CN109971004A - A kind of perfluorinated sulfonic acid ion exchange membrane and its preparation method and application - Google Patents
A kind of perfluorinated sulfonic acid ion exchange membrane and its preparation method and application Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1466—Monomers containing sulfur
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- H01M8/102—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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
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- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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- Y02E60/30—Hydrogen technology
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention belongs to high molecular functional field of membrane material, and in particular to a kind of perfluorinated sulfonic acid ion exchange membrane and its preparation method and application.The method that the present invention uses emulsion polymerization, obtains the relatively narrow polymer of molecular weight distribution by the polymerization reaction of perfluorinated sulfonic acid ether monomer and chain-transferring agent, and perfluorinated sulfonic acid ion exchange membrane is made using curtain coating casting method.The perfluorinated sulfonic acid ion exchange membrane narrow molecular weight distribution, molecular weight is controllable, has bigger crystallization area and crystallinity, has ion selectivity good, mechanical performance is excellent, can preferably apply in flow battery.The preparation process of perfluorinated sulfonic acid ion exchange membrane of the present invention is simple, mild condition, is suitble to large-scale production.
Description
Technical field
The invention belongs to high molecular functional field of membrane material, and in particular to flow battery amberplex and its preparation side
Method and application.
Background technique
After E.I.Du Pont Company in 1984 announces perfluorinated sulfonic acid ion exchange membrane patent of invention US 4433082, largely
Research work concentrates on the modification using perfluorinated sulfonic resin, compound and technique is expanded to prepare perfluorosulfonic acid ion exchange
Film.It is disclosed in Chinese patent CN 103044698B and a kind of perfluorinated sulfonic resin is dissolved in less toxic low boiling point solvent, is dry
Perfluorinated sulfonic resin powder is obtained, high solids content high viscosity then is made in high boiling solvent in the direct stirring and dissolving of powder
Preparation liquid, then operation is filmed；Chinese patent CN 102336924B, which is disclosed, a kind of to be drawn using low-temperature plasma body method
It is modified in (per) fluoropolymer film progress situ-formed graft to send out fluorinated sulfonyl fluorides based compound or sulfonic fluoropolymer (salt), then by adding
Basic hydrolysis and H+The method that ion exchange obtains perfluorinated sulfonic acid ion exchange membrane.Perfluorinated sulfonic acid type is referred in above-mentioned patent
The use of resin, and there are also very much, the propositions such as DuPont Corporation scientist Connolly in 1966 for similar patent document
Perfluorinated sulfonic resin is prepared using the method for the monomers such as perfluor sulfonyl vinyl ethers and tetrafluoroethene copolymerization, these resins are all
It is carried out under high temperature (typically larger than 200 DEG C), high pressure (~20MPa) using common free radical (co) polymerization method, therefore not
Make the molecular weight distribution of the perfluorinated sulfonic resin of synthesis wider avoidablely, controllability is deteriorated, for macromolecule, molecular weight
Distribution width means that the molecular weight difference of component is big, and strand length is unevenly distributed, and under the same conditions, will cause crystalline rate
It is inconsistent, be hardly formed more regular crystal, uniformity is poor, cause its mechanical property also can sharp fall, and then it is right
The performance of perfluorinated sulfonic acid ion exchange membrane has adverse effect on.
Currently, the membrane material used both at home and abroad is mainly the Nation series membranes of DuPont Corporation's exploitation, Nation film
Chemical property and in terms of there is excellent performance, but since its synthesis technology is considerably complicated, and
Nation series membranes not aim at the special development & production preparation of all-vanadium flow battery, therefore have the shortcomings that ion selectivity difference, from
And the film is limited in the further industrial applications in liquid flow energy storage battery field.
Summary of the invention
To make up the deficiencies in the prior art, first purpose of the invention is to provide that a kind of ion selectivity is good, mechanical strength
The preparation method of high perfluorinated sulfonic acid ion exchange membrane.
Inventive point of the invention is: active free radical polymerization is carried out using the method for emulsion polymerization, by adding into lotion
Entering stabilizer can make reaction system form heterogeneous system under violent mechanical agitation, by dithioesters, three thio
Carbonic ester or xanthate are applied to the emulsion polymerization of fluorochemical monomer as chain-transferring agent, and available molecular weight distribution is relatively
Narrow polymer, the polymer wide compared to the molecular weight distribution that traditional free radical polymerization obtains, narrow molecular weight distribution are advantageous
In the crystallinity for improving synthesized amberplex, to improve the mechanical strength of film.In addition, high crystallinity to polymerize
The intermolecular force of object is bigger, and intermolecular distance is short, and amberplex is made to have good effect for the barrier of metal ion.
