CN103833622A - Maleimide ionic liquid, and preparation method and application thereof - Google Patents
Maleimide ionic liquid, and preparation method and application thereof Download PDFInfo
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- CN103833622A CN103833622A CN201210486537.4A CN201210486537A CN103833622A CN 103833622 A CN103833622 A CN 103833622A CN 201210486537 A CN201210486537 A CN 201210486537A CN 103833622 A CN103833622 A CN 103833622A
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- maleimide
- ionic liquid
- organic solvent
- alkyl
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 56
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 7
- 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
- -1 alkyl maleimide derivative Chemical class 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
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 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
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 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
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 7
- 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
- 150000001875 compounds Chemical class 0.000 claims description 5
- USICVVZOKTZACS-UHFFFAOYSA-N 3-butylpyrrole-2,5-dione Chemical group CCCCC1=CC(=O)NC1=O USICVVZOKTZACS-UHFFFAOYSA-N 0.000 claims description 4
- MXVZVCCKUVRGQC-UHFFFAOYSA-N 3-hexylpyrrole-2,5-dione Chemical compound CCCCCCC1=CC(=O)NC1=O MXVZVCCKUVRGQC-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical group CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 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
- 0 C*(C(C=C1)=O)(C1=O)O Chemical compound C*(C(C=C1)=O)(C1=O)O 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 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
- 238000009776 industrial production Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000003990 capacitor Substances 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
- 238000002156 mixing Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Pyrrole Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention relates to a maleimide 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 maleimide 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 supercapacitors or lithium ionic batteries with high specific capacity. Furthermore, the invention also relates to a preparation method and application of the maleimide ionic liquid.
Description
[technical field]
The present invention relates to a kind of capacitor electrolyte field, relate in particular to a kind of maleimide ionic liquid and preparation method thereof, also relate to a kind of electrolytic solution and compound method and ultracapacitor that uses this maleimide 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 maleimide ionic liquid providing a kind of not halogen-containing element and preparation method thereof.
A kind of maleimide ionic liquid, 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 maleimide 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 maleimide ionic liquid, comprises the steps:
Under inert atmosphere protection, alkyl maleimide 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 alkyl maleimide derivative is 0.8: 1～1.4: 1, be stirring reaction 3 hours～15 hours under 60 DEG C～80 DEG C conditions in temperature, then remove excessive described alkyl maleimide derivative and described organic solvent, collect colourless liquid, after washing, vacuum-drying obtains maleimide ionic liquid, wherein, described alkyl maleimide derivative is ethyl maleimide, propyl group maleimide, butyl maleimide, amyl group maleimide or hexyl maleimide, 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 maleimide derivative and described organic solvent and is specially: remove excessive alkyl maleimide derivative and described organic solvent by the mode of underpressure distillation, the condition of described underpressure distillation is that temperature is 120 DEG C～200 DEG C, 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 maleimide 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 maleimide ionic liquid and organic solvent,
Wherein, the structural formula of described maleimide ionic liquid is as follows:
R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-;
Maleimide 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 maleimide ionic liquid in the mass ratio ratio of 1: 5～2: 1 of organic solvent and maleimide ionic liquid; be uniformly mixed; obtain described electrolytic solution; wherein, the structural formula of described maleimide 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 maleimide ionic liquid is high, fusing point is low, Heat stability is good and not halogen-containing impurity, particularly the decomposition voltage of electrolytic solution is high, can be widely used in the preparation field of ultracapacitor, obtain 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 maleimide ionic liquid to there is higher charging/discharging voltage, and under high charge-discharge voltage conditions, electrolytic solution is highly stable.
[brief description of the drawings]
Fig. 1 is the preparation method's of the prepared maleimide ionic liquid of the embodiment of the present invention schema.
[embodiment]
Mainly in conjunction with specific embodiments maleimide ionic liquid and its preparation method and application is described in further detail below.
The maleimide 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 maleimide 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 maleimide 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 maleimide 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 alkyl maleimide derivative is 0.8: 1～1.4: 1, is stirring reaction 3 hours～15 hours under 60 DEG C～80 DEG C conditions in temperature.
Wherein, alkyl maleimide derivative is ethyl maleimide, propyl group maleimide, butyl maleimide, amyl group maleimide or hexyl maleimide.
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 maleimide derivative and described organic solvent, collect colourless liquid.
