CN104716353B - Porous membrane used for liquid flow cell and preparation and application thereof - Google Patents
Porous membrane used for liquid flow cell and preparation and application thereof Download PDFInfo
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- CN104716353B CN104716353B CN201310693038.7A CN201310693038A CN104716353B CN 104716353 B CN104716353 B CN 104716353B CN 201310693038 A CN201310693038 A CN 201310693038A CN 104716353 B CN104716353 B CN 104716353B
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- solvent
- perforated membrane
- polymer resin
- organic polymer
- 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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
- H01M8/0289—Means for holding the electrolyte
- H01M8/0293—Matrices for immobilising electrolyte solutions
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a porous membrane used for a liquid flow cell and preparation and application thereof, the porous membrane is prepared from raw materials of one or more than two kinds of organic polymer resin and one or more than two degradable organic or inorganic components in the electrolyte; the degradable component content is 5 to 40 wt% by mass of the organic polymer resin; and the porous membrane is prepared by the preparation process in the condition of constant temperature and constant humidity. The porous membrane has a multi-stage pore structure, and can effectively achieve the separation between ions with different valences, and the ion-passing-selectivity of the ionic membrane of the membrane can be kept. The composite membrane is simple and environmentally-friendly in process, controllable in pore structure, and low in cost, and mass production is easy to realize.
Description
Technical field
The present invention relates to a kind of flow battery perforated membrane, more particularly to a kind of perforated membrane with hierarchical porous structure and its
Prepare and apply.
Background technology
Flow battery is a kind of electrochemical energy storage new technique, compared with other energy storage technologies, with energy conversion efficiency it is high,
System design is flexible, capacitance of storage is big, addressing is free, can deep discharge, safety and environmental protection, the low advantage of maintenance cost, Ke Yiguang
It is general to be applied to the renewable energy power generation energy storage such as wind energy, solar energy, emergency power system, stand-by station and power system peak clipping and fill out
The aspects such as paddy.All-vanadium flow battery（Vanadium flow battery,VFB）Due to safe, good stability, efficiency high,
Life-span length（Life-span>15 years）, low cost and other advantages, be considered to have good application prospect.
Battery diaphragm is the important component part in flow battery, and it plays obstruct positive and negative electrode electrolyte, there is provided proton is passed
The effect of defeated passage.The proton-conducting of film, chemical stability and ion selectivity etc. will directly affect the electrochemistry of battery
Energy and service life；Therefore it is required that film has relatively low active substance permeability (having higher selectivity) and relatively low face electricity
Resistance (having higher ionic conductance), while should also have preferable chemical stability and relatively low cost.Now both at home and abroad
The membrane material for using is mainly the Nafion membrane of du pont company's exploitation, and Nafion membrane is in chemical property and service life etc.
Aspect has excellent performance, but due to expensive, there is ion selectivity poor in being especially applicable to all-vanadium flow battery
The shortcomings of, so as to limit the industrial applications of the film.Therefore, electricity of the exploitation with high selectivity, high stability and low cost
Pond barrier film is most important.
In VFB, vanadium ion and proton are in the form of hydrated ion.Due to vanadium ion and hydrion hydration radius
Difference, can be realized by porous diffusion barrier to vanadium ion and hydrionic Selective Separation.Using perforated membrane as VFB every
Film, with chemical stability is good, material selection wide ranges, technical maturity easily amplify, the advantages of low production cost.But perforated membrane pair
The selectivity and proton-conducting of hydrion and vanadium ion is difficult to take into account, therefore improves perforated membrane selectivity, ionic conductivity, enters
And realize that its sizable application has great importance.
Electrolyte is full of in envisioning a kind of hole with honeycomb structure barrier film, be conducive to transmission of the proton in film.
If little duct is constructed on its hole wall, by the sieving actoion of hole wall layer by layer, the ion that can effectively improve film is selected
Property, while with good proton-conducting.Shape of the exchange rate and gel time of solvent and non-solvent to the pore structure of film
Into playing conclusive effect, therefore can be formed it into by controlling the relative steam content and temperature of the non-solvent in air
With cellular pore structure.Add the organic or inorganic composition of degradable in the electrolytic solution simultaneously in casting solution, can be with shape
Into hierarchical porous structure, the ion selectivity and proton-conducting of film can be effectively improved, so as to obtain more preferable battery performance.
