CN103833661A - Oxazolidine ionic liquid, and preparation method and application thereof - Google Patents
Oxazolidine ionic liquid, and preparation method and application thereof Download PDFInfo
- Publication number
- CN103833661A CN103833661A CN201210486641.3A CN201210486641A CN103833661A CN 103833661 A CN103833661 A CN 103833661A CN 201210486641 A CN201210486641 A CN 201210486641A CN 103833661 A CN103833661 A CN 103833661A
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- ionic liquid
- azoles
- organic solvent
- alkyl
- alkanes
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 title abstract 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 7
- -1 azoles alkanes Chemical class 0.000 claims description 89
- 239000003960 organic solvent Substances 0.000 claims description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 239000008151 electrolyte solution Substances 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 239000011737 fluorine Substances 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 11
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000003252 repetitive effect Effects 0.000 claims description 8
- 238000005201 scrubbing Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 230000001035 methylating effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 150000002917 oxazolidines Chemical class 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 9
- 229910052736 halogen Inorganic materials 0.000 abstract description 8
- 150000002367 halogens Chemical class 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 6
- 239000003990 capacitor Substances 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 229910018928 (FSO2)2N Inorganic materials 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000011244 liquid electrolyte Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
-
- 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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Microelectronics & Electronic Packaging (AREA)
Abstract
The invention relates to an oxazolidine ionic liquid. The chemical structural formula of the ionic liquid is shown as the specification, wherein R is alkyl of C2-C6; Y<-> is (CF3SO2)2N<-> or (FSO2)2N<->. The oxazolidine ionic liquid is completely formed by ions at room temperature or under a situation close to the room temperature, has the advantages of high electrical conductivity, low melting point, wide electrochemical window, no volatilization or inflammability, good thermal stability and no halogen impurities or toxicity, and can be applied to the field of preparation of super-capacitors or lithium ionic batteries with high specific capacity. Furthermore, the invention also relates to a preparation method and application of the oxazolidine ionic liquid.
Description
[technical field]
The present invention relates to a kind of capacitor electrolyte field, relate in particular to a kind of azoles alkanes ionic liquid and preparation method thereof, also relate to a kind of electrolytic solution and compound method and ultracapacitor that uses this azoles alkanes ionic liquid simultaneously.
[background technology]
Ultracapacitor is a kind of novel energy device between rechargeable battery and electrical condenser, have that volume is little, capacity is large, charge velocities 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 electromobile etc.The energy that ultracapacitor is stored be proportional to applied voltage square, thereby, improve the voltage that applies and can increase considerably the specific energy of ultracapacitor.But the ionic liquid that adopts two-step approach to prepare inevitably all can be introduced halogens, these halogen impurities ions can cause the stability of ionic liquid to reduce, the shortcoming that Melting point elevation and electrochemical window narrow.
[summary of the invention]
Based on this, be necessary azoles alkanes ionic liquid providing a kind of not halogen-containing element and preparation method thereof.
A kind of azoles alkanes ionic liquid, chemical structural formula is as follows:
Wherein, R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3s0
2)
2n
-or (FSO
2)
2n
-.
This azoles alkanes ionic liquid is in room temperature or approach under the condition of room temperature and be made up of ion completely, specific conductivity is high, fusing point is low, electrochemical window is wide, non-volatile, non-combustible, Heat stability is good and not contain halogen impurities nontoxic, particularly decomposition voltage is high, under high voltage condition, be difficult to decompose, thereby can be applied in ultracapacitor or the lithium ion battery field of manufacturing height ratio capacity.
A preparation method for azoles alkanes ionic liquid, comprises the steps:
Under inert atmosphere protection, alkyl oxazolidine derivative and methylating reagent MY are added in organic solvent for 1: 1 in molar ratio～1.2: 1, the mass ratio of described organic solvent and described alkyl oxazolidine derivative is 0.8: 1～1.4: 1, be stirring reaction 3 hours～15 hours under 60 ℃～80C condition in temperature, then remove excessive described alkyl oxazolidine derivative and described organic solvent, collect colourless liquid, after washing, vacuum-drying obtains azoles alkanes ionic liquid, wherein, described alkyl oxazolidine derivative is ethyl azoles alkane, propyl group azoles alkane, butyl azoles alkane, amyl group azoles alkane or hexyl azoles alkane, described methylating reagent MY is N-methyl-bis-(fluoroform sulphonyl) amine or N-methyl-bis-(fluorine sulphonyl) amine, its chemical structural formula is as follows:
Wherein, R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-.
