CN103012826B - 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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- CN103012826B CN103012826B CN201210552089.3A CN201210552089A CN103012826B CN 103012826 B CN103012826 B CN 103012826B CN 201210552089 A CN201210552089 A CN 201210552089A CN 103012826 B CN103012826 B CN 103012826B
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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 ion-exchange membrane preparation field used for all-vanadium redox flow battery, particularly a kind of preparation technology of the poly-vinylidene-fluoride composite film that can be used for 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, as wind energy, sun power, sea energy etc.But it is larger that these novel energies are affected by the factors such as weather environment, in power generation process, can not ensure the output of continous-stable, in the exploitation of new forms of energy, the storage of energy and transform into restriction its development key.
That in energy storage technology, has applied at present, mainly contains draw water energy storage and chemical storage batteries energy storage.Wherein, chemical energy storage is used widely because of without geographical constraints.In 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 different valence state vanadium ion, avoid inhomogeneity active substance between battery plus-negative plate, to interpenetrate the crossed contamination of generation, and there is long service life, the advantages such as manufacture scale is large, specific energy height, have very large using value in 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 and intercepts electrolytic solution between positive and negative electrode in vanadium cell, conducting ion simultaneously, 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 resistance to chemical attack oxidation resistent susceptibility is good are one of critical materials in all-vanadium flow battery.At present, vanadium cell barrier film adopts perfluorinated sulfonic acid ionic membrane more, because it has good electric chemical property and stability, but its resistance vanadium performance is bad, the self-discharge phenomenon of battery is improved, cause 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 good ion-exchange membrane plays very important application to the commercial applications of vanadium cell.
Summary of the invention
The object of the present invention is to provide a kind of preparation technology of the poly-vinylidene-fluoride composite film that can be used for vanadium cell, the ion-exchange membrane of preparing by this method has good mechanical stability, and cheap feature is applicable to being applied in all-vanadium flow battery.
Technical scheme of the present invention is:
A 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 dry with deionized water;
(2) the alkalization polyvinylidene fluoride resin obtaining in (1) is dissolved in organic solvent, strength of solution 3 ~ 20wt%,, dry and make polyvinylidene difluoride (PVDF) basement membrane in clean solid surface film forming with curtain coating, knifing or spraying method, dry metacneme thickness 20 ~ 80 μ m;
(3) monomer that contains sulfonic acid group is dissolved in organic solvent or water, strength of solution 15 ~ 30wt%, is sprayed at the two sides of polyvinylidene difluoride (PVDF) basement membrane, is placed in baking oven and dries and obtain poly-vinylidene-fluoride composite film, sulphonic layer thickness 5 ~ 25 μ m of every one side.
In 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 DEG C, and the reaction times is 5 ~ 60min.
In the present invention, organic solvent is the one or more kinds of mixtures in dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone.
In step (2), the film-forming temperature of polyvinylidene difluoride (PVDF) basement membrane is 80 ~ 160 DEG C.
In step (3), the monomer that contains sulfonic acid group is one or more the mixture in polystyrolsulfon acid, sodium allyl sulfonate, methylpropene sodium sulfonate.
In the described solution of step (3), can add initiator, the mass percent that the add-on of initiator accounts for sulfonic acid group monomer is 0.5 ~ 2%.
In 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, peroxy dicarbonate diethyl ethyl phosphonate.
In step (3), the bake out temperature of sulphonic layer is 40 ~ 80 DEG C.
Advantage of the present invention and beneficial effect are:
1, the present invention selects the skeleton of polyvinylidene fluoride resin as film, and polyvinylidene difluoride (PVDF) is carried out to alkalinisation treatment make it to generate carbon-carbon double bond, select have ionicconductive function containing the material of sulfonic acid group as modified material, add initiator make containing 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 chemical stability and the mechanical stability that polyvinylidene difluoride (PVDF) is good, 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, easily realize and 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 development of vanadium flow battery provides the foundation.
Embodiment
Embodiment 1
Polyvinylidene fluoride resin is infiltrated in the potassium hydroxide solution of 1mol/L, soak 10min at 60 DEG C, take out with deionized water and clean, put into 80 ± 2 DEG C of baking ovens and dry and to obtain alkalization polyvinylidene difluoride (PVDF).Alkalization polyvinylidene difluoride (PVDF) is dissolved in dimethyl formamide and prepares homogeneous solution, strength of solution 20wt%, casting film-forming on clean sheet glass, dries in 140 DEG C of baking ovens, film thickness 30 μ m after drying.Methylpropene sodium sulfonate is dissolved in dimethyl sulfoxide (DMSO), and strength of solution 18wt%, sprays to the two sides of polyvinylidene difluoride (PVDF) basement membrane, and in 50 DEG C of baking ovens, 16h is dried film forming, one side sulphonic layer thickness 15 μ m, composite membrane thickness 60 μ m.
