CN120574253B - Method, apparatus, and lithium difluorooxalate borate solution for continuous preparation - Google Patents
Method, apparatus, and lithium difluorooxalate borate solution for continuous preparationInfo
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- CN120574253B CN120574253B CN202511091418.2A CN202511091418A CN120574253B CN 120574253 B CN120574253 B CN 120574253B CN 202511091418 A CN202511091418 A CN 202511091418A CN 120574253 B CN120574253 B CN 120574253B
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Abstract
The application discloses a method and a device for continuously preparing lithium difluoro oxalate borate, and a lithium difluoro oxalate borate solution, belonging to the technical field of electrolyte salt synthesis, wherein the method comprises the steps of continuously pumping a first mixed solution formed by oxalate and an ester solvent and chlorosilane into a first dynamic microchannel reactor, and carrying out a first reaction to obtain a reaction product, wherein the mass flow ratio of the first mixed solution to the chlorosilane is (4-10): 1; continuously pumping the reaction product into a second dynamic micro-channel reactor, continuously pumping a second mixed solution formed by lithium tetrafluoroborate and an ester solvent into the second dynamic micro-channel reactor, performing a second reaction at the temperature of 20-70 ℃ and the rotating speed of 200-400 r/min to obtain a mixed reaction solution, and separating the reaction product in the mixed reaction solution to obtain lithium difluoroborate. The method for continuously preparing the lithium bifluoride oxalate borate can realize continuous production of the lithium bifluoride oxalate borate, and the quality of the lithium bifluoride oxalate borate is high.
Description
Technical Field
The application belongs to the technical field of electrolyte salt synthesis, and particularly relates to a method and a device for continuously preparing lithium difluoro oxalate borate, and a lithium difluoro oxalate borate solution.
Background
Lithium bifluoride oxalate (LiODFB) is an important high-performance lithium ion battery electrolyte additive, has the advantages of lithium bifluoride oxalate and lithium tetrafluoroborate, has good electrochemical properties and thermal stability, and is beneficial to forming a more stable SEI film on the surface of a negative electrode, so that the high-temperature cycle performance and the high-temperature storage performance of a battery are improved. In addition, the SEI film formed by LiODFB can prevent the co-embedding of electrolyte solvent (especially propylene carbonate) on the surface of the anode, and prevent the damage of SEI film structure.
There are related arts in which oxalate such as sodium oxalate is reacted with chlorosilane to obtain silica oxalate, and then the silica oxalate is reacted with lithium tetrafluoroborate to obtain a synthetic route of lithium difluorooxalate borate, which is generally divided into two steps, the first step of oxalate is reacted with chlorosilane to generate silica oxalate, the second step of silica oxalate is reacted with lithium tetrafluoroborate to generate lithium difluorooxalate, after synthesizing silica oxalate, the generated chloride salt such as sodium chloride is subjected to double decomposition reaction with the second step of lithium tetrafluoroborate to cause high acidity and excessive chloride ion content of the reaction product, therefore, it is generally necessary to separate solid chloride salt such as sodium chloride, otherwise continuous production of lithium difluorooxalate borate cannot be realized.
Disclosure of Invention
The present application aims to solve at least one of the technical problems in the related art to some extent. To this end, an object of the present application is to propose a method and a device for the continuous preparation of lithium difluorooxalato borate, a solution of lithium difluorooxalato borate. The method for continuously preparing the lithium bifluoride oxalate borate provided by the application can realize continuous production of the lithium bifluoride oxalate borate, improves the production efficiency and ensures that the prepared lithium bifluoride oxalate borate has high quality.
The first aspect of the application provides a method for continuously preparing lithium difluoro oxalate borate, which comprises the steps of continuously pumping a first mixed solution formed by oxalate and an ester solvent and chlorosilane into a first dynamic micro-channel reactor, carrying out a first reaction to obtain a reaction product, wherein the mass flow ratio of the first mixed solution to the chlorosilane is (4-10): 1, continuously pumping the reaction product into a second dynamic micro-channel reactor, continuously pumping a second mixed solution formed by lithium tetrafluoroborate and the ester solvent into the second dynamic micro-channel reactor, carrying out a second reaction at the temperature of 20-70 ℃ and the rotating speed of 200-400 r/min to obtain the mixed reaction solution, and separating the reaction product in the mixed reaction solution to obtain the lithium difluoro oxalate borate.
