CN102867930A - Composite film for flow energy storage battery and application thereof - Google Patents
Composite film for flow energy storage battery and application thereof Download PDFInfo
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Abstract
The invention discloses a composite film for a flow energy storage battery and an application thereof. The composite film disclosed herein is characterized by using one or more than two of organic polymer resin as raw material to prepare a porous film as a matrix, and then compounding a layer of the organic resin on the surface of the porous matrix to prepare a compact film, wherein the organic resin comprises one or more than two of N-containing heterocyclic high-molecular polymers or high-molecular polymers containing amino functional group. According to the invention, the composite film disclosed herein uses a porous separator without ion-exchange group as matrix; by adding a layer of the compact positively charged film, the permselectivity of the porous separator on ions is further enhanced; the composite film disclosed herein has controllable aperture, is easy to realize batch production; and simultaneously, the variety and application range of porous membrane material for the flow energy storage battery are expanded.
Description
Technical field
The present invention relates to a kind of liquid flow energy storage battery polyelectrolyte diaphragm material, particularly a kind of liquid flow energy storage battery is with composite membrane and preparation method thereof, with and application in liquid flow energy storage battery.
Background technology
Liquid flow energy storage battery is a kind of electrochemical energy storage new technology, compare with other energy storage technology, have the energy conversion efficiency height, an advantage such as system is flexible, capacitance of storage is large, but the free deep discharge of addressing, safety and environmental protection, maintenance cost are low, can be widely used in the aspects such as the renewable energy power generation energy storage such as wind energy, solar energy, emergency power system, stand-by station and electric power system peak load shifting.All-vanadium liquid flow energy storage battery (Vanadium redox battery, VRB) because safe, good stability, efficient is high, the life-span is long (life-span＞15 year), low cost and other advantages, is considered to have most in the liquid flow energy storage battery prospect and representational a kind of liquid flow energy storage battery.
Battery diaphragm is the important component part in the liquid flow energy storage battery, and it plays and intercepts positive and negative electrode electrolyte, and the effect of proton transport passage is provided.The proton-conducting of film, chemical stability and ion selectivity etc. will directly affect chemical property and the useful life of battery; Therefore require film to have lower active material permeability (higher selectivity is namely arranged) and lower surface resistance (higher ionic conductance is namely arranged), also should have simultaneously preferably chemical stability and lower cost.The membrane material that uses both at home and abroad now mainly is the Nafion film of du pont company exploitation, the Nafion film has excellent performance at aspects such as chemical property and useful lifes, but because expensive, particularly be applied to exist in the all-vanadium liquid flow energy storage battery shortcoming such as ion selectivity is poor, thereby limited the industrial applications of this film.Therefore, exploitation has high selectivity, high stability and battery diaphragm is most important cheaply.
At present exploitation and the liquid flow energy storage battery barrier film that uses, be amberplex, be that membrane material is comprised of the polymer that contains ion-exchange group, mainly be divided into perfluorinated ion-exchange membrane, half fluorine ion exchange membrane and non-fluorine ion exchange membrane, because problems such as fluoropolymer membrane are expensive, and ion selectivity is poor, the researcher has carried out a large amount of research-and-development activitys for non-fluorine ion exchange membrane material, common non-fluorinated polymer is sulfonated poly aryl ether ketone, polyether sulphone, the materials such as polyimides.Wherein ion-exchange group plays a part transmission ion, isolation vanadium ion, and main polymer chain guarantees the mechanical performance of film.But to the non-fluorine ion exchange membrane of the overwhelming majority, the introducing of ion-exchange group greatly reduces the oxidation stability of film, has limited the useful life of film in VRB.
The film separation process sees through film as separating medium take selectivity, and when there was certain motive force (such as pressure differential, concentration difference, potential difference etc.) in the film both sides, feed side compositional selecting ground saw through film, with the purpose that reaches separation, purifies.The structure of diffusion barrier is generally the perforated film structure, and according to the size of membrane aperture, the molecule of different size can optionally see through film, thereby realizes the purpose of separating-purifying.The pore separation membrane that has used in the industry generally obtains by the method for inversion of phases, basic skills is that the solution with polymer is layered on dull and stereotyped upper (such as glass plate), then as required, with solvent evaporates a period of time, the non-solvent that flat board is immersed polymer solidifies in bathing, and forms the perforated film of polymer.
