CN111943969B - Preparation method of lithium difluoroborate - Google Patents
Preparation method of lithium difluoroborate Download PDFInfo
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- CN111943969B CN111943969B CN202010914074.1A CN202010914074A CN111943969B CN 111943969 B CN111943969 B CN 111943969B CN 202010914074 A CN202010914074 A CN 202010914074A CN 111943969 B CN111943969 B CN 111943969B
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- 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 System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of lithium difluoro (oxalato) borate, belonging to the technical field of preparation of lithium ion battery electrolyte. The preparation method comprises the following steps: 1) Mixing lithium tetrafluoroborate, lithium oxalate, an organic solvent and an auxiliary agent, and reacting the obtained mixed solution to obtain a reaction solution containing LiODFB; the auxiliary agent is niobium pentachloride, niobium pentafluoride or antimony pentafluoride; 2) Filtering the reaction solution containing LiODFB, and concentrating the filtrate to obtain a crude product of lithium difluoro-oxalato-borate; 3) And recrystallizing and drying the crude lithium difluoro oxalate borate to obtain the lithium difluoro oxalate borate. The preparation method provided by the invention has the advantages of high conversion rate, high product purity and yield, and no corrosive gas generated in the reaction process.
Description
Technical Field
The invention relates to the technical field of lithium ion battery electrolyte preparation, in particular to a preparation method of lithium difluoroborate.
Background
The lithium ion battery is a novel high-energy secondary battery, and has the excellent performances of small volume, light weight, high-rate discharge, high specific energy, no memory effect and the like. Lithium ion batteries are widely used in the fields of electronics, automobiles, household appliances and the like. The electrolyte is one of the main components of the lithium ion battery and is also one of the key materials influencing the performance of the lithium ion battery. The electrolyte of a commonly used lithium ion battery is mainly lithium hexafluorophosphate (LiPF 6), but lithium hexafluorophosphate is easy to absorb water and deliquesce, a decomposition product HF can corrode an electrode, lithium hexafluorophosphate must be used together with Ethylene Carbonate (EC) to form a stable solid electrolyte phase interface film, and the melting point of EC is low, so that the low-temperature use effect of the battery is poor.
The research on novel lithium salts is mainly focused on lithium borate complexes and lithium phosphate complexes, and lithium difluorooxalato borate (LiODFB) is the most attractive. The special chemical structure of the lithium bis (oxalato) borate and the lithium tetrafluoroborate combines the advantages of the lithium bis (oxalato) borate and the lithium tetrafluoroborate, and has good high and low temperature performance, rate capability and cycle performance. According to the difference of boron source selection, the current mainstream preparation method of LiODFB is classified as BF 3 Complex method and LiBF 4 The method is carried out. BF (BF) generator 3 The complexing method is BF 3 Complexes and Li 2 C 2 O 4 Taking diethyl ether or carbonate as a solvent as a raw material, heating and refluxing to obtain a crude product of LiODFB, and performing multiple crystallization to obtain a target product. The method has the advantages that the raw material is cheap, no catalyst is needed,the cost is relatively low, but the main raw material boron trifluoride is flammable, has strong irritation and corrosivity, has high requirements on equipment, has certain danger and has high requirements on the safety of the device; and the reaction can produce a by-product lithium tetrafluoroborate, the solubility of main and side products in a solvent is similar, the separation is difficult, and the yield and the purity of the product are reduced. LiBF 4 The method takes lithium tetrafluoroborate, oxalic acid and organic solvent as raw materials, and takes HF and AlCl 3 And reacting with metal halide as an auxiliary agent, and recrystallizing and purifying to prepare the lithium difluoro oxalate borate. However, when HF is used as a reaction auxiliary agent, the HF is corrosive gas, so that equipment is easily corroded, the requirement on the tightness of the equipment is high, unreacted HF easily pollutes the environment, and the use risk degree is high; and adopts AlCl 3 As a reaction auxiliary agent, HCl generated in the reaction process can cause corrosion to reaction equipment.
