CN110240610A - A kind of preparation method of the double borate difluoroborates of polyalcohol - Google Patents
A kind of preparation method of the double borate difluoroborates of polyalcohol Download PDFInfo
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- CN110240610A CN110240610A CN201910447963.9A CN201910447963A CN110240610A CN 110240610 A CN110240610 A CN 110240610A CN 201910447963 A CN201910447963 A CN 201910447963A CN 110240610 A CN110240610 A CN 110240610A
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- polyalcohol
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- double
- borate
- difluoroborates
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- 150000005846 sugar alcohols Polymers 0.000 title claims abstract description 36
- -1 borate difluoroborates Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 238000011049 filling Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000012043 crude product Substances 0.000 claims abstract description 8
- 150000004673 fluoride salts Chemical class 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 10
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 6
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 238000003682 fluorination reaction Methods 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 claims description 2
- 229960000367 inositol Drugs 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 150000002221 fluorine Chemical class 0.000 claims 2
- 239000011737 fluorine Substances 0.000 claims 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 239000013078 crystal Substances 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims 1
- 229960002675 xylitol Drugs 0.000 claims 1
- 235000010447 xylitol Nutrition 0.000 claims 1
- 239000000811 xylitol Substances 0.000 claims 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000654 additive Substances 0.000 abstract description 6
- 230000000996 additive effect Effects 0.000 abstract description 6
- 229910015900 BF3 Inorganic materials 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 150000001875 compounds Chemical group 0.000 abstract description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract 1
- 229910001425 magnesium ion Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 229910001415 sodium ion Inorganic materials 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 239000007787 solid Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- CHNLPLHJUPMEOI-UHFFFAOYSA-N oxolane;trifluoroborane Chemical compound FB(F)F.C1CCOC1 CHNLPLHJUPMEOI-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229960002645 boric acid Drugs 0.000 description 4
- 235000010338 boric acid Nutrition 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- LCIDHOOTSZBDBI-UHFFFAOYSA-N O1CCCC1.[B].B(F)(F)F Chemical compound O1CCCC1.[B].B(F)(F)F LCIDHOOTSZBDBI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- OKVJWADVFPXWQD-UHFFFAOYSA-N difluoroborinic acid Chemical compound OB(F)F OKVJWADVFPXWQD-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of preparation methods of the double borate difluoroborates of polyalcohol, comprise the following steps: (1) polyalcohol being added in the reaction kettle A for filling nonaqueous solvents and boron trifluoride carries out reacting the double borate boron difluoride intermediates of obtained polyalcohol；(2) the double borate boron difluoride intermediates of obtained polyalcohol are continued to put into the reaction kettle B for filling nonaqueous solvents and be added fluoride salt and is reacted to obtain the double borate difluoroborate crude products of polyalcohol；(3) the double borate difluoroborate fine work of polyalcohol are obtained after crude product being filtered and being recrystallized drying.The compound structure of this method preparation is novel, product purity is high, raw material cost is low, waste is easily processed, entire reaction process Atom economy is high, reactor product can be used for lithium ion battery, Magnesium ion battery, sodium-ion battery electrolysis additive, and significantly improve the high temperature circulation and high-temperature storage performance of battery.
Description
[technical field]
The present invention relates to lithium-ion battery electrolytes additive technology fields, and in particular to a kind of double borates two of polyalcohol
The preparation method of borofluoride.
[background technique]
Ternary material (LiNi1-x-yCoxMnyO2,0 < x, y < 1) is relative to LiFePO 4 material gram volume with higher
And electronic conductivity, therefore ternary battery has higher energy density and cryogenic property and is widely used in new energy and multiplies
With vehicle field.The content for improving nickel element in ternary material, can further improve the gram volume of ternary material, and then electricity can be improved
The energy density in pond.The energy density that wherein NCM811 matches graphite cell can reach 280Wh/kg, and it is negative that NCM811 matches SiO-C
The battery energy density of pole can reach 300Wh/kg.For the energy density for further increasing battery, some research institutions in recent years
And Materials Co., Ltd is developing ternary material of the nickel content 0.9 or more, but the Thermodynamically stable performance of such material is with nickel
The raising of content and constantly decline, while there are the Ni4+ of high concentration at positive electrode interface in full electricity for battery, to electrolyte
Catalysis oxidation ability become strong, therefore the high temperature circulation of nickelic ternary battery and high-temperature storage performance are deteriorated.
