CN104377042A - Ion selective membrane for pseudo-electric super capacitor - Google Patents
Ion selective membrane for pseudo-electric super capacitor Download PDFInfo
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- CN104377042A CN104377042A CN201410551665.1A CN201410551665A CN104377042A CN 104377042 A CN104377042 A CN 104377042A CN 201410551665 A CN201410551665 A CN 201410551665A CN 104377042 A CN104377042 A CN 104377042A
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- ion selective
- membrane
- selective separator
- ion
- separator according
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- 239000012528 membrane Substances 0.000 title abstract description 23
- 239000003990 capacitor Substances 0.000 title abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000012452 mother liquor Substances 0.000 claims abstract description 18
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 17
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 11
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000012546 transfer Methods 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims description 49
- 230000000873 masking effect Effects 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- 235000013312 flour Nutrition 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- JSAIENUMNDAGTD-UHFFFAOYSA-N benzene ethene styrene Chemical compound C1=CC=CC=C1.C=C.C=C.C=CC1=CC=CC=C1 JSAIENUMNDAGTD-UHFFFAOYSA-N 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000012456 homogeneous solution Substances 0.000 abstract 4
- 239000012749 thinning agent Substances 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 14
- 229910001456 vanadium ion Inorganic materials 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 230000010220 ion permeability Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000004695 Polyether sulfone Substances 0.000 description 4
- 229920006393 polyether sulfone Polymers 0.000 description 4
- 239000003011 anion exchange membrane Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 thioether sulfone Chemical class 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 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
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004758 underpotential deposition Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Cell Separators (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention discloses an ion selective membrane for a pseudo-electric super capacitor. A method for preparing the ion selective membrane for the pseudo-electric super capacitor comprises the steps that (1) raw material ion exchange resin, a forming agent, a thinning agent and a filling agent are stirred for thirty hours to eighty hours at the temperature ranging from 20 DEG C to 90 DEG C, so that a homogeneous solution is formed; (2) rotary evaporation is conducted on the homogeneous solution till the viscosity of the homogeneous solution reaches 2 Pa.s-10Pa.s, so that membrane mother liquor is prepared, wherein membrane forming is facilitated by controlling the viscosity of the homogeneous solution between 2 Pa.s and 10 Pa.s, and the viscosity is measured through a viscosimeter at the room temperature; (3) the humidity condition is controlled, the prepared membrane mother liquor is prepared into a liquid membrane according to the flowing spread membrane forming method or the transfer membrane coating method or the scarper membrane coating method; (4) the liquid membrane is dipped in sulfuric acid after being dried, so that the ion selective membrane is obtained. According to the ion selective membrane for the pseudo-electric super capacitor, the raw materials are low in price and easy to obtain, the preparing method is simple and easy to implement, continuous preparation can be achieved, and cost of the membrane is greatly reduced; the ion selective membrane is applied to the pseudo-electric super capacitor and has high mechanical strength and good electrochemical performance.
Description
Technical field
The present invention relates to counterfeit electric-type ultracapacitor production technical field, particularly one counterfeit electric-type ultracapacitor ion selective separator.
Background technology
Ultracapacitor can be divided into double electric layer capacitor, Faradic pseudo-capacitor (also known as counterfeit electric-type ultracapacitor), hybrid super capacitor by energy storage principle.Counterfeit electric-type ultracapacitor be electrode surface and body mutually in two dimension or accurate two-dimensional space on, electroactive material carries out underpotential deposition, there is chemical adsorption desorption or the redox reaction of height, make electrode store high-density electric charge and form counterfeit electric-type ultracapacitor.For counterfeit electric-type electric capacity, it stores process of electric charge and not only comprises storage on electric double layer, and comprise electrolyte intermediate ion in electrode active material due to redox reaction by charge storage in electrode.Super capacitor is the novel energy-storing electric elements between traditional capacitance and secondary cell, have that power density is high, the life-span be long, Maintenance free and discharge and recharge rapidly, the advantage such as environmental protection, make it be widely used as power power-supply or accumulation power supply in fields such as industrial electronic, communications and transportation, the renewable energy resources, military affairs.Industry authoritative expert think, greatly develops ultracapacitor, has important and far-reaching strategic importance for construction Low Carbon World and development green economy.
Barrier film is as one of layer assembly in counterfeit electric-type ultracapacitor, and its status is very important.It can effectively stop the physical contact between positive pole and negative pole to prevent battery short circuit on the one hand, blocks electric transmission, suppresses ultracapacitor self-discharge phenomenon.On the other hand allow ion conducting selectively again, thus complete the transmitting procedure of electric current, form a complete current circuit.As the important component part of counterfeit electric-type electric capacity, the quality of membrane properties decides the internal resistance of capacitor, interfacial property and high stability, and then the capacity affecting capacitor, life-span and fail safe.
