CN103130779B - Maleimide ionic liquid of carbonate-containing group and its preparation method and application - Google Patents
Maleimide ionic liquid of carbonate-containing group and its preparation method and application Download PDFInfo
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- CN103130779B CN103130779B CN201110393397.1A CN201110393397A CN103130779B CN 103130779 B CN103130779 B CN 103130779B CN 201110393397 A CN201110393397 A CN 201110393397A CN 103130779 B CN103130779 B CN 103130779B
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 55
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 44
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 6
- 159000000002 lithium salts Chemical class 0.000 abstract description 6
- 125000005587 carbonate group Chemical group 0.000 abstract description 5
- 238000010494 dissociation reaction Methods 0.000 abstract description 3
- 230000005593 dissociations Effects 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- -1 1-ethyl-3-methylimidazole tetrafluoroborate ion Chemical class 0.000 description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 239000007788 liquid Substances 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000000605 extraction Methods 0.000 description 18
- 238000001291 vacuum drying Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 101710134784 Agnoprotein Proteins 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- RMLHVYNAGVXKKC-UHFFFAOYSA-N [SH2]=N.C(F)(F)F Chemical class [SH2]=N.C(F)(F)F RMLHVYNAGVXKKC-UHFFFAOYSA-N 0.000 description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 5
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- AGQKYUPKNZGEQS-UHFFFAOYSA-N C(C)(=O)OC=C.C(O)(=O)Cl Chemical compound C(C)(=O)OC=C.C(O)(=O)Cl AGQKYUPKNZGEQS-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 229910013075 LiBF Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- MYXJUONNAJPJJT-UHFFFAOYSA-N carbonochloridic acid;prop-1-ene Chemical group CC=C.OC(Cl)=O MYXJUONNAJPJJT-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UCDPSMXXZQJIAN-UHFFFAOYSA-N 4-bromo-5-methyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1Br UCDPSMXXZQJIAN-UHFFFAOYSA-N 0.000 description 1
- 0 C*(*)(C(C=C1)=O)C1=O Chemical compound C*(*)(C(C=C1)=O)C1=O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- PSEXDQCGOVHUCE-UHFFFAOYSA-N [K].[SH2]=N.C(F)(F)F Chemical compound [K].[SH2]=N.C(F)(F)F PSEXDQCGOVHUCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- DIMLTXLBYNIQRI-UHFFFAOYSA-N but-1-ene carbonochloridic acid Chemical class CCC=C.OC(Cl)=O DIMLTXLBYNIQRI-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—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
Landscapes
- Pyrrole Compounds (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to field of ionic liquid, it discloses maleimide ionic liquid of a kind of carbonate-containing group and its preparation method and application; This ionic liquid has following structural formula:
in formula, R is
0≤n≤4; Y
-be selected from BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -.The maleimide ionic liquid of carbonate-containing group provided by the invention, by introducing carbonate group in positively charged ion, the performance of ionic liquid is improved, and on the one hand in the electrolytic solution containing lithium salts, this structural carbonate has good dissolving and dissociation to lithium salts; Ionic liquid on the other hand containing structural carbonate can generate SEI film preferably, thus improves the electrochemical stability of il electrolyte.
Description
Technical field
The present invention relates to field of ionic liquid, particularly relate to maleimide ionic liquid of a kind of carbonate-containing group and its preparation method and application.
Background technology
Ionic liquid (Ionic liquids) refers to that in room temperature range, (be generally less than 100 DEG C) is in a liquid state, and is made up of organic cation and inorganic anion (or organic anion).Ionic liquid has adjustability, and need to change the object that its zwitterion structure can reach planner according to difference, thus ionic liquid is called as the solvent of planner.First ionic liquid has just been found as far back as 1914----nitro ethamine; But thereafter, the progress in this field is slow.Until 1992, the research group of Wikes leader has synthesized low melting point, resistant to hydrolysis, 1-ethyl-3-methylimidazole tetrafluoroborate ion liquid ([EMIM] BF that stability is strong
4) after, the research of ionic liquid is just developed rapidly, have developed a series of ion liquid system subsequently.Initial ionic liquid is mainly used in electrochemical research, and ionic liquid comes into one's own for organic and Polymer Synthesizing as green solvent in recent years.Compare with ionogen with traditional organic solvent, ionic liquid has a series of outstanding advantage: (1) fusing point lower than or close to room temperature, the temperature range be in a liquid state is wide; (2) steam force down, hardly volatilize, colourless, odorless; (3) there is larger equilibrium temperature scope, good chemical stability and wider electrochemical stability potential window; (4) good dissolution characteristics, all shows good dissolving power to a lot of inorganics and organism; (5) nonflammable without point of ignition; (6) can be recycled, free from environmental pollution etc.