In all-vanadium liquid flow energy storage battery, vanadium ion and proton all exist with the form of hydrated ion.The stokes radius of pentavalent vanadium ion is greatly between 2.5-3A °.According to the computing formula (formula 1) of Stokes radius, the stokes radius of ion in solution and the infiltration coefficient relation of being inversely proportional to of ion.And hydrionic infiltration coefficient is far longer than the vanadium ion infiltration coefficient in solution.Therefore, in the solution, the Stokes radius of vanadium ion is far longer than hydrionic Stokes radius.
(k
BBe Boltzmann constant, T is kelvin degree, and the D ion is infiltration coefficient, and η is the viscosity of solution)
Difference according to vanadium ion and hydrogen ion Stokes radius, if we can realize vanadium ion is separated with hydrionic by pore separation membrane is arranged imagination, by the control membrance casting condition, the size in control perforated film aperture, realization is to the Selective Separation of different material, make that hydrogen ion can freely pass through in the film, and vanadium ion is trapped, and can realize that amberplex is in the function of VRB.Because this film does not need to introduce ion-exchange group, need only the function that just can realize film by simple aperture adjustment, greatly widened the range of choice of liquid flow energy storage battery with membrane material, reduce the production cost of film.
But this perforated film is little to a certain degree the time when the aperture, continues to reduce relatively difficulty of aperture again, and the ion-selective permeability that how further to improve perforated film becomes a major issue that solves this class film.Because nitrogenous heterocyclic high molecular polymer all shows positive charge with the high molecular polymer molecule that contains amido functional group, its film has good interception capacity to high-valence cationic, and wherein some polymer itself just has good proton conductivity.If macromolecule membrane and the perforated membrane of these aobvious positive charges are combined with each other, the ion-selective permeability of former perforated membrane will be improved greatly.
Summary of the invention
The object of the invention is to overcome the problem that existing ion-exchange membrane for liquid flow energy-storing batteries exists, a kind of liquid flow energy storage battery organic substance thin layer composite perforated film is provided, by surface recombination one deck nitrogen heterocyclic ring or the amino macromolecule membrane at perforated film, can in the situation of not obvious raising pellicular front resistance, greatly improve the ion-selective permeability of perforated film, thereby obtain the diaphragm material that extremely cheap, the suitable liquid flow energy storage battery of cost is used.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of liquid flow energy storage battery organic substance thin layer composite perforated film, take by one or two or more kinds porous septum that is prepared from as raw material in the organic polymer resin as matrix, the dense film that then is prepared from by the organic substance resin at surface recombination one deck of this porous matrix;
The membrane aperture of porous septum is of a size of 0.1～100nm, and porosity is 6～70%;
Described organic substance resin is to contain the high molecular polymer of azacyclo-or contain in the high molecular polymer of amido functional group one or two or more kinds.
Described organic polymer resin is polysulfones, polyacrylonitrile, polyimides, polyether-ketone, polybenzimidazoles, polytetrafluoroethylene, Kynoar, poly-aliphatic hydrocarbon or polystyrene pyridine;
This high molecular polymer that contains azacyclo-is a kind of homopolymers or the copolymer more than two kinds in benzimidazole, ethene imidazoles, pyridine, vinylpyridine, pyrazoles, pyrimidine, thiazole, benzothiazole, oxazole, benzoxazole, oxadiazole, quinoline, quinoxaline, thiadiazoles, four purine;
This high molecular polymer that contains amido functional group is the aliphat high molecular polymer with secondary amine, tertiary amine, quaternary amines.Described aliphat high molecular polymer is the polymer of one or two or more kinds mixing in polyimides, Polyetherimide, polyethyene diamine, quaternary ammoniated polyether-ether-ketone, the polymine.
