WO2014106362A1 - Preparation method of imidodisulfuryl fluoride lithium - Google Patents

Abstract

The present invention provides a preparation method of imidodisulfuryl fluoride lithium, comprising: obtaining an imidodisulfuryl fluoride lithium product by a metathesis reaction of lithium bis(oxalate)borate or lithium difluoro(oxalato)borate and bis(fluorosulfonyl)imide potassium salt in a solvent. The preparation method of imidodisulfuryl fluoride lithium in the present invention is simple in process route and easy to realize industrialized preparation.

Description

 The present invention claims to be submitted to the Chinese Intellectual Property Office on January 5, 2013, entitled "Preparation Method of Lithium Difluorosulfonimide Lithium" (China Application No. 201310002647.3) Priority of the Invention The content of the invention is hereby incorporated by reference in its entirety. Technical field

 The invention relates to a preparation method of lithium bisfluorosulfonimide, in particular to preparing a difluorosulfonamide by a metathesis exchange reaction of lithium bis(oxalate)borate or lithium oxalate difluoroborate with a potassium salt of bisfluorosulfonimide. Lithium amine. Background technique

 Difluorosulfonimide lithium can be used in various fields, for example, it can be used as a lithium ion battery electrolyte additive to improve the cycle performance of lithium ion batteries, and can also be used as a primary battery electrolyte; as a polymerization catalyst; Use of antistatic agents in the industrial field.

 The bisfluorosulfonamide compound referred to in the present invention:

 Now studies have shown that lithium bisfluoro sulfonimide is used in the electrolyte of rechargeable lithium battery, which can effectively reduce the high and low temperature resistance of the SEI layer formed on the surface of the electrode plate at low temperature, and reduce the lithium battery during the placement process. The capacity loss, thereby providing a high-capacity battery, improves the electrochemical performance of the battery.

For the preparation technology of lithium bisfluorosulfonimide, it has been reported at home and abroad that the bis-difluorosulfonimide potassium salt is metathesized and exchanged with lithium perchlorate or lithium tetrafluoroborate in an aprotic polar solvent. However, it has the following disadvantages: Lithium perchlorate and lithium tetrafluoroborate as raw materials for the reaction have a large solubility in a solvent, resulting in lithium perchlorate and tetra contained in the final lithium difluorosulfonimide product. Lithium fluoroborate is difficult to separate and the product is not easily purified. Moreover, lithium perchlorate friction or impact is liable to cause burning or explosion, Come to a big security risk.

 In view of the above disadvantages, the present invention utilizes lithium bis(oxalate)borate or lithium oxalate difluoroborate and bis-fluorosulfonimide potassium salt in a solvent (dimethyl carbonate, acetonitrile, nitromethane, etc.) to form a difluorosulfonamide. Lithium amine, which has a lower solubility than lithium perchlorate or lithium tetrafluoroborate, such as lithium bis(oxalate)borate is almost insoluble in dimethyl carbonate; and there is no safety problem.

The inventors of the present invention have found a new process suitable for the preparation of lithium bisfluorosulfonimide after intensive research on the problems existing in the prior art. In the present invention, lithium bis(sulfonate) borate or lithium oxalate difluoroborate and potassium bisfluorosulfonimide are complex-dissociated in a solvent (dimethyl carbonate, acetonitrile, nitromethane, etc.) to obtain lithium bisfluorosulfonimide.

 Specifically, the present invention provides a method for preparing lithium bisfluorosulfonimide, the method comprising: performing lithium bis(oxalate)borate or lithium oxalate difluoroborate and potassium bisfluorosulfonimide in a solvent. The metathesis exchange reaction yields a lithium bisfluorosulfonimide product.

 The formula is:

 In one embodiment of the invention, the method further comprises extracting, filtering, washing and drying the lithium bisfluorosulfonamide product using an extraction solvent. In the present invention, the extraction solvent used for the extraction includes a nonpolar solvent such as dichloromethane, toluene or cyclohexane.

-2— Replacement page (Article 26) In the present invention, the purpose of the extraction is to extract the solvent which is not completely evaporated, and directly granulate, so that the amount (volume amount) of the extraction solvent may be large or small.

 In one embodiment of the invention, the solvent is selected from the group consisting of linear carbonates. In one embodiment of the present invention, the solvent is selected from the group consisting of dimethyl carbonate, acetonitrile, nitroformamidine, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl acetate, tetrahydrofuran, acetone, and double Trifluoroethyl carbonate, methyl trifluoroethyl carbonate, ethyl trifluoroethyl carbonate, 1,2-dimethoxyacetamidine, 1, 3-dioxolan and methyl formate.