At present, the synthesis of novel ion liquid, the sign of ionic liquid physics and chemistry characteristic and as the aspect such as solvent and electrolytical applied research are mainly concentrated on to the research of ionic liquid.Ionic liquid, as novel solvent, medium, the catalyzer of a class, achieves many gratifying results in the research in the fields such as organic synthesis, catalyzed reaction, extracting and separating, material preparation, natural polymer, electrochemistry, receives and pay close attention to widely.
Summary of the invention
Based on the problems referred to above, an object of the present invention is the maleimide ionic liquid providing a kind of novel carbonate-containing group.
A maleimide ionic liquid for carbonate-containing group, it comprises following structural formula:
In formula, R is
0≤n≤4; Y
-be selected from BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -.
Another object of the present invention is to the preparation method of the maleimide ionic liquid that above-mentioned carbonate-containing group is provided, comprise the steps:
S1, by mol ratio be 1: 1.1 ~ 1.2 N-methylmaleimido and RX carry out building-up reactions, reaction terminates rear obtained structural formula and is
the N-methylmaleimido halogenide of carbonate-containing group; Wherein, R is
0≤n≤4; X is halogen element, is selected from Cl or Br;
S2, the maleimide halogenide of described carbonate-containing group obtained by step S1 and inorganic salt MY carry out ion exchange reaction according to the mol ratio of 1: 1, and reaction terminates rear obtained structural formula and is
the maleimide ionic liquid of described carbonate-containing group; Wherein, in MY, M
+for processable positively charged ion, be selected from Na
+, K
+or NH
4 +; Y
-be selected from BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -.
In above-mentioned preparation method, the building-up reactions in step S1 is carried out in an inert atmosphere; This inert atmosphere comprises by least one gas composition in nitrogen and argon gas; In described step S1, described building-up reactions stirs 48 ~ 72h and carries out at 60 ~ 80 DEG C.
Another object of the present invention is to provide the maleimide ionic liquid of above-mentioned carbonate-containing group in ultracapacitor or lithium ion battery as the application of electrolytic solution.
The maleimide ionic liquid of carbonate-containing group provided by the invention, by introducing carbonate group in positively charged ion, makes the performance of ionic liquid improve, and is containing lithium salts (e.g., LiBF on the one hand
4, LiPF
6, LiTFSI, (CF
3sO
2)
2nLi or CF
3sO
3li), in electrolytic solution, this structural carbonate has good dissolving and dissociation to lithium salts; Ionic liquid on the other hand containing structural carbonate can generate SEI film (i.e. solid-electrolyte interface film) preferably, thus improves the electrochemical stability of il electrolyte.
The maleimide ionic liquid preparation method of carbonate group provided by the invention, preparation technology is simple, is suitable for scale operationization and produces.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of the maleimide ionic liquid of carbonate-containing group of the present invention;
Fig. 2 is the charging and discharging curve of button cell prepared by the embodiment of the present invention 6.
Embodiment
The maleimide ionic liquid of carbonate-containing group provided by the invention, it comprises following structural formula:
In formula, R is
0≤n≤4; Y
-be selected from BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -.
The preparation method of the maleimide ionic liquid of above-mentioned carbonate-containing group, as shown in Figure 1, comprises the steps:
S1, by mol ratio be 1: 1.1 ~ 1.2 N-methylmaleimido and RX (halocarbonate) carry out building-up reactions, reaction terminates rear obtained structural formula and is
the N-methylmaleimido halogenide (or being called the maleimide halogen of carbonate-containing group) of carbonate-containing group; Wherein, R is
0≤n≤4; X is halogen element, is selected from Cl or Br; Its reaction formula is as follows:
Wherein, RX is
be selected from chlorocarbonic acid vinyl acetate, chlorocarbonic acid propylene, chlorocarbonic acid butene esters, chlorocarbonic acid amylene ester, chlorocarbonic acid hexene ester, bromo NSC 11801, bromo propylene carbonate, bromo butylene, bromo carbonic acid amylene ester or bromo carbonic acid hexene ester etc.; When n is 0, it is exactly chlorocarbonic acid vinyl acetate; When n is 4, it is chlorocarbonic acid hexene ester.All the other, analogize;
S2, the N-methylmaleimido halogenide of described carbonate-containing group obtained by step S1 and inorganic salt MY carry out ion exchange reaction according to the mol ratio of 1: 1, and reaction terminates rear obtained structural formula and is
the maleimide ionic liquid of described carbonate-containing group; Wherein, in MY, M
+for processable positively charged ion, be selected from Na
+, K
+or NH
4 +; Y
-be selected from BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -; Its reaction formula is as follows:
In above-mentioned preparation method, in step S1: building-up reactions is carried out in an inert atmosphere; This inert atmosphere is the inert atmosphere comprised by nitrogen or the arbitrary gas composition of argon gas, and described building-up reactions stirs 48 ~ 72h at 60 ~ 80 DEG C carries out.
