CN106117473B - A kind of sulfonated polyether-ether-ketone and its preparation method and application can be used as cross-linked proton exchange membrane material - Google Patents
A kind of sulfonated polyether-ether-ketone and its preparation method and application can be used as cross-linked proton exchange membrane material Download PDFInfo
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- CN106117473B CN106117473B CN201610505938.8A CN201610505938A CN106117473B CN 106117473 B CN106117473 B CN 106117473B CN 201610505938 A CN201610505938 A CN 201610505938A CN 106117473 B CN106117473 B CN 106117473B
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- 0 C**c(cc(cc1)OC(C)(C)C(C=C2)=CCC2OC(C=C2)=CCC2OC(C=C2)=C(*)CC2OC(C)(C)C)c1Oc(cc1)ccc1[N+](C1C=CC(C(C)(C)Oc(cc2)cc([N+]([O-])=C)c2Oc(cc2)ccc2C(c2ccc(C(C)(C)Oc(cc3)ccc3Oc(cc3)ccc3[N+](c3ccc(C)cc3)[O-])cc2)=*)=CC1)[O-] Chemical compound C**c(cc(cc1)OC(C)(C)C(C=C2)=CCC2OC(C=C2)=CCC2OC(C=C2)=C(*)CC2OC(C)(C)C)c1Oc(cc1)ccc1[N+](C1C=CC(C(C)(C)Oc(cc2)cc([N+]([O-])=C)c2Oc(cc2)ccc2C(c2ccc(C(C)(C)Oc(cc3)ccc3Oc(cc3)ccc3[N+](c3ccc(C)cc3)[O-])cc2)=*)=CC1)[O-] 0.000 description 1
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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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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- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0239—Organic resins; Organic polymers
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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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to macromolecule member material fields, more particularly to a kind of polymer and its preparation method and application that can be used as cross-linked proton exchange membrane material.The present invention provides a kind of polymer, and the polymer is the sulfonated polyether-ether-ketone of the tertiary amine functional group grafting of crosslinking.Cross-linked proton exchange membrane in the present invention has low methanol and vanadium ion permeability, excellent oxidation stability and higher proton conductivity, the comprehensive performance of sulfonated polyether-ether-ketone resin can be improved in the preparation method provided through the invention, and the cross-linked proton exchange membrane prepared phenomena such as being not in cracking in the process for preparing membrane electrode, deforming or fall off, to guarantee the stabilization of direct methanol fuel cell and all-vanadium flow battery performance.
Description
Technical field
The present invention relates to macromolecule member material field, more particularly to a kind of cross-linked proton exchange membrane material that can be used as
Polymer and its preparation method and application.
Background technique
Proton exchange membrane is the critical material of direct methanol fuel cell (DMFC) and all-vanadium flow battery (VRB), it rises
Barrier fuel and proton conducting effect.Diaphragm commercially available at present is perfluorosulfonic acid proton exchange film, such as Chemours
Nafion series of company etc., this kind of film proton conductivity with higher, excellent chemical stability and dimensional stability etc.
Advantage.But Nafion membrane fancy price, lower operating temperature, higher ion transmission and fluorine material preparation process
Middle bring problem of environmental pollution etc. limits its extensive use.
For the above problem of perfluorosulfonic acid proton exchange film, current research is concentrated mainly on two aspects: first is that right
Perfluorosulfonic acid proton exchange film surface is modified, and to reduce fuel infiltration, but this method of modifying still uses perfluor sulphur
Sour proton exchange membrane, leads to high expensive；Second is that the novel low-cost non-fluorine sulfonation polyaromatic proton exchange membrane of exploitation, such as sulphur
Change polyether-ether-ketone, sulfonated polyether sulphone, sulfonated polyimide, sulfonated polyphenyl, sulfonated polypyrrone etc..It is such by many years effort
The research of non-fluorine proton exchange membrane makes great progress, but its poor chemical stability, film hygroscopic swelling when high temperature, low humidity
It spends the low disadvantage of lower conductivity and still seriously hinders the practical application of such film in the battery.
To obtain the non-fluorine proton exchange membrane haveing excellent performance, people inhibit sulfonation polyaromatic film using the method for crosslinking
Swelling, improves the chemical stability of film.Crosslinking method can be covalent or ionomer.On the one hand covalent cross-linking causes film more
It is close, the swelling of film, while migration of the restraint of liberty base in film are significantly inhibited, the service life of film is extended.On the other hand, it is crosslinked
The entanglement between macromolecular chain can be increased, adjust the size of ion channel, improve the selected area update strategy performance of film, but covalent cross-linking
Film is caused to become fragile, or even broken.Kim etc. by being chemically crosslinked to carboxylic poly(aryl ether ketone) with benzidine disulfonic acid, with
The degree of cross linking increase to 30% from 0, the chemical stability of film improves, and the methanol permeability of cross linking membrane is from 6.1 × 10-7cm2s-1
It is down to 3.0 × 10-7cm2s-1, room temperature water absorption rate is reduced to 10% from 24%, and the swelling of film is obviously suppressed, and the Proton conducting of film
Rate is not substantially reduced (J.Membr.Sci.2012,405-406,176-184)；And film then both can be effectively suppressed in ionomer
Swelling, and the ductility of film can be retained, but be easy to be destroyed in high temperature.Wang etc. find coupled ion crosslinking and covalently
Crosslinking, can effectively improve the mechanical performance of film, keep the proton conductivity and morphology stability of film, and Fenton reagent tests table
The oxidation life of the bright film was up to 152 minutes (J.Membr.Sci.2010,363,112-119).This illustrates that effective coupled ion is handed over
Joint covalent cross-linking can improve the swelling behavior of film, improve the chemical stability of film.However these methods are both needed to open from monomer
Beginning to modify upper particular functional group, then is chemically crosslinked through polycondensation, and using the particular functional group, step is more, higher cost,
It is difficult to large scale preparation.
