WO2013029237A1 - 双中心联吡啶阳离子类离子液体及其制备方法和应用 - Google Patents

双中心联吡啶阳离子类离子液体及其制备方法和应用 Download PDF

Info

Publication number
WO2013029237A1
WO2013029237A1 PCT/CN2011/079118 CN2011079118W WO2013029237A1 WO 2013029237 A1 WO2013029237 A1 WO 2013029237A1 CN 2011079118 W CN2011079118 W CN 2011079118W WO 2013029237 A1 WO2013029237 A1 WO 2013029237A1
Authority
WO
WIPO (PCT)
Prior art keywords
bipyridyl
ionic liquid
bipyridine
center
salt
Prior art date
Application number
PCT/CN2011/079118
Other languages
English (en)
French (fr)
Inventor
周明杰
刘大喜
王要兵
Original Assignee
海洋王照明科技股份有限公司
深圳市海洋王照明工程有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 海洋王照明科技股份有限公司, 深圳市海洋王照明工程有限公司 filed Critical 海洋王照明科技股份有限公司
Priority to CN201180072278.4A priority Critical patent/CN103732587B/zh
Priority to PCT/CN2011/079118 priority patent/WO2013029237A1/zh
Priority to EP11871780.0A priority patent/EP2752409B1/en
Priority to US14/234,384 priority patent/US9196424B2/en
Priority to JP2014527454A priority patent/JP5796128B2/ja
Publication of WO2013029237A1 publication Critical patent/WO2013029237A1/zh

