CN103787981A - Imidazoles ionic liquid and ionic liquid electrolytic solution, and preparation methods and applications thereof - Google Patents

Imidazoles ionic liquid and ionic liquid electrolytic solution, and preparation methods and applications thereof Download PDF

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CN103787981A
CN103787981A CN201210428463.9A CN201210428463A CN103787981A CN 103787981 A CN103787981 A CN 103787981A CN 201210428463 A CN201210428463 A CN 201210428463A CN 103787981 A CN103787981 A CN 103787981A
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methylimidazole
ratio
ion liquid
organic solvent
glyoxaline ion
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周明杰
刘大喜
王要兵
钟辉
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Shenzhen Oceans King Lighting Engineering Co Ltd
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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
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    • H01—ELECTRIC ELEMENTS
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Abstract

The invention relates to an imidazoles ionic liquid having the following structural formula defined in the description, wherein R represents CH3O(CH2)n, n is 2, 3 or 4, and Y<-> represents BF4<->, PF6<->, (CF3SO2)2N<-> or CF3SO3<->. The imidazoles ionic liquid has lower melting point than a traditional alkyl imidazoles ionic liquid; moreover, introduction of methoxy alkyl allows the imidazoles ionic liquid to have a functionalizated ether bond, and the ability of the imidazoles ionic liquid to dissolve corresponding substances can be increased; at the same time, the imidazoles ionic liquid also has common advantages of ionic liquids. The invention also provides a preparation method of the imidazoles ionic liquid. The preparation method has the advantages of simple process, easily controlled reaction and higher product yield, and is suitable for industrialized production. In addition, the imidazoles ionic liquid has excellent electrochemical performance, and can be used for preparation of an electrolytic solution of a lithium ion battery.

Description

Glyoxaline ion liquid, il electrolyte and preparation method and application
Technical field
The present invention relates to Ionic liquids technologies field, particularly relate to a kind of glyoxaline ion liquid, il electrolyte and preparation method and application.
Background technology
Ionic liquid (Ionic liquids) refers in room temperature range and (is generally below 100 ℃) and is in a liquid state, the ionic compound being made up of organic cation and inorganic anion.As far back as 1914, people have just found the first ionic liquid-nitro ethamine, but the progress of ionic liquid is slow thereafter, until 1992, Wikes leader's research group has synthesized ionic liquid-1-ethyl-3-methylimidazole a tetrafluoro borate ([EMIM] BF of advantages such as having low melting point, resistant to hydrolysis, stability are strong 4) after, the research of ionic liquid is just developed rapidly, has developed subsequently a series of ion liquid system.
Ionic liquid has advantages of a series of outstanding: (1) fusing point lower than or approach room temperature, the temperature range being in a liquid state is wide; (2) steam force down, hardly volatilization, colourless, odorless; (3) there is 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.
Initial ionic liquid is mainly used in electrochemical research, along with scientific and technological development ionic liquid is as a class novel green solvent, medium, catalyzer, 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.But different field requires differently to ionic liquid, and for meeting the requirement of every field, investigator's work mainly concentrates on the aspect such as synthesizing new ionic liquid and the application to synthetic novel ion liquid.Traditional ionic liquid ubiquity specific storage for electrochemical field and the not high problem of specific conductivity, limited it and further applied.
Summary of the invention
Based on this, be necessary to provide glyoxaline ion liquid that a kind of specific storage and specific conductivity are higher and preparation method thereof.
A kind of glyoxaline ion liquid, has following structural formula:
Figure BDA00002341363400021
Wherein, R is CH 3o (CH 2) n, n is 2,3 or 4; Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -.
A preparation method for glyoxaline ion liquid, comprises the steps:
Under shielding gas atmosphere, be the ratio of 1: 1.05 ~ 1:1.2 according to the mol ratio of 3-Methylimidazole and haloalkane, the stirring reaction at 60 ~ 80 ℃ by 3-Methylimidazole and haloalkane, obtains the 1-methoxyl group alkyl 3-Methylimidazole halogenide of following structural formula:
Figure BDA00002341363400022
Wherein, R is CH 3o (CH 2) n, n be 2,3 or 4, X be halogen;
Be 1:1 ~ 1:1.1 according to mol ratio, by described 1-methoxyl group alkyl 3-Methylimidazole halogenide and inorganic salt M +y -and at room temperature stirring reaction of deionized water, obtain having the glyoxaline ion liquid of following structural formula:
Figure BDA00002341363400023
Wherein, M +for Na +, K +or NH 4 +, Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -, the ratio of the volume of the described 1-methoxyl group alkyl halid molar weight of 3-Methylimidazole and described deionized water is 1mol:200 ~ 300mL.
