CN103390502A - Morpholine ionic liquid/gel polymer electrolyte membrane and preparation method thereof - Google Patents
Morpholine ionic liquid/gel polymer electrolyte membrane and preparation method thereof Download PDFInfo
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- methoxyethoxyethyl
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- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 title claims abstract description 220
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 117
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 59
- 239000012528 membrane Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 17
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 68
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 32
- -1 methoxyethoxyethyl chloroethane Chemical compound 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- ODTKBCUBSAPRBP-UHFFFAOYSA-N 1-bromo-1-(2-methoxyethoxy)ethane Chemical compound COCCOC(C)Br ODTKBCUBSAPRBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- YRAQORMETFHQDS-UHFFFAOYSA-N 4-methylmorpholin-4-ium;iodide Chemical compound [I-].C[NH+]1CCOCC1 YRAQORMETFHQDS-UHFFFAOYSA-N 0.000 claims description 3
- ANWRFECLRNZBHC-UHFFFAOYSA-N 4-methylmorpholine;hydrobromide Chemical compound [Br-].C[NH+]1CCOCC1 ANWRFECLRNZBHC-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- BTJRKNUKPQBLAL-UHFFFAOYSA-N hydron;4-methylmorpholine;chloride Chemical compound Cl.CN1CCOCC1 BTJRKNUKPQBLAL-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- JAMHLMVWVXACEH-UHFFFAOYSA-N 3-bromo-1-(2-methoxyethoxy)butane Chemical compound COCCOCCC(C)Br JAMHLMVWVXACEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002027 dichloromethane extract Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000004927 fusion Effects 0.000 abstract 1
- 238000000935 solvent evaporation Methods 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 239000003990 capacitor Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011244 liquid electrolyte Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- KAVQCBPUWVUKQF-UHFFFAOYSA-N 1-chloro-1-(2-methoxyethoxy)ethane Chemical compound COCCOC(C)Cl KAVQCBPUWVUKQF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material 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
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- 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
- Y02E60/10—Energy storage using batteries
-
- 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
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
A morpholine ionic liquid/gel polymer electrolyte membrane comprises a polyacrylonitrile substrate and morpholine ionic liquid mixed and dissolved in the polyacrylonitrile. The morpholine ionic liquid has the following structural formula: , wherein Y- is selected from one of BF4-, PF6-, (CF3SO2)2N- and CF3SO3-. The mass ratio of the polyacrylonitrile and the morpholine ionic liquid is 100:30-100:50. The morpholine ionic liquid has the advantages of being high in conductivity, low in fusion point and wide in electrochemical window, and in addition, the morpholine ionic liquid is free of volatilization, incombustible and good in heat stability, so that the morpholine ionic liquid is suitable for preparing an electrolyte with high safety. The morpholine ionic liquid is mixed in the polyacrylonitrile to form the morpholine ionic liquid/gel polymer electrolyte membrane, and the morpholine ionic liquid/gel polymer electrolyte membrane integrates the advantages of the morpholine ionic liquid and gel polymers. The gel polymer electrolyte membrane with the morpholine ionic liquid compound is free of the phenomena such as solvent evaporation and liquid leakage, and the safety is greatly improved.
Description
Technical Field
The invention relates to a morpholine ionic liquid/gel polymer electrolyte membrane and a preparation method thereof.
Background
The super capacitor is a novel energy device between a rechargeable battery and a capacitor, has the advantages of small volume, large capacity, high charging speed, long cycle life, high discharging efficiency, wide working temperature range, good reliability, no pollution, no maintenance and the like, is a novel, high-efficiency and practical energy storage device, and is widely applied to the military field, mobile communication devices, computers, hybrid power supplies of electric automobiles and the like.
The working electrolyte of the super capacitor is divided into an aqueous electrolyte, an organic liquid electrolyte and a polymer electrolyte. Aqueous electrolytes have been studied less frequently because of their low decomposition voltage. The liquid electrolyte widely used at present has the advantage of high conductivity, but contains flammable and volatile organic solvents, so that flammable gas is released in the charging and discharging process, and particularly, the generation of a large amount of heat under certain unconventional working conditions (such as high-power charging and discharging, overcharge and overdischarge) can accelerate the generation of gas, so that the internal pressure of a battery is increased, the gas is leaked, and even the battery is ignited and exploded, thereby having serious potential safety hazards. The polymer electrolyte super capacitor is regarded by researchers because of its advantages of safety, no leakage, small leakage current, etc. Solid polymer electrolytes have low conductivity at room temperature (10)-5~10-4s/cm), the use applications are limited, and thus gel polymer electrolytes are the focus of research.
