CN106699666A - Ionic liquid and preparation method and application of ionic liquid - Google Patents
Ionic liquid and preparation method and application of ionic liquid Download PDFInfo
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- CN106699666A CN106699666A CN201611206229.6A CN201611206229A CN106699666A CN 106699666 A CN106699666 A CN 106699666A CN 201611206229 A CN201611206229 A CN 201611206229A CN 106699666 A CN106699666 A CN 106699666A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- 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
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Abstract
The invention relates to the field of electrolyte materials and discloses ionic liquid and a preparation method and application of the ionic liquid. The method comprises the following steps: 1) carrying out first reaction on methanesulfonyl chloride and at least one substance with a structure shown as a formula (2); 2) carrying out second reaction on an organic product obtained by the first reaction of the step 1) and a substance with a structure shown as a formula (3). According to the ionic liquid disclosed by the invention, defects that a traditional ionic liquid preparation process is complicated and the safety is low are overcome; the method provided by the invention is simple and feasible; preparation parameters have high controllability; the preparation method has the advantages of low cost and high efficiency; polymerized ionic liquid prepared from the ionic liquid has relatively high ionic conductivity and a wide electrochemical window, and has a very good industrial application prospect. (The formula (2) and the formula (3) are shown as the description.).
Description
Technical field
The present invention relates to electrolyte field, in particular it relates to a kind of ionic liquid, a kind of preparation side of ionic liquid
The application of method, the ionic liquid as obtained in the preparation method, and the ionic liquid.
Background technology
Lithium ion battery since the beginning of the nineties in last century successfully develops, just with its specific energy it is high, operating voltage is high, should
With temperature range it is wide, self-discharge rate is low, have extended cycle life, the unique advantage such as pollution-free and receive much attention, and in mobile phone, digital phase
Extensive use in the small-sized portable electronic product such as machine, notebook computer.In recent years, for reply auto industry fast development brings
Environmental pollution, petroleum resources the country such as negative effect, the U.S., Japan, China such as drastically consume and all adopt actively developing
With the R＆D work of the electric automobile EV and hybrid electric vehicle HEV of clean energy resource.And lithium ion battery is used as following electronic vapour
The topmost candidate's electrical source of power of car, the characteristics of with low cost, excellent performance, it has also become the master in international electrokinetic cell field
Study hotspot is wanted, wherein the electrolyte of the function admirable as one of the key factor for improving lithium ion battery safety performance
Exploitation become in order to research emphasis.
Solid electrolyte is a class safe electrolyte, does not possess combustibility, is to solve the problems, such as lithium ion battery security
Core.It is high that polymeric ionic liquid solid electrolyte combines good polymer machinery performance, easy processing and ionic liquid electrical conductivity
Feature, is of concern.And ionic liquid is the key factor for influenceing solid electrolyte performance, similarly, the system of ionic liquid
Preparation Method can cause that electrolyte meter reveals different conductivity characteristics.
At present, reacted with imidazoles using halogenated hydrocarbons more than the preparation of glyoxaline ion liquid, then carry out ion exchange, the party
Method generally uses bromo-hydrocarbons, and the building-up process of bromo-hydrocarbons is complicated and there is unsafe factor, in addition, the ion that prior art is provided
Liquid further carry out being polymerized obtained polymeric ionic liquid solid electrolyte electrical conductivity it is poor.
Therefore, a kind of polymeric ionic liquid with high ionic conductivity and electrochemical window wide of exploitation is needed badly.
The content of the invention
The invention aims to overcome prior art to exist polymeric material ionic conductivity is low, electrochemical window
It is not wide enough, and preparation process is complicated, a kind of low defect of security, there is provided ionic liquid, a kind of preparation side of ionic liquid
The application of method, the ionic liquid as obtained in the preparation method, and the ionic liquid.
The present inventor has found in research process, first by the organic material with hydroxyl as end and monosubstituted acyl
Chlorine (methylsufonyl chloride) carry out reaction generation ester, esterification products and imidazoles material are carried out into ion salt-forming reaction, obtain from
Polymeric ionic liquid obtained in sub- liquid has ionic conductivity higher and electrochemical window wide, if in ion salt-forming reaction
After proceed anion exchange reaction, the more preferable ionic liquid of chemical property can be obtained, the ionic liquid is gathered
The polymeric ionic liquid that conjunction is obtained has electrical conductivity and electrochemical window wider higher.
Based on this, the invention provides a kind of ionic liquid, the ionic liquid has the formula shown in formula (1),
Wherein, n is selected from the integer of 1-10, R1It is H, C1-C6Alkyl, R2It is hydrogen, C1-C6Saturated hydrocarbyl or C1-C6Unsaturated alkyl, R3And R5Each solely
It is on the spot hydrogen or C1-C6Alkyl, R4And R6It is each independently C1-C6Alkylidene, R7It is C1-C6Saturated hydrocarbyl or C1-C6No
Saturated hydrocarbyl,
X—It is Cl—、ClO4 —、
The present invention provides a kind of preparation method of ionic liquid, and the method includes：
1) methylsufonyl chloride is carried out into the first reaction with the material of structure shown at least one formula (2)；
2) by step 1) the first organic product for obtaining of reaction carries out the second reaction with the material of structure shown in formula (3)；
Wherein, n is selected from the integer of 1-10, R8It is H, C1-C6Alkyl, R2It is hydrogen, C1-C6Saturated hydrocarbyl or C1-C6Unsaturated alkyl, R3And R5Each solely
It is on the spot hydrogen or C1-C6Alkyl, R4And R6It is each independently C1-C6Alkylidene, R7It is C1-C6Saturated hydrocarbyl or C1-C6No
Saturated hydrocarbyl.
