CN104282923A - Anode/enhanced/cathode amphoteric composite membrane for all-vanadium redox flow battery and preparation method of composite membrane - Google Patents
Anode/enhanced/cathode amphoteric composite membrane for all-vanadium redox flow battery and preparation method of composite membrane Download PDFInfo
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- CN104282923A CN104282923A CN201410528904.1A CN201410528904A CN104282923A CN 104282923 A CN104282923 A CN 104282923A CN 201410528904 A CN201410528904 A CN 201410528904A CN 104282923 A CN104282923 A CN 104282923A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to the field of ion exchange membranes for vanadium redox batteries (VRB) and in particular relates to an anode/enhanced/cathode amphoteric composite membrane for an all-vanadium redox flow battery and a preparation method of the composite membrane. The problem that the conventional used proton exchange membrane is high in vanadium ion penetration rate and high in price and the like is solved. The preparation method comprises the following steps: performing chloromethylation on an anion exchange resin, performing quaternized modification, preparing quaternized anion exchange resins of different ion exchange capacities, respectively dissolving the modified anion exchange resin and a perfluorinated sulfonic acid resin through an organic solvent, further utilizing step-by-step tape casting, taking a base film as a connecting layer, adjusting the film forming temperature, concentration and time, thereby preparing the perfluorinated sulfonic acid anode/enhanced/cathode amphoteric composite membrane. The composite membrane prepared by the invention has the advantages of good vanadium resistance, good mechanical property, high chemical stability and good single VRB battery performance, low cost and the like and can be widely applied to the field of vanadium redox batteries.
Description
Technical field
The present invention relates to vanadium redox battery (VRB) and use amberplex field, particularly one sun/enhancing used for all-vanadium redox flow battery/cloudy both sexes composite membrane and preparation method thereof.
Background technology
New forms of energy such as exploitation wind energy, solar energy etc. are the important channels solving energy resources shortage, represent the direction of energy future development.But be limited by time and region dependence, off-grid wind energy, solar power generation must use energy-storage system, otherwise be difficult to round-the-clock utilization; And direct grid-connected also must adopt energy-storage system to carry out peak regulation and frequency modulation to electrical network, otherwise larger impact can be brought to grid power and frequency.Therefore, efficient, large-scale energy storage technologies just becomes the key core of its development and application.
Vanadium cell (vanadium oxide reduction flow battery/Vanadium redox flow battery) is that stored energy is in electrolyte based on VO2+/VO2+ and V2+/V3+ electricity right liquid flow energy storage battery technology.Compared with traditional storage battery, vanadium cell can big current fast charging and discharging, self-discharge rate low, realize the massive store of energy, be meet intelligent grid and wind energy, solar power generation to the desirable stored energy form of extensive energy storage demand, the vanadium resource advantage of China's abundant is also for development vanadium cell energy storage technology provides condition.
Barrier film (proton exchange membrane) is one of the critical material and significant components of vanadium cell, is the passage of electrolyte ion transmission, plays again the effect of separating both positive and negative polarity, preventing battery short circuit.Therefore, barrier film decides the coulombic efficiency of vanadium cell, energy efficiency and cycle life to a great extent.A kind of good proton exchange membrane should possess good chemical stability, resistance to electrochemistry oxygen voltinism, low vanadium ion permeability and low cost.At present, main employing Nafion series membranes both at home and abroad, although Nafion membrance chemistry good stability, proton conductivity are high, some shortcomings of such film are that vanadium ion transmitance is high, and self-discharge of battery phenomenon is comparatively remarkable, reason is this barrier film is cation-exchange membrane, containing hydrophilic sulfonic acid group, be very easy to swelling in water, dimensional stability is bad, it is high that such channel diameter increase causes vanadium ion to permeate, and its fancy price also makes the cost of vanadium cell remain high.Therefore, how to prepare low-cost and high-performance vanadium cell diaphragm material and become one of critical bottleneck of restriction vanadium cell through engineering approaches and technical development.Also carried out multinomial diagram modification research both at home and abroad, although enhance some performances of barrier film, the price of barrier film is still high, governs the business processes of VRB.In addition, its modifying process has complex process, and raw material such as not easily to obtain at the shortcoming.
But theoretically, the ion-exchange group of cation-exchange membrane is azochlorosulfonate acid anion, comparatively large to vanadium ion permeability in vanadium battery solution, although the permeability by can reduce vanadium ion to a certain extent to the modification of film, the infiltration of vanadium ion fundamentally can not be stoped.
