CN106276829B - A kind of synthetic method of double fluorine sulfimide lithiums - Google Patents
A kind of synthetic method of double fluorine sulfimide lithiums Download PDFInfo
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Abstract
The present invention, which provides, synthesizes a kind of method of double fluorine sulfimide lithiums, and steps are as follows：A kind of synthetic method of double fluorine sulfimide lithiums, which is characterized in that synthetic method includes the following steps：1）In nitrogen atmosphere, after double chlorine sulfimides and organic solvent are sufficiently mixed in reactor of the merging with condenser, then to lithium fluoride is sequentially added in reactor, liquid hydrogen fluoride heating is reacted；2）It reduces temperature of reaction system and removes remaining hydrogen fluoride gas completely with nitrogen decompression displacement, and filtering reacting liquid removing insoluble matter obtains filtrate under nitrogen atmosphere；3）Filtrate is concentrated 4 using high vacuum decompression precipitation method）Weak polar solvent low temperature recrystallization is added after concentrate is cooled down, it filters and obtains pure double fluorine sulfimide lithiums after being dried under reduced pressure processing at 40 DEG C, the present invention is cheap and easy to get using reagent, preparation process is simple, it is swift in response and thoroughly, by-product it is few and it is easy remove, post processing mode it is easy, product purity is high, is very suitable for industrialized production.
Description
Technical field
The invention belongs to the field of chemical synthesis, and in particular to a kind of synthetic method of double fluorine sulfimide lithiums.
Background technology
Double fluorine sulfimide lithiums have that stability high and low temperature is had excellent performance, hydrolytic stability is good and more environment-friendly etc. excellent
Point can be used as excellent serondary lithium battery electrolyte, simultaneously because it, with excellent electric conductivity, can be used for ultracapacitor
And aluminium electrolutic capacitor etc.；Lewis acid catalyst use is also acted as, there is important industrial production value.
In the prior art, mainly there is following report for the preparation of bis- (fluorine sulphonyl) imine lithiums:
Chinese CN101747242 reports the preparation method of bis- (fluorine sulphonyl) imine lithiums, by amino under the protection of nitrogen
It is double that sulfonic acid, thionyl chloride, chlorosulfonic acid carry out reaction generation（Chlorine sulphonyl）Imines, yield 82%；It again will be double（Chlorine sulphonyl）Imines exists
It is double with anhydrous antimony trifluoride, acetonitrile reaction generation under nitrogen protection（Fluorine sulphonyl）Imines potassium, yield 78%；Then by 91.5 grams
Bis- (fluorine sulphonyl) imines potassium of (- 0.42mol) are reacted with the second eyeball solution 150ml (containing 36.2 grams of lithium perchlorates) of lithium perchlorate,
62 grams (0.33mol) bis- (fluorine sulphonyl) imine lithiums, yield 79%, final products total recovery are obtained after recrystallizing, drying
50.5%.The method must operate in vacuum tank, of high cost, and the yield of bis- (fluorine sulphonyl) imine lithiums is only（50.5%）, raw material is easy
It is dissolved in organic solvent, bis- (fluorine sulphonyl) imine lithiums of high-purity can not be obtained.
The patent application that Chinese Patent Application No. is 201280010507.4 discloses a kind of system of fluorine-containing sulfimide salt
Method is made, the manufacturing method is by making N, fluorine-containing sulfimide ammonium salt and the hydroxide such as N- bis- (fluorosulfonyl) imines ammonium salt
Under reduced pressure, 40 DEG C or so of low temperature is reacted the alkali metal hydroxides such as lithium, potassium hydroxide, sodium hydroxide, obtains N, N-
Two (fluorosulfonyl) imines lithium salts, N, N- bis- (fluorine sulphur lithium base) imide, N, N- bis- (fluorine sulfonephthalein base) imines sodium salt etc. are fluorine-containing
Sulfonephthalein imine alkali metal salt.But the manufacturing method, there are the defect that raw material is difficult to obtain, reaction process generates a large amount of
Heat, product have the possibility thermally decomposed, are not suitable for industrialized production.