The ionic liquid has the advantages of high conductivity, low melting point, wide electrochemical window, non-volatility, non-flammability, good thermal stability and the like. In recent years, ionic liquid/gel polymer electrolytes have become more and more attractive.
Disclosure of Invention
Therefore, it is necessary to provide a morpholine ionic liquid/gel polymer electrolyte membrane with high safety and a preparation method thereof, aiming at the problem that the existing liquid electrolyte is not high in safety.
A morpholine ionic liquid/gel polymer electrolyte membrane comprising a polyacrylonitrile substrate and a morpholine ionic liquid miscible in the polyacrylonitrile, the morpholine ionic liquid having the following structural formula:
wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -One of (1); the mass ratio of the polyacrylonitrile to the morpholine ionic liquid is 100: 30-100: 50.
In one embodiment, the polyacrylonitrile has a relative molecular weight of 10-60 ten thousand.
The morpholine ionic liquid/gel polymer electrolyte membrane is applied to a super capacitor or a lithium ion battery.
A preparation method of a morpholine ionic liquid/gel polymer electrolyte membrane comprises the following steps:
the method comprises the following steps: mixing polyacrylonitrile, morpholine ionic liquid and an organic solvent according to the mass ratio of 100: 30-50: 20-40, heating to 40-60 ℃, stirring to dissolve the polyacrylonitrile to form a homogeneous mixed solution, wherein the morpholine ionic liquid has the following structural formula:
wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -One of (1);
step two: and casting the homogeneous mixed solution on a substrate, then drying the substrate on which the homogeneous mixed solution is cast in vacuum at 80-100 ℃ for 24-28 hours, cooling to room temperature, and stripping a film on the substrate to obtain the morpholine ionic liquid/gel polymer electrolyte film.
In one embodiment, the polyacrylonitrile has a relative molecular weight of 10-60 ten thousand.
In one embodiment, the organic solvent is dimethylformamide, N-methylpyrrolidone, or ethylene carbonate.
In one embodiment, the morpholine ionic liquid is prepared as follows:
mixing one of methoxyethoxyethyl chloroethane, methoxyethoxy bromoethane and methoxyethoxyethyl iodoethane with N-methylmorpholine according to a molar ratio of 1.05: 1-1.2: 1, heating by microwave radiation for 20-40 seconds, stirring for 10-15 seconds, repeating the heating and stirring steps for 3-6 times to obtain halogenated N-methoxyethoxyethyl-N-methylmorpholine, wherein the halogenated N-methoxyethoxyethyl-N-methylmorpholine is N-methoxyethoxyethyl chloride-N-methylmorpholine, N-methoxyethoxyethyl bromide-N-methylmorpholine or N-methoxyethoxyethyl iodide-N-methylmorpholine;
reacting the halogenated N-methoxyethoxyethyl-N-methylmorpholine with a compound represented by the general formula M+Y-Mixing the salts according to the mol ratio of 1: 1-1: 1.1, adding the mixed salts into deionized water, stirring the mixture to perform an ion exchange reaction, and separating and purifying the mixture to obtain the morpholine ionic liquid with the following structural formula:
wherein M is+Selected from Na+、K+And NH4 +One of (1); y is-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -One kind of (1).
In one embodiment, the mixture of N-methylmorpholine and one of methoxyethoxyethyl chloroethane, methoxyethoxyethyl bromoethane and methoxyethoxyethyl iodoethane is heated under the microwave radiation power of 200-300W, the heating and stirring steps are repeated for 3-6 times, the obtained reactant is cooled and washed by ethyl acetate, and then the washed product is dried in vacuum to obtain purified halogenated N-methoxyethoxyethyl-N-methylmorpholine.
In one embodiment, the temperature of the ion exchange reaction is 15-30 ℃ and the time is 8-24 hours.
