CN105742548A - Application of porous membrane in neutral system zinc-iron flow battery - Google Patents
Application of porous membrane in neutral system zinc-iron flow battery Download PDFInfo
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- CN105742548A CN105742548A CN201410768172.3A CN201410768172A CN105742548A CN 105742548 A CN105742548 A CN 105742548A CN 201410768172 A CN201410768172 A CN 201410768172A CN 105742548 A CN105742548 A CN 105742548A
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Abstract
The invention relates to an application of a porous membrane in a neutral system zinc-iron flow battery. The porous membrane is a porous conductive membrane which is prepared from more than one or two organic polymer resins as a raw material through a phase inversion method, wherein the membrane aperture size of the porous conductive membrane is 0.1-100nm; and the porosity is 5%-70%. Compared with original other ion exchange membranes, the porous conductive membrane has relatively high ionic selectivity, can effectively inhibit the migration problem of an electrolyte solution; the cycle lifetime of the battery is prolonged; the battery performance is improved; and meanwhile, the production cost of a membrane material for the system flow battery is greatly reduced.
Description
Technical field
The present invention relates to a kind of polyelectrolyte diaphragm material to use at neutral system zinc-iron flow battery.
Background technology
Flow battery is a kind of electrochemical energy storage new technique, compared with other energy storage technology, there is energy conversion efficiency height, system flexible design, capacitance of storage is big, addressing is free, can the advantage such as deep discharge, safety and environmental protection, maintenance cost be low, it is possible to 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 power system peak load shifting.Neutral system zinc-iron flow battery is due to safety height, good stability, life-span length (life-span > 15 year), low cost and other advantages, it is believed that be a kind of flow battery with significantly high development potentiality.
Battery diaphragm is the important component part in flow battery, and it plays obstruct positive and negative electrode electrolyte, it is provided that the effect of proton transmitting channel.The proton-conducting of film, chemical stability and ion selectivity etc. will directly affect chemical property and the service life of battery；Therefore it is required that film has relatively low active substance permeability (namely having higher selectivity) and relatively low surface resistance (namely having higher ionic conductance), also should have good chemical stability and relatively low cost simultaneously.The membrane material used both at home and abroad now is mainly the Nafion membrane of du pont company's exploitation, Nafion membrane has the performance of excellence in chemical property and service life etc., but due to expensive, it is especially applicable in neutral system zinc-iron flow battery and there is the shortcomings such as ion poor selectivity, thus limiting the industrial applications of this film.Therefore, the battery diaphragm with high selectivity, high stability and low cost is developed most important.
Exploitation at present and the neutral system zinc-iron flow battery barrier film used, it is ion exchange membrane, namely membrane material is made up of the polymer containing ion-exchange group, it is broadly divided into perfluorinated ion-exchange membrane, half fluorine ion exchange membrane and non-fluorine ion exchange membrane, owing to fluoropolymer membrane is expensive, the problem such as ion poor selectivity, research worker has carried out a large amount of research-and-development activity for non-fluorine ion exchange membrane material, common non-fluorinated polymer is the materials such as sulfonated poly aryl ether ketone, polyether sulphone, polyimides.Wherein ion-exchange group plays a part transmission ion, isolation zinc/iron ion, and main polymer chain ensures the mechanical performance of film.But to most non-fluorine ion exchange membranes, the introducing of ion-exchange group, greatly reduce the oxidation stability of film, limit film service life in neutral system zinc-iron flow battery.
Membrane separating process passes through film for separating medium with selectivity, and when film both sides exist certain motive force (such as pressure differential, concentration difference, potential difference etc.), feed side compositional selecting ground is through film, to reach the purpose separating, purifying.The structure separating film is generally perforated film structure, and the size according to membrane aperture, various sizes of molecule can optionally pass through film, thus realizing the purpose of separating-purifying.The pore separation membrane that has used in industry obtains typically via the method for inversion of phases, basic skills is to be layered on flat board by the solution of polymer (such as glass plate), then as required, solvent is volatilized a period of time, flat board is immersed in the non-solvent bath of polymer and solidify, form the perforated film of polymer.
In neutral system zinc-iron flow battery, zinc ion, iron ion and proton all exist with the form of hydrated ion.Computing formula (formula 1) according to Stokes radius, the infiltration coefficient of ion stokes radius in the solution and ion is inversely.And hydrionic infiltration coefficient is far longer than zinc/iron ion infiltration coefficient in the solution.Therefore, in solution, the Stokes radius of zinc/iron 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)
Difference according to zinc/iron ion and hydrion Stokes radius, if it is contemplated that can by there being pore separation membrane to realize zinc/iron ion and hydrionic separation, by controlling membrance casting condition, control the size in perforated film aperture, realize the Selective Separation to different material, make hydrion in film to pass freely through, and zinc/iron ion is trapped, it is possible to achieve ion exchange membrane is in the function of VFB.Owing to this film need not introduce ion-exchange group, as long as just can be realized the function of film by simple aperture adjustment, significantly widen the range of choice of neutral system zinc-iron flow battery membrane material, reduce the production cost of film.