Summary of the invention
In view of the foregoing deficiencies of prior art, it can be used as crosslinking proton the purpose of the present invention is to provide one kind to hand over
The polymer and its preparation method and application for changing membrane material, for solving the problems of the prior art.
In order to achieve the above objects and other related objects, first aspect present invention provides a kind of polymer, the polymer
It can be cross-linked proton exchange membrane material, the cross-linked proton exchange membrane material is that the sulfonation of the tertiary amine functional group grafting of crosslinking is poly-
Ether ether ketone (tertiary-aminated sulfonated polyether-ether-ketone).
Non-grafted sulfonated polyether-ether-ketone can be passed through in the sulfonated polyether-ether-ketone of the tertiary amine functional group grafting of the crosslinking
It prepares, non-grafted sulfonated polyether-ether-ketone, structure is as follows:
Sulfonated polyether-ether-ketone:
Sulfonated polyether-ether-ketone can be formed by commercialized polyether-ether-ketone sulfonation respectively, for example, sulphur used in the present invention
Change polyether-ether-ketone and reacts acquisition through concentrated acid sulfonation by polyether-ether-ketone resin.
The various polyether-ether-ketone resins in this field can be selected in the polyether-ether-ketone resin, specific workable polyether-ether-ketone resin
Including but not limited to, such as the 450P of Victrex and 450PF, the 4000P of Evonik Degussa grinds high-performance work in Jilin Province
The 770PF of engineering plastics Co., Ltd, 550PF, 330UPF etc..
It is furthermore preferred that the number-average molecular weight of the sulfonated polyether-ether-ketone is 40~50kDa.
It is furthermore preferred that the polymer molecular weight profile exponent of the sulfonated polyether-ether-ketone is 1.3~2.1.
It is furthermore preferred that the sulfonation degree of the sulfonated polyether-ether-ketone is 40~85%.
Specifically, the sulfonated polyether-ether-ketone of the tertiary amine functional group grafting refers specifically to the sulfonated polyether for being grafted with tertiary amine molecule
At least part sulfonic acid group of ether ketone, more specifically finger sulfonated polyether-ether-ketone is grafted to form tertiary amine functional group by tertiary amine molecule.
Preferably, the tertiary amine molecule is while having the compound of primary amine functional group and tertiary amine functional group, specifically, institute
State at least part sulfonic acid that tertiary amine molecule refers specifically to sulfonated polyether-ether-ketone by primary amine functional group and sulfonated polyether-ether-ketone grafting
Primary amine group on group and tertiary amine molecule is grafted, further the activated rear and uncle of the sulfonic acid group of specially sulfonated polyether-ether-ketone
Primary amine group grafting on amine molecule, forms stable sulfonamide structure.
Preferably, the tertiary amine molecule is selected from N, N- dimethyl-p-phenylenediamine, N, N- dimethyl -1,3- propane diamine, N, N-
Dimethyl -1,3- propane diamine, N, N- dimethyl -1,4- butanediamine, N, one of N- dimethyl -1,5- pentanediamine or a variety of
Combination.
Preferably, the grafting rate of the tertiary amine molecule is 5~50%, preferably 40~50%.
Specifically, the crosslinking refers specifically to be crosslinked between at least part tertiary amine functional group, it is more particularly at least a part of
It is crosslinked between tertiary amine functional group by corsslinking molecular, more specifically one tertiary amine functional group of finger passes through corsslinking molecular and another tertiary amine function
Group's crosslinking, more specifically covalent cross-linking.It is described be crosslinked also refer specifically at least part of uncrosslinked tertiary amine functional group with polymerize
At least part of remaining sulfonic acid group forms crosslinking, more specifically ionomer on object.
Preferably, the corsslinking molecular is polyhalo corsslinking molecular, and the polyhalo corsslinking molecular is with two or more
The compound of halo groups.The sulphur for referring specifically to tertiary amine functional group grafting is crosslinked between tertiary amine functional group by polyhalo corsslinking molecular
The different tertiary amine functional groups changed on polyether-ether-ketone strand can be reacted with the halo groups of polyhalo corsslinking molecular, and reaction can
To form quaternary ammonium structure, to realize crosslinking.
It is furthermore preferred that the polyhalo corsslinking molecular be selected from α, α '-dichloro-p-xylene, α, α '-dibromo paraxylene, 1,
One of 3,5- trisbromomethyl benzene, 1,2,4,5- tetrabromo methylbenzene or a variety of combinations.