Present invention also offers ionic liquid obtained in the above method and the ionic liquid of present invention offer in lithium ion
Application in battery.
The ionic liquid that the present invention is provided overcomes conventional ion liquid preparation technology complexity, the low defect of security, sheet
Invent the method for providing simple and easy to apply, preparation parameter controllability is strong, with low cost, the advantage of efficiency high, and the ion for obtaining
Polymeric ionic liquid obtained in liquid has ionic conductivity higher and electrochemical window wide, before good commercial Application
Scape.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with following tool
Body implementation method is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the ionic conductivity-hygrogram of polymeric ionic liquid obtained in ionic liquid that embodiment 2 is obtained
Fig. 2 is the ionic conductivity-hygrogram of polymeric ionic liquid obtained in product B-2 that embodiment 2 is obtained.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific
Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
One or more can be obtained with combination with one another between the endpoint value of individual scope and single point value, and individually between point value
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of ionic liquid, and the ionic liquid has the formula shown in formula (1),
Wherein, n is selected from the integer of 1-10, R1It is H, C1-C6Alkyl, R2It is hydrogen, C1-C6Saturated hydrocarbyl or C1-C6Unsaturated alkyl, R3And R5Each solely
It is on the spot hydrogen or C1-C6Alkyl, R4And R6It is each independently C1-C6Alkylidene, R7It is C1-C6Saturated hydrocarbyl or C1-C6No
Saturated hydrocarbyl,
X—It is Cl—、ClO4 —、
The present invention is to n, R1、R2、X—Range of choice it is wider, for example, R1Can be H, C1-C6Alkyl, or contain
There is the group of ketone group, ester group.
In order to further improve the chemical property of ionic liquid, it is preferable that n is selected from the integer of 1-7；R1It is H or C1-
C3Alkyl orIt is further preferred that n is equal to 3 or 4, R1For H, methyl,
A preferred embodiment of the invention, R2It is hydrogen, C1-C3Saturated hydrocarbyl or C1-C3Unsaturated alkyl, enters one
Walk preferably, R2It is vinyl or ethyl.
A preferred embodiment of the invention, works as R2During for H or saturated hydrocarbyl, R1ForThis kind of preferred embodiment R1There is provided unsaturated group, it is ensured that the ionic liquid
Polymeric ionic liquid is obtained in follow-up smoothly polymerization.
To X in the present invention—Range of choice it is wider, its can be ionic liquid commonly used in the art it is any cloudy from
Son, it is preferable that X—ForStill more preferably X—ForThe preferred anion molecule amount is larger, and delocalized degree is higher, is more beneficial for improving
The chemical property of ionic liquid.
The present invention provides a kind of preparation method of ionic liquid, and the method includes：1) by methylsufonyl chloride and at least one
The material of structure carries out the first reaction shown in formula (2)；
2) by step 1) the first organic product for obtaining of reaction carries out the second reaction with the material of structure shown in formula (3)；
Wherein, n is selected from the integer of 1-10, R8It is H, C1-C6Alkyl, R2It is hydrogen, C1-C6Saturated hydrocarbyl or C1-C6Unsaturated alkyl, R3And R5Each solely
It is on the spot hydrogen or C1-C6Alkyl, R4And R6It is each independently C1-C6Alkylidene, R7It is C1-C6Saturated hydrocarbyl or C1-C6No
Saturated hydrocarbyl.
N and R2Selection as described above, will not be repeated here.
In the present invention, it is preferred to R8It is H or C1-C3Alkyl, further preferred R8It is H or methyl.
The present invention is wider with the range of choice of the mol ratio of the material of structure shown in formula (2) to the methylsufonyl chloride, is
Further improve the chemical property of obtained ionic liquid, it is preferable that methylsufonyl chloride and structure shown in formula (2)
The mol ratio of material is 1-3:1, more preferably 1-2:1.When the two mol ratio is smaller, it is unfavorable for structure shown in formula (2)
The substitution of hydrogen on material hydroxyl, and then the chemical property of ionic liquid is influenceed, when the two mol ratio is larger, that is, cause resource
Waste, and introduce excessive impurity to subsequent step.
In order that obtain first reaction more smoothly carrying out, preferably described first reaction is in acid binding agent and/or dilution
Carried out in the presence of agent.There is no particular limitation for species of the present invention to the acid binding agent and diluent, and those skilled in the art can
To be selected as the case may be.
In the present invention, acid binding agent is mainly used in neutralizing the acidic materials in course of reaction, for example, described tie up acid
Agent can be triethylamine.
