CN107394240A - A kind of sulfonated poly aryl ether ketone amberplex preparation method and application - Google Patents
A kind of sulfonated poly aryl ether ketone amberplex preparation method and application Download PDFInfo
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- CN107394240A CN107394240A CN201710407864.9A CN201710407864A CN107394240A CN 107394240 A CN107394240 A CN 107394240A CN 201710407864 A CN201710407864 A CN 201710407864A CN 107394240 A CN107394240 A CN 107394240A
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- ether ketone
- film
- aryl ether
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- sulfonated poly
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- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 55
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000007731 hot pressing Methods 0.000 claims abstract description 7
- 230000004888 barrier function Effects 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052582 BN Inorganic materials 0.000 claims description 28
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 28
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000006277 sulfonation reaction Methods 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000007766 curtain coating Methods 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- -1 aryl ether ketone Chemical class 0.000 claims description 5
- 238000003490 calendering Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000002242 deionisation method Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000010025 steaming Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 3
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims 1
- 239000012312 sodium hydride Substances 0.000 claims 1
- 229910000104 sodium hydride Inorganic materials 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 abstract description 5
- 229910001456 vanadium ion Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000003729 cation exchange resin Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 239000012779 reinforcing material Substances 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- 229920000557 Nafion® Polymers 0.000 description 13
- BWQOPMJTQPWHOZ-UHFFFAOYSA-N (2,3-difluorophenyl)-phenylmethanone Chemical compound FC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1F BWQOPMJTQPWHOZ-UHFFFAOYSA-N 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000005059 solid analysis Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 206010058490 Hyperoxia Diseases 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000000222 hyperoxic effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229920001059 synthetic polymer Polymers 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- 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
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a kind of preparation method based on sulfonated poly aryl ether ketone amberplex and its application in all-vanadium flow battery, it is related to ion exchange membrane material field, sulfonated poly aryl ether ketone (SFPAEK) amberplex can be prepared by sulfonic polymeric thing and reinforcing material composite, by being cast wet method, hot pressing dry method, extrude dry method, extrusion-blown modling dry method, the techniques such as film stretching orientation are in membrane-film preparation process, inorganic nano sheet is dispersed in the matrix of cationic ion-exchange resin, form the barrier layer of vanadium ion, effectively inhibit the shuttle effect of all-vanadium flow battery vanadium ion adjoint in charge and discharge process；The method technique is simple, and green, cost is low, film is not damaged in itself in implementation process, so the film of shaping possesses preferable mechanical strength, the electrical conductivity and swellbility of film are ensured.
Description
Technical field
The present invention relates to liquid flow energy storage battery seperation film and the ion exchange membrane material field of fuel cell, and in particular to
A kind of sulfonated poly aryl ether ketone (SFPAEK) amberplex preparation method and application.
Background technology
Vanadium redox battery (VRFB) is by the electrochemical reaction of the vanadium ion of different valence state, realizes electric energy
With the mutual conversion of chemical energy.Due to its long lifespan (>15 years), can depth discharge and recharge, security and stability height (charge and discharge cycles>
16000 times), the advantages that energy efficiency is high, turn into one of most potential energy storage device available for extensive energy storage.
In all-vanadium flow battery, the core material of most critical is exactly the barrier film in pile, and barrier film is that amberplex is born
Duty separates both positive and negative polarity electrolyte, avoids self discharge caused by the phase counterdiffusion of both positive and negative polarity electrolyte, proton conducting or sulfuric acid
Root or anion hydrogen sulphate form the effect of circuit in battery.The transfer rate of ion is improved, the internal resistance of battery is reduced, is to carry
Rise one of key of flow battery performance.Applying the amberplex in all-vanadium flow battery should have the following characteristics that：1st, it is high
Ion conductivity；The surface resistance of film is small, reduces the loss of voltage of battery, improves the efficiency for charge-discharge of battery；2nd, it is high
Ion selectivity；The selectivity of film determines the coulombic efficiency of pile, and high ion selectivity can greatly avoid both positive and negative polarity electric
Solution liquid interpenetrates, and thus reduces battery capacity loss；3rd, low water migration amount, the irreversible migration of electrolyte reclaimed water can make
Into the solution concentration change in electrolyte storage tank, the stability of pile will be influenceed.4th, outstanding electrochemical corrosion resistant, full vanadium liquid
The running environment of galvanic battery is acid medium-sulfuric acid, and the V of hyperoxia can be produced in the charging process of battery5+Ion,
Amberplex must possess excellent corrosion resistance, just can ensure that the stable of pile.