In an embodiment, the mol ratio of described 3-Methylimidazole and described haloalkane is 1:1.2 therein.
In an embodiment, the mol ratio of described 1-methoxyl group alkyl 3-Methylimidazole halogenide and described inorganic salt is 1:1.05 therein.
Therein in an embodiment, be also included in the step that described 1-methoxyl group alkyl 3-Methylimidazole halogenide and inorganic salt and deionized water are at room temperature carried out to separation and purification to ionic liquid after stirring reaction, the process of described separation and purification comprises the steps:
By the mixed solution dichloromethane extraction obtaining after reaction repeatedly, after combining extraction liquid, then the extraction liquid being combined with deionized water carries out back extraction until use Ag +titration detects without precipitation and produces, and collects methylene dichloride phase;
Described methylene dichloride is rotated to evaporation process mutually and removes methylene dichloride, after being dried, obtain the described glyoxaline ion liquid of purifying.
The organic cation of above-mentioned glyoxaline ion liquid is 1-methoxyl group alkyl 3-Methylimidazole ion, with respect to traditional glyoxaline ion liquid, in the situation that carbon atom number is identical, the introducing of methoxyl group alkyl has increased the asymmetry of the organic cations structure of glyoxaline ion liquid, make zwitterion can not be piled into regularly crystal, thereby the reactive force between weakening zwitterion, fusing point also declines thereupon, therefore, the fusing point of the more traditional alkyl imidazole ionic liquid of above-mentioned glyoxaline ion liquid is lower; And the introducing of methoxyl group alkyl makes above-mentioned glyoxaline ion liquid have the ehter bond of functionalization, can increase the dissolving power of above-mentioned glyoxaline ion liquid to material.Above-mentioned glyoxaline ion liquid also has advantages of that ionic liquid is total simultaneously, as wide in liquid state temperature range, steam forces down, not volatile, chemical stability and wider electrochemical stability potential window preferably, a large amount of inorganic and organic substances is had to good dissolving power, and there is the dual-use function of solvent and catalyzer, can be used as solvent or the catalytic activity carrier etc. of many chemical reactions.Through performance detects, and above-mentioned glyoxaline ion liquid has the specific conductivity higher than conventional ion liquid and specific storage.
The preparation method of above-mentioned glyoxaline ion liquid, first prepare 1-methoxyl group alkyl 3-Methylimidazole halogenide by 3-Methylimidazole and haloalkane reaction, then the inorganic salt that contain target negatively charged ion and 1-methoxyl group alkyl 3-Methylimidazole halogenide are carried out to ion exchange reaction, product after the dry ion exchange reaction of purifying, obtains glyoxaline ion liquid.Aforesaid method technique is simple, reaction is easy to control, product yield higher (80%-85%), is suitable for suitability for industrialized production, and the glyoxaline ion liquid preparing has good chemical property, can be applied to the field such as ultracapacitor, lithium ion battery.
In addition, be also necessary to provide a kind of il electrolyte with higher specific conductivity and specific storage and preparation method thereof.
A kind of il electrolyte, comprises organic solvent and is dispersed in glyoxaline ion liquid and the lithium salts in described organic solvent; The mass ratio of described glyoxaline ion liquid and described organic solvent is 1:10 ~ 1:1, and the mass ratio of described lithium salts and described organic solvent is 1:20 ~ 1: 10; Wherein, described glyoxaline ion liquid has following structural formula:
Figure BDA00002341363400041
R is CH 3o (CH 2) n, n is 2,3 or 4; Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -;
Described organic solvent is the mixed solution being made up of NSC 11801 and Methyl ethyl carbonate, and wherein, the volume ratio of NSC 11801 and Methyl ethyl carbonate is 1:1 ~ 4;
Described lithium salts is LiBF 4, LiPF 6, LiSO 3cF 3or LiTFSI.