The content of the invention
For achieving the above object, the technical solution used in the present invention is as follows：
A kind of flow battery perforated membrane, described porous composite film by the one kind in organic polymer resin or two kinds with
Above and in the electrolytic solution one or two or more kinds of the organic or inorganic composition of degradable is prepared from for raw material；Degradable into
Divide content for 5～40wt% of organic polymer resin quality；
Described organic polymer resin is polysulfones, polyketone, polyacrylonitrile, polyimides, polyethers ketone, polytetrafluoroethyl-ne
One or two or more kinds in alkene, Kynoar, polybenzimidazoles or polyvinyl pyridine；
Described inorganic constituentss be silicon oxide, zirconium oxide, titanium oxide, lead oxide, tungsten oxide or zirconium phosphate in one kind or
More than two kinds；Organic principle is polyvinylpyrrolidone, one or two or more kinds in Polyethylene Glycol.
The hierarchical porous structure that the perforated membrane is made up of macropore and the aperture being distributed on macropore hole wall；Porous film thickness
For 20～500 μm, porosity is 5～60%；Wherein the aperture size of macropore is 50nm～2 micron, the wherein aperture size of aperture
For 2～10nm, wherein, aperture accounts for the 0.1～5% of perforated membrane mesopore volume.
Described composite membrane is prepared from using humidity phase inversion.
Described porous septum is prepared using following process：
（1）By organic polymer resin and in the electrolytic solution the composition dissolving of degradable in organic solvent, in temperature it is
0.5～10h is sufficiently stirred at 20～100 DEG C and makes blend solution；Wherein organic polymer resin concentration be 5～40wt% between,
5～40wt% of the component content of degradable for organic polymer resin quality；
Effumability solvent is added without or can be also added in above-mentioned solvent, mixed solvent is formed, and effumability solvent is mixed
Concentration in bonding solvent is 0～50wt%；
（2）By step（1）The blend solution of preparation is poured over nonwoven fabric base bottom or is poured directly on glass plate, volatilizees molten
Agent 0～60 second, is then integrally placed in climatic chamber, and in climatic chamber, the relative steam of the poor solvent of resin is wet
Degree prepares film forming in 10%～100%, temperature at -20～100 DEG C；The thickness of film is between 20～500 μm；Optimum condition is temperature
50 degree of degree, humidity 100%；
（3）Prepared film is placed in flow battery electrolyte solution and is soaked more than 24 hours, obtain required perforated membrane.
The flow battery electrolyte solution can be all-vanadium flow battery pentavalent vanadium solution, zinc-bromine flow battery bromine list
Ferric iron or hexavalent chromium solution in matter, siderochrome flow battery.
The organic solvent is one or two or more kinds in DMSO, DMAC, NMP, DMF；The effumability non-solvent
For in methanol, tetrahydrofuran or normal hexane one or two or more kinds, the poor solvent of resin is water, methanol, ethanol, propanol or different
One or two or more kinds in propanol.
The composite membrane can be used in flow battery, and the flow battery includes all-vanadium flow battery, zinc/bromine liquid stream electricity
Pond, sodium polysulfide/bromine redox flow cell, ferrum/chrome liquor galvanic battery, vanadium/bromine flow battery or zinc/cerium flow battery.
The useful achievement of the present invention：
1. the composite membrane that prepared by the present invention is applied in flow battery, by the relative steam for controlling the non-solvent in air
Content and temperature can be formed multistage adjusting the relativeness of both the exchange rate and gel time of solvent and non-solvent
Hole, can effectively improve the selectivity and proton-conducting of film, so as to obtain more preferable battery performance.
2. the composite membrane that prepared by the present invention can regulate and control this by changing non-solvent species, the species of biodegradable component
The selectivity and conductivity of class film.
3. the composite membrane that prepared by the present invention, pore structure is adjustable, with low cost, easily realizes producing in enormous quantities.
4. the present invention has widened the species and use range of flow battery membrane material.
5. the present invention is capable of achieving the controllability to flow battery efficiency.
Such film has hierarchical porous structure, by the sieving actoion of hole wall layer by layer, can effectively improve the ion choosing of film
Selecting property and proton-conducting.