Widely used commercialization barrier film mainly comprises Nafion film, Selemion film, Daramic film in the market, commercial amberplex generally has good conductivity and electrochemical stability, but film is expensive, and effectively can not stop the infiltration of other ion in electrolyte, therefore voltage efficiency and the energy efficiency of super capacitor reduce greatly.
Summary of the invention
The object of the present invention is to provide a kind of counterfeit electric-type ultracapacitor ion selective separator, cheaper starting materials is easy to get, preparation method is simple, can serialization prepare, greatly reduce the cost of barrier film, ion selective separator of the present invention is applied to counterfeit electric-type ultracapacitor, has high mechanical strength and good chemical property.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of counterfeit electric-type ultracapacitor ion selective separator, described ion selective separator is prepared from by following methods:
(1) by raw material ion exchange resin, forming agent, diluent and filler, at 20-90 DEG C, stir 30-80h and form homogeneous phase solution;
(2) by homogeneous phase solution rotary evaporation, be that 2-10Pa.s obtains masking mother liquor to viscosity; Control viscosity is 2-10Pa.s, is beneficial to film forming, and viscosity is adopt viscometer determining to obtain under room temperature.
(3) controlled humidity condition, adopts a kind of method in casting film-forming, transfer film, scraper film to make liquid film by masking mother liquor;
(4) (60-100 DEG C of dry 30min-90min) after liquid film drying process, soak with sulfuric acid, obtain ion selective separator.
Gained ion selective separator of the present invention has ion and selects on state characteristic, and its ion selectivity part is anion-exchange membrane, has the filter membrane of loose structure; Amberplex with sulfonic group, phosphate, phosphorous acid base, carboxylic acid group, phenolic group one or more; The filter membrane with loose structure is the one of milipore filter, miillpore filter, NF membrane, microfiltration membranes, hollow fiber ultrafiltration membrane, Sai Er filter membrane.The channel diameter with the filter membrane of loose structure is 0.1-20 nanometer, and energy selectivity is through hydrogen ion.
Its maximum feature of gained ion selective separator of the present invention is exactly with low cost, selecting and simplifying production technology and realize, being applicable to acidic electrolysis liquid system by controlling raw material.
As preferably, the weight percent proportioning of each component of described raw material is: ion exchange resin 2%-10%, forming agent 5%-20%, filler 0.1%-1%, and surplus is diluent.Preferably, the weight percent proportioning of each component of described raw material is: ion exchange resin 3%-5%, forming agent 11%-14%, filler 0.1%-1%, and surplus is diluent.
Ion exchange resin, forming agent, filler etc. that the present invention is prepared selected by ion selective separator are electronic body; Ion exchange resin ensure that ion selectivity, and the proportioning controlling feed components makes ion selective separator achieve ion selectivity conducting and electronic isolation two kinds of functions so simultaneously.
As preferably, described ion exchange resin selects one or more in styrene diethylene benzene copoly mer, polysulfones, polystyrene, Kynoar.Polysulfones can be polyether sulfone, polyaryl thioether sulfone.Ion exchange resin of the present invention is all introduce the resin changing anion.
As preferably, described forming agent is selected from one or more in sodium carboxymethylcellulose, polyvinylpyrrolidone, hydroxypropyl methylcellulose.
As preferably, described filler is selected from one or more in titanium dioxide, carbon black, graphite, glass microballoon, silica flour.
As preferably, described diluent is selected from one or more in dimethyl formamide, dimethylacetylamide, dibutyl phthalate, dioctyl phthalate.
The resin that the present invention selects has excellent thermal endurance, physical and mechanical properties, insulation property, excellent dimensional stability, and good chemical-resistant; Forming agent is water soluble polymer, contributes to the hydrophily of film forming and pore-forming and increase film; Filler can reduce coefficient of linear expansion and shrinkage, improves dimensional stability and the mechanical strength of barrier film, changes the mobility of glue and regulates viscosity.
As preferably, in step (2), the parameter of rotary evaporation is: vacuum degree control is-0.1MPa ~-0.85MPa, temperature 60-100 DEG C.
As preferably, the humid control in step (3) is 1%-40%.Relative humidities is 1% ~ 40%, is for controlling steam to the impact of film quality, being held in film quality.
