CN102993120B - Morpholine-containing ionic liquid and preparation method thereof as well as electrolyte and application thereof - Google Patents

Morpholine-containing ionic liquid and preparation method thereof as well as electrolyte and application thereof Download PDF

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CN102993120B
CN102993120B CN201110278317.8A CN201110278317A CN102993120B CN 102993120 B CN102993120 B CN 102993120B CN 201110278317 A CN201110278317 A CN 201110278317A CN 102993120 B CN102993120 B CN 102993120B
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electrolytic solution
ion liquid
methyl
morpholine
organic solvent
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CN102993120A (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 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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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention is applicable to the technical field of new materials and provides morpholine-containing ionic liquid and a preparation method thereof as well as electrolyte and an application thereof, wherein the morpholine-containing ionic liquid can be shown as the structural formula (I) (described in the specification). According to the morpholine-containing ionic liquid provided by the invention, a C-O ether bond is introduced into a positive ion, on the one hand, melting point of the ionic liquid is obviously reduced, and on the other hand, the viscosity of the ionic liquid is reduced; and the electrolyte provided by the embodiment of the invention has higher ionic conductivity by utilizing the low melting point and low viscosity characteristics of the morpholine-containing ionic liquid provided by the invention, and the solubility of the electrolyte is greatly increased, so that an energy space of a battery or capacitor applying the electrolyte is greatly increased.

Description

Containing morpholinium ion liquid and preparation method thereof, electrolytic solution and application thereof
Technical field
The invention belongs to new material technology field, particularly relate to a kind of containing morpholinium ion liquid and preparation method thereof, a kind of electrolytic solution and application thereof.
Background technology
At present, in ultracapacitor or battery, great majority use water quality electrolytic solution.But under high voltage condition, aqueous electrolyte easily decomposes, internal resistance is caused sharply to increase and electrical capacity reduces rapidly.Therefore the decomposition voltage of electrolytic solution is one of key factor limiting its specific energy always.Compared with aqueous electrolyte, organic electrolyte has higher decomposition voltage, and is easy to encapsulation because of its corrosion-free protection question, and available aluminum, as collector electrode and packaged material, significantly reduces material cost.But, organic electrolyte solubleness lower (25 DEG C of solubleness in PC are 1mol/L), solubleness will be lower at lower temperatures, and this improves the space of ultracapacitor specific energy under just constraining low temperature, meanwhile, the problem of electrolyte decomposition low voltage is also constrained.
Summary of the invention
In view of this, the invention provides a kind of containing morpholinium ion liquid and preparation method, containing this electrolytic solution containing morpholinium ion liquid, solve the technical problem of the low and electrolyte decomposition low voltage of organic electrolyte solubleness in prior art.
The present invention is achieved in that
A kind of containing morpholinium ion liquid, there is following structural formula (I):
Wherein, Y is negatively charged ion, is selected from BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -.
And,
A kind of containing morpholinium ion liquid preparation method, comprise the steps:
By N-methylmorpholine and 1: the 1.05-1.2 mixing in molar ratio of methoxy ethoxy methyl halide, heat 20-40 second under microwave irradiation power is 200-300W after, take out stirring reaction to room temperature, repeat this microwave heating and taking-up is stirred to ambient operation more than 3 times, washing reaction liquid, obtain the N-methyl-N-methoxy ethoxyl methyl morpholine halogenide that structural formula (III) represents, reaction formula is:
In reaction formula, RX is methoxy ethoxy methyl halide, wherein, R representation methoxy ethoxyl methyl, X represents halogen, is selected from Cl, Br or I;
The N-methyl-N-methoxy ethoxyl methyl morpholine halogenide represented by this structural formula (III) and inorganic salt solution, carry out ion exchange reaction, and to obtain structural formula be (I) containing morpholinium ion liquid; Reaction formula is expressed as:
In reaction formula, MY represents this inorganic salt; Wherein, M is positively charged ion, is selected from Na +, K +or NH 4 +; Y is negatively charged ion, is selected from BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -.
