CN106241757A - A kind of preparation method of imidodisulfuryl fluoride lithium salt - Google Patents
A kind of preparation method of imidodisulfuryl fluoride lithium salt Download PDFInfo
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Abstract
The present invention relates to the field of chemical synthesis, be specifically related to the preparation method of a kind of imidodisulfuryl fluoride lithium salt.The present invention more provides the preparation method of a kind of imidodisulfuryl fluoride lithium salt, comprises the steps: that double fluorine sulfimides are carried out displacement reaction with LiX by (1), and wherein, X is selected from Cl, Br or I；(2) appropriate fluohydric acid gas is mixed with displacement reaction gained reactant liquor；(3) by step (2) gained reactant liquor solid-liquid separation, liquid phase concentrates, and adds poor solvent crystallize, and solid-liquid separation i.e. obtains imidodisulfuryl fluoride lithium salt.The preparation method of imidodisulfuryl fluoride lithium salt provided by the present invention can prepare highly purified LiFSI, and constant product quality, yield are high, effectively reduce in product the impurity contents such as potassium ion, sodium ion, chloride ion, sulfate ion and moisture, and operating procedure is simple, production cost is reasonable, safety is high, and is more suitable for industrialized production.
Description
Technical field
The present invention relates to the field of chemical synthesis, be specifically related to the preparation method of a kind of imidodisulfuryl fluoride lithium salt.
Background technology
Double fluorine sulfimide lithium, are called for short LiFSI, as crucial in the new energy devices such as lithium ion battery, ultracapacitor
High-performance electrolyte, there is the highest commercial application and be worth.But this product is hygroscopic and decomposes, moisture and miscellaneous
Its performance of verifying adversely affects.Using requirement for meeting electrolyte, LiFSI has for the index such as moisture, various foreign ions
Considered critical, and there is no effective purifying products method at present, impurity is once introduced just very difficult being touched the mark by purification and wants
Ask.
Patent US2013331609, US2012041233 etc. report the synthetic method of LiFSI, are all first to prepare metal
Or double fluorine sulfimide salt intermediate of organic base, then with LiOH or Li2CO3Carry out cation exchange reaction and prepare LiFSI, lack
Point is, exchange reaction is difficult to proceed after reaching a balance, and conversion ratio is on the low side；And the intermediate MSFI (M that unreacted is complete
Refer to metal cation, organic base cation) similar to LiFSI character, it is difficult to be kept completely separate, causes LiFSI quality the highest, it is impossible to
Directly apply to cell electrolyte.
And Electrochemical Society Transactions, 2009,24, the 91-98 page；With
Polyhedron, 2006,25, the method for the 1292-1298 page report, the lithium salts of HFSI is by the potassium salt of HFSI (i.e.,
KFSI) displacement reaction with lithium perchlorate (LiClO4) synthesizes, and this reaction is easily caused potassium ion in product and exceeds standard, and
The potassium hyperchlorate (KClO4) that LiClO4 and reaction produce, is explosive compound, and these methods are not suitable for commercial scale
Synthesis.
United States Patent (USP) US2004097757 uses HClSI directly to react preparation LiFSI, salt exchange and halogen exchange with LiF
Reaction is carried out simultaneously, and by-product is many, quality purity is poor.
Japan's catalyst patent CN102917979A, by the butyl acetate solution of double fluorine sulfimide ammoniums, with Lithium hydrate water
Solution reaction obtains the butyl acetate solution of LiFSI.By concentrating, add poor solvent toluene and produce precipitation, after filtration drying
Obtain LiFSI.The method of this patent report there is problems of product purity and yield is the lowest, and consumption of raw materials and garbage produce
Too much, manufacturing cost is the highest.
Patent CN103391896A, first by double fluorine sulfimide ammonium salts, be made into after butyl acetate solution with Lithium hydrate
After reactant aqueous solution, organic layer removing solvent obtains LiFSI.The problem that the method for this patent report exists is product purity equally
The lowest with yield, consumption of raw materials and garbage produce too many, and manufacturing cost is the highest.