The ion-exchange membrane assembling vanadium flow battery that uses the present embodiment to prepare, at 70mA/cm
2under current density, carry out charge-discharge test, internal resistance of cell 41.2m Ω, coulomb efficiency 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, soak 25min at 45 DEG C, take out with deionized water and clean, put into 80 ± 2 DEG C of baking ovens and dry and to obtain alkalization polyvinylidene difluoride (PVDF).Alkalization polyvinylidene difluoride (PVDF) is dissolved in dimethyl formamide and prepares homogeneous solution, strength of solution 20wt%, casting film-forming on clean sheet glass, dries in 140 DEG C of baking ovens, film thickness 40 μ m after drying.Methylpropene sodium sulfonate is dissolved in dimethyl sulfoxide (DMSO), and strength of solution 18wt%, sprays to the two sides of polyvinylidene difluoride (PVDF) basement membrane, and in 50 DEG C of baking ovens, 16h is dried film forming, one side sulphonic layer thickness 10 μ m, composite membrane thickness 60 μ m.
The ion-exchange membrane assembling vanadium flow battery that uses the present embodiment to prepare, at 70mA/cm
2under current density, carry out charge-discharge test, internal resistance of cell 45.8m Ω, coulomb efficiency 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, soak 10min at 60 DEG C, take out with deionized water and clean, put into 80 ± 2 DEG C of baking ovens and dry and to obtain alkalization polyvinylidene difluoride (PVDF).Alkalization polyvinylidene difluoride (PVDF) is dissolved in dimethyl formamide and prepares homogeneous solution, strength of solution 20wt%, casting film-forming on clean sheet glass, dries in 140 DEG C of baking ovens, film thickness 30 μ m after drying.Sodium allylsulfonate is dissolved in dimethyl sulfoxide (DMSO), strength of solution 18wt%, add the benzoyl peroxide that accounts for sodium allylsulfonate massfraction 1% as initiator, stir and spray to the two sides of polyvinylidene difluoride (PVDF) basement membrane, in 80 DEG C of baking ovens, 8h is dried film forming, one side sulphonic layer thickness 15 μ m, composite membrane thickness 60 μ m.
The ion-exchange membrane assembling vanadium flow battery that uses the present embodiment to prepare, at 70mA/cm
2under current density, carry out charge-discharge test, internal resistance of cell 39.2m Ω, coulomb efficiency 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, soak 10min at 60 DEG C, take out with deionized water and clean, put into 80 ± 2 DEG C of baking ovens and dry and to obtain alkalization polyvinylidene difluoride (PVDF).Alkalization polyvinylidene difluoride (PVDF) is dissolved in dimethyl formamide and prepares homogeneous solution, strength of solution 20wt%, casting film-forming on clean sheet glass, dries in 140 DEG C of baking ovens, film thickness 40 μ m after drying.Methylpropene sodium sulfonate is dissolved in the water, strength of solution 30wt%, add the benzoyl peroxide that accounts for methylpropene sodium sulfonate massfraction 1% as initiator, stir and spray to the two sides of polyvinylidene difluoride (PVDF) basement membrane, in 80 DEG C of baking ovens, 8h is dried film forming, one side sulphonic layer thickness 10 μ m, composite membrane thickness 60 μ m.
The ion-exchange membrane assembling vanadium flow battery that uses the present embodiment to prepare, at 70mA/cm
2under current density, carry out charge-discharge test, internal resistance of cell 46.2m Ω, coulomb efficiency 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, soak 10min at 60 DEG C, take out with deionized water and clean, put into 80 ± 2 DEG C of baking ovens and dry and to obtain alkalization polyvinylidene difluoride (PVDF).Alkalization polyvinylidene difluoride (PVDF) is dissolved in dimethyl sulfoxide (DMSO) and prepares homogeneous solution, strength of solution 20wt%, casting film-forming on clean sheet glass, dries in 140 DEG C of baking ovens, film thickness 50 μ m after drying.Methylpropene sodium sulfonate is dissolved in the water, strength of solution 20wt%, add the benzoyl peroxide that accounts for methylpropene sodium sulfonate massfraction 2% as initiator, stir and spray to the two sides of polyvinylidene difluoride (PVDF) basement membrane, in 80 DEG C of baking ovens, 8h is dried film forming, one side sulphonic layer thickness 5 μ m, composite membrane thickness 60 μ m.