 In one embodiment of the invention, the metathesis exchange reaction is carried out at a temperature below the boiling point of the solvent.

 In one embodiment of the invention, the metathesis exchange reaction is carried out at a temperature of from 5 to 60 °C. In one embodiment of the present invention, after the metathesis exchange reaction is carried out for 1 hour, the reaction is completed at 90% or more.

 In one embodiment of the invention, the metathesis exchange reaction is carried out for 0.5 to 24 hours, preferably for 1 to 12 hours.

 In one embodiment of the present invention, the lithium bis(oxalate)borate or lithium oxalate difluoroborate is reacted with a potassium salt of bisfluorosulfonimide in an equimolar ratio. In the present invention, an equimolar ratio is considered in consideration of the potassium residual amount, but lithium bis(oxalate)borate or lithium difluoroborate may be used in excess, except that an excessive amount of the raw material remains in the product.

 In one embodiment of the invention, the drying is carried out at a temperature of from 20 to 60 ° C and a pressure of from 10 to 30 kPa.

 Compared with the prior art method using lithium perchlorate or lithium tetrafluoroborate, the method for preparing lithium bis sulfonimide of the present invention has the following technical advantages:

 (1) Lithium bis(oxalate) borate or lithium oxalate diborate has lower solubility than lithium perchlorate or lithium tetrafluoroborate, such as lithium bis(oxalate)borate which is almost insoluble in dimethyl carbonate; thus, difluorosulfonate The final product of lithium imide is easy to purify, has a lower purification cost, and contains less impurities.

 (2) Lithium bis(oxalate) borate or lithium oxalate diborate does not have the safety hazard of burning or explosion caused by friction or impact of lithium perchlorate, and has a better prospect in the safety of industrial production.

(3) The preparation method of the lithium bisfluorosulfonimide of the present invention has a simple process route and is easy to realize industrial preparation. DRAWINGS

 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an infrared spectrum chart of lithium bisfluorosulfonimide of the present invention.

 Figure 2 is a F (19) R spectrum of the bisfluorosulfonimide lithium of the present invention (ZCIRI 1-400; F19-WLYP-6338; pulase sequence: s2pul; solvent: acetone; room temperature; INOVA -400 "ZC400"; relaxation time delay (relax. Delay): 3.000 seconds; pulse: 45.0 degrees; acquisition time (Acq. time): 1.812 seconds; width: 144.7 kHz; 32 repetitions; observation: F19, 376.3177408 MHz Data processing: FT size (FT size) 524288; total time: 2 minutes, 34 seconds). detailed description

 The invention will be further described in detail below with reference to the specific embodiments, and the advantages of the invention will be more clearly understood. It is to be understood that the contents are merely illustrative and are not intended to limit the scope of the invention. The experimental methods in the following examples, which do not specify the specific conditions, are usually carried out according to the usual conditions or according to the conditions recommended by the manufacturer. Unless otherwise stated, all parts are by weight and all percentages are by weight. Example 1

 219 g (lmol) of bisfluorosulfonimide potassium salt, 194 g (lmol) of lithium oxalate borate and 1000 ml of dimethyl carbonate were added to a three-necked flask under a dry nitrogen atmosphere, and the reaction was stirred at room temperature for 12 hours, and filtered under reduced pressure to remove insoluble. The filtrate was concentrated to about 150 ml under reduced pressure, and then an equal volume of methylene chloride was added thereto. After being cooled to room temperature, it was filtered, washed, and dried to obtain 150 g of lithium bisfluorosulfonimide.

The product was inspected by infrared light at 1387cm- ¹ , 1223cm" ¹ , 1185cm" ¹ , 852cm" ¹ , 777cm" ¹ , S Scm was determined as a difluorosulfonamide by comparison with the standard spectrum of bisfluorosulfonimide. A characteristic group of lithium amine. Example 2

219 g (lmol) of bisfluorosulfonimide potassium salt, 144 g (lmol) of lithium oxalate diborate and 1000 ml of dimethyl carbonate were added to a three-necked flask under a dry nitrogen atmosphere, and the reaction was stirred at room temperature for 12 hours. The insoluble matter was removed by pressure filtration, and the filtrate was concentrated to about 150 ml under reduced pressure, and then an equal volume of methylene chloride was added thereto. After being cooled to room temperature, it was filtered, washed, and dried to obtain 138 g of lithium bisfluorosulfonimide.