Description of the drawings
Fig. 1 is perforated membrane SEM photograph prepared by embodiment 1；
Monocell charging and discharging curves of the Fig. 2 for perforated membrane prepared by embodiment 1.
Specific embodiment
The following examples are that the present invention is further illustrated, rather than limit the scope of the present invention.
Embodiment 1
8 grams of polyether sulfones and 4 grams of polyvinylpyrrolidones are dissolved in 20mLDMAC, stir 8 hours, and the polymer of formation is molten
Liquid, is laid in glass plate, is then put into rapidly during wetness is the climatic chamber that 100%, temperature is 50 DEG C, solidification 10
Minute, perforated membrane is formed, film thickness is 130 μm.48 will be soaked in sulfuric acid solution of the prepared film as the 3M of 1.5M pentavalent vanadiums
Hour.The porous diffusion barrier with hierarchical porous structure is obtained as can be seen from Figure 1.
Using prepared porous composite film assembling all-vanadium flow battery, wherein Catalytic Layer is activated carbon-fiber felt, and bipolar plates are
Graphite cake, the effective area of film is 6cm-2, both positive and negative polarity electrolyte volume is 30mL, and wherein vanadium ion concentration is 1.50mol L-1, H2SO4Concentration is 3mol L-1.Can be seen that from Fig. 2 charging and discharging curves, battery charging and discharging electric current density is 80mA cm-2,
Battery coulombic efficiency is 93%, and energy efficiency is 79%.
Embodiment 2
With embodiment 1, polyether sulfone is changed into polyacrylonitrile, prepare porous composite film.The flow battery current efficiency of assembling
For 89%, energy efficiency is 76%.
Embodiment 3
With embodiment 1, polyvinylpyrrolidone is changed into silicon oxide, prepare porous composite film.The flow battery electricity of assembling
Stream efficiency is 91%, and energy efficiency is 78.5%.
Embodiment 4
With embodiment 1, vapor is changed into alcohol vapor, prepare porous composite film.The flow battery current efficiency of assembling
For 92%, energy efficiency is 76%.
Embodiment 5
Humidity is changed to into 90% with embodiment 1.The flow battery current efficiency of assembling is 95%, and energy efficiency is 76%.
Embodiment 6
Humidity is changed to into 80% with embodiment 1.The flow battery current efficiency of assembling is 96%, and energy efficiency is 75%.
Claims (6)
1. a kind of flow battery perforated membrane, it is characterised in that：Described perforated membrane by the one kind in organic polymer resin or
It is prepared from for raw material with one or two or more kinds of the organic or inorganic composition of degradable in the electrolytic solution for more than two kinds；Can drop
5～40wt% of the component content of solution for organic polymer resin quality；Described organic polymer resin be polysulfones, polyketone,
In polyacrylonitrile, polyimides, polyethers ketone, politef, Kynoar, polybenzimidazoles or polyvinyl pyridine one
Plant or more than two kinds；Described inorganic constituentss are in silicon oxide, zirconium oxide, titanium oxide, lead oxide, tungsten oxide or zirconium phosphate
Plant or more than two kinds；Organic principle is polyvinylpyrrolidone, the one kind in Polyethylene Glycol or two kinds；
The perforated membrane is with the hierarchical porous structure being made up of macropore and the aperture being distributed on macropore hole wall；Porous film thickness is
20～500mm, porosity are 5～60%；Wherein the aperture size of macropore is 50nm～2 micron, the wherein aperture size of aperture
For 2～10nm, wherein, aperture accounts for the 0.1～5% of perforated membrane mesopore volume；
The perforated membrane is prepared using following steps：
(1) by organic polymer resin and in the electrolytic solution degradable composition dissolve in organic solvent, temperature be 20～
0.5～10h is sufficiently stirred at 100 DEG C and makes blend solution；Wherein organic polymer resin concentration be 5～40wt% between, can
5～40wt% of the component content of degraded for organic polymer resin quality；It is added without or can also add easily waving in above-mentioned solvent
The property sent out solvent, forms mixed solvent, and concentration of the effumability solvent in mixed solvent is 0～50wt%；
(2) blend solution prepared by step (1) is poured over into nonwoven fabric base bottom or is poured directly on glass plate, solvent flashing 0
～60 seconds, then it is integrally placed in climatic chamber, the poor solvent relative steam in resin in climatic chamber is wet
Spend and prepare film forming for 10%～100%, temperature under the conditions of -20～100 DEG C；The thickness of film is between 20～500 μm；
(3) prepared film is placed in flow battery electrolyte solution and is soaked more than 24 hours, obtain required perforated membrane.