A preparation method for il electrolyte, comprises the steps:
Under shielding gas atmosphere, be the ratio of 1: 1.05 ~ 1:1.2 according to the mol ratio of 3-Methylimidazole and haloalkane, the stirring reaction at 60 ~ 80 ℃ by 3-Methylimidazole and haloalkane, obtains the 1-methoxyl group alkyl 3-Methylimidazole halogenide of following structural formula:
Wherein, R is CH 3o (CH 2) n, n be 2,3 or 4, X be halogen;
Be 1:1 ~ 1:1.1 according to mol ratio, by described 1-methoxyl group alkyl 3-Methylimidazole halogenide and inorganic salt M +y -and at room temperature stirring reaction of deionized water, obtain having the glyoxaline ion liquid of following structural formula:
Figure BDA00002341363400043
Wherein, M +for Na +, K +or NH4 +, Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -, the ratio of the volume of the described 1-methoxyl group alkyl halid molar weight of 3-Methylimidazole and described deionized water is 1mol:200 ~ 300mL;
Be that described NSC 11801 and Methyl ethyl carbonate are mixed with organic solvent by 1: 1 ~ 4 ratio according to the volume ratio of NSC 11801 and Methyl ethyl carbonate;
The ratio that according to the mass ratio of described glyoxaline ion liquid and described organic solvent is 1: 10 ~ 1:1 adds glyoxaline ion liquid in described organic solvent, the ratio that is 10:1 ~ 20:1 according to the mass ratio of organic solvent and lithium salts again after being uniformly mixed adds lithium salts in described organic solvent, continuing to be stirred to lithium salts dissolves completely, obtain described il electrolyte, wherein, described lithium salts is LiBF 4, LiPF 6, LiSO 3cF 3or LiTFSI.
In an embodiment, the mol ratio of described 3-Methylimidazole and described haloalkane is 1:1.2 therein.
In an embodiment, the mol ratio of described 1 methoxyl group alkyl 3-Methylimidazole halogenide and described inorganic salt is 1:1.05 therein.
Above-mentioned il electrolyte, compared with traditional lithium-ion battery electrolytes, owing to having added a large amount of ionic liquids, can improve the stability of electrolytic solution greatly, thereby improves the safety performance of battery; And above-mentioned il electrolyte may be used in lithium ion battery, as electrolytic solution, having good chemical property.
Preparation method's technique of above-mentioned il electrolyte is simple, reaction is easy to control, be suitable for suitability for industrialized production, the il electrolyte preparing has good chemical property, stability is high, security good, can be applied to the field such as ultracapacitor, lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the preparation method's of the glyoxaline ion liquid of an embodiment schema;
Fig. 2 is the preparation method's of the il electrolyte of an embodiment schema.
Embodiment
Below in conjunction with drawings and the specific embodiments, glyoxaline ion liquid, il electrolyte and preparation method and application are further detailed.
The glyoxaline ion liquid of one embodiment, has following structural formula:
Figure BDA00002341363400061
Wherein, R is CH 3o (CH 2) n, n is 2,3 or 4; Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -.
The organic cation of this glyoxaline ion liquid is 1-methoxyl group alkyl 3-Methylimidazole ion, with respect to traditional glyoxaline ion liquid, in the situation that carbon atom number is identical, the introducing of methoxyl group alkyl has increased the asymmetry of the organic cations structure of glyoxaline ion liquid, make zwitterion can not be piled into regularly crystal, thereby the reactive force between weakening zwitterion, fusing point also declines thereupon, therefore, the fusing point of the more traditional alkyl imidazole ionic liquid of above-mentioned glyoxaline ion liquid is lower.And the introducing of methoxyl group alkyl makes above-mentioned glyoxaline ion liquid have the ehter bond of functionalization, can increase the dissolving power of above-mentioned glyoxaline ion liquid to material.Above-mentioned glyoxaline ion liquid also has advantages of that ionic liquid is total simultaneously, as wide in liquid state temperature range, steam forces down, not volatile, chemical stability and wider electrochemical stability potential window preferably, a large amount of inorganic and organic substances is had to good dissolving power, and there is the dual-use function of solvent and catalyzer, can be used as solvent or the catalytic activity carrier etc. of many chemical reactions.Through performance detects, and above-mentioned glyoxaline ion liquid has the specific conductivity higher than conventional ion liquid and specific storage.