The thickness of described perforated film matrix is 20～500 μ m; The film that is prepared from by the organic substance resin is dense film, and thickness is 0.1～100 μ m.
The preparation method of above-mentioned composite membrane, the method adopt the following steps preparation:
(1) organic polymer resin being dissolved in one or two or more kinds the solvent among DMSO, DMAC, NMP, the DMF, is that 20～100 ℃ of lower 0.5～10h that fully stir make blend solution in temperature; Wherein organic polymer resin concentration is between 5～70wt%;
Also can add the effumability solvent in the above-mentioned solvent, form mixed solvent, the concentration of effumability solvent in mixed solvent is 0～50wt%;
(2) blend solution that step (1) is prepared is poured at the bottom of the nonwoven fabric base or is poured directly on the glass plate, solvent flashing 0～60 second, then its mass-impregnation is entered 5～600s in the poor solvent of resin, under-20～100 ℃ of temperature, be prepared into porous septum; The thickness of film is between 20～500 μ m;
(3) be made into certain density solution in the solvent with one or two or more kinds in DMSO, DMAC, NMP, DMF, chloroform, dichloroethanes, water, ethanol of organic substance resin, this solution evenly be coated in the film surface of (2) preparation with the mode of spraying, dipping or spin-coating;
(4) film with (3) preparation descended dry 1～24 hour at 0～200 ℃, formed composite membrane.
Described effumability solvent is in methyl alcohol, oxolane or the n-hexane one or two or more kinds; The poor solvent of resin is one or two or more kinds in water, methyl alcohol, ethanol, propyl alcohol or the isopropyl alcohol.
Described composite membrane can be used in the liquid flow energy storage battery, and described liquid flow energy storage battery comprises all-vanadium liquid flow energy storage battery, zinc/bromine flow battery, sodium polysulfide/bromine redox flow cell, iron/chrome liquor galvanic battery, vanadium/bromine flow battery or zinc/cerium flow battery.
Useful result of the present invention:
(1) traditional liquid flow energy storage battery adopts ion-exchange group to realize conduction mechanism between the ion with diaphragm material, the perforated film that the present invention will not contain ion-exchange group is applied in the liquid flow energy storage battery, has strengthened the selection permeability of perforated film to ion by the positively charged film that increases one deck densification.The composite membrane preparation method of the present invention's preparation is simple, is conducive to improve the ion selectivity of film.
(2) it is controlled that the preparation method of such membrane material has the aperture, realizes easily producing in enormous quantities.
(3) the present invention has expanded kind and the scope of application of all-vanadium liquid flow energy storage battery with porous film material.
Description of drawings
Fig. 1 is the application principle figure of organic substance thin layer composite perforated film of the present invention in VRB;
Fig. 2 is that the prepared film of embodiment 1 and comparative example close lower charge-discharge performance of 80 electricity in VRB contrast.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
7.5 the gram polyacrylonitrile is dissolved among 30mlDMSO and the 10mlTHF, stirred 5 hours, the polymer solution that forms, be tiled in glass plate, thickness is 250 μ m, then immerses rapidly in the 5L water, solidify, form [Dan, Fig. 4 provides the section S EM picture of prepared membrane material, shows the pore structure of rule.
The [Dan that makes was processed 55 minutes at the sodium hydrate aqueous solution of 10wt.%, and treatment temperature is 55 ℃.Then film is cleaned up with deionized water, in ethanol, soak 2h, displace water wherein.
Compound concentration is the DMAC solution of the polybenzimidazole resin of 2wt.%, and is coated in the perforated film surface with whirler.High Rotation Speed is dry to coating liquid.
Utilize the composite membrane assembling all-vanadium liquid flow energy storage battery of preparation, wherein Catalytic Layer is activated carbon-fiber felt, and bipolar plates is graphite cake, and the effective area of film is 9cm
2, current density is 80mA cm
-2, vanadium ion concentration is 1.50mol L in the electrolyte
-1, H
2SO
4Concentration is 3mol L
-1The all-vanadium liquid flow energy storage battery current efficiency of assembling is 94.7%, and voltage efficiency is 81.1%, and energy efficiency is 76.8%.
