CN102324566A - A kind of preparation method of ionic liquid electrolyte - Google Patents
A kind of preparation method of ionic liquid electrolyte Download PDFInfo
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- CN102324566A CN102324566A CN201110278427A CN201110278427A CN102324566A CN 102324566 A CN102324566 A CN 102324566A CN 201110278427 A CN201110278427 A CN 201110278427A CN 201110278427 A CN201110278427 A CN 201110278427A CN 102324566 A CN102324566 A CN 102324566A
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- lithium
- ionic liquid
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- electrolyte
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 66
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 31
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 31
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000003063 flame retardant Substances 0.000 claims abstract description 11
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract 6
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 102
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 38
- 229910001416 lithium ion Inorganic materials 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- OZHJEQVYCBTHJT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-methylbenzene Chemical compound CC1=C(Br)C(Br)=C(Br)C(Br)=C1Br OZHJEQVYCBTHJT-UHFFFAOYSA-N 0.000 claims description 6
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 claims description 6
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000005486 organic electrolyte Substances 0.000 claims description 3
- CHHOPPGAFVFXFS-UHFFFAOYSA-M [Li+].[O-]S(F)(=O)=O Chemical compound [Li+].[O-]S(F)(=O)=O CHHOPPGAFVFXFS-UHFFFAOYSA-M 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 238000010494 dissociation reaction Methods 0.000 claims description 2
- 230000005593 dissociations Effects 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims 3
- 229920000058 polyacrylate Polymers 0.000 claims 3
- JZVUAOCDNFNSGQ-UHFFFAOYSA-N 7-methoxy-2-phenyl-1h-quinolin-4-one Chemical compound N=1C2=CC(OC)=CC=C2C(O)=CC=1C1=CC=CC=C1 JZVUAOCDNFNSGQ-UHFFFAOYSA-N 0.000 claims 2
- WCXIRBYEIYUFJL-UHFFFAOYSA-M lithium;2,2,3,3,3-pentafluoropropanoate Chemical compound [Li+].[O-]C(=O)C(F)(F)C(F)(F)F WCXIRBYEIYUFJL-UHFFFAOYSA-M 0.000 claims 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims 1
- OAJNZFCPJVBYHB-UHFFFAOYSA-N 2,5,8,11-tetraoxabicyclo[10.4.0]hexadeca-1(16),12,14-triene Chemical compound O1CCOCCOCCOC2=CC=CC=C21 OAJNZFCPJVBYHB-UHFFFAOYSA-N 0.000 claims 1
- SULCYVPOJZHGRY-UHFFFAOYSA-M [Li+].[O-]C(F)=O Chemical compound [Li+].[O-]C(F)=O SULCYVPOJZHGRY-UHFFFAOYSA-M 0.000 claims 1
- 150000001450 anions Chemical class 0.000 claims 1
- CDRXHPHCGLPMFV-UHFFFAOYSA-N carbonic acid pent-2-ene Chemical compound OC(O)=O.CCC=CC CDRXHPHCGLPMFV-UHFFFAOYSA-N 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 238000004880 explosion Methods 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- 239000000446 fuel Substances 0.000 claims 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims 1
- 238000013021 overheating Methods 0.000 claims 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 6
- 150000003984 12-crown-4 derivatives Chemical class 0.000 abstract 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 238000003756 stirring Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 26
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 24
- 150000002148 esters Chemical class 0.000 description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 16
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 12
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 12
- NBVMCMSJGNOOCF-UHFFFAOYSA-N lithium;2,2,2-trifluoroacetic acid Chemical compound [Li].OC(=O)C(F)(F)F NBVMCMSJGNOOCF-UHFFFAOYSA-N 0.000 description 10
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 8
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- PZSXCNWLLFEOPM-UHFFFAOYSA-N [F].C(CC)(=O)O Chemical compound [F].C(CC)(=O)O PZSXCNWLLFEOPM-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ANLVEXKNRYNLDH-UHFFFAOYSA-N 1,3-dioxonan-2-one Chemical compound O=C1OCCCCCCO1 ANLVEXKNRYNLDH-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
Classifications
-
- 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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- Secondary Cells (AREA)
Abstract
The present invention discloses a preparation method for an ionic liquid electrolyte. According to the method, a lithium salt, a carbonate, ionic liquid, 12-crown-4 and a 12-crown-4 derivative, a polymethacrylic acid long chain alkyl ester, a polyacrylic acid long chain alkyl ester and a fire retardant agent are adopted as raw materials. The preparation method comprises: mixing the raw materials according to a certain ratio, wherein the raw materials comprise, by mass, 0.001-95% of the lithium salt, 0.001-95% of the carbonate, 0.001-95% of the ionic liquid, 0.001-95% of the 12-crown-4 and the 12-crown-4 derivative, 0.001-15% of the polymethacrylic acid long chain alkyl ester, 0.001-15% of the polyacrylic acid long chain alkyl ester and 0.001-15% of the fire retardant agent; carrying out stirring until all the materials are completely dissolved to obtain the ionic liquid electrolyte.
