KR101890787B1 - Process for producing lithium bisfluorosulfonylimide - Google Patents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
- C01B21/0935—Imidodisulfonic acid; Nitrilotrisulfonic acid; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
- C01B21/096—Amidosulfonic acid; Salts thereof
Abstract
(1) Fluorination reaction: Synthesizing bis (chlorosulfonyl) imide (HClSI) and hydrogen fluoride (HF) with an intermediate bisfluorosulfonylimide (HFSI) under catalysis; And
(2) reacting the bis-fluorosulfonylimide (HFSI) obtained in the step (1) with basic lithium, and subjecting the reaction mixture to solid-liquid separation to obtain a LiFSI product, wherein the lithium bisfluorosulfonylimide And a manufacturing method thereof. The above production method is suitable for industrial production because the cost is low, the amount of by-products is small, the post treatment is simple, and the quality and purity of the product can be ensured.
Description
The present invention relates to the field of lithium batteries and lithium capacitors, and more particularly to a process for producing lithium bisfluorosulfonylimide and its use.
In the Periodic Table of the Elements, fluorine is the largest element of electronegativity. The introduction of a fluorine element into a single compound usually results in a significant change in its physical and chemical properties. Thus, numerous fluorine-containing compounds such as lithium bis (trifluoromethylsulfonyl) imide (LiTFST) and lithium hexafluorophosphate (LiPF 6 ) are widely used to improve the electrical properties of batteries and capacitors do. U.S. Patent No. 5,916,475 discloses lithium bisfluorosulfonylimide (LiFSI), a fluorine-containing lithium salt having better thermal stability and chemical stability, higher conductivity and lower corrosion rate than LiTFSI and LiPF 6 , It is a fluorine-containing lithium salt that can replace LiPF 6 , and is considered to have good application prospects in lithium battery and super capacitor applications.
Most of the synthesis methods of LiFSI are all synthesized first with bis (chlorosulfonyl) imide (HClSI) and then reacted with MFn (M is a group of 11-15 and 4-6 cyclic elements) to obtain a corresponding metal or organic base To prepare a salt intermediate of bis-fluorosulfonylimide followed by a cation exchange reaction with LiOH or Li 2 CO 3 to produce LiFSI (U.S. Patent Application Publication No. 2013331609, U.S. Patent Application Publication No. 2012041233, European Patent No. 2415757, U.S. Patent Application Publication No. 2011034716). The disadvantage of this method is that when the exchange reaction reaches equilibrium, it is hard to react completely and the completely unreacted intermediate MSFI (M means metal cation, organic base cation ) Is completely separated from LiSFI, making it difficult to obtain a high-quality product.
When LiFSI is produced by directly reacting HClSI with LiF (U.S. Patent Application Publication No. 2004097757), a large amount of corrosive gas HF can be generated, and at the same time, it is difficult to separate excessive LiF from LiFSI.
There are studies to produce LiFSI by metal exchange of purified potassium bis-fluorosulfonylimide (KFSI) and LiClO 4 , but it has a high potassium ion content in the product and affects practical applications. Also, LiClO 4 and produced KClO 4 all have a constant explosion risk [Electrochimical Acta, 2012, 66, pp. 320-324, Polyhedron, 2006, 25, PP. 1292-1298, Chinese Patent No. 101747242, Chinese Patent No. 101747243, Chinese Patent No. 101654229]. In addition, in general, a slight excess of LiClO 4 is required for the reaction, but LiClO 4 itself is highly hygroscopic and can not remove a small amount of LiClO 4 containing the final product, so that the purity of the final product, LiFSI, can not be guaranteed.
U.S. Patent No. 8377406 discloses a method for producing LiFSI by reacting bisfluorosulfonylimide (HFSI) with lithium carbonate in an aqueous solution. However, when the HFSI is dissolved in water, a violent exothermic reaction occurs and HFSI The patent has solved the technical problem of causing a vigorous exothermic reaction by dissolving HFSI in water using a method of producing HFSI aqueous solution at a very low temperature (-78 ° C), but this method has a problem in that the energy consumption , And more importantly, LiFSI has very good water solubility, so the extraction efficiency is very low and is not suitable for industrial production.