According to the method for continuously preparing the lithium difluoroborate in the embodiment of the application, the first dynamic microchannel reactor and the second dynamic microchannel reactor are combined, the tolerance of the dynamic microchannel reactors to solid matters is fully utilized, the two dynamic microchannel reactors are high in heat and mass transfer efficiency, high in safety and high in reaction efficiency, however, in the two dynamic microchannel reactors, the reaction time of the first reaction is longer, the reaction time of the second reaction is shorter, so that the reaction time of the two steps of reaction is not matched, the production efficiency is low, the quality of the lithium difluoroborate is poor, on one hand, the ratio of reaction raw materials of the first reaction is controlled, the reaction time of the first reaction is shortened, the matching of the two reaction time of the first dynamic microchannel reactor and the second dynamic microchannel reactor is realized, on the other hand, the temperature and the rotating speed of the second reaction are controlled, the solid and liquid reactants of the second reaction are layered under the centrifugal force effect, so that solid chloride salt such as sodium chloride is accumulated on the inner wall of the second dynamic microchannel reactor, the probability of the fourth fluoroborate in the second reaction is reduced, and the second reaction time is matched with the first reaction time of the second reaction time, and the first reaction time and the second reaction time of the second reaction time is fast. Furthermore, the solid-containing reaction liquid obtained by the first reaction in the first dynamic microchannel reactor directly enters the second dynamic microchannel reactor to carry out the second reaction without separating chloride salt such as sodium chloride, and the uniform separation is carried out after the reaction, so that the quality of the obtained lithium difluorooxalato borate can be ensured, and on the other hand, as the solvent adopted by the two-step reaction is an ester solvent, the ester solvent can dissolve the product lithium difluorooxalato borate, and the byproducts such as sodium chloride, lithium chloride and sodium tetrafluoroborate are not easy to dissolve, so that the solution of the ester solvent of the lithium difluorooxalato borate with qualified acidity and chloride ion content can be obtained. In conclusion, the method for continuously preparing the lithium bifluoride oxalate borate provided by the application can realize continuous production of the lithium bifluoride oxalate borate, improves the production efficiency, and has the advantages of high quality and low impurity content.
In some embodiments of the present application, the pressure of the first reaction and the second reaction is 0.5mpa to 1mpa. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the application, the temperature of the first reaction is 50 ℃ to 120 ℃. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the application, the mass ratio of oxalate in the first mixed solution is less than or equal to 20%. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the application, the mass ratio of lithium tetrafluoroborate in the second mixed solution is less than or equal to 20%. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the present application, the ratio of the amount of the substance of the silicon oxalate in the reaction product to the amount of the substance of the lithium tetrafluoroborate in the second mixed solution is 1 (1-1.05). Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the application, the oxalate comprises at least one of sodium oxalate and potassium oxalate. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the application, the ester solvent comprises at least one of dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the application, the stirring speed of the first reaction is 200r/min to 400r/min. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the application, the reynolds number of the fluid in the first dynamic microchannel reactor is greater than or equal to 10000. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the application, the time of the first reaction is 1min to 30min. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the application, the reynolds number of the fluid in the second dynamic microchannel reactor is greater than or equal to 15000. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the application, the second reaction time is 1min to 10min. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the application, the step of separating the reaction products in the mixed reaction solution comprises flash evaporation of the mixed reaction solution to obtain a solid-liquid mixture and gas, continuous centrifugation of the solid-liquid mixture, and separation and removal of solids to obtain a solution of lithium difluorooxalato borate and an ester solvent. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the application, the flash vaporization is at a temperature of 110 ℃ to 120 ℃. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the application, the rotational speed of the continuous centrifugation is 60r/min to 120r/min. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the present application, the pressure of the flash evaporation is 0.5mpa to 1mpa. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In some embodiments of the present application, the pressure of the continuous centrifugation is 0.5mpa to 1mpa. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In a second aspect, the application provides an apparatus for continuously preparing lithium difluorooxalato borate, said apparatus being used for carrying out the process according to the first aspect of the application. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
The third aspect of the application provides a lithium difluorooxalate borate solution, which comprises lithium difluorooxalate borate and an ester solvent, and is prepared by adopting the continuous preparation method of the lithium difluorooxalate borate. Therefore, the lithium bifluoride oxalate borate solution has high production efficiency, high quality and low impurity content.
In some embodiments of the application, the lithium bifluoride oxalate borate comprises 10% -35% by mass based on the total mass of the lithium bifluoride oxalate borate solution. Therefore, the lithium bifluoride oxalate borate solution has high production efficiency, high quality and low impurity content.
In some embodiments of the application, the lithium chloride mass ratio is less than or equal to 15ppm based on the total mass of the lithium difluorooxalato borate solution. Therefore, the lithium bifluoride oxalate borate solution has high production efficiency, high quality and low impurity content.
In some embodiments of the application, the mass ratio of tetrafluoroborate is less than or equal to 15ppm based on the total mass of the lithium difluorooxalato borate solution. Therefore, the lithium bifluoride oxalate borate solution has high production efficiency, high quality and low impurity content.
Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.
Drawings
The foregoing and/or additional aspects and advantages of the application will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a flow chart of a method for continuously preparing lithium difluorooxalato borate according to one embodiment of the present application.
Fig. 2 is a block diagram of an apparatus for continuously preparing lithium difluorooxalato borate according to an embodiment of the present application.
FIG. 3 is a chromatographic test chart of a solution of lithium difluorooxalato borate with an ester solvent obtained by the process of example 1 of the present application.
Reference numerals illustrate:
1 chlorosilane storage tank, 2 oxalate storage tank, 3 first feed pump, 4 second feed pump, 5 first dynamic micro-channel reactor, 6 lithium tetrafluoroborate tank, 7 third feed pump, 8 second dynamic micro-channel reactor, 9 flash tank and 10 continuous centrifuge.
Detailed Description
The following detailed description of embodiments of the application is exemplary and intended to be illustrative of the application and not to be construed as limiting the application.
The lithium bifluoride oxalate borate is an important high-performance lithium ion battery electrolyte additive, has the advantages of the lithium bifluoride oxalate borate and the lithium tetrafluoroborate, and has good electrochemical properties and thermal stability.
