CN111099566A - Preparation method of co-produced bis (chlorosulfonyl) imide acid and bis (fluorosulfonyl) imide lithium - Google Patents
Preparation method of co-produced bis (chlorosulfonyl) imide acid and bis (fluorosulfonyl) imide lithium Download PDFInfo
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Abstract
The invention discloses a preparation method of coproduced dichlorosulfonyl imide acid and lithium difluorosulfonyl imide, which comprises the following steps: s1, adding sulfuryl chloride into the first solvent, dropwise adding octamethylcyclotetrasilazane, reacting, and purifying to obtain bischlorosulfonimidyl acid; s2, reacting the dichlorosulfonimide acid and anhydrous hydrofluoric acid under the action of a catalyst to obtain the difluorosulfonimide acid; s3, reacting the bis-fluorosulfonyl imide acid and lithium fluoride in a second solvent, and purifying to obtain the bis-fluorosulfonyl imide lithium. The method selects appropriate raw materials and is matched with a solvent method to coproduce and prepare the bis-chlorosulfonyl imide acid and the bis-fluorosulfonyl imide lithium, the preparation process is simple, the byproducts are few and can be recycled, the yield is high, no water is involved in the production process, the obtained bis-chlorosulfonyl imide acid and the bis-fluorosulfonyl imide lithium have high purity, no waste water is generated, the process route is green and environment-friendly, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of new energy materials, in particular to a preparation method of co-produced bis (chlorosulfonyl) imide acid and bis (fluorosulfonyl) imide lithium.
Background
The lithium ion battery as a portable high-specific energy chemical power source is widely applied to the fields of portable instruments, notebook computers, military, mobile communication, cameras and the like, is a preferred matching power source of power automobiles at present, can also be widely applied to the field of energy storage batteries, and is widely researched and applied in the world. The lithium ion battery mainly comprises an anode, a cathode, a diaphragm, electrolyte, a battery system and the like, wherein the electrolyte mainly comprises electrolyte and an organic solvent, is an active component for connecting the anode and the cathode and is an important factor for the performance of the battery. The additive is the most important component in the lithium ion battery electrolyte except for electrolyte and organic solvent, and the proper additive can play a key role in enhancing the performance of the lithium battery.
The bis (chlorosulfonyl) imide acid (HClSI) is an important intermediate, has high economic value, and can be used for synthesizing bis (chlorosulfonyl) imide salt, bis (fluorosulfonyl) imide salt, bis (perfluorododecanol) sulfonyl imide and salts thereof and the like.
Lithium bis (fluorosulfonyl) imide (LiFSI) is an important novel fluorine-containing material, is a key high-performance electrolyte material in lithium ion batteries, supercapacitors and ionic liquids, and has extremely high industrial application value. Compared with the traditional lithium salt lithium hexafluorophosphate, the lithium bis (fluorosulfonyl) imide has the advantages of higher decomposition temperature, better safety performance, higher conductivity, small probability of side reaction, proper conductivity, high thermal stability, high electrochemical stability and the like, and is a novel electrolyte material with wide application prospect. The preparation methods of the bischlorosulfonimide acid and the lithium bisfluorosulfonimide in the prior literatures and patents have certain defects as follows:
in patent CN101747242A, sulfamide reacts with thionyl chloride and chlorosulfonic acid to generate dichlorosulfimide, so that a lot of byproducts exist, the dichlorosulfimide cannot be recycled, and the industrial cost is high.
In patent CN104495767A, sulfuryl chloride and ammonia gas are reacted in the presence of an organic base to obtain an organic base salt of bis (chlorosulfonyl) imide, which has the problems that bis (chlorosulfonyl) imide is difficult to separate from the organic base salt, the use of bis (chlorosulfonyl) imide is limited, and the purity is not high.
