CN104716355A - Liquid flow cell composite membrane and application thereof - Google Patents
Liquid flow cell composite membrane and application thereof Download PDFInfo
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- CN104716355A CN104716355A CN201310694635.1A CN201310694635A CN104716355A CN 104716355 A CN104716355 A CN 104716355A CN 201310694635 A CN201310694635 A CN 201310694635A CN 104716355 A CN104716355 A CN 104716355A
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- composite membrane
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- flow battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0239—Organic resins; Organic polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
-
- 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
Abstract
The invention relates to a liquid flow cell composite membrane and application thereof in liquid flow cells, a pore membrane prepared from raw materials of one or two or more kinds of organic polymer resin is used as a matrix, one side surface of the matrix is composited with a dense membrane prepared from cation exchange resin, and the composite membrane is simple in preparation method and environmental friendly in process. Compared with the original pore membrane, the composite membrane has higher hydrophily and ionic selectivity, and can effectively inhibit the electrolyte solution migration problem, and the type and use scope of the liquid flow cell pore membrane material can be expanded.
Description
Technical field
The present invention relates to a kind of flow battery polyelectrolyte diaphragm material, particularly a kind of flow battery composite membrane and its application in flow battery.
Background technology
Flow battery is a kind of electrochemical energy storage new technology, compared with other energy storage technology, have that energy conversion efficiency is high, system is flexible, capacitance of storage is large, addressing is free, can the advantage such as deep discharge, safety and environmental protection, maintenance cost be low, the aspects such as the energy storage of the renewable energy power generation such as wind energy, solar energy, emergency power system, stand-by station and electric power system peak load shifting can be widely used in.All-vanadium flow battery (vanadium flow battery, VFB) because fail safe is high, good stability, efficiency are high, the life-span is long (life-span >15), low cost and other advantages, be considered in flow battery, have prospect and representational a kind of flow battery most.
Battery diaphragm is the important component part in flow battery, and it plays and intercepts positive and negative electrode electrolyte, provides the effect of proton transmitting channel.Proton-conducting, the chemical stability and ion selectivity etc. of film directly will affect chemical property and the useful life of battery; Therefore require that film has lower active material permeability (namely having higher selectivity) and lower surface resistance (namely having higher ionic conductance), also should have good chemical stability and lower cost simultaneously.The Nafion film of the membrane material both at home and abroad used now mainly du pont company's exploitation, Nafion film has excellent performance in chemical property and useful life etc., but due to expensive, particularly be applied in all-vanadium flow battery shortcomings such as there is ion selectivity difference, thus limit the industrial applications of this film.Therefore, the battery diaphragm with high selectivity, high stability and low cost is developed most important.
The flow battery barrier film of current exploitation and use, be amberplex, namely membrane material is made up of the polymer containing ion-exchange group, mainly be divided into perfluorinated ion-exchange membrane, half fluorine ion exchange membrane and non-fluorine ion exchange membrane, because fluoropolymer membrane is expensive, the problems such as ion selectivity difference, researcher has carried out a large amount of research-and-development activity 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 ensures 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, limit the useful life of film in VFB.
Membrane separating process with selectivity through film for separating medium, when there are certain motive force (as pressure differential, concentration difference, potential difference etc.) in film both sides, feed side compositional selecting ground through film, with reach separations, purification object.The structure of diffusion barrier is generally perforated film structure, and according to the size of membrane aperture, the molecule of different size optionally through film, thus can realize the object of separating-purifying.The pore separation membrane that has used in industry is generally obtained by the method for inversion of phases, basic skills is layered on by the solution of polymer dull and stereotyped upper (as glass plate), then as required, by solvent evaporates a period of time, flat board is immersed in the non-solvent bath of polymer and solidify, form the perforated film of polymer.
In all-vanadium flow 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 infiltration coefficient of ion stokes radius in the solution and ion inversely.And hydrionic infiltration coefficient is far longer than vanadium ion infiltration coefficient in the solution.Therefore, in solution, the Stokes radius of vanadium ion is far longer than hydrionic Stokes radius.
