CN104282923B - Sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane and preparation method thereof - Google Patents
Sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane and preparation method thereof Download PDFInfo
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- CN104282923B CN104282923B CN201410528904.1A CN201410528904A CN104282923B CN 104282923 B CN104282923 B CN 104282923B CN 201410528904 A CN201410528904 A CN 201410528904A CN 104282923 B CN104282923 B CN 104282923B
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- 239000012528 membrane Substances 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 37
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 210000004379 membrane Anatomy 0.000 claims abstract description 83
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 42
- 239000011347 resin Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 238000007265 chloromethylation reaction Methods 0.000 claims abstract description 21
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 23
- 238000009835 boiling Methods 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000005728 strengthening Methods 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- -1 poly (aryl ether sulfone ketone Chemical class 0.000 claims description 10
- 239000004695 Polyether sulfone Substances 0.000 claims description 9
- 229920006393 polyether sulfone Polymers 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003011 anion exchange membrane Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000004745 nonwoven fabric Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 238000005349 anion exchange Methods 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- YUMNZEWYPUBSQA-UHFFFAOYSA-N 1-(chloromethoxy)octane Chemical compound CCCCCCCCOCCl YUMNZEWYPUBSQA-UHFFFAOYSA-N 0.000 claims description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 claims description 2
- 229940061627 chloromethyl methyl ether Drugs 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 30
- 229910001456 vanadium ion Inorganic materials 0.000 abstract description 20
- 150000002500 ions Chemical group 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 150000001450 anions Chemical class 0.000 abstract description 3
- 150000003460 sulfonic acids Chemical class 0.000 abstract description 3
- 239000003014 ion exchange membrane Substances 0.000 abstract description 2
- 238000010345 tape casting Methods 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 description 14
- 230000010220 ion permeability Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000011324 bead Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 230000008595 infiltration Effects 0.000 description 6
- 238000001764 infiltration Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001768 cations Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000002596 correlated effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000003026 anti-oxygenic effect Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NEHMKBQYUWJMIP-OUBTZVSYSA-N chloromethane Chemical group Cl[13CH3] NEHMKBQYUWJMIP-OUBTZVSYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- LFETXMWECUPHJA-UHFFFAOYSA-N methanamine;hydrate Chemical compound O.NC LFETXMWECUPHJA-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- PSDQQCXQSWHCRN-UHFFFAOYSA-N vanadium(4+) Chemical compound [V+4] PSDQQCXQSWHCRN-UHFFFAOYSA-N 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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (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 present invention relates to vanadium redox battery (VRB) and use ion exchange membrane field, particularly to a kind of sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane and preparation method thereof, solve the problems such as currently used PEM vanadium ion transmitance is high, expensive.By anion exchange resin chloromethylation, again carry out quaternised modified, the quaternized anion exchange resin of preparation different ions exchange capacity, respectively modified anion exchanger resin and perfluorinated sulfonic resin are dissolved by organic solvent, and then utilize substep the tape casting, with basement membrane as articulamentum, by being adjusted to film temperature, concentration, time prepare perfluorinated sulfonic acid sun/strengthen/cloudy both sexes composite membrane.Composite diaphragm prepared by the present invention has good resistance vanadium performance, mechanical performance, chemical stability and good single VRB battery performance, the advantage such as with low cost, can be widely used in vanadium redox battery field.
Description
Technical field
The present invention relates to vanadium redox battery (VRB) and use ion exchange membrane field, particularly to one
Plant sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane and preparation method thereof.
Background technology
The exploitation new forms of energy such as wind energy, solar energy are the important channels solving energy resources shortage, represent the energy not
The direction developed.But being limited by time and region dependency, off-grid wind energy, solar electrical energy generation must use
Energy-storage system, is otherwise difficult to round-the-clock utilization；And direct grid-connected also must use energy-storage system to adjust electrical network
Peak and frequency modulation, otherwise can bring bigger impact to grid power and frequency.Therefore, energy efficient, large-scale
Amount memory technology just becomes the key core of its development and application.
