CN108218782A - A kind of secondary cell ionic liquid and its synthetic method and application - Google Patents
A kind of secondary cell ionic liquid and its synthetic method and application Download PDFInfo
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- CN108218782A CN108218782A CN201611145796.5A CN201611145796A CN108218782A CN 108218782 A CN108218782 A CN 108218782A CN 201611145796 A CN201611145796 A CN 201611145796A CN 108218782 A CN108218782 A CN 108218782A
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- 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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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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Abstract
The present invention provides a kind of secondary cell ionic liquid and its synthetic method and application, and the secondary cell ionic liquid is the ionic liquid of the side chain containing hetero atom, and positively charged functional group is quaternary ammonium salt, one kind in imidazole salts, pyrroles's salt, pyridiniujm；Y is O in side chain, is the alkyl chain of length C1 C3 between Y and positively charged functional group, Y is far from the alkyl chain that positively charged functional group side is C1 C3 or the oxygen-containing alkyl chain of C2 C7；To anion X‑For Cl‑、Br‑、I‑、BF4 ‑Or TFSI‑One or more of (bis trifluoromethyl sulfimide).Compared with prior art, the adjustability of structure of the ionic liquid is preferable, the modulation ionic liquid chemical constitution of substituent group can be passed through according to demand, optimize ionic liquid character, the conductivity of ionic liquid can realize the preparation of different ionic liquid by the optimization of the alternative condition of catalyst in more than 1mS/cm, preparation process using substances such as environmental protection alcohol ethers, it is easy to operate, it is easy to accomplish.
Description
Technical field
The invention belongs to secondary cell field of ionic liquid；The present invention relates to one kind to have compared with high ionic conductivity, good
Good electrochemical stability has the synthesis of the ionic liquid of side chain containing hetero atom of favorable compatibility and its characterization, survey with electrolyte
Examination.
Background technology
It is exploitation clean environment firendly, efficient renewable with the increasingly depleted of fossil energy and the increasingly exacerbation of environmental pollution
New energy has been increasingly becoming the hot spot of whole world research.Advanced energy storage and secondary cell also become wherein indispensable important set
Into part.Lithium ion battery due to its higher energy density, the high circulation service life, it is environmentally protective the advantages that become research and development
Hot spot.In recent years, due to the rise of new-energy automobile, lithium rechargeable battery has obtained applying to a certain extent.However, at present
The course continuation mileage of lithium-ion electric electrical automobile is relatively low (general<300km), cost is higher.In order to solve asking in terms of lithium ion battery
Topic, researchers have carried out a large amount of research work.On the one hand, it by optimizing battery cathode material and electrolyte, is gradually increased
The capacity of lithium ion battery；On the other hand, by study using lithium metal as anode lithium/sky and (or) lithium/sulphur battery have compared with
High theoretical energy density shows certain application prospect.However, the fusing point of lithium metal is low, active higher, have most of
There are problems that Li dendrite precipitation in machine electrolyte, there are serious security risks for the application in large-sized power battery, hinder
It is commercialized process.Therefore, exploitation becomes with more high-energy-density, mechanism of new electrochemical power sources system pollution-free, at low cost and works as
The important content of preceding research and advanced probing direction.
Currently, the new secondary battery using metals such as magnesium, aluminium, sodium, calcium as anode is increasingly becoming the hot spot studied at present.Especially
Using magnesium metal as anode, its theoretical specific capacity is up to 2205mAhg for it-1, electrode potential is about -2.37V (Vs.SHE), is had good
Good electric conductivity, mechanical performance, higher safety, particularly its price are the 1/25 of lithium so that magnesium cell in safety and
Two aspect of cost has significant advantage simultaneously, is considered being expected to be used for the green secondary cell of electric vehicle and energy-storage system.
In addition, the magnesium resource reserves in China occupy the first in the world, compared to other countries, exploitation rechargeable magnesium cell has considerable excellent
Gesture.
The research history of rechargeable magnesium cell and lithium battery are almost suitable, but it is relatively slow to compare with lithium battery its development,
It is different to be primarily due to the properties of interfacial film that magnesium metal and lithium are formed in most aprotic, polar organic electrolytes.