As preferably, described in step (4), the concentration of sulfuric acid is 1mol/L-3mol/L, and soak time is 2-10 days.Sulfonic group can be introduced on film surface while adopting sulfuric acid to be immersed in formation pore structure, increase the hydrophily of film.
As preferably, the thickness of described ion selective separator is 50-200 micron.
The invention has the beneficial effects as follows:
1, ion selective separator of the present invention can in acidic electrolysis liquid system, and selectivity, through hydrogen ion, improves the stability of counterfeit electric-type capacitor system.
2, ion selective separator of the present invention achieves ion selectivity conducting and electronic isolation two kinds of functions simultaneously, overcomes the defect of original barrier film single type electronic isolation function.
3, ion selective separator preparation method of the present invention is simple, and cheaper starting materials is easy to get, and preparation cost is low.
Accompanying drawing explanation
Fig. 1 is the counterfeit electric-type ultracapacitor discharge and recharge schematic diagram adopting ion selective separator of the present invention assembling.
Embodiment
Below by specific embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.
In the present invention, if not refer in particular to, the raw material adopted and equipment etc. all can be buied from market or this area is conventional.Method in following embodiment, if no special instructions, is the conventional method of this area.
Embodiment 1:
(1) by styrene diethylene benzene copoly mer (commercially available) 10kg, sodium carboxymethylcellulose 10kg, hydroxypropyl methylcellulose 10kg, dibutyl phthalate 40kg, dioctyl phthalate 29.9kg, carbon black 0.05kg and graphite 0.05kg, at 20 DEG C, stir 80h and form homogeneous phase solution.
(2) by homogeneous phase solution rotary evaporation, the parameter of rotary evaporation is: vacuum degree control is-0.1MPa, temperature 60 C, is that 2Pa.s obtains masking mother liquor to viscosity.
(3) controlling relative humidity is 1%, adopts casting film-forming method (existing method) to make liquid film in masking mother liquor.
(4), after liquid film 60 DEG C of dry 90min, soak 10 days with the sulfuric acid that concentration is 1mol/L, obtained thickness is the ion selective separator of 100 microns, carries out the determination experiment of mechanical performance, moisture content, vanadium ion permeability and film resistance.By the graphite felt of thickness 1mm as positive and negative electrode, 2MVOSO
4/ (VO
2)
2sO
4+ 1M H
2sO
4as anode electrolyte, 2M VSO
4/ V
2(SO
4)
3+ 1MH
2sO
4as electrolyte liquid, be assembled into ultracapacitor monomer.
Under the charge-discharge magnification of 60C, adopt the fake capacitance initial specific capacities 3450mAh/kg of ion selective separator of the present invention, specific energy is 4.14Wh/kg, and cycle life reaches more than 100,000 times.
Embodiment 2:
(1) by polyether sulfone 2kg, polyvinylpyrrolidone 5kg, dimethyl formamide 92kg and titanium dioxide 1kg, at 90 DEG C, stir 30h and form homogeneous phase solution.
(2) by homogeneous phase solution rotary evaporation, the parameter of rotary evaporation is: vacuum degree control is-0.85MPa, temperature 100 DEG C, is that 10Pa.s obtains masking mother liquor to viscosity.
(3) controlling relative humidity is 40%, adopts scraper coating method (existing method) to make liquid film in masking mother liquor.
(4), after liquid film 100 DEG C of dry 30min, soak 2 days with the sulfuric acid that concentration is 3mol/L, obtained thickness is the ion selective separator of 100 microns, carries out the determination experiment of mechanical performance, moisture content, vanadium ion permeability and film resistance.By the graphite felt of thickness 1mm as positive and negative electrode, 2MVOSO
4/ (VO
2)
2sO
4+ 1M H
2sO
4as anode electrolyte, 2M VSO
4/ V
2(SO
4)
3+ 1MH
2sO
4as electrolyte liquid, be assembled into ultracapacitor monomer.
Under the charge-discharge magnification of 60C, adopt the fake capacitance initial specific capacities 3500mAh/kg of ion selective separator of the present invention, specific energy is 4.20Wh/kg, and cycle life reaches more than 100,000 times.
Embodiment 3:
(1) by polyether sulfone 5kg, Kynoar (trade mark 2801) 0.1kg, polyvinylpyrrolidone 10kg, dimethylacetylamide 84kg and silica flour 0.9kg, at 45 DEG C, stir 70h and form homogeneous phase solution.
(2) by homogeneous phase solution rotary evaporation, the parameter of rotary evaporation is: vacuum degree control is-0.9MPa, temperature 80 DEG C, is that 3Pa.s obtains masking mother liquor to viscosity.
