CN109438489A - A kind of preparation method of difluorine oxalic acid boracic acid lithium - Google Patents
A kind of preparation method of difluorine oxalic acid boracic acid lithium Download PDFInfo
- Publication number
- CN109438489A CN109438489A CN201811506049.9A CN201811506049A CN109438489A CN 109438489 A CN109438489 A CN 109438489A CN 201811506049 A CN201811506049 A CN 201811506049A CN 109438489 A CN109438489 A CN 109438489A
- Authority
- CN
- China
- Prior art keywords
- lithium
- oxalic acid
- added
- preparation
- difluorine oxalic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 131
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 51
- 235000006408 oxalic acid Nutrition 0.000 title claims abstract description 43
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title claims abstract description 28
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229960002645 boric acid Drugs 0.000 title claims abstract description 28
- 235000010338 boric acid Nutrition 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 8
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012043 crude product Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims description 16
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000005352 clarification Methods 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- RHFUXPCCELGMFC-UHFFFAOYSA-N n-(6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-4-yl)-n-phenylmethoxyacetamide Chemical compound OC1C(C)(C)OC2=CC=C(C#N)C=C2C1N(C(=O)C)OCC1=CC=CC=C1 RHFUXPCCELGMFC-UHFFFAOYSA-N 0.000 claims description 2
- XURZGOTTZHKXTQ-UHFFFAOYSA-N acetonitrile;lithium Chemical compound [Li].CC#N XURZGOTTZHKXTQ-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 238000001953 recrystallisation Methods 0.000 abstract description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 7
- 239000005049 silicon tetrachloride Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910013098 LiBF2 Inorganic materials 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 1
- XJGIGXYFHBOWDQ-UHFFFAOYSA-N B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+].[F] Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+].[F] XJGIGXYFHBOWDQ-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BYKSDPYYTJQZOA-UHFFFAOYSA-N difluoro oxalate Chemical compound FOC(=O)C(=O)OF BYKSDPYYTJQZOA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000001291 vacuum drying 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)
Abstract
The present invention relates to a kind of preparation methods of difluorine oxalic acid boracic acid lithium.Its technical solution be the following steps are included: 1. into reactor be added specified amount acetonitrile, slowly add LiBF4, after the completion of feeding intake, heat stirring and dissolving；2. quantitative oxalic acid is added into four lithium fluophosphate acetonitrile solutions, it is uniformly mixed；3. alchlor reaction promoter is added, thermotonus is controlled, aluminum fluoride is filtered out；4. decrease temperature crystalline after the reaction was completed, separation of solid and liquid obtains crude product difluorine oxalic acid boracic acid lithium；5. obtaining target product in DMC dissolving-recrystallization.Beneficial effect is: simple process provided by the invention, it is easily operated, raw material sources are reliable, yield reaches 85% or more, consumption of raw materials is reduced, production cost is effectively reduced, avoids the pollution to environment well, the risk of production is also reduced, lower cost can promote the sound development of downstream New Energy Industry.
Description
Technical field
The present invention relates to a kind of preparation of the electrolyte in new energy lithium battery material field, in particular to a kind of difluoro oxalate
The preparation method of lithium borate.
Background technique
Difluorine oxalic acid boracic acid lithium, novel lithium battery electrolyte lithium salt, chemical formula LiBF2(CO2)2.English name:
LiDFOB, CAS:409071-16-5.It can be used in lithium battery electrolytes making as film for additive or substitution lithium hexafluoro phosphate
Conductive salt uses, for can greatly promote the cycle life of battery in lithium battery electrolytes and improve the high and low temperature of battery
Energy.
Preparation method general at present:
1, the first step is using LiBF4, oxalic acid, organic solvent and auxiliary agent hydrogen fluoride gas as reaction raw materials, control reaction temperature
Degree, obtains the mixture containing difluorine oxalic acid boracic acid lithium after reaction；Aforementioned obtained mixture is removed into organic solvent, then is tied again
Difluorine oxalic acid boracic acid lithium is obtained after crystalline substance purification.Referring in particular to Chinese patent literature Publication No. 103113396B, patent name is
" preparation method of difluorine oxalic acid boracic acid lithium ", comprising the following steps: (one) with LiBF4, oxalic acid, organic solvent and auxiliary agent
Hydrogen fluoride gas is reaction raw materials, and control reaction temperature is 0~20 DEG C, and the mixing containing difluorine oxalic acid boracic acid lithium is obtained after reaction
Object；(2) mixture for obtaining step (1) removes organic solvent, then obtains difluorine oxalic acid boracic acid lithium after recrystallization purification；
The organic solvent is tetrahydrofuran, dimethyl carbonate, diethyl carbonate, propene carbonate, butylene, methyl ethyl carbonate
At least one of ester, acetonitrile, propionitrile, butyronitrile, acetone.