In one embodiment, the separation and purification steps are as follows: reacting a halogenated N-methoxyethoxyethyl-N-methylmorpholine with a compound of the formula M+Y-The mixed solution obtained after the salt is stirred and reacted is extracted by dichloromethane, and then the dichloromethane is used for back extraction until the obtained water phase is saturated AgNO3And titrating the aqueous solution until no precipitate is generated, evaporating and concentrating a dichloromethane extract, and drying in vacuum to obtain the morpholine ionic liquid.
The morpholine ionic liquid/gel polymer electrolyte membrane comprises a polyacrylonitrile substrate and morpholine ionic liquid which is miscible with polyacrylonitrile, the morpholine ionic liquid has the advantages of high conductivity, low melting point and wide electrochemical window, the conductivity is 2-6ms/cm, the melting point is about-30 ℃, the electrochemical window is about 5.0V, the morpholine ionic liquid is non-volatile, non-flammable and good in thermal stability, and the decomposition temperature is higher than 320 ℃. Therefore, the morpholine ionic liquid is suitable for preparing electrolyte with high safety. The morpholine ionic liquid is mixed and dissolved in polyacrylonitrile to form the morpholine ionic liquid/gel polymer electrolyte membrane, the morpholine ionic liquid/gel polymer electrolyte membrane has the advantages of morpholine ionic liquid and gel polymer, the ionic liquid compounded gel polymer electrolyte membrane does not have the phenomena of solvent volatilization, liquid leakage and the like any more, and compared with an organic liquid electrolyte which is inflammable, volatile and has potential explosion safety hazard, the safety of the ionic liquid/gel polymer electrolyte membrane is greatly improved.
Drawings
FIG. 1 is a flow chart of a method for preparing morpholine ionic liquid according to one embodiment;
fig. 2 is a flow chart of a method for preparing a morpholine ionic liquid/gel polymer electrolyte membrane according to an embodiment.
Detailed Description
The morpholine ionic liquid/gel polymer electrolyte membrane and the preparation method thereof are further explained by the attached drawings and the detailed description.
A morpholine ionic liquid having the following structural formula:
wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -One kind of (1).
The morpholine ionic liquid has the advantages of high conductivity, low melting point and wide electrochemical window, the conductivity is 2-6ms/cm, the melting point is about-30 ℃, the electrochemical window is about 5.0V, the morpholine ionic liquid is non-volatile, non-flammable and good in thermal stability, and the decomposition temperature is higher than 320 ℃. Therefore, the morpholine ionic liquid is suitable for preparing electrolyte with better safety.
Referring to fig. 1, a method for preparing morpholine ionic liquid according to an embodiment includes the following steps:
step S110: mixing one of methoxyethoxyethyl chloroethane, methoxyethoxy bromoethane and methoxyethoxyethyl iodoethane with N-methylmorpholine according to a molar ratio of 1.05: 1-1.2: 1, heating by microwave radiation for 20-40 seconds, stirring for 10-15 seconds, repeating the heating and stirring steps for 3-6 times to obtain halogenated N-methoxyethoxyethyl-N-methylmorpholine, wherein the halogenated N-methoxyethoxyethyl-N-methylmorpholine is N-methoxyethoxyethyl chloride-N-methylmorpholine, N-methoxyethoxyethyl bromide-N-methylmorpholine or N-methoxyethoxyethyl iodide-N-methylmorpholine.
Heating a mixture of N-methylmorpholine and one of methoxyethoxy chloroethane, methoxyethoxy bromoethane and methoxyethoxy iodoethane under the microwave radiation power of 200-300W. Compared with the traditional heating, the microwave heating can greatly accelerate the reaction rate of organic synthesis, shorten the reaction time and improve the production efficiency. Heating for 20-40 seconds, stirring for 10-15 seconds, repeating the heating and stirring steps for 3-6 times, stirring to room temperature, and washing with ethyl acetate for three times. Vacuum drying at 80 deg.c to obtain halogenated N-methoxyethoxyethyl-N-methylmorpholine. The halogenated N-methoxyethoxyethyl-N-methylmorpholine was a pale yellow solid.