The production technology of above LiFSI, requires higher to consersion unit, and consumption of raw materials and garbage are more, industrial operation
Complexity, there is safety problem in some；And product yield is low, moisture, potassium ion, sodium ion, calcium ion, chloride ion, sulfur in product
The impurity such as acid ion cannot be effectively controlled, and causes poor product quality, makes LiFSI difficult quality meet requirement, inapplicable
In industrial applications.Therefore, this area is in the urgent need to a kind of preparation and purification method of LiFSI, and the method is prone to reaction thoroughly,
Product purification processes convenient；React with the industrial raw material being easier to buy, economical and practical, the three wastes are few, can be with higher yields
Prepare LiFSI product with high-purity, industrialization can be realized simultaneously.
Summary of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide a kind of imidodisulfuryl fluoride lithium salt
Preparation method, is used for solving the problems of the prior art.
For achieving the above object and other relevant purposes, the present invention provides the preparation side of a kind of imidodisulfuryl fluoride lithium salt
Method, comprises the steps:
(1) with LiX, double fluorine sulfimides (HFSI) being carried out displacement reaction, wherein, X is selected from Cl, Br or I；
(2) appropriate fluohydric acid gas is mixed with displacement reaction gained reactant liquor；
(3) by step (2) gained reactant liquor solid-liquid separation, liquid phase concentrates, and adds making beating solvent crystallization, solid-liquid separation and get final product
Imidodisulfuryl fluoride lithium salt.
In some embodiments of the present invention, in described step (1), the mol ratio of LiX and double fluorine sulfimides be 0.9～
1:1, preferably 0.95～1:1.
In some embodiments of the present invention, in described step (1), reaction temperature is 0～50 DEG C, preferably 10～40
DEG C, more preferably 25～40 DEG C.
In some embodiments of the present invention, in described step (1), react and carry out under conditions of reaction dissolvent exists,
Described reaction dissolvent is organic solvent.
In some embodiments of the present invention, in described step (1), described organic solvent is ketone, alcohols, esters or ether
The combination of one or more in kind solvent.
In some embodiments of the present invention, in described step (1), described ketones solvent selected from N-Methyl pyrrolidone,
The combination of one or more in acetone, methyl ethyl ketone, butanone, methyl tertbutyl ketone, 4-methyl-2 pentanone etc.；Described alcohol
Kind solvent can be selected from the combination of one or more in such as methanol, ethanol, isopropanol, isoamyl alcohol；Described esters solvent selects
From dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethylene carbonate, Allyl carbonate, methyl acetate, ethyl acetate, second
The combination of one or more in propyl propionate, isopropyl acetate, butyl acetate, isobutyl acetate, vinylacetate；Described ethers
Solvent is selected from ether, propyl ether, diisopropyl ether, butyl ether, diisobutyl ether, oxolane, methyltetrahydrofuran, cyclopentyl methyl ether, dioxy six
The combination of one or more in ring, dioxolane, glycol dimethyl ether.
In some embodiments of the present invention, in described step (1), reaction is carried out under conditions of gas shield.
In some embodiments of the present invention, in described step (2), fluohydric acid gas is 0.1%～4% with the mol ratio of LiX:
1, preferably 1%～4%:1.
In some embodiments of the present invention, in described step (2), fluohydric acid gas is mixed with displacement reaction gained reactant liquor
Method particularly as follows: hydrogen fluoride gas is passed through in displacement reaction gained reactant liquor；
Or, fluohydric acid gas is dissolved in appropriate solvent, then by anti-with displacement reaction gained for the solvent that is dissolved with fluohydric acid gas
Answer liquid to mix, be organic solvent for dissolving the solvent of fluohydric acid gas.
In some embodiments of the present invention, in described step (2), the solvent for dissolving fluohydric acid gas be ketone, alcohols,
The combination of one or more in esters or ether solvent.
In some embodiments of the present invention, in described step (2), described ketones solvent selected from N-Methyl pyrrolidone,
The combination of one or more in acetone, methyl ethyl ketone, butanone, methyl tertbutyl ketone, 4-methyl-2 pentanone；Described alcohols
Solvent can be selected from the combination of one or more in such as methanol, ethanol, isopropanol, isoamyl alcohol etc.；Described esters solvent selects
From dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate, ethylene carbonate, Allyl carbonate, methyl acetate, ethyl acetate, second
The combination of one or more in propyl propionate, isopropyl acetate, butyl acetate, isobutyl acetate, vinylacetate；Described ethers
Solvent is selected from ether, propyl ether, diisopropyl ether, butyl ether, diisobutyl ether, oxolane, methyltetrahydrofuran, cyclopentyl methyl ether, dioxy six
The combination of one or more in ring, dioxolane, glycol dimethyl ether.