In the present invention, diluent is mainly used in providing the ring of methylsufonyl chloride and the substance reaction of structure shown in formula (2)
Border, various diluents commonly used in the art are used equally to the present invention, and preferably described diluent is selected from dichloromethane, two chloroethenes
At least one in alkane and dichloropropane, most preferably dichloromethane.
Therefore, a preferred embodiment of the invention, methods described also includes：By at least one formula (2) Suo Shi
The material of structure mixes with the diluent and acid binding agent successively, and the first reaction is carried out to treat to be contacted with methylsufonyl chloride.
A preferred embodiment of the invention, the condition of first reaction includes：30- is stirred under condition of ice bath
60min, is subsequently placed in room temperature to stirring 6-12h at 60 DEG C.Using this kind of preferred hybrid mode, be conducive to methylsufonyl chloride and formula
(2) the uniform mixing of the material of structure shown in and being smoothed out for reaction.
In the present invention, the mode of methylsufonyl chloride is preferably added to be added dropwise, and be preferably added dropwise over, be added dropwise using this kind
Mode, can control reaction rate, and ensure that reaction is smoothed out, it is to avoid the generation of impurity.
The present invention it is wider to the range of choice of the consumption of the acid binding agent, as long as so that step 1) reaction be smoothed out i.e.
Can, it is preferable that the acid binding agent is 2-4 with the volume ratio of the material of structure shown in formula (2):1.
The present invention is wider to the range of choice of the consumption of the diluent, as long as being capable of structure enough shown in dissolution type (2)
Material, it is preferable that the volume ratio of the diluent and the material of structure shown in formula (2) is 3-5:1.
There is no particular limitation for condition of the present invention to the described first mixing, as long as by diluent and structure shown in formula (2)
Material mixing it is uniform, it is preferred to use the mode of stirring.
In the present invention, in the case of being not particularly illustrated, to stir condition there is no particular limitation, for example, stirring
Speed can be 50rpm-1000rpm.
According to preparation method of the present invention, in step 1) first reaction after the completion of, can select add watery hydrochloric acid use
In the carrying out of terminating reaction.
In the present invention, it is preferred to the concrete mode that the organic product of the first reaction is obtained includes：It is anti-to terminate
Should after add in the mixture that obtains the diluent (can be divided into and add twice, each addition can be the material of structure shown in formula (2)
20-40 times of volume) mixture system is layered, collect the organic product that lower organic layer is obtained as the first reaction.It is preferred that
Diluent and the step 1 of addition) in carry out that the diluent species that the first reaction used is identical, this kind of preferred embodiment will not
Introduce new impurity.
A preferred embodiment of the invention, the preparation method also includes removing trace using anhydrous sodium sulfate
Water, this kind of preferred embodiment is more beneficial for subsequent step 2) carrying out.
A preferred embodiment of the invention, the preparation method also includes entering the mixture after removal trace water
Row is filtered, and then vacuum revolving obtains the organic product.Condition to vacuum revolving has no particular limits, preferably very
Below the boiling point of used diluent, the temperature of still more preferably described vacuum revolving is 40-60 DEG C to the temperature of sky revolving,
Time is 20-60min.
It should be noted that working as R2During for hydrogen or saturated hydrocarbyl, in order to the further application of the ionic liquid is obtained polymerization
Ionic liquid, can be to step 1) unsaturated group is introduced in the first organic product for obtaining of reaction, step 2 is then carried out again).
The present invention is to step 1) specific method and not of unsaturated group is introduced in the first organic product for obtaining of reaction
There is no particular limitation for the species of saturated group, and those skilled in the art can make suitable selection according to actual conditions.
In accordance with the present invention it is preferred that, work as R2During for H or saturated hydrocarbyl, R8It is H, the method also includes：By step 1) first
The organic product that obtains of reaction is with acrylic acid and/or metering system acid reaction with to step 1) organic product that obtains of the first reaction
Middle introducingAnd/orIt is highly preferred that by step 1) having of obtaining of the first reaction
Machine product and metering system acid reaction are with to step 1) introduce in the organic product that obtains of the first reaction
For example, can be by step 1) the first organic product for obtaining of reaction and organic solvent, acrylic acid and/or metering system
Acid, cesium carbonate and polymerization inhibitor haptoreaction.The polymerization inhibitor is used to prevent the polymerization of acrylic acid and/or methacrylic acid, excellent
The polymerization inhibitor is selected for hydroquinones, preferably the addition of polymerization inhibitor is the 0.5-3 matter of acrylic acid and/or methacrylic acid
Amount %.
The present invention to the organic solvent, there is no particular limitation, be mainly used in provide step 1) first reaction obtain have
Machine product and acrylic acid and/or the reaction environment of methacrylic acid, preferably described organic solvent is DMF.
There is no particular limitation to the catalytic condition for the present invention, excellent as long as unsaturated bond can be introduced
Selection of land, the catalytic temperature is 30-50 DEG C, and the time is 30-60h.