(kB is Boltzmann constant, and T is kelvin degree, and D ion is infiltration coefficient, and η is the viscosity of solution)
According to the difference of vanadium ion and hydrogen ion Stokes radius, if we can be separated with hydrionic vanadium ion by having pore separation membrane to realize imagination, by controlling membrance casting condition, control the size in perforated film aperture, realize the Selective Separation to different material, hydrogen ion in film can freely be passed through, and vanadium ion is trapped, and can realize the function of amberplex at VFB.Because this film does not need to introduce ion-exchange group, as long as just can be realized the function of film by simple aperture adjustment, greatly widen the range of choice of flow battery membrane material, reduce the production cost of film.
But this perforated film when aperture little to a certain extent time, then continue to reduce aperture can be more difficult, the ion-selective permeability how improving perforated film further becomes the major issue solving this kind of film.Because cation high molecular itself has good proton conductivity.If these cation exchange resin films and perforated film are combined with each other, by greatly improve original pore membrane ion-selective permeability while, the selectivity of film can be improved.
Summary of the invention
The object of the invention is to overcome existing flow battery amberplex Problems existing, a kind of flow battery organic substance thin layer composite perforated film is provided, by the dense film be prepared from by cation exchange resin at surface recombination one deck of perforated film, greatly can improve the ion-selective permeability of perforated film when not obvious raising pellicular front resistance, thus obtain the diaphragm material that cost is extremely cheap, be applicable to flow battery.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of flow battery composite membrane, with the perforated film be prepared from for raw material by one or two or more kinds in organic polymer resin for matrix, in the dense film that side surface recombination one deck of this matrix is prepared from by cation exchange resin;
Perforated film aperture size is 0.1 ~ 20nm, and porosity is 6 ~ 70%;
Described organic polymer resin is by one or more in polysulfones, polyketone, polyimides, polybenzimidazoles, Kynoar, polyvinyl pyridine, polyacrylonitrile, polypropylene, polyethylene, polybutadiene or cellulose acetate;
Described cation exchange resin is one or two or more kinds in fluorinated polymer, sulfonated polyether-ether-ketone, SPSF, sulfonated polyether sulfone, sulfonated polystyrene or polyacrylic acid.
The thickness of described perforated film matrix is 20 ~ 500 μm; The film be prepared from by organic substance resin is dense film, and thickness is 0.1 ~ 20 μm.
The preparation method of above-mentioned composite membrane, the method adopts following steps preparation:
(1) organic polymer resin is dissolved in the solvent of one or two or more kinds in DMSO, DMAC, NMP, DMF, at temperature is 20 ~ 100 DEG C, fully stirs 0.5 ~ 10h makes blend solution; Wherein organic polymer resin concentration is between 5 ~ 70wt%;
Do not add in above-mentioned solvent or also can add effumability solvent, form mixed solvent, the concentration of effumability solvent in mixed solvent is 0 ~ 50wt%; Described effumability solvent is one or two or more kinds in methyl alcohol, oxolane or n-hexane;
(2) be poured at the bottom of nonwoven fabric base by blend solution prepared by step (1) or be poured directly on flat board, solvent flashing 0 ~ 2 minute, then enters 5 ~ 600s in the poor solvent of resin by its mass-impregnation; The thickness of film is between 20 ~ 500 μm;
(3) be made in the solvent of one or two or more kinds of cation exchange resin in DMSO, DMAC, NMP, DMF, chloroform, dichloroethanes, water, ethanol the solution that concentration is 0.1 ~ 10wt%, this dissolution homogeneity be coated in the film surface of (2) preparing by the mode of spraying, dipping or spin-coating;
(4) film prepared by (3) at 0 ~ 200 DEG C dry 1 ~ 24 hour, obtained composite membrane; Organic substance resin is prepared from dense film thickness between 0.1 ~ 100 μm.
Described composite membrane can be used in flow battery, and described flow battery comprises all-vanadium flow 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.
Beneficial outcomes of the present invention:
(1) perforated film by the aperture control of film realize to the obstruct of vanadium ion and to hydrionic selectivity through.On the basis in regulation and control aperture, the present invention, by the method for the cationic membrane of compound one deck densification, improves the ionic selection abilities of film further, increases the hydrophily of film simultaneously, thus makes film have better combination property in VFB application.
(2) composite membrane prepared of the present invention, aperture is adjustable; The resin cation kind thickness of compound is controlled.By modulation above-mentioned parameter, the controllable adjustment of battery performance can be realized.