It preferably, is 5~100%, preferably 10 by the degree of cross linking that corsslinking molecular is crosslinked between the tertiary amine functional group
~100%.Those skilled in the art can adjust the degree of cross linking being crosslinked between tertiary amine functional group by corsslinking molecular, example as needed
The inventory of corsslinking molecular realizes the adjustment to the degree of cross linking when such as can be by being crosslinked.Usually, when the degree of cross linking rises, matter
Proton exchange oxidation stability can increase, and proton conductivity can decline；When degree of cross linking decline, oxidation stability can be reduced, matter
Electron conductivity can increase.
Preferably, its structural formula of the polymer is shown in formula I, wherein x=n1+n2+ m, 0.4≤x≤0.85, (x/20)
≤(n1+n2)≤(x/2), 0.05≤n2/(n1+n2)≤1；
It is furthermore preferred that (2x/5)≤(n1+n2)≤(x/2)。
It is furthermore preferred that 0.1≤n2/(n1+n2)≤1。
The preparation method of the polymer of cross-linked proton exchange membrane material, packet are provided described in second aspect of the present invention offer
Include following steps:
1) sulfonated polyether-ether-ketone is grafted tertiary amine molecule；
2) step 1) products therefrom is reacted with polyhalo corsslinking molecular, prepares the crosslinking proton that can be used as and hands over
Change the polymer of membrane material.
Preferably, in the step 1), the tertiary amine molecule be selected from N, N- dimethyl-p-phenylenediamine, N, dimethyl -1 N-,
3- propane diamine, N, N- dimethyl -1,3- propane diamine, N, N- dimethyl -1,4- butanediamine, N, in N- dimethyl -1,5- pentanediamine
One or more combinations.
Preferably, in the step 1), the method by sulfonated polyether-ether-ketone grafting tertiary amine molecule includes the following steps:
By N, N'- carbonyl dimidazoles (CDI) are reacted with sulfonated polyether-ether-ketone, CDI reacted with sulfonated polyether-ether-ketone gained intermediate again with
Tertiary amine molecule reaction.
It is furthermore preferred that CDI is reacted with sulfonated polyether-ether-ketone to carry out in the presence of a solvent, institute in the step 1)
It states solvent and is selected from polar non-solute, polar non-solute is often referred to that proton itself cannot be provided, and has very strong dissolution
The polar solvent of ability.
It is further preferred that the solvent is selected from n,N-Dimethylformamide, N, N- dimethylacetamide in the step 1)
One of amine, N-Methyl pyrrolidone, dimethyl sulfoxide or a variety of combinations.
It is furthermore preferred that in the step 1), CDI reacts products therefrom with sulfonated polyether-ether-ketone and reacts again with tertiary amine molecule
It carries out in the presence of a solvent, the solvent is selected from polar non-solute.
It is further preferred that the solvent is selected from n,N-Dimethylformamide, N, N- dimethylacetamide in the step 1)
One of amine, N-Methyl pyrrolidone, dimethyl sulfoxide or a variety of combinations.
Usually, the solvent that CDI reacts that products therefrom is reacted with tertiary amine molecule again with sulfonated polyether-ether-ketone can be with CDI
It is identical as the reaction dissolvent of sulfonated polyether-ether-ketone.
It is furthermore preferred that those skilled in the art can adjust tertiary amine according to the dosage of CDI and tertiary amine molecule in the step 1)
The ratio of the amount of the substance of sulfonic acid group is (0.1~1) in the grafting rate of molecule, CDI and sulfonated polyether-ether-ketone: 1, tertiary amine molecule
Ratio with the amount of the substance of sulfonic acid group in sulfonated polyether-ether-ketone is (0.1~1): 1.
It is further preferred that in the step 1), the ratio of the amount of the substance of sulfonic acid group in CDI and sulfonated polyether-ether-ketone
For (0.5~0.75): 1, in tertiary amine molecule and sulfonated polyether-ether-ketone the ratio of the amount of the substance of sulfonic acid group be (0.5~
0.75): 1.
It is further preferred that the ratio of the amount of the substance of tertiary amine molecule and CDI is (0.7~1) in the step 1): 1,
In the embodiment of the invention, the ratio of the amount of the substance of tertiary amine molecule and CDI is 1:1.
It is furthermore preferred that the reaction temperature of CDI and sulfonated polyether-ether-ketone is 20~100 DEG C in the step 1).
It is furthermore preferred that in the step 1), CDI reacts products therefrom with sulfonated polyether-ether-ketone and reacts again with tertiary amine molecule
Temperature is 20~100 DEG C.
It is further preferred that the reaction temperature of CDI and sulfonated polyether-ether-ketone is 40~60 DEG C in the step 1).
It is further preferred that in the step 1), CDI reacted with sulfonated polyether-ether-ketone products therefrom again with tertiary amine molecule
Reaction temperature is 40~60 DEG C.
Those skilled in the art can adjust the reaction time according to reaction process, such as can be by monitoring reaction system Central Plains
The conversion situation of material adjusts the reaction time, and monitoring method can be such as nuclear magnetic resonance spectroscopy, is embodied in the present invention one
During scheme is, reaction time of CDI and sulfonated polyether-ether-ketone can for 1~for 24 hours, can also be 1~3h, CDI and sulfonated polyether
Ether reactive ketone products therefrom again with the reaction time of tertiary amine molecule can for 1~for 24 hours, can also be 2~4h.