Japanese Patent Application Laid-Open No. 2013091524 has systematically studied the stability of LiFSI, and found that LiFSI decomposes rapidly in an environment where the temperature exceeds 40 ° C, and decomposes rapidly as the water content increases. Therefore, it is possible to obtain reagents inexpensively and easily in the field, react quickly and completely, have high yield, have few byproducts and can be easily removed, can not easily decompose the synthesized lithium salt, The use of the process for the preparation of the fluorosulfonylimide desperately demands that the cost of the product be significantly reduced and to be more suitable for industrial production.
In view of the disadvantages of the prior art, it is an object of the present invention to provide a process for producing lithium bisfluorosulfonylimide (LiFSI) which solves the problems of the prior art.
In order to achieve the above and other related objects, the present invention provides a process for producing lithium bisfluorosulfonylimide (LiFSI) comprising the following steps.
(1) Fluorination reaction: Synthesizing bis (chlorosulfonyl) imide (HClSI) and hydrogen fluoride (HF) with an intermediate bis-fluorosulfonylimide (HFSI) under catalysis;
(2) reacting the bis-fluorosulfonylimide (HFSI) obtained in the step (1) with basic lithium, and performing solid-liquid separation after completion of the reaction to obtain a LiFSI product.
The reaction scheme of step (1) is as follows:
Preferably, in the step (1), a specific method of the fluorination reaction is carried out by introducing HClSI and a catalyst into a reactor and introducing HF gas.
Preferably, in the above step (1), the catalyst is preferably a Lewis acid, and more preferably from SbCl 5, TiCl 4, SnCl 4 , MoCl combination of one or more of the five kinds.
Preferably, in the step (1), the molar ratio of HClSI to the catalyst is preferably 1: 0.05 to 1: 1, more preferably 1: 0.1 to 1: 0.5.
Preferably, in said step (1), the molar ratio of HClSI to HF is preferably from 1: 1.4 to 1: 4, more preferably from 1: 1.7 to 1: 2.
Preferably, in the step (1), the reaction temperature of the reaction system is 90 to 110 ° C, more preferably 100 to 105 ° C.
Preferably, in step (1) above, an intermediate HFSI is synthesized under catalysis by HClSI and HF, and after completion of the reaction, the HF and HCl gases in the reaction system are removed to obtain an intermediate bisfluorosulfonylimide.
More preferably, the method of removing HF and HCl gas in the reaction system is to conduct distillation to the reaction system or to conduct the blowing and distillation to the reaction system.
More preferably, the temperature at blowing is room temperature, the blowing time is 10 to 20 hours, and the distillation is vacuum distillation.
Preferably, in the above step (2), wherein the basic lithium is a combination LiOH, LiHCO 3, or Li 2 CO 3 at least one of.
Preferably, the molar ratio of HFSI to lithium in the basic lithium is preferably 1: 0.8 to 1: 1, more preferably 1: 0.9 to 1: 0.98.
When the basic lithium is LiOH, the reaction is as follows:
When the basic lithium is Li 2 CO 3 , the reaction formula is as follows:
When the basic lithium is LiHCO 3 , the reaction is as follows:
Preferably, in step (2) above, the product obtained in step (1) is added to a basic lithium / solvent system and cooling is preferably performed on the reaction system during the addition and / or the reaction, It is dropping.
More preferably, the reaction temperature of the reaction system is 0 to 20 캜, more preferably 0 to 5 캜.
More preferably, the basic lithium / solvent-based solvent is a low-polarity solvent, and more preferably a combination of at least one of hexane, cyclohexane, dichloromethane, dichloroethane, toluene, xylene, chlorobenzene and dichlorobenzene .
Preferably, in step (2), the bis-fluorosulfonylimide (HFSI) obtained in step (1) is reacted with basic lithium, and SOCl 2 is added dropwise to the reaction system so that the water in the reaction system is completely reacted And subjected to solid-liquid separation to obtain a LiFSI product.
More preferably, SOCl 2 is added dropwise at room temperature.
Preferably, in step (2), the LiFSI product obtained by reacting the bisfluorosulfonylimide (HFSI) obtained in the step (1) with basic lithium, and solid-liquid separation after completion of the reaction is further triturated, .
More preferably, as a specific method of the pulverization treatment, LiFSI obtained by solid-liquid separation is put into a pulverizing solvent and a metal ion removing agent and pulverized to obtain a purified LiFSI product.
More preferably, the pulverizing solvent is a low polarity solvent, and more preferably at least one of hexane, cyclohexane, dichloromethane, dichloroethane, toluene, xylene, chlorobenzene and dichlorobenzene.