Transition metal oxide, fluoride (such as Al are coated on the surface of the material2O3, ZrO2, TiO2, LiF, AlF3) or material
Miscellaneous element (such as Mg, Al, F, Ca, Zr) is adulterated in body phase can be improved interface and the phase stabilizer of material, slow down and electrolyte
Side reaction, to improve the cycle performance of battery.Relative to the modification of positive electrode, film forming is added in the electrolytic solution and adds
Add agent to improve the mode of the cycle performance of ternary battery more simple possible.
Difluorine oxalic acid boracic acid lithium (LiDFOB) is a kind of common electrolysis additive, can be at positive and negative pole material interface
The formation for participating in interfacial film, to improve the interface stability of material and reduce corrosion of the electrolyte to material.It should but contain
The battery of additive battery in high temperature storage and high temperature circulation is easy to happen flatulence, to influence the service life and peace of battery
Quan Xing.It how to be that scientific circles and industry need asking for breakthrough from structural point modification and redesign lithium borate salt additive
Topic.
[summary of the invention]
In view of this, the double borate difluoroborates of polyalcohol are as a kind of lithium-ion battery electrolytes additive, this adds
Add in agent structure without containing oxalate structure, stable structure, thus participates in SEI the and CEI membrane structure to be formed and stablize, in high temperature item
It is not easy to produce gas under part, therefore difluorine oxalic acid boracic acid lithium can be substituted, improves the high temperature storage and high temperature cyclic performance of battery.
The purpose of the present invention is to provide a kind of safe operation, production cost is low and the double borates of the polyalcohol of high income
The preparation method of difluoroborate.The compound product structure are as follows:
For achieving the above object, the preparation method of the double borate difluoroborates of polyalcohol provided by the invention includes
Following steps:
(1) non-aqueous organic solvent is added into reaction vessel, polyalcohol is added in reaction vessel in batches, is then pressed
Fluorination reagent is slowly added in reaction vessel and opens heating by certain proportion to react, and has in reaction process a large amount of white
Color solid generates.
(2) it is separated by solid-liquid separation after the reaction was completed, filtrate is obtained after filtering；Distillation obtains crude product after removing solvent, uses
The production of polyalcohol borate boron difluoride white solid is obtained after being dried in vacuo after poor solvent washing and at a certain temperature
Product.
(3) obtained polyalcohol borate boron difluoride is continued to put into the reaction kettle for filling solvent, and is added one
Quantitative fluoride salt is reacted to obtain polyalcohol borate boron difluoride hydrochlorate crude product, and crude product is filtered and is recrystallized
And polyalcohol borate boron difluoride hydrochlorate product is obtained after drying.
Preferably, in the above preparation method, the polyalcohol is antierythrite, pentaerythrite, inositol, xylose
One of alcohol, sorbierite are a variety of, preferably antierythrite and pentaerythrite.
Preferably, in the above preparation method, the non-aqueous organic solvent be acetonitrile, tetrahydrofuran, methylene chloride,
Ethyl acetate, one of dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate or a variety of mixed solvents, preferably acetonitrile,
Tetrahydrofuran.
Preferably, in the above preparation method, fluorination reagent general formula used is LBF3, wherein L is ether or four
One of hydrogen furans or more than one mixture, preferably tetrahydrofuran solution.
Preferably, in the above preparation method, the molar ratio of the fluorination reagent and polyalcohol is 1.9:1~2.5:
1, preferably 1.95:1~2.1:1.
Preferably, in the above preparation method, the fluoride salt is lithium fluoride, in sodium fluoride, potassium fluoride, magnesium fluoride
One or more, preferably lithium fluoride, sodium fluoride.
Preferably, in the above preparation method, the molar ratio of the fluoride salt and polyalcohol borate boron difluoride
For 0.9:1~1.5:1, preferably 1.05:1~1.2:1.
Preferably, in the above preparation method, the reaction temperature is 50~100 DEG C, preferably 60~80 DEG C；
Reaction time is 10~18 hours, preferably 12~15 hours.