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/035—Liquid electrolytes, e.g. impregnating materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to an ionic liquid, and more particularly to a bi-centered bipyridyl cation-based ionic liquid, a process for producing the same, an organic electrolyte comprising the bi-bipyridine cation-based ionic liquid, and a process for preparing the organic electrolytic solution.
  • Ionic liquids are liquids in the range of room temperature (generally below 100 °C) composed of organic cations and inorganic anions (or organic anions).
  • the ionic liquid is tunable, and the anion-cation structure can be changed according to different needs to achieve the designer's purpose, and thus the ionic liquid is called a designer's solvent.
  • the first ionic liquid, mononitroethylamine, was discovered as early as 1914, but research in this area has been slow. Until 1992, the team led by Wikes synthesized a low melting point, hydrolysis resistant, and stable 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid ([EMIM]BF 4 ), followed by ionic liquids.
  • the research was developed rapidly, and a series of ionic liquid systems were developed.
  • the initial ionic liquids were mainly used in electrochemical research. In recent years, ionic liquids have been valued as green solvents for organic and polymer synthesis.
  • ionic liquids Compared with traditional organic solvents and electrolytes, ionic liquids have a series of outstanding advantages: (1) The melting point is lower or close to room temperature, and the liquid temperature range is wide; (2) The vapor pressure is low, almost non-volatile, colorless, and (3) Has a large stable temperature range, good chemical stability and a wide electrochemical stability potential window; (4) Good solubility characteristics, showing good solubility for many inorganic and organic substances (5) No ignition point and not easy to burn; (6) Recyclable, no pollution to the environment. Therefore, ionic liquids have a good development prospect as electrolytes for electric double layer capacitors.
  • the conventional organic electrolyte is easily decomposed at a high voltage, causing a sharp increase in the internal resistance of the capacitor and a rapid decrease in the capacitance.
  • the stability of organic electrolytes has been a key factor limiting the specific energy of capacitors.
  • a monocentric bipyridine cationic ionic liquid having the following structural formula: Wherein Y is BF 4 , PF 6 , (CF 3 S0 2 ) 2 N- or (FS0 2 ) 2 N -.
  • a preparation method of a bicenter bipyridylcation ionic liquid comprises the following steps:
  • Step 1 Under a protective gas atmosphere, the bipyridyl is mixed with an alkylene molar ratio of 1:2-1:2.5, heated to 60 ° C ⁇ 80 ° C, and stirred to obtain a dialkyl bipyridyl compound;
  • Said alkane is methoxyethoxychloromethane or methoxyethoxymethyl bromide;
  • Step 2 the dialkyl bipyridyl halide prepared in the first step and the salt of the formula M+Y- are mixed at a molar ratio of 1: 2, added to deionized water, and stirred to cause an ion exchange reaction to obtain a double having the following structural formula. center Wherein ⁇ + is Na+, K+ or NH 4 +, Y- is BF 4 -, PF 6 -, (CF 3 S0 2 ) 2 N- or (FS0 2 ) 2 N-.
  • step 1 the reaction time of the bipyridine and the alkylene is stirred for 24h ⁇ 72h, the reaction liquid is cooled, washed with ethyl acetate, and the washed product is vacuum dried to obtain a purified dialkylbipyridine.
  • the reaction time of the bipyridine and the alkylene is stirred for 24h ⁇ 72h, the reaction liquid is cooled, washed with ethyl acetate, and the washed product is vacuum dried to obtain a purified dialkylbipyridine.
  • the shielding gas atmosphere is a nitrogen atmosphere or an argon atmosphere.
  • the temperature of the ion exchange reaction is room temperature, and the reaction time is 8 h to 24 h.
  • the second step further comprises the step of separating and purifying the bi-center bipyridylcation-based ionic liquid, and the separating and purifying steps are as follows: stirring the dialkyl bipyridyl compound with a salt having the general formula M+Y- The resulting mixture was extracted with dichloromethane until the aqueous phase obtained was saturated with AgN0 3 The aqueous solution was titrated without precipitation, and the dichloromethane extract was concentrated by evaporation and dried under vacuum to obtain a purified bi-centered pyridine ionic liquid.
  • An organic electrolyte comprising a bi-centered bipyridine cationic ionic liquid, an organic solvent and a lithium salt, and the double-heart bipyridyl cation-based ionic liquid has the following structural formula: Wherein, ⁇ - is BF 4 -, PF 6 -, (CF 3 S0 2 ) 2 N- or (FS0 2 ) 2 N-, the mass ratio of the organic solvent to the bi-center bipyridyl cation-based ionic liquid is 0 to 100, the concentration of the lithium salt is 0.3 to 1.2 mol/L.
  • the lithium salt is at least one of lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, and lithium bis(fluorosulfonyl)imide.
  • the organic solvent is at least one of ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate and ethyl propionate.
  • a method for preparing an organic electrolyte comprising the steps of:
  • Step 1 Under a protective gas atmosphere, the bipyridyl is mixed with an alkylene molar ratio of 1:2-1:2.5, heated to 60 ° C to 80 ° C, and stirred to obtain a dialkylbipyridyl compound; Said alkane is methoxyethoxychloromethane or methoxyethoxymethyl bromide;
  • Step 2 the dialkyl bipyridyl halide prepared in the first step and the salt of the formula M+Y- are mixed at a molar ratio of 1: 2, added to deionized water, and stirred to cause an ion exchange reaction to obtain a double having the following structural formula.
  • Step 3 providing an organic solvent,
  • the double-phase bipyridyl cation-based ionic liquid is added to the organic solvent and stirred uniformly, and the mass ratio of the organic solvent to the bi-center bipyridyl cation-based ionic liquid is 0-100;
  • Step 4 adding a lithium salt to the mixed solution of the organic solvent and the bi-center bipyridyl cation-based ionic liquid and stirring to obtain the organic electrolyte; the lithium salt in the organic electrolyte
  • the concentration is 0.3 ⁇ 1.2mol/L.
  • the double-centered bipyridylcation ionic liquid has an electrochemical window of more than 4 V, has good electrochemical stability, and is not easily decomposed under high voltage.
  • the organic electrolyte containing the bi-centered bipyridine cationic ionic liquid has better stability at a higher charging voltage.
  • Fig. 1 is a standard charge and discharge curve obtained by conventionally testing an organic electrolyte prepared in Example 6 and an electrode material composed of a supercapacitor.
  • bi-centered bipyridine cationic ionic liquid and its preparation method and application are further clarified below with reference to the accompanying drawings and specific examples.
  • ⁇ - is BF 4 -, PF 6 -, (CF 3 S0 2 ) 2 N- or (FS0 2 ) 2 N -.
  • the double-centered bipyridylcation ionic liquid has an electrochemical window of more than 4 V, has good electrochemical stability, and is not easily decomposed under high voltage.
  • the alkoxy structure introduced into the side chain of the bi-bipyridine ion-based ionic liquid can reduce the viscosity of the ionic liquid on the one hand.
  • such an oxygen-containing functional group can facilitate complexation with lithium ions in the electrolyte to increase the solubility of the lithium salt.
  • the invention provides a preparation method of the above-mentioned bi-centered bipyridyl cation-based ionic liquid, which comprises the following steps: Step S11: Mixing bipyridyl with alkane in a protective gas atmosphere formed by nitrogen or argon 1: 2-1: 2.5 After mixing, it is heated to 60 ° C ⁇ 80 ° C, and the reaction is stirred to obtain a dialkyl bipyridyl halide.
  • the reaction formula is: ; RX is a halogenated alkane.
  • Haloalkoxy may methoxyethoxy chloride (CI A 0 ⁇ ° ⁇ ) or methoxyethoxy methyl bromide (80 ⁇ 0 ⁇ ).
  • the stirring reaction time can be 24 to 72 hours. In general, it is sufficient to react the double-centered quaternary ammonium salt with the alkyl halide.
  • reaction of bipyridine with alkane is not limited to a protective gas atmosphere formed by nitrogen or argon, and it is only carried out under the protection of an inert gas.
  • the reaction solution After the reaction solution is cooled, it is not limited to the purification of the dialkylbipyridine by washing three times with ethyl acetate, and the dialkylbipyridine halide can also be purified by other methods in the art.
  • Step S12 the dialkyl bipyridyl halide prepared in the step S11 and the salt of the formula M+Y- are mixed at a molar ratio of 1: 2 and then added to deionized water at a reaction temperature of room temperature, and the reaction time is 8-24.
  • the dialkylbipyridine halide is stirred with a salt of the formula ⁇ + ⁇ -, and the mixture obtained after the ion exchange reaction is extracted with dichloromethane until the obtained deionized water phase is saturated with AgN0 3
  • the aqueous solution was titrated without precipitation.
  • the dichloromethane phase was concentrated by evaporation and dried under vacuum at 80 ° C for 48 h to obtain a double having the following structural formula.
  • M + is Na +, K + or NH 4 +
  • Y is BF 4, PF 6, (CF 3 S0 2) 2 N- or (FS0 2) 2 N-.
  • the reaction formula is:
  • the time of the ion exchange reaction is not limited to 8 to 24 hours, as long as the dialkylbipyridine halide is ion-exchanged with the salt having the general formula M+Y-; separation and purification of the double center