More preferably, the metal ion removing agent is at least one selected from the group consisting of 12-crown-4, 15-crown-5, 18-crown-6 and dicyclohexano-18-crown-6.
The process for producing lithium bisfluorosulfonylimide (LiFSI) according to the present invention has the following advantages:
1. Because HF is used as a fluorination reagent, the cost is low, raw materials can be easily obtained, fully fluorinated under catalysis, less by-products, and HCI as a by-product only needs to be absorbed as a base. After completion of the reaction, most of the HF and HCI in the reaction system can be removed by nitrogen blowing and a small portion can be removed by distillation to ensure the purity and quality of the intermediate HFSI.
2. By reacting bis (fluorosulfonyl) imide (HFSI) with LiOH or LiHCO 3 , Li 2 CO 3 , the rate is fast and fully reacted, and the by-product produced is water (water has a solubility in LiFSI Very good, and the product is difficult to precipitate when water is present). The water can be removed gently at low temperature by SOCl 2 and the product can be slowly precipitated so as to simplify the separation after water removal and at the same time produce SO 2 as a byproduct and HCl (or CO 2 ) And there are no other complicated by-products.
3. At the same time, the equivalent number of bis-fluorosulfonylimide (HFSI) is greater than the equivalent number of lithium, ensuring that all basic lithium is fully reacted, and since excess HFSI is liquid, the remaining SOCl 2 (Liquid), SO 2 (gas), HCI (gas) or CO 2 (gas) are all removed by filtration and grinding, thus ensuring the purity of the product.
4. Since the product is very sensitive to temperature and easily decomposes at high temperatures, the present invention ensures product quality and purity by avoiding successful heating operations in all important salt forming steps.
5. Since the present invention uses a non-aqueous system (non-aqueous system), it is economically efficient because it has few wastewater, waste gas and solid waste, has a high yield and can easily recover and recycle all the solvents. In the post treatment, crown ether can be used to remove metal ions such as potassium and sodium that can be introduced into the reaction system, thereby improving the quality and performance of LiFSI.
As can be seen from the above, the present invention provides a high-quality, high-purity product suitable for industrial production and an economically efficient production method.
The inventors of the present invention have found that by using anhydrous hydrogen fluoride (HF) and bis (chlorosulfonyl) imide (HClSI) as raw materials and fluorinating under catalysis to obtain an intermediate bisfluorosulfonylimide (HFSI) Quality LiFSI (Lithium Bifluorosulfonylimide, CAS: 171611-11-3) product by obtaining a high-quality and high-purity LiFSI (CAS: 171611-11-3) product by reacting with a certain amount of basic lithium , Thereby completing the present invention.
The present invention provides a process for preparing lithium bisfluorosulfonylimide (LiFSI) comprising the following steps.
Step (1), fluorination reaction: Bis (chlorosulfonyl) imide (HClSI) and hydrogen fluoride (HF) are synthesized with catalytic intermediate bisfluorosulfonylimide (HFSI) Is as follows:
In the step (1), a specific method of the fluorination reaction is carried out by introducing HClSI and a catalyst into a reaction apparatus and introducing HF gas.
In the above step (1), the catalyst is preferably a Lewis acid, more preferably a combination of at least one of SbCl 5 , TiCl 4 , SnCl 4 and MoCl 5 , and the molar ratio of HClSI to the catalyst is preferably 1: 0.05 ‰ to 1: 1 ‰, more preferably from 1: 0.1 ‰ to 1: 0.5 ‰.
In the above step (1), the molar ratio of HClSI to HF is preferably 1: 1.4 to 1: 4, more preferably 1: 1.7 to 1: 2.
In the step (1), the reaction temperature of the reaction system is preferably 90 to 110 ° C, more preferably 100 to 105 ° C. Those skilled in the art can control the reaction time according to the progress of the reaction in the reaction system, and the preferable reaction time is 15 to 25 hours.
In the step (1), an intermediate HFSI is synthesized under catalysis by HClSI and HF, and HF and HCl gas in the reaction system are removed after completion of the reaction to obtain an intermediate bis-fluorosulfonylimide. The method of removing HF and HCl gas in the reaction system is to conduct distillation to the reaction system or to conduct the blowing and distillation to the reaction system. In a preferred embodiment of the present invention, a method for removing HF and HCl gas in a reaction system is a method in which the reaction system is first subjected to blowing, and then distillation proceeds. The temperature for blowing is preferably room temperature, and the gas usable for blowing includes, but is not limited to, a combination of at least one of nitrogen and various inert gases, and those skilled in the art will appreciate that depending on the size of the reaction system, And the blowing time can be adjusted. The preferable blowing time is 10 to 20 hours. The specific conditions for the distillation are not particularly limited as long as the object of the present invention is not limited, and preferably, the distillation is a reduced pressure distillation.