A kind of electrolytic solution, comprise lithium salts, this electrolytic solution also comprises containing morpholinium ion liquid, should have following structural formula (I) containing morpholinium ion liquid:
Wherein, Y is negatively charged ion, is selected from BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -.
The present invention further provides the application of above-mentioned electrolytic solution in ultracapacitor, lithium ion battery.
The present invention, containing morpholinium ion liquid, by introducing C-O ehter bond in positively charged ion, makes the performance of ionic liquid obtain obvious improvement, on the one hand its fusing point is significantly reduced, and reduces the viscosity of ionic liquid on the other hand; Electrolytic solution of the present invention, by the above-mentioned low melting point containing morpholinium ion liquid and low viscosity characteristics, can ionize fully containing morpholinium ion liquid (even under cryogenic) in electrolytic solution and form positively charged ion and negatively charged ion, achieve embodiment of the present invention electrolytic solution has higher ionic conductivity, simultaneously, owing to containing the lower fusing point of morpholinium ion liquid, lower viscosity, the solubleness of electrolytic solution is promoted greatly, the energy space of the battery or electrical condenser applying this electrolytic solution is improved greatly.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention contains morpholinium ion liquid preparation method schematic flow sheet;
Fig. 2 is the lithium ion battery charging and discharging curve of electrolytic solution prepared by the application embodiment of the present invention 4.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The embodiment of the present invention provides a kind of containing morpholinium ion liquid, has following structural formula (I):
Wherein, Y is negatively charged ion, is selected from BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -.
Particularly, the embodiment of the present invention is containing morpholinium ion liquid, and comprise positively charged ion and negatively charged ion, wherein, cationic structural formula (II) is negatively charged ion is selected from BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -in one;
The embodiment of the present invention, containing morpholinium ion liquid, by introducing C-O ehter bond in positively charged ion, makes the performance of ionic liquid greatly strengthen, and on the one hand its fusing point is significantly reduced, and reduces the viscosity of ionic liquid on the other hand; By reducing fusing point and the viscosity of ionic liquid, improving the low-temperature conductive rate of ionic liquid, significantly promoting this ionic liquid as solvent use or low-temperature performance when using in electrochemistry.
Refer to Fig. 1, it is above-mentioned containing morpholinium ion liquid preparation method schema that Fig. 1 shows the embodiment of the present invention, comprises the steps:
Step S01, preparation N-methyl-N-methoxy oxyethyl group morpholine halogenide
By N-methylmorpholine and 1: the 1.05-1.2 mixing in molar ratio of methoxy ethoxy methyl halide, heat 20-40 second under microwave irradiation power is 200-300W after, take out stirring reaction to room temperature, repeat this microwave heating and taking-up is stirred to ambient operation more than 3 times, washing reaction liquid, obtain the N-methyl-N-methoxy ethoxyl methyl morpholine halogenide that structural formula (III) represents, reaction formula is:
In reaction formula, RX is methoxy ethoxy methyl halide, wherein, R representation methoxy ethoxyl methyl, X represents halogen, is selected from Cl, Br or I;
Step S02, preparation is containing morpholinium ion liquid
The N-methyl-N-methoxy ethoxyl methyl morpholine halogenide represented by this structural formula (III) and inorganic salt solution, carry out ion exchange reaction, and to obtain structural formula be (I) containing morpholinium ion liquid; Reaction formula is expressed as:
In reaction formula, MY represents this inorganic salt; Wherein, M is positively charged ion, is selected from Na +, K +or NH 4 +; Y is negatively charged ion, is selected from BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -.
