CN102952098B - Pyrazine ionic liquid and its preparation method and application - Google Patents

Pyrazine ionic liquid and its preparation method and application Download PDF

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CN102952098B
CN102952098B CN201110253200.4A CN201110253200A CN102952098B CN 102952098 B CN102952098 B CN 102952098B CN 201110253200 A CN201110253200 A CN 201110253200A CN 102952098 B CN102952098 B CN 102952098B
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pyrazine
ionic liquid
methoxvethoxvmethvl
lithium
hours
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CN102952098A (en
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周明杰
刘大喜
王要兵
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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Abstract

The present invention relates to a kind of pyrazine ionic liquid, its chemical structural formula is as follows: wherein, Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -, (FSO 2) 2n -or CF 3sO 3 -.This pyrazine ionic liquid room temperature or close to the condition of room temperature under be composed entirely of ions, specific conductivity is high, fusing point is low, electrochemical window is wide, non-volatile, non-combustible, Heat stability is good and nontoxic, particularly decomposition voltage is high, be difficult under high voltage condition decompose, thus the ultracapacitor or field of lithium ion battery that manufacture height ratio capacity can be applied in.In addition, the invention still further relates to preparation method and the application thereof of this pyrazine ionic liquid.

Description

Pyrazine ionic liquid and its preparation method and application
[technical field]
The present invention relates to a kind of capacitor electrolyte field, particularly relate to a kind of pyrazine ionic liquid and preparation method thereof, also relate to simultaneously a kind of use this pyrazine ionic liquid electrolytic solution and compound method and ultracapacitor.
[background technology]
Ultracapacitor is a kind of novel energy storage component between rechargeable battery and electrical condenser, have that volume is little, capacity is large, charge velocities is fast, have extended cycle life, discharging efficiency is high, operating temperature range is wide, the advantage such as good reliability and contaminant-free maintenance-free, be a kind of novel, efficient, practical energy accumulating device, be thus widely used in the AC-battery power source etc. of military field, device for mobile communication, computer and electromobile.The energy that ultracapacitor stores be proportional to applied voltage square, thus, improve the specific energy that the voltage that applies can increase considerably ultracapacitor.But under high voltage condition, traditional aqueous electrolyte easily decomposes, cause that the internal resistance of electrical condenser sharply increases, electrical capacity reduces rapidly.
[summary of the invention]
Based on this, be necessary to provide one not easily to decompose, the good pyrazine ionic liquid of stability and preparation method thereof.
A kind of pyrazine ionic liquid, chemical structural formula is as follows:
Wherein, Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -, (FSO 2) 2n -or CF 3sO 3 -.
This pyrazine ionic liquid room temperature or close to the condition of room temperature under be composed entirely of ions, specific conductivity is high, fusing point is low, electrochemical window is wide, non-volatile, non-combustible, Heat stability is good and nontoxic, particularly decomposition voltage is high, be difficult under high voltage condition decompose, thus the ultracapacitor or field of lithium ion battery that manufacture height ratio capacity can be applied in.
A preparation method for pyrazine ionic liquid, comprises the steps:
Step one: pyrazine and methoxy ethoxy methyl halide to be reacted in molar ratio at 1: 1 ~ 1: 1.2, generates methoxvethoxvmethvl-pyrazine halogeno salt;
Step 2: described methoxvethoxvmethvl-pyrazine halogeno salt and the inorganic salt containing organic anion are in deionized water carried out ion exchange reaction in molar ratio at 1: 1, and generate described pyrazine ionic liquid, its chemical structural formula is as follows:
Wherein, Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -, (FSO 2) 2n -or CF 3sO 3 -.
In a preferred embodiment, described methoxy ethoxy methyl halide is methoxy ethoxy methyl chloride or methoxy ethoxy methyl bromide; Described inorganic salt cationic is Na +, K +or NH 4 +.
In a preferred embodiment; step one comprises the steps: pyrazine to mix with methoxy ethoxy methyl halide; under protection of inert gas; be warming up to 60 ~ 80 DEG C; room temperature is cooled to after stirring reaction; dry with ethyl acetate washing final vacuum, obtain methoxvethoxvmethvl-pyrazine halogeno salt.