Step (2) Salt formation reaction: The bisfluorosulfonylimide (HFSI) obtained in step (1) is reacted with basic lithium, and after completion of the reaction, solid-liquid separation is carried out to obtain a LiFSI product.
In the step (2), the basic lithium is preferably a combination of at least one of LiOH, LiHCO 3 or Li 2 CO 3 , and the molar ratio of HFSI to lithium in basic lithium is preferably 1: 0.8 to 1: 1 , More preferably from 1: 0.9 to 1: 0.98. The LiOH may be LiOH · H 2 O.
When the basic lithium is LiOH, the reaction is as follows:
When the basic lithium is Li 2 CO 3 , the reaction formula is as follows:
When the basic lithium is LiHCO 3 , the reaction equation is as follows:
In step (2), the product obtained in step (1) is preferably added to the basic lithium / solvent system and the reaction system is further cooled during the addition and / or the reaction. More preferably, the reaction temperature of the reaction system is 0 to 20 캜, more preferably 0 to 5 캜. Those skilled in the art can control the reaction time depending on the progress of the reaction in the reaction system, and the preferable reaction time is 1 to 5 hours. The solvent in the basic lithium / solvent system is preferably a low polarity solvent and specifically includes a combination of at least one of hexane, cyclohexane, dichloromethane, dichloroethane, toluene, xylene, chlorobenzene and dichlorobenzene, It does not. One skilled in the art can adjust the amount of solvent used in the basic lithium / solvent system depending on the actual situation, and the preferred amount is 3 to 4 times the weight of the product LiFSI.
In step (2), preferably bis (fluorosulfonyl) imide (HFSI) obtained in the step (1) is reacted with basic lithium, and after completion of the reaction, SOCl 2 Is added dropwise, and solid-liquid separation is carried out to obtain a LiFSI product. SOCl 2 is preferably added dropwise at room temperature, and a person skilled in the art can adjust the amount of SOCl 2 to be used depending on the actual conditions of the reaction system. Preferably, the molar ratio of HFSI to SOCl 2 is 1: 05 to 1: 4, The ratio of LiOH to H 2 O is 1: 2.4 to 1: 3.2, LiOHCO 3 is 1: 1.2 to 1: 1.6, and Li 2 CO 3 is 1: 0.6 to 1: 0.8.
In the step (2), the LiFSI product obtained by reacting the bisfluorosulfonylimide (HFSI) obtained in the step (1) with basic lithium, and solid-liquid separation after completion of the reaction is further pulverized, Specifically, LiFSI obtained by solid-liquid separation is put in a pulverizing solvent and a metal ion removing agent and pulverized to obtain a purified LiFSI product. The pulverizing solvent is a low polar solvent and specifically includes, but is not limited to, a combination of at least one of hexane, cyclohexane, dichloromethane, dichloroethane, toluene, xylene, chlorobenzene and dichlorobenzene. Those skilled in the art can adjust the amount of the pulverizing solvent to be used depending on the actual situation, and the amount of the pulverizing solvent is preferably 3 to 6 times the weight of LiFSI. The metal ion removing agent may be various metal ion removing agents of the present invention. Preferably, the metal ion removing agent is 12-crown-4, 15-crown-5, 18-crown-6, dicyclohexano- -6, but is not limited thereto. Those skilled in the art can adjust the amount of the metal ion removing agent to be used depending on the actual situation, and the amount of the metal ion removing agent is preferably 0.02% to 0.2% by weight of LiFSI.
The present invention further provides the use of the lithium bisfluorosulfonylimide in the field of producing lithium bisfluorosulfonylimide.
The method of producing LiFSI according to the present invention is a method of producing HClSI using a method of fluorinating under catalysis with HF, reacting the latter completely with basic lithium and conducting a simple and economical post-treatment to obtain a high quality and high purity LiFSI The product can be obtained by purification. The process is simple, cost-effective, and suitable for large-scale industrialization.