Technical solution of the present invention is as follows, a kind of perfluorinated sulfonic acid ion exchange membrane preparation method, comprising the following steps:
(1) perfluorinated sulfonic acid ether monomer, chain-transferring agent, initiator and emulsifier are distributed to deionized water under mechanical stirring
Middle carry out emulsion polymerization reacts 18-52h, preferably 80 DEG C under the conditions of 70-100 DEG C of (in vacuum or atmosphere of inert gases), then
Crosslinking agent is added, continues to be stirred to react, emulsion polymerization terminates preceding cooling, and blowing air stops reaction；
(2) intermediate product obtained by step (1) is centrifuged, removes supernatant liquor, lower layer's organic phase is washed, will be produced after washing
Object is heated to being completely dissolved to obtain perfluor sulfoacid resin solution in organic solvent；
(3) perfluor sulfoacid resin solution obtained in step (2) is made down on flat plate mold by being cast casting method
Perfluorinated sulfonic acid ion exchange membrane；
The molar ratio of the perfluorinated sulfonic acid ether monomer and chain-transferring agent is (90-300): 1；What emulsion polymerization initial stage was added draws
The molar ratio for sending out agent and chain-transferring agent is 1:(1-5), preferably 1:3；Emulsifier accounts for the 1.5- of perfluorinated sulfonic acid ether monomer mole
2.5%, preferably 2%, the molar ratio of crosslinking agent and chain-transferring agent is (1.5-5): 1；The crosslinking agent be containing there are two or two
The fluorine-containing crosslinking agent of the above double bond, preferably perfluor divinylbenzene；Chain-transferring agent is dithioesters, trithiocarbonate or Huang
One of ortho esters, it is furthermore preferred that the dithiocarbonates can be the thio phenyl ester of 1- cyano -1- phenylethyl two, two sulphur
For benzoic acid isopropyl phenyl ester, dithiobenzoic acid isopropyl hydrocyanic ester etc.；The trithiocarbonate can be 4- cyano -4 '-(ethyl
Sulfanyl thiocarbonyl group) sulfanyl valeric acid, 4- cyano -4 '-(dodecyl sulfanyl thiocarbonyl group) sulfanyl valeric acid, 2- (dodecane
Base trithiocarbonic acid ester group) -2 Methylpropionic acid etc.；The xanthate can be 4- cyano -4 '-(isopropyl oxyalkyl thiocarbonyl group)
Sulfanyl valeric acid or curing isopropyl methyl xanthate.
As the preferred embodiment of the invention, the chain-transferring agent is the thio phenyl ester of 1- cyano -1- phenylethyl two, 4-
Cyano -4 '-(Ethylsulfanyl thiocarbonyl group) sulfanyl valeric acid or 4- cyano -4 '-(isopropyl oxyalkyl thiocarbonyl group) sulfanyl penta
Acid.
The perfluorinated sulfonic acid ether monomer can be any monomer of perfluorinated sulfonic acid ethers, such as perfluor [2- (1- fluorine sulphonyl
Ethyoxyl)-ethyl vinyl ether], perfluor [2- (1- fluorine sulphonyl diethoxy)-propyl vinyl ether], perfluor [2- (1- fluorine sulphur
Acyl ethyoxyl)-propyl vinyl ether] etc., the preferred perfluor of the embodiment of the present invention [2- (1- fluorine nyl ethoxy)-propyl ethylene base
Ether].
The emulsifier is dodecyl sodium sulfate, lauryl sodium sulfate, perfluoro carboxylic acid (CnF2n+1COOH) and
Its sodium, sylvite, wherein perfluoro carboxylic acid and its sodium, sylvite refer to C atom number more than or equal to 6 perfluoro carboxylic acid or
Perfluoro carboxylic acid sodium (CnF2n+1) or perfluoro carboxylic acid potassium (C COONanF2n+1COOK), wherein (n >=6, and n is integer).
Such as perfluoro capryl carboxylic acid sodium, perfluoro decyl carboxylic acid potassium.
The initiator can be any in peroxide initiator, redox initiator or azo-initiator
Kind, preferably azodiisobutyronitrile.
