CN103456504A - Gel polymer electrolyte film, and manufacturing method and application for same - Google Patents
Gel polymer electrolyte film, and manufacturing method and application for same Download PDFInfo
- Publication number
- CN103456504A CN103456504A CN2012101756341A CN201210175634A CN103456504A CN 103456504 A CN103456504 A CN 103456504A CN 2012101756341 A CN2012101756341 A CN 2012101756341A CN 201210175634 A CN201210175634 A CN 201210175634A CN 103456504 A CN103456504 A CN 103456504A
- Authority
- CN
- China
- Prior art keywords
- polymer electrolyte
- gel polymer
- electrolyte film
- ionic liquid
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 239000002608 ionic liquid Substances 0.000 claims abstract description 37
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 13
- -1 iodo propene carbonate Chemical compound 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 19
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 6
- 125000001475 halogen functional group Chemical group 0.000 claims description 6
- 101710134784 Agnoprotein Proteins 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 238000004448 titration Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- IWZMSZQCVAFYHL-UHFFFAOYSA-N C(O)(O)=O.BrC=CC Chemical compound C(O)(O)=O.BrC=CC IWZMSZQCVAFYHL-UHFFFAOYSA-N 0.000 claims description 4
- MYXJUONNAJPJJT-UHFFFAOYSA-N carbonochloridic acid;prop-1-ene Chemical group CC=C.OC(Cl)=O MYXJUONNAJPJJT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 229920000307 polymer substrate Polymers 0.000 abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 229910021389 graphene Inorganic materials 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000005030 aluminium foil Substances 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Images
Classifications
-
- 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
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
An embodiment of the invention discloses a gel polymer electrolyte film. The gel polymer electrolyte film is made of a mixed material. A polymer substrate material and ionic liquid are mixed to form the mixed material, a mass ratio of the polymer substrate material to the ionic liquid is 100:30-50, the polymer substrate material is polyacrylonitrile-methyl methacrylate, and the ionic liquid is N-methylpiperidine ionic liquid. The embodiment of the invention further discloses a manufacturing method and application for the gel polymer electrolyte film. The gel polymer electrolyte film, the manufacturing method and the application have the advantages that the safety performance is excellent, environments are protected, large-scale manufacturing is facilitated, and the like.
Description
Technical field
The present invention relates to the electrochemical device association area, relate in particular to a kind of gel polymer electrolyte film and its production and use.
Background technology
Ultracapacitor is a kind of novel energy device between rechargeable battery and capacitor, have that volume is little, capacity is large, charging rate is fast, have extended cycle life, the advantage such as discharging efficiency is high, operating temperature range is wide, good reliability and contaminant-free maintenance-free, be a kind of novel, efficient, practical energy accumulating device, thereby be widely used in AC-battery power source of military field, device for mobile communication, computer and electric automobile etc.
The ultracapacitor working electrolyte is divided into aqueous electrolyte, organic liquid electrolyte and polymer dielectric.The decomposition voltage of aqueous electrolyte is low, thereby studies less.The advantage of now widely used liquid electrolyte is that conductivity is high, but inflammable owing to containing, volatile organic solvent, it discharges fuel gas in charge and discharge process, particularly under some unconventional condition of work, (as high-power, discharge and recharge, super-charge super-discharge etc.) produces the generation that gas is accelerated in large calorimetric meeting, cause inner pressure of battery to increase, Leakage Gas, blast even on fire, thereby have serious potential safety hazard.The studied persons of advantage such as polymer dielectric ultracapacitor and polymer electrolyte lithium-ion battery are safe because having, nothing is leaked, leakage current is little pay attention to.But under the solid polymer electrolyte room temperature, conductivity is lower by (10
-5~ 10
-4s/cm), use application to be restricted, thereby gel polymer electrolyte become research emphasis.
Summary of the invention
Given this, the embodiment of the present invention aims to provide a kind of gel polymer electrolyte film and preparation method thereof, has that security performance is high, environmental friendliness, is conducive to the characteristics such as extensive preparation, can be for the preparation of ultracapacitor.
The embodiment of the present invention provides a kind of gel polymer electrolyte film, the material of described gel polymer electrolyte film comprises the composite material that Polymers bottom material and ionic liquid are mixed to form, the mass ratio of described Polymers bottom material and described ionic liquid is 100:30 ~ 50, described Polymers bottom material is polyacrylonitrile-methyl methacrylate, and described ionic liquid is for having the compound as shown in structural formula (1):
In formula, Y
-for BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -.
