion-conducting polymer is a diphenyl sulfide group", then diphenyl sulfide is selected as the first monomer.
It will be appreciated that the second monomer in the first component is correspondingly selected based on the second aryl group in the ion conducting polymer described above, e.g., when the "second aryl group of the ion conducting polymer is p-terphenyl", then p-terphenyl is selected as the second monomer.
It is understood that the molar ratio of the third monomer, the fourth monomer, the fifth monomer and the sixth monomer in the second component is n: x: m: p, which is identical to n: x: m: p in the ion-conducting polymer provided above, and will not be described herein.
It should be noted that when R a1 or R b1 has the structural formulaWhen the third component selects the first substance; when R a1 or R b1 has the structural formulaThe third component selects the second substance when it is.
In some alternative embodiments of the application, R 13、R7 and R 8 are both halogen atoms; as an example, R 13、R7 and R 8 are each independently a fluorine atom, a bromine atom, a chlorine atom, or the like.
As an example, the first substance is selected from at least one of methyl iodide, dimethyl carbonate, dimethyl sulfate, methyl bromide, methyl chloride, ethyl bromide, ethyl chloride, and ethyl iodide.
In some alternative embodiments of the application, a method of preparing an ion conducting polymer comprises: in the presence of a catalyst, a system comprising a first component, a second component and a first solvent is subjected to a copolymerization reaction.
As an example, the first solvent includes at least one of dichloromethane, chloroform, nitrobenzene, chloroform, 1, 2-dichloroethane, carbon disulfide, petroleum ether, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide. The first solvent is selected from the substances, so that the first component, the second component and the catalyst can be well dissolved and dispersed.
In some alternative embodiments of the application, the copolymerization is carried out at-10 to 100 ℃ (e.g., under ice bath conditions); further, the copolymerization is carried out at the temperature of-10 ℃ to 70 ℃, which is favorable for better carrying out the copolymerization.
In some alternative embodiments of the application, a method of preparing an ion conducting polymer comprises: and adding a catalyst into a system containing the first component, the second component and the first solvent at the temperature of-10 ℃ to 100 ℃ and then carrying out copolymerization reaction. Further, the time of the copolymerization reaction is 5-24 hours. Under the above copolymerization conditions, the copolymerization reaction can be made to proceed well.
As an example, the temperature of the copolymerization reaction may be-10 ℃, -5 ℃,0 ℃,10 ℃, 20 ℃,50 ℃, 70 ℃ and 100 ℃ or a range value between any two; the time of the copolymerization reaction may be any one point value or a range value between any two of 5h, 8h, 10h, 12h, 15h, 17h, 20h, 22h and 24 h.
In some alternative embodiments of the application, the molar ratio of catalyst to first component is (2-5): 1; is beneficial to improving the efficiency of the copolymerization reaction.
As an example, the molar ratio of catalyst to first component may be any one point value or a range value between any two of 2:1, 2.5:1, 3:1, 3.5:1, 4:14.5:1 and 5:1.
In some alternative embodiments of the application, the molar ratio of the first component to the second component is 1 (0.8-1.2); is beneficial to improving the efficiency of the copolymerization reaction.
As an example, the molar ratio of the first component to the second component may be any one point value or a range value between any two of 1:0.8, 1:0.9, 1:1, 1:1.1 and 1:1.2.
In some optional embodiments of the application, the temperature of the salifying reaction is 0-100 ℃, and the time of the salifying reaction is 12-36 h; under the above copolymerization conditions, the salt formation reaction can be made to proceed well.
As an example, the temperature of the salification reaction may be any one point value or a range value between any two of 0 ℃,5 ℃, 10 ℃, 20 ℃,50 ℃, 75 ℃ and 100 ℃; the salt formation reaction time may be any one point value or a range value between any two of 12h, 15h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h and 36 h.
In some alternative embodiments of the application, a method of preparing an ion conducting polymer comprises: slowly dripping the system after the copolymerization reaction into a second solvent before the salification reaction, and filtering to obtain a first solid; then immersing the first solid in an alkaline solution, and filtering to obtain a second solid; mixing the dried second solid with a third solvent to obtain a mixed system; and adding a third component into the mixed system to carry out salt forming reaction. Wherein the second solvent comprises at least one of ethanol, methanol, water, ethyl acetate and tetrahydrofuran; the alkaline solution comprises at least one of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate; the third solvent includes at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
It should be noted that the ion-conducting polymer provided above may be prepared without using the preparation method of the ion-conducting polymer provided above, as long as the structure corresponding to the ion-conducting polymer provided above can be prepared.
The application provides a preparation method of an ion conduction cross-linked product, which comprises the following steps: the ion-conducting polymer provided above is subjected to a crosslinking reaction in the presence of a crosslinking agent.