The concrete maleimide derivatives of removing excessive described alkyl and the step of described organic solvent are to remove maleimide derivatives 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 DEG C～200 DEG C, and pressure is 0.1Pa～5Pa.
Step S3: after washing, it is as follows that vacuum-drying obtains its chemical structural formula of maleimide 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 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 maleimide 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 maleimide ionic liquid and organic solvent,
Wherein, the structural formula of maleimide ionic liquid is as follows:
R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-;
Maleimide 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 maleimide 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 maleimide ionic liquid in the mass ratio ratio of 1: 5～2: 1 of organic solvent and maleimide ionic liquid; be uniformly mixed; obtain described electrolytic solution; wherein, the structural formula of described maleimide 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 maleimide ionic liquid is high, fusing point is low, Heat stability is good and do not contain halogen impurities, particularly the decomposition voltage of electrolytic solution is high, can be widely used in the preparation field of ultracapacitor, obtain 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 maleimide 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 taking nitrogen and argon atmosphere as representative.
Embodiment 1:
In the flask of 500mL, add respectively 110g chloroform, (137.6g, 1.1mol) ethyl maleimide, (295g, 1.0mol) N-methyl-bis-(fluoroform sulphonyl) amine, under nitrogen atmosphere, be warming up to 70 DEG C, stirring reaction 10 hours.Leave standstill cooling, it is 150 DEG C 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 DEG C 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 1-ethyl-1-methyl maleimide, productive rate 87%.
Its hydrogen spectrum data are as follows:
1H?NMR(CDCl
3，400MHz，ppm)：6.92(d，2H)，3.43(m，2H)，2.92(s，3H)，0.97(s，3H).
Under inert atmosphere protection, take out two (fluoroform sulphonyl) inferior amine salts of 10g1-ethyl-1-methyl maleimide, then add wherein 30g acetonitrile, and be uniformly mixed, thereby obtain object ion liquid electrolyte.
Embodiment 2:
In the flask of 500mL, add respectively 139g methylene dichloride, (139g, 1.0mol) propyl group maleimide, (195g, 1.0mol) N-methyl-bis-(fluorine sulphonyl) amine, under nitrogen atmosphere, be warming up to 60 DEG C, stirring reaction 3 hours.Leave standstill cooling, it is 120 DEG C 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 70 DEG C 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 1-propyl group-1-methyl maleimide, productive rate 88%.
Its hydrogen spectrum data are as follows:
1H?NMR(CDCl
3，400MHz，ppm)：6.93(d，2H)，3.45(m，2H)，2.94(s，3H)，1.58(m，2H)，0.95(s，3H).
At N
2(or Ar
2) under atmosphere protection, take out two (fluorine sulphonyl) inferior amine salts of 10g1-propyl group-1-methyl maleimide, 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 205g tetracol phenixin, (183.8g, 1.2mol) butyl maleimide, (195g, 1.0mol) N-methyl-bis-(fluorine sulphonyl) amine, under nitrogen atmosphere, be warming up to 80 DEG C, stirring reaction 15 hours.Leave standstill cooling, it is 200 DEG C 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 90 DEG C 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 1-butyl-1-methyl maleimide, productive rate 86%.
Its hydrogen spectrum data are as follows:
1H?NMR(CDCl
3，400MHz，ppm)：6.92(d，2H)，3.45(m，2H)，2.94(s，3H)，1.56(m，2H)，1.35(m，2H)，0.97(s，3H).
At N
2(or Ar
2) under atmosphere protection, take out two (fluorine sulphonyl) inferior amine salts of 10g1-butyl-1-methyl maleimide, then add wherein 5g acetonitrile, and be uniformly mixed, thereby obtain object ion liquid electrolyte.
Embodiment 4:
In the flask of 500mL, add respectively 228g chloroform, (175.5g, 1.05mol) amyl group maleimide, (295g, 1.0mol) N-methyl-bis-(fluoroform sulphonyl) amine, under nitrogen atmosphere, be warming up to 65 DEG C, stirring reaction 7 hours.Leave standstill cooling, it is 180 DEG C 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 DEG C 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 1-amyl group-1-methyl maleimide, productive rate 85%.
Its hydrogen spectrum data are as follows:
1H?NMR(CDCl
3，400MHz，ppm)：6.93(d，2H)，3.45(m，2H)，2.95(s，3H)，1.56(m，2H)，1.33(m，4H)，0.96(s，3H).
