CN103130777A - Pyridines ionic liquid containing carbonic ester group and preparation method and application thereof - Google Patents
Pyridines ionic liquid containing carbonic ester group and preparation method and application thereof Download PDFInfo
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- CN103130777A CN103130777A CN2011103931798A CN201110393179A CN103130777A CN 103130777 A CN103130777 A CN 103130777A CN 2011103931798 A CN2011103931798 A CN 2011103931798A CN 201110393179 A CN201110393179 A CN 201110393179A CN 103130777 A CN103130777 A CN 103130777A
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 58
- 150000003222 pyridines Chemical class 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 125000004185 ester group Chemical group 0.000 title abstract description 13
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 38
- -1 pyridinium halide Chemical class 0.000 claims description 30
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 6
- 159000000002 lithium salts Chemical class 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 2
- 238000010494 dissociation reaction Methods 0.000 abstract 1
- 230000005593 dissociations Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 239000007788 liquid Substances 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000000605 extraction Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
- 239000007864 aqueous solution Substances 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
- 230000002194 synthesizing effect Effects 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical class CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- 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
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 4
- 125000005587 carbonate group Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- GIEFFCXIJRRYFW-UHFFFAOYSA-N Br[BrH]Br.c1ccncc1 Chemical compound Br[BrH]Br.c1ccncc1 GIEFFCXIJRRYFW-UHFFFAOYSA-N 0.000 description 2
- 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
- PZWVRLQNJUKLAI-UHFFFAOYSA-N C(F)(F)F.N1=CC=CC=C1 Chemical compound C(F)(F)F.N1=CC=CC=C1 PZWVRLQNJUKLAI-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 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 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
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 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
- UCDPSMXXZQJIAN-UHFFFAOYSA-N 4-bromo-5-methyl-1,3-dioxolan-2-one Chemical compound CC1OC(=O)OC1Br UCDPSMXXZQJIAN-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N CCC(CO1)OC1=O Chemical compound CCC(CO1)OC1=O ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 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
- 150000001449 anionic compounds Chemical class 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
- 239000012141 concentrate Substances 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
- 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
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Pyridine Compounds (AREA)
Abstract
The invention belongs to the field of ionic liquids, and discloses a pyridines ionic liquid containing a carbonic ester group, and a preparation method and application of the pyridines ionic liquid. The ionic liquid has the following structural formula. In the formula, R is 0<=n<=4, Y- is selected from BF4-, PF6- and (CF3SO2)2N- or CF3SO3-. According to the pyridines ionic liquid containing the carbonic ester group, through the method of introducing the carbonic ester group into positive ions, the performance of the ionic liquid can be improved. On one hand, in an electrolyte solution containing lithium salt, the carbonic ester structure has a good dissolving and dissociation function to the lithium salt; and on the other hand, the ionic liquid containing the carbonic ester structure can generate an SEI film well, so that electrochemical stability of the ionic liquid electrolyte solution is improved.
Description
Technical field
The present invention relates to the ionic liquid field, relate in particular to pyridines ionic liquid of a kind of carbonate-containing group and its preparation method and application.
Background technology
Ionic liquid (Ionic liquids) refers to (be generally below 100 ℃) in room temperature range and is in a liquid state, and is made of organic cation and inorganic anion (or organic anion).Ionic liquid has adjustability, change according to different needs the purpose that its zwitterion structure can reach the planner, thereby ionic liquid is called as planner's solvent.Just found first ionic liquid----nitro ethamine as far back as 1914; But thereafter, the progress in this field is slow.Until 1992, Wikes leader's research group has synthesized low melting point, resistant to hydrolysis, stable strong 1-ethyl-3-methylimidazole tetrafluoroborate ion liquid ([EMIM] BF
4) after, the research of ionic liquid is just developed rapidly, has developed subsequently a series of ion liquid system.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 advantages of a series of outstanding: (1) fusing point lower than or near room temperature, the temperature range that is in a liquid state is wide; (2) steam force down, hardly the volatilization, colourless, odorless; (3) has larger equilibrium temperature scope, preferably chemical stability and wider electrochemical stability potential window; (4) good dissolution characteristics all shows good dissolving power to a lot of inorganicss and organism; (5) without point of ignition and nonflammable; (6) can be recycled, free from environmental pollution etc.