In above-mentioned preparation method, after the building-up reactions in step S1 terminates, also comprise the halid purification step of the maleimide of carbonate-containing group:
Reaction solution is left standstill cooling, then washs repeatedly by ethyl acetate; Vacuum-drying at 80 DEG C subsequently, obtains lurid neat solid, i.e. the maleimide halogenide of carbonate-containing group;
In above-mentioned preparation method, after the ion exchange reaction in step S2 terminates, also comprise the purification step of the maleimide ionic liquid to carbonate-containing group:
Reaction mixture with 250mL dichloromethane extraction repeatedly, combining extraction liquid; Then use deionized water back extraction until with saturated AgNO at every turn
3till aqueous solution titration aqueous phase produces without precipitation; Then, methylene dichloride Rotary Evaporators concentrates, and obtains colourless liquid after 80 DEG C of vacuum-drying 48h, is the maleimide ionic liquid of carbonate-containing group.
The maleimide ionic liquid of above-mentioned carbonate-containing group in ultracapacitor or lithium ion battery as the application of electrolytic solution.
The maleimide ionic liquid of carbonate-containing group provided by the invention, by introducing carbonate group in positively charged ion, makes the performance of ionic liquid improve, and is containing lithium salts (e.g., LiBF on the one hand
4, LiPF
6, LiTFSI, (CF
3sO
2)
2nLi or CF
3sO
3li), in electrolytic solution, this structural carbonate has good dissolving and dissociation to lithium salts; Ionic liquid on the other hand containing structural carbonate can generate SEI film (i.e. solid-electrolyte interface film) preferably, thus improves the electrochemical stability of il electrolyte.
The maleimide ionic liquid preparation method of carbonate group provided by the invention, preparation technology is simple, is suitable for scale operationization and produces.
Below preferred embodiment of the present invention is described in further detail.
The synthesis of embodiment 1 N-propylene carbonate ester group-N-methylmaleimido a tetrafluoro borate
1, in the flask of 250mL, add (111g, 1mol) N-methylmaleimido and (149.6g, 1.1mol) chlorocarbonic acid propylene respectively; Then at N
2under atmosphere protection, be warming up to 60 DEG C, stir building-up reactions 72h; Leave standstill cooling subsequently, wash resultant 3 times by ethyl acetate, and vacuum-drying at 80 DEG C, obtain lurid N-propylene carbonate ester group-N-methylmaleimido villaumite, yield is 73%;
2, by above-mentioned obtained N-propylene carbonate ester group-N-methylmaleimido villaumite (123.5g, 0.5mol), NaBF
4(or KBF
4) (55g, 0.5mol) and 100mL deionized water add in the flask of 500mL, at room temperature stirring reaction 10h; After having reacted, obtain mixed solution; Then, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid; Then use the back extraction of 60mL deionized water until with saturated AgNO at every turn
3till aqueous solution titration aqueous phase produces without precipitation; After methylene dichloride is concentrated with Rotary Evaporators, 80 DEG C of vacuum-drying 48h obtain colourless liquid, are N-propylene carbonate ester group-N-methylmaleimido tetrafluoroborate ion liquid.
The nuclear magnetic resonance spectrum diagram data of N-propylene carbonate ester group-N-methylmaleimido a tetrafluoro borate is as follows:
1H NMR(CDCl
3，400MHz，ppm)：6.92(d，2H)，4.82(m，1H)，4.28(d，2H)，3.85(d，2H)，3.18(s，3H).