In a preferred embodiment, step 2 to comprise the steps: methoxvethoxvmethvl-pyrazine halogeno salt and the inorganic salt containing organic anion in deionized water, carry out ion exchange reaction under room temperature after, reaction mixture dichloromethane extraction, obtain methylene dichloride phase, again described methylene dichloride deionized water is stripped, until with saturated AgNO 3aqueous solution titration aqueous phase is to producing without precipitation, and finally concentrated by the methylene dichloride phase rotary evaporation after reextraction, vacuum-drying obtains described pyrazine ionic liquid.
The large-scale industrial production that above-mentioned preparation process efficiency is high, pollution-free, be conducive to pyrazine ionic liquid.
Meanwhile, there is a need to provide a kind of use above-mentionedly not easily to decompose, the electrolytic solution of the good ionic liquid of stability and compound method thereof and ultracapacitor.
A kind of electrolytic solution, comprises pyrazine ionic liquid, lithium salts and carbonate based organic solvent,
Wherein, the structural formula of described pyrazine ionic liquid is as follows:
Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -, (FSO 2) 2n -or CF 3sO 3 -;
In electrolytic solution, the concentration of lithium salts is 0.3-1.2mol/L, is preferably 1mol/L;
Carbonate based organic solvent is less than or equal to 100 than scope for being more than or equal to 0 with the quality of pyrazine ionic liquid.
In a preferred embodiment, described lithium salts is at least one in LiBF4, lithium hexafluoro phosphate, trifluoromethanesulfonic acid lithium, two (fluoroform sulphonyl) imine lithium and two (fluorine sulphonyl) imine lithium.
In a preferred embodiment, described carbonate based organic solvent is at least one in NSC 11801, Methyl ethyl carbonate, methylcarbonate and diethyl carbonate.
A compound method for electrolytic solution, comprises the steps:
Get NSC 11801, Methyl ethyl carbonate, at least one in methylcarbonate and diethyl carbonate is as carbonate based organic solvent, be more than or equal to 0 ratio being less than or equal to 100 in the mass ratio of carbonate based organic solvent and pyrazine ionic liquid and add pyrazine ionic liquid in described carbonate based organic solvent, be uniformly mixed at 40 DEG C, LiBF4 is added again in the organic phase mixed, lithium hexafluoro phosphate, trifluoromethanesulfonic acid lithium, two (fluoroform sulphonyl) imine lithium and at least one lithium salts in two (fluorine sulphonyl) imine lithium, stir until lithium salts dissolves completely, obtain described electrolytic solution, wherein, in organic phase, the concentration of lithium salts is 0.3-1.2mol/L, be preferably 1mol/L.
Electrolytic conductivity containing pyrazine ionic liquid is high, fusing point is low, the decomposition voltage of Heat stability is good, particularly electrolytic solution is high, can be widely used in the preparation field of ultracapacitor, obtains the ultracapacitor of high-energy-density.Meanwhile, its process for preparation is simple, uses cheaper starting materials to be easy to get, can large-scale industrial production.
A kind of ultracapacitor, the electrolytic solution of described ultracapacitor comprises the ionic liquid with following structure:
Wherein, Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -, (FSO 2) 2n -or CF 3sO 3 -.
By test, use the above-mentioned ultracapacitor containing pyrazine ionic liquid to have higher charging/discharging voltage, and under high charge-discharge voltage conditions, electrolytic solution is highly stable.
[accompanying drawing explanation]
Fig. 1 is the constant current charge-discharge test curve figure of the ultracapacitor using embodiment 6 obtained.
[embodiment]
Mainly in conjunction with the drawings and the specific embodiments pyrazine ionic liquid and its preparation method and application is described in further detail below.
The pyrazine ionic liquid of present embodiment, chemical structural formula is as follows:
Wherein, Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -, (FSO 2) 2n -or CF 3sO 3 -.
This pyrazine ionic liquid room temperature or close to the condition of room temperature under be composed entirely of ions, specific conductivity is high, fusing point is low, electrochemical window is wide, non-volatile, non-combustible, Heat stability is good and nontoxic, particularly decomposition voltage is high, be difficult under high voltage condition decompose, thus the ultracapacitor or field of lithium ion battery that manufacture height ratio capacity can be applied in.
A preparation method for above-mentioned pyrazine ionic liquid, preparation flow is as follows:
Pyrazine → methoxvethoxvmethvl-pyrazine halogeno salt → pyrazine ionic liquid
Wherein RX represents haloalkane or containing in the inorganic salt MY of organic anion, positively charged ion M +can be Na +, K +and NH 4 +deng; Negatively charged ion Y -can be BF 4 -, PF 6 -, (CF 3sO 2) 2n -, CF 3sO 3 -or (FSO 2) 2n -deng.