The passivating film that metallic lithium surface is formed is the excellence conductor of lithium ion, and the passivating film of magnesium surface generation is the bad of magnesium ion
Conductor causes magnesium ion that can not pass through this layer of passivating film, so as to limit magnesium metal electro-chemical activity.It can be said that magnesium electricity can be filled
It is related all to obtain big breakthrough with electrolyte for each step development in pond.
Important component of the electrolyte as battery is referred to as " blood " of battery, is played between battery cathode and anode
It conveys ion and conducts the effect of electric current, be one of key factor for improving battery performance.Electrolyte includes electrolyte
With solvent two parts, a large amount of work is done, and have made some progress about the performance study persons for improving electrolyte, proposed
New system, including machine Grignard Reagent and its derivative system, organic-magnesium halogen aluminium salt system, molten salt system, solid electrolytic plastid
System etc..However most of presently used solvent is acetonitrile, ethers and lipid, is low boiling point using most of organic reagent, easy
Volatilization, environmental pollution is not only resulted in, and can cause electrolyte since the volatilization of solvent causes its viscosity to increase, conductivity
It reduces.At the same time, the electrochemical window of organic reagent is narrow, and electrochemical stability is poor, causes the voltage window of battery
Smaller, the poor-performing of mouth.
Ionic liquid, as a kind of organic molecule salt of liquid at room temperature, since its conductivity is higher, electrochemical window
It is wide and electrolyte or solvent is used as to receive and widely pay close attention to.However, ionic liquid is still deposited as secondary cell electrolyte at present
In some shortcomings：(1) viscosity is larger, and the conductivity that this not only results in entire electrolyte is low, and the ohmic polarization of battery is larger, and
And the transmission difficulty of magnesium can be also caused, the multiplying power of battery is small；(2) it is not suitable for the complexing of magnesium.If the work of ionic liquid and magnesium
With larger, the ability that magnesium is complexed is stronger, and the reduction of magnesium can be caused to deposit relatively difficult, as a result cause the invertibity of Mg secondary cell
It is poor；If the complexing with magnesium is weaker, the ability for carrying magnesium ion is weaker, and the transmission of magnesium will encounter difficulties.So how to open
Hair synthesis viscosity is low, conductivity is high, electrochemical stability window is wide, there is suitable complexing power with magnesium can with effectively realize magnesium
The novel ion liquid of inverse deposition/dissolution becomes the hot spot studied at present and difficult point.
Invention content
It is in view of the above-mentioned problems, a kind of with compared with low viscosity, high conductance, wider electrification it is an object of the invention to synthesize
Window, the ionic liquid of reversible deposition/dissolution suitable to magnesium complexing power, can realizing magnesium；It characterizes and tests this ion
The physical and chemical performance of liquid；Evaluate its application prospect in the secondary battery.
The structural representation letter of the ionic liquid of the side chain containing hetero atom of synthesis is as follows：
Wherein, positively charged functional group is quaternary ammonium salt, imidazole salts (the straight chain alkane that the nitrogen N1 positions of imidazole salts are C1-C4
Hydrocarbon and/or carbon C2 positions are methyl), pyrroles's salt, one kind in pyridiniujm；Y is O in side chain, between Y and positively charged functional group
For the alkyl chain of length C1-C3, Y contains oxyalkyl far from the alkyl chain or C2-C7 that positively charged functional group side is C1-C3
Chain；To anion X-For Cl-、Br-、I-、BF4 -Or TFSI-One kind in (bis trifluoromethyl sulfimide).
A kind of synthesis of the ionic liquid of the side chain containing hetero atom includes the following steps：
(1) the halogenated synthesis containing heteroatom species
The halogenated synthesis containing heteroatom species includes two steps：The first step is the substance of tosylation containing hetero atom
Synthesis；Second step is the synthesis of the halogenated compound containing hetero atom.