Preferably, the matter average molecular weight of polyacrylonitrile-methyl methacrylate (P (AN-MMA)) is 10 ~ 500,000.
Correspondingly, the embodiment of the present invention also provides a kind of preparation method of gel polymer electrolyte film, comprises the following steps:
(1) ratio that is 1:1.05 ~ 1.2 with the halo propene carbonate according to mol ratio by the N-methyl piperidine is mixed, and is heated to 60 ℃ ~ 80 ℃ under inert gas shielding, and stirring reaction 48 ~ 72 hours obtains having the compd A that following structural formula means:
In formula, X
-for Cl
-, Br
-, I
-;
(2) by described compd A and general formula, be M
+y
-salt according to the ratio of mol ratio 1: 1 ~ 1.1, mix, add deionized water, at room temperature stirring reaction is 4 ~ 24 hours, obtains having the ionic liquid meaned as structural formula (1):
Wherein, M
+for Na
+, K
+or NH
4 +; Y
-for BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -;
(3) by described ionic liquid, with polyacrylonitrile-methyl methacrylate, according to mass ratio, be that 30 ~ 50:100 mixes; add organic solvent; under anhydrous and inert gas shielding; be heated to 40 ℃ ~ 60 ℃; the formation viscous solution that stirs, cast in described viscous solution on glass plate, 80 ℃ ~ 100 ℃ lower vacuumizes 24 hours ~ 48 hours; after cooling, peel off and obtain described gel polymer electrolyte film.
Step (1) is for to make the N-methyl piperidine react the process that makes compd A with the halo propene carbonate, and reaction equation is as follows:
Wherein, RX is the halo propene carbonate.
Preferably, the halo propene carbonate is chlorocarbonic acid propylene, bromo propene carbonate or iodo propene carbonate.
Wherein, the structural formula of chlorocarbonic acid propylene, bromo propene carbonate and iodo propene carbonate is respectively:
Preferably, described inert gas is nitrogen (N
2) or argon gas (Ar
2).
Preferably, step (1) also comprises the following purification process to compd A: after completion of the reaction, that the reactant liquor of described reaction is standing cooling, use the ethyl acetate washed product, and, 80 ℃ ~ 100 ℃ lower vacuumizes 24 hours ~ 48 hours, obtain the compd A of purifying.
Step (2) is M for making compd A and general formula
+y
-reactant salt make ionic liquid, reaction equation is as follows:
In formula, M
+for Na
+, K
+or NH
4 +; Y
-for BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -.
Preferably, step (2) also comprises the following purification process to described ionic liquid: after completion of the reaction, with carrene or chloroform extraction reactant liquor 1 ~ 5 time, collect extract, strip to using saturated AgNO with deionized water
3aqueous solution titration water by after the organic phase evaporation and concentration, and, 80 ℃ ~ 100 ℃ lower vacuumizes 24 hours ~ 48 hours, obtains the described ionic liquid of purifying till producing without precipitation.
Ionic liquid has the characteristics such as conductivity high (about 5ms/cm), fusing point low (30 ℃ of left and right), electrochemical window wide (5V left and right), has the advantages such as non-volatile, non-combustible, Heat stability is good with respect to inflammable, volatile, shortcoming, the ionic liquid such as thermal stability is bad of organic liquid.Therefore, in gel polymer electrolyte, mixed ionic liquid can reduce the use amount of organic liquid, has reduced electrolytical inflammability and volatility, has not only improved the fail safe of gel polymer electrolyte film, stability, and environmental friendliness.
Step (3) is for making N-methyl piperidine ionic liquid/polyacrylonitrile-methyl methacrylate (P (AN-MMA)) gel polymer electrolyte film.
Preferably, the matter average molecular weight of polyacrylonitrile-methyl methacrylate (P (AN-MMA)) is 10 ~ 500,000.
Preferably, organic solvent is the DMSO(dimethyl sulfoxide (DMSO)), the NMP(N-methyl pyrrolidone) or DMF(N, dinethylformamide).
Preferably, the mass ratio of organic solvent and polyacrylonitrile-methyl methacrylate is 20% ~ 30%.
In addition, the embodiment of the present invention also provides the purposes of the gel polymer electrolyte film prepared by said method in ultracapacitor.