The ion conduction cross-linked matter prepared by the preparation method of the ion conduction cross-linked matter provided by the application can not only improve the ion conductivity of the anion exchange membrane prepared by the ion conduction cross-linked matter, so that the anion exchange membrane has better electrochemistry; the swelling rate of the anion exchange membrane can be reduced, and the oxidation resistance of the anion exchange membrane can be improved, so that the anion exchange membrane has longer service life, and the application range of the anion exchange membrane is widened to a great extent.
In some alternative embodiments of the application, the crosslinking agent comprises at least one of a first crosslinking agent and an olefinic crosslinking agent; wherein the first crosslinking agent contains at least two crosslinking groups, and the crosslinking groups are at least one of halogen atoms and pseudohalogen groups. The ion-conducting polymer may be allowed to undergo a cross-linking reaction to form an ion-conducting cross-link.
In the present application, the olefinic crosslinking agent means a crosslinking agent having a carbon-carbon double bond.
In some alternative embodiments of the present application, the aforementioned first crosslinking agent has the following structural formula:
; wherein R 15 is selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl; r 16 and R 17 are each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and hydrogen; r 18 and R 19 are each independently selected from at least one of halogen, trifluoromethanesulfonyl and p-toluenesulfonyl.
Further, in some alternative embodiments of the present application, the first crosslinking agent is selected from at least one of dibromopropane, dibromobutane, dibromopentane, and dibromohexane.
In some alternative embodiments of the application, the olefinic crosslinking agent has the formula:
; wherein R 20 is selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl; r 21 is at least one selected from halogen atom, trifluoromethanesulfonyl and p-toluenesulfonyl.
Further, in some alternative embodiments of the present application, the olefinic crosslinking agent is selected from at least one of chloromethylstyrene and allyl chloride.
In some alternative embodiments of the application, a method of making an ion-conducting cross-link comprises: the system comprising the ion-conducting polymer provided above and the fourth solvent is subjected to a crosslinking reaction in the presence of a crosslinking agent.
As an example, the fourth solvent includes at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone. The fourth solvent is selected from the substances, so that the ion conducting polymer and the cross-linking agent can be well dissolved and dispersed.
In some alternative embodiments of the application, the time of the crosslinking reaction is 12-36 hours, and the temperature of the crosslinking reaction is 20-120 ℃. The conditions for the crosslinking reaction can be such that the crosslinking reaction proceeds well.
As an example, the time of the crosslinking reaction may be any one point value or a range value between any two of 12h, 15h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, and 36 h; the temperature of the crosslinking reaction may be any one point value or a range value between any two of 20 ℃, 30 ℃, 50 ℃,70 ℃, 90 ℃, 100 ℃ and 120 ℃.
In some alternative embodiments of the present application, the molar ratio of the crosslinking agent to the second component is (0.01 to 0.5): 1, which may allow the crosslinking reaction to proceed well.
As an example, the molar ratio of crosslinker to second component may be any one point value or a range value between any two of 0.01:1, 0.02:1, 0.05:1, 0.07:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, and 0.5:1.
In some alternative embodiments of the application, the method of making an ion-conducting cross-link further comprises: after the crosslinking reaction, adding the system after the crosslinking reaction into a fifth solvent, and taking out the precipitated solid phase to obtain the ion conduction crosslinked product. When the ion-conducting crosslinked material is used to prepare the anion-exchange membrane, the ion-conducting crosslinked material in a solid phase is dissolved in dimethyl sulfoxide, and then the anion-exchange membrane is prepared.
As an example, the fifth solvent includes at least one of tetrahydrofuran, ethyl acetate, petroleum ether, toluene, chlorobenzene, dichloromethane, dichloroethane, and chloroform. The sixth solvent is selected from the solvents, so that the prepared ion conduction cross-linked matter can be separated out in the fifth solvent, and the purification of the ion conduction cross-linked matter is facilitated.
The application also provides an ion conduction cross-linked object which is prepared by adopting the preparation method of the ion conduction cross-linked object.
The application provides an anion exchange membrane, the material of which comprises an ion conduction system; wherein the ion conducting system comprises: the ion-conducting polymer provided above or/and the ion-conducting cross-linked material provided above.
The anion exchange membrane provided by the application has higher ion conductivity, lower swelling rate and higher oxidation resistance, namely the anion exchange membrane has better electrochemical performance and longer service life, and is beneficial to widening the application range of the anion exchange membrane to a great extent.
In some alternative embodiments of the application, the anion exchange membrane comprises four means:
Mode one: the anion exchange membrane comprises a membrane matrix, and the membrane matrix is made of the ion conduction system.
As an exemplary example, the method for preparing an anion exchange membrane according to mode one includes: casting a liquid phase containing an ion conduction system onto a planar substrate, and drying to obtain a film-like substance positioned on the planar substrate; and immersing the dried film-shaped substance in a KOH solution of 1M to obtain the hydroxide anion exchange membrane. Wherein the planar substrate can be polyethylene, polypropylene, polyethylene terephthalate, polytetrafluoroethylene or glass, etc.; the drying temperature can be about 80 ℃, and the drying time can be 1-20 h. Further, the planar substrate is selected from polyethylene terephthalate.