Description
Technical field
The present invention relates to a kind of preparation method of il electrolyte, belong to the lithium ion battery material field.
Background technology
Advantages such as lithium ion battery has the operating voltage height, energy density is big, temperature limit is wide, self-discharge rate is low, have extended cycle life, memory-less effect.Along with increasingly sharpening of world energy sources crisis and environmental crisis; Lithium ion battery is compared with conventional batteries to has significantly advantage and receives the extensive concern of countries in the world; Be described as one of environmental protection energy of 21 century; This makes lithium ion battery develop rapidly becomes a huge industry, in global economy, occupies an important position and acts on.
At present; Lithium ion battery has been widely used in pocket household electrical appliance such as portable computer and the mobile phone; Also obtained extensive use in Aeronautics and Astronautics, artificial satellite and military domain of communication equipment; Especially in recent years the application in the electric bicycle field has obtained developing rapidly; Following lithium ion battery will be brought into play the effect that conventional batteries is difficult to substitute as electrokinetic cell in auto industry, make automobile become the vehicles of clean environment firendly, will play an important role for the protection world environments.
Electrolyte is one of lithium ion battery four big critical materials (positive electrode, negative material, barrier film, electrolyte); Be " blood " of lithium ion battery; In lithium ion battery, playing the effect of conduction electron between the both positive and negative polarity, is the assurance that lithium ion battery obtains performances such as high voltage, high specific energy.At present, lithium-ion battery electrolytes is generally by highly purified organic solvent, electrolyte lithium salt, other necessary raw material such as additive, and is under certain condition, formulated by a certain percentage.Organic solvent adopts carbonic ester series high-purity organic solvent more; Like ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, methyl carbonic acid propylene ester, ethyl carbonate propylene ester etc., electrolyte lithium salt is actual, and what use mainly is lithium hexafluoro phosphate.
Lithium hexafluoro phosphate exists problems such as the preparation process is complicated, process conditions are harsh, cost an arm and a leg, and particularly has problems such as thermal stability is poor, poor water resistance.When lithium hexafluoro phosphate is met water or steam; Decomposition reaction takes place rapidly generate phosphorus pentafluoride; Phosphorus pentafluoride is colourless foul gas at normal temperatures and pressures; Skin, eyes, mucous membrane are had intense stimulus property, and in humid air or meet the hydrogen fluoride that water can vigorous reaction generates severe toxicity and very corrosive, this has had a strong impact on the stability and the safety in utilization of lithium ion battery.
Lithium ion battery relies on the comprehensive advantage of himself coming into a more huge industrial colony---automobile power cell field.In order to adapt to this huge industrial colony, lithium-ion battery electrolytes material development in future trend will mainly concentrate on aspects such as ionic liquid, novel lithium salts.Therefore; The electrolyte material that the positive and negative electrode material of research and development and lithium ion battery is complementary; To make lithium ion battery safer; Have higher power and bigger capacity, be applied to electric motor car, energy storage, space flight and field widely with finally making the lithium ion battery safe ready, significant to promoting the lithium ion battery industrial expansion.