Step S120: reacting the halogenated N-methoxyethoxyethyl-N-methylmorpholine prepared in step 110 with a compound of formula M+Y-Mixing the salts according to the mol ratio of 1: 1-1: 1.1, adding the mixed salts into deionized water, stirring for reaction, and separating and purifying to obtain the morpholine ionic liquid with the following structural formula:
wherein M is+Selected from Na+、K+And NH4 +One of (1); y is-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -One kind of (1).
Halogenated N-methoxyethoxyethyl-N-methylmorpholine and a compound of formula M+Y-Salts ofStirring the mixture in deionized water at 15-30 ℃ to perform ion exchange reaction, reacting for 8-24 hours to obtain a mixed solution, extracting the mixed solution for 3 times by using dichloromethane, combining extract liquor, and performing back extraction by using the deionized water each time until saturated AgNO is used3Until no precipitate is generated in the aqueous phase by aqueous titration, the dichloromethane phase is concentrated by a rotary evaporator and dried under vacuum at 80 ℃ for 48 hours to obtain colorless liquid, namely morpholine ionic liquid with the following structural formula:
wherein M is+Selected from Na+、K+And NH4 +One of (1); y is-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -One kind of (1).
It is understood that the reaction time is not limited to 8 to 24 hours, as long as the halogenated N-methoxyethoxyethyl-N-methylmorpholine is reacted with the compound of the formula M+Y-The salt reaction is complete.
Step S120 uses deionized water as a reaction solvent, reduces the use of organic solvents, is environment-friendly and has low cost.
The total reaction formula of the preparation of the morpholine ionic liquid is as follows:
wherein,
is composed of 
M+Selected from Na+、K+And NH4 +One of (1); y is-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -One kind of (1).
The preparation method of the morpholine ionic liquid has the advantages of simple preparation process, mild reaction conditions, short reaction time, high reaction efficiency, lower cost and easy large-scale preparation.
The morpholine ionic liquid is prepared from N-methylmorpholine and methoxyethoxy halogenated ethane as raw materials, and is easy to obtain, relatively low in price and easy to popularize and apply.
An embodiment of morpholine ionic liquid/gel polymer electrolyte membrane comprises a polyacrylonitrile substrate and morpholine ionic liquid miscible with polyacrylonitrile, wherein the morpholine ionic liquid has the following structural formula:
wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -One of (1); the mass ratio of the polyacrylonitrile to the morpholine ionic liquid is 100: 30-100: 50.
The polyacrylonitrile has the advantages of good film forming property, high film strength, wide electrochemical stability window and no decomposition in organic electrolyte, and is a gel polymer electrolyte framework supporting material with excellent performance.
In the embodiment, the relative molecular weight of polyacrylonitrile is 10-60 ten thousand. In order to meet the application requirements of supercapacitors or lithium batteries, etc., the electrolyte membrane must have good mechanical properties and electrode adhesion. Polyacrylonitrile as a framework support carrier of the ionic liquid/gel polymer electrolyte should have good mechanical properties and electrode adhesion to meet the requirements of the electrolyte membrane. Polyacrylonitrile with the molecular weight of 10-60 ten thousand has good strength and proper viscosity, so that the gel polymer electrolyte based on polyacrylonitrile has good mechanical property and electrode adhesion.
The morpholine ionic liquid at room temperature is introduced into polyacrylonitrile with good mechanical property to form morpholine ionic liquid/gel polymer electrolyte, so that the gel polymer electrolyte has the advantages of both morpholine ionic liquid and gel polymer electrolyte. The ionic liquid compounded gel polymer electrolyte membrane has no phenomena of solvent volatilization, liquid leakage and the like, and the safety is greatly improved compared with the organic liquid electrolyte which is inflammable, volatile and has potential explosion safety hazards, so that the safety of the supercapacitor and the lithium battery of the morpholine ionic liquid/gel polymer electrolyte membrane is improved.
The morpholine ionic liquid is dispersed into polyacrylonitrile, and the morpholine ionic liquid and the polyacrylonitrile form a stable membrane structure, have good mechanical properties, and are convenient to assemble in other electrochemical devices such as a super capacitor. The morpholine ionic liquid/gel polymer electrolyte membrane can be processed into any shape, is suitable for electrochemical devices of different shapes, and is beneficial to preparing various ultrathin electrochemical devices.
