CN113135554A - Preparation method of lithium bis (fluorosulfonyl) imide - Google Patents
Preparation method of lithium bis (fluorosulfonyl) imide Download PDFInfo
- Publication number
- CN113135554A CN113135554A CN202110382664.9A CN202110382664A CN113135554A CN 113135554 A CN113135554 A CN 113135554A CN 202110382664 A CN202110382664 A CN 202110382664A CN 113135554 A CN113135554 A CN 113135554A
- Authority
- CN
- China
- Prior art keywords
- imide
- fluorosulfonyl
- bis
- lithium
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
Abstract
In order to overcome the problems of easy explosion of active lithium metal compounds, more product impurities and complex reaction water removal process existing in the existing preparation method of the lithium bis (fluorosulfonyl) imide, the invention provides a preparation method of the lithium bis (fluorosulfonyl) imide, which comprises the following operation steps: obtaining bis-fluorosulfonyl imide; mixing and reacting the bifluorosulfonyl imide and a basic lithium source in a non-aqueous solvent capable of forming an azeotrope with water, wherein the non-aqueous solvent is selected from chloroethanol, and filtering to obtain a crude solution of the bifluorosulfonyl imide lithium, and the basic lithium source comprises LiOH and LiHCO3And Li2CO3One or more of; decompressing and drying the crude lithium bis (fluorosulfonyl) imide solution in an environment with the vacuum degree of 1000-100 Pa and the temperature of 30-80 ℃, and reducing the vacuum degree to 10 when the product is pasty‑2Drying under Pa to obtain a crude product of the lithium bis (fluorosulfonyl) imide. The preparation method of the lithium bis (fluorosulfonyl) imide provided by the invention has the advantages that the reaction process is safe and controllable, and the separation process of water in the product is simplified.
Description
Technical Field
The invention belongs to the technical field of synthesis of lithium bis (fluorosulfonyl) imide, and particularly relates to a preparation method of lithium bis (fluorosulfonyl) imide.
Background
The lithium bis (fluorosulfonyl) imide is a key high-performance electrolyte material in new energy devices such as lithium ion batteries and supercapacitors, and has a very high industrial application value. The prior patent documents disclose that the preparation method of lithium bis (fluorosulfonyl) imide has certain defects.
For example, CN101747242A, the scientific and technical university of china, firstly, reacting sulfonamide with thionyl chloride and chlorosulfonic acid to obtain bis (chlorosulfonyl) imide, then reacting it with antimony trifluoride to obtain bis (fluorosulfonyl) imide, then reacting it with potassium carbonate (rubidium or cesium) to obtain potassium (rubidium or cesium) bis (fluorosulfonyl) imide salt, and finally performing a double decomposition exchange reaction with lithium (or sodium) perchlorate or lithium (or sodium) tetrafluoroborate in an aprotic polar solvent to obtain lithium (or sodium) bis (fluorosulfonyl) imide salt. The method reported in this patent suffers from the following problems: involving four chemical reactions and related purification steps, the process flow is too long; antimony fluoride, lithium perchlorate or lithium tetrafluoroborate and the like are relatively expensive, and the cost of raw materials is too high; the raw materials are consumed greatly and generate a large amount of wastes, including antimony trichloride, carbon dioxide, potassium perchlorate, organic solvent and the like; the product has more impurities, and is difficult to purify and meets the practical application standard.
In Shanghai Kangpeng chemical company CN 104925765A, firstly, bis (fluorosulfonyl) imide is obtained by reacting bis (chlorosulfonyl) imide with hydrogen fluoride, then, bis (fluorosulfonyl) imide is reacted with lithium hydroxide or lithium carbonate in a low-polarity solvent to generate lithium bis (fluorosulfonyl) imide, the product is subjected to water removal by adding thionyl chloride, then, solid-liquid separation is performed, and the solid product is further purified by pulping and the like. The problem that reactants and products are not soluble in a solvent exists in the method, so that the product yield can be greatly reduced, and thionyl chloride is used for removing water, so that the content of chloride ions in the products is high, and the requirement of a lithium battery on the content of the chloride ions in lithium salts is difficult to achieve.
In Shanghai Kangpeng chemical company CN 106044728A, firstly, bis (fluorosulfonyl) imide is obtained by reacting bis (chlorosulfonyl) imide with hydrogen fluoride, then, bis (fluorosulfonyl) imide is reacted with lithium metal, lithium hydride or lithium aminohydride in a non-aqueous polar solvent to generate lithium bis (fluorosulfonyl) imide and hydrogen or ammonia, and then, the product is obtained by directly drying the reaction product. Although the patent adopts lithium metal, lithium hydride or lithium ammonium hydride to carry out reaction so as to avoid the problem of generating water in the reaction process, the risk of the reaction is that the lithium metal, the lithium hydride or the lithium ammonium hydride are all extremely active metal compounds, the possibility of runaway explosion exists in the reaction process, and the generated hydrogen is flammable and explosive gas, so that great potential safety hazard is brought to production.