It is furthermore preferred that CDI reacts products therefrom with sulfonated polyether-ether-ketone and reacts again with tertiary amine molecule in the step 1)
Afterwards, also by products therefrom submerged, filter, be dried to obtain the sulfonated polyether-ether-ketone of tertiary amine molecule grafting.
Preferably, in the step 2), step 1) products therefrom reacts the item existing for solvent with polyhalo corsslinking molecular
It is carried out under part, the solvent is selected from polar non-solute.In an embodiment of the present invention, what the step 2) prepared
To include the polymer solution that can be used as cross-linked proton exchange membrane material, usually, solution evaporation is (for example, can be with
For drying etc.) after, the polymeric film material can be obtained.
Polar non-solute can be selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- crassitude
One of ketone, dimethyl sulfoxide or a variety of combinations.
Preferably, in the step 2), those skilled in the art can adjust according to the grafting rate of polyhalo corsslinking molecular and walk
The dosage of rapid 1) products therefrom and polyhalo corsslinking molecular, the official of step 1) products therefrom tertiary amine group and polyhalo corsslinking molecular
It is 1:(0.05~1 that (for example, halogen group) the mass ratio of the material, which can be rolled into a ball).
It is furthermore preferred that the polyhalo corsslinking molecular is selected from α, α '-dichloro-p-xylene, α, α '-two in the step 2)
One of bromine paraxylene, 1,3,5- trisbromomethyl benzene, 1,2,4,5- tetrabromo methylbenzene or a variety of combinations.
Preferably, in the step 2), the reaction temperature of step 1) products therefrom and polyhalo corsslinking molecular is 20~100
℃。
It is furthermore preferred that in the step 2), the reaction temperature of step 1) products therefrom and polyhalo corsslinking molecular is 20~
30℃。
Those skilled in the art can adjust the reaction time according to reaction process, such as can be by monitoring reaction system Central Plains
The conversion situation of material adjusts the reaction time, and monitoring method can be such as nuclear magnetic resonance spectroscopy, is embodied in the present invention one
During scheme is, the reaction time that step 1) products therefrom is reacted with polyhalo corsslinking molecular can be 1~12h, can also for 1~
2h。
The present invention provides the polymer in the purposes of cross-linked proton exchange membrane preparation field to the third aspect.
Fourth aspect present invention provides a kind of cross-linked proton exchange membrane, and the cross-linked proton exchange membrane includes the polymerization
Object.
Fifth aspect present invention provides the preparation method of the cross-linked proton exchange membrane, includes the following steps: above-mentioned system
Standby acquisition includes that the polymer solution that can be used as cross-linked proton exchange membrane material forms a film as casting solution (for example, will
Casting solution is coated on glass plate), it dries after film up to crosslinking proton exchange membrane.
Those skilled in the art can adjust the specific method and condition for drying film according to the film forming situation of membrane material, for example, can
Material to be dried, drying temperature can be 25~100 DEG C, can also be 60~70 DEG C, and drying time can be 1~
For 24 hours, it is also possible to 4~12h；For another example can also be heat-treated to material, heat treatment usually carries out under vacuum conditions,
The temperature of heat treatment can be 100~160 DEG C, can also be 80~120 DEG C, time of heat treatment can for 1~for 24 hours, may be used also
To be 8~12h.
The present invention provides the cross-linked proton exchange membrane in direct methanol fuel cell and/or all-vanadium flow to the 6th aspect
Purposes in battery preparation.
In the preparation method of cross-linked proton exchange membrane of the invention, the sulfonic acid group on sulfonated polyether-ether-ketone is activated through CDI
After processing, it is easy to react to obtain stable sulfonamide structure with the compound of tertiary amine functional group with having primary amine simultaneously.By
This single step reaction, the tertiary amine group on sulfonated polyether-ether-ketone strand can be easy to that addition reaction occurs and generates with halides
Quaternary ammonium, and when halides have 2 and the above degree of functionality, that is, it can be considered corsslinking molecular.Uncle on sulfonated polyether-ether-ketone strand
After amine groups are reacted with crosslinking agent, part tertiary amine becomes quaternary ammonium, this is covalent cross-linking；And retain tertiary amine can on polymer
Remaining sulfonic acid group forms ionomer, can further improve the crosslinking degree of film, is the further supplement to chemical crosslinking.
Crosslinking proton exchange membrane initial reactant provided by the present invention is at low cost, thermal stability is good, Proton conducting
The high sulfonated polyether-ether-ketone of rate, the proton exchange membrane price prepared is only 1/10th of perfluoro sulfonic acid membrane, and is applied
Its methanol and vanadium ion permeability are low when in direct methanol fuel cell and all-vanadium flow battery, chemical stability is good, size
Stability is high.Cross-linked proton exchange membrane of the invention, proton conductivity is 0.005~0.075S cm at 25 DEG C-1；With a thickness of 20
~160 μm, it can be regulated and controled by changing solid content and the drying temperature of casting solution.
In conclusion the invention has the following advantages that
1) crosslinking agent is while being crosslinked tertiary amine functionalized polymer, also tertiary amine group has been carried out it is quaternized,
Chemistry and ionomer are realized in film forming procedure, the method is simple and quick, which will not introduce the substance without ionic group,
The film ensured has high ion exchange volume (IEC).
