CN108373143A - A kind of dechlorination method of purification of double fluorine sulfimide lithiums - Google Patents
A kind of dechlorination method of purification of double fluorine sulfimide lithiums Download PDFInfo
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- CN108373143A CN108373143A CN201810242600.7A CN201810242600A CN108373143A CN 108373143 A CN108373143 A CN 108373143A CN 201810242600 A CN201810242600 A CN 201810242600A CN 108373143 A CN108373143 A CN 108373143A
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Abstract
The invention discloses a kind of dechlorination methods of purification of double fluorine sulfimide lithiums.Temperature for removing water in the present invention is relatively low, and using the deicer thionyl chloride with water response type, it can guarantee in removal process, what is generated is all gas and product can't be caused to occur to go bad, since dehydration reagent directly instead react with water by life, so the even molecular complex crystallization water, also can smoothly remove.After the present invention dissolves crude product with organic solvent, be adjusted to be more than 7 using anhydrous alkali being added by system pH, the anhydrous alkali for being conducive to being spin-dried for for system after removing acid, and using so that water will not be generated after reaction again, while again can effectively in removing system chlorine.
Description
Technical field
The invention belongs to electrochemical energy system technical fields, and in particular to a kind of dechlorination purification of double fluorine sulfimide lithiums
Method.
Background technology
Since nineteen nineties propose lithium-ion electric pool concept and realize its commercial applications, lithium ion battery
Basis and related application research be increasingly becoming internationalization electrochemical research one of hot spot.Double fluorine sulfimide lithiums have
The advantages (such as United States Patent (USP) US5916475) such as electrochemical stability is high, thermal stability is good, electric conductivity is high, corrosion rate is low, can be
It is generally used in electrolyte, there is good foreground in the application of lithium battery.
The method of domestic and international pairing fluorine sulfimide lithium in pairs has been reported that (such as United States Patent (USP) US4315935, Chinese patent more
Document CN103384641A, CN103347811A, CN101980955, CN101654229), prior art majority is first to be prepared into
It to double fluorine sulfimides, then using double fluorine sulfimides as raw material, is reacted with lithium carbonate or lithium hydroxide, double fluorine sulphurs is prepared
Imide li.But it is prepared with existing method, has by-product water generation, and double fluorine sulfimide lithiums easily absorb water so that most
Water or even double fluorine sulfimide lithiums can be contained in obtained crude product afterwards can be complexed a crystallization water so that product does not meet electricity
Pond uses standard.After double fluorine sulfimide lithiums absorb water, thermal stability can be deteriorated, unsuitable long-term preservation (such as Japan Patent
JP2013091524A), therefore generally require to carry out removing water process.But when double fluorine sulfimide lithiums are aqueous, pole at high temperature
It easily decomposes, therefore conventional physical method can not effectively remove moisture substantially, it is most at present to be occurred with water by the way that deicer is added
The mode of chemical reaction is removed water.
Thionyl chloride can directly be reacted with water, generate HCl and sulfur dioxide gas, and thionyl chloride property is more living
It sprinkles, high to water-sensitive sensitivity, good water removal effect is more common deicer.But the HCl meetings generated using thionyl chloride water removal
Chlorion in product is caused to have apparent residual.Likewise, using some other deicers to water sensitive, such as some acyls
The substance of chlorine, sulfonic acid chloride class equally has apparent Chloride residue although water removal effect is good.Residual chlorine ion is higher,
It can lead to the drastically decline of performance of lithium ion battery.
The related patents about double fluorine sulfimide lithiums are concentrated mainly on compound direction at present, used method of purification
The mode that mostly directly crude product is recrystallized, lack it is special remove chlorine process, frequently can lead in this way in product chlorine from
Sub- content fluctuation is big, and properties of product are unstable.Given this situation, the present invention propose it is a kind of it is relatively simple, effect is good removes for dechlorination
Chlorine method of purification.
Invention content
It is an object of the invention to overcome prior art defect, a kind of dechlorination purification side of double fluorine sulfimide lithiums is provided
Method.
Technical scheme is as follows：
A kind of dechlorination method of purification of double fluorine sulfimide lithiums, includes the following steps：
(1) the first small polar solvent of double fluorine sulfimide lithium crude products is disperseed, while deicer thionyl chloride is added 0
20~25h is stirred at~30 DEG C, is obtained precipitating after resulting material filtering and be washed again with the above-mentioned first small polar solvent, filtering is taken out
Do to obtain the first solid；
(2) solid of gained in step (1) is dissolved with organic solvent, anhydrous alkali is added and adjusts pH more than 7, is filtered to remove
Insoluble matter obtains filtrate；
(3) after being crystallized the filtrate obtained by step (2), the second solid is filtered to obtain, the second small pole of second solid
Property organic solvent washing, filters to obtain third solid；
(4) by can be to get double fluorine sulfimide lithiums after purification after above-mentioned third solid vacuum drying；
Moisture in above-mentioned small polar solvent is less than or equal to 10ppm.