A kind of specific embodiment of the invention, the process can be：By step 1) first reaction obtain it is organic
Product is added in organic solvent, then sequentially adds methacrylic acid and/or acrylic acid, cesium carbonate and hydroquinones, will be obtained
Mixture react 30-60h at 30-50 DEG C, preferably also include the filtering, vacuum revolving and the column chromatography chromatogram that are carried out after reaction
Separate (can be carried out according to conventional meanses), preferred steps 1) the first organic product for obtaining of reaction and methacrylic acid and/or third
Olefin(e) acid, the mol ratio of cesium carbonate are 2:1:1, this kind of preferred embodiment can cause step 1) first organic product for obtaining of reaction
The unilateral introducing unsaturated bond of thing, another side meets the requirement that the second reaction is carried out with the material of structure shown in formula (3).In above-mentioned
It is only to provide a kind of specific embodiment for introducing double bond to hold, and the present invention includes but is not limited to this.
The present invention is to the step 1) mol ratio of the first organic product for obtaining of reaction and the material of structure shown in formula (3)
Range of choice it is wider, in order to further improve the chemical property of obtained ionic liquid, it is preferable that step 1) first
The organic product that reaction is obtained is 1 with the mol ratio of the material of structure shown in formula (2):1-3, more preferably 1:1-2, it is optimal
Elect 1 as:1.Carrying out reaction using the preferred mol ratio can make reaction more complete, and further reduce subsequent reactions product
Processing load.
A preferred embodiment of the invention, the condition of second reaction includes：At 80-120 DEG C, stirring
6-12h。
According to the preparation method that the present invention is provided, the preferably preparation method also includes to step 2) the second reaction obtain it is mixed
Compound carries out washing the product for obtaining the second reaction, it is preferred to use ethyl acetate is to step 2) the second mixture for obtaining of reaction enters
Row washing 1-2 times.
In order to further improve the chemical property of ionic liquid, preferably the method also includes：By step 2) it is second anti-
The product that should be obtained carries out anion exchange reaction.
Not carrying out anion exchange can improve the chemical property of ionic liquid, but, by step 2) the second reaction
The product for obtaining carries out anion exchange reaction and can further improve the chemical property of ionic liquid.
The present invention described anion exchange reaction is not limited specifically, step 2) second reaction obtain product tool
Just like the structure shown in formula (4),Formula (4), the anion exchange reaction is only
WillSpecific required anion is exchanged for, the present invention has no particular limits to this, this area
Technical staff can be selected according to actual needs.
A preferred embodiment of the invention, the specific embodiment of the anion exchange reaction includes：Will
Step 2) the second product for obtaining of reaction contacts (can carry out at room temperature) with lithium salts.Further preferably, first to step 2) the
Deionized water is added in the product that two reactions are obtained, the lithium salts is subsequently adding.
The present invention is wider with the range of choice of the mol ratio of lithium salts to the described second product for obtaining of reaction, if by the moon from
Sub- exchange reaction is carried out completely, and the product and the mol ratio of lithium salts that preferably described second reaction is obtained are 1:1-5, further
Preferably 1:1-3, most preferably 1:1.
The present invention has no particular limits to the anion of the lithium salts, is selected from double trifluoromethanesulfonimide lithiums
(LiTFSI), at least one in lithium perchlorate and lithium chloride.
The present invention preferably willIt is exchanged for that molecular weight is larger, and delocalized degree anion higher.
Therefore, most preferably lithium salts is double trifluoromethanesulfonimide lithiums.
According to the method that the present invention is provided, preferably the method also includes to the mixed system after above-mentioned anion exchange reaction
Extracted (preferably carry out 3-4 times), go trace water, filtering and vacuum revolving to obtain ionic liquid.
A preferred embodiment of the invention, the extraction use and step 1) described in identical type dilution
Agent is carried out, and impurity is not easily introduced using this kind of preferred embodiment, is conducive to obtaining the product of high-purity.
The present invention is wider to the range of choice of vacuum revolving, and preferably the temperature of vacuum revolving is in used diluent
Below boiling point, the temperature of still more preferably described vacuum revolving is 40-60 DEG C, and the time is 20-60min.
Present invention also offers the ionic liquid as obtained in above-mentioned preparation method and the ionic liquid in lithium ion battery
In application.
Below will the present invention will be described in detail by embodiment.
In the examples below, " room temperature " refers to " 25 DEG C "；The computational methods of molar yield are：
Molar yield, the actual molar yields of %=/theoretical molar yield × 100%
Theoretical molar yield refers to that ideally whole raw materials are converted into the mole of target product.