At present, to the research of ionic liquid mainly concentrate on novel ion liquid synthetic, ionic liquid physics and chemistry characteristic sign and as aspects such as solvent and electrolytical applied researcies.Ionic liquid is as the novel solvent of a class, medium, catalyzer, and the research in fields such as organic synthesis, catalyzed reaction, extracting and separating, material preparation, natural polymer, electrochemistry has obtained many gratifying results, has been subject to paying close attention to widely.
Summary of the invention
Based on the problems referred to above, one of purpose of the present invention is to provide a kind of pyridines ionic liquid of novel carbonate-containing group.
A kind of pyridines ionic liquid of 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 provide the preparation method of the pyridines ionic liquid of above-mentioned carbonate-containing group, comprise the steps:
S1, be that 1: 1.1～1.2 pyridine and RX carry out building-up reactions with mol ratio, make structural formula after reaction finishes and be
The pyridinium halide of carbonate-containing group; Wherein, R is
0≤n≤4; X is halogen element, is selected from Cl or Br;
Pyridinium halide and the inorganic salt MY of S2, described carbonate-containing group that step S1 is made carry out ion exchange reaction according to the mol ratio of 1: 1, make structural formula after reaction finishes and are
The pyridines ionic liquid of described carbonate-containing group; Wherein, in MY, M
+For the 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 under inert atmosphere; This inert atmosphere is to comprise by at least a gas composition in nitrogen and argon gas; In described step S1, described building-up reactions stirs 48～72h and carries out under 60～80 ℃.
The pyridines ionic liquid that another purpose of the present invention is to provide above-mentioned carbonate-containing group in ultracapacitor or lithium ion battery as the application of electrolytic solution.
The pyridines ionic liquid of carbonate-containing group provided by the invention by introduce carbonate group in positively charged ion, improves the performance of ionic liquid, is on the one hand containing lithium salts (as, LiBF
4, LiPF
6, LiTFSI, (CF
3SO
2)
2NLi or CF
3SO
3Li) in electrolytic solution, this carbonic ether structure has good dissolving and the effect of dissociating to lithium salts; The ionic liquid that contains on the other hand the carbonic ether structure can generate SEI film (being solid-electrolyte interface film) preferably, thereby improves the electrochemical stability of il electrolyte.
The pyridines ionic liquid preparation method of carbonate group provided by the invention, preparation technology is simple, is suitable for scale operation production.
Description of drawings
Fig. 1 is preparation technology's schema of the pyridines ionic liquid of carbonate-containing group of the present invention;
Fig. 2 is the charging and discharging curve of the button cell of the embodiment of the present invention 6 preparations.
Embodiment
The pyridines 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 pyridines ionic liquid of above-mentioned carbonate-containing group as shown in Figure 1, comprises the steps:
S1, be that 1: 1.1～1.2 pyridine and RX (being the halo carbonic ether) carry out building-up reactions with mol ratio, make structural formula after reaction finishes and be
The pyridinium halide pyridine halogen of carbonate-containing group (or be called) 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 the chlorocarbonic acid vinyl acetate; N is 4 o'clock, is chlorocarbonic acid hexene ester.All the other are analogized;
Pyridinium halide and the inorganic salt MY of S2, described carbonate-containing group that step S1 is made carry out ion exchange reaction according to the mol ratio of 1: 1, make structural formula after reaction finishes and are
The pyridines ionic liquid of described carbonate-containing group; Wherein, in MY, M
+For the 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, the building-up reactions in step S1 is carried out under inert atmosphere; This inert atmosphere is the inert atmosphere that comprises by nitrogen or the arbitrary gas composition of argon gas; In described step S1, described building-up reactions stirs 48～72h and carries out under 60～80 ℃.