Specifically comprise the steps:
Step S1: pyrazine and methoxy ethoxy methyl halide to be reacted in molar ratio at 1: 1 ~ 1: 1.2, generates methoxvethoxvmethvl-pyrazine halogeno salt.
Specific as follows: pyrazine and methoxy ethoxy methyl halide to be mixed in molar ratio at 1: 1 ~ 1: 1.2; under protection of inert gas, be warming up to 60 ~ 80 DEG C, after stirring reaction, be cooled to room temperature; dry with ethyl acetate washing final vacuum, obtain methoxvethoxvmethvl-pyrazine halogeno salt.
Step S2: methoxvethoxvmethvl-pyrazine halogeno salt and the inorganic salt containing organic anion are in deionized water carried out ion exchange reaction in molar ratio at 1: 1, generates pyrazine ionic liquid.
Specific as follows: by methoxvethoxvmethvl-pyrazine halogeno salt and the inorganic salt containing organic anion in deionized water, carry out ion exchange reaction under room temperature after, reaction mixture dichloromethane extraction, obtain methylene dichloride phase, again methylene dichloride deionized water is stripped, until with saturated AgNO 3aqueous solution titration aqueous phase is to producing without precipitation, and finally concentrated by the methylene dichloride phase rotary evaporation after reextraction, vacuum-drying obtains pyrazine ionic liquid.
The large-scale industrial production that above-mentioned preparation process efficiency is high, pollution-free, be conducive to pyrazine ionic liquid.
Meanwhile, present invention also offers a kind of use above-mentionedly not easily to decompose, the electrolytic solution of the good ionic liquid of stability and compound method thereof and ultracapacitor.
The electrolytic solution of one embodiment comprises pyrazine ionic liquid, lithium salts and carbonate based organic solvent,
Wherein, the structural formula of pyrazine ionic liquid is as follows:
Y -for BF 4 -, PF 6 -, (CF 3sO 2) 2n -, (FSO 2) 2n -or CF 3sO 3 -.
Lithium salts is preferably at least one in LiBF4, lithium hexafluoro phosphate, trifluoromethanesulfonic acid lithium, two (fluoroform sulphonyl) imine lithium and two (fluorine sulphonyl) imine lithium, and the concentration of lithium salts is 0.3-1.2mol/L in electrolytic solution, be preferably 1mol/L;
Carbonate based organic solvent is preferably at least one in NSC 11801, Methyl ethyl carbonate, methylcarbonate and diethyl carbonate, and carbonate based organic solvent is less than or equal to 100 than scope for being more than or equal to 0 with the quality of pyrazine ionic liquid.
The process for preparation of this electrolytic solution, comprises the steps:
Get NSC 11801, Methyl ethyl carbonate, at least one in methylcarbonate and diethyl carbonate is as carbonate based organic solvent, be more than or equal to 0 ratio being less than or equal to 100 in the mass ratio of carbonate based organic solvent and pyrazine ionic liquid and add pyrazine ionic liquid in carbonate based organic solvent, be uniformly mixed at 40 DEG C, LiBF4 is added again in the organic phase mixed, lithium hexafluoro phosphate, trifluoromethanesulfonic acid lithium, two (fluoroform sulphonyl) imine lithium and at least one lithium salts in two (fluorine sulphonyl) imine lithium, stir until lithium salts dissolves completely, obtain electrolytic solution, wherein, in organic phase, the concentration of lithium salts is 0.3-1.2mol/L, be preferably 1mol/L.
Electrolytic conductivity containing pyrazine ionic liquid is high, fusing point is low, the decomposition voltage of Heat stability is good, particularly electrolytic solution is high, can be widely used in the preparation field of ultracapacitor, obtains the ultracapacitor of high-energy-density.Meanwhile, its process for preparation is simple, uses cheaper starting materials to be easy to get, can large-scale industrial production.
By test, use the above-mentioned ultracapacitor prepared containing pyrazine ionic liquid to have higher charging/discharging voltage, and under high charge-discharge voltage conditions, electrolytic solution is highly stable.