Comparatively speaking, the ion-exchange group of anion-exchange membrane is cation, due to Dannon effect, thus selectivity is higher, the infiltration of vanadium ion will be restricted, currently reported polyether sulphone and copolymerization aryl ether sulfone material are by carrying out the modifications such as chloromethylation/quaternized to it, obtained anion-exchange membrane has lower vanadium ion permeability.But being used alone cavity block, to be applied in vanadium cell its internal resistance comparatively large, can affect battery performance to a certain extent.Therefore, if make barrier film both have cationic membrane characteristic, having again the characteristic that anionic membrane ion-selective permeability is good, anions and canons film advantage separately rolled into one, will be the research tendency of following all-vanadium flow battery barrier film.
Summary of the invention
The object of this invention is to provide a kind of sun/enhancing used for all-vanadium redox flow battery/cloudy both sexes composite membrane and preparation method thereof, in order to solve the proton exchange membrane of use at present in problems such as vanadium ion transmitance are high, expensive, therefore perfluorinated sulfonic acid sun/enhancing/cloudy both sexes composite membrane is prepared, this composite membrane had both had cationic membrane good conductivity, feature that chemical stability is good, there is again the characteristic that anionic membrane ion-selective permeability is good, improve barrier film intensity again simultaneously, be applicable to vanadium redox battery (VRB).
Technical scheme of the present invention:
A kind of sun/enhancing used for all-vanadium redox flow battery/cloudy both sexes composite membrane, it is characterized in that, perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite membrane, comprise and strengthen basement membrane, perfluoro sulfonic acid membrane, cavity block, the both sides strengthening basement membrane are respectively perfluoro sulfonic acid membrane and cavity block, in composite membrane, each interracial contact is good, non-division phenomenon; Perfluoro sulfonic acid membrane/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, and cavity block thickness is 40 ~ 100 microns, the thickness of enhancing basement membrane is 20 ~ 40 microns.
The preparation method of described sun/enhancing used for all-vanadium redox flow battery/cloudy both sexes composite membrane, comprises the steps and process conditions:
(1) 1 ~ 5g anion exchange resin is added high boiling organic solvent, anion exchange resin is dissolved completely; Chloromethylation is carried out in 0 ~ 50 DEG C of different temperatures, 4 ~ 20ml different proportion chloromethylation reagents, 2 ~ 12h differential responses time; It is precipitation reagent that reaction terminates rear ethanol, resulting polymer is separated out, more repeatedly washs with distilled water, and to cleaning solution not chloride ion-containing, vacuumize, obtains the cavity block resin of chloromethylation;
(2) the cavity block resin of chloromethylation in step (1) is placed in the four-hole boiling flask that blender and thermometer are housed, then adds high boiling organic solvent and make to dissolve completely; Adding mass concentration is in the trimethylamine aqueous solution of 20% ~ 45%, reacts 24 ~ 72h, carry out quaternised modified at 30 ~ 60 DEG C, the quaternized anion exchange resin preparation liquid of preparation different ions exchange capacity, and mass percent is 3 ~ 35%;
(3) perfluorinated sulfonic resin is dissolved in high boiling organic solvent, in a kettle. heating for dissolving, is made into the perfluor sulfoacid resin solution that mass percent is 3 ~ 25%, and heating for dissolving temperature conditions is 170 DEG C ~ 260 DEG C;
(4) enhancing basement membrane is fixing on the glass plate of cleaning, adopt solution casting method, the perfluor sulfoacid resin solution of step (3) is cast in and strengthens on basement membrane, in 60 ~ 140 DEG C of different temperatures, 0.5 ~ 3h different time solvent evaporates film forming, by film fixed placement conversely;
(5) the more quaternized anion exchange resin preparation liquid of step (2) is cast on film prepared by step (4), continue dry at 60 ~ 100 DEG C of different temperatures, 1 ~ 4h different time, prepare perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite membrane.
The preparation method of described sun/enhancing used for all-vanadium redox flow battery/cloudy both sexes composite membrane, high boiling organic solvent is dimethyl sulfoxide (DMSO), DMF, DMA, 1-METHYLPYRROLIDONE or carrene.