The ion-exchange membrane assembling vanadium flow battery that uses the present embodiment to prepare, at 70mA/cm
2under current density, carry out charge-discharge test, internal resistance of cell 56m Ω, coulomb efficiency 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, soak 10min at 60 DEG C, take out with deionized water and clean, put into 80 ± 2 DEG C of baking ovens and dry and to obtain alkalization polyvinylidene difluoride (PVDF).Alkalization polyvinylidene difluoride (PVDF) is dissolved in dimethyl sulfoxide (DMSO) and prepares homogeneous solution, strength of solution 20wt%, casting film-forming on clean sheet glass, dries in 140 DEG C of baking ovens, film thickness 70 μ m after drying.Sodium allylsulfonate is dissolved in the water, strength of solution 30wt%, add the benzoyl peroxide that accounts for sodium allylsulfonate massfraction 1% as initiator, stir and spray to the two sides of polyvinylidene difluoride (PVDF) basement membrane, in 80 DEG C of baking ovens, 6h is dried film forming, one side sulphonic layer thickness 5 μ m, composite membrane thickness 80 μ m.
The ion-exchange membrane assembling vanadium flow battery that uses the present embodiment to prepare, at 70mA/cm
2under current density, carry out charge-discharge test, internal resistance of cell 98m Ω, coulomb efficiency 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, soak 30min at 60 DEG C, take out with deionized water and clean, put into 80 ± 2 DEG C of baking ovens and dry and to obtain alkalization polyvinylidene difluoride (PVDF).Alkalization polyvinylidene difluoride (PVDF) is dissolved in N,N-DIMETHYLACETAMIDE and prepares homogeneous solution, strength of solution 20wt%, knifing on clean sheet glass, dries in 140 DEG C of baking ovens, film thickness 70 μ m after drying.Styrene sulfonic acid is dissolved in N,N-DIMETHYLACETAMIDE, strength of solution 20wt%, add the benzoyl peroxide that accounts for styrene sulfonic acid massfraction 2% as initiator, stir and spray to the two sides of polyvinylidene difluoride (PVDF) basement membrane, in 80 DEG C of baking ovens, 6h is dried film forming, one side sulphonic layer thickness 10 μ m, composite membrane thickness 90 μ m.
The ion-exchange membrane assembling vanadium flow battery that uses the present embodiment to prepare, at 70mA/cm
2under current density, carry out charge-discharge test, internal resistance of cell 79m Ω, coulomb efficiency 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 by polyvinylidene difluoride (PVDF) and obtains the polyvinylidene difluoride (PVDF) that alkalizes, alkalization polyvinylidene difluoride (PVDF) and the monomer with sulfonic acid group are dissolved in respectively and in solvent, make homogeneous solution, with spraying method prepare MULTILAYER COMPOSITE barrier film, centre is polyvinylidene difluoride (PVDF) basement membrane, two sides sprays the material with sulfonic acid group as conductive layer, acquisition can be used for the ion-exchange membrane of vanadium cell, overcome perfluorinated sulfonic acid ion exchange membrane swelling set large, the shortcoming such as expensive, there is technological process simple, the advantage such as with low cost.
Claims (4)
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 dry with deionized water;
(2) the alkalization polyvinylidene fluoride resin obtaining in (1) is dissolved in organic solvent, strength of solution 3 ~ 20wt%,, dry and make polyvinylidene difluoride (PVDF) basement membrane in clean solid surface film forming with curtain coating, knifing or spraying method, basement membrane thickness 20 ~ 80 μ m after drying;
(3) monomer that contains sulfonic acid group is dissolved in organic solvent or water, strength of solution 15 ~ 30wt%, is sprayed at the two sides of polyvinylidene difluoride (PVDF) basement membrane, is placed in baking oven and dries and obtain poly-vinylidene-fluoride composite film, sulphonic layer thickness 5 ~ 25 μ m of every one side;
In 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 DEG C, and the reaction times is 5 ~ 60min;
Organic solvent is the one or more kinds of mixtures in dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone;
In step (2), the film-forming temperature of polyvinylidene difluoride (PVDF) basement membrane is 80 ~ 160 DEG C;
In the described solution of step (3), add initiator, the mass percent that the add-on of initiator accounts for sulfonic acid group monomer is 0.5 ~ 2%.
2. according to the preparation technology of the poly-vinylidene-fluoride composite film that can be used for vanadium cell described in right 1, it is characterized in that, in step (3), the monomer that contains sulfonic acid group is one or more the mixture in styrene sulfonic acid, sodium allyl sulfonate, methylpropene sodium sulfonate.
3. according to the preparation technology of the poly-vinylidene-fluoride composite film that can be used for vanadium cell described in right 1, 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, peroxy dicarbonate diethyl ethyl phosphonate.
4. according to the preparation technology of the poly-vinylidene-fluoride composite film that can be used for vanadium cell described in right 1, it is characterized in that, in step (3), the bake out temperature of sulphonic layer is 40 ~ 80 DEG C.
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| 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 |
| 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 |
| 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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