The amberplex that liquid flow energy storage battery uses at present is mostly the perfluoro sulfonic acid membrane (Nafion) of du pont company.
The film of Nafion series possesses excellent ionic conductance and remarkable electrochemical stability, but the preparation technology of film it is complicated and
It is and expensive.Directly applied in all-vanadium flow battery, because what Nafion sulfonic acid group was formed in the electrolytic solution
Reversed phase micelle is more conducive to vanadium ion shuttle, so as to cause the self discharge of battery, reduces battery capacity.How the wearing of vanadium ion is reduced
Shuttle effect, developing low-cost, high conductivity, the amberplex of high selectivity will be the keys that solve all-vanadium flow battery
One.
The content of the invention
Answered the technical problem to be solved in the present invention is to provide a kind of with high ion selectivity, high ionic conductance
Close PEM and preparation method and the application in all-vanadium flow battery.
To solve the above problems, the present invention adopts the following technical scheme that：
The invention provides a kind of preparation method of sulfonated poly aryl ether ketone amberplex, it is concretely comprised the following steps：
(1) sulfonation 4,4 '-difluoro benzophenone：4,4 '-difluoro benzophenone of a quality is added and carries returned cold
In two mouthfuls of round-bottomed flasks of 250ml of solidifying pipe, the oleum that the concentration of the pure level of analysis of a volume is 20%, magnetic force are added
Stir and be warming up to 110 DEG C and reacted；Reaction is cooled to room temperature after terminating, and the frozen water that product is poured slowly into 5 parts of volumes mixes
In compound, stirring adds the sodium chloride of 5 parts of quality, and simultaneously drying solid is filtered after being separated out to white solid；Solid after drying, it is molten
Solution is slowly added to sodium hydroxide in the deionized water of 1-2 part volumes, and solution is adjusted into neutrality, adds sodium chloride and was formed
Saturated solution, white solid separate out, and filter, and dry；Dried solid is dissolved by heating with dimethyl sulfoxide (DMSO) again, filtered off while hot
Insoluble impurity, filtrate decompression is distilled, and is obtained product and is cleaned with acetone, absolute ethyl alcohol washing, is filtered, is obtained white powder
Solid, 80 DEG C of vacuum drying obtain 3 for one day, 5 '-sodium disulfonate base -4,4 '-difluoro benzophenone；
(2) preparation of sulfonating polymers PAEK：By 3,5 '-sodium disulfonate base -4,4 '-difluoro benzophenone, 4,4 ' -
Difluoro benzophenone, bisphenol AF are added to equipped with mechanical agitation, water knockout drum and nitrogen air guide according to certain mol proportion example
In 100ml three neck round bottom flask, the steaming toluene again of anhydrous DMAc and 0.5-0.75 parts volume of 20% volume is added；First it is heated to
130 DEG C, kept for 3-4 hours, then pouring out for water knockout drum will be flowed into, be to slowly warm up to 160-190 DEG C, kept for 20-24 hours；Will production
In the methanol solution of thing 15 parts of volumes of importing and continue to stir, the fibrous solids of precipitation are filtered, and is cleaned with deionized water
To neutrality, 80 DEG C of vacuum drying obtains the polymer in one day；
(3) sulfonating polymers PAEK film forming：Sulfonating polymers PAEK film forming is prepared using curtain coating wet method, specifically
It is as follows：Take a certain amount of step (2) resulting polymers to add the coating solution that DMAc is made into 10-12%, coating solution is poured over one
On the clean glass of block, 60-80 DEG C of drying 12 hours in vacuum drying chamber, it is dried in vacuo 12 hours at 80 DEG C, will be dried
Film be immersed in 1M hydrochloric acid solution one day, then film is washed till neutrality with deionized water, and preserve in deionized water.
As another preferred scheme of the present invention, the sulfonating polymers PAEK film forming can also be done using hot pressing
It is prepared by method, extrusion curtain coating dry method, extrusion calendaring dry method, extrusion-blown modling dry method, film stretching orientation process.