Comparative Examples 1
Compare with embodiment 1, change film into virgin pp nitrile perforated film, other conditions are constant.Battery current efficient is 90%, and voltage efficiency is 85.1%, and energy efficiency is 76.6%.Compare with virgin pp nitrile perforated film, current efficiency and the energy efficiency of the perforated film of polybenzimidazoles Film laminated all increase significantly.The introducing of polybenzimidazoles film is described, has effectively improved the ion selectivity of film, its coulomb efficient reaches the level (enclosed pasture efficient 95%) of commercialization Nafion115 film.
Composite membrane preparation method of the present invention is simple, and composite bed thickness is controlled, realizes easily producing in enormous quantities.The composite membrane of preparation effectively raises the ion selectivity of perforated film.In addition, such membrane material has been expanded the range of choice of liquid flow energy storage battery membrane material, and can greatly have been reduced the battery diaphragm cost not needing to regard it as any ion-exchange group and can realize the transmission of ion.
Claims (6)
1. liquid flow energy storage battery composite membrane is characterized in that:
Take by one or two or more kinds porous septum that is prepared from as raw material in the organic polymer resin as matrix, the dense film that then is prepared from by the organic substance resin at surface recombination one deck of this porous matrix;
The membrane aperture of porous septum is of a size of 0.1～100nm, and porosity is 6～70%;
Described organic substance resin is to contain the high molecular polymer of azacyclo-or contain in the high molecular polymer of amido functional group one or two or more kinds.
2. composite membrane according to claim 1 is characterized in that:
Described organic polymer resin is polysulfones, polyacrylonitrile, polyimides, polyether-ketone, polybenzimidazoles, polytetrafluoroethylene, Kynoar, poly-aliphatic hydrocarbon or polystyrene pyridine;
This high molecular polymer that contains azacyclo-is a kind of homopolymers or the copolymer more than two kinds in benzimidazole, ethene imidazoles, pyridine, vinylpyridine, pyrazoles, pyrimidine, thiazole, benzothiazole, oxazole, benzoxazole, oxadiazole, quinoline, quinoxaline, thiadiazoles, four purine;
This high molecular polymer that contains amido functional group is the aliphat high molecular polymer with secondary amine, tertiary amine, quaternary amines; Described aliphat high molecular polymer is the polymer of one or two or more kinds mixing in polyimides, Polyetherimide, polyethyene diamine, quaternary ammoniated polyether-ether-ketone, the polymine.
3. composite membrane according to claim 1, it is characterized in that: the thickness of described perforated film matrix is 20～500 μ m; The film that is prepared from by the organic substance resin is dense film, and thickness is 0.1～100 μ m.
4. composite membrane according to claim 1, it is characterized in that: described composite membrane is prepared from according to the following procedure,
(1) organic polymer resin being dissolved in one or two or more kinds the solvent among DMSO, DMAC, NMP, the DMF, is that 20～100 ℃ of lower 0.5～10h that fully stir make blend solution in temperature; Wherein organic polymer resin concentration is between 5～70wt%;
Also can add the effumability solvent in the above-mentioned solvent, form mixed solvent, the concentration of effumability solvent in mixed solvent is 0～50wt%;
(2) blend solution that step (1) is prepared is poured at the bottom of the nonwoven fabric base or is poured directly on the flat board, solvent flashing 0～60 second, then its mass-impregnation is entered 5～600s in the poor solvent of resin, under-20～100 ℃ of temperature, be prepared into porous septum; The thickness of film is between 20～500 μ m;
(3) be made into the solution that concentration is 0.1～10wt% in the solvent with one or two or more kinds in DMSO, DMAC, NMP, DMF, chloroform, dichloroethanes, water, ethanol of organic substance resin, this solution evenly be coated in the film surface of (2) preparation with the mode of spraying, dipping or spin-coating;
(4) film with (3) preparation descended dry 1～24 hour at 0～200 ℃, made composite membrane; The organic substance resin is prepared from dense film thickness between 0.1～100 μ m.