Embodiment 1
1) TEG monomethyl ether (1mL, 5.11mmol) is dissolved in 3mL dichloromethane, and is stirred, in 0 DEG C of ice
Under the conditions of bath, 2.14mL triethylamines are added, be then added dropwise over methylsufonyl chloride (0.585g, 5.11mmol), keep 0 DEG C of ice bath
Condition stirs 45min, and 10h is then stirred at room temperature, adds watery hydrochloric acid (0.1M, 20ml) terminating reaction, then adds at twice
Enter dichloromethane, each 30mL so that system layering collects lower organic layer, removes trace water using anhydrous sodium sulfate, finally
Oil product (1.448g, 5.059mmol) is obtained by filtering, vacuum revolving (50 DEG C, 20min), molar yield is 99%；
With1H-NMR analyzes the structure of the product,1H-NMR(400MHz,DMSO-D6):δ=3.03 (s, 3H), 3.33 (s,
3H),3.50(m,2H),3.61(m,10H),3.74(m,2H),4.34(m,2H)；
2) by step 1) oil product (1g, 3.492mmol) and vinyl imidazole (0.34ml, 3.492mmol) that obtain
Mixing, stirs 10 hours under the conditions of 100 DEG C, obtains the grease of clear, 3 times is washed with ethyl acetate and obtains product B-
1 (1.288g, 3.387mmol), molar yield is 97%；
With1H-NMR analyzes the structure of the product,1H-NMR(400MHz,DMSO-D6):δ=3.00 (s, 3H), 3.55 (s,
3H), 3.75 (m, 2H), 3.85 (m, 10H), 4.11 (t, J1=4.3Hz, J2=4.5Hz, 2H), 4.80 (t, J1=4.2Hz, J2
=4.4Hz, 2H), 5.60 (dd, J1=8.6Hz, J2=2.5Hz, 1H), 6.10 (dd, J1=15.6Hz, J2=2.5Hz, 1H),
7.5(m,1H),7.9(s,1H),8.0(s,1H),10.3(s,1H)；
3) at room temperature, to deionized water (30mL) is added in product B-1 (1g, 2.630mmol), it is subsequently adding LiTFSI
(0.755g, 2.630mmol, 1 times of equivalent) carries out ion-exchange reactions and obtains mixed system, using dichloromethane to mixed system
Extraction 4 times, collects lower organic layer, and removes trace water with anhydrous sodium sulfate, after filtering, vacuum revolving (50 DEG C, 20min)
Pale yellow oily liquid (1.487g, 2.630mmol) is obtained, molar yield is 100%；
With1H-NMR analyzes the structure of the product,1H-NMR(400MHz,DMSO-D6):δ=3.24 (s, 3H), 3.44 (dd,
J1=5.7Hz, J2=3.4Hz, 2H), 3.52 (dd, J1=6.7Hz, J2=4.1Hz, 10H), 3.83 (m, 2H), 4.4 (m,
2H), 5.45 (dd, J1=8.7Hz, J2=2.3Hz, 1H), 6.0 (dd, J1=15.6Hz, J2=2.4Hz, 1H), 7.3 (dd, J1
=15.6Hz, J2=8.7Hz, 1H), 7.9 (s, 1H), 8.2 (s, 1H), 9.4 (s, 1H).
The zwitterion of the product is analyzed by mass spectrum, analysis result shows, the anion relative molecular mass
It is 279.9, cation relative molecular mass is 285.1.
Pass through1H-NMR spectrum is tested and mass spectrometry results understand that the product has the formula shown in formula (1), wherein, R1
It is methyl, n is equal to 4, R2It is vinyl, X—For
Pass through1Knowable to H-NMR spectrum test result, the material and methyl sulphur of structure shown in the formula (2) with hydroxyl as end
Acyl chloride reaction generates ester, and esterification products and imidazoles material have carried out ion salt-forming reaction, after anion exchange, willIt is exchanged forIonic liquid obtained in the method that the present invention is provided is evaded
Tradition prepares the process of bromo raw material, it is to avoid should during uneasy full response, method full safety that the present invention provides,
Controllability is strong, yield is high.
Embodiment 2
1) tetraethylene-glycol (1ml, 5.81mmol) is dissolved in 4mL dichloromethane, and is stirred, in 0 DEG C of ice bath
Under the conditions of, 2.43mL triethylamines are added, methylsufonyl chloride (1.33g, 11.62mmol) is then added dropwise over, keep 0 DEG C of ice bath bar
Part stirs 30min, then in 12h is stirred at 40 DEG C, adds watery hydrochloric acid (0.1M, 30ml) terminating reaction, then adds at twice
Dichloromethane, each 30mL so that system layering collects lower organic layer, and trace water is removed using anhydrous sodium sulfate, most passes through afterwards
Filtering, vacuum revolving (40 DEG C, 60min) obtain oil product 5.75mmol, and molar yield is 99%；
With1H-NMR analyzes the structure of the product,1H-NMR(400MHz,DMSO-D6):δ=3.07 (d, J=0.8Hz,
3H), 3.65 (m, 8H), 3.76 (m, 4H), 4.37 (dd, J1=3.70Hz, J2=4.70Hz, 4H).
2) by step 1) oil product (1g, 2.853mmol, 2 times of equivalent) that obtains adds DMF
(DMF) in, methacrylic acid (0.13mL, 1.427mmol, 1 times of equivalent) is then sequentially added, cesium carbonate (0.465g,
1.427mmol, 1 times of equivalent) and hydroquinones (being added by methacrylic acid mass fraction 1%), the mixture that will be obtained exists
48h is heated at 32 DEG C, then filtered, vacuum revolving (40 DEG C, 60min), eventually pass the isolated Huang of column chromatography chromatogram
Color oil product (0.437g, 1.283mmol, 45%)；
With1H-NMR analyzes the structure of the product,1H-NMR(400MHz,DMSO-D6):δ1.95(m,3H),3.08(d,
3H), 3.65 (m, 6H), 3.76 (m, 4H), 4.30 (m, 2H), 4.38 (m, 4H), 5.58 (m, 1H), 6.13 (dd, J1=
0.93Hz, J2=1.44Hz, 1H).