2) in cross-linked proton exchange membrane of the invention, the sulfonic acid group on sulfonated polyether-ether-ketone strand reacts one with CDI
As can carry out completely, and the tertiary amine that generates can also carry out completely with reacting for halides after activating, therefore being referred to
Stoichiometry is learned, film quality electron conductivity, dimensional stability and resistance to oxidation stability are realized by the method accurately to feed
Regulation.
3) cross-linked proton exchange membrane in the present invention has low methanol and vanadium ion permeability, excellent oxidation stability
With higher proton conductivity, the comprehensive of sulfonated polyether-ether-ketone resin is can be improved in the preparation method provided through the invention
Can, and the cross-linked proton exchange membrane prepared is not in cracking in the process for preparing membrane electrode, deforms or fall off
Phenomena such as, to guarantee the stabilization of DMFC and VRB performance.
Detailed description of the invention
Fig. 1 is the synthetic route chart of 1 cross-linked proton exchange membrane of the embodiment of the present invention；
Fig. 2 is the infrared spectrogram for the proton exchange membrane that the embodiment of the present invention 1 obtains；
Fig. 3 is the direct methanol fuel cell polarization curve of 1 cross-linked proton exchange membrane of embodiment and Nafion115 film；
Fig. 4 is the all-vanadium flow battery charge-discharge performance of 2 cross-linked proton exchange membrane of embodiment.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
It should be clear that in the following example not specifically dated process equipment or device be all made of conventional equipment in the art or
Device.
In addition, it should also be understood that, one or more method and step mentioned in the present invention does not repel before and after the combination step
It can also be inserted into other methods step there may also be other methods step or between these explicitly mentioned steps, unless separately
It is described；It should also be understood that the combination connection relationship between one or more equipment/device mentioned in the present invention is not repelled
The two equipment/devices specifically mentioned before and after the unit equipment/device there may also be other equipment/device or at these it
Between can also be inserted into other equipment/device, unless otherwise indicated.Moreover, unless otherwise indicated, the number of various method steps is only
Identify the convenient tool of various method steps, rather than for the arrangement order of limitation various method steps or limits the enforceable model of the present invention
It encloses, relativeness is altered or modified, and without material changes in technical content, when being also considered as, the present invention is enforceable
Scope.
Embodiment 1
(1) it takes 10.00g sulfonated polyether-ether-ketone (sulfonation degree 60%) to be dissolved in 100mL DMSO, 1.46g CDI is added,
After 50 DEG C of reaction 2h, it is added 1.23g N, N- dimethyl-p-phenylenediamine, by polymer submerged after 50 DEG C of reaction 3h, suction filtration,
Filter cake is collected, washing obtains tertiary-aminated sulfonated polyether-ether-ketone, grafting rate 50% after dry；
(2) it takes the above-mentioned tertiary-aminated sulfonated polyether-ether-ketone of 8.00g to be dissolved in 100mL DMSO, 0.06g α, α '-dichloro is added
Dimethylbenzene stirs 2h at 25 DEG C and dissolves to obtain casting solution；
(3) on a glass by above-mentioned casting solution curtain coating, 8h is dried under 60 DEG C of convection ovens, is finally placed in 120 DEG C of vacuum and dries
It is heat-treated 12h in case, can be prepared by the proton exchange membrane of 10% degree of cross linking (covalent), synthetic route is as shown in Figure 1, wherein x=
0.6, n1=0.27, n2=0.03, m=0.3.The proton exchange membrane of the 10% obtained degree of cross linking is carried out infrared spectroscopy by the present invention
Test, as shown in fig. 2, it can be seen that containing carbonyl, methylene, sulfonamide and sulphur in the polymer architecture that the present embodiment obtains
Acid groups.
Embodiment 2
(1) it takes 10.00g sulfonated polyether-ether-ketone (sulfonation degree 40%) to be dissolved in 100mL DMSO, 1.01g CDI is added,
After 50 DEG C of reaction 2h, 0.64g N, N- dimethyl -1,3- propane diamine, by polymer submerged, pumping after 50 DEG C of reaction 3h is added
Filter, collects filter cake, and washing obtains tertiary-aminated sulfonated polyether-ether-ketone, grafting rate 47% after dry；
(2) it takes the above-mentioned tertiary-aminated sulfonated polyether-ether-ketone of 8.00g to be dissolved in 100mL DMSO, 0.24g α, α '-dibromo is added
Dimethylbenzene stirs 2h at 25 DEG C and dissolves to obtain casting solution；
(3) on a glass by above-mentioned casting solution curtain coating, 8h is dried under 60 DEG C of convection ovens, is finally placed in 110 DEG C of vacuum and dries
It is heat-treated 12h in case, can be prepared by the proton exchange membrane of 40% degree of cross linking.Examination of infrared spectrum indicates that the present embodiment obtains poly-
It closes and contains carbonyl, methylene, sulfonamide and sulfonic acid group in object structure.
