CN102167759A - Preparation method, product and application of a kind of ionic liquid - Google Patents
Preparation method, product and application of a kind of ionic liquid Download PDFInfo
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- CN102167759A CN102167759A CN201010615962XA CN201010615962A CN102167759A CN 102167759 A CN102167759 A CN 102167759A CN 201010615962X A CN201010615962X A CN 201010615962XA CN 201010615962 A CN201010615962 A CN 201010615962A CN 102167759 A CN102167759 A CN 102167759A
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Abstract
The invention provides a preparation method of an ionic liquid electrolyte, which comprises the following steps: (1) preparation of intermediate brominated 1-ethyl-3-methylimidazolium salt: synthesizing an intermediate brominated 1-ethyl-3-methylimidazolium salt by using bromoethane and 1-methylimidazole as raw materials; (2) preparing hydrophilic ionic liquid tetrafluoroborate 1-ethyl-3-methylimidazole: reacting the brominated 1-ethyl-3-methylimidazolium salt with NaBF4 to obtain hydrophilic ionic liquid tetrafluoroborate 1-ethyl-3-methylimidazole; (3) and (3) purification: adding CH2Cl2 for extraction, and removing CH2Cl2 and water to obtain a product; (4) preparation of PAN-EMIMBF 4: and polymerizing a polyacrylonitrile monomer and equimolar EMIMBF4TMS, and adding TMS as an initiator to obtain a product PAN-EMIMBF 4-TMS. The conductivity of the PAN-EMIMBF4 prepared by the invention reaches 15mS cm-1It is applied to capacitor electrolyte and has high capacitance.
Description
Technical field
The present invention relates to technical field of electrochemistry, relate to a kind of preparation method of ionic liquid and ionic liquid electrolyte especially.
Background technology
Ionic liquid is called ionic liquid at room temperature, room temperature melting salt, organic ion liquid again, is meant only to be made up of ion to be the salt of liquid under room temperature or low temperature.Compare with ionogen with traditional organic solvent, ionic liquid has a series of outstanding advantages: (1) does not almost have vapour pressure, non-volatile, colourless, tasteless; (2) bigger equilibrium temperature scope is arranged, the electrochemical stability potential window of better chemical stability and broad; (3) can regulate its solvability by the design of zwitterion, and its acidity is adjustable to super acid to inorganics, water, organism and polymkeric substance.
The ion liquid positive ion of current research has 4 classes: quaternary ammonium alkyl ion [NH
NH
4N]
+, Wan Ji quaternary phosphine ion [PR
NH
4N]
+, 1, the imidazol ion that the 3-dialkyl group replaces or claim N, the pyridinium ion that the luxuriant son of imidazoles that N '-dialkyl group replaces, N-alkyl replace.
Difference according to negative ion can be divided into ionic liquid two big classes: a class is that halide salt (positive ion still is above-mentioned 4 kinds) adds AlCl
3Wherein the also available Br of Cl replaces.Another kind of ionic liquid is also referred to as new ionic liquid, and its composition is a fixed, and wherein many kinds are to water, to air-stable, and its positive ion mostly is the imidazol ion that alkyl replaces.
Ionic liquid is of a great variety, changes positively charged ion and anionic various combination, can design different ionic liquids.General positively charged ion is that cation type common in the organic composition ionic liquid has alkyl ammonium cation, Wan Ji phosphonium cation, N, imidazol ion, N-alkyl pyridine positively charged ion that N '-dialkyl group replaces, wherein modal is N, the imidazol ion that N '-dialkyl group replaces.
In recent years, novel energy-storing material based on ion liquid medium continues to bring out, it is the plastic crystal grid that Macfadane etc. design ionic liquid, can be with wherein lithium ion doped, since the rotation randomness of this lattice, and have the room, and lithium ion is quick travel therein, its good conductivity makes the application of ionic liquid on secondary cell that prospect be arranged very much.Yasu shi etc. are with [emim] Cl-FeCl2]-the FeCI3 system is applied in the battery, and this system has the feature of low melting point and reversible redox reaction, is expected to further be used in rechargeable battery.Yasuhiko etc. have carried out systematically research to special battery electrolyte, adopt ionic liquid to be used for the double-embedded type molten salt electrolyte battery, can replace organic solvent and volatile matter.