(3) controlling relative humidity is 20%, adopts transfer coating method (existing method) to make liquid film in masking mother liquor.
(4), after liquid film 80 DEG C of dry 60min, soak 7 days with the sulfuric acid that concentration is 1.5mol/L, obtained thickness is the ion selective separator of 100 microns, carries out the determination experiment of mechanical performance, moisture content, vanadium ion permeability and film resistance.By the graphite felt of thickness 1mm as positive and negative electrode, 2MVOSO
4/ (VO
2)
2sO
4+ 1M H
2sO
4as anode electrolyte, 2M VSO
4/ V
2(SO
4)
3+ 1MH
2sO
4as electrolyte liquid, be assembled into ultracapacitor monomer.Under the charge-discharge magnification of 60C, adopt the fake capacitance initial specific capacities 3650mAh/kg of ion selective separator of the present invention, specific energy is 4.38Wh/kg, and cycle life reaches more than 100,000 times.Cycle-index-capability retention relation as shown in Figure 1.
Embodiment 4:
(1) by polyether sulfone 3kg, Kynoar (trade mark 2801) 0.05kg, polyvinylpyrrolidone 12kg, dimethylacetylamide 84.45kg and silica flour 0.5kg, at 35 DEG C, stir 70h and form homogeneous phase solution.
(2) by homogeneous phase solution rotary evaporation, the parameter of rotary evaporation is: vacuum degree control is-0.9MPa, temperature 85 DEG C, is that 2800mPa.s obtains masking mother liquor to viscosity.
(3) controlling relative humidity is 20%, adopts transfer coating method (existing method) to make liquid film in masking mother liquor.
(4), after liquid film 85 DEG C of dry 60min, soak 7 days with the sulfuric acid that concentration is 2.5mol/L, obtained thickness is the ion selective separator of 100 microns, carries out the determination experiment of mechanical performance, moisture content, vanadium ion permeability and film resistance.By the graphite felt of thickness 1mm as positive and negative electrode, 2MVOSO
4/ (VO
2)
2sO
4+ 1M H
2sO
4as anode electrolyte, 2M VSO
4/ V
2(SO
4)
3+ 1MH
2sO
4as electrolyte liquid, be assembled into ultracapacitor monomer.Under the charge-discharge magnification of 60C, adopt the fake capacitance initial specific capacities 3600mAh/kg of ion selective separator, specific energy is 4.32Wh/kg, and cycle life reaches more than 100,000 times.
Embodiment 5:
(1) by polyaryl thioether sulfone 5kg, Kynoar (trade mark 2801) 0.15kg, sodium carboxymethylcellulose 10kg, dimethyl formamide 84.75kg and silica flour 0.1kg, at 40 DEG C, stir 70h and form homogeneous phase solution.
(2) by homogeneous phase solution rotary evaporation, the parameter of rotary evaporation is: vacuum degree control is-0.9MPa, temperature 80 DEG C, is that 2900mPa.s obtains masking mother liquor to viscosity.
(3) controlling relative humidity is 20%, adopts transfer coating method (existing method) to make liquid film in masking mother liquor.
(4), after liquid film 80 DEG C of dry 60min, soak 7 days with the sulfuric acid that concentration is 2mol/L, obtained thickness is the ion selective separator of 100 microns, carries out the determination experiment of mechanical performance, moisture content, vanadium ion permeability and film resistance.By the graphite felt of thickness 1mm as positive and negative electrode, 2M VOSO
4/ (VO
2)
2sO
4+ 1M H
2sO
4as anode electrolyte, 2M VSO
4/ V
2(SO
4)
3+ 1M H
2sO
4as electrolyte liquid, be assembled into ultracapacitor monomer.Under the charge-discharge magnification of 60C, adopt the fake capacitance initial specific capacities 3750mAh/kg of ion selective separator, specific energy is 4.5Wh/kg, and cycle life reaches more than 100,000 times.
Embodiment 6:
(1) by polyaryl thioether sulfone 3kg, Kynoar (trade mark 2801) 0.1kg, sodium carboxymethylcellulose 12kg, dimethyl formamide 84.8kg and silica flour 0.1kg, at 40 DEG C, stir 70h and form homogeneous phase solution.
(2) by homogeneous phase solution rotary evaporation, the parameter of rotary evaporation is: vacuum degree control is-0.9MPa, temperature 80 DEG C, is that 3Pa.s obtains masking mother liquor to viscosity.
(3) controlling relative humidity is 20%, adopts transfer coating method (existing method) to make liquid film in masking mother liquor.