Be below specific embodiment part:
Salt containing organic anion in following examples mainly represents with sodium salt and sylvite, in other embodiments, can also use corresponding ammonium salt, lithium salts etc.; Atmosphere of inert gases with nitrogen and argon atmosphere for representative.
The synthesis of pyrazine ionic liquid
The synthesis of embodiment 1:1-methoxvethoxvmethvl pyrazine a tetrafluoro borate
In the flask of 250mL, add the pyrazine of 80g, 1mol and the methoxy ethoxy methyl chloride of 136.4g, 1.1mol respectively, under nitrogen atmosphere, be warming up to 60 DEG C, stirring reaction 72 hours.Leave standstill cooling, wash three times by ethyl acetate.Vacuum-drying at 80 DEG C, obtains lurid solid, i.e. 1-methoxvethoxvmethvl pyrazine villaumite, and yield is 81%.
102g is added, 0.5mol chlorination 1-methoxvethoxvmethvl pyrazine, 55g, 0.5mol NaBF in 500mL flask 4with 150mL deionized water, at room temperature stir 24 hours.After having reacted, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid.Then strip with 60mL deionized water until with saturated AgNO at every turn 3till aqueous solution titration aqueous phase produces without precipitation.After the methylene dichloride Rotary Evaporators obtained is concentrated, 80 DEG C of vacuum-dryings obtain lurid liquid in 48 hours, i.e. 1-methoxvethoxvmethvl pyrazine a tetrafluoro borate, and its hydrogen modal data is as follows:
1H NMR(CDCl3，400MHz，ppm)：8.78(d，2H)，8.65(d，2H)，5.92(s，2H)，3.84(m，2H)，3.38(m，2H)，3.24(s，3H).
The synthesis of embodiment 2:1-methoxvethoxvmethvl pyrazine hexafluorophosphate
In the flask of 250mL, add the pyrazine of 81g, 1mol and the methoxy ethoxy monobromethane of 184.8g, 1.2mol respectively, under argon atmosphere, be warming up to 80 DEG C, stirring reaction 48 hours.Leave standstill cooling, wash three times by ethyl acetate.Vacuum-drying at 80 DEG C, obtains lurid solid, i.e. 1-methoxvethoxvmethvl pyrazine bromine salt, and yield is 83%.
0.5mol1-methoxvethoxvmethvl pyrazine bromine salt, 92g, 0.5molKPF is added in 500mL flask 6with 100mL deionized water, at room temperature stir 8 hours.After having reacted, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid.Then strip with 60mL deionized water until with saturated AgNO at every turn 3till aqueous solution titration aqueous phase produces without precipitation.After the methylene dichloride Rotary Evaporators obtained is concentrated, 80 DEG C of vacuum-dryings obtain colourless liquid in 48 hours, i.e. 1-methoxvethoxvmethvl pyrazine hexafluorophosphate.
The proton nmr spectra test result of 1-methoxvethoxvmethvl pyrazine hexafluorophosphate prepared by the present embodiment is as follows:
1H NMR(CDCl3，400MHz，ppm)：8.79(d，2H)，8.67(d，2H)，5.93(s，2H)，3.85(m，2H)，3.38(m，2H)，3.25(s，3H).
The synthesis of embodiment 3:1-methoxy ethoxy pyrazine fluoroform sulfimide salt
The synthesis of 1-methoxvethoxvmethvl pyrazine villaumite is with embodiment 1.
In 500mL flask, add 102.5g, 0.5mol 1-methoxvethoxvmethvl pyrazine villaumite, 159.5g, 0.5mol fluoroform sulfimide potassium TFSI-K and 125mL deionized water, at room temperature stir 16 hours.After having reacted, mixed solution 250mL dichloromethane extraction 2 times, combining extraction liquid.Then strip with 60mL deionized water until with saturated AgNO at every turn 3till aqueous solution titration aqueous phase produces without precipitation.After the methylene dichloride Rotary Evaporators obtained is concentrated, 80 DEG C of vacuum-dryings obtain colourless liquid in 48 hours, i.e. 1-methoxy ethoxy pyrazine fluoroform sulfimide salt.
The proton nmr spectra test result of 1-methoxy ethoxy pyrazine fluoroform sulfimide salt prepared by the present embodiment is as follows:
1H NMR(CDCl3，400MHz，ppm)：8.80(d，2H)，8.68(d，2H)，5.93(s，2H)，3.85(m，2H)，3.39(m，2H)，3.26(s，3H).