3) yellow oil product (1g, 2.936mmol) and ethyl imidazol(e) (0.33mL, 2.936mmol) are mixed, in 80 DEG C
Under the conditions of stir 12 hours, obtain the grease of clear, washed with ethyl acetate obtain for 3 times product B-2 (1.217g,
2.789mmol), molar yield is 95%；
With1H-NMR analyzes the structure of the product,1H-NMR(400MHz,DMSO-D6):δ=1.57 (m, 3H), 1.94 (s,
3H),2.75(s,3H),3.64(m,12H),4.32(m,4H),4.52(m,2H),5.59(s,1H),6.11(s,1H),7.34
(s,1H),7.65(s,1H),9.77(s,1H).4) at room temperature, to addition deionized water in product B-2 (1g, 2.291mmol)
(30mL), is subsequently adding LiTFSI (0.658g, 2.291mmol, 1 times of equivalent) and carries out ion-exchange reactions and obtain mixed system,
Mixed system is extracted 3 times using dichloromethane, collects lower organic layer, and trace water is removed with anhydrous sodium sulfate, through filtering,
Pale yellow oily liquid (1.351g, 2.176gmmol) is obtained after vacuum revolving (40 DEG C, 60min), molar yield is 95%；
With1H-NMR analyzes the structure of the product,1H-NMR(400MHz,DMSO-D6):δ=1.44 (t, J1=7.2Hz, J2
=6.2Hz, 3H), 1.89 (s, 3H), 3.63 (m, 12H), 4.23 (d, J=5.9Hz, 4H), 4.35 (m, 2H), 5.70 (s, 1H),
6.04(s,1H),7.76(s,1H),7.81(s,1H),9.14(s,1H)。
The zwitterion of the product is analyzed by mass spectrum, analysis result shows, the anion relative molecular mass
It is 279.9, cation relative molecular mass is 341.2.
Pass through1H-NMR spectrum is tested and mass spectrometry results understand that the product has the formula shown in formula (1), wherein, R1
ForN is equal to 4, R2It is ethyl, X—ForCompared with the final product,
B-2 is without anion exchange reaction, anionThe R of B-21ForN is equal to 4,
R2It is ethyl.
Embodiment 3
1) tetraethylene-glycol (1ml, 5.81mmol) is dissolved in 5mL dichloromethane, and is stirred, in 0 DEG C of ice bath
Under the conditions of, 4mL triethylamines are added, then it is added dropwise over methylsufonyl chloride (1.33g, 11.62mmol)), keep 0 DEG C of condition of ice bath
Stirring 60min, then in 6h is stirred at 60 DEG C, adds watery hydrochloric acid (0.1M, 30ml) terminating reaction, and dichloro is then added at twice
Methane, each 30mL so that system layering collects lower organic layer, and trace water is removed using anhydrous sodium sulfate, eventually passes
Filter, vacuum revolving (60 DEG C, 40min) obtain oil product 5.76mmol, and molar yield is 99%；
2) by step 1) oil product (2.853mmol, 2 times of equivalents) that obtains adds DMF (DMF)
In, then sequentially add acrylic acid (1.427mmol, 1 times of equivalent), cesium carbonate (1.427mmol, 1 times of equivalent) and to benzene two
Phenol (is added) by acrylic acid mass fraction 1%, and the mixture that will be obtained heats 48h at 32 DEG C, then filtered, vacuum rotation
Steam (60 DEG C, 40min), eventually pass the isolated yellow oil product of column chromatography chromatogram (1.321mmol, 46%)；
3) yellow oil product 2.936mmol and ethyl imidazol(e) 2.936mmol is mixed, 6 is stirred under the conditions of 120 DEG C small
When, the grease of clear is obtained, 3 times to be washed with ethyl acetate and obtains product B-3 2.818mmol, molar yield is
96%；
4) at room temperature DEG C, to deionized water (30mL) is added in product B-3 2.600mmol, it is subsequently adding LiTFSI
(0.748g, 2.600mmol, 1 times of equivalent) carries out ion-exchange reactions and obtains mixed system, using dichloromethane to mixed system
Extraction 4 times, collects lower organic layer, and removes trace water with anhydrous sodium sulfate, after filtering, vacuum revolving (60 DEG C, 40min)
Pale yellow oily liquid 2.548mmol is obtained, molar yield is 98%.
Pass through1H-NMR spectrum is tested and mass spectrometry results understand that the product has the formula shown in formula (1), wherein, R1
ForN is equal to 4, R2It is ethyl, X—For
Embodiment 4
According to the method for embodiment 1, unlike, substitute LiTFSI, step 3 with the lithium chloride of same molar) rub
Your yield is 93%.
