CN108373143B - Dechlorination purification method of lithium bis (fluorosulfonyl) imide - Google Patents
Dechlorination purification method of lithium bis (fluorosulfonyl) imide Download PDFInfo
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- CN108373143B CN108373143B CN201810242600.7A CN201810242600A CN108373143B CN 108373143 B CN108373143 B CN 108373143B CN 201810242600 A CN201810242600 A CN 201810242600A CN 108373143 B CN108373143 B CN 108373143B
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Abstract
The invention discloses a dechlorination purification method of lithium bis (fluorosulfonyl) imide. The dehydration temperature in the invention is lower, and the water-reactive water scavenger thionyl chloride is adopted, so that the gas is generated in the dehydration process, the product is not deteriorated, and the dehydration reagent directly reacts with water, so that even molecular complex crystal water can be smoothly removed. According to the invention, after the crude product is dissolved by an organic solvent, the pH value of the system is adjusted to be more than 7 by adding anhydrous alkali, the spin-drying of the system is facilitated after the acid is removed, and the anhydrous alkali is adopted, so that water is not produced again after the reaction, and chlorine in the system can be effectively removed.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy systems, and particularly relates to a dechlorination purification method of lithium bis (fluorosulfonyl) imide.
Background
Since the concept of lithium ion batteries was proposed and commercialized in the nineties of the twentieth century, research on the basis of lithium ion batteries and related applications became one of the hot spots of international electrochemical research. The lithium bis (fluorosulfonyl) imide has the advantages of high electrochemical stability, good thermal stability, high conductivity, low corrosion rate and the like (for example, U.S. Pat. No. 5,5916475), can be generally used in electrolyte, and has good prospects in application of lithium batteries.
Many methods for synthesizing lithium bis (fluorosulfonyl) imide have been reported at home and abroad (for example, US4315935, chinese patent documents CN103384641A, CN103347811A, CN101980955, and CN101654229), and most of the prior art methods are to prepare bis (fluorosulfonyl) imide first, and then react bis (fluorosulfonyl) imide with lithium carbonate or lithium hydroxide to prepare lithium bis (fluorosulfonyl) imide. However, the product prepared by the existing method generates water as a byproduct, and the lithium bis (fluorosulfonyl) imide is very easy to absorb water, so that the finally obtained crude product contains water, and even the lithium bis (fluorosulfonyl) imide is complexed with crystal water, so that the product does not meet the use standard of the battery. When lithium bis (fluorosulfonyl) imide absorbs water, thermal stability is deteriorated and long-term storage is not preferable (e.g., Japanese patent JP2013091524A), and therefore water removal treatment is often required. However, when lithium bis (fluorosulfonyl) imide contains water, it is very easily decomposed at high temperature, so that conventional physical methods cannot remove water effectively basically, and most of the methods for removing water include a method of adding a water removing agent to react with water chemically.
Thionyl chloride can directly react with water to generate HCl and sulfur dioxide gas, and thionyl chloride is active, high in sensitivity to water and good in water removal effect, and is a common water removal agent. However, HCl generated by removing water with thionyl chloride causes obvious residue of chloride ions in the product. Similarly, some other water-sensitive water removing agents, such as some acyl chlorides and sulfonyl chlorides, are used, although the water removing effect is good, the obvious chloride ion residue is also generated. The high residual amount of chloride ions can lead to a sharp decrease in the performance of the lithium ion battery.
At present, related patents about lithium bis (fluorosulfonyl) imide are mainly focused on the synthesis direction, most of purification methods are methods for directly recrystallizing a crude product, and a special dechlorination process is lacked, so that the content of chloride ions in the product is large in fluctuation and the product performance is unstable. Under the circumstances, the invention provides a chlorine removal purification method which is simpler and has good chlorine removal effect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a dechlorination purification method of lithium bis (fluorosulfonyl) imide.
