CN103012826A - Preparing process for polyvinylidene fluoride compound membrane for vanadium battery - Google Patents
Preparing process for polyvinylidene fluoride compound membrane for vanadium battery Download PDFInfo
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Abstract
The invention relates to the preparation field of ion exchange membranes for all-vanadium redox flow batteries, in particular to a preparing process for a polyvinylidene fluoride compound membrane for a vanadium battery. The preparation process comprises the steps as follows: polyvinylidene fluoride is subjected to alkali treatment to obtain alkalized polyvinylidene fluoride, alkalized polyvinylidene fluoride and monomers with sulfonic acid groups are respectively dissolved in a solvent to prepare uniform solutions, a spraying method is adopted to prepare multiple layers of compound diaphragms, a base polyvinylidene fluoride membrane is in the middle, and two sides are sprayed with substances with the sulfonic acid groups to be taken as conducting layers. The prepared ion exchange membrane for the vanadium battery overcomes the defects that a perfluorosulfonic acid ion exchange membrane is large in swelling deformation and high in price and the like. The ion exchange membrane prepared by the process has the characteristics of good mechanical stability and low price and is suitable for being applied to the all-vanadium redox flow batteries.
Description
Technical field
The present invention relates to used for all-vanadium redox flow battery ion-exchange membrane preparation field, particularly a kind of preparation technology who can be used for the poly-vinylidene-fluoride composite film of vanadium cell.
Background technology
Sustainable development has become the theme of the world today, and the development of novel energy industry enjoys countries in the world to pay close attention to.Large-scale develop and utilize renewable energy source both at home and abroad and obtained important breakthrough, such as wind energy, sun power, sea energy etc.Factor affecting is larger but these novel energies are subjected to weather environment etc., can not guarantee the output of continous-stable in power generation process, in the development and use of new forms of energy, and the storage of energy and transform into the key of its development of restriction.
That has used in energy storage technology at present, mainly contains draw water energy storage and chemical storage batteries energy storage.Wherein, chemical energy storage is not because being used widely by geographic restrictions.In the chemical storage batteries energy storage, vanadium flow battery is unique a kind of elementary composition battery system of the same race that uses in numerous chemical power sources, it realizes storage and the release of electric energy by the mutual conversion between the different valence state vanadium ion, avoided the inhomogeneity active substance between battery plus-negative plate, to interpenetrate the crossed contamination of generation, and has long service life, the manufacturing scale is large, and the advantages such as specific energy height have very large using value in the energy storage field.
The key components of all-vanadium flow battery mainly contain electrode, bipolar plates, ion-exchange membrane and electrolytic solution, ion-exchange membrane plays in vanadium cell and intercepts electrolytic solution between positive and negative electrode, the while conducting ion, form the effect of cell circuit, requirement has that resistance vanadium performance is good, and resistance is little, and physical strength is high, the features such as the resistance to chemical attack oxidation resistent susceptibility is good are one of critical materials in the all-vanadium flow battery.At present, the vanadium cell barrier film adopts the perfluorinated sulfonic acid ionic membrane more, because it has good electric chemical property and stability, but its resistance vanadium performance is bad, so that the self-discharge phenomenon of battery improves, causes power loss, swelling set is large, affect the assembling sealing of vanadium cell, and it is expensive, is unfavorable for the commercial applications of vanadium cell.Therefore, develop a kind of cheap, deformation is little, resistance vanadium performance is good ion-exchange membrane the commercial applications of vanadium cell is played very important application.
Summary of the invention
The object of the present invention is to provide a kind of preparation technology who can be used for the poly-vinylidene-fluoride composite film of vanadium cell, the ion-exchange membrane for preparing with this method has good mechanical stability, and cheap characteristics are fit to be applied in the all-vanadium flow battery.
Technical scheme of the present invention is:
A kind of preparation technology who can be used for the poly-vinylidene-fluoride composite film of vanadium cell comprises following steps:
(1) polyvinylidene fluoride resin is processed with alkaline solution, obtained the polyvinylidene fluoride resin that alkalizes, clean and oven dry with deionized water;
(2) the alkalization polyvinylidene fluoride resin that obtains in (1) is dissolved in the organic solvent, strength of solution 3 ~ 20wt%, with curtain coating, knifing or the spraying method solid surface film forming in cleaning, the polyvinylidene difluoride (PVDF) basement membrane is made in oven dry, oven dry metacneme thickness 20 ~ 80 μ m;
The monomer that (3) will contain sulfonic acid group is dissolved in organic solvent or the water, and strength of solution 15 ~ 30wt% is sprayed at the two sides of polyvinylidene difluoride (PVDF) basement membrane, places the baking oven oven dry to obtain poly-vinylidene-fluoride composite film, sulphonic layer thickness 5 ~ 25 μ m of every one side.