Mode two: the anion exchange membrane comprises a porous support layer and a filler filled in the pores of the porous support layer, wherein the filler is the ion conduction system provided by the above.
As an exemplary example, the method of preparing the anion exchange membrane of mode two includes: casting the liquid phase containing the ion conduction system into the pores of the porous supporting layer and drying; and immersing the dried film-shaped substance in a KOH solution of 1M to obtain the hydroxide anion exchange membrane. Wherein the porous supporting layer is made of at least one of polypropylene, polyethylene, polysulfone, polyphenylene sulfide, polyamide, polyether sulfone, polyphenylene sulfone, polyethylene terephthalate, polyether ether ketone, sulfonated polyether ether ketone, expanded polytetrafluoroethylene, chlorotrifluoroethylene, copolymer of ethylene and tetrafluoroethylene, copolymer of ethylene and chlorotrifluoroethylene, polyimide, polyetherimide and meta-aromatic polyamide; the drying temperature can be about 80 ℃, and the drying time can be 1-20 h; the porosity of the porous supporting layer is 40% -90%; the thickness of the porous support layer is 1-60 μm. Further, the porous supporting layer is made of expanded polytetrafluoroethylene; the porosity of the porous supporting layer is 50% -80%; the thickness of the porous support layer is 2-40 μm.
Mode three: the anion exchange membrane comprises a porous support layer and a filler filled in the pores of the porous support layer, the filler comprising inorganic hydrophilic particles and an ion conducting system as provided above.
As an exemplary example, the method for preparing an anion exchange membrane of mode three includes: casting liquid phase containing inorganic hydrophilic particles and an ion conduction system into pores of a porous supporting layer, and drying; and immersing the dried film-shaped substance in a KOH solution of 1M to obtain the hydroxide anion exchange membrane. The drying temperature can be about 80 ℃, and the drying time can be 1-20 hours; the inorganic hydrophilic particles comprise at least one of zirconia, barium sulfate, hydrotalcite, titanium dioxide, zinc carbonate, magnesium hydroxide, nickel hydroxide and hydrotalcite materials; the particle size of the inorganic hydrophilic particles is 1 nm-1 mu m; the inorganic hydrophilic particles account for less than or equal to 60% of the mass fraction of the ion conduction system; the porous supporting layer is made of at least one of polypropylene, polyethylene, polysulfone, polyphenylene sulfide, polyamide, polyether sulfone, polyphenylene sulfone, polyethylene terephthalate, polyether ether ketone, sulfonated polyether ether ketone, expanded polytetrafluoroethylene, chlorotrifluoroethylene, copolymer of ethylene and tetrafluoroethylene, copolymer of ethylene and chlorotrifluoroethylene, polyimide, polyetherimide and meta-aromatic polyamide; the porosity of the porous supporting layer is 40% -90%; the thickness of the porous support layer is 1-60 μm. Further, the inorganic hydrophilic particles are selected from zirconium oxide or barium sulfate, the particle size of the inorganic hydrophilic particles is 5-500 nm, the inorganic hydrophilic particles account for 10-30% of the mass fraction of the ion conduction system, the porous support layer is selected from expanded polytetrafluoroethylene, the porosity of the porous support layer is 50-80%, and the thickness of the porous support layer is 2-40 mu m.
Mode four: the anion exchange membrane comprises a membrane matrix, and the material of the membrane matrix comprises the anion conduction system and the inorganic hydrophilic particles.
As an exemplary example, the method for preparing an anion exchange membrane of mode four includes: casting a liquid phase containing inorganic hydrophilic particles and an ion conduction system onto a planar substrate, and drying to obtain a film-like substance positioned on the planar substrate; and immersing the dried film-shaped substance in a KOH solution of 1M to obtain the hydroxide anion exchange membrane. Wherein the planar substrate can be polyethylene, polypropylene, polyethylene terephthalate, polytetrafluoroethylene or glass, etc.; the inorganic hydrophilic particles comprise at least one of zirconia, barium sulfate, hydrotalcite, titanium dioxide, zinc carbonate, magnesium hydroxide, nickel hydroxide and hydrotalcite materials; the particle size of the inorganic hydrophilic particles is 1 nm-1 mu m; the inorganic hydrophilic particles account for less than or equal to 60% of the mass fraction of the ion conduction system; the drying temperature can be about 80 ℃, and the drying time can be 1-20 h. Further, the plane substrate is made of polyethylene terephthalate, the inorganic hydrophilic particles are made of zirconium oxide or barium sulfate, the particle size of the inorganic hydrophilic particles is 5 nm-500 nm, and the mass fraction of the inorganic hydrophilic particles in the ion conduction system is 10% -30%.