In a preferred embodiment, described organic solvent is chloroform, methylene dichloride or tetracol phenixin.
In a preferred embodiment, step is removed excessive described alkyl oxazolidine derivative and described organic solvent and is specially: remove excessive alkyl oxazolidine derivative and described organic solvent by the mode of underpressure distillation, the condition of described underpressure distillation is that temperature is 120 ℃～200C, and pressure is 0.1Pa～5Pa.
In a preferred embodiment, described washing step is specially: by colourless liquid repetitive scrubbing in the solution of ethyl acetate or methyl tertiary butyl ether of collecting.
Above-mentioned preparation process adopts the large-scale industrial production that single stage method efficiency is high, pollution-free, be conducive to azoles alkanes ionic liquid.
Meanwhile, be also necessary to provide a kind of electrolytic solution and compound method and ultracapacitor that uses above-mentioned difficult decomposition, the good ionic liquid of stability.
A kind of electrolytic solution, comprises azoles alkanes ionic liquid and organic solvent,
Wherein, the structural formula of described azoles alkanes ionic liquid is as follows:
R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-;
Azoles alkanes ionic liquid is 1: 5～2: 1 with the quality of organic solvent than scope.
In a preferred embodiment, described organic solvent is at least one in acetonitrile, NSC 11801, Methyl ethyl carbonate, propylene carbonate, gamma-butyrolactone and ethyl propionate.
A compound method for electrolytic solution, comprises the steps:
Under inert atmosphere protection; get at least one in acetonitrile, NSC 11801, Methyl ethyl carbonate, propylene carbonate, gamma-butyrolactone and ethyl propionate as organic solvent; in described organic solvent, add azoles alkanes ionic liquid in the mass ratio ratio of 1: 5～2: 1 of organic solvent and azoles alkanes ionic liquid; be uniformly mixed; obtain described electrolytic solution; wherein, the structural formula of described azoles alkanes ionic liquid is as follows:
R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-.
The electrolytic conductivity that contains azoles alkanes ionic liquid is high, fusing point is low, the decomposition voltage of Heat stability is good and not halogen-containing impurity, particularly electrolytic solution is high, can be widely used in the preparation field of ultracapacitor, obtains the ultracapacitor of high-energy-density.Meanwhile, its process for preparation is simple, uses raw material cheap and easy to get, can large-scale industrial production.
A kind of ultracapacitor, the electrolytic solution of described ultracapacitor comprises the ionic liquid with following structure:
R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-.
By test, use the above-mentioned ultracapacitor that contains azoles alkanes ionic liquid to there is higher charging/discharging voltage, and under high charge-discharge voltage conditions, electrolytic solution is highly stable.
[accompanying drawing explanation]
Fig. 1 is the preparation method's of the prepared azoles alkanes of embodiment of the present invention ionic liquid schema.
[embodiment]
Mainly in conjunction with specific embodiments azoles alkanes ionic liquid and its preparation method and application is described in further detail below.
The azoles alkanes ionic liquid of present embodiment, chemical structural formula is as follows:
Wherein, R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-.
This azoles alkanes ionic liquid is in room temperature or approach under the condition of room temperature and be made up of ion completely, specific conductivity is high, fusing point is low, electrochemical window is wide, non-volatile, non-combustible, Heat stability is good and not halogen-containing impurity nontoxic, particularly decomposition voltage is high, under high voltage condition, be difficult to decompose, thereby can be applied in ultracapacitor or the lithium ion battery field of manufacturing height ratio capacity.
A preparation method for above-mentioned azoles alkanes ionic liquid, preparation flow is as follows:
Wherein MY is N-methyl-bis-(fluoroform sulphonyl) amine or N-methyl-bis-(fluorine sulphonyl) amine; R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-.
Specifically comprise the steps:
Step S1: under inert atmosphere protection; alkyl oxazolidine derivative and methylating reagent MY are added in organic solvent for 1: 1 in molar ratio～1.2: 1; the mass ratio of described organic solvent and described alkyl oxazolidine derivative is 0.8: 1～1.4: 1, is stirring reaction 3 hours～15 hours under 60C～80C condition in temperature.