CN 106829892A applied by Wuhanhai Spulin science and technology development Limited company firstly reacts chlorosulfonic acid isocyanate with fluorosulfonic acid to obtain difluoride sulfimide, and then reacts with lithium carbonate in an aqueous solution system to generate the difluoride sulfimide lithium. The reaction has the problems that the bifluorosulfonyl imide is in contact with water and can be decomposed violently in an exothermic mode, so that the impurity content of the product is high, and the bifluorosulfonyl imide lithium has very good solubility in water, so that the product is difficult to dry.
U.S. Pat. No. 4, 2018/0141901, 1, issued to Lonza Ltd, U.S. Pat. No. 4,89, first, bis (fluorosulfonyl) imide is reacted with hydrogen fluoride to produce bis (fluorosulfonyl) imide, then the bis (fluorosulfonyl) imide is mixed with water and triethylamine, the pH value is adjusted, valeronitrile is added for extraction, the organic phase is washed with water and then ammonia water is added, the organic phase is collected and then reacted with the aqueous solution of lithium hydroxide, triethylamine is added as an acid-binding agent to obtain a lithium bis (fluorosulfonyl) imide/valeronitrile/triethylamine solution, and then the solution is dried under reduced pressure and purified to obtain a product. The patent has the problems that the reaction flow is too long, the waste is too much, the reaction is carried out in an aqueous solution system, and the industrialization is difficult.
As described above, the methods disclosed in the prior patent documents are often used to synthesize bischlorosulfimide (ret al, chem. Ber.1962,95,625; m.goehring et al, inorg.synth.1966,8,105; ruff, inorg. chem.1967,6,2108; m. berran et al, z.anorg. allg.chem.2005,631,55), followed by fluorination and lithiation to prepare lithium bis (fluorosulfonyl) imide. However, the methods reported in these patent documents generally have the problems of long production process flow, necessity of using an aqueous solution system for lithiation reaction or using an active lithium metal compound which is easily exploded and out of control, large consumption of raw materials, more generation of waste, low product yield, difficult purification and high production cost, and partially use Li2CO3In the production process of the alkaline lithium source, a water removing agent is additionally added to remove moisture generated in the reaction.
Disclosure of Invention
Aiming at the problems that active lithium metal compounds are easy to explode, product impurities are more and the process for removing reaction water is complex in the existing preparation method of lithium bis (fluorosulfonyl) imide, the invention provides a preparation method of lithium bis (fluorosulfonyl) imide.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a preparation method of lithium bis (fluorosulfonyl) imide, which comprises the following operation steps:
obtaining bis-fluorosulfonyl imide;
mixing and reacting the bifluorosulfonyl imide and a basic lithium source in a non-aqueous solvent capable of forming an azeotrope with water, wherein the non-aqueous solvent is selected from chloroethanol, and filtering to obtain a crude solution of the bifluorosulfonyl imide lithium, and the basic lithium source comprises LiOH and LiHCO3And Li2CO3One or more of;
decompressing and drying the crude lithium bis (fluorosulfonyl) imide solution in an environment with the vacuum degree of 1000-100 Pa and the temperature of 30-80 ℃, and reducing the vacuum degree to 10 when the product is pasty-2Drying under Pa to obtain a crude product of the lithium bis (fluorosulfonyl) imide.
In the preparation method of the lithium bis (fluorosulfonyl) imide provided by the invention, chloroethanol is adopted as a reaction environment, and LiOH and LiHCO are adopted simultaneously3And Li2CO3As a source of alkaline lithium and bifluorosulphonateThe imide reaction is safe and controllable in reaction process, the generation of side reaction products can be effectively reduced, and the yield of finished products is improved.
The method comprises the steps of dissolving water produced in the reaction process into chloroethanol in time to form an azeotrope, removing the azeotrope through subsequent decompression drying operation, decompressing and drying crude lithium bis (fluorosulfonyl) imide solution in an environment with the vacuum degree of 1000-100 Pa and the temperature of 30-80 ℃ based on the chloroethanol non-aqueous solvent adopted and the characteristics of subsequent removal of the azeotrope and a large amount of experimental results, and reducing the vacuum degree to 10 when the product is pasty-2Drying below Pa, and controlling drying conditions to prevent generated lithium bis (fluorosulfonyl) imide from being decomposed in the drying process to a certain extent, so as to quickly remove moisture on the premise of ensuring that the product is not decomposed, and controlling the moisture content in the crude lithium bis (fluorosulfonyl) imide to be less than or equal to 50ppm, so that the yield of the finished product and the content of the lithium bis (fluorosulfonyl) imide in the crude lithium bis (fluorosulfonyl) imide are improved, and the drying method does not need to additionally add a water removal agent for removing water, so that the separation process of the moisture in the product is greatly simplified.
Optionally, the operation of obtaining bis-fluorosulfonyl imide comprises:
adding sulfamic acid, thionyl chloride and chlorosulfonic acid into a reaction vessel for reaction, then carrying out reduced pressure distillation, and collecting the fraction of the dichlorosulfimide;
and introducing hydrogen fluoride gas into the obtained bis (chlorosulfonyl) imide, carrying out reduced pressure distillation on the liquid after reaction, and collecting the fraction of the bis (chlorosulfonyl) imide.
Optionally, chlorosulfonic acid isocyanate and chlorosulfonic acid are added into a reaction container for reaction, then reduced pressure distillation is carried out, and the fraction of the bischlorosulfonimide is collected;
and introducing hydrogen fluoride gas into the obtained bis (chlorosulfonyl) imide, carrying out reduced pressure distillation on the liquid after reaction, and collecting the fraction of the bis (chlorosulfonyl) imide.
