CN109053786A - A kind of preparation method of di-oxalate lithium borate - Google Patents
A kind of preparation method of di-oxalate lithium borate Download PDFInfo
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- CN109053786A CN109053786A CN201811089625.4A CN201811089625A CN109053786A CN 109053786 A CN109053786 A CN 109053786A CN 201811089625 A CN201811089625 A CN 201811089625A CN 109053786 A CN109053786 A CN 109053786A
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- oxalate
- lithium borate
- lithium
- preparation
- oxalate lithium
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- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 54
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 11
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004327 boric acid Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- WVQUCYVTZWVNLV-UHFFFAOYSA-N boric acid;oxalic acid Chemical compound OB(O)O.OC(=O)C(O)=O WVQUCYVTZWVNLV-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 150000002641 lithium Chemical class 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000005217 methyl ethers Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- XJGIGXYFHBOWDQ-UHFFFAOYSA-N B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+].[F] Chemical class B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+].[F] XJGIGXYFHBOWDQ-UHFFFAOYSA-N 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910013188 LiBOB Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000004255 ion exchange chromatography Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- RKLWISLCSWAWJI-UHFFFAOYSA-L dilithium;difluoride Chemical compound [Li+].[Li+].[F-].[F-] RKLWISLCSWAWJI-UHFFFAOYSA-L 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000003869 coulometry Methods 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- -1 boron trifluoride Tetrafluoro boric acid Chemical compound 0.000 description 1
- WYWLPUYJUPVXSK-UHFFFAOYSA-N boron;oxalic acid Chemical compound [B].OC(=O)C(O)=O WYWLPUYJUPVXSK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction 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 di-oxalate lithium borate, generate tetrafluoro boric acid this method comprises: boron trifluoride is dissolved in anhydrous hydrofluoric acid；Lithium oxalate is added, the di-oxalate lithium borate product containing lithium fluoride is obtained by filtration in heating removal hydrofluoric acid；It is added to the biggish solvent of di-oxalate lithium borate solubility, the solution for containing only di-oxalate lithium borate is obtained by filtration, evaporate solution and be dried to obtain di-oxalate lithium borate.The method of the present invention technological operation is simple, is easily purified, low cost, low energy consumption, is suitble to large-scale industrial production.
Description
Technical field
The present invention relates to lithium ion battery material manufacturing technology field, more particularly to a kind of di-oxalate lithium borate
Preparation method.
Background technique
Operating voltage is high, energy density is big, self-discharge rate is low, memory-less effect, cycle life because having for lithium ion battery
Long, spry and light the advantages that facilitating, is widely applied as portable power.Electrolyte is the basis of lithium-ion battery electrolytes
One of raw material directly affects the working performance of lithium ion battery.Lithium salts used in lithium ion battery is generally LiPF at this stage6。
But LiPF6Extremely sensitive to moisture, micro-moisture can react with it, while LiPF6Thermal stability it is poor, at high temperature, meeting
It decomposes and generates HF, corroding electrode material and collector.Therefore it develops chemical stability and thermal stability is good, there is good high temperature
The new lithium salts of performance become current research hotspot.
Di-oxalate lithium borate LiBOB has good chemical stability and thermostabilization as a kind of novel electrolytes lithium salts
Property, thermal decomposition temperature is higher, up to 300 DEG C, enhances the safety of battery；Without containing F element, will not generate HF causes to corrode
Electrode material and collector reduce the cost of battery to improve the cycle life of battery；It can be in Carbon anode surface shape
At more stable SEI film, it can be used in pure PC solvent, widen battery use temperature range；Synthesis material is cheap and easy to get,
Preparation process is simple, environmentally friendly；And conductivity with higher and wider electrochemical window, cause numerous concerns.
Currently, being mainly the following to the research of the preparation method of di-oxalate lithium borate.
Solid phase-gas phase contact method is at high temperature, to be synthesized using basic lithium salts as raw material, this method is to equipment requirement
Higher, process control requirements are stringent, and synthesis difficulty is big, and reaction efficiency is low, it is difficult to accomplish scale production.
German patent DE 19829030 proposes the compound such as LiOH or Li for containing lithium with raw material2CO3, oxalic acid or oxalic acid
The method that the oxide of salt, boric acid or boron prepares LiBOB.Using this, preparation method is simple, and raw material is cheap and easy to get.But by
In entire reaction process all along with the presence of a large amount of water, and water negatively affects the LiBOB for being used as lithium ion battery electrolyte
It is huge, therefore how to guarantee that product is anhydrous as the key for preparing LiBOB with this method.In addition, this method is made
It is easily lower containing the complete raw material of unreacteds, product purities such as oxalic acid in LiBOB product.