The synthesis of embodiment 4:1-methoxy ethoxy pyrazine fluoroform sulphonate
The synthesis of 1-methoxvethoxvmethvl pyrazine bromine salt is with embodiment 2.
0.5mol 1-methoxvethoxvmethvl pyrazine bromine salt, 86g, 0.5molCF is added in 500mL flask 3sO 3na and 130mL deionized water, at room temperature stirs 20 hours.After having reacted, mixed solution 250mL dichloromethane extraction 4 times, combining extraction liquid.Then strip with 60mL deionized water until with saturated AgNO at every turn 3till aqueous solution titration aqueous phase produces without precipitation.The methylene dichloride Rotary Evaporators obtained concentrates, and obtains water white liquid, i.e. 1-methoxy ethoxy pyrazine fluoroform sulphonate after 80 DEG C of vacuum-drying 48h.
The proton nmr spectra test result of 1-methoxy ethoxy pyrazine fluoroform sulphonate prepared by the present embodiment is as follows:
1H NMR(CDCl3，400MHz，ppm)：8.79(d，2H)，8.68(d，2H)，5.92(s，2H)，3.85(m，2H)，3.39(m，2H)，3.25(s，3H).
The synthesis of two (fluorine sulphonyl) inferior amine salt of embodiment 5:1-methoxvethoxvmethvl pyrazine
Detailed preparation process, only need by 55g, 0.5mol NaBF with embodiment 1 4be changed to the 93.5g of equimolar amount, two (fluorine sulphonyl) imines potassium (FSO of 0.5mol 2) 2nK.
The proton nmr spectra test result of two (fluorine sulphonyl) inferior amine salt of 1-methoxvethoxvmethvl pyrazine prepared by the present embodiment is as follows:
1H NMR(CDCl3，400MHz，ppm)：8.78(d，2H)，8.67(d，2H)，5.93(s，2H)，3.86(m，2H)，3.38(m，2H)，3.26(s，3H).
Electrolyte quota containing pyrazine ionic liquid:
Embodiment 6
Under nitrogen atmosphere protection, NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), diethyl carbonate (DEC) are configured to organic solvent (referred to as mixed solvent with the volume ratio of 2: 3: 1: 1 eC+EMC+DMC+DEC).Then mixed solvent is compared according to quality eC+EMC+DMC+DEC: pyrazine ionic liquid be 10: 1 proportioning add the obtained 1-methoxvethoxvmethvl pyrazine tetrafluoroborate ion liquid of embodiment 1, and be heated to 40 DEG C of stirrings and obtain uniform organic phase.Finally add LiBF 4, make the volumetric molar concentration of lithium salts in electrolytic solution be that 1mol/L is (namely based on the volume V of organic phase eC+EMC+DMC+DEC+ Pyrazine ionic liquid bodydecide the consumption of lithium salts), continue stirring and lithium salts is dissolved completely, thus obtain target organic electrolyte.
Take Graphene as electrode materials, the target organic electrolyte obtained with the present embodiment is electrolytic solution, be assembled into button ultracapacitor, CHI660A electrochemical workstation is utilized to carry out constant current charge-discharge test to it, in the electrochemical window of 0 ~ 2.8V, its charging and discharging curve is recorded, as shown in Figure 1 with the electric current of 1A/g.As seen from Figure 1, the charging and discharging curve of this ultracapacitor is comparatively stable, illustrates that up under the discharge voltage condition of 2.8V, capacitor performance is still stablized, thus the electrolyte decomposition voltage containing methoxvethoxvmethvl-pyrazine tetrafluoroborate ion liquid is high, stability is better.
Embodiment 7
Under argon atmosphere protection, add the 1-methoxvethoxvmethvl pyrazine tetrafluoroborate ion liquid that 100mL embodiment 1 is obtained, and be heated to 40 DEG C of stirrings, then add LiSO 3cF 3, make the volumetric molar concentration of lithium salts be 0.3mol/L, continue stirring and lithium salts is dissolved completely, thus obtain target organic electrolyte.
