CN110197919A - A kind of ionic conduction type porous septum used for all-vanadium redox flow battery and its preparation method and purposes - Google Patents
A kind of ionic conduction type porous septum used for all-vanadium redox flow battery and its preparation method and purposes Download PDFInfo
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- porous septum
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000005266 casting Methods 0.000 claims abstract description 47
- 239000004094 surface-active agent Substances 0.000 claims abstract description 40
- 229920000620 organic polymer Polymers 0.000 claims abstract description 35
- 239000002952 polymeric resin Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 48
- 239000004088 foaming agent Substances 0.000 claims description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000001112 coagulating effect Effects 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 229920002521 macromolecule Polymers 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003093 cationic surfactant Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 150000003384 small molecules Chemical group 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 229940113088 dimethylacetamide Drugs 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002480 polybenzimidazole Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229920001652 poly(etherketoneketone) Polymers 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical class CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 229910001456 vanadium ion Inorganic materials 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 230000010148 water-pollination Effects 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical group [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XXJLQQRZZGAIGT-UHFFFAOYSA-N benzyl(methyl)azanium;bromide Chemical compound [Br-].C[NH2+]CC1=CC=CC=C1 XXJLQQRZZGAIGT-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical compound O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 1
- 229920006120 non-fluorinated polymer Polymers 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
-
- 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
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/10—Fuel cells in stationary systems, e.g. emergency power source in plant
-
- 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
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a kind of ionic conduction type porous septums used for all-vanadium redox flow battery and its preparation method and application；The porous septum is applied in all-vanadium flow battery, it is prepared by using the casting solution of the organic polymer resin containing high concentration, and changing porous septum exchange rate of solvent and non-solvent in film forming procedure by addition surfactant influences the final structure of porous septum.The present invention passes through control addition surfactant, to control the size in the porous septum duct of preparation, so as under the premise of keeping high vanadium ion selectivity, effectively increase the proton conductive of film, realize film to the selectivity of vanadium ion and the balance of high proton conductivity.After introducing surfactant, the hydrophily of porous septum is substantially improved porous septum of the invention, is effectively reduced the interface resistance between porous septum and electrolyte, is reduced the polarity effect of battery.
Description
Technical field
The present invention relates to all-vanadium flow battery technical fields, and in particular to a kind of ionic conduction type used for all-vanadium redox flow battery is more
Hole diaphragm and its preparation method and application.
Background technique
Flow battery is a kind of novel electrochemical energy storage technology, has high-efficient, modularized design, safety and environmental protection, dimension
The advantages such as shield is simple, operating cost is low, in wind-power electricity generation, photovoltaic power generation, power grid peak load shifting, distribution power station, smart grid etc.
Field shows application prospect outstanding.All-vanadium flow battery (Vanadium flow battery, VFB) is due to charge and discharge
High-efficient, environmental-friendly, flexible design, the advantages that highly-safe, self discharge is low, the service life is long, are most had in current flow battery
A kind of flow battery of prospect.
Battery diaphragm is one of critical material of all-vanadium flow battery, the battery diaphragm on the one hand by positive and negative anodes electrolyte every
It opens, to avoid positive and negative anodes active ion cross contamination, self discharge occurs；On the other hand the conductive ions such as proton are allowed to pass through, shape
At circuit in battery.The battery diaphragm of VFB should have the following characteristics that high ionic conductivity, make battery voltage with higher
Efficiency, to reduce the polarization phenomena of battery；High vanadium ion selectivity, makes battery coulombic efficiency with higher, reduces battery
Self discharge；Resistant to chemical etching with preferable mechanical performance, resistance to electrochemical oxidation guarantees longer service life.
The diaphragm material that commercialized vanadium cell uses both at home and abroad at present is still mainly the Nafion of E.I.Du Pont Company's exploitation
Film.In flow battery, although Nafion membrane price is more expensive and ion selectivity is poor, in ionic conductivity, mechanicalness
Energy, chemical property and service life etc. are still that current many commercialization films are incomparable.But due to Nafion membrane
Price is more expensive and ion selectivity is poor, limits the use of the film.In view of the above problems, non-fluorine ion exchange membrane becomes
The hot spot of people's research, common non-fluorinated polymer are the materials such as sulfonated poly aryl ether ketone, polyether sulphone and polyimides, however right
For most of non-fluorine ion exchange membranes, the structure of material can be destroyed when introducing ion-exchange group, greatly reduces film
Oxidation stability, to limit service life of the film in VFB.Therefore, exploitation has high ionic conductivity, high selection
Property, high stability and low cost porous septum used as battery diaphragm, for pushing the commercialization process of all-vanadium flow battery
It is most important.