The existing preparation method of the lithium difluoro-oxalato-borate mainly comprises the steps of synthesizing lithium tetrafluoroborate by using lithium oxalate and boron trifluoride, and then reacting the lithium tetrafluoroborate with oxalic acid to obtain the lithium difluoro-oxalato-borate. In the production process of the method, corrosive materials such as boron trifluoride and oxalic acid exist, so that high requirements are put on a reaction system, and the equipment cost and the maintenance difficulty are increased. In addition, the reaction route has gas-liquid reaction, the reaction efficiency is low, a large amount of corrosive tail gas is generated, and the continuous difficulty is high.
There are related art proposals at present that oxalate such as sodium oxalate is used to react with chlorosilane to obtain silicon oxalate, and then the silicon oxalate is reacted with lithium tetrafluoroborate to obtain a synthetic route of lithium difluorooxalate borate, the route is generally divided into two steps, solid chloride such as sodium chloride needs to be separated after the silicon oxalate is synthesized, otherwise, sodium chloride and unreacted chlorosilane can undergo double decomposition reaction with lithium tetrafluoroborate, resulting in high acidity of reaction products and exceeding standard of chloride ion content. On the other hand, when the silicon oxalate is subjected to the second-step reaction, lithium tetrafluoroborate and a solvent are added, and evaporation separation is performed again after the reaction, and the problems of long solid-liquid reaction time, complex post-treatment and mismatching of the working hours of the fast reaction of the first step and the second step exist in the route, so that the process efficiency is low and the product quality is unstable.
In view of this, the first aspect of the present application proposes a method for continuously preparing lithium difluorooxalato borate. Referring to fig. 1, the method for continuously preparing lithium difluorooxalato borate according to an embodiment of the present application includes:
S1, continuously pumping a first mixed solution formed by oxalate and an ester solvent and chlorosilane into a first dynamic microchannel reactor, and performing a first reaction to obtain a reaction product, wherein the mass flow ratio of the first mixed solution to the chlorosilane is (4-10): 1;
s2, continuously pumping the reaction product into a second dynamic micro-channel reactor, continuously pumping a second mixed solution formed by lithium tetrafluoroborate and an ester solvent into the second dynamic micro-channel reactor, and performing a second reaction at 20-70 ℃ to obtain a mixed reaction solution;
s3, separating reaction products in the mixed reaction liquid to obtain the lithium difluoro oxalate borate.
The following describes the beneficial effects that can be achieved by the method for continuously preparing lithium difluoro oxalate borate:
The application provides a method for continuously preparing lithium difluoro oxalate borate, which adopts a first dynamic micro-channel reactor 5 and a second dynamic micro-channel reactor 8 to be combined, fully utilizes the tolerance of the dynamic micro-channel reactors to solid matters, and has high heat and mass transfer efficiency, high safety and high reaction efficiency, however, in the two dynamic micro-channel reactors, the reaction time of a first reaction is longer, the reaction time of a second reaction is shorter, so that the reaction time of the two steps of reactions is not matched, the production efficiency is low, the quality of the product lithium difluoro oxalate borate is not good, therefore, on one hand, the application controls the ratio of reaction raw materials of the first reaction, the reaction time of the first reaction is shortened, the matching of the two reaction time in the first dynamic micro-channel reactor and the second dynamic micro-channel reactor is realized, on the other hand, the temperature and the rotating speed of the second reaction are controlled, the rotating speed ensures that the reaction materials of the second reaction are subjected to solid-liquid delamination under the action of centrifugal force, so that solid chloride salt such as sodium chloride is gathered on the inner wall of the second dynamic micro-channel reactor, the probability of double decomposition reaction of lithium tetrafluoroborate in the liquid materials and the lithium tetrafluoroborate is reduced, and the reaction temperature ensures that the main reaction of the second reaction is rapidly carried out in a central cavity and matched with the working time of the first reaction. Furthermore, the solid-containing reaction liquid obtained by the first reaction in the first dynamic micro-channel reactor 5 directly enters the second dynamic micro-channel reactor 8 to carry out the second reaction without separating chloride salt such as sodium chloride, and uniform separation is carried out after the reaction, so that the quality of the obtained lithium difluorooxalate borate can be ensured. In conclusion, the method for continuously preparing the lithium bifluoride oxalate borate provided by the application can realize continuous production of the lithium bifluoride oxalate borate, improves the production efficiency, and has the advantages of high quality and low impurity content.
It can be understood that for the reaction of the reaction containing solids (such as oxalate, chloride, lithium tetrafluoroborate and the like), the general micro-reactor or pipeline reactor is easy to have the conditions of solid blockage and the like, so the application adopts the dynamic micro-channel reactor, combines the external jacket and the internal stirring mode, has the heat exchange function while the internal stirring shaft rotates at high speed, is an option of solid-liquid continuous reaction, and is not easy to have the condition of solid blockage.
The temperature of the second reaction is 20-70 ℃. For example, the temperature of the second reaction can be controlled to be 20 ℃,40 ℃,50 ℃,70 ℃ and the like, the temperature of the second reaction is controlled to be within the range, the influence on the main reaction rate is small within the temperature range, the double decomposition reaction rate of chloride salt such as sodium chloride is extremely slow, the product selectivity is higher than 99%, the quality of lithium bifluoride oxalate borate is improved, the impurity content is reduced, the generation process of fluorosilane is reduced, the generation of bubbles is reduced, the average residence time of materials is influenced, and the efficient performance of the reaction is ensured.