In above-mentioned preparation method, the building-up reactions in step S1 also comprises the purification step to the pyridinium halide of carbonate-containing group after finishing:
Reaction solution is standing cooling, then with the ethyl acetate washing repeatedly; 80 ℃ of lower vacuum-dryings, obtain lurid pure solid, i.e. the pyridinium halide of carbonate-containing group subsequently;
In above-mentioned preparation method, the ion exchange reaction in step S2 also comprises the purification step to the pyridines ionic liquid of carbonate-containing group after finishing:
Reaction mixture is used the 250mL dichloromethane extraction repeatedly, combining extraction liquid; Then at every turn with the deionized water back extraction until with saturated AgNO
3Till aqueous solution titration water produces without precipitation; Then, methylene dichloride is concentrated with Rotary Evaporators, obtains colourless liquid after 80 ℃ of vacuum-drying 48h, is the pyridines ionic liquid of carbonate-containing group.
The pyridines ionic liquid of above-mentioned carbonate-containing group in ultracapacitor or lithium ion battery as the application of electrolytic solution.
The pyridines ionic liquid of carbonate-containing group provided by the invention by introduce carbonate group in positively charged ion, improves the performance of ionic liquid, is on the one hand containing lithium salts (as, LiBF
4, LiPF
6, LiTFSI, (CF
3SO
2)
2NLi or CF
3SO
3Li) in electrolytic solution, this carbonic ether structure has good dissolving and the effect of dissociating to lithium salts; The ionic liquid that contains on the other hand the carbonic ether structure can generate SEI film (being solid-electrolyte interface film) preferably, thereby improves the electrochemical stability of il electrolyte.
The pyridines ionic liquid preparation method of carbonate group provided by the invention, preparation technology is simple, is suitable for scale operation production.
The below is described in further detail preferred embodiment of the present invention.
Embodiment 1
Synthesizing of 1-propylene carbonate yl pyridines a tetrafluoro borate
1, add respectively (79g, 1mol) pyridine and (149.6g, 1.1mol) chlorocarbonic acid propylene in the flask of 250mL; Then at N
2Under the atmosphere protection, be warming up to 60 ℃, stir building-up reactions 72h; Standing cooling subsequently, wash resultant three times with ethyl acetate, and 80 ℃ of lower vacuum-dryings, obtain lurid 1-propylene carbonate yl pyridines villaumite, yield is 75%;
2, with above-mentioned 1-propylene carbonate yl pyridines villaumite (107.5g, 0.5mol), the NaBF that makes
4(or KBF
4) (55g, 0.5mol) and 100mL deionized water add in the flask of 500mL, stirring reaction 10h at room temperature; After reaction is completed, obtain mixed solution; Then, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid; Then at every turn with 60mL deionized water back extraction until with saturated AgNO
3Till aqueous solution titration water produces without precipitation; After methylene dichloride was concentrated with Rotary Evaporators, 80 ℃ of vacuum-drying 48h obtained colourless liquid, are 1-propylene carbonate yl pyridines tetrafluoroborate ion liquid.
The nuclear magnetic resonance spectrum diagram data of 1-propylene carbonate yl pyridines a tetrafluoro borate is as follows:
1H?NMR(CDCl
3，400MHz，ppm)：9.12(d，2H)，8.60(t，1H)，8.15(t，2H)，4.88(d，2H)，4.82(m，1H)，4.72(d，2H)
Embodiment 2
Synthesizing of 1-NSC 11801 yl pyridines hexafluorophosphate
1, add respectively (79g, 1mol) pyridine and (182.6g, 1.1mol) bromo NSC 11801 in the flask of 250mL; Then at Ar
2Under the atmosphere protection, be warming up to 80 ℃, stir building-up reactions 48h; Standing cooling subsequently, with ethyl acetate washing three times, and 80 ℃ of lower vacuum-dryings, obtain lurid 1-NSC 11801 yl pyridines bromine salt, yield is 76%;
2, with above-mentioned 1-NSC 11801 yl pyridines bromine salt (122.5g, 0.5mol), the KPF that makes
6(92g, 0.5mol) and 150mL deionized water add in the 500mL flask, at room temperature stir ion exchange reaction 24h; The reaction complete after, or mixing solutions; Then, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid; Then at every turn with 60mL deionized water back extraction until with saturated AgNO
3Till aqueous solution titration water produces without precipitation; After methylene dichloride was concentrated with Rotary Evaporators, 80 ℃ of vacuum-drying 48h obtained colourless liquid, are 1-NSC 11801 yl pyridines hexafluorophosphate ionic liquid.