Hereinafter, embodiments of the present invention will be described with reference to specific embodiments, and those skilled in the art can easily understand other advantages and effects of the present invention by disclosing the present invention. The present invention may also be practiced or embodied in other, different specific embodiments, and each of the details herein may be modified or altered within the spirit and scope of the invention, on the basis of different views and applications.
It should be understood that any process equipment or apparatus not specifically mentioned in the following examples is a generic equipment or apparatus used in the art.
It should also be understood that one or more method steps referred to in the present invention may have other method steps before or after the combining step, or that other method steps may be added between these explicitly mentioned steps, do. It should also be understood that the combination relationship of one or more of the equipment / devices mentioned in the present invention means that there are other equipment / devices before or after the combination equipment / device, Other equipment / devices may be added between the devices / devices.
Experiments: Sulfamic acid, thionyl chloride and chlorosulfonic acid, which are commercially available, are mixed by the steps of literature (Chinese Patent Application Laid-Open No. 103935970, U.S. Patent Application Publication No. 2011034716, U.S. Patent No. 4350685) And all other reagents are commercially available.
Example 1
To a 1000 mL reaction flask was added 1235 g of HClSI, 0.5 g of SbCl 5 , the temperature was raised to 100-105 ° C, about 230 g of HF gas was slowly introduced with stirring, reacted for 20 hours, And nitrogen gas was bubbled for 15 hours to obtain about 900 g of a preparation and distilled for a short time to obtain 865.6 g of a product with a yield of 82.8%.
Example 2
To a 1000 mL reaction flask was added 1230 g of HClSI and 0.47 g of MoCl 5 and the temperature was raised to 100-105 DEG C and about 216 g of HF gas was slowly introduced with stirring and allowed to react for 22 hours and then cooled to room temperature And nitrogen gas was bubbled for 15 hours to obtain about 896 g of a preparation, which was distilled for a short time to obtain 864.8 g of a product having a yield of 83.1%.
Example 3
To a 1000 mL reaction flask, 543 g of dichloroethane and 42.0 g of LiOH.H 2 O were added, the temperature was lowered to 0-5 캜, and 192.5 g of HFSI (Example 1) was added dropwise with stirring and stirred for 2 hours The temperature is raised to 20-25 ° C, 357 g of SOCl 2 is added dropwise, and the mixture is stirred for 16 hours. After filtration, the filter cake was pulverized with 600 g of dichloroethane and 0.17 g of 18-crown-6, filtered and dried to obtain 169.2 g of product, the yield being 90.4%.
Detection results: AAS (ppm): Na: 5.6, K: 2.3, Fe <1, Ca <1. IC (ppm): Cl -: 4.7, F -: 27, SO 4 2-: 17.
Example 4
To a 1000 mL reaction flask, 550 g of toluene and 36 g of Li 2 CO 3 were added and the temperature was lowered to 0 to 5 캜. 181 g of HFSI (Example 2) was added dropwise with stirring, and after stirring for 2 hours, Is raised to 20-25 ° C, 95 g of SOCl 2 is added dropwise, and the mixture is stirred for 16 hours. After filtration, the filter cake was pulverized with 600 g of toluene and 0.15 g of 15-crown-5, filtered and dried to obtain 170.6 g of product, and the yield was 91.2%.
Detection results: AAS (ppm): Na: 3.7, K: 3.5, Fe <1, Ca <1. IC (ppm): Cl -: 7.8, F -: 14, SO 4 2-: 20.
Example 5
500 g of cyclohexane and 68 g of LiHCO 3 were added to a 1000 mL reaction flask, the temperature was lowered to 0 to 5 캜, 188.5 g of HFSI (Example 1) was added dropwise with stirring, and the mixture was stirred for 2 hours, Was raised to 20-25 ° C, 161 g of SOCl 2 was added dropwise, and the mixture was stirred for 16 hours. After filtration, the filter cake was pulverized with 500 g of cyclohexane and 0.17 g of 18-crown-6, filtered and dried to obtain 170.2 g of product, the yield being 91.0%.
Detection results: AAS (ppm): Na: 4.4, K: 3.0, Fe <1, Ca <1. IC (ppm): Cl -: 6.1, F -: 21, SO 4 2-: 15.
In summary, the present invention overcomes various problems of the prior art and has a very high value for industrial use.
The foregoing embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Those skilled in the art may make modifications or alterations to the above embodiments within the spirit and scope of the present invention. Accordingly, any equivalent modifications or alterations made by those skilled in the art without departing from the spirit and scope of the invention disclosed in the present invention are intended to be included within the scope of the present invention.