5. composite membrane according to claim 5, it is characterized in that: described effumability solvent is in methyl alcohol, oxolane or the n-hexane one or two or more kinds;
The poor solvent of resin is one or two or more kinds in water, methyl alcohol, ethanol, propyl alcohol or the isopropyl alcohol.
6. the application of the described composite membrane of one of claim 1-6, it is characterized in that: described composite membrane can be used in the liquid flow energy storage battery, and described liquid flow energy storage battery comprises all-vanadium liquid flow energy storage battery, zinc/bromine flow battery, sodium polysulfide/bromine redox flow cell, iron/chrome liquor galvanic battery, vanadium/bromine flow battery or zinc/cerium flow battery.
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| CN104143613A (en) * | 2013-05-09 | 2014-11-12 | 中国科学院大连化学物理研究所 | Self-assembled layers composite membrane and preparation and application thereof |
| CN104300101A (en) * | 2013-07-18 | 2015-01-21 | 中国科学院大连化学物理研究所 | Difunctional composite porous membrane and preparation and application thereof |
| CN104716355A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Liquid flow cell composite membrane and application thereof |
| CN108134107A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of perforated membrane is in the application of Alkaline Zinc iron liquid galvanic battery |
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| CN108400365A (en) * | 2018-03-01 | 2018-08-14 | 犀望新能源科技（昆山）有限公司 | zinc-bromine flow battery |
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| CN111261911A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Flow battery composite membrane and application thereof |
| CN111261912A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Application of porous ion-conducting membrane in neutral zinc-iron flow battery |
| CN111378988A (en) * | 2020-03-31 | 2020-07-07 | 山东东岳高分子材料有限公司 | Preparation method of pre-swelling perfluorinated ion exchange membrane |
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| CN104300101A (en) * | 2013-07-18 | 2015-01-21 | 中国科学院大连化学物理研究所 | Difunctional composite porous membrane and preparation and application thereof |
| CN104300101B (en) * | 2013-07-18 | 2017-05-03 | 中国科学院大连化学物理研究所 | Difunctional composite porous membrane and preparation and application thereof |
| CN104716355A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Liquid flow cell composite membrane and application thereof |
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| CN108400365A (en) * | 2018-03-01 | 2018-08-14 | 犀望新能源科技（昆山）有限公司 | zinc-bromine flow battery |
| CN108400365B (en) * | 2018-03-01 | 2021-11-12 | 南京瑞贻电子科技有限公司 | Zinc-bromine flow battery |
| CN110940770A (en) * | 2018-09-21 | 2020-03-31 | 中国科学院大连化学物理研究所 | Method for screening parameters of solvent treatment process of polymer porous ion-conducting membrane for flow battery |
| CN111261911A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Flow battery composite membrane and application thereof |
| CN111261912A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Application of porous ion-conducting membrane in neutral zinc-iron flow battery |
| CN111261911B (en) * | 2018-11-30 | 2021-07-13 | 中国科学院大连化学物理研究所 | Flow battery composite membrane and application thereof |
| CN109786796B (en) * | 2019-01-17 | 2021-01-26 | 深圳大学 | High-temperature proton exchange membrane and preparation method thereof |
| CN109786796A (en) * | 2019-01-17 | 2019-05-21 | 深圳大学 | A kind of high temperature proton exchange film and preparation method thereof |
| CN112940321A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Cross-linked composite membrane for flow battery and preparation and application thereof |
| CN112940321B (en) * | 2019-12-10 | 2022-04-15 | 中国科学院大连化学物理研究所 | Cross-linked composite membrane for flow battery and preparation and application thereof |
| CN111378988A (en) * | 2020-03-31 | 2020-07-07 | 山东东岳高分子材料有限公司 | Preparation method of pre-swelling perfluorinated ion exchange membrane |
| CN111378988B (en) * | 2020-03-31 | 2021-10-22 | 山东东岳高分子材料有限公司 | Preparation method of pre-swelling perfluorinated ion exchange membrane |
| CN114621496A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation and application of Daramic composite ion conduction membrane with bromine blocking and fixing functions |
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Application publication date: 20130109 |