The preparation method of described sun/enhancing used for all-vanadium redox flow battery/cloudy both sexes composite membrane, enhancing basement membrane is nonwoven fabrics, porous PP film or porous PE film.
The preparation method of described sun/enhancing used for all-vanadium redox flow battery/cloudy both sexes composite membrane, anion exchange resin 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/cloudy both sexes composite membrane, chloromethylation reagents refers to trim,ethylchlorosilane, Isosorbide-5-Nitrae-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/cloudy 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/cloudy 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/cloudy 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/cloudy both sexes composite membrane, in step (5), temperature is preferably 80 ~ 100 DEG C, and the time is preferably 2 ~ 3h.
Advantage of the present invention and beneficial effect as follows:
1, the present invention utilizes the ion-exchange group of anion-exchange membrane for cation, and due to Dannon effect, the feature that thus ion selectivity is higher, the infiltration of vanadium ion will be restricted, and greatly reduce the infiltration of vanadium ion.
2, the present invention utilizes the feature that porous basement membrane porosity is large, aperture is large, a large amount of perfluor sulfoacid resin solution and a small amount of cavity block resin solution is made effectively to permeate and combine closely, avoid because molecular skeleton is different, due to the lamination that dimensional stability difference causes in V electrolyte water-based system, this structure composite film solves layering that the reason such as conventional composite film Yin Wendu, electrolyte oxidation produces and to come off problem.
3, the present invention is due to the electric conductivity adding reduction film of basement membrane, by penetrating in porous basement membrane containing the perfluor sulfoacid resin solution in a large number with hydrophilic radical, proton conducting, effectively improves the conductivity of composite membrane.
4, composite diaphragm of the present invention greatly reduces due to perfluorinated sulfonic resin consumption, therefore this composite diaphragm cost comparatively Nafion series membranes significantly reduce.
In a word, scientifically combine the advantage of anode membrane and cavity block, prepare sun/enhancing/cloudy both sexes composite membrane, in use PSFA layer is applied in anode (anode electrolyte oxidizability is strong), the non-oxidizability of composite membrane is improved while ensureing conductivity, cavity block layer is applied in battery cathode (electrolyte liquid oxygen voltinism is weak) and utilizes Dannon effect, improves the resistance vanadium of composite membrane.Overcome anode membrane as perfluoro sulfonic acid membrane resistance vanadium poor performance and expensive shortcoming, cavity block internal resistance is large and antioxygenic property is poor shortcoming, effectively raise antioxygenic property and the resistance vanadium performance of barrier film, and reduce barrier film cost, for the preparation of vanadium cell barrier film provides new approaches.
Accompanying drawing explanation
Fig. 1 masking glass plate of the present invention schematic diagram.In figure, 1, strengthen basement membrane; 2, glazing bead; 3, anchorage clip; 4, glass plate.
Fig. 2 composite membrane result schematic diagram of the present invention.In figure, 1, strengthen basement membrane; 5, perfluoro sulfonic acid membrane; 6, cavity block.
Fig. 3 composite membrane charge-discharge performance of the present invention.
Embodiment
As shown in Figure 1, masking glass plate mainly comprises enhancing basement membrane 1, glazing bead 2, anchorage clip 3, glass plate 4 etc., strengthening basement membrane 1 is placed on glass plate 4, and the edge strengthening basement membrane 1 is installed with glazing bead 2, and anchorage clip 3 is in the edge clamping glass press strip 2 of glass plate 4.
In a specific embodiment, the preparation method of the present invention's sun/enhancing used for all-vanadium redox flow battery/cloudy both sexes composite membrane, comprises the steps and process conditions:
(1) 1 ~ 5g anion exchange resin is added high boiling organic solvent, anion exchange resin is dissolved completely; Chloromethylation is carried out in 0 ~ 50 DEG C of different temperatures, 4 ~ 20ml different proportion chloromethylation reagents, 2 ~ 12h differential responses time.It is precipitation reagent that reaction terminates rear ethanol, resulting polymer is separated out, more repeatedly washs with distilled water, and to cleaning solution not chloride ion-containing, vacuumize, obtains the cavity block resin of chloromethylation.
(2) the cavity block resin of chloromethylation in step (1) is placed in the four-hole boiling flask that blender and thermometer are housed, then adds high boiling organic solvent and make to dissolve completely; Adding mass concentration is in the trimethylamine aqueous solution of 20% ~ 45%, 24 ~ 72h is reacted at 30 ~ 60 DEG C, carry out quaternised modified, the quaternized anion exchange resin preparation liquid of preparation different ions exchange capacity, mass percent is 3 ~ 35% (being preferably 7% ~ 20%).
