CN114891031A - Preparation method of lithium difluoro (oxalato) borate - Google Patents
Preparation method of lithium difluoro (oxalato) borate Download PDFInfo
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- CN114891031A CN114891031A CN202210396542.XA CN202210396542A CN114891031A CN 114891031 A CN114891031 A CN 114891031A CN 202210396542 A CN202210396542 A CN 202210396542A CN 114891031 A CN114891031 A CN 114891031A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
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- 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, which relates to the technical field of battery electrolyte additives. According to the invention, the lithium bis (oxalato) borate and the lithium fluoride are used as raw materials to react to generate the lithium difluoro (oxalato) borate and the lithium oxalate by adopting a two-step method, the middle part does not need to be treated, and boron trifluoride diethyl etherate is directly added to react with the lithium oxalate generated in the first step to generate the lithium difluoro (oxalato) borate continuously, so that the technical process is simple, the reaction condition is mild, and the method is more suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of battery electrolyte additives, in particular to a preparation method of lithium difluoroborate.
Background
The lithium ion battery is a new type high-energy secondary battery developed in 90 s of 20 th century because ofThe power supply has the advantages of high energy density, long cycle life, high working voltage and the like, and becomes one of the most attractive power supplies. The electrolyte salt is an important component of the lithium ion battery, and the research and development of the electrolyte salt are very important for the performance and development of the lithium ion secondary battery. In contrast, a great deal of research is being conducted on lithium ion battery electrolyte lithium salts at home and abroad, and lithium hexafluorophosphate (LiPF) is currently mainly developed 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium bis (oxalato) borate (Li-BOB), lithium difluoro (oxalato) borate (LiBF) 2 C 2 O 4 ) And the like lithium salts. Wherein, LiPF 6 The problems of sensitivity to moisture, unstable high-temperature performance, corrosion of a decomposition product HF to an electrode material and the like exist, so that the safety performance of the lithium battery is poor. LiBF 2 C 2 O 4 Has relatively high solubility in a chain carbonate solvent, high conductivity and LiBF 2 C 2 O 4 The lithium ion battery electrolyte has good film forming property and good cycle performance, can be used as an additive of lithium ion battery electrolyte, can also be used as a film forming additive in lithium battery electrolyte, has good thermal stability and electrochemical stability, becomes an important component material of the lithium ion battery electrolyte, and has wide application prospect in the field of power batteries.
Existing LiBF 2 C 2 O 4 The preparation process takes boron trifluoride and lithium oxalate as raw materials to directly react, and then the lithium difluoro oxalate borate is obtained through recrystallization and purification, but the reaction has the defects of long reaction time, low yield, low product purity and the like. Therefore, the development of a LiBF which has mild reaction conditions and is easy for industrial production is urgently needed 2 C 2 O 4 And (3) a synthesis process.
Disclosure of Invention
The invention aims to provide a preparation method of lithium difluoroborate, which aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of lithium difluoro (oxalato) borate comprises the steps of taking lithium bis (oxalato) borate and lithium fluoride to perform a first-step reaction under the action of a catalyst consisting of silicon tetrachloride and aluminum trichloride together in an inert gas protection and anhydrous environment, slowly dropwise adding boron trifluoride diethyl etherate after the reaction is completed, performing a second-step reaction again, filtering while hot after the reaction is completed, concentrating filtrate to dryness, and recrystallizing by using an ethyl acetate-dichloromethane mixed solution to obtain the lithium difluoro (oxalato) borate, wherein the specific chemical reaction formula is as follows:
further, the preparation method comprises the following specific steps:
under the protection of inactive gas and in an anhydrous environment, dissolving lithium bis (oxalato) borate and lithium fluoride in an organic solvent, cooling to a temperature below 5 ℃, adding aluminum trichloride, slowly dropwise adding silicon tetrachloride, slowly heating to 55-60 ℃ after dropwise adding to perform a first-step reaction, cooling to a temperature below 5 ℃ after completing the reaction, dropwise adding boron trifluoride diethyl etherate, slowly heating to 50-55 ℃ after dropwise adding to perform a second-step reaction, filtering while hot after completing the reaction, concentrating the filtrate to dryness, and recrystallizing by using an ethyl acetate-dichloromethane mixed solution to obtain the lithium difluoro (oxalato) borate.
Further, the molar ratio of the lithium bis (oxalato) borate to the lithium fluoride is 1-1.1: 2.
further, the weight ratio of the lithium fluoride to the aluminum trichloride to the silicon tetrachloride is 1: 0.05-0.08: 0.1 to 0.12.