As another preferred scheme of the present invention, the step (3) can also be replaced with following steps：：
(301) preparation of porous boron nitride nanometer sheet：By diboron trioxide and guanidine hydrochloride according to mol ratio 1:5 be added to it is suitable
Quick stirring forms colourless transparent solution in the methanol of amount, and quick stirring one day, white solid is formed, and is poured into silica crucible
In, 1100 DEG C are heated in tube furnace, 10 DEG C/min, is kept for 2 hours at 1100 DEG C, and be passed through in heating process
Nitrogen, the hydrogen mixed gas of the nitrogen of 15% hydrogen/85%, obtain white solid powder porous boron nitride nanometer sheet；
(302) preparation of sulfonated porous boron nitride：Take the white powder porous boron nitride nanometer sheet of 0.04 part of quality, 2 parts
The toluene of volume, the propane sultone of 0.08 part of quality are added in two mouthfuls of round-bottomed flasks equipped with reflux condensing tube, and magnetic force stirs
Mix and be warming up to 110 DEG C, kept for 110 DEG C, react 24 hours, after reaction terminates, be cooled to room temperature, 8000rpm, centrifuge 5 minutes,
Liquid is removed, then is washed with ethanol, then is centrifuged, repeats this process 3 times, then is centrifuged after being washed with deionization, this step also repeats 3
Time, yellow solid is finally obtained, is freeze-dried to obtain sulfonated porous boron nitride；
(303) preparation of sulfonated poly aryl ether ketone amberplex：By be cast wet method, hot pressing dry method, extrusion curtain coating dry method,
The techniques such as extrusion calendaring dry method, extrusion-blown modling dry method, film stretching orientation prepare film.With regard to curtain coating wet method citing：Sulfonation is taken to gather
The polymer of aryl ether ketone is made into 10% coating solution, is adding 1%, 3%, 5%, 7%, the sulfonation nitridation of 10% mass fraction
Boron, ultrasonic 1-5 hours, quick stirring 12 hours, coating solution are poured on one block of clean glass, in vacuum drying chamber afterwards
Middle 60-80 DEG C of drying 12 hours, it is dried in vacuo 12 hours at 80 DEG C.Dried film is immersed in 1M hydrochloric acid solution one day,
Film is washed till neutrality with deionized water again, and preserved in deionized water.
As another preferred scheme of the present invention, the step (5) can also be：Take 60% hydrogen of 0.08 part of quality
Change sodium to be added to equipped with nitrogen airway tube, in the three neck round bottom flask of drying tube, the dimethyl sulfoxide (DMSO) nitrogen for pouring into 5 parts of volumes is protected
75 DEG C are heated under shield, 1 hour, the white powder porous boron nitride nanometer sheet of 0.04 part of quality is added it when being cooled to 40 DEG C
In, stir 12 hours, then, the PS for adding 0.08 part of quality adds reaction and reacts 24 hours at 40 DEG C, instead
After should terminating, room temperature is cooled to, 8000rpm, centrifuges 5 minutes, removes liquid, then washed with ethanol, then centrifuged, repeat this process
3 times, then centrifuged after being washed with deionization, this step also repeats 3 times, finally obtains yellow solid, is freeze-dried.
As present invention further optimization scheme, a quality is preferably 5g, and a volume is preferably 20ml.
As another preferred scheme of the present invention, 3 in the step B, 5 '-sodium disulfonate base -4,4 '-difluorodiphenyl first
Ketone, 4,4 '-difluoro benzophenone, the molar ratio of bisphenol AF is 4：6：10 or 5：5：10 or 6：4：10 or 7：3：10.
Present invention also offers a kind of preparation method of the sulfonated poly aryl ether ketone amberplex in all-vanadium flow battery
And its application of fuel cell field, its use the sulfonated poly aryl ether ketone amberplex of synthesis as all-vanadium flow battery every
Film.
Further, the barrier film as all-vanadium flow battery use for compound sulfonated poly aryl ether ketone ion exchange
Film.
Compared with prior art, the beneficial effects of the present invention are：
The present invention carries out the mode synthetic polymer of polycondensation again by using earlier sulfonation synthesis sulfonated monomer, so can be compared with
The sulfonation degree of the polymer product of synthesis is adequately controlled, so can be with the swellbility and proton of conveniently regulating and controlling polymer film
The balance of electrical conductivity.So as to obtain it is a kind of there is high proton conductivity, relatively low surface resistance and have good ion again
The proton exchange polymer membrane of selectivity.It is used for using the film in all-vanadium flow battery, coulombic efficiency and energy dose-effect can be obtained
Rate is all higher than business Nafion 117 performance.
