CN110407724A - A kind of double ion is to ionic liquid and preparation method thereof - Google Patents
A kind of double ion is to ionic liquid and preparation method thereof Download PDFInfo
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- CN110407724A CN110407724A CN201910669333.6A CN201910669333A CN110407724A CN 110407724 A CN110407724 A CN 110407724A CN 201910669333 A CN201910669333 A CN 201910669333A CN 110407724 A CN110407724 A CN 110407724A
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- ion
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- potassium
- ionic liquid
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 149
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 93
- -1 salt compound Chemical class 0.000 claims abstract description 64
- 150000002500 ions Chemical class 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 23
- 239000012046 mixed solvent Substances 0.000 claims abstract description 21
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 21
- 235000019441 ethanol Nutrition 0.000 claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 4
- 150000002466 imines Chemical class 0.000 claims description 31
- 150000001412 amines Chemical class 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 239000011737 fluorine Substances 0.000 claims description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 10
- 229910001415 sodium ion Inorganic materials 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000001455 metallic ions Chemical class 0.000 claims description 5
- 125000005999 2-bromoethyl group Chemical group 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 3
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- UMJJNXFVAMHNIE-UHFFFAOYSA-N ClCC[Na] Chemical compound ClCC[Na] UMJJNXFVAMHNIE-UHFFFAOYSA-N 0.000 claims description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052740 iodine Chemical group 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- LOBZGFYXHNXAKE-UHFFFAOYSA-N [S]CCBr Chemical compound [S]CCBr LOBZGFYXHNXAKE-UHFFFAOYSA-N 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 34
- 239000003792 electrolyte Substances 0.000 abstract description 15
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 150000002170 ethers Chemical class 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 150000001298 alcohols Chemical class 0.000 description 15
- 229960000935 dehydrated alcohol Drugs 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 15
- 239000003643 water by type Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 9
- QRMLKVVWCJUMPR-UHFFFAOYSA-N BrCC[Na] Chemical compound BrCC[Na] QRMLKVVWCJUMPR-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- ZSBXGIUJOOQZMP-UHFFFAOYSA-N Isomatrine Natural products C1CCC2CN3C(=O)CCCC3C3C2N1CCC3 ZSBXGIUJOOQZMP-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- UXCXDXQIWXBVNI-UHFFFAOYSA-N ethanesulfonic acid;potassium Chemical compound [K].CCS(O)(=O)=O UXCXDXQIWXBVNI-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 229930014456 matrine Natural products 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- 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
- H01M10/052—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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
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- Chemical & Material Sciences (AREA)
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Abstract
The present invention relates to Ionic liquids technologies, it is desirable to provide a kind of double ion is to ionic liquid and preparation method thereof.Include: to take three substitutional amine-group compounds and halogenosulfonic acid salt compound, is dissolved in water-ethanol in the mixed solvent and back flow reaction；Rotary evaporation removes water and ethyl alcohol；Then water is added to be extracted with dichloromethane again three times, retains water phase；After rotary evaporation removes most of water, salt compounds are added；It is stood after stirring, takes drying under lower layer's solution vacuum, the double ion of purifying is made to ionic liquid.Product of the invention can be mixed in all proportions new electrolyte with carbonates or ethers electrolyte, improve the safety of the thermal stability and lithium ion battery of electrolyte.The additive amount that respective metal ion can be reduced when using as electrolyte, even without the corresponding metal ion of addition.Operation of the present invention is simple, and step is few, and yield is high, does not generate toxic by-product, is suitble to large-scale production.
Description
Technical field
The present invention relates to Ionic liquids technologies, in particular to a kind of double ion is to ionic liquid and preparation method thereof.
Background technique
Ionic liquid is a kind of ionic compound being made of zwitterion, and flowable liquid is presented at normal temperature, therefore
Also referred to as ionic liquid at room temperature.Ionic liquid boiling point generally with higher and thermal decomposition temperature and higher ion-conductance
The advantages that conductance and wider electrochemical window.The above advantage makes ionic liquid solve lithium ion battery using security issues
Aspect can be applied.
Chinese invention patent CN109627227A reports a kind of preparation method of piperidines type ionic liquid, and this method is normal
Temperature is lower to be carried out, and yield is high, economical, easy to operate.Synthesizing obtained ionic liquid can be applied to the electrolyte group of lithium ion battery
Point, show better noninflammability and chemical stability and low electrochemical impedance.But the reaction in organic solution into
Row, it is environmentally protective not enough.Chinese invention patent CN109575023A reports a kind of matrine long chain fatty acids ionic liquid
And preparation method thereof, which has good solubility, trap and stability, but the preparation method reaction condition
Harshness needs to react under atmosphere of inert gases, and last handling process needs vacuum environment again.
Therefore, novel ionic liquid is invented, the further investigation and its application to ionic liquid are of great significance.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiency in the prior art, provide a kind of double ion to ionic liquid
Body and preparation method thereof.
In order to solve the technical problem, solution of the invention is:
A kind of double ion is provided to ionic liquid, which has the following structure ionic liquid:
Wherein, R1For the ethylene oxide chain CH of terminal methyl3(OCH2CH2)n, n=2~6；R2For alkane chain-(CH2CH2)n,
N=2-6；R-Be negative univalent anion, is perchlorate, two (trimethyl fluoride sulfonyl) imines, bis- (fluorine sulphonyl) imines, tetrafluoro boron
Any one in acid group or dioxalic acid borate；M+ is positive monovalent metallic ion, is sodium ion (Na+), lithium ion (Li+) or
Potassium ion (K+)。
Invention further provides aforementioned double ions to the preparation method of ionic liquid, comprising the following steps:
(1) three substitutional amine-group compound M1 and halogenosulfonic acid salt compound M2 are taken, water-ethanol in the mixed solvent is dissolved in；In
Back flow reaction 72 hours under the conditions of 100 DEG C；
(2) after reaction, rotary evaporation removes the water and ethyl alcohol in reaction solution；Then water is added, then uses dichloromethane
Alkane extracts three times, retains water phase；
(3) water phase after removing 80% water, is added into salt compounds M3 by rotary evaporation；It is quiet after stirring 6 hours
It sets, after solution layering, takes lower layer's solution；It is dried under vacuum 24 hours, the double ion of purifying is made to ionic liquid；
The dosage relation of each reagent: the molar ratio of compound M1, M2, M3 are M1: M2: M3=1: 1: 1；It is mixed in water-ethanol
In solvent, the volume ratio of water and ethyl alcohol is 5: 1；Using 1 mole of compound M1 as mete-wand, water-ethanol in the mixed solvent water
Volume is 880 milliliters, and the volume that water is added before methylene chloride extraction is 750 milliliters, every time methylene chloride volume used when extraction
It is 750 milliliters.
In the present invention, the chemical structural formula of the three substitutional amine-group compounds M1 are as follows:
Wherein R1For the ethylene oxide chain CH of terminal methyl3(OCH2CH2)n, n=2~6.
In the present invention, the three substitutional amine-group compounds M1 is three (3,6- dioxaheptyl) amine (i.e. preferred n=2), three
(3,6,9,12- tetra- oxa- tridecyl) amine (i.e. n=4) or three (3,6,9,12,15,18- six oxa- nonadecyl) amine (i.e. n
=6).
In the present invention, the chemical structural formula of the halogenosulfonic acid salt compound M2 are as follows:
X-R2-SO3 -M+
Wherein X is chlorine atom (Cl), bromine atom (Br) or iodine atom (I), R2For alkane chain-(CH2CH2)n, n=2~
6；M+Be positive monovalent metallic ion, is sodium ion (Na+), lithium ion (Li+) or potassium ion (K+)。
In the present invention, the halogenosulfonic acid salt compound M2 is 2- bromoethyl sodium sulfonate, 2- bromoethyl Sulfonic Lithium or 2- bromine
(i.e. preferred n=2 and X is bromine atom Br to ethylsulfonic acid potassium；Particularly preferred 2- bromoethyl Sulfonic Lithium).
In the present invention, the chemical structural formula of the salt compounds M3 are as follows:
M+R-
Wherein, M+Be positive monovalent metallic ion, is sodium ion (Na+), lithium ion (Li+) or potassium ion (K+)；R-For negative one
Valence anion is perchlorate, two (trimethyl fluoride sulfonyl) imines, bis- (fluorine sulphonyl) imines, tetrafluoroborate or dioxalic acid boron
Acid group.