In patent CN104925765A, a two-step method is adopted, in the first step, bis-chlorosulfonyl imide reacts with hydrogen fluoride to obtain bis-fluorosulfonyl imide, in the second step, bis-fluorosulfonyl imide reacts with lithium carbonate or lithium hydroxide in a low-polarity solvent to generate lithium bis-fluorosulfonyl imide, thionyl chloride is added to remove moisture, and the solid is further purified after solid-liquid separation. The preparation method has the problems that reaction raw materials and target products are not dissolved in a solvent, the product yield is low, and thionyl chloride used in the dehydration process can bring chloride ions, so that the chloride ions in the products exceed the standard, and the technical indexes of novel lithium salt electrolytes in lithium batteries are difficult to meet.
In patent CN101747242A, sulfonamide reacts with thionyl chloride and chlorosulfonic acid to generate bis (chlorosulfonyl) imide, which reacts with antimony trifluoride to obtain bis (fluorosulfonyl) imide, then reacts with potassium carbonate (cesium or rubidium) to obtain potassium bis (fluorosulfonyl) imide (cesium or rubidium) salt, and finally reacts with lithium (sodium) tetrafluoroborate or lithium perchlorate in an aprotic polar solvent to obtain the product lithium (sodium) bis (fluorosulfonyl) imide. The method has the advantages of overlong process flow, high raw material cost, more byproducts and low purity, and is difficult to realize industrialization.
In the US patent US8377406, bis-fluorosulfonyl imide (HFSI) and lithium carbonate are directly reacted in an aqueous solution to synthesize the product of lithium bis-fluorosulfonyl imide, which is characterized in that the decomposition of the bis-fluorosulfonyl imide is caused by the violent heat release of the HFSI when the HFSI is dissolved in water, and the lithium bis-fluorosulfonyl imide is very hygroscopic and is easily decomposed under the condition of water in the system, so that the product has low purity, low extraction efficiency, increased cost and the like, and is not suitable for industrial production.
In patent CN201710032620.7, fluorosulfonic acid isocyanate and fluorosulfonic acid are reacted to prepare bis-fluorosulfonylimide, and then bis-fluorosulfonylimide is reacted with lithium carbonate to prepare lithium bis-fluorosulfonylimide. The method has the defects that the price of the raw material fluorosulfonic acid isocyanate is high, so that the product cost is too high, and the industrial production is difficult.
In conclusion, the method for preparing the high-efficiency bis-chlorosulfonyl imide acid and the high-efficiency bis-fluorosulfonyl imide lithium is provided, so that the bis-chlorosulfonyl imide acid and the bis-fluorosulfonyl imide lithium are low in production cost, less in three wastes and high in purity, and the problems to be solved by the technical personnel in the field are solved urgently.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of co-production of bischlorosulfonimide acid and lithium bifluorosulfonimide, the preparation method selects appropriate raw materials and is matched with a solvent method to co-produce and prepare the bischlorosulfonimide acid and the lithium bifluorosulfonimide, the preparation process is simple, byproducts are few and can be recycled, the yield is high, no water is involved in the production process, the purity of the obtained bischlorosulfonimide acid and the lithium bifluorosulfonimide is high, no waste water is generated, the process route is green and environment-friendly, and the preparation method is suitable for industrial production.
The invention provides a preparation method of coproduced bis (chlorosulfonyl) imide acid and bis (fluorosulfonyl) imide lithium, which comprises the following steps:
s1, adding sulfuryl chloride into the first solvent, dropwise adding octamethylcyclotetrasilazane, reacting, and purifying to obtain bischlorosulfonimidyl acid;
s2, reacting the dichlorosulfonimide acid and anhydrous hydrofluoric acid under the action of a catalyst to obtain the difluorosulfonimide acid;
s3, reacting the bis-fluorosulfonyl imide acid and lithium fluoride in a second solvent, and purifying to obtain the bis-fluorosulfonyl imide lithium.
Preferably, in S1, the first solvent is at least one of dimethyl carbonate, ethyl acetate, propyl acetate, butyl acetate, acetonitrile, propionitrile, N-dimethylformamide, N-methylpyrrolidone.
Preferably, in S3, the second solvent is at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and acetonitrile.