Vanadium cell (vanadium oxide reduction flow battery/Vanadium redox flow battery) is based on VO2+/VO2+
With V2+/V3+ electricity to liquid flow energy storage battery technology, energy is stored in electrolyte.Compared with traditional accumulator,
Vanadium cell can electric current fast charging and discharging, self-discharge rate greatly low, it is achieved the massive store of energy, is to meet intelligence
Electrical network and wind energy, the solar electrical energy generation preferable stored energy form to extensive energy storage demand, the vanadium money of China's abundant
Source advantage also provides condition for development vanadium cell energy storage technology.
Barrier film (PEM) is critical material and one of significant components of vanadium cell, is electrolyte ion
The passage of transmission, plays again the effect separating both positive and negative polarity, preventing battery short circuit.Therefore, barrier film is to a great extent
On decide the coulombic efficiency of vanadium cell, energy efficiency and cycle life.A kind of good PEM should
Possess good chemical stability, resistance to electrochemical oxidation, low vanadium ion permeability and low cost.At present,
Main employing Nafion series membranes, although Nafion membrane chemical stability is good, proton conductivity is high, but
Be some shortcomings of such film be that vanadium ion transmitance is high, self-discharge of battery phenomenon is more notable, reason be this every
Film is cation exchange membrane, containing hydrophilic sulfonic acid group, is very easy to swelling in water, and dimensional stability is not
Good, the increase of such channel diameter causes vanadium ion infiltration height, and its fancy price also makes the cost of vanadium cell occupy
Height not under.Therefore, how to prepare low-cost and high-performance vanadium cell diaphragm material and become restriction vanadium cell through engineering approaches
One of critical bottleneck with technology development.Be also carried out both at home and abroad multinomial diagram modification research, although enhance every
Some performances of film, but the price of barrier film is the highest, governs the business processes of VRB.It addition, it changes
Property process has complex process, and raw material is difficult to the shortcomings such as acquisition.
But theoretically, the ion-exchange group of cation exchange membrane is azochlorosulfonate acid anion, molten at vanadium cell
In liquid bigger to vanadium ion permeability, although by the modification of film can be reduced to a certain extent vanadium from
The permeability of son, but can not fundamentally stop the infiltration of vanadium ion.
Comparatively speaking, the ion-exchange group of anion exchange membrane is cation, due to Dannon effect, thus
Selectivity is higher, and the infiltration of vanadium ion will be restricted, currently reported polyether sulphone and copolymerization aryl ether sulfone material
Expect that the anion exchange membrane prepared has relatively low vanadium ion by it is carried out chloromethylation/quaternized modification such as grade
Permeability.But it is single use cavity block and is applied in vanadium cell its internal resistance relatively greatly, battery can be affected to a certain extent
Performance.Therefore, if making barrier film both have cationic membrane characteristic, there is again anionic membrane ion-selective permeability good
Characteristic, respective for anions and canons film advantage is rolled into one, it will be following all-vanadium flow battery barrier film
Research tendency.
Summary of the invention
It is an object of the invention to provide a kind of sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane and preparation thereof
Method, in order to solve currently used PEM in vanadium ion transmitance the problem such as high, expensive, because of
This prepares perfluorinated sulfonic acid sun/strengthen/cloudy both sexes composite membrane, this composite membrane both had cationic membrane good conductivity,
The feature that chemical stability is good, has again a characteristic that anionic membrane ion-selective permeability is good, improve again simultaneously every
Film-strength, is applicable to vanadium redox battery (VRB).
Technical scheme:
A kind of sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane, it is characterised in that perfluoro sulfonic acid membrane/increasing
Strong basis film/cavity block both sexes composite membrane, including strengthening basement membrane, perfluoro sulfonic acid membrane, cavity block, the both sides strengthening basement membrane are divided
Not Wei perfluoro sulfonic acid membrane and cavity block, in composite membrane, each interracial contact is good, non-division phenomenon；Perfluoro sulfonic acid membrane/
Strengthening basement membrane/cavity block both sexes composite film thickness is 160～240 μm, and the thickness of perfluoro sulfonic acid membrane is 40～100 micro-
Rice, cavity block thickness is 40～100 microns, the thickness that strengthens basement membrane is 20～40 microns.