Summary of the invention
Present invention aim to overcome that existing neutral system zinc-iron flow battery ion exchange membrane Problems existing, it is provided that a kind of neutral system zinc-iron flow battery Organic substance perforated membrane.The ion-selective permeability of perforated film can be greatly improved, thus obtaining the diaphragm material that cost is extremely cheap, be suitable for neutral system zinc-iron flow battery when inconspicuous raising pellicular front resistance.
For achieving the above object, the technical solution used in the present invention is as follows:
By one or more machine macromolecule resins are raw material, by the porous conductive membranes that phase inversion method is prepared from；
The membrane aperture of porous conductive membranes is of a size of 0.1～100nm, and porosity is 5～70%.
Described organic polymer resin is by polysulfones, polyketone, polyimides, polybenzimidazoles, Kynoar, polyvinyl pyridine, polyacrylonitrile, polypropylene, polyethylene, polybutadiene or cellulose acetate；
The preparation method of above-mentioned perforated membrane, the method adopts following steps to prepare:
(1), in the solvent of one or two or more kinds organic polymer resin being dissolved in DMSO, DMAC, NMP, DMF, it is be sufficiently stirred for 0.5～10h at 20～100 DEG C to make blend solution in temperature；Wherein organic polymer resin concentration is between 5～70wt%；
Also can adding effumability solvent in above-mentioned solvent, form mixed solvent, effumability solvent concentration in mixed solvent is 0～50wt%；
(2) blend solution prepared by step (1) it is poured at the bottom of nonwoven fabric base or is poured directly on flat board, solvent flashing 0～20 minute/60 seconds, then its mass-impregnation is entered 5～600s in the poor solvent of resin, at-20～100 DEG C of temperature, prepares into porous septum；The thickness of film is between 20～500 μm；
Described perforated membrane is used in neutral system zinc-iron flow battery,
The beneficial outcomes of the present invention:
(1) porous conductive membranes can realize zinc/iron ion and hydrionic selectivity are passed through by the aperture control of film.
(2) perforated membrane prepared by the present invention, aperture is adjustable, and thickness is controlled.By modulation above-mentioned parameter, it may be achieved the controllable adjustment of battery performance.
(3) present invention has expanded kind and the use scope of neutral system zinc-iron flow battery membrane material.
Such method for preparing porous film is simple, and technique environmental protection, ion is selectively adjustable.Compared with former ion exchange membrane, porous conductive membranes film has good hydrophilic and zinc/iron ion obstructing capacity, has higher combination property with the neutral system zinc-iron flow battery that this assembles.
Accompanying drawing explanation
Fig. 1 is the perforated membrane of present invention application principle figure in neutral system zinc-iron flow battery；
Fig. 2 is that perforated membrane prepared by embodiment 1 contrasts with comparative example 80 close lower charge-discharge performances of electricity in neutral system zinc-iron flow battery.
Detailed description of the invention
The following examples are further illustrating the present invention, rather than restriction the scope of the present invention.Embodiment 1
7.5 grams of polyacrylonitrile are dissolved in 30mlDMSO and 10mlTHF, stir 5 hours, the polymer solution of formation, are laid in glass plate, and thickness is 250 μm, then immerse rapidly in 5L water, solidify, form pseudoseptum.
Being processed 55 minutes at the sodium hydrate aqueous solution of 10wt.% by prepared pseudoseptum, treatment temperature is 55 DEG C.Then film deionized water is cleaned up, soak 2h in ethanol, displace water therein.
The perforated membrane utilizing preparation assembles neutral system zinc-iron flow battery, and wherein Catalytic Layer is activated carbon-fiber felt, and bipolar plates is graphite cake, and the effective area of film is 48cm2, electric current density is 80mAcm-2, in electrolyte, zinc ion concentration is 0.5molL-1, the concentration of ferrous ion is 1molL-1.Neutral system zinc-iron flow battery coulombic efficiency (CE) assembled is 98.8%, and voltage efficiency (VE) is 81.1%, and energy efficiency (EE) is 80.1%.Battery life > 100 circulations.Comparative example 1
Compared with embodiment 1, film changing the Nafion115 ion exchange membrane that E.I.Du Pont Company produces into, other conditions are constant,.Battery coulombic efficiency is 88.6%, and voltage efficiency is 83.3%, and energy efficiency is 73.8%.Battery life < 20 circulations.