(3) perfluorinated sulfonic resin is dissolved in high boiling organic solvent, heating for dissolving in a kettle., be made into the perfluor sulfoacid resin solution that mass percent is 3 ~ 25% (being preferably 5% ~ 15%), heating for dissolving temperature conditions is 170 DEG C ~ 260 DEG C.
(4) enhancing basement membrane is fixing on the glass plate of cleaning, adopt solution casting method, the perfluor sulfoacid resin solution of step (3) is cast in and strengthens on basement membrane, in 60 ~ 140 DEG C of (being preferably 100 ~ 140 DEG C) different temperatures, 0.5 ~ 3h (being preferably 1 ~ 1.5h) different time solvent evaporates film forming.When solvent does not have bone dry, by film fixed placement conversely.
(5) the more quaternized anion exchange resin preparation liquid of step (2) is cast on film prepared by step (4), continue dry at 60 ~ 100 DEG C of (being preferably 80 ~ 100 DEG C) different temperatures, 1 ~ 4h (being preferably 2 ~ 3h) different time, prepare perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite membrane.
Wherein, high boiling organic solvent is dimethyl sulfoxide (DMSO), N, dinethylformamide, N, N-dimethylacetylamide, 1-METHYLPYRROLIDONE or carrene etc., enhancing basement membrane is nonwoven 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., and chloromethylation reagents refers to trim,ethylchlorosilane, Isosorbide-5-Nitrae-dichloro methyl butyl ether, chloromethyl octyl ether or chloromethyl methyl ether etc.
As shown in Figure 2, prepared perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite membrane, comprises and strengthens basement membrane 1, perfluoro sulfonic acid membrane 5, cavity block 6, and the both sides strengthening basement membrane 1 are respectively perfluoro sulfonic acid membrane 5 and cavity block 6.Perfluoro sulfonic acid membrane/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, and cavity block thickness is 40 ~ 100 microns, the thickness of enhancing basement membrane is 20 ~ 40 microns.In composite membrane, each interracial contact is good, and non-division phenomenon, mechanical strength is good.
Be described in further detail below by embodiment technical scheme of the present invention.
Embodiment 1
1, weigh 3g polyethersulfone resin and be placed in the four-hole boiling flask that blender and thermometer are housed, add 15mL carrene, polyether sulfone is dissolved completely, then adds the chloromethylation reagents (the present embodiment is chloromethyl octyl ether) of 5mL, under room temperature (25 DEG C), react 4h.It is precipitation reagent that reaction terminates rear ethanol, and resulting polymer is separated out, more repeatedly washs with distilled water, to cleaning solution not chloride ion-containing, vacuumize, obtains chloromethylation polyether sulfone.
2, take 2g chloromethylation polyether sulfone, be placed in the four-hole boiling flask that blender and thermometer are housed, then add the DMF (DMF) of 30mL, make to dissolve completely; Adding mass concentration is in the trimethylamine aqueous solution of 25%, stirs at 40 DEG C, after making quaterisation 48h, stops stirring, obtains quaternized polyether sulfone preparation liquid.
3, taking 2g perfluorinated sulfonic resin is dissolved in DMF (DMF), and 200 DEG C of heating for dissolving in a kettle., are made into the perfluor sulfoacid resin solution that mass percent is 7%.
4, as shown in Figure 1, nonwoven fabrics is strengthened basement membrane 1 anchorage clip 3 and glazing bead 2 and be fixed on clean glass plate 4, adopt solution casting method, perfluor sulfoacid resin solution 60ml is cast in and strengthens on basement membrane, 140 DEG C of solvent evaporates 1.5h film forming.When solvent does not have bone dry, film is fixed on glass plate 4 with anchorage clip 3 and glazing bead 2 conversely again.
5, more quaternized polyether sulfone preparation liquid 50ml is cast on film prepared by above-mentioned steps (4), continues dry 3h at 100 DEG C, prepare perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite membrane.
In the present embodiment, the perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite film thickness of acquisition is 190 μm, and the thickness of perfluoro sulfonic acid membrane is 90 microns, and cavity block thickness is 70 microns, the thickness of nonwoven fabrics is 30 microns.In composite membrane, each interracial contact is good, and non-division phenomenon, mechanical strength is good.