Optionally, the water content of the bis-fluorosulfonyl imide, the water content of the alkaline lithium source, and the water content of the non-aqueous solvent are less than 10000 ppm.
Optionally, the mixing temperature of the bis-fluorosulfonyl imide, the alkaline lithium source and the non-aqueous solvent is-60 ℃ to 60 ℃, the reaction temperature is-20 ℃ to 50 ℃, and the reaction time is 2h to 48 h.
Alternatively, in the operation of carrying out mixed reaction of the bifluorosulfonimide and the basic lithium source in a non-aqueous solvent capable of forming an azeotrope with water,
firstly, mixing the bis-fluorosulfonyl imide with a non-aqueous solvent, and then adding the alkaline lithium source solid in batches;
or firstly mixing the alkaline lithium source solid with a non-aqueous solvent, and then dropwise adding the bis-fluorosulfonyl imide.
Optionally, the molar ratio of the lithium element in the bis-fluorosulfonyl imide and the alkaline lithium source is 1: 0.9-1: 2.
Optionally, the crude product of lithium bis (fluorosulfonyl) imide is dissolved in an aprotic solvent, then is subjected to adsorption and purification by an ionic resin, and is filtered to obtain a lithium bis (fluorosulfonyl) imide solution.
Optionally, the ionic resin is a polymer matrix grafted with one or more of primary amine, secondary amine and tertiary amine.
Optionally, drying the lithium bis (fluorosulfonyl) imide solution to remove the aprotic solvent to obtain solid lithium bis (fluorosulfonyl) imide.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of lithium bis (fluorosulfonyl) imide, which comprises the following operation steps:
obtaining bis-fluorosulfonyl imide;
mixing and reacting the bifluorosulfonyl imide and a basic lithium source in a non-aqueous solvent capable of forming an azeotrope with water, wherein the non-aqueous solvent is selected from chloroethanol, and filtering to obtain a crude solution of the bifluorosulfonyl imide lithium, and the basic lithium source comprises LiOH and LiHCO3And Li2CO3One or more of;
the fluorine is removedThe lithium sulfimide crude product solution is decompressed and dried under the environment that the vacuum degree is 1000 Pa-100 Pa and the temperature is 30 ℃ to 80 ℃, and when the product is pasty, the vacuum degree is reduced to 10-2Drying under Pa to obtain a crude product of the lithium bis (fluorosulfonyl) imide.
The bis-fluorosulfonylimide can be obtained by different reactions.
In one embodiment, the "obtaining bis-fluorosulfonylimide" operation comprises:
adding sulfamic acid, thionyl chloride and chlorosulfonic acid into a reaction vessel for reaction, then carrying out reduced pressure distillation, and collecting the fraction of the dichlorosulfonimide.
Specifically, sulfamic acid, thionyl chloride and chlorosulfonic acid are put into a reaction kettle at room temperature, the heating speed is controlled by controlling the gas generation speed, heat preservation is carried out for 24 hours at 130 ℃ after no gas is generated, then reduced pressure distillation is carried out, and a fraction at 95 ℃ below 650pa is collected, wherein the fraction is the bischlorosulfonimide.
The reaction chemical equation is as follows:
NH2SO3H+2SOCl2+ClSO3H→HN(SO2Cl)2+2SO2↑+3HCl↑
and introducing hydrogen fluoride gas into the obtained bis (chlorosulfonyl) imide, carrying out reduced pressure distillation on the liquid after reaction, and collecting the fraction of the bis (chlorosulfonyl) imide.
Specifically, bis-chlorosulfonyl imide is added into a Hastelloy high-pressure reaction kettle at 50 ℃, then hydrogen fluoride gas is added by a pressure pump, the molar ratio of HClSI to HF is 1:10, the temperature is raised to 80-110 ℃ for reaction, the hydrogen fluoride gas is liquefied and separated by a compressor after the gas after the reaction is discharged, and the hydrogen fluoride is recovered and continuously used for the fluorination reaction. And (3) carrying out reduced pressure distillation on the reacted liquid to collect a fraction at 58-60 ℃ under 600pa, wherein the fraction is the fraction of the bis (fluorosulfonyl) imide.
The reaction equation is as follows:
HN(SO2Cl)2+2HF→HN(SO2F)2+2HCl
in another embodiment, the "obtaining bis-fluorosulfonylimide" operation comprises:
adding chlorosulfonic acid isocyanate and chlorosulfonic acid into a reaction vessel for reaction, then carrying out reduced pressure distillation, and collecting the fraction of the bischlorosulfonimide.
Specifically, chlorosulfonic acid isocyanate and chlorosulfonic acid are put into a reaction kettle at room temperature, slowly heated to 110 ℃, reacted for 12 hours under slight reflux, then heated to 130 ℃, insulated for 24 hours, distilled under reduced pressure, and collected at 95 ℃ below 650pa, wherein the fraction is the bischlorosulfonimide.
The reaction equation is as follows:
ClSO2NCO+ClSO3H→(ClSO2)2NH+CO2↑
and introducing hydrogen fluoride gas into the obtained bis (chlorosulfonyl) imide, carrying out reduced pressure distillation on the liquid after reaction, and collecting the fraction of the bis (chlorosulfonyl) imide.