United States Patent (USP) US0034235A1 uses Li [B (OCH3)4] and (CH3)3SiOOCCSi(CH3) anti-in acetonitrile solvent
LiBOB should be prepared.Water will not be generated using the preparation method during the reaction, and products obtained therefrom purity is higher.The disadvantage is that closing
It is difficult to obtain at route raw material, higher cost, is not suitable for industrialized production.
Chinese patent CN200510011555.7 uses Solid phase synthesis LiBOB, but there are energy consumption height, synthesis effects for this method
Rate is low, the drawback of industrialized production difficulty.
Therefore, in conjunction with the above problem, a kind of preparation method of di-oxalate lithium borate is provided, is that those skilled in the art need
It solves the problems, such as.
Summary of the invention
In view of this, method process operation is simple the present invention provides a kind of preparation method of di-oxalate lithium borate, easily mention
Pure, inexpensive, low energy consumption is suitble to large-scale industrial production.
The object of the present invention is to provide a kind of preparation method of di-oxalate lithium borate, specific method is to dissolve boron trifluoride
Tetrafluoro boric acid is generated in anhydrous hydrofluoric acid；Lithium oxalate is added, double grass containing lithium fluoride are obtained by filtration in heating removal hydrofluoric acid
Sour lithium borate product；Wherein synthesis equation is as follows:
HBF4+2Li2C2O4→LiB(C2O4)2+3LiF+HF
It adds to the biggish solvent of di-oxalate lithium borate solubility, is obtained by filtration and contains only the molten of di-oxalate lithium borate
Liquid, dry solution obtain di-oxalate lithium borate.
To achieve the goals above, The technical solution adopted by the invention is as follows:
Anhydrous hydrofluoric acid is added in reaction kettle, is passed through boron trifluoride, is sufficiently stirred under confined conditions by S1, boron trifluoride
It is dissolved in anhydrous hydrofluoric acid and generates tetrafluoro boric acid, pressure control is in 0.01MPa hereinafter, stirring 4-6h；
S2 is slowly added to lithium oxalate into reaction kettle and is stirred continuously, and low-temperature cooling media is passed through in collet, and control is anti-
Answering temperature in the kettle is 0 DEG C, and charging finishes, and is sufficiently reacted, and stirring a period of time is continued；
S3, the product that S2 is obtained heat, and remove hydrofluoric acid, and filtering obtains double oxalic acid boric acid containing lithium fluoride
Lithium product；
S4 is added to the biggish solvent of di-oxalate lithium borate solubility, filters off fluorinated lithium, obtains containing only double oxalic acid
The solution of lithium borate evaporates solution and drying, obtains di-oxalate lithium borate.
Preferably, raw material, HF solvent and reaction unit used in the step S1~S4 are by removing water process.
By using above-mentioned preferred embodiment, the beneficial effects of the present invention are: the water in reaction system can be with double oxalic acid boron
Sour lithium combines, and generates hydrate, influences product purity, therefore, in order to ensure that high product purity, the present invention is carried out except water process.
Preferably, the mass ratio of boron trifluoride and anhydrous hydrofluoric acid is 1~2:10 in the step S1.
Preferably, the mass ratio of boron trifluoride and anhydrous hydrofluoric acid is 3:25 in the step S1.
Preferably, it is -10~10 DEG C that reaction temperature is controlled in the step S1.
By using above-mentioned preferred embodiment, the beneficial effects of the present invention are: control reaction temperature, can in OK range
Boron trifluoride is generated to prevent tetrafluoro boric acid from decomposing.
Preferably, the molar ratio of boron trifluoride and lithium oxalate is 1:2~2.1 in the step S2.
Preferably, the molar ratio of boron trifluoride and lithium oxalate is 1:2.05 in the step S2.
Preferably, after sufficiently reacting 2~4h in the step S2, continue 4~6h of stirring.
Preferably, heating removal hydrofluoric acid, the hydrofluoric acid steamed will be recycled by condensing mode in the step S3,
Condensation temperature is set as -50~-10 DEG C, preferably -25 DEG C, and the hydrofluoric acid of recycling is reused.
Preferably, the filter type of products obtained therefrom is carried out using filters pressing mode after evaporative crystallization in the step S3.