Particularly, gel polymer electrolyte film is assembled into to ultracapacitor: by Graphene, (specific area is about 700m
2/ g), acetylene black and PVDF are Graphene according to mass ratio: the ratio of acetylene black: PVDF=85 ~ 90:3 ~ 7:3 ~ 10 is mixed, and Graphene: NMP=1:2 ~ 20 add NMP in mass ratio, fully stirs and makes it to become the slurry mixed; Then by the slurry blade coating on the aluminium foil cleaned through ethanol, under the vacuum of 0.01MPa, 100 ℃ are dried to constant weight, and are pressed into Graphene electrodes in 10 ~ 15MPa pressure lower roll, and are cut into the electrode disk; The gel polymer electrolyte film prepared is placed between two Graphene electrodes, and on stamping machine, the button capacitor is made in sealing.
Implement the embodiment of the present invention, there is following beneficial effect:
(1) gel polymer electrolyte film security performance provided by the invention is high, stability is high and environmental friendliness, is applicable to the electrochemical devices such as ultracapacitor;
(2) preparation method of gel polymer electrolyte film provided by the invention is easy and simple to handle, is conducive to realize large-scale production.
The accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, below will the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is preparation method's schematic flow sheet of gel polymer electrolyte film provided by the invention;
Fig. 2 is the constant current charge-discharge curve of the ultracapacitor of the embodiment of the present invention one.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making under the creative work prerequisite the every other embodiment obtained, belong to the scope of protection of the invention.
Embodiment 1
A kind of preparation method of gel polymer electrolyte film, comprise the steps:
(1) prepare chlorination N-propylene carbonate ester group-N-methyl piperidine
Add respectively (99g, 1mol) N-methyl piperidine and (149.6g, 1.1mol) chlorocarbonic acid propylene in the flask of 250mL, after mixing, at N
2under protection, be heated to 60 ℃, stirring reaction 72h, after completion of the reaction, the standing room temperature that is cooled to, use ethyl acetate washed product 3 times, and at 80 ℃ of lower vacuumize 48h, obtain lurid solid, be chlorination N-propylene carbonate ester group-N-methyl piperidine, yield is 70%;
(2) prepare N-propylene carbonate ester group-N-methyl piperidine tetrafluoroborate ion liquid
By the above-mentioned chlorination N-propylene carbonate ester group made-N-methyl piperidine (117.5g, 0.5mol) and NaBF
4(55g, 0.5mol) is dissolved in the 100mL deionized water, stirring reaction 4h at room temperature, after completion of the reaction, by 250mL dichloromethane extraction 3 times for reactant liquor, combining extraction liquid; Then at every turn with 60mL deionized water back extraction until with saturated AgNO
3till aqueous solution titration water produces without precipitation, after carrene is concentrated with Rotary Evaporators, at 80 ℃ of vacuumize 48h, obtain colourless liquid, be N-propylene carbonate ester group-N-methyl piperidine tetrafluoroborate ion liquid.
N-propylene carbonate ester group-N-methyl piperidine tetrafluoroborate ion liquid synthetic reaction formula is as follows:
The nuclear magnetic resoance spectrum diagram data of N-propylene carbonate ester group-N-methyl piperidine tetrafluoroborate is as follows: 1H NMR (CDCl3,400MHz, ppm): 4.92 (m, 1H), 4.40 (d, 2H), (3.73 d, 2H), 3.26 (m, 4H), 2.95 (s, 3H), 1.74 (m, 4H), 1.29 (m, 2H).
(3) prepare N-propylene carbonate ester group-N-methyl piperidine tetrafluoroborate ion liquid/P (AN-MMA) gel polymer electrolyte film:
Add successively 100g P (AN-MMA) (matter average molecular weight 300,000), 50g N-propylene carbonate ester group-N-methyl piperidine tetrafluoroborate and 25g dimethyl sulfoxide (DMSO) in the there-necked flask of 500mL.Under the protection of dry inert nitrogen gas, be heated to 40 ℃, and stir and to allow P (AN-MMA) dissolve, make system become even viscous solution.The viscous solution that gained is mixed casts on clean glass plate, is transferred to rapidly in vacuum drying chamber, and under 80 ℃, dry 48h, slough solvent.After being cooled to room temperature, separating elastic membrane transparent on sheet glass and be N-propylene carbonate ester group-N-methyl piperidine tetrafluoroborate ion liquid/P (AN-MMA) gel polymer electrolyte film in glove box.