Claims (9)
(2) reacting the bis-fluorosulfonylimide (HFSI) obtained in the step (1) with basic lithium, and performing solid-liquid separation after completion of the reaction to obtain a LiFSI product
Lt; / RTI >
In the above step (2), a basic lithium LiOH, LiHCO 3, or Li 2 CO 3, and one or more of;
In the step (2), the product obtained in the step (1) is added to a basic lithium solvent system, and the solvent of the basic lithium solvent system is a low polar solvent; Wherein the low polarity solvent is at least one selected from the group consisting of hexane, cyclohexane, dichloromethane, dichloroethane, toluene, xylene, chlorobenzene, and dichlorobenzene.
In the step (1), a specific method of the fluorination reaction is to introduce HClSI and a catalyst into a reaction apparatus, and to introduce the HF gas to proceed the reaction.
In the above step (1), the catalyst is a Lewis acid; And / or
In the above step (1), the molar ratio of HClSI to the catalyst is 1: 0.05 ‰ to 1: 1 ‰; And / or
In step (1) above, the molar ratio of HClSI to HF is 1: 1.4 to 1: 4; And / or
In the step (1), the reaction temperature of the reaction system is 90 to 110 占 폚.
In the step (1), HClSI and HF are reacted under catalysis to synthesize an intermediate HFSI, and HF and HCl gas in the reaction system are removed after completion of the reaction.
The method for removing HF and HCl gas in the reaction system is preferably a method in which distillation is carried out for the reaction system or blowing and distillation are carried out for the reaction system.
The temperature at the time of blowing is room temperature; And / or the distillation is a vacuum distillation.
In step (2), the molar ratio of HFSI to lithium in basic lithium is 1: 0.8 to 1: 1; And /
In the step (2), the reaction temperature of the reaction system is 0 to 20 占 폚; And / or
In step (2), SOCl 2 is added dropwise to the reaction system so that the bis-fluorosulfonylimide obtained in step (1) is reacted with basic lithium and the water in the reaction system is completely reacted after completion of the reaction. ≪ / RTI > and separating the lithium bisfluorosulfonylimide.
In the step (2), the LiFSI product obtained by reacting the bis-fluorosulfonylimide obtained in the step (1) with basic lithium, and solid-liquid separation after completion of the reaction is further subjected to pulverization treatment,
As a specific method of the pulverization treatment, LiFSI obtained by solid-liquid separation is added to a pulverizing solvent and a metal ion removing agent and pulverized to obtain a purified LiFSI product.
The pulverizing solvent is a low polarity solvent; And / or
The metal ion removing agent is at least one selected from the group consisting of 12-crown-4, 15-crown-5, 18-crown-6, and dicyclohexano- Lt; / RTI >
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| CN201510261089.1A CN104925765B (en) | 2015-05-21 | 2015-05-21 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
| PCT/CN2016/073420 WO2016184176A1 (en) | 2015-05-21 | 2016-02-04 | Preparation method for bis-(fluoro-sulfonyl) imide lithium salt |
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| CN104925765B (en) * | 2015-05-21 | 2017-08-08 | 上海康鹏科技有限公司 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
| JP2018535181A (en) * | 2015-11-13 | 2018-11-29 | ロンザ・リミテッド | Bis (fluorosulfonyl) -imide and process for preparing the salt |
| JP6873997B2 (en) * | 2015-12-04 | 2021-05-19 | エスイーエス ホールディングス ピーティーイー．エルティーディー． | Method for producing hydrogenbis (fluorosulfonyl) imide |
| CN105858626B (en) * | 2016-03-31 | 2017-02-08 | 南京远淑医药科技有限公司 | A preparing method of lithium bis(fluorosulfonyl)imide |