(3) the present invention has expanded kind and the scope of application of perforated film material used for all-vanadium redox flow battery.
Such composite membrane preparation method is simple, and technique environmental protection, ion selectivity is adjustable.Compared with original pore membrane, composite membrane has good hydrophily and vanadium ion obstructing capacity, and the flow battery assembled with this has higher combination property.
Accompanying drawing explanation
Fig. 1 is the application principle figure of organic substance thin layer composite perforated film of the present invention in VFB;
Charge-discharge performance under the film of Fig. 2 prepared by embodiment 1 and comparative example 80 electricity in VFB are close contrasts.
Embodiment
The following examples further illustrate of the present invention, instead of limit the scope of the invention.
Embodiment 1
7.5 grams of polyacrylonitrile are dissolved in 30mlDMSO and 10mlTHF, and stir 5 hours, the polymer solution of formation, is laid in glass plate, and thickness is 250 μm, and then immerse rapidly in 5L water, solidification, forms pseudoseptum.
By the sodium hydrate aqueous solution process 55 minute of obtained pseudoseptum at 10wt.%, treatment temperature is 55 DEG C.Then film is clean by washed with de-ionized water, soak 2h in ethanol, displace water wherein.
Compound concentration is the DMAC solution of the Nafion resin of 2wt.%, and is coated in perforated film surface with whirler.High Rotation Speed is dry to coating liquid, obtains and is compounded with pore membrane (A)
Utilize the composite membrane assembling all-vanadium flow battery of preparation, wherein Catalytic Layer is activated carbon-fiber felt, and bipolar plates is graphite cake, and the effective area of film is 48cm
2, current density is 80mA cm
-2, in electrolyte, vanadium ion concentration is 1.50mol L
-1, H
2sO
4concentration is 3mol L
-1.The all-vanadium flow battery coulombic efficiency (CE) of assembling is 93.8%, and voltage efficiency (VE) is 81.1%, and energy efficiency (EE) is 76.1%.
Comparative example 1
Compared with embodiment 1, film is changed into virgin pp nitrile perforated film, other conditions are constant, obtained virgin pp nitrile perforated film (B).Battery coulombic efficiency is 88.6%, and voltage efficiency is 83.3%, and energy efficiency is 73.8%.
As can be seen from Figure 2, compared with virgin pp nitrile perforated film, coulombic efficiency and the energy efficiency of the perforated film of Nafion Film laminated all increase significantly.The introducing of Nafion film is described, effectively improves the ion selectivity of film, intercepted the mutual string of vanadium ion in positive and negative end electrolyte, thus improve the coulombic efficiency of battery.
Embodiment 2
With embodiment 1, change polymer into polysulfones, other conditions are constant.
Embodiment 3
With embodiment 1, change polymer into polyimides, solvent changes NMP into, and other conditions are constant.
Embodiment 4
With embodiment 1, cation exchange resin is replaced to sulfonated polyether-ether-ketone, other conditions are constant.
Embodiment 5
With embodiment 1, cation exchange resin is replaced to sulfonated polyether sulfone, other conditions are constant.
Claims (5)
1. a flow battery composite membrane, is characterized in that:
With the perforated film be prepared from for raw material by one or two or more kinds in organic polymer resin for matrix, in the dense film that side surface recombination one deck of this matrix is prepared from by cation exchange resin;
Perforated film aperture size is 0.1 ~ 20nm, and porosity is 6 ~ 70%;
Described composite membrane is prepared from according to the following procedure,
(1) organic polymer resin is dissolved in the solvent of one or two or more kinds in DMSO, DMAC, NMP, DMF, at temperature is 20 ~ 100 DEG C, fully stirs 0.5 ~ 10h makes blend solution; Wherein organic polymer resin concentration is between 5 ~ 70wt%;
Do not add in above-mentioned solvent or also can add effumability solvent, form mixed solvent, the concentration of effumability solvent in mixed solvent is 0 ~ 50wt%;
(2) be poured at the bottom of nonwoven fabric base by blend solution prepared by step (1) or be poured directly on flat board, solvent flashing 0 ~ 2 minute, then enters 5 ~ 600s in the poor solvent of resin by its mass-impregnation; The thickness of film is between 20 ~ 500 μm;
(3) be made in the solvent of one or two or more kinds of cation exchange resin in DMSO, DMAC, NMP, DMF, chloroform, dichloroethanes, water, ethanol the solution that concentration is 0.1 ~ 10wt%, this dissolution homogeneity be coated in the film surface of (2) preparing by the mode of spraying, dipping or spin-coating;
(4) film prepared by (3) at 0 ~ 200 DEG C dry 1 ~ 24 hour, obtained composite membrane; Organic substance resin is prepared from dense film thickness between 0.1 ~ 100 μm.