Boron nitride inorganic nano sheet, porous nitrogen of the present invention also by adding 1-10% mass fractions in PEM
Change boron inorganic nano sheet, sulfonation boron nitride inorganic nano sheet, porous sulfonation boron nitride inorganic nano sheet, enter the resistance vanadium performance of film
One step improves, and its battery is possessed more preferable coulombic efficiency, voltage efficiency and energy efficiency be all higher than undoped with film and business
The films of Nafion 117.And the capacity attenuation of its battery is also below the films of Nafion 117 of business.Because its raw material sources is extensive,
Preparation process is simple, so perfluoro sulfonic acid membrane of the cost of film well below the Nafion series of business.
Composite membrane can be applied not only to all-vanadium flow battery, moreover it is possible to applied to fuel cell.The nitridation of the sulfonation of addition
Boron nanometer sheet has the heat-conductive characteristic of brilliance, and the good selectivity of ion is realized in the aperture of regulation and control porous boron nitride nanometer sheet,
Heat management and water management to fuel cell have beneficial contribution.
Brief description of the drawings
Fig. 1 is the molecular formula figure of sulfonated poly aryl ether ketone amberplex in the embodiment of the present invention 1；
Fig. 2 is the FTIR spectrum figure of sulfonated poly aryl ether ketone amberplex in embodiment 1 in the present invention；
Fig. 3 is the proton conductivity of the sulfonated poly aryl ether ketone amberplex of different sulfonation degrees in embodiment 1 in the present invention
Comparison diagram.S4 represents sulfonated poly aryl ether ketone component (mol ratio/sodium disulfonate base difluoro benzophenone：Difluoro benzophenone：Bis-phenol
AF=4：6：10), water absorption rate 15.0%, swelling ratio 4.5%, ion exchange capacity are 1.58 mMs/gram；S5 represents sulphur
Change PAEK component (mol ratio/sodium disulfonate base difluoro benzophenone：Difluoro benzophenone：Bisphenol AF=5：5：10), inhale
Water rate is 16.8%, and swelling ratio 5.8%, ion exchange capacity is 1.87 mMs/gram；S6 represents sulfonated poly aryl ether ketone component
(mol ratio/sodium disulfonate base difluoro benzophenone：Difluoro benzophenone：Bisphenol AF=6：4：10), water absorption rate 30.5%, it is molten
Swollen rate is 7.1%, and ion exchange capacity is 2.21 mMs/gram；S7 represents sulfonated poly aryl ether ketone component (mol ratio/disulfonic acid
Sodium base difluoro benzophenone：Difluoro benzophenone：Bisphenol AF=7：3：10), water absorption rate 58.1%, swelling ratio 14.0%,
Ion exchange capacity is 2.40 mMs/gram.
Fig. 4 is the schematic diagram of boron nitride in the embodiment of the present invention 2；
Fig. 5 is the X-ray diffractogram of boron nitride in the embodiment of the present invention 2；
Fig. 6 is the transmission electron microscope figure of porous boron nitride in embodiment 2；
Fig. 7 is sulfonated poly aryl ether ketone amberplex compound in the embodiment of the present invention 2, in embodiment 1 undoped with sulphur
Change PAEK amberplex and business Nafion 117 in 80mA/cm2Coulombic efficiency under current density, voltage efficiency and
The comparison figure of energy efficiency；
Fig. 8 is sulfonated poly aryl ether ketone amberplex compound in embodiment 2, in embodiment 1 undoped with the poly- virtue of sulfonation
Ether ketone amberplex and business Nafion 117 are in 80mA/cm2Charging and discharging curve figure under current density；
Fig. 9 is sulfonated poly aryl ether ketone amberplex compound in embodiment 2 in 80mA/cm2Current density under circulate
Coulombic efficiency under 100 cycles, voltage efficiency and energy efficiency；
Figure 10 is sulfonated poly aryl ether ketone amberplex and business Nafion117 films compound in the embodiment of the present invention 2
Discharge capacity with the decay of cycle-index comparison figure.
Embodiment
Further detailed description is done to the present invention with reference to specific embodiment, but embodiments of the present invention are not limited to
This.