The synthesis of embodiment 2 N-ethylene carbonate ester group-N-methylmaleimido hexafluorophosphate
1, in the flask of 250mL, add (111g, 1mol) N-methylmaleimido and (182.6g, 1.1mol) bromo NSC 11801 respectively; Then at Ar
2under atmosphere protection, be warming up to 80 DEG C, stir building-up reactions 48h; Leave standstill cooling subsequently, wash 3 times by ethyl acetate, and vacuum-drying at 80 DEG C, obtain lurid N-ethylene carbonate ester group-N-methylmaleimido bromine salt, yield is 74%;
2, by above-mentioned obtained N-ethylene carbonate ester group-N-methylmaleimido bromine salt (138.5g, 0.5mol), KPF
6(92g, 0.5mol) and 150mL deionized water add in 500mL flask, at room temperature stir ion exchange reaction 24h; After having reacted, or mixing solutions; Then, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid; Then use the back extraction of 60mL deionized water until with saturated AgNO at every turn
3till aqueous solution titration aqueous phase produces without precipitation; After methylene dichloride is concentrated with Rotary Evaporators, 80 DEG C of vacuum-drying 48h obtain colourless liquid, are N-ethylene carbonate ester group-N-methylmaleimido phosphofluoric acid ionic liquid.
The synthesis of two (fluoroform sulfimide) salt of embodiment 3 N-butylene carbonate ester group-N-methylmaleimido
1, in the flask of 250mL, add (111g, 1mol) N-methylmaleimido and (213.4g, 1.1mol) bromo butylene respectively.At N
2under atmosphere protection, be warming up to 65 DEG C, stirring reaction 60h; Leave standstill cooling, wash 3 times by ethyl acetate.Vacuum-drying at 80 DEG C, obtain lurid N-butylene carbonate ester group-N-methylmaleimido bromine salt, yield is 78%.
2, in 500mL flask, add (152.5g, 0.5mol) N-butylene carbonate ester group-N-methylmaleimido bromine salt, (159.5g, 0.5mol) fluoroform sulfimide potassium (CF
3sO
2)
2nK and 120mL deionized water, at room temperature stirring reaction 12h.After having reacted, obtain mixing solutions; Then, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid; Then use the back extraction of 60mL deionized water until with saturated AgNO at every turn
3till aqueous solution titration aqueous phase produces without precipitation; After methylene dichloride is concentrated with Rotary Evaporators, 80 DEG C of vacuum-drying 48h obtain colourless liquid, are two (fluoroform sulfimide) ionic liquid of N-butylene carbonate ester group-N-methylmaleimido.
The synthesis of embodiment 4 N-carbonic acid amylene ester group-N-methylmaleimido fluoroform sulphonate
1, in the flask of 250mL, add (111g, 1mol) N-methylmaleimido and (196.8g, 1.2mol) chlorocarbonic acid amylene ester respectively.At N
2under atmosphere protection, be warming up to 70 DEG C, stirring reaction 50h; Leave standstill cooling, wash 3 times by ethyl acetate; Vacuum-drying at 80 DEG C, obtain lurid N-carbonic acid amylene ester group-N-methylmaleimido villaumite, yield is 77%.
2, in a 250mL flask, add (136.5g, 0.5mol) N-carbonic acid amylene ester group-N-methylmaleimido villaumite, (86g, 0.5mol) CF
3sO
3na and 140mL deionized water, at room temperature stirring reaction 18h.After having reacted, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid; Then use the back extraction of 60mL deionized water until with saturated AgNO at every turn
3till aqueous solution titration aqueous phase produces without precipitation.Methylene dichloride Rotary Evaporators concentrates, and obtains colourless liquid after 80 DEG C of vacuum-drying 48h, is N-carbonic acid amylene ester group-N-methylmaleimido trifluoromethanesulfonic acid ionic liquid.
The synthesis of embodiment 5 N-carbonic acid hexene ester group-N-methylmaleimido a tetrafluoro borate
1, in the flask of 250mL, add (111g, 1mol) N-methylmaleimido and (266.4g, 1.2mol) bromo carbonic acid hexene ester respectively.At N
2and Ar
2under the protection of composition mixed gas atmosphere, be warming up to 60 DEG C, stirring reaction 72h.Leave standstill cooling, wash 3 times by ethyl acetate.Vacuum-drying at 80 DEG C, obtain lurid N-carbonic acid hexene ester group-N-methylmaleimido bromine salt, yield is 79%.
2, in a 250mL flask, add (166.5g, 0.5mol) N-carbonic acid hexene ester group-N-methylmaleimido bromine salt, (52.5g, 0.5mol) NH
4bF
4with 130mL deionized water, at room temperature stirring reaction 15h; After having reacted, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid; Then use the back extraction of 60mL deionized water until with saturated AgNO at every turn
3till aqueous solution titration aqueous phase produces without precipitation.Methylene dichloride Rotary Evaporators concentrates, and obtains colourless liquid after 80 DEG C of vacuum-drying 48h, is N-carbonic acid hexene ester group-N-methylmaleimido tetrafluoroborate ion liquid.