The N-propylene carbonate ester group that makes-N-methyl piperidine tetrafluoroborate ion liquid/P (AN-MMA) gel polymer electrolyte film is assembled into to ultracapacitor: (specific area is about 700m to take the 9g Graphene
2/ g), 0.5g acetylene black and 0.5g PVDF, and add 80g NMP, fully stir and make it to become the slurry mixed.Then by its blade coating on the aluminium foil cleaned through ethanol, under the vacuum of 0.01MPa, 100 ℃ are dried to constant weight, and are pressed into Graphene electrodes in 10MPa pressure lower roll, and are cut into the electrode disk.The above-mentioned gel polymer electrolyte prepared is placed between two Graphene electrodes, and on stamping machine, the button capacitor is made in sealing.
Utilize the charge-discharge test instrument to carry out the constant current charge-discharge test to the ultracapacitor assembled in the present embodiment, in the electrochemical window of 0 ~ 2.7V, with the electric current of 0.5A/g, record its charging and discharging curve as shown in Figure 2.
As can be seen from Figure 2, the prepared gel polymer electrolyte of the embodiment of the present invention is suitable for the electrolyte of ultracapacitor, and has stability preferably in the electrochemical window of 0 ~ 2.7V.
Embodiment 2
A kind of preparation method of gel polymer electrolyte film, comprise the steps:
(1) prepare bromination N-propylene carbonate ester group-N-methyl piperidine
Add respectively (99g, 1mol) N-methyl piperidine and (216g, 1.2mol) bromo propene carbonate in the flask of 250mL, after mixing, at N
2under protection, be heated to 70 ℃, stirring reaction 60h, after completion of the reaction, the standing room temperature that is cooled to, use ethyl acetate washed product 3 times, and at 90 ℃ of lower vacuumize 36h, obtain lurid solid, be bromination N-propylene carbonate ester group-N-methyl piperidine, yield is 75%;
(2) prepare N-propylene carbonate ester group-N-methyl piperidine hexafluorophosphate ionic liquid
By the above-mentioned bromination N-propylene carbonate ester group made-N-methyl piperidine (140.1g, 0.5mol) and KPF
6(101.2g, 0.55mol) is dissolved in the 100mL deionized water, stirring reaction 10h at room temperature, after completion of the reaction, by 250mL chloroform extraction 3 times for reactant liquor, combining extraction liquid; Then at every turn with 60mL deionized water back extraction until with saturated AgNO
3till aqueous solution titration water produces without precipitation, after carrene is concentrated with Rotary Evaporators, at 90 ℃ of vacuumize 36h, obtain colourless liquid, be N-propylene carbonate ester group-N-methyl piperidine hexafluorophosphate ionic liquid.
N-propylene carbonate ester group-N-methyl piperidine hexafluorophosphate ionic liquid synthetic reaction formula is as follows:
The nuclear magnetic resoance spectrum diagram data of N-propylene carbonate ester group-N-methyl piperidine hexafluorophosphate is as follows: 1HNMR (CDCl3,400MHz, ppm): 4.95 (m, 1H), 4.42 (d, 2H), (3.74 d, 2H), 3.27 (m, 4H), 2.97 (s, 3H), 1.76 (m, 4H), 1.31 (m, 2H).
(3) prepare N-propylene carbonate ester group-N-methyl piperidine hexafluorophosphate ionic liquid/P (AN-MMA) gel polymer electrolyte film:
Add successively 100g P (AN-MMA) (matter average molecular weight 100,000), 40g N-propylene carbonate ester group-N-methyl piperidine hexafluorophosphate and 20g NMP in the there-necked flask of 500mL.Under the protection of dry inert gas Ar2, be heated to 50 ℃, and stir and to allow P (AN-MMA) dissolve, make system become even viscous solution.The viscous solution that gained is mixed casts on clean glass plate, is transferred to rapidly in vacuum drying chamber, and under 90 ℃, dry 36h, slough solvent.After being cooled to room temperature, separating elastic membrane transparent on sheet glass and be N-propylene carbonate ester group-N-methyl piperidine hexafluorophosphate ionic liquid/P (AN-MMA) gel polymer electrolyte film in glove box.