Disclosure of Invention
Aiming at the technical problems that the preparation of lithium difluoro (oxalato) borate in the background technology has high requirements on reaction equipment, main and side reaction products are not easy to separate, corrosive gas is generated in the reaction process, and the danger degree is high, the invention provides the preparation method of the lithium difluoro (oxalato) borate, the method has high reaction conversion rate, high product purity and yield, and the corrosive gas cannot be generated in the reaction process.
In order to solve the technical problem, the invention provides a preparation method of lithium difluoro (oxalato) borate, which comprises the following steps:
1) Mixing lithium tetrafluoroborate, lithium oxalate, an organic solvent and an auxiliary agent, and reacting the obtained mixed solution to obtain a reaction solution containing LiODFB;
the auxiliary agent is niobium pentachloride, niobium pentafluoride or antimony pentafluoride;
2) Filtering the reaction solution containing LiODFB in the step 1), and concentrating the filtrate to obtain a crude product of lithium difluoro oxalato borate;
3) Recrystallizing and drying the crude lithium difluoro (oxalato) borate product obtained in the step 2) to obtain the lithium difluoro (oxalato) borate.
Preferably, the reaction temperature in the step 1) is 5-45 ℃ and the reaction time is 4-24 h.
Preferably, the molar ratio of lithium tetrafluoroborate to lithium oxalate in the step 1) is 1:1.0 to 1.5; the molar ratio of the lithium tetrafluoroborate to the auxiliary agent is 1-1.5.
Preferably, the organic solvent comprises one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, acetonitrile, butyronitrile, acetone, diethyl ether, ethylene carbonate and propylene carbonate.
Preferably, the concentration mode in the step 2) is to perform reduced pressure distillation on the filtrate, cool the filtrate for crystallization when the solution is turbid, and filter the solution.
Preferably, the pressure during the reduced pressure distillation is 0.005 to 0.02MPa.
Preferably, the crystallization temperature of the temperature-reducing crystallization is-5 to 5 ℃, and the time is 3 to 5 hours.
Preferably, the step 3) is performed by recrystallization using dimethyl carbonate.
Preferably, the drying mode in the step 3) is vacuum drying, the temperature of the vacuum drying is 80-150 ℃, and the vacuum degree is 80-100 Kpa.
Preferably, the method further comprises the steps of recovering the filtrate obtained after the temperature reduction crystallization and the filtration and the solution obtained after the recrystallization in the step 3), and sequentially concentrating, recrystallizing and vacuum-drying the recovered solution to obtain the residual lithium difluoro-oxalato-borate.
Compared with the prior art, the invention achieves the following technical effects:
the lithium tetrafluoroborate and the lithium oxalate are used as main raw materials, and niobium pentachloride, niobium pentafluoride or antimony pentafluoride is selected as an auxiliary agent to prepare the lithium difluorooxalato borate, so that the reaction can be initiated, and the reaction process is accelerated; the reaction conversion rate is improved, and the additive amount is small, the cost is low, and the conversion rate is high. Meanwhile, the obtained main and side reaction products are easy to separate, so that the product purity is greatly improved;
further, the method recovers the solution obtained by recrystallizing the filtrate obtained after temperature reduction crystallization and filtration and the crude lithium difluoro oxalato borate, and sequentially performs concentration, recrystallization and vacuum drying on the recovered solution to obtain the residual lithium difluoro oxalato borate, so that the reaction yield is improved, and the recrystallized solution can be reused.
Detailed Description
The invention provides a preparation method of lithium difluoro (oxalato) borate, which comprises the following steps:
1) Mixing lithium tetrafluoroborate, lithium oxalate, an organic solvent and an auxiliary agent, and reacting the obtained mixed solution to obtain a reaction solution containing LiODFB;
the auxiliary agent is niobium pentachloride, niobium pentafluoride or antimony pentafluoride;
2) Filtering the reaction solution containing LiODFB in the step 1), and concentrating the filtrate to obtain a crude product of lithium difluoro oxalato borate;
3) Recrystallizing and drying the crude lithium difluoro oxalate borate in the step 2) to obtain the lithium difluoro oxalate borate.