In addition, present embodiment also provides a kind of preparation method of glyoxaline ion liquid, as shown in Figure 1, comprises the steps:
Step S110; under shielding gas atmosphere; the ratio that is 1:1.05 ~ 1:1.2 according to the mol ratio of 3-Methylimidazole and haloalkane, the stirring reaction at 60 ~ 80 ℃ by 3-Methylimidazole and haloalkane, obtains having the 1-methoxyl group alkyl 3-Methylimidazole halogenide of following structural formula:
Figure BDA00002341363400062
Wherein, RX is haloalkane, and R is CH 3o (CH 2) n, n be 2,3 or 4, X be halogen.
What obtain contains product 1-methoxyl group alkyl 3-Methylimidazole halogenide and can wash after 2 ~ 3 times by ethyl acetate, dry under 80 ℃ of vacuum, obtains the 1-methoxyl group alkyl-3 Methylimidazole halogenide of purifying.
Other preferred embodiment in, the mol ratio of 3-Methylimidazole and haloalkane is 1: 1.2.
Step S120, by 1-methoxyl group alkyl 3-Methylimidazole halogenide and inorganic salt and at room temperature stirring reaction of deionized water, obtains having the ionic liquid of following structural formula:
Figure BDA00002341363400071
Wherein, MY is inorganic salt, M +for N a +, K +or NH 4 +, Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -, the mol ratio of 1-methoxyl group alkyl 3-Methylimidazole halogenide and inorganic salt is 1:1 ~ 1: the ratio of the volume of 1.1, the 1-methoxyl group alkyl halid molar weight of 3-Methylimidazole and deionized water is 1mol:200 ~ 300mL.
In addition, the preparation method of this glyoxaline ion liquid is also included in the step that 1-methoxyl group alkyl 3-Methylimidazole halogenide and inorganic salt and deionized water are at room temperature carried out to separation and purification to ionic liquid after stirring reaction.The process of this separation and purification comprises the steps:
By the mixed solution dichloromethane extraction obtaining after reaction repeatedly, after combining extraction liquid, then the extraction liquid being combined with deionized water carries out back extraction until use Ag +titration detects without precipitation and produces, and collects methylene dichloride phase, wherein Ag +titration detects the silver salt that can use the water-solubles such as nitrate;
Methylene dichloride is rotated to evaporation process mutually and removes methylene dichloride, after being dried, obtain the glyoxaline ion liquid of purifying.
Other preferred embodiment in, the mol ratio of 1-methoxyl group alkyl 3-Methylimidazole halogenide and inorganic salt is 1:1.05.
The preparation method of this glyoxaline ion liquid, first prepare 1-methoxyl group alkyl 3-Methylimidazole halogenide by 3-Methylimidazole and haloalkane reaction, then the inorganic salt that contain target negatively charged ion and 1-methoxyl group alkyl 3-Methylimidazole halogenide are carried out to ion exchange reaction, product after the dry ion exchange reaction of purifying, obtains glyoxaline ion liquid.Aforesaid method technique is simple, reaction is easy to control, product yield higher (80%-85%), is suitable for suitability for industrialized production, and the glyoxaline ion liquid preparing has good chemical property, can be applied to the field such as ultracapacitor, lithium ion battery.
In addition, present embodiment also provides a kind of il electrolyte with higher specific conductivity and specific storage and preparation method thereof.
This il electrolyte comprises the ionic liquid and the lithium salts that are dispersed in organic solvent.Wherein, ionic liquid is above-mentioned glyoxaline ion liquid.Organic solvent is the mixed solution of NSC 11801 (EC) and Methyl ethyl carbonate (EMC), and wherein, the volume ratio of NSC 11801 and Methyl ethyl carbonate is 1:1 ~ 4.Lithium salts is LiBF 4, LiPF 6, LiSO 3cF 3or LiTFSI.The mass ratio of ionic liquid and organic solvent is 1:10 ~ 1:1, and the mass ratio of lithium salts and organic solvent is 1:20 ~ 1:10.
This il electrolyte, compared with traditional lithium-ion battery electrolytes, owing to having added a large amount of ionic liquids, can improve the stability of electrolytic solution greatly, thereby improves the safety performance of battery; And above-mentioned il electrolyte is applied to and has good chemical property in lithium ion battery.
The preparation method of this il electrolyte, as shown in Figure 2, comprises the steps:
Step S210, prepares above-mentioned glyoxaline ion liquid.