The mass flow ratio of the first mixed solution to the chlorosilane is (4-10): 1, for example, the mass flow ratio of the first mixed solution to the chlorosilane can be 4:1,5:1,7:1,9:1,10:1 and the like, the mass flow ratio of the first mixed solution to the chlorosilane is controlled within the above range, the molar ratio of oxalate such as sodium oxalate to the chlorosilane can be 1 (1.01-1.05), the sodium oxalate is completely reacted after the reaction, a small amount of chlorosilane remains, the reaction can be fully performed, and the generation of byproducts is avoided.
The stirring rotation speed of the second reaction is 200 r/min-400 r/min, for example, 200r/min,300r/min,400r/min and the like, and the stirring rotation speed is controlled within the above range, so that the fluid in the second reaction is in a turbulent state, and the mass transfer efficiency and the reaction rate are improved.
The following details the method for continuously preparing lithium difluorooxalate borate provided by the application:
the heat and mass transfer efficiency is high, the first dynamic micro-channel reactor 5 and the second dynamic micro-channel reactor 8 can perform high-efficiency temperature control in the reaction cavity, the liquid and the solid are kept to be pushed to one direction under the high-speed rotation of the stirring paddle, the back mixing phenomenon is reduced, the average reaction residence time is ensured, the second mixed liquid is added in the serial connection process of the two dynamic micro-channel reactors, the second-level mixing of the two-phase liquid is realized in the dynamic micro-channel reactors, the materials are rapidly reacted according to the mole ratio, the reaction selectivity of synthesizing the lithium difluorooxalato borate is high, and the double decomposition reaction is less.
The safety is high, the liquid holdup of the first dynamic micro-channel reactor 5 and the second dynamic micro-channel reactor 8 is small, and the solid-liquid reaction working condition can be borne. After the reaction starts, the blades can force the solid to move, the risk of overpressure caused by solid blocking equipment is avoided, heat exchange media are arranged in the stirring shafts and the outer sleeves of the first dynamic micro-channel reactor 5 and the second dynamic micro-channel reactor 8, the temperature of the materials is accurately controlled, and the materials can flow rapidly during stirring to avoid local temperature runaway or hot spot generation.
The reaction efficiency is high, namely, the ester solvent is used in the reaction raw materials, the solution of the lithium difluoro oxalate borate dissolved in the ester solvent is directly generated after the solid-liquid separation is carried out after the reaction, the solution is matched with the electrolyte solvent, no additional configuration process is needed, the production efficiency is high, the reaction time is short when the lithium difluoro oxalate borate is synthesized, and the double decomposition reaction of the chloride salt such as sodium chloride and lithium tetrafluoroborate is less.
The product purity is high, the solubility of inorganic matters such as byproduct lithium chloride and ammonium tetrafluoroborate generated by the reaction of the chloride salt such as sodium chloride and lithium tetrafluoroborate in the ester solvent is low, and the industrial byproduct sodium chloride is obtained by simple drying along with wet solids. The solubility of the product lithium difluoro oxalate borate in the ester solvent is higher, so that during solid-liquid separation, impurities enter sodium chloride to be treated as industrial sodium chloride, and the insoluble substances, chloride ions and acidity of the solution of the lithium difluoro oxalate borate dissolved in the ester solvent are controllable.
In addition, the application can realize the optimization of reaction conditions and further improve the purity and yield of the product. The reaction process has few steps, and the chlorine ion and acidity value in the lithium bifluoride oxalate borate solution product are controllable, and the quality is controllable.
Specifically, taking oxalate as sodium oxalate as an example, the reaction equation in the first dynamic microchannel reactor 5 is:
Na2C2O4+2Si(CH3)3Cl→(Si(CH3)3)2C2O4+2NaCl.
The reaction equation in the second dynamic microchannel reactor 8 is:
(Si(CH3)3)2C2O4+LiBF4→LiC2O4BF2+2Si(CH3)3F.
According to some embodiments of the application, the pressure of the first reaction and the second reaction is 0.5mpa to 1mpa. As an example, the pressures of the first reaction and the second reaction may be 0.5mpa,0.6mpa,0.7mpa,0.8mpa,0.9mpa,1mpa, etc., specifically, nitrogen may be used to raise the pressures of the first reaction and the second reaction to 0.5mpa to 1mpa, and the pressures of the first reaction and the second reaction are stabilized by a back pressure system, so that the reaction processes of the two dynamic microchannel reactors are ensured to be performed under high pressure conditions, and the first dynamic microchannel reactor 5 and the second dynamic microchannel reactor 8 are caused to react thoroughly, so as to improve the reaction efficiency and the product purity, and improve the stability of the whole apparatus for continuously preparing lithium difluoroborate.
According to some embodiments of the application, the temperature of the first reaction is 50 ℃ to 120 ℃, for example, 50 ℃,70 ℃,90 ℃,100 ℃,120 ℃ and the like. The temperature of the first reaction is controlled within the range, the reaction temperature is higher, the rapid reaction of oxalate such as sodium oxalate and chlorosilane can be promoted, the reaction time is shortened by controlling, the rapid reaction can be matched with the rapid reaction of the second dynamic microchannel reaction, the continuous production of the lithium difluorooxalate borate is realized, the production efficiency is improved, and the quality of the prepared lithium difluorooxalate borate is high.
According to some embodiments of the application, the first mixed solution has an oxalate mass ratio of 20% or less, for example, the oxalate mass ratio may be 1%,5%,10%,15%,20%, etc., and the oxalate mass ratio is controlled within the above range, so that the reaction can be sufficiently performed while avoiding the formation of by-products.
