CN111233772A - High-capacity imidazole ionic liquid and preparation method and application thereof - Google Patents
High-capacity imidazole ionic liquid and preparation method and application thereof Download PDFInfo
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 254
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 155
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims description 86
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 239000003960 organic solvent Substances 0.000 claims description 26
- -1 chloroalkyl ester Chemical class 0.000 claims description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims description 24
- 159000000002 lithium salts Chemical class 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 150000005215 alkyl ethers Chemical class 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical class [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical group COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- MMYKTRPLXXWLBC-UHFFFAOYSA-N 1-bromo-2-ethoxyethane Chemical compound CCOCCBr MMYKTRPLXXWLBC-UHFFFAOYSA-N 0.000 claims description 2
- JAMFGQBENKSWOF-UHFFFAOYSA-N bromo(methoxy)methane Chemical group COCBr JAMFGQBENKSWOF-UHFFFAOYSA-N 0.000 claims description 2
- CYYWAXVARNZFBI-UHFFFAOYSA-N bromomethoxyethane Chemical compound CCOCBr CYYWAXVARNZFBI-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 30
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 25
- 239000007774 positive electrode material Substances 0.000 abstract description 8
- 125000004185 ester group Chemical group 0.000 abstract description 6
- 125000001033 ether group Chemical group 0.000 abstract description 6
- 239000002000 Electrolyte additive Substances 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 13
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 12
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 12
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 8
- 229910001290 LiPF6 Inorganic materials 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 6
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000006259 organic additive Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- JDIIGWSSTNUWGK-UHFFFAOYSA-N 1h-imidazol-3-ium;chloride Chemical compound [Cl-].[NH2+]1C=CN=C1 JDIIGWSSTNUWGK-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910013188 LiBOB Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- FOZVXADQAHVUSV-UHFFFAOYSA-N 1-bromo-2-(2-bromoethoxy)ethane Chemical compound BrCCOCCBr FOZVXADQAHVUSV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001348 alkyl chlorides Chemical class 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- GOKUDEWVRNZXDZ-UHFFFAOYSA-N 1-bromo-3-(3-bromopropoxy)propane Chemical compound BrCCCOCCCBr GOKUDEWVRNZXDZ-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000275 quality assurance Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
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Classifications
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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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic 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
Abstract
The invention relates to a high-capacity imidazole ionic liquid and a preparation method and application thereof. The structural formula of the ionic liquid is shown as the following, wherein R1Is CH2(CH2)aO(CH2)bCH3A is 0 or 1, b is 0 or 1; r2Is CH2(CH2)cCOO(CH2)dCH3C is 0 or 1, d is 0 or 1; y is‑Is BF4 ‑，PF6 ‑，TFSI‑，FSI‑Or N (CN)2 ‑. In the preparation of the imidazole ionic liquid, through ternary substitution, an ether group is introduced into an N-1 position on an imidazole ring, so that the viscosity of the ionic liquid is reduced; ester group is introduced into N-3 position on imidazole ring, and electrochemical window and electrochemistry of ionic liquid are improvedAnd (4) stability. The imidazole ionic liquid is used as an electrolyte additive, is applied to a lithium ion battery taking a ternary material (NCM523) as a positive electrode material, and has good safety performance and electrochemical performance.
Description
Technical Field
The invention relates to the technical field of ionic liquid, and mainly researches novel imidazole ionic liquid, ionic liquid electrolyte and application of the ionic liquid electrolyte in lithium ion battery electrolyte.
Background
In 2012, haze weather is continuous, PM2.5 index is in high imminent, and environmental pollution is generally discussed and concerned by public opinions of various communities. Air pollution brings serious influence to life and traveling of people, and simultaneously gives an alarm to Chinese environmental problems again, so that the current unreasonable energy structure in China and the emission of a large amount of urban motor vehicle tail gas are the main causes. The PM of automobile emission is over 90 percent, and the CO is over 70 percent. In order to avoid excessive deterioration of the environment, new energy vehicles are gradually developed. However, in terms of the current development trend of new energy vehicles in our country, for the new energy vehicles to achieve excellent planning of quality and quality assurance, the new energy vehicles themselves need to find the right track for realizing industrialized development as soon as possible. The main factor restricting the marketability of electric vehicles is the power battery, which is the "engine" component of electric vehicles. Most of the power batteries used at present are lithium ion batteries, which have the characteristics of high working voltage, high energy density, environmental friendliness and the like.
However, as a mobile energy storage system, the lithium ion power battery needs to have safety. In recent years, ignition events of electric vehicles caused by lithium ion batteries are continuous, ignition events are initiated by Honda hybrid electric vehicles in 2008, spontaneous combustion is caused by battery overheating of 825-path pure electric buses in Shanghai in 2011, and public nerves are also started to be dragged due to collision ignition lethal events in BYD in 2012, so that the safety of the lithium ion batteries is imperative. In addition, as the demand of people for modern digital technology is increasing, high energy density will be another essential point for the development of lithium ion batteries.
The positive electrode material is an important component of the lithium ion battery, and the improvement of the energy density of the battery can be achieved from this point forward. Ternary materials (NCM) are a new type of positive electrode material. It integrates LiCoO2、LiNiO2And LiMnO2The advantages of the three materials are that due to the obvious synergistic effect among Ni, Co and Mn, the performance of NCM is better than that of a single-component layered cathode material, and the NCM is considered to be one of the novel cathode materials with the most application prospect. The three elements have different influences on the electrochemical performance of the material, and in general, Co can effectively stabilize the layered structure of the ternary material and inhibit cation mixing, thereby improving the electronic conductivity of the material and improving the cycle performance; mn can reduce the cost and improve the structural stability and safety of the material; the presence of Ni contributes to the increase in energy. In the ternary material, the elements can be classified into NCM333, NCM424, NCM523, NCM622, NCM811, and the like in order of nickel, cobalt, and manganese according to different element ratios.
The ionic liquid is a liquid low-melting-point ionic compound, is a salt substance which is composed of anions and cations and is in a liquid state at room temperature or near room temperature, generally is composed of organic cations and inorganic or organic anions, the cations mainly comprise imidazoles, quaternary ammonium salts, guanidines and the like, and the anions mainly comprise halogen anions, hexafluorophosphate anions and the like. Different combinations of anions and cations of the ionic liquid can be designed and synthesized into various ionic liquids. With the increasing research of ionic liquid, the ionic liquid is widely applied to various fields such as organic synthesis, catalysis, extraction separation, electrochemistry and the like. However, according to the needs of practical application, different functional groups are introduced into the cation instead of alkyl groups, and the design and synthesis of ionic liquids with specific functions are one of the main directions for research.
The ionic liquid is a non-volatile solvent, has strong thermal stability and electrochemical stability, and has very low vapor pressure and very high non-flammability, which makes it used as a safe electrolyte in lithium ion batteries. However, the electrolyte using ionic liquid alone has poor cycle stability and rate performance with a lithium negative electrode, and therefore, a pure ionic liquid electrolyte cannot achieve satisfactory electrochemical effects. The literature shows that the addition of suitable organic solvents to ionic liquids allows better performance to be achieved without compromising safety. Guerf et al, by mixing commercial organic solvents with ionic liquids, these mixtures can exhibit low viscosity, high conductivity, and they are also non-flammable. In addition, VC is a promising additive for SEI film formation, which can effectively passivate the surface of a lithium negative electrode by increasing capacity retention.
Therefore, a novel imidazole ionic liquid is developed and functionalized in a targeted manner, so that the imidazole ionic liquid has a specific function, and the imidazole ionic liquid is used as an electrolyte additive to be added into a lithium ion battery taking a ternary material as a positive electrode material, so that the safety and the energy density of the battery are improved, and the development of the lithium ion battery is a new step.
Disclosure of Invention
The invention mainly aims to provide a novel imidazole ionic liquid, an ionic liquid electrolyte, a preparation method and application aiming at the defects in the prior art. The imidazole ionic liquid is subjected to ternary substitution, and an ether group is introduced into an N-1 position on an imidazole ring, so that the viscosity of the ionic liquid is reduced; an ester group is introduced into the N-3 position on the imidazole ring, so that the electrochemical window and the electrochemical stability of the ionic liquid are improved. The imidazole ionic liquid is used as an electrolyte additive, is applied to a lithium ion battery taking a ternary material (NCM523) as a positive electrode material, and has good safety performance and electrochemical performance.
The technical scheme of the invention is as follows:
an imidazole ionic liquid, wherein the structural formula of the ionic liquid is as follows:
wherein R is1Is CH2(CH2)aO(CH2)bCH3A is 0 or 1, bIs 0 or 1; r2Is CH2(CH2)cCOO(CH2)dCH3C is 0 or 1, d is 0 or 1; y is-Is BF4 -，PF6 -，TFSI-，FSI-Or N (CN)2 -。
The preparation method of the imidazole ionic liquid comprises the following steps:
(1) dissolving 2-methylimidazole and bromo-alkyl ether in a solvent, and reacting at 100-150 ℃ for 24-48 hours; extracting after the reaction is finished, adding triethylamine into the organic phase, and reacting for 16-24 hours at the temperature of 100-130 ℃ to obtain 1-alkoxy alkyl-2-methylimidazole with the following structural formula:
wherein, the molar ratio is 2-methylimidazole: brominated alkyl ethers: triethylamine is 1: 1-1.1: 1; the solvent is absolute ethyl alcohol or dichloromethane, and 100-200 ml of solvent is added to each mol of 2-methylimidazole; the brominated alkyl ether is bromomethyl methyl ether, bromomethyl ethyl ether, 2-bromoethyl methyl ether or 2-bromoethyl ethyl ether; the extractant is a mixed solution of absolute ethyl alcohol and absolute ethyl ether, and the volume ratio of the absolute ethyl alcohol to the absolute ethyl ether is as follows: anhydrous ether 1: 4;
wherein R is1Is CH2(CH2)aO(CH2)bCH3A is 0 or 1, b is 0 or 1;
(2) dissolving 1-alkoxy alkyl-2-methylimidazole in a solvent under the atmosphere of protective gas, and reacting with chloroalkyl ester at 60 ℃ for 24-48 hours to obtain 1-alkoxy alkyl-2-methyl-3-ester imidazole halide with the following structure:
wherein R is1Is CH2(CH2)aO(CH2)bCH3A is 0 or 1, b is 0 or 1; r2Is CH2(CH2)cCOO(CH2)dCH3C is 0 or 1, d is 0 or 1; x is halogen; the molar ratio is 1-alkoxy alkyl-2-methylimidazole: a chloroalkyl ester 1:1 to 1.2; the solvent is dichloromethane, and 100-200 ml of solvent is added to each mol of 1-alkoxy alkyl-2-methylimidazole;
the chloroalkyl ester is methyl chloroacetate or ethyl chloroacetate;
(3) dissolving the 1-alkoxy alkyl-2-methyl-3-ester imidazole halide in dichloromethane, and then reacting with an inorganic salt M at 20-25 ℃ under the protection of inert gas+Y-Reacting for 5-12 hours to obtain the 1-alkoxy alkyl-2-methyl-3-ester imidazole bis (trifluoromethyl sulfonyl) imide ionic liquid with the following structural formula:
wherein M is+Is Li; y is-Is BF4 -，PF6 -，TFSI-，FSI-Or N (CN)2 -Adding 100-200 ml of dichloromethane, 1-alkoxyalkyl-2-methyl-3-ester imidazole halide and inorganic salt M into each mole of 1-alkoxyalkyl-2-methyl-3-ester imidazole halide+Y-The molar ratio of (A) to (B) is 1: 1-1.1;
the molar ratio of the 2-methylimidazole to the brominated alkyl ether is preferably 1: 1.05.
The molar ratio of the 1-alkoxyalkyl-2-methylimidazole to the chloroalkyl ester is preferably 1: 1.05.
The molar ratio of the 1-alkoxyalkyl-2-methyl-3-esterimidazole halide to the inorganic salt is preferably 1: 1.05.
And (3) the protective atmosphere in the step (2) and the step (3) is nitrogen or argon.
In the step (3), the method further comprises the following steps: the ionic liquid separation and purification method comprises the following steps of:
filtering white LiCl precipitate in a reaction product, washing and drying the filtrate by using sodium sulfate, and then washing by using deionized water until no precipitate is generated by using a saturated silver nitrate solution; and (3) removing the volatile solvent from the treated solution through rotary evaporation, and drying to obtain the purified imidazole ionic liquid.
The application of the imidazole ionic liquid is used for preparing the electrolyte of the lithium ion battery.
The electrolyte comprises: organic solvent, lithium salt and ionic liquid; wherein the ionic liquid accounts for 10-80% of the electrolyte by mass, the lithium salt accounts for 0.2-9% of the electrolyte by mass, and the balance is an organic solvent.
The imidazole ionic liquid has the following structure:
wherein R is1Is CH2(CH2)aO(CH2)bCH3A is 0 or 1, b is 0 or 1; r2Is CH2(CH2)cCOO(CH2)dCH3C is 0 or 1, d is 0 or 1; y is-Is BF4 -，PF6 -，TFSI-，FSI-Or N (CN)2 -。
The organic solvent is a mixed solution of ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and vinylene carbonate and phenyl sulfone organic additives are added into the organic solvent, wherein the volume ratio of the ethylene carbonate to the diethyl carbonate to the methyl ethyl carbonate is 2:2: 1-2: 2:3, and the vinylene carbonate and the phenyl sulfone are respectively added in a volume ratio of 1-3%.
The lithium salt is LiTFSI or LiPF6、LiBF4Or LiBOB.
The preparation method of the imidazole ionic liquid electrolyte is characterized by comprising the following steps:
according to the volume ratio of ethylene carbonate, diethyl carbonate and methyl ethyl carbonate being 2:2: 1-2: 2:3, vinylene carbonate and phenylsulfone are respectively added in the volume ratio of 1-3%, and are mixed to prepare an organic solvent;
adding the lithium salt into the organic solvent according to the mass percent of 0.2-9%, stirring until the lithium salt is completely dissolved, and adding imidazole ionic liquid into the solution according to the mass percent of 10-80% of the ionic liquid to obtain the ionic liquid electrolyte.
The invention has the substantive characteristics that:
the cation of the imidazole ionic liquid obtained by the invention is a 1-alkoxy alkyl-2-methyl-3-ester group imidazole cation, and compared with the traditional imidazole ionic liquid, an ether group is introduced into the N-1 position on the imidazole ring of the imidazole ionic liquid, so that the viscosity of the ionic liquid is reduced; an ester group is introduced into the N-3 position on the imidazole ring, so that the electrochemical window and the electrochemical stability of the ionic liquid are improved; in addition, after the active hydrogen on the 2-position of the imidazole ring is replaced by methyl, the electrochemical window is wider and the electrochemical stability is obviously improved. Through performance detection, the imidazole ionic liquid has better cyclicity and electrochemical stability than the traditional ionic liquid.
The preparation method of the imidazole ionic liquid comprises the steps of firstly preparing 1-alkoxy alkyl-2-methylimidazole by reacting 2-methylimidazole with bromo-alkyl ether, secondly, 1-alkoxy alkyl-2-methylimidazole reacts with alkyl chloride to prepare 1-alkoxy alkyl-2-methyl-3-ester imidazole halide, finally inorganic salt containing target anions and 1-alkoxy alkyl-2-methyl-3-ester imidazole halide are subjected to ion exchange, and the product after the ion exchange reaction is purified and dried, the preparation method is simple and convenient, the operation is simple, the yield is high (80-90%), and the prepared imidazole ionic liquid has good electrochemical performance and is suitable for the application of lithium ion battery electrolyte taking ternary materials as anode materials.
The invention has the beneficial effects that:
the preparation method of the bifunctional novel imidazole ionic liquid is simple and convenient, the operation is simple, the yield is high, the prepared imidazole ionic liquid electrolytes with different concentrations have good electrochemical performance, high safety, good cycle performance and high stability, and the proportion of organic solvents and organic additives which are not adopted before in the electrolytes is applied, so that all parts are suitable for the application of lithium ion battery electrolytes taking ternary materials as anode materials. The concrete expression is as follows:
the prepared imidazole electrolyte has low viscosity, high conductivity and good thermal stability, and is suitable for being used as a high-capacity lithium ion battery electrolyte, and the dissolving capacity of the imidazole ionic liquid is improved due to the introduction of an ether group at the N-1 position on the imidazole ring of the imidazole ionic liquid; an ester group is introduced into the N-3 position on the imidazole ring, so that the electrochemical window and the electrochemical stability of the ionic liquid are improved; in addition, after the active hydrogen on the No. 2 position of the imidazole ring is replaced by methyl, the electrochemical window is wider, the electrochemical stability is obviously improved, and the obtained electrolyte has good cycle performance and high safety.
Compared with the traditional organic electrolyte, the imidazole ionic liquid electrolyte has higher electrochemical performance and improves the safety performance of the lithium ion battery due to the introduction of the ionic liquid. In order to clarify the influence of ionic liquid electrolyte on the safety performance of the battery, flammability tests were performed on electrolytes with different ionic liquid contents, the electrolytes with different concentrations were ignited for 3 seconds, the combustion conditions after 5 seconds and after 8 seconds were observed, and self-extinguishing time (SET, extinguishing time normalized according to sample mass) was calculated (table 1). As a result, the electrolyte added with the ionic liquid is not easy to burn, and the higher the concentration of the ionic liquid is, the shorter the burning time is, even the ionic liquid does not burn, which shows that the ionic liquid electrolyte has high flame retardance and meets the requirement of the safety of the lithium ion battery. Meanwhile, ethylene carbonate, diethyl carbonate and methyl ethyl carbonate are mixed according to the volume ratio of 2:2: 1-2: 2:3, and vinylene carbonate and phenylsulfone which are organic additives are added according to the volume ratio of 1-3%, so that the formation of an SEI film of the battery is promoted, and the cycle performance of the battery is improved.
In addition, the ternary material (NCM) is a novel positive electrode material, and due to the obvious synergistic effect among Ni, Co and Mn in the structure of the ternary material, the performance of the NCM is better than that of a single-component layered positive electrode material, and Co can effectively stabilize the layered structure of the ternary material, inhibit cation mixing and discharge, improve the electronic conductivity of the material and improve the cycle performance; mn can reduce the cost and improve the structural stability and safety of the material; the presence of Ni contributes to the increase in energy. The imidazole ionic liquid lithium ion battery electrolyte is prepared by taking a ternary material as a positive material, the specific discharge capacity of the ionic liquid electrolyte with each concentration obtained after 50 charge-discharge cycles is higher (above 172 mAh/g) and almost exceeds the specific discharge capacity value (168.1mAh/g) of the commercial electrolyte, wherein the specific discharge capacity of the ionic liquid electrolyte with 10 percent is the highest and is 182.4mAh/g, and the capacity retention rate of the ionic liquid with each concentration is above 95 percent. In conclusion, the electrolyte prepared from the ionic liquid has good circulation performance, high specific capacity, safety and nonflammability, and is suitable for the requirements of industrialization on high energy density and safety of batteries.
Drawings
FIG. 1 is an infrared spectrum of the ionic liquid obtained in example 1;
FIG. 2 is a charge-discharge cycle test chart of the lithium ion battery obtained in example 1;
Detailed Description
The preparation of the imidazole ionic liquid and the application of the imidazole ionic liquid in the lithium ion battery electrolyte taking the ternary material as the anode material are further explained with reference to the attached drawings and specific embodiments.
An embodiment of an imidazolium ionic liquid has the following structural formula:
wherein R is1Is CH2(CH2)aO(CH2)bCH3A is 0 or 1, b is 0 or 1; r2Is CH2(CH2)cCOO(CH2)dCH3C is 0 or 1, d is 0 or 1; y is-Is BF4 -，PF6 -，TFSI-，FSI-Or N (CN)2 -。
The cation of the imidazole ionic liquid obtained by the invention is a 1-alkoxy alkyl-2-methyl-3-ester group imidazole cation, and compared with the traditional imidazole ionic liquid, an ether group is introduced into the N-1 position on the imidazole ring of the imidazole ionic liquid, so that the viscosity of the ionic liquid is reduced; an ester group is introduced into the N-3 position on the imidazole ring, so that the electrochemical window and the electrochemical stability of the ionic liquid are improved; in addition, after the active hydrogen on the 2-position of the imidazole ring is replaced by methyl, the electrochemical window is wider and the electrochemical stability is obviously improved. Through performance detection, the imidazole ionic liquid has better cyclicity and electrochemical stability than the traditional ionic liquid.
In addition, the embodiment also provides a preparation method of the imidazole ionic liquid, which comprises the following steps:
step S110, dissolving 2-methylimidazole and bromoalkyl ether in a solvent according to the molar ratio of 1: 1-1: 1.1 of 2-methylimidazole to bromoalkyl ether, and reacting at 100-150 ℃ for 24-48 hours; after the reaction is finished, extracting for 2-3 times by using a mixed solution of absolute ethyl alcohol and absolute ethyl ether, adding triethylamine with the same molar weight as 2-methylimidazole into the organic phase, and reacting for 16-24 hours at 100-130 ℃ to obtain 1-alkoxyalkyl-2-methylimidazole with the following structural formula:
wherein R is1Is CH2(CH2)aO(CH2)bCH3A is 0 or 1, b is 0 or 1;
and (3) carrying out suction filtration on the obtained 1-alkoxy alkyl-2-methylimidazole to remove white salt impurities generated in the reaction, collecting filtrate, then carrying out reduced pressure distillation and collecting fractions to obtain the purified 1-alkoxy alkyl-2-methylimidazole.
In other preferred embodiments, the molar ratio of 2-methylimidazole to bromoalkyl ether is preferably 1: 1.05.
Step S120, under the protective gas atmosphere, dissolving 1-alkoxyalkyl-2-methylimidazole in a solvent according to the molar ratio of 1: 1-1: 1.2 of 1-alkoxyalkyl-2-methylimidazole to chloroalkyl ester, and reacting the solution with chloroalkyl ester at 60 ℃ for 24-48 hours to obtain 1-alkoxyalkyl-2-methyl-3-esterimidazole halide with the following structure:
wherein R is1Is CH2(CH2)aO(CH2)bCH3A is 0 or 1, b is 0 or 1; r2Is CH2(CH2)cCOO(CH2)dCH3C is 0 or 1, d is 0 or 1; x is halogen.
The chloroalkyl ester is methyl chloroacetate and ethyl chloroacetate.
The resulting product containing 1-alkoxyalkyl-2-methyl-3-acylimidazole halide was distilled under reduced pressure and dried under vacuum at 60 ℃ to give a purified 1-alkoxyalkyl-2-methyl-3-acylimidazole halide.
In other preferred embodiments, the molar ratio of 1-alkoxyalkyl-2-methylimidazole to the chloroalkyl ester is preferably 1: 1.05.
Step S130, dissolving the 1-alkoxy alkyl-2-methyl-3-ester imidazole halide in dichloromethane according to the molar ratio of 1: 1-1: 1.1, and then reacting the obtained solution with an inorganic salt M under the protection of inert gas+Y-Reacting for 5-12 hours to obtain the imidazole ionic liquid with the following structural formula:
wherein M is+Is Li; y is-Is BF4 -，PF6 -，TFSI-，FSI-Or N (CN)2 -Adding 100-200 ml of dichloromethane, 1-alkoxyalkyl-2-methyl-3-ester imidazole halide and inorganic salt M into each mole of 1-alkoxyalkyl-2-methyl-3-ester imidazole halide+Y-The molar ratio of (A) to (B) is 1:1 to 1.1.
In other preferred embodiments, the molar ratio of 1-alkoxyalkyl-2-methyl-3-esterimidazole halide to inorganic salt is 1: 1.05.
In addition, the preparation method of the imidazole ionic liquid also comprises the step of separating and purifying the ionic liquid after the 1-alkoxy alkyl-2-methyl-3-ester imidazole halide, inorganic salt and dichloromethane are stirred and reacted at the temperature of 60 ℃, and the separation and purification process comprises the following steps:
filtering white LiCl precipitate in a reaction product, washing and drying the filtrate by using sodium sulfate, and then washing by using deionized water until no precipitate is generated by using a saturated silver nitrate solution; and (3) removing the volatile solvent from the treated solution through rotary evaporation, and drying to obtain the purified imidazole ionic liquid.
The imidazole ionic liquid is prepared by reacting 2-methylimidazole with alkyl ether bromide to prepare 1-alkoxy alkyl-2-methylimidazole, secondly, 1-alkoxy alkyl-2-methylimidazole reacts with alkyl chloride to prepare 1-alkoxy alkyl-2-methyl-3-ester imidazole halide, finally inorganic salt containing target anions and 1-alkoxy alkyl-2-methyl-3-ester imidazole halide are subjected to ion exchange, and the product after the ion exchange reaction is purified and dried, the preparation method is simple and convenient, the operation is simple, the yield is high (80-90%), and the prepared imidazole ionic liquid has good electrochemical performance and is suitable for the application of lithium ion battery electrolyte taking ternary materials as anode materials.
In addition, the embodiment also provides an imidazole ionic liquid electrolyte for the lithium ion battery and a preparation method thereof.
The ionic liquid electrolyte comprises lithium salt, an organic solvent and ionic liquid. Wherein the ionic liquid is the imidazole ionic liquid. The organic solvent is a mixed solution of ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and vinylene carbonate and phenyl sulfone organic additives are added into the organic solvent, wherein the volume ratio of the ethylene carbonate to the diethyl carbonate to the methyl ethyl carbonate is 2:2: 1-2: 2:3, and the vinylene carbonate and the phenyl sulfone are respectively added in a volume ratio of 1-3%. The lithium salt is LiTFSI or LiPF6、LiBF4Or LiBOB.
Compared with the traditional organic electrolyte, the ionic liquid electrolyte has good cycle performance and wide electrochemical window, and the lithium ion battery has higher electrochemical performance due to the introduction of the ionic liquid, so that the safety performance of the battery is improved; meanwhile, the formation of an SEI film of the lithium negative electrode is promoted, and the cycle performance of the battery is improved.
The preparation method of the ionic liquid electrolyte comprises the following steps:
step S210, preparing the imidazole ionic liquid.
Step S220, adding vinylene carbonate and phenyl sulfone respectively in a volume ratio of 1-3% according to the volume ratio of 2:2: 1-2: 2:3 of ethylene carbonate, diethyl carbonate and methyl ethyl carbonate, and mixing to prepare an organic solvent;
and step S230, adding the lithium salt into the organic solvent according to the mass percent of 0.2-9%, and stirring until the lithium salt is completely dissolved. And then adding imidazole ionic liquid into the solution according to the mass percent of 10-80% of the ionic liquid to obtain the ionic liquid electrolyte. The lithium salt is LiTFSI or LiPF6、LiBF4Or LiBOB.
The preparation method of the imidazole ionic liquid electrolyte is simple and convenient, simple to operate and high in yield, and the prepared imidazole ionic liquid electrolyte has good electrochemical performance, good cycle performance and high stability, and is suitable for application of lithium ion battery electrolyte taking ternary materials as anode materials.
The following describes the preparation of imidazole ionic liquid and its application in lithium ion battery electrolyte using ternary material as anode material, and describes the test of the electrolyte in the aspects of performance and the like, with reference to specific examples.
Example 1
Mixing and dissolving 0.1mol of 2-methylimidazole, 0.105mol of 2-bromoethyl methyl ether and 20mL of absolute ethyl alcohol, transferring the mixture into a 250mL reaction kettle, and reacting for 48 hours at 140 ℃; extracting the brown solution generated by the reaction for three times by using 10mL of mixed solution (1:4, v/v) of anhydrous ethanol and anhydrous ether, retaining the organic phase solution, mixing with 0.1mol of triethylamine, transferring to a 250mL reaction kettle, and reacting for 16 hours at 130 ℃; and (3) filtering to remove white salt substances of a reaction product, collecting filtrate, carrying out reduced pressure distillation, and collecting fractions to obtain the 1-methoxyethyl-2-methylimidazole.
Wherein R is1Is CH2(CH2)aO(CH2)bCH3A is 1, b is 0;
under the atmosphere of nitrogen protection gas, 0.083mol of 1-methoxyethyl-2-methylimidazole is dissolved in 15mL of dichloromethane, then mixed and dissolved with 0.087mol of methyl chloroacetate, and then the mixture is reacted for 48 hours at 60 ℃ to obtain a reaction product; and carrying out reduced pressure distillation on the product, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain a brown yellow viscous liquid, namely the 1-methoxyethyl-2-methyl-3-ester imidazole chloride salt.
Wherein R is1Is CH2(CH2)aO(CH2)bCH3A is 1, b is 0; r2Is CH2(CH2)cCOO(CH2)dCH3C is 0 and d is 0; x is halogen.
Respectively adding 0.068mol of 1-methoxyethyl-2-methyl-3-ester imidazole chloride, 0.07mol of LiTFSI and 10mL of dichloromethane into a 100mL flask to obtain a mixed solution, placing the mixed solution at 60 ℃ for reacting for 12 hours, generating LiCl as a white precipitate, filtering the white precipitate, washing and drying the filtrate by using 0.068mol of sodium sulfate, and then washing the filtrate by using 10mL of deionized water for five times until no precipitate is generated by using a saturated silver nitrate solution; and (3) removing the volatile solvent from the treated solution by rotary evaporation, and drying the solution in vacuum at the temperature of 60 ℃ to obtain brown yellow viscous liquid 1-methoxyethyl-2-methyl-3-ester imidazole bis (trifluoromethylsulfonyl) imide ionic liquid.
Wherein R is1Is CH2(CH2)aO(CH2)bCH3A is 1, b is 0; r2Is CH2(CH2)cCOO(CH2)dCH3C is 0 and d is 0; y is-Is TFSI-。
According to the volume ratio of 2:2:1 of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, vinylene carbonate and phenylsulfone are respectively added in the volume ratio of 1.5%, the materials are mixed to prepare an organic solvent, the organic solvent is added in the mass ratio of 3% of lithium salt, and the mixture is stirred until the lithium salt is completely dissolved. And then adding imidazole ionic liquid into the solution according to the mass percent of 0-100% of the ionic liquid to obtain the ionic liquid electrolytes with different concentrations. The lithium salt being LiPF6。
FIG. 1 is an infrared spectrum of the imidazole ionic liquid. From fig. 1, the characteristic peaks of the ionic liquid described in example 1 can be derived, and the stretching vibration peak of C — H on the unsaturated carbon on the imidazole ring is: 3149.64 cm-1; the stretching vibration peaks of CH 3-and CH 2-on saturated carbon on the imidazole substituted ring are respectively as follows: 2995.34cm-1 and 2945.19 cm-1; bending vibration of-CH 3 and-CH 2 was 1435 cm-1; the stretching vibration of the side chain C ═ O is: 1756cm-1, the stretching vibration of the side chain C-O-C is: 1210cm-1, and the asymmetric stretching vibration of C-O-C is a strong and wide peak called as an ester band, so the stretching vibration absorption of C ═ O is at 1756cm-1 in the spectrogram; the stretching vibration and the aromatic skeleton vibration of C ═ N on the imidazole ring are as follows: 1533.35cm-1 and 1421.48 cm-1; the telescopic vibration absorption peak of C ═ C on the imidazole ring is as follows: 1456.20 cm-1; the C-N telescopic vibration absorption peak on the imidazole ring is 1355.91cm < -1 >; the absorption peak of the stretching vibration of the side chain C-N is as follows: 1271.04cm-1 and 1199.67 cm-1; the stretching vibration peak of the imidazole ring is as follows: 1136.03 cm-1; the stretching vibration peak of TFSI-is: 1055.02 cm-1; the stretching vibration peak of C-O-C on the imidazole ring is as follows: 1012.59 cm-1; the C-H in-plane rocking bending vibration peak on the imidazole ring is as follows: 993.30 cm-1; the peak of the C-H out-of-plane rocking bending vibration on the imidazole ring is as follows: 740.64 cm-1. From the above description, 1-methoxyethyl-2-methyl-3-allylimidazolium bis (trifluoromethylsulfonyl) imide salt was obtained.
The 1-methoxyethyl-2-methyl-3-ester imidazole bis (trifluoromethyl sulfonyl) imide ionic liquid is obtained.
As can be seen from table 1, when the electrolyte was exposed to a free flame, the 0% IL electrolyte (blank electrolyte) ignited instantaneously and kept the flame above 19.5s, in contrast to the mixed electrolytes 10% IL, 20% IL, 40% IL extinguished in 11.4s, 8.7s, 2.1s, respectively; the non-flammability threshold is reached when the ionic liquid in the mixed electrolyte reaches above 60%. In addition, the short extinguishing time has strong flame retardance, and then the SET of ionic liquid with various concentrations is observed, the SET of 0% IL of the organic electrolyte is 88.6s/g, and the SET of 10% IL, 20% IL and 40% IL of the mixed electrolyte is 51.8s/g, 39.5s/g and 9.5s/g respectively; compared with 0% IL electrolyte (blank electrolyte), the addition of 10%, 20% and 40% IL shortens the extinguishing time by 41.5%, 55.4% and 89.3%, respectively, and has high safety performance. The incombustibility of the mixed electrolyte meets the requirement of industrialization. Meanwhile, ethylene carbonate, diethyl carbonate and methyl ethyl carbonate are mixed according to the volume ratio of 2:2: 1-2: 2:3, and vinylene carbonate and phenylsulfone which are organic additives are added according to the volume ratio of 1-3%, so that the formation of a lithium cathode SEI film is promoted, and the cycle performance of the battery is improved.
Table 1 combustion calculations for ionic liquid electrolytes of different concentrations obtained in example 1.
LiNi0.5Co0.2Mn0.3O2The charge-discharge cycle test of the/Li battery is mainly completed by a CT2001A type blue charge-discharge test system.
The lithium ion battery was subjected to charge and discharge tests, and the test results are shown in fig. 2.
For example, fig. 2 is a graph of 50 charge-discharge cycle performance of ionic liquid electrolytes with different concentrations at 0.1C. The highest specific discharge capacity of the 0% IL electrolyte (blank electrolyte) is 168.1mAh/g, the specific discharge capacity of 50 cycles is 166.6mAh/g, the capacity retention rate is 97%, and the capacity retention rate is far lower than the theoretical specific capacity of the ternary material (NCM 523); the conductivity of the mixed electrolyte solution of 10% IL, 20% IL, 40% IL and 60% IL is higher than that of a blank electrolyte solution, wherein the specific discharge capacity of the electrolyte solution of 10% IL is the highest and is 182.4mAh/g, the oxidative decomposition of an organic solvent in the circulation process is inhibited due to the addition of the ionic liquid, the solution is completely solvated into free anions and cations, the conductivity of the electrolyte solution is increased along with the increase of the number of ions, and the charge and discharge of a battery are facilitated. The specific discharge capacity of 80% IL and 100% IL is relatively low, which is caused by the fact that the viscosity of the electrolyte is high due to the fact that the content of IL in the electrolyte is too high and the viscosity of the ionic liquid is high; in addition, the electrolyte has high viscosity, so that the wettability of the electrolyte and an electrode material is poor, and the electrolyte and the electrode material have combined action, so that the capacity of the battery is seriously attenuated in the circulating process, and the circulating performance of the battery is reduced. Generally, the ionic liquid electrolyte with various concentrations has higher specific discharge capacity which is more than 172mAh/g, is higher than that of a commercial electrolyte (a blank electrolyte), has good safety performance, and is suitable for the requirements of industrialization on high energy density and safety of batteries.
Example 2
Mixing and dissolving 0.1mol of 2-methylimidazole, 0.105mol of 2-bromoethyl ether and 20mL of absolute ethyl alcohol, transferring the mixture into a 250mL reaction kettle, and reacting for 48 hours at 140 ℃; washing the brown solution generated by the reaction with 10mL of mixed solution (1:4, v/v) of anhydrous ethanol and anhydrous ether for three times, mixing with 0.1mol of triethylamine, transferring to a 250mL reaction kettle, and reacting for 16 hours at 130 ℃; and (3) filtering to remove white salt substances of a reaction product, collecting filtrate, carrying out reduced pressure distillation, and collecting fractions to obtain the 1-ethoxyethyl-2-methylimidazole.
Under the atmosphere of nitrogen protection gas, 0.083mol of 1-ethoxyethyl-2-methylimidazole is dissolved in 15mL of dichloromethane, then mixed and dissolved with 0.087mol of methyl chloroacetate, and then the mixture reacts for 48 hours at 60 ℃ to obtain a reaction product; and carrying out reduced pressure distillation on the product, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain a brown yellow viscous liquid, namely the 1-methoxyethyl-2-methyl-3-ester imidazole chloride salt.
According to the volume ratio of 2:2:1 of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, vinylene carbonate and phenylsulfone are respectively added in the volume ratio of 1.5%, the materials are mixed to prepare an organic solvent, the organic solvent is added in the mass ratio of 3% of lithium salt, and the mixture is stirred until the lithium salt is completely dissolved. And then adding imidazole ionic liquid into the solution according to the mass percent of 0-100% of the ionic liquid to obtain the ionic liquid electrolytes with different concentrations. The lithium salt being LiPF6。
Example 3
Mixing and dissolving 0.1mol of 2-methylimidazole, 0.105mol of 2-bromoethyl ether and 20mL of absolute ethyl alcohol, transferring the mixture into a 250mL reaction kettle, and reacting for 48 hours at 140 ℃; washing the brown solution generated by the reaction with 10mL of mixed solution (1:4, v/v) of anhydrous ethanol and anhydrous ether for three times, mixing with 0.1mol of triethylamine, transferring to a 250mL reaction kettle, and reacting for 16 hours at 130 ℃; and (3) filtering to remove white salt substances of a reaction product, collecting filtrate, carrying out reduced pressure distillation, and collecting fractions to obtain the 1-ethoxyethyl-2-methylimidazole.
Under the atmosphere of nitrogen protection gas, 0.083mol of 1-ethoxyethyl-2-methylimidazole is dissolved in 15mL of dichloromethane, then mixed and dissolved with 0.087mol of ethyl chloroacetate, and then the mixture reacts for 48 hours at 60 ℃ to obtain a reaction product; and carrying out reduced pressure distillation on the product, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain a brown yellow viscous liquid, namely the 1-methoxyethyl-2-methyl-3-ester imidazole chloride salt.
Respectively adding 0.068mol of 1-ethoxyethyl-2-methyl-3-ester imidazole chloride, 0.07mol of LiTFSI and 10mL of dichloromethane into a 100mL flask to obtain a mixed solution, reacting the mixed solution at 60 ℃ for 12 hours to generate LiCl which is a white precipitate, filtering the white precipitate, washing and drying the filtrate by using 0.068mol of sodium sulfate, and then washing the filtrate by using 10mL of deionized water for five times until no precipitate is generated by using a saturated silver nitrate solution; and (3) removing the volatile solvent from the treated solution by rotary evaporation, and drying the solution in vacuum at the temperature of 60 ℃ to obtain brown yellow viscous liquid 1-ethoxyethyl-2-methyl-3-ester imidazole bis (trifluoromethylsulfonyl) imide ionic liquid.
According to the volume ratio of 2:2:1 of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, vinylene carbonate and phenylsulfone are respectively added in the volume ratio of 1.5%, the materials are mixed to prepare an organic solvent, the organic solvent is added in the mass ratio of 3% of lithium salt, and the mixture is stirred until the lithium salt is completely dissolved. And then adding imidazole ionic liquid into the solution according to the mass percent of 0-100% of the ionic liquid to obtain the ionic liquid electrolytes with different concentrations. The lithium salt being LiPF6。
Example 4
Mixing and dissolving 0.1mol of 2-methylimidazole, 0.105mol of 2-bromomethyl ethyl ether and 20mL of absolute ethyl alcohol, transferring the mixture into a 250mL reaction kettle, and reacting for 48 hours at 140 ℃; washing the brown solution generated by the reaction with 10mL of mixed solution (1:4, v/v) of anhydrous ethanol and anhydrous ether for three times, mixing with 0.1mol of triethylamine, transferring to a 250mL reaction kettle, and reacting for 16 hours at 130 ℃; and (3) filtering to remove white salt substances of a reaction product, collecting filtrate, carrying out reduced pressure distillation, and collecting fractions to obtain the 1-methoxyethyl-2-methylimidazole.
Under the atmosphere of nitrogen protection gas, 0.083mol of 1-methoxyethyl-2-methylimidazole is dissolved in 15mL of dichloromethane, then the dichloromethane and 0.087mol of ethyl chloroacetate are mixed and dissolved, and then the mixture reacts for 48 hours at 60 ℃ to obtain a reaction product; and carrying out reduced pressure distillation on the product, and carrying out vacuum drying at 60 ℃ for 24 hours to obtain a brown yellow viscous liquid, namely the 1-methoxyethyl-2-methyl-3-ester imidazole chloride salt.
Respectively adding 0.068mol of 1-methoxyethyl-2-methyl-3-ester imidazole chloride, 0.07mol of LiTFSI and 10mL of dichloromethane into a 100mL flask to obtain a mixed solution, placing the mixed solution at 60 ℃ for reacting for 12 hours, generating LiCl as a white precipitate, filtering the white precipitate, washing and drying the filtrate by using 0.068mol of sodium sulfate, and then washing the filtrate by using 10mL of deionized water for five times until no precipitate is generated by using a saturated silver nitrate solution; and (3) removing the volatile solvent from the treated solution by rotary evaporation, and drying the solution in vacuum at the temperature of 60 ℃ to obtain brown yellow viscous liquid 1-methoxyethyl-2-methyl-3-ester imidazole bis (trifluoromethylsulfonyl) imide ionic liquid.
According to the volume ratio of 2:2:1 of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, vinylene carbonate and phenylsulfone are respectively added in the volume ratio of 1.5%, the materials are mixed to prepare an organic solvent, the organic solvent is added in the mass ratio of 3% of lithium salt, and the mixture is stirred until the lithium salt is completely dissolved. And then adding imidazole ionic liquid into the solution according to the mass percent of 0-100% of the ionic liquid to obtain the ionic liquid electrolytes with different concentrations. The lithium salt being LiPF6。
And (3) performance testing:
application of the Ionic liquid electrolyte prepared in example 1 to LiNi0.5Co0.2Mn0.3O2In the Li lithium ion battery, the cyclic charge and discharge performance test is carried out, and the steps are as follows:
respectively and accurately weighing LiNi according to the mass ratio of 85:10:50.5Co0.2Mn0.3O2Putting PVDF into a cleaned agate mortar, adding N-methylpyrrolidone (NMP) according to the mass ratio of the PVDF to the N-methylpyrrolidone being 1:51, and grinding for 20 minutes to obtain a transparent and uniform paste; then weighing the LiNi0.5Co0.2Mn0.3O2The active material and acetylene black are put into a mortar and continuously ground for 40 minutes, and the active material and the acetylene black are uniformly mixed to prepare slurry.
Uniformly coating the slurry on aluminum foil cleaned with ethanol by a four-side coater, drying in a thermostat at 60 deg.C for 12 hr, and rolling under 12MPa to obtain LiNi0.5Co0.2Mn0.3O2And finally, drying the electrode in a vacuum drying oven at 120 ℃ for 24 hours, removing the volatile solvent NMP, and preparing the positive plate. Punching the prepared pole piece into the pole piece with the diameter of 16mmThe wafer is used as the anode of the lithium ion battery and is sealed and stored in a glove box filled with argon; selecting polypropylene as a lithium battery diaphragm; and selecting a lithium sheet as the negative electrode of the lithium battery. In a glove box, the electrolyte prepared in example 1 was placed in the positive and negative electrodes, an LIR2032 type button cell was used and assembled, and then mechanically sealed on a sealing machine.
LiNi0.5Co0.2Mn0.3O2The charge-discharge cycle test of the/Li battery is mainly completed by a CT2001A type blue charge-discharge test system.
The lithium ion battery was subjected to charge and discharge tests, and the test results are shown in fig. 2.
As can be seen from fig. 2, the highest specific discharge capacity of the 0% IL electrolyte (blank electrolyte) is 168.1mAh/g, the specific discharge capacity of 50 cycles is 166.6mAh/g, the capacity retention rate is 97%, which is far lower than the theoretical specific capacity of the ternary material (NCM 523); the conductivity of the mixed electrolyte solution of 10% IL, 20% IL, 40% IL and 60% IL is higher than that of a blank electrolyte solution, wherein the specific discharge capacity of the electrolyte solution of 10% IL is the highest and is 182.4mAh/g, the oxidative decomposition of an organic solvent in the circulation process is inhibited due to the addition of the ionic liquid, the solution is completely solvated into free anions and cations, the conductivity of the electrolyte solution is increased along with the increase of the number of ions, and the charge and discharge of a battery are facilitated. The specific discharge capacity of 80% IL and 100% IL is relatively low, which is caused by the fact that the viscosity of the electrolyte is high due to the fact that the content of IL in the electrolyte is too high and the viscosity of the ionic liquid is high; in addition, the electrolyte has high viscosity, so that the wettability of the electrolyte and an electrode material is poor, and the electrolyte and the electrode material have combined action, so that the capacity of the battery is seriously attenuated in the circulating process, and the circulating performance of the battery is reduced. Generally, the ionic liquid electrolyte with various concentrations has higher specific discharge capacity which is more than 172mAh/g, is higher than that of a commercial electrolyte (a blank electrolyte), has good safety performance, and is suitable for the requirements of industrialization on high energy density and safety of batteries.
The prepared imidazole electrolyte has low viscosity and good electrochemical performance, and the dissolving capacity of the imidazole ionic liquid is improved because an ether group is introduced into the N-1 position on the imidazole ring of the imidazole ionic liquid; an ester group is introduced into the N-3 position on the imidazole ring, so that the electrochemical window and the electrochemical stability of the ionic liquid are improved; and after the active hydrogen on the 2-position of the imidazole ring is substituted by methyl, the electrochemical window is wider and the electrochemical stability is obviously improved. When the imidazole ionic liquid is used as an additive and a ternary material is used as a positive electrode material, the obtained electrolyte has good cycle performance and a wide electrochemical window.
It should be understood that the above description is illustrative of the preferred embodiment of the invention and is not to be construed as limiting the scope of the invention.
The invention is not the best known technology.
Claims (10)
1. An imidazole ionic liquid, characterized in that the ionic liquid has the following structural formula:
wherein R is1Is CH2(CH2)aO(CH2)bCH3A is 0 or 1, b is 0 or 1; r2Is CH2(CH2)cCOO(CH2)dCH3C is 0 or 1, d is 0 or 1; y is-Is BF4 -，PF6 -，TFSI-，FSI-Or N (CN)2 -。
2. A process for the preparation of imidazolium ionic liquids according to claim 1, characterized in that it comprises the following steps:
(1) dissolving 2-methylimidazole and bromo-alkyl ether in a solvent, and reacting at 100-150 ℃ for 24-48 hours; extracting after the reaction is finished, adding triethylamine into the organic phase, and reacting for 16-24 hours at the temperature of 100-130 ℃ to obtain 1-alkoxy alkyl-2-methylimidazole with the following structural formula:
wherein, the molar ratio is 2-methylimidazole: brominated alkyl ethers: triethylamine is 1: 1-1.1: 1; the solvent is absolute ethyl alcohol or dichloromethane, and 100-200 ml of solvent is added to each mol of 2-methylimidazole; the brominated alkyl ether is bromomethyl methyl ether, bromomethyl ethyl ether, 2-bromoethyl methyl ether or 2-bromoethyl ethyl ether;
wherein R is1Is CH2(CH2)aO(CH2)bCH3A is 0 or 1, b is 0 or 1;
(2) dissolving 1-alkoxy alkyl-2-methylimidazole in a solvent under the atmosphere of protective gas, and reacting with chloroalkyl ester at 60 ℃ for 24-48 hours to obtain 1-alkoxy alkyl-2-methyl-3-ester imidazole halide with the following structure:
wherein R is1Is CH2(CH2)aO(CH2)bCH3A is 0 or 1, b is 0 or 1; r2Is CH2(CH2)cCOO(CH2)dCH3C is 0 or 1, d is 0 or 1; x is halogen; the molar ratio is 1-alkoxy alkyl-2-methylimidazole: a chloroalkyl ester 1:1 to 1.2; the solvent is dichloromethane, and 100-200 ml of solvent is added to each mol of 1-alkoxy alkyl-2-methylimidazole;
the chloroalkyl ester is methyl chloroacetate or ethyl chloroacetate;
(3) dissolving the 1-alkoxy alkyl-2-methyl-3-ester imidazole halide in dichloromethane, and then reacting with an inorganic salt M at 20-25 ℃ under the protection of inert gas+Y-Reacting for 5-12 hours to obtain the 1-alkoxy alkyl-2-methyl-3-ester imidazole bis (trifluoromethyl sulfonyl) imide ionic liquid with the following structural formula:
wherein M is+Is Li; y is-Is BF4 -，PF6 -，TFSI-，FSI-Or N (CN)2 -Adding 100-200 ml of dichloromethane, 1-alkoxyalkyl-2-methyl-3-ester imidazole halide and inorganic salt M into each mole of 1-alkoxyalkyl-2-methyl-3-ester imidazole halide+Y-The molar ratio of (A) to (B) is 1:1 to 1.1.
3. The method for preparing imidazole ionic liquid according to claim 2, wherein the extractant is a mixed solution of absolute ethyl alcohol and absolute ethyl ether, and the volume ratio of absolute ethyl alcohol: anhydrous ether ═ 1: 4.
4. The process for preparing imidazolium ionic liquids according to claim 2, characterized in that the molar ratio of the 2-methylimidazole to the brominated alkyl ether is preferably 1: 1.05.
5. The process for preparing imidazolium ionic liquids according to claim 2, wherein the molar ratio of the 1-alkoxyalkyl-2-methylimidazole to the chloroalkyl ester is preferably 1: 1.05.
6. The method for preparing imidazole ionic liquid according to claim 2, wherein the molar ratio of the 1-alkoxyalkyl-2-methyl-3-esterimidazole halide to the inorganic salt is preferably 1: 1.05.
7. The method for preparing imidazole ionic liquid according to claim 2, wherein the protective atmosphere in step (2) and step (3) is nitrogen or argon.
8. The method for preparing imidazole ionic liquid according to claim 2, characterized in that in the step (3), the method further comprises the following steps: the ionic liquid separation and purification method comprises the following steps of:
filtering white LiCl precipitate in a reaction product, washing and drying the filtrate by using sodium sulfate, and then washing by using deionized water until no precipitate is generated by using a saturated silver nitrate solution; and (3) removing the volatile solvent from the treated solution through rotary evaporation, and drying to obtain the purified imidazole ionic liquid.
9. Use of the imidazolium ionic liquids according to claim 1 for the production of electrolytes for lithium ion batteries.
10. The use of an imidazolium ionic liquid according to claim 1, wherein the electrolyte comprises: organic solvent, lithium salt and ionic liquid; wherein the ionic liquid accounts for 10-80% of the electrolyte by mass, the lithium salt accounts for 0.2-9% of the electrolyte by mass, and the balance is an organic solvent.
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| CN111592609A (en) * | 2020-06-23 | 2020-08-28 | 中国科学院兰州化学物理研究所 | Ether-group-containing imidazole polymerization ionic liquid and preparation method and application thereof |
| CN111592609B (en) * | 2020-06-23 | 2021-03-16 | 中国科学院兰州化学物理研究所 | Ether-group-containing imidazole polymerization ionic liquid and preparation method and application thereof |
| CN113270644A (en) * | 2021-05-17 | 2021-08-17 | 惠州亿纬锂能股份有限公司 | Electrolyte and preparation method and application thereof |
| CN114105907A (en) * | 2021-12-14 | 2022-03-01 | 河北工业大学 | Pyrrolidine ionic liquid and preparation method and application thereof |
| CN115960494A (en) * | 2023-02-20 | 2023-04-14 | 杭州米娅嗨米文化有限公司 | Application of ionic liquid, pigment and preparation method of pigment |
| CN116315065A (en) * | 2023-02-20 | 2023-06-23 | 安徽瑞柏新材料有限公司 | Preparation method of electrolyte and application of electrolyte in lithium ion battery |
| CN116315065B (en) * | 2023-02-20 | 2023-10-03 | 安徽瑞柏新材料有限公司 | Preparation method of electrolyte and application of electrolyte in lithium ion battery |
| CN115960494B (en) * | 2023-02-20 | 2023-12-15 | 杭州米娅嗨米文化有限公司 | Application of ionic liquid, pigment and preparation method thereof |
| CN116626788A (en) * | 2023-07-24 | 2023-08-22 | 季华实验室 | Electrowetting zoom lens based on high-refractive-index ionic liquid |
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