| CN105967159B (en) * | 2016-04-29 | 2018-06-01 | 南京远淑医药科技有限公司 | A kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine |
| CN105836719B (en) * | 2016-04-29 | 2018-06-01 | 南京远淑医药科技有限公司 | A kind of method for synthesizing imidodisulfuryl fluoride lithium salt using fragrant methyl amine |
| CN105731399B (en) * | 2016-04-29 | 2018-03-27 | 多氟多化工股份有限公司 | A kind of preparation method of double fluorine sulfimide lithiums |
| CN109311669B (en) * | 2016-05-26 | 2022-04-19 | 株式会社日本触媒 | Method for producing alkali metal salt of bis (fluorosulfonyl) imide, and alkali metal salt composition of bis (fluorosulfonyl) imide |
| CN106006586B (en) * | 2016-05-27 | 2018-10-19 | 上海康鹏科技有限公司 | A kind of preparation method of double fluorine sulfimide potassium |
| JP6663986B2 (en) * | 2016-05-27 | 2020-03-13 | 株式会社日本触媒 | Method for producing alkali metal bis (fluorosulfonyl) imide |
| CN106044728B (en) * | 2016-05-27 | 2018-07-27 | 上海康鹏科技有限公司 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
| DE102016209982A1 (en) * | 2016-06-07 | 2017-12-07 | Robert Bosch Gmbh | Hybrid supercapacitor with increased lifespan |
| CN106241757B (en) * | 2016-07-27 | 2018-09-18 | 上海康鹏科技有限公司 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
| FR3059993A1 (en) * | 2016-12-08 | 2018-06-15 | Arkema France | PROCESS FOR DRYING AND PURIFYING BIS (FLUOROSULFONYL) IMIDE LITHIUM SALT |
| CN106800280B (en) * | 2016-12-29 | 2018-11-27 | 衢州康鹏化学有限公司 | It is a kind of double（Fluorosulfonyl）The preparation method of inferior amine salt |
| KR101926856B1 (en) * | 2017-03-22 | 2018-12-10 | 제이투에이치바이오텍 (주) | Method for preparing extrapure fluorosulfonylimide with removing methallic cation |
| CN106976849B (en) * | 2017-04-20 | 2020-05-26 | 江苏国泰超威新材料有限公司 | Purification method of lithium bis (fluorosulfonyl) imide |
| CN107055493B (en) * | 2017-05-10 | 2019-02-26 | 浙江永太科技股份有限公司 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
| CN109264682B (en) * | 2017-07-18 | 2019-11-29 | 九江天赐高新材料有限公司 | A kind of preparation method of high-purity difluoro sulfimide |
| CN107662908A (en) * | 2017-10-27 | 2018-02-06 | 江苏理文化工有限公司 | A kind of preparation method of double fluorine sulfimide lithiums |
| CN108002355B (en) * | 2017-12-20 | 2019-10-22 | 厦门大学 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
| FR3081866B1 (en) | 2018-06-01 | 2020-05-08 | Arkema France | PROCESS FOR THE PREPARATION OF A SALT OF IMIDES CONTAINING A FLUOROSULFONYL GROUP |
| CN109264683B (en) * | 2018-10-16 | 2021-07-27 | 广州理文科技有限公司 | Method for extracting and purifying bis (fluorosulfonyl) imide |
| CN109592655B (en) * | 2019-01-17 | 2020-07-28 | 联化科技股份有限公司 | Method for efficiently preparing bis (fluorosulfonyl) imide through catalytic fluorination |
| CN109776362B (en) * | 2019-03-08 | 2022-02-15 | 如鲲(山东)新材料科技有限公司 | Novel process of bis (trifluorosulfonyl) imide salt |
| CN109721037B (en) * | 2019-03-11 | 2019-12-24 | 上海如鲲新材料有限公司 | Novel process of bis (fluorosulfonyl) imide salt |
| KR102259985B1 (en) * | 2019-03-28 | 2021-06-03 | 주식회사 천보 | Method for producing bis (fluorosulfonyl) imide lithium salt (LiFSI) with reduced fluorine anion content |
| KR102285464B1 (en) * | 2019-03-28 | 2021-08-03 | 주식회사 천보 | Method for producing bis (fluorosulfonyl) imide lithium salt (LiFSI) with reduced fluorine anion content |
| US11267707B2 (en) | 2019-04-16 | 2022-03-08 | Honeywell International Inc | Purification of bis(fluorosulfonyl) imide |
| FR3095439B1 (en) * | 2019-04-25 | 2021-04-02 | Arkema France | Process for the preparation of bis (fluorosulfonyl) imide |