The application provides an application of the anion exchange membrane provided above in preparing an electrolyzed water device, an electrodialysis device, a fuel cell or an electrochemical energy storage device; the electrochemical energy storage device comprises a flow battery.
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a preparation method of an anion exchange membrane, which comprises the following steps:
(1) 2.07g of p-terphenyl, 1.13g of N-methylpiperidone, 0.186g of diphenyl sulfide and 7mL of methylene dichloride are added into a reaction bottle and mixed to obtain a mixed system; then the reaction bottle is transferred into an ice bath environment, 7mL of trifluoromethanesulfonic acid is slowly added into the reaction bottle, and the reaction is carried out for 24 hours in the ice bath environment, so as to obtain a viscous solution. Slowly dripping tetrahydrofuran solution into the viscous solution to precipitate solid, and drying to obtain initial polymer.
Wherein the structural formula of the initial polymer is as follows:
。
(2) Soaking the initial polymer obtained in the step (1) in 1M potassium carbonate aqueous solution, stirring for 8 hours, filtering and drying, taking 1g of dried solid into a reaction bottle, adding 20mL of dimethyl sulfoxide into the reaction bottle, adding 1mL of methyl iodide, reacting at 25 ℃ for 12 hours, dripping the obtained system into ethyl acetate, precipitating solid, and drying the solid at 60 ℃ to obtain the ion-conducting polymer.
Wherein the ion conducting polymer has the following structural formula:
。
(3) 1g of the ion-conducting polymer obtained in the step (2) was dissolved in 20mL of dimethyl sulfoxide to obtain a casting solution. Casting the casting solution on a glass substrate, drying at 80 ℃ for 12 hours to form a film-shaped substance, then soaking the film-shaped substance in a KOH solution of 1M for 12 hours, completely replacing chloride ions into hydroxyl ions, and then demolding to obtain the anion exchange membrane.
Example 2
This example provides a method for preparing an anion exchange membrane, and the difference between this example and example 1 is that: 0.186g of diphenyl sulfide from example 1 was replaced with 0.202g of diphenyl sulfoxide; the corresponding initial polymer has the following structural formula:
。
the corresponding ion conducting polymer has the following structural formula:
。
Example 3
This example provides a method for preparing an anion exchange membrane, and the difference between this example and example 1 is that: 2.07g of p-terphenyl from example 1 was replaced with 1.94g of 9, 9-dimethylfluorene; the corresponding initial polymer has the following structural formula:
。
the corresponding ion conducting polymer has the following structural formula:
。
Example 4
This example provides a method for preparing an anion exchange membrane, and the difference between this example and example 1 is that: 2.07g of p-terphenyl from example 1 was replaced by 1.54g of biphenyl; the corresponding initial polymer has the following structural formula:
。
the corresponding ion conducting polymer has the following structural formula:
。
Example 5
The embodiment provides a preparation method of an anion exchange membrane, which comprises the following steps:
(1) 2.07g of p-terphenyl, 1.13g of N-methylpiperidone, 0.186g of diphenyl sulfide and 7mL of methylene dichloride are added into a reaction bottle and mixed to obtain a mixed system; then the reaction bottle is transferred into an ice bath environment, 7mL of trifluoromethanesulfonic acid is slowly added into the reaction bottle, and the reaction is carried out for 24 hours in the ice bath environment, so as to obtain a viscous solution. Slowly dripping tetrahydrofuran solution into the viscous solution to precipitate solid, and drying to obtain initial polymer.
Wherein the structural formula of the initial polymer is as follows:
。
(2) Soaking the initial polymer obtained in the step (1) in 1M potassium carbonate aqueous solution, stirring for 8 hours, filtering and drying, taking 1g of dried solid into a reaction bottle, adding 20mL of dimethyl sulfoxide into the reaction bottle, adding 1mL of methyl iodide, reacting at 25 ℃ for 12 hours, dripping the obtained system into ethyl acetate, precipitating solid, and drying the solid at 60 ℃ to obtain the ion-conducting polymer.
Wherein the ion conducting polymer has the following structural formula:
。/>
(3) Taking 1g of the ion-conducting polymer obtained in the step (1) in a reaction bottle, adding 20mL of dimethyl sulfoxide into the reaction bottle, adding 10mg of dibromopropane, and reacting for 12 hours at 50 ℃; then, the reacted system is added into ethyl acetate drop by drop to obtain a solid product, and then the solid product is dried at 60 ℃ to obtain the ion conduction cross-linked product.
(4) 1G of the ion-conducting crosslinked material obtained in the step (3) was dissolved in 20mL of dimethyl sulfoxide to obtain a casting solution. Casting the casting solution on a glass substrate, drying at 80 ℃ for 12 hours to form a film-shaped substance, then soaking the film-shaped substance in a KOH solution of 1M for 12 hours, completely replacing chloride ions into hydroxyl ions, and then demolding to obtain the anion exchange membrane.