Further, the molar ratio of the lithium fluoride to the boron trifluoride diethyl etherate is 1: 1.05 to 1.1.
Further, the volume ratio of ethyl acetate to dichloromethane in the mixed solution of ethyl acetate and dichloromethane is 2.5-3: 1.
further, the organic solvent is dimethyl acetate.
Further, the time length of the first-step reaction is 10-12 hours.
Further, the time length of the second step reaction is 5-6 h.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the lithium bis (oxalato) borate and the lithium fluoride are used as raw materials to react to generate the lithium difluoro (oxalato) borate and the lithium oxalate, the middle part does not need to be treated, the boron trifluoride diethyl etherate is directly added to react with the lithium oxalate generated in the first step to generate the lithium difluoro (oxalato) borate continuously, the process is simple, the reaction condition is mild, and the method is more suitable for industrial production;
in the reaction process, the catalyst consisting of silicon tetrachloride and aluminum trichloride is added at one time, so that the forward reaction can be accelerated.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
the preparation method of the lithium difluoro oxalato borate comprises the following preparation processes:
under the protection of nitrogen and in an anhydrous environment, 203.47g (1.05mol) of lithium bis (oxalato) borate and 51.88g (2mol) of lithium fluoride are dissolved in 700mL of dimethyl acetate, the mixture is cooled to 0 ℃, 3.11g of aluminum trichloride is added, 5.71g of silicon tetrachloride is slowly dripped, after the dripping is finished, the temperature is slowly increased to 58 ℃ for carrying out a first-step reaction for 11 hours, after the reaction is finished, the mixture is cooled to 0 ℃, 305.15g (2.15mol) of boron trifluoride diethyl etherate is slowly dripped, after the dripping is finished, the mixture is slowly heated to 50 ℃ for carrying out a second-step reaction for 6 hours, after the reaction is finished, the mixture is filtered while hot, the filtrate is concentrated to be dry, and then a 3-time ethyl acetate-dichloromethane mixed solution (the volume ratio of ethyl acetate to dichloromethane is 3: 1) is used for recrystallization, thus obtaining 261.23g of lithium difluoro (oxalato) borate, wherein the yield is 90.86%, the purity is 99.6%, and the specific chemical reaction formula is as follows:
example two:
the preparation method of the lithium difluoro oxalato borate comprises the following preparation processes:
under the protection of nitrogen and in an anhydrous environment, 213.16g (1.1mol) of lithium bis (oxalato) borate and 51.88g (2mol) of lithium fluoride are dissolved in 700mL of dimethyl acetate, the mixture is cooled to 5 ℃, 4.15g of aluminum trichloride is added, 5.19g of silicon tetrachloride is slowly dripped, after the dripping is finished, the temperature is slowly increased to 55 ℃ for carrying out the first-step reaction for 12 hours, after the reaction is finished, the mixture is cooled to 5 ℃, 312.25g (2.2mol) of boron trifluoride diethyl etherate is slowly dripped, after the dripping is finished, the mixture is slowly heated to 52 ℃ for carrying out the second-step reaction for 5.5 hours, after the reaction is finished, the mixture is filtered while hot, filtrate is concentrated to be dry, and then 3.4 times of ethyl acetate-dichloromethane mixed solution (the volume ratio of ethyl acetate to dichloromethane is 2.7: 1) is used for recrystallization, so that 260.74g of lithium difluoro (oxalato) borate is obtained, the yield is 90.69%, and the purity is 99.4%.
Example three:
the preparation method of the lithium difluoro oxalato borate comprises the following preparation processes:
under the protection of nitrogen and in an anhydrous environment, 193.78g (1mol) of lithium bis (oxalato) borate and 51.88g (2mol) of lithium fluoride are dissolved in 750mL of dimethyl acetate, the mixture is cooled to 2 ℃, 3.63g of aluminum trichloride is added, 5.45g of silicon tetrachloride is slowly dripped, after the dripping is finished, the temperature is slowly increased to 60 ℃ for carrying out the first-step reaction for 10 hours, after the reaction is finished, the mixture is cooled to 2 ℃, 298.05g (2.1mol) of boron trifluoride diethyl etherate is slowly dripped, after the dripping is finished, the mixture is slowly heated to 55 ℃ for carrying out the second-step reaction for 5.4 hours, after the reaction is finished, the mixture is filtered while hot, the filtrate is concentrated to be dry, and then 3.1 time of ethyl acetate-dichloromethane mixed solution (the volume ratio of ethyl acetate to dichloromethane is 2.9: 1) is used for recrystallization, so that 260.07g of lithium difluoro (oxalato) borate is obtained, the yield is 90.45%, and the purity is 99.3%.