The N-propylene carbonate ester group that makes-N-methyl piperidine hexafluorophosphate ionic liquid/P (AN-MMA) gel polymer electrolyte film is assembled into to ultracapacitor: take 8.5g Graphene (specific area is about 700m2/g), 0.4g acetylene black and 0.4g PVDF, and add 60g NMP, fully stir and make it to become the slurry mixed.Then by its blade coating on the aluminium foil cleaned through ethanol, under the vacuum of 0.01MPa, 100 ℃ are dried to constant weight, and are pressed into Graphene electrodes in 15MPa pressure lower roll, and are cut into the electrode disk.The above-mentioned N-propylene carbonate ester group prepared-N-methyl piperidine hexafluorophosphate ionic liquid/P (AN-MMA) gel polymer electrolyte film is placed between two Graphene electrodes, and on stamping machine, the button capacitor is made in sealing.
Utilize the charge-discharge test instrument to carry out the constant current charge-discharge test to the ultracapacitor assembled in the present embodiment, there is stability preferably in the electrochemical window of 0 ~ 2.7V.
Embodiment 3
A kind of preparation method of gel polymer electrolyte film, comprise the steps:
(1) prepare iodate N-propylene carbonate ester group-N-methyl piperidine
Add respectively (99g, 1mol) N-methyl piperidine and (239.4g, 1.05mol) iodo propene carbonate in the flask of 250mL, after mixing, at N
2under protection, be heated to 80 ℃, stirring reaction 48h, after completion of the reaction, the standing room temperature that is cooled to, use ethyl acetate washed product 5 times, and at 100 ℃ of lower vacuumize 24h, obtain lurid solid, be chlorination N-propylene carbonate ester group-N-methyl piperidine, yield is 80%;
(2) prepare two (fluoroform sulphonyl) the inferior amine salt ionic liquids of N-propylene carbonate ester group-N-methyl piperidine
By the above-mentioned iodate N-propylene carbonate ester group made-N-methyl piperidine (117.5g, 0.5mol) and two (fluoroform sulphonyl) imines potassium KTFSI (173.4g, 0.53mol) be dissolved in the 100mL deionized water, stirring reaction 24h at room temperature, after completion of the reaction, by reactant liquor 250mL dichloromethane extraction 3 times, combining extraction liquid; Then at every turn with 60mL deionized water back extraction until with saturated AgNO
3till aqueous solution titration water produces without precipitation, after carrene is concentrated with Rotary Evaporators, at 100 ℃ of vacuumize 24h, obtain colourless liquid, be two (fluoroform sulphonyl) the inferior amine salt ionic liquids of N-propylene carbonate ester group-N-methyl piperidine.
Two (fluoroform sulphonyl) the inferior amine salt ionic liquid synthetic reaction formulas of N-propylene carbonate ester group-N-methyl piperidine are as follows:
The nuclear magnetic resoance spectrum diagram data of two (fluoroform sulphonyl) inferior amine salts of N-propylene carbonate ester group-N-methyl piperidine is as follows: 4.96 (m, 1H), 4.44 (d, 2H), 3.75 (d, 2H), 3.28 (m, 4H), 2.99 (s, 3H), 1.77 (m, 4H), 1.33 (m, 2H).
(3) prepare two (fluoroform sulphonyl) inferior amine salt ionic liquid/P (AN-MMA) gel polymer electrolyte films of N-propylene carbonate ester group-N-methyl piperidine:
Add successively 100g P (AN-MMA) (matter average molecular weight 300,000), two (fluoroform sulphonyl) inferior amine salts of 30g N-propylene carbonate ester group-N-methyl piperidine and 30g DMF in the there-necked flask of 500mL.Under the protection of dry inert gas N2, be heated to 60 ℃, and stir and to allow P (AN-MMA) dissolve, make system become even viscous solution.The viscous solution that gained is mixed casts on clean glass plate, is transferred to rapidly in vacuum drying chamber, and under 100 ℃, dry 24h, slough solvent.After being cooled to room temperature, separating elastic membrane transparent on sheet glass and be two (fluoroform sulphonyl) inferior amine salt ionic liquid/P (AN-MMA) gel polymer electrolyte films of N-propylene carbonate ester group-N-methyl piperidine in glove box.