The preparation method of bis- (fluorine sulphonyl) imine lithiums of Chinese patent CN103524387A report, first using thionyl chloride,
Sulfamic acid, chlorosulfonic acid are reacted in a reaction vessel, without double chlorine sulfimine compounds (HN [SOzCl]
Z) separation of product, is directly added into thionyl chloride and anhydrous lithium salts carries out reaction and double chlorine sulfimide lithium salts are made, and removes chlorination
After sulfoxide solvent, add people's organic solvent, a small amount of triethylamine carries out fluorination reaction, filtering using anhydrous zinc fluoride, filtrate be evaporated or
It recrystallizes and obtains imidodisulfuryl fluoride lithium salt after being dried under reduced pressure.Reaction step is excessively cumbersome, and reagent type is more, there is bigger
Probability introduces other impurities, and the fluorization agent zinc fluoride of this reaction reacts the zinc chloride to be formed and easily remains in solvent, makes final obtain
The product arrived is impure.
The preparation method of bis- (fluorine sulphonyl) imine lithiums of Chinese CN103664712A reports, the concentrated sulfuric acid, KN (SO2F) 2, two
Silica is mixed, and is passed through nitrogen, air-distillation obtains crude product HFSI, and then destilling tower rectifying obtains sterling HFSI, carbonic acid
Lithium is made into suspension with deionized water, and HFSI aqueous solutions are then slowly added dropwise, 50 DEG C or so, PH=6-6.3, stop reaction, will be anti-
It answers liquid to be spray-dried, obtains solid powder, be then dried in vacuo in about 200 DEG C of height, 1-6Pa, finally obtain sterling LiFSI.
HFSI is reacted with lithium carbonate in water environment, exothermic heat of reaction, and product is easy to reaction of decomposing, and the band of water in aqueous solution
Enter to make precipitation drying to become highly difficult.
JP2013091524 has carried out compared with systematic research the stability of LiFSI, and discovery LiFSI is more than 40 DEG C in temperature
Environment in, decomposition rate is accelerated, and moisture is bigger, decomposes faster.
Invention content
In order to overcome above-mentioned technical problem, the present invention provides a kind of preparation method of double fluorine sulfimide lithiums, the present invention
Cheap and easy to get using reagent, preparation process is simple, is swift in response and thoroughly, by-product it is few and it is easy remove, post processing mode it is easy,
Product purity is high, is very suitable for industrialized production.
A kind of synthetic method of double fluorine sulfimide lithiums, synthetic method include the following steps：
1）In nitrogen atmosphere, reacting with condenser is placed in after double chlorine sulfimides are sufficiently mixed with organic solvent
In device, the addition of the organic solvent is 2 ~ 4 times of the weight of double chlorine sulfimides, then to sequentially adding fluorine in reactor
Change lithium, liquid hydrogen fluoride, then heat to 40 ~ 60 DEG C, reacts 8 ~ 12 hours, reaction equation is as follows：HN(SO2Cl)2+LiF+HF→
LiN(SO2F)2+2HCl；
2）Temperature of reaction system is reduced to 20 ~ 25 DEG C, remaining hydrogen fluoride gas is removed completely with nitrogen decompression displacement,
And the reaction solution retained in filtration reactor under nitrogen atmosphere, it removes insoluble matter and obtains filtrate；
3）Precipitation method is depressurized at 40 ~ 60 DEG C by step 2 using high vacuum）In filtrate be concentrated into step（1）Middle raw material
1 ~ 2 times of double chlorine sulfimide quality obtains concentrate；
4）By step 3）Concentrate be cooled to 20 ~ 25 DEG C, into concentrate above-mentioned be added weak polar solvent low temperature weight
Crystallization, mixing speed are 500 ~ 1000r/min, and the weak polar solvent is the organic solvent of polarity≤3.4, weak polar solvent
Temperature be 10 ~ 25 DEG C, the volume ratio of the concentrate and weak polar solvent is 1：3 ~ 10, preferably 1：4 ~ 7, most preferably 1：5, mistake
It filters and obtains pure double fluorine sulfimide lithiums after being dried under reduced pressure processing at 40 DEG C.
Further, the purity of double chlorine sulfimides of the present invention is more than 99%, and the purity of lithium fluoride is more than 99%, hydrogen fluoride
Purity be more than 99%.
Further, step 3 of the present invention）It is middle by step 2）In filtrate be concentrated into the double chlorine sulphurs of raw material using thin film evaporation
1.2 times of acid imide quality.
Further, step of the present invention（1）Described in organic solvent be esters, ethers, one kind in nitrile or several
The mixture of kind.