The preparation method of described sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane, comprises the steps
And process conditions:
(1) 1～5g anion exchange resin is added high boiling organic solvent, make anion exchange resin complete
Dissolve；In 0～50 DEG C of different temperatures, 4～20ml different proportion chloromethylation reagents, 2～12h differential responses
Time carries out chloromethylation；Reaction is precipitant with ethanol after terminating, and makes resulting polymer separate out, then uses
Distilled water repeatedly washs, to cleaning mixture not chloride ion-containing, vacuum drying, it is thus achieved that the cavity block resin of chloromethylation；
(2) the cavity block resin of chloromethylation in step (1) is placed in four mouthfuls of burnings equipped with agitator and thermometer
In Ping, add high boiling organic solvent and make to be completely dissolved；Add the trimethylamine that mass concentration is 20%～45%
In aqueous solution, react 24～72h at 30～60 DEG C, carry out quaternised modified, prepare different ions exchange capacity
Quaternized anion exchange resin preparation liquid, mass percent is 3～35%；
(3) during perfluorinated sulfonic resin is dissolved in high boiling organic solvent, heating for dissolving in a kettle., it is made into quality
Percent is the perfluor sulfoacid resin solution of 3～25%, and heating for dissolving temperature conditions is 170 DEG C～260 DEG C；
(4) fix strengthening basement membrane on clean glass plate, use solution casting method, by step (3)
Perfluor sulfoacid resin solution casts on enhancing basement membrane, at 60～140 DEG C of different temperatures, 0.5～3h different time
Solvent volatilization film forming, by film fixed placement in turn；
(5) the more quaternized anion exchange resin preparation liquid of step (2) is cast to prepared by step (4)
On film, continue to be dried at 60～100 DEG C of different temperatures, 1～4h different time, prepare perfluoro sulfonic acid membrane/increasing
Strong basis film/cavity block both sexes composite membrane.
The preparation method of described sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane, high boiling point is organic molten
Agent is dimethyl sulfoxide, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone
Or dichloromethane.
The preparation method of described sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane, enhancing basement membrane is nothing
Spin cloth, porous PP film or porous PE film.
The preparation method of described sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane, anion exchange tree
Fat is polyphenylene oxide, polysulfones, poly (aryl ether sulfone ketone), polyether sulfone or polyimides.
The preparation method of described sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane, chloromethylation reagents
Refer to trim,ethylchlorosilane, 1,4-dichloro methyl butyl ether, chloromethyl octyl ether or chloromethyl methyl ether.
The preparation method of described sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane, in step (2),
The mass percent of quaternized anion exchange resin is preferably 7%～20%.
The preparation method of described sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane, in step (3),
The mass percent of perfluorinated sulfonic resin is preferably 5%～15%.
The preparation method of described sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane, in step (4),
Temperature is preferably 100～140 DEG C, and the time is preferably 0.5～3h.
The preparation method of described sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane, in step (5),
Temperature is preferably 80～100 DEG C, and the time is preferably 2～3h.
Advantages of the present invention and having the beneficial effect that:
1, the present invention utilizes the ion-exchange group of anion exchange membrane to be cation, due to Dannon effect,
Thus the feature that ion selectivity is higher, the infiltration of vanadium ion will be restricted, and be substantially reduced the infiltration of vanadium ion.
2, the present invention utilizes the feature that porous basement membrane porosity is big, aperture is big, makes a large amount of perfluor sulfoacid resin solution
Effectively permeate with a small amount of cavity block resin solution and combine closely, it is to avoid because molecular skeleton is different, at V electrolyte
The lamination caused due to dimensional stability difference in water-based system, this structure composite film solves conventional composite
Film comes off problem because of layering that the reason such as temperature, electrolyte oxidation produces.