Composite membrane conductivity is tested:
At room temperature, by film to be measured at VOSO
4in solution fully after dipping, between two Room being fixed on measuring cell.Under the effect of external pump, VOSO
4solution circulates between fluid reservoir and two Room of measuring cell, and this measures resistance R between two Room
1.Identical with above-mentioned condition, measure the resistance R between measuring cell two Room of not installing film to be measured
2.Then film resistance R=R
1-R
2, the conductivity of membrane is calculated according to δ=L/AR.
The test of composite membrane vanadium (IV) ion permeability:
Test employing two and half pond is carried out, and in right half pond, the initial concentration of vanadium (IV) ion is 1.5mol/LVOSO
4+ 2mol/LH
2sO
4, volume is that in 150ml, Zuo Banchi, initial concentration is 1.5mol/LMgSO
4+ 2mol/LH
2sO
4, volume is 150ml, and centre separates with barrier film to be measured.Solution in two Room, respectively under the effect of external pump, is flowed into from measuring cell flow liquid frame, then is flowed out by barrier film, circulate.After running certain hour, ultraviolet specrophotometer is utilized to survey the concentration of different time vanadium ion (IV) in left half pond.
Wherein, V represent left and right half pond fill the initial volume of solution, ml; A and L refers to the effective area (mm of film respectively
2) and thickness (mm); P refers to the permeability of vanadium (IV) ion, %; C
rrefer to the initial concentration of vanadium ion in right half pond, mol/L; C
lrefer to the concentration of vanadium (IV) ion in left half pond, mol/L.
Film is cut into certain length L by the swelling test of film of preparation
b(mm) in deionized water 25 DEG C soak after 48h and take out, measure three film length LA (mm) blot the water on film surface with blotting paper after immediately, then the linear expansion rate L of film, can be drawn by following formula:
L＝(L
A-L
B)/L
B×100％
The correlated performance data of the present embodiment is as follows:
Recording the conductivity of barrier film in vanadium redox battery under room temperature is 0.0085s/cm, composite diaphragm conductivity prepared by this ratio is smaller, but the performance of rechargable battery discharge and recharge can meet the demands substantially, and energy efficiency and coulombic efficiency are higher than Nafion212 film.
The 48h vanadium ion permeability 6.57cm of composite diaphragm prepared by this ratio
2/ min, Nafion212 film 48h vanadium ion permeability 8.07cm
2/ min.
Single VRB system charge-discharge test data are shown in accompanying drawing 3, as seen from Figure 3, the single VRB battery of perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite membrane is housed, there is in charge and discharge process very high coulombic efficiency, energy efficiency, wherein through more than 20 circulation 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 composite membrane 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, all the other steps are identical with embodiment 1.
In the present embodiment, the perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite film thickness of acquisition is 160 μm, and the thickness of perfluoro sulfonic acid membrane is 60 microns, and cavity block thickness is 70 microns, the thickness of nonwoven fabrics is 30 microns.In composite membrane, 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 the conductivity of barrier film in vanadium redox battery under room temperature is 0.0072s/cm, composite diaphragm Conductivity Ratio example 1 prepared by this ratio little, analysis reason is that the ratio of perfluorinated sulfonic acid rete and cavity block diminishes, and causes hydrophilic radical ratio to reduce, the transmission of H ion is slowed down.
The 48h vanadium ion permeability 6.02cm of composite diaphragm prepared by this ratio
2/ min, vanadium ion permeability is better than example 1, and reason is that cavity block ratio is large, utilizes Dannon effect, stops cation to enter barrier film, thus improves the resistance vanadium of composite membrane.
Embodiment 3
Difference from Example 1 is:
1, quaternized polyether sulfone preparation liquid 30ml is measured.
2, all the other steps are identical with embodiment 1.
In the present embodiment, the perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite film thickness of acquisition is 160 μm, and the thickness of perfluoro sulfonic acid membrane is 90 microns, and cavity block thickness is 40 microns, the thickness of nonwoven fabrics is 30 microns.In composite membrane, 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 the conductivity of barrier film in vanadium redox battery under room temperature is 0.0105s/cm, composite diaphragm Conductivity Ratio example 1 prepared by this ratio little, analysis reason is that the ratio of perfluorinated sulfonic acid rete and cavity block becomes greatly, causes hydrophilic radical ratio to increase, the transmission of H ion is accelerated.