The product was subjected to infrared detection at 1387 cm - ¹ , 1223 cm " ¹ , 1185 cm " ¹ , 852 cm " ¹ , cm - ^ Scm - ¹ by comparison with the standard spectrum of bisfluorosulfonimide to determine the difluorosulfonamide Characteristic group of lithium amine. Example 3

 Under a dry nitrogen atmosphere, 219 g (1 mol) of bisfluorosulfonimide potassium salt, 194 g (lmol) of lithium oxalate borate and 1200 ml of ethyl methyl carbonate were added to the three-necked flask, and the reaction was stirred at room temperature for 12 hours, and filtered under reduced pressure to remove insoluble. The filtrate was concentrated under reduced pressure to about 165 ml, and then an equal volume of methylene chloride was added thereto. After being cooled to room temperature, it was filtered, washed, and dried to obtain 158 g of lithium bisfluorosulfonimide.

The product was inspected by infrared light at 1387cm- ¹ , 1223cm" ¹ , 1185cm" ¹ , 852cm" ¹ , 777cm" ¹ , S Scm was determined as a difluorosulfonamide by comparison with the standard spectrum of bisfluorosulfonimide. A characteristic group of lithium amine. Example 4

 Under a dry nitrogen atmosphere, 219 g (1 mol) of bisfluorosulfonimide potassium salt, 194 g (lmol) of lithium oxalate borate and 1200 ml of ethyl acetate were added to the three-necked flask, and the reaction was stirred at room temperature for 12 hours, and the insoluble matter was removed by filtration under reduced pressure. The filtrate was concentrated under reduced pressure to about 140 ml, and then an equal volume of methylene chloride was added thereto. After being cooled to room temperature, it was filtered, washed, and dried to obtain 126 g of lithium bisfluorosulfonimide.

The product was inspected by infrared light at 1387cm- ¹ , 1223cm" ¹ , 1185cm" ¹ , 852cm" ¹ , 777cm" ¹ , S Scm was determined as a difluorosulfonamide by comparison with the standard spectrum of bisfluorosulfonimide. A characteristic group of lithium amine. It is to be understood that various changes and modifications may be made by those skilled in the art in the <RTIgt;

Claims

Rights request

 A method for preparing a lithium bisfluorosulfonimide, the method comprising: performing a metathesis exchange reaction of lithium bis(oxalate)borate or lithium oxalate difluoroborate with a potassium salt of bisfluorosulfonimide in a solvent, Lithium difluorosulfonimide product.

2. The method for preparing lithium bisfluorosulfonate according to claim 1, wherein the structural formula of the lithium oxalate borate is:

\一₀ \ — Z

 Z— The structural formula of the lithium oxalate difluoroborate is:

 The method for producing lithium bisfluorosulfonate according to claim 1, wherein the method further comprises extracting, filtering, washing and drying the lithium bisfluorosulfonimide product using an extraction solvent.

The method for producing lithium bisfluorosulfonimide according to claim 1 or 3, wherein the solvent is selected from the group consisting of linear carbonates.

The method for preparing lithium bisfluorosulfonimide according to claim 1 or 3, wherein the solvent is selected from the group consisting of dimethyl carbonate, acetonitrile, nitromethane, ethyl methyl carbonate, and diethyl carbonate. Ester, methyl propyl carbonate, ethyl acetate, tetrahydrofuran, acetone, bistrifluoroethyl carbonate, methyl trifluoroethyl carbonate, ethyl trifluoroethyl carbonate, 1,2-dimethoxyethane, 1, 3-dioxolane and methyl formate.

The process for producing lithium bisfluorosulfonate according to claim 1 or 3, wherein the metathesis exchange reaction is carried out at a temperature lower than the boiling point of the solvent.

Replacement page (Article 26)

The method for producing lithium bisfluorosulfonate according to claim 1 or 3, wherein the metathesis exchange reaction is carried out at a temperature of from 5 to 60 °C.

The method for producing lithium bisfluorosulfonate according to claim 1 or 3, wherein after the metathesis exchange reaction is carried out for 1 hour, the reaction is completed at 90% or more.

The process for producing lithium bisfluorosulfonate according to claim 1 or 3, wherein the metathesis exchange reaction is carried out for 0.5 to 24 hours, preferably for 1 to 12 hours.

The method for producing lithium bisfluorosulfonimide according to claim 1 or 3, wherein the lithium bis(oxalate) borate or lithium oxalate difluoroborate and a potassium salt of bisfluorosulfonimide are waitable The molar ratio is reacted.

The method for producing lithium bisfluorosulfonimide according to claim 3, wherein the drying is carried out at a temperature of 20 to 60 ° C and a pressure of 10 to 30 kPa.