Test example 1
Ionic conductivity to the ionic liquid obtained by embodiment 1-4 is tested.
The method of testing of ionic conductivity is as follows：
Ionic liquid is positioned in 70 DEG C of drying boxes and dries 10h, conductivity meter is then inserted into ionic liquid (ionic liquid
Body is completely by platinized platinum submergence on conductivity meter), conductivity meter is accessed into electrochemical workstation, carry out testing impedance and obtain impedance value
R, ionic conductivity is measured by formula σ=d/ (RA), wherein, d is the distance between two platinized platinums, and A is platinized platinum area, R
It is impedance value.
The conductivity meter is using the model DDSJ-308A's of thunder magnetic-Shanghai INESA Scientific Instrument Co., Ltd.
Conductivity meter.
The test result of ionic conductivity is listed in table 1.
The ionic conductivity of ionic liquid at 1 30 DEG C of table
| Ionic conductivity, Scm-1 | |
| Embodiment 1 | 1.79×10-3 |
| Embodiment 2 | 1.89×10-3 |
| Embodiment 2 (B-2) | 1.55×10-3 |
| Embodiment 3 | 1.90×10-3 |
| Embodiment 4 | 1.35×10-3 |
Test example 2
Polymeric ionic liquid has ionic conductivity and electrochemical window higher obtained in the ionic liquid that the present invention is provided
Mouthful.
The preparation of polymeric ionic liquid：
The ionic liquid and the intermediate product B-2 (not carrying out anion exchange) of embodiment 2 that embodiment 2 is obtained are gathered
Conjunction obtains polymeric ionic liquid, and the specific embodiment of polymerization includes：To adding initiator azodiisobutyronitrile in ionic liquid
(AIBN), azodiisobutyronitrile and the mass ratio of ionic liquid are 5:100, under the conditions of 50 DEG C heating obtain within 16 hours being polymerized from
Sub- liquid.
Chemical property (ionic conductivity and electrochemical window) to polymeric ionic liquid is tested, ionic conductivity
Method of testing and electrochemical window method of testing are as follows.
Ionic conductivity：Polymeric ionic liquid is used into mortar grinder 10min, bubble present in system to be measured is eliminated,
As more uniform electro-chemical test system, mould is put into, filled up, multilayer is coated with preservative film, be placed on 30 points in isoperibol
Clock, is then tested.
Tested using the structure of " ss | polymeric ionic liquids | ss ", ss represents inert electrode (Pt electrodes), passes through
Below equation calculates the electrical conductivity of polymeric ionic liquid,
σ=d/ (RA), wherein, d is the thickness of tested material, and R is to test gained bulk resistance by AC impedence method,
When Z is when locally minimum value is obtained, corresponding Z ' is resistance-R needed for test, and A is material and electrode in test structure
Facing area.
Electrochemical window：Carried out using linear sweep voltammetry, polymeric ionic liquid is tamped into the battery in CR2032
In shell, it is put into mould, accesses electrochemical workstation and tested, assembles " ss | polymeric ionic liquids | ss " structure, " ss " table
Show aluminum alloy sheet, with 0.1mVS-1Sweep speed, from low-voltage scanning to high voltage in 2-7V is interval.
The ionic conductivity of polymeric ionic liquid test at different temperatures obtained in the ionic liquid that embodiment 2 is obtained
Result is shown in Fig. 1, step 3 in embodiment 2) test at different temperatures of the ionic conductivity of the polymer of product B-2 that obtains
Result is shown in Fig. 2.σ represents ionic conductivity in Fig. 1 and Fig. 2, and the unit of σ is Scm-1。
Ionic liquid and the step 3 of embodiment 2 that embodiment 2 is obtained) polymerization that obtains by polymerization of the product B-2 that obtains from
Ionic conductivity and electrochemical window test result of the sub- liquid at 30 DEG C are shown in Table 2, though it is not entirely shown, other implementations
Ionic conductivity and electrochemical window test result of the polymeric ionic liquid that example is obtained at 30 DEG C are similar to Example 2.
The ionic conductivity and electrochemical window result of polymeric ionic liquid at 2 30 DEG C of table
| Ionic conductivity, Scm-1 | Electrochemical window, V | |
| Embodiment 2 | 4.22×10-4 | 7.5 |
| Embodiment 2 (B-2) | 1.95×10-4 | 7.3 |
It is complicated that the ionic liquid that the present invention is provided overcomes conventional ion liquid preparation technology, the low defect of security, and
Ionic conductivity is high.Polymeric ionic liquid obtained in the ionic liquid that the method provided using the present invention is obtained, with higher
Ionic conductivity and electrochemical window wider, and ionic liquid obtained in the method that provides of the present invention evaded tradition and prepared bromine
For the process of raw material, it is to avoid should during uneasy full response, method full safety that the present invention is provided, controllability is strong, produce
Rate is high.
By the contrast of embodiment 1-3 and embodiment 4, anion friendship is carried out using most preferably lithium salts of the invention
Change, can further improve ionic conductivity, widen electrochemical window.