Preferably, filter pressure by absolute pressure is calculated as 0.5~2 atmospheric pressure in the step S3.
By using above-mentioned preferred embodiment, the beneficial effects of the present invention are: select suitable filter type and filtration pressure
Power, it can be ensured that most of hydrofluoric acid is conducive to the reuse of subsequent recovery hydrofluoric acid by filtering discharge.
It preferably, include but is not limited to tetrahydro furan to the biggish solvent of di-oxalate lithium borate solubility in the step S4
It mutters, the double methyl ethers of the double alcohol of acetonitrile, dimethyl ether and second.
Preferably, the lithium fluoride that removal is filtered in the step S4 can be used as the use of LITHIUM BATTERY product.
Preferably, the step S4 is in a kettle dried product using hot inert gas.
Preferably, the drying process of the step S4 carries out in drying atmosphere of the water content less than 10ppm.
Preferably, it is dried in the step S4 method particularly includes: cold inert gas is warming up to 40~60 DEG C, is held
Continue after being passed through hot inert gas 3h, inert gas is warming up to 100~150 DEG C, continues dry 4~8h.
Preferably, inert gas includes but is not limited to one or more of nitrogen, argon gas, helium in the step S4.
Preferably, the reaction kettle be band solid feeding device, collet, thermometer, pressure gauge, blow vent, pressure relief opening and
The capacity of filter device is the stainless steel cauldron of 316L.
As can be seen from the above technical solutions, compared with prior art, beneficial effects of the present invention are as follows:
1, the sufficient raw selected, it is cheap.
2, process flow is easy to operate, without complicated experimental facilities.
3, the productivity of product improves, and is suitble to large-scale industrial production.
3, purification of products be easy, low energy consumption, it is environmental-friendly.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1:
The embodiment of the invention discloses a kind of preparation methods of di-oxalate lithium borate, the technical solution adopted is as follows:
Band solid feeding device, collet, thermometer, pressure gauge, blow vent, pressure release is added in 150g anhydrous hydrofluoric acid by S1
The capacity of mouth and filter device is to be passed through 18g boron trifluoride in the stainless steel cauldron of 316L, and control reaction temperature is -10 DEG C,
In 0.01MPa hereinafter, 4h is sufficiently stirred under confined conditions, boron trifluoride, which is dissolved in anhydrous hydrofluoric acid, generates tetrafluoro for pressure control
Boric acid；
S2 is slowly added to 55.45g lithium oxalate into reaction kettle and is stirred continuously, low-temperature cooling media is passed through in collet,
Controlling reactor temperature is 0 DEG C, and charging finishes, and after sufficiently reacting 2h, continues to stir 4h；
S3, the product that S2 is obtained heat, and remove hydrofluoric acid, and filtering obtains double oxalic acid boric acid containing lithium fluoride
Lithium product；
S4 is added dimethyl ether, filters off fluorinated lithium, obtains the solution for containing only di-oxalate lithium borate, evaporates solution, and
Product is dried using hot nitrogen, first by cold nitrogen temperature to 40 DEG C, after being continually fed into hot nitrogen 3h, extremely by nitrogen temperature
100 DEG C, continues dry 4h, obtain di-oxalate lithium borate 48.72g, purity 99.97%, water content 20ppm.
Table one
| Project | Index | Analysis method |
| Product purity | 99.97% | NMR, Atomic absorption |
| Moisture | 20ppm | Fischer coulometry |
| Ca2+ | 0.5ppm | Ion chromatography |
| Fe3+ | 5.2ppm | Ion chromatography |
Embodiment 2:
The embodiment of the invention discloses a kind of preparation methods of di-oxalate lithium borate, the technical solution adopted is as follows:
Band solid feeding device, collet, thermometer, pressure gauge, blow vent, pressure release is added in 180g anhydrous hydrofluoric acid by S1
The capacity of mouth and filter device is to be passed through 18g boron trifluoride in the stainless steel cauldron of 316L, and control reaction temperature is 0 DEG C, is pressed
In 0.01MPa hereinafter, 5h is sufficiently stirred under confined conditions, boron trifluoride is dissolved in generation tetrafluoro boron in anhydrous hydrofluoric acid for power control
Acid；
S2 is slowly added to 55.46g lithium oxalate into reaction kettle and is stirred continuously, low-temperature cooling media is passed through in collet,
Controlling reactor temperature is 0 DEG C, and charging finishes, and after sufficiently reacting 3h, continues to stir 5h；
S3, the product that S2 is obtained heat, and remove hydrofluoric acid, and filtering obtains double oxalic acid boric acid containing lithium fluoride
Lithium product；
S4 is added dimethyl ether, filters off fluorinated lithium, obtains the solution for containing only di-oxalate lithium borate, evaporates solution, and
Product is dried using hot argon gas, cold argon gas is first warming up to 50 DEG C, after being continually fed into hot argon gas 3h, argon gas is warming up to