In some embodiments of the present invention, in described step (3), poor solvent is selected from saturated hydrocarbons, halogenated hydrocarbon, virtue
The combination of one or more in fragrant hydro carbons and Polyhalogenated aromatic hydrocarbons low polar solvent.
In some embodiments of the present invention, in described step (3), poor solvent is selected from normal hexane, hexamethylene, dichloromethane
Alkane, dichloroethanes, toluene, dimethylbenzene, chlorobenzene, the combination of one or more in dichloro-benzenes.
In some embodiments of the present invention, in described step (3), the temperature of concentration is 10～80 DEG C, preferably 25～
60℃。
In some embodiments of the present invention, the preparation method of described imidodisulfuryl fluoride lithium salt comprises the steps: double
The reaction under conditions of catalyst exists of chlorine sulfimide (HClSI) and fluohydric acid gas (HF) obtains double fluorine sulfimide (HFSI).
In some embodiments of the present invention, described catalyst is Bronsted acid and/or lewis acid.
In some embodiments of the present invention, described lewis acid is selected from SbCl5、TiCl4、SnCl4、MoCl5In one
Or multiple combination.
In some embodiments of the present invention, described Bronsted acid is selected from concentrated sulphuric acid and/or oleum.
In some embodiments of the present invention, HClSI Yu HF mol ratio is 1:1.4～1:4, preferably 1:1.7～1:
2.5。
In some embodiments of the present invention, in the preparation method of described imidodisulfuryl fluoride lithium salt, the temperature of reaction system
Degree is 90～110 DEG C, preferably 100～105 DEG C.
The preparation method of imidodisulfuryl fluoride lithium salt provided by the present invention can prepare highly purified LiFSI, and
Constant product quality, yield are high, effectively reduce in product the impurity such as potassium ion, sodium ion, chloride ion, sulfate ion and moisture
Content, and operating procedure is simple, production cost is reasonable, safety is high, and it is more suitable for industrialized production.
Detailed description of the invention
Inventor is that raw material prepares highly purified pair of fluorine sulphonyl of high-quality with double chlorine sulfimides (HClSI)
Imines lithium salts (LiFSI, CAS:171611-11-3), thus provide a kind of simple process, method that low cost, yield are high is come
Preparation high-quality LiFSI, completes the present invention on this basis.
One aspect of the present invention provides the preparation method of a kind of imidodisulfuryl fluoride lithium salt, described imidodisulfuryl fluoride lithium salt
Preparation method may include that and with LiX, double fluorine sulfimides are carried out displacement reaction, and wherein, X is selected from Cl, Br or I.
In above-mentioned course of reaction, the usage amount of double fluorine sulfimides can be relative to LiX excess, such as, and LiX and double fluorine sulphurs
Imido mol ratio can be 0.9～1:1, it is also possible to is 0.95～1:1.
In above-mentioned course of reaction, reaction temperature can be room temperature, and such as, reaction temperature can be 0～50 DEG C, it is also possible to for
10～40 DEG C, it is also possible to be 25～40 DEG C.It is not particularly limited, as long as not to this for changing the method for temperature of reaction system
Bright goal of the invention produces and limits, such as, the methods such as water-bath can be used to be controlled the temperature of reaction system.Ability
Field technique personnel can adjust the response time of above-mentioned reaction according to reaction process, such as can be by monitoring the response situation of raw material
Judging reaction process, in some detailed description of the invention of the present invention, the response time of above-mentioned reaction can be 10～40 hours, also
It can be 15～20 hours.