By taking all-vanadium flow battery as an example, since vanadium ion and proton (hydrogen ion) are all with hydrated ion in the electrolytic solution
Form exists, and the former stokes radius is much larger than the latter, therefore can be by adjusting the aperture of porous septum or charged
Property, proton is passed freely through, and vanadium ion is trapped, to realize the separation to vanadium ion and proton.Such porous septum
It is not only cheap, but also the limitation that ion-exchange group is introduced on macromolecule is got rid of, it is arranged by aperture screening or Donnan
The mechanism of reprimand realizes the separation of ion, greatly improves the stability of film, is the hot spot researched and developed at present.
The preparation of porous septum has to pass film properties frequently with immersion precipitation phase-inversion technologies, the aperture of film and pore structure
Important influence.It is many to the regulation method of the parameters such as aperture and pore structure during film preparation, including solvent/non-
Pore creating material is added in the selection of solvent in casting solution, adds the methods of easy volatile solvent, control membrance casting condition.However in adjustment hole
During diameter, since the too small resistance that can make diaphragm in aperture is too big, serious polarization phenomena are caused, aperture is too big, the selection of film
Property it is poor, generate self discharge, thus solve perforated membrane ionic conductivity and selectivity contradiction become the key to solve the problem.
Summary of the invention
In order to improve the deficiencies in the prior art, it is an object of the invention to solve the ionic conductivity of porous septum and selection
The problems such as property is poor, by introducing surfactant in porous septum, adjusts the structure of the porous septum, what is be prepared is porous
Diaphragm can effectively improve porous septum and improve its proton conductivity to the wellability of electrolyte, and due to surface-active
Agent is adsorbed on the surface of the porous septum, passes through electrostatic repulsion or the cation (such as vanadium ion) of formation hydrogen bond and high price, performance
Good selectivity is gone out to obtain low in cost, function admirable porous septum used for all-vanadium redox flow battery.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of preparation method of ionic conduction type porous septum used for all-vanadium redox flow battery, includes the following steps:
Using organic polymer resin as raw material, it is mixed and made into casting solution with pore-foaming agent, surfactant, passes through immersion precipitation
The ionic conduction type porous septum used for all-vanadium redox flow battery is prepared in phase inversion.
In a preferred embodiment of the invention, the preparation method includes the following steps:
(1) organic polymer resin, pore-foaming agent and surfactant are dissolved in organic solvent, obtain mixed solution, i.e.,
Casting solution；
(2) casting solution of step (1) is coated in substrate surface, immerses in coagulating bath and solidify after standing, institute is prepared
State ionic conduction type porous septum used for all-vanadium redox flow battery.
In a preferred embodiment of the invention, the mass concentration of organic polymer resin is 10- in the casting solution
50wt%, the mass concentration of pore-foaming agent are 1-10%, and the mass concentration of surfactant is greater than 0 and to be less than or equal to 40wt%.
It is further preferred that the mass concentration of organic polymer resin is 20-40wt% in the casting solution, the mass concentration of pore-foaming agent is
1.5-8%, the mass concentration of surfactant are 0.5-20wt%.It is further preferred that organic polymer in the casting solution
The mass concentration of resin is 30-35wt%, and the mass concentration of pore-foaming agent is 2-5%, and the mass concentration of surfactant is 1-
10wt%.
In a preferred embodiment of the invention, the molecular weight of the organic polymer resin is more than or equal to 700,000 g/
mol；Preferably, the organic polymer resin is selected from Kynoar, polysulfones, polyether sulfone, polyacrylonitrile, polyimides, gathers
At least one of ether ketone ketone, polytetrafluoroethylene (PTFE), polybenzimidazoles or polyvinyl pyridine.
In a preferred embodiment of the invention, the pore-foaming agent is selected from macromolecule pore-foaming agent, or is selected from small molecule pore
Agent；Preferably, the macromolecule pore-foaming agent is selected from one of polyvinylpyrrolidone (PVP), polyethylene glycol or polyvinyl alcohol
Or it is two or more.Preferably, the small molecule pore-foaming agent be selected from one or both of lithium chloride, lithium bromide or aluminium chloride with
On.
In a preferred embodiment of the invention, the surfactant be selected from cationic surfactant and/or yin from
Sub- surfactant；It is further preferred that the cationic surfactant is selected from hexadecyltrimethylammonium chloride, dodecyl two
The one or two quaternary ammonium salt such as methylbenzyl ammonium bromide；The anionic surfactant is selected from neopelex, ten
The one or two sulfonate such as dialkyl sulfonates.