This method the problem is that: it is more difficult to control to prepare each material rate, and uses auxiliary agent hydrogen fluoride gas operation danger
Danger, target product remove hydrogen fluoride complexity and higher cost.
2, lithium oxalate and boron trifluoride ether are prepared by a certain percentage, referring to Chinese patent literature Publication No.
102070661B, patent name are " a kind of preparation method of high-purity lithium oxalyldifluoroborate ", are molten with carbonic ester, acetonitrile etc.
Agent, be added catalyst carries out isothermal reaction 1h~12h at 20 DEG C~100 DEG C, be then filtered to remove side reaction solid and not instead
The lithium oxalate answered obtains the solution containing LiODFB, using 30 DEG C~150 DEG C vacuum distillation slough solvent, -50 DEG C~10 DEG C it is low
Warm crystallization, obtained LiODFB crystallization obtain pure LiODFB solid in 40 DEG C~150 DEG C vacuum drying 1h~48h.
But this method the problem is that: more white precipitate can be generated after the completion of preparation, need to be mentioned through repeatedly dissolving
Pure to obtain difluorine oxalic acid boracic acid lithium, raw materials market supply is few, and at high cost and supply is difficult to ensure, is difficult to realize large-scale work
Industry metaplasia produces.
In addition, there are also use to prepare under the effect of auxiliary agent silicon tetrachloride with LiBF4 and anhydrous oxalic acid in the prior art
LiBF2 (C2O4), the problem is that: silicon tetrachloride strong corrosive is made using degree of danger height, and using silicon tetrachloride
For raw material, ocratation is produced, product degree of danger is high, cannot be only absorbed by the water, and processing cost is high.
Summary of the invention
The purpose of the present invention is to drawbacks described above of the existing technology, and providing one kind can be with the two of industrialized production
The preparation method of fluorine Lithium bis (oxalate) borate, low in raw material price, and also hazardous degree is lower.
A kind of preparation method for difluorine oxalic acid boracic acid lithium that the present invention mentions, technical solution be the following steps are included:
(1) acetonitrile solvent is added into reactor, no more than the 50% of reactor total measurement (volume), slowly adds LiBF4, feeds intake
After the completion, it is warming up to 40-45 DEG C, stirring and dissolving 4 hours, dissolves and finishes after solution clarification, acetonitrile solvent and LiBF4 matter
Amount compares 5:1；
(2) oxalic acid is added into four lithium fluophosphates and acetonitrile solution, the molar ratio with four lithium fluophosphates is 1.5 ~ 2.0: 1.5
~ 2.0, it is uniformly mixed；
(3) it is added 1 part of alchlor reaction promoter, temperature is controlled at 40 DEG C -45 DEG C, continues to be stirred to react 4 hours；
(4) it filters after the reaction was completed, solution is gone into crystallizer, carries out decrease temperature crystalline；Solution temperature is down to 5 DEG C, solid-liquid point
From obtaining crude product difluorine oxalic acid boracic acid lithium；
(5) it is dissolved in dimethyl carbonate solvent, is recrystallized to give target product.
Preferably, in step (3), alchlor reaction promoter is added, controls reaction temperature, after being stirred to react, filters out
The aluminum fluoride of generation.
Preferably, the reaction equation of four lithium fluophosphates and oxalic acid and alchlor are as follows:
3LiBF4+3H2C2O4+2AlCl3=3LiB(C2O4)F2+2AlF3 +6HCl 。
Preferably, quantitative oxalic acid, quantitative oxalic acid and four fluorophosphoric acid are added in step (2), in four lithium fluophosphate acetonitrile solutions
The preferable molar ratio of lithium is 1:0.95.