Embodiment 1
A kind of preparation method of sulfonated poly aryl ether ketone amberplex is provided in this example, it is concretely comprised the following steps：
1) sulfonation 4,4 '-difluoro benzophenone：The 4,4 ' of 5g-difluoro benzophenone is added with reflux condensing tube
In two mouthfuls of round-bottomed flasks of 250ml, the oleum that the concentration of the 20ml pure level of analysis is 20% is added, magnetic agitation simultaneously heats up
Reacted to 110 DEG C；Reaction is cooled to room temperature after terminating, and product is poured slowly into 100ml mixture of ice and water, and stirring adds
Enter 25g sodium chloride, simultaneously drying solid is filtered after being separated out to white solid；Will dry after solid, be dissolved in 20-40ml go from
In sub- water, sodium hydroxide is slowly added to, solution is adjusted to neutrality, sodium chloride is added and forms supersaturated solution, white solid analysis
Go out, filter, dry；Dried solid is dissolved by heating with dimethyl sulfoxide (DMSO) again, insoluble impurity is filtered off while hot, filtrate is subtracted
Pressure distillation, obtains product and is cleaned with acetone, absolute ethyl alcohol washing, filters, obtains white powdery solids, be dried in vacuo 80 DEG C one
It obtains 3,5 '-sodium disulfonate base -4,4 '-difluoro benzophenone；
2) preparation of sulfonating polymers PAEK：By 3,5 '-sodium disulfonate base -4,4 '-difluoro benzophenone, 4,4 ' -
Difluoro benzophenone, bisphenol AF is according to molar ratio 6：4：10 are added to equipped with mechanical agitation, water knockout drum and nitrogen air guide
In 100ml three neck round bottom flask, the anhydrous DMAc and 10-15ml of 20% volume steaming toluene again are added；130 DEG C are first heated to,
Kept for 3-4 hours, then pouring out for water knockout drum will be flowed into, be to slowly warm up to 160-190 DEG C, kept for 20-24 hours；Product is imported
In 300ml methanol solution and continue to stir, the fibrous solids of precipitation are filtered, and cleaned with deionized water to neutrality, very
Sky dries 80 DEG C and obtains the polymer in；
3) sulfonating polymers PAEK film forming：By being cast wet method, hot pressing dry method, extrusion curtain coating dry method, extrusion calendaring
The techniques such as dry method, extrusion-blown modling dry method, film stretching orientation prepare film.With regard to curtain coating wet method citing：Take a certain amount of step 2)
Resulting polymers add the coating solution that DMAc is made into 10-12%, and coating solution is poured on one block of clean glass, done in vacuum
60-80 DEG C of drying 12 hours in dry case, is dried in vacuo 12 hours at 80 DEG C, dried film is immersed in one in 1M hydrochloric acid solution
My god, then film is washed till neutrality with deionized water, and preserve in deionized water.
In this example, using it is above-mentioned undoped with sulfonated poly aryl ether ketone amberplex as all-vanadium flow battery every
Film.
Embodiment 2
A kind of preparation method of sulfonated poly aryl ether ketone amberplex is provided in this example, it is concretely comprised the following steps：
1) sulfonation 4,4 '-difluoro benzophenone：The 4,4 ' of 5g-difluoro benzophenone is added with reflux condensing tube
In two mouthfuls of round-bottomed flasks of 250ml, the oleum that the concentration of the 20ml pure level of analysis is 20% is added, magnetic agitation simultaneously heats up
Reacted to 110 DEG C；Reaction is cooled to room temperature after terminating, and product is poured slowly into 100ml mixture of ice and water, and stirring adds
Enter 25g sodium chloride, simultaneously drying solid is filtered after being separated out to white solid；Will dry after solid, be dissolved in 20-40ml go from
In sub- water, sodium hydroxide is slowly added to, solution is adjusted to neutrality, sodium chloride is added and forms supersaturated solution, white solid analysis
Go out, filter, dry；Dried solid is dissolved by heating with dimethyl sulfoxide (DMSO) again, insoluble impurity is filtered off while hot, filtrate is subtracted
Pressure distillation, obtains product and is cleaned with acetone, absolute ethyl alcohol washing, filters, obtains white powdery solids, be dried in vacuo 80 DEG C one
It obtains 3,5 '-sodium disulfonate base -4,4 '-difluoro benzophenone；
2) preparation of sulfonating polymers PAEK：By 3,5 '-sodium disulfonate base -4,4 '-difluoro benzophenone, 4,4 ' -
Difluoro benzophenone, bisphenol AF is according to molar ratio 6：4：10 are added to equipped with mechanical agitation, water knockout drum and nitrogen air guide
In 100ml three neck round bottom flask, the anhydrous DMAc and 10-15ml of 20% volume steaming toluene again are added；130 DEG C are first heated to,