The chemical reaction equation of the invention is as follows:
2Cl2O2S+C8H28N4Si4＝ClSO2NHSO2Cl+C8H27N3Si4Cl2；
ClSO2NHSO2Cl+2HF＝FSO2NHSO2F+2HCl(g)；
FSO2NHSO2F+LiF＝FSO2NLiSO2F+HF(g)。
preferably, in S1, the step of purifying is: the remaining raw materials and by-products are distilled off first, and then the first solvent is distilled off.
In the above S1, the distilled residual raw material is sulfuryl chloride, the byproduct is octamethylchlorosilane, and the first solvent can be recovered and reused.
The recovered byproduct octamethylchlorosilazane can be reacted with ammonia gas to obtain octamethylcyclotetrasilazane, which is recycled as a raw material in S1.
Preferably, in S3, the purification step is: filtering, taking the filtrate, concentrating, adding an anti-solvent, precipitating a solid, and drying to obtain the lithium bis (fluorosulfonyl) imide.
The HCl gas generated in the reaction in the S2 and the HF gas generated in the reaction in the S3 can be absorbed by alkali liquor, so that the environmental pollution is avoided.
Preferably, the anti-solvent is a non-polar solvent or a weakly polar solvent.
Preferably, the anti-solvent is at least one of dichloromethane, dichloroethane, n-hexane and toluene.
Preferably, the weight ratio of antisolvent to lithium bis (fluorosulfonyl) imide is from 1 to 4: 1.
preferably, in S1, the reaction temperature is 30-120 ℃.
Preferably, in S1, the reaction time is 2-12 h.
Preferably, in S2, the reaction temperature is 90-110 ℃.
Preferably, in S2, the reaction temperature is 95-105 ℃.
Preferably, in S2, the reaction time is 10-20 h.
Preferably, in S3, the reaction temperature is 0-50 ℃.
Preferably, in S3, the reaction temperature is 20-40 ℃.
Preferably, in S3, the reaction time is 1-12 h.
Preferably, in S2, the catalyst is antimony pentachloride.
Preferably, in S1, the molar ratio of sulfuryl chloride to octamethylcyclotetrasilazane is 2 to 4: 1.
preferably, in S2, the molar ratio of the bischlorosulfonimide acid to anhydrous hydrofluoric acid is 1: 2-2.1.
Preferably, in S3, the molar ratio of bis-fluorosulfonyl imide acid to lithium fluoride is 1: 1-1.1.
Preferably, in S1, the volume molar (L/mol) ratio of the first solvent to octamethylcyclotetrasilazane is 0.2 or more.
Preferably, in S3, the volume molar (L/mol) ratio of the second solvent to the bis-fluorosulfonylimide acid is 0.2 or more.
Preferably, the water content of the first solvent and the water content of the second solvent are both less than or equal to 5 ppm.
The lining of the reaction equipment for the reaction is at least one of PFA or PTFE, the water content of a system before the reaction of the reaction equipment is less than or equal to 1ppm, and the reaction equipment is provided with a cooling system.
According to the invention, appropriate raw materials are selected and a solvent method is matched for coproduction of the bis-chlorosulfonyl imide acid and the bis-fluorosulfonyl imide lithium, the preparation process is simple, the byproducts are few and can be recycled, the high-quality bis-chlorosulfonyl imide acid is prepared in S1, the byproducts can be recycled, and the yield is over 97%; the yield of the bis (fluorosulfonyl) imide acid in S2 is more than 90%; the yield of the lithium bis (fluorosulfonyl) imide in the S3 is high, the yield reaches more than 96%, no water is involved in the production process, the obtained bis (chlorosulfonyl) imide acid and the lithium bis (fluorosulfonyl) imide have high purity, no waste water is generated, the process route is green and environment-friendly, and the lithium bis (fluorosulfonyl) imide is suitable for industrial production; the method has the advantages of simple process, easy operation and reliable raw material source, effectively reduces the consumption of raw and auxiliary materials, effectively reduces the production cost, well avoids environmental pollution, reduces the production risk, has low cost and can effectively promote the healthy development of downstream new energy industries.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of coproduced bis (chlorosulfonyl) imide acid and bis (fluorosulfonyl) imide lithium comprises the following steps:
s1, adding 0.25L of anhydrous acetonitrile into a PTFE-lined stainless steel reaction kettle, then adding 135g of sulfuryl chloride, slowly dropwise adding 73.2g of octamethylcyclotetrasilazane by using a pneumatic diaphragm pump while stirring, stirring and reacting at 120 ℃ for 2 hours after dropwise adding is finished, respectively recovering the residual sulfuryl chloride and byproduct octamethylchlorosilane by pressure distillation, and recovering acetonitrile by reduced pressure distillation after recovery is finished to obtain 53g of bischlorosulfonimide acid;
s2, adding 53.5g of bis (chlorosulfonyl) imide acid and 0.042g of antimony pentachloride into a PTFE-lined stainless steel reaction kettle, heating to 90 ℃, slowly introducing 10g of anhydrous hydrofluoric acid gas while stirring, reacting for 20 hours, cooling to room temperature, blowing nitrogen for 10 hours to obtain about 42g of crude product, and performing short-path distillation to obtain 40g of bis (fluorosulfonyl) imide acid with the yield of 90.2%;
s3, adding 0.1L of dimethyl carbonate and 45.3g of bis (fluorosulfonyl) imide acid into a PTFE-lined stainless steel reaction kettle, fully stirring, adding 7.13g of lithium fluoride, reacting at 0 ℃ for 12 hours, absorbing hydrogen fluoride gas generated by the reaction by alkali liquor, filtering to remove residual lithium fluoride, concentrating the filtrate, adding 184g of dichloromethane, separating out solids due to different solubility of substances, and drying in vacuum to obtain 46g of bis (fluorosulfonyl) imide lithium.
Example 2
A preparation method of coproduced bis (chlorosulfonyl) imide acid and bis (fluorosulfonyl) imide lithium comprises the following steps:
s1, adding 0.2L N N-dimethylformamide into a PFA-lined stainless steel reaction kettle, then adding 135g of sulfuryl chloride, slowly dropwise adding 146.4g of octamethylcyclotetrasilazane by using a pneumatic diaphragm pump while stirring, stirring and reacting at 30 ℃ for 12 hours after dropwise adding is finished, respectively recovering the residual sulfuryl chloride and byproduct octamethylcyclosilane by pressure distillation, and recovering acetonitrile by reduced pressure distillation after recovery is finished to obtain 104.6g of bischlorosulfonimidyl acid;
s2, adding 107g of bis (chlorosulfonyl) imide acid and 0.084g of antimony pentachloride into a PTFE (polytetrafluoroethylene) lined stainless steel reaction kettle, heating to 110 ℃, slowly introducing 20g of anhydrous hydrofluoric acid gas while stirring, reacting for 10 hours, cooling to room temperature, blowing nitrogen for 15 hours to obtain about 86g of crude product, and performing short-path distillation to obtain 84.6g of bis (fluorosulfonyl) imide acid with the yield of 93.4%;
s3, adding 0.2L of dimethyl carbonate and 90.57g of bis (fluorosulfonyl) imide acid into a PFA-lined stainless steel reaction kettle, fully stirring, adding 12.97g of lithium fluoride, reacting at 50 ℃ for 1h, absorbing hydrogen fluoride gas generated by the reaction by alkali liquor, filtering to remove residual lithium fluoride, concentrating the filtrate, adding 87.8g of dichloroethane, precipitating solids due to different solubility of substances, and vacuum drying to obtain 87.8g of bis (fluorosulfonyl) imide lithium.