Further, the application of the morpholine ionic liquid/gel polymer electrolyte membrane in a super capacitor or a lithium ion battery is provided.
Referring to fig. 2, a method for preparing a morpholine ionic liquid/gel polymer electrolyte membrane according to an embodiment includes the following steps:
step S220: mixing polyacrylonitrile, morpholine ionic liquid and an organic solvent according to the mass ratio of 100: 30-50: 20-40, heating and stirring to dissolve the polyacrylonitrile, so that the polyacrylonitrile, the morpholine ionic liquid and the organic solvent are mixed to form a homogeneous mixed solution, wherein the morpholine ionic liquid has the following structural formula:
wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -One kind of (1).
The morpholine ionic liquid is prepared according to the preparation method of the morpholine ionic liquid. The preparation method of the morpholine ionic liquid has lower cost, and can reduce the cost of the morpholine ionic liquid/gel polymer electrolyte membrane.
The molecular weight of the polyacrylonitrile is 10-60 ten thousand. Heating and stirring to dissolve polyacrylonitrile, wherein the heating temperature is 40-60 ℃. The viscosity of polyacrylonitrile is moderate at 40-60 ℃, and the subsequent casting film forming is facilitated.
The organic solvent is Dimethylformamide (DMF), N-methylpyrrolidone (NMP) or Ethylene Carbonate (EC). The organic solvent is used for dissolving polyacrylonitrile and morpholine ionic liquid, forming pores on polyacrylonitrile, and has the functions of both the solvent and the plasticizer. Mixing the organic solvent, polyacrylonitrile and morpholine ionic liquid, removing the organic solvent after film formation, and leaving micropores for adsorbing the morpholine ionic liquid. Dimethylformamide (DMF), N-methylpyrrolidone (NMP) or Ethylene Carbonate (EC) and polyacrylonitrile have good miscibility and high plasticizing efficiency.
The higher the content of the organic solvent is, the more micropores are formed on the polyacrylonitrile, and the more morpholine ionic liquid can be adsorbed, so that the conductivity of the morpholine ionic liquid/gel polymer electrolyte membrane can be effectively improved. However, the more micropores there are, the lower the mechanical properties of polyacrylonitrile. When the mass ratio of the polyacrylonitrile to the morpholine ionic liquid to the organic solvent is 100: 30-50: 20-40, moderate mechanical properties and conductivity can be obtained.
Step S220 is performed in a dry inert gas atmosphere, which may be nitrogen, argon, helium, or the like.
Step S240: and (5) casting the homogeneous mixed liquid obtained in the step (S220) on a substrate, then carrying out vacuum drying on the substrate on which the homogeneous mixed liquid is cast for 24-28 hours, cooling to room temperature, and stripping off a film on the substrate to obtain the morpholine ionic liquid/gel polymer electrolyte film.
The substrate is a clean glass sheet or a polytetrafluoroethylene mold. The temperature of vacuum drying is 80-100 ℃. And (3) after the substrate cast with the homogeneous phase mixed liquid is dried for 24-28 hours in vacuum, a transparent elastic film is formed on the substrate. And stripping the elastic membrane from the substrate in a glove box filled with inert gas to obtain the ionic liquid/gel polymer electrolyte membrane.
The glove box provides an oxygen-free, water-free and dust-free environment, and prevents moisture and dust from affecting the morpholine ionic liquid/gel polymer electrolyte membrane.
The preparation method of the morpholine ionic liquid/gel polymer electrolyte membrane has the advantages of simple process and low manufacturing cost, is suitable for large-scale industrial preparation, and is beneficial to developing various ultrathin and ultra-large-area electrochemical devices such as various special-shaped super capacitors, lithium batteries and the like.
The following are specific examples.