In above-mentioned course of reaction, reaction can be carried out under conditions of reaction dissolvent exists, and described reaction dissolvent can be
Organic solvent, described organic solvent can be the combination of one or more in ketone, alcohols, esters or ether solvent；Described
Ketones solvent can be selected from such as N-Methyl pyrrolidone, acetone, methyl ethyl ketone, butanone, methyl tertbutyl ketone, 4-methyl-
The combination of one or more in 2 pentanone etc.；Described alcohols solvent can be selected from such as methanol, ethanol, isopropanol, isoamyl alcohol
The combination of one or more in Deng；Described esters solvent can be selected from such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate
Ester, ethylene carbonate, Allyl carbonate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, acetic acid
The combination of one or more in isobutyl ester, vinylacetate etc..Described ether solvent can be selected from such as ether, propyl ether, different
Propyl ether, butyl ether, diisobutyl ether, oxolane, methyltetrahydrofuran, cyclopentyl methyl ether, dioxane, dioxolane, ethylene glycol bisthioglycolate
The combination of one or more in methyl ether etc..Those skilled in the art can be according to concrete reaction system and the kind of reaction dissolvent
Adjusting the consumption of reaction dissolvent, such as, the consumption of solvent can be 1～6 times of HFSI weight, it is also possible to for HFSI weight
1.5～3 times.
In above-mentioned course of reaction, reaction can be carried out under conditions of gas shield, and described gas generally may refer to not
There is the gaseous material of chemical reaction, Ke Yishi in the main component (the most double fluorine sulfimides, LiX etc.) easily and in reaction system
The such as combination of one or more in nitrogen, helium, neon, argon, Krypton, xenon etc..
The preparation method of described imidodisulfuryl fluoride lithium salt can also include: by anti-with displacement reaction gained for appropriate fluohydric acid gas
Liquid is answered to mix.
In above-mentioned course of reaction, LiX can be with the usage amount typically catalytic amount of hydrogen fluoride reaction generation LiF, HF
, such as, fluohydric acid gas can be 0.1%～4%:1 with the mol ratio of LiX, it is also possible to is 1%～4%:1.The reaction temperature of reaction
Degree is not particularly limited, as long as the goal of the invention not to the present invention produces limits.Those skilled in the art can be according to reaction
The practical situation of system adjusts the response time, such as, can judge reaction process by the response situation of monitoring LiX.
In above-mentioned course of reaction, those skilled in the art may select suitable method by appropriate fluohydric acid gas and displacement reaction institute
Obtain reactant liquor mixing, for example, it is possible to hydrogen fluoride gas is passed through in displacement reaction gained reactant liquor, then for example, it is possible to will fluorination
Hydrogen is dissolved in appropriate solvent, then is mixed with displacement reaction gained reactant liquor by the solvent being dissolved with fluohydric acid gas.For dissolving
The solvent of fluohydric acid gas can be organic solvent, and described organic solvent can be the one in ketone, alcohols, esters or ether solvent
Or multiple combination；Described ketones solvent can be selected from such as N-Methyl pyrrolidone, acetone, methyl ethyl ketone, butanone, methyl
The combination of one or more in tert-butyl group ketone, 4-methyl-2 pentanone etc.；Described alcohols solvent can be selected from such as methanol, second
The combination of one or more in alcohol, isopropanol, isoamyl alcohol etc.；Described esters solvent can be selected from such as dimethyl carbonate, carbon
Diethyl phthalate, Ethyl methyl carbonate, ethylene carbonate, Allyl carbonate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate
The combination of one or more in ester, butyl acetate, isobutyl acetate, vinylacetate etc..Described ether solvent can be selected from
Such as ether, propyl ether, diisopropyl ether, butyl ether, diisobutyl ether, oxolane, methyltetrahydrofuran, cyclopentyl methyl ether, dioxane, two
The combination of one or more in oxygen five rings, glycol dimethyl ether etc..Can also be anti-with displacement for dissolving the solvent of fluohydric acid gas
Solvent phase used in Ying is same.Those skilled in the art can adjust for dissolving the molten of fluohydric acid gas according to the usage amount of fluohydric acid gas
The consumption of agent, for example, it is possible to be dissolved in fluohydric acid gas in appropriate solvent to form the saturated solution of fluohydric acid gas.
The preparation method of described imidodisulfuryl fluoride lithium salt can also include: by anti-with displacement reaction gained for appropriate fluohydric acid gas
Answering the reactant liquor solid-liquid separation of liquid mixing gained, liquid phase concentrates, and adds poor solvent crystallize, and it is sub-that solid-liquid separation i.e. obtains double fluorine sulphonyl
Amine lithium salts.