Example 3
A preparation method of coproduced bis (chlorosulfonyl) imide acid and bis (fluorosulfonyl) imide lithium comprises the following steps:
s1, adding 0.1L of ethyl acetate into a PTFE-lined stainless steel reaction kettle, then adding 135g of sulfuryl chloride, slowly dropwise adding 117.1g of octamethylcyclotetrasilazane by using a pneumatic diaphragm pump while stirring, stirring and reacting at 60 ℃ for 8 hours after dropwise adding, respectively recovering the residual sulfuryl chloride and byproduct octamethylcyclosilane by pressure distillation, and recovering acetonitrile by reduced pressure distillation after recovering to obtain 84.7g of bischlorosulfonimide acid;
s2, adding 85.6g of bis (chlorosulfonyl) imide acid and 0.067g of antimony pentachloride into a PTFE (polytetrafluoroethylene) lined stainless steel reaction kettle, heating to 95 ℃, slowly introducing 16.8g of anhydrous hydrofluoric acid gas while stirring, reacting for 18 hours, cooling to room temperature, blowing nitrogen for 15 hours to obtain about 69g of crude product, and performing short-path distillation to obtain 68.47g of bis (fluorosulfonyl) imide acid with the yield of 94.5%;
s3, adding 0.1L of anhydrous acetonitrile and 72.5g of bis (fluorosulfonyl) imide acid into a PTFE-lined stainless steel reaction kettle, fully stirring, adding 10.4g of lithium fluoride, reacting at 20 ℃ for 4 hours, absorbing hydrogen fluoride gas generated by the reaction by alkali liquor, filtering to remove residual lithium fluoride, concentrating the filtrate, adding 146.4g of n-hexane, separating out solids due to different solubility of substances, and drying in vacuum to obtain 73.2g of bis (fluorosulfonyl) imide lithium.
Example 4
A preparation method of coproduced bis (chlorosulfonyl) imide acid and bis (fluorosulfonyl) imide lithium comprises the following steps:
s1, adding 0.2L of anhydrous propionitrile into a PTFE-lined stainless steel reaction kettle, then adding 135g of sulfuryl chloride, slowly dropwise adding 146.4g of octamethylcyclotetrasilazane by using a pneumatic diaphragm pump while stirring, stirring and reacting for 6 hours at 80 ℃ after dropwise adding, respectively recovering the residual sulfuryl chloride and byproduct octamethylcyclosilane by pressure distillation, and recovering propionitrile by reduced pressure distillation after recovering to obtain 105.6g of difluorosulfonimide acid;
s2, adding 107g of bis (chlorosulfonyl) imide acid and 0.084g of antimony pentachloride into a PTFE (polytetrafluoroethylene) lined stainless steel reaction kettle, heating to 105 ℃, slowly introducing 21g of anhydrous hydrofluoric acid gas while stirring, reacting for 15 hours, cooling to room temperature, blowing nitrogen for 15 hours to obtain about 88g of crude product, and carrying out short-path distillation to obtain 86.2g of bis (fluorosulfonyl) imide acid with the yield of 95.2%;
s3, adding 0.2L of methyl ethyl carbonate and 90.57g of bis (fluorosulfonyl) imide acid into a PTFE-lined stainless steel reaction kettle, fully stirring, adding 14.2g of lithium fluoride, reacting at 40 ℃ for 3 hours, absorbing hydrogen fluoride gas generated by the reaction by alkali liquor, filtering to remove residual lithium fluoride, concentrating the filtrate, adding 367.2g of toluene, precipitating solids due to different solubility of substances, and drying in vacuum to obtain 91.8g of bis (fluorosulfonyl) imide lithium.
The bischlorosulfonimide acid and lithium bisfluorosulfonimide prepared in examples 1 to 4 were tested and the yields were counted, and the results are shown in tables 1 and 2:
TABLE 1 detection and analysis table for bischlorosulfonimide acid
TABLE 2 lithium bis (fluorosulfonyl) imide test Table
As can be seen from tables 1 and 2, the bischlorosulfonimide acid and the lithium bisfluorosulfonimide prepared by the co-production method have good purity and high yield.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A preparation method of co-produced bis (chlorosulfonyl) imide acid and bis (fluorosulfonyl) imide lithium is characterized by comprising the following steps:
s1, adding sulfuryl chloride into the first solvent, dropwise adding octamethylcyclotetrasilazane, reacting, and purifying to obtain bischlorosulfonimidyl acid;
s2, reacting the dichlorosulfonimide acid and anhydrous hydrofluoric acid under the action of a catalyst to obtain the difluorosulfonimide acid;
s3, reacting the bis-fluorosulfonyl imide acid and lithium fluoride in a second solvent, and purifying to obtain the bis-fluorosulfonyl imide lithium.