Step S220, NSC 11801 and Methyl ethyl carbonate are mixed with organic solvent by the ratio that is 1:1 ~ 4 according to the volume ratio of NSC 11801 and Methyl ethyl carbonate.
Step S230, the ratio that is 1:10 ~ 1:1 according to the mass ratio of glyoxaline ion liquid and organic solvent adds glyoxaline ion liquid in organic solvent, the ratio that is 10:1 ~ 20:1 according to the mass ratio of organic solvent and lithium salts again after being uniformly mixed adds lithium salts in organic solvent, continue to be stirred to lithium salts and dissolve completely, obtain il electrolyte.Wherein, lithium salts is LiBF 4, LiPF 6, LiSO 3cF 3or LiTFSI.
Preparation method's technique of this il electrolyte is simple, reaction is easy to control, be suitable for suitability for industrialized production, the il electrolyte preparing has good chemical property, stability is high, security good, can be applied to the field such as ultracapacitor, lithium ion battery.
Illustrate glyoxaline ion liquid and its preparation method and application below in conjunction with specific embodiment, with and the test of the aspect such as performance.
Embodiment 1
In the flask of 250mL, add respectively 1mol 3-Methylimidazole and 1.1mol methoxychlor ethane, obtain mixture; At N 2under the protection of atmosphere, by said mixture stirring reaction 40 hours under 70 ℃ of conditions, obtain reaction product; Above-mentioned reaction product is left standstill and is cooled to room temperature, then with ethyl acetate washing three times; Reaction product after ethyl acetate washing is placed in to vacuum-drying at 80 ℃, obtains lurid solid, be 1-methoxy ethyl 3-Methylimidazole villaumite.Calculated yield, yield is 82%.
In 250mL flask, add 0.53mol NaBF 4, 130mL deionized water and the above-mentioned 1-methoxy ethyl 3-Methylimidazole villaumite preparing of 0.5mol, obtain mixed solution; Above-mentioned mixed solution is stirred under room temperature condition anti-8 hours, obtain reacted solution; Divide the solution after extractive reaction 3 times with 250mL methylene dichloride, merge extraction phase, then use the deionized water back extraction of 60mL repeatedly, until with saturated AgNO 3aqueous solution titration water detects without precipitation and produces position, collect methylene dichloride phase, by concentrated this methylene dichloride phase of Rotary Evaporators, then after concentrating, obtain product and be placed at 80 ℃ vacuum-drying 48 hours, obtain colourless 1-methoxy ethyl 3-methyl imidazolium tetrafluoroborate.
At N 2under atmosphere protection, in the above-mentioned 1-of the preparing methoxy ethyl of 10g 3-methyl imidazolium tetrafluoroborate, add 50g organic solvent, obtain mixture; And said mixture is heated to 40 ℃, the organic phase that obtains mixing under the condition stirring; Then in the organic phase mixing, add 3.5g LiBF4, continue to stir until lithium salts dissolves completely, obtain il electrolyte, wherein, organic solvent is that NSC 11801 and the ratio of Methyl ethyl carbonate take volume ratio as 1:3 are mixed to get.
Embodiment 2
In the flask of 250mL, add respectively 1mol 3-Methylimidazole and 1.05mol methoxyl group N-PROPYLE BROMIDE, obtain mixture; Under the protection of Ar atmosphere, by said mixture stirring reaction 60 hours under 60 ℃ of conditions, obtain reaction product; Above-mentioned reaction product is left standstill and is cooled to room temperature, then with ethyl acetate washing three times; Reaction product after ethyl acetate washing is placed in to vacuum-drying at 80 ℃, obtains lurid solid, be 1-methoxy-propyl 3-Methylimidazole bromine salt; Calculated yield, yield is 80%.
In 250mL flask, add 0.5mol KPF 6, 100mL deionized water and the above-mentioned 1-methoxy-propyl 3-Methylimidazole bromine salt preparing of 0.5mol, obtain mixed solution; Above-mentioned mixed solution is stirred under room temperature condition anti-20 hours, obtain reacted solution; Divide the solution after extractive reaction 3 times with 250mL methylene dichloride, merge extraction phase, then use the deionized water back extraction of 60mL repeatedly, until with saturated AgNO 3aqueous solution titration water detects without precipitation and produces position, collect methylene dichloride phase, by concentrated this methylene dichloride phase of Rotary Evaporators, then after concentrating, obtain product and be placed at 80 ℃ vacuum-drying 48 hours, obtain colourless 1-methoxy-propyl 3-Methylimidazole hexafluorophosphate.