Embodiment 3
(1) it takes 10.00g sulfonated polyether-ether-ketone (sulfonation degree 60%) to be dissolved in 100mL DMSO, 1.46g CDI is added,
After 50 DEG C of reaction 2h, 1.05g N, N- dimethyl-Putriscine, by polymer submerged, pumping after 50 DEG C of reaction 3h is added
Filter, collects filter cake, and washing obtains tertiary-aminated sulfonated polyether-ether-ketone, grafting rate 42% after dry；
(2) it takes the above-mentioned tertiary-aminated sulfonated polyether-ether-ketone of 8.00g to be dissolved in 100mL DMSO, 0.44g α, α '-dibromo is added
Dimethylbenzene stirs 2h at 25 DEG C and dissolves to obtain casting solution；
(3) on a glass by above-mentioned casting solution curtain coating, 8h is dried under 60 DEG C of convection ovens, is finally placed in 100 DEG C of vacuum and dries
It is heat-treated 12h in case, can be prepared by the proton exchange membrane of 60% degree of cross linking.Examination of infrared spectrum indicates that the present embodiment obtains poly-
It closes and contains carbonyl, methylene, sulfonamide and sulfonic acid group in object structure.
Embodiment 4
(1) it takes 10.00g sulfonated polyether-ether-ketone (sulfonation degree 85%) to be dissolved in 100mL DMSO, 1.93g CDI is added,
After 50 DEG C of reaction 2h, 1.39g N, N- dimethyl-Putriscine, by polymer submerged, pumping after 50 DEG C of reaction 3h is added
Filter, collects filter cake, and washing obtains tertiary-aminated sulfonated polyether-ether-ketone, grafting rate 45% after dry；
(2) it takes the above-mentioned tertiary-aminated sulfonated polyether-ether-ketone of 8.00g to be dissolved in 100mL DMSO, 0.74g 1,3,5- tri- is added
Bromomethyl benzene stirs 2h at 25 DEG C and dissolves to obtain casting solution；
(3) on a glass by above-mentioned casting solution curtain coating, 8h is dried under 60 DEG C of convection ovens, is finally placed in 100 DEG C of vacuum and dries
It is heat-treated 12h in case, can be prepared by the proton exchange membrane of 80% degree of cross linking.Examination of infrared spectrum indicates that the present embodiment obtains poly-
It closes and contains carbonyl, methylene, sulfonamide and sulfonic acid group in object structure.
Embodiment 5
(1) it takes 10.00g sulfonated polyether-ether-ketone (sulfonation degree 60%) to be dissolved in 100mL DMSO, 1.46g CDI is added,
After 50 DEG C of reaction 2h, 1.18g N, N- dimethyl -1,5- pentanediamine, by polymer submerged, pumping after 50 DEG C of reaction 3h is added
Filter, collects filter cake, and washing obtains tertiary-aminated sulfonated polyether-ether-ketone, grafting rate 40% after dry；
(2) it takes the above-mentioned tertiary-aminated sulfonated polyether-ether-ketone of 8.00g to be dissolved in 100mL DMSO, 0.60g 1,2,4,5- is added
Tetrabromo methylbenzene stirs 2h at 25 DEG C and dissolves to obtain casting solution；
(3) on a glass by above-mentioned casting solution curtain coating, 8h is dried under 60 DEG C of convection ovens, is finally placed in 100 DEG C of vacuum and dries
It is heat-treated 12h in case, can be prepared by the proton exchange membrane of 100% degree of cross linking.Examination of infrared spectrum indicates what the present embodiment obtained
Contain carbonyl, methylene, sulfonamide and sulfonic acid group in polymer architecture.
Cross-linked proton exchange membrane made from Examples 1 to 5 with a thickness of 80~90 μm, as clear as crystal, thickness is uniform, without bright
Aobvious defect.Cross-linked proton exchange membrane made from the above method and Nafion115 film are subjected to conductivity test, water absorption rate at 25 DEG C
Accelerated oxidation survey is carried out through test and in 80 DEG C of Fenton reagents with the test of length direction swelling ratio, methanol and vanadium ion
Examination, the results are shown in Table 1:
The performance test results of proton exchange membrane and Nafion115 film that 1 embodiment of the present invention 1~5 of table obtains
Note: a is with the measured value under the conditions of 25 DEG C；
Note: b is Fenton reagent (2ppm, 30%H2O2) 80 DEG C, under the conditions of 4h, utilize the oxidation of mass change evaluated for film
Stability.
The result shows that cross-linked proton exchange membrane made from Examples 1 to 5 has and the comparable resistance to oxidation of Nafion115 film
Stability, and water absorption rate and swelling ratio are lower, show good dimensional stability.It is by embodiment 1,3,5 as can be seen that same
With the raising of the degree of cross linking under sulfonation degree, proton conductivity, water absorption rate and the swelling ratio of film, methanol and vanadium ion permeability also with
Reduction, methanol permeability and vanadium ion permeability, an order of magnitude lower than Nafion115 film show excellent barrier property
Energy.
Cross-linked proton exchange membrane in embodiment 1 is assembled into direct methanol fuel cell, the effective area of membrane electrode is
4cm-2, the catalyst loading of positive and negative anodes is 4mg cm-2, use the concentration of methanol solution for 4M.As shown in figure 3, it is multiple to measure multilayer
The polarization curve and power density curve of film and business Nafion115 film are closed, maximum power density is respectively 30.3 and 29.0mW
cm-2；Open-circuit voltage is respectively 0.82 and 0.83V.The performance of cross-linked proton exchange membrane is relatively preferable, this is attributed in embodiment 1
The preferable alcohol-rejecting ability of cross-linked proton exchange membrane and sufficiently high proton conductivity.
