CN102024928A - Nafion ion exchange membrane used for enhanced vanadium redox battery and preparation method thereof - Google Patents
Nafion ion exchange membrane used for enhanced vanadium redox battery and preparation method thereof Download PDFInfo
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- CN102024928A CN102024928A CN2009101875673A CN200910187567A CN102024928A CN 102024928 A CN102024928 A CN 102024928A CN 2009101875673 A CN2009101875673 A CN 2009101875673A CN 200910187567 A CN200910187567 A CN 200910187567A CN 102024928 A CN102024928 A CN 102024928A
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- ion exchange
- sulfonic acid
- acid ion
- perfluorinated sulfonic
- exchange membrane
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- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 50
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 37
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920000557 Nafion® Polymers 0.000 title abstract 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 67
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 67
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 40
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 24
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000012779 reinforcing material Substances 0.000 claims abstract description 7
- 150000003460 sulfonic acids Chemical class 0.000 claims description 64
- 239000004744 fabric Substances 0.000 claims description 59
- 239000000463 material Substances 0.000 claims description 15
- 229920006361 Polyflon Polymers 0.000 claims description 12
- 239000003365 glass fiber Substances 0.000 claims description 12
- 238000005728 strengthening Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 238000000935 solvent evaporation Methods 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 30
- 230000004888 barrier function Effects 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
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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
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Abstract
The invention relates to the field of an ion exchange membrane used for a vanadium redox battery (VRB), in particular to a Nafion ion exchange membrane used for enhanced vanadium redox battery and a preparation method thereof. A Nafion ion exchange resin containing sulfonic group is taken as forming resin; the resin is dissolved into organic solvent to obtain forming solvent; and the Nafion ion exchange membrane is formed by the forming solvent; a layer of polytetrafluoroethylene mesh in the middle of the Nafion ion exchange membrane is taken as reinforcing material; or a layer of Nafion ion exchange membrane is arranged between two layers of polytetrafluoroethylene meshes. The membrane has high chemical stability and high current density, and compared with the Nafion membrane, the Nafion ion exchange membrane has higher mechanical strength, higher exchange capacity and lower cost, and the problems that the Nafion ion exchange membrane in the prior art has high exchange capacity and low mechanical strength or high mechanical strength and low exchange capacity are solved, and the Nafion ion exchange membrane is mainly applied to the vanadium redox battery (VRB).
Description
Technical field
The present invention relates to vanadium redox battery (VRB) and use the amberplex field, particularly a kind of enhancement mode vanadium cell perfluorinated sulfonic acid ion exchange membrane and preparation method thereof.
Background technology
Along with the national economy fast development, the contradiction between the energy, resource and environmental protection becomes increasingly conspicuous, and impels urgent the changing to regenerative resource of traditional energy resource system.
Adjust the current power energy resource structure, the exploitation scale utilizes renewable and clean energy resources such as wind energy, solar energy, has become the fundamental state policy of China's electric power energy development.Renewable energy power generation such as wind energy, solar energy process has discontinuous and unsettled characteristics, needs to be equipped with the electric power storage energy storage device, could realize continuous, stable electric energy output, to avoid that partial electric grid is produced the extensive serious accident of impacting and causing.Up to the present, in the new battery technology of worldwide being developed, vanadium redox battery (Redox flow cell) is the most promising beyond doubt, advantage such as this battery has that the use scale is big, the life-span is long, energy efficiency is high, environmental friendliness, current continuity are good, " peak load shifting " that can be implemented in the existing network system by the vanadium redox battery energy storage acts on, can relax imbalance between power supply and demand, improve the generating equipment utilance, reduce the thermal power generation energy consumption.