Embodiment 3
Synthesizing of two (fluoroform sulfimide) salt of 1-butylene yl pyridines
1, add respectively (79g, 1mol) pyridine and (213.4g, 1.1mol) bromo butylene in the flask of 250mL.At N
2Under the atmosphere protection, be warming up to 65 ℃, stirring reaction 60h; Standing cooling, with ethyl acetate washing three times.80 ℃ of lower vacuum-dryings, obtain lurid 1-butylene yl pyridines bromine salt, yield is 78%.
2, add (136.5g, 0.5mol) 1-butylene yl pyridines bromine salt, (159.5g, 0.5mol) fluoroform sulfimide potassium (CF in the 500mL flask
3SO
2)
2NK and 120mL deionized water, at room temperature stirring reaction 12h.After reaction is completed, obtain mixing solutions; Then, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid; Then at every turn with 60mL deionized water back extraction until with saturated AgNO
3Till aqueous solution titration water produces without precipitation.After methylene dichloride was concentrated with Rotary Evaporators, 80 ℃ of vacuum-drying 48h obtained colourless liquid, were two (fluoroform sulfimide) the salt ion liquid of 1-butylene yl pyridines.
Embodiment 4
Synthesizing of 1-carbonic acid amylene ester group pyridine fluoroform sulphonate
1, add respectively (79g, 1mol) pyridine and (196.8g, 1.2mol) chlorocarbonic acid amylene ester in the flask of 250mL.At N
2Under the atmosphere protection, be warming up to 70 ℃, stirring reaction 50h; Standing cooling, with ethyl acetate washing three times; 80 ℃ of lower vacuum-dryings, obtain lurid 1-carbonic acid amylene ester group pyridine villaumite, yield is 78%.
2, add (121.5g, 0.5mol) 1-carbonic acid amylene ester group pyridine villaumite, (86g, 0.5mol) CF in a 250mL flask
3SO
3Na and 140mL deionized water, at room temperature stirring reaction 18h.After reaction is completed, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid; Then at every turn with 60mL deionized water back extraction until with saturated AgNO
3Till aqueous solution titration water produces without precipitation.Methylene dichloride is concentrated with Rotary Evaporators, obtains colourless liquid after 80 ℃ of vacuum-drying 48h, is 1-carbonic acid amylene ester group pyridine fluoroform sulphonate ionic liquid.
Embodiment 5
Synthesizing of 1-carbonic acid hexene ester group pyridinium tetrafluoroborate salt
1, add respectively (79g, 1mol) pyridine and (266.4g, 1.2mol) bromo carbonic acid hexene ester in the flask of 250mL.At N
2And Ar
2Form under the protection of mixed gas atmosphere, be warming up to 60 ℃, stirring reaction 72h.Standing cooling, with ethyl acetate washing three times.80 ℃ of lower vacuum-dryings, obtain lurid 1-carbonic acid hexene ester group pyridinium tribromide salt, yield is 79%.
2, add (150.5g, 0.5mol) 1-carbonic acid hexene ester group pyridinium tribromide salt, (52.5g, 0.5mol) NH in a 250mL flask
4BF
4With the 130mL deionized water, stirring reaction 15h at room temperature; After reaction is completed, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid; Then at every turn with 60mL deionized water back extraction until with saturated AgNO
3Till aqueous solution titration water produces without precipitation.Methylene dichloride is concentrated with Rotary Evaporators, obtains colourless liquid after 80 ℃ of vacuum-drying 48h, is 1-carbonic acid hexene ester group pyridinium tetrafluoroborate salt ion liquid.
Embodiment 6
The present embodiment with two (fluoroform sulfimide) salt of the 1-butylene yl pyridines in embodiment 3 as ionic liquid.