Compared with Nafion115 ion exchange membrane, the cycle life of the coulombic efficiency of perforated membrane, energy efficiency and battery all increases significantly.Illustrate by the different pore size size sieving actoion to different ions in perforated membrane, being effectively improved the ion selectivity of film, intercepted the mutual string of zinc/iron ion in positive and negative end electrolyte, thus improve the coulombic efficiency of battery and the stable new of battery.
Embodiment 2
With embodiment 1, changing polymer into polysulfones, other conditions are constant.
Embodiment 3
With embodiment 1, polymer changing polyimides into, solvent changes NMP into, and other conditions are constant.
Embodiment 4
With embodiment 1, polymer changing the mixture of poly-polyacrylonitrile and sulfonated polyether-ether-ketone into, other conditions are constant.
Claims (5)
1. the perforated membrane application in neutral system zinc-iron flow battery, it is characterised in that:
Described perforated membrane is with one or more organic polymer resins for raw material, by the porous conductive membranes that phase inversion method is prepared from；
The membrane aperture of porous conductive membranes is of a size of 0.1～100nm, and porosity is 5～70%.
2. application according to claim 1, it is characterised in that:
Described organic polymer resin is one or two or more kinds in polysulfones, polyketone, polyimides, polybenzimidazoles, Kynoar, polyvinyl pyridine, polyacrylonitrile, polypropylene, polyethylene, polybutadiene or cellulose acetate.
3. application according to claim 1 and 2, it is characterised in that: described perforated membrane is prepared from according to the following procedure,
(1), in the solvent of one or two or more kinds one or two or more kinds in organic polymer resin being dissolved in DMSO, DMAC, NMP, DMF, it is be sufficiently stirred for 0.5～10h at 20～100 DEG C to make blend solution in temperature；Wherein organic polymer resin concentration is between 5～70wt%；
Also can adding effumability solvent in above-mentioned solvent, form mixed solvent, effumability solvent concentration in mixed solvent is 0～50wt%；
(2) blend solution prepared by step (1) it is poured at the bottom of nonwoven fabric base or is poured directly on flat board, solvent flashing 0～20 minute, then its mass-impregnation is entered 5～600s in the poor solvent of resin, at-20～100 DEG C of temperature, prepares into porous septum.
4. application according to claim 3, it is characterised in that: described effumability solvent is one or two or more kinds in methanol, oxolane or normal hexane；
The poor solvent of resin is one or two or more kinds in water, methanol, ethanol, propanol or isopropanol.
5. application according to claim 3, it is characterised in that: the thickness of the porous septum prepared is between 20～500 μm.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108123155A (en) * | 2016-11-28 | 2018-06-05 | 中国科学院金属研究所 | A kind of preparation method of non-fluorine porous composite film used for all-vanadium redox flow battery |
| 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 |
| WO2018103517A1 (en) * | 2016-12-10 | 2018-06-14 | 中国科学院大连化学物理研究所 | Alkaline zinc-iron flow battery |
| CN110165308A (en) * | 2018-02-13 | 2019-08-23 | 中国科学院大连化学物理研究所 | Application of porous ion conducting membrane with negative charges in alkaline zinc-based 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 |
| CN111106398A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院上海硅酸盐研究所 | Low-cost aqueous zinc-iron secondary battery |
| 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 |
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| CN102867928A (en) * | 2011-07-05 | 2013-01-09 | 中国科学院大连化学物理研究所 | Composite film for flow energy storage battery and application thereof |
| CN103682387A (en) * | 2012-09-06 | 2014-03-26 | 中国科学院大连化学物理研究所 | Application of polymer porous separation membrane in liquid flow energy storage battery |
| CN103846012A (en) * | 2012-12-04 | 2014-06-11 | 中国科学院大连化学物理研究所 | Method for preparing porous separation membrane |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108123155A (en) * | 2016-11-28 | 2018-06-05 | 中国科学院金属研究所 | A kind of preparation method of non-fluorine porous composite film used for all-vanadium redox flow battery |
| 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 |
| WO2018103517A1 (en) * | 2016-12-10 | 2018-06-14 | 中国科学院大连化学物理研究所 | Alkaline zinc-iron flow battery |
| CN108461784A (en) * | 2016-12-10 | 2018-08-28 | 中国科学院大连化学物理研究所 | A kind of Alkaline Zinc iron liquid galvanic battery |
| CN110165308A (en) * | 2018-02-13 | 2019-08-23 | 中国科学院大连化学物理研究所 | Application of porous ion conducting membrane with negative charges in alkaline zinc-based battery |
| CN110165308B (en) * | 2018-02-13 | 2021-06-29 | 中国科学院大连化学物理研究所 | Application of porous ion conducting membrane with negative charges in alkaline zinc-based 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 |
| CN111106398A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院上海硅酸盐研究所 | Low-cost aqueous zinc-iron secondary battery |
| 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 |
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