2. the preparation method of the perforated membrane described in a kind of claim 1, it is characterised in that：The perforated membrane adopts following steps system
It is standby：
(1) by organic polymer resin and in the electrolytic solution degradable composition dissolve in organic solvent, temperature be 20～
0.5～10h is sufficiently stirred at 100 DEG C and makes blend solution；Wherein organic polymer resin concentration be 5～40wt% between, can
5～40wt% of the component content of degraded for organic polymer resin quality；It is added without or can also add easily waving in above-mentioned solvent
The property sent out solvent, forms mixed solvent, and concentration of the effumability solvent in mixed solvent is 0～50wt%；
(2) blend solution prepared by step (1) is poured over into nonwoven fabric base bottom or is poured directly on glass plate, solvent flashing 0
～60 seconds, then it is integrally placed in climatic chamber, the poor solvent relative steam in resin in climatic chamber is wet
Spend and prepare film forming for 10%～100%, temperature under the conditions of -20～100 DEG C；The thickness of film is between 20～500 μm；
(3) prepared film is placed in flow battery electrolyte solution and is soaked more than 24 hours, obtain required perforated membrane.
3. preparation method according to claim 2, it is characterised in that：The flow battery electrolyte solution is all-vanadium flow
Ferric iron or hexavalent chromium solution in battery pentavalent vanadium solution, zinc-bromine flow battery bromine simple substance, siderochrome flow battery.
4. preparation method according to claim 2, it is characterised in that：The organic solvent is DMSO, DMAC, NMP, DMF
In one or two or more kinds；The effumability solvent is one or two or more kinds in methanol, tetrahydrofuran or normal hexane, is set
The poor solvent of fat is one or two or more kinds in water, methanol, ethanol, propanol or isopropanol.
5. preparation method according to claim 2, it is characterised in that：50 DEG C of step (2) thermostat temperature, constant humidity humidity
100%.
6. the application of perforated membrane described in a kind of claim 1, it is characterised in that：Described flow battery includes all-vanadium flow electricity
Pond, vanadium/bromine flow battery or ferrum/chrome liquor galvanic battery.
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| CN104716353B true CN104716353B (en) | 2017-05-03 |
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| CN106532104B (en) * | 2015-09-09 | 2019-03-19 | 中国科学院大连化学物理研究所 | A kind of lithium-sulfur cell gel electrolyte porous electrode and its preparation and application |
| CN107546399B (en) * | 2016-06-29 | 2020-04-07 | 中国科学院大连化学物理研究所 | Ion exchange membrane with main chain separated from ion exchange group and preparation and application thereof |
| CN107546397B (en) * | 2016-06-29 | 2020-02-21 | 中国科学院大连化学物理研究所 | Porous ion conduction membrane for flow battery and preparation and application thereof |
| 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 |
| CN108129612B (en) * | 2016-12-01 | 2020-01-14 | 中国科学院大连化学物理研究所 | Preparation of phosphoric acid functionalized multistage pore hybrid monolithic material, and material and application thereof |
| CN109659589A (en) * | 2017-10-11 | 2019-04-19 | 中国科学院大连化学物理研究所 | The screening technique of flow battery polyalcohol stephanoporate ion-conductive membranes in a kind of solvent treatment process |
| CN110943238B (en) * | 2018-09-21 | 2020-11-20 | 中国科学院大连化学物理研究所 | Ion-conducting membrane for flow battery and preparation and application thereof |
| CN112447994B (en) * | 2019-08-28 | 2022-03-08 | 中国科学院大连化学物理研究所 | Application of ion-conducting membrane containing chlorinated polyvinyl chloride in flow battery |
| CN114044853B (en) * | 2021-11-15 | 2022-09-09 | 湖北工程学院 | Biomass-based EC-g-PSSA graft copolymer and preparation method and application thereof |
| CN117317331A (en) * | 2023-11-28 | 2023-12-29 | 华中科技大学 | Positive electrode electrolyte of chromium chelate and flow battery |
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