The 48h vanadium ion permeability 7.35cm2/min of composite diaphragm prepared by this ratio, vanadium ion permeability comparatively example 1 is deteriorated, and reason is that anode membrane ratio is large, and this composite membrane hydrophily increases, and anode membrane structure ion bunch channel diameter is increased, causes vanadium ion to permeate high.
Experimental result shows: the present invention by anion exchange resin chloromethylation, again carry out quaternised modified, prepare quaternized anion exchange resin solution, perfluorinated sulfonic resin is passed through organic solvent dissolution, and then utilize substep the tape casting, with basement membrane as articulamentum, prepare perfluorinated sulfonic acid sun/enhancing/cloudy both sexes composite membrane.Composite diaphragm electric conductivity prepared by the present invention meets vanadium cell instructions for use, there is good resistance vanadium performance, mechanical performance, chemical stability and good battery performance, the advantage such as with low cost simultaneously, can be widely used in vanadium redox battery field.
Claims (10)
1. sun/enhancing used for all-vanadium redox flow battery/cloudy both sexes composite membrane, it is characterized in that, perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite membrane, comprise and strengthen basement membrane, perfluoro sulfonic acid membrane, cavity block, the both sides strengthening basement membrane are respectively perfluoro sulfonic acid membrane and cavity block, in composite membrane, each interracial contact is good, non-division phenomenon; Perfluoro sulfonic acid membrane/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, and cavity block thickness is 40 ~ 100 microns, the thickness of enhancing basement membrane is 20 ~ 40 microns.
2., according to the preparation method of sun/enhancing used for all-vanadium redox flow battery according to claim 1/cloudy both sexes composite membrane, it is characterized in that, comprise the steps and process conditions:
(1) 1 ~ 5g anion exchange resin is added high boiling organic solvent, anion exchange resin is dissolved completely; Chloromethylation is carried out in 0 ~ 50 DEG C of different temperatures, 4 ~ 20ml different proportion chloromethylation reagents, 2 ~ 12h differential responses time; It is precipitation reagent that reaction terminates rear ethanol, resulting polymer is separated out, more repeatedly washs with distilled water, and to cleaning solution not chloride ion-containing, vacuumize, obtains the cavity block resin of chloromethylation;
(2) the cavity block resin of chloromethylation in step (1) is placed in the four-hole boiling flask that blender and thermometer are housed, then adds high boiling organic solvent and make to dissolve completely; Adding mass concentration is in the trimethylamine aqueous solution of 20% ~ 45%, reacts 24 ~ 72h, carry out quaternised modified at 30 ~ 60 DEG C, the quaternized anion exchange resin preparation liquid of preparation different ions exchange capacity, and mass percent is 3 ~ 35%;
(3) perfluorinated sulfonic resin is dissolved in high boiling organic solvent, in a kettle. heating for dissolving, is made into the perfluor sulfoacid resin solution that mass percent is 3 ~ 25%, and heating for dissolving temperature conditions is 170 DEG C ~ 260 DEG C;
(4) enhancing basement membrane is fixing on the glass plate of cleaning, adopt solution casting method, the perfluor sulfoacid resin solution of step (3) is cast in and strengthens on basement membrane, in 60 ~ 140 DEG C of different temperatures, 0.5 ~ 3h different time solvent evaporates film forming, by film fixed placement conversely;
(5) the more quaternized anion exchange resin preparation liquid of step (2) is cast on film prepared by step (4), continue dry at 60 ~ 100 DEG C of different temperatures, 1 ~ 4h different time, prepare perfluoro sulfonic acid membrane/enhancing basement membrane/cavity block both sexes composite membrane.
3. according to the preparation method of sun/enhancing used for all-vanadium redox flow battery according to claim 2/cloudy both sexes composite membrane, it is characterized in that, high boiling organic solvent is dimethyl sulfoxide (DMSO), DMF, DMA, 1-METHYLPYRROLIDONE or carrene.
4. according to the preparation method of sun/enhancing used for all-vanadium redox flow battery according to claim 2/cloudy both sexes composite membrane, it is characterized in that, enhancing basement membrane is nonwoven fabrics, porous PP film or porous PE film.