Preferably, in the above preparation method, poor solvent is ether, methylene chloride, dichloroethanes, chloroform, just
One of hexane, hexamethylene, benzene or a variety of mixing, preferably methylene chloride, n-hexane.Preferably, in above-mentioned preparation
In method, the vacuum drying temperature is 50~100 DEG C, preferably 60~80 DEG C；Drying time is 5~10 hours, preferably
It is 6~8 hours.
[specific embodiment]
It is as follows that embodiment is enumerated in invention, and illustrated embodiment is used only for helping to understand the present invention, is not intended to limit this hair
Bright range.
Specific embodiment is set forth below to be explained in detail.
Embodiment 1:
122g antierythrite and 300g anhydrous acetonitrile is added into 2000mL there-necked flask at room temperature, 0.5h is stirred at room temperature, this
When erythrol dissolve on a small quantity, solution is suspension.The boron trifluoride tetrahydrofuran solution that 615g mass fraction is 45.5% is passed through
Dropping funel is slowly added dropwise in there-necked flask, and with the dropwise addition of boron trifluoride ether solution, erythrol gradually dissolves, to borontrifluoride
Boron tetrahydrofuran solution is added dropwise to complete that rear solution is colorless and transparent, and reaction temperature is risen to 60 DEG C at this time, and the reaction was continued completely
Light yellow transparent solution is obtained after 12h, the hydrogen fluoride gas for reacting generation is absorbed by external sodium hydrate aqueous solution.
Faint yellow solid is obtained after light yellow transparent solution air-distillation obtained above is removed acetonitrile, this is faint yellow
Solid is placed in 80 DEG C of vacuum ovens after being washed twice using methylene chloride and is dried in vacuo 6h, and white powdery solids are obtained
151g, yield 88%.
The white powder for continuing to obtain, which is added in another single port bottle for filling 200mL ethyl acetate, to be dissolved,
Then be gradually added into 44g lithium fluoride into reaction flask, reaction temperature be increased to 80 DEG C, with the progress of reaction, lithium fluoride by
It gradually dissolves, stops reaction after the reaction was continued until completely dissolved 12h.After ethyl acetate being removed using vacuum distillation obtain white
Powder solid is placed in 80 DEG C of vacuum oven after being recrystallized using methylene chloride and 6h is dried, finally obtained
The double borate difluoro lithium borate 176g of tetrahydroxylic alcohol, yield 90%.
Embodiment 2:
122g antierythrite and 300g tetrahydrofuran is added into 2000mL there-necked flask at room temperature, 0.5h is stirred at room temperature, this
When erythrol dissolve on a small quantity, solution is suspension.The boron trifluoride tetrahydrofuran solution that 615g mass fraction is 45.5% is passed through
Dropping funel is slowly added dropwise in there-necked flask, and with the dropwise addition of boron trifluoride ether solution, erythrol gradually dissolves, to borontrifluoride
Boron tetrahydrofuran solution is added dropwise to complete that rear solution is colorless and transparent, and reaction temperature is risen to 60 DEG C at this time, and the reaction was continued completely
Light yellow transparent solution is obtained after 12h, the hydrogen fluoride gas for reacting generation is absorbed by external sodium hydrate aqueous solution.
Faint yellow solid is obtained after light yellow transparent solution air-distillation obtained above is removed tetrahydrofuran, this is light
Yellow solid is placed in 80 DEG C of vacuum ovens after being washed twice using methylene chloride and is dried in vacuo 6h, and white powder is obtained
Solid 151g, yield 88%.
The white powder for continuing to obtain, which is added in another single port bottle for filling 200mL ethyl acetate, to be dissolved,
Then be gradually added into 72g sodium fluoride into reaction flask, reaction temperature be increased to 70 DEG C, with the progress of reaction, sodium fluoride by
It gradually dissolves, stops reaction after the reaction was continued until completely dissolved 12h.After ethyl acetate being removed using vacuum distillation obtain white
Powder solid is placed in 80 DEG C of vacuum oven after being recrystallized using ether and 6h is dried, finally obtains quaternary
The double borate difluoro Boratex 178g of alcohol, yield 80%.