At N
2(or Ar
2) under atmosphere protection, take out two (fluoroform sulphonyl) inferior amine salts of 10g1-amyl group-1-methyl maleimide, 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 279g tetracol phenixin, (199.3g, 1.1mol) hexyl maleimide, (295g, 1.0mol) N-methyl-bis-(fluoroform sulphonyl) amine, under nitrogen atmosphere, be warming up to 75 DEG C, stirring reaction 12 hours.Leave standstill cooling, it is 170 DEG C 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 DEG C 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 1-hexyl-1-methyl maleimide, productive rate 84%.
Its hydrogen spectrum data are as follows:
1H?NMR(CDCl
3，400MHz，ppm)：6.94(d，2H)，3.45(m，2H)，2.95(s，3H)，1.56(m，2H)，1.32(m，6H)，0.95(s，3H).
At N
2(or Ar
2) under atmosphere protection, take out two (fluoroform sulphonyl) inferior amine salts of 10g1-hexyl-1-methyl maleimide, 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 is about 2000m to take 9g gac
2/ g), 0.45g acetylene black and 0.55g 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 DEG C are dried to constant weight, and are pressed into activated carbon electrodes in 13MPa 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) | 122 | 115 | 100 | 106 | 110 |
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. a maleimide 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 maleimide ionic liquid, is characterized in that, comprises the steps:
Under inert atmosphere protection, alkyl maleimide 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 alkyl maleimide derivative is 0.8: 1～1.4: 1, be stirring reaction 3 hours～15 hours under 60 DEG C～80 DEG C conditions in temperature, then remove excessive described alkyl maleimide derivative and described organic solvent, collect colourless liquid, after washing, vacuum-drying obtains maleimide ionic liquid, wherein, described alkyl maleimide derivative is ethyl maleimide, propyl group maleimide, butyl maleimide, amyl group maleimide or hexyl maleimide, 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 maleimide 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 maleimide ionic liquid as claimed in claim 2, it is characterized in that, maleimide derivatives and described organic solvent that step is removed excessive described alkyl are specially: maleimide derivatives 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 DEG C～200 DEG C, and pressure is 0.1Pa～5Pa.
5. the preparation method of maleimide 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 maleimide ionic liquid and organic solvent,
Wherein, the structural formula of described maleimide ionic liquid is as follows:
R is that carbonatoms is 2～6 alkyl, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-;
Maleimide 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 maleimide ionic liquid in the mass ratio ratio of 1: 5～2: 1 of organic solvent and maleimide ionic liquid; be uniformly mixed; obtain described electrolytic solution; wherein, the structural formula of described maleimide 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, Y
-for (CF
3sO
2)
2n
-or (FSO
2)
2n
-.
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|---|---|---|---|---|
| US4624755A (en) * | 1985-06-05 | 1986-11-25 | Mcmanis Iii George E | Preparation of ionic liquids for electrodeposition |
| CN101054360A (en) * | 2007-05-23 | 2007-10-17 | 浙江工业大学 | Method for preparing N-substituted acryloyl-2,5-pyrrole-dione compound |
| CN101268057A (en) * | 2005-09-22 | 2008-09-17 | 纳幕尔杜邦公司 | Ionic liquids |
| CN101492422A (en) * | 2009-03-06 | 2009-07-29 | 华东师范大学 | Alkyl imidazole succinimide ionic liquid and method for preparing the same |
| WO2012120420A1 (en) * | 2011-03-04 | 2012-09-13 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Surface functionalization of a substrate in an ionic liquid medium |
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2012
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| US4624755A (en) * | 1985-06-05 | 1986-11-25 | Mcmanis Iii George E | Preparation of ionic liquids for electrodeposition |
| CN101268057A (en) * | 2005-09-22 | 2008-09-17 | 纳幕尔杜邦公司 | Ionic liquids |
| CN101054360A (en) * | 2007-05-23 | 2007-10-17 | 浙江工业大学 | Method for preparing N-substituted acryloyl-2,5-pyrrole-dione compound |
| CN101492422A (en) * | 2009-03-06 | 2009-07-29 | 华东师范大学 | Alkyl imidazole succinimide ionic liquid and method for preparing the same |
| WO2012120420A1 (en) * | 2011-03-04 | 2012-09-13 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Surface functionalization of a substrate in an ionic liquid medium |
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