3, due to the fact that basement membrane add reduce film electric conductivity, by will containing a large amount of band hydrophilic groups,
The perfluor sulfoacid resin solution of proton conducting penetrates in porous basement membrane, is effectively improved the electric conductivity of composite membrane.
4, composite diaphragm of the present invention greatly reduces due to perfluorinated sulfonic resin consumption, and therefore this composite diaphragm cost is relatively
Nafion series membranes is greatly lowered.
In a word, the advantage scientifically combining anode membrane and cavity block, it is prepared for sun/enhancing/the moon both sexes composite membrane, makes
During with, PSFA layer is applied anode (anode electrolyte oxidisability is strong), it is ensured that while electric conductivity
Improving the non-oxidizability of composite membrane, cavity block layer is applied and is utilized in battery cathode (electrolyte liquid oxidation is weak)
Dannon effect, improves the resistance vanadium of composite membrane.Anode membrane such as perfluoro sulfonic acid membrane resistance vanadium poor performance and price is overcome to hold high
Expensive shortcoming, the shortcoming that cavity block internal resistance is big and antioxygenic property is poor, effectively raise the antioxygenic property of barrier film
With resistance vanadium performance, and reduce barrier film cost, prepare providing new approaches for vanadium cell barrier film.
Accompanying drawing explanation
Fig. 1 masking of the present invention glass plate schematic diagram.In figure, 1, strengthen basement membrane；2, glazing bead；3, fastening
Folder；4, glass plate.
Fig. 2 composite membrane of the present invention result schematic diagram.In figure, 1, strengthen basement membrane；5, perfluoro sulfonic acid membrane；6, cloudy
Film.
Fig. 3 composite membrane of the present invention charge-discharge performance.
Detailed description of the invention
As it is shown in figure 1, masking glass plate mainly includes strengthening basement membrane 1, glazing bead 2, anchorage clip 3, glass
Plates 4 etc., strengthen basement membrane 1 and are placed on glass plate 4, and the edge pressure strengthening basement membrane 1 sets glazing bead 2,
Anchorage clip 3 clamps glazing bead 2 in the edge of glass plate 4.
In a specific embodiment, the preparation side of present invention sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane
Method, comprises the steps and process conditions:
(1) 1～5g anion exchange resin is added high boiling organic solvent, make anion exchange resin complete
Dissolve；In 0～50 DEG C of different temperatures, 4～20ml different proportion chloromethylation reagents, 2～12h differential responses
Time carries out chloromethylation.Reaction is precipitant with ethanol after terminating, and makes resulting polymer separate out, then uses
Distilled water repeatedly washs, to cleaning mixture not chloride ion-containing, vacuum drying, it is thus achieved that the cavity block resin of chloromethylation.
(2) the cavity block resin of chloromethylation in step (1) is placed in four mouthfuls of burnings equipped with agitator and thermometer
In Ping, add high boiling organic solvent and make to be completely dissolved；Add the trimethylamine that mass concentration is 20%～45%
In aqueous solution, react 24～72h at 30～60 DEG C, carry out quaternised modified, prepare different ions exchange capacity
Quaternized anion exchange resin preparation liquid, mass percent is 3～35% (preferably 7%～20%).
(3) during perfluorinated sulfonic resin is dissolved in high boiling organic solvent, heating for dissolving in a kettle., it is made into quality
Percent is 3～the perfluor sulfoacid resin solution of 25% (preferably 5%～15%), heating for dissolving temperature conditions
It it is 170 DEG C～260 DEG C.
(4) fix strengthening basement membrane on clean glass plate, use solution casting method, by step (3)
Perfluor sulfoacid resin solution casts on enhancing basement membrane, different at 60～140 DEG C (preferably 100～140 DEG C)
Temperature, 0.5～3h (preferably 1～1.5h) different time solvent volatilization film forming.When solvent is not completely dried
Time, by film fixed placement in turn.