In above-mentioned course of reaction, poor solvent can select low polar solvent, can be more specifically saturated hydrocarbons, halogenated hydrocarbons
The combination of one or more in the low polar solvents such as class, arene and Polyhalogenated aromatic hydrocarbons, preferably normal hexane, hexamethylene
Alkane, dichloromethane, dichloroethanes, toluene, dimethylbenzene, chlorobenzene, the combination of one or more in dichloro-benzenes etc..Art technology
Personnel can adjust number of times and the consumption of poor solvent of making beating according to making beating system, in some detailed description of the invention of the present invention
In, the consumption of poor solvent can be 1.5～8 times of HFSI weight, it is also possible to is 2～4 times, and the number of times of making beating can be at least
Once.
In above-mentioned course of reaction, the method concentrated for liquid phase is not particularly limited, if the invention mesh not to the present invention
Generation limit.Such as, the method for concentration can be concentrating under reduced pressure, and the temperature of concentration can be 10～80 DEG C, it is also possible to
It it is 25～60 DEG C.
In the preparation method of described imidodisulfuryl fluoride lithium salt, double fluorine sulfimides can pass through such as CN
The preparation method of the double fluorine sulfimides in 104925765A prepares.More specifically, described imidodisulfuryl fluoride lithium salt
Preparation method can also include: double chlorine sulfimides (HClSI) and fluohydric acid gas (HF) react under conditions of catalyst exists and obtains
Obtaining double fluorine sulfimides (HFSI), reaction equation is as follows:
In above-mentioned course of reaction, described catalyst can be acid, more specifically, described catalyst can be Bronsted acid with/
Or lewis acid.Concrete available lewis acidic example includes but not limited to SbCl5、TiCl4、SnCl4、MoCl5In one
Kind or multiple combination；The example of concrete available Bronsted acid includes but not limited to concentrated sulphuric acid and/or oleum.Described dense
Sulphuric acid is often referred to the sulfuric acid solution of the sulfuric acid solution of mass percent >=70%, more specifically mass percent >=98%.Described
Oleum (H2SO4·xSO3) it is often referred to the sulfuric acid solution of sulfur trioxide, it is specifically as follows three oxygen of mass percent >=20%
Change sulfur sulfuric acid solution, can be more specifically mass percent be the sulphuric acid of the sulfur trioxide of 20%, 40%, 60% or 66%
Solution.
In above-mentioned course of reaction, the usage amount of catalyst is not particularly limited, as long as not producing the goal of the invention of the present invention
Raw limiting, the usage amount of described catalyst is usually catalytic amount, specifically used amount ratio, can be HClSI and
The mol ratio of catalyst is 1:0.05 ‰～1:1 ‰, it is also possible to for 1:0.1 ‰～1:0.5 ‰.
In above-mentioned course of reaction, ratio, the usage amount of HF is commonly angled relative to HClSI excess, and specifically used amount is pressed
Molar ratio computing, can be HClSI Yu HF mol ratio be 1:1.4～1:4, it is also possible to for 1:1.7～1:2.5.
In above-mentioned course of reaction, the temperature of reaction system can be 90～110 DEG C, it is also possible to is 100～105 DEG C.Ability
Field technique personnel can control reaction process according to real reaction situation, such as, can judge anti-by the response situation of monitoring raw material
Answer process, the more such as response time can be 10～25 hours.
In above-mentioned course of reaction, the concrete grammar of reaction can be: is passed through by HF and includes the anti-of HClSI and/or catalyst
Answer in system and react, such as, can be that HClSI, catalyst are placed in reaction unit, be passed through HF gas and react.
In above-mentioned course of reaction, after having reacted, generally can remove HF and the HCl gas in reaction system, remove reaction
The method of HF and the HCl gas in system should be known to those skilled in the art, such as, can be to reaction
System is advertised and/or distills, more such as, the temperature advertised typically room temperature, the time of advertising can be that 10-20 is little
Time, more such as, distill distillation of typically reducing pressure.
As it has been described above, the preparation method of imidodisulfuryl fluoride lithium salt provided by the present invention is reacted by HFSI and LiCl,
Through the post processing of simple economy, preparing highly purified LiFSI, constant product quality, yield are high, effectively reduce in product potassium from
The impurity contents such as son, sodium ion, chloride ion, sulfate ion and moisture, and operating procedure is simple, production cost reasonable, peace
Quan Xinggao, and it is more suitable for industrialized production.