In order to improve perfluorinated sulfonic acid ion exchange membrane comprehensive performance, to reaction system in step (1) emulsion polymerization process
After addition crosslinking agent is stirred to react, adds excess initiator and continue to be stirred to react, the excess initiator and chain-transferring agent of addition
Molar ratio be (5-50): 1.Excess initiator is added in the reaction process to refer to: in initiator and chain-transferring agent mole
Than (5-50): enough initiators are added in the range of 1 reacts it sufficiently with sulfur-bearing end group, reaches in removal reaction system
The purpose of the sulfur-bearing end group of polymer.
Step (2) organic solvent is any polar high-boiling solvent, such as dimethyl sulfoxide (DMSO), N, N '-two
Methylformamide, metacresol or N-Methyl pyrrolidone.
Preferably, the step (1) are as follows: by perfluor [2- (1- fluorine nyl ethoxy)-propyl vinyl ether], chain tra nsfer
Agent, azodiisobutyronitrile and emulsifier are distributed under mechanical stirring in the deionized water for accounting for ten times of monomer mass, in indifferent gas
Body protects lower 70-100 DEG C of reaction 18-52h, and perfluor divinylbenzene is first added and continues to stir 20-40min, more preferable 30min,
Excessive azodiisobutyronitrile is added, to remove sulfur-bearing end group, continues to stir 1-3h, more preferable 2h, cooling, blowing air stops
Reaction.
The step (2) specifically: supernatant liquor, lower layer's organic phase will be removed after the centrifugation of intermediate product obtained by step (1)
It is first washed with deionized, then is washed with DMSO, then products therefrom is transferred in three neck round bottom flask, it is molten that DMSO is added
Agent is heated to being completely dissolved under inert gas shielding, obtains the perfluorinated resin solution of stable homogeneous.
The step (3) specifically: keep flat plate mold horizontal, by perfluorinated resin solution slowly down on flat plate mold, and
Slowly drying in an oven, is then heat-treated, and adds 40-50 DEG C of heat after heat treatment after slow cooling to film surface again
Film is removed after water, then is handled with 3% hydrogen peroxide and 0.5mol/L dilute sulfuric acid, neutrality is finally washed with distilled water to, is obtained complete
Fluosulfonic acid amberplex.
Another object of the present invention is the perfluorinated sulfonic acid ion exchange membrane that above method preparation is claimed.
Third purpose of the present invention is that the perfluorinated sulfonic acid ion exchange membrane of above method preparation is claimed in flow battery
In application, the application especially in all-vanadium flow battery.
Molecular weight distribution to solve the problems, such as perfluorinated sulfonic resin in the prior art is wider, poor controllability, and the present invention adopts
Use dithioesters, trithiocarbonate or xanthate as chain-transferring agent, these chain-transferring agents can be in free radical polymerization
Reversible addition and fracture are carried out with the living radical end group reacted, number of free radical in effective control system slows down
The speed of molecule chain growth is to achieve the purpose that control molecular weight, more importantly keeping molecular weight distribution controllable.And it is traditional
Chain-transferring agent generally use the compound of thio-alcohol, although this kind of compound has the function of certain control molecular weight,
It is that effect of the invention is unable to reach substantially without too big effect to polymer molecular weight distribution.And the chain that the present invention uses turns
Molecular weight distribution sharp can be made by moving agent, keep the length of each strand in polymer very close, this is for polymer
Crystallization be it is highly beneficial, chain length is close, and the crystalline region that polymer crystallization is formed is bigger, its mechanics of the bigger polymer of crystallinity
Performance is also more excellent.And if polymer molecular chain length is unevenly distributed, crystalline rate is inconsistent, is hardly formed more regular
Crystal, uniformity can be poorer, cause the mechanical property of the amberplex obtained also can sharp fall.