  • the preparation method of the bi-center bipyridyl cation-based ionic liquid has less toxicity and the preparation process is simpler, so that the cost is lower and it is easy to be prepared on a large scale.
  • the organic electrolytic solution of one embodiment includes a bi-centered bipyridine cationic ionic liquid, an organic solvent, and a lithium salt.
  • the double-heart bipyridyl cation-based ionic liquid has the following structural formula: Wherein, ⁇ is BF 4 , PF 6 , (CF 3 S0 2 ) 2 N- or (FS0 2 ) 2 N -.
  • the mass ratio of the organic solvent to the bi-centered bipyridine ionic liquid is greater than or equal to 0 and less than 100.
  • the organic solvent may be at least one selected from the group consisting of ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), and ethyl propionate (EP).
  • the concentration of the lithium salt in the organic electrolyte is 0.3 to 1.2 mol/L.
  • the concentration of the lithium salt in the organic electrolyte is 1 mol/L.
  • the lithium salt may be selected from lithium tetrafluoroborate (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and lithium bis(fluorosulfonyl)imide (LiFSI). At least one.
  • a method for preparing the above organic electrolyte comprising the steps of:
  • the washed product was dried under vacuum at 80 ° C for 48 h to give purified dialkyl bipyridyl compound.
  • the alkyl halide can be methoxyethoxychloromethane (c ⁇ o ⁇ ° ⁇ ) or methoxyethoxymethyl bromide
  • the stirring reaction time can be 24 to 72 hours. In general, it is sufficient to react the double-centered quaternary ammonium salt with the alkyl halide.
  • reaction of bipyridine with alkane is not limited to a protective gas atmosphere formed by nitrogen or argon, and it is only carried out under the protection of an inert gas.
  • the reaction liquid After the reaction liquid is cooled, it is not limited to the purification of the dialkylbipyridine by washing three times with ethyl acetate, and the dialkyl bipyridyl compound may be purified by other methods in the art.
  • the dialkyl bipyridyl halide prepared in step S21 and the salt of the formula M+Y- are mixed at a molar ratio of 1: 2 and then added to deionized water at a reaction temperature of room temperature, and the reaction time is 8 to 24 hours.
  • the dialkylbipyridine halide is stirred with a salt of the formula ⁇ + ⁇ -, and the mixture obtained after the ion exchange reaction is extracted with dichloromethane until the obtained deionized water phase is saturated with the AgN0 3 aqueous solution. No precipitation occurred in the titration.
  • the methylene chloride phase was concentrated by evaporation and dried under vacuum at 80 ° C for 48 h to obtain a double centered structure having the following structural formula.
  • ⁇ + is Na+, K+ or NH 4 +
  • Y- is BF 4 -, PF 6 -, (CF 3 S0 2 ) 2 N- or (FS0 2 ) 2 N-.
  • the time of the ion exchange reaction is not limited to 8 to 24 hours, as long as the dialkylbipyridine halide is ion-exchanged with the salt of the formula M+Y-; the separation and purification of the double center
  • the organic solvent is at least one selected from the group consisting of ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), and ethyl propionate (EP).
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • EP ethyl propionate
  • step S23 is performed under the protection of an inert gas, which may be nitrogen or argon.
  • Step S24 adding a lithium salt to the mixed solution of the organic solvent and the bi-centered bipyridine ion-based ionic liquid, and stirring and dissolving to obtain an organic electrolytic solution.
  • concentration of the lithium salt in the organic electrolyte is 0.3 to 1.2 mol/L.
  • the lithium salt has a concentration of 1 mol/L.
  • the lithium salt may be selected from lithium tetrafluoroborate (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and lithium bis(fluorosulfonyl)imide (LiFSI). At least one.
  • the electrochemical window of the bicenter bipyridylcation ionic liquid in the above organic electrolyte exceeds 4V, has good electrochemical stability, and is not easily decomposed under high voltage, so that the organic electrolyte has a higher charging voltage. Good stability.
  • Lithium salts provide lithium ions in applications such as lithium ion batteries or lithium ion capacitors, and organic solvents can reduce the viscosity of the electrolyte. The following is a specific embodiment.
  • the mixture was extracted three times with 250 mL of dichloromethane, and the extracts were combined. It was then stripped with 60 mL of deionized water each time until the aqueous phase was titrated with a saturated aqueous solution of AgN0 3 without precipitation.
  • the methylene chloride phase was concentrated on a rotary evaporator and dried in vacuo at 80 ° C for 48 h to give a pale-yellow solid as a di-bibi- pyridine hexafluorophosphate.
  • the methylene chloride phase was concentrated using a rotary evaporator and dried in vacuo at 80 ° C for 48 h to afford a pale-yellow solid as a bi-bibi-bi-trifluoromethanesulfonimide salt.
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), and ethyl propionate (EP) are arranged in a volume ratio of 2:5:2:3.
  • organic solvent cylinder called mixed solvent EC + EMC + DMC + EP.
  • EMC + EMC + DMC + EP organic solvent
  • the ratio of 10:1 is added to the bi-center bipyridyl tetrafluoroborate (prepared in Example 1) ionic liquid, and heated to 40°. C is stirred to obtain a homogenous organic phase.
  • lithium salt LiBF 4 in this example
  • a certain amount of lithium salt LiBF 4 in this example is added to make the molar concentration of the lithium salt 1 mol/L (based on the volume of the organic phase V EC + EMC + DMC + ⁇ + , ⁇ « sub-liquid to determine the lithium salt The amount of the), continue to stir to dissolve the lithium salt completely, thereby obtaining the target organic electrolyte.
  • Figure 1 shows the use of graphene as the electrode material.
  • the organic electrolyte prepared in this example is used as the electrolyte, assembled into a button cell, and subjected to constant current charge and discharge test using a CHI660A electrochemical workstation, at 0 ⁇ 3.2V.
  • the charge-discharge curve of the button cell measured at a current of 0.25 A/g in the electrochemical window.
  • the organic electrolyte prepared in this embodiment is suitable for the electrolyte of a supercapacitor, and the organic electrolyte has good stability in a charging voltage of up to 3.2 V.
  • Example 7
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), and ethyl propionate (EP) are arranged in a volume ratio of 2:5:2:3.
  • organic solvent cylinder called mixed solvent EC + EMC + DMC + EP .
  • EMC + EMC + DMC + EP organic solvent
  • the ratio of 1:100 is added to the bi-center bipyridyl bis(trifluoromethanesulfonyl)imide salt (prepared in Example 3).
  • the liquid was heated and heated to 40 ° C to obtain a homogeneous organic phase.
  • lithium salt LiTFSI in this example
  • LiTFSI lithium salt
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), and ethyl propionate (EP) are arranged in a volume ratio of 2:5:2:3.
  • Organic solvent (cylinder called mixed solvent EC+EMC + DMC + EP) °
  • Bicenter bipyridyl ionic liquid is 1:10 ratio added to the bi-center bipyridyl double (Fluorosyl)imide salt (prepared in Example 4)
  • An ionic liquid and heated to 40 ° C to obtain a homogenous organic phase.
  • LiFSI lithium salt
  • Ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate under N 2 atmosphere protection (DMC), ethyl propionate (EP) is configured as an organic solvent in a volume ratio of 2:5:2:3 (the cartridge is referred to as a mixed solvent EC+ EMC + DMC + EP).
  • the mass is then mixed solvent EC + EMC + DMC + EP: bis-bipyridine center "is defined ionic liquid 1: 1 ratio of the bis-bipyridine a given center tetrafluoroborate ionic liquid was heated to 40 ° C and stirred The homogenous organic phase is obtained.
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), and ethyl propionate (EP) are arranged in a volume ratio of 2:5:2:3.
  • Organic solvent (cylinder called mixed solvent EC + EMC + DMC + EP ) °
  • bi-center bipyridyl ionic liquid 40 1 ratio of the addition of bi-bipyridine ion
  • the liquid (this example is a bi-center bipyridyl tetrafluoroborate with a molar ratio of 1:1 and a bi-center bipyridyl hexafluorophosphate) and heated to 40 ° C to obtain a homogenous organic phase.
  • lithium salt in this example, LiTFSI and LiFSI with a molar ratio of 1:1
  • LiTFSI and LiFSI with a molar ratio of 1:1
  • Sub-liquid determines the amount of lithium salt
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), and ethyl propionate (EP) are arranged in a volume ratio of 2:5:2:3.
  • Organic solvent (cylinder called mixed solvent EC + EMC + DMC + EP ) °
  • the mass ratio mixed solvent EC + EMC + DMC + EP double-phase bipyridyl ionic liquid 70: 1 ratio of the addition of bi-bipyridine ion Liquid (this example is a bis-bipyridyl bis(trifluoromethanesulfonyl)imide salt and a bi-bipyridine bis(fluorosulfonyl)imide salt in a molar ratio of 1:1) and heated to 40 ° C for stirring.
  • ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), and ethyl propionate (EP) are arranged in a volume ratio of 2:5:2:3.
  • organic solvent cylinder called mixed solvent EC + EMC + DMC + EP .
  • EMC + EMC + DMC + EP organic solvent
  • the ratio of 100:1 is added to the bi-center bipyridyl bis(trifluoromethanesulfonyl)imide salt ionic liquid, and heated to 40 The mixture was stirred at ° C to obtain a homogenous organic phase.
  • lithium salt LiTFSI in this example
  • LiTFSI lithium salt