In the step (1), alkaline solution is sodium hydroxide solution or potassium hydroxide solution, and concentration is 0.5 ~ 1.5mol/L, and temperature of reaction is 30 ~ 80 ℃, and the reaction times is 5 ~ 60min.
Among the present invention, organic solvent is the one or more kinds of mixtures in dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE, the N-Methyl pyrrolidone.
In the step (2), the film-forming temperature of polyvinylidene difluoride (PVDF) basement membrane is 80 ~ 160 ℃.
In the step (3), the monomer that contains sulfonic acid group is one or more the mixture in polystyrolsulfon acid, sodium allyl sulfonate, the methylpropene sodium sulfonate.
Can add initiator in the described solution of step (3), the mass percent that the add-on of initiator accounts for the sulfonic acid group monomer is 0.5 ~ 2%.
Among the present invention, initiator is one or more the mixture in the special butyl ester of peroxidation two acyls, benzoyl peroxide, benzoyl peroxide formic acid, the peroxy dicarbonate diethyl ethyl phosphonate.
In the step (3), the bake out temperature of sulphonic layer is 40 ~ 80 ℃.
Advantage of the present invention and beneficial effect are:
1, the present invention selects polyvinylidene fluoride resin as the skeleton of film, and polyvinylidene difluoride (PVDF) is carried out alkalinisation treatment make it to generate carbon-carbon double bond, select the material that contains sulfonic acid group with ionicconductive function as modified material, add initiator make contain the polymerization of sulfonic acid group material and with alkalinisation treatment after the crosslinked barrier film with ion exchanging function of preparing of polyvinylidene difluoride (PVDF).This barrier film had both had the good chemical stability of polyvinylidene difluoride (PVDF) and mechanical stability, and contained sulfonic acid group has ionic conductivity, greatly reduced the internal resistance of film.
2, film-forming method of the present invention is simple for process, realize easily commercially producing, compare than perfluorinated sulfonic acid ion exchange membrane, the prepared barrier film mechanical stability of the present invention is better, cost reduces greatly, for the large-scale commercial applications development of vanadium flow battery provides the foundation.
Embodiment
Embodiment 1
Polyvinylidene fluoride resin is infiltrated in the potassium hydroxide solution of 1mol/L, and 60 ℃ of lower 10min that soak take out with deionized water and clean, and put into 80 ± 2 ℃ of baking ovens and dry to get the alkalization polyvinylidene difluoride (PVDF).The polyvinylidene difluoride (PVDF) that will alkalize is dissolved in and prepares homogeneous solution in the dimethyl formamide, strength of solution 20wt%, and casting film-forming on the sheet glass of cleaning is dried in 140 ℃ of baking ovens, film thickness 30 μ m after the oven dry.Methylpropene sodium sulfonate is dissolved in the dimethyl sulfoxide (DMSO), and strength of solution 18wt% sprays to the two sides of polyvinylidene difluoride (PVDF) basement membrane, 16h oven dry film forming in 50 ℃ of baking ovens, single face sulphonic layer thickness 15 μ m, composite membrane thickness 60 μ m.
Use the ion-exchange membrane assembling vanadium flow battery of present embodiment preparation, at 70mA/cm
2Carry out charge-discharge test under the current density, internal resistance of cell 41.2m Ω, enclosed pasture efficient is 88.7%, and energy efficiency is 74.8%, and voltage efficiency is 84.3%.
Embodiment 2
Polyvinylidene fluoride resin is infiltrated in the potassium hydroxide solution of 1mol/L, and 45 ℃ of lower 25min that soak take out with deionized water and clean, and put into 80 ± 2 ℃ of baking ovens and dry to get the alkalization polyvinylidene difluoride (PVDF).The polyvinylidene difluoride (PVDF) that will alkalize is dissolved in and prepares homogeneous solution in the dimethyl formamide, strength of solution 20wt%, and casting film-forming on the sheet glass of cleaning is dried in 140 ℃ of baking ovens, film thickness 40 μ m after the oven dry.Methylpropene sodium sulfonate is dissolved in the dimethyl sulfoxide (DMSO), and strength of solution 18wt% sprays to the two sides of polyvinylidene difluoride (PVDF) basement membrane, 16h oven dry film forming in 50 ℃ of baking ovens, single face sulphonic layer thickness 10 μ m, composite membrane thickness 60 μ m.