Take Graphene as electrode materials, electrolytic solution used is two (fluoroform sulfimide) salt of 1mol/L LiTFSI/1-butylene yl pyridines and 10wt.% acetonitrile, is assembled into button cell.
The process for preparation of electrolytic solution: under nitrogen protection; LiTFSI is joined in two (fluoroform sulfimide) salt of 1-butylene yl pyridines; stir, making the concentration of LiTFSI (i.e. two (trimethyl fluoride sulfonyl) imine lithium) is 1mol/L.Then, add the acetonitrile that accounts for total mass 10% in system, and mix.
Utilize the CHI660A electrochemical workstation to carry out the constant current charge-discharge test to it, in the electrochemical window of 0～3.2V, electric current with 0.75A/g records its charging and discharging curve, as can be seen from Figure 2, the electrolytic solution prepared of the embodiment of the present invention has cyclical stability preferably in the charging voltage up to 3.2V.
Should be understood that, above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. the pyridines ionic liquid of a carbonate-containing group, is characterized in that, it comprises following structural formula:
In formula, R is
0≤n≤4; Y
-Be BF
4 -, PF
6 -, (CF
3SO
2)
2N
-Or CF
3SO
3 -
2. the preparation method of the pyridines ionic liquid of a carbonate-containing group, is characterized in that, comprises the steps:
S1, be that 1: 1.1～1.2 pyridine and RX carry out building-up reactions with mol ratio, make structural formula to be
The pyridinium halide of carbonate-containing group; Wherein, R is
0≤n≤4; X is halogen element;
Pyridinium halide and the inorganic salt MY of S2, described carbonate-containing group that step S1 is made carry out ion exchange reaction according to the mol ratio of 1: 1, make structural formula and are
The pyridines ionic liquid of described carbonate-containing group; Wherein, in MY, M
+Be processable positively charged ion, Y
-Be BF
4 -, PF
6 -, (CF
3SO
2)
2N
-Or CF
3SO
3 -
3. the preparation method of the pyridines ionic liquid of carbonate-containing group according to claim 2, is characterized in that, in step S1, X is Cl or Br.
4. the preparation method of the pyridines ionic liquid of carbonate-containing group according to claim 2, is characterized in that, the building-up reactions in step S1 is carried out under inert atmosphere.
5. the preparation method of the pyridines ionic liquid of carbonate-containing group according to claim 4, is characterized in that, described inert atmosphere is to comprise by at least a gas composition in nitrogen and argon gas.
According to claim 2 to 5 arbitrary described carbonate-containing group the preparation method of pyridines ionic liquid, it is characterized in that, in described step S1, described building-up reactions stirs 48～72h and carries out under 60～80 ℃.
7. the preparation method of the pyridines ionic liquid of carbonate-containing group according to claim 2, is characterized in that, the building-up reactions in described step S1 also comprises the step of the pyridinium halide of described carbonate-containing group being carried out purification process after finishing.
8. the preparation method of the pyridines ionic liquid of carbonate-containing group according to claim 2, is characterized in that, in described step S2, M+ is selected from Na
+, K
+Or NH
4 +
9. the preparation method of the pyridines ionic liquid of according to claim 2 or 8 described carbonate-containing groups, it is characterized in that, ion exchange reaction in described step S2 also comprises the step of the pyridines ionic liquid of described carbonate-containing group being carried out purification process after finishing.
The pyridines ionic liquid of carbonate-containing group claimed in claim 1 in ultracapacitor or lithium ion battery as the application of electrolytic solution.
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| 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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| WO2005027157A2 (en) * | 2003-09-09 | 2005-03-24 | Nat Inst Of Advanced Ind Scien | Salt fusible at ordinary temperature and electrochemical device |
| CN1934212A (en) * | 2004-04-19 | 2007-03-21 | Lg化学株式会社 | Gel polymer electrolyte containing ionic liquid and electrochromic device using the same |
| US20060210876A1 (en) * | 2005-03-17 | 2006-09-21 | Takashi Kuboki | 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 |
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