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Pyridine Compounds (AREA)
  • Secondary Cells (AREA)

Abstract

本发明公开了一种双中心联吡啶阳离子类离子液体，通过联吡啶与卤代烷反应合成二烷基联吡啶卤化物，再通过离子交换反应将二烷基吡啶卤化物中的卤素离子转换为目标阴离子，最终得到目标离子液体。本发明还公开了一种包含有上述双中心联吡啶阳离子类离子液体的有机电解液及其制备方法。

Description

双中心联吡啶阳离子类离子液体及其制备方法和应用
【技术领域】
本发明涉及离子液体， 尤其涉及一种双中心联吡啶阳离子类离子液体， 其 制备方法、 包括该双中心联吡啶阳离子类离子液体的有机电解液及该有机电解 液的制备方法。
【背景技术】
离子液体（Ionic liquids)是指在室温范围内 （一般为 100 °C以下）呈液态， 由 有机阳离子和无机阴离子 （或有机阴离子）构成的。 离子液体具有可调性， 根 据不同需要改变其阴阳离子结构可以达到设计者的目的， 因而离子液体被称为 设计者的溶剂。 早在 1914年就发现了第一个离子液体一硝基乙胺， 但其后该领 域的研究进展緩慢。 直到 1992年， Wikes领导的研究小组合成了低熔点、 抗 水解、 稳定性强的 1-乙基 -3-甲基咪唑四氟硼酸盐离子液体 ([EMIM]BF4)后， 离 子液体的研究才得以迅速发展， 随后开发出了一系列的离子液体体系。 最初的 离子液体主要用于电化学研究， 近年来离子液体作为绿色溶剂用于有机及高分 子合成受到重视。
与传统的有机溶剂和电解质相比， 离子液体具有一系列突出的优点： （1) 熔 点低于或接近室温， 呈液态的温度范围宽； （2 )蒸气压低、 几乎不挥发、 无色、 无嗅； （3) 具有较大的稳定温度范围， 较好的化学稳定性及较宽的电化学稳定电 位窗口；（4) 良好的溶解特性，对很多无机物和有机物都表现出良好的溶解能力； ( 5 )无着火点且不易燃烧； （6 )可循环使用， 不污染环境等。 因此， 离子液体 作为双电层电容器的电解液具有良好的发展前景。
然而传统的有机电解液在高电压下容易分解， 引起电容器内阻急剧增大且 电容量迅速降低。 有机电解液的稳定性一直是限制电容器的比能量的关键因素。
【发明内容】 基于此， 有必要提供一种在高电压下不容易分解的双中心联吡啶阳离子类 离子液体。
此外， 还有必要提供一种上述双中心联吡啶阳离子类离子液体的制备方法。 此外， 还有必要提供一种包含有上述双中心联吡啶阳离子类离子液体的有 机电解液中及其制备方法。
一 心联吡啶阳离子类离子液体， 具有如下结构式：
Figure imgf000004_0001
， 其中， Y为 BF4、 PF6、 (CF3S02)2N-或 (FS02)2N -。
一种双中心联吡啶阳离子类离子液体的制备方法， 包括如下步骤：
步骤一、 在保护气体氛围下， 将联吡啶与 代烷按摩尔比 1: 2-1 : 2.5混合 后加热至 60°C ~80°C , 搅拌反应得到二烷基联吡啶 化物； 其中， 所述 代烷为 甲氧基乙氧基氯甲烷或甲氧基乙氧基溴甲烷；
步骤二、 将步骤一中制备的二烷基联吡啶卤化物与通式为 M+Y-的盐以摩尔 比 1: 2混合后加入去离子水中， 搅拌发生离子交换反应得到具有如下结构式的 双中心
Figure imgf000004_0002
其中， Μ+为 Na+、 K+或 NH4+, Y-为 BF4-、 PF6-、 （CF3S02)2N—或 (FS02)2N―。 优选的， 步骤一中， 所述联吡啶与所述 代烷搅拌反应的时间为 24h~72h, 反应液冷却后用乙酸乙酯洗涤， 将洗涤得到的产物真空干燥得到纯化的二烷基 联吡啶 化物。
优选的， 步骤一中， 所述保护气体氛围为氮气氛围或氩气氛围。
优选的，步骤二中，所述离子交换反应的温度为室温，反应时间为 8 h ~24 h。 优选的，步骤二还包括将所述双中心联吡啶阳离子类离子液体进行分离纯化 的步骤， 所述分离纯化步骤如下： 将二烷基联吡啶 化物与具有通式 M+Y—的盐 搅拌反应后得到的混合液用二氯甲烷萃取， 直至所得到的水相用饱和的 AgN03 水溶液滴定无沉淀产生为止， 将二氯甲烷萃取物蒸发浓缩后真空干燥得到纯化 的双中心联吡啶阳离子类离子液体。
一种有机电解液， 包括双中心联吡啶阳离子类离子液体、 有机溶剂和锂盐， 所述双 心联吡啶阳离子类离子液体具有如下结构式：
Figure imgf000005_0001
其中， Υ-为 BF4-、 PF6-、 （CF3S02)2N—或 (FS02)2N—, 所述有机溶剂与所述双中 心联吡啶阳离子类离子液体的质量比为 0~100,所述锂盐的浓度为 0.3~1.2mol/L。
优选的， 所述锂盐为四氟硼酸锂、 六氟磷酸锂、 双 (三氟甲磺酰)亚胺锂和双 (氟磺酰）亚胺锂中的至少一种。
优选的， 所述有机溶剂为碳酸乙烯酯、 碳酸甲乙酯、 碳酸二甲酯和丙酸乙 酯中的至少一种。
一种有机电解液的制备方法， 其特征在于， 包括如下步骤：
步骤一、 在保护气体氛围下， 将联吡啶与 代烷按摩尔比 1: 2-1: 2.5混合 后加热至 60°C ~80°C , 搅拌反应得到二烷基联吡啶 化物； 其中， 所述 代烷为 甲氧基乙氧基氯甲烷或甲氧基乙氧基溴甲烷；
步骤二、 将步骤一中制备的二烷基联吡啶卤化物与通式为 M+Y-的盐以摩尔 比 1: 2混合后加入去离子水中， 搅拌发生离子交换反应得到具有如下结构式的 双中心 其中， Μ+为 Na+、 K+或 NH4+, Y-为 BF4-、 PF6-、 （CF3S02)2N—或 (FS02)2N—； 步骤三、 提供有机溶剂， 向所述有机溶剂中加入所述双中心联吡啶阳离子 类离子液体并搅拌均匀 , 所述有机溶剂与所述双中心联吡啶阳离子类离子液体 的质量比为 0~100；
步骤四、 向所述有机溶剂及所述双中心联吡啶阳离子类离子液体形成的混 合液中加入锂盐并搅拌溶解得到所述有机电解液； 所述有机电解液中所述锂盐 的浓度为 0.3~1.2mol/L。
该双中心联吡啶阳离子类离子液体的电化学窗口超过 4V, 具有较好的电化 学稳定性， 在高电压下不容易分解。 从而， 包含该双中心联吡啶阳离子类离子 液体的有机电解液在较高的充电电压内具有较好的稳定性。
【附图说明】
图 1为实施例 6制备的有机电解液与电极材料组成超级电容器进行常规测 试得到的标准的充放电曲线。
【具体实施方式】
下面结合附图和具体实施例对双中心联吡啶阳离子类离子液体及其制备方 法和应用进一步阐明。
一
Figure imgf000006_0001
其中， Υ-为 BF4-、 PF6-、 （CF3S02)2N-或 (FS02)2N -。
该双中心联吡啶阳离子类离子液体的电化学窗口超过 4V, 具有较好的电化 学稳定性， 在高电压下不容易分解。
该双中心联吡啶阳离子类离子液体侧链引入的烷氧基结构， 一方面能够降 低离子液体的粘度。 另一方面， 这种含氧官能团能够有利于与电解液中锂离子 的络合， 增加锂盐的溶解度。
提供一种上述双中心联吡啶阳离子类离子液体的制备方法， 包括以下步骤： 步骤 Sll、在氮气或氩气形成的保护气体氛围下， 将联吡啶与 代烷按摩尔 比 1: 2-1: 2.5混合后加热至 60°C ~80°C , 搅拌反应得到二烷基联吡啶卤化物。 反应式为：
Figure imgf000007_0001
； RX为卤代烷。
洗涤后的产物在 80 °C下真空干燥 48h得到纯化的二烷基联吡啶 化物。 卤代烷可以为甲氧基乙氧基氯甲烷（ CIA0〜°\ )或甲氧基乙氧基溴甲烷 ( 八0^^0\ )。
搅拌反应时间可以为 24~72小时。 一般的， 只要使双中心季铵盐与卤代烷反 应完全即可。
联吡啶与 代烷的反应不限于在氮气或氩气形成的保护气体氛围下进行，只 要在惰性气体保护下进行即可。
反应液冷却后不限于用乙酸乙酯洗涤三次提纯二烷基联吡啶 化物，也可用 本领域中其他方法提纯二烷基联吡啶卤化物。