According to some embodiments of the application, the oxalate comprises at least one of sodium oxalate and potassium oxalate, which is susceptible to reaction with chlorosilanes under heating with few side reactions.
According to some embodiments of the present application, the ester solvent includes at least one of dimethyl carbonate (DMC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC), and the above ester solvent can dissolve the product lithium difluorooxalato borate without being easily dissolved by-products such as sodium chloride, lithium chloride and sodium tetrafluoroborate, so that a solution of the ester solvent of lithium difluorooxalato borate having acceptable acidity and chloride ion content can be obtained, and the prepared lithium difluorooxalato borate has high quality and low impurity content.
According to some embodiments of the present application, the first mixed solution and the second mixed solution are identical in the ester solvent, for example, the first mixed solution is dimethyl carbonate, and the second mixed solution is dimethyl carbonate, so that a solution of the ester solvent of lithium difluoroborate oxalate with high purity can be obtained.
According to some specific embodiments of the present application, the stirring rotation speed of the first reaction is 200r/min to 400r/min, for example, may be 200r/min,300r/min,400r/min, etc., and the stirring rotation speed is controlled within the above range, so that the fluid in the first reaction is in a turbulent state, and the mass transfer efficiency and the reaction rate are improved.
According to some embodiments of the present application, the reynolds number of the fluid in the first dynamic micro-channel reactor 5 is greater than or equal to 10000, for example, the reynolds number may be 10000,50000,60000,70000,80000,90000,100000,150000, and the reynolds number of the fluid in the first dynamic micro-channel reactor 5 is controlled within the above range, so that the fluid therein is in a turbulent state, and mass transfer efficiency and reaction rate are improved.
According to some embodiments of the present application, the time of the first reaction is 1min to 30min, for example, may be 1min,5min,10min,20min,30min, etc., and the time of the first reaction is controlled within the above range, so that the reaction can be ensured to be sufficiently performed, and meanwhile, the formation of byproducts caused by too long residence time is avoided, so that the prepared lithium difluorooxalato borate has high quality and low impurity content.
According to some embodiments of the application, in the second mixed solution, the mass ratio of lithium tetrafluoroborate is less than or equal to 20%, for example, may be 1%,5%,10%,15%,20%, etc., and the mass ratio of lithium tetrafluoroborate is controlled within the above range, so that the reaction can be ensured to be sufficiently performed while avoiding the formation of by-products.
The ratio of the amount of the substance of the silicon oxalate in the first dynamic micro-channel reactor to the amount of the substance of the lithium tetrafluoroborate in the second mixed solution is 1 (1-1.05). For example, the ratio of the amounts of the two substances may be 1:1.01,1:1.02,1:1.03,1:1.04,1:1.05, etc., and the ratio of the amounts of the two substances may be controlled within the above range, whereby the reaction can be ensured to proceed sufficiently while avoiding the formation of by-products.
According to some embodiments of the present application, the reynolds number of the fluid in the second dynamic micro-channel reactor 8 is greater than or equal to 15000, for example, the reynolds number may be 15000,20000,50000,70000,80000,90000,100000,150000, and the reynolds number of the fluid in the second dynamic micro-channel reactor 8 is controlled within the above range, so that the fluid therein is in a turbulent state, and mass transfer efficiency and reaction rate are improved.
According to some embodiments of the application, the second reaction time is 1 min-10 min. For example, the second reaction time may be 1min,5min,10min, etc., and the second reaction time may be controlled within the above range, so that the reaction is sufficiently carried out while avoiding the formation of by-products due to an excessively long residence time, and the produced lithium difluorooxalato borate has high quality and a low impurity content.
According to some embodiments of the application, step S3 comprises:
S31, flash evaporating the mixed reaction liquid to obtain a solid-liquid mixture and gas;
S32, continuously centrifuging the solid-liquid mixture, and separating and removing solids to obtain a solution of lithium difluoro oxalate borate and an ester solvent.
Specifically, the flash evaporation can be performed by using a flash evaporation tank, the continuous centrifugation can be performed by using a continuous centrifuge, the materials after the reaction continuously enter the flash evaporation tank 9, the gas mixture of the fluorosilane, the chlorosilane and the volatile gases of the solvent is discharged from the gas phase, the liquid enters the continuous centrifuge 10 to form a chloride salt with 15% moisture content such as sodium chloride solid and a solution of the product lithium difluorooxalato borate and the ester solvent, and the chloride salt solid with 15% moisture content is dried to obtain a chloride salt byproduct.
According to some embodiments of the present application, the flash evaporation temperature is 110 ℃ to 120 ℃, for example, 110 ℃,112 ℃,115 ℃,117 ℃,120 ℃ and the like, and the flash evaporation temperature is controlled within the above range, so that mixed gas of fluorosilane, chlorosilane, volatilized gas of solvent and the like in the product in the second dynamic microchannel reactor 8 can be discharged from the gas phase, separation of impurities is realized, fluorosilane, chlorosilane and the like in the reaction product can be removed conveniently, and the quality of the prepared lithium difluorooxalato borate is high, and the content of impurities is low.
According to some specific embodiments of the present application, the flash evaporation pressure is 0.5mpa to 1mpa, for example, may be 0.5mpa,0.6mpa,0.7mpa,0.8mpa,0.9mpa,1mpa, etc., so that the quality of the prepared lithium difluorooxalate borate is high, and the impurity content is low.