In a preferred embodiment of the invention, the organic solvent is selected from dimethylformamide (DMF), dimethylacetamide
One or more of amine (DMAC), N-methyl pyrrolidones (NMP) or dimethyl sulfoxide (DMSO).
In a preferred embodiment of the invention, in step (2), the coagulating bath is selected from water, ethyl alcohol, propyl alcohol, butanol, different
One or more of propyl alcohol, methanol, acetone, DMF or DMAC.
In a preferred embodiment of the invention, in step (2), the cured time is 1-60min.
The present invention provides a kind of ionic conduction type porous septum used for all-vanadium redox flow battery, and the porous septum is by above-mentioned
Method be prepared.
In a preferred embodiment of the invention, the porous septum with a thickness of 50-500 μm, it is further preferred that described more
Hole diaphragm with a thickness of 150-300 μm.Preferably, the pore size of the porous septum is 0.5-100nm, the porous septum
Porosity 20-80%.
The present invention provides a kind of purposes of ionic conduction type porous septum, is used for all-vanadium flow battery.
The present invention provides a kind of all-vanadium flow battery comprising above-mentioned porous septum.
Beneficial outcomes:
It is by using having containing high concentration 1. porous septum of the invention is applied in all-vanadium flow battery
What the casting solution of machine macromolecule resin was prepared, porous septum solvent in film forming procedure is changed by addition surfactant
With the exchange rate of non-solvent and then the final structure of influence porous septum, the content of surfactant is added by control, obtains
The porous septum controllable to structure and performance.
2. the present invention controls the big of the porous septum duct of preparation by control addition surfactant and its additional amount
It is small, the proton conductive of porous septum can be effectively increased under the premise of keeping highly selective to vanadium ion, realized porous
Highly selective and high proton conductivity balance of the diaphragm to vanadium ion.
3. porous septum of the invention is after introducing surfactant, the hydrophily of film is substantially improved, effectively
The interface resistance between porous septum and electrolyte is reduced, the polarity effect of battery is reduced.
4. the preparation method of porous septum of the invention is simple, aperture is adjustable, and the additional amount of surfactant is controllable, passes through
The adjusting to porous septum performance can be realized by adjusting above-mentioned parameter, and then realize the adjusting to battery performance.
5. porous septum of the invention prepares lower cost for material, chemical stability is excellent.
6. the present invention has expanded porous septum to the method for modifying of electrolyte wellability.
7. the present invention realizes the controllability to all-vanadium flow battery efficiency.
Detailed description of the invention
Fig. 1 is charging and discharging curve of the porous septum of the preparation of embodiment 1 in all-vanadium flow battery.
Fig. 2 is the SEM cross section structure figure of porous septum prepared by comparative example 1 and embodiment 1.
Specific embodiment
[preparation method of ionic conduction type porous septum used for all-vanadium redox flow battery]
As previously mentioned, the present invention provides a kind of preparation method of ionic conduction type porous septum used for all-vanadium redox flow battery, packet
Include following steps:
Using organic polymer resin as raw material, it is mixed and made into casting solution with pore-foaming agent, surfactant, passes through immersion precipitation
The ionic conduction type porous septum used for all-vanadium redox flow battery is prepared in phase inversion.
In a preferred embodiment of the invention, the preparation method includes the following steps:
(1) organic polymer resin, pore-foaming agent and surfactant are dissolved in organic solvent, obtain mixed solution, i.e.,
Casting solution；
(2) casting solution of step (1) is coated in substrate surface, immerses in coagulating bath and solidify after standing, institute is prepared
State ionic conduction type porous septum used for all-vanadium redox flow battery.
In the preferred embodiment of the invention, in step (1), the mixing temperature of the mixed solution, i.e. casting solution
Preparation temperature does not limit specifically, it will be understood by those skilled in the art that it will meet the organic polymer resin, cause
Hole agent and surfactant mixing completely, guarantee that the mixed time is unlikely to too long again, improve the preparation of the porous septum
Efficiency；Preferably, the temperature of the mixed solution mixing is 50-100 DEG C, at this temperature, described organic after 6-10 hours
Macromolecule resin, pore-foaming agent and surfactant can be dissolved completely in organic solvent, and can form uniform and stable mixing
Solution；It will be understood by those skilled in the art that the mixed mode does not limit specifically, ultrasonic mixing, magnetic force can be
Be stirred, mechanical stirring mixing etc., as long as the mixed solution can be prepared.