Research aspect electrical condenser, external, especially day present technique is leading, and China also is in the starting stage.The main manufacturer of domestic V-Chip AEC all changes into company's import electrolytic solution from SANYO GS, though V-Chip AEC quality product guarantees to some extent but profit is meagre, more domestic in recent years companies also have this type of electrolytic solution product to sell, though price is low, but it uses character and quality all relatively poor, it is said that what use in prescription is a kind of second-rate quaternary ammonium salt.
Summary of the invention
The object of the present invention is to provide a kind of specific conductivity height, preparation technology is simple, the ionic liquid electrolyte that cost is low.
The present invention solves the problems of the technologies described above the technical scheme that is adopted to be:
A kind of preparation method of ionic liquid electrolyte may further comprise the steps,
(1) preparation intermediate bromination 1-ethyl-3-methylimidazole salt: with monobromethane and 1-Methylimidazole is that raw material has synthesized intermediate bromination 1-ethyl-3-methylimidazole salt;
(2) preparation wetting ability hydrophilic ionic-liquid Tetrafluoroboric acid 1-ethyl-3-Methylimidazole: bromination 1-ethyl-3-methylimidazole salt and NaBF4 react hydrophilic ionic-liquid Tetrafluoroboric acid 1-ethyl-3-Methylimidazole;
(3) purifying: add CH2Cl2 and extract, remove CH2Cl2 and water, get product;
(4) preparation PAN-EMIMBF4: with the EMIMBF4TMS polymerization of polyacrylonitrile monomer and equimolar amount, add TMS, make PAN-EMIMBF4-TMS as initiator.
Described step (1) also comprises: temperature control in pressure kettle is 110 ℃ with 1-Methylimidazole and monobromethane, generates bromination 1-ethyl-3-methylimidazole salt by quaternarization.
Described step (2) comprising: bromination 1-ethyl-3-methylimidazole salt and NaBF4 are mixed in the Erlenmeyer flask, the adding acetone solvent, magnetic agitation 24h, suction filtration is removed insoluble NaBr, and solvent acetone is then removed with rotary evaporation, gets Tetrafluoroboric acid 1-ethyl-3-Methylimidazole at last.
Described step (3) also comprises: adding CH2Cl2 extracts in the described hydrophilic ionic-liquid Tetrafluoroboric acid of step (2) 1-ethyl-3-Methylimidazole, rotary evaporation is removed CH2Cl2 and water wherein.
Described step (4) also comprises: with the EMIMBF4TMS polymerization of polyacrylonitrile monomer and equimolar amount, add TMS as initiator, at 80 ℃ of reaction 12h.
By the ionic liquid electrolyte that above-mentioned preparation method makes, comprise following feed composition: monobromethane, 1-Methylimidazole, NaBF4, polyacrylonitrile monomer, TMS initiator.
Ionic liquid electrolyte of the present invention is applied to electrical condenser electrolysis matter.
The beneficial effect of the invention
Ionic liquid electrolyte of the present invention has good electrochemical properties as electrical condenser electrolysis matter, can arrive 50-170F/g based on the specific capacitance of the electrical condenser of high-specific surface area carbon material.Specific conductivity by the PAN-EMIMBF4 of the present invention preparation has reached 15mScm
-1Traditional ionic liquid is that viscosity is too high as the shortcoming of electrolytic solution, sneak into a small amount of organic solvent with the reduction viscosity, and improve its ionic conductivity.Ionic liquid electrolyte of the present invention by its boiling point height of high-molecular weight compound, the steam that ionic liquid and polymer polymerizing form force down, broad advantages such as electrochemical stability electrochemical window, make it be suitable for very much the electrolytic solution of photoelectrochemistry solar cell.
Below in conjunction with embodiment, the present invention is further described.