Example 1
The morpholine ionic liquid N-methoxyethoxyethyl-N-methylmorpholine tetrafluoroborate is prepared by the following reaction process:
mixing N-methylmorpholine (101 g, 1mol) and methoxyethoxy chloroethane (145.5g,1.05mol), stirring uniformly, heating for 30 seconds under the microwave radiation power of 240W, taking out, stirring for 15 seconds, repeating the steps for 3 times, stirring to room temperature, and washing with ethyl acetate for three times. Vacuum drying at 80 deg.C to obtain pale yellow solid, i.e. N-methoxyethoxyethyl-N-methylmorpholine chloride, with a yield of 82%;
the N-methoxyethoxyethyl-N-methylmorpholine chloride (119.9g, 0.5mol) and NaBF were mixed4(60.5g, 0.55mol) was dissolved in 100mL of deionized water, stirred at 15 ℃ for 8 hours to give a mixture, the mixture was extracted 3 times with 250mL of dichloromethane, the extracts were combined and then back-extracted with 60mL of deionized water each time until saturated AgNO was used3Until no precipitate is generated in the aqueous solution titration water phase, concentrating the dichloromethane phase by using a rotary evaporator, and performing vacuum drying for 48 hours at the temperature of 80 ℃ to obtain colorless liquid, namely N-methoxyethoxyethyl-N-methylmorpholine tetrafluoroborate;
the prepared morpholine ionic liquid N-methoxyethoxyethyl-N-methylmorpholine tetrafluoroborate has the following nuclear magnetic spectrum: 1H NMR (CDCl3,400MHz, ppm) 3.84(m,2H),3.73(m,2H),3.62(m,2H),3.57(m,2H),3.38(m,2H),3.24(s,3H),2.95(s,3H),2.78(m,2H),2.65(m,2H),2.56(m,2H).
Preparation of morpholine ionic liquid N-methoxyethoxyethyl-N-methylmorpholine tetrafluoroborate/gel polymer electrolyte membrane:
100g of polyacrylonitrile having a relative molecular weight of 50 ten thousand, 50g N-methoxyethoxyethyl-N-methylimidazolium tetrafluoroborate and 20g of dimethylformamide were placed in a 500mL three-necked flask in this order. Under the protection of dry nitrogen, the temperature is raised to 40 ℃, and the polyacrylonitrile is dissolved by stirring, so that the system becomes homogeneous. And casting the uniformly mixed solution on a clean glass sheet, quickly transferring the glass sheet to a vacuum drying oven, drying the glass sheet for 24 hours at the temperature of 100 ℃, and removing the organic solvent. After cooling to room temperature, the transparent elastic membrane on the glass sheet is peeled off in a glove box filled with nitrogen, namely the morpholine ionic liquid N-methoxyethoxyethyl-N-methylmorpholine tetrafluoroborate/gel polymer electrolyte membrane.
Example 2
The morpholine ionic liquid N-methoxyethoxyethyl-N-methylmorpholine hexafluorophosphate is prepared by the following reaction process:
mixing N-methylmorpholine (101 g, 1mol) and methoxyethoxy bromoethane (201.3g,1.1mol), stirring uniformly, heating for 40 seconds under the microwave radiation power of 200W, taking out and stirring for 10 seconds, repeating the steps for 4 times, stirring to room temperature, and washing with ethyl acetate for three times. Vacuum drying at 80 deg.C to obtain pale yellow solid, i.e. brominated N-methoxyethoxyethyl-N-methylmorpholine, with a yield of 85%;
the brominated N-methoxyethoxyethyl-N-methylmorpholine (142.1g, 0.5mol) and (96.6g, 0.53mol) KPF were mixed6Dissolving in 120mL deionized water, stirring at 25 deg.C for 16 hr to obtain a mixture, extracting the mixture with 250mL dichloromethane for 4 times, combining the extracts, and back-extracting with 60mL deionized water each time until saturated AgNO3Until no precipitate is generated in the aqueous solution titration aqueous phase, concentrating the dichloromethane phase by using a rotary evaporator, and performing vacuum drying at 80 ℃ for 48 hours to obtain colorless liquid, namely N-methoxyethoxyethyl-N-methylmorpholine hexafluorophosphate;
the nuclear magnetic spectrum of the prepared morpholine ionic liquid N-methoxyethoxyethyl-N-methylmorpholine hexafluorophosphate is as follows:
1H NMR(CDCl3,400MHz,ppm):3.85(m,2H),3.74(m,2H),3.64(m,2H),3.59(m,2H),3.40(m,2H),3.24(s,3H),2.96(s,3H),2.78(m,2H),2.67(m,2H),2.58(m,2H).