In a preferred embodiment of the invention, in step (1), organic polymer resin, pore-foaming agent in the casting solution
It is not limited specifically with the mixed proportion of surfactant, meets the mixed solution being prepared, i.e., casting solution is through solidifying
After bath solidification, ionic conduction type porous septum used for all-vanadium redox flow battery of the invention can be prepared.Preferably, the casting film
The mass concentration of organic polymer resin is 10-50wt% in liquid, and the mass concentration of pore-foaming agent is 1-10%, surfactant
Mass concentration is greater than 0 and to be less than or equal to 40wt%.It is further preferred that in the casting solution organic polymer resin mass concentration
For 20-40wt%, the mass concentration of pore-foaming agent is 1.5-8%, and the mass concentration of surfactant is 0.5-20wt%.Further
Preferably, the mass concentration of organic polymer resin is 30-35wt% in the casting solution, and the mass concentration of pore-foaming agent is 2-
5%, the mass concentration of surfactant is 1-10wt%.Select the organic polymer resin of above-mentioned mass concentration, pore-foaming agent and
Surfactant be on the one hand because highly selective porous septum can be made in the casting solution of the polymer containing high concentration,
And it can also guarantee high mechanical performance；It on the other hand is because realizing the micro- of device to hole by the dosage of control surfactant
It adjusts, so that porous septum reaches the balance to ion selectivity and proton conduction.
In a preferred embodiment of the invention, in step (1), the molecular weight and the degree of polymerization of the organic polymer resin
It does not limit specifically, can be known to the skilled in the art any can be dissolved in the organic solvent is had
Molecular weight and the degree of polymerization.There is no particular limitation for the selection of the organic polymer resin, and can be can be prepared institute
Any organic polymer resin of porous septum is stated, and is able to achieve the use mesh of the porous septum used for all-vanadium redox flow battery
's.Preferably, the molecular weight of the organic polymer resin is more than or equal to 700,000 g/mol；It selects organic high within the scope of this
Molecule resin is to can satisfy the requirement of all-vanadium flow porous septum because it is with preferable mechanical performance；It is preferred that
Ground, the organic polymer resin are selected from Kynoar, polysulfones, polyether sulfone, polyacrylonitrile, polyimides, polyether ketone ketone, gather
At least one of tetrafluoroethene, polybenzimidazoles or polyvinyl pyridine.
In a preferred embodiment of the invention, in step (1), the selection of the pore-foaming agent is not limited specifically,
It can be used cooperatively with organic polymer resin, and realize that pore acts on.Preferably, the pore-foaming agent is selected from macromolecule pore-foaming agent,
Or it is selected from small molecule pore-foaming agent；The macromolecule pore-foaming agent be selected from as known to those skilled in the art it is any can with it is organic high
The macromolecule pore-foaming agent that molecule resin complex uses.Preferably, the macromolecule pore-foaming agent is selected from polyvinylpyrrolidone
(PVP), one or more of polyethylene glycol or polyvinyl alcohol.The small molecule pore-foaming agent is selected from those skilled in the art
Any small molecule pore-foaming agent that can be used cooperatively with organic polymer resin known.Preferably, the small molecule
Pore-foaming agent is selected from one or more of lithium chloride, lithium bromide or aluminium chloride.
In a preferred embodiment of the invention, in step (1), the selection of the surfactant is not limited specifically
It is fixed, it can be used cooperatively with organic polymer resin, and the surface for the porous septum being prepared can be adsorbed on, and then realize logical
It crosses electrostatic repulsion and good selectivity is shown to the cation (such as vanadium ion) of high price, moreover, the surface-active
Agent can change the porous septum exchange rate of solvent and non-solvent and then final structure of influence porous septum in film forming procedure；
Preferably, the surfactant is selected from cationic surfactant and/or anionic surfactant；It is further preferred that described
Cationic surfactant is selected from the one or two such as hexadecyltrimethylammonium chloride, dodecyl dimethyl benzyl ammonium bromide
Quaternary ammonium salt；The anionic surfactant is selected from one or two kinds of sulphurs such as neopelex, dodecyl sodium sulfate
Hydrochlorate.
In a preferred embodiment of the invention, in step (1), the selection of the organic solvent is not limited specifically,
It, which can be, can dissolve organic polymer resin, pore-foaming agent and surfactant, and the mixing that stable homogeneous can be prepared is molten
Any organic solvent as known to those skilled in the art of liquid, it is preferable that the organic solvent is selected from dimethylformamide
(DMF), one or both of dimethyl acetamide (DMAC), N-methyl pyrrolidones (NMP) or dimethyl sulfoxide (DMSO) with
On.
In a preferred embodiment of the invention, in step (2), the substrate be can be as known to those skilled in the art
The substrate of any surfacing or out-of-flatness of diaphragm can be prepared, the size and shape of the substrate does not also limit specifically
It is fixed, it can reasonably be selected according to the size and shape for the diaphragm to be prepared, as known to those skilled in the art
Select a kind of compatible substrate of size and shape.Preferably, the substrate is glass plate, stainless steel plate or non-woven fabrics.