Particularly, in step S01, this methoxy ethoxy methyl halide (RX) is selected from methoxy ethoxy methyl chloride, methoxy ethoxy monobromethane or methoxy ethoxy methyl iodide, and particularly, R is methoxvethoxvmethvl, and X is chlorine, bromine or iodine; The molar ratio of this morpholine and methoxy ethoxy methyl halide is 1: 1.05-1.2, is preferably 1: 1.2;
This methoxy ethoxy methyl chloride structural formula is:
This methoxy ethoxy monobromethane structural formula is:
This methoxy ethoxy methyl iodide structural formula is:
This step S01 reaction is carried out under microwave heating condition, and the power of this microwave heating is 200-300W, is preferably 240W; Microwave heating time is 20-40 second, is preferably 30 seconds; Taken out from microwave heating equipment by reactant after microwave heating, be stirred to system temperature and be reduced to room temperature, churning time does not limit, such as 15 seconds;
The operation of microwave heating in this step S01, taking-up stirring reaction repeats more than 3 times, until react completely, is preferably 3-6 time;
The process of this step S01 is:
Methoxy ethoxy methyl halide and N-methylmorpholine are added in reactor and mix, stir, obtain mixture, this mixture is put into microwave heating installation microwave heating, heat rear taking-up mixture, stirred, reacted to room temperature, and then put into microwave heating installation and carry out microwave heating, heat rear taking-up mixture, stirred, reacted to room temperature, repeat more than 3 times, be preferably 3-6 time;
After the microwave heating of this step has been reacted, reaction product ethyl acetate is washed more than 3 times, then completely dry in vacuum environment more than 80 DEG C, namely obtain light yellow solid is the N-methyl-N-methoxy ethoxyl methyl morpholine halogenide that formula II I represents.
This step S01 reaction formula is expressed as:
Particularly, in step S02, by ion exchange reaction, change the halide-ions in N-methyl-N-methoxy ethoxyl methyl morpholine halogenide into desired anion, generate target product.Positively charged ion (M in these inorganic salt (MY) +) be selected from Na +, K +or NH 4 +in one, negatively charged ion (Y -) be selected from BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -in one, the array mode of this positively charged ion and negatively charged ion does not limit, such as, NaBF 4, Na (CF 3sO 2) 2n, K PF 6, K CF 3sO 3, NH 4cF 3sO 3;
This step S02 temperature of reaction is room temperature, does not specifically limit, such as 15-30 DEG C, and the reaction times is 8-24 hour, is preferably 8-16 hour; The N-methyl-N-methoxy ethoxyl methyl morpholine halogenide that this formula II I represents and inorganic salt mol ratio are 1: 1, and this reaction is also carried out under agitation, and concrete alr mode does not limit.
After having reacted, reaction product carried out extract, strip, concentrated and dry, be specially, after product dichloromethane extraction will be reacted more than three times, combining extraction liquid, then strips with deionized water, until with saturated silver nitrate aqueous solution titration aqueous phase, till not precipitating generation, collect organic phase (methylene dichloride phase), will concentrate with Rotary Evaporators, then more than 80 DEG C in vacuum environment drying 48 hours, obtain colourless liquid, namely containing morpholinium ion liquid.
The embodiment of the present invention is containing morpholinium ion liquid preparation method, by in preparation N-methyl-N-methoxy ethoxyl methyl morpholine halogenide step, ehter bond (C-O) is introduced in N-methyl-N-methoxy oxyethyl group morpholine halogenide, make prepared greatly strengthening containing morpholinium ion liquid properties, on the one hand its fusing point is significantly reduced, reduce the viscosity of ionic liquid on the other hand; By reducing fusing point and the viscosity of ionic liquid, significantly promote this ionic liquid as solvent use or low-temperature performance when using in electrochemistry.
The embodiment of the present invention provides a kind of electrolytic solution further, comprises lithium salts, and this electrolytic solution also comprises containing morpholinium ion liquid, should have following structural formula (I) containing morpholinium ion liquid:
Wherein, Y is negatively charged ion, is selected from BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -.
Particularly, embodiment of the present invention electrolytic solution, by the above-mentioned low melting point containing morpholinium ion liquid and low viscosity characteristics, can ionize fully containing morpholinium ion liquid (even under cryogenic) in electrolytic solution and form positively charged ion and negatively charged ion, achieve embodiment of the present invention electrolytic solution has higher ionic conductivity, simultaneously, should containing the electrochemical window of morpholinium ion liquid more than 4V, there is good electrochemical stability, be not easy under high voltages to decompose, in higher charging voltage, there is good stability.Meanwhile, owing to containing the lower fusing point of morpholinium ion liquid, lower viscosity, makes the solubleness of electrolytic solution greatly promote, and the energy space of the battery or electrical condenser applying this electrolytic solution is improved greatly.