(5) the more quaternized anion exchange resin preparation liquid of step (2) is cast to prepared by step (4)
On film, at 60～100 DEG C of (preferably 80～100 DEG C) different temperatures, 1～4h (preferably 2～3h) no
Continue to be dried with the time, prepare perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite membrane.
Wherein, high boiling organic solvent is dimethyl sulfoxide, DMF, N, N-dimethyl
Acetamide, N-Methyl pyrrolidone or dichloromethane etc., enhancing basement membrane is non-woven fabrics, porous PP film or porous
PE film etc., anion exchange resin is polyphenylene oxide, polysulfones, poly (aryl ether sulfone ketone), polyether sulfone or polyimides etc.,
Chloromethylation reagents refers to trim,ethylchlorosilane, 1,4-dichloro methyl butyl ether, chloromethyl octyl ether or chloromethyl first
Ether etc..
As in figure 2 it is shown, prepared perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite membrane, including strengthening basement membrane
1, perfluoro sulfonic acid membrane 5, cavity block 6, the both sides strengthening basement membrane 1 are respectively perfluoro sulfonic acid membrane 5 and cavity block 6.Entirely
Fluosulfonic acid film/enhancing basement membrane/cavity block both sexes composite film thickness is 160～240 μm, and the thickness of perfluoro sulfonic acid membrane is
40～100 microns, cavity block thickness is 40～100 microns, the thickness that strengthens basement membrane is 20～40 microns.Compound
In film, each interracial contact is good, and non-division phenomenon, mechanical strength is good.
It is described in further detail below by embodiment technical scheme.
Embodiment 1
1, weigh 3g polyethersulfone resin to be placed in the four-hole boiling flask equipped with agitator and thermometer, add 15mL
Dichloromethane, makes polyether sulfone be completely dissolved, and (the present embodiment is chloromethane to add the chloromethylation reagents of 5mL
Base octyl ether), under room temperature (25 DEG C), react 4h.Reaction is precipitant with ethanol after terminating, and makes resulting polymer
Separate out, more repeatedly wash with distilled water, to cleaning mixture not chloride ion-containing, vacuum drying, obtain chloromethylation and gather
Ether sulfone.
2, weigh 2g chloromethylation polyether sulfone, be placed in the four-hole boiling flask equipped with agitator and thermometer, then add
Enter the DMF (DMF) of 30mL, make to be completely dissolved；Adding mass concentration is the three of 25%
In methylamine water solution, stir at 40 DEG C, after making quaterisation 48h, stop stirring, obtain quaternized
Polyether sulfone preparation liquid.
3, weigh 2g perfluorinated sulfonic resin to be dissolved in DMF (DMF), 200 DEG C in a kettle.
Heating for dissolving, is made into the perfluor sulfoacid resin solution that mass percent is 7%.
4 as it is shown in figure 1, strengthen basement membrane 1 anchorage clip 3 and glazing bead 2 is fixed on cleaning by non-woven fabrics
On glass plate 4, use solution casting method, perfluor sulfoacid resin solution 60ml cast on enhancing basement membrane,
140 DEG C of solvents volatilization 1.5h film forming.When solvent is not completely dried, by film the most again with anchorage clip 3
It is fixed on glass plate 4 with glazing bead 2.
5, more quaternized polyether sulfone preparation liquid 50ml is cast on film prepared by above-mentioned steps (4), at 100 DEG C
Continue to be dried 3h, prepare perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite membrane.
In the present embodiment, it is thus achieved that perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite film thickness be 190 μm,
The thickness of perfluoro sulfonic acid membrane is 90 microns, and cavity block thickness is 70 microns, the thickness of non-woven fabrics is 30 microns.Multiple
Closing each interracial contact in film good, non-division phenomenon, mechanical strength is good.