Kept for 3-4 hours, then pouring out for water knockout drum will be flowed into, be to slowly warm up to 160-190 DEG C, kept for 20-24 hours；Product is imported
In 300ml methanol solution and continue to stir, the fibrous solids of precipitation are filtered, and cleaned with deionized water to neutrality, very
Sky dries 80 DEG C and obtains the polymer in；
3) preparation of porous boron nitride nanometer sheet：By diboron trioxide and guanidine hydrochloride according to mol ratio 1:5 are added in right amount
Methanol in quick stirring form colourless transparent solution, quick stirring one day, white solid is formed, and is poured into silica crucible
In, 1100 DEG C are heated in tube furnace, 10 DEG C/min, is kept for 2 hours at 1100 DEG C, and be passed through in heating process
Nitrogen, the hydrogen mixed gas of the nitrogen of 15% hydrogen/85%, obtain white solid powder porous boron nitride nanometer sheet；
4) preparation of sulfonated porous boron nitride：Take 0.2g white powder porous boron nitride nanometer sheet, 40ml toluene,
0.4g propane sultone is added in two mouthfuls of round-bottomed flasks equipped with reflux condensing tube, and magnetic agitation is simultaneously warming up to 110 DEG C, guarantor
110 DEG C are held, is reacted 24 hours, after reaction terminates, room temperature is cooled to, 8000rpm, centrifuges 5 minutes, remove liquid, then use ethanol
Washing, then centrifuge, repeat this process 3 times, then centrifuged after being washed with deionization, this step also repeats 3 times, finally obtains yellow and consolidates
Body, it is freeze-dried to obtain sulfonated porous boron nitride；
5) preparation of sulfonated poly aryl ether ketone amberplex：Dry method is cast by being cast wet method, hot pressing dry method, extrusion, is squeezed
Go out to roll the techniques such as dry method, extrusion-blown modling dry method, film stretching orientation and prepare film.With regard to curtain coating wet method citing：Take the poly- virtue of sulfonation
The polymer of ether ketone is made into 10% coating solution, add 1%, 3%, 5%, 7%, the sulfonation boron nitride of 10% mass fraction,
Ultrasonic 1-5 hours, quick stirring 12 hours, coating solution are poured on one block of clean glass, in vacuum drying chamber afterwards
60-80 DEG C of drying 12 hours, it is dried in vacuo 12 hours at 80 DEG C.Dried film is immersed in 1M hydrochloric acid solution one day, then
Film is washed till neutrality with deionized water, and preserved in deionized water.
In this example, using compound above-mentioned sulfonated poly aryl ether ketone amberplex as all-vanadium flow battery every
Film.
It is the molecular formula of sulfonated poly aryl ether ketone amberplex in embodiment 1 as shown in Figure 1 based on above-mentioned；Such as Fig. 2 institutes
It is shown as, the FTIR spectrum figure of sulfonated poly aryl ether ketone amberplex in embodiment 1；It is illustrated in figure 3, in embodiment 1
The proton conductivity comparison diagram of the sulfonated poly aryl ether ketone amberplex of different sulfonation degrees.It is illustrated in figure 4, it is more in embodiment 2
The schematic diagram of hole boron nitride；It is illustrated in figure 5, the X-ray diffractogram of porous boron nitride in embodiment 2；It is illustrated in figure 6, it is real
Apply the transmission electron microscope figure of porous boron nitride in example 2；Be illustrated in figure 7, in embodiment 2 compound sulfonated poly aryl ether ketone from
Proton exchange, in embodiment 1 undoped with sulfonated poly aryl ether ketone amberplex and business Nafion 117 coulombic efficiency, electricity
Press the comparison figure of efficiency and energy efficiency；It is illustrated in figure 8, compound sulfonated poly aryl ether ketone amberplex in embodiment 2, it is real
Apply in example 1 undoped with sulfonated poly aryl ether ketone amberplex and business Nafion 117 in 80mA/cm2Filling under current density
Discharge curve；It is illustrated in figure 9, compound sulfonated poly aryl ether ketone amberplex is in 80mA/cm in embodiment 22Electric current is close
The coulombic efficiency in degree lower 100 cycles of circulation, voltage efficiency and energy efficiency figure；It is as shown in Figure 10, it is compound in embodiment 2
The discharge capacity of sulfonated poly aryl ether ketone amberplex and the films of business Nafion 117 with the decay of cycle-index comparison figure.From
It can be seen from the figure that, sulfonated poly aryl ether ketone amberplex its coulombic efficiency, voltage efficiency obtained by the present invention and can dose-effect
Rate is above the film of the Nafion series used in the prior art, and is handed over sulfonated poly aryl ether ketone ion compound in the present invention
It is optimal to change film.