Example 6
This example provides a method for preparing an anion exchange membrane, and differs from example 5 only in that: 10mg of dibromopropane from example 5 was replaced with 15.2mg of p-chloromethylstyrene.
Example 7
The embodiment provides a preparation method of an anion exchange membrane, which comprises the following steps:
(1) 2.07g of p-terphenyl, 1.13g of N-methylpiperidone, 0.186g of diphenyl sulfide, 0.174g of trifluoroacetophenone and 7mL of dichloromethane are added into a reaction bottle and mixed to obtain a mixed system; then the reaction bottle is transferred into an ice bath environment, 7mL of trifluoromethanesulfonic acid is slowly added into the reaction bottle, and the reaction is carried out for 24 hours in the ice bath environment, so as to obtain a viscous solution. Slowly dripping tetrahydrofuran solution into the viscous solution to precipitate solid, and drying to obtain initial polymer.
Wherein the structural formula of the initial polymer is as follows:
。
(2) Soaking the initial polymer obtained in the step (1) in 1M potassium carbonate aqueous solution, stirring for 8 hours, filtering and drying, taking 1g of dried solid into a reaction bottle, adding 20mL of dimethyl sulfoxide into the reaction bottle, adding 1mL of methyl iodide, reacting at 25 ℃ for 12 hours, dripping the obtained system into ethyl acetate, precipitating solid, and drying the solid at 60 ℃ to obtain the ion-conducting polymer.
Wherein the ion conducting polymer has the following structural formula:
。
(3) 1g of the ion-conducting polymer obtained in the step (2) was dissolved in 20mL of dimethyl sulfoxide to obtain a casting solution. Casting the casting solution on a glass substrate, drying at 80 ℃ for 12 hours to form a film-shaped substance, then soaking the film-shaped substance in a KOH solution of 1M for 12 hours, completely replacing chloride ions into hydroxyl ions, and then demolding to obtain the anion exchange membrane.
Example 8
This example provides a method for preparing an anion exchange membrane, and the difference between this example and example 1 is that: the difference of the step (3); in this embodiment, step (3) is as follows:
1g of the ion-conducting polymer obtained in the step (2) was dissolved in 20mL of dimethyl sulfoxide to obtain a casting solution. Flatly paving a swelling polytetrafluoroethylene film with the thickness of 10 mu M and the porosity of 70% on a glass substrate, filling the prepared casting film liquid into pores of the swelling polytetrafluoroethylene film in a coating mode, drying at 80 ℃ for 12 hours to form a film-shaped substance with the filler in the pores of the swelling polytetrafluoroethylene film, soaking the dried film-shaped substance in a KOH solution of 1M for 12 hours, completely replacing chloride ions into hydroxyl ions, and demolding to obtain the anion exchange film.
Example 9
This example provides a method for preparing an anion exchange membrane, and the difference between this example and example 1 is that: the difference of the step (3); in this embodiment, step (3) is as follows:
1g of the ion-conducting polymer obtained in the step (2) and 0.1g of zirconia powder having an average particle diameter of 30 μm were dissolved in 20mL of dimethyl sulfoxide to obtain a casting solution. Flatly paving a swelling polytetrafluoroethylene film with the thickness of 10 mu M and the porosity of 70% on a glass substrate, filling the prepared casting film liquid into pores of the swelling polytetrafluoroethylene film in a coating mode, drying at 80 ℃ for 12 hours to form a film-shaped substance with the filler in the pores of the swelling polytetrafluoroethylene film, soaking the dried film-shaped substance in a KOH solution of 1M for 12 hours, completely replacing chloride ions into hydroxyl ions, and demolding to obtain the anion exchange film.
Comparative example
The comparative example provides a method for preparing an anion exchange membrane, comprising the following steps:
(1) 2.3g of terphenyl, 1.13g of N-methyl-4-piperidone and 7mL of methylene dichloride are added into a reaction bottle and mixed to obtain a mixed system; then the reaction bottle is transferred into an ice bath environment, 7mL of trifluoromethanesulfonic acid is slowly added into the reaction bottle, and the reaction is carried out for 24 hours in the ice bath environment, so as to obtain a viscous solution. Slowly dripping tetrahydrofuran solution into the viscous solution to precipitate solid, and drying to obtain initial polymer.
Wherein the structural formula of the initial polymer is as follows:
。
(2) Soaking the initial polymer obtained in the step (1) in 1M potassium carbonate aqueous solution, stirring for 8 hours, filtering and drying, taking 1g of dried solid in a reaction bottle, adding 20mL of dimethyl sulfoxide and 1mL of methyl iodide into the reaction bottle, reacting at 25 ℃ for 12 hours, dripping the reacted system into ethyl acetate to obtain a solid product, and drying at 60 ℃ to obtain the ion-conducting polymer.