Specifically, bis-chlorosulfonyl imide is added into a Hastelloy high-pressure reaction kettle at 50 ℃, then hydrogen fluoride gas is added by a pressure pump, the molar ratio of HClSI to HF is 1:10, the temperature is raised to 80-110 ℃ for reaction, the hydrogen fluoride gas is liquefied and separated by a compressor after the gas after the reaction is discharged, and the hydrogen fluoride is recovered and continuously used for the fluorination reaction. And (3) carrying out reduced pressure distillation on the reacted liquid to collect a fraction at 58-60 ℃ under 600pa, wherein the fraction is the fraction of the bis (fluorosulfonyl) imide.
The reaction equation is as follows:
HN(SO2Cl)2+2HF→HN(SO2F)2+2HCl
in some embodiments, the water content of the bis-fluorosulfonylimide, the water content of the alkaline lithium source, and the water content of the non-aqueous solvent are less than 10000 ppm.
More preferably, the water content of the bis-fluorosulfonylimide, the water content of the basic lithium source, and the water content of the nonaqueous solvent are less than 5000 ppm.
Theoretically, the lesser the amount of moisture carried by the bis-fluorosulfonyl imide, the alkaline lithium source, and the non-aqueous solvent itself, the more favorable the reaction and subsequent removal of moisture.
In some embodiments, the mixing temperature of the bis-fluorosulfonyl imide, the alkaline lithium source and the non-aqueous solvent is-60 ℃ to 60 ℃, the reaction temperature is-20 ℃ to 50 ℃, and the reaction time is 2h to 48 h.
After the reaction is finished, the solid impurities are removed by filtering, the treatment can be one-stage or multi-stage filtering membrane treatment, and the aperture of the filtering membrane is 0.1 um-5 um, preferably 0.1 um-2 um.
In one embodiment, the "mixed reaction of bis-fluorosulfonylimide and basic lithium source in a non-aqueous solvent that can form an azeotrope with water" operation involves first mixing bis-fluorosulfonylimide with a non-aqueous solvent and then adding the basic lithium source solid in portions.
The temperature for mixing the bis-fluorosulfonyl imide and the non-aqueous solvent is-40 ℃ to 10 ℃, preferably-20 ℃ to-10 ℃, and the temperature of the solid alkaline lithium source fed-batch system is controlled to be-40 ℃ to 10 ℃, preferably-20 ℃ to 0 ℃; after the addition is finished, the reaction temperature is controlled to be-20-50 ℃, and preferably 20-30 ℃.
In another embodiment, the "mixed reaction of the bis-fluorosulfonylimide and the basic lithium source in a non-aqueous solvent that can form an azeotrope with water" operation is to mix the basic lithium source solid with the non-aqueous solvent and then add the bis-fluorosulfonylimide dropwise.
The temperature for mixing the solid alkaline lithium source and the non-aqueous solvent is-40 ℃ to 40 ℃, and the optimal temperature is-20 ℃ to 10 ℃; the temperature of the system in the dripping process of the bis (fluorosulfonyl) imide is controlled to be-40-20 ℃, and is preferably-20-5 ℃; the reaction temperature after the completion of the dropwise addition should be controlled at-20 ℃ to 50 ℃, preferably 20 ℃ to 30 ℃.
In some embodiments, the molar ratio of the lithium element in the bis-fluorosulfonyl imide and the basic lithium source is 1:0.9 to 1: 2.
The alkaline lithium source is selected from Li2CO3When bis (fluorosulfonyl) imide is used with Li2CO3The molar ratio of (A) to (B) is 1: 0.5-1: 1;
when the alkaline lithium source is LiOH, the molar ratio of the bis-fluorosulfonyl imide to the LiOH is 1: 1-1: 2;
the alkaline lithium source is selected from LiHCO3When bis (fluorosulfonyl) imide is used with LiHCO3In a molar ratio of 1:1 ℃1:2。
The boiling point of the blend of the non-aqueous solvent and the water can be reduced by reducing the pressure, so that the removal of the non-aqueous solvent and the moisture is facilitated, the drying temperature is controlled between 30 ℃ and 80 ℃, the moisture can be removed on the premise of ensuring that the product is not decomposed, and the moisture content in the crude product of the lithium bis (fluorosulfonyl) imide is controlled to be less than or equal to 50 ppm.
Further preferably, the drying temperature is 40 to 60 ℃.
In some embodiments, the obtained crude product of lithium bis (fluorosulfonyl) imide can be further purified, the crude product of lithium bis (fluorosulfonyl) imide is dissolved in an aprotic solvent, insoluble substances are precisely filtered, the purity of lithium bis (fluorosulfonyl) imide in the solution is detected, and the lithium bis (fluorosulfonyl) imide can be used as a lithium bis (fluorosulfonyl) imide solution after the detection is qualified.
If the detection is unqualified, the lithium bis (fluorosulfonyl) imide solution is obtained by adsorption and purification through ion resin and filtration.
The ionic resin is a polymer matrix grafted with one or more of primary amine, secondary amine and tertiary amine.
If the final product is a lithium bis (fluorosulfonyl) imide solution, the aprotic solvent includes one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and acetonitrile.