According to some specific embodiments of the application, the rotational speed of the continuous centrifugation is 60r/min to 120r/min. For example, the rotational speed of continuous centrifugation can be controlled within the above range at 60r/min,80r/min,100r/min,120r/min and the like, so that the solution separation of solid chloride salt such as sodium chloride and lithium difluoro oxalato borate from an ester solvent can be realized, the moisture content in the solid chloride salt can be lower than 15%, and the subsequent drying is facilitated.
According to some specific embodiments of the present application, the pressure of the continuous centrifugation is 0.5mpa to 1mpa, for example, may be 0.5mpa,0.6mpa,0.7mpa,0.8mpa,0.9mpa,1mpa, etc., so that the quality of the prepared lithium difluorooxalato borate is high, and the impurity content is low.
In a second aspect of the application, the application proposes a device for the continuous preparation of lithium difluorooxalato borate for carrying out the process according to the first aspect of the application. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
According to some embodiments of the present application, referring to fig. 2, the apparatus for continuously preparing lithium bifluoride oxalate borate includes a first dynamic micro-channel reactor 5, a second dynamic micro-channel reactor 8 and a separation device, wherein a first mixed solution formed by oxalate and ester solvent and chlorosilane are continuously pumped into the first dynamic micro-channel reactor 5, the second dynamic micro-channel reactor 8 is disposed downstream of the first dynamic micro-channel reactor 5, a reaction product in the first dynamic micro-channel reactor 5 is continuously pumped into the second dynamic micro-channel reactor 8, a second mixed solution formed by lithium tetrafluoroborate and ester solvent is continuously pumped into the second dynamic micro-channel reactor 8, and a separation device is disposed downstream of the second dynamic micro-channel reactor 8 for separating the reaction product in the second dynamic micro-channel reactor 8 to obtain lithium bifluoride oxalate borate.
Referring to fig. 2, the apparatus for continuously preparing lithium difluorooxalato borate further includes a chlorosilane storage tank 1, an oxalate storage tank 2 and a lithium tetrafluoroborate tank 6, wherein the chlorosilane storage tank 1 is disposed upstream of the first dynamic microchannel reactor 5, chlorosilane in the chlorosilane storage tank 1 is pumped into the first dynamic microchannel reactor 5 by a first feed pump 3, the oxalate storage tank 2 is disposed upstream of the first dynamic microchannel reactor 5, a first mixed solution formed by oxalate and an ester solvent is stored in the oxalate storage tank 2, the first mixed solution is pumped into the first dynamic microchannel reactor 5 by a second feed pump 4, the lithium tetrafluoroborate tank 6 is disposed upstream of the second dynamic microchannel reactor 8, a second mixed solution formed by lithium tetrafluoroborate and an ester solvent is stored in the lithium tetrafluoroborate tank 6, and the second mixed solution is pumped into the second dynamic microchannel reactor 8 by a third feed pump 7. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
In summary, the device for continuously preparing lithium difluorooxalate borate provided by the application utilizes the two-stage dynamic microchannel reactor to promote the rapid synthesis of solid chloride and silica oxalate in the first dynamic microchannel reactor 5, reduces the separation procedure after synthesis, directly enters the second step of rapid reaction, the gas phase is rectified and separated for application, the liquid is continuously separated, the impurities enter the solid industrial grade sodium chloride, the liquid is a qualified product, and the lithium difluorooxalate borate is a solution of an ester solvent.
In a third aspect of the present application, the present application provides a lithium difluorooxalato borate solution, wherein the lithium difluorooxalato borate solution comprises lithium difluorooxalato borate and an ester solvent, and the lithium difluorooxalato borate solution is prepared by adopting the continuous preparation method of the first aspect of the present application. Therefore, the lithium bifluoride oxalate borate solution provided by the application can realize continuous production, improves the production efficiency, and has high quality and low impurity content.
According to some embodiments of the present application, the lithium difluorooxalato borate solution has a mass ratio of 10% -35%, such as 10%,15%,16%,17%,18%,19%,20%,30%,35%, etc., based on the total mass of the lithium difluorooxalato borate solution. Therefore, the continuous production of the lithium bifluoride oxalate borate can be realized, the production efficiency is improved, and the prepared lithium bifluoride oxalate borate has high quality and low impurity content.
According to some specific embodiments of the present application, the mass ratio of lithium chloride is less than or equal to 15ppm, for example, may be 0,1ppm,5ppm,10ppm,15ppm, etc., based on the total mass of the lithium difluorooxalato borate solution, thereby controlling the mass ratio of the impurity lithium chloride in the lithium difluorooxalato borate solution within the above range, realizing continuous production of lithium difluorooxalato borate, improving the production efficiency, and the produced lithium difluorooxalato borate has high quality and low impurity content.
According to some embodiments of the application, the tetrafluoroborate comprises a mass ratio of less than or equal to 15ppm based on the total mass of the lithium difluorooxalato borate solution. For example, the content of tetrafluoroborate in the lithium difluorooxalato borate solution can be controlled to be in the above range, such as 0,1ppm,5ppm,10ppm,15ppm, etc., the quality of the lithium difluorooxalato borate is high, the content of impurities is low, and when the lithium difluorooxalato borate solution is used in a battery, the high-temperature cycle performance and the high-temperature storage performance of the battery can be better improved.