步骤 S12、 将步骤 S11 中制备的二烷基联吡啶卤化物与通式为 M+Y—的盐以 摩尔比 1： 2混合后加入去离子水中， 反应温度为室温， 反应时间为 8~24小时， 将二烷基联吡啶卤化物与通式为 Μ+Υ—的盐搅拌， 发生离子交换反应后得到的混 合液用二氯甲烷萃取， 直至所得到的去离子水相用饱和的 AgN03水溶液滴定无 沉淀产生， 将二氯甲烷相蒸发浓缩后在 80°C下真空干燥 48h得到具有如下结构 式的双
Figure imgf000007_0002
其中， M+为 Na+、 K+或 NH4+, Y为 BF4、 PF6、 (CF3S02)2N—或 (FS02)2N―。 反应式为：
Figure imgf000008_0001
可以理解， 所述离子交换反应的时间不限于为 8~24小时， 只要使二烷基联 吡啶卤化物与具有通式 M+Y—的盐发生离子交换反应完全即可； 分离提纯双中心 上述双中心联吡啶阳离子类离子液体制备方法， 使用的溶剂毒性较小， 制 备工艺较为筒单， 从而成本较低易于大规模制备。
一实施方式的有机电解液， 包括双中心联吡啶阳离子类离子液体、 有机溶 剂及锂盐。
双 心联吡啶阳离子类离子液体具有如下结构式：
Figure imgf000008_0002
其中， Υ为 BF4 、 PF6 、 (CF3S02)2N-或 (FS02)2N -。
有机溶剂与双中心联吡啶阳离子类离子液体的质量比大于等于 0且小于等 于 100。 有机溶剂可以为选自碳酸乙烯酯 （EC )、 碳酸甲乙酯 （EMC )、 碳酸二 甲酯（DMC )、 丙酸乙酯（EP ) 中的至少一种。
有机电解液中锂盐的浓度为 0.3~1.2 mol/L。
在优选的实施例中， 有机电解液中锂盐的浓度为 l mol/L。
锂盐可以为选自四氟硼酸锂 ( LiBF4 )、 六氟磷酸锂 ( LiPF6 )、 双 (三氟甲磺 酰)亚胺锂 ( LiTFSI )和双（氟磺酰） 亚胺锂（ LiFSI ) 中的至少一种。
提供一种上述有机电解液的配制方法， 包括以下步骤：
S21、 在氮气或氩气形成的保护气体氛围下， 将联吡啶与卤代烷按摩尔比 1: 2-1: 2.5混合后加热至 60°C ~80°C , 搅拌反应得到二烷基联吡啶卤化物。
洗涤后的产物在 80 °C下真空干燥 48h得到纯化的二烷基联吡啶 化物。 卤代烷可以为甲氧基乙氧基氯甲烷（ c^o〜°\ )或甲氧基乙氧基溴甲烷
( Β^0^^0\ )。
搅拌反应时间可以为 24~72小时。 一般的， 只要使双中心季铵盐与卤代烷反 应完全即可。
联吡啶与 代烷的反应不限于在氮气或氩气形成的保护气体氛围下进行，只 要在惰性气体保护下进行即可。
反应液冷却后不限于用乙酸乙酯洗涤三次提纯二烷基联吡啶 化物， 也可 用本领域中其他方法提纯二烷基联吡啶 化物。
522、将步骤 S21中制备的二烷基联吡啶卤化物与通式为 M+Y—的盐以摩尔比 1: 2混合后加入去离子水中， 反应温度为室温， 反应时间为 8~24小时， 将二烷 基联吡啶卤化物与通式为 Μ+Υ—的盐搅拌， 发生离子交换反应后得到的混合液用 二氯甲烷萃取， 直至所得到的去离子水相用饱和的 AgN03水溶液滴定无沉淀产 生， 将二氯甲烷相蒸发浓缩后在 80°C下真空干燥 48h得到具有如下结构式的双 中心联
Figure imgf000009_0001
其中， Μ+为 Na+、 K+或 NH4+, Y-为 BF4-、 PF6-、 （CF3S02)2N—或 (FS02)2N―。 可以理解， 所述离子交换反应的时间不限于为 8~24小时， 只要使二烷基联 吡啶卤化物与具有通式 M+Y—的盐发生离子交换反应完全即可； 分离提纯双中心
523、 提供有机溶剂， 向有机溶剂中加入双中心联吡啶阳离子类离子液体并 搅拌均匀， 有机溶剂与双中心联吡啶阳离子类离子液体的质量比为 0~100。
有机溶剂选自碳酸乙烯酯（ EC )、碳酸甲乙酯（ EMC )、碳酸二甲酯（ DMC )、 丙酸乙酯 （EP ) 中的至少一种。
优选的， 步骤 S23在惰性气体的保护下进行， 惰性气体可为氮气或氩气。 步骤 S24、向有机溶剂及双中心联吡啶阳离子类离子液体形成的混合液中加 入锂盐并搅拌溶解得到有机电解液。 有机电解液中锂盐的浓度为 0.3~1.2 mol/L。
在优选的实施例中， 锂盐的浓度为 1 mol/L。
锂盐可以为选自四氟硼酸锂 ( LiBF4 )、 六氟磷酸锂 ( LiPF6 )、 双 (三氟甲磺 酰)亚胺锂 ( LiTFSI )和双（氟磺酰） 亚胺锂（ LiFSI ) 中的至少一种。
上述有机电解液中双中心联吡啶阳离子类离子液体的电化学窗口超过 4V , 具有较好的电化学稳定性， 在高电压下不容易分解， 从而有机电解液在较高的 充电电压内具有较好的稳定性。 锂盐在锂离子电池或锂离子电容器等的应用中 提供锂离子， 有机溶剂能够降低电解液的粘度。 下面为具体实施例。
实施例 1
双中心联吡啶四氟硼酸盐的合成。
在 250 mL的烧瓶中分别加入 1 mol联吡啶和 2.1 mol甲氧基乙氧基氯甲烷, 在 N2氛围保护下， 升温至 70°C , 搅拌反应 36h。 静置冷却， 用乙酸乙酯洗涤三 次。 在 80°C下真空干燥， 得到浅黄色的固体为二烷基联吡啶氯盐， 收率为 78%。
向 500 mL烧瓶中加入 0.5 mol二烷基联吡啶氯盐、 1 mol NaBF4和 120 mL 去离子水， 在室温下搅拌 16 h。反应完成后， 混合液用 250 mL二氯甲烷萃取 3 次， 合并萃取液。 然后每次用 60 mL去离子水反萃直至用饱和的 AgN03水溶液 滴定水相无沉淀产生为止。 二氯甲烷相用旋转蒸发仪浓缩后， 80°C真空干燥 48h 得到浅黄色的固体为双中心联吡啶四氟硼酸盐。
本实施例双中心联吡啶四氟硼酸盐的核磁共振氢谱测试结果如下： NMR ((CD3)2CO, 400 MHz, ppm): 8.69 (d, 4H), 7.63 (d, 4H), 5.92 (s, 4H), 3.64 (m, 8H), 3.24 (s, 6H)。 实施例 2
双中心联吡啶六氟磷酸盐的合成。
在 250 mL的烧瓶中分别加入 1 mol联吡啶和 2.1 mol 甲氧基乙氧基溴甲烷。 在 Ar氛围保护下， 升温至 70°C , 搅拌反应 36h。 静置冷却， 用乙酸乙酯洗涤三 次。 在 80°C下真空干燥， 得到浅黄色的固体为二烷基联吡啶溴盐， 收率为 80%。 向 500 mL烧瓶中加入 0.5 mol二烷基联吡啶溴盐、 1 mol KPF6和 120 mL去 离子水， 在室温下搅拌 16 h。 反应完成后， 混合液用 250 mL二氯甲烷萃取 3 次， 合并萃取液。 然后每次用 60 mL去离子水反萃直至用饱和的 AgN03水溶液 滴定水相无沉淀产生为止。 二氯甲烷相用旋转蒸发仪浓缩后， 80 °〇真空干燥 48 h得到浅黄色的固体为双中心联吡啶六氟磷酸盐。
本实施例双中心联吡啶双中心联吡啶六氟磷酸盐的核磁共振氢谱测试结果 如下： !H NMR ((CD3)2CO, 400 MHz, ppm): 8.70 (d, 4H), 7.63 (d, 4H), 5.93 (s, 4H),
3.64 (m, 8H), 3.25 (s, 6H)。 实施例 3
双中心联吡啶三氟甲磺酰亚胺盐的合成。
向 500 mL烧瓶中加入 0.5 mol二烷基联吡啶氯盐（实施例 1制备)、 1 mol三 氟甲磺酰亚胺钾 KTFSI和 120 mL去离子水， 在室温下搅拌 16h。 反应完成后， 混合液用 250 mL二氯甲烷萃取 3次， 合并萃取液。 然后每次用 60 mL去离子 水反萃直至用饱和的 AgN03水溶液滴定水相无沉淀产生为止。 二氯甲烷相用旋 转蒸发仪浓缩后， 80°C真空干燥 48 h得到浅黄色的固体为双中心联吡啶三氟甲 磺酰亚胺盐。
本实施例双中心联吡啶三氟甲磺酰亚胺盐的核磁共振氢谱测试结果如下： ¾ NMR ((CD3)2CO, 400 MHz, ppm): 8.71 (d, 4H), 7.65 (d, 4H), 5.95 (s, 4H), 3.66 (m, 8H), 3.26 (s, 6H)。 实施例 4
双中心联吡啶三氟甲磺酸盐的合成。