The beneficial effects of the present invention are: production method provided by the invention using alchlor be used as reaction promoter, with show
The silicon tetrachloride for having technology to use is compared: 1, AlCl3 is easy to get, cheap；2, use AlCl3 for raw material, the product of generation
AlF3 is insoluble to be can be easily separated with acetonitrile, and silicon tetrachloride is used to produce ocratation, product degree of danger as raw material
Height cannot be only absorbed by the water, and processing cost is high；3, compared with silicon tetrachloride, silicon tetrachloride strong corrosive uses degree of danger
It is high；
Simple process provided by the invention, easily operated, raw material sources are reliable, and yield reaches 85% or more, reduce raw material and disappear
Consumption, effectively reduces production cost, avoids the pollution to environment well, also reduces the risk of production, it is lower at
Originally it can promote the sound development of downstream New Energy Industry.
Detailed description of the invention
Attached drawing 1 is structural schematic diagram of the invention；
Attached drawing 2 is the F spectrogram of difluorine oxalic acid boracic acid lithium；
Attached drawing 3 is the B spectrogram of difluorine oxalic acid boracic acid lithium.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment 1, a kind of preparation method for difluorine oxalic acid boracic acid lithium that the present invention mentions, technical solution be include following
Step:
(1) acetonitrile solvent is added into reactor, no more than the 50% of reactor total measurement (volume), slowly adds LiBF4, feeds intake
After the completion, it is warming up to 40-45 DEG C, stirring and dissolving 4 hours, dissolves and finishes after solution clarification, acetonitrile solvent and LiBF4 matter
Amount compares 5:1；
(2) oxalic acid is added into four lithium fluophosphates and acetonitrile solution, the molar ratio with four lithium fluophosphates is 1:0.95, and stirring is mixed
It closes uniform；
(3) it is added 1 part of alchlor reaction promoter, temperature is controlled at 42 DEG C, continues to be stirred to react 4 hours；
(4) solution is gone to crystallizer, carries out decrease temperature crystalline by the aluminum fluoride for filtering out generation after the reaction was completed；By solution temperature
5 DEG C are down to, separation of solid and liquid obtains crude product difluorine oxalic acid boracic acid lithium；
(5) it is dissolved in dimethyl carbonate solvent, is recrystallized to give target product.
Wherein, the reaction equation of four lithium fluophosphates and oxalic acid and alchlor are as follows:
3LiBF4+3H2C2O4+2AlCl3=3LiB(C2O4)F2+2AlF3 +6HCl 。
Referring to attached drawing 2, which is the F spectrum of the nuclear magnetic resonance chemical analyser of difluorine oxalic acid boracic acid lithium LIDFOB,
Wherein the place X=- 63 is standard specimen peak, and integral area is set as 300.The place X=- 153.9 is LIDFOB.
Judged by F spectrum without other substances containing F (the chemical shift details of other substances containing F are shown in annex 2)
Referring to attached drawing 3, which is the B spectrum of the nuclear magnetic resonance chemical analyser of difluorine oxalic acid boracic acid lithium LIDFOB,
It is wherein LIDFOB at X=2, integral area is set as 100.It is LIBOB at X=6.5.LIBOB if it exists, should be at X=
- 2.42 places.
By B spectrum judgement with the presence of impurity LIBOB, and exist without LIBF4.
As a result it calculates
It is calculated by analyzing result, obtains following result:
Embodiment 2, a kind of preparation method for difluorine oxalic acid boracic acid lithium that the present invention mentions, technical solution be include following step
It is rapid:
(1) acetonitrile solvent is added into reactor, no more than the 50% of reactor total measurement (volume), slowly adds LiBF4, feeds intake
After the completion, it is warming up to 40-45 DEG C, stirring and dissolving 4 hours, dissolves and finishes after solution clarification, acetonitrile solvent and LiBF4 matter
Amount compares 5:1；
(2) oxalic acid is added into four lithium fluophosphates and acetonitrile solution, the molar ratio with four lithium fluophosphates is 1.5:2.0, stirring
It is uniformly mixed；
(3) it is added 1 part of alchlor reaction promoter, temperature is controlled at 40 DEG C, continues to be stirred to react 4 hours；
(4) solution is gone to crystallizer, carries out decrease temperature crystalline by the aluminum fluoride for filtering out generation after the reaction was completed；By solution temperature
5 DEG C are down to, separation of solid and liquid obtains crude product difluorine oxalic acid boracic acid lithium；
(5) it is dissolved in dimethyl carbonate solvent, is recrystallized to give target product.