Wherein the ion conducting polymer has the following structural formula:
。
(3) 1g of the ion-conducting polymer obtained in the step (2) was dissolved in 20mL of dimethyl sulfoxide to obtain a casting solution. Casting the casting solution on a glass substrate, drying at 80 ℃ for 12 hours to form a film-shaped substance, then soaking the film-shaped substance in a KOH solution of 1M for 12 hours, completely replacing chloride ions into hydroxyl ions, and then demolding to obtain the anion exchange membrane.
Experimental example 1
The ion conductive polymer obtained in step (2) of example 1, the ion conductive polymer obtained in step (2) of example 2, the ion conductive polymer obtained in step (2) of example 3, the ion conductive polymer obtained in step (2) of example 4, the ion conductive polymer obtained in step (2) of example 7 and the ion conductive polymer obtained in step (2) of comparative example were subjected to structural characterization, and nuclear magnetic hydrogen spectra are shown in fig. 1 to 6.
As can be seen from fig. 1, the nuclear magnetic hydrogen spectrum of the ion conducting polymer prepared in step (2) of example 1 is consistent with the expected structure; in the nuclear magnetic resonance spectrum (the solvent is deuterated dimethyl sulfoxide), the peak with the displacement of 7.59-7.79ppm corresponds to the signal of H on terphenyl, the peak with the displacement of 7.27-7.51ppm corresponds to the signal of H on diphenyl sulfide, the peak with the displacement of 3.39ppm corresponds to the signal of methylene connected on N, the peak with the displacement of 3.17ppm corresponds to the signal of methyl connected on N, and the peak with the displacement of 2.88ppm corresponds to the signal of two methylene not connected with N.
As can be seen from fig. 2, the nuclear magnetic hydrogen spectrum of the ion conducting polymer prepared in step (2) of example 2 is consistent with the expected structure; in the nuclear magnetic resonance spectrum (the solvent is deuterated dimethyl sulfoxide), the peak with the displacement of 7.58-7.73ppm corresponds to the signal of H on the aromatic ring of the terphenyl and the signal of H of the diphenyl sulfoxide, the peak with the displacement of 3.36ppm corresponds to the signal of methylene on N, the peak with the displacement of 3.16ppm corresponds to the signal of methyl on N, and the peak with the displacement of 2.91 corresponds to the signal of H of methylene which is not connected with N on the piperidine ring.
As can be seen from fig. 3, the nuclear magnetic hydrogen spectrum of the ion conducting polymer prepared in step (2) of example 3 is consistent with the expected structure; in the nuclear magnetic resonance spectrum (the solvent is deuterated dimethyl sulfoxide), the peak shifted to 7.34-7.80ppm corresponds to the signal of H on the aromatic ring of fluorene, the peak shifted to 7.26ppm corresponds to the signal of H on the aromatic ring of diphenyl sulfide (in addition, part of H on diphenyl sulfide is covered by the aromatic signal of fluorene), the peak shifted to 3.34ppm corresponds to the signal of methylene on N (overlapping with the water peak), the peak shifted to 3.13ppm corresponds to the signal of methyl on N, and the peak shifted to 2.87 corresponds to the signal of H on methylene not connected to N on piperidine ring.
As can be seen from fig. 4, the nuclear magnetic hydrogen spectrum of the ion conducting polymer prepared in step (2) of example 4 is consistent with the expected structure; in the nuclear magnetic resonance spectrum (the solvent is deuterated dimethyl sulfoxide), the peak with the displacement of 7.52-7.60ppm corresponds to the signal of H on the aromatic ring of fluorene, the peak with the displacement of 7.26-7.28ppm corresponds to the signal of H on the aromatic ring of diphenyl sulfide (in addition, part of H on diphenyl sulfide is covered by the aromatic signal of fluorene), the peak with the displacement of 3.47ppm corresponds to the signal of methylene on N, the peak with the displacement of 3.14ppm corresponds to the signal of methyl on N, and the peak with the displacement of 2.85 corresponds to the signal of H on the methylene which is not connected with N on the piperidine ring.
As can be seen from fig. 5, the nuclear magnetic hydrogen spectrum of the ion conducting polymer prepared in step (2) of example 7 is consistent with the expected structure; in the nuclear magnetic resonance spectrum (the solvent is deuterated dimethyl sulfoxide), the peak with the displacement of 7.60-7.79ppm corresponds to the signal of H on terphenyl, the peak with the displacement of 7.27-7.51ppm corresponds to the signal of H on diphenyl sulfide, the peak with the displacement of 7.16-7.21ppm corresponds to the signal of aromatic ring of trifluoroacetophenone, the peak with the displacement of 3.35ppm corresponds to the signal of methylene connected on N, the peak with the displacement of 3.16-3.17ppm corresponds to the signal of methyl connected on N, and the peak with the displacement of 2.87ppm corresponds to the signals of two methylene not connected with N.