In a preferred embodiment of the invention, in step (2), the mode of the coating is not limited specifically, is used
Any coating method that can prepare porous septum as known to those skilled in the art, it is preferable that the coating method
It can be at least one of roller coating, blade coating, spraying, impregnating.As illustrative, the smearing with a thickness of 50-500 μm is utilized
Casting solution is applied on the substrate with surfacing by scraper.
In a preferred embodiment of the invention, in step (2), the standing is to be coated with the substrate of casting solution suitable
Suitable temperature (boiling point of the temperature lower than each component in casting solution, the boiling point of organic solvent preferably shorter than in casting solution,
Such as the temperature can be 0-100 DEG C) and air atmosphere under stand placement, the purpose is to use up the organic solvent in casting solution
Possible volatilization is complete, in order to which it solidifies in coagulating bath.It will be understood by those skilled in the art that the time of the standing does not have
There is specific restriction, it is related in the coating thickness of substrate surface and the environment temperature of the standing with casting solution, work as casting solution
It is thicker in the coating thickness of substrate surface and stand environment temperature it is lower when, the time of the standing is then extended, and casting is worked as
Film liquid it is relatively thin in the coating thickness of substrate surface and stand environment temperature it is higher when, the time of the standing is then shortened；
Preferably, the time of the standing is 1-30min.
In a preferred embodiment of the invention, in step (2), the casting solution is not specific in the thickness of substrate surface
Restriction, it will be understood by those skilled in the art that its can be it is related with the thickness of porous septum that is prepared is needed, if needing
When the thickness for the porous septum to be prepared is thicker, casting solution at this time is equally thicker in the thickness of substrate surface, similarly, if
When the thinner thickness for the porous septum for needing to be prepared, casting solution at this time is equally relatively thin in the thickness of substrate surface；Ability
Field technique personnel it should be understood that the casting solution in substrate surface after standing and solidification, thickness can change.It is preferred that
Ground, the casting solution the thickness of substrate surface to meet the porous septum being prepared with a thickness of 50-500 μm, further preferably
It is 150-300 μm.
In a preferred embodiment of the invention, in step (2), the selection of the coagulating bath is not limited specifically, this
What field technical staff knew any can make casting solution in the liquid being wherein cured.Preferably, the solidification
Bath is selected from one or more of water, ethyl alcohol, propyl alcohol, butanol, isopropanol, methanol, acetone, DMF or DMAC.It is exemplary
, the coagulating bath is the mixed solution of water and DMF；Or the mixed solution for water and DMAC, or be ethyl alcohol, or be water etc..
In a preferred embodiment of the invention, in step (2), the solidification temperature and time in coagulating bath be not specific
Restriction, the temperature and time that casting solution can be made to be cured as known to those skilled in the art, and also need guarantee prepare
Obtained porous septum used for all-vanadium redox flow battery realizes that it uses purpose.Preferably, the cured time is 1-60min.
[ionic conduction type porous septum used for all-vanadium redox flow battery]
As previously mentioned, the present invention provides a kind of ionic conduction type porous septum used for all-vanadium redox flow battery, the porous septum
It is to be prepared by above-mentioned method.
In a preferred embodiment of the invention, the porous septum is by adding the method for surfactant to containing
Obtained by the regulation of the conductive porous diaphragm of low proton of the casting solution preparation of high-concentration polymer, which both has height
The ion selectivity that has had again of ionic conductivity, show superior chemical property.It simultaneously can also be by adjusting table
The dosage of face activating agent realizes the controllable adjustment to the porous septum chemical property.
In a preferred embodiment of the invention, the thickness of the porous septum, aperture size and porosity be not specific
Restriction, can be selected with its use environment, and meet its as porous septum used for all-vanadium redox flow battery use mesh
's.Preferably, the porous septum with a thickness of 50-500 μm, it is further preferred that the porous septum with a thickness of 150-300 μ
m.Preferably, the pore size of the porous septum is 0.5-100nm, the porosity 20-80% of the porous septum.
[purposes of ionic conduction type porous septum used for all-vanadium redox flow battery]
As previously mentioned, the present invention provides a kind of purposes of ionic conduction type porous septum, it to be used for all-vanadium flow battery.
[all-vanadium flow battery]
As previously mentioned, the present invention provides a kind of all-vanadium flow battery comprising above-mentioned porous septum.
In a preferred embodiment of the invention, the coulombic efficiency of the all-vanadium flow battery is 89% or more, voltage effect
Rate is 80% or more, and energy efficiency is 75% or more.