Use the ion-exchange membrane assembling vanadium flow battery of present embodiment preparation, at 70mA/cm
2Carry out charge-discharge test under the current density, internal resistance of cell 45.8m Ω, enclosed pasture efficient is 92.9%, and energy efficiency is 77.7%, and voltage efficiency is 83.6%.
Embodiment 3
Polyvinylidene fluoride resin is infiltrated in the potassium hydroxide solution of 1mol/L, and 60 ℃ of lower 10min that soak take out with deionized water and clean, and put into 80 ± 2 ℃ of baking ovens and dry to get the alkalization polyvinylidene difluoride (PVDF).The polyvinylidene difluoride (PVDF) that will alkalize is dissolved in and prepares homogeneous solution in the dimethyl formamide, strength of solution 20wt%, and casting film-forming on the sheet glass of cleaning is dried in 140 ℃ of baking ovens, film thickness 30 μ m after the oven dry.Sodium allylsulfonate is dissolved in the dimethyl sulfoxide (DMSO), strength of solution 18wt%, add and account for the benzoyl peroxide of sodium allylsulfonate massfraction 1% as initiator, stir and spray to the two sides of polyvinylidene difluoride (PVDF) basement membrane, 8h oven dry film forming in 80 ℃ of baking ovens, single face sulphonic layer thickness 15 μ m, composite membrane thickness 60 μ m.
Use the ion-exchange membrane assembling vanadium flow battery of present embodiment preparation, at 70mA/cm
2Carry out charge-discharge test under the current density, internal resistance of cell 39.2m Ω, enclosed pasture efficient is 88.3%, and energy efficiency is 76.4%, and voltage efficiency is 86.5%.
Embodiment 4
Polyvinylidene fluoride resin is infiltrated in the potassium hydroxide solution of 1mol/L, and 60 ℃ of lower 10min that soak take out with deionized water and clean, and put into 80 ± 2 ℃ of baking ovens and dry to get the alkalization polyvinylidene difluoride (PVDF).The polyvinylidene difluoride (PVDF) that will alkalize is dissolved in and prepares homogeneous solution in the dimethyl formamide, strength of solution 20wt%, and casting film-forming on the sheet glass of cleaning is dried in 140 ℃ of baking ovens, film thickness 40 μ m after the oven dry.Methylpropene sodium sulfonate is dissolved in the water, strength of solution 30wt%, add and account for the benzoyl peroxide of methylpropene sodium sulfonate massfraction 1% as initiator, stir and spray to the two sides of polyvinylidene difluoride (PVDF) basement membrane, 8h oven dry film forming in 80 ℃ of baking ovens, single face sulphonic layer thickness 10 μ m, composite membrane thickness 60 μ m.
Use the ion-exchange membrane assembling vanadium flow battery of present embodiment preparation, at 70mA/cm
2Carry out charge-discharge test under the current density, internal resistance of cell 46.2m Ω, enclosed pasture efficient is 91.7%, and energy efficiency is 77.4%, and voltage efficiency is 84.4%.
Embodiment 5
Polyvinylidene fluoride resin is infiltrated in the potassium hydroxide solution of 1mol/L, and 60 ℃ of lower 10min that soak take out with deionized water and clean, and put into 80 ± 2 ℃ of baking ovens and dry to get the alkalization polyvinylidene difluoride (PVDF).The polyvinylidene difluoride (PVDF) that will alkalize is dissolved in and prepares homogeneous solution in the dimethyl sulfoxide (DMSO), strength of solution 20wt%, and casting film-forming on the sheet glass of cleaning is dried in 140 ℃ of baking ovens, film thickness 50 μ m after the oven dry.Methylpropene sodium sulfonate is dissolved in the water, strength of solution 20wt%, add and account for the benzoyl peroxide of methylpropene sodium sulfonate massfraction 2% as initiator, stir and spray to the two sides of polyvinylidene difluoride (PVDF) basement membrane, 8h oven dry film forming in 80 ℃ of baking ovens, single face sulphonic layer thickness 5 μ m, composite membrane thickness 60 μ m.