Ionic liquid (Ionic Liquids) is exactly to be made up of ion fully, and the salt that under low temperature (＜100 ℃), is in a liquid state is also referred to as watery fusion salt, and it generally is made up of organic cation and inorganic anion.The material that is made up of ion that under near temperature room temperature or the room temperature, is in a liquid state is called ionic liquid at room temperature, generally abbreviates ionic liquid as.Because ionic liquid has good conductivity, difficult volatilizees, does not burn, electrochemical window is more much bigger than other electrolyte aqueous solution; Ionic liquid is applied to battery can alleviates self discharge, ionic liquid is applied to make novel high-performance battery, solar cell and capacitor etc. as electrolyte and all has significant advantage.Therefore, ionic liquid not only can be widened the serviceability temperature scope of lithium ion battery as lithium-ion battery electrolytes; And can improve the fail safe of lithium ion battery under high-energy-density; Be the desirable electrolyte of following power lithium-ion battery, thereby, receive extensive concern in recent years.
The present invention is a raw material with lithium salts, carbonic ester, ionic liquid, 12-crown-4 and derivative thereof, polymethylacrylic acid long-chain alkyl groups, polyacrylic acid long-chain alkyl groups and fire retardant etc.; The preparation steam forces down, thermally-stabilised good, chemical stability is good, electrochemical window is wide, the il electrolyte of cleaning, environmental protection, safety and excellent performance; Contain lithium hexafluoro phosphate electrolyte with what substitute that present lithium ion battery uses; Fundamentally solve problems such as the existing poor water resistance of traditional organic electrolyte, poor heat stability, improve the performances such as capacity, cryogenic property and battery cycle life of lithium ion battery.
Adopt il electrolyte cheap, the Chemical Physics stable performance; Substitute the lithium hexafluoro phosphate electrolyte of lithium ion battery in the market; It is one of inexorable trend of lithium ion battery industrial development; To help significantly reducing the production cost of lithium ion battery, improve the performance of lithium ion battery, very favourable to large tracts of land developing lithium ion battery produce market.
Summary of the invention
The preparation method of a kind of il electrolyte of the present invention; Providing a kind of is raw material with lithium salts, carbonic ester, ionic liquid, 12-crown-4 and derivative thereof, polymethylacrylic acid long-chain alkyl groups, polyacrylic acid long-chain alkyl groups and fire retardant; According to certain quality percentage, the method for preparation lithium-ion battery electrolytes.
The preparation method of a kind of il electrolyte of the present invention, adopt following technical scheme:
Mass percent according to lithium salts, carbonic ester, ionic liquid, 12-crown-4 and derivative thereof, polymethylacrylic acid long-chain alkyl groups, polyacrylic acid long-chain alkyl groups and fire retardant is (0.001%～95%): (0.001%～95%): (0.001%～95%): (0.001%～95%): (0.001%～15%): (0.001%～15%): the ratio of (0.001%～15%); Lithium salts, carbonic ester, ionic liquid, 12-crown-4 and derivative thereof, polymethylacrylic acid long-chain alkyl groups, polyacrylic acid long-chain alkyl groups and fire retardant are mixed; After being stirred to all materials and dissolving fully, promptly obtain il electrolyte.