Two (fluoroform sulphonyl) inferior amine salt ionic liquid/P (AN-MMA) gel polymer electrolyte films of the N-propylene carbonate ester group that makes-N-methyl piperidine are assembled into to ultracapacitor: (specific area is about 700m to take the 9g Graphene
2/ g), 0.6g acetylene black and 0.8g PVDF, and add 150g NMP, fully stir and make it to become the slurry mixed.Then by its blade coating on the aluminium foil cleaned through ethanol, under the vacuum of 0.01MPa, 100 ℃ are dried to constant weight, and are pressed into Graphene electrodes in 15MPa pressure lower roll, and are cut into the electrode disk.The above-mentioned N-propylene carbonate ester group prepared-N-methyl piperidine hexafluorophosphate ionic liquid/P (AN-MMA) gel polymer electrolyte film is placed between two Graphene electrodes, and on stamping machine, the button capacitor is made in sealing.
Utilize the charge-discharge test instrument to carry out the constant current charge-discharge test to the ultracapacitor assembled in the present embodiment, there is stability preferably in the electrochemical window of 0 ~ 2.7V.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.
Claims (10)
1. a gel polymer electrolyte film, it is characterized in that, the material of described gel polymer electrolyte film is the composite material that Polymers bottom material and ionic liquid are mixed to form, the mass ratio of described Polymers bottom material and described ionic liquid is 100:30 ~ 50, described Polymers bottom material is polyacrylonitrile-methyl methacrylate, and described ionic liquid is for having the compound as shown in structural formula (1):
Y in formula
-for BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -.
2. gel polymer electrolyte film as claimed in claim 1, is characterized in that, the matter average molecular weight of described polyacrylonitrile-methyl methacrylate is 10 ~ 500,000.
3. the preparation method of a gel polymer electrolyte film, is characterized in that, comprises the following steps:
(1) ratio that is 1:1.05 ~ 1.2 with the halo propene carbonate according to mol ratio by the N-methyl piperidine is mixed, and is heated to 60 ℃ ~ 80 ℃ under inert gas shielding, and stirring reaction 48 ~ 72 hours obtains having the compd A that following structural formula means:
In formula, X
-for Cl
-, Br
-, I
-;
(2) by described compd A and general formula, be M
+y
-salt according to mol ratio, be 1:1 ~ 1.1 ratio is mixed, add deionized water, at room temperature stirring reaction is 4 ~ 24 hours, obtains having the ionic liquid meaned as structural formula (1):
Wherein, M
+for Na
+, K
+or NH
4 +; Y
-for BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -;
(3) ratio that is 30 ~ 50:100 with polyacrylonitrile-methyl methacrylate according to mass ratio by described ionic liquid is mixed; add organic solvent; under anhydrous and inert gas shielding; be heated to 40 ℃ ~ 60 ℃; the formation viscous solution that stirs, cast in described viscous solution on glass plate, 80 ℃ ~ 100 ℃ lower vacuumizes 24 hours ~ 48 hours; after cooling, peel off and obtain described gel polymer electrolyte film.
4. the preparation method of gel polymer electrolyte film as claimed in claim 3, is characterized in that, halo propene carbonate described in step (1) is chlorocarbonic acid propylene, bromo propene carbonate or iodo propene carbonate.
5. the preparation method of gel polymer electrolyte film as claimed in claim 3, is characterized in that, described inert gas is nitrogen or argon gas.
6. the preparation method of gel polymer electrolyte film as claimed in claim 3, it is characterized in that, step (1) also comprises the following purification process to described compd A: after completion of the reaction described, the reactant liquor of described reaction is standing cooling, use the ethyl acetate washed product, and, 80 ℃ ~ 100 ℃ lower vacuumizes 24 hours ~ 48 hours, obtain the described compd A of purifying.
7. the preparation method of gel polymer electrolyte film as claimed in claim 3, it is characterized in that, step (2) also comprises the following purification process to described ionic liquid: after completion of the reaction described, with carrene or chloroform extraction reactant liquor 1 ~ 5 time, collect extract, strip to using saturated AgNO with deionized water
3aqueous solution titration water by after the organic phase evaporation and concentration, and, 80 ℃ ~ 100 ℃ lower vacuumizes 24 hours ~ 48 hours, obtains the described ionic liquid of purifying till producing without precipitation.
8. the preparation method of gel polymer electrolyte film as claimed in claim 3, is characterized in that, the matter average molecular weight of described polyacrylonitrile-methyl methacrylate is 10 ~ 500,000.
9. the preparation method of gel polymer electrolyte film as claimed in claim 3, it is characterized in that, described in step (3), organic solvent is dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE or N, dinethylformamide, the mass ratio of described organic solvent and polyacrylonitrile-methyl methacrylate is 20% ~ 30%.