It is detected by result,
Embodiment 3, a kind of preparation method for difluorine oxalic acid boracic acid lithium that the present invention mentions, technical solution be include following step
It is rapid:
(1) acetonitrile solvent is added into reactor, no more than the 50% of reactor total measurement (volume), slowly adds LiBF4, feeds intake
After the completion, it is warming up to 40-45 DEG C, stirring and dissolving 4 hours, dissolves and finishes after solution clarification, acetonitrile solvent and LiBF4 matter
Amount compares 5:1；
(2) oxalic acid is added into four lithium fluophosphates and acetonitrile solution, the molar ratio with four lithium fluophosphates is 2:1.5, and stirring is mixed
It closes uniform；
(3) it is added 1 part of alchlor reaction promoter, temperature is controlled at 45 DEG C, continues to be stirred to react 4 hours；
(4) solution is gone to crystallizer, carries out decrease temperature crystalline by the aluminum fluoride for filtering out generation after the reaction was completed；By solution temperature
5 DEG C are down to, separation of solid and liquid obtains crude product difluorine oxalic acid boracic acid lithium；
(5) it is dissolved in dimethyl carbonate solvent, is recrystallized to give target product.
It is detected by result,
The above is only part preferred embodiment of the invention, and anyone skilled in the art is possibly also with upper
Equivalent technical solution is modified or be revised as to the technical solution for stating elaboration.Therefore, technical solution according to the present invention
Any simple modification carried out or substitute equivalents, belong to the greatest extent the scope of protection of present invention.
Claims (4)
1. a kind of preparation method of difluorine oxalic acid boracic acid lithium, it is characterized in that the following steps are included:
(1) acetonitrile solvent is added into reactor, no more than the 50% of reactor total measurement (volume), slowly adds LiBF4, feeds intake
After the completion, it is warming up to 40-45 DEG C, stirring and dissolving 4 hours, dissolves and finishes after solution clarification, acetonitrile solvent and LiBF4 matter
Amount compares 5:1；
(2) oxalic acid is added into four lithium fluophosphates and acetonitrile solution, the molar ratio with four lithium fluophosphates is 1.5 ~ 2.0: 1.5
~ 2.0, it is uniformly mixed；
(3) it is added 1 part of alchlor reaction promoter, temperature is controlled at 40 DEG C -45 DEG C, continues to be stirred to react 4 hours；
(4) it filters after the reaction was completed, solution is gone into crystallizer, carries out decrease temperature crystalline；Solution temperature is down to 5 DEG C, solid-liquid point
From obtaining crude product difluorine oxalic acid boracic acid lithium；
(5) it is dissolved in dimethyl carbonate solvent, is recrystallized to give target product.
2. the preparation method of difluorine oxalic acid boracic acid lithium according to claim 1, it is characterized in that: trichlorine is added in step (3)
Change reactive aluminum auxiliary agent, controls reaction temperature, after being stirred to react, filter out the aluminum fluoride of generation.
3. the preparation method of difluorine oxalic acid boracic acid lithium according to claim 1, it is characterized in that: four lithium fluophosphates and oxalic acid and
The reaction equation of alchlor are as follows:
3LiBF4+3H2C2O4+2AlCl3=3LiB(C2O4)F2+2AlF3 +6HCl 。
4. the preparation method of difluorine oxalic acid boracic acid lithium according to claim 1, it is characterized in that: in step (2), four fluorophosphoric acid
Quantitative oxalic acid is added in lithium acetonitrile solution, quantitatively the molar ratio of oxalic acid and four lithium fluophosphates is 1:0.95.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811506049.9A CN109438489A (en) | 2018-12-10 | 2018-12-10 | A kind of preparation method of difluorine oxalic acid boracic acid lithium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811506049.9A CN109438489A (en) | 2018-12-10 | 2018-12-10 | A kind of preparation method of difluorine oxalic acid boracic acid lithium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109438489A true CN109438489A (en) | 2019-03-08 |
Family