Embodiment
Embodiment
A kind of preparation method of ionic liquid electrolyte may further comprise the steps,
(1) preparation intermediate bromination 1-ethyl-3-methylimidazole salt
Temperature control in adding pressure kettle is 110 ℃ with 100ml1-Methylimidazole and 30.0 monobromethanes, and 1-Methylimidazole and monobromethane generate intermediate bromination 1-ethyl-3-methylimidazole salt by quaternarization, and promptly quaternary ammonium halide is synthetic:
R
1R
2R
3N+R
4I—→R
1R
2R
3R
4N
++I
-
(2) preparation wetting ability hydrophilic ionic-liquid Tetrafluoroboric acid 1-ethyl-3-Methylimidazole
Bromination 1-ethyl-3-methylimidazole salt and NaBF4 are mixed in the Erlenmeyer flask, the adding acetone solvent, magnetic agitation 24h, suction filtration is removed insoluble NaBr, and solvent acetone is then removed with rotary evaporation, gets hydrophilic ionic-liquid Tetrafluoroboric acid 1-ethyl-3-Methylimidazole at last.
(3) purifying: adding CH2Cl2 extracts in the described hydrophilic ionic-liquid Tetrafluoroboric acid of step (2) 1-ethyl-3-Methylimidazole, rotary evaporation is removed CH2Cl2 and water wherein, gets product;
(4) preparation PAN-EMIMBF4: with the EMIMBF4TMS polymerization of polyacrylonitrile monomer and equimolar amount, add TMS,, make PAN-EMIMBF4-TMS at 80 ℃ of reaction 12h as initiator.
Performance Detection
1. specific conductivity test: the specific conductivity that records the ionic liquid electrolyte of present embodiment preparation has reached 15mScm
-1
2. be applied to the ionogen of electrical condenser: ionic liquid electrolyte of the present invention is become electrolytic solution according to table 1 formulation, and be prepared into and be made into the 400V operating voltage, capacity is the electrical condenser of 220uf, and its initial performance and shelf characteric see Table 2.
Table 1
| Ethylene glycol | 86g |
| Ionic liquid electrolyte | 12g |
| Ammonium borate | 1g |
| Ammonium hypophosphite | 0.3g |
| P-nitrophenyl methyl alcohol | 0.4 |
| Special auxiliary agent | 0.3g |
Table 2
From the data of tabulation as can be seen, the prepared electrical condenser tg of the electrolyte prescription that uses this ionogen to prepare δ, Δ C/C, Lc and have the shelf characteric of load, real load fabulous, its electrical capacity height.
The present invention is not limited to above-mentioned embodiment, and every all embodiments that are equal to that can realize the object of the invention are all within protection scope of the present invention.
Claims (7)
1. the preparation method of an ionic liquid electrolyte is characterized in that, may further comprise the steps,
(1) preparation intermediate bromination 1-ethyl-3-methylimidazole salt: with monobromethane and 1-Methylimidazole is that raw material has synthesized intermediate bromination 1-ethyl-3-methylimidazole salt;
(2) preparation wetting ability hydrophilic ionic-liquid Tetrafluoroboric acid 1-ethyl-3-Methylimidazole: bromination 1-ethyl-3-methylimidazole salt and NaBF4 react hydrophilic ionic-liquid Tetrafluoroboric acid 1-ethyl-3-Methylimidazole;
(3) purifying: add CH2Cl2 and extract, remove CH2Cl2 and water, get product;
(4) preparation PAN-EMIMBF4: with the EMIMBF4TMS polymerization of polyacrylonitrile monomer and equimolar amount, add TMS, make PAN-EMIMBF4-TMS as initiator.
2. the preparation method of ionic liquid electrolyte according to claim 1, it is characterized in that, described step (1) also comprises: temperature control in pressure kettle is 110 ℃ with 1-Methylimidazole and monobromethane, generates bromination 1-ethyl-3-methylimidazole salt by quaternarization.