As can be seen from fig. 6, the nuclear magnetic hydrogen spectrum of the ion conducting polymer prepared in step (2) of the comparative example is consistent with the expected structure; in the nuclear magnetic resonance spectrum (the solvent is deuterated dimethyl sulfoxide), the peak with the displacement of 7.58-7.76ppm corresponds to the signal of H on the terphenyl aromatic ring, the peak with the displacement of 3.43ppm corresponds to the signal of methylene on N (overlapped with the water peak), the peak with the displacement of 3.16ppm corresponds to the signal of methyl on N, and the peak with the displacement of 2.87ppm corresponds to the signal of H on the piperidine ring which is not connected with N (the peak of 2.87 is an impurity interference signal and is not the signal in the product).
Experimental example 2
The swelling properties and ion conductivity of the anion exchange membranes prepared in examples 1 to 9 and comparative examples were measured, respectively, and the measurement results are shown in table 1.
The swelling performance test method is as follows: and cutting the prepared anion exchange membrane into a square-sized (3 cm multiplied by 3 cm) membrane sample, soaking the membrane sample in deionized water for 12 hours at 25 ℃, taking out the membrane sample, rapidly wiping off residual liquid on the surface of the membrane sample by using filter paper, measuring four side lengths of the membrane sample, taking an average value of the four side lengths, and marking the average value as L1. Then, the film sample was baked at 60℃for 0.5 hours, four side lengths of the film sample in a dry film state were measured, and an average value of the four side lengths was taken and recorded as L2. The swelling ratio of the anion exchange membrane is calculated as follows: swelling ratio = [ (L2-L1)/L1 ] ×100%.
The ion conductivity test method is as follows: hydroxyl ion conductivity was tested by a vantolab PGSTAT128N electrochemical workstation in switzerland. The prepared anion exchange membrane is soaked in 1M KOH aqueous solution for 12 hours, and then is repeatedly washed by deionized water until the KOH solution on the surface is completely washed, and then hydroxide ion conductivity test is carried out by a four-probe method.
The method for testing the antioxidant stability is as follows: the prepared anion exchange membrane was immersed in an aqueous solution containing 3wt% of H 2O2 and 2ppmFe 2+, left at 80 ℃ for 96 hours, then dried at 60 ℃ for 0.5 hours, and then the mass of the anion exchange membrane was weighed, and the mass difference before and after the anion exchange membrane was immersed was calculated, and oxidation stability (%) = (mass of anion exchange membrane after immersion/mass of anion exchange membrane before immersion) ×100%.
TABLE 1
As can be seen from Table 1, the swelling ratios of the anion-exchange membranes prepared in examples 1 to 9 are lower than those of the anion-exchange membranes prepared in comparative examples, the ion conductivities of the anion-exchange membranes prepared in examples 1 to 9 are higher than those of the anion-exchange membranes prepared in comparative examples, and the oxidation stabilities of the anion-exchange membranes prepared in examples 1 to 9 are higher than those of the comparative examples, which indicates that the anion-exchange membranes prepared in examples 1 to 9 have better electrochemistry and longer service lives.
In summary, the application selects aryl containing thioether bond, sulfoxide bond or/and phosphine bond as aryl in the main chain of the ion conducting polymer, and the ion conducting polymer is used for preparing the anion exchange membrane, so that the ion conductivity of the anion exchange membrane can be improved, and the anion exchange membrane has better electrochemistry; the swelling rate of the anion exchange membrane can be reduced, and the oxidation resistance of the anion exchange membrane can be improved, so that the anion exchange membrane has longer service life, and the application range of the anion exchange membrane is widened to a great extent.
The embodiments described above are some, but not all embodiments of the application. The detailed description of the embodiments of the application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Claims (8)
1. An ion conducting polymer, characterized in that the ion conducting polymer has the expression formula: ax-Bm-Cn-Dp, the ion conducting polymer has the following structural formula:
；
wherein x is more than or equal to 0, m is more than or equal to 0, n is more than 0, and p is more than 0;
r 1 and R 3 are phenyl groups;
R 2 and R 4 are trifluoromethyl;
Ar 1、Ar2、Ar3 and Ar 4 are each independently selected from the group consisting of a first aryl group or a second aryl group;
The ion conducting polymer contains the first aryl group and the second aryl group at the same time;
The first aryl is selected from at least one of diphenyl sulfide group and diphenyl sulfoxide group; the second aryl group does not contain thioether linkages, sulfoxide linkages, and phosphine linkages; the second aryl is selected from biphenyl, p-terphenyl, m-terphenyl, o-terphenyl, fluorenyl, dimethylfluorenyl and diethylfluorenyl;
The structural formulae of R a and R b are each independently as follows:
Or/> ；
R 5 and R 6 are both C 1~C3 alkyl; x 1 - and X 2 - are halogen ions; y is a natural number of 1 to 6.