Embodiment 8
Under nitrogen atmosphere protection, NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), diethyl carbonate (DEC) are configured to organic solvent (referred to as mixed solvent with the volume ratio of 2: 3: 1: 1 eC+EMC+DMC+DEC).Then mixed solvent is compared according to quality eC+EMC+DMC+DEC: pyrazine ionic liquid be 1: 100 proportioning add above-mentioned obtained 1-methoxvethoxvmethvl pyrazine phosphofluoric acid ionic liquid, and be heated to 40 DEG C of stirrings and obtain uniform organic phase.Finally add LiPF 6, make the volumetric molar concentration of lithium salts in electrolytic solution be 0.5mol/L, continue stirring and lithium salts is dissolved completely, thus obtain target organic electrolyte.
Embodiment 9
Under nitrogen atmosphere protection, NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), diethyl carbonate (DEC) are configured to organic solvent (referred to as mixed solvent with the volume ratio of 2: 3: 1: 1 eC+EMC+DMC+DEC).Then mixed solvent is compared according to quality eC+EMC+DMC+DEC: pyrazine ionic liquid be 1: 10 proportioning add above-mentioned obtained 1-methoxy ethoxy pyrazine fluoroform sulfimide ionic liquid, and be heated to 40 DEG C of stirrings and obtain uniform organic phase.Finally add LiTFSI, make the volumetric molar concentration of lithium salts in electrolytic solution be 0.7mol/L, continue stirring and lithium salts is dissolved completely, thus obtain target organic electrolyte.
Embodiment 10
At N 2(or Ar 2) atmosphere protection under, NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), diethyl carbonate (DEC) are configured to organic solvent (referred to as mixed solvent with the volume ratio of 2: 3: 1: 1 eC+EMC+DMC+DEC).Then mixed solvent is compared according to quality eC+EMC+DMC+DEC: pyrazine ionic liquid be 1: 1 proportioning add above-mentioned obtained 1-methoxy ethoxy pyrazine trifluoromethanesulfonic acid ionic liquid, and be heated to 40 DEG C of stirrings and obtain uniform organic phase.Finally add a certain amount of lithium salts (as LiBF 4, LiPF 6, LiSO 3cF 3, LiTFSI, LiFSI), make the volumetric molar concentration of lithium salts be that 0.9mol/L is (based on the volume V of organic phase eC+EMC+DMC+DEC+ pyrazine ionic liquiddecide the consumption of lithium salts), continue stirring and lithium salts is dissolved completely, thus obtain target organic electrolyte.
Embodiment 11
Under argon atmosphere protection, NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), diethyl carbonate (DEC) are configured to organic solvent (referred to as mixed solvent with the volume ratio of 2: 3: 1: 1 eC+EMC+DMC+DEC).Then mixed solvent is compared according to quality eC+EMC+DMC+DEC: pyrazine ionic liquid be 40: 1 proportioning add two (fluorine sulphonyl) the inferior amine salt ionic liquid of above-mentioned obtained 1-methoxvethoxvmethvl pyrazine, and be heated to 40 DEG C of stirrings and obtain uniform organic phase.Finally add LiFSI, make the volumetric molar concentration of lithium salts in electrolytic solution be 1mol/L, continue stirring and lithium salts is dissolved completely, thus obtain target organic electrolyte.
Embodiment 12
Under nitrogen atmosphere protection, NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), diethyl carbonate (DEC) are configured to organic solvent (referred to as mixed solvent with the volume ratio of 2: 3: 1: 1 eC+EMC+DMC+DEC).Then mixed solvent is compared according to quality eC+EMC+DMC+DEC: pyrazine ionic liquid be 70: 1 proportioning add above-mentioned obtained 1-methoxvethoxvmethvl pyrazine tetrafluoroborate ion liquid, and be heated to 40 DEG C of stirrings and obtain uniform organic phase.Finally add LiBF 4, make the volumetric molar concentration of lithium salts in electrolytic solution be 1.1mol/L, continue stirring and lithium salts is dissolved completely, thus obtain target organic electrolyte.