Further, step 1 of the present invention）Described in organic solvent purity be more than 99%, and water content be less than 50ppm.
Further, step 1 of the present invention）The reaction temperature is 40 DEG C, and the reaction time is 10 hours.
Further, step 1 of the present invention）Described in double chlorine sulfimides, lithium fluoride, hydrogen fluoride molar ratio be 1:（1
~1.2）：（1~1.4）.
Further, step 1 of the present invention）Described in double chlorine sulfimides, lithium fluoride, hydrogen fluoride molar ratio be 1：
1.1：1.2.
Further, step 4 of the present invention）Described in weak polar solvent, dichloromethane, carbon tetrachloride, toluene, just oneself
The mixed solvent of one or more of alkane.
Further, double chlorine sulfimides of the present invention are mixed to prepare reaction by sulfamic acid, thionyl chloride, chlorosulfonic acid
Temperature is 120~140 DEG C, and the reaction time is 20~30 hours.
The beneficial effects of the present invention are：1. the method for the preparation imidodisulfuryl fluoride lithium salt, inexpensive easily using reagent
, it is simple for process, it is swift in response and thoroughly.2. the present invention rationally controls reaction temperature, concentration, crystallization, drying temperature
System, overcomes technical barrier, avoids product to greatest extent and decompose during post-processing, and ensure that high yield can
Can, while obtaining the product of high-purity.3. the technical process of the present invention strictly controls the introducing of water, the complete raw material fluorinated lithium of unreacted
Be easy to remove insoluble in organic solvent, by-product it is few and it is easy remove, the lithium salts of synthesis is not easily decomposed, post processing mode is easy, from
And the cost of product is significantly reduced, and it is made to be more suitable for industrialized production.
Specific implementation mode
Embodiment 1
A kind of preparation method of double fluorine sulfimide lithiums, includes the following steps：
1）In nitrogen atmosphere, 214g is taken（1mol）Double chlorine sulfimides, 428g ethyl acetate, are placed in after being sufficiently mixed
It is stirred in the 1000ml four-hole boiling flasks for carrying condenser pipe, stirring, tail gas absorption full of nitrogen, wherein the purity of ethyl acetate
99.9%, water content 30ppm.Then to sequentially adding 27.3g in four-hole boiling flask（1.05mol）Lithium fluoride, 24g（1.2mol）Liquid
State hydrogen fluoride is warming up to 40 DEG C and reacts 10 hours, and reaction equation is as follows：HN (SO2Cl) 2+LiF+HF → LiN (SO2F) 2+2HCl,
The purity of the double chlorine sulfimides of reactant, lithium fluoride, hydrogen fluoride used in the present embodiment is all higher than 99%.
2）Temperature of reaction system is reduced to 20 DEG C, is replaced with nitrogen decompression and removes remaining hydrogen fluoride gas completely, and
The reaction solution retained in filtration reactor under nitrogen atmosphere is filtered to remove a small amount of solid impurity being wherein mixed with and obtains filtrate.
3）Precipitation method is depressurized at 50 DEG C by step 2 using high vacuum）In filtrate to be concentrated into the double chlorine sulphonyl of middle raw material sub-
1.2 times of amine quality obtain concentrate.
4）By step 3）Concentrate be cooled to 20 DEG C, into concentrate above-mentioned be added 900ml toluene low temperature tie again
Crystalline substance, mixing speed 600r/min, the temperature of toluene are 10 DEG C, filter and are dried under reduced pressure to obtain pure 170g at 40 DEG C bis-
Fluorine sulfimide lithium solid powder, it is 135-137 DEG C to measure fusing point, purity 99.92%, water content 42ppm, Na+ 、K+Content is small
In 5ppm.
Embodiment 2
A kind of preparation method of double fluorine sulfimide lithiums, includes the following steps：
1）In nitrogen atmosphere, 214g is taken（1mol）Double chlorine sulfimides, 428g acetonitriles are placed in after being sufficiently mixed and are full of
It is stirred in the 1000ml four-hole boiling flasks for carrying condenser pipe, stirring, tail gas absorption of nitrogen, wherein the purity 99.9% of acetonitrile, it is aqueous
40ppm is measured, then to sequentially adding 27.3g in four-hole boiling flask（1.05mol）Lithium fluoride, 24g（1.2mol）Liquid hydrogen fluoride rises
Temperature to 40 DEG C react 10 hours, reaction equation is as follows：HN (SO2Cl) 2+LiF+HF → LiN (SO2F) 2+2HCl, institute in the present embodiment
The double chlorine sulfimides of the reactant that uses, lithium fluoride, hydrogen fluoride purity be all higher than 99%.