Below by way of specific instantiation, embodiments of the present invention being described, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also be by the most different concrete realities
The mode of executing is carried out or applies, the every details in this specification can also based on different viewpoints and application, without departing from
Various modification or change is carried out under the spirit of the present invention.
It should be clear that conventional equipment in the concrete process equipment indicated or device all use this area in the following example or
Device.
In addition, it is to be understood that the one or more method steps mentioned in the present invention do not repel before and after described combination step
Additive method step can also be there is or additive method step can also be inserted between these steps specifically mentioned, unless separately
It is described；Should also be understood that the combination annexation between the one or more equipment/devices mentioned in the present invention is not repelled
Can also exist before and after described unit equipment/device other equipment/devices or these two equipment/devices specifically mentioned it
Between can also insert other equipment/devices, except as otherwise noted.And, except as otherwise noted, the numbering of various method steps is only
Differentiate the convenient tool of various method steps, rather than for limiting the ordering of various method steps or limiting the enforceable model of the present invention
Enclose, being altered or modified of its relativeness, in the case of without essence change technology contents, enforceable when being also considered as the present invention
Category.
Embodiment 1
In 1000mL reaction bulb, add dimethyl carbonate 300g, lithium chloride 20.8g, be cooled to 15～25 DEG C, stir lower
Add 90g HFSI.Stirring 18 hours, the dropping dimethyl carbonate solution containing 0.1g fluohydric acid gas, after stirring reaction, filter, filtrate subtracts
Pressure-off is molten, obtains thick concentrate.Adding 400g dichloromethane in concentrate, product separates out, through filtering, dried must produce
Product 90.6g, yield 98%.Testing result: AAS:Na+(7ppm), K+(5ppm), Fe+＜ 1ppm, Ca+<1ppm；IC:Cl-
(5ppm), SO42-(21ppm).Product is white powdery solids, fusing point 124-128 DEG C.
Embodiment 2
In 500mL reaction bulb, adding propyl ether 150g, LiCl 20.1g, control temperature is to 25～30 DEG C, and stirring is lower to be dripped
90g HFSI.Stir 20 hours, the dropping propyl ether solution containing 0.15g fluohydric acid gas, stirring reaction, filter, filtrate decompression precipitation,
To thick concentrate.Adding 200g dichloroethanes in concentrate, product separates out, through filtering, dried product 87g.(inspection
Survey result: AAS (ppm): Na+(4ppm), K+(4ppm), Fe+＜ 1ppm, Ca+<1ppm；IC:Cl-(7ppm), SO42-
(23ppm))。
Embodiment 3
In 500mL reaction bulb, adding methyl ethyl ketone 200g, LiCl 21g, control temperature, to 35～40 DEG C, stirs lower
Add 90g HFSI.Stirring reaction 18 hours, the dropping diisopropyl ether solution containing 0.15g fluohydric acid gas, stir, filter, filtrate decompression takes off
Molten, obtain thick concentrate.Adding 150g normal hexane in concentrate, product separates out, through filtering, dried product
89.4g.(testing result: AAS (ppm): Na+(7ppm), K+(4ppm), Fe+＜ 1ppm, Ca+<1ppm；IC:Cl-(5ppm),
SO42-(18ppm))。
Embodiment 4:
In 500mL reaction bulb, adding methanol 200g, LiCl 19.8g, control temperature is to 25～30 DEG C, and stirring is lower to be dripped
90g HFSI.Stirring reaction 20 hours, the dropping methanol solution containing 0.3g fluohydric acid gas, stir 21 hours, filter, filtrate decompression takes off
Molten, obtain thick concentrate.Adding 200g dichloroethanes in concentrate, product separates out, through filtering, dried product
85.6g.(testing result: AAS (ppm): Na+(5ppm), K+(4ppm), Fe+＜ 1ppm, Ca+<1ppm；IC:Cl-(8ppm),
SO42-(21ppm))。
Embodiment 5
In 500mL reaction bulb, adding THF 200g, LiCl 21.2g, control temperature is to 25～35 DEG C, and stirring is lower to be dripped
90g HFSI.Stirring reaction 15 hours, adds 0.3g fluohydric acid gas, stirs, filters, and filtrate decompression precipitation obtains thick concentration