The building-up process of the substance of tosylation containing hetero atom is：It is sequentially added in the organic solvent A of certain volume
The alcohol ether of certain volume and the organic weak base of certain volume, after mixing at a certain temperature add in certain mass to first
Benzene sulfonyl chloride is cleaned up with certain density aqueous slkali after reacting a period of time under certain temperature, is fully dried to obtain and contains
Hetero atom tosylation substance a；
The building-up process of the halogenated compound containing hetero atom is：By the tolysulfonyl containing hetero atom of the above-mentioned preparation of certain mass
Compound a is dissolved in the organic solvent B of certain volume, the halide of certain mass is added in after dissolving completely, at a certain temperature instead
After a period of time, it should fully be dried to obtain the b of halogenated compound containing hetero atom.
(2) synthesis of the ionic liquid of the side chain containing hetero atom
The synthesis of the ionic liquid of the side chain containing hetero atom includes two steps：The first step be the halogen-type of side chain containing hetero atom from
The synthesis of sub- liquid；Second step is the conversion of ionic liquid different anions.
The building-up process of the halogen-type ionic liquid of side chain containing hetero atom is：It will be synthesized in certain mass step (1) containing miscellaneous
(the nitrogen N1 positions of glyoxaline compound are C1-C4's for the tertiary amine of atom halogenated compound b and certain volume, glyoxaline compound
Linear paraffin and/or carbon C2 positions are methyl), pyrroles or pyridine be dissolved in the organic solvent C of certain volume, in certain temperature item
A period of time is reacted under part, the halogen-type ionic liquid of side chain containing hetero atom is dried to obtain after then fully being washed with organic solvent D；
The conversion process of ionic liquid different anions is：By the halogen-type ionic liquid of side chain containing hetero atom of above-mentioned synthesis
It is dissolved in the solvent E of certain volume, adds in the corresponding inorganic salts of certain mass anion, removed after stirring a period of time at room temperature
Solvent obtains the crude samples of the ionic liquid of different anions after fully being washed with dichloromethane or water；
(3) purifying of the ionic liquid of side chain containing hetero atom
The purity level of ionic liquid is to the electrochemistry of ionic liquid physicochemical properties in itself and application ionic liquid
Device performance is affected, thus the purifying of ionic liquid be ionic liquid application premise, be it is particularly significant also compare have
The operation of difficulty.Purification process is：Activated carbon is added in the above-mentioned ionic liquid fully washed, stirs mistake after a period of time
Filter, is subsequently poured into fill and is filtered in diatomaceous funnel, finally using revolving method it is fully dry at a certain temperature after
It is put into spare in glove box.
The synthesis of the ionic liquid of the above-mentioned side chain containing hetero atom：
Alcohol ether described in step (1) is diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, five second
One kind in glycol monomethyl ether, six glycol monoethyl ethers and poly glycol monomethyl ether -350；
Organic weak base described in step (1) is pyridine, triethylamine, N, N- diisopropylethylamine, DABCO (1,4- diazas
One or more of two rings [2.2.2] octane)；
Solvent A described in step (1) is dichloromethane, dichloroethanes, chloroform, acetone, acetonitrile, ethyl alcohol, propyl alcohol, isopropanol
In one kind；
Aqueous slkali described in step (1) is sodium carbonate, one kind in sodium bicarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide
It is or several；A concentration of 0.1-10mol/L of the aqueous slkali；
The volume of alcohol ether described in step (1) and the volume ratio of solvent A are 1:0-1:10；The volume of the alcohol ether with it is organic
The volume ratio of weak base is 1:0.3-1:1.5；The volume of the alcohol ether and the mass ratio of paratoluensulfonyl chloride are 1:0.5-1:5mL/
g；
0-10 DEG C of the temperature of solution when paratoluensulfonyl chloride is added in described in step (1)；0-40 DEG C of the reaction temperature；Institute