2. composite membrane according to claim 1, is characterized in that:
Described organic polymer resin is by one or two or more kinds in polysulfones, polyketone, polyimides, polybenzimidazoles, Kynoar, polyvinyl pyridine, polyacrylonitrile, polypropylene, polyethylene, polybutadiene or cellulose acetate;
Described cation exchange resin is one or two or more kinds in fluorinated polymer, sulfonated polyether-ether-ketone, SPSF, sulfonated polyether sulfone, sulfonated polystyrene or polyacrylic acid.
3. composite membrane according to claim 1, is characterized in that: the thickness of described perforated film matrix is 20 ~ 500 μm; The dense film thickness be prepared from by resin cation is 0.1 ~ 20 μm.
4. composite membrane according to claim 1, is characterized in that: described effumability solvent is one or two or more kinds in methyl alcohol, oxolane or n-hexane;
The poor solvent of resin is one or two or more kinds in water, methyl alcohol, ethanol, propyl alcohol or isopropyl alcohol.
5. the application of the arbitrary described composite membrane of claim 1-4, it is characterized in that: described composite membrane can be used in flow battery, described flow battery comprises all-vanadium flow 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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| Application Number | Priority Date | Filing Date | Title |
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| CN201310694635.1A CN104716355A (en) | 2013-12-15 | 2013-12-15 | Liquid flow cell composite membrane and application thereof |
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| CN201310694635.1A CN104716355A (en) | 2013-12-15 | 2013-12-15 | Liquid flow cell composite membrane and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106558712A (en) * | 2015-09-21 | 2017-04-05 | 中国科学院大连化学物理研究所 | A kind of application of composite membrane in neutral system zinc-iron flow battery |
| CN107240704A (en) * | 2017-06-21 | 2017-10-10 | 大连理工大学 | A kind of method of accurate control composite membrane skin thickness |
| CN107591545A (en) * | 2016-07-07 | 2018-01-16 | 中国科学院大连化学物理研究所 | A kind of application of blended porous membrane in flow battery |
| 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 |
| CN111106373A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院大连化学物理研究所 | Zinc-bromine storage 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 |
| CN111886735A (en) * | 2018-04-09 | 2020-11-03 | 米兰理工大学 | Flow battery with membranes having different selectivities |
| CN112968190A (en) * | 2019-12-12 | 2021-06-15 | 中国科学院大连化学物理研究所 | Processing method of zinc-bromine flow battery diaphragm, diaphragm and application |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106558712A (en) * | 2015-09-21 | 2017-04-05 | 中国科学院大连化学物理研究所 | A kind of application of composite membrane in neutral system zinc-iron flow battery |
| CN107591545A (en) * | 2016-07-07 | 2018-01-16 | 中国科学院大连化学物理研究所 | A kind of application of blended porous membrane in flow battery |
| CN107240704A (en) * | 2017-06-21 | 2017-10-10 | 大连理工大学 | A kind of method of accurate control composite membrane skin thickness |
| 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 |
| CN111886735A (en) * | 2018-04-09 | 2020-11-03 | 米兰理工大学 | Flow battery with membranes having different selectivities |
| CN111106373A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院大连化学物理研究所 | Zinc-bromine storage battery |
| CN111106373B (en) * | 2018-10-25 | 2021-05-25 | 中国科学院大连化学物理研究所 | Zinc-bromine storage 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 |
| 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 |
| CN112968190A (en) * | 2019-12-12 | 2021-06-15 | 中国科学院大连化学物理研究所 | Processing method of zinc-bromine flow battery diaphragm, diaphragm and application |
| CN112968190B (en) * | 2019-12-12 | 2022-06-07 | 中国科学院大连化学物理研究所 | Processing method of zinc-bromine flow battery diaphragm, diaphragm and application |
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Application publication date: 20150617 |