In a preferred embodiment of the invention, the described first small polar solvent is dichloromethane, chloroform, two
At least one of chloroethanes, benzene, toluene, chlorobenzene, petroleum ether and n-hexane.
In a preferred embodiment of the invention, the anhydrous alkali is anhydrous ammonia, triethylamine, diethylamine, pyrrole
At least one of pyridine and tetramethylethylenediamine.
In a preferred embodiment of the invention, the described second small polar solvent is dichloromethane, dichloroethanes, three
At least one of chloromethanes, benzene, toluene, petroleum ether and n-hexane.
In a preferred embodiment of the invention, the organic solvent be ether, ethyl acetate, dimethyl carbonate,
At least one of methyl tertiary butyl ether(MTBE), butyl acetate, ethylene carbonate, n,N-Dimethylformamide and dimethyl sulfoxide (DMSO).
In a preferred embodiment of the invention, is appropriate dry toluene is added in the crystallization, in -17~-14 DEG C
20~25h of crystallisation by cooling.
It is further preferred that the crystallization is the appropriate dry toluene of addition, for 24 hours in -15 DEG C of crystallisation by cooling.
The beneficial effects of the invention are as follows：
1, the temperature for removing water in the present invention is relatively low, and using the deicer thionyl chloride with water response type, it is ensured that
In removal process, generation be all gas and that product can't be caused to occur is rotten, due to dehydration reagent directly with water is counter gives birth to
Reaction, so the even molecular complex crystallization water, also can smoothly remove.
2, after the present invention dissolves crude product with organic solvent, system pH is more than 7 using anhydrous alkali is added, is removed by acid
Be conducive to being spin-dried for for system afterwards, and the anhydrous alkali used so that after reacting water will not be generated again, while can effectively remove again
Chlorine in system.
3, the present invention is required except the cheap and dosage of chloride material anhydrous alkali is few when being dechlorinated, and is adopted
Detection method is also extremely simple, and pH tests are carried out to system.When pH is adjusted to be more than 7, the salt for the generation that dechlorinates can be direct
It is filtered to remove, and product is washed again after finally obtaining solid, can guarantee that dechlorination is complete, obtained product chlorinity
Extremely low and fluctuation is small, product purity height and stable quality.
4, the time is short, at low cost, the simple characteristic of operating procedure except chlorine process has by the present invention, is suitable for industrial production,
Double fluorine sulfimide lithium products that purity is high, chlorinity is low can efficiently be obtained.
Specific implementation mode
Technical scheme of the present invention is further detailed and is described below by way of specific implementation mode.
Embodiment 1
Double sulfuryl fluoride imines crude products 187g in total is added into the reaction bulb of 500mL, dichloromethane 300g in total is added, stirs
Mixing is mixed to disperse crude product.Weighing thionyl chloride, 150g is added in system in total, temperature is controlled at 30 DEG C hereinafter, in connection
Device for absorbing tail gas, tail gas are absorbed with sodium hydrate aqueous solution.After being stirred to react for 24 hours, the water in crude product is removed, then by body
System's filtering, obtains filter cake.
Obtained filter cake is transferred in the reaction bulb of 500mL, is washed and is filtered with the anhydrous methylene chloride of 200g, it will
Filter cake drains to obtain white solid.White solid is placed into the single-necked flask of 500mL, the total 150g of anhydrous ether, stirring is added
0.5h is dissolved, triethylamine is added, pHpH is adjusted to 7.4, be filtered to remove insoluble matter, obtain water white transparency filtrate, nothing is added into filtrate
Water-toluene 150g, crystallisation by cooling for 24 hours, is filtered and is washed, after vacuum drying with 100g dichloromethane in a low temperature of being placed into -15 DEG C
Solid is obtained, ultimate yield 85.3%, after testing, the purity of product is 99.87%, chloride ion content 23ppm.