Embodiment 6
The present embodiment with embodiment 3 /two (fluoroform sulfimide) salt of N-butylene carbonate ester group-N-methylmaleimido is for ionic liquid.
Take Graphene as electrode materials, electrolytic solution used is two (fluoroform sulfimide) salt+10wt.% acetonitrile of 1mol/L LiTFSI/N-butylene carbonate ester group-N-methylmaleimido, is assembled into button cell.
The process for preparation of electrolytic solution: under nitrogen protection; LiTFSI (i.e. two (trimethyl fluoride sulfonyl) imine lithium) is joined in two (fluoroform sulfimide) salt of N-butylene carbonate ester group-N-methylmaleimido; stir, make the concentration of LiTFSI be 1mol/L.Then, in system, add the acetonitrile accounting for total mass 10%, and be uniformly mixed.
CHI660A electrochemical workstation is utilized to carry out constant current charge-discharge test to it, in the electrochemical window of 0 ~ 2.7V, its charging and discharging curve is recorded with the electric current of 0.75A/g, as can be seen from Figure 2, the electrolytic solution prepared of the embodiment of the present invention is having good cyclical stability up in the charging voltage of 2.7V.
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (7)
1. a preparation method for the maleimide ionic liquid of carbonate-containing group, is characterized in that, comprise the steps:
S1, be that the N-methylmaleimido of 1:1.1 ~ 1.2 and RX carry out building-up reactions by mol ratio, reaction terminates rear obtained structural formula and is
the N-methylmaleimido halogenide of carbonate-containing group; Wherein, R is
0≤n≤4; X is halogen element;
S2, the N-methylmaleimido halogenide of described carbonate-containing group obtained by step S1 and inorganic salt MY carry out ion exchange reaction according to the mol ratio of 1:1, and reaction terminates rear obtained structural formula and is
the maleimide ionic liquid of described carbonate-containing group; Wherein, in MY, M
+for Na
+, K
+or NH
4 +; Y
-be selected from BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -.
2. the preparation method of the maleimide ionic liquid of carbonate-containing group according to claim 1, is characterized in that, in step S1, X is Cl or Br.
3. the preparation method of the maleimide ionic liquid of carbonate-containing group according to claim 1, is characterized in that, the building-up reactions in step S1 is carried out in an inert atmosphere.
4. the preparation method of the maleimide ionic liquid of carbonate-containing group according to claim 3, is characterized in that, described inert atmosphere comprises by least one gas composition in nitrogen and argon gas.
5., according to the preparation method of the maleimide ionic liquid of the arbitrary described carbonate-containing group of Claims 1-4, it is characterized in that, in described step S1, described building-up reactions stirs 48 ~ 72h and carries out at 60 ~ 80 DEG C.
6. the preparation method of the maleimide ionic liquid of carbonate-containing group according to claim 5, it is characterized in that, after building-up reactions in described step S1 terminates, also comprise the halid purification step of maleimide to described carbonate-containing group.
7. the preparation method of the maleimide ionic liquid of carbonate-containing group according to claim 1, it is characterized in that, after ion exchange reaction in described step S2 terminates, also comprise the purification step to the described maleimide ionic liquid containing carbonate-containing group.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005027157A2 (en) * | 2003-09-09 | 2005-03-24 | Nat Inst Of Advanced Ind Scien | Salt fusible at ordinary temperature and electrochemical device |
| CN101640291A (en) * | 2008-07-29 | 2010-02-03 | 三星Sdi株式会社 | Electrolyte and lithium ion secondary battery including the same |
| CN101679292A (en) * | 2007-06-12 | 2010-03-24 | 日宝化学株式会社 | Ionic liquid and method for producing the same |
| CN102138235A (en) * | 2008-08-29 | 2011-07-27 | 法国原子能及替代能源委员会 | Lithium-ion rechargeable batteries containing ionic liquid electrolytes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005027157A2 (en) * | 2003-09-09 | 2005-03-24 | Nat Inst Of Advanced Ind Scien | Salt fusible at ordinary temperature and electrochemical device |
| CN101679292A (en) * | 2007-06-12 | 2010-03-24 | 日宝化学株式会社 | Ionic liquid and method for producing the same |
| CN101640291A (en) * | 2008-07-29 | 2010-02-03 | 三星Sdi株式会社 | Electrolyte and lithium ion secondary battery including the same |
| CN102138235A (en) * | 2008-08-29 | 2011-07-27 | 法国原子能及替代能源委员会 | Lithium-ion rechargeable batteries containing ionic liquid electrolytes |
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| 邓友全.新型阳离子.《离子液体—性质、制备与应用》.中国石化出版社,2006, * |
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