In the embodiment, the ionic resin is adopted to adsorb the ionic impurities in the lithium bis (fluorosulfonyl) imide solution, and compared with other existing purification modes, the ionic resin adsorption mode effectively improves the purity of the lithium bis (fluorosulfonyl) imide in the lithium bis (fluorosulfonyl) imide solution, so that the adverse effect of the ionic impurities in the lithium bis (fluorosulfonyl) imide on the application of the lithium bis (fluorosulfonyl) imide in a lithium ion battery or a capacitor is avoided, and meanwhile, the ionic resin adsorption mode can simplify the purification process.
In the process of adding the crude product of the lithium bis (fluorosulfonyl) imide into the aprotic solvent, the temperature of the system should be controlled at-10 ℃ to 10 ℃, and preferably at-10 ℃ to 5 ℃.
The filtration is one-stage or multi-stage filtration membrane treatment, and the aperture of the filtration membrane is 0.1 um-5 um, preferably 0.1 um-2 um.
In some embodiments, the lithium bis (fluorosulfonyl) imide solution obtained above is dried to remove the aprotic solvent to obtain solid lithium bis (fluorosulfonyl) imide.
Specifically, the lithium bis (fluorosulfonyl) imide solution is concentrated and dried under reduced pressure, and the vacuum degree is less than or equal to 10-2Pa, the temperature of the drying system is 30-80 ℃, and preferably 40-60 ℃.
If the final product is solid lithium bis (fluorosulfonyl) imide, the aprotic solvent includes one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, acetonitrile, ethanol, diethyl ether, acetone, ethyl acetate, butyl acetate, ethylene glycol dimethyl ether, toluene, and dichloromethane.
The present invention will be further illustrated by the following examples.
Adding sulfamic acid, thionyl chloride and chlorosulfonic acid into a reaction kettle at room temperature, controlling the heating speed by controlling the gas generation speed, keeping the temperature at 130 ℃ for 24 hours after no gas is generated, then carrying out reduced pressure distillation, and collecting the fraction at 95 ℃ below 650pa, wherein the fraction is the bischlorosulfonimide.
Adding bis (chlorosulfonyl) imide into a Hastelloy high-pressure reaction kettle at 50 ℃, then adding hydrogen fluoride gas by using a pressure pump, wherein the molar ratio of HClSI to HF is 1:10, heating to 80-110 ℃ for reaction, discharging the gas after the reaction, liquefying and separating the hydrogen fluoride gas by using a compressor, and recovering the hydrogen fluoride for further use in the fluorination reaction. And (3) carrying out reduced pressure distillation on the reacted liquid to collect a fraction at 58-60 ℃ under 600pa, wherein the fraction is the fraction of the bis (fluorosulfonyl) imide.
The prepared bis (fluorosulfonyl) imide (HFSI) is used for the preparation of lithium bis (fluorosulfonyl) imide in examples 1-2.
Example 1
This example is used to illustrate a method for preparing lithium bis (fluorosulfonyl) imide disclosed in the present invention, which includes the following steps:
under the protection of nitrogen and with stirring, 402.5g of anhydrous chloroethanol (5mol) and 40.7g of anhydrous lithium carbonate (0.55mol) were added into a dry 1L three-necked flask, and an ice bath was started to cool the system to-20 ℃. To a dry, constant pressure dropping funnel under nitrogen blanket was added 181g of HFSI (1mol) and then to a three-necked flaskThe dripping speed is controlled, and the internal temperature of the system is kept to be less than or equal to-10 ℃. After the dropwise addition, the mixture is continuously stirred for 2 hours at the temperature of minus 10 ℃, and then the temperature is slowly increased to 25 ℃ for continuous reaction for 4 hours. Filtering, drying under reduced pressure at 50 deg.C with vacuum degree of 1000Pa, and drying under high vacuum degree of 10 or less when the product is pasty-2Pa, 184g of crude product of lithium bis (fluorosulfonyl) imide is obtained.
The obtained crude product of lithium bis (fluorosulfonyl) imide was detected to have a moisture content of 23ppm and a yield of 98.39%. The major content of IC detection is 98.56%.
Example 2
This example is used to illustrate a method for preparing lithium bis (fluorosulfonyl) imide disclosed in the present invention, which includes the following steps:
under the protection of nitrogen and with stirring, 402.5g of anhydrous chloroethanol (5mol) and 44.4g of anhydrous lithium carbonate (0.60mol) were added into a dry 1L three-necked flask, and an ice bath was started to cool the system to-20 ℃. Under the protection of nitrogen, 181g HFSI (1mol) is added into a dry constant pressure dropping funnel, and then is dropped into a three-necked bottle, the dropping speed is controlled, and the internal temperature of a system is maintained to be less than-10 ℃. After the dropwise addition, the mixture is continuously stirred for 2 hours at the temperature of minus 10 ℃, and then the temperature is slowly increased to 25 ℃ for continuous reaction for 4 hours. Filtering, drying under reduced pressure at 50 deg.C with vacuum degree of 1000Pa, and drying under high vacuum degree of 10 or less when the product is pasty-2Pa, obtaining 183g of crude product of the lithium bis (fluorosulfonyl) imide.