The method mixes lithium tetrafluoroborate, lithium oxalate, organic solvent and auxiliary agent, and reacts the obtained mixed solution to obtain the reaction solution containing LiODFB. In the present invention, the molar ratio of the lithium tetrafluoroborate to the lithium oxalate is preferably 1:1.0 to 1.5, more preferably 1.1 to 1.2. In the present invention, the molar ratio of the lithium tetrafluoroborate to the auxiliary is preferably 1 to 1.5, more preferably 1.2 to 1.3. In the present invention, the organic solvent preferably includes one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, acetonitrile, butyronitrile, acetone, diethyl ether, ethylene carbonate, and propylene carbonate, more preferably acetonitrile. The amount of the organic solvent used in the present invention is not particularly limited. In the present invention, it is preferable to mix lithium tetrafluoroborate, lithium oxalate, an organic solvent and an auxiliary agent, and then stir the mixture. The stirring time is preferably 60min. In the present invention, the temperature of the reaction is preferably 5 to 45 ℃, more preferably 10 to 25 ℃; the reaction time is preferably 4 to 24 hours, more preferably 16 to 20 hours. In the invention, niobium pentachloride, niobium pentafluoride or antimony pentafluoride is used as an auxiliary agent to initiate reaction and accelerate the reaction process, and the auxiliary agent has strong acidity, small addition amount and little influence on equipment.
The sources of the lithium tetrafluoroborate, the lithium oxalate, the organic solvent and the auxiliary agent are not particularly limited, and the conventional commercial products in the field can be adopted.
After the reaction liquid containing the LiODFB is obtained, the reaction liquid containing the LiODFB is filtered, and the filtrate is concentrated to obtain a crude lithium difluoro-oxalato-borate product. In the present invention, the pore size of the filter mesh for filtration is preferably 20 to 80 μm, and more preferably 30 to 50 μm. In the present invention, the concentration method is preferably to distill the filtrate under reduced pressure, cool and crystallize when the solution is turbid, and filter. In the present invention, the pressure at the time of the reduced pressure distillation is preferably 0.005 to 0.02MPa, more preferably 0.01MPa. In the invention, the crystallization temperature of the cooling crystallization is preferably-5 ℃; the time for cooling crystallization is preferably 3-5 h.
After a crude lithium difluoro (oxalato) borate product is obtained, recrystallizing and drying the crude lithium difluoro (oxalato) borate product to obtain the lithium difluoro (oxalato) borate product. In the present invention, recrystallization is preferably carried out using dimethyl carbonate as an organic solvent. In the present invention, the drying is preferably performed by vacuum drying; the temperature of the vacuum drying is preferably 80-150 ℃, and more preferably 100-120 ℃; the degree of vacuum for the vacuum drying is preferably 80 to 100Kpa, more preferably 90Kpa.
In order to further improve the yield, the invention preferably further comprises the steps of recovering the filtrate obtained after the temperature reduction crystallization and filtration and the solution obtained after the recrystallization, and sequentially concentrating, recrystallizing and vacuum drying the recovered solution to obtain the residual lithium difluoro-oxalato-borate. In the invention, the concentration mode is preferably reduced pressure distillation, and when the solution is turbid, the temperature is reduced, the solution is crystallized and filtered. In the present invention, the pressure at the time of the reduced pressure distillation is preferably 0.005 to 0.02MPa, more preferably 0.01MPa. In the invention, the crystallization temperature of the cooling crystallization is preferably-5 ℃; the time for cooling crystallization is preferably 3-5 h. The conditions of recrystallization and drying in the invention are the same as those of recrystallization and drying of the crude lithium difluoro (oxalato) borate. In the present invention, it is preferable to recycle the recrystallized solution.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Adding 320g of acetonitrile solvent into a reaction container, adding 31.25g of lithium tetrafluoroborate and 40.76g of lithium oxalate under stirring, continuing stirring for 60min, and adjusting the temperature of the solution to 10 ℃;
(2) After the temperature is constant, 6.0g of niobium pentachloride is added into the solution, and the reaction is finished after 16 hours to obtain a reaction solution containing the lithium difluoro-oxalato-borate.