10. select as described in one as claim 3 ~ 9 purposes of gel polymer electrolyte film in ultracapacitor that method prepares.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101756341A CN103456504A (en) | 2012-05-31 | 2012-05-31 | Gel polymer electrolyte film, and manufacturing method and application for same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101756341A CN103456504A (en) | 2012-05-31 | 2012-05-31 | Gel polymer electrolyte film, and manufacturing method and application for same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103456504A true CN103456504A (en) | 2013-12-18 |
Family
ID=49738765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101756341A Pending CN103456504A (en) | 2012-05-31 | 2012-05-31 | Gel polymer electrolyte film, and manufacturing method and application for same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103456504A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060210876A1 (en) * | 2005-03-17 | 2006-09-21 | Takashi Kuboki | Electrochemical device |
| CN1934212A (en) * | 2004-04-19 | 2007-03-21 | Lg化学株式会社 | Gel polymer electrolyte containing ionic liquid and electrochromic device using the same |
-
2012
- 2012-05-31 CN CN2012101756341A patent/CN103456504A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1934212A (en) * | 2004-04-19 | 2007-03-21 | Lg化学株式会社 | Gel polymer electrolyte containing ionic liquid and electrochromic device using the same |
| US20060210876A1 (en) * | 2005-03-17 | 2006-09-21 | Takashi Kuboki | Electrochemical device |
Non-Patent Citations (2)
| Title |
|---|
| G P PANDEY等: "Ionic liquid incorporated polymer electrolytes for supercapacitor application", 《INDIAN JOURNAL OF CHEMISTRY》 * |
| WEN LU等: "Incorporating Ionic Liquid Electrolytes into Polymer Gels for Solid-State Ultracapacitors", 《JOURNAL OF ELECTROCHEMICAL SOCIETY》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103779568B (en) | A kind of post quinone positive electrode for lithium ion battery and application thereof | |
| CN107069079A (en) | A kind of solid state electrolyte and its preparation and application | |
| JP2014531415A (en) | Bisquaternary ammonium salt ionic liquid having two centers, process for its preparation and use | |
| CN102195091A (en) | Ionic liquid electrolyte for lithium secondary battery | |
| CN108586348A (en) | A kind of glyoxaline ion liquid and its preparation method and application | |
| CN101587777A (en) | Difunctional electrolyte and preparation method thereof | |
| CN101420053A (en) | Guanidinium type ionic liquid electrolyzing solution for lithium secondary cell | |
| CN102952099B (en) | Pyrrole ionic liquid, and preparation method and application thereof | |
| CN103387742A (en) | Imidazole ionic liquid/gel polymer electrolyte membrane and preparation method thereof | |
| CN103787996A (en) | Triazoles ionic liquid and ionic liquid electrolytic solution, and preparation methods and applications thereof | |
| CN113540563B (en) | Additive and modification method of lithium battery electrolyte | |
| CN103450610A (en) | Gel polymer electrolyte membrane, and preparation method and application thereof | |
| CN103896828B (en) | Two centers bipyridyliums ionic liquid and its preparation method and electrolytic solution and lithium ion battery | |
| CN102952097A (en) | Double-centre piperazine ionic liquid, and preparation method and application thereof | |
| CN103387731A (en) | Gel polymer electrolyte membrane and preparation method thereof | |
| CN103794818A (en) | Pyrroles ionic liquid and ionic liquid electrolytic solution, and preparation methods and applications thereof | |
| CN103390502B (en) | Morpholine ionic liquid/gel polymer electrolyte membrane and preparation method thereof | |
| CN103732587B (en) | Two centers bipyridine cation class ionic liquid and its preparation method and application | |
| CN103390501B (en) | Gel polymer electrolyte film and preparation method thereof | |
| CN111211327B (en) | Compound for lithium ion battery anode material and preparation method and application thereof | |
| CN103456504A (en) | Gel polymer electrolyte film, and manufacturing method and application for same | |
| CN114105907A (en) | Pyrrolidine ionic liquid and preparation method and application thereof | |
| CN111416150A (en) | Preparation method of fluorine-containing sulfonate lithium ion battery additive | |
| CN111116388A (en) | Preparation method of polyether-based ionic liquid, preparation method and application of high-voltage electrolyte | |
| CN102952092B (en) | Oxazolidine ionic liquid and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131218 |