Use the ion-exchange membrane assembling vanadium flow battery of present embodiment preparation, at 70mA/cm
2Carry out charge-discharge test under the current density, internal resistance of cell 56m Ω, enclosed pasture efficient is 95.8%, and energy efficiency is 78.1%, and voltage efficiency is 81.5%.
Embodiment 6
Polyvinylidene fluoride resin is infiltrated in the potassium hydroxide solution of 1mol/L, and 60 ℃ of lower 10min that soak take out with deionized water and clean, and put into 80 ± 2 ℃ of baking ovens and dry to get the alkalization polyvinylidene difluoride (PVDF).The polyvinylidene difluoride (PVDF) that will alkalize is dissolved in and prepares homogeneous solution in the dimethyl sulfoxide (DMSO), strength of solution 20wt%, and casting film-forming on the sheet glass of cleaning is dried in 140 ℃ of baking ovens, film thickness 70 μ m after the oven dry.Sodium allylsulfonate is dissolved in the water, strength of solution 30wt%, add and account for the benzoyl peroxide of sodium allylsulfonate massfraction 1% as initiator, stir and spray to the two sides of polyvinylidene difluoride (PVDF) basement membrane, 6h oven dry film forming in 80 ℃ of baking ovens, single face sulphonic layer thickness 5 μ m, composite membrane thickness 80 μ m.
Use the ion-exchange membrane assembling vanadium flow battery of present embodiment preparation, at 70mA/cm
2Carry out charge-discharge test under the current density, internal resistance of cell 98m Ω, enclosed pasture efficient is 96.0%, and energy efficiency is 69.7%, and voltage efficiency is 72.6%.
Embodiment 7
Polyvinylidene fluoride resin is infiltrated in the sodium hydroxide solution of 1.5mol/L, and 60 ℃ of lower 30min that soak take out with deionized water and clean, and put into 80 ± 2 ℃ of baking ovens and dry to get the alkalization polyvinylidene difluoride (PVDF).The polyvinylidene difluoride (PVDF) that will alkalize is dissolved in and prepares homogeneous solution in the N,N-DIMETHYLACETAMIDE, strength of solution 20wt%, and knifing on the sheet glass of cleaning is dried in 140 ℃ of baking ovens, film thickness 70 μ m after the oven dry.Styrene sulfonic acid is dissolved in the N,N-DIMETHYLACETAMIDE, strength of solution 20wt%, add and account for the benzoyl peroxide of styrene sulfonic acid massfraction 2% as initiator, stir and spray to the two sides of polyvinylidene difluoride (PVDF) basement membrane, 6h oven dry film forming in 80 ℃ of baking ovens, single face sulphonic layer thickness 10 μ m, composite membrane thickness 90 μ m.
Use the ion-exchange membrane assembling vanadium flow battery of present embodiment preparation, at 70mA/cm
2Carry out charge-discharge test under the current density, internal resistance of cell 79m Ω, enclosed pasture efficient is 96.2%, and energy efficiency is 75.6%, and voltage efficiency is 78.6%.
Embodiment result shows, the present invention carries out alkaline purification with polyvinylidene difluoride (PVDF) and obtains the polyvinylidene difluoride (PVDF) that alkalizes, alkalization polyvinylidene difluoride (PVDF) and monomer with sulfonic acid group be dissolved in respectively make homogeneous solution in the solvent, method with spraying prepares the MULTILAYER COMPOSITE barrier film, the centre is the polyvinylidene difluoride (PVDF) basement membrane, the two sides spraying has the material of sulfonic acid group as conductive layer, acquisition can be used for the ion-exchange membrane of vanadium cell, it is large to have overcome the perfluorinated sulfonic acid ion exchange membrane swelling set, the shortcoming such as expensive, the advantages such as it is simple to have technological process, with low cost.
Claims (8)
1. a preparation technology who can be used for the poly-vinylidene-fluoride composite film of vanadium cell is characterized in that, comprises following steps:
(1) polyvinylidene fluoride resin is processed with alkaline solution, obtained the polyvinylidene fluoride resin that alkalizes, clean and oven dry with deionized water;
(2) the alkalization polyvinylidene fluoride resin that obtains in (1) is dissolved in the organic solvent, strength of solution 3 ~ 20wt%, with curtain coating, knifing or the spraying method solid surface film forming in cleaning, the polyvinylidene difluoride (PVDF) basement membrane is made in oven dry, oven dry metacneme thickness 20 ~ 80 μ m;
The monomer that (3) will contain sulfonic acid group is dissolved in organic solvent or the water, and strength of solution 15 ~ 30wt% is sprayed at the two sides of polyvinylidene difluoride (PVDF) basement membrane, places the baking oven oven dry to obtain poly-vinylidene-fluoride composite film, sulphonic layer thickness 5 ~ 25 μ m of every one side.