The technical scheme of the invention is as follows:
a dechlorination purification method of lithium bis (fluorosulfonyl) imide comprises the following steps:
(1) dispersing the crude product of the lithium bis (fluorosulfonyl) imide with a first small polar solvent, adding a water removing agent thionyl chloride, stirring at 0-30 ℃ for 20-25 h, filtering the obtained material to obtain a precipitate, washing the precipitate with the first small polar solvent, filtering, and draining to obtain a first solid;
(2) dissolving the solid obtained in the step (1) by using an organic solvent, adding anhydrous alkali to adjust the pH value to be more than 7, and filtering to remove insoluble substances to obtain filtrate;
(3) crystallizing the filtrate obtained in the step (2), filtering to obtain a second solid, washing the second solid with a second small polar organic solvent, and filtering to obtain a third solid;
(4) vacuum drying the third solid to obtain purified lithium bis (fluorosulfonyl) imide;
the water content in the small polar solvent is 10ppm or less.
In a preferred embodiment of the present invention, the first small polar solution is at least one of dichloromethane, chloroform, dichloroethane, benzene, toluene, chlorobenzene, petroleum ether and n-hexane.
In a preferred embodiment of the present invention, the anhydrous base is at least one of anhydrous ammonia gas, triethylamine, diethylamine, pyridine and tetramethylethylenediamine.
In a preferred embodiment of the present invention, the second small polar solution is at least one of dichloromethane, dichloroethane, chloroform, benzene, toluene, petroleum ether and n-hexane.
In a preferred embodiment of the present invention, the organic solvent is at least one of diethyl ether, ethyl acetate, dimethyl carbonate, methyl t-butyl ether, butyl acetate, ethylene carbonate, N-dimethylformamide, and dimethyl sulfoxide.
In a preferred embodiment of the invention, the crystallization is carried out by adding a proper amount of anhydrous toluene and cooling and crystallizing for 20-25 h at-17 to-14 ℃.
Further preferably, the crystallization is carried out by adding a proper amount of anhydrous toluene and cooling and crystallizing for 24 hours at-15 ℃.
The invention has the beneficial effects that:
1. the dehydration temperature in the invention is lower, and the water-reactive water scavenger thionyl chloride is adopted, so that the gas is generated in the dehydration process, the product is not deteriorated, and the dehydration reagent directly reacts with water, so that even molecular complex crystal water can be smoothly removed.
2. According to the invention, after the crude product is dissolved by an organic solvent, the pH value of the system is more than 7 by adding anhydrous alkali, the system is favorably dried after the acid is removed, and the anhydrous alkali is adopted, so that water is not produced again after the reaction, and chlorine in the system can be effectively removed.
3. When the method is used for dechlorinating, the needed dechlorinating substance anhydrous alkali is low in price and small in using amount, the adopted detection method is very simple, and the pH value of the system can be tested. When the pH value is adjusted to be more than 7, the salt generated by dechlorination can be directly filtered and removed, and the product is washed again after the solid is finally obtained, so that the dechlorination is completely ensured, the obtained product has extremely low chlorine content and small fluctuation, and the product has high purity and stable quality.
4. The dechlorination process has the characteristics of short time, low cost and simple operation steps, is suitable for industrial production, and can efficiently obtain the lithium bis (fluorosulfonyl) imide product with high purity and low chlorine content.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1
To a 500mL reaction flask, 187g in total of crude bissulfonylmonof luoride was added, 300g in total of methylene chloride was added, and the crude product was dispersed with stirring and mixing. Weighing total 150g of thionyl chloride, adding the thionyl chloride into the system, controlling the temperature below 30 ℃, connecting a tail gas absorption device, and absorbing the tail gas by using a sodium hydroxide aqueous solution. After stirring and reacting for 24h, removing water in the crude product, and then filtering the system to obtain a filter cake.
The resulting filter cake was transferred to a 500mL reaction flask, washed with 200g of anhydrous dichloromethane and filtered with suction, and the filter cake was dried with suction to give a white solid. Placing the white solid into a 500mL single-neck flask, adding 150g of anhydrous ether, stirring and dissolving for 0.5h, adding triethylamine to adjust the pH value to 7.4, filtering to remove insoluble substances to obtain colorless transparent filtrate, adding 150g of anhydrous toluene into the filtrate, placing the filtrate at the low temperature of-15 ℃ for cooling and crystallizing for 24h, filtering, washing with 100g of dichloromethane, and drying in vacuum to obtain the solid, wherein the final yield is 85.3%, the purity of the product is 99.87% and the chloride ion content is 23 ppm.