In a preferred embodiment of the invention, the charging voltage of the all-vanadium flow battery is lower than 1.4V, discharge voltage
Higher than 1.3V.
The voltage efficiency refers to the ratio of the average voltage of discharge voltage and the average voltage of charging voltage.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read content disclosed in this invention, ability
Field technique personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within protection defined by the present invention
Within the scope of.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Embodiment 1
By the hexadecyltrimethylammonium chloride ultrasonic disperse of the PVP of 0.5g and 0.4g in 16mL dimethyl acetamide,
Uniform solution is formed, the Kynoar that 8.4g is then added is prepared into uniform polymer solution in 80 DEG C of heating stirrings,
That is casting solution, using the mixed liquor (volume ratio 1:1) of second alcohol and water is that coagulating bath is controlled on a glass using hand scaler
The film that casting solution processed is formed with a thickness of 250 μm, the film which forms first is evaporated into 10min in air, then immerse solidifying
Gu solidifying 30min in bath, the PVDF porous septum being prepared is put and is saved backup in water.
The mass concentration of organic polymer resin is 34.6wt%, pore-foaming agent in the mixed solution in the mixed solution
Mass concentration be 2.05wt%, the mass concentration of cationic surfactant is 1.6wt% in the mixed solution.
All-vanadium flow battery is assembled into using the above-mentioned PVDF porous septum being prepared, wherein Catalytic Layer is activated carbon
Felt, bipolar plates are graphite plate, and the effective area of the PVDF porous septum is 4cm-2, current density 80mAcm-2, electrolysis
Vanadium ion concentration is 1.5molL in liquid-1, sulfuric acid concentration 3molL-1。
Fig. 1 is charging and discharging curve of the porous septum of the preparation of embodiment 1 in all-vanadium flow battery.It can know from Fig. 1
Road, the initial charge voltage of the battery assembled with the porous septum are lower than 1.38V, and initial discharge voltage is higher than 1.4V, illustrates this
The proton conductivity that porous septum has had, so that the battery of assembling has weak polarization phenomena.
The all-vanadium flow battery coulombic efficiency of the PVDF porous septum assembling is 94%, voltage efficiency 80.2%, energy
Amount efficiency is 75.4%.
Embodiment 2
For other conditions with embodiment 1, difference is that the quality of hexadecyltrimethylammonium chloride is 0.6g.
The mass concentration of organic polymer resin is 34.3wt%, pore-foaming agent in the mixed solution in the mixed solution
Mass concentration be 2.04wt%, the mass concentration of cationic surfactant is 2.45wt% in the mixed solution.
Test condition is with embodiment 1, as a result: coulombic efficiency 93.8%, voltage efficiency 85.2%, and energy efficiency is
80%.
Embodiment 3
For other conditions with embodiment 1, difference is that the quality of hexadecyltrimethylammonium chloride is 0.8g.
The mass concentration of organic polymer resin is 34wt% in the mixed solution, pore-foaming agent in the mixed solution
Mass concentration is 2.02wt%, and the mass concentration of cationic surfactant is 3.23wt% in the mixed solution.
Test condition is with embodiment 1, as a result: coulombic efficiency 89.6%, voltage efficiency 83.7%, and energy efficiency is
75%.
Comparative example 1
By the PVP ultrasonic disperse of 0.5g in 16mL dimethyl acetamide, uniform solution is formed, is then added 8.4g's
Kynoar is prepared into uniform polymer solution, i.e. casting solution in 80 DEG C of heating stirrings, using the mixed liquor of second alcohol and water
(volume ratio 1:1) is coagulating bath, using hand scaler, control on a glass the film that casting solution is formed with a thickness of 250 μm,
The film that casting solution is formed first is evaporated into 10min in air, then immerses and solidifies 30min in coagulating bath, the PVDF that will be prepared
Porous septum is put to be saved backup in water.
The mass concentration of organic polymer resin is 35wt% in the mixed solution, pore-foaming agent in the mixed solution
Mass concentration is 2.09wt%, and the mass concentration of surfactant is 0wt% in the mixed solution.
All-vanadium flow battery is assembled using the above-mentioned PVDF porous septum being prepared, wherein Catalytic Layer is activated carbon-fiber felt,
Bipolar plates are graphite plate, and the effective area of the PVDF porous septum is 4cm-2, current density 80mAcm-2, in electrolyte
Vanadium ion concentration is 1.5molL-1, sulfuric acid concentration 3molL-1。
The all-vanadium flow battery of assembling can not carry out charge-discharge test due to larger resistance.