Wherein, alkyl oxazolidine derivative is ethyl azoles alkane, propyl group azoles alkane, butyl azoles alkane, amyl group azoles alkane or hexyl azoles alkane.
Wherein, methylating reagent MY is N-methyl-bis-(fluoroform sulphonyl) amine or N-methyl-bis-(fluorine sulphonyl) amine.
Step S2: then remove excessive described alkyl oxazolidine derivative and described organic solvent, collect colourless liquid.
The concrete oxazolidine derivative of removing excessive described alkyl and the step of described organic solvent are to remove oxazolidine derivative and the described organic solvent of excessive alkyl by the mode of underpressure distillation, the condition of described underpressure distillation is that temperature is 120 ℃～200C, and pressure is 0.1Pa～5Pa.
Step S3: after washing, it is as follows that vacuum-drying obtains its chemical structural formula of azoles alkanes ionic liquid:
Wherein, R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-.
Wherein, the mode of washing is for adopting ethyl acetate or methyl tertiary butyl ether 50ml repetitive scrubbing more than 3 times.
The large-scale industrial production that above-mentioned preparation process efficiency is high, pollution-free, be conducive to azoles alkanes ionic liquid.
Meanwhile, the present invention also provides a kind of electrolytic solution and compound method and ultracapacitor that uses above-mentioned difficult decomposition, the good ionic liquid of stability.
The electrolytic solution of one embodiment comprises azoles alkanes ionic liquid and organic solvent,
Wherein, the structural formula of azoles alkanes ionic liquid is as follows:
R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-;
Azoles alkanes ionic liquid is 1: 5～2: 1 with the quality of organic solvent than scope.
Organic solvent is preferably at least one in acetonitrile, NSC 11801, Methyl ethyl carbonate, propylene carbonate, gamma-butyrolactone and ethyl propionate, and the mass ratio of organic solvent and azoles alkanes ionic liquid 1: 5～2: 1.
The process for preparation of this electrolytic solution, comprises the steps:
Under inert atmosphere protection; get at least one in acetonitrile, NSC 11801, Methyl ethyl carbonate, propylene carbonate, gamma-butyrolactone and ethyl propionate as organic solvent; in described organic solvent, add azoles alkanes ionic liquid in the mass ratio ratio of 1: 5～2: 1 of organic solvent and azoles alkanes ionic liquid; be uniformly mixed; obtain described electrolytic solution; wherein, the structural formula of described azoles alkanes ionic liquid is as follows:
R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-.
The electrolytic conductivity that contains azoles alkanes ionic liquid is high, fusing point is low, Heat stability is good and not contain the decomposition voltage of halogen impurities, particularly electrolytic solution high, can be widely used in the preparation field of ultracapacitor, obtains the ultracapacitor of high-energy-density.Meanwhile, its process for preparation is simple, uses raw material cheap and easy to get, can large-scale industrial production.
By test, use and above-mentionedly contain the ultracapacitor that azoles alkanes ionic liquid prepares and there is higher charging/discharging voltage, and under high charge-discharge voltage conditions, electrolytic solution is highly stable.
Be below specific embodiment part:
In following examples, contain atmosphere of inert gases take nitrogen and argon atmosphere as representative.
Embodiment 1:
In the flask of 500mL, add respectively 110g chloroform, (111.3g, 1.1mol) ethyl azoles alkane, (295g, 1.0mol) N-methyl-bis-(fluoroform sulphonyl) amine, under nitrogen atmosphere, be warming up to 70C, stirring reaction 10 hours.Leave standstill cooling, it is 150 ℃ in temperature, pressure is to carry out underpressure distillation under the condition of 3.0Pa, remove excessive reactant, collecting colourless liquid 50ml ethyl acetate repetitive scrubbing three times, is then 80 ℃ in temperature, and vacuum tightness is under 0.01MPa condition, to carry out vacuum-drying, obtain two (fluoroform sulphonyl) inferior amine salts of colourless liquid N-ethyl-N-methyl azoles alkane, productive rate 90%.
Its hydrogen spectrum data are as follows:
1H NMR(CDCl
3，400MHz，ppm)：4.48(s，2H)，3.62(m，2H)，2.59(m，2H)，2.45(m，2H)，2.32(s，3H)，0.97(s，3H).