The following detailed description of embodiments of the application is provided for the purpose of illustration only and is not to be construed as limiting the application. In addition, all reagents employed in the examples below are commercially available or may be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
The pressure of the whole system is increased to 0.6MPa by high-pressure nitrogen, and the pressure of the whole device is stabilized to 0.8MPa by a back pressure system.
The temperature of the first dynamic microchannel reactor was raised to 90℃and the stirring speed was 300r/min. The temperature of the second dynamic microchannel reactor was raised to 40 ℃, the temperature of the flash tank was set to 110 ℃, and the continuous centrifuge was maintained at a rotational speed of 90r/min.
In a feeding system, sodium oxalate and DMC solvent are stirred in a kettle to form uniform liquid (first mixed liquid) with the mass ratio of 10% of sodium oxalate, and then the first mixed liquid and chlorosilane simultaneously enter a first dynamic micro-channel reactor, wherein the mass flow ratio of the two groups is 6:1, and the reaction residence time is 20min. And then the reacted mixed solution enters a second dynamic micro-channel reactor, meanwhile, a lithium tetrafluoroborate solution is added into the second dynamic micro-channel reactor, the mass ratio of lithium tetrafluoroborate in DMC solution of lithium tetrafluoroborate is 9%, the mass ratio of silicon oxalate to lithium tetrafluoroborate is 1:1.02, and the reaction residence time is 5min.
In the post-treatment unit, the materials from the second dynamic microchannel reactor enter a flash tank, the chlorosilane, fluorosilane and DMC mixed gas are discharged from a gas phase, the liquid enters a continuous centrifuge to form sodium chloride solids with 15% of moisture content and a product solution, the sodium chloride solids with 15% of moisture content are dried to obtain sodium chloride byproducts, the mass ratio of the sodium chloride is 99.55%, the mass ratio of the lithium chloride is 0.07%, and the mass ratio of the sodium tetrafluoroborate is 0.38%. The product solution was tested as 19.9% by mass of lithium bifluoride oxalate borate, 4ppm by mass of lithium chloride, 10ppm by mass of tetrafluoroborates (lithium tetrafluoroborate and sodium tetrafluoroborate), the remainder being solvent DMC.
Examples 2 to 36
The method for continuously preparing lithium difluorooxalato borate in examples 2 to 36 is the same as that in example 1, and the differences are shown in table 1. The tetrafluoroborate in example 30 was lithium tetrafluoroborate and potassium tetrafluoroborate, and the byproduct obtained was potassium chloride. That is, in table 2, the chloride salt in example 30 was potassium chloride, and the chloride salts of the remaining examples and comparative examples were sodium chloride.
Comparative example 1
And (3) stirring sodium oxalate and DMC solvent in a kettle to form uniform liquid (first mixed liquid) with the mass ratio of 10% of sodium oxalate, then mixing the first mixed liquid with chlorosilane, and reacting the two groups at the mass ratio of 6:1 at 90 ℃ for 20min under 0.8Mpa to obtain mixed liquid.
And (3) separating sodium chloride from the mixed solution to obtain a silicon oxalate solution, wherein the mass ratio of lithium tetrafluoroborate in the DMC solution of lithium tetrafluoroborate is 10%, and the silicon oxalate and the lithium tetrafluoroborate are mixed in a molar ratio of 1:1.02 and react for 5min at 40 ℃ to obtain a reaction solution.
And (3) flash evaporating the reaction liquid, wherein the flash evaporation temperature is 110 ℃, discharging the mixed gas of chlorosilane, fluorosilane and DMC from a gas phase, enabling the liquid to enter a centrifugal machine, enabling the rotating speed to be 90r/min, forming sodium chloride solid with 15% moisture content and a product solution, and drying the sodium chloride solid with 15% moisture content to obtain a sodium chloride byproduct, wherein the product solution is a solution of lithium difluorooxalato borate and an ester solvent.
Comparative examples 2 to 7
The method for continuously preparing lithium difluorooxalato borate in comparative examples 2 to 7 is the same as that in example 1, and the differences are shown in table 1. Wherein the ratio of the mass flow rate of the first mixed solution to the chlorosilane of comparative examples 2 and 3 is not within the range defined by the present application, the reaction temperature in the second dynamic microchannel reactor of comparative examples 4 and 5 is not within the range defined by the present application, and the rotational speed in the second dynamic microchannel reactor of comparative examples 6 and 7 is not within the range defined by the present application.
The solution chromatogram of the lithium difluoroborate prepared in example 1 and the ester solvent is shown in fig. 3, and it can be seen that the solution of the lithium difluoroborate prepared in example 1 and the ester solvent has higher quality.
The sodium chloride by-products and the solutions of lithium difluorooxalato borate and ester solvents of examples 1 to 36 and comparative examples 1 to 7 were subjected to component measurement, respectively, and the test results are shown in table 2.
1. And (3) measuring the components of the sodium chloride byproduct:
Sample pretreatment (deionized water dilution/filtration), detection of Li + (column: CS 12A) using ICP inductively coupled plasma, detection of BF 4 - (column: AS 11-HC) using IC anion mode, and corresponding conversion to lithium chloride mass ratio and tetrafluoroborate mass ratio.
2. Determination of solution components of lithium difluoro oxalate borate and an ester solvent:
Sample pretreatment (deionized water dilution/filtration) and detection of F-and oxalate content using an IC ion chromatograph, corresponding to conversion to lithium difluorooxalato borate mass ratio.
The test results are shown in Table 2.
Conclusion:
As can be seen from Table 2, in examples 1 to 36, the method for continuously preparing lithium difluorooxalate borate according to the examples of the present application is adopted, and simultaneously the ratio of the reaction materials of the first reaction is controlled, the temperature and the rotation speed of the second reaction are controlled, so that the continuous production of lithium difluorooxalate borate can be realized, the production efficiency is improved, the quality of the prepared lithium difluorooxalate borate is high, and sodium chloride or potassium chloride byproducts can be obtained. Comparative example 1 was not prepared by a continuous method, and the quality of the obtained lithium difluorooxalato borate was low, while comparative examples 2 to 7 were not prepared by simultaneously controlling the ratio of the reaction materials of the first reaction, controlling the temperature and the rotation speed of the second reaction, and the obtained lithium difluorooxalato borate was low in quality and high in impurity content.
Compared with example 1, the first reaction time is shorter in example 10, the second reaction time is shorter in example 23, and thus the reaction is insufficient, resulting in mismatching of the working hours of the first dynamic microchannel reactor and the second dynamic microchannel reactor, reduced lithium difluorooxalato borate content in the solution of lithium difluorooxalato borate and the ester solvent, reduced mass ratio of oxalate in example 6, reduced mass ratio of lithium tetrafluoroborate in example 19, and thus the reaction is insufficient, resulting in mismatching of the working hours of the first dynamic microchannel reactor and the second dynamic microchannel reactor, and reduced lithium difluorooxalato borate content in the solution of lithium difluorooxalato borate and the ester solvent.
Compared with example 1, the first reaction time and the second reaction time in example 25 are both longer, which causes an increase in side reaction, and therefore the content of byproducts such as lithium fluoride and tetrafluoroborate is increased in the solution of lithium difluoroborate and the ester solvent obtained, the ratio of the amounts of the substances such as silicon oxalate and lithium tetrafluoroborate in example 35 is increased, the flash evaporation temperature is increased, and the rotational speed of continuous centrifugation is increased, which causes an increase in side reaction, and therefore the content of byproducts such as lithium fluoride and tetrafluoroborate is increased in the solution of lithium difluoroborate and the ester solvent obtained, the ratio of the amounts of the substances such as silicon oxalate and lithium tetrafluoroborate is decreased in example 36, the flash evaporation temperature is decreased, and the rotational speed of continuous centrifugation is also decreased, which causes an increase in side reaction, and therefore the content of byproducts such as lithium fluoride and tetrafluoroborate is increased in the solution of lithium difluoroborate and the ester solvent obtained.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.
Claims (5)
1. A method for continuously preparing lithium bifluoride oxalate borate, which is characterized by comprising the following steps:
continuously pumping a first mixed solution formed by oxalate and an ester solvent and chlorosilane into a first dynamic microchannel reactor, and performing a first reaction to obtain a reaction product, wherein the mass flow ratio of the first mixed solution to the chlorosilane is (4-10): 1;
Continuously pumping the reaction product into a second dynamic micro-channel reactor, continuously pumping a second mixed solution formed by lithium tetrafluoroborate and an ester solvent into the second dynamic micro-channel reactor, and performing a second reaction at the temperature of 20-70 ℃ and the rotating speed of 200-400 r/min to obtain a mixed reaction solution;
Separating reaction products in the mixed reaction liquid to obtain lithium difluoro oxalate borate;
in the first mixed solution, the mass ratio of oxalate is less than or equal to 20%;
In the second mixed solution, the mass ratio of lithium tetrafluoroborate is less than or equal to 20%;
the ratio of the amount of the silicon oxalate in the reaction product to the amount of the lithium tetrafluoroborate in the second mixed solution is 1 (1-1.05).
2. The continuous process for preparing lithium difluorooxalato borate according to claim 1, wherein said process satisfies at least one of the following conditions:
The pressure of the first reaction and the second reaction is 0.5-1 MPa;
the temperature of the first reaction is 50-120 ℃.
3. The continuous process for preparing lithium difluorooxalato borate according to claim 1, wherein said process satisfies at least one of the following conditions:
the oxalate is at least one selected from sodium oxalate and potassium oxalate;
the ester solvent is at least one selected from dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate;
the stirring rotating speed of the first reaction is 200 r/min-400 r/min;
the reynolds number of the fluid in the first dynamic microchannel reactor is greater than or equal to 10000;
The time of the first reaction is 1 min-30 min;
the reynolds number of the fluid in the second dynamic microchannel reactor is greater than or equal to 15000;
the second reaction time is 1 min-10 min.
4. The method for continuously preparing lithium difluoroborate according to any one of claims 1 to 3, wherein the step of separating the reaction product in the mixed reaction solution comprises:
Flash evaporating the mixed reaction liquid to obtain a solid-liquid mixture and gas;
And continuously centrifuging the solid-liquid mixture, and separating and removing solids to obtain a solution of lithium difluoro oxalate borate and an ester solvent.
5. The continuous process for preparing lithium difluorooxalato borate according to claim 4, wherein said process satisfies at least one of the following conditions:
the flash evaporation temperature is 110-120 ℃;
the rotating speed of the continuous centrifugation is 60 r/min-120 r/min;
the pressure of the flash evaporation is 0.5-1 MPa;
the pressure of the continuous centrifugation is 0.5-1 MPa.
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