向 500 mL烧瓶中加入 0.5 mol二烷基联吡啶溴盐 （实施例 2制备）、 1 mol CF3S03Na和 120 mL去离子水，在室温下搅拌 16 h。反应完成后，混合液用 250 mL二氯甲烷萃取 3次， 合并萃取液。 然后每次用 60 mL去离子水反萃直至用 饱和的 AgN03水溶液滴定水相无沉淀产生为止。二氯甲烷相用旋转蒸发仪浓缩， 80 °C真空干燥 48 h后得到浅黄色的固体为双中心联吡啶三氟甲磺酸盐。
本实施例双中心联吡啶三氟甲磺酸盐的核磁共振氢谱测试结果如下： ¾ NMR ((CD3)2CO, 400 MHz, ppm): 8.70 (d, 4H), 7.63 (d, 4H), 5.93 (s, 4H), 3.65 (m, 8H), 3.23 (s, 6H)。 实施例 5
双中心联吡啶双（氟橫酰）亚胺盐的合成。
详细制备过程同实施例 1 , 只需将 1 mol的 NaBF4换为 1 mol的双 (氟磺酰） 亚胺钾 (FS02)2NK即可。
本实施例双中心联吡啶双（氟磺酰）亚胺盐的核磁共振氢谱测试结果如下： ¾ NMR ((CD3)2CO, 400 MHz, ppm): 8.70 (d, 4H), 7.64 (d, 4H), 5.92 (s, 4H), 3.66 (m, 8H), 3.25 (s, 6H)。 实施例 6
在 N2氛围保护下， 将碳酸乙烯酯（EC )、 碳酸甲乙酯（EMC )、 碳酸二甲酯 ( DMC )、 丙酸乙酯（EP ) 以 2: 5: 2: 3的体积比配置成有机溶剂 （筒称为混 合溶剂 EC+ EMC + DMC + EP )。 然后根据质量比混合溶剂 EC+ EMC + DMC + EP： 双中心联 吡啶离子液体为 10: 1的配比加入双中心联吡啶四氟硼酸盐 （实施例 1制备） 离子液体， 并加热到 40°C搅拌得到均勾的有机相。 最后加入一定量的锂盐 （本 实施例为 LiBF4 ),使锂盐的摩尔浓度为 1 mol/L (基于有机相的体积 VEC+ EMC + DMC + ΕΡ+ ,^« 子液体来决定锂盐的用量 ) , 继续搅拌使锂盐溶解完全， 从而得到目标 有机电解液。
图 1 为以石墨烯为电极材料， 以本实施例制得的有机电解液为电解液， 组 装成扣式电池，利用 CHI660A电化学工作站对其进行恒流充放电测试，在 0~3.2V 的电化学窗口内， 以 0.25 A/g的电流测得到的扣式电池的充放电曲线。
由图 1 可以看出， 本实施例制备的有机电解液适合用于超级电容器的电解 液， 且在高达 3.2 V的充电电压内有机电解液具有较好的稳定性。 实施例 7
在 Ar氛围保护下， 加入 100 mL双中心联吡啶六氟磷酸盐（实施例 2制备） 离子液体， 并加热到 40°C搅拌， 然后加入一定量的锂盐（本实施例为 LiPF6)使 锂盐的摩尔浓度为 0.3 mol/L, 继续搅拌使锂盐溶解完全， 从而得到目标有机电 解液。 实施例 8
在 N2氛围保护下， 将碳酸乙烯酯（EC)、 碳酸甲乙酯（EMC)、 碳酸二甲酯 (DMC)、 丙酸乙酯（EP) 以 2: 5: 2: 3的体积比配置成有机溶剂 （筒称为混 合溶剂 EC+EMC + DMC + EP)。 然后根据质量比混合溶剂 EC+EMC + DMC + EP:双中心联吡 啶离子液体为 1: 100的配比加入双中心联吡啶双 (三氟甲磺酰)亚胺盐（实施例 3 制备） 离子液体， 并加热到 40°C搅拌得到均匀的有机相。 最后加入一定量的锂 盐 （本实施例为 LiTFSI), 使锂盐的摩尔浓度为 0.5 mol/L (基于有机相的体积 VEC+EMC + DMC + EP+5^,^«¾子液体来决定锂盐的用量），继续搅拌使锂盐溶解完全，从 而得到目标有机电解液。 实施例 9
在 Ar 氛围保护下， 将碳酸乙烯酯（EC)、 碳酸甲乙酯（EMC)、 碳酸二甲 酯（DMC)、 丙酸乙酯（EP) 以 2: 5: 2: 3的体积比配置成有机溶剂 （筒称为 混合溶剂 EC+ EMC + DMC + EP )° 然后才艮据质量比混合溶剂 EC+ EMC + DMC + EP： 双中心 联吡啶离子液体为 1: 10 的配比加入双中心联吡啶双（氟橫酰）亚胺盐 （实施 例 4制备） 离子液体， 并加热到 40°C搅拌得到均勾的有机相。 最后加入一定量 的锂盐 （本实施例为 LiFSI), 使锂盐的摩尔浓度为 0.7mol/L (基于有机相的体 积 VEC+EMC + DMC + EP+5R†,^tt^ 液体来决定锂盐的用量），继续搅拌使锂盐溶解完全， 从而得到目标有机电解液。 实施例 10
在 N2氛围保护下， 将碳酸乙烯酯（EC)、 碳酸甲乙酯（EMC)、 碳酸二甲酯 (DMC)、 丙酸乙酯（EP) 以 2: 5: 2: 3的体积比配置成有机溶剂 （筒称为混 合溶剂 EC+ EMC + DMC + EP )。 然后根据质量比混合溶剂 EC+ EMC + DMC + EP： 双中心联 吡"定离子液体为 1: 1的配比加入双中心联吡1定四氟硼酸盐离子液体， 并加热到 40°C搅拌得到均勾的有机相。 最后加入一定量的锂盐 （本实施例为摩尔比为 1: 1的 LiBF4和 LiPF6；),使锂盐的摩尔浓度为 0.9 mol/L(基于有机相的体积 VEC+EMC
+ DMC + EP+ ^^«子液体来决定锂盐的用量）， 继续搅拌使锂盐溶解完全， 从而得到 目标有机电解液。 实施例 11
在 Ar 氛围保护下， 将碳酸乙烯酯（EC)、 碳酸甲乙酯（EMC)、 碳酸二甲 酯 （DMC)、 丙酸乙酯（EP) 以 2: 5: 2: 3的体积比配置成有机溶剂 （筒称为 混合溶剂 EC+ EMC + DMC + EP )° 然后才艮据质量比混合溶剂 EC+ EMC + DMC + EP： 双中心 联吡啶离子液体为 40： 1 的配比加入双中心联吡啶离子液体（本实施例为摩尔 比 1: 1的双中心联吡啶四氟硼酸盐和双中心联吡啶六氟磷酸盐 ),并加热到 40°C 搅拌得到均勾的有机相。 最后加入一定量的锂盐 （本实施例为摩尔比 1: 1 的 LiTFSI和 LiFSI),使锂盐的摩尔浓度为 1 mol/L (基于有机相的体积 VEC+EMC + DMC + ΕΡ+ ,^« 子液体来决定锂盐的用量）， 继续搅拌使锂盐溶解完全， 从而得到目标 有机电解液。 实施例 12
在 Ar 氛围保护下， 将碳酸乙烯酯（EC)、 碳酸甲乙酯（EMC)、 碳酸二甲 酯（DMC)、 丙酸乙酯（EP) 以 2: 5: 2: 3的体积比配置成有机溶剂 （筒称为 混合溶剂 EC+ EMC + DMC + EP )° 然后才艮据质量比混合溶剂 EC+ EMC + DMC + EP： 双中心 联吡啶离子液体为 70： 1 的配比加入双中心联吡啶离子液体（本实施例为摩尔 比 1: 1 的双中心联吡啶双 (三氟甲磺酰)亚胺盐和双中心联吡啶双（氟磺酰） 亚 胺盐）， 并加热到 40°C搅拌得到均勾的有机相。 最后加入一定量的锂盐（本实施 例为摩尔比 1: 1的 LiPF6和 LiTFSI), 使锂盐的摩尔浓度为 1.1 mol/L (基于有 机相的体积 VEC+EMC + DMC + EP+5R†,dt^«fr来决定锂盐的用量）， 继续搅拌使锂盐 溶解完全， 从而得到目标有机电解液。 实施例 13
在 N2氛围保护下， 将碳酸乙烯酯（EC)、 碳酸甲乙酯（EMC)、 碳酸二甲酯 (DMC)、 丙酸乙酯（EP) 以 2: 5: 2: 3的体积比配置成有机溶剂 （筒称为混 合溶剂 EC+EMC + DMC + EP)。 然后根据质量比混合溶剂 EC+EMC + DMC + EP:双中心联吡 啶离子液体为 100: 1的配比加入双中心联吡啶双 (三氟甲磺酰)亚胺盐离子液体， 并加热到 40 °C搅拌得到均勾的有机相。 最后加入一定量的锂盐 （本实施例为 LiTFSI), 使锂盐的摩尔浓度为 1.2 mol/L (基于有机相的体积 VEC+EMC + DMC + EP+ 中心联 子液体来决定锂盐的用量）， 继续搅拌使锂盐溶解完全， 从而得到目标有机 电解液。
但并不能因此而理解为对本发明专利范围的限制。 应当指出的是， 对于本领域 的普通技术人员来说， 在不脱离本发明构思的前提下， 还可以做出若干变形和 改进， 这些都属于本发明的保护范围。 因此， 本发明专利的保护范围应以所附 权利要求为准。