125 DEG C, continues dry 6h, obtain di-oxalate lithium borate 49.02g, purity 99.99%, water content 16ppm.
Table two
| Project | Index | Analysis method |
| Product purity | 99.99% | NMR, Atomic absorption |
| Moisture | 16ppm | Fischer coulometry |
| Ca2+ | 0.3ppm | Ion chromatography |
| Fe3+ | 4.8ppm | Ion chromatography |
Embodiment 3:
The embodiment of the invention discloses a kind of preparation methods of di-oxalate lithium borate, the technical solution adopted is as follows:
Band solid feeding device, collet, thermometer, pressure gauge, blow vent, pressure relief opening is added in 90g anhydrous hydrofluoric acid by S1
Capacity with filter device is to be passed through 18g boron trifluoride in the stainless steel cauldron of 316L, and control reaction temperature is 10 DEG C, pressure
In 0.01MPa hereinafter, 6h is sufficiently stirred under confined conditions, boron trifluoride is dissolved in generation tetrafluoro boron in anhydrous hydrofluoric acid for power control
Acid；
S2 is slowly added to 55.45g lithium oxalate into reaction kettle and is stirred continuously, low-temperature cooling media is passed through in collet,
Controlling reactor temperature is 0 DEG C, and charging finishes, and after sufficiently reacting 4h, continues to stir 6h；
S3, the product that S2 is obtained heat, and remove hydrofluoric acid, and filtering obtains double oxalic acid boric acid containing lithium fluoride
Lithium product；
S4 is added dimethyl ether, filters off fluorinated lithium, obtains the solution for containing only di-oxalate lithium borate, evaporates solution, and
Product is dried using hot helium, cold helium is first warming up to 60 DEG C, after being continually fed into hot helium 3h, helium is warming up to
150 DEG C, continues dry 8h, obtain di-oxalate lithium borate 49.07g, purity 99.98%, water content 12ppm.
Table three
| Project | Index | Analysis method |
| Product purity | 99.98% | NMR, Atomic absorption |
| Moisture | 12ppm | Fischer coulometry |
| Ca2+ | 0.3ppm | Ion chromatography |
| Fe3+ | 5.0ppm | Ion chromatography |
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of preparation method of di-oxalate lithium borate, which is characterized in that specific step is as follows:
Anhydrous hydrofluoric acid is added in reaction kettle, is passed through boron trifluoride, is sufficiently stirred under confined conditions by S1, boron trifluoride dissolution
Tetrafluoro boric acid is generated in anhydrous hydrofluoric acid, pressure control is in 0.01MPa hereinafter, stirring 4-6h；
S2 is slowly added to lithium oxalate into reaction kettle and is stirred continuously, and low-temperature cooling media is passed through in collet, controls reaction kettle
Interior temperature is 0 DEG C, and charging finishes, and is sufficiently reacted, and stirring a period of time is continued；
S3, the product that S2 is obtained heat, and remove hydrofluoric acid, and filtering obtains the di-oxalate lithium borate containing lithium fluoride and produces
Product；
S4 is added to the biggish solvent of di-oxalate lithium borate solubility, filters off fluorinated lithium, obtains containing only double oxalic acid boric acid
The solution of lithium evaporates solution and drying, obtains di-oxalate lithium borate.
2. a kind of preparation method of di-oxalate lithium borate according to claim 1, which is characterized in that three in the step S1
The mass ratio of boron fluoride and anhydrous hydrofluoric acid is 1~2:10.
3. a kind of preparation method of di-oxalate lithium borate according to claim 1, which is characterized in that controlled in the step S1
Reaction temperature processed is -10~10 DEG C.
4. a kind of preparation method of di-oxalate lithium borate according to claim 1, which is characterized in that three in the step S2
The molar ratio of boron fluoride and lithium oxalate is 1:2~2.1.
5. a kind of preparation method of di-oxalate lithium borate according to claim 1, which is characterized in that filled in the step S2
After dividing 2~4h of reaction, continue 4~6h of stirring.