The preparation method of a kind of il electrolyte of the present invention has following characteristics:
1, uses fluorocarboxylic acid lithium salts and fluoro sulfonic acid lithium salts,, can effectively improve the conductivity of il electrolyte like trifluoroacetic acid lithium, five fluorine propionic acid lithiums and TFMS lithium;
2, substitute lithium hexafluoro phosphate with ionic liquid, both can reduce the production cost of il electrolyte, can eliminate the problem of electrolyte poor water resistance again, also can effectively improve the conductivity of il electrolyte;
3, because 12-crown-4 and derivative thereof can form complex compound with the lithium ion complexing; Thereby increase the degree of dissociation of lithium salts; Reduce the interaction between lithium ion and solvent molecule, realized effective separation that the lithium salts zwitterion is right, therefore; Use 12-crown-4 and derivative thereof as complexing agent, can further improve the conductivity of il electrolyte;
4, use polymethylacrylic acid long-chain alkyl groups and polyacrylic acid long-chain alkyl groups can effectively reduce the solidifying point of il electrolyte, make the serviceability temperature scope of il electrolyte become wideer, help widening its application;
5, the organic solvent in the lithium-ion battery electrolytes can be gasified; Lithium ion battery is is excessively discharging and recharging, is emitting a large amount of heat under the situation that short circuit and big electric current work long hours; Cause flammable electrolyte to have potential safety hazard, even cause battery to be blasted, the purpose of using fire retardant is to make inflammable organic electrolyte become difficult combustion or non-flammable electrolyte; Avoid battery under overheated condition, to burn or explode, eliminate the potential safety hazard of electrolyte.
The preparation method of a kind of il electrolyte of the present invention, used lithium salts is any one or more in trifluoroacetic acid lithium, five fluorine propionic acid lithiums and the TFMS lithium.
The preparation method of a kind of il electrolyte of the present invention, used carbonic ester is any one or more in ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbonic acid first propyl ester, methyl carbonic acid propylene ester and the ethyl carbonate propylene ester.
The preparation method of a kind of il electrolyte of the present invention; Used ionic liquid is 1-methyl-3-ethyl imidazol(e) hexafluorophosphate, 1-methyl-3-ethyl imidazol(e) tetrafluoroborate, 1-methyl-3-butyl imidazole hexafluorophosphate, 1-methyl-3-butyl imidazole tetrafluoroborate, 1-methyl-3-hexyl imidazoles hexafluorophosphate, 1-methyl-3-hexyl tetrafluoroborate, 1; 2-dimethyl-3-ethyl imidazol(e) hexafluorophosphate, 1; 2-dimethyl-3-ethyl imidazol(e) tetrafluoroborate, 1; 2-dimethyl-3-butyl imidazole hexafluorophosphate, 1; 2-dimethyl-3-butyl imidazole tetrafluoroborate, 1; 2-dimethyl-3-hexyl imidazoles hexafluorophosphate, 1, any one or more in 2-dimethyl-3-hexyl tetrafluoroborate, N-ethylpyridine hexafluorophosphate, N-ethylpyridine tetrafluoroborate, N-butyl-pyridinium hexafluorophosphate, N-butyl-pyridinium tetrafluoroborate, N-hexyl pyridine hexafluorophosphate and the N-hexyl pyridinium tetrafluoroborate salt.
The preparation method of a kind of il electrolyte of the present invention; Used 12-crown-4 and derivative thereof are 12-crown-4, phendioxin 2-hat-4,2-methylol-12-crown-4,1, any one or more in 2-cyclohexyl-12-crown-4 and the 4-methyl benzo 12-crown-4.
The preparation method of a kind of il electrolyte of the present invention, used polymethylacrylic acid long-chain alkyl groups is any one or more in polymethylacrylic acid n-tetradecane base ester, polymethylacrylic acid dodecyl ester, the polymethylacrylic acid n-octyl.
The preparation method of a kind of il electrolyte of the present invention, used polyacrylic acid long-chain alkyl groups is any one or more in polyacrylic acid n-tetradecane base ester, polyacrylic acid dodecyl ester, the polyacrylic acid n-octyl.
The preparation method of a kind of il electrolyte of the present invention, used fire retardant is any one or more in deca-BDE, pentabromotoluene, HBCD, triphenyl phosphate, the tricresyl phosphate.
Embodiment
Be the preparation method's of a kind of il electrolyte of the present invention non-limiting example below.Providing of these instances only is for illustrative purposes, can not be interpreted as qualification of the present invention.Because on the basis that does not break away from the spirit and scope of the present invention, can carry out many conversion to the present invention.In these embodiment, unless stated otherwise, all percentage all is meant mass percent.
Embodiment 1
Trifluoroacetic acid lithium: 8%
Ethylene carbonate: 40%
Ethyl carbonate propylene ester: 15%
1-methyl-3-ethyl imidazol(e) hexafluorophosphate: 15%
N-hexyl pyridinium tetrafluoroborate salt: 5%
12-crown-4: 15%
Polymethylacrylic acid n-tetradecane base ester: 0.3%
Polyacrylic acid n-octyl: 0.2%
Deca-BDE: 1.5%
Preparing process: according to above-mentioned mass percent; Trifluoroacetic acid lithium, ethylene carbonate, ethyl carbonate propylene ester, 1-methyl-3-ethyl imidazol(e) hexafluorophosphate, N-hexyl pyridinium tetrafluoroborate salt, 12-crown-4, polymethylacrylic acid n-tetradecane base ester, polyacrylic acid n-octyl and deca-BDE are mixed; After being stirred to all materials and dissolving fully, promptly obtain il electrolyte.
Embodiment 2
TFMS lithium: 10%
Propene carbonate: 31%
Butylene: 26%
1-methyl-3-ethyl imidazol(e) tetrafluoroborate: 12%
N-hexyl pyridine hexafluorophosphate: 7%
Phendioxin 2-hat-4:12%
Polymethylacrylic acid dodecyl ester: 0.2%
Polyacrylic acid dodecyl ester: 0.1%
Pentabromotoluene: 1.7%
Preparing process: according to above-mentioned mass percent; TFMS lithium, propene carbonate, butylene, 1-methyl-3-ethyl imidazol(e) tetrafluoroborate, N-hexyl pyridine hexafluorophosphate, phendioxin 2-hat-4, polymethylacrylic acid dodecyl ester, polyacrylic acid dodecyl ester and pentabromotoluene are mixed; After being stirred to all materials and dissolving fully, promptly obtain il electrolyte.
Embodiment 3
Trifluoroacetic acid lithium: 11%
Butylene: 50%
1-methyl-3-butyl imidazole hexafluorophosphate: 6%
N-butyl-pyridinium tetrafluoroborate: 13%
2-methylol-12-crown-4: 18%
Polymethylacrylic acid n-octyl: 0.2%
Polyacrylic acid n-tetradecane base ester: 0.2%
HBCD: 1.6%
Preparing process: according to above-mentioned mass percent; Trifluoroacetic acid lithium, butylene, 1-methyl-3-butyl imidazole hexafluorophosphate, N-butyl-pyridinium tetrafluoroborate, 2-methylol-12-crown-4, polymethylacrylic acid n-octyl, polyacrylic acid n-tetradecane base ester and HBCD are mixed; After being stirred to all materials and dissolving fully, promptly obtain il electrolyte.
Embodiment 4
TFMS lithium: 9%
Dimethyl carbonate: 45%
Butylene: 10%
1-methyl-3-butyl imidazole tetrafluoroborate: 7%
N-butyl-pyridinium hexafluorophosphate: 11%
1,2-cyclohexyl-12-crown-4: 15.5%
Polymethylacrylic acid n-tetradecane base ester: 0.1%
Polyacrylic acid n-octyl: 0.5%
Triphenyl phosphate: 1.9%
Preparing process: according to above-mentioned mass percent; With TFMS lithium, dimethyl carbonate, butylene, 1-methyl-3-butyl imidazole tetrafluoroborate, N-butyl-pyridinium hexafluorophosphate, 1; 2-cyclohexyl-12-crown-4, polymethylacrylic acid n-tetradecane base ester, polyacrylic acid n-octyl and triphenyl phosphate mix; After being stirred to all materials and dissolving fully, promptly obtain il electrolyte.
Embodiment 5
TFMS lithium: 3%
Trifluoroacetic acid lithium: 7%
Diethyl carbonate: 20%
Propene carbonate: 31%
1-methyl-3-hexyl imidazoles hexafluorophosphate: 10%
N-ethylpyridine tetrafluoroborate: 10%
4-methyl benzo 12-crown-4: 17%
Polymethylacrylic acid dodecyl ester: 0.2%
Polyacrylic acid dodecyl ester: 0.2%
Tricresyl phosphate: 1.6%
Preparing process: according to above-mentioned mass percent; TFMS lithium, trifluoroacetic acid lithium, diethyl carbonate, propene carbonate, 1-methyl-3-hexyl imidazoles hexafluorophosphate, N-ethylpyridine tetrafluoroborate, 4-methyl benzo 12-crown-4, polymethylacrylic acid dodecyl ester, polyacrylic acid dodecyl ester and tricresyl phosphate are mixed; After being stirred to all materials and dissolving fully, promptly obtain il electrolyte.
Embodiment 6
TFMS lithium: 12%
Methyl ethyl carbonate: 17%
Propene carbonate: 30%
1-methyl-3-hexyl tetrafluoroborate: 6%
N-ethylpyridine hexafluorophosphate: 11%
Phendioxin 2-hat-4:21%
Polymethylacrylic acid n-octyl: 0.3%
Polyacrylic acid n-tetradecane base ester: 0.3%
Deca-BDE: 2.4%
Preparing process: according to above-mentioned mass percent; TFMS lithium, methyl ethyl carbonate, propene carbonate, 1-methyl-3-hexyl tetrafluoroborate, N-ethylpyridine hexafluorophosphate, phendioxin 2-hat-4, polymethylacrylic acid n-octyl, polyacrylic acid n-tetradecane base ester and deca-BDE are mixed; After being stirred to all materials and dissolving fully, promptly obtain il electrolyte.
Embodiment 7
Five fluorine propionic acid lithiums: 13%
Carbonic acid first propyl ester: 28%
Methyl ethyl carbonate: 19%
1,2-dimethyl-3-ethyl imidazol(e) hexafluorophosphate: 7%
1-methyl-3-butyl imidazole hexafluorophosphate: 8%
2-methylol-12-crown-4: 23%
Polymethylacrylic acid n-tetradecane base ester: 0.1%
Polyacrylic acid n-octyl: 0.3%
Pentabromotoluene: 1.7%
Preparing process: according to above-mentioned mass percent; With five fluorine propionic acid lithiums, carbonic acid first propyl ester, methyl ethyl carbonate, 1; 2-dimethyl-3-ethyl imidazol(e) hexafluorophosphate, 1-methyl-3-butyl imidazole hexafluorophosphate, 2-methylol-12-crown-4, polymethylacrylic acid n-tetradecane base ester, polyacrylic acid n-octyl and pentabromotoluene mix; After being stirred to all materials and dissolving fully, promptly obtain il electrolyte.
Embodiment 8
Trifluoroacetic acid lithium: 5%
Five fluorine propionic acid lithiums: 7%
Methyl carbonic acid propylene ester: 13%
Dimethyl carbonate: 38%
1,2-dimethyl-3-butyl imidazole hexafluorophosphate: 9%
1-methyl-3-ethyl imidazol(e) tetrafluoroborate: 6%
1,2-cyclohexyl-12-crown-4: 19%
Polymethylacrylic acid n-octyl: 0.2%
Polyacrylic acid dodecyl ester: 0.4%
HBCD: 2.3%
Preparing process: according to above-mentioned mass percent; With trifluoroacetic acid lithium, five fluorine propionic acid lithiums, methyl carbonic acid propylene ester, dimethyl carbonate, 1; 2-dimethyl-3-butyl imidazole hexafluorophosphate, 1-methyl-3-ethyl imidazol(e) tetrafluoroborate, 1; 2-cyclohexyl-12-crown-4, polymethylacrylic acid n-octyl, polyacrylic acid dodecyl ester and HBCD mix, and after being stirred to all materials and dissolving fully, promptly obtain il electrolyte.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912383A (en) * | 2012-10-31 | 2013-02-06 | 南京工业大学 | Method for preparing porous nickel powder by electrodepositing Ni-Al-Mg-Li alloy |