Under the protection of Ar atmosphere, in the above-mentioned 1-of the preparing methoxy-propyl of 10g 3-Methylimidazole hexafluorophosphate, add 10g organic solvent, obtain mixture; And said mixture is heated to 40 ℃, the organic phase that obtains mixing under the condition stirring; Then in the organic phase mixing, add 1.0g LiPF 6, continue to stir until lithium salts dissolves completely, obtain il electrolyte, wherein, organic solvent is that NSC 11801 and the ratio of Methyl ethyl carbonate take volume ratio as 1:4 are mixed to get.
Embodiment 3
In the flask of 250mL, add respectively 1mol 3-Methylimidazole and 1.2mol methoxyl group butyl iodide, obtain mixture; At N 2under the protection of atmosphere, by said mixture stirring reaction 20 hours under 80 ℃ of conditions, obtain reaction product; Above-mentioned reaction product is left standstill and is cooled to room temperature, then with ethyl acetate washing three times; Reaction product after ethyl acetate washing is placed in to vacuum-drying at 80 ℃, obtains lurid solid, be 1-methoxyl group butyl 3-Methylimidazole salt compounded of iodine; Calculated yield, yield is 85%.
In 250mL flask, add 0.55mol (CF 3sO 2) 2the above-mentioned 1-methoxyl group butyl 3-Methylimidazole salt compounded of iodine preparing of NK, 150mL deionized water and 0.5mol, obtains mixed solution; Above-mentioned mixed solution is stirred under room temperature condition anti-5 hours, obtain reacted solution; Divide the solution after extractive reaction 3 times with 250mL methylene dichloride, merge extraction phase, then use the deionized water back extraction of 60mL repeatedly, until with saturated AgNO 3aqueous solution titration water detects without precipitation and produces position, collect methylene dichloride phase, by concentrated this methylene dichloride phase of Rotary Evaporators, then after concentrating, obtain product and be placed at 80 ℃ vacuum-drying 48 hours, obtain colourless 1-methoxyl group butyl 3-Methylimidazole fluoroform sulfimide salt.
At N 2under atmosphere protection, in the above-mentioned 1-of the preparing methoxyl group of 10g butyl 3-Methylimidazole fluoroform sulfimide salt, add 100g organic solvent, obtain mixture; And said mixture is heated to 40 ℃, the organic phase that obtains mixing under the condition stirring; Then in the organic phase mixing, add 5gLiTFSI, continue to stir until lithium salts dissolves completely, obtain il electrolyte, wherein, organic solvent is that NSC 11801 and Methyl ethyl carbonate are mixed to get take volume ratio as the ratio of 1: 1.
Embodiment 4
In the flask of 250mL, add respectively 1mol 3-Methylimidazole and 1.1mol methoxychlor propane, obtain mixture; At N 2under the protection of atmosphere, by said mixture stirring reaction 45 hours under 65 ℃ of conditions, obtain reaction product; Above-mentioned reaction product is left standstill and is cooled to room temperature, then with ethyl acetate washing three times; Reaction product after ethyl acetate washing is placed in to vacuum-drying at 80 ℃, obtains lurid solid, be 1-methoxy-propyl 3-Methylimidazole villaumite; Calculated yield, yield is 82%.
In 250mL flask, add 0.52mol CF 3sO 3nH 4, 120mL deionized water and the above-mentioned 1-methoxy-propyl 3-Methylimidazole villaumite preparing of 0.5mol, obtain mixed solution; Above-mentioned mixed solution is stirred under room temperature condition anti-15 hours, obtain reacted solution; Divide the solution after extractive reaction 3 times with 250mL methylene dichloride, merge extraction phase, then use the deionized water back extraction of 60mL repeatedly, until with saturated AgNO 3aqueous solution titration water detects without precipitation and produces position, collect methylene dichloride phase, by concentrated this methylene dichloride phase of Rotary Evaporators, then after concentrating, obtain product and be placed at 80 ℃ vacuum-drying 48 hours, obtain colourless 1-methoxy-propyl 3-Methylimidazole fluoroform sulphonate.