Cross-linked proton exchange membrane in embodiment 2 is assembled into all-vanadium flow battery, activated carbon-fiber felt is Catalytic Layer, and graphite plate is
Bipolar plates, film effective area are 10.5cm-2, current density is 80mA cm-2, vanadium ion concentration is 1.6mol L in electrolyte-1,
H2SO4Concentration is 4mol L-1.As shown in figure 4, battery current efficiency is 99.2% after battery operation 400 circulations, voltage effect
Rate is 82.4%, and energy efficiency 81.7% shows good long-time stability.This is because drawing on one side polymer chain
The quaternary ammonium group for entering positive charge can prevent VO2+Infiltration (road south effect), on the other hand retain sulfonic acid group can provide
Certain proton conductivity, to take into account resistance vanadium ion performance and proton conduction property.
In conclusion the present invention effectively overcomes various shortcoming in the prior art and has high industrial utilization value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (18)
1. a kind of polymer, the polymer is the sulfonated polyether-ether-ketone of the tertiary amine functional group grafting of crosslinking, the sulfonated polyether
The sulfonation degree of ether ketone is 40~85%, and the sulfonated polyether-ether-ketone of the tertiary amine functional group grafting refers specifically to sulfonated polyether-ether-ketone extremely
Few a part of sulfonic acid group is grafted to form tertiary amine functional group by tertiary amine molecule, and the tertiary amine molecule is while having primary amine functional group
With the compound of tertiary amine functional group, the grafting rate of the tertiary amine molecule is 5~50%；
The crosslinking refers specifically to be crosslinked between at least part tertiary amine functional group by corsslinking molecular；
At least part of uncrosslinked tertiary amine functional group and at least part of sulfonic acid group remaining on polymer formed from
Son crosslinking by the degree of cross linking that corsslinking molecular be crosslinked is 5~100% between the tertiary amine functional group.
2. a kind of polymer as described in claim 1, the number-average molecular weight of the sulfonated polyether-ether-ketone is 40~50kDa；
And/or the polymer molecular weight profile exponent of the sulfonated polyether-ether-ketone is 1.3~2.1.
3. a kind of polymer as described in claim 1, which is characterized in that the tertiary amine molecule is selected from N, and N- dimethyl is to benzene two
Amine, N, N- dimethyl -1,3- propane diamine, N, N- dimethyl -1,4- butanediamine, N, one of N- dimethyl -1,5- pentanediamine
Or a variety of combination；
And/or the grafting rate of the tertiary amine molecule is 40~50%.
4. a kind of polymer as described in claim 1, which is characterized in that the corsslinking molecular is polyhalo corsslinking molecular, institute
Stating polyhalo corsslinking molecular is the compound with more than two halo groups.
5. a kind of polymer as claimed in claim 4, which is characterized in that the polyhalo corsslinking molecular is selected from α, α '-dichloro
Paraxylene, α, α '-dibromo paraxylene, 1,3,5- trisbromomethyl benzene, one of 1,2,4,5- tetrabromo methylbenzene or a variety of
Combination.
6. a kind of polymer as described in claim 1, which is characterized in that handed between the tertiary amine functional group by corsslinking molecular
The degree of cross linking of connection is 10~100%.
7. the polymer as described in claim 1-6 any claim, structural formula are shown in formula I, wherein x=n1+n2+ m,
0.4≤x≤0.85, (x/20)≤(n1+n2)≤(x/2), 0.05≤n2/(n1+n2)≤1:
8. the preparation method of the polymer as described in claim 1~7 any claim, includes the following steps:
1) sulfonated polyether-ether-ketone is grafted tertiary amine molecule；
2) step 1) products therefrom is reacted with polyhalo corsslinking molecular, prepares the polymer.
9. preparation method as claimed in claim 8, which is characterized in that in the step 1), the tertiary amine molecule is selected from N, N-
Dimethyl-p-phenylenediamine, N, N- dimethyl -1,3- propane diamine, N, N- dimethyl -1,4- butanediamine, N, N- dimethyl -1,5- penta
One of diamines or a variety of combinations；
And/or in the step 1), the method by sulfonated polyether-ether-ketone grafting tertiary amine molecule includes the following steps: N,
N'- carbonyl dimidazoles are reacted with sulfonated polyether-ether-ketone, and it is anti-with tertiary amine molecule again that CDI reacts products therefrom with sulfonated polyether-ether-ketone
It answers.
10. preparation method as claimed in claim 9, which is characterized in that in the step 1), CDI is anti-with sulfonated polyether-ether-ketone
It should carry out in the presence of a solvent, the solvent is selected from polar non-solute；
And/or in the step 1), CDI reacts products therefrom with sulfonated polyether-ether-ketone and reacts again with tertiary amine molecule in solvent
It is carried out under the conditions of existing, the solvent is selected from polar non-solute；
And/or in the step 1), CDI reacted with sulfonated polyether-ether-ketone solvent that products therefrom is reacted with tertiary amine molecule again with
CDI is identical as the reaction dissolvent of sulfonated polyether-ether-ketone；
And/or in the step 1), the ratio of the amount of the substance of sulfonic acid group is (0.1~1) in CDI and sulfonated polyether-ether-ketone:
1, the ratio of the amount of the substance of sulfonic acid group is (0.1~1) in tertiary amine molecule and sulfonated polyether-ether-ketone: 1；
And/or in the step 1), the ratio of the amount of the substance of tertiary amine molecule and CDI is (0.7~1): 1；
And/or in the step 1), the reaction temperature of CDI and sulfonated polyether-ether-ketone is 20~100 DEG C；
And/or in the step 1), CDI reacts products therefrom with sulfonated polyether-ether-ketone and is with the reaction temperature of tertiary amine molecule again
20~100 DEG C；
And/or in the step 1), CDI is reacted with sulfonated polyether-ether-ketone after products therefrom reacts with tertiary amine molecule again, then by institute
Product submerged is obtained, the sulfonated polyether-ether-ketone of tertiary amine molecule grafting is filtered, is dried to obtain.