5. according to the preparation method of sun/enhancing used for all-vanadium redox flow battery according to claim 2/cloudy both sexes composite membrane, it is characterized in that, anion exchange resin is polyphenylene oxide, polysulfones, poly (aryl ether sulfone ketone), polyether sulfone or polyimides.
6. according to the preparation method of sun/enhancing used for all-vanadium redox flow battery according to claim 2/cloudy both sexes composite membrane, it is characterized in that, chloromethylation reagents refers to trim,ethylchlorosilane, Isosorbide-5-Nitrae-dichloro methyl butyl ether, chloromethyl octyl ether or chloromethyl methyl ether.
7. according to the preparation method of sun/enhancing used for all-vanadium redox flow battery according to claim 2/cloudy both sexes composite membrane, it is characterized in that, in step (2), the mass percent of quaternized anion exchange resin is preferably 7% ~ 20%.
8. according to the preparation method of sun/enhancing used for all-vanadium redox flow battery according to claim 2/cloudy both sexes composite membrane, it is characterized in that, in step (3), the mass percent of perfluorinated sulfonic resin is preferably 5% ~ 15%.
9. according to the preparation method of sun/enhancing used for all-vanadium redox flow battery according to claim 2/cloudy both sexes composite membrane, it is characterized in that, in step (4), temperature is preferably 100 ~ 140 DEG C, and the time is preferably 0.5 ~ 3h.
10. according to the preparation method of sun/enhancing used for all-vanadium redox flow battery according to claim 2/cloudy both sexes composite membrane, it is characterized in that, in step (5), temperature is preferably 80 ~ 100 DEG C, and the time is preferably 2 ~ 3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410528904.1A CN104282923B (en) | 2014-10-09 | 2014-10-09 | Sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410528904.1A CN104282923B (en) | 2014-10-09 | 2014-10-09 | Sun/enhancing used for all-vanadium redox flow battery/the moon both sexes composite membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN104282923A true CN104282923A (en) | 2015-01-14 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106972186A (en) * | 2016-01-14 | 2017-07-21 | 中国科学院金属研究所 | It is used for all-vanadium redox flow battery that there is catalysis to be combined membrane preparation method to positive and negative electrode |
| CN108461787A (en) * | 2017-02-17 | 2018-08-28 | 中国科学院金属研究所 | A kind of preparation method of integrated composite membrane used 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 |
| CN109758917A (en) * | 2018-09-18 | 2019-05-17 | 张伟 | A kind of preparation method of bivalent cation selective 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 |
| CN113544886A (en) * | 2019-03-08 | 2021-10-22 | 旭化成株式会社 | Electrolyte membrane for redox flow battery, and method for producing electrolyte membrane |
| TWI766614B (en) * | 2020-04-24 | 2022-06-01 | 日商旭化成股份有限公司 | Redox flow battery separator, method for producing redox flow battery separator, redox flow battery separator electrode assembly, redox flow battery cell, and redox flow battery |
| CN114976165A (en) * | 2022-06-17 | 2022-08-30 | 上海恩捷新材料科技有限公司 | Composite ion exchange membrane and preparation method thereof |
| CN117199465A (en) * | 2023-11-07 | 2023-12-08 | 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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| CN106972186A (en) * | 2016-01-14 | 2017-07-21 | 中国科学院金属研究所 | It is used for all-vanadium redox flow battery that there is catalysis to be combined membrane preparation method to positive and negative electrode |
| 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 |
| CN108461787A (en) * | 2017-02-17 | 2018-08-28 | 中国科学院金属研究所 | A kind of preparation method of integrated composite membrane used 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 |
| CN109758917A (en) * | 2018-09-18 | 2019-05-17 | 张伟 | A kind of preparation method of bivalent cation selective ion exchange membrane |
| CN113544886A (en) * | 2019-03-08 | 2021-10-22 | 旭化成株式会社 | Electrolyte membrane for redox flow battery, and method for producing electrolyte membrane |
| TWI766614B (en) * | 2020-04-24 | 2022-06-01 | 日商旭化成股份有限公司 | Redox flow battery separator, method for producing redox flow battery separator, redox flow battery separator electrode assembly, redox flow battery cell, and redox flow battery |
| CN114976165A (en) * | 2022-06-17 | 2022-08-30 | 上海恩捷新材料科技有限公司 | Composite ion exchange membrane and preparation method thereof |
| 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 |
| CN117199465A (en) * | 2023-11-07 | 2023-12-08 | 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 |
| 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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