Under the protection of Ar atmosphere, in the above-mentioned 1-of the preparing methoxy-propyl of 10g 3-Methylimidazole fluoroform sulphonate, add 60g organic solvent, obtain mixture; And said mixture is heated to 40 ℃, the organic phase that obtains mixing under the condition stirring; Then in the organic phase mixing, add 3.7gLiSO 3cF 3, continue stirring and make, until lithium salts dissolves completely, to obtain il electrolyte, wherein, organic solvent is that NSC 11801 and the ratio of Methyl ethyl carbonate take volume ratio as 1:2 are mixed to get.
Comparative example
At N 2under atmosphere protection, in 50g organic solvent, add 3.5g LiBF 4, obtain mixture; And said mixture is heated to 40 ℃, the electrolytic solution that obtains mixing under the condition stirring; Wherein, organic solvent is that NSC 11801 and the ratio of Methyl ethyl carbonate take volume ratio as 1:3 are mixed to get.
Performance test:
(1) specific conductivity of the il electrolyte of preparing in employing DDS-11C conductivitimeter test implementation example 1-4, and the specific conductivity of the electrolytic solution of preparing in comparative example, conductivity data is listed in table 1.
(2) by the il electrolyte of preparing in embodiment 1-4, and the electrolytic solution of preparing in comparative example is applied in lithium ion battery, and tests the specific storage of each lithium ion battery, and specific storage data are listed in table 1.Concrete steps are as follows:
By the 9.0g LiFeO taking 4, 0.55g acetylene black, 0.35g polyvinylidene difluoride (PVDF) (PVDF) and 20g N-Methylimidazole alkane ketone (NMP) mixes and fully stirs, and prepares the slurry mixing; Slurry blade coating, on the aluminium foil cleaning through ethanol, is then dried to constant weight by lower 80 ℃ of vacuum condition scraping the aluminium foil that scribbles slurry and be placed in 0.01MPa; The aluminium foil that is dried to scraping of constant weight and scribbles slurry is pressed into LiFeO in 12MPa pressure lower roll 4electrode; And by LiFeO 4electrode is cut into disk, as the positive pole of lithium ion battery; Select the barrier film of polypropylene (PP) as lithium ion battery, lithium sheet is as lithium ion battery negative; The electrolytic solution having prepared in embodiment 1-4 and comparative example is placed between positive and negative electrode, and on stamping machine, button cell is made in sealing.Then in the voltage range of 2.5 ~ 4.2V, utilize charge-discharge test instrument to carry out 0.1C charge-discharge test to the above-mentioned lithium ion battery assembling.
Table 1: performance test data
Embodiment 1 2 3 4 Comparative example
Specific conductivity (ms/cm) 17 15 16 13 8
First discharge specific capacity (mAh/g) 115 104 107 113 107
Performance test data shows, the il electrolyte that embodiment 1-4 prepares has relatively good specific conductivity; The il electrolyte that embodiment 1-4 is prepared is applied to lithium ion battery, has equally relatively good specific storage.Illustrate that the il electrolyte that embodiment 1-4 prepares has relatively good chemical property.
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 (10)

1. a glyoxaline ion liquid, is characterized in that, has following structural formula:
Figure FDA00002341363300011
Wherein, R is CH 3o (CH 2) n, n is 2,3 or 4; Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -.
2. a preparation method for glyoxaline ion liquid, is characterized in that, comprises the steps:
Under shielding gas atmosphere, be the ratio of 1: 1.05 ~ 1:1.2 according to the mol ratio of 3-Methylimidazole and haloalkane, the stirring reaction at 60 ~ 80 ℃ by 3-Methylimidazole and haloalkane, obtains the 1-methoxyl group alkyl 3-Methylimidazole halogenide of following structural formula:
Wherein, R is CH 3o (CH 2) n, n be 2,3 or 4, X be halogen;
Be 1:1 ~ 1:1.1 according to mol ratio, by described 1-methoxyl group alkyl 3-Methylimidazole halogenide and inorganic salt M +y -and at room temperature stirring reaction of deionized water, obtain having the glyoxaline ion liquid of following structural formula:
Wherein, M +for Na +, K +or NH 4 +, Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -, the ratio of the volume of the described 1-methoxyl group alkyl halid molar weight of 3-Methylimidazole and described deionized water is 1mol:200 ~ 300mL.
3. the preparation method of glyoxaline ion liquid as claimed in claim 2, is characterized in that, the mol ratio of described 3-Methylimidazole and described haloalkane is 1:1.2.