preparing morpholine ionic liquid N-methoxyethoxyethyl-N-methylmorpholine hexafluorophosphate/gel polymer electrolyte membrane:
100g of polyacrylonitrile having a relative molecular weight of 10 ten thousand, 45g N-methoxyethoxyethyl-N-methylimidazolium hexafluorophosphate and 30g N-methylpyrrolidone were sequentially charged in a 500mL three-necked flask. Under the protection of dry argon, the temperature is raised to 60 ℃, and the polyacrylonitrile is dissolved by stirring, so that the system becomes homogeneous. And casting the uniformly mixed solution on a clean glass sheet, quickly transferring the glass sheet to a vacuum drying oven, drying the glass sheet for 48 hours at the temperature of 80 ℃, and removing the organic solvent. And cooling to room temperature, and stripping the transparent elastic membrane on the glass sheet in a glove box filled with argon, wherein the elastic membrane is the morpholine ionic liquid N-methoxyethoxyethyl-N-methylmorpholine hexafluorophosphate/gel polymer electrolyte membrane.
Example 3
The morpholine ionic liquid N-methoxyethoxyethyl-N-methylmorpholine bis (trifluoromethanesulfonyl) imide salt is prepared through the following reaction process:
mixing N-methylmorpholine (101 g, 1mol) and methoxyethoxy iodoethane (276g,1.2mol), stirring uniformly, heating for 20 seconds under the microwave radiation power of 300W, taking out and stirring for 10 seconds, repeating the process for 6 times, stirring to room temperature, and washing with ethyl acetate for three times. Vacuum drying at 80 deg.C to give a pale yellow solid, i.e., N-methoxyethoxyethyl-N-methylmorpholine iodide) in 84% yield;
dissolving the N-methoxyethoxyethyl-N-methylmorpholine iodide (165.6g, 0.5mol) and (159.5g, 0.5mol) potassium bis (trifluoromethanesulfonyl) imide in 150mL of deionized water, stirring at 30 ℃ for 24 hours to obtain a mixture, extracting the mixture 6 times with 250mL of dichloromethane, combining the extracts, and back-extracting with 60mL of deionized water each time until saturated AgNO is used3Until no precipitate is generated in the aqueous solution titration aqueous phase, concentrating the dichloromethane phase by using a rotary evaporator, and performing vacuum drying at 80 ℃ for 48 hours to obtain colorless liquid, namely N-methoxyethoxyethyl-N-methylmorpholine bis (trifluoromethanesulfonyl) imide;
the nuclear magnetic spectrum of the prepared morpholine ionic liquid N-methoxyethoxyethyl-N-methylmorpholine bis (trifluoromethanesulfonyl) imide salt is as follows:
1H NMR(CDCl3,400MHz,ppm):3.86(m,2H),3.75(m,2H),3.64(m,2H),3.59(m,2H),3.42(m,2H),3.26(s,3H),2.97(s,3H),2.78(m,2H),2.67(m,2H),2.59(m,2H).
preparing morpholine ionic liquid N-methoxyethoxyethyl-N-methylmorpholine bis (trifluoromethanesulfonyl) imide salt/gel polymer electrolyte salt membrane:
100g of polyacrylonitrile having a relative molecular weight of 60 ten thousand, 30g of N-methoxyethoxyethyl-N-methylimidazolium bis (trifluoromethanesulfonyl) imide salt and 20g of ethylene carbonate were placed in a 500mL three-necked flask in this order. Under the protection of dry helium, the temperature is raised to 50 ℃, and the polyacrylonitrile is dissolved by stirring, so that the system becomes homogeneous. The uniformly mixed solution was cast on a clean glass slide, quickly transferred to a vacuum drying oven, dried at 90 ℃ for 36 hours, and the organic solvent was removed. And cooling to room temperature, and stripping the transparent elastic membrane on the glass sheet in a helium-filled glove box to obtain the morpholine ionic liquid N-methoxyethoxyethyl-N-methylmorpholine bis (trifluoromethanesulfonyl) imide salt/gel polymer electrolyte membrane.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A morpholine ionic liquid/gel polymer electrolyte membrane, which is characterized by comprising a polyacrylonitrile substrate and morpholine ionic liquid miscible with the polyacrylonitrile, wherein the morpholine ionic liquid has the following structural formula:
wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -One of (1); the mass ratio of the polyacrylonitrile to the morpholine ionic liquid is 100: 30-100: 50.