State the reaction time>12h；
Drying mode described in step (1) is vacuum drying or revolving；The drying temperature is 100-140 DEG C；It is described dry
The dry time is>12h；
Halide described in step (1) is lithium chloride, one kind in lithium bromide, potassium bromide, potassium iodide, sodium iodide；
Solvent B described in step (1) is one or more of acetone, acetonitrile, dichloromethane, dichloroethanes；
The quality of the compound of tolysulfonyl containing hetero atom a described in step (1) and the mass ratio of halide are 5:1-1:3；
The quality of the compound of tolysulfonyl containing hetero atom a described in step (1) is 1 with the volume ratio of solvent B:5-3:1g/mL；
The reaction temperature of the compound a of tolysulfonyl containing hetero atom and halide described in step (1) is -80 DEG C of room temperature；Institute
State the reaction time>12h；The drying condition is identical with the drying condition of hetero atom tolysulfonyl compound a；
Step (2) described solvent C is one or more of ethyl alcohol, methanol, isopropanol, propyl alcohol；The solvent D is
One or both of ethyl acetate, ether；
The quality of the b of halogenated compound containing hetero atom described in step (2) and tertiary amine, glyoxaline compound (glyoxaline compound
Nitrogen N1 positions be C1-C4 linear paraffin and/or carbon C2 positions be methyl), the volume ratio of pyrroles or pyridine be 4:1-1:2g/
mL；The quality of the b of halogenated compound containing hetero atom and the volume ratio of solvent C are 1:0-1:10g/mL；
Step (2) described reaction temperature is -100 DEG C of room temperature；The reaction time is>12h；
Step (2) described inorganic salts are sodium tetrafluoroborate, potassium tetrafluoroborate, LiBF4, lithium hexafluoro phosphate, bis- (three
Fluoromethane sulfimide) one kind in lithium；
Step (2) the solvent E is one or more of water, acetone, acetonitrile, chloroform, methanol；
The mass ratio of the quality of the halogen-type ionic liquid of side chain containing hetero atom and inorganic salts described in step (2) is 5:1-1:5；
The quality of the halogen-type of side chain containing the hetero atom ionic liquid is 1 with the volume ratio of solvent E:10-1:100；
Step (2) described mixing time is>24h；
Step (3) described mixing time is>12h；The revolving temperature is 100-140 DEG C；It is described revolving the time be>48h.
The synthesis of the ionic liquid of the side chain of the present invention containing hetero atom has the following advantages that：
(1) adjustability of structure of ionic liquid is preferable, can pass through the modulation ionic liquid chemistry knot of substituent group according to demand
Structure optimizes ionic liquid character；
(2) conductivity of the ionic liquid of the side chain containing hetero atom of synthesis disclosure satisfy that novel secondary in more than 1mS/cm
Requirement of the magnesium cell to conductivity；
(3) ionic liquid of the side chain containing hetero atom of synthesis is theoretically moderate to the complexing power of magnesium, and can realize magnesium can
Inverse dissolving/deposition process, cycle performance of battery are preferable.
Description of the drawings
Fig. 1 is the synthetic route of the ionic liquid of the side chain containing hetero atom in embodiment 1.
Fig. 2 is the nucleus magnetic hydrogen spectrum of the substance of tosylation containing hetero atom synthesized in embodiment 1.
Fig. 3 is the nucleus magnetic hydrogen spectrum of the halogenated compound containing hetero atom synthesized in embodiment 1.
Fig. 4 is the nucleus magnetic hydrogen spectrum of the ionic liquid of the side chain containing hetero atom in embodiment 1.
Specific embodiment
Embodiment 1
Under room temperature, 20mL diethylene glycol monomethyl ethers and 30mL pyridines are added in into 100mL single-necked flasks, and is stirred equal
It is even.Then (4 DEG C) the addition 40g paratoluensulfonyl chlorides under conditions of ice-water bath, stir 0.5h, Ran Hou under the conditions of ice-water bath
30h is reacted under the conditions of 30 DEG C.It is washed 4 times with 10M sodium bicarbonate aqueous solutions after reaction solution restores to room temperature, 120 after liquid separation
DEG C dry 48h of revolving, obtains diethylene glycol monomethyl ether tolysulfonyl compound.
The diethylene glycol monomethyl ether tolysulfonyl compound of the above-mentioned synthesis of 25g is dissolved in 30mL acetone, while stirring slowly
Slow to add in 15g sodium iodide solids, 60 DEG C of condensing refluxes react 48h.Restore after reaction solution to room temperature, 40 DEG C of revolvings dry and remove
A large amount of acetone, then 120 DEG C of revolvings are dry for 24 hours, obtain diethylene glycol monomethyl ether iodide.
The diethylene glycol monomethyl ether halogenated compound of the above-mentioned synthesis of 20g and 10mL 1- methylimidazoles are added to 50mL to burn
In bottle, 80 DEG C of magnetic agitations react 60h.Restore after reaction solution to room temperature, fully washed with ethyl acetate, tangerine is obtained after liquid separation
It is obtained 1- methyl -3- diethylene glycol monomethyl ether imidazolium iodides after 120 DEG C of vacuum drying, is put by yellow viscous liquid
It is spare in glove box.
1- methyl -3- diethylene glycol monomethyl ether the imidazolium iodides of above-mentioned synthesis are converted into TFSI-For anionic
Ionic liquid.10g1- methyl -3- diethylene glycol monomethyl ethers imidazolium iodide, 15g LiTFSI are weighed in glove box, is added in
100mL water, is sufficiently stirred, and isolates upper water, is fully washed with water (when adding in AgNO into upper water3It does not precipitate, table
Bright washes clean).Then TFSI types ionic liquid is transferred to after 130 DEG C of revolving 72h to be measured in glove box.
1- methyl -3- diethylene glycol monomethyl ether the imidazolium iodides of above-mentioned synthesis are converted into BF4 -For anionic from
Sub- liquid.10g 1- methyl -3- diethylene glycol monomethyl ethers imidazolium iodide, 8g NaBF are weighed in glove box4, add in 200mL
Acetonitrile stirs 48h at room temperature.Filter out extra NaBF4It carries out revolving and removes acetonitrile solvent, obtain orange clear solution.It will
Dichloromethane is added in solution, and a large amount of white flock precipitates are precipitated, and solution is rotated after filtering and removes dichloromethane.Then again to molten
Dichloromethane is added in liquid, white precipitate is precipitated, refilters revolving, is so performed repeatedly until into solution and adds in dichloromethane
Generation is not precipitated.130 DEG C of revolving 72h obtain dry BF again after 40 DEG C of revolving removing dichloromethane4 -Type ionic liquid, and shift
It is to be measured into glove box.
Using Bruker ACIII 400 to diethylene glycol monomethyl ether tolysulfonyl compound, diethylene glycol monomethyl ether iodate
Object, the structure of diethylene glycol monomethyl ether imidazolium iodide and purity are characterized, resonant frequency 400.13MHz.During experiment,
A small amount of diethylene glycol monomethyl ether tolysulfonyl compound, diethylene glycol monomethyl ether iodide are dissolved with deuterochloroform, diethylene glycol
Monomethyl ether imidazolium iodide is dissolved in heavy water, in acquisition sample in Nuclear Magnetic Resonance1H NMR spectras.Wherein with deuterochloroform
Test sample for solvent is using tetramethylsilane (TMS) as internal standard.Fig. 2 is diethylene glycol monomethyl ether tolysulfonyl compound
's1H NMR, Fig. 3 are diethylene glycol monomethyl ether iodide1H NMR, Fig. 4 are diethylene glycol monomethyl ether imidazolium iodide1H
NMR.By in Fig. 2, Fig. 3, Fig. 41Characteristic peak positions and hydrogen peak peak type, which can be seen that, in H NMR successfully synthesizes diethylene glycol list first
Ether tolysulfonyl compound, diethylene glycol monomethyl ether iodide and diethylene glycol monomethyl ether imidazolium iodide, and the sample synthesized
The purity of product is higher.
The conductivity of ionic liquid and electrolyte is tested using plum Teller FE30 conductivity meters, measurement range is：
0-199.9mS cm-1.Entire experiment carries out in the glove box of argon gas atmosphere, and test temperature is room temperature.TFSI-Anion corresponds to
The corresponding conductivity of diethylene glycol monomethyl ether imidazole ion liquid close to 3mScm-1, secondary cell is substantially met to ionic liquid
Conductivity requirement (>1mScm-1)。
We use TFSI-Full phenyl magnalium lattice are configured for solvent in anionic diethylene glycol monomethyl ether imidazole ion liquid
Family name's reagent electrolyte simultaneously tests its conductivity.Full phenyl magnalium Grignard Reagent is prepared according to document, and process is：In glove box
Middle weighing 0.564g alchlors, are dissolved with 6mLTHF, obtain orange-yellow clear solution, and it is complete that 4mL 1M are then slowly added dropwise
Phenyl-magnesium-chloride is uniformly mixing to obtain yellow transparent solution.Then the ionic liquid of different proportion is added in into this clear solution,
Solution measures conductivity after restoring to room temperature.Table 1 is the corresponding conductivity value of electrolyte for the amount for adding in different ionic liquid.Table
Middle n is the ratio of the amount of the substance of ionic liquid and the amount of the substance of alchlor.To data analysis in table, it can be seen that ion
The addition of liquid significantly improves the conductivity of electrolyte, but as the conductivity of the increase electrolyte of the ionic liquid scale of construction is no longer bright
It is aobvious to improve, illustrate that influence of the amount of ionic liquid to the conductivity of electrolyte is smaller.
1 different proportion diethylene glycol monomethyl ether imidazoles TFSI of table-The conductivity of type il electrolyte.
Embodiment 2
Under room temperature, 30mL triethylamines, 10mL poly glycol monomethyl ethers -350 and 6mL pyridines are sequentially added into 100mL
In flask, stir evenly.15g paratoluensulfonyl chlorides are added at a temperature of 6 DEG C, are then stirred to react 48h under the conditions of 25 DEG C.
It is washed 6 times, then fully washed with water with 4M wet chemicals after reaction solution restores to room temperature, in 130 DEG C of revolvings after liquid separation
Dry 60h, obtains poly glycol monomethyl ether tolysulfonyl compound.
The poly glycol monomethyl ether tolysulfonyl compound of the above-mentioned synthesis of 15g is dissolved in 20mL acetonitriles, is slowly added into 6g
Lithium bromide, 80 DEG C of condensing refluxes react 28h.80 DEG C of revolvings dry and remove acetonitrile solvent, and then the dry 48h of 130 DEG C of revolvings, obtains
Poly glycol monomethyl ether iodide.
The poly glycol monomethyl ether halogenated compound of the above-mentioned synthesis of 12g and 5mL trimethylamines alcoholic solution (33%) are added to
In 50mL flasks, 40 DEG C of magnetic agitations react 48h.Restore after reaction solution to room temperature, fully washed to obtain orange with ether and be glued
Thick liquid.1- methyl -3- poly glycol monomethyl ether imidazolium bromides finally are obtained after dry 72h in 130 DEG C of vacuum drying chambers,
It is put into spare in glove box.
1- methyl -3- poly glycol monomethyl ether the imidazolium iodides of above-mentioned synthesis are converted into TFSI-For anionic
Ionic liquid.10g 1- methyl -3- poly glycol monomethyl ethers imidazolium iodide, 10g LiTFSI are weighed in glove box, is added in
30mL water, is sufficiently stirred, and removes upper water, is fully washed with water (when adding in AgNO into upper water3It does not precipitate, shows
Washes clean).Then TFSI types ionic liquid is transferred to after 130 DEG C of revolving 72h in glove box and carries out conductivity and other
The measure of parameter.TFSI-The conductivity of anion 1- methyl -3- poly glycol monomethyl ether imidazole ion liquids is 0.7mScm-1。
The conductivity of this ionic liquid is significantly less than the ionic liquid conductivity synthesized in embodiment 1, and analysis reason is side chain molecular weight
Increase, cationic removable reduced capability, ionic liquid conductivity decline.
Claims (6)
1. a kind of secondary cell ionic liquid, for the ionic liquid of the side chain containing hetero atom, structural representation is as follows：
Wherein, positively charged functional group is one kind in quaternary ammonium salt, imidazole salts, pyrroles's salt, pyridiniujm；In side chain Y be O, Y with
It is the alkyl chain of length C1-C3 between positively charged functional group, Y is far from the alkyl chain that positively charged functional group side is C1-C3
Or the oxygen-containing alkyl chain of C2-C7；To anion X-For Cl-、Br-、I-、BF4 -Or TFSI-In (bis trifluoromethyl sulfimide)
It is one or more kinds of.
2. a kind of synthetic method of secondary cell ionic liquid described in claim 1, it is characterised in that：Include the following steps：
(1) the halogenated synthesis containing heteroatom species
The halogenated synthesis containing heteroatom species includes two steps：The first step is the conjunction of the substance of tosylation containing hetero atom
Into；Second step is the synthesis of the halogenated compound containing hetero atom.
The building-up process of the substance of tosylation containing hetero atom is：Alcohol ether and organic weak is sequentially added in organic solvent A
Alkali is adding in paratoluensulfonyl chloride after mixing, is being cleaned up, be fully dried to obtain containing hetero atom pair with aqueous slkali after reaction
Tosylated species a；
The building-up process of the halogenated compound containing hetero atom is：The compound of tolysulfonyl containing the hetero atom a of above-mentioned preparation, which is dissolved in, to be had
In solvent B, halide is added in after dissolving completely, after reaction, is fully dried to obtain the b of halogenated compound containing hetero atom；
(2) synthesis of the ionic liquid of the side chain containing hetero atom
The synthesis of the ionic liquid of the side chain containing hetero atom includes two steps：The first step is the halogen-type ionic liquid of side chain containing hetero atom
The synthesis of body；Second step is the conversion of ionic liquid different anions；
The building-up process of the halogen-type ionic liquid of side chain containing hetero atom is：The halogenated chemical combination containing hetero atom that will be synthesized in step (1)
(linear paraffin and/or carbon C2 positions that the nitrogen N1 positions of glyoxaline compound are C1-C4 be for object b and tertiary amine, glyoxaline compound
Methyl), pyrroles or pyridine be dissolved in organic solvent C, react, be dried to obtain after then fully being washed with organic solvent D containing miscellaneous original
Sub- side chain halogen-type ionic liquid；
The conversion process of ionic liquid different anions is：The halogen-type ionic liquid of side chain containing hetero atom of above-mentioned synthesis is dissolved in
In solvent E, the corresponding inorganic salts of anion are added in, stirring at room temperature removes solvent, after fully being washed with dichloromethane or water
To the crude samples of the ionic liquid of different anions；
(3) purifying of the ionic liquid of side chain containing hetero atom
Purification process is：Activated carbon is added in the above-mentioned ionic liquid fully washed, is filtered after stirring, is subsequently poured into and fills
It is filtered, is put into after finally fully being dried using revolving method spare in glove box in diatomaceous funnel.
3. according to the synthetic method of secondary cell ionic liquid described in claim 2, it is characterised in that：
Alcohol ether described in step (1) is diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, five ethylene glycol
One kind in monomethyl ether, six glycol monoethyl ethers and poly glycol monomethyl ether -350；
Organic weak base described in step (1) is pyridine, triethylamine, N, N- diisopropylethylamine, DABCO (1,4- diazabicylos
One or more of [2.2.2] octane)；
Solvent A described in step (1) is dichloromethane, in dichloroethanes, chloroform, acetone, acetonitrile, ethyl alcohol, propyl alcohol, isopropanol
It is a kind of；
Aqueous slkali described in step (1) is sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide, one kind in potassium hydroxide or several
Kind；A concentration of 0.1-10mol/L of the aqueous slkali；
The volume of alcohol ether described in step (1) and the volume ratio of solvent A are 1:0-1:10；The volume and organic weak base of the alcohol ether
Volume ratio be 1:0.3-1:1.5；The volume of the alcohol ether and the mass ratio of paratoluensulfonyl chloride are 1:0.5-1:5mL/g；
0-10 DEG C of the temperature of solution when paratoluensulfonyl chloride is added in described in step (1)；0-40 DEG C of the reaction temperature；It is described anti-
Between seasonable>12h；
Drying mode described in step (1) is vacuum drying or revolving；The drying temperature is 100-140 DEG C；When described dry
Between be>12h；
Halide described in step (1) is lithium chloride, one kind in lithium bromide, potassium bromide, potassium iodide, sodium iodide；
Solvent B described in step (1) is one or more of acetone, acetonitrile, dichloromethane, dichloroethanes；
The quality of the compound of tolysulfonyl containing hetero atom a described in step (1) and the mass ratio of halide are 5:1-1:3；Step
(1) quality of the compound of tolysulfonyl containing hetero atom described in a is 1 with the volume ratio of solvent B:5-3:1g/mL；
The reaction temperature of the compound a of tolysulfonyl containing hetero atom and halide described in step (1) is -80 DEG C of room temperature；It is described anti-
Between seasonable>12h；The drying condition is identical with the drying condition of hetero atom tolysulfonyl compound a.
4. according to the synthetic method of secondary cell ionic liquid described in claim 2, it is characterised in that：
Step (2) described solvent C is one or more of ethyl alcohol, methanol, isopropanol, propyl alcohol；The solvent D is acetic acid
One or both of ethyl ester, ether；
The quality of the b of halogenated compound containing hetero atom described in step (2) and tertiary amine, the glyoxaline compound (nitrogen of glyoxaline compound
The linear paraffin and/or carbon C2 positions that N1 positions are C1-C4 are methyl), the volume ratio of pyrroles or pyridine be 4:1-1:2g/mL；
The quality of the b of halogenated compound containing hetero atom and the volume ratio of solvent C are 1:0-1:10g/mL；
Step (2) described reaction temperature is -100 DEG C of room temperature；The reaction time is>12h；
Step (2) described inorganic salts are sodium tetrafluoroborate, potassium tetrafluoroborate, LiBF4, lithium hexafluoro phosphate, bis- (fluoroforms
Alkane sulfimide) one kind in lithium；
Step (2) the solvent E is one or more of water, acetone, acetonitrile, chloroform, methanol；
The mass ratio of the quality of the halogen-type ionic liquid of side chain containing hetero atom and inorganic salts described in step (2) is 5:1-1:5；It is described
The quality of the halogen-type ionic liquid of side chain containing hetero atom is 1 with the volume ratio of solvent E:10-1:100；
Step (2) described mixing time is>24h.
5. according to the synthetic method of secondary cell ionic liquid described in claim 2, it is characterised in that：
Step (3) described mixing time is>12h；The revolving temperature is 100-140 DEG C；It is described revolving the time be>48h.
6. a kind of electrolyte of the ionic liquid as secondary cell described in claim 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012048874A (en) * | 2010-08-25 | 2012-03-08 | Yamaguchi Univ | Electrolyte for magnesium secondary battery, and magnesium secondary battery using the same |
| CN103387742A (en) * | 2012-05-08 | 2013-11-13 | 海洋王照明科技股份有限公司 | Imidazole ionic liquid/gel polymer electrolyte membrane and preparation method thereof |
-
2016
- 2016-12-13 CN CN201611145796.5A patent/CN108218782A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012048874A (en) * | 2010-08-25 | 2012-03-08 | Yamaguchi Univ | Electrolyte for magnesium secondary battery, and magnesium secondary battery using the same |
| CN103387742A (en) * | 2012-05-08 | 2013-11-13 | 海洋王照明科技股份有限公司 | Imidazole ionic liquid/gel polymer electrolyte membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MARTIN B. DURISKA，等: ""Synthesis and Characterization of Novel Ionic Liquids: N-Substituted Aziridinium Salts"", 《JOURNAL OF HETEROCYCLIC CHEMISTRY》 * |
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|---|---|---|---|---|
| CN110429334A (en) * | 2019-07-16 | 2019-11-08 | 中国电子新能源（武汉）研究院有限责任公司 | Electrolyte and preparation method thereof and battery |
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