CN1312788C - Proton exchange composite membrane for all vanadium redox flow battery and its preparing method - Google Patents
Proton exchange composite membrane for all vanadium redox flow battery and its preparing method Download PDFInfo
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- CN1312788C CN1312788C CNB2005100865479A CN200510086547A CN1312788C CN 1312788 C CN1312788 C CN 1312788C CN B2005100865479 A CNB2005100865479 A CN B2005100865479A CN 200510086547 A CN200510086547 A CN 200510086547A CN 1312788 C CN1312788 C CN 1312788C
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- 239000012528 membrane Substances 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims description 15
- 150000007524 organic acids Chemical class 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000002033 PVDF binder Substances 0.000 claims abstract description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 239000003495 polar organic solvent Substances 0.000 claims description 10
- 239000011256 inorganic filler Substances 0.000 claims description 9
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 5
- 210000002700 urine Anatomy 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 4
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 4
- 239000008240 homogeneous mixture Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims 3
- 239000000126 substance Substances 0.000 abstract description 7
- 229910001456 vanadium ion Inorganic materials 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000000149 penetrating effect Effects 0.000 abstract 1
- 230000035515 penetration Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 210000000352 storage cell Anatomy 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Fuel Cell (AREA)
Abstract
The present invention relates to a proton exchanging composite membrane for a full-vanadium redox flow battery, and a preparation method thereof. The proton exchanging composite membrane uses a polymetafluoroethylene membrane mixed with inorganic nano stuffing as a base body, organic acid containing sulfonic acid radicle is led into the base body then, and a target product is obtained by automatic polymerization. Organic and inorganic composite proton exchanging membranes of polyvinylidene fluoride made by the preparing method provided by the present invention have the advantages of excellent proton conducting performance, excellent vanadium ion preventing penetrating performance and chemical stability, simple preparing technology and low cost. The electric conductivity of the membranes can reach the magnitude of 0.01 S/cm, and the penetration rate of vanadium ions can reach the magnitude of 0.0000001 square centimeter /min.
Description
Technical field
The present invention relates to the redox flow batteries technology in the electrochemical field, proton exchange composite membrane that particularly a kind of vanadium redox battery is used and preparation method thereof.
Background technology
Vanadium redox battery is with the sulfuric acid solution of the different valence state vanadium ion novel energy storage cell as electrolyte.Proton exchange membrane (barrier film) is as one of vanadium redox battery critical material, and the quality of its performance directly influences the performance of battery.Vanadium redox battery is strong with corrosivity, the proton conductivity that proton exchange membrane requires to have anti-strong oxidizing property, anti-strong acid, and can stop characteristics such as different valence state vanadium ion infiltration effectively.The battery diaphragm that uses mainly contains cation-exchange membrane at present, once uses Selemion CMV, CMS, AMV, DMV, ASS, the DSV film of Asahi Glass company as people such as T.Mohammadi [Journal of Membrane science, 107 (35) 1995]; Dow XUSI 3204.10 films of U.S. Dow chemical company.But these films are degraded easily in the electrolyte of pentavalent vanadium, poor chemical stability.And people such as Skyllas-Kazacos report that the Nafion film of du pont company production has shown good chemical stability and proton conductive [Journal of Applied Electrochemistry, 27 (153) 1996], but there is the production cost height, to problem [the The Electrochemical Society such as obstructing capacity difference of vanadium ion, Honolulu, USA, Oct.1998, Proc.Vol.88-11, p363].Some vanadium cells of Yan Zhikaifaing have long-time stability with barrier film in recent years, but its price is still too high, are not suitable for extensive use [SEI Tech.ReV.45 (88) 1998].Therefore, good, the high-performance of development chemical stability, barrier film becomes one of key technology that improves the vanadium redox battery performance cheaply.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art and defective, proton exchange composite membrane for all vanadium redox flow battery and preparation method thereof is provided, make it have excellent proton conduction performance and good resistance vanadium ion permeance property, and chemical stability is good, cheap.