Claims

1、 一种双中心联吡啶阳离子类离子液体， 其特征在于， 具有如下结构式：
Figure imgf000016_0001
其中， Υ-为 BF4-、 PF6-、 （CF3S02)2N-或 (FS02)2N -。
2、 一种双中心联吡啶阳离子类离子液体的制备方法， 其特征在于， 包括如 下步骤：
步骤一、 在保护气体氛围下， 将联吡啶与 代烷按摩尔比 1: 2-1: 2.5混合 后加热至 60°C~80°C , 搅拌反应得到二烷基联吡啶 化物； 其中， 所述 代烷为 甲氧基乙氧基氯甲烷或甲氧基乙氧基溴甲烷；
步骤二、 将步骤一中制备的二烷基联吡啶卤化物与通式为 M+Y-的盐以摩尔 比 1: 2混合后加入去离子水中， 搅拌发生离子交换反应得到具有如下结构式的 双中心联吡啶阳离子类离子液体：
Figure imgf000016_0002
其中， Μ+为 Na+、 K+或 NH4+, Y-为 BF4-、 PF6-、 （CF3S02)2N—或 (FS02)2N―。
3、 如权利要求 2所述的双中心联吡啶阳离子类离子液体的制备方法， 其特 征在于， 步骤一中， 所述联吡啶与所述 代烷搅拌反应的时间为 24h~72h , 反应 液冷却后用乙酸乙酯洗涤， 将洗涤得到的产物真空干燥得到纯化的二烷基联吡 p定卤化物。
4、 如权利要求 2所述的双中心联吡啶阳离子类离子液体的制备方法， 其特 征在于， 步骤一中， 所述保护气体氛围为氮气氛围或氩气氛围。
5、 如权利要求 2所述的双中心联吡啶阳离子类离子液体的制备方法， 其特 征在于， 步骤二中， 所述离子交换反应的温度为室温， 反应时间为 8 h ~24 h。
6、 如权利要求 2所述的双中心联吡啶阳离子类离子液体的制备方法， 其特 征在于， 步骤二还包括将所述双中心联吡啶阳离子类离子液体进行分离纯化的 步骤， 所述分离纯化步骤如下： 将二烷基联吡啶卤化物与具有通式 M+Y—的盐搅 拌反应后得到的混合液用二氯甲烷萃取， 直至所得到的水相用饱和的 AgN03水 溶液滴定无沉淀产生为止， 将二氯甲烷萃取物蒸发浓缩后真空干燥得到纯化的 双中心联吡啶阳离子类离子液体。
7、 一种有机电解液， 其特征在于， 包括双中心联吡啶阳离子类离子液体、 有机溶
Figure imgf000017_0001
其中， Y-为 BF4-、 PF6-、 （CF3S02)2N—或 (FS02)2N—, 所述有机溶剂与所述双中 心联吡啶阳离子类离子液体的质量比为 0~100 , 所述锂盐的浓度为 0.3~1.2 mol/L。
8、如权利要求 7所述的有机电解液， 其特征在于， 所述锂盐为四氟硼酸锂、 六氟磷酸锂、 双 (三氟甲磺酰)亚胺锂和双（氟磺酰）亚胺锂中的至少一种。
9、 如权利要求 7所述的有机电解液， 其特征在于， 所述有机溶剂为碳酸乙 烯酯、 碳酸甲乙酯、 碳酸二甲酯和丙酸乙酯中的至少一种。
10、 一种有机电解液的制备方法， 其特征在于， 包括如下步骤：
步骤一、 在保护气体氛围下， 将联吡啶与 代烷按摩尔比 1: 2-1: 2.5混合 后加热至 60°C ~80°C , 搅拌反应得到二烷基联吡啶 化物； 其中， 所述 代烷为 甲氧基乙氧基氯甲烷或甲氧基乙氧基溴甲烷；
步骤二、 将步骤一中制备的二烷基联吡啶卤化物与通式为 M+Y-的盐以摩尔 比 1: 2混合后加入去离子水中， 搅拌发生离子交换反应得到具有如下结构式的 双中心
Figure imgf000017_0002
其中， Μ+为 Na+、 K+或 NH4+, Y-为 BF4-、 PF6-、 （CF3S02)2N—或 (FS02)2N—； 步骤三、 提供有机溶剂， 向所述有机溶剂中加入所述双中心联吡啶阳离子 类离子液体并搅拌均匀 , 所述有机溶剂与所述双中心联吡啶阳离子类离子液体 的质量比为 0~100；
步骤四、 向所述有机溶剂及所述双中心联吡啶阳离子类离子液体形成的混 合液中加入锂盐并搅拌溶解得到所述有机电解液； 所述有机电解液中所述锂盐 的浓度为 0.3~1.2mol/L。
PCT/CN2011/079118 2011-08-30 2011-08-30 双中心联吡啶阳离子类离子液体及其制备方法和应用 WO2013029237A1 (zh)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201180072278.4A CN103732587B (zh) 2011-08-30 2011-08-30 双中心联吡啶阳离子类离子液体及其制备方法和应用
PCT/CN2011/079118 WO2013029237A1 (zh) 2011-08-30 2011-08-30 双中心联吡啶阳离子类离子液体及其制备方法和应用
EP11871780.0A EP2752409B1 (en) 2011-08-30 2011-08-30 Double-center bipyridyl cationic ionic liquid, preparation method therefor and use thereof
US14/234,384 US9196424B2 (en) 2011-08-30 2011-08-30 Double-center bipyridyl cationic ion liquid, preparation method therefor and use thereof
JP2014527454A JP5796128B2 (ja) 2011-08-30 2011-08-30 ２つの中心を有するビピリジルカチオン系イオン液体、その調製方法及び使用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2011/079118 WO2013029237A1 (zh) 2011-08-30 2011-08-30 双中心联吡啶阳离子类离子液体及其制备方法和应用