Embodiment 2
Double sulfuryl fluoride imines crude products 187g in total is added into the reaction bulb of 500mL, dichloroethanes 300g in total is added, stirs
Mixing is mixed to disperse crude product.Weighing thionyl chloride, 150g is added in system in total, temperature is controlled at 30 DEG C hereinafter, in connection
Device for absorbing tail gas, tail gas are absorbed with sodium hydrate aqueous solution.After being stirred to react for 24 hours, the water in crude product is removed, then by body
System's filtering, obtains filter cake.
Obtained filter cake is transferred in the reaction bulb of 500mL, with the anhydrous hexane of 200g and is filtered, by filter cake
Drain to obtain white solid.White solid is placed into the single-necked flask of 500mL, the total 150g of anhydrous ether, stirring and dissolving is added
0.5h is added anhydrous pyridine and pH is adjusted to alkalinity 8, is filtered to remove insoluble matter, obtains water white transparency filtrate, be added into filtrate anhydrous
Toluene 150g, crystallisation by cooling for 24 hours, is filtered and is washed with 100g dichloroethanes, obtained after vacuum drying in a low temperature of being placed into -15 DEG C
Solid, ultimate yield 87.1%, after testing, the purity of product is 99.85%, chloride ion content 22ppm.
Embodiment 3
Double sulfuryl fluoride imines crude products 187g in total is added into the reaction bulb of 500mL, toluene 300g in total is added, stirring is mixed
Conjunction disperses crude product.Weighing thionyl chloride, 150g is added in system in total, temperature is controlled at 30 DEG C hereinafter, the upper tail gas of connection
Absorption plant, tail gas are absorbed with sodium hydrate aqueous solution.After being stirred to react for 24 hours, the water in crude product is removed, then by system mistake
Filter, obtains filter cake.
Obtained filter cake is transferred in the reaction bulb of 500mL, is washed and is filtered with the dry toluene of 200g, by filter cake
Drain to obtain white solid.White solid is placed into the single-necked flask of 500mL, the total 150g of anhydrous ether, stirring and dissolving is added
0.5h is passed through dry ammonia and pH is adjusted to alkalinity 12, is filtered to remove insoluble matter, obtains water white transparency filtrate, be added into filtrate
Dry toluene 150g, crystallisation by cooling for 24 hours, is filtered and is washed with 100g toluene, obtained after vacuum drying in a low temperature of being placed into -15 DEG C
Solid, ultimate yield 86.5%, after testing, the purity of product is 99.91%, chloride ion content 19ppm.
Embodiment 4
Double sulfuryl fluoride imines crude products 187g in total is added into the reaction bulb of 500mL, n-hexane 300g in total, stirring is added
Mixing disperses crude product.Weighing thionyl chloride, 150g is added in system in total, temperature is controlled at 30 DEG C hereinafter, the upper tail of connection
Aspiration receiving apparatus, tail gas are absorbed with sodium hydrate aqueous solution.After being stirred to react for 24 hours, the water in crude product is removed, then by system
Filtering, obtains filter cake.
Obtained filter cake is transferred in the reaction bulb of 500mL, is washed and is filtered with the anhydrous n-hexane of 200g, will filtered
Cake drains to obtain white solid.White solid is placed into the single-necked flask of 500mL, the total 150g of anhydrous ether is added, stirring is molten
0.5h is solved, diethylamine is added, pH is adjusted to alkalinity 7.6, be filtered to remove insoluble matter, obtain water white transparency filtrate, nothing is added into filtrate
Water-toluene 150g, crystallisation by cooling for 24 hours, is filtered and is washed with 100g n-hexanes, obtained after vacuum drying in a low temperature of being placed into -15 DEG C
Solid, ultimate yield 85.9%, after testing, the purity of product is 99.88%, chloride ion content 22ppm.
Embodiment 5
Double sulfuryl fluoride imines crude products 187g in total is added into the reaction bulb of 500mL, petroleum ether 300g in total, stirring is added
Mixing disperses crude product.Weighing thionyl chloride, 150g is added in system in total, temperature is controlled at 30 DEG C hereinafter, the upper tail of connection
Aspiration receiving apparatus, tail gas are absorbed with sodium hydrate aqueous solution.After being stirred to react for 24 hours, the water in crude product is removed, then by system
Filtering, obtains filter cake.
Obtained filter cake is transferred in the reaction bulb of 500mL, is washed and is filtered with the dry oil ether of 200g, will filtered
Cake drains to obtain white solid.White solid is placed into the single-necked flask of 500mL, the total 150g of anhydrous ether is added, stirring is molten
0.5h is solved, tetramethylethylenediamine is added, pH is adjusted to alkalinity 10, be filtered to remove insoluble matter, water white transparency filtrate obtained, into filtrate
Dry toluene 150g is added, crystallisation by cooling for 24 hours, is filtered and dried with 100g petroleum ethers, vacuum in a low temperature of being placed into -15 DEG C
Solid is obtained after dry, ultimate yield 86.1%, after testing, the purity of product is 99.90%, chloride ion content 23ppm.