11. preparation method as claimed in claim 10, which is characterized in that in the step 1), CDI is anti-with sulfonated polyether-ether-ketone
When should carry out in the presence of a solvent, the solvent is selected from n,N-Dimethylformamide, n,N-dimethylacetamide, N- first
One of base pyrrolidones, dimethyl sulfoxide or a variety of combinations；
And/or in the step 1), in CDI and sulfonated polyether-ether-ketone the ratio of the amount of the substance of sulfonic acid group be (0.5~
0.75): 1, the ratio of the amount of the substance of sulfonic acid group is (0.5~0.75) in tertiary amine molecule and sulfonated polyether-ether-ketone: 1；
And/or in the step 1), the reaction temperature of CDI and sulfonated polyether-ether-ketone is 40~60 DEG C；
And/or in the step 1), CDI reacts products therefrom with sulfonated polyether-ether-ketone and is with the reaction temperature of tertiary amine molecule again
40~60 DEG C.
12. preparation method as claimed in claim 10, which is characterized in that in the step 1), CDI is anti-with sulfonated polyether-ether-ketone
Products therefrom is answered to carry out in the presence of a solvent with reacting for tertiary amine molecule again, the solvent is selected from N, N- dimethyl formyl
One of amine, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide or a variety of combinations.
13. preparation method as claimed in claim 9, which is characterized in that in the step 2), step 1) products therefrom and more halogen
It is carried out in the presence of a solvent for corsslinking molecular reaction, the solvent is selected from polar non-solute；
And/or in the step 2), halogen functional group's object of step 1) products therefrom tertiary amine functional group and polyhalo corsslinking molecular
The amount ratio of matter is 1:(0.05~1)；
And/or in the step 2), the polyhalo corsslinking molecular is selected from α, and α '-dichloro-p-xylene, α, α '-dibromo is to two
Toluene；
And/or in the step 2), the reaction temperature of step 1) products therefrom and polyhalo corsslinking molecular is 20~100 DEG C.
14. preparation method as claimed in claim 13, which is characterized in that in the step 2), solvent is selected from N, N- dimethyl
One of formamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide；
And/or in the step 2), the reaction temperature of step 1) products therefrom and polyhalo corsslinking molecular is 20~30 DEG C.
15. polymer as described in claim 1~7 any claim is in the purposes of cross-linked proton exchange membrane preparation field.
16. a kind of cross-linked proton exchange membrane, the cross-linked proton exchange membrane includes such as claim 1~7 any claim institute
The polymer stated.
17. the preparation method of cross-linked proton exchange membrane as claimed in claim 16, including the following steps: will be comprising having the right to want
The solution for the polymer for asking 8~14 any claims to prepare forms a film as casting solution, up to cross-linking type proton after baking film
Exchange membrane.
18. cross-linked proton exchange membrane as claimed in claim 16 is in direct methanol fuel cell and/or all-vanadium flow battery
Purposes.
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| CN108598533B (en) * | 2018-04-25 | 2020-11-03 | 同济大学 | Coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane and preparation method thereof |
| CN108912361B (en) * | 2018-07-16 | 2020-11-24 | 中国地质大学（武汉） | Method for constructing efficient proton transfer channel in proton exchange membrane |
| CN109053979B (en) * | 2018-09-05 | 2020-11-03 | 九江天赐高新材料有限公司 | Preparation method of crosslinked sulfonated polyether-ether-ketone |
| CN110483711A (en) * | 2019-08-12 | 2019-11-22 | 杭州中科氢能科技有限公司 | A kind of novel high-stability sexual intercourse connection sulfonated polyether-ether-ketone and preparation method and purposes |
| CN113896847B (en) * | 2021-08-26 | 2023-08-25 | 国家电投集团科学技术研究院有限公司 | Amphoteric polyether-ether-ketone organic matter, preparation method, amphoteric polyether-ether-ketone ion exchange membrane and iron-chromium redox flow battery |
| CN113817197B (en) * | 2021-08-26 | 2023-10-13 | 北京和瑞储能科技有限公司 | Amphoteric polyether-ether-ketone ion exchange membrane and preparation method thereof |
| CN114085402A (en) * | 2021-10-14 | 2022-02-25 | 湖北大学 | Base-crosslinked sulfonated polyether-ether-ketone ion exchange membrane and preparation method thereof |
| CN114573934B (en) * | 2022-03-04 | 2023-12-12 | 国家电投集团氢能科技发展有限公司 | Sulfonated polymer/modified polystyrene composite and ion exchange membrane |
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