Example 2
To a 500mL reaction flask, 187g in total of crude bissulfonylmonof luoride was added, 300g in total of dichloroethane was added, and the crude product was dispersed with stirring and mixing. Weighing total 150g of thionyl chloride, adding the thionyl chloride into the system, controlling the temperature below 30 ℃, connecting a tail gas absorption device, and absorbing the tail gas by using a sodium hydroxide aqueous solution. After stirring and reacting for 24h, removing water in the crude product, and then filtering the system to obtain a filter cake.
The resulting filter cake was transferred to a 500mL reaction flask, washed with 200g of anhydrous ethane and filtered with suction, and the filter cake was dried with suction to give a white solid. Placing the white solid into a 500mL single-neck flask, adding 150g of anhydrous ether, stirring and dissolving for 0.5h, adding anhydrous pyridine to adjust the pH value to be alkaline 8, filtering to remove insoluble substances to obtain colorless transparent filtrate, adding 150g of anhydrous toluene into the filtrate, placing the filtrate at the low temperature of-15 ℃ for cooling and crystallizing for 24h, filtering, washing with 100g of dichloroethane, and drying in vacuum to obtain the solid, wherein the final yield is 87.1%, the purity of the product is 99.85% and the chloride ion content is 22ppm through detection.
Example 3
To a 500mL reaction flask, 187g in total of crude bissulfonylmonofimide and 300g in total of toluene were added, and the crude product was dispersed with stirring and mixing. Weighing total 150g of thionyl chloride, adding the thionyl chloride into the system, controlling the temperature below 30 ℃, connecting a tail gas absorption device, and absorbing the tail gas by using a sodium hydroxide aqueous solution. After stirring and reacting for 24h, removing water in the crude product, and then filtering the system to obtain a filter cake.
The resulting filter cake was transferred to a 500mL reaction flask, washed with 200g of anhydrous toluene and filtered with suction, and the filter cake was dried with suction to give a white solid. Placing the white solid into a 500mL single-neck flask, adding 150g of anhydrous ether, stirring and dissolving for 0.5h, introducing dry ammonia gas to adjust the pH value to be alkaline 12, filtering to remove insoluble substances to obtain colorless transparent filtrate, adding 150g of anhydrous toluene into the filtrate, placing the filtrate at the low temperature of-15 ℃ for cooling and crystallizing for 24h, filtering, washing with 100g of toluene, and drying in vacuum to obtain the solid, wherein the final yield is 86.5%, the purity of the product is 99.91% and the content of chloride ions is 19 ppm.
Example 4
To a 500mL reaction flask, a total of 187g of crude bissulfonylmonoimide was added, a total of 300g of n-hexane was added, and the crude was dispersed with stirring and mixing. Weighing total 150g of thionyl chloride, adding the thionyl chloride into the system, controlling the temperature below 30 ℃, connecting a tail gas absorption device, and absorbing the tail gas by using a sodium hydroxide aqueous solution. After stirring and reacting for 24h, removing water in the crude product, and then filtering the system to obtain a filter cake.
The obtained filter cake was transferred to a 500mL reaction flask, washed with 200g of anhydrous n-hexane and filtered with suction, and the filter cake was dried with suction to obtain a white solid. Placing the white solid into a 500mL single-neck flask, adding 150g of anhydrous ether, stirring and dissolving for 0.5h, adding diethylamine to adjust the pH value to be alkaline 7.6, filtering to remove insoluble substances to obtain colorless transparent filtrate, adding 150g of anhydrous toluene into the filtrate, placing the filtrate at the low temperature of-15 ℃ for cooling and crystallizing for 24h, filtering, washing with 100g of n-hexane, and drying in vacuum to obtain the solid, wherein the final yield is 85.9%, the purity of the product is 99.88% and the chloride ion content is 22 ppm.
Example 5
To a 500mL reaction flask, 187g in total of crude bissulfonylmonof luoride was added, 300g in total of petroleum ether was added, and the crude product was dispersed with stirring and mixing. Weighing total 150g of thionyl chloride, adding the thionyl chloride into the system, controlling the temperature below 30 ℃, connecting a tail gas absorption device, and absorbing the tail gas by using a sodium hydroxide aqueous solution. After stirring and reacting for 24h, removing water in the crude product, and then filtering the system to obtain a filter cake.