| CN110155967A (en) * | 2019-06-18 | 2019-08-23 | 山东安博新材料研究院有限公司 | A kind of preparation method of double fluorine sulfimide lithiums |
| CN110407184B (en) * | 2019-08-27 | 2021-04-06 | 刘大凡 | Preparation method of bis (fluorosulfonyl) imide alkali metal salt |
| CN110745795B (en) * | 2019-11-07 | 2022-08-26 | 兰州大学 | Method for synthesizing lithium bis (fluorosulfonyl) imide by using electrochemistry |
| CN110697668B (en) | 2019-11-20 | 2021-08-06 | 上海如鲲新材料有限公司 | Preparation method of high-purity bis (fluorosulfonyl) imide salt |
| CN111057079A (en) * | 2019-12-16 | 2020-04-24 | 江苏华盛锂电材料股份有限公司 | Purification method of lithium bis (oxalato) borate and lithium bis (oxalato) borate |
| CN112978690B (en) * | 2019-12-18 | 2022-12-09 | 浙江蓝天环保高科技股份有限公司 | Water removal and screening method for powdery lithium bis (fluorosulfonyl) imide |
| CN111620315A (en) * | 2020-07-22 | 2020-09-04 | 上海华谊（集团）公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN112479165B (en) * | 2020-11-27 | 2023-08-08 | 湖北迈可凯科技有限公司 | Method for synthesizing lithium difluorosulfimide by one-step method |
| CN113104823A (en) * | 2021-03-26 | 2021-07-13 | 广州理文科技有限公司 | Synthesis method of bis (fluorosulfonyl) imide |
| KR20220156229A (en) | 2021-05-18 | 2022-11-25 | 임광민 | Mass Production Method of Metal bis(fluorosulfonyl)imide |
| CN113979454B (en) * | 2021-11-23 | 2023-09-26 | 山东永浩新材料科技有限公司 | Preparation method of alkali metal fluorosulfonate |
| US20230178804A1 (en) * | 2021-12-02 | 2023-06-08 | Honeywell International Inc. | Processes for producing lithium bis(fluorosulfonyl) imide |
| KR20230085823A (en) | 2021-12-07 | 2023-06-14 | 주식회사 이브이에스텍 | Economical Mass Production Method of Metal bis(fluorosulfonyl)imide solution |
| CN114436226A (en) * | 2021-12-30 | 2022-05-06 | 石家庄康坦福化工科技有限公司 | Preparation and application of potassium bis (fluorosulfonyl) imide |
| CN114560452B (en) * | 2022-03-29 | 2023-06-23 | 多氟多新材料股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN114804043A (en) * | 2022-05-17 | 2022-07-29 | 临沂小篆新材料科技有限公司 | Process for preparing lithium bis (fluorosulfonyl) imide |
| CN115448267B (en) * | 2022-09-19 | 2023-04-07 | 安徽新宸新材料有限公司 | Method for preparing lithium bis (fluorosulfonyl) imide |
| CN116022748B (en) * | 2022-12-16 | 2024-02-27 | 山东惟普新能源有限公司 | Water removal method for aqueous lithium bis (fluorosulfonyl) imide |
| CN115974015A (en) * | 2022-12-28 | 2023-04-18 | 无锡威孚环保催化剂有限公司 | Synthetic method of sodium bis (fluorosulfonyl) imide |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8377406B1 (en) * | 2012-08-29 | 2013-02-19 | Boulder Ionics Corporation | Synthesis of bis(fluorosulfonyl)imide |
| FR2998297B1 (en) * | 2012-11-22 | 2014-11-14 | Arkema France | PROCESS FOR PREPARING SALT OF IMIDES CONTAINING FLUOROSULFONYL GROUP |
| CN103910346B (en) * | 2013-01-05 | 2016-07-06 | 江苏华盛精化工股份有限公司 | Preparation method of difluoro lithium sulfimide |
| US8722005B1 (en) * | 2013-07-26 | 2014-05-13 | Boulder Ionics Corporation | Synthesis of hydrogen bis(fluorosulfonyl)imide |
| CN103935970A (en) * | 2014-03-24 | 2014-07-23 | 深圳新宙邦科技股份有限公司 | Preparation methods of bis(fluorosulfonyl)imide and alkali metal salts thereof |
| FR3020060B1 (en) * | 2014-04-18 | 2016-04-01 | Arkema France | PREPARATION OF IMIDES CONTAINING FLUOROSULFONYL GROUP |
| CN104495767B (en) * | 2014-11-21 | 2017-01-04 | 湖南博氟新材料科技有限公司 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
| JP6691740B2 (en) * | 2015-04-24 | 2020-05-13 | ステラケミファ株式会社 | Method for producing fluorosulfonylimide compound |
| CN104925765B (en) * | 2015-05-21 | 2017-08-08 | 上海康鹏科技有限公司 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
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