Particularly, this lithium salts is selected from LiBF4 (LiBF 4), lithium hexafluoro phosphate (LiPF 6) or two (fluoroform sulphonyl) imine lithium (LiTFSI);
Further, this electrolytic solution also comprises organic solvent, this organic solvent is preferably n: 1 with being somebody's turn to do containing morpholinium ion liquid mass ratio, wherein, n is greater than 0, is less than or equal to 100, and this organic solvent is made up of according to volume ratio 2 ~ 3: 1 ~ 3: 1 ~ 2: 1 ~ 1.5 NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC) and propylene carbonate (PC).
The consumption of this lithium salts is make this lithium salts concentration in the electrolytic solution be 0.3-1.2mol/L, and be preferably 1mol/L, this lithium salt is obtained compared with the volume of organic solvent by the molar weight of lithium salts.
The embodiment of the present invention provides above-mentioned preparation method of electrolyte further, comprises the steps:
By lithium salts and above-mentioned containing morpholinium ion liquid mixing, stir and obtain electrolytic solution, following structural formula (I) should be had containing morpholinium ion liquid:
Wherein, Y is negatively charged ion, is selected from BF 4 -, PF 6 -, (CF 3sO 2) 2n -, CF 3sO 3 -.
This is by as follows to lithium salts, organic solvent and the above-mentioned step containing morpholinium ion liquid mixing:
Lithium salts is added to this containing in morpholinium ion liquid, the concentration making lithium salts is 0.3-1.2mol/L, is stirred to lithium salts and dissolves completely, namely obtain electrolytic solution.
If also comprise organic solvent in this electrolytic solution, this electrolytic solution preparation process is as follows:
A: prepare organic solvent
Under oxygen free condition, NSC 11801, Methyl ethyl carbonate, methylcarbonate and propylene carbonate are mixed according to volume ratio 2 ~ 3: 1 ~ 3: 1 ~ 2: 1 ~ 1.5, stir and obtain organic solvent; This oxygen free condition is identical with aforementioned, does not repeat to set forth at this.
B: add containing morpholinium ion liquid in organic solvent
To containing morpholinium ion liquid be added in this organic solvent containing morpholinium ion liquid mass than 0.001-100: 1 with being somebody's turn to do by organic solvent, and temperature being adjusted to 40 DEG C, stirring;
C: add lithium salts;
In the mixing solutions that step B obtains, add lithium salts, the concentration making lithium salts is 0.3-1.2mol/L, is stirred to lithium salts and dissolves completely, namely obtain electrolytic solution.
The embodiment of the present invention provides above-mentioned containing the application of morpholine electrolytic solution in ultracapacitor or lithium ion battery further.
Below in conjunction with specific embodiment, above-mentioned preparation method of electrolyte is described in detail.
Embodiment one
Embodiment of the present invention preparation method of electrolyte, comprises the steps:
Preparation is containing morpholinium ion liquid (N-methoxvethoxvmethvl-N-methylmorpholine a tetrafluoro borate):
By N-methylmorpholine (101g, 1mol) and methoxy ethoxy methyl chloride (130.2g, 1.05mol) mixing, stir, under microwave irradiation power 240W, after heating 30s, after taking-up, stir 15s, repetition like this 3 times, is stirred to room temperature, washs three times by ethyl acetate.Vacuum-drying at 80 DEG C, obtain lurid solid (chlorination N-methoxvethoxvmethvl-N-methylmorpholine), productive rate is 82%;
By this chlorination N-methoxvethoxvmethvl-N-methylmorpholine (112.5g, 0.5mol) and NaBF 4(55g, 0.5mol) is dissolved in 100mL deionized water, stirs 8h and obtain mixed solution at 15 DEG C, and by this mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid, then uses the back extraction of 60mL deionized water until with saturated AgNO at every turn 3till aqueous solution titration aqueous phase produces without precipitation, after methylene dichloride is concentrated with Rotary Evaporators, 80 DEG C of vacuum-drying 48h obtain colourless liquid and N-methoxvethoxvmethvl-N-methylmorpholine a tetrafluoro borate;
H NMR(CDCl 3，400MHz，ppm)：4.68(s，2H)，3.84(m，2H)，3.73(m，2H)，3.62(m，2H)，3.38(m，2H)，3.24(s，3H)，2.95(s，3H)，2.78(m，2H)，2.56(m，2H)；
Prepare electrolytic solution:
At N 2under atmosphere protection, by NSC 11801, Methyl ethyl carbonate, methylcarbonate and propylene carbonate by the volume ratio mixing of 2: 3: 1: 1, stir and obtain organic solvent (referred to as organic solvent eC+EMC+DMC+PC);
By organic solvent eC+EMC+DMC+PCcontain morpholinium ion liquid mass for enter N-methoxvethoxvmethvl-N-methylmorpholine a tetrafluoro borate than 10: 1 in this organic solvent with this, and be heated to 40 DEG C, stir, add LiBF 4, make LiBF 4volumetric molar concentration be 1mol/L, continue stirring and lithium salts dissolved completely, obtain electrolytic solution.
Refer to Fig. 2, the button cell charging and discharging curve of the electrolytic solution of Fig. 2 display application embodiment of the present invention one preparation:
Take Graphene as electrode materials, with embodiment one obtain electrolytic solution for electrolytic solution, be assembled into button cell, CHI660A electrochemical workstation is utilized to carry out constant current charge-discharge test to it, in the electrochemical window of 0 ~ 3.2V, its charging and discharging curve is recorded with the electric current of 1A/g, as can be seen from Figure 2, the electrolytic solution that the embodiment of the present invention one prepares at higher voltages, electrolytic solution does not decompose, there is satisfactory stability, be suitable for the electrolytic solution of ultracapacitor, and there is good stability up to organic electrolyte in the charging voltage of 3.2V.
Embodiment two
Embodiment of the present invention preparation method of electrolyte, comprises the steps:
Preparation is containing morpholinium ion liquid (N-methoxvethoxvmethvl-N-methylmorpholine hexafluorophosphate):
By N-methylmorpholine (101g, 1mol) and methoxy ethoxy monobromethane (184.8g, 1.1mol) mixing, stir, under microwave irradiation power 200W, after heating 40s, take out and stir 10s, repetition like this 4 times, is stirred to room temperature, washs three times by ethyl acetate.Vacuum-drying at 80 DEG C, obtain lurid solid (chlorination N-methoxvethoxvmethvl-N-methylmorpholine), productive rate is 85%;
By this bromination N-methoxvethoxvmethvl-N-methylmorpholine (134.5g, 0.5mol) and (92g, 0.5mol) KPF 6be dissolved in 120mL deionized water, stir 16h and obtain mixed solution at 25 DEG C, by this mixed solution 250mL dichloromethane extraction 4 times, combining extraction liquid, then uses the back extraction of 60mL deionized water until with saturated AgNO at every turn 3till aqueous solution titration aqueous phase produces without precipitation, after methylene dichloride is concentrated with Rotary Evaporators, 80 DEG C of vacuum-drying 48h obtain colourless liquid and N-methoxvethoxvmethvl-N-methylmorpholine hexafluorophosphate;
Prepare electrolytic solution:
At N 2under atmosphere protection, by NSC 11801, Methyl ethyl carbonate, methylcarbonate and propylene carbonate by the volume ratio mixing of 3: 3: 2: 1, stir and obtain organic solvent (referred to as organic solvent eC+EMC+DMC+PC);
By organic solvent eC+EMC+DMC+PCcontain morpholinium ion liquid mass for enter N-methoxvethoxvmethvl-N-methylmorpholine hexafluorophosphate than 1: 100 in this organic solvent with this, and be heated to 40 DEG C, stir, add LiPF 6, make LiPF 6volumetric molar concentration be 0.3mol/L, continue stirring make LiPF 6dissolve completely, obtain electrolytic solution.
Embodiment three
Embodiment of the present invention preparation method of electrolyte, comprises the steps:
Preparation is containing morpholinium ion liquid (two (fluoroform sulphonyl) inferior amine salt of N-methoxvethoxvmethvl-N-methylmorpholine):
By N-methylmorpholine (101g, 1mol) and methoxy ethoxy methyl iodide (259.2g, 1.2mol) mixing, stir, under microwave irradiation power 300W, after heating 20s, take out and stir 10s, repetition like this 6 times, is stirred to room temperature, washs three times by ethyl acetate.Vacuum-drying at 80 DEG C, obtain lurid solid (chlorination N-methoxvethoxvmethvl-N-methylmorpholine), productive rate is 84%;
By this iodate N-methoxvethoxvmethvl-N-methylmorpholine (158.5g, 0.5mol) and (159.5g, 0.5mol) two (fluoroform sulphonyl) imines potassium is dissolved in 150mL deionized water, at 30 DEG C, stir 24h obtain mixed solution, by this mixed solution 250mL dichloromethane extraction 6 times, combining extraction liquid, then uses the back extraction of 60mL deionized water until with saturated AgNO at every turn 3till aqueous solution titration aqueous phase produces without precipitation, after methylene dichloride is concentrated with Rotary Evaporators, 80 DEG C of vacuum-drying 48h obtain colourless liquid and two (fluoroform sulphonyl) inferior amine salt of N-methoxvethoxvmethvl-N-methylmorpholine;
Prepare electrolytic solution:
At N 2under atmosphere protection, by NSC 11801, Methyl ethyl carbonate, methylcarbonate and propylene carbonate by the volume ratio mixing of 2: 1: 1: 1.5, stir and obtain organic solvent (referred to as organic solvent eC+EMC+DMC+PC);
By organic solvent eC+EMC+DMC+PCmorpholinium ion liquid mass is contained for entering two (fluoroform sulphonyl) inferior amine salt of N-methoxvethoxvmethvl-N-methylmorpholine in this organic solvent than 1: 10 with this, and be heated to 40 DEG C, stir, add LiTFSI, the volumetric molar concentration of LiTFSI is made to be 0.7mol/L, continuing stirring makes LiTFSI dissolve completely, obtains electrolytic solution.
Embodiment four
The embodiment of the present invention four preparation method of electrolyte, with reference to embodiment one, wherein, is preparing NaBF in ionic liquid 4(55g, 0.5mol) changes (86g, 0.5mol) trifluoromethanesulfonic acid sodium CF into 3sO 3na; Preparing in electrolytic solution step, by organic solvent eC+EMC+DMC+PCcontain morpholinium ion liquid mass for enter N-methoxvethoxvmethvl-N-methylmorpholine fluoroform sulphonate than 1: 1 in this organic solvent with this, and be heated to 40 DEG C, stir, add LiCF 3sO 3, make LiCF 3sO 3volumetric molar concentration be 0.9mol/L, continue stirring make LiCF 3sO 3dissolve completely, obtain electrolytic solution.
Embodiment five
The embodiment of the present invention five preparation method of electrolyte, with reference to embodiment one, wherein, preparing in electrolytic solution step, by organic solvent eC+EMC+DMC+PCcontain morpholinium ion liquid mass for enter N-methoxvethoxvmethvl-N-methylmorpholine a tetrafluoro borate than 100: 1 in this organic solvent with this, and be heated to 40 DEG C, stir, add LiBF 4, make LiBF 4volumetric molar concentration be 1.2mol/L, continue stirring and lithium salts dissolved completely, obtain electrolytic solution.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1., containing a morpholinium ion liquid, there is following structure formula I:
Wherein, Y is negatively charged ion, is selected from BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -.
2., containing a morpholinium ion liquid preparation method, comprise the steps:
By N-methylmorpholine and the 1:1.05-1.2 mixing in molar ratio of methoxy ethoxy methyl halide, heat 20-40 second under microwave irradiation power is 200-300W after, take out stirring reaction to room temperature, repeat described microwave heating and take out the operation more than 3 times being stirred to room temperature, washing reaction liquid, obtain the N-methyl-N-methoxy ethoxyl methyl morpholine halogenide that structure formula III represents, reaction formula is:
In reaction formula, RX is methoxy ethoxy methyl halide, wherein, R representation methoxy ethoxyl methyl, X represents halogen, is selected from Cl, Br or I;
The N-methyl-N-methoxy ethoxyl methyl morpholine halogenide represented by described structure formula III and inorganic salt solution carry out ion exchange reaction, change the halide-ions in N-methyl-N-methoxy ethoxyl methyl morpholine halogenide into desired anion, to obtain structural formula be (I) containing morpholinium ion liquid; Reaction formula is expressed as:
In reaction formula, MY represents described inorganic salt; Wherein, M is positively charged ion, is selected from Na +, K +or NH 4 +; Y is negatively charged ion, is selected from BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -.
3. as claimed in claim 2 containing morpholinium ion liquid preparation method, it is characterized in that, in described carry out microwave radiation heating process, radiation power is 240W, and the radiation heating time is 30 seconds.
4. as claimed in claim 2 containing morpholinium ion liquid preparation method, it is characterized in that, described N-methyl-N-methoxy ethoxyl methyl morpholine halogenide and described inorganic salt mol ratio are 1:1.
5. an electrolytic solution, comprises lithium salts, it is characterized in that, described electrolytic solution also comprises containing morpholinium ion liquid, and described have following structure formula I containing morpholinium ion liquid:
Wherein, Y is negatively charged ion, is selected from BF 4 -, PF 6 -, (CF 3sO 2) 2n -or CF 3sO 3 -.
6. electrolytic solution as claimed in claim 5, it is characterized in that, described electrolytic solution also comprises organic solvent, and described organic solvent contains morpholinium ion liquid mass than being n:1 with described,
Wherein, n is greater than 0, is less than or equal to 100; Described lithium salts concentration is in the electrolytic solution 0.3-1.2mol/L.
7. electrolytic solution as claimed in claim 6, is characterized in that, described organic solvent contains morpholinium ion liquid mass than being 10:1 with described.
8. electrolytic solution as claimed in claim 7, it is characterized in that, described organic solvent is made up of according to volume ratio 2 ~ 3:1 ~ 3:1 ~ 2:1 ~ 1.5 NSC 11801, Methyl ethyl carbonate, methylcarbonate and propylene carbonate.
9. electrolytic solution as claimed in claim 5, is characterized in that, described lithium salts be selected from LiBF4, lithium hexafluoro phosphate, two (fluoroform sulphonyl) imine lithium one or more.
10. the application of the electrolytic solution as described in any one of claim 5-9 in ultracapacitor or lithium ion battery.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060210876A1 (en) * 2005-03-17 2006-09-21 Takashi Kuboki Electrochemical device
CN1950338A (en) * 2004-03-05 2007-04-18 霍尼韦尔国际公司 Polymer ionic electrolytes
CN101085762A (en) * 2007-07-05 2007-12-12 上海交通大学 Ionic liquid containing N-cyanoalkyl-N-alkylmorphinone cation and preparation method thereof
CN102015666A (en) * 2008-04-29 2011-04-13 默克专利有限公司 Reactive ionic liquids

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1950338A (en) * 2004-03-05 2007-04-18 霍尼韦尔国际公司 Polymer ionic electrolytes
US20060210876A1 (en) * 2005-03-17 2006-09-21 Takashi Kuboki Electrochemical device
CN101085762A (en) * 2007-07-05 2007-12-12 上海交通大学 Ionic liquid containing N-cyanoalkyl-N-alkylmorphinone cation and preparation method thereof
CN102015666A (en) * 2008-04-29 2011-04-13 默克专利有限公司 Reactive ionic liquids

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