(4), after liquid film 80 DEG C of dry 60min, soak 7 days with the sulfuric acid that concentration is 2mol/L, obtained thickness is the ion selective separator of 100 microns, carries out the determination experiment of mechanical performance, moisture content, vanadium ion permeability and film resistance.By the graphite felt of thickness 1mm as positive and negative electrode, 2M VOSO
4/ (VO
2)
2sO
4+ 1M H
2sO
4as anode electrolyte, 2M VSO
4/ V
2(SO
4)
3+ 1M H
2sO
4as electrolyte liquid, be assembled into ultracapacitor monomer.Under the charge-discharge magnification of 60C, adopt the fake capacitance initial specific capacities 3800mAh/kg of ion selective separator, specific energy is 4.56Wh/kg, and cycle life reaches more than 100,000 times.
Comparative example
Employing Nafion 117 thickness is the contrast test film that the film of 100 microns is tested as vanadium ion mechanical performance, moisture content, permeability and film resistance.The results are shown in Table 1.
The mensuration reference literature " research of quaternized Phthalazinone polyether-ketone anion-exchange membrane used for all-vanadium redox flow battery " (author: the fragrant unit in Yichun: Dalian University of Technology delivers the time: 2009) of vanadium ion mechanical performance, moisture content, permeability.
The mensuration of film resistance adopts the method for testing in document " performance of all-vanadium flow battery barrier film in vanadium solution " (author: Tan Ning unit: Central South University delivers the time: 2004) to carry out.
The performance test of table 1 anion-exchange membrane
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (10)
1. a counterfeit electric-type ultracapacitor ion selective separator, is characterized in that: described ion selective separator is prepared from by following methods:
(1) by raw material ion exchange resin, forming agent, diluent and filler, at 20-90 DEG C, stir 30-80h and form homogeneous phase solution;
(2) by homogeneous phase solution rotary evaporation, be that 2-10Pa.s obtains masking mother liquor to viscosity;
(3) controlled humidity condition, adopts a kind of method in casting film-forming, transfer film, scraper film to make liquid film by masking mother liquor;
(4), after liquid film drying process, soak with sulfuric acid, obtain ion selective separator.
2. ion selective separator according to claim 1, is characterized in that: the weight percent proportioning of each component of described raw material is: ion exchange resin 2%-10%, forming agent 5%-20%, filler 0.1%-1%, and surplus is diluent.
3. ion selective separator according to claim 1 and 2, is characterized in that: described ion exchange resin selects one or more in styrene diethylene benzene copoly mer, polysulfones, polystyrene, Kynoar.
4. ion selective separator according to claim 1 and 2, is characterized in that: described forming agent is selected from one or more in sodium carboxymethylcellulose, polyvinylpyrrolidone, hydroxypropyl methylcellulose.
5. ion selective separator according to claim 1 and 2, is characterized in that: described filler is selected from one or more in titanium dioxide, carbon black, graphite, glass microballoon, silica flour.
6. ion selective separator according to claim 1 and 2, is characterized in that: described diluent is selected from one or more in dimethyl formamide, dimethylacetylamide, dibutyl phthalate, dioctyl phthalate.
7. ion selective separator according to claim 1 and 2, is characterized in that: in step (2), the parameter of rotary evaporation is: vacuum degree control is-0.1MPa ~-0.85MPa, temperature 60-100 DEG C.
8. ion selective separator according to claim 1 and 2, is characterized in that: the humid control in step (3) is 1%-40%.
9. ion selective separator according to claim 1 and 2, is characterized in that: described in step (4), the concentration of sulfuric acid is 1mol/L-3mol/L, and soak time is 2-10 days.
10. ion selective separator according to claim 1 and 2, is characterized in that: the thickness of described ion selective separator is 50-200 micron.
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| CN105719848A (en) * | 2016-01-29 | 2016-06-29 | 佛山市聚成生化技术研发有限公司 | Preparation method for long-cycling-life supercapacitor and supercapacitor prepared by same |
| CN110165125A (en) * | 2019-05-21 | 2019-08-23 | 吉林大学 | A kind of preparation method of fly ash float coating nonwoven cloth diaphragm |
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| US20110242730A1 (en) * | 2010-03-31 | 2011-10-06 | Xiangyang Zhou | Solid state energy storage device and method |
| CN103441230A (en) * | 2013-08-21 | 2013-12-11 | 东莞新能源科技有限公司 | Organic/inorganic composite porous isolating membrane, preparation method thereof and electrochemical device |
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| US20110242730A1 (en) * | 2010-03-31 | 2011-10-06 | Xiangyang Zhou | Solid state energy storage device and method |
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