Composite membrane electrical conductivity is tested:
At room temperature, by film to be measured at VOSO4After solution is sufficiently impregnated with, it is fixed between two Room of measuring cell.
Under the effect of external pump, VOSO4Solution is circulated flowing between fluid reservoir and two Room of measuring cell, this
Measure resistance R between two Room1.Identical with above-mentioned condition, measure the electricity between measuring cell two Room not installing film to be measured
Resistance R2.Then membrane resistance R=R1-R2, the electrical conductivity of membrane is calculated according to δ=L/AR.
The test of composite membrane vanadium (IV) ion permeability:
Test uses two and half ponds to carry out, and in right half pond, the initial concentration of vanadium (IV) ion is
1.5mol/LVOSO4+2mol/LH2SO4, volume is 150ml, and in Zuo Banchi, initial concentration is 1.5
mol/LMgSO4+2mol/LH2SO4, volume is 150ml, and centre separates with barrier film to be measured.Solution in two Room
Respectively under the effect of external pump, flow into from measuring cell flow liquid frame, then flowed out by barrier film, be circulated flowing.
After running certain time, ultraviolet spectrophotometer is utilized to survey the concentration of different time vanadium ion (IV) in left half pond.
Wherein, V represents the initial volume of left and right half the filled solution in pond, ml；A and L refers to the effective of film respectively
Area (mm2) and thickness (mm)；P refers to the permeability of vanadium (IV) ion, %；CRRefer to vanadium ion in right half pond
Initial concentration, mol/L；CLRefer to the concentration of vanadium (IV) ion, mol/L in left half pond.
Film is cut into certain length L by the swelling test of film of preparationB(mm) in deionized water 25 DEG C soak after 48h and take
Go out, blot the water on film surface with absorbent paper after, measure three film length LA (mm), the then linear expansions of film immediately
Rate L, can be drawn by following formula:
L=(LA-LB)/LB× 100%
The correlated performance data of the present embodiment is as follows:
Recording barrier film electrical conductivity in vanadium redox battery under room temperature is 0.0085s/cm, this ratio
The composite diaphragm electrical conductivity of preparation is smaller, but the performance of rechargable battery discharge and recharge can substantially meet requirement, and energy
Amount efficiency and coulombic efficiency are higher than Nafion212 film.
48h vanadium ion permeability 6.57cm of composite diaphragm prepared by this ratio2/ min, Nafion212 film 48h
Vanadium ion permeability 8.07cm2/min。
Single VRB system charge-discharge test data are shown in accompanying drawing 3, as seen from Figure 3, equipped with perfluoro sulfonic acid membrane
The single VRB battery of/enhancing basement membrane/cavity block both sexes composite membrane, has the highest coulombic efficiency in charge and discharge process,
Energy efficiency, wherein through circulate for more than 20 times coulombic efficiency average out to 95%, energy efficiency be average 83%,
Voltage efficiency average out to 88%.Through repeatedly circulating, its battery efficiency does not decay.So, secondary optimum compound
Film can be good at adapting to vanadium cell system, has good application prospect.
Embodiment 2
Difference from Example 1 is:
1, perfluor sulfoacid resin solution 40ml is measured.
2, remaining step is same as in Example 1.
In the present embodiment, it is thus achieved that perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite film thickness be 160 μm,
The thickness of perfluoro sulfonic acid membrane is 60 microns, and cavity block thickness is 70 microns, the thickness of non-woven fabrics is 30 microns.Multiple
Closing each interracial contact in film good, non-division phenomenon, mechanical strength is good.
The correlated performance data of the present embodiment is as follows:
Recording barrier film electrical conductivity in vanadium redox battery under room temperature is 0.0072s/cm, this ratio
Composite diaphragm Conductivity Ratio example 1 little of preparation, analyzes the ratio that reason is perfluoro sulfonic acid membrane layer and cavity block
Diminish, cause hydrophilic group ratio to reduce, make the transmission of H ion slow down.