Technical scheme of the present invention is as follows:
A kind of proton exchange composite membrane for all vanadium redox flow battery, it is characterized in that: described proton exchange composite membrane is that the polyvinylidene fluoride film with the doping inorganic filler is a matrix, this matrix is polymerized with the organic acid that has sulfonate radical again, thickness is 50～400 microns, and preparation with the following method:
1) is 1～20: 1 mixing with Kynoar powder and inorganic filler by mass ratio, is dissolved in the non-polar organic solvent that be mixed with homogeneous mixture solotion, the concentration of mixed-powder in solvent is 0.05～0.3 grams per milliliter; Described inorganic filler is nano silicon oxide, zirconia, aluminium oxide, zinc oxide, molecular sieve or their mixture; Described non-polar organic solvent adopts dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), triethyl phosphate, cyclopentanone, N-methyl pyrrolidone, tetramethyl urine, propene carbonate or their mixture;
2) described mixed solution is heated in 50～150 ℃ water-bath and stir, obtain viscosity solution; Again this viscosity solution is cast on the glass plate and and dries film forming down, use washed with de-ionized water then at 60～100 ℃;
3) film after will cleaning immerses in 60～120 ℃ the organic acid that has sulfonate radical and soaked 5～24 hours, makes film enter in the film and autohemagglutination with wherein residual exchange of solvent, uses the acid of deionized water clean surface again, promptly obtains described proton exchange composite membrane.
The present invention also provides the preparation method of the proton exchange composite membrane that described vanadium redox battery uses, and this method is carried out as follows:
1) is 1～20: 1 mixing with Kynoar powder and inorganic filler by mass ratio, is dissolved in the non-polar organic solvent that be mixed with homogeneous mixture solotion, the concentration of mixed-powder in solvent is 0.05～0.3 grams per milliliter; Described inorganic filler is nano silicon oxide, zirconia, aluminium oxide, zinc oxide, molecular sieve or their mixture; Described non-polar organic solvent adopts dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), triethyl phosphate, cyclopentanone, N-methyl pyrrolidone, tetramethyl urine, propene carbonate or their mixture;
2) described mixed solution is heated in 50～150 ℃ water-bath and stir, obtain viscosity solution; Again this viscosity solution is cast on the glass plate and and dries film forming down, use washed with de-ionized water then at 60～100 ℃;
3) film after will cleaning immerses in 60～120 ℃ the organic acid that has sulfonate radical and soaked 5～24 hours, makes film enter in the film and autohemagglutination with wherein residual exchange of solvent, uses the acid of deionized water clean surface then, promptly obtains described proton exchange composite membrane.
The organic acid that has sulfonate radical of the present invention adopts vinyl sulfonic acid, styrene sulfonic acid, methacrylic acid sulfonic acid, allyl sulphonic acid, 2-acrylamide-2-methyl propane sulfonic acid or their mixture.
The present invention has following technique effect and high-lighting progress compared with prior art: the Kynoar proton exchange composite membrane that utilizes preparation method proposed by the invention to make has excellent proton conduction performance and good resistance vanadium ion permeance property, and its conductance reaches 10
-2The order of magnitude of S/cm; Because Kynoar has partially fluorinated carbon carbon skeleton structure, the proton exchange composite membrane that adopts this method to make has stable physical property and chemical property, and preparation technology of the present invention is simple simultaneously, and cost of material is cheap, system film cost is low, is suitable for large-scale production.
Description of drawings
Fig. 1 is the all-vanadium flow battery stable performance linearity curve of proton exchange composite membrane.
Fig. 2 is 60mA/cm for the all-vanadium flow battery of proton exchange composite membrane in current density
2The time charging and discharging curve.
Embodiment
Is 1～20: 1 mixing with Kynoar powder and inorganic filler by mass ratio, is dissolved in the non-polar organic solvent, stirs and makes it even; Described inorganic filler is nano silicon oxide, zirconia, aluminium oxide, zinc oxide, molecular sieve etc. or their mixture; Described non-polar organic solvent adopts dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), triethyl phosphate, cyclopentanone, N-methyl pyrrolidone, tetramethyl urine, propene carbonate or their mixture; Described mixed solution is heated in 50～100 ℃ water-bath and stir, general mixing time is 2～6 hours, obtains even viscosity solution; Again this viscosity solution is cast on the glass plate and and dries film forming down, use washed with de-ionized water then at 60～150 ℃; Soaked 5～24 hours in the organic acid that has sulfonate radical with 60～120 ℃ of the film immersions after cleaning, make film enter in the film and autohemagglutination, use the acid of deionized water clean surface then, promptly obtain described proton exchange composite membrane with wherein residual exchange of solvent.
Organic acid of the present invention adopts vinyl sulfonic acid, styrene sulfonic acid, methacrylic acid sulfonic acid, allyl sulphonic acid, 2-acrylamide-2-methyl propane sulfonic acid or their mixture.
The invention will be further described below by embodiment.
Embodiment 1:
30 gram Kynoar and the nano oxidized Si powder of 30 grams are dissolved in 500 milliliters of dimethylacetamide solvents.This mixed solution heated in 60 ℃ water-bath stir, obtain viscosity solution.This viscosity solution is cast on the glass plate and 60 ℃ of oven dry film forming down, with the film oven dry and in deionized water, clean.Soaked 5 hours in the styrene sulfonic acid liquid with 80 ℃ of this film immersions afterwards.Film is taken out, promptly obtain the composite membrane of Kynoar with the deionized water clean surface
Effect: under the room temperature condition, conductivity is 1.02 * 10
-2S/cm.
Embodiment 2:
25 gram Kynoar and 5 gram molecules sieve powder are dissolved in 100 milliliters of dimethyl sulfoxide solvents.This mixed solution heated in 80 ℃ water-bath stir, obtain viscosity solution.This viscosity solution is cast on the glass plate and 150 ℃ of oven dry film forming down, with the film oven dry and in deionized water, clean.Soaked 8 hours in 2-acrylamide-2-methyl propane sulfonic acid liquid with 70 ℃ of this film immersions afterwards.Film is taken out, promptly obtain the composite membrane of Kynoar with the deionized water clean surface
Effect: under the room temperature condition, conductivity is 2.04 * 10
-2S/cm.
Embodiment 3:
30 gram Kynoar and 3 gram nano aluminium oxide powder are dissolved in 200 milliliters of propylene carbonate solvents.This mixed solution heated in 50 ℃ water-bath stir, obtain viscosity solution.This viscosity solution is cast on the glass plate and 120 ℃ of oven dry film forming down, with the film oven dry and in deionized water, clean.Soaked 16 hours in the vinyl sulfonic acid azochlorosulfonate acid liquid with 60 ℃ of this film immersions afterwards.Film is taken out, promptly obtain the composite membrane of Kynoar with the deionized water clean surface
Effect: under the room temperature condition, conductivity is 3.05 * 10
-2S/cm.
Embodiment 4:
30 gram Kynoar and 10 gram nano zirconium oxide powders are dissolved in 600 milliliters of N-crassitude ketone solvents.This mixed solution heated in 100 ℃ water-bath stir, obtain viscosity solution.This viscosity solution is cast on the glass plate and 120 ℃ of oven dry film forming down, with the film oven dry and in deionized water, cleaned 10 minutes.Soaked 20 hours in the allyl sulphonic acid solution with 90 ℃ of this film immersions afterwards.Film is taken out, promptly obtain the composite membrane of Kynoar with the deionized water clean surface.
Effect: under the room temperature condition, conductivity is 3.19 * 10
-2S/cm charging and discharging currents density 60mA/cm
2The time, energy efficiency reaches 60%.
Embodiment 5:
30 gram Kynoar and 1.5 gram nano aluminium oxide powder are dissolved in the mixed solution of 300 milliliters of dimethyl formamides and propylene carbonate acid, and wherein both volume ratios are 1: 1.This mixed solution heated in 90 ℃ water-bath stir, obtain viscosity solution.This viscosity solution is cast on the glass plate and 100 ℃ of oven dry film forming down, with the film oven dry and in deionized water, clean.Soaked 24 hours in the allyl sulphonic acid solution with 120 ℃ of this film immersions afterwards.Film is taken out, promptly obtain the composite membrane of Kynoar with the deionized water clean surface.
Effect: under the room temperature condition, conductivity is 3.46 * 10
-2S/cm; Charging and discharging currents density 60mA/cm
2The time, discharge capacity can remain between 1400～1510mAh for a long time.(see figure 2), energy efficiency reaches 75%.(see figure 3)
Claims (3)
1. proton exchange composite membrane for all vanadium redox flow battery, it is characterized in that: described proton exchange composite membrane is that the polyvinylidene fluoride film with the doping inorganic nano-filler is a matrix, in matrix, introduce again and have the organic acid of sulfonate radical by being polymerized, thickness is 50～400 microns, and preparation with the following method:
1) is 1～20: 1 mixing with Kynoar powder and inorganic nano-filler by mass ratio, is dissolved in the non-polar organic solvent that be mixed with homogeneous mixture solotion, the concentration of mixed-powder in solvent is 0.05～0.3 grams per milliliter; Described inorganic nano-filler is nano silicon oxide, zirconia, aluminium oxide, zinc oxide, molecular sieve or their mixture; Described non-polar organic solvent adopts dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), triethyl phosphate, cyclopentanone, N-methyl pyrrolidone, tetramethyl urine, propene carbonate or their mixture;
2) described mixed solution is heated in 50～100 ℃ water-bath and stir, obtain viscosity solution; Again this viscosity solution is cast on the glass plate and and dries film forming down, use washed with de-ionized water then at 60～150 ℃;
3) film after will cleaning immerses in 60～120 ℃ the organic acid that has sulfonate radical and soaked 5～24 hours, make exchange of solvent residual in organic acid and the film and in film autohemagglutination, use the acid of deionized water clean surface again, promptly obtain described proton exchange composite membrane.
2. the preparation method of the proton exchange composite membrane used of a vanadium redox battery is characterized in that this method carries out as follows:
1) is 1～20: 1 mixing with Kynoar powder and inorganic filler by mass ratio, is dissolved in the non-polar organic solvent that be mixed with homogeneous mixture solotion, the concentration of mixed-powder in solvent is 0.05～0.3 grams per milliliter; Described inorganic filler is nano silicon oxide, zirconia, aluminium oxide, zinc oxide, molecular sieve; Described non-polar organic solvent adopts dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), triethyl phosphate, cyclopentanone, N-methyl pyrrolidone, tetramethyl urine, propene carbonate or their mixture;
2) described mixed solution is heated in 50～100 ℃ water-bath and stir, obtain viscosity solution; Again this viscosity solution is cast on the glass plate and and dries film forming down, use washed with de-ionized water then at 60～150 ℃;
3) film after will cleaning immerses in 60～120 ℃ the organic acid that has sulfonate radical and soaked 5～24 hours, makes film enter in the film and autohemagglutination with wherein residual exchange of solvent, uses the acid of deionized water clean surface then, promptly obtains described proton exchange composite membrane.
3. the preparation method of the proton exchange composite membrane of using according to the described vanadium redox battery of claim 2, it is characterized in that: the organic acid that has sulfonate radical described in the step 3) adopts vinyl sulfonic acid, styrene sulfonic acid, methacrylic acid sulfonic acid, allyl sulphonic acid, 2-acrylamide-2-methyl propane sulfonic acid or their mixture.
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Cited By (1)
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| WO2012075810A1 (en) * | 2010-12-10 | 2012-06-14 | 中国科学院大连化学物理研究所 | Use of porous membrane and composite membrane thereof in redox flow energy storage battery |
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| CN101383404B (en) * | 2007-09-05 | 2010-09-01 | 中国科学院大连化学物理研究所 | Fluorine/hydrocarbon composite ion exchange film and preparation thereof |
| CN101220161B (en) * | 2007-12-11 | 2010-06-30 | 天津商业大学 | Molecular sieve filling degradable polyalcohol group compound film and method for producing the same |
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| US9960443B2 (en) | 2010-09-28 | 2018-05-01 | Battelle Memorial Institute | Redox flow batteries having multiple electroactive elements |
| US8771856B2 (en) * | 2010-09-28 | 2014-07-08 | Battelle Memorial Institute | Fe-V redox flow batteries |
| US8628880B2 (en) | 2010-09-28 | 2014-01-14 | Battelle Memorial Institute | Redox flow batteries based on supporting solutions containing chloride |
| DE102012016317A1 (en) | 2012-08-14 | 2014-02-20 | Jenabatteries GmbH | Redox flow cell for storing electrical energy |
| AU2015328395B2 (en) | 2014-10-06 | 2020-05-07 | Battelle Memorial Institute | All-vanadium sulfate acid redox flow battery system |
| CN108075091B (en) * | 2016-11-18 | 2019-10-22 | 中国科学院金属研究所 | A kind of preparation method of functional porous polyvinylidene fluoride film used for all-vanadium redox flow battery |
| CN115939477B (en) * | 2023-03-13 | 2023-05-23 | 杭州德海艾科能源科技有限公司 | High proton transmission exchange membrane for vanadium battery and preparation method and application thereof |
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| EP0790658B1 (en) * | 1996-02-19 | 2000-11-02 | Kashima-Kita Electric Power Corporation | Redox flow cell battery with vanadium electrolyte and a polysulfone-based semipermeable membrane |
| JP2002200618A (en) * | 2000-12-28 | 2002-07-16 | Toyo Tire & Rubber Co Ltd | Mold for molding resin foam |
| CN1330425A (en) * | 2001-06-29 | 2002-01-09 | 清华大学 | Process for preparing proton exchange membrane of polymetafluoethyene grafted polystyrene sulfonate |
| CN1416186A (en) * | 2001-10-29 | 2003-05-07 | 中国科学院大连化学物理研究所 | Method for preparing complex film of proton exchange film for fuel cell |
| CN1598063A (en) * | 2003-09-18 | 2005-03-23 | 攀枝花钢铁有限责任公司钢铁研究院 | Process for electrolyzing preparing electrolyte of full vanadium ion flow battery |
| CN1585153A (en) * | 2004-06-11 | 2005-02-23 | 中山大学 | Modified proton exchanging film of direct alcohol fuel battery and preparing method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012075810A1 (en) * | 2010-12-10 | 2012-06-14 | 中国科学院大连化学物理研究所 | Use of porous membrane and composite membrane thereof in redox flow energy storage battery |
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