CN116040593A - Preparation method of difluoro-sulfonyl imide, lithium difluoro-sulfonyl imide, preparation method and application thereof - Google Patents
Preparation method of difluoro-sulfonyl imide, lithium difluoro-sulfonyl imide, preparation method and application thereof Download PDFInfo
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- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical group FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000013067 intermediate product Substances 0.000 claims abstract description 22
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims abstract description 18
- XPVRBHCXMWRJEY-UHFFFAOYSA-N difluoro(imino)-$l^{4}-sulfane Chemical compound FS(F)=N XPVRBHCXMWRJEY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 238000005191 phase separation Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 5
- -1 bis-fluorosulfonyl imide Chemical class 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000007791 liquid phase Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 11
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 10
- CTIKAHQFRQTTAY-UHFFFAOYSA-N fluoro(trimethyl)silane Chemical compound C[Si](C)(C)F CTIKAHQFRQTTAY-UHFFFAOYSA-N 0.000 claims description 9
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a preparation method of difluoro-sulfonyl imide, lithium difluoro-sulfonyl imide, a preparation method and application thereof, wherein the preparation method of difluoro-sulfonyl imide comprises the following steps: the sulfonyl fluoride and hexamethyl silazane react in inert atmosphere to obtain an intermediate product, and the intermediate product is subjected to gas phase separation to obtain the difluoro sulfonyl imide. According to the invention, sulfonyl fluoride and hexamethyl silazane are used as raw materials to prepare the difluoro sulfonyl imide by a one-step method, so that the cost is reduced, and the production safety is improved. The prepared difluoro sulfimide is used as a high-quality raw material for preparing difluoro sulfimide lithium, so that the difluoro sulfimide lithium is applied to a lithium ion battery and has excellent electrochemical performance.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, relates to a preparation method of difluoro-sulfonyl imide, and in particular relates to a preparation method of difluoro-sulfonyl imide, a difluoro-sulfonyl-imide lithium and a preparation method and application thereof.
Background
The lithium hexafluorophosphate has stable performance, is a core material in the fields of current digital lithium batteries and power lithium batteries, but is used as lithium salt in the use process of the batteries, and HF is easy to generate. The lithium bis (fluorosulfonyl) imide has higher stability, and meanwhile, the lithium bis (fluorosulfonyl) imide has the advantages of excellent low-temperature performance, high conductivity, environmental friendliness and high safety, and is the material most likely to be a lithium hexafluorophosphate substitute on electrolyte at present. The difluoro-sulfonyl imide is an important intermediate for synthesizing the difluoro-sulfonyl imide lithium, and can be synthesized with reagents such as metal lithium, inorganic lithium salt, organic lithium or lithium hydride and the like to obtain the difluoro-sulfonyl imide lithium.
CN110436424a discloses a process for preparing bis-fluorosulfonyl imide, preparing s.nhf complex, mixing s.nhf complex with bis-chlorosulfonyl imide, reacting to form a mixture containing bis-fluorosulfonyl imide, distilling the mixture, and collecting the fraction of bis-fluorosulfonyl imide. However, the preparation process is costly for the distillation process of mixtures containing bisfluorosulfonyl imide.
CN114604832a discloses a preparation method of bis (fluorosulfonyl) imide and application of bis (fluorosulfonyl) imide lithium. And purifying the fluorosulfonic acid isocyanate and the fluorosulfonic acid obtained by the fluorination reaction under the catalysis to obtain the difluoro sulfimide. However, the fluorination reaction process of the fluorosulfonic acid isocyanate and the fluorosulfonic acid is complex, and the production cost of the whole process can be increased.
The existing method for preparing the difluoro sulfonyl imide has complicated process, high three wastes, low safety and high cost, so how to prepare the difluoro sulfonyl imide with low cost and high safety is an important research direction in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of difluoro-sulfonyl imide, lithium difluoro-sulfonyl imide, and a preparation method and application thereof. The difluoro sulfimide is prepared by one-step low-cost preparation.
To achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a preparation method of difluoro-sulfonyl imide, which comprises the following steps: the sulfonyl fluoride and hexamethyl silazane react in inert atmosphere to obtain an intermediate product, and the intermediate product is subjected to gas phase separation to obtain the difluoro sulfonyl imide.