In order to further increase the mechanical performance and crystallinity of perfluorinated sulfonic acid ion exchange membrane, the present invention is in monomer polymerization mistake
It is slightly cross-linked as crosslinking agent progress high polymer main chain that perfluor divinylbenzene is added in journey, has on perfluor divinyl benzene molecular
There are two carbon-carbon double bonds, can be during the free radical polymerization of fluorochemical monomer in main polymer chain addition reaction, two carbon
Carbon double bond can guarantee that the main chain of two polymer is connected with each other, and then not influence molecular weight distribution and polymer crystallization performance
Under the premise of, improve the mechanical performance of amberplex.And if using non-fluorine type crosslinking agent, such as divinylbenzene,
It can not have preferable molecule compatibility with perfluorinated sulfonic acid monomer or polymer, cannot achieve itself and fluoropolymer main chain
It is copolymerized addition, is unable to reach the purpose of crosslinking.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) the present invention provides a kind of synthetic molecular weight narrow distribution, the controllable perfluorinated sulfonic acid ion exchange membranes of molecular weight
Preparation method, due to the narrow molecular weight distribution of polymer, polymer middle-molecular-weihydroxyethyl compositional difference is small, in identical crystallization condition
Under, bigger crystallization area and crystallinity easy to form obtain the perfluor of more excellent mechanical performance so that uniformity is preferable
Sulfonic acid ion exchange membrane；
(2) amberplex that the method prepared through the invention obtains has bigger crystallization area and crystallization due to it
Degree, uniformity is preferable, and macromolecular chain arrangement is close in film, is unfavorable for that there is large volume of water and metal ion to pass through, therefore
With preferable ion selectivity；
(3) preparation process of perfluorinated sulfonic acid ion exchange membrane provided by the invention is relatively easy, mild condition, is suitble to scale
Metaplasia produces.
Specific embodiment
The present invention is described in detail below by specific embodiment, but is not limited the scope of the invention.Unless otherwise specified, originally
Experimental method used by inventing is conventional method, and experiment equipment used, material, reagent etc. can chemically company be bought.
Embodiment 1
By 138.6g (0.3mol) perfluor [2- (1- fluorine nyl ethoxy)-propyl vinyl ether] monomer, 0.943g
The thio phenyl ester (CDB) of (3.33mmol) 1- cyano -1- phenylethyl two, 0.182g (1.11mmol) azodiisobutyronitrile and
1.632g (6mmol) dodecyl sodium sulfate is distributed in 1386g water under strong mechanical stirring, is carried out to reaction system
Deoxygenation-filling with inert gas operation, reacts 18h under the conditions of 80 DEG C, 1.55g (5.00mmol) perfluor divinyl is then added
Benzene continues to stir 30min, 5.468g (33.3mmol) azodiisobutyronitrile is added, and continues to stir 2h, cooling, blowing air stops
Reaction；
Supernatant liquor is removed after cooling reaction system is centrifuged, lower layer is washed with deionized three times, then is washed with DMSO
It washs three times, to remove the impurity such as monomer remaining in sample and water, then resulting sample is transferred in three neck round bottom flask, is added
Enter DMSO solvent, be heated to sample at 120 DEG C under inert gas shielding and be completely dissolved, it is uniform steady to obtain mass fraction 7wt%
Fixed solution.
Make plate glass die horizontal, by perfluorinated resin solution that concentration is 7wt% slowly down on plate glass mold,
And slowly dried in baking oven at 70 DEG C, it then heats to 150 DEG C and carries out heat treatment 1h, add again to film surface after slow cooling
Film is removed after 40-50 DEG C of hot water, then is handled with 3% hydrogen peroxide and 0.5mol/L dilute sulfuric acid, is finally washed with distilled water to
Neutrality obtains the perfluorinated sulfonic acid ion exchange membrane with a thickness of 50 ± 2 μm.
In the present embodiment, perfluor [2- (1- fluorine nyl ethoxy)-propyl vinyl ether]: chain-transferring agent=90:1；Perfluor
Divinylbenzene: chain-transferring agent=1.5:1, emulsifier account for the 2% of perfluorinated sulfonic acid monomer molar amount, and excess initiator azo two is different
The ratio of butyronitrile and chain-transferring agent is 10:1.
Embodiment 2
The present embodiment the difference from embodiment 1 is that: perfluor [2- (1- fluorine nyl ethoxy)-propyl vinyl ether] is single
The scale of construction is changed to 277.2g (0.60mol) and dodecyl sodium sulfate amount is changed to 3.264g (12mmol), and deionized water quality is changed to
2772g, reaction time are for 24 hours, to obtain the perfluorinated sulfonic acid ion exchange membrane with a thickness of 50 ± 2 μm.
In the present embodiment, perfluor [2- (1- fluorine nyl ethoxy)-propyl vinyl ether]: chain-transferring agent=180:1；Perfluor
Divinylbenzene: chain-transferring agent=1.5:1.