3. the preparation method of ionic liquid electrolyte according to claim 1, it is characterized in that, described step (2) comprising: bromination 1-ethyl-3-methylimidazole salt and NaBF4 are mixed in the Erlenmeyer flask, the adding acetone solvent, magnetic agitation 24h, suction filtration is removed insoluble NaBr, solvent acetone is then removed with rotary evaporation, gets Tetrafluoroboric acid 1-ethyl-3-Methylimidazole at last.
4. the preparation method of ionic liquid electrolyte according to claim 1, it is characterized in that described step (3) also comprises: adding CH2Cl2 extracts in the described hydrophilic ionic-liquid Tetrafluoroboric acid of step (2) 1-ethyl-3-Methylimidazole, rotary evaporation is removed CH2Cl2 and water wherein.
5. the preparation method of ionic liquid electrolyte according to claim 1 is characterized in that, described step (4) also comprises: with the EMIMBF4TMS polymerization of polyacrylonitrile monomer and equimolar amount, add TMS as initiator, at 80 ℃ of reaction 12h.
6. the ionic liquid electrolyte that makes of the preparation method of an ionic liquid electrolyte according to claim 1 is characterized in that, comprises following feed composition: monobromethane, 1-Methylimidazole, NaBF4, polyacrylonitrile monomer, TMS initiator.
7. ionic liquid electrolyte according to claim 6 is characterized in that, is applied to electrical condenser electrolysis matter.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103247447A (en) * | 2012-10-24 | 2013-08-14 | 苏州大学 | Polyelectrolyte film of supercapacitor and preparation method |
| CN108933289A (en) * | 2018-07-06 | 2018-12-04 | 武汉霖泉环保科技有限公司 | Lithium-air battery ionic liquid electrolyte and air cell preparation method |
| CN112133964A (en) * | 2020-09-23 | 2020-12-25 | 杭州怡莱珂科技有限公司 | Magnesium ion electrolyte solution and preparation method thereof |
| CN112898458A (en) * | 2021-01-15 | 2021-06-04 | 中国科学院兰州化学物理研究所 | Polymeric ionic liquid, preparation method and application thereof, and supercapacitor electrolyte |
| CN113772687A (en) * | 2021-11-01 | 2021-12-10 | 郑州中科新兴产业技术研究院 | A method for recovering sodium bromide and sodium tetrafluoroborate from synthetic 1-butyl-3-methylimidazolium tetrafluoroborate by-product wastewater |
-
2010
- 2010-12-27 CN CN201010615962XA patent/CN102167759A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103247447A (en) * | 2012-10-24 | 2013-08-14 | 苏州大学 | Polyelectrolyte film of supercapacitor and preparation method |
| CN108933289A (en) * | 2018-07-06 | 2018-12-04 | 武汉霖泉环保科技有限公司 | Lithium-air battery ionic liquid electrolyte and air cell preparation method |
| CN112133964A (en) * | 2020-09-23 | 2020-12-25 | 杭州怡莱珂科技有限公司 | Magnesium ion electrolyte solution and preparation method thereof |
| CN112898458A (en) * | 2021-01-15 | 2021-06-04 | 中国科学院兰州化学物理研究所 | Polymeric ionic liquid, preparation method and application thereof, and supercapacitor electrolyte |
| CN112898458B (en) * | 2021-01-15 | 2022-01-07 | 中国科学院兰州化学物理研究所 | A kind of polymeric ionic liquid and its preparation method and application, supercapacitor electrolyte |
| CN113772687A (en) * | 2021-11-01 | 2021-12-10 | 郑州中科新兴产业技术研究院 | A method for recovering sodium bromide and sodium tetrafluoroborate from synthetic 1-butyl-3-methylimidazolium tetrafluoroborate by-product wastewater |
| CN113772687B (en) * | 2021-11-01 | 2022-10-18 | 郑州中科新兴产业技术研究院 | A method for recovering sodium bromide and sodium tetrafluoroborate from synthetic 1-butyl-3-methylimidazolium tetrafluoroborate by-product wastewater |
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Application publication date: 20110831 |