Publications (1)

Publication Number Publication Date
WO2013029237A1 true WO2013029237A1 (zh) 2013-03-07

Family

ID=47755196

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2011/079118 WO2013029237A1 (zh) 2011-08-30 2011-08-30 双中心联吡啶阳离子类离子液体及其制备方法和应用

Country Status (5)

Country Link
US (1) US9196424B2 (zh)
EP (1) EP2752409B1 (zh)
JP (1) JP5796128B2 (zh)
CN (1) CN103732587B (zh)
WO (1) WO2013029237A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110204473A (zh) * 2019-05-22 2019-09-06 常州乾艺智能制造科技有限公司 一种用于锂电池的双中心阳离子液体及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109012043A (zh) * 2018-09-19 2018-12-18 河南师范大学 一种双功能螯合型离子液体吸收二氧化硫气体的方法
CN114105907A (zh) * 2021-12-14 2022-03-01 河北工业大学 一种吡咯烷类离子液体及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54143783A (en) * 1978-04-28 1979-11-09 Canon Inc Image display device
CN1326936A (zh) * 2000-05-30 2001-12-19 默克专利股份有限公司 离子液体
CN1838469A (zh) * 2006-04-20 2006-09-27 武汉大学 锂－硫电池电解液及其可充锂－硫电池

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE793156A (fr) * 1971-12-23 1973-06-21 Philips Nv Cellule reproductrice d'images
DE2811803A1 (de) * 1978-03-15 1979-09-27 Schering Ag Verfahren zur herstellung von 4.4'-bipyridyl und dessen alkylderivaten
JPH0233702B2 (ja) * 1986-01-29 1990-07-30 Nippon Mining Co Shinkijipirijiniumuenjudotai
JP4583582B2 (ja) 2000-11-08 2010-11-17 株式会社クラレ 電気二重層キャパシタ
JPWO2003091198A1 (ja) 2002-04-24 2005-09-02 日清紡績株式会社 イオン性液体および脱水方法ならびに電気二重層キャパシタおよび二次電池
JP2003321425A (ja) * 2002-05-02 2003-11-11 Daikin Ind Ltd フッ素化合物の製造方法、及びフッ素化剤前駆体の回収又は再生方法
AU2003256281A1 (en) 2002-06-21 2004-01-06 The Regents Of The University Of California Electrolytes for electrooptic devices comprising ionic liquids
JP2004029433A (ja) * 2002-06-26 2004-01-29 Nippon Oil Corp エレクトロクロミック素子
US7875732B2 (en) 2005-01-12 2011-01-25 Otsuka Chemical Co., Ltd. Quaternary ammonium salt, electrolyte, electrolyte, solution and electrochemical device
JP4499594B2 (ja) 2005-03-29 2010-07-07 第一工業製薬株式会社 超高純度イオン性液体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54143783A (en) * 1978-04-28 1979-11-09 Canon Inc Image display device
CN1326936A (zh) * 2000-05-30 2001-12-19 默克专利股份有限公司 离子液体
CN1838469A (zh) * 2006-04-20 2006-09-27 武汉大学 锂－硫电池电解液及其可充锂－硫电池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHANDRASEKARAN K. ET AL.: "Photoelectrochemical Cells Based on Hydrogen-Atom Abstraction and Electron-Transfer Reactions in Solution: Systems Based on Benzophenone, 2-Propanol, Trialkylamines, and Methyl Viologen", J. AM. CHEM. SOC., vol. 103, no. 24, 1981, pages 1270 - 7215, XP055140819 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110204473A (zh) * 2019-05-22 2019-09-06 常州乾艺智能制造科技有限公司 一种用于锂电池的双中心阳离子液体及其制备方法
CN110204473B (zh) * 2019-05-22 2023-03-10 常州乾艺智能制造科技有限公司 一种用于锂电池的双中心阳离子液体及其制备方法

Also Published As

Publication number Publication date
JP5796128B2 (ja) 2015-10-21
EP2752409A1 (en) 2014-07-09
EP2752409B1 (en) 2017-01-11
JP2014525419A (ja) 2014-09-29
US9196424B2 (en) 2015-11-24
CN103732587A (zh) 2014-04-16
CN103732587B (zh) 2015-09-16
US20140166921A1 (en) 2014-06-19
EP2752409A4 (en) 2015-04-29

Similar Documents

Publication Publication Date Title
JP5667328B2 (ja) ２つの中心を有するビス第四級アンモニウム塩のイオン液体、その調製方法及び使用
CN103787981A (zh) 咪唑类离子液体、离子液体电解液及制备方法和应用
CN102952097B (zh) 双中心哌嗪离子液体及其制备方法和应用
CN102952099B (zh) 吡咯类离子液体及其制备方法和应用
WO2013029237A1 (zh) 双中心联吡啶阳离子类离子液体及其制备方法和应用
CN103896828B (zh) 双中心联吡啶类离子液体及其制备方法与电解液及锂离子电池
CN103787996A (zh) 三氮唑类离子液体、离子液体电解液及制备方法和应用
CN102952058B (zh) 马来酰亚胺类离子液体及其制备方法和应用
CN115440506A (zh) 非对称结构环状季铵盐制备方法及其产品和应用
CN113540563B (zh) 一种添加剂以及锂电池电解液的改性方法
CN110204473B (zh) 一种用于锂电池的双中心阳离子液体及其制备方法
CN103450610B (zh) 一种凝胶聚合物电解质膜及其制备方法和用途
CN102952092B (zh) 唑烷类离子液体及其制备方法和应用
CN102952116B (zh) 双中心烟碱离子液体及其制备方法和应用
CN103130783B (zh) 含碳酸酯基团的四氢噻吩类离子液体及其制备方法和应用
CN103130786B (zh) 含碳酸酯基团的唑烷类离子液体及其制备方法和应用
CN111599609B (zh) 一种超级电容器电解液添加剂、电解液及其应用
CN102956917A (zh) 三氮唑离子液体及其制备方法和应用
CN103130778B (zh) 含碳酸酯基团的吡嗪类离子液体及其制备方法和应用
CN103130779B (zh) 含碳酸酯基团的马来酰亚胺类离子液体及其制备方法和应用
CN103787957A (zh) 吡啶类离子液体、离子液体电解液及制备方法和应用
CN104505264B (zh) 一种无卤素螺环季铵盐的合成方法
CN103130764A (zh) 含碳酸酯基团的季铵盐类离子液体及其制备方法和应用
CN102952098B (zh) 吡嗪类离子液体及其制备方法和应用
CN103130765A (zh) 含碳酸酯基团的哌啶类离子液体及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11871780

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2011871780

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2011871780

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 14234384

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2014527454

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE