CN103833677A - Pyrrole ionic liquid, and preparation method and application thereof - Google Patents
Pyrrole ionic liquid, and preparation method and application thereof Download PDFInfo
- Publication number
- CN103833677A CN103833677A CN201210486689.4A CN201210486689A CN103833677A CN 103833677 A CN103833677 A CN 103833677A CN 201210486689 A CN201210486689 A CN 201210486689A CN 103833677 A CN103833677 A CN 103833677A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- organic solvent
- lithium
- pyroles
- electrolytic solution
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/037—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements with quaternary ring nitrogen atoms
-
- 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
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a pyrrole ionic liquid. The chemical structural formula of the ionic liquid is shown as the specification, wherein R is alkyl of C1-C4; Y<-> is CF3SO3<-> or CF3CO2<->. The pyrrole ionic liquid is completely formed by ions at room temperature or under a situation close to the room temperature, has the advantages of high electrical conductivity, low melting point, wide electrochemical window, no volatilization or inflammability, good thermal stability and no halogen impurities or toxicity, and can be applied to the field of preparation of supercapacitors or lithium ionic batteries with high specific capacity. Furthermore, the invention also relates to a preparation method and application of the pyrrole ionic liquid.
Description
[technical field]
The present invention relates to a kind of lithium-ion battery electrolytes field, relate in particular to a kind of pyroles ionic liquid and preparation method thereof, also relate to a kind of electrolytic solution and compound method and lithium ion battery that uses this pyroles ionic liquid simultaneously.
[background technology]
The advantage such as lithium ion battery has that capacity is high, memory-less effect, volume are little, lightweight and pollution-free.Volume with the ferric phosphate lithium cell of equal-specification capacity is 2/3rds of lead-acid cell volume, and weight is 1/3rd of lead-acid cell.Thereby be widely used in military field, device for mobile communication, computer and electromobile etc.The energy of storing of lithium ion battery increases with the rising of voltage, thereby the voltage that raising applies can increase substantially the specific energy of lithium ion battery.
But, the ionic liquid that adopts two-step approach to prepare inevitably all can be introduced halogens, these halogen impurities ions can cause the shortcomings such as the stability of ionic liquid reduces, and Melting point elevation and electrochemical window narrow, thereby are unfavorable for that it is applied to the electrolytic solution of lithium ion battery.
[summary of the invention]
Based on this, be necessary pyroles ionic liquid providing a kind of not halogen-containing element and preparation method thereof.
A kind of pyroles ionic liquid, chemical structural formula is as follows:
Wherein, R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -.
This pyroles ionic liquid is in room temperature or approach under the condition of room temperature and be made up of ion completely, specific conductivity is high, fusing point is low, electrochemical window is wide, non-volatile, non-combustible, Heat stability is good and not contain halogen impurities nontoxic, particularly decomposition voltage is high, under high voltage condition, be difficult to decompose, thereby can be applied in ultracapacitor or the lithium ion battery field of manufacturing height ratio capacity.
A preparation method for pyroles ionic liquid, comprises the steps:
Under inert atmosphere protection, by N-crassitude and alkylating reagent RY in molar ratio 1:1 ~ 1.2:1 be added in organic solvent, the mass ratio of described organic solvent and described N-crassitude is 0.8:1 ~ 1.4:1, be stirring reaction 5 hours ~ 30 hours under 50 ℃ ~ 90 ℃ conditions in temperature, then remove excessive described N-crassitude and described organic solvent, collect colourless liquid, after washing, vacuum-drying obtains pyroles ionic liquid, described alkylating reagent RY is trifluoromethanesulfonic acid methyl esters, trifluoromethanesulfonic acid ethyl ester, trifluoromethanesulfonic acid propyl ester, trifluoromethanesulfonic acid butyl ester, trifluoro-acetate, Trifluoroacetic Acid Ethyl Ester, trifluoroacetic acid propyl ester or TAB, its chemical structural formula is as follows:
Wherein, R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -.
In a preferred embodiment, described organic solvent is chloroform, tetrahydrofuran (THF) or acetonitrile.
In a preferred embodiment, step is removed excessive described N-crassitude and described organic solvent and is specially: remove excessive N-crassitude and described organic solvent by the mode of underpressure distillation, the condition of described underpressure distillation is that temperature is 80 ℃～150 ℃, and pressure is 0.1Pa～5Pa.
In a preferred embodiment, described washing step is specially: described vacuum drying step is specially, and vacuum drying temperature is 60 ℃～100 ℃, and vacuum tightness is 0.01MPa.
Above-mentioned preparation process adopts the large-scale industrial production that single stage method efficiency is high, pollution-free, be conducive to pyroles ionic liquid.
Meanwhile, be also necessary to provide a kind of electrolytic solution and compound method and lithium ion battery that uses above-mentioned difficult decomposition, the good ionic liquid of stability.
A kind of electrolytic solution, comprises pyroles ionic liquid, lithium salts and organic solvent,
Wherein, the structural formula of described pyroles ionic liquid is as follows:
R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -;
Described lithium salts is 1:20～1:10 with the quality of described organic solvent than scope;
Described pyroles ionic liquid is 1:10～1 with the quality of described organic solvent than scope: 1.
In a preferred embodiment, described organic solvent is the mixing solutions of NSC 11801, Methyl ethyl carbonate and methylcarbonate, and wherein, the volume ratio of described NSC 11801, Methyl ethyl carbonate and methylcarbonate is 1～3:3～6:1.
A compound method for electrolytic solution, comprises the steps:
Under inert atmosphere protection, get NSC 11801, Methyl ethyl carbonate is that 1～3:3～6:1 mixes as organic solvent with methylcarbonate by volume, the ratio that than scope is in described pyroles ionic liquid and the quality of described organic solvent adds pyroles ionic liquid in described organic solvent, be to be uniformly mixed under 20 ℃ ~ 50 ℃ conditions in temperature, then add lithium salts, described lithium salts is LiBF4, lithium hexafluoro phosphate, trifluoromethanesulfonic acid lithium or two (trimethyl fluoride sulfonyl) imine lithium, described lithium salts is 1:20～1:10 with the quality of described organic solvent than scope, obtain described electrolytic solution, wherein, the structural formula of described pyroles ionic liquid is as follows:
R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -.
The electrolytic conductivity that contains pyroles ionic liquid is high, fusing point is low, the decomposition voltage of Heat stability is good and not halogen-containing impurity, particularly electrolytic solution is high, can be widely used in the preparation field of lithium ion battery, obtains the lithium ion battery of high-energy-density.Meanwhile, its process for preparation is simple, uses raw material cheap and easy to get, can large-scale industrial production.
A kind of lithium ion battery, the electrolytic solution of described lithium ion battery comprises the ionic liquid with following structure:
R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -.
By test, use the above-mentioned lithium ion battery that contains pyroles ionic liquid to there is higher charging/discharging voltage, and under high charge-discharge voltage conditions, electrolytic solution is highly stable.
[accompanying drawing explanation]
Fig. 1 is the preparation method's of the prepared pyroles ionic liquid of the embodiment of the present invention schema;
Fig. 2 is the preparation method's of the prepared pyroles ion of embodiment of the present invention electrolytic solution schema;
[embodiment]
Mainly in conjunction with specific embodiments pyroles ionic liquid and its preparation method and application is described in further detail below.
The pyroles ionic liquid of present embodiment, chemical structural formula is as follows:
Wherein, R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -.
This pyroles ionic liquid is in room temperature or approach under the condition of room temperature and be made up of ion completely, specific conductivity is high, fusing point is low, electrochemical window is wide, non-volatile, non-combustible, Heat stability is good and not halogen-containing impurity nontoxic, particularly decomposition voltage is high, under high voltage condition, be difficult to decompose, thereby can be applied in ultracapacitor or the lithium ion battery field of manufacturing height ratio capacity.
A preparation method for above-mentioned pyroles ionic liquid, preparation flow is as follows:
Wherein RY is trifluoromethanesulfonic acid methyl esters, trifluoromethanesulfonic acid ethyl ester, trifluoromethanesulfonic acid propyl ester, trifluoromethanesulfonic acid butyl ester, trifluoro-acetate, Trifluoroacetic Acid Ethyl Ester, trifluoroacetic acid propyl ester or TAB; R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -.
Specifically comprise the steps:
Step S1: under inert atmosphere protection; N-crassitude and 1: 1 in molar ratio ~ 1.2:1 of alkylating reagent RY are added in organic solvent; the mass ratio of described organic solvent and described N-crassitude is 0.8:1 ~ 1.4:1, is stirring reaction 5 hours ~ 30 hours under 50 ℃ ~ 90 ℃ conditions in temperature.
Wherein, alkylating reagent RY is trifluoromethanesulfonic acid methyl esters, trifluoromethanesulfonic acid ethyl ester, trifluoromethanesulfonic acid propyl ester, trifluoromethanesulfonic acid butyl ester, trifluoro-acetate, Trifluoroacetic Acid Ethyl Ester, trifluoroacetic acid propyl ester or TAB.
Wherein, organic solvent is chloroform, tetrahydrofuran (THF) or acetonitrile.
Step S2: then remove excessive described N-crassitude and described organic solvent, collect colourless liquid.
Wherein, the concrete step of removing excessive described N-crassitude and described organic solvent is to remove excessive N-crassitude and described organic solvent by the mode of underpressure distillation, the condition of described underpressure distillation is that temperature is 80 ℃～150 ℃, and pressure is 0.1Pa～5Pa.
Step S3: after washing, it is as follows that vacuum-drying obtains its chemical structural formula of pyroles ionic liquid:
Wherein, vacuum drying temperature is 60 ℃～100 ℃, and vacuum tightness is 0.01MPa;
Wherein, R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -.
Wherein, the mode of washing is for adopting methyl tertiary butyl ether 50ml repetitive scrubbing more than 3 times.
The large-scale industrial production that above-mentioned preparation process efficiency is high, pollution-free, be conducive to pyroles ionic liquid.
Meanwhile, the present invention also provides a kind of electrolytic solution and compound method and lithium ion battery that uses above-mentioned difficult decomposition, the good ionic liquid of stability.
The electrolytic solution of one embodiment comprises pyroles ionic liquid, lithium salts and organic solvent,
Wherein, the structural formula of pyroles ionic liquid is as follows:
R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -;
Described lithium salts is 1:20～1:10 with the quality of described organic solvent than scope;
Described pyroles ionic liquid is 1:10～1 with the quality of described organic solvent than scope: 1.
Organic solvent is preferably the mixing solutions of NSC 11801, Methyl ethyl carbonate and methylcarbonate, and wherein, the volume ratio of described NSC 11801, Methyl ethyl carbonate and methylcarbonate is 1～3:3～6:1.
With reference to the accompanying drawings 2, the process for preparation of this electrolytic solution, comprises the steps:
Step S4: under inert atmosphere protection; get NSC 11801, Methyl ethyl carbonate is that 1～3:3～6:1 mixes as organic solvent with methylcarbonate by volume; the ratio that than scope is in described pyroles ionic liquid and the quality of described organic solvent adds pyroles ionic liquid in described organic solvent; be to be uniformly mixed under 20 ℃ ~ 50 ℃ conditions in temperature
Step S5: then add lithium salts, described lithium salts is LiBF4, lithium hexafluoro phosphate, trifluoromethanesulfonic acid lithium or two (trimethyl fluoride sulfonyl) imine lithium, described lithium salts is 1:20～1:10 with the quality of described organic solvent than scope, obtain described electrolytic solution, wherein, the structural formula of described pyroles ionic liquid is as follows:
R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -.
The electrolytic conductivity that contains pyroles ionic liquid is high, fusing point is low, Heat stability is good and not contain the decomposition voltage of halogen impurities, particularly electrolytic solution high, can be widely used in the preparation field of lithium ion battery, obtains the lithium ion battery of high-energy-density.Meanwhile, its process for preparation is simple, uses raw material cheap and easy to get, can large-scale industrial production.
The electrolytic solution of the lithium ion battery of one embodiment comprises the ionic liquid with following structure:
R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -.
By test, use and above-mentionedly contain the lithium ion battery that pyroles ionic liquid prepares and there is higher charging/discharging voltage, and under high charge-discharge voltage conditions, electrolytic solution is highly stable.
Be below specific embodiment part:
In following examples, contain atmosphere of inert gases take nitrogen and argon atmosphere as representative.
Embodiment 1:
In the flask of 500mL, add respectively 105g chloroform, (93.6g, 1.1mol) N-crassitude, (164.1g, 1.0mol) trifluoromethanesulfonic acid methyl esters, under nitrogen atmosphere, be warming up to 70 ℃, stirring reaction 20 hours.Leave standstill cooling, it is 100 ℃ in temperature, pressure is to carry out underpressure distillation under the condition of 3.0Pa, removing excessive reactant, collect colourless liquid 50ml methyl tertiary butyl ether repetitive scrubbing three times, is then 80 ℃ in temperature, vacuum tightness is under 0.01MPa condition, to carry out vacuum-drying, obtain colourless liquid N, N-dimethyl pyrrolidine fluoroform sulphonate, productive rate 87%.
Its hydrogen spectrum data are as follows:
1H?NMR(CDCl
3,400MHz,ppm):3.36(s,6H),3.28(m,4H),1.77(m,4H).
Under inert atmosphere protection; take out 10g; N-dimethyl pyrrolidine fluoroform sulphonate; then add wherein the mixed solvent of 30g NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC); wherein; volume ratio between NSC 11801, Methyl ethyl carbonate and methylcarbonate is 2:5:1, and is heated to 40 ℃ and is uniformly mixed, and then adds 3.5g LiBF4 (LiBF
4), continue stirring it is all dissolved, thereby obtain object ion liquid electrolyte.
Embodiment 2:
In the flask of 500mL, add respectively 68g tetrahydrofuran (THF), (85.1g, 1.0mol) N-crassitude, (178.1g, 1.0mol) trifluoromethanesulfonic acid ethyl ester, under nitrogen atmosphere, be warming up to 50 ℃, stirring reaction 30 hours.Leave standstill cooling, it is 80 ℃ in temperature, pressure is to carry out underpressure distillation under the condition of 0.1Pa, remove excessive reactant, collecting colourless liquid 50ml methyl tertiary butyl ether repetitive scrubbing three times, is then 60 ℃ in temperature, and vacuum tightness is under 0.01MPa condition, to carry out vacuum-drying, obtain colourless liquid N-ethyl-N-crassitude fluoroform sulphonate, productive rate 88%.
Its hydrogen spectrum data are as follows:
1H?NMR(CDCl
3,400MHz,ppm):3.36(s,3H),3.28(m,6H),1.77(m,4H),1.27(s,3H)
Under inert atmosphere protection; take out 10g N-ethyl-N-crassitude fluoroform sulphonate; then add wherein the mixed solvent of 100g NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC); wherein; volume ratio between NSC 11801, Methyl ethyl carbonate and methylcarbonate is 1:3:1; and be heated to 20 ℃ and be uniformly mixed, then add 5.0g lithium hexafluoro phosphate (LiPF
6), continue stirring it is all dissolved, thereby obtain object ion liquid electrolyte.
Embodiment 3
In the flask of 500mL, add respectively 120g acetonitrile, (102.1g, 1.2mol) N-crassitude, (156.1g, 1.0mol) trifluoroacetic acid propyl ester, under nitrogen atmosphere, be warming up to 80 ℃, stirring reaction 5 hours.Leave standstill cooling, it is 150 ℃ in temperature, pressure is to carry out underpressure distillation under the condition of 5.0Pa, remove excessive reactant, collecting colourless liquid 50ml methyl tertiary butyl ether repetitive scrubbing three times, is then 100 ℃ in temperature, and vacuum tightness is under 0.01MPa condition, to carry out vacuum-drying, obtain colourless liquid N-propyl group-N-crassitude trifluoroacetate, productive rate 90%.
Its hydrogen spectrum data are as follows:
1H?NMR(CDCl
3,400MHz,ppm):3.36(s,3H),3.28(m,6H),1.77(m,6H),0.96(s,3H)
Under inert atmosphere protection; take out 10g N-propyl group-N-crassitude trifluoroacetate; then add wherein the mixed solvent of 10g NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC); wherein; volume ratio between NSC 11801, Methyl ethyl carbonate and methylcarbonate is 3:6:1; and be heated to 50 ℃ and be uniformly mixed, then add 1.0g trifluoromethanesulfonic acid lithium (LiSO
3cF
3), continue stirring it is all dissolved, thereby obtain object ion liquid electrolyte.
Embodiment 4:
In the flask of 500mL, add respectively 131g chloroform, (93.6g, 1.1mol) N-crassitude, (170.1g, 1.0mol) TAB, under nitrogen atmosphere, be warming up to 90 ℃, stirring reaction 25 hours.Leave standstill cooling, it is 120 ℃ in temperature, pressure is to carry out underpressure distillation under the condition of 4.0Pa, remove excessive reactant, collecting colourless liquid 50ml methyl tertiary butyl ether repetitive scrubbing three times, is then 90 ℃ in temperature, and vacuum tightness is under 0.01MPa condition, to carry out vacuum-drying, obtain colourless liquid N-butyl-N-crassitude trifluoroacetate, productive rate 84%.
Its hydrogen spectrum data are as follows:
1H?NMR(CDCl
3,400MHz,ppm):3.36(s,3H),3.28(m,6H),1.77(m,6H),1.36(m,2H),0.96(s,3H)
Under inert atmosphere protection; take out 10g N-butyl-N-crassitude trifluoroacetate; then add wherein the mixed solvent of 30g NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC); wherein; volume ratio between NSC 11801, Methyl ethyl carbonate and methylcarbonate is 1:4:1; and be heated to 30 ℃ and be uniformly mixed; then add 2.2g bis-(trimethyl fluoride sulfonyl) imine lithium (LiTFSI); continue stirring it is all dissolved, thereby obtain object ion liquid electrolyte.
Application Example
Electrolytic solution in application above-described embodiment 1 ~ 4 is assembled into lithium ion battery
Take 9g LiNi
0.8co
0.2o
2, 0.5g acetylene black and 0.7g PVDF, and add 20g NMP, fully stir and make it to become the slurry mixing.Then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 80 ℃ are dried to constant weight, and are pressed into LiNi in 10MPa pressure lower roll
0.8co
0.2o
2electrode, and be cut into electrode disk.In the glove box that is full of argon gas, the electrolytic solution electrolytic solution in pp barrier film and above-described embodiment 1 ~ 4 is placed between two activated carbon electrodes disks, on stamping machine, fastening lithium ionic cell is made in sealing.
In the voltage range of 2.5 ~ 4.2V, utilize charge-discharge test instrument to carry out 0.2C charge-discharge test to the lithium ion battery assembling in the present embodiment, its performance data is listed in the table below:
| Embodiment | 1 | 2 | 3 | 4 |
| First discharge specific capacity mAh/g | 120 | 122 | 115 | 117 |
| Discharging efficiency | 96% | 97% | 95% | 96% |
As can be seen from the table, the prepared il electrolyte of the embodiment of the present invention is suitable for the electrolytic solution of lithium ion battery, and assembled lithium ion battery has good specific storage and efficiency for charge-discharge while being applied to electrolytic solution.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a pyroles ionic liquid, is characterized in that, chemical structural formula is as follows:
Wherein, R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -.
2. a preparation method for pyroles ionic liquid, is characterized in that, comprises the steps:
Under inert atmosphere protection, by N-crassitude and alkylating reagent RY in molar ratio 1:1 ~ 1.2:1 be added in organic solvent, the mass ratio of described organic solvent and described N-crassitude is 0.8:1 ~ 1.4:1, be stirring reaction 5 hours ~ 30 hours under 50 ℃ ~ 90 ℃ conditions in temperature, then remove excessive described N-crassitude and described organic solvent, collect colourless liquid, after washing, vacuum-drying obtains pyroles ionic liquid, wherein, described alkylating reagent RY is trifluoromethanesulfonic acid methyl esters, trifluoromethanesulfonic acid ethyl ester, trifluoromethanesulfonic acid propyl ester, trifluoromethanesulfonic acid butyl ester, trifluoro-acetate, Trifluoroacetic Acid Ethyl Ester, trifluoroacetic acid propyl ester or TAB, its chemical structural formula is as follows:
Wherein, R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -.
3. the preparation method of pyroles ionic liquid as claimed in claim 2, is characterized in that, described organic solvent is chloroform, tetrahydrofuran (THF) or acetonitrile.
4. the preparation method of pyroles ionic liquid as claimed in claim 2, it is characterized in that, step is removed excessive described N-crassitude and described organic solvent and is specially: remove excessive N-crassitude and described organic solvent by the mode of underpressure distillation, the condition of described underpressure distillation is that temperature is 80 ℃～150 ℃, and pressure is 0.1Pa～5Pa.
5. the preparation method of pyroles ionic liquid as claimed in claim 2, is characterized in that, described vacuum drying step is specially, and vacuum drying temperature is 60 ℃～100 ℃, and vacuum tightness is 0.01MPa.
6. an electrolytic solution, is characterized in that, comprises pyroles ionic liquid, lithium salts and organic solvent,
Wherein, the structural formula of described pyroles ionic liquid is as follows:
R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -;
Described lithium salts is 1:20～1:10 with the quality of described organic solvent than scope;
Described pyroles ionic liquid is 1:10～1 with the quality of described organic solvent than scope: 1.
7. electrolytic solution as claimed in claim 6, it is characterized in that, described organic solvent is the mixing solutions of NSC 11801, Methyl ethyl carbonate and methylcarbonate, and wherein, the volume ratio of described NSC 11801, Methyl ethyl carbonate and methylcarbonate is 1～3:3～6:1.
8. electrolytic solution as claimed in claim 6, is characterized in that, described lithium salts is LiBF4, lithium hexafluoro phosphate, trifluoromethanesulfonic acid lithium or two (trimethyl fluoride sulfonyl) imine lithium.
9. a compound method for electrolytic solution, is characterized in that, comprises the steps:
Under inert atmosphere protection, get NSC 11801, Methyl ethyl carbonate is that 1～3:3～6:1 mixes as organic solvent with methylcarbonate by volume, the ratio that than scope is in described pyroles ionic liquid and the quality of described organic solvent adds pyroles ionic liquid in described organic solvent, be to be uniformly mixed under 20 ℃ ~ 50 ℃ conditions in temperature, then add lithium salts, described lithium salts is LiBF4, lithium hexafluoro phosphate, trifluoromethanesulfonic acid lithium or two (trimethyl fluoride sulfonyl) imine lithium, described lithium salts is 1:20～1:10 with the quality of described organic solvent than scope, obtain described electrolytic solution, wherein, the structural formula of described pyroles ionic liquid is as follows:
r is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -.
10. a lithium ion battery, is characterized in that, the electrolytic solution of described lithium ion battery comprises the ionic liquid with following structure:
R is that carbonatoms is 1～4 alkyl, Y
-for CF
3sO
3 -or CF
3cO
2 -.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210486689.4A CN103833677A (en) | 2012-11-26 | 2012-11-26 | Pyrrole ionic liquid, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210486689.4A CN103833677A (en) | 2012-11-26 | 2012-11-26 | Pyrrole ionic liquid, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103833677A true CN103833677A (en) | 2014-06-04 |
Family
ID=50797616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210486689.4A Pending CN103833677A (en) | 2012-11-26 | 2012-11-26 | Pyrrole ionic liquid, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103833677A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496928A (en) * | 2014-11-21 | 2015-04-08 | 绍兴佳华高分子材料股份有限公司 | Method for preparing quaternary ammonium salt ionic liquid without halogen ions and sodium ions |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102037600A (en) * | 2008-05-19 | 2011-04-27 | 日本电气株式会社 | Secondary battery |
-
2012
- 2012-11-26 CN CN201210486689.4A patent/CN103833677A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102037600A (en) * | 2008-05-19 | 2011-04-27 | 日本电气株式会社 | Secondary battery |
Non-Patent Citations (1)
| Title |
|---|
| NIKOLAI V.IGNAT’EV等: "A Convenient Synthesis of Triflate Anion Ionic Liquids and Their Properties", 《MOLECULES》, vol. 17, 7 May 2012 (2012-05-07) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496928A (en) * | 2014-11-21 | 2015-04-08 | 绍兴佳华高分子材料股份有限公司 | Method for preparing quaternary ammonium salt ionic liquid without halogen ions and sodium ions |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11177507B2 (en) | Electrolyte for lithium secondary battery and lithium secondary battery including the same | |
| WO2021110165A1 (en) | Lithium secondary battery electrolyte with low internal resistance and lithium secondary battery | |
| CN107732304B (en) | Method for cooperatively using organic silicon electrolyte and silicon-based electrode material | |
| CN106946925B (en) | Lithium fluoroalkoxytrifluoroborate salt, and preparation method and application thereof | |
| CN105800582B (en) | The preparation method and lithium ion battery non-aqueous electrolyte of a kind of difluorophosphate | |
| CN110148787B (en) | Electrolyte for improving capacity of lithium-sulfur battery and lithium-sulfur battery | |
| CN105206873B (en) | A kind of electrolyte containing phosphonitrile oroalkane sulfonyl imine lithium and the battery using the electrolyte | |
| CN103641751A (en) | Alkali metal salts of binary or ternary fluorine-containing sulfimide and ionic liquid and applications thereof | |
| CN111788732A (en) | Lithium secondary battery electrolyte and lithium secondary battery comprising same | |
| KR101298868B1 (en) | Nonaqueous electrolyte and lithium-ion secondary battery using thereof | |
| CN110797574A (en) | Non-aqueous electrolyte for lithium ion battery and lithium ion battery thereof | |
| CN110838595B (en) | Lithium ion battery electrolyte and application thereof | |
| CN105762410B (en) | A kind of nonaqueous electrolytic solution and the lithium ion battery using the nonaqueous electrolytic solution | |
| CN105742701A (en) | Electrolyte and lithium secondary battery | |
| KR100371403B1 (en) | New electrolytes and lithium ion battery using the same | |
| KR102100244B1 (en) | Electrolyte for Lithium Secondary Battery and Lithium Secondary Battery Containing the Same | |
| WO2023092885A1 (en) | Isocyanate electrolyte additive based on imidazole structural group and application thereof | |
| CN114156526A (en) | High-voltage electrolyte for lithium battery | |
| CN106898817B (en) | Lithium ion battery electrolyte and lithium ion battery | |
| CN110635166B (en) | Electrolyte, battery containing electrolyte and electric vehicle | |
| CN116706233A (en) | Bio-based lithium battery additive, electrolyte and lithium ion battery | |
| CN105009346A (en) | Electrolyte for lithium secondary battery, and lithium secondary battery including same | |
| CN103833558B (en) | Ion liquid of quaternaries and its preparation method and application | |
| CN109659618A (en) | A kind of electrolysis additive, electrolyte and preparation method thereof, lithium ion battery and equipment | |
| CN103833677A (en) | Pyrrole ionic liquid, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140604 |