Thing.Adding 300g dichloromethane in concentrate, product separates out, through filtering, dried product 89.8g.(testing result: AAS
(ppm): Na+(6ppm), K+(4ppm), Fe+＜ 1ppm, Ca+<1ppm；IC:Cl-(7ppm), SO42-(15ppm))。
Embodiment 6
In 1000mL reaction bulb, adding ethyl acetate 400g, LiBr 42g, control temperature is to 30-40 DEG C, and stirring is lower to be dripped
90g HFSI.Stir 25 hours, add 0.35g fluohydric acid gas, stirring reaction, filter, filtrate decompression precipitation, obtain thick concentration
Thing.Adding 300g toluene in concentrate, product separates out, through filtering, dried product 89.5g.(testing result: AAS
(ppm): Na+(4ppm), K+(6ppm), Fe+＜ 1ppm, Ca+<1ppm；IC:Br-(7ppm), SO42-(19ppm))。
Embodiment 7
The preparation of double fluorine sulfimides
In 1000mL tetrafluoro reaction bulb, add HClSI 1000g, SbCl51g, is warming up to 100～105 DEG C, and stirring is lower slow
Slowly being passed through HF gas about 220g, be cooled to room temperature, advertise nitrogen, obtain crude product about 833g after reacting 15 hours, short steaming is produced
Product 750g.Product is colourless liquid, and fusing point is about 17 DEG C.
In sum, the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Any ripe
Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by the personage knowing this technology.Cause
This, have usually intellectual such as complete with institute under technological thought without departing from disclosed spirit in art
All equivalences become are modified or change, and must be contained by the claim of the present invention.
Claims (10)
1. a preparation method for imidodisulfuryl fluoride lithium salt, comprises the steps:
(1) with LiX, double fluorine sulfimides being carried out displacement reaction, wherein, X is selected from Cl, Br or I；
(2) appropriate fluohydric acid gas is mixed with displacement reaction gained reactant liquor；
(3) by step (2) gained reactant liquor solid-liquid separation, liquid phase concentrates, and adds poor solvent crystallize, and solid-liquid separation i.e. obtains double fluorine
Sulfimide lithium salts.
2. the preparation method of imidodisulfuryl fluoride lithium salt as claimed in claim 1, it is characterised in that in described step (1),
LiX is 0.9～1:1 with the mol ratio of double fluorine sulfimides；
And/or, in described step (1), reaction temperature is 0～50 DEG C；
And/or, in described step (1), reacting and carry out under conditions of reaction dissolvent exists, described reaction dissolvent is organic molten
Agent；
And/or, in described step (1), reaction is carried out under conditions of gas shield.
3. the preparation method of imidodisulfuryl fluoride lithium salt as claimed in claim 2, it is characterised in that in described step (1),
LiX is 0.95～1:1 with the mol ratio of double fluorine sulfimides；
And/or, in described step (1), reaction temperature is 10～40 DEG C；
And/or, in described step (1), described organic solvent is one or more in ketone, alcohols, esters or ether solvent
Combination.
4. the preparation method of imidodisulfuryl fluoride lithium salt as claimed in claim 1, it is characterised in that in described step (2), fluorine
The mol ratio changing hydrogen and LiX is 0.1%～4%:1；
And/or, in described step (2), the method that mixed with displacement reaction gained reactant liquor by fluohydric acid gas is particularly as follows: by fluohydric acid gas
Gas is passed through in displacement reaction gained reactant liquor；
And/or, in described step (2), the method that mixed with displacement reaction gained reactant liquor by fluohydric acid gas is particularly as follows: by fluohydric acid gas
It is dissolved in appropriate solvent, then the solvent being dissolved with fluohydric acid gas is mixed with displacement reaction gained reactant liquor, be used for dissolving fluorine
The solvent changing hydrogen is organic solvent.
5. the preparation method of imidodisulfuryl fluoride lithium salt as claimed in claim 4, it is characterised in that in described step (2), fluorine
The mol ratio changing hydrogen and LiX is 1%～4%:1；
And/or, in described step (2), it is in ketone, alcohols, esters or ether solvent for dissolving the solvent of fluohydric acid gas
Kind or multiple combination.