Example four:
the preparation method of the lithium difluoro oxalato borate comprises the following preparation processes:
under the protection of nitrogen and in an anhydrous environment, 197.66g (1.02mol) of lithium bis (oxalato) borate and 51.88g (2mol) of lithium fluoride are dissolved in 800mL of dimethyl acetate, the mixture is cooled to the temperature of minus 5 ℃, 2.59g of aluminum trichloride is added, 6.23g of silicon tetrachloride is slowly dripped, after the dripping is finished, the temperature is slowly increased to 57 ℃ for carrying out the first-step reaction for 11.5h, after the reaction is finished, the mixture is cooled to the temperature of minus 5 ℃, 300.89g (2.12mol) of boron trifluoride diethyl etherate is slowly dripped, after the dripping is finished, the mixture is slowly heated to 54 ℃ for carrying out the second-step reaction for 5h, after the reaction is finished, the mixture is filtered while hot, the filtrate is concentrated to be dry, and then 3.6 times of ethyl acetate-dichloromethane mixed solution (the volume ratio of ethyl acetate to dichloromethane is 2.5: 1) is used for recrystallization, and 261.12g of lithium difluoro (oxalato) borate is obtained, the yield is 90.82%, and the purity is 99.5%.
Example five:
the preparation method of the lithium difluoro oxalato borate comprises the following preparation processes:
under the protection of nitrogen and in an anhydrous environment, 205.41g (1.06mol) of lithium bis (oxalato) borate and 51.88g (2mol) of lithium fluoride are dissolved in 800mL of dimethyl acetate, the mixture is cooled to 0 ℃, 3.11g of aluminum trichloride is added, 5.97g of silicon tetrachloride is slowly dripped, after the dripping is finished, the temperature is slowly increased to 59 ℃ for carrying out the first-step reaction for 10.5h, after the reaction is finished, the mixture is cooled to 0 ℃, 306.57g (2.16mol) of boron trifluoride diethyl etherate is slowly dripped, after the dripping is finished, the mixture is slowly heated to 53 ℃ for carrying out the second-step reaction for 5.6h, after the reaction is finished, the mixture is filtered while hot, the filtrate is concentrated to be dry, and then 3.7 times of ethyl acetate-dichloromethane mixed solution (the volume ratio of ethyl acetate to dichloromethane is 2.6: 1) is used for recrystallization, thus obtaining 260.14g of lithium difluoro (oxalato) borate, the yield is 90.48%, and the purity is 99.4%.
Comparative example:
the finished lithium difluoro (oxalato) borate product is purchased in the market, and the product yield is 81.2 percent and the purity is 95.0 percent.
The yields and purities of the finished products of examples one to five were compared with those of the comparative example, and the comparison results are shown in table 1:
as can be seen from Table 1, the yield and purity of the lithium difluoroborate prepared by the method are higher than those of the commercially available products.
TABLE 1
| Item | Total yield (%) | Purity (%) |
| Example one | 90.86 | 99.6 |
| Example two | 90.69 | 99.4 |
| EXAMPLE III | 90.45 | 99.3 |
| Example four | 90.82 | 99.5 |
| EXAMPLE five | 90.48 | 99.4 |
| Comparative example | 81.2 | 95.0 |
Application experiments:
ternary material NCM (622) lithium is used as a positive electrode material, a negative electrode adopts mesocarbon microbeads, current collectors of the positive electrode and the negative electrode are distributed into aluminum foils and copper foils, a diaphragm adopts a ceramic diaphragm to form a soft package battery, after electrolyte is injected, the soft package battery is assembled in a glove box, and the test is carried out after the soft package battery is kept stand for 8 hours. And (3) respectively carrying out charging and discharging at the constant temperature of 25 ℃ and at the voltage of more than 1/10 C3.0V-4.2V to activate the battery, thus obtaining the battery to be tested.
The electrolytes tested included base electrolyte E1 and electrolyte E2, the compositions of which are as follows:
1. basic electrolyte E1
EC：Solution-1：DEC＝3：3：4(v:v:v)，LiPF 6 ：1.0M，0.5％LiFSI，1％VC
2. Electrolyte E2
EC: solution-1: DEC ═ 3: 3: 4(v: v: v), lithium difluorooxalato borate: 1.0M, 0.5% LiFSI, 1% VC
And (3) testing results:
1. the test results after 60 ℃ cycling were as follows:
TABLE 2
2. And (3) placing the battery in a low-temperature box, respectively controlling the temperature to be-30 ℃ or-40 ℃, placing for 240min, and then measuring the capacity retention rate of the battery.