The structural formula of the sulfonyl fluoride is shown as a formula 1,
the structural formula of the hexamethyl-silazane is shown as formula 2, and the formula is->
In the formula 2, sulfonyl fluoride and hexamethyl-silazane are used as raw materials to prepare the difluoro sulfonyl imide by a one-step method, so that the cost is reduced, the production safety is improved, the introduction of impurities can be effectively avoided, the moisture is isolated, and the product quality is improved. />
In the present invention, the reaction of sulfonyl fluoride and hexamethyl silazane is carried out in the absence of a solvent.
As a preferable technical scheme of the invention, the molar ratio of the sulfonyl fluoride to the hexamethyl-silazane is (1.8-5): 1, wherein the molar ratio may be 1.8: 1. 1.9: 1. 2.0: 1. 2.5: 1. 3: 1. 3.5: 1. 4: 1. 4.5:1 or 5:1, etc., but not limited to the recited values, other non-recited values within the range are equally applicable, preferably (1.8-3): 1.
as a preferred embodiment of the present invention, the inert atmosphere includes an argon atmosphere and/or a nitrogen atmosphere.
The temperature of the reaction is preferably 40 to 110 ℃, wherein the temperature may be 40 ℃, 50 ℃, 60 ℃, 70 ℃,80 ℃,90 ℃,100 ℃, 110 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range are equally applicable, and further preferably 80 to 110 ℃.
Preferably, the reaction time is 1 to 14h, wherein the time may be 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The reaction time is 1-14 h, the excessive impurity in the reaction time affects the yield, and the short reaction time does not affect the yield completely.
As a preferred embodiment of the present invention, the intermediate product comprises trimethylfluorosilane in the gas phase and bisfluorosulfonimide in the liquid phase.
The temperature of the gas phase separation is preferably 17 to 80 ℃, wherein the temperature may be 17 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃,40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃,80 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the gas phase separation time is 1 to 4 hours, wherein the time can be 1 hour, 2 hours, 3 hours or 4 hours, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the invention, the liquid phase bis-fluorosulfonyl imide is subjected to rectification treatment to obtain the bis-fluorosulfonyl imide.
The temperature of the rectification treatment is preferably 125 to 165 ℃, wherein the temperature may be 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the time of the rectification treatment is 1-6 h, wherein the time can be 1h, 2h, 3h, 4h, 5h or 6h, etc., but is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
the molar ratio is (1.8-5): 1 and hexamethyl silazane react for 1-14 h at 40-110 ℃ in inert atmosphere to obtain an intermediate product, and the intermediate product is subjected to gas phase separation to obtain the difluoro sulfonimide.
The second object of the present invention is to provide a lithium difluorosulfonimide, wherein the raw material of the lithium difluorosulfonimide is difluorosulfonimide, and the difluorosulfonimide is prepared by the preparation method according to one of the objects.
It is a third object of the present invention to provide a method for producing lithium difluorosulfimide as defined in the second object, comprising:
and (3) carrying out reaction on the difluoro-sulfonyl imide and lithium fluoride to complete ion exchange, thereby obtaining the difluoro-sulfonyl imide lithium.
As a preferred embodiment of the present invention, the molar ratio of the bis-fluorosulfonyl imide to the lithium fluoride is 1:1 to 1:2, wherein the molar ratio may be 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, or 1:2, etc., but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Preferably, the temperature of the reaction is 100 to 150 ℃, wherein the temperature may be 100 ℃,105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the atmosphere of the reaction is an argon atmosphere and/or a nitrogen atmosphere.
Preferably, the hydrogen fluoride gas as a by-product is evaporated after the reaction is completed.
Preferably, the evaporating temperature is 100 to 150 ℃, wherein the temperature may be 100 ℃,105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The lithium fluoride in the invention has enough solubility in hydrogen fluoride, can fully react with the difluoro-sulfonyl imide, and can be obtained by evaporating hydrogen fluoride gas after the reaction is finished, and the preparation process is simple.
It is a fourth object of the present invention to provide the use of lithium bis-fluorosulfonyl imide as defined in the second object, for use in lithium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, sulfonyl fluoride and hexamethyl-silazane are used as raw materials to prepare the difluoro-sulfonyl imide by a one-step method, so that the cost is reduced, the production safety is improved, the introduction of impurities can be effectively avoided under the inert gas atmosphere, the moisture is isolated, the product quality is improved, the yield of the prepared difluoro-sulfonyl imide is high and can reach more than 90