Embodiment 13
Under argon atmosphere protection, NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), diethyl carbonate (DEC) are configured to organic solvent (referred to as mixed solvent with the volume ratio of 2: 3: 1: 1 eC+EMC+DMC+DEC).Then mixed solvent is compared according to quality eC+EMC+DMC+DEC: pyrazine ionic liquid be 100: 1 proportioning add above-mentioned obtained 1-methoxvethoxvmethvl pyrazine phosphofluoric acid ionic liquid, and be heated to 40 DEG C of stirrings and obtain uniform organic phase.Finally add LiPF 6, make the volumetric molar concentration of lithium salts in electrolytic solution be 1.2mol/L, continue stirring and lithium salts is dissolved completely, thus obtain target organic electrolyte.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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 (2)

1. a preparation method for pyrazine ionic liquid, is characterized in that, comprises the steps:
In the flask of 250mL, add the pyrazine of 80g, 1mol and the methoxy ethoxy methyl chloride of 136.4g, 1.1mol respectively, under nitrogen atmosphere, be warming up to 60 DEG C, stirring reaction 72 hours; Leave standstill cooling, wash three times by ethyl acetate; Vacuum-drying at 80 DEG C, obtains lurid solid, i.e. 1-methoxvethoxvmethvl pyrazine villaumite;
102g is added, 0.5mol chlorination 1-methoxvethoxvmethvl pyrazine, 55g, 0.5mol NaBF in 500mL flask 4with 150mL deionized water, at room temperature stir 24 hours; After having reacted, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid; Then strip with 60mL deionized water until with saturated AgNO at every turn 3till aqueous solution titration aqueous phase produces without precipitation; After the methylene dichloride Rotary Evaporators obtained is concentrated, 80 DEG C of vacuum-dryings obtain lurid liquid in 48 hours, i.e. 1-methoxvethoxvmethvl pyrazine a tetrafluoro borate.
2. a compound method for electrolytic solution, is characterized in that, comprises the steps:
In the flask of 250mL, add the pyrazine of 80g, 1mol and the methoxy ethoxy methyl chloride of 136.4g, 1.1mol respectively, under nitrogen atmosphere, be warming up to 60 DEG C, stirring reaction 72 hours; Leave standstill cooling, wash three times by ethyl acetate; Vacuum-drying at 80 DEG C, obtains lurid solid, i.e. 1-methoxvethoxvmethvl pyrazine villaumite;
102g is added, 0.5mol chlorination 1-methoxvethoxvmethvl pyrazine, 55g, 0.5mol NaBF in 500mL flask 4with 150mL deionized water, at room temperature stir 24 hours; After having reacted, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid; Then strip with 60mL deionized water until with saturated AgNO at every turn 3till aqueous solution titration aqueous phase produces without precipitation; After the methylene dichloride Rotary Evaporators obtained is concentrated, 80 DEG C of vacuum-dryings obtain lurid liquid in 48 hours, i.e. pyrazine ionic liquid: 1-methoxvethoxvmethvl pyrazine a tetrafluoro borate;
Get NSC 11801, Methyl ethyl carbonate, at least one in methylcarbonate and diethyl carbonate is as carbonate based organic solvent, be greater than 0 ratio being less than or equal to 100 in the mass ratio of carbonate based organic solvent and pyrazine ionic liquid and add pyrazine ionic liquid in described carbonate based organic solvent, be uniformly mixed at 40 DEG C, LiBF4 is added again in the organic phase mixed, lithium hexafluoro phosphate, trifluoromethanesulfonic acid lithium, two (fluoroform sulphonyl) imine lithium and at least one lithium salts in two (fluorine sulphonyl) imine lithium, stir until lithium salts dissolves completely, obtain described electrolytic solution, wherein, in organic phase, the concentration of lithium salts is 0.3-1.2mol/L.
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CN101516829A (en) * 2006-09-19 2009-08-26 大塚化学株式会社 Method for producing high-purity quaternary ammonium salt
CN101640291A (en) * 2008-07-29 2010-02-03 三星Sdi株式会社 Electrolyte and lithium ion secondary battery including the same
CN101679292A (en) * 2007-06-12 2010-03-24 日宝化学株式会社 Ionic liquid and method for producing the same
CN101918368A (en) * 2007-12-14 2010-12-15 巴斯夫欧洲公司 Method for improving the hydrolysis stability of ionic liquids

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101516829A (en) * 2006-09-19 2009-08-26 大塚化学株式会社 Method for producing high-purity quaternary ammonium salt
CN101679292A (en) * 2007-06-12 2010-03-24 日宝化学株式会社 Ionic liquid and method for producing the same
CN101918368A (en) * 2007-12-14 2010-12-15 巴斯夫欧洲公司 Method for improving the hydrolysis stability of ionic liquids
CN101640291A (en) * 2008-07-29 2010-02-03 三星Sdi株式会社 Electrolyte and lithium ion secondary battery including the same

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