Embodiment 3:
136g pentaerythrite and 400g anhydrous acetonitrile is added into 2000mL there-necked flask at room temperature, 0.5h is stirred at room temperature, this
When pentaerythrite it is insoluble.The boron trifluoride tetrahydrofuran solution that 645g mass fraction is 45.5% is slowly dripped through dropping funel
It is added in there-necked flask, with the dropwise addition of boron trifluoride ether solution, pentaerythrite gradually dissolves, molten to boron trifluoride tetrahydrofuran
It is colorless and transparent that liquid is added dropwise to complete rear solution completely, reaction temperature is risen to 80 DEG C the reaction was continued after 15h at this time obtain it is yellowish
Color clear solution, the hydrogen fluoride gas for reacting generation are absorbed by external sodium hydrate aqueous solution.
Faint yellow solid is obtained after light yellow transparent solution air-distillation obtained above is removed acetonitrile, this is faint yellow
Solid is placed in 80 DEG C of vacuum ovens after being washed twice using methylene chloride and is dried in vacuo 8h, and white powdery solids are obtained
153g, yield 80%.
The white powder for continuing to obtain, which is added in another single port bottle for filling 200mL ethyl acetate, to be dissolved,
Then be gradually added into 42g lithium fluoride into reaction flask, reaction temperature be increased to 80 DEG C, with the progress of reaction, lithium fluoride by
It gradually dissolves, stops reaction until completely dissolved.White powder solid is obtained after removing ethyl acetate using vacuum distillation, is used
Methylene chloride is placed in 80 DEG C of vacuum oven after being recrystallized and 6h is dried, and finally obtains the double boric acid of pentaerythrite
Ester difluoro lithium borate 165g, yield 85%.
Embodiment 4:
136g pentaerythrite and 400g anhydrous acetonitrile is added into 2000mL there-necked flask at room temperature, 0.5h is stirred at room temperature, this
When pentaerythrite it is insoluble.The boron trifluoride tetrahydrofuran solution that 645g mass fraction is 45.5% is slowly dripped through dropping funel
It is added in there-necked flask, with the dropwise addition of boron trifluoride ether solution, pentaerythrite gradually dissolves, molten to boron trifluoride tetrahydrofuran
It is colorless and transparent that liquid is added dropwise to complete rear solution completely, reaction temperature is risen to 80 DEG C the reaction was continued after 15h at this time obtain it is yellowish
Color clear solution, the hydrogen fluoride gas for reacting generation are absorbed by external sodium hydrate aqueous solution.
Faint yellow solid is obtained after light yellow transparent solution air-distillation obtained above is removed acetonitrile, this is faint yellow
Solid is placed in 80 DEG C of vacuum ovens after being washed twice using methylene chloride and is dried in vacuo 8h, and white powdery solids are obtained
153g, yield 80%.
The white powder for continuing to obtain, which is added in another single port bottle for filling 200mL ethyl acetate, to be dissolved,
Then be gradually added into 42g sodium fluoride into reaction flask, reaction temperature be increased to 80 DEG C, with the progress of reaction, lithium fluoride by
It gradually dissolves, stops reaction until completely dissolved.White powder solid is obtained after removing ethyl acetate using vacuum distillation, is used
Methylene chloride is placed in 80 DEG C of vacuum oven after being recrystallized and 8h is dried, and finally obtains the double boric acid of pentaerythrite
Ester difluoro Boratex 165g, yield 75%.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the present invention in any form；It is all
The those of ordinary skill of the industry can implement the present invention by the above and swimmingly；But all technologies for being familiar with this profession
Personnel without departing from the scope of the present invention, a little change for being made using disclosed above technology contents,
Modification and the equivalent variations developed, are equivalent embodiment of the invention；Meanwhile all substantial technologicals according to the present invention are to above
The variation, modification and evolution etc. of any equivalent variations made by embodiment still fall within the protection model of technical solution of the present invention
Within enclosing.