48h vanadium ion permeability 6.02cm of composite diaphragm prepared by this ratio2/ min, vanadium ion permeability is good
In example 1, reason is that cavity block ratio is big, utilizes Dannon effect, stops cation to enter barrier film, thus carries
The resistance vanadium of high composite membrane.
Embodiment 3
Difference from Example 1 is:
1, quaternized polyether sulfone preparation liquid 30ml is measured.
2, remaining step is same as in Example 1.
In the present embodiment, it is thus achieved that perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite film thickness be 160 μm, entirely
The thickness of fluosulfonic acid film is 90 microns, and cavity block thickness is 40 microns, the thickness of non-woven fabrics is 30 microns.Compound
In film, each interracial contact is good, and non-division phenomenon, mechanical strength is good.
The correlated performance data of the present embodiment is as follows:
Recording barrier film electrical conductivity in vanadium redox battery under room temperature is 0.0105s/cm, this ratio
Composite diaphragm Conductivity Ratio example 1 little of preparation, analyzes the ratio that reason is perfluoro sulfonic acid membrane layer and cavity block
Become big, cause hydrophilic group ratio to increase, make the transmission of H ion accelerate.
48h vanadium ion permeability 7.35cm2/min of composite diaphragm prepared by this ratio, vanadium ion permeability is relatively
Example 1 is deteriorated, and reason is that anode membrane ratio is big, and this composite membrane hydrophilic increases so that anode membrane structure ion bunch leads to
Road diameter increases, and causes vanadium ion infiltration height.
Test result indicate that: the present invention by anion exchange resin chloromethylation, again carry out quaternised modified, system
Standby quaternized anion exchange resin solution, is dissolved perfluorinated sulfonic resin by organic solvent, and then utilization point
Step the tape casting, with basement membrane as articulamentum, prepares perfluorinated sulfonic acid sun/enhancing/cloudy both sexes composite membrane.System of the present invention
Standby composite diaphragm electric conductivity meets vanadium cell and uses requirement, has good resistance vanadium performance, mechanicalness simultaneously
Can, chemical stability and good battery performance, the advantage such as with low cost, can be widely used in the oxidation of full vanadium
Reducing solution galvanic battery field.
Claims (9)
1. the preparation method of sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane, it is characterized in that, described composite membrane is perfluoro sulfonic acid membrane/enhancing basement membrane/anion exchange membrane both sexes composite membrane, including strengthening basement membrane, perfluoro sulfonic acid membrane, anion exchange membrane, the both sides strengthening basement membrane are respectively perfluoro sulfonic acid membrane and anion exchange membrane, in composite membrane, each interracial contact is good, non-division phenomenon；Perfluoro sulfonic acid membrane/enhancing basement membrane/anion exchange membrane both sexes composite film thickness is 160～240 m, and the thickness of perfluoro sulfonic acid membrane is 40～100 microns, and anion exchange film thickness is 40～100 microns, the thickness that strengthens basement membrane is 20～40 microns；
The preparation of described composite membrane comprises the steps:
(1) 1～5g anion exchange resin is added high boiling organic solvent, make anion exchange resin be completely dissolved；Chloromethylation is carried out in 0～50 DEG C of temperature, 4～20ml chloromethylation reagents, 2～12h response time；Reaction is precipitant with ethanol after terminating, and makes resulting polymer separate out, more repeatedly washs with distilled water, to cleaning mixture not chloride ion-containing, is vacuum dried, it is thus achieved that the anion exchange film resin of chloromethylation；
(2) by during the anion exchange film resin of chloromethylation is placed in the four-hole boiling flask equipped with agitator and thermometer in step (1), add high boiling organic solvent and make to be completely dissolved；Adding in the trimethylamine aqueous solution that mass concentration is 20%～45%, react 24～72h, carry out quaternised modified, prepare quaternized anion exchange resin preparation liquid at 30～60 DEG C, mass percent is 3～35%；
(3) during perfluorinated sulfonic resin is dissolved in high boiling organic solvent, heating for dissolving in a kettle., it is made into the perfluor sulfoacid resin solution that mass percent is 3～25%, heating for dissolving temperature conditions is 170 DEG C～260 DEG C；
(4) fix strengthening basement membrane on clean glass plate, use solution casting method, the perfluor sulfoacid resin solution of step (3) is cast on enhancing basement membrane, in 60～140 DEG C of temperature, 0.5～3h time solvent volatilization film forming, by film fixed placement in turn；
(5) the more quaternized anion exchange resin preparation liquid of step (2) is cast on film prepared by step (4), continues to be dried in 60～100 DEG C of temperature, 1～4h time, prepare perfluoro sulfonic acid membrane/enhancing basement membrane/anion exchange membrane both sexes composite membrane.