Embodiment 3
The present embodiment the difference from embodiment 1 is that: perfluor [2- (1- fluorine nyl ethoxy)-propyl vinyl ether] is single
The scale of construction is changed to 462g (1.00mol) and dodecyl sodium sulfate amount is changed to 5.439g (20mmol), and deionized water quality is changed to
4620g, reaction time 30h obtain the perfluorinated sulfonic acid ion exchange membrane with a thickness of 50 ± 2 μm.
In the present embodiment, perfluor [2- (1- fluorine nyl ethoxy)-propyl vinyl ether]: chain-transferring agent=300:1；Perfluor
Divinylbenzene: chain-transferring agent=1.5:1.
Embodiment 4
The present embodiment the difference from embodiment 1 is that: the amount of crosslinking agent perfluor divinylbenzene is changed to 3.1g
(10.0mmol) obtains the perfluorinated sulfonic acid ion exchange membrane with a thickness of 50 ± 2 μm.
In the present embodiment, perfluor [2- (1- fluorine nyl ethoxy)-propyl vinyl ether]: chain-transferring agent=90:1；Perfluor
Divinylbenzene: chain-transferring agent=3:1.
Embodiment 5
The present embodiment the difference from embodiment 1 is that: the amount of crosslinking agent perfluor divinylbenzene is changed to 5.16g
(16.6mmol) obtains the perfluorinated sulfonic acid ion exchange membrane with a thickness of 50 ± 2 μm.
In the present embodiment, perfluor [2- (1- fluorine nyl ethoxy)-propyl vinyl ether]: chain-transferring agent=90:1；Perfluor
Divinylbenzene: chain-transferring agent=5:1.
Embodiment 6
The present embodiment the difference from embodiment 1 is that: 30h will be changed in the reaction time, obtain the perfluor with a thickness of 50 ± 2 μm
Sulfonic acid ion exchange membrane.
Embodiment 7
The present embodiment the difference from embodiment 1 is that: 45h will be changed in the reaction time, obtain the perfluor with a thickness of 50 ± 2 μm
Sulfonic acid ion exchange membrane.
Embodiment 8
The present embodiment the difference from embodiment 1 is that: 6mmol emulsifier dodecyl sodium sulfate is replaced with into 4.5mmol
Perfluoro capryl carboxylic acid sodium accounts for the 1.5% of perfluorinated sulfonic acid monomer molar amount, obtains the perfluorosulfonic acid ion with a thickness of 50 ± 2 μm
Exchange membrane.
Embodiment 9
The present embodiment the difference from embodiment 1 is that: it is complete that 6mmol emulsifier dodecyl sodium sulfate is replaced with into 10mmol
Fluorine decyl carboxylic acid potassium, accounts for the 2.5% of perfluorinated sulfonic acid monomer molar amount, obtains handing over a thickness of 50 ± 2 μm of perfluorosulfonic acid ion
Change film.
Embodiment 10
The present embodiment the difference from embodiment 1 is that: thio phenyl ester of chain-transferring agent 1- cyano -1- phenylethyl two etc. is rubbed
You replace with 4- cyano -4 '-(Ethylsulfanyl thiocarbonyl group) sulfanyl valeric acid (have trithiocarbonic acid ester structure), initiator by
1.11mmol becomes 0.667mmol, and chain-transferring agent is 5:1 with the initiator ratio reacted at this time, and reaction temperature is 70 DEG C, reaction
Time becomes 52h, and excess initiator azodiisobutyronitrile mole is changed to 16.6mmol, it is with the ratio of chain-transferring agent at this time
5:1 obtains the perfluorinated sulfonic acid ion exchange membrane with a thickness of 50 ± 2 μm.
Embodiment 11
The present embodiment the difference from embodiment 1 is that: thio phenyl ester of chain-transferring agent 1- cyano -1- phenylethyl two etc. is rubbed
You replace with 4- cyano -4 '-(isopropyl oxyalkyl thiocarbonyl group) sulfanyl valeric acid (have xanthate structure), initiator by
1.11mmol becomes 3.33mmol, and chain-transferring agent is 1:1 with the initiator ratio reacted at this time, and reaction temperature is 100 DEG C, reaction
Time becomes 35h, and excess initiator azodiisobutyronitrile mole is changed to 166mmol, it is with the ratio of chain-transferring agent at this time
50:1 obtains the perfluorinated sulfonic acid ion exchange membrane with a thickness of 50 ± 2 μm.