Under inert atmosphere protection, take out two (fluoroform sulphonyl) inferior amine salts of 10g N-ethyl-N-methyl azoles alkane, then add wherein 30g acetonitrile, and be uniformly mixed, thereby obtain object ion liquid electrolyte.
Embodiment 2:
In the flask of 500mL, add respectively 92g methylene dichloride, (115.2g, 1.0mol) propyl group azoles alkane, (195g, 1.0mol) N-methyl-bis-(fluorine sulphonyl) amine, under nitrogen atmosphere, be warming up to 60 ℃, stirring reaction 3 hours.Leave standstill cooling, be 120C in temperature, pressure is to carry out underpressure distillation under the condition of 0.1Pa, remove excessive reactant, collecting colourless liquid 50ml methyl tertiary butyl ether repetitive scrubbing three times, is then 70C in temperature, and vacuum tightness is under 0.01MPa condition, to carry out vacuum-drying, obtain two (fluorine sulphonyl) inferior amine salts of colourless liquid N-propyl group-N-methyl azoles alkane, productive rate 89%.
Its hydrogen spectrum data are as follows:
1H NMR(CDCl
3，400MHz，ppm)：4.47(s，2H)，3.62(m，2H)，2.58(m，2H)，2.41(m，2H)，2.32(s，3H)，1.46(m，2H)，0.96(s，3H)
At N
2(or Ar
2) under atmosphere protection, take out two (fluorine sulphonyl) inferior amine salts of 10g N-propyl group-N-methyl azoles alkane, then add wherein 50g propylene carbonate, and be uniformly mixed, thereby obtain object ion liquid electrolyte.
Embodiment 3
In the flask of 500mL, add respectively 170g tetracol phenixin, (155.0g, 1.2mol) butyl azoles alkane, (195g, 1.0mol) N-methyl-bis-(fluorine sulphonyl) amine, under nitrogen atmosphere, be warming up to 80 ℃, stirring reaction 15 hours.Leave standstill cooling, it is 200 ℃ in temperature, pressure is to carry out underpressure distillation under the condition of 5.0Pa, remove excessive reactant, collecting colourless liquid 50ml ethyl acetate repetitive scrubbing three times, is then 90C in temperature, and vacuum tightness is under 0.01MPa condition, to carry out vacuum-drying, obtain two (fluorine sulphonyl) inferior amine salts of colourless liquid N-butyl-N-methyl azoles alkane, productive rate 87%.
Its hydrogen spectrum data are as follows:
1HNMR(CDCl
3，400MHz，ppm)：4.48(s，2H)，3.63(m，2H)，2.59(m，2H)，2.41(m，2H)，2.33(s，3H)，1.45(m，2H)，1.37(m，2H)，0.97(s，3H)
At N
2(or Ar
2) under atmosphere protection, take out two (fluorine sulphonyl) inferior amine salts of 10g N-butyl-N-methyl azoles alkane, then add wherein 5g acetonitrile, and be uniformly mixed, thereby obtain object ion liquid electrolyte.
Embodiment 4:
In the flask of 500mL, add respectively 180g chloroform, (150.3g, 1.05mol) amyl group azoles alkane, (195g, 1.0mol) N-methyl-bis-(fluorine sulphonyl) amine, under nitrogen atmosphere, be warming up to 65C, stirring reaction 7 hours.Leave standstill cooling, be 180C in temperature, pressure is to carry out underpressure distillation under the condition of 2.0Pa, remove excessive reactant, collecting colourless liquid 50ml methyl tertiary butyl ether repetitive scrubbing three times, is then 100 ℃ in temperature, and vacuum tightness is under 0.01MPa condition, to carry out vacuum-drying, obtain two (fluorine sulphonyl) inferior amine salts of colourless liquid N-amyl group-N-methyl azoles alkane, productive rate 83%.
Its hydrogen spectrum data are as follows:
1H NMR(CDCl
3，400MHz，ppm)：4.47(s，2H)，3.62(m，2H)，2.58(m，2H)，2.41(m，2H)，2.32(s，3H)，1.43(m，2H)，1.33(m，4H)，0.96(s，3H).