TABLE 3
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A preparation method of lithium difluoro (oxalato) borate is characterized by comprising the following steps: the preparation method comprises the steps of taking lithium bis (oxalato) borate and lithium fluoride to perform a first-step reaction under the action of a catalyst consisting of silicon tetrachloride and aluminum trichloride together under the protection of an inert gas and in an anhydrous environment, slowly dropwise adding boron trifluoride diethyl etherate after the reaction is completed, performing a second-step reaction again, filtering while hot after the reaction is completed, concentrating the filtrate to dryness, and recrystallizing by using an ethyl acetate-dichloromethane mixed solution to obtain the lithium difluoro (oxalato) borate, wherein the specific chemical reaction formula is as follows:
2. the method for producing lithium difluoroborate as claimed in claim 1, wherein: the preparation method comprises the following specific steps:
under the protection of inactive gas and in an anhydrous environment, dissolving lithium bis (oxalato) borate and lithium fluoride in an organic solvent, cooling to a temperature below 5 ℃, adding aluminum trichloride, slowly dropwise adding silicon tetrachloride, slowly heating to 55-60 ℃ after dropwise adding to perform a first-step reaction, cooling to a temperature below 5 ℃ after completing the reaction, dropwise adding boron trifluoride diethyl etherate, slowly heating to 50-55 ℃ after dropwise adding to perform a second-step reaction, filtering while hot after completing the reaction, concentrating the filtrate to dryness, and recrystallizing by using an ethyl acetate-dichloromethane mixed solution to obtain the lithium difluoro (oxalato) borate.
3. The method for producing lithium difluoroborate according to claim 1 or 2, characterized in that: the molar ratio of the lithium bis (oxalato) borate to the lithium fluoride is 1-1.1: 2.
4. the method for producing lithium difluoroborate according to claim 1 or 2, characterized in that: the weight ratio of the lithium fluoride to the aluminum trichloride to the silicon tetrachloride is 1: 0.05-0.08: 0.1 to 0.12.
5. The method for producing lithium difluoroborate according to claim 1 or 2, characterized in that: the molar ratio of lithium fluoride to boron trifluoride diethyl etherate is 1: 1.05 to 1.1.
6. The method for producing lithium difluoroborate according to claim 1 or 2, characterized in that: the volume ratio of ethyl acetate to dichloromethane in the mixed solution of ethyl acetate and dichloromethane is 2.5-3: 1.
7. the method for producing lithium difluoroborate according to claim 1 or 2, characterized in that: the organic solvent is dimethyl acetate.
8. The method for producing lithium difluoroborate according to claim 1 or 2, characterized in that: the reaction time of the first step is 10-12 h.
9. The method for producing lithium difluoroborate according to claim 1 or 2, characterized in that: the time of the second step reaction is 5-6 h.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20030100761A1 (en) * | 2001-11-05 | 2003-05-29 | Central Glass Company, Limited | Process for synthesizing ionic metal complex |
| 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 |
| CN104557995A (en) * | 2013-10-12 | 2015-04-29 | 陈琛 | Preparation method of lithium oxalyldifluoroborate |
| CN107226821A (en) * | 2017-06-12 | 2017-10-03 | 上海如鲲新材料有限公司 | A kind of synthesis technique that difluorine oxalic acid boracic acid lithium is prepared with di-oxalate lithium borate |
| CN109232628A (en) * | 2018-11-13 | 2019-01-18 | 九江天赐高新材料有限公司 | A kind of method of one pot process difluorine oxalic acid boracic acid lithium |
| CN111808128A (en) * | 2020-08-24 | 2020-10-23 | 山东海科创新研究院有限公司 | Preparation method of lithium difluoro (oxalato) borate |
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- 2022-04-15 CN CN202210396542.XA patent/CN114891031A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030100761A1 (en) * | 2001-11-05 | 2003-05-29 | Central Glass Company, Limited | Process for synthesizing ionic metal complex |
| 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 |
| CN104557995A (en) * | 2013-10-12 | 2015-04-29 | 陈琛 | Preparation method of lithium oxalyldifluoroborate |
| CN107226821A (en) * | 2017-06-12 | 2017-10-03 | 上海如鲲新材料有限公司 | A kind of synthesis technique that difluorine oxalic acid boracic acid lithium is prepared with di-oxalate lithium borate |
| CN109232628A (en) * | 2018-11-13 | 2019-01-18 | 九江天赐高新材料有限公司 | A kind of method of one pot process difluorine oxalic acid boracic acid lithium |
| CN111808128A (en) * | 2020-08-24 | 2020-10-23 | 山东海科创新研究院有限公司 | Preparation method of lithium difluoro (oxalato) borate |
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