Comparative example 1
The present embodiment the difference from embodiment 1 is that: be added without chain-transferring agent, obtain the perfluor sulphur with a thickness of 50 ± 2 μm
Acid ion exchange membrane.
Comparative example 2
The present embodiment the difference from example 2 is that: be added without chain-transferring agent, obtain the perfluor sulphur with a thickness of 50 ± 2 μm
Acid ion exchange membrane.
Comparative example 3
The present embodiment and the difference of embodiment 3 are: being added without chain-transferring agent, obtain the perfluor sulphur with a thickness of 50 ± 2 μm
Acid ion exchange membrane.
Comparative example 4
The present embodiment the difference from embodiment 1 is that: be added without crosslinking agent perfluor divinylbenzene, obtain with a thickness of 50 ±
2 μm of perfluorinated sulfonic acid ion exchange membrane.
The perfluorinated sulfonic acid ion exchange membrane of 1-11 of the embodiment of the present invention, comparative example 1-4 preparation and DuPont Corporation are opened
The Nation series membranes of hairIt is tested for the property by taking all-vanadium flow battery as an example, test result is as shown in table 1.
The performance data of film prepared by 1 embodiment 1-11 of table and comparative example 1-4
From table 1 it follows that the molecular weight of polymer is higher, the mechanical performance for synthesizing film is better, vanadium ion migration
Rate is lower, therefore can promote the mechanicalness of synthesis film by the ratio of adjusting reaction time or adjustment monomer and chain-transferring agent
It can and hinder vanadium efficiency；Using suitable crosslinking agent film can be improved under the premise of will not influence the molecular weight distribution of polymer substantially
Mechanical strength.Embodiment 1-11 narrow molecular weight distribution for comparative example 1-3 is conducive to the crystallization for improving synthesized film
Degree, so that the mechanical strength of film is improved, by comparative example 4 it is found that when being added without crosslinking agent perfluor divinylbenzene, although film
Narrow molecular weight distribution, resistance vanadium efficiency preferably but mechanical performance and crystallinity are decreased obviously；In addition, high crystallinity makes
The intermolecular force for obtaining polymer is bigger, and intermolecular distance is short, this can be to the hydration vanadium ion with larger ionic radius
Saying has preferable shielding action, so that the mobility of vanadium ion reduces, resistance vanadium performance has greatly improved；Compared to close to together
ThicknessFilm, the narrow molecular weight distribution of the perfluorinated sulfonic acid ion exchange membrane of the method for the invention preparation, mechanicalness
It is more excellent and to hinder vanadium efficiency.
The preferable specific embodiment of the above, only the invention, but the protection scope of the invention is not
It is confined to this, anyone skilled in the art is in the technical scope that the invention discloses, according to the present invention
The technical solution of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection scope it
It is interior.
Claims (14)
1. a kind of perfluorinated sulfonic acid ion exchange membrane preparation method, which comprises the following steps:
(1) by perfluorinated sulfonic acid ether monomer, chain-transferring agent, initiator and emulsifier be distributed in deionized water under mechanical stirring into
Row emulsion polymerization reacts 18-52h under the conditions of 70-100 DEG C in vacuum or atmosphere of inert gases, crosslinking agent is then added and continues
It is stirred to react, emulsion polymerization terminates preceding cooling, and blowing air stops reaction；
(2) intermediate product obtained by step (1) is centrifuged, removes supernatant liquor, lower layer's organic phase is washed, by product after washing in
It is heated to being completely dissolved to obtain perfluor sulfoacid resin solution in organic solvent；
(3) perfluor is made by being cast casting method down on flat plate mold in perfluor sulfoacid resin solution obtained in step (2)
Sulfonic acid ion exchange membrane；
The molar ratio of the perfluorinated sulfonic acid ether monomer and chain-transferring agent is (90-300): 1；The molar ratio of initiator and chain-transferring agent
For 1:(1-5)；Emulsifier accounts for the 1.5-2.5% of perfluorinated sulfonic acid ether monomer mole, and the molar ratio of crosslinking agent and chain-transferring agent is
(1.5-5): 1；Chain-transferring agent is one of dithioesters, trithiocarbonate or xanthate；The crosslinking agent be containing
The fluorine-containing crosslinking agent of two or more double bonds.