2. according to the preparation method described in claim 1, it is characterised in that high boiling organic solvent is dimethyl sulfoxide, DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone or dichloromethane.
3. according to the preparation method described in claim 1, it is characterised in that enhancing basement membrane is non-woven fabrics, porous PP film or porous PE film.
4. according to the preparation method described in claim 1, it is characterised in that anion exchange resin is polyphenylene oxide, polysulfones, poly (aryl ether sulfone ketone), polyether sulfone or polyimides.
5. according to the preparation method described in claim 1, it is characterised in that chloromethylation reagents refers to trim,ethylchlorosilane, Isosorbide-5-Nitrae-dichloro methyl butyl ether, chloromethyl octyl ether or chloromethyl methyl ether.
6., according to the preparation method described in claim 1, it is characterised in that in step (2), the mass percent of quaternized anion exchange resin is 7%～20%.
7., according to the preparation method described in claim 1, it is characterised in that in step (3), the mass percent of perfluorinated sulfonic resin is 5%～15%.
8. according to the preparation method described in claim 1, it is characterised in that in step (4), temperature is 100～140 DEG C, and the time is 0.5～3h.
9. according to the preparation method described in claim 1, it is characterised in that in step (5), temperature is 80～100 DEG C, and the time is 2～3h.
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| CN106972186B (en) * | 2016-01-14 | 2020-01-03 | 中国科学院金属研究所 | Preparation method of composite membrane with catalytic function on positive electrode and negative electrode for all-vanadium redox flow battery |
| CN108461787B (en) * | 2017-02-17 | 2020-01-03 | 中国科学院金属研究所 | Preparation method of integrated composite membrane for all-vanadium redox flow battery |
| CN109428101A (en) * | 2017-09-05 | 2019-03-05 | 哈尔滨工业大学（威海） | A kind of amphoteric ion exchange membrane and preparation method thereof based on perfluorinated sulfonic acid ion exchange membrane |
| CN109873188A (en) * | 2017-12-01 | 2019-06-11 | 中国科学院大连化学物理研究所 | Application of the cluster ion exchange membrane in alkaline system zinc-iron flow battery |
| CN109758917B (en) * | 2018-09-18 | 2021-07-02 | 张伟 | Preparation method of divalent cation selective ion exchange membrane |
| KR102534907B1 (en) * | 2019-03-08 | 2023-05-26 | 아사히 가세이 가부시키가이샤 | Electrolyte membrane for redox flow battery, redox flow battery, and manufacturing method of electrolyte membrane |
| WO2021215126A1 (en) * | 2020-04-24 | 2021-10-28 | 旭化成株式会社 | Diaphragm for redox flow batteries, method for producing diaphragm for redox flow batteries, diaphragm electrode assembly for redox flow batteries, cell for redox flow batteries, and redox flow battery |
| CN114976165B (en) * | 2022-06-17 | 2024-02-02 | 上海恩捷新材料科技有限公司 | Composite ion exchange membrane and preparation method thereof |
| CN117199465B (en) * | 2023-11-07 | 2024-02-06 | 杭州德海艾科能源科技有限公司 | High ion selectivity ionic membrane for vanadium redox flow battery and preparation method thereof |
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