6. the preparation method of imidodisulfuryl fluoride lithium salt as claimed in claim 1, it is characterised in that in described step (3), no
One or more in saturated hydrocarbons, halogenated hydrocarbon, arene and Polyhalogenated aromatic hydrocarbons low polar solvent of good solvent
Combination；
And/or, in described step (3), the temperature of concentration is 10～80 DEG C.
7. the preparation method of imidodisulfuryl fluoride lithium salt as claimed in claim 6, it is characterised in that in described step (3), no
Good solvent is selected from normal hexane, hexamethylene, dichloromethane, dichloroethanes, toluene, dimethylbenzene, chlorobenzene, the one or many in dichloro-benzenes
The combination planted；
And/or, in described step (3), the temperature of concentration is 25～60 DEG C.
8. the preparation method of imidodisulfuryl fluoride lithium salt as claimed in claim 1, it is characterised in that described pair of fluorine sulfimide
The preparation method of lithium salts comprises the steps: that the reaction under conditions of catalyst exists of double chlorine sulfimide and fluohydric acid gas obtains double
Fluorine sulfimide.
9. the preparation method of imidodisulfuryl fluoride lithium salt as claimed in claim 8, it is characterised in that described catalyst is proton
Acid and/or lewis acid；
And/or, HClSI Yu HF mol ratio is 1:1.4～1:4；
And/or, in the preparation method of described imidodisulfuryl fluoride lithium salt, the temperature of reaction system is 90～110 DEG C.
10. the preparation method of imidodisulfuryl fluoride lithium salt as claimed in claim 9, it is characterised in that described lewis acid selects
From SbCl5、TiCl4、SnCl4、MoCl5In the combination of one or more；
And/or, described Bronsted acid is selected from concentrated sulphuric acid and/or oleum；
And/or, HClSI Yu HF mol ratio is 1:1.7～1:2.5；
And/or, in the preparation method of described imidodisulfuryl fluoride lithium salt, the temperature of reaction system is 100～105 DEG C.
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| CN111320151A (en) * | 2020-02-18 | 2020-06-23 | 白银科奥夫化学科技有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN112739652A (en) * | 2020-06-05 | 2021-04-30 | 珠海理文新材料有限公司 | Preparation method of lithium fluorosulfonate |
| EP3825278A1 (en) | 2019-11-20 | 2021-05-26 | Shanghai Rolechem Co., Ltd. | Method for preparing high-purity bisfluorosulfonylimide salt |
| CN114044497A (en) * | 2022-01-13 | 2022-02-15 | 江苏笃行致远新材料科技有限公司 | Synthesis method of bis (fluorosulfonyl) imide |
| US11267707B2 (en) | 2019-04-16 | 2022-03-08 | Honeywell International Inc | Purification of bis(fluorosulfonyl) imide |
| CN114408883A (en) * | 2022-01-29 | 2022-04-29 | 宁德时代新能源科技股份有限公司 | Method for recovering lithium bis (fluorosulfonyl) imide |
| CN114436226A (en) * | 2021-12-30 | 2022-05-06 | 石家庄康坦福化工科技有限公司 | Preparation and application of potassium bis (fluorosulfonyl) imide |
| CN114524422A (en) * | 2022-03-31 | 2022-05-24 | 河南省氟基新材料科技有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
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| CN106800280A (en) * | 2016-12-29 | 2017-06-06 | 衢州康鹏化学有限公司 | It is a kind of double（Fluorosulfonyl）The preparation method of inferior amine salt |
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| CN111320151A (en) * | 2020-02-18 | 2020-06-23 | 白银科奥夫化学科技有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
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| CN114436226A (en) * | 2021-12-30 | 2022-05-06 | 石家庄康坦福化工科技有限公司 | Preparation and application of potassium bis (fluorosulfonyl) imide |
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| CN114408883A (en) * | 2022-01-29 | 2022-04-29 | 宁德时代新能源科技股份有限公司 | Method for recovering lithium bis (fluorosulfonyl) imide |
| CN114524422A (en) * | 2022-03-31 | 2022-05-24 | 河南省氟基新材料科技有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN115231532A (en) * | 2022-08-05 | 2022-10-25 | 金石资源集团股份有限公司 | Preparation method and application of lithium bis (fluorosulfonyl) imide |
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