2. The method for preparing the coproduction of the bischlorosulfonimide acid and the lithium bisfluorosulfonimide according to claim 1, wherein in S1, the first solvent is at least one of dimethyl carbonate, ethyl acetate, propyl acetate, butyl acetate, acetonitrile, propionitrile, N-dimethylformamide, and N-methylpyrrolidone; preferably, in S3, the second solvent is at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and acetonitrile.
3. The method for producing bis (chlorosulfonyl) imide acid and lithium bis (fluorosulfonyl) imide as claimed in claim 1 or 2, wherein the purification step in S1 is: the remaining raw materials and by-products are distilled off first, and then the first solvent is distilled off.
4. The method for preparing the coproduction of the bischlorosulfonimide acid and the lithium bisfluorosulfonimide according to any one of claims 1 to 3, wherein in S3, the purification step is: filtering, concentrating the filtrate, adding an anti-solvent, separating out a solid, and drying to obtain lithium bis (fluorosulfonyl) imide; preferably, the anti-solvent is a non-polar solvent or a weakly polar solvent; preferably, the antisolvent is at least one of dichloromethane, dichloroethane, n-hexane and toluene; preferably, the weight ratio of antisolvent to lithium bis (fluorosulfonyl) imide is from 1 to 4: 1.
5. the method for preparing the coproduction of the bischlorosulfonimide acid and the lithium bisfluorosulfonimide acid as claimed in any one of claims 1 to 4, wherein in S1, the reaction temperature is 30 to 120 ℃; preferably, in S1, the reaction time is 2-12 h.
6. The method for preparing the coproduction of the bischlorosulfonimide acid and the lithium bisfluorosulfonimide acid as claimed in any one of claims 1 to 5, wherein in S2, the reaction temperature is 90 to 110 ℃; preferably, in S2, the reaction temperature is 95-105 ℃; preferably, in S2, the reaction time is 10-20 h.
7. The method for preparing the coproduction of the bischlorosulfonimide acid and the lithium bisfluorosulfonimide acid as claimed in any one of claims 1 to 6, wherein in S3, the reaction temperature is 0 to 50 ℃; preferably, in S3, the reaction temperature is 20-40 ℃; preferably, in S3, the reaction time is 1-12 h.
8. The method for preparing the coproduction of the bischlorosulfonimide acid and the lithium bisfluorosulfonimide acid as claimed in any one of claims 1 to 7, wherein in S2, the catalyst is antimony pentachloride.
9. The method for producing bis (chlorosulfonyl) imide acid and lithium bis (fluorosulfonyl) imide as claimed in any one of claims 1 to 8, wherein the molar ratio of sulfuryl chloride to octamethylcyclotetrasilazane at S1 is 2 to 4: 1; preferably, in S2, the molar ratio of the bischlorosulfonimide acid to anhydrous hydrofluoric acid is 1: 2-2.1; preferably, in S3, the molar ratio of bis-fluorosulfonyl imide acid to lithium fluoride is 1: 1-1.1.
10. The method for preparing the coproduction of the bischlorosulfonimidyl acid and the lithium bisfluorosulfonylimide according to any one of claims 1 to 9, wherein in S1, the volume molar (L/mol) ratio of the first solvent to octamethylcyclotetrasilazane is not less than 0.2; preferably, in S3, the volume molar (L/mol) ratio of the second solvent to the bis-fluorosulfonyl imide acid is 0.2 or more; preferably, the water content of the first solvent and the water content of the second solvent are both less than or equal to 5 ppm.
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| CN111573639A (en) * | 2020-05-12 | 2020-08-25 | 广州理文科技有限公司 | Method for preparing lithium bis (fluorosulfonyl) imide by using organic metal lithium reagent |
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| CN113979454B (en) * | 2021-11-23 | 2023-09-26 | 山东永浩新材料科技有限公司 | Preparation method of alkali metal fluorosulfonate |
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| CN115304039B (en) * | 2022-10-10 | 2022-12-06 | 山东海科新源材料科技股份有限公司 | Purification device and method for bis (chlorosulfonyl) imide |
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