ID=65557664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811506049.9A Pending CN109438489A (en) | 2018-12-10 | 2018-12-10 | A kind of preparation method of difluorine oxalic acid boracic acid lithium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109438489A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533763A (en) * | 2020-07-09 | 2020-08-14 | 山东海科创新研究院有限公司 | Preparation method and preparation device of lithium difluoroborate |
| CN114864888A (en) * | 2022-04-07 | 2022-08-05 | 湖南金硅科技有限公司 | Lithium difluorooxalato borate doped and coated SiO/C composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648963A (en) * | 2009-08-28 | 2010-02-17 | 张家港市国泰华荣化工新材料有限公司 | Synthesizing process for obtaining lithium difluoro-oxalato-borate and lithium tetrafluoroborate |
| CN102702243A (en) * | 2012-06-12 | 2012-10-03 | 中南大学 | Method for preparation and purifying lithium difluoroborate |
| CN103265569A (en) * | 2013-05-17 | 2013-08-28 | 太原理工大学 | Lithium difluoro(oxalato)borate synthesis method |
| CN105481887A (en) * | 2015-12-31 | 2016-04-13 | 苏州润禾化学材料有限公司 | Preparation method of lithium oxalyldifluroborate |
-
2018
- 2018-12-10 CN CN201811506049.9A patent/CN109438489A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648963A (en) * | 2009-08-28 | 2010-02-17 | 张家港市国泰华荣化工新材料有限公司 | Synthesizing process for obtaining lithium difluoro-oxalato-borate and lithium tetrafluoroborate |
| CN102702243A (en) * | 2012-06-12 | 2012-10-03 | 中南大学 | Method for preparation and purifying lithium difluoroborate |
| CN103265569A (en) * | 2013-05-17 | 2013-08-28 | 太原理工大学 | Lithium difluoro(oxalato)borate synthesis method |
| CN105481887A (en) * | 2015-12-31 | 2016-04-13 | 苏州润禾化学材料有限公司 | Preparation method of lithium oxalyldifluroborate |
Non-Patent Citations (2)
| Title |
|---|
| 王永勤等: ""二氟草酸硼酸锂的制备与性能研究"", 《无机盐工业》 * |
| 秘军林等: ""新型锂盐二氟草酸硼酸锂制备的实验性研究"", 《无机盐工业》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533763A (en) * | 2020-07-09 | 2020-08-14 | 山东海科创新研究院有限公司 | Preparation method and preparation device of lithium difluoroborate |
| CN114864888A (en) * | 2022-04-07 | 2022-08-05 | 湖南金硅科技有限公司 | Lithium difluorooxalato borate doped and coated SiO/C composite material and preparation method and application thereof |
| CN114864888B (en) * | 2022-04-07 | 2023-08-01 | 湖南金硅科技有限公司 | Lithium difluoro oxalate borate doped coated SiO/C composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5315971B2 (en) | Method for producing difluorobis (oxalato) lithium phosphate solution | |
| CN104495767A (en) | Preparation method of lithium bis(fluorosulfonyl)amide | |
| CA2874610A1 (en) | High-purity lithium hexafluorophosphate | |
| US10294418B2 (en) | Complex fluoride phosphor and method for producing same | |
| CA2874608A1 (en) | Preparation of high-purity lithium fluoride | |
| CN104387411A (en) | Series one-pot synthesis method of lithium oxalyldifluroborate | |
| CN114655939B (en) | Preparation method of lithium bis (fluorosulfonyl) imide | |
| CN103374023A (en) | Co-production method for lithium oxalyldifluoroborate and lithium tetrafluoroborate | |
| JP2013249261A (en) | Method for producing tetrafluoro(oxalato)phosphate solution | |
| US20130066115A1 (en) | Methods and systems for forming boronic acids and intermediates thereof | |
| CN109836444A (en) | A kind of preparation method of difluorine oxalic acid boracic acid lithium | |
| CN109438489A (en) | A kind of preparation method of difluorine oxalic acid boracic acid lithium | |
| CN106749361A (en) | A kind of high efficiency preparation method of high-purity difluorine oxalic acid boracic acid lithium | |
| CN105399761A (en) | Preparation method of lithium difluoro(oxalato)borate | |
| CN106976853A (en) | A kind of preparation method of difluorophosphate | |
| CN112919441A (en) | Method for coproducing lithium difluorophosphate and lithium difluorooxalate phosphate | |
| CN108912155A (en) | A kind of preparation method of difluoro oxalate borate | |
| CN109678898A (en) | A kind of preparation method of difluorine oxalic acid boracic acid lithium | |
| US20160130286A1 (en) | Method for producing salts having monofluoro-tricyanoborate anions | |
| CN112591727B (en) | Preparation method of lithium difluorophosphate | |
| CN106632437B (en) | The separation method of LiODFB and LiBF4 | |
| EP1400525B1 (en) | Process for preparing tetrakis (fluoroaryl) borate derivatives | |
| CN106674261B (en) | The method of purification of LiODFB | |
| CN102910638A (en) | Preparation method of anhydrous lithium metaborate | |
| CN115650201B (en) | Preparation method of lithium difluorophosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190308 |
|
| RJ01 | Rejection of invention patent application after publication |