It should be understood by those skilled in the art that the present invention is not limited to the above embodiments, above-described embodiment and explanation
Merely illustrating the principles of the invention described in book, without departing from the spirit and scope of the present invention, the present invention also have
Various changes and modifications, these changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention
By appended claims and its equivalent thereof.
Claims (8)
1. a kind of preparation method of sulfonated poly aryl ether ketone amberplex, it is characterised in that concretely comprise the following steps：
(1) preparation of sulfonation 4,4 '-difluoro benzophenone：4,4 '-difluoro benzophenone of a quality is added with backflow
In two mouthfuls of round-bottomed flasks of 250ml of condenser pipe, the oleum that the concentration of the pure level of analysis of a volume is 20%, magnetic are added
Power, which stirs and is warming up to 110 DEG C, is reacted；Reaction is cooled to room temperature after terminating, and product is poured slowly into the frozen water of 5 parts of volumes
In mixture, stirring adds the sodium chloride of 5 parts of quality, and simultaneously drying solid is filtered after being separated out to white solid；Solid after drying,
It is dissolved in the deionized water of 1-2 part volumes, is slowly added to sodium hydroxide, solution is adjusted to neutrality, adds sodium chloride and formed
Supersaturated solution, white solid separate out, and filter, and dry；Dried solid is dissolved by heating with dimethyl sulfoxide (DMSO) again, filtered while hot
Insoluble impurity is removed, filtrate decompression is distilled, product is obtained and is cleaned with acetone, absolute ethyl alcohol washing, filters, obtains white powder
Shape solid, 80 DEG C of vacuum drying obtain 3 for one day, 5 '-sodium disulfonate base -4,4 '-difluoro benzophenone；
(2) preparation of sulfonating polymers PAEK：By 3,5 '-sodium disulfonate base -4,4 '-difluoro benzophenone, 4,4 '-difluoro
Benzophenone, bisphenol AF are added to the 100ml equipped with mechanical agitation, water knockout drum and nitrogen airway tube according to certain mol proportion example
In three neck round bottom flask, the steaming toluene again of anhydrous DMAc and 0.5-0.75 parts volume of 20% volume is added；First it is heated to 130
DEG C, kept for 3-4 hours, then the liquid for flowing into water knockout drum is poured out, 160-190 DEG C is to slowly warm up to, is kept for 20-24 hours；Will
In the methanol solution of product 15 parts of volumes of importing and continue to stir, the fibrous solids of precipitation are filtered, and it is clear with deionized water
Neutrality is washed till, 80 DEG C is dried in vacuo one day, obtains the polymer；
(3) sulfonating polymers PAEK film forming：Sulfonating polymers PAEK film forming is prepared using curtain coating wet method, specifically such as
Under：Take a certain amount of step (2) resulting polymers to add the coating solution that DMAc is made into 10-12%, coating solution is poured over one piece
On clean glass, 60-80 DEG C of drying 12 hours in vacuum drying chamber, it is dried in vacuo 12 hours at 80 DEG C, will be dried
Film is immersed in 1M hydrochloric acid solution one day, then film is washed till into neutrality with deionized water, and is preserved in deionized water.
2. the preparation method of a kind of sulfonated poly aryl ether ketone amberplex according to claim 1, it is characterised in that described
Sulfonating polymers PAEK film forming can also use hot pressing dry method, extrusion curtain coating dry method, extrusion calendaring dry method, extrusion-blown modling to do
It is prepared by method, film stretching orientation process.