Claims (10)
1. a kind of preparation method of the double borate difluoroborates of polyalcohol, which is characterized in that its preparation process includes following step
It is rapid:
Polyalcohol and fluorination reagent are added in the reaction kettle A for filling nonaqueous solvents, control is in certain temperature and carries out reaction system
The double borate boron difluoride crude products of polyalcohol are obtained, obtain white crystal after concentrated wash crystallization, by the double boron of obtained polyalcohol
Acid esters boron difluoride intermediate continue to put into the reaction kettle B for filling nonaqueous solvents and be added fluoride salt reacted to obtain it is more
The double borate difluoroborate crude products of first alcohol；Crude product is filtered and is recrystallized and obtains the double boric acid of polyalcohol after being dried in vacuo
Ester difluoroborate fine work.
It reacts shown in the double borate difluoroborate structural formula as I of polyalcohol obtained:
2. the preparation method of the double borate difluoroborates of polyalcohol according to claim 1, which is characterized in that described more
First alcohol is one of antierythrite, pentaerythrite, inositol, xylitol, sorbierite or a variety of.
3. the preparation method of the double borate difluoroborates of polyalcohol according to claim 1, which is characterized in that described non-
Aqueous organic solvent is acetonitrile, tetrahydrofuran, methylene chloride, ethyl acetate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate
One of or a variety of mixed solvents.
4. the preparation method of the double borate difluoroborates of polyalcohol according to claim 1, which is characterized in that fluorine used
Change reagent general formula is LBF3, wherein L is one of ether or tetrahydrofuran or more than one mixture.
5. the preparation method of the double borate difluoroborates of polyalcohol according to claim 1, which is characterized in that the fluorine
The molar ratio for changing reagent and polyalcohol is 1.9:1~2.5:1.
6. the preparation method of the double borate difluoroborates of polyalcohol according to claim 1, which is characterized in that the fluorine
Salt dissolving is one of lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride or a variety of.
7. the preparation method of the double borate difluoroborates of polyalcohol according to claim 1, which is characterized in that the fluorine
Salt dissolving and the molar ratio of polyalcohol borate boron difluoride are 0.9:1~1.5:1.
8. the preparation method of the double borate difluoroborates of polyalcohol according to claim 1, which is characterized in that described
Reaction temperature is 50~100 DEG C, and the reaction time is 10~18 hours.
9. poor solvent according to claim 1 be ether, methylene chloride, dichloroethanes, chloroform, n-hexane, hexamethylene,
One of benzene or a variety of mixing.
10. the preparation method of the double borate difluoroborates of polyalcohol according to claim 1, which is characterized in that described
Vacuum drying temperature be 50~100 DEG C；Drying time is 5~10 hours.
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| CN115763981A (en) * | 2022-12-28 | 2023-03-07 | 蜂巢能源科技(马鞍山)有限公司 | Electrolyte for lithium ion battery and application |
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| US20020107419A1 (en) * | 1997-03-10 | 2002-08-08 | Nippon Shokubai Co., Ltd. | Purifying process of tetrakis (fluoroaryl) borate.magnesium halide, tetrakis (fluoroaryl) borate.ether complex and producing process of the same, and producing process of tetrakis (fluoroaryl) borate derivative |
| CN104387411A (en) * | 2014-11-07 | 2015-03-04 | 周阳 | Series one-pot synthesis method of lithium oxalyldifluroborate |
| CN109627256A (en) * | 2018-11-02 | 2019-04-16 | 珠海市赛纬电子材料股份有限公司 | A kind of preparation method of the double borate boron difluorides of pentaerythrite |
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| US20020107419A1 (en) * | 1997-03-10 | 2002-08-08 | Nippon Shokubai Co., Ltd. | Purifying process of tetrakis (fluoroaryl) borate.magnesium halide, tetrakis (fluoroaryl) borate.ether complex and producing process of the same, and producing process of tetrakis (fluoroaryl) borate derivative |
| CN104387411A (en) * | 2014-11-07 | 2015-03-04 | 周阳 | Series one-pot synthesis method of lithium oxalyldifluroborate |
| CN109627256A (en) * | 2018-11-02 | 2019-04-16 | 珠海市赛纬电子材料股份有限公司 | A kind of preparation method of the double borate boron difluorides of pentaerythrite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115763981A (en) * | 2022-12-28 | 2023-03-07 | 蜂巢能源科技(马鞍山)有限公司 | Electrolyte for lithium ion battery and application |
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