2. The morpholine ionic liquid/gel polymer electrolyte membrane according to claim 1, wherein the polyacrylonitrile has a relative molecular weight of 10-60 ten thousand.
3. Use of a morpholine ionic liquid/gel polymer electrolyte membrane according to any one of claims 1 or 2 in a supercapacitor or lithium ion battery.
4. The preparation method of the morpholine ionic liquid/gel polymer electrolyte membrane is characterized by comprising the following steps:
the method comprises the following steps: mixing polyacrylonitrile, morpholine ionic liquid and an organic solvent according to the mass ratio of 100: 30-50: 20-40, heating to 40-60 ℃, and stirring to form a homogeneous mixed solution, wherein the morpholine ionic liquid has the following structural formula:
wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -One of (1);
step two: and casting the homogeneous mixed solution on a substrate, then drying the substrate on which the homogeneous mixed solution is cast in vacuum at 80-100 ℃ for 24-28 hours, cooling to room temperature, and stripping a film on the substrate to obtain the morpholine ionic liquid/gel polymer electrolyte film.
5. The method for preparing a morpholine ionic liquid/gel polymer electrolyte membrane according to claim 4, wherein the relative molecular weight of polyacrylonitrile is 10-60 ten thousand.
6. The method for preparing morpholine ionic liquid/gel polymer electrolyte membrane according to claim 4, wherein the organic solvent is dimethylformamide, N-methylpyrrolidone or ethylene carbonate.
7. The method for preparing morpholine ionic liquid/gel polymer electrolyte membrane according to claim 4, wherein the morpholine ionic liquid is prepared according to the following method:
mixing one of methoxyethoxyethyl chloroethane, methoxyethoxy bromoethane and methoxyethoxyethyl iodoethane with N-methylmorpholine according to a molar ratio of 1.05: 1-1.2: 1, heating by microwave radiation for 20-40 seconds, stirring for 10-15 seconds, repeating the heating and stirring steps for 3-6 times to obtain halogenated N-methoxyethoxyethyl-N-methylmorpholine, wherein the halogenated N-methoxyethoxyethyl-N-methylmorpholine is N-methoxyethoxyethyl chloride-N-methylmorpholine, N-methoxyethoxyethyl bromide-N-methylmorpholine or N-methoxyethoxyethyl iodide-N-methylmorpholine;
reacting the halogenated N-methoxyethoxyethyl-N-methylmorpholine with a compound represented by the general formula M+Y-Mixing the salts according to the mol ratio of 1: 1-1: 1.1, adding the mixed salts into deionized water, stirring the mixture to perform an ion exchange reaction, and separating and purifying the mixture to obtain the morpholine ionic liquid with the following structural formula:
wherein M is+Selected from Na+、K+And NH4 +One of (1); y is-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -One kind of (1).
8. The preparation method of the morpholine ionic liquid/gel polymer electrolyte membrane according to claim 7, wherein the mixture of N-methylmorpholine and one of methoxyethoxyethyl chloroethane, methoxyethoxyethyl bromoethane and methoxyethoxyethyl iodoethane is heated under microwave radiation power of 200-300W, the heating and stirring steps are repeated for 3-6 times, the obtained reactant is cooled and washed with ethyl acetate, and then the washed product is dried in vacuum to obtain purified halogenated N-methoxyethoxyethyl-N-methylmorpholine.
9. The method for preparing morpholine ionic liquid/gel polymer electrolyte membrane according to claim 7, wherein the temperature of the ion exchange reaction is 15-30 ℃ and the time is 8-24 hours.
10. The method for preparing morpholine ionic liquid/gel polymer electrolyte membrane according to claim 7, wherein the separation and purification steps are as follows: reacting a halogenated N-methoxyethoxyethyl-N-methylmorpholine with a compound of the formula M+Y-The mixed solution obtained after the salt is stirred and reacted is extracted by dichloromethane, and then the dichloromethane is used for back extraction until the obtained water phase is saturated AgNO3And titrating the aqueous solution until no precipitate is generated, evaporating and concentrating a dichloromethane extract, and drying in vacuum to obtain the morpholine ionic liquid.
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