(3) Filtering the reaction liquid containing the lithium difluoro-oxalato-borate obtained in the step (2) to remove insoluble substances, distilling under reduced pressure of 0.005Mpa until the solution becomes turbid, cooling to-5 ℃, crystallizing for 3 hours, and filtering to obtain a crude product of the lithium difluoro-oxalato-borate; and dissolving the crude product by using dimethyl carbonate for recrystallization, and drying in vacuum at the temperature of 150 ℃ and the vacuum degree of 90Kpa to obtain the lithium difluoro-oxalato-borate.
(4) And (4) recovering and enriching the solution crystallized and filtered in the step (3) and the solution recrystallized, concentrating, recrystallizing and drying in vacuum, purifying the residual lithium difluoro (oxalato) borate in the solution, and calculating to obtain the product with the yield of 94.37% (yield = actual production of the target product/theoretical production of the target product: 100%) and the purity of 99.7% (the purity is detected by using a gas chromatograph). The recrystallized solution is recycled.
Example 2
(1) Adding 400g of acetonitrile solvent into a reaction container, adding 35g of lithium tetrafluoroborate and 38g of lithium oxalate under stirring, continuing stirring for 60min, and adjusting the temperature of the solution to 15 ℃;
(2) After the temperature is constant, 4.18g of niobium pentafluoride is added into the solution, and the continuous reaction is finished after 24 hours to obtain the reaction solution containing the lithium difluoro-oxalato-borate.
(3) Filtering the reaction liquid containing the lithium difluoro-oxalato-borate obtained in the step (2) to remove insoluble substances, distilling under reduced pressure of 0.02Mpa until the solution becomes turbid, cooling to 5 ℃, crystallizing for 5 hours, and filtering to obtain a crude product of the lithium difluoro-oxalato-borate; and dissolving the crude product by using dimethyl carbonate for recrystallization, and drying in vacuum at the temperature of 80 ℃ and the vacuum degree of 80Kpa to obtain the lithium difluoro oxalate borate.
(4) And (4) recovering and enriching the solution subjected to the decrystallization and filtration and the solution subjected to recrystallization in the step (3), and purifying residual lithium difluoro (oxalato) borate in the solution after concentration, crystallization, recrystallization and vacuum drying, wherein the calculated product yield is 93.28% (yield = actual production amount of target product/theoretical production amount of target product: 100%) and the purity is 99.5% (the purity is detected by using a gas chromatograph). The recrystallized solution is recycled.
Example 3
(1) Preparing a composite solvent from 200g of acetonitrile and 300g of dimethyl carbonate, adding the composite solvent into a reaction container, adding 35g of lithium tetrafluoroborate and 53.26g of lithium oxalate under stirring, continuing stirring for 60min after the addition is finished, and adjusting the temperature of the solution to 45 ℃;
(2) And after the temperature is constant, adding 7.24g of antimony pentafluoride into the solution, and finishing the continuous reaction for 4 hours to obtain the reaction solution containing the lithium difluoro-oxalate borate.
(3) Filtering the reaction liquid containing the lithium difluoro-oxalato-borate obtained in the step (2) to remove insoluble substances, distilling under reduced pressure of 0.01Mpa until the solution becomes turbid, cooling to-5 ℃, crystallizing for 4 hours, and filtering to obtain a crude product of the lithium difluoro-oxalato-borate; and dissolving the crude product by using dimethyl carbonate for recrystallization, and drying in vacuum at the temperature of 110 ℃ and the vacuum degree of 100Kpa to obtain the lithium difluoro oxalate borate.