The foregoing is only a preferred embodiment of the present invention, therefore cannot limit the scope of implementation of the present invention according to this, i.e.,
According to equivalent changes and modifications made by the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.
Claims (7)
1. a kind of dechlorination method of purification of double fluorine sulfimide lithiums, it is characterised in that：Include the following steps：
(1) the first small polar solvent of double fluorine sulfimide lithium crude products is disperseed, while deicer thionyl chloride is added 0~30
20~25h is stirred at DEG C, is obtained precipitating after resulting material filtering and be washed again with the above-mentioned first small polar solvent, filters, drains
First solid；
(2) solid of gained in step (1) is dissolved with organic solvent, anhydrous alkali is added and adjusts pH more than 7, is filtered to remove insoluble
Object obtains filtrate；
(3) after being crystallized the filtrate obtained by step (2), the second solid is filtered to obtain, which has with the second small polarity
Solvent is washed, and third solid is filtered to obtain；
(4) by can be to get double fluorine sulfimide lithiums after purification after above-mentioned third solid vacuum drying；
Moisture in above-mentioned small polar solvent is less than or equal to 10ppm.
2. dechlorination method of purification as described in claim 1, it is characterised in that：The first small polar solvent be dichloromethane,
At least one of chloroform, dichloroethanes, benzene, toluene, chlorobenzene, petroleum ether and n-hexane.
3. dechlorination method of purification as described in claim 1, it is characterised in that：The anhydrous alkali be anhydrous ammonia, triethylamine,
At least one of diethylamine, pyridine and tetramethylethylenediamine.
4. dechlorination method of purification as described in claim 1, it is characterised in that：The second small polar solvent be dichloromethane,
At least one of dichloroethanes, chloroform, benzene, toluene, petroleum ether and n-hexane.
5. dechlorination method of purification as described in claim 1, it is characterised in that：The organic solvent is ether, ethyl acetate, carbon
In dimethyl phthalate, methyl tertiary butyl ether(MTBE), butyl acetate, ethylene carbonate, n,N-Dimethylformamide and dimethyl sulfoxide (DMSO) extremely
Few one kind.
6. the dechlorination method of purification as described in any claim in Claims 1-4, it is characterised in that：The crystallization is to add
Enter appropriate dry toluene, in -17~-14 DEG C of 20~25h of crystallisation by cooling.
7. dechlorination method of purification as claimed in claim 5, it is characterised in that：The crystallization is the appropriate dry toluene of addition, in-
15 DEG C of crystallisation by cooling are for 24 hours.
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| CN201810242600.7A CN108373143B (en) | 2018-03-22 | 2018-03-22 | Dechlorination purification method of lithium bis (fluorosulfonyl) imide |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113912028A (en) * | 2021-11-30 | 2022-01-11 | 深圳鑫宸新能源科技有限公司 | Method for purifying bis (fluorosulfonyl) imide |
| 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 |
| CN115321498A (en) * | 2022-08-16 | 2022-11-11 | 浙江中硝康鹏化学有限公司 | Method for preparing lithium bis (fluorosulfonyl) imide from fluorosulfonic acid |
| CN116022748A (en) * | 2022-12-16 | 2023-04-28 | 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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| US20130323155A1 (en) * | 2011-03-03 | 2013-12-05 | Nippon Soda Co., Ltd. | Process for producing fluorine-containing sulfonylimide salt |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113912028A (en) * | 2021-11-30 | 2022-01-11 | 深圳鑫宸新能源科技有限公司 | Method for purifying bis (fluorosulfonyl) imide |
| 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 |
| CN115321498A (en) * | 2022-08-16 | 2022-11-11 | 浙江中硝康鹏化学有限公司 | Method for preparing lithium bis (fluorosulfonyl) imide from fluorosulfonic acid |
| CN115321498B (en) * | 2022-08-16 | 2024-04-30 | 浙江中硝康鹏化学有限公司 | Method for preparing lithium bis (fluorosulfonyl) imide by taking fluorosulfonic acid as raw material |
| CN116022748A (en) * | 2022-12-16 | 2023-04-28 | 山东惟普新能源有限公司 | Water removal method for aqueous 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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