2）Temperature of reaction system is reduced to 20 DEG C, is replaced with nitrogen decompression and removes remaining hydrogen fluoride gas completely, and
The reaction solution retained in filtration reactor under nitrogen atmosphere is filtered to remove a small amount of solid impurity being wherein mixed with and obtains filtrate.
3）Precipitation method is depressurized at 50 DEG C by step 2 using high vacuum）In filtrate to be concentrated into the double chlorine sulphonyl of middle raw material sub-
1.2 times of amine quality obtain concentrate, and using thin film evaporation, such precipitation mode, residence time of material is short, are particularly suitable for heat
The processing of quick property material.
5）By step 3）Concentrate be cooled to 20 DEG C, into concentrate above-mentioned be added 900ml carbon tetrachloride low temperature
The temperature of recrystallization, mixing speed 800r/min, carbon tetrachloride is 25 DEG C, filters and is dried under reduced pressure to obtain at 40 DEG C pure
The bis- fluorine sulfimide lithium solid powders of 168g, measure fusing point be 135-137 DEG C, purity 99.91%, water content 44ppm, Na+ 、K+Content is less than 5ppm.
Embodiment 3
A kind of preparation method of double fluorine sulfimide lithiums, includes the following steps：
1）In nitrogen atmosphere, 214g is taken（1mol）Double chlorine sulfimides, 642g ethyl acetate, are placed in after being sufficiently mixed
It is stirred in the 1000ml four-hole boiling flasks for carrying condenser pipe, stirring, tail gas absorption full of nitrogen, wherein the purity of ethyl acetate
99.9%, water content 30ppm, then to sequentially adding 28.6g in four-hole boiling flask（1.1mol）Lithium fluoride, 24g（1.2mol）Liquid
Hydrogen fluoride is warming up to 40 DEG C and reacts 10 hours, and reaction equation is as follows：HN (SO2Cl) 2+LiF+HF → LiN (SO2F) 2+2HCl, this
The purity of the double chlorine sulfimides of reactant, lithium fluoride, hydrogen fluoride used in embodiment is all higher than 99%.
2）Temperature of reaction system is reduced to 20 DEG C, is replaced with nitrogen decompression and removes remaining hydrogen fluoride gas completely, and
The reaction solution retained in filtration reactor under nitrogen atmosphere is filtered to remove a small amount of solid impurity being wherein mixed with and obtains filtrate.
3）Precipitation method is depressurized at 50 DEG C by step 2 using high vacuum）In filtrate to be concentrated into the double chlorine sulphonyl of middle raw material sub-
1.2 times of amine quality obtain concentrate.
4）By step 3）Concentrate be cooled to 20 DEG C, into concentrate above-mentioned be added by 450ml carbon tetrachloride and
The temperature of the mixed solvent low temperature recrystallization of 450ml toluene composition, mixing speed 1000r/min, mixed solvent is 20 DEG C, mistake
The bis- fluorine sulfimide lithium solid powders of pure 172g are filtered and are dried under reduced pressure to obtain at 40 DEG C, it is 135-137 DEG C to measure fusing point,
Purity 99.93%, water content 34ppm, Na+ 、K+Content is less than 5ppm.
Embodiment 4
A kind of preparation method of double fluorine sulfimide lithiums, includes the following steps：
1）In nitrogen atmosphere, 214g is taken（1mol）Double chlorine sulfimides, 642g tetrahydrofurans, are placed in after being sufficiently mixed
It is stirred in the 1000ml four-hole boiling flasks for carrying condenser pipe, stirring, tail gas absorption full of nitrogen, wherein the purity of tetrahydrofuran
99.9%, water content 40ppm, then to sequentially adding 26g in four-hole boiling flask（1mol）Lithium fluoride, 24g（1.2mol）It is liquid fluorinated
Hydrogen is warming up to 40 DEG C and reacts 10 hours, and reaction equation is as follows：HN (SO2Cl) 2+LiF+HF → LiN (SO2F) 2+2HCl, this implementation
Example used in reactant lithium fluoride, hydrogen fluoride purity be all higher than 99%, wherein double chlorine sulfimides by by sulfamic acid,
It is 120~140 DEG C that thionyl chloride, chlorosulfonic acid, which are mixed to prepare reaction temperature, and the reaction time is 20~30 hours, obtained by the reaction double
Chlorine sulfimide is by the Methods For Purification of rectifying, and purity is more than 99%.