2. according to the right 1 described preparation technology who can be used for the poly-vinylidene-fluoride composite film of vanadium cell, it is characterized in that, in the step (1), alkaline solution is sodium hydroxide solution or potassium hydroxide solution, concentration is 0.5 ~ 1.5mol/L, and temperature of reaction is 30 ~ 80 ℃, and the reaction times is 5 ~ 60min.
3. according to the right 1 described preparation technology who can be used for the poly-vinylidene-fluoride composite film of vanadium cell, it is characterized in that described organic solvent is the one or more kinds of mixtures in dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE, the N-Methyl pyrrolidone.
4. according to the right 1 described preparation technology who can be used for the poly-vinylidene-fluoride composite film of vanadium cell, it is characterized in that in the step (2), the film-forming temperature of polyvinylidene difluoride (PVDF) basement membrane is 80 ~ 160 ℃.
5. according to the right 1 described preparation technology who can be used for the poly-vinylidene-fluoride composite film of vanadium cell, it is characterized in that, in the step (3), the monomer that contains sulfonic acid group is one or more the mixture in polystyrolsulfon acid, sodium allyl sulfonate, the methylpropene sodium sulfonate.
6. according to the right 1 described preparation technology who can be used for the poly-vinylidene-fluoride composite film of vanadium cell, it is characterized in that add initiator in the described solution of step (3), the mass percent that the add-on of initiator accounts for the sulfonic acid group monomer is 0.5 ~ 2%.
7. according to the right 6 described preparation technologies that can be used for the poly-vinylidene-fluoride composite film of vanadium cell, it is characterized in that described initiator is one or more the mixture in the special butyl ester of peroxidation two acyls, benzoyl peroxide, benzoyl peroxide formic acid, the peroxy dicarbonate diethyl ethyl phosphonate.
8. according to the right 1 described preparation technology who can be used for the poly-vinylidene-fluoride composite film of vanadium cell, it is characterized in that in the step (3), the bake out temperature of sulphonic layer is 40 ~ 80 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103223304A (en) * | 2013-04-24 | 2013-07-31 | 浙江大学宁波理工学院 | Polyvinylidene fluoride/polyalkenes sulfonate cation exchange alloy membrane preparation method |
| CN107629366A (en) * | 2017-11-02 | 2018-01-26 | 宝应县润华静电涂装工程有限公司 | A kind of preparation method of perfluorinated ionic membrane |
| CN111718505A (en) * | 2020-06-24 | 2020-09-29 | 常州大学 | Sulfonated polyether-ether-ketone/polyvinylidene fluoride composite ion exchange membrane for all-vanadium redox flow battery and preparation method thereof |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1224730A (en) * | 1998-07-20 | 1999-08-04 | 天津纺织工学院膜天膜技术工程公司 | Method of producing composite porous polymetafluoroethylene film |
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- 2012-12-18 CN CN201210552089.3A patent/CN103012826B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1224730A (en) * | 1998-07-20 | 1999-08-04 | 天津纺织工学院膜天膜技术工程公司 | Method of producing composite porous polymetafluoroethylene film |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103223304A (en) * | 2013-04-24 | 2013-07-31 | 浙江大学宁波理工学院 | Polyvinylidene fluoride/polyalkenes sulfonate cation exchange alloy membrane preparation method |
| CN107629366A (en) * | 2017-11-02 | 2018-01-26 | 宝应县润华静电涂装工程有限公司 | A kind of preparation method of perfluorinated ionic membrane |
| CN111718505A (en) * | 2020-06-24 | 2020-09-29 | 常州大学 | Sulfonated polyether-ether-ketone/polyvinylidene fluoride composite ion exchange membrane for all-vanadium redox flow battery and preparation method thereof |
| CN111718505B (en) * | 2020-06-24 | 2022-12-16 | 常州大学 | Sulfonated polyether-ether-ketone/polyvinylidene fluoride composite ion exchange membrane for all-vanadium redox flow battery and preparation method thereof |
| 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 |
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