Fig. 2 is the SEM cross section structure figure of porous septum prepared by comparative example 1 and embodiment 1.From Fig. 2 it is recognised that with right
The aperture (as shown in Figure 2 a) for the porous septum that ratio 1 is prepared is compared, and the porous septum that embodiment 1 is prepared is adding
The aperture of the caudacoria of surfactant is (as shown in Figure 2 b) to increase, and facilitates transmission of the porous septum to proton.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of ionic conduction type porous septum, which comprises the steps of:
Using organic polymer resin as raw material, it is mixed and made into casting solution with pore-foaming agent, surfactant, is turned by immersion precipitation phase
The ionic conduction type porous septum is prepared in change method.
2. preparation method according to claim 1, which is characterized in that the preparation method includes the following steps:
(1) organic polymer resin, pore-foaming agent and surfactant are dissolved in organic solvent, obtain mixed solution, i.e. casting film
Liquid；
(2) casting solution of step (1) is coated in substrate surface, immerses in coagulating bath after standing and solidify, be prepared it is described from
Sub- conduction type porous septum.
3. preparation method according to claim 1 or 2, which is characterized in that organic high in the casting solution in step (1)
The mass concentration of molecule resin is 10-50wt%, and the mass concentration of pore-foaming agent is 1-10%, and the mass concentration of surfactant is
Greater than 0 and it is less than or equal to 40wt%.
Preferably, the mass concentration of organic polymer resin is 20-40wt% in the casting solution, and the mass concentration of pore-foaming agent is
1.5-8%, the mass concentration of surfactant are 0.5-20wt%.
Preferably, the mass concentration of organic polymer resin is 30-35wt% in the casting solution, and the mass concentration of pore-foaming agent is
2-5%, the mass concentration of surfactant are 1-10wt%.
4. preparation method according to claim 1-3, which is characterized in that the molecule of the organic polymer resin
Amount is more than or equal to 700,000 g/mol；Preferably, the organic polymer resin is selected from Kynoar, polysulfones, polyether sulfone, gathers
At least one of acrylonitrile, polyimides, polyether ketone ketone, polytetrafluoroethylene (PTFE), polybenzimidazoles or polyvinyl pyridine.
5. preparation method according to claim 1-4, which is characterized in that the pore-foaming agent is selected from macromolecule pore
Agent, or it is selected from small molecule pore-foaming agent；Preferably, the macromolecule pore-foaming agent is selected from polyvinylpyrrolidone (PVP), polyethylene glycol
Or one or more of polyvinyl alcohol.Preferably, the small molecule pore-foaming agent is selected from lithium chloride, lithium bromide or aluminium chloride
One or more of.
Preferably, the surfactant is selected from cationic surfactant and/or anionic surfactant；It is further preferred that
The cationic surfactant be selected from hexadecyltrimethylammonium chloride, dodecyl dimethyl benzyl ammonium bromide etc. it is a kind of or
Two kinds of quaternary ammonium salts；The anionic surfactant is selected from the one kind such as neopelex, dodecyl sodium sulfate or two
Kind sulfonate.
Preferably, the organic solvent is selected from dimethylformamide (DMF), dimethyl acetamide (DMAC), N-methyl pyrrolidines
One or more of ketone (NMP) or dimethyl sulfoxide (DMSO).
6. according to the described in any item preparation methods of claim 2-5, which is characterized in that in step (2), the coagulating bath is selected from
One or more of water, ethyl alcohol, propyl alcohol, butanol, isopropanol, methanol, acetone, DMF or DMAC.
Preferably, in step (2), the cured time is 1-60min.
7. a kind of ionic conduction type porous septum, which is characterized in that the porous septum is by any one of claim 1-6 institute
What the method stated was prepared.
8. porous septum according to claim 7, which is characterized in that the porous septum with a thickness of 50-500 μm, also
Preferably, the porous septum with a thickness of 150-300 μm.
Preferably, the pore size of the porous septum is 0.5-100nm, the porosity 20-80% of the porous septum.
9. the purposes of porous septum described in claim 7 or 8, is used for all-vanadium flow battery.