2）Temperature of reaction system is reduced to 20 DEG C, is replaced with nitrogen decompression and removes remaining hydrogen fluoride gas completely, and
The reaction solution retained in filtration reactor under nitrogen atmosphere is filtered to remove a small amount of solid impurity being wherein mixed with and obtains filtrate.
3）Precipitation method is depressurized at 60 DEG C by step 2 using high vacuum）In filtrate to be concentrated into the double chlorine sulphonyl of middle raw material sub-
1.2 times of amine quality obtain concentrate.
4）By step 3）Concentrate be cooled to 20 DEG C, into concentrate above-mentioned be added 900ml n-hexane low temperature weight
The temperature of crystallization, mixing speed 1000r/min, n-hexane is 15 DEG C, filters and is dried under reduced pressure to obtain at 40 DEG C pure
The bis- fluorine sulfimide lithium solid powders of 166g, it is 135-137 DEG C to measure fusing point, purity 99.85%, water content 44ppm, Na+ 、K+
Content is less than 5ppm.
Embodiment 5
A kind of preparation method of double fluorine sulfimide lithiums, includes the following steps：
1）In nitrogen atmosphere, 214g is taken（1mol）Double chlorine sulfimides, 642g ethyl acetate, are placed in after being sufficiently mixed
It is stirred in the 1000ml four-hole boiling flasks for carrying condenser pipe, stirring, tail gas absorption full of nitrogen, wherein the purity of ethyl acetate
99.9%, water content 30ppm, then to sequentially adding 28.6g in four-hole boiling flask（1.1mol）Lithium fluoride, 26g（1.3mol）Liquid
Hydrogen fluoride is warming up to 40 DEG C and reacts 10 hours, and reaction equation is as follows：HN (SO2Cl) 2+LiF+HF → LiN (SO2F) 2+2HCl, this
The purity of reactant lithium fluoride, hydrogen fluoride used in embodiment is all higher than 99%, wherein double chlorine sulfimides are by by amino sulphur
It is 120~140 DEG C that acid, thionyl chloride, chlorosulfonic acid, which are mixed to prepare reaction temperature, and the reaction time is 20~30 hours, is obtained by the reaction
Double chlorine sulfimides by the Methods For Purification of rectifying, purity is more than 99%.
2）Temperature of reaction system is reduced to 20 DEG C, is replaced with nitrogen decompression and removes remaining hydrogen fluoride gas completely, and
The reaction solution retained in filtration reactor under nitrogen atmosphere is filtered to remove a small amount of solid impurity being wherein mixed with and obtains filtrate.
3）Precipitation method is depressurized at 50 DEG C by step 2 using high vacuum）In filtrate to be concentrated into the double chlorine sulphonyl of middle raw material sub-
1.2 times of amine quality obtain concentrate.
4）By step 3）Concentrate be cooled to 20 DEG C, into concentrate above-mentioned be added by 450ml carbon tetrachloride and
The temperature of the mixed solvent low temperature recrystallization of 450ml toluene composition, mixing speed 1000r/min, mixed solvent is 18 DEG C, mistake
The bis- fluorine sulfimide lithium solid powders of pure 173g are filtered and are dried under reduced pressure to obtain at 40 DEG C, it is 135-137 DEG C to measure fusing point,
Purity 99.93%, water content 34ppm, Na+ 、K+Content is less than 5ppm.
Embodiment 6
A kind of preparation method of double fluorine sulfimide lithiums, includes the following steps：
1）In nitrogen atmosphere, 214g is taken（1mol）Double chlorine sulfimides, 642g ethyl acetate, are placed in after being sufficiently mixed
It is stirred in the 1000ml four-hole boiling flasks for carrying condenser pipe, stirring, tail gas absorption full of nitrogen, wherein the purity of ethyl acetate
99.9%, water content 30ppm, then to sequentially adding 28.6g in four-hole boiling flask（1.1mol）Lithium fluoride, 26g（1.3mol）Liquid
Hydrogen fluoride is warming up to 60 DEG C and reacts 10 hours, and reaction equation is as follows：HN (SO2Cl) 2+LiF+HF → LiN (SO2F) 2+2HCl, this
The purity of reactant lithium fluoride, hydrogen fluoride used in embodiment is all higher than 99%, wherein double chlorine sulfimides are by by amino sulphur
It is 120~140 DEG C that acid, thionyl chloride, chlorosulfonic acid, which are mixed to prepare reaction temperature, and the reaction time is 20~30 hours, is obtained by the reaction
Double chlorine sulfimides by the Methods For Purification of rectifying, purity is more than 99%.