2. the method according to claim 1, wherein the step (1) further include: being added, crosslinking agent stirring is anti-
Ying Hou adds excess initiator and continues to be stirred to react, and the excess initiator of addition and the molar ratio of chain-transferring agent are (5-50):
1。
3. method according to claim 1 or 2, which is characterized in that the molar ratio of initiator and chain-transferring agent is 1:3.
4. method according to claim 1 or 2, which is characterized in that step (1) reaction temperature is 80 DEG C.
5. method according to claim 1 or 2, which is characterized in that the crosslinking agent is perfluor divinylbenzene.
6. method according to claim 1 or 2, which is characterized in that the chain-transferring agent is 1- cyano -1- phenylethyl
Two thio phenyl esters, dithiobenzoic acid isopropyl phenyl ester, dithiobenzoic acid isopropyl hydrocyanic ester, 4- cyano -4 '-(Ethylsulfanyl
Thiocarbonyl group) sulfanyl valeric acid, 4- cyano -4 '-(dodecyl sulfanyl thiocarbonyl group) sulfanyl valeric acid, 2- (dodecyl trithio
For carbonate group) -2 Methylpropionic acid, 4- cyano -4 '-(isopropyl oxyalkyl thiocarbonyl group) sulfanyl valeric acid or curing methyl it is different
One of xanthogen ester.
7. method according to claim 1 or 2, which is characterized in that the perfluorinated sulfonic acid ether monomer is perfluor [2- (1-
Fluorine nyl ethoxy)-ethyl vinyl ether], perfluor [2- (1- fluorine sulphonyl diethoxy)-propyl vinyl ether] or perfluor [2-
One of (1- fluorine nyl ethoxy)-propyl vinyl ether].
8. method according to claim 1 or 2, which is characterized in that the emulsifier is dodecyl sodium sulfate, 12
One of sodium alkyl sulfate, perfluoro carboxylic acid, perfluoro carboxylic acid sodium salt, perfluoro carboxylic acid sylvite.
9. method according to claim 1 or 2, which is characterized in that the initiator is peroxide initiator, aoxidizes also
One of former initiator or azo-initiator.
10. method according to claim 1 or 2, which is characterized in that step (2) organic solvent be dimethyl sulfoxide,
N, one of N '-dimethyl formamide, metacresol or N-Methyl pyrrolidone.
11. according to the method described in claim 2, it is characterized in that, the step (1) specifically: by perfluor [2- (1- fluorine sulphur
Acyl ethyoxyl)-propyl vinyl ether], chain-transferring agent, azodiisobutyronitrile and emulsifier be distributed to account for monomer under mechanical stirring
In the deionized water that ten times of quality, 70-100 DEG C of reaction 18-52h under inert gas protection, be added perfluor divinylbenzene after
Continuous stirring 20-40min, then excessive azodiisobutyronitrile is added into reaction system and continues to stir 1-3h, cooling, blowing air stops
Only react.
12. method according to claim 1 or 2, which is characterized in that the step (2) specifically: will be obtained by step (1)
Supernatant liquor is removed after intermediate product centrifugation, lower layer's organic phase is first washed with deionized, then is washed with dimethyl sulfoxide, then
Products therefrom is shifted to and is added dimethyl sulfoxide solvent, is heated to being completely dissolved under inert gas shielding, obtains perfluorinated resin
Solution.
13. the perfluorinated sulfonic acid ion exchange membrane of any method preparation of claim 1-12.
14. application of the perfluorinated sulfonic acid ion exchange membrane of any method preparation of claim 1-12 in flow battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113948746A (en) * | 2021-10-12 | 2022-01-18 | 南京工业大学 | Metal organic framework film with organic layer and application thereof |
| CN116217780A (en) * | 2022-12-22 | 2023-06-06 | 福建科润世纪氢能材料有限公司 | Preparation method of perfluoropolymer and application of perfluoropolymer in ion exchange membrane |
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| CN101220120A (en) * | 2007-01-12 | 2008-07-16 | 山东东岳神舟新材料有限公司 | Fluor resin with sulfuryl fluoride and aether terminal group lateral group, synthesizing method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113948746A (en) * | 2021-10-12 | 2022-01-18 | 南京工业大学 | Metal organic framework film with organic layer and application thereof |
| CN116217780A (en) * | 2022-12-22 | 2023-06-06 | 福建科润世纪氢能材料有限公司 | Preparation method of perfluoropolymer and application of perfluoropolymer in ion exchange membrane |
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