10. a kind of all-vanadium flow battery comprising porous septum described in claim 7 or 8.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522042A (en) * | 2021-08-07 | 2021-10-22 | 南开大学 | Preparation method and application of homogeneous cation exchange membrane containing alkylbenzene sulfonate |
| CN113522043A (en) * | 2021-08-07 | 2021-10-22 | 南开大学 | Preparation method and application of homogeneous cation exchange membrane of anionic surfactant |
| CN118420970A (en) * | 2024-06-18 | 2024-08-02 | 液流储能科技有限公司 | Ion conductive film, and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60257076A (en) * | 1984-06-01 | 1985-12-18 | Sumitomo Electric Ind Ltd | Redox flow battery |
| WO2005023921A1 (en) * | 2003-09-03 | 2005-03-17 | Toagosei Co., Ltd. | Method for continuous production of functional film |
| CN101174705A (en) * | 2006-11-01 | 2008-05-07 | 中国科学院金属研究所 | Method for preparing all vanadium ion redox flow battery electrolyte |
| CN102299353A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Application of organic-inorganic composite membrane in acid electrolyte redox energy storage battery |
| CN103025411A (en) * | 2010-05-21 | 2013-04-03 | 阿德里安·布罗曾尔 | Self-assembled surfactant structures |
| CN103682210A (en) * | 2012-09-06 | 2014-03-26 | 中国科学院大连化学物理研究所 | Application of organic-inorganic porous composite diaphragm in flow energy storage battery |
| CN105304847A (en) * | 2014-07-30 | 2016-02-03 | 中国科学院大连化学物理研究所 | Application of heat-resistant porous diaphragm to lithium ion battery |
| CN105789534A (en) * | 2014-12-26 | 2016-07-20 | 上海交通大学 | Preparation method for sulfonated polystyrene/polyolefin microporous film cross-linking composite membrane |
| KR20170063008A (en) * | 2015-11-30 | 2017-06-08 | 전남대학교산학협력단 | Polymer electrolyte composite membrane with low permeability and high proton conductivity for redox flow battery and redox flow battery comprising the same |
| CN107528079A (en) * | 2016-06-20 | 2017-12-29 | 中国科学院大连化学物理研究所 | A kind of solvent processing method of flow battery polyalcohol stephanoporate ion-conductive membranes |
-
2018
- 2018-02-27 CN CN201810162374.1A patent/CN110197919B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60257076A (en) * | 1984-06-01 | 1985-12-18 | Sumitomo Electric Ind Ltd | Redox flow battery |
| WO2005023921A1 (en) * | 2003-09-03 | 2005-03-17 | Toagosei Co., Ltd. | Method for continuous production of functional film |
| CN101174705A (en) * | 2006-11-01 | 2008-05-07 | 中国科学院金属研究所 | Method for preparing all vanadium ion redox flow battery electrolyte |
| CN103025411A (en) * | 2010-05-21 | 2013-04-03 | 阿德里安·布罗曾尔 | Self-assembled surfactant structures |
| CN102299353A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Application of organic-inorganic composite membrane in acid electrolyte redox energy storage battery |
| CN103682210A (en) * | 2012-09-06 | 2014-03-26 | 中国科学院大连化学物理研究所 | Application of organic-inorganic porous composite diaphragm in flow energy storage battery |
| CN105304847A (en) * | 2014-07-30 | 2016-02-03 | 中国科学院大连化学物理研究所 | Application of heat-resistant porous diaphragm to lithium ion battery |
| CN105789534A (en) * | 2014-12-26 | 2016-07-20 | 上海交通大学 | Preparation method for sulfonated polystyrene/polyolefin microporous film cross-linking composite membrane |
| KR20170063008A (en) * | 2015-11-30 | 2017-06-08 | 전남대학교산학협력단 | Polymer electrolyte composite membrane with low permeability and high proton conductivity for redox flow battery and redox flow battery comprising the same |
| CN107528079A (en) * | 2016-06-20 | 2017-12-29 | 中国科学院大连化学物理研究所 | A kind of solvent processing method of flow battery polyalcohol stephanoporate ion-conductive membranes |
Non-Patent Citations (1)
| Title |
|---|
| RAHIMPOUR等: ""The effect of anionic, non-ionic and cationic surfactants on morphology and performance of polyethersulfone ultrafiltration membranes for milk concentration"", 《JOURNAL OF MEMBRANE SCIENCE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522042A (en) * | 2021-08-07 | 2021-10-22 | 南开大学 | Preparation method and application of homogeneous cation exchange membrane containing alkylbenzene sulfonate |
| CN113522043A (en) * | 2021-08-07 | 2021-10-22 | 南开大学 | Preparation method and application of homogeneous cation exchange membrane of anionic surfactant |
| CN118420970A (en) * | 2024-06-18 | 2024-08-02 | 液流储能科技有限公司 | Ion conductive film, and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN110197919B (en) | 2021-08-17 |
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Denomination of invention: An ion conductive porous membrane for vanadium flow batteries and its preparation method and application Granted publication date: 20210817 Pledgee: Pudong Development Bank of Shanghai Limited by Share Ltd. Changsha branch Pledgor: HUNAN YINFENG NEW ENERGY Co.,Ltd. Registration number: Y2024980027570 |