6. a kind of preparation method of di-oxalate lithium borate according to claim 1, which is characterized in that right in the step S4
The biggish solvent of di-oxalate lithium borate solubility includes but is not limited to the double methyl ethers of the double alcohol of tetrahydrofuran, acetonitrile, dimethyl ether and second.
7. a kind of preparation method of di-oxalate lithium borate according to claim 1, which is characterized in that the step S4 is anti-
It answers in kettle and product is dried using hot inert gas.
8. drying process according to claim 7, which is characterized in that the drying process method particularly includes: will be cold lazy
Inert gas after being continually fed into hot inert gas 3h, is warming up to 100~150 DEG C, continues to do by property gas heating to 40~60 DEG C
Dry 4~8h.
9. drying process according to claim 7, which is characterized in that the inert gas includes but is not limited to nitrogen, argon
One or more of gas, helium.
10. a kind of preparation method of double fluorine Lithium bis (oxalate) borates according to claim 1, which is characterized in that the reaction kettle
It is the stainless of 316L for the capacity with solid feeding device, collet, thermometer, pressure gauge, blow vent, pressure relief opening and filter device
Steel reaction kettle.
Priority Applications (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964045A (en) * | 2019-12-16 | 2020-04-07 | 江苏华盛锂电材料股份有限公司 | Method for reducing acid value of lithium bis (oxalato) borate and lithium bis (oxalato) borate with low acid value |
| CN116040641A (en) * | 2023-01-17 | 2023-05-02 | 福建德尔科技股份有限公司 | Preparation method of lithium tetrafluoroborate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127218A (en) * | 1994-10-11 | 1996-07-24 | 埃尔夫阿托化学有限公司 | Production of aqueous solutions of fluoboric acid |
| CN1687081A (en) * | 2005-04-11 | 2005-10-26 | 北京科技大学 | Method for synthesizing dioxalate group lithium borate |
| CN101643481A (en) * | 2009-08-28 | 2010-02-10 | 张家港市国泰华荣化工新材料有限公司 | Synthesis technique for obtaining difluoro oxalate lithium borate and di-oxalate lithium borate |
| CN102766151A (en) * | 2011-05-05 | 2012-11-07 | 中国科学院福建物质结构研究所 | Method for purifying lithium bis(oxalate)borate |
| CN103951689A (en) * | 2014-05-16 | 2014-07-30 | 北京化学试剂研究所 | Preparation method of liquid lithium bisoxalate borate |
| CN104447827A (en) * | 2014-10-30 | 2015-03-25 | 重庆富地宝科技有限责任公司 | Purification method of lithium bis(oxalato)borate |
| WO2017218616A1 (en) * | 2016-06-17 | 2017-12-21 | 3M Innovative Properties Company | Electrolyte solutions and electrochemical cells containing same |
-
2018
- 2018-09-18 CN CN201811089625.4A patent/CN109053786B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127218A (en) * | 1994-10-11 | 1996-07-24 | 埃尔夫阿托化学有限公司 | Production of aqueous solutions of fluoboric acid |
| CN1687081A (en) * | 2005-04-11 | 2005-10-26 | 北京科技大学 | Method for synthesizing dioxalate group lithium borate |
| CN101643481A (en) * | 2009-08-28 | 2010-02-10 | 张家港市国泰华荣化工新材料有限公司 | Synthesis technique for obtaining difluoro oxalate lithium borate and di-oxalate lithium borate |
| CN102766151A (en) * | 2011-05-05 | 2012-11-07 | 中国科学院福建物质结构研究所 | Method for purifying lithium bis(oxalate)borate |
| CN103951689A (en) * | 2014-05-16 | 2014-07-30 | 北京化学试剂研究所 | Preparation method of liquid lithium bisoxalate borate |
| CN104447827A (en) * | 2014-10-30 | 2015-03-25 | 重庆富地宝科技有限责任公司 | Purification method of lithium bis(oxalato)borate |
| WO2017218616A1 (en) * | 2016-06-17 | 2017-12-21 | 3M Innovative Properties Company | Electrolyte solutions and electrochemical cells containing same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964045A (en) * | 2019-12-16 | 2020-04-07 | 江苏华盛锂电材料股份有限公司 | Method for reducing acid value of lithium bis (oxalato) borate and lithium bis (oxalato) borate with low acid value |
| CN116040641A (en) * | 2023-01-17 | 2023-05-02 | 福建德尔科技股份有限公司 | Preparation method of lithium tetrafluoroborate |
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