At N
2(or Ar
2) under atmosphere protection, take out two (fluorine sulphonyl) inferior amine salts of 10g N-amyl group-N-methyl azoles alkane, then add wherein 10g gamma-butyrolactone, and be uniformly mixed, thereby obtain object ion liquid electrolyte.
Embodiment 5:
In the flask of 500mL, add respectively 242g tetracol phenixin, (172.9g, 1.1mol) hexyl azoles alkane, (295g, 1.0mol) N-methyl-bis-(fluoroform sulphonyl) amine, under nitrogen atmosphere, be warming up to 75 ℃, stirring reaction 12 hours.Leave standstill cooling, it is 170 ℃ in temperature, pressure is to carry out underpressure distillation under the condition of 0.6Pa, remove excessive reactant, collecting colourless liquid 50ml ethyl acetate repetitive scrubbing three times, is then 90 ℃ in temperature, and vacuum tightness is under 0.01MPa condition, to carry out vacuum-drying, obtain two (fluoroform sulphonyl) inferior amine salts of colourless liquid N-hexyl-N-methyl azoles alkane, productive rate 81%.
Its hydrogen spectrum data are as follows:
1HNMR(CDCl
3，400MHz，ppm)：4.48(s，2H)，3.62(m，2H)，2.59(m，2H)，2.43(m，2H)，2.32(s，3H)，1.43(m，2H)，1.32(m，6H)，0.97(s，3H).
At N
2(or Ar
2) under atmosphere protection, take out two (fluoroform sulphonyl) inferior amine salts of 10g N-hexyl-N-methyl azoles alkane, then add wherein 20g gamma-butyrolactone, and be uniformly mixed, thereby obtain object ion liquid electrolyte.
Application Example
Electrolytic solution in application above-described embodiment 1～5 is assembled into ultracapacitor
(specific surface area of nitrogen-doped graphene is about 1000m to take 9g nitrogen-doped graphene
2/ g, nitrogen content is 8%), 0.5g acetylene black and 0.5g PVDF, and add 60g NMP, fully stir and make it to become the slurry mixing.Then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 80 ℃ are dried to constant weight, and are pressed into nitrogen-doped graphene electrode in 12MPa pressure lower roll, and are cut into electrode disk.In the glove box that is full of argon gas, pp barrier film and above-mentioned il electrolyte are placed between two activated carbon electrodes disks, on stamping machine, button electrical condenser is made in sealing.
Utilize charge-discharge test instrument to carry out constant current charge-discharge test to the ultracapacitor assembling in the present embodiment, in the electrochemical window of 0～3.0V, record as follows than capacitance data with the electric current of 0.5A/g:
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| Than electric capacity (F/g) | 125 | 118 | 103 | 110 | 114 |
As can be seen from the table, the prepared il electrolyte of the embodiment of the present invention is suitable for the electrolytic solution of ultracapacitor, and in the electrochemical window of 3.0V, has good capacitance characteristic.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. an azoles alkanes ionic liquid, is characterized in that, chemical structural formula is as follows:
Wherein, R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-.
2. a preparation method for azoles alkanes ionic liquid, is characterized in that, comprises the steps:
Under inert atmosphere protection, alkyl oxazolidine derivative and methylating reagent MY are added in organic solvent for 1: 1 in molar ratio～1.2: 1, the mass ratio of described organic solvent and described alkyl oxazolidine derivative is 0.8: 1～1.4: 1, be stirring reaction 3 hours～15 hours under 60 ℃～80 ℃ conditions in temperature, then remove excessive described alkyl oxazolidine derivative and described organic solvent, collect colourless liquid, after washing, vacuum-drying obtains azoles alkanes ionic liquid, wherein, described alkyl oxazolidine derivative is ethyl azoles alkane, propyl group azoles alkane, butyl azoles alkane, amyl group azoles alkane or hexyl azoles alkane, described methylating reagent MY is N-methyl-bis-(fluoroform sulphonyl) amine or N-methyl-bis-(fluorine sulphonyl) amine, its chemical structural formula is as follows:
Wherein, R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-.
3. the preparation method of azoles alkanes ionic liquid as claimed in claim 2, is characterized in that, described organic solvent is chloroform, methylene dichloride or tetracol phenixin.