2. The ion conducting polymer of claim 1, wherein x, m and p are not 0 at the same time;
Or/and, R a and R b are respectively ; R 5 and R 6 are both C 1~C3 alkyl;
or/and, in the ion conducting polymer, the ratio of the molar quantity of the first aryl group to the molar quantity of the second aryl group is less than or equal to 0.3;
Or/and, 30 percent is more than or equal to (x+m)/(x+m+n+p) is more than or equal to 0, and 100 percent is more than or equal to (n+p)/(x+m+n+p) is more than or equal to 70 percent;
Or/and the number average molecular weight of the ion conducting polymer is 10000 Da-1000000 Da.
3. The ion conducting polymer of claim 1, wherein the ion conducting polymer has the structural formula:
、、、 Or (b) ; Wherein, M 2 and M 4 are p-terphenyl groups, and M 1 and M 3 are diphenyl sulfide groups.
4. A method for preparing the ion conducting polymer according to any one of claims 1 to 3, comprising: copolymerizing the first component and the second component in the presence of a catalyst; then adding a third component into the system after the copolymerization reaction to carry out salification reaction;
The catalyst comprises at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, concentrated sulfuric acid, p-toluenesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, perfluoropropionic acid, heptafluorobutyric acid and phosphotungstic acid;
the first component comprises a first monomer and a second monomer;
The second component comprises a third monomer and a sixth monomer; or, the second component comprises a third monomer and a sixth monomer, and the second component further comprises at least one of a fourth monomer and a fifth monomer;
The first monomer is selected from at least one of diphenyl sulfide and diphenyl sulfoxide;
the second monomer is selected from biphenyl, para-terphenyl, meta-terphenyl, ortho-terphenyl, fluorene, dimethylfluorene and diethylfluorene;
the structural formula of the third monomer is as follows:
；
the structural formula of the fourth monomer is as follows:
；
the structural formula of the fifth monomer is as follows:
；
The structural formula of the sixth monomer is as follows:
；
Wherein R 1 and R 3 are both phenyl;
R 2 and R 4 are trifluoromethyl;
The structural formulae of R a1 and R b1 are each independently as follows:
Or/> ; R 5 is C 1~C3 alkyl;
The third component comprises a first substance or/and a second substance; the structural formula of the first substance is R 6-R13, and the structural formula of the second substance is Wherein R 6 is an alkyl group of C 1~C3, R 13、R7 and R 8 are each independently selected from halogen atoms, and y is a natural number of 1 to 6.
5. A method of preparing an ion-conducting cross-link comprising: the ion-conducting polymer according to any one of claims 1 to 3 is subjected to a crosslinking reaction in the presence of a crosslinking agent.
6. An ion-conducting crosslinked material, which is produced by the method for producing an ion-conducting crosslinked material according to claim 5.
7. An anion exchange membrane, wherein the material of the anion exchange membrane comprises an ion conduction system;
Or, the anion exchange membrane comprises a porous support layer and a filler filled in the pores of the porous support layer; wherein the filler comprises inorganic hydrophilic particles and an ion conducting system;
Or, the anion exchange membrane comprises a porous support layer and a filler filled in the pores of the porous support layer; wherein the filler comprises an ion conducting system;
or, the anion exchange membrane comprises inorganic hydrophilic particles and an ion conducting system;
wherein the ion conducting system comprises: ion-conducting polymers or/and ion-conducting crosslinks;
The ion-conducting polymer is the ion-conducting polymer according to any one of claims 1 to 3, or the ion-conducting polymer is prepared by the ion-conducting polymer preparation method according to claim 4;
The ion-conducting crosslinked material is an ion-conducting crosslinked material produced by the method for producing an ion-conducting crosslinked material according to claim 5, or the ion-conducting crosslinked material is an ion-conducting crosslinked material according to claim 6.
8. Use of an anion exchange membrane according to claim 7 for the preparation of an electrolyzed water device, an electrodialysis device or an electrochemical energy storage device;
the electrochemical energy storage device includes a flow battery and a fuel cell.
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| CN116948153A (en) * | 2023-07-26 | 2023-10-27 | 嘉庚创新实验室 | Polymer, anion exchange membrane, and preparation method and application thereof |
| CN117181316A (en) * | 2023-07-28 | 2023-12-08 | 浙江工业大学 | Preparation method of monovalent anion selective solvent-resistant ion exchange membrane |
| CN117024924A (en) * | 2023-10-08 | 2023-11-10 | 佛山科学技术学院 | Ultralow-swelling anti-free radical polyaryl anion exchange membrane and preparation method thereof |
| CN117304536A (en) * | 2023-10-27 | 2023-12-29 | 安徽大学 | Polyarylacridine anion exchange membrane with high ion conductivity and high dimensional stability, and preparation method and application thereof |
| CN117343289A (en) * | 2023-10-30 | 2024-01-05 | 广东智宇天成精密制造有限公司 | High-alkali-resistance polyarylpiperidine anion exchange membrane containing fluorocarbon side chain and application thereof |
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