The obtained crude product of lithium bis (fluorosulfonyl) imide is detected, and the water content is 21ppm, and the yield is 97.86%. The IC detection main content is 98.50%.
From the test results of the above examples 1-2, it can be seen that the preparation method of lithium bis (fluorosulfonyl) imide provided by the present invention simplifies the water removal process, can effectively control the water content of the crude lithium bis (fluorosulfonyl) imide to be less than 50ppm, and simultaneously improves the yield and the main content.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the lithium bis (fluorosulfonyl) imide is characterized by comprising the following operation steps:
obtaining bis-fluorosulfonyl imide;
mixing and reacting the bifluorosulfonyl imide and a basic lithium source in a non-aqueous solvent capable of forming an azeotrope with water, wherein the non-aqueous solvent is selected from chloroethanol, and filtering to obtain a crude solution of the bifluorosulfonyl imide lithium, and the basic lithium source comprises LiOH and LiHCO3And Li2CO3One or more of;
decompressing and drying the crude lithium bis (fluorosulfonyl) imide solution in an environment with the vacuum degree of 1000-100 Pa and the temperature of 30-80 ℃, and reducing the vacuum degree to 10 when the product is pasty-2Drying under Pa to obtain a crude product of the lithium bis (fluorosulfonyl) imide.
2. The method for preparing lithium bis (fluorosulfonyl) imide according to claim 1, wherein said operation of obtaining bis (fluorosulfonyl) imide comprises:
adding sulfamic acid, thionyl chloride and chlorosulfonic acid into a reaction vessel for reaction, then carrying out reduced pressure distillation, and collecting the fraction of the dichlorosulfimide;
and introducing hydrogen fluoride gas into the obtained bis (chlorosulfonyl) imide, carrying out reduced pressure distillation on the liquid after reaction, and collecting the fraction of the bis (chlorosulfonyl) imide.
3. The method for preparing lithium bis (fluorosulfonyl) imide according to claim 1, wherein said operation of obtaining bis (fluorosulfonyl) imide comprises:
adding chlorosulfonic acid isocyanate and chlorosulfonic acid into a reaction container for reaction, then carrying out reduced pressure distillation, and collecting the fraction of the dichlorosulfonimide;
and introducing hydrogen fluoride gas into the obtained bis (chlorosulfonyl) imide, carrying out reduced pressure distillation on the liquid after reaction, and collecting the fraction of the bis (chlorosulfonyl) imide.
4. The method for producing lithium bis (fluorosulfonyl) imide according to claim 1, wherein the water content of bis (fluorosulfonyl) imide, the water content of alkaline lithium source and the water content of nonaqueous solvent are less than 10000 ppm.
5. The method for preparing lithium bis (fluorosulfonyl) imide according to claim 1, wherein the mixing temperature of said bis (fluorosulfonyl) imide, said alkaline lithium source and said non-aqueous solvent is-60 ℃ to 60 ℃, the reaction temperature is-20 ℃ to 50 ℃, and the reaction time is 2h to 48 h.
6. The method for producing lithium bis (fluorosulfonyl) imide according to claim 1, wherein said "mixed reaction of bis (fluorosulfonyl) imide and a basic lithium source in a non-aqueous solvent capable of forming an azeotrope with water",
firstly, mixing the bis-fluorosulfonyl imide with a non-aqueous solvent, and then adding the alkaline lithium source solid in batches;
or firstly mixing the alkaline lithium source solid with a non-aqueous solvent, and then dropwise adding the bis-fluorosulfonyl imide.
7. The method for preparing lithium bis (fluorosulfonyl) imide according to claim 1, wherein the molar ratio of lithium element in said lithium bis (fluorosulfonyl) imide to said basic lithium source is 1: 0.9-1: 2.
8. The preparation method of lithium bis (fluorosulfonyl) imide according to claim 1, wherein crude lithium bis (fluorosulfonyl) imide is dissolved in an aprotic solvent, then purified by adsorption on an ionic resin, and filtered to obtain a lithium bis (fluorosulfonyl) imide solution.
9. The method for preparing lithium bis (fluorosulfonyl) imide according to claim 8, wherein said ionic resin is a polymer matrix grafted with one or more of primary amine, secondary amine, and tertiary amine.