4. the preparation method of azoles alkanes ionic liquid as claimed in claim 2, it is characterized in that, oxazolidine derivative and described organic solvent that step is removed excessive described alkyl are specially: oxazolidine derivative and the described organic solvent of removing excessive alkyl by the mode of underpressure distillation, the condition of described underpressure distillation is that temperature is 120 ℃～200 ℃, and pressure is 0.1Pa～5Pa.
5. the preparation method of azoles alkanes ionic liquid as claimed in claim 2, is characterized in that, described washing step is specially: by colourless liquid repetitive scrubbing in the solution of ethyl acetate or methyl tertiary butyl ether of collecting.
6. an electrolytic solution, is characterized in that, comprises azoles alkanes ionic liquid and organic solvent,
Wherein, the structural formula of described azoles alkanes ionic liquid is as follows:
R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-;
Azoles alkanes ionic liquid is 1: 5～2: 1 with the quality of organic solvent than scope.
7. electrolytic solution as claimed in claim 6, is characterized in that, described organic solvent is at least one in acetonitrile, NSC 11801, Methyl ethyl carbonate, propylene carbonate, gamma-butyrolactone and ethyl propionate.
8. a compound method for electrolytic solution, is characterized in that, comprises the steps:
Under inert atmosphere protection; get at least one in acetonitrile, NSC 11801, Methyl ethyl carbonate, propylene carbonate, gamma-butyrolactone and ethyl propionate as organic solvent; in described organic solvent, add azoles alkanes ionic liquid in the mass ratio ratio of 1: 5～2: 1 of organic solvent and azoles alkanes ionic liquid; be uniformly mixed; obtain described electrolytic solution; wherein, the structural formula of described azoles alkanes ionic liquid is as follows:
R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-.
9. a ultracapacitor, is characterized in that, the electrolytic solution of described ultracapacitor comprises the ionic liquid with following structure:
R is that carbonatoms is 2～6 alkyl, and Y-is (CF
3sO
2)
2n
-or (FSO
2)
2n
-.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1854129A (en) * | 2005-03-29 | 2006-11-01 | 第一工业制药株式会社 | Superhigh purity ionic liquid |
| CN101747243A (en) * | 2008-11-28 | 2010-06-23 | 华中科技大学 | Ionic liquid prepared through diimine (vikane) and (perfluoroalkglsulfonyl fluorosulfonyl group) imine alkali salt |
| CN101841064A (en) * | 2010-05-20 | 2010-09-22 | 中南大学 | High capacity and Coulomb-efficiency lithium-ion capacitance battery anode system |
| JP2011236161A (en) * | 2010-05-11 | 2011-11-24 | Mazda Motor Corp | Ionic liquid, method for producing the same, power storage device using the same |
-
2012
- 2012-11-26 CN CN201210486641.3A patent/CN103833661B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1854129A (en) * | 2005-03-29 | 2006-11-01 | 第一工业制药株式会社 | Superhigh purity ionic liquid |
| CN101747243A (en) * | 2008-11-28 | 2010-06-23 | 华中科技大学 | Ionic liquid prepared through diimine (vikane) and (perfluoroalkglsulfonyl fluorosulfonyl group) imine alkali salt |
| JP2011236161A (en) * | 2010-05-11 | 2011-11-24 | Mazda Motor Corp | Ionic liquid, method for producing the same, power storage device using the same |
| CN101841064A (en) * | 2010-05-20 | 2010-09-22 | 中南大学 | High capacity and Coulomb-efficiency lithium-ion capacitance battery anode system |
Non-Patent Citations (1)
| Title |
|---|
| MACIEJ GALINSKI等: "Morpholinium-based ionic liquid mixtures as electrolytes in electrochemical double layer capacitors", 《JOURNAL OF APPLIED ELECTROCHEMISTRY》, vol. 39, no. 10, 30 April 2009 (2009-04-30), pages 1949 - 1953, XP019749458, DOI: 10.1007/s10800-009-9904-4 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111477469A (en) * | 2020-04-17 | 2020-07-31 | 贵州梅岭电源有限公司 | Preparation method of high-voltage electrolyte and application of high-voltage electrolyte in super capacitor |
| CN111477469B (en) * | 2020-04-17 | 2022-05-17 | 贵州梅岭电源有限公司 | Preparation method of high-voltage electrolyte and application of high-voltage electrolyte in super capacitor |
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| CN103833661B (en) | 2016-04-20 |
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