The resulting filter cake was transferred to a 500mL reaction flask, washed with 200g of anhydrous petroleum ether and filtered with suction, and the filter cake was dried with suction to give a white solid. Placing the white solid into a 500mL single-neck flask, adding 150g of anhydrous ether, stirring and dissolving for 0.5h, adding tetramethylethylenediamine to adjust the pH value to be alkaline 10, filtering to remove insoluble substances to obtain colorless transparent filtrate, adding 150g of anhydrous toluene into the filtrate, placing the filtrate at the low temperature of-15 ℃ for cooling and crystallizing for 24h, filtering, washing with 100g of petroleum ether, and drying in vacuum to obtain the solid, wherein the final yield is 86.1%, and the purity of the product is 99.90% and the content of chloride ions is 23ppm through detection.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (3)
1. A dechlorination purification method of lithium bis (fluorosulfonyl) imide is characterized by comprising the following steps: the method comprises the following steps:
(1) dispersing the crude product of the lithium bis (fluorosulfonyl) imide with a first small polar solvent, adding a water removing agent thionyl chloride, stirring at 0-30 ℃ for 20-25 h, filtering the obtained material to obtain a precipitate, washing the precipitate with the first small polar solvent, filtering, and draining to obtain a first solid; the first small polar solution is at least one of dichloromethane, trichloromethane, dichloroethane, benzene, toluene, chlorobenzene, petroleum ether and n-hexane;
(2) dissolving the solid obtained in the step (1) by using an organic solvent, adding anhydrous alkali to adjust the pH value to be more than 7, and filtering to remove insoluble substances to obtain filtrate; the anhydrous alkali is at least one of anhydrous ammonia gas, triethylamine, diethylamine, pyridine and tetramethyl ethylenediamine;
(3) crystallizing the filtrate obtained in the step (2), filtering to obtain a second solid, washing the second solid with a second small polar organic solvent, and filtering to obtain a third solid; the second small polar solution is at least one of dichloromethane, dichloroethane, chloroform, benzene, toluene, petroleum ether and n-hexane; adding a proper amount of anhydrous toluene into the crystals, and cooling and crystallizing the crystals for 20 to 25 hours at a temperature of between 17 ℃ below zero and 14 ℃ below zero;
(4) drying the third solid in vacuum to obtain purified lithium bis (fluorosulfonyl) imide;
the water content in the small polar solvent is 10ppm or less.
2. The dechlorination purification method according to claim 1, characterized in that: the organic solvent is at least one of diethyl ether, ethyl acetate, dimethyl carbonate, methyl tert-butyl ether, butyl acetate, ethylene carbonate, N-dimethylformamide and dimethyl sulfoxide.
3. The dechlorination purification method according to claim 1, characterized in that: the crystallization is to add a proper amount of anhydrous toluene and cool and crystallize for 24 hours at the temperature of minus 15 ℃.
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| CN110361339A (en) * | 2019-05-31 | 2019-10-22 | 衢州康鹏化学有限公司 | The detection method of chloride in imidodisulfuryl fluoride lithium 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 |
| 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 |
| CN113912028B (en) * | 2021-11-30 | 2024-01-26 | 安徽新宸新材料有限公司 | Method for purifying difluoro sulfimide |
| CN114852977A (en) * | 2022-05-06 | 2022-08-05 | 佳化化学科技发展（上海）有限公司 | Purification method of high-purity 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 |
| CN116143087A (en) * | 2022-12-30 | 2023-05-23 | 浙江研一新能源科技有限公司 | Preparation method of sodium bis (fluorosulfonyl) imide |
| CN116283671A (en) * | 2023-03-17 | 2023-06-23 | 浙江大学 | Preparation method of low-water-content lithium bis (trifluoromethanesulfonyl) imide |
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| CN105523530B (en) * | 2014-10-23 | 2018-09-07 | 浙江蓝天环保高科技股份有限公司 | A kind of preparation method of bis- (fluorine sulphonyl) imines potassium |
| 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 |
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