10. The method for preparing lithium bis (fluorosulfonyl) imide according to claim 8, wherein the solution of lithium bis (fluorosulfonyl) imide is dried to remove the aprotic solvent, thereby obtaining solid lithium bis (fluorosulfonyl) imide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110382664.9A CN113135554A (en) | 2019-02-14 | 2019-02-14 | Preparation method of lithium bis (fluorosulfonyl) imide |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910113983.2A CN109734061A (en) | 2019-02-14 | 2019-02-14 | A kind of preparation method of double fluorine sulfimide lithiums |
| CN202110382664.9A CN113135554A (en) | 2019-02-14 | 2019-02-14 | Preparation method of lithium bis (fluorosulfonyl) imide |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910113983.2A Division CN109734061A (en) | 2019-02-14 | 2019-02-14 | A kind of preparation method of double fluorine sulfimide lithiums |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113135554A true CN113135554A (en) | 2021-07-20 |
Family
ID=66367381
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110382664.9A Pending CN113135554A (en) | 2019-02-14 | 2019-02-14 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN201910113983.2A Pending CN109734061A (en) | 2019-02-14 | 2019-02-14 | A kind of preparation method of double fluorine sulfimide lithiums |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910113983.2A Pending CN109734061A (en) | 2019-02-14 | 2019-02-14 | A kind of preparation method of double fluorine sulfimide lithiums |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN113135554A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114560452A (en) * | 2022-03-29 | 2022-05-31 | 多氟多新材料股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN114590785A (en) * | 2022-04-18 | 2022-06-07 | 湖北万润新能源科技股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide and lithium ion battery |
| CN114604832A (en) * | 2022-03-19 | 2022-06-10 | 珠海市赛纬电子材料股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide and application of lithium bis (fluorosulfonyl) imide |
| CN114873571A (en) * | 2022-06-28 | 2022-08-09 | 河南省氟基新材料科技有限公司 | Preparation method of bis (fluorosulfonyl) imide salt |
| CN115159479A (en) * | 2022-08-11 | 2022-10-11 | 衢州市九洲化工有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN115490619A (en) * | 2022-09-02 | 2022-12-20 | 衢州市九洲化工有限公司 | Preparation method of bis (trifluoromethylsulfonyl) imide salt |
| CN116462166A (en) * | 2023-03-03 | 2023-07-21 | 山东惟普新能源有限公司 | Method for removing water in lithium bis (fluorosulfonyl) imide synthesis process |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110436424A (en) * | 2019-07-04 | 2019-11-12 | 湖南福邦新材料有限公司 | A kind of preparation method of double fluorine sulfimides and double fluorine sulfimide lithiums |
| 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 |
| CN112978689B (en) * | 2019-12-18 | 2022-05-24 | 浙江蓝天环保高科技股份有限公司 | Continuous preparation method of bis (fluorosulfonyl) imide |
| CN111547689A (en) * | 2020-04-26 | 2020-08-18 | 广州理文科技有限公司 | Chemical drying and purifying method of diimine lithium |
| CN113511639B (en) * | 2021-06-17 | 2023-03-14 | 深圳市研一新材料有限责任公司 | Lithium bis (fluorosulfonyl) imide and preparation method and application thereof |
| CN115611245B (en) * | 2021-07-13 | 2024-02-02 | 湖南福邦新材料有限公司 | Preparation method of dichloro sulfonyl imide acid and difluoro sulfonyl imide lithium |
| CN115611244B (en) * | 2021-07-14 | 2024-02-02 | 湖南福邦新材料有限公司 | Preparation method of alkali metal salt of dichloro-sulfonyl imide and alkali metal salt of difluoro-sulfonyl imide |
| WO2023025776A1 (en) | 2021-08-27 | 2023-03-02 | Solvay Sa | Reactive distillation process for preparing fluorosulfonylimide salts |
| CN113800485B (en) * | 2021-09-18 | 2023-05-02 | 多氟多新材料股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| WO2023142025A1 (en) * | 2022-01-29 | 2023-08-03 | 宁德时代新能源科技股份有限公司 | Lithium bis(fluorosulfonyl)imide, method for preparing same, electrolyte, and secondary battery |
| CN114572945A (en) * | 2022-04-18 | 2022-06-03 | 湖北万润新能源科技股份有限公司 | Preparation method and application of sodium bis (fluorosulfonyl) imide |
| CN115818591A (en) * | 2022-06-16 | 2023-03-21 | 时代思康新材料有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN115367718B (en) * | 2022-08-31 | 2023-03-24 | 安徽新宸新材料有限公司 | Purification method of lithium bis (fluorosulfonyl) imide |
| CN115677543B (en) * | 2022-10-14 | 2023-10-20 | 衢州市九洲化工有限公司 | Synthesis method of (difluoromethyl sulfonyl) (trifluoro methylsulfonyl) lithium imine |
| CN115744844B (en) * | 2022-10-31 | 2024-01-09 | 浙江巨化技术中心有限公司 | Preparation method of sulfonyl lithium salt |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105731399A (en) * | 2016-04-29 | 2016-07-06 | 多氟多化工股份有限公司 | Preparation method of difluoro-sulfonyl imide lithium |
| CN106006586A (en) * | 2016-05-27 | 2016-10-12 | 上海康鹏科技有限公司 | Preparation method of potassium bis(fluorosulfonyl)imide |
| CN106365132A (en) * | 2016-08-31 | 2017-02-01 | 中国船舶重工集团公司第七八研究所 | Preparation method of difluoro-sulfimide and lithium difluoro-sulfimide |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP3090984A1 (en) * | 2015-05-07 | 2016-11-09 | Lonza Ltd | Method for preparation of the salts of certain amines and bis(fluorosulfonyl)-imide |