Vanadium redox battery is the H with V (II)/V (III) and V (IV)/V (V) oxidation-reduction pair
2SO
4Solution is made positive and negative half-cell electrolyte respectively.H
2SO
4Be ionized into H
+And SO
4 2-, H in the electrolyte then
+Continue the H in the replacement amberplex
+, and enter in another chamber electrolyte, finish conducting process.When discharge, the VO in the anode electrolyte
2 +Ion is reduced to VO
2+Ion, the V in the negative pole electrolyte
2+Ion is oxidized to V
3+Ion.When charging, process is just opposite.
The vanadium cell electrode reaction is as follows:
Anodal:
E
0=1.00V
Negative pole:
E
0=-0.26V
Vanadium cell develops into today, reached a more advanced level, but still there are many key issues to press for solution, wherein key material barrier film is exactly one of them, the vanadium cell septation has the positive and negative electrode of isolation electrolyte solution, stops the interpenetrative effect of different valence state vanadium ion, the cross pollution that prevents positive and negative electrode electrolyte improves ion selectivity, and proton can freely pass through, and the vanadium of different valence state is had high selectivity.Through a large amount of evidences, perfluorinated sulfonic acid ion exchange membrane has high chemical stability, high current density, ionic conduction resistance is little.Wherein, by Nafion117 barrier film various aspects of performance the best in numerous barrier films of company of Du group production, but this barrier film cost is more expensive; Though homemade barrier film cost is low, performance is not as good as the Nafion117 film.At present, all there is the exchange capacity height in perfluorinated sulfonic acid ion exchange membrane and mechanical strength is low, mechanical strength is high and problem that exchange capacity is low.And when utilizing wind energy, solar energy scale assembling area battery in actual applications, quite high to the requirement in useful life of barrier film mechanical strength and intensity, can existing perfluorinated sulfonic acid ion exchange membrane meet the demands and query.
Summary of the invention:
The purpose of this invention is to provide a kind of enhancement mode vanadium cell with perfluorinated sulfonic acid ion exchange membrane and preparation method thereof, solve that all there is the exchange capacity height in the perfluorinated sulfonic acid ion exchange membrane that exists in the prior art and mechanical strength is low, mechanical strength is high and problem that exchange capacity is low.This enhancement mode perfluorinated sulfonic acid ion exchange membrane is the barrier film that is applied to vanadium redox battery (VRB), compare with present perfluorinated sulfonic acid ion exchange membrane, promptly have high chemical stability, high current density, simultaneously can also satisfy high mechanical strength, high exchange capacity, and cost reduces.
Technical scheme of the present invention is:
A kind of enhancement mode vanadium cell perfluorinated sulfonic acid ion exchange membrane is a film-forming resin by the perfluorinated sulfonic acid ion exchange resin that contains sulfonic acid group, and resin dissolves obtains film forming solution in organic solvent, form perfluorinated sulfonic acid ion exchange membrane by film forming solution; In the middle of perfluorinated sulfonic acid ion exchange membrane, one deck polytetrafluoroethylene (PTFE) screen cloth is arranged as reinforcing material; Perhaps, one deck perfluorinated sulfonic acid ion exchange membrane is arranged in the middle of two-layer polytetrafluoroethylene (PTFE) screen cloth.
The film forming solution of described perfluorinated sulfonic acid ion exchange resin is by smearing, heat and strengthening the net strong bonded.
Described polytetrafluoroethylene (PTFE) screen cloth is that the employing glass fibre is that base material is woven into netted base cloth, applies polyflon again; The grid of screen cloth is 0.3 * 0.3mm-10 * 10mm, and thickness is 0.01mm-1.2mm.Wherein,
Polytetrafluoroethylene is the polymer of tetrafluoroethene.Basic structure is:
-CF2-CF2-CF2-CF2-CF2-CF2-CF2-CF2-CF2-CF2-。
The structure of perfluorinated sulfonic acid ion exchange resin is:
Wherein, X 〉=1, Y 〉=0, Z=0-3, n 〉=1, the exchange capacity of perfluorinated sulfonic acid ion exchange resin is IEC=0.67-1.3mmol/g.
The above-mentioned enhancement mode vanadium cell preparation method of perfluorinated sulfonic acid ion exchange membrane, concrete steps are as follows:
(1) perfluorinated sulfonic acid ion exchange resin (exchange capacity IEC=0.67-1.3mmol/g) is dissolved in the organic solvent by mass ratio w=5%-30%, reactor is heated to 110 ℃-250 ℃ insulation 1-4h dissolving resins, obtains even, limpid film forming solution.
Wherein, organic solvent is dimethylbenzene, N, dinethylformamide, N, N-dimethyl second formamide, dimethyl sulfoxide (DMSO) or N-base pyrrolidones.
(2) film forming solution of producing is shaken 30min-60min in the ultrasonic oscillation device, make solution refinement and expeling micro-bubble wherein.
(3) get of the mould top casting of a certain amount of film forming solution in cleaning, be heated to 100 ℃-120 ℃, constant temperature 1-2h, and then with smooth being placed on the film forming solution of polytetrafluoroethylene (PTFE) screen cloth, to be left film forming solution at last and spread upon on the polytetrafluoroethylene (PTFE) screen cloth, by heat 120 ℃-180 ℃, constant temperature 1-4h with solvent evaporation, be cooled to room temperature, the film that obtains cleans with distilled water, 50-70 ℃ of oven dry, the type vanadium cell of being enhanced perfluorinated sulfonic acid ion exchange membrane.
Perhaps, film forming solution is spread upon on one deck polytetrafluoroethylene screen cloth, on film forming solution, cover one deck polytetrafluoroethylene screen cloth again, by heat 120 ℃-180 ℃, constant temperature 1-4h with solvent evaporation, be cooled to room temperature, the film that obtains cleans with distilled water, 50-70 ℃ of oven dry, the type vanadium cell of being enhanced perfluorinated sulfonic acid ion exchange membrane.
Described mold materials is glass plate, aluminium sheet, corrosion resistant plate, polyfluortetraethylene plate or pvc material.
Among the present invention, mass fraction is that to prepare thickness be that 70 μ m, area are 165mm for 10% film forming solution 20ml
2Film, the thickness of adding the polytetrafluoroethylene (PTFE) screen cloth is the gross thickness of perfluorinated sulfonic acid ion exchange membrane.
Advantage of the present invention:
1. the present invention uses the reinforcing material of polytetrafluoroethylene (PTFE) screen cloth as perfluorinated sulfonic acid ion exchange membrane; can significantly improve the perfluorinated sulfonic acid ion exchange membrane mechanical strength; thereby when guaranteeing to utilize in actual applications wind energy, solar energy scale assembling large tracts of land all-vanadium flow battery; the mechanical strength and the useful life of suitable high request; to avoid in the assembled battery process or after operation a period of time; because of the barrier film mechanical strength causes the membrane ruptures phenomenon inadequately; destroy the operation of entire cell; thereby improve maintenance work, also promptly improve the battery cost battery.
2. present, perfluorinated sulfonic acid ion exchange membrane has the mechanical strength height, then the low problem of exchange capacity.Therefore, the present invention is because of using the reinforcing material of polytetrafluoroethylene (PTFE) screen cloth as perfluorinated sulfonic acid ion exchange membrane, can use the high perfluorinated sulfonic acid ion exchange resin of exchange capacity to be prepared into coating solution, make barrier film that high mechanical strength promptly be arranged, have simultaneously high exchange capacity again, improve the all-vanadium flow battery performance.
3. the present invention uses the reinforcing material of polytetrafluoroethylene (PTFE) screen cloth as perfluorinated sulfonic acid ion exchange membrane, under the situation that satisfies the diaphragm electrochemical performance, reduces the consumption of perfluorinated sulfonic acid ion exchange resin, and the cost for preparing barrier film like this reduces greatly.
Description of drawings
Fig. 1 is a kind of structural representation of enhancement mode vanadium cell of the present invention with perfluorinated sulfonic acid ion exchange membrane.
Fig. 2 is the another kind of structural representation of enhancement mode vanadium cell of the present invention with perfluorinated sulfonic acid ion exchange membrane.
Among the figure, 1 film; 2 polytetrafluoroethylene (PTFE) screen cloths.
Embodiment
Below by embodiment, and in conjunction with the accompanying drawings, technical scheme of the present invention is described in further detail.
(exchange capacity IEC=0.7mmol/g) is dissolved in 20ml N, N with 1.89g perfluorinated sulfonic acid ion exchange resin
2In-the dimethyl formamide (DMF), be heated to 140 ℃ of insulation 3h dissolving resins, obtain even, limpid film forming solution, as film forming solution at reactor.
At first, the film forming solution of producing is shaken 1h in the ultrasonic oscillation device, make solution refinement and expeling micro-bubble wherein.Then, get the mould top casting of 10ml film forming solution in cleaning, be heated to 100 ℃, constant temperature 1h is again with 2 smooth the placing on the film forming solution of polytetrafluoroethylene (PTFE) screen cloth.At last, remaining 10ml film forming solution is spread upon on the polytetrafluoroethylene (PTFE) screen cloth 2, be heated to 140 ℃, constant temperature 2h, naturally cool to room temperature, form a skim 1 respectively, the film that obtains is cleaned with distilled water on two surfaces of polytetrafluoroethylene (PTFE) screen cloth 2,60 ℃ of oven dry, the type that is enhanced vanadium cell perfluorinated sulfonic acid ion exchange membrane (Fig. 1).
In addition, can also get the 20ml film forming solution earlier spreads upon on one deck polytetrafluoroethylene (PTFE) screen cloth 2, on film forming solution, cover one deck polytetrafluoroethylene (PTFE) screen cloth 2 again, by being heated to 140 ℃, constant temperature 2h naturally cools to room temperature, and the film that obtains is cleaned with distilled water, 60 ℃ of oven dry, the type that is enhanced vanadium cell perfluorinated sulfonic acid ion exchange membrane (Fig. 2).
In the present embodiment, strengthening net is the polytetrafluoroethylene (PTFE) screen cloth, is that the employing glass fibre is that base material is woven into netted base cloth, applies polyflon again and makes.The grid of screen cloth is 0.3 * 0.3mm, and thickness is 0.03mm.
Basic identical with example 1, different is that 0.63g perfluorinated sulfonic acid ion exchange resin is dissolved in 6.67mlN, N
2In-the dimethyl formamide (DMF), as film forming solution.
In the present embodiment, strengthening net is the polytetrafluoroethylene (PTFE) screen cloth, is that the employing glass fibre is that base material is woven into netted base cloth, applies polyflon again and makes.The grid of screen cloth is 0.5 * 0.5mm, and thickness is 0.05mm.
Embodiment 3
Basic identical with example 1, different is that 2.83g perfluorinated sulfonic acid ion exchange resin is dissolved in 30ml N, N
2In-the dimethyl formamide (DMF), as film forming solution.
In the present embodiment, strengthening net is the polytetrafluoroethylene (PTFE) screen cloth, is that the employing glass fibre is that base material is woven into netted base cloth, applies polyflon again and makes.The grid of screen cloth is 1 * 1mm, and thickness is 0.1mm.
Embodiment 4
Basic identical with example 1, different is that 5.67g perfluorinated sulfonic acid ion exchange resin is dissolved in 60ml N, N
2In-the dimethyl formamide (DMF), as film forming solution.
In the present embodiment, strengthening net is the polytetrafluoroethylene (PTFE) screen cloth, is that the employing glass fibre is that base material is woven into netted base cloth, applies polyflon again and makes.The grid of screen cloth is 2 * 2mm, and thickness is 0.2mm.
Embodiment 5
Basic identical with example 1, different is that 1.89g perfluorinated sulfonic acid ion exchange resin is dissolved in 10ml N, N
2In-the dimethyl formamide (DMF), as film forming solution.
In the present embodiment, strengthening net is the polytetrafluoroethylene (PTFE) screen cloth, is that the employing glass fibre is that base material is woven into netted base cloth, applies polyflon again and makes.The grid of screen cloth is 0.3 * 0.3mm, and thickness is 0.03mm.
Embodiment 6
Basic identical with example 1, different is that 1.89g perfluorinated sulfonic acid ion exchange resin is dissolved in 30ml N, N
2In-the dimethyl formamide (DMF), as film forming solution.
In the present embodiment, strengthening net is the polytetrafluoroethylene (PTFE) screen cloth, is that the employing glass fibre is that base material is woven into netted base cloth, applies polyflon again and makes.The grid of screen cloth is 1 * 1mm, and thickness is 0.1mm.
Embodiment 7
Basic identical with example 1, different is that 1.89g perfluorinated sulfonic acid ion exchange resin is dissolved in 50ml N, N
2In-the dimethyl formamide (DMF), as film forming solution.
In the present embodiment, strengthening net is the polytetrafluoroethylene (PTFE) screen cloth, is that the employing glass fibre is that base material is woven into netted base cloth, applies polyflon again and makes.The grid of screen cloth is 2 * 2mm, and thickness is 0.2mm.
Embodiment 8
Basic identical with example 1, that different is the exchange capacity IEC=0.9mmol/g of perfluorinated sulfonic acid ion exchange resin.
In the present embodiment, strengthening net is the polytetrafluoroethylene (PTFE) screen cloth, is that the employing glass fibre is that base material is woven into netted base cloth, applies polyflon again and makes.The grid of screen cloth is 0.3 * 0.3mm, and thickness is 0.03mm.
Embodiment 9
Basic identical with example 1, that different is the exchange capacity IEC=1.1mmol/g of perfluorinated sulfonic acid ion exchange resin.
In the present embodiment, strengthening net is the polytetrafluoroethylene (PTFE) screen cloth, is that the employing glass fibre is that base material is woven into netted base cloth, applies polyflon again and makes.The grid of screen cloth is 1 * 1mm, and thickness is 0.1mm.
Embodiment 10
Basic identical with example 1, that different is the exchange capacity IEC=1.3mmol/g of perfluorinated sulfonic acid ion exchange resin.
In the present embodiment, strengthening net is the polytetrafluoroethylene (PTFE) screen cloth, is that the employing glass fibre is that base material is woven into netted base cloth, applies polyflon again and makes.The grid of screen cloth is 2 * 2mm, and thickness is 0.2mm.
The result shows, the present invention has one deck polytetrafluoroethylene (PTFE) screen cloth as one deck perfluorinated sulfonic acid ion exchange membrane is arranged in the middle of reinforcing material or the two-layer polytetrafluoroethylene (PTFE) screen cloth in the middle of perfluorinated sulfonic acid ion exchange membrane, can make amberplex promptly have high chemical stability, high current density, it is low to have mechanical strength height, exchange capacity height, cost again, can be applicable to vanadium redox battery (VRB).
Claims (8)
1. enhancement mode vanadium cell perfluorinated sulfonic acid ion exchange membrane, it is characterized in that: by the perfluorinated sulfonic acid ion exchange resin that contains sulfonic acid group is film-forming resin, resin dissolves obtains film forming solution in organic solvent, form perfluorinated sulfonic acid ion exchange membrane by film forming solution; In the middle of perfluorinated sulfonic acid ion exchange membrane, one deck polytetrafluoroethylene screen cloth is arranged as reinforcing material; Perhaps, one deck perfluorinated sulfonic acid ion exchange membrane is arranged in the middle of two-layer polytetrafluoroethylene screen cloth.
2. according to the described enhancement mode vanadium cell of claim 1 perfluorinated sulfonic acid ion exchange membrane, it is characterized in that: the film forming solution of described perfluorinated sulfonic acid ion exchange resin is by smearing, heat and strengthening the net strong bonded.
3. according to the described enhancement mode vanadium cell of claim 1 perfluorinated sulfonic acid ion exchange membrane, it is characterized in that: described polytetrafluoroethylene screen cloth is that the employing glass fibre is that base material is woven into netted base cloth, applies polyflon again; The grid of screen cloth is 0.3 * 0.3mm-10 * 10mm, and thickness is 0.01mm-1.2mm.
4. according to the described enhancement mode vanadium cell of claim 1 perfluorinated sulfonic acid ion exchange membrane, it is characterized in that: described polytetrafluoroethylene is the polymer of tetrafluoroethene, and basic structure is:
-CF2-CF2-CF2-CF2-CF2-CF2-CF2-CF2-CF2-CF2-。
5. according to the described enhancement mode vanadium cell of claim 1 perfluorinated sulfonic acid ion exchange membrane, it is characterized in that: the structure of described perfluorinated sulfonic acid ion exchange resin is:
Wherein, X 〉=1, Y 〉=0, Z=0-3, n 〉=1.
6. according to the described enhancement mode vanadium cell of claim 1 perfluorinated sulfonic acid ion exchange membrane, it is characterized in that: the exchange capacity of perfluorinated sulfonic acid ion exchange resin is IEC=0.67-1.3mmol/g.
7. according to the preparation method of the described enhancement mode vanadium cell of claim 1, it is characterized in that concrete steps are as follows with perfluorinated sulfonic acid ion exchange membrane:
(1) perfluorinated sulfonic acid ion exchange resin is dissolved in the organic solvent by mass ratio w=5%-30%, reactor is heated to 110 ℃-250 ℃ insulation 1-4h dissolving resins, obtains even, limpid film forming solution;
(2) film forming solution of producing is shaken 30min-60min in the ultrasonic oscillation device, make solution refinement and expeling micro-bubble wherein;
(3) get the mould top casting of film forming solution in cleaning, be heated to 80 ℃-120 ℃, constant temperature 1-2h, and then with smooth being placed on the film forming solution of polytetrafluoroethylene screen cloth, to be left film forming solution at last and spread upon on the polytetrafluoroethylene screen cloth, by heat 120 ℃-180 ℃, constant temperature 1-4h with solvent evaporation, be cooled to room temperature, the film that obtains cleans with distilled water, 50-70 ℃ of oven dry, the type vanadium cell of being enhanced perfluorinated sulfonic acid ion exchange membrane.
8. according to the preparation method of the described enhancement mode vanadium cell of claim 1, it is characterized in that concrete steps are as follows with perfluorinated sulfonic acid ion exchange membrane:
(1) perfluorinated sulfonic acid ion exchange resin is dissolved in the organic solvent by mass ratio w=5%-30%, reactor is heated to 110 ℃-250 ℃ insulation 1-4h dissolving resins, obtains even, limpid film forming solution;
(2) film forming solution of producing is shaken 30min-60min in the ultrasonic oscillation device, make solution refinement and expeling micro-bubble wherein;
(3) film forming solution is spread upon on one deck polytetrafluoroethylene screen cloth, on film forming solution, cover one deck polytetrafluoroethylene screen cloth again, by heat 120 ℃-180 ℃, constant temperature 1-4h with solvent evaporation, be cooled to room temperature, the film that obtains cleans with distilled water, 50-70 ℃ of oven dry, the type vanadium cell of being enhanced perfluorinated sulfonic acid ion exchange membrane.
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| CN103762375A (en) * | 2014-01-10 | 2014-04-30 | 清华大学深圳研究生院 | Polyfluortetraethylene sandwich layer protective ion exchange membrane, preparation method of membrane and liquid flow battery |
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