4. the preparation method of glyoxaline ion liquid as claimed in claim 2, is characterized in that, the mol ratio of described 1-methoxyl group alkyl 3-Methylimidazole halogenide and described inorganic salt is 1:1.05.
5. the preparation method of glyoxaline ion liquid as claimed in claim 2, it is characterized in that, also be included in the step that described 1-methoxyl group alkyl 3-Methylimidazole halogenide and inorganic salt and deionized water are at room temperature carried out to separation and purification to ionic liquid after stirring reaction, the process of described separation and purification comprises the steps:
By the mixed solution dichloromethane extraction obtaining after reaction repeatedly, after combining extraction liquid, then the extraction liquid being combined with deionized water carries out back extraction until use Ag +titration detects without precipitation and produces, and collects methylene dichloride phase;
Described methylene dichloride is rotated to evaporation process mutually and removes methylene dichloride, after being dried, obtain the described glyoxaline ion liquid of purifying.
6. an il electrolyte, is characterized in that, comprises organic solvent and is dispersed in glyoxaline ion liquid and the lithium salts in described organic solvent; The mass ratio of described glyoxaline ion liquid and described organic solvent is 1:10 ~ 1:1, and the mass ratio of described lithium salts and described organic solvent is 1:20 ~ 1:10; Wherein, described glyoxaline ion liquid has following structural formula:
Figure FDA00002341363300021
R is CH 3o (CH 2) n, n is 2,3 or 4; Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -;
Described organic solvent is the mixed solution being made up of NSC 11801 and Methyl ethyl carbonate, and wherein, the volume ratio of NSC 11801 and Methyl ethyl carbonate is 1:1 ~ 4;
Described lithium salts is LiBF 4, LiPF 6, LiSO 3cF 3or LiTFSI.
7. a preparation method for il electrolyte, is characterized in that, comprises the steps:
Under shielding gas atmosphere, be the ratio of 1: 1.05 ~ 1:1.2 according to the mol ratio of 3-Methylimidazole and haloalkane, the stirring reaction at 60 ~ 80 ℃ by 3-Methylimidazole and haloalkane, obtains the 1-methoxyl group alkyl 3-Methylimidazole halogenide of following structural formula:
Figure FDA00002341363300031
Wherein, R is CH 3o (CH 2) n, n be 2,3 or 4, X be halogen;
Be 1:1 ~ 1:1.1 according to mol ratio, by described 1-methoxyl group alkyl 3-Methylimidazole halogenide and inorganic salt M +y -and at room temperature stirring reaction of deionized water, obtain having the glyoxaline ion liquid of following structural formula:
Figure FDA00002341363300032
Wherein, M +for Na +, K +or NH 4 +, Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -, the ratio of the volume of the described 1-methoxyl group alkyl halid molar weight of 3-Methylimidazole and described deionized water is 1mol:200 ~ 300mL;
Described NSC 11801 and Methyl ethyl carbonate are mixed with organic solvent by the ratio that is 1:1 ~ 4 according to the volume ratio of NSC 11801 and Methyl ethyl carbonate;
The ratio that is 1:10 ~ 1:1 according to the mass ratio of described glyoxaline ion liquid and described organic solvent adds glyoxaline ion liquid in described organic solvent, the ratio that is 10:1 ~ 20:1 according to the mass ratio of organic solvent and lithium salts again after being uniformly mixed adds lithium salts in described organic solvent, continuing to be stirred to lithium salts dissolves completely, obtain described il electrolyte, wherein, described lithium salts is LiBF 4, LiPF 6, LiSO 3cF 3or LiTFSI.
8. the preparation method of il electrolyte as claimed in claim 7, is characterized in that, the mol ratio of described 3-Methylimidazole and described haloalkane is 1:1.2.
9. the preparation method of il electrolyte as claimed in claim 7, is characterized in that, the mol ratio of described 1 methoxyl group alkyl 3-Methylimidazole halogenide and described inorganic salt is 1:1.05.
10. a lithium ion battery, is characterized in that, the electrolytic solution of described lithium ion battery is il electrolyte claimed in claim 6.
CN201210428463.9A 2012-10-31 2012-10-31 Imidazoles ionic liquid and ionic liquid electrolytic solution, and preparation methods and applications thereof Pending CN103787981A (en)

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