The comparing result of the polymeric ionic liquid obtained by embodiment 2 and the intermediate product B-2 of embodiment 2, will be with
Hydroxyl carries out reaction generation ester for the organic material and monosubstituted acyl chlorides of end, and esterification products and imidazoles material are carried out into ion
Salt-forming reaction can to a certain extent improve ionic conductivity, widen electrochemical window, proceed preferred anion and hand over
Change the chemical property that reaction is more beneficial for improving ionic liquid.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method
Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (13)
1. a kind of ionic liquid, it is characterised in that the ionic liquid has the formula shown in formula (1),
Wherein, n is selected from the integer of 1-10, R1It is H, C1-C6Alkyl, R2
It is hydrogen, C1-C6Saturated hydrocarbyl or C1-C6Unsaturated alkyl, R3And R5It is each independently hydrogen or C1-C6Alkyl, R4And R6Each
It independently is C1-C6Alkylidene, R7It is C1-C6Saturated hydrocarbyl or C1-C6Unsaturated alkyl,
X—It is Cl—、ClO4 —、
2. ionic liquid according to claim 1, wherein, n is selected from the integer of 1-7；R1It is H, C1-C3Alkyl orR2It is hydrogen, C1-C3Saturated hydrocarbyl or C1-C3Unsaturated alkyl；
X—For
Preferably, n is equal to 3 or 4；R1For H, methyl,R2For vinyl or
Ethyl；X—For
It is further preferred that working as R2During for H or saturated hydrocarbyl, R1For
3. a kind of preparation method of ionic liquid, it is characterised in that the method includes：
1) methylsufonyl chloride is carried out into the first reaction with the material of structure shown at least one formula (2)；
2) by step 1) the first organic product for obtaining of reaction carries out the second reaction with the material of structure shown in formula (3)；
Wherein, n is selected from the integer of 1-10, R8It is H, C1-C6Alkyl,
R2It is hydrogen, C1-C6Saturated hydrocarbyl or C1-C6Unsaturated alkyl, R3And R5It is each independently hydrogen or C1-C6Alkyl, R4And R6Respectively
From independently being C1-C6Alkylidene, R7It is C1-C6Saturated hydrocarbyl or C1-C6Unsaturated alkyl.
4. preparation method according to claim 3, wherein, n is selected from the integer of 1-7；R8It is H or C1-C3Alkyl；R2For
Hydrogen, C1-C3Saturated hydrocarbyl or C1-C3Unsaturated alkyl；
Preferably, n is equal to 3 or 4；R8It is H or methyl；R2It is vinyl or ethyl.
5. preparation method according to claim 3, wherein,
Methylsufonyl chloride is 1-3 with the mol ratio of the material of structure shown in formula (2):1, preferably 1-2:1；
Step 1) the first organic product for obtaining of reaction and the mol ratio of the material of structure shown in formula (3) be 1:1-3, preferably 1:
1-2。
6. the preparation method according to any one in claim 3-5, wherein, first reaction in acid binding agent and/or
Carried out in the presence of diluent；
Preferably, the acid binding agent be triethylamine, the diluent be selected from dichloromethane, dichloroethanes and dichloropropane in extremely
Few one kind.
7. preparation method according to claim 6, wherein, methods described also includes：By structure shown at least one formula (2)
Material mix with the diluent and acid binding agent successively, carry out the first reaction to treat to be contacted with methylsufonyl chloride；
Preferably, the condition of first reaction includes：30-60min is stirred under condition of ice bath, room temperature is subsequently placed in at 60 DEG C
Stirring 6-12h.
8. preparation method according to claim 3, wherein, work as R2During for H or saturated hydrocarbyl, R8It is H, the method also includes：
By step 1) the first organic product for obtaining of reaction with acrylic acid and/or metering system acid reaction with to step 1) first react
To organic product in introduce
Preferably, by step 1) the first organic product for obtaining of reaction and organic solvent, acrylic acid and/or methacrylic acid, carbon
Sour caesium and polymerization inhibitor haptoreaction；
It is further preferred that the catalytic temperature is 30-50 DEG C, the time is 30-60h.
9. the preparation method according to any one in claim 3-5, wherein, the condition of second reaction includes：
At 80-120 DEG C, 6-12h is stirred.
10. the preparation method according to any one in claim 3-9, wherein, the method also includes：By step 2) second
The product that reaction is obtained carries out anion exchange reaction；
Preferably, the specific embodiment of the anion exchange reaction includes：By step 2) the second product for obtaining of reaction with
Lithium salts is contacted.
11. preparation methods according to claim 10, wherein,
The product that second reaction is obtained and the mol ratio of lithium salts are 1:1-5, preferably 1:1-3；
The lithium salts is selected from least one in double trifluoromethanesulfonimide lithiums, lithium perchlorate and lithium chloride, preferably double three
Fluoromethane sulfimide lithium.
Ionic liquid obtained in 12. preparation method as described in any one in claim 3-11.
The application of ionic liquid described in 13. claims 1,2 and 12 in lithium ion battery.
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| US20120082903A1 (en) * | 2010-09-30 | 2012-04-05 | Zhengcheng Zhang | Functionalized ionic liquid electrolytes for lithium ion batteries |
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