| CN110870125A (en) * | 2017-01-31 | 2020-03-06 | 塞斯欧化学制品有限公司 | Method for producing hygroscopic alkali metal salt electrolyte solution |
| CN107188138B (en) * | 2017-05-02 | 2019-05-14 | 惠州市大道新材料科技有限公司 | A kind of preparation method of double fluorine sulfimide lithiums |
| CN107215853B (en) * | 2017-07-20 | 2019-08-06 | 苏州华一新能源科技有限公司 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
| CN108946686A (en) * | 2018-07-31 | 2018-12-07 | 九江天赐高新材料有限公司 | A kind of preparation method of double fluorine sulfimide lithiums |
-
2019
- 2019-02-14 CN CN202110382664.9A patent/CN113135554A/en active Pending
- 2019-02-14 CN CN201910113983.2A patent/CN109734061A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105731399A (en) * | 2016-04-29 | 2016-07-06 | 多氟多化工股份有限公司 | Preparation method of difluoro-sulfonyl imide lithium |
| CN106006586A (en) * | 2016-05-27 | 2016-10-12 | 上海康鹏科技有限公司 | Preparation method of potassium bis(fluorosulfonyl)imide |
| CN106365132A (en) * | 2016-08-31 | 2017-02-01 | 中国船舶重工集团公司第七八研究所 | Preparation method of difluoro-sulfimide and lithium difluoro-sulfimide |
Non-Patent Citations (1)
| Title |
|---|
| 金懋昌, 东南大学出版社 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114604832A (en) * | 2022-03-19 | 2022-06-10 | 珠海市赛纬电子材料股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide and application of lithium bis (fluorosulfonyl) imide |
| CN114560452A (en) * | 2022-03-29 | 2022-05-31 | 多氟多新材料股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN114590785A (en) * | 2022-04-18 | 2022-06-07 | 湖北万润新能源科技股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide and lithium ion battery |
| CN114590785B (en) * | 2022-04-18 | 2023-01-06 | 湖北万润新能源科技股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide and lithium ion battery |
| CN114873571A (en) * | 2022-06-28 | 2022-08-09 | 河南省氟基新材料科技有限公司 | Preparation method of bis (fluorosulfonyl) imide salt |
| CN114873571B (en) * | 2022-06-28 | 2023-11-21 | 河南省氟基新材料科技有限公司 | Preparation method of difluoro sulfonyl imide salt |
| CN115159479A (en) * | 2022-08-11 | 2022-10-11 | 衢州市九洲化工有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN115159479B (en) * | 2022-08-11 | 2024-01-30 | 衢州市九洲化工有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN115490619A (en) * | 2022-09-02 | 2022-12-20 | 衢州市九洲化工有限公司 | Preparation method of bis (trifluoromethylsulfonyl) imide salt |
| CN115490619B (en) * | 2022-09-02 | 2023-08-18 | 衢州市九洲化工有限公司 | Preparation method of bis (trifluoromethyl sulfonyl) imide salt |
| CN116462166A (en) * | 2023-03-03 | 2023-07-21 | 山东惟普新能源有限公司 | Method for removing water in lithium bis (fluorosulfonyl) imide synthesis process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109734061A (en) | 2019-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113135554A (en) | Preparation method of lithium bis (fluorosulfonyl) imide | |
| CN106044728B (en) | A kind of preparation method of imidodisulfuryl fluoride lithium salt | |
| CN105731399B (en) | A kind of preparation method of double fluorine sulfimide lithiums | |
| CN113511639B (en) | Lithium bis (fluorosulfonyl) imide and preparation method and application thereof | |
| CN104495767A (en) | Preparation method of lithium bis(fluorosulfonyl)amide | |
| WO2015143866A1 (en) | Preparation method for bis-fluorosulfonyl imide and alkali metal salts thereof | |
| WO2016184176A1 (en) | Preparation method for bis-(fluoro-sulfonyl) imide lithium salt | |
| CN107986248B (en) | Preparation method of bis (fluorosulfonyl) imide | |
| CN106276829B (en) | A kind of synthetic method of double fluorine sulfimide lithiums | |
| CN107720717B (en) | Preparation method of lithium difluorophosphate | |
| KR102036924B1 (en) | Method for producing alkali metal hexafluorophosphate, alkali metal hexafluorophosphate, method for producing electrolyte concentrate comprising alkali metal hexafluorophosphate, and method for producing secondary battery | |
| CN108155434B (en) | Method for recovering lithium from waste electrolyte of lithium ion battery | |
| CN107033119A (en) | A kind of preparation method of high-purity fluorinated ethylene carbonate | |
| CN112707418B (en) | Preparation method of lithium hexafluorophosphate | |
| CN113800485B (en) | Preparation method of lithium bis (fluorosulfonyl) imide | |
| CN114506829A (en) | Preparation method of lithium bis (fluorosulfonyl) imide | |
| SG177287A1 (en) | Method for producing tetrafluoroborate | |
| CN105859760A (en) | A synthetic method of electronic grade lithium difluoro(oxalato)borate | |
| CN110921640A (en) | Preparation method of lithium bis (fluorosulfonyl) imide | |
| CN111989295A (en) | Production of lithium hexafluorophosphate | |
| CN115231531A (en) | Method and system for continuously synthesizing lithium bis (fluorosulfonyl) imide by using microreactor | |
| CN115676855B (en) | Preparation method of sodium ion battery electrolyte sodium salt | |
| JP5151121B2 (en) | Method for producing electrolytic solution for lithium ion battery and lithium ion battery using the same | |
| CN109369474B (en) | Preparation method of lithium bis (trifluoromethylsulfonyl) imide | |
| CN115872370A (en) | Preparation method of bis (fluorosulfonyl) imide and bis (fluorosulfonyl) imide salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210720 |