| CN103756754A (en) * | 2014-02-19 | 2014-04-30 | 南京林业大学 | Lubricating oil added with modified nano-Zn powder and ionic liquid and preparation method of lubricating oil |
| CN103814468A (en) * | 2013-09-27 | 2014-05-21 | 惠州亿纬锂能股份有限公司 | Electrolyte for lithium battery and lithium battery using the electrolyte |
| RU2592646C2 (en) * | 2014-11-14 | 2016-07-27 | Открытое Акционерное Общество " Научно-исследовательский и проектно-технологический институт электроугольных изделий" | Low-temperature lithium-fluocarbon element |
| CN107946646A (en) * | 2017-04-14 | 2018-04-20 | 云南锡业集团（控股）有限责任公司 | A kind of square low-temperature lithium ion battery and preparation method thereof |
| WO2018096889A1 (en) * | 2016-11-24 | 2018-05-31 | 日本電気株式会社 | Non-aqueous electrolyte solution and lithium ion secondary battery |
| CN111293356A (en) * | 2018-12-10 | 2020-06-16 | 张家港市国泰华荣化工新材料有限公司 | Crown ether electrolyte and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5110694A (en) * | 1990-10-11 | 1992-05-05 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Secondary Li battery incorporating 12-Crown-4 ether |
| CN101640291A (en) * | 2008-07-29 | 2010-02-03 | 三星Sdi株式会社 | Electrolyte and lithium ion secondary battery including the same |
| CN102130364A (en) * | 2011-02-12 | 2011-07-20 | 中南大学 | A kind of gel-type polymer electrolyte for lithium-sulfur secondary battery system and preparation method thereof |
-
2011
- 2011-09-20 CN CN2011102784274A patent/CN102324566B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5110694A (en) * | 1990-10-11 | 1992-05-05 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Secondary Li battery incorporating 12-Crown-4 ether |
| CN101640291A (en) * | 2008-07-29 | 2010-02-03 | 三星Sdi株式会社 | Electrolyte and lithium ion secondary battery including the same |
| CN102130364A (en) * | 2011-02-12 | 2011-07-20 | 中南大学 | A kind of gel-type polymer electrolyte for lithium-sulfur secondary battery system and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| G.NAGASUBRAMANIAN,ET AL.: "12-Crown-4 Ether-Assisted Enhancement of Ionic Conductivity and Interfacial Kinetics in Polyethylene Oxide Electrolytes", 《J. ELECTROCHEM. SOC.》 * |
| 郑洪河等: "锂离子电池电解液添加剂的发展与展望", 《化学通报》 * |
| 黄再波等: "离子液体用作锂二次电池电解液的研究进展", 《电源技术》 * |
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| CN102912383A (en) * | 2012-10-31 | 2013-02-06 | 南京工业大学 | Method for preparing porous nickel powder by electrodepositing Ni-Al-Mg-Li alloy |
| CN102912383B (en) * | 2012-10-31 | 2015-02-25 | 南京工业大学 | Method for preparing porous nickel powder by electrodepositing Ni-Al-Mg-Li alloy |
| CN103814468A (en) * | 2013-09-27 | 2014-05-21 | 惠州亿纬锂能股份有限公司 | Electrolyte for lithium battery and lithium battery using the electrolyte |
| WO2015042851A1 (en) * | 2013-09-27 | 2015-04-02 | 惠州亿纬锂能股份有限公司 | Electrolyte for lithium battery and lithium battery using same |
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| RU2592646C2 (en) * | 2014-11-14 | 2016-07-27 | Открытое Акционерное Общество " Научно-исследовательский и проектно-технологический институт электроугольных изделий" | Low-temperature lithium-fluocarbon element |
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| CN107946646A (en) * | 2017-04-14 | 2018-04-20 | 云南锡业集团（控股）有限责任公司 | A kind of square low-temperature lithium ion battery and preparation method thereof |
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