2）Temperature of reaction system is reduced to 20 DEG C, is replaced with nitrogen decompression and removes remaining hydrogen fluoride gas completely, and
The reaction solution retained in filtration reactor under nitrogen atmosphere is filtered to remove a small amount of solid impurity being wherein mixed with and obtains filtrate.
3）Precipitation method is depressurized at 40 DEG C by step 2 using high vacuum）In filtrate to be concentrated into the double chlorine sulphonyl of middle raw material sub-
1.5 times of amine quality obtain concentrate.
4）By step 3）Concentrate be cooled to 20 DEG C, into concentrate above-mentioned be added it is low by 1200ml dichloromethane
The temperature of temperature recrystallization, mixing speed 1000r/min, dichloromethane is 20 DEG C, filters and is dried under reduced pressure to obtain at 40 DEG C
The bis- fluorine sulfimide lithium solid powders of pure 162g, it is 135-137 DEG C to measure fusing point, purity 99.93%, water content 40ppm,
Na+ 、K+Content is less than 5ppm.
Embodiment 7
A kind of preparation method of double fluorine sulfimide lithiums, includes the following steps：
1）In nitrogen atmosphere, 214g is taken（1mol）Double chlorine sulfimides, 642g ethyl acetate, are placed in after being sufficiently mixed
It is stirred in the 1000ml four-hole boiling flasks for carrying condenser pipe, stirring, tail gas absorption full of nitrogen, wherein the purity of ethyl acetate
99.9%, water content 30ppm, then to sequentially adding 28.6g in four-hole boiling flask（1.1mol）Lithium fluoride, 26g（1.3mol）Liquid
Hydrogen fluoride is warming up to 50 DEG C and reacts 10 hours, and reaction equation is as follows：HN (SO2Cl) 2+LiF+HF → LiN (SO2F) 2+2HCl, this
The purity of reactant lithium fluoride, hydrogen fluoride used in embodiment is all higher than 99%, wherein double chlorine sulfimides are by by amino sulphur
It is 120~140 DEG C that acid, thionyl chloride, chlorosulfonic acid, which are mixed to prepare reaction temperature, and the reaction time is 20~30 hours, is obtained by the reaction
Double chlorine sulfimides by the Methods For Purification of rectifying, purity is more than 99%.
2）Temperature of reaction system is reduced to 20 DEG C, is replaced with nitrogen decompression and removes remaining hydrogen fluoride gas completely, and
The reaction solution retained in filtration reactor under nitrogen atmosphere is filtered to remove a small amount of solid impurity being wherein mixed with and obtains filtrate.
3）Precipitation method is depressurized at 40 DEG C by step 2 using high vacuum）In filtrate to be concentrated into the double chlorine sulphonyl of middle raw material sub-
2 times of amine quality obtain concentrate.
4）By step 3）Concentrate be cooled to 20 DEG C, be added into concentrate above-mentioned by 800ml dichloromethane and
The temperature of the mixed solvent low temperature recrystallization of 800ml toluene composition, mixing speed 1000r/min, mixed solvent is 20 DEG C, mistake
The bis- fluorine sulfimide lithium solid powders of pure 155g are filtered and are dried under reduced pressure to obtain at 40 DEG C, it is 135-137 DEG C to measure fusing point,
Purity 99.96%, water content 44ppm, Na+ 、K+Content is less than 5ppm.