(4) And (4) recovering and enriching the solution crystallized and filtered in the step (3) and the solution recrystallized, concentrating, crystallizing, recrystallizing and drying in vacuum, purifying the residual lithium difluoro (oxalato) borate in the solution, and calculating to obtain the product with the yield of 92.96% (yield = actual production of the target product/theoretical production of the target product of 100%) and the purity of 99.8% (the purity is detected by using a gas chromatograph). The recrystallized solution is recycled.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A preparation method of lithium difluoro (oxalato) borate is characterized by comprising the following steps: 1) Mixing lithium tetrafluoroborate, lithium oxalate, an organic solvent and an auxiliary agent, and reacting the obtained mixed solution to obtain a reaction solution containing LiODFB; the auxiliary agent is niobium pentachloride, niobium pentafluoride or antimony pentafluoride; 2) Filtering the reaction solution containing LiODFB in the step 1), and concentrating the filtrate to obtain a crude product of lithium difluoro (oxalato) borate; 3) Recrystallizing and drying the crude lithium difluoro (oxalato) borate in the step 2) to obtain lithium difluoro (oxalato) borate; the reaction temperature in the step 1) is 5-45 ℃, and the reaction time is 4-24 h; the molar ratio of the lithium tetrafluoroborate to the lithium oxalate in the step 1) is 1:1.0 to 1.5; the molar ratio of the lithium tetrafluoroborate to the auxiliary agent is 1-1.5; the organic solvent is one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, acetonitrile, butyronitrile, acetone, diethyl ether, ethylene carbonate and propylene carbonate.
2. The preparation method according to claim 1, wherein the concentration in the step 2) is performed by distilling the filtrate under reduced pressure, cooling and crystallizing when the solution is turbid, and filtering.
3. The method according to claim 2, wherein the pressure at the time of the reduced pressure distillation is 0.005 to 0.02MPa.
4. The preparation method according to claim 2, wherein the crystallization temperature of the temperature-reducing crystallization is-5 to 5 ℃ and the time is 3 to 5 hours.
5. The method according to claim 1, wherein the recrystallization is carried out using dimethyl carbonate as an organic solvent in the step 3).
6. The preparation method according to claim 1, wherein the drying manner in the step 3) is vacuum drying, the temperature of the vacuum drying is 80-150 ℃, and the vacuum degree is 80-100 Kpa.
7. The preparation method according to claim 2, further comprising recovering the filtrate obtained after the temperature reduction crystallization and filtration and the solution obtained after the recrystallization in the step 3), and sequentially concentrating, recrystallizing and vacuum-drying the recovered solution to obtain the residual lithium difluoro-oxalato-borate.
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| CN104628754A (en) * | 2015-02-01 | 2015-05-20 | 湖南省正源储能材料与器件研究所 | Preparation method of lithium ion battery electrolyte salt LiODFB (lithium oxalyldifluroborate) |
| WO2016002771A1 (en) * | 2014-07-02 | 2016-01-07 | セントラル硝子株式会社 | Complex center formation agent, ionic complex and production method thereof |
| WO2016157870A1 (en) * | 2015-03-27 | 2016-10-06 | 凸版印刷株式会社 | Contact-type two-dimensional image sensor |
| CN109836444A (en) * | 2017-11-29 | 2019-06-04 | 东莞东阳光科研发有限公司 | A kind of preparation method of difluorine oxalic acid boracic acid lithium |
| CN110343125A (en) * | 2019-03-13 | 2019-10-18 | 杉杉新材料（衢州）有限公司 | A kind of method and this application for mixing lithium salts in lithium ion battery of low cost preparation high-purity certainty ratio mixing lithium salts |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016002771A1 (en) * | 2014-07-02 | 2016-01-07 | セントラル硝子株式会社 | Complex center formation agent, ionic complex and production method thereof |
| CN104628754A (en) * | 2015-02-01 | 2015-05-20 | 湖南省正源储能材料与器件研究所 | Preparation method of lithium ion battery electrolyte salt LiODFB (lithium oxalyldifluroborate) |
| WO2016157870A1 (en) * | 2015-03-27 | 2016-10-06 | 凸版印刷株式会社 | Contact-type two-dimensional image sensor |
| CN109836444A (en) * | 2017-11-29 | 2019-06-04 | 东莞东阳光科研发有限公司 | A kind of preparation method of difluorine oxalic acid boracic acid lithium |
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