3. the preparation method of a kind of sulfonated poly aryl ether ketone amberplex according to claim 1, it is characterised in that specific
Step is：The step (3) can also be replaced with following steps：
(301) preparation of porous boron nitride nanometer sheet：By diboron trioxide and guanidine hydrochloride according to mol ratio 1:5 be added to it is appropriate
Quick stirring forms colourless transparent solution in methanol, and quick stirring one day, white solid is formed, and is poured into silica crucible,
1100 DEG C are heated in tube furnace, 10 DEG C/min, is kept for 2 hours at 1100 DEG C, and 15% hydrogen is being passed through in heating process
Nitrogen, the hydrogen mixed gas of the nitrogen of gas/85%, obtain white solid powder porous boron nitride nanometer sheet；
(302) preparation of sulfonated porous boron nitride：Take the white powder porous boron nitride nanometer sheet of 0.04 part of quality, 2 parts of volumes
Toluene, the propane sultone of 0.08 part of quality is added in two mouthfuls of round-bottomed flasks equipped with reflux condensing tube, and magnetic agitation is simultaneously
110 DEG C are warming up to, is kept for 110 DEG C, is reacted 24 hours, after reaction terminates, room temperature is cooled to, 8000rpm, centrifuges 5 minutes, go
Liquid, then washed with ethanol, then centrifuge, repeats this process 3 times, then is centrifuged after being washed with deionization, and this step also repeats 3 times, most
After obtain yellow solid, be freeze-dried to obtain sulfonated porous boron nitride；
(303) preparation of sulfonated poly aryl ether ketone ion-exchange composite membranes：By be cast wet method, hot pressing dry method, extrusion curtain coating dry method,
The techniques such as extrusion calendaring dry method, extrusion-blown modling dry method, film stretching orientation prepare film.With regard to curtain coating wet method citing：Sulfonation is taken to gather
The polymer of aryl ether ketone is made into 10% coating solution, is adding 1%, 3%, 5%, 7%, the sulfonation nitridation of 10% mass fraction
Boron, ultrasonic 1-5 hours, quick stirring 12 hours, coating solution are poured on one block of clean glass, in vacuum drying chamber afterwards
Middle 60-80 DEG C of drying 12 hours, it is dried in vacuo 12 hours at 80 DEG C.Dried film is immersed in 1M hydrochloric acid solution one day,
Film is washed till neutrality with deionized water again, and preserved in deionized water.
4. the preparation method of a kind of sulfonated poly aryl ether ketone amberplex according to claim 2, it is characterised in that described
Step (302) can also be：60% sodium hydride of 0.08 part of quality is taken to be added to equipped with nitrogen airway tube, three mouthfuls of drying tube
In round-bottomed flask, pour under the dimethyl sulfoxide (DMSO) nitrogen protection of 5 parts of volumes and be heated to 75 DEG C, 1 hour, incited somebody to action when being cooled to 40 DEG C
The white powder porous boron nitride nanometer sheet of 0.04 part of quality is added thereto, and stirs 12 hours, then, 0.08 part of quality of addition
PS adds reaction and reacted 24 hours at 40 DEG C, after reaction terminates, is cooled to room temperature, 8000rpm, centrifuges 5 points
Clock, liquid is removed, then washed with ethanol, then centrifuged, repeat this process 3 times, then centrifuged after being washed with deionized water, this step also weighs
It is multiple 3 times, yellow solid is finally obtained, is freeze-dried.
A kind of 5. preparation method of sulfonated poly aryl ether ketone amberplex according to claim 1 or 2, it is characterised in that
A quality is 5g, and a volume is 20ml.
A kind of 6. preparation method of sulfonated poly aryl ether ketone amberplex according to claim 1 or 2, it is characterised in that
3 in the step (2), 5 '-sodium disulfonate base -4,4 '-difluoro benzophenone, 4,4 '-difluoro benzophenone, mole of bisphenol AF
Ratio is 4：6：10 or 5：5：10 or 6：4：10 or 7：3：10.
7. a kind of preparation method of sulfonated poly aryl ether ketone amberplex as claimed in claim 1 or 2 is in all-vanadium flow battery
The application in field, it is characterised in that using barrier film of the sulfonated poly aryl ether ketone amberplex of synthesis as all-vanadium flow battery.
8. a kind of sulfonated poly aryl ether ketone ion exchange membrane preparation method according to claim 7 is in all-vanadium flow battery field
Application, it is characterised in that what the barrier film as all-vanadium flow battery used hands over for compound sulfonated poly aryl ether ketone ion
Change film.
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| CN110534682A (en) * | 2019-08-05 | 2019-12-03 | 长沙理工大学 | A kind of preparation method of alkaline oxygenated reduction flow battery amberplex |
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