Claims (8)
1. a kind of synthetic method of double fluorine sulfimide lithiums, which is characterized in that synthetic method includes the following steps：
1）In nitrogen atmosphere, after double chlorine sulfimides and organic solvent are sufficiently mixed in reactor of the merging with condenser,
The organic solvent is the mixture of one or more of esters, ethers, nitrile, and the addition of the organic solvent is double
2 ~ 4 times of the weight of chlorine sulfimide, then to lithium fluoride, liquid hydrogen fluoride is sequentially added in reactor, then heat to 40 ~
60 DEG C, react 8 ~ 12 hours, double chlorine sulfimides, lithium fluoride, hydrogen fluoride molar ratio be 1:（1~1.2）：（1~1.4）；
2）Temperature of reaction system is reduced to 20 ~ 25 DEG C, is replaced with nitrogen decompression and removes remaining hydrogen fluoride gas completely, and
The reaction solution retained in filtration reactor under nitrogen atmosphere removes insoluble matter and obtains filtrate；
3）Precipitation method is depressurized at 40 ~ 60 DEG C by step 2 using high vacuum）In filtrate be concentrated into step（1）The double chlorine of middle raw material
1 ~ 2 times of sulfimide quality obtains concentrate；
4）By step 3）Concentrate be cooled to 20 ~ 25 DEG C, into concentrate above-mentioned be added weak polar solvent low temperature tie again
Crystalline substance, mixing speed are 500 ~ 1000r/min, and the weak polar solvent is the organic solvent of polarity≤3.4, weak polar solvent
Temperature is 10 ~ 25 DEG C, and the volume ratio of the concentrate and weak polar solvent is 1：3 ~ 10, it filters and is dried under reduced pressure place at 40 DEG C
Pure double fluorine sulfimide lithiums are obtained after reason.
2. a kind of synthetic method of double fluorine sulfimide lithiums according to claim 1, it is characterised in that：Double chlorine sulfimides
Purity be more than 99%, the purity of lithium fluoride is more than 99%, and the purity of hydrogen fluoride is more than 99%.
3. a kind of synthetic method of double fluorine sulfimide lithiums according to claim 1, it is characterised in that：Step（1）Middle institute
The organic solvent purity stated is more than 99%, and water content is less than 50ppm.
4. a kind of synthetic method of double fluorine sulfimide lithiums according to any claim in claims 1 or 2 or 3,
It is characterized in that：Step 3）It is middle by step 2）In filtrate the 1.2 of the double chlorine sulfimide quality of raw material are concentrated into using thin film evaporation
Times.
5. a kind of synthetic method of double fluorine sulfimide lithiums according to any claim in claims 1 or 2 or 3,
It is characterized in that：Step 1）The reaction temperature is 40 DEG C, and the reaction time is 10 hours.
6. a kind of synthetic method of double fluorine sulfimide lithiums according to any claim in claims 1 or 2 or 3,
It is characterized in that：Step 1）Described in double chlorine sulfimides, lithium fluoride, hydrogen fluoride molar ratio be 1：1.1：1.2.
7. a kind of synthetic method of double fluorine sulfimide lithiums according to any claim in claims 1 or 2 or 3,
It is characterized in that：Step 4）Described in weak polar solvent be dichloromethane, carbon tetrachloride, toluene, one kind in n-hexane or several
The mixed solvent of kind.
8. a kind of synthetic method of double fluorine sulfimide lithiums according to any claim in claims 1 or 2 or 3,
It is characterized in that：Double chlorine sulfimides by sulfamic acid, thionyl chloride, chlorosulfonic acid be mixed to prepare reaction temperature be 120~
140 DEG C, the reaction time is 20~30 hours.
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| JP6921464B2 (en) * | 2018-04-10 | 2021-08-18 | エルジー・ケム・リミテッド | Method for producing lithium bis (fluorosulfonyl) imide salt |
| US11267707B2 (en) | 2019-04-16 | 2022-03-08 | Honeywell International Inc | Purification 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 |
| CN112174101A (en) * | 2020-09-23 | 2021-01-05 | 湖南博信新能源科技有限公司 | Preparation method of high-purity lithium bis (fluorosulfonyl) imide |
| CN112320772A (en) * | 2020-11-24 | 2021-02-05 | 泰兴华盛精细化工有限公司 | 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 |
| CN112850667A (en) * | 2021-02-05 | 2021-05-28 | 广东巨氟节能技术有限公司 | Synthetic method of liquid-cooled fluorinated liquid of data center |
| CN113104823A (en) * | 2021-03-26 | 2021-07-13 | 广州理文科技有限公司 | Synthesis method of bis (fluorosulfonyl) imide |
| CN113247871B (en) * | 2021-06-04 | 2021-09-24 | 江苏华盛锂电材料股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
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