In the present invention, the salt compounds M3 is sodium perchlorate, two (trimethyl fluoride sulfonyl) imines sodium, bis- (fluorine sulphonyl)
Imines sodium, sodium tetrafluoroborate, dioxalic acid Boratex, lithium perchlorate, two (trimethyl fluoride sulfonyl) imine lithiums, bis- (fluorine sulphonyl) imines
Lithium, LiBF4, dioxalic acid lithium borate, potassium hyperchlorate, two (trimethyl fluoride sulfonyl) imines potassium, bis- (fluorine sulphonyl) imines potassium,
Any one in potassium tetrafluoroborate or dioxalic acid potassium borate.Wherein, particularly preferred two (trimethyl fluoride sulfonyl) imine lithium.
Inventive principle description:
By three substitutional amine-group compound M1 and halogenosulfonic acid salt compound M2 quaternization reaction occurs for the present invention, obtains season
Ammonium salt is reacted by subsequent with salt compounds M3, and halide anion is replaced with the biggish anion of volume, such as perchloric acid
Root, two (trimethyl fluoride sulfonyl) imines, bis- (fluorine sulphonyl) imines, tetrafluoroborate or dioxalic acid borate；Due to zwitterion
Volume it is larger, so resulting product can present at normal temperature liquid to get to the double ion to ionic liquid.
Compared with prior art, the beneficial effects of the present invention are:
1, product of the invention can be mixed in all proportions new electrolyte with carbonates or ethers electrolyte,
Improve the safety of the thermal stability and lithium ion battery of electrolyte.
2, double ion of the invention inherently has sodium ion, lithium ion or potassium ion to ionic liquid, there is presently no
Similar report, the additive amount of respective metal ion can be reduced when using as electrolyte, even without the corresponding gold of addition
Belong to ion.
3, operation of the present invention is simple, and step is few, and yield is high, does not generate toxic by-product, is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is nuclear magnetic spectrogram of the resulting double ion of embodiment 8 to ionic liquid.
Fig. 2 is the relationship using lithium/ferric phosphate lithium cell specific discharge capacity and charge and discharge cycles number in example 1,2
Curve.
Specific embodiment
Present invention is further described in detail with specific embodiment with reference to the accompanying drawing.Following example can make this
The present invention, but do not limit the invention in any way is more fully understood in the professional technician of profession.
Embodiment 1
By 1 mole of three (3,6- dioxaheptyl) amine and 1 mole of 2- bromoethyl sodium sulfonate be dissolved in 880 ml deionized waters and
In the mixed solvent made of 176 milliliters of dehydrated alcohols is stirred at reflux 72 hours under 100 DEG C of oil bath.Then revolving removes water
And dehydrated alcohol.750 milliliters of water are added, are then extracted with dichloromethane three times, every time with 750 milliliters of methylene chloride, stay water phase
Product.The water that water-phase product removes methylene chloride and 80% is rotated, 1 mole of bis- (trimethyl fluoride sulfonyl) imine lithium is then added,
Stirring 6 hours, filtered after standing, rotary evaporation remove water, in a vacuum drying oven dry 24 hours to get to double ion to from
Sub- liquid.
Embodiment 2
By 1 mole of three (3,6- dioxaheptyl) amine and 1 mole of 2- bromoethyl sodium sulfonate be dissolved in 880 ml deionized waters and
In the mixed solvent made of 176 milliliters of dehydrated alcohols is stirred at reflux 72 hours under 100 DEG C of oil bath.Then revolving removes water
And dehydrated alcohol.750 milliliters of water are added, are then extracted with dichloromethane three times, every time with 750 milliliters of methylene chloride, stay water phase
Product.The water that water-phase product removes methylene chloride and 80% is rotated, 1 mole of lithium perchlorate is then added, is stirred 6 hours, is stood
After filter, rotary evaporation remove water, in a vacuum drying oven dry 24 hours to get to double ion to ionic liquid.
Embodiment 3
By 1 mole of three (3,6- dioxaheptyl) amine and 1 mole of 2- bromine hexyl Sulfonic Lithium be dissolved in 880 ml deionized waters and
In the mixed solvent made of 176 milliliters of dehydrated alcohols is stirred at reflux 72 hours under 100 DEG C of oil bath.Then revolving removes water
And dehydrated alcohol.750 milliliters of water are added, are then extracted with dichloromethane three times, every time with 750 milliliters of methylene chloride, stay water phase
Product.The water that water-phase product removes methylene chloride and 80% is rotated, 1 mole of LiBF4 is then added, is stirred 6 hours, it is quiet
Filtering is postponed, rotary evaporation removes water, dries 24 hours in a vacuum drying oven to get double ion is arrived to ionic liquid.
Embodiment 4
By 1 mole of three (3,6- dioxaheptyl) amine and 1 mole of 2- bromoethyl sodium sulfonate be dissolved in 880 ml deionized waters and
In the mixed solvent made of 176 milliliters of dehydrated alcohols is stirred at reflux 72 hours under 100 DEG C of oil bath.Then revolving removes water
And dehydrated alcohol.750 milliliters of water are added, are then extracted with dichloromethane three times, every time with 750 milliliters of methylene chloride, stay water phase
Product.The water that water-phase product removes methylene chloride and 80% is rotated, 1 mole of sodium tetrafluoroborate is then added, is stirred 6 hours, it is quiet
Filtering is postponed, rotary evaporation removes water, dries 24 hours in a vacuum drying oven to get double ion is arrived to ionic liquid.
Embodiment 5
0.5 mole of three (3,6- dioxaheptyl) amine and 0.5 mole of 2- bromoethyl sodium sulfonate are dissolved in 440 milliliters of deionizations
In the mixed solvent made of water and 88 milliliters of dehydrated alcohols, is stirred at reflux 72 hours under 100 DEG C of oil bath.Then revolving removes
Water and dehydrated alcohol.375 milliliters of water are added, are then extracted with dichloromethane three times, every time with 375 milliliters of methylene chloride, stay water
Phase product.The water that water-phase product removes methylene chloride and 80% is rotated, 0.5 mole of bis- (fluorine sulphonyl) imines potassium is then added, stirs
It mixes 6 hours, is filtered after standing, rotary evaporation removes water, dries 24 hours in a vacuum drying oven to get double ion is arrived to ion
Liquid.
Embodiment 6
By 2 mole of three (3,6- dioxaheptyl) amine and 2 moles of 2- bromines, base sodium sulfonate is dissolved in 1760 ml deionized waters
With in the mixed solvent made of 352 milliliters of dehydrated alcohols, it is stirred at reflux under 100 DEG C of oil bath 72 hours.Then revolving removes
Water and dehydrated alcohol.1500 milliliters of water are added, are then extracted with dichloromethane three times, every time with 1500 milliliters of methylene chloride, stay
Water-phase product.The water that water-phase product removes methylene chloride and 80% is rotated, 2 moles of bis- (fluorine sulphonyl) imines sodium are then added, stir
It mixes 6 hours, is filtered after standing, rotary evaporation removes water, dries 24 hours in a vacuum drying oven to get double ion is arrived to ion
Liquid.
Embodiment 7
By 1 mole of three (3,6- dioxaheptyl) amine and 1 mole of 2- brombutyl potassium sulfonate be dissolved in 880 ml deionized waters and
In the mixed solvent made of 176 milliliters of dehydrated alcohols is stirred at reflux 72 hours under 100 DEG C of oil bath.Then revolving removes water
And dehydrated alcohol.750 milliliters of water are added, are then extracted with dichloromethane three times, every time with 750 milliliters of methylene chloride, stay water phase
Product.The water that water-phase product removes methylene chloride and 80% is rotated, 1 mole of dioxalic acid potassium borate is then added, is stirred 6 hours,
It is filtered after standing, rotary evaporation removes water, dries 24 hours in a vacuum drying oven to get double ion is arrived to ionic liquid.
Embodiment 8
By 0.25 mole of three (3,6- dioxaheptyl) amine and 0.25 mole of 2- bromoethyl Sulfonic Lithium be dissolved in 220 milliliters go from
In the mixed solvent made of sub- water and 44 milliliters of dehydrated alcohols, is stirred at reflux 72 hours under 100 DEG C of oil bath.Then revolving is removed
Remove water and dehydrated alcohol.187.5 milliliters of water are added, are then extracted with dichloromethane three times, every time with 187.5 milliliters of dichloromethanes
Alkane stays water-phase product.The water that water-phase product removes methylene chloride and 80% is rotated, 0.25 mole of lithium perchlorate is then added, stirs
It mixes 6 hours, is filtered after standing, rotary evaporation removes water, dries 24 hours in a vacuum drying oven to get double ion is arrived to ion
Liquid.Resulting double ion is as shown in Figure 1 to the nuclear magnetic spectrogram of ionic liquid.
Embodiment 9
By 1 mole of three (3,6- dioxaheptyl) amine and 1 mole of 2- bromoethyl potassium sulfonate be dissolved in 880 ml deionized waters and
In the mixed solvent made of 176 milliliters of dehydrated alcohols is stirred at reflux 72 hours under 100 DEG C of oil bath.Then revolving removes water
And dehydrated alcohol.750 milliliters of water are added, are then extracted with dichloromethane three times, every time with 750 milliliters of methylene chloride, stay water phase
Product.The water that water-phase product removes methylene chloride and 80% is rotated, 1 mole of bis- (trimethyl fluoride sulfonyl) imines potassium is then added,
Stirring 6 hours, filtered after standing, rotary evaporation remove water, in a vacuum drying oven dry 24 hours to get to double ion to from
Sub- liquid.
Embodiment 10
By 1 mole of three (3,6- dioxaheptyl) amine and 1 mole of 2- bromoethyl sodium sulfonate be dissolved in 880 ml deionized waters and
In the mixed solvent made of 176 milliliters of dehydrated alcohols is stirred at reflux 72 hours under 100 DEG C of oil bath.Then revolving removes water
And dehydrated alcohol.750 milliliters of water are added, are then extracted with dichloromethane three times, every time with 750 milliliters of methylene chloride, stay water phase
Product.The water that water-phase product removes methylene chloride and 80% is rotated, 1 mole of bis- (trimethyl fluoride sulfonyl) imines sodium is then added,
Stirring 6 hours, filtered after standing, rotary evaporation remove water, in a vacuum drying oven dry 24 hours to get to double ion to from
Sub- liquid.
Embodiment 11
By 1 mole of three (3,6- dioxaheptyl) amine and 1 mole of 2- chloroethyl sodium sulfonate be dissolved in 880 ml deionized waters and
In the mixed solvent made of 176 milliliters of dehydrated alcohols is stirred at reflux 72 hours under 100 DEG C of oil bath.Then revolving removes water
And dehydrated alcohol.750 milliliters of water are added, are then extracted with dichloromethane three times, every time with 750 milliliters of methylene chloride, stay water phase
Product.The water that water-phase product removes methylene chloride and 80% is rotated, 1 mole of bis- (trimethyl fluoride sulfonyl) imines sodium is then added,
Stirring 6 hours, filtered after standing, rotary evaporation remove water, in a vacuum drying oven dry 24 hours to get to double ion to from
Sub- liquid.
Embodiment 12
By 0.25 mole of three (3,6- dioxaheptyl) amine and 0.25 mole of 2- iodine ethylsulfonic acid lithium be dissolved in 220 milliliters go from
In the mixed solvent made of sub- water and 44 milliliters of dehydrated alcohols, is stirred at reflux 72 hours under 100 DEG C of oil bath.Then revolving is removed
Remove water and dehydrated alcohol.187.5 milliliters of water are added, are then extracted with dichloromethane three times, every time with 187.5 milliliters of dichloromethanes
Alkane stays water-phase product.The water that water-phase product removes methylene chloride and 80% is rotated, 0.25 mole of bis- (trifluoromethyl is then added
Sulphonyl) imine lithium, stir 6 hours, filtered after standing, rotary evaporation remove water, in a vacuum drying oven dry 24 hours to get
To double ion to ionic liquid.
Embodiment 13
0.25 mole of three (3,6,9,12- tetra- oxa- tridecyl) amine and 0.25 mole of 2- iodine ethylsulfonic acid lithium are dissolved in
In the mixed solvent made of 220 ml deionized waters and 44 milliliters of dehydrated alcohols, it is small under 100 DEG C of oil bath to be stirred at reflux 72
When.Then revolving removes water and dehydrated alcohol.187.5 milliliters of water are added, are then extracted with dichloromethane three times, use every time
187.5 milliliters of methylene chloride, stay water-phase product.The water that water-phase product removes methylene chloride and 80% is rotated, is then added 0.25
Mole bis- (trimethyl fluoride sulfonyl) imine lithiums are stirred 6 hours, are filtered after standing, and rotary evaporation removes water, in a vacuum drying oven
24 hours are dried to get double ion is arrived to ionic liquid.
Embodiment 14
1 mole of three (3,6,9,12,15,18- six oxa- nonadecyl) amine and 1 mole of 2- bromine hexyl Sulfonic Lithium are dissolved in
In the mixed solvent made of 880 ml deionized waters and 176 milliliters of dehydrated alcohols, it is small under 100 DEG C of oil bath to be stirred at reflux 72
When.Then revolving removes water and dehydrated alcohol.750 milliliters of water are added, are then extracted with dichloromethane three times, every time with 750 millis
Methylene chloride is risen, water-phase product is stayed.The water that water-phase product removes methylene chloride and 80% is rotated, 1 mole of perchloric acid is then added
Lithium is stirred 6 hours, is filtered after standing, and rotary evaporation removes water, dries 24 hours in a vacuum drying oven to get double ion is arrived
To ionic liquid.
Embodiment 15
By 1 mole of three (3,6- dioxaheptyl) amine and 1 mole of 2- brombutyl Sulfonic Lithium be dissolved in 880 ml deionized waters and
In the mixed solvent made of 176 milliliters of dehydrated alcohols is stirred at reflux 72 hours under 100 DEG C of oil bath.Then revolving removes water
And dehydrated alcohol.750 milliliters of water are added, are then extracted with dichloromethane three times, every time with 750 milliliters of methylene chloride, stay water phase
Product.The water that water-phase product removes methylene chloride and 80% is rotated, 1 mole of dioxalic acid lithium borate is then added, is stirred 6 hours,
It is filtered after standing, rotary evaporation removes water, dries 24 hours in a vacuum drying oven to get double ion is arrived to ionic liquid.
Products application example:
Using example 1
Double ion prepared by 9.0 milliliters of embodiments 8 is to ionic liquid, 0.5 milliliter of ethylene carbonate and 0.5 milliliter of carbonic acid
Acrylic ester is uniformly mixed in the glove box of anhydrous and oxygen-free, is configured to electrolyte.The electrolyte is used to assemble lithium/LiFePO4
Battery carries out the charge-discharge test under 0.5C to gained battery.
In the electrolyte obtained by the present embodiment, volume fraction shared by propene carbonate is 5%, shared by ethylene carbonate
Volume fraction is 5%, and double ion is 90% to volume fraction shared by ionic liquid.
Using example 2
Double ion prepared by 8.5 milliliters of embodiments 8 is to ionic liquid, 0.5 milliliter of ethylene carbonate and 1.0 milliliters of carbonic acid
Acrylic ester is uniformly mixed in the glove box of anhydrous and oxygen-free and is configured to electrolyte.The electrolyte is used to assemble lithium/LiFePO4
Battery carries out the charge-discharge test under 0.5C to gained battery.
In the electrolyte obtained by the present embodiment, volume fraction shared by propene carbonate is 10%, shared by ethylene carbonate
Volume fraction be 5%, double ion to volume fraction shared by ionic liquid be 85%.
Using the relation curve of lithium/ferric phosphate lithium cell specific discharge capacity and charge and discharge cycles number in example 1,2
As shown in Figure 2.
Finally it should be noted that the above enumerated are only specific embodiments of the present invention.It is clear that the invention is not restricted to
Above embodiments can also have many variations.Those skilled in the art can directly lead from present disclosure
Out or all deformations for associating, it is considered as protection scope of the present invention.
Claims (8)
1. a kind of double ion is to ionic liquid, which is characterized in that the double ion has the following structure ionic liquid:
Wherein, R1For the ethylene oxide chain CH of terminal methyl3(OCH2CH2)n, n=2~6；R2For alkane chain-(CH2CH2)n, n=2
~6；R-Be negative univalent anion, is perchlorate, two (trimethyl fluoride sulfonyl) imines, bis- (fluorine sulphonyl) imines, tetrafluoro boric acid
Any one in root or dioxalic acid borate；M+ is positive monovalent metallic ion, is sodium ion, lithium ion or potassium ion.
2. double ion described in claims 1 is to the preparation method of ionic liquid, which comprises the following steps:
(1) three substitutional amine-group compound M1 and halogenosulfonic acid salt compound M2 are taken, water-ethanol in the mixed solvent is dissolved in；100
Back flow reaction 72 hours under the conditions of DEG C；
(2) after reaction, rotary evaporation removes the water and ethyl alcohol in reaction solution；Then water is added, then is extracted with methylene chloride
It takes three times, retains water phase；
(3) water phase after removing 80% water, is added into salt compounds M3 by rotary evaporation；Stirring is stood after 6 hours,
After solution layering, lower layer's solution is taken；It is dried under vacuum 24 hours, the double ion of purifying is made to ionic liquid；
The dosage relation of each reagent: the molar ratio of compound M1, M2, M3 are M1: M2: M3=1: 1: 1；In water-ethanol mixed solvent
In, the volume ratio of water and ethyl alcohol is 5: 1；Using 1 mole of compound M1 as mete-wand, the volume of water-ethanol in the mixed solvent water
It is 880 milliliters, the volume that water is added before methylene chloride extraction is 750 milliliters, and methylene chloride volume used is 750 when extraction every time
Milliliter.
3. method according to claim 2, which is characterized in that the chemical structural formula of the three substitutional amine-group compounds M1
Are as follows:
Wherein R1For the ethylene oxide chain CH of terminal methyl3(OCH2CH2)n, n=2~6.
4. method according to claim 2, which is characterized in that the three substitutional amine-group compounds M1 is three (3,6- bis-
Oxa- heptyl) amine, three (3,6,9,12- tetra- oxa- tridecyl) amine or three (3,6,9,12,15,18- six oxa- nonadecyls)
Amine.
5. method according to claim 2, which is characterized in that the chemical structural formula of the halogenosulfonic acid salt compound M2
Are as follows:
X-R2-SO3 -M+
Wherein X is chlorine atom, bromine atom or iodine atom, R2For alkane chain-(CH2CH2)n, n=2~6；M+Be positive monovalent metal
Ion is sodium ion, lithium ion or potassium ion.
6. method according to claim 2, which is characterized in that the halogenosulfonic acid salt compound M2 is 2- bromoethyl sulphur
Sour sodium, 2- bromoethyl Sulfonic Lithium or 2- bromoethyl potassium sulfonate, 2- iodine ethylsulfonic acid lithium, 2- chloroethyl sodium sulfonate, 2- brombutyl sulphur
Sour potassium, 2- bromine hexyl Sulfonic Lithium.
7. method according to claim 2, which is characterized in that the chemical structural formula of the salt compounds M3 are as follows:
M+R-
Wherein, M+Be positive monovalent metallic ion, is sodium ion, lithium ion or potassium ion；R-Be negative univalent anion, is perchloric acid
Root, two (trimethyl fluoride sulfonyl) imines, bis- (fluorine sulphonyl) imines, tetrafluoroborate or dioxalic acid borate.
8. compound M3 according to claim 2, which is characterized in that the salt compounds M3 is sodium perchlorate, two
(trimethyl fluoride sulfonyl) imines sodium, bis- (fluorine sulphonyl) imines sodium, sodium tetrafluoroborate, dioxalic acid Boratex, lithium perchlorate, two (three
Methyl fluoride sulphonyl) imine lithium, bis- (fluorine sulphonyl) imine lithiums, LiBF4, dioxalic acid lithium borate, potassium hyperchlorate, two (fluoroforms
Base sulphonyl) any one in imines potassium, bis- (fluorine sulphonyl) imines potassium, potassium tetrafluoroborate or dioxalic acid potassium borate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112968209A (en) * | 2021-02-24 | 2021-06-15 | 珠海中科先进技术研究院有限公司 | Ionic liquid gel electrolyte and preparation method and application thereof |
| CN112968210A (en) * | 2021-02-24 | 2021-06-15 | 珠海中科先进技术研究院有限公司 | Zwitterionic liquid gel electrolyte and preparation method and application thereof |
| WO2021187625A1 (en) * | 2020-03-19 | 2021-09-23 | 三菱ケミカル株式会社 | Nonaqueous electrolytic solution secondary battery and nonaqueous electrolytic solution |
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| US3813422A (en) * | 1970-07-23 | 1974-05-28 | H Marumo | Surface modifier for synthetic high polymers |
| JP2001272788A (en) * | 2000-03-24 | 2001-10-05 | Toshiba Corp | Solution material for underlayer film and pattern forming method using the same |
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| WO2021187625A1 (en) * | 2020-03-19 | 2021-09-23 | 三菱ケミカル株式会社 | Nonaqueous electrolytic solution secondary battery and nonaqueous electrolytic solution |
| CN112968209A (en) * | 2021-02-24 | 2021-06-15 | 珠海中科先进技术研究院有限公司 | Ionic liquid gel electrolyte and preparation method and application thereof |
| CN112968210A (en) * | 2021-02-24 | 2021-06-15 | 珠海中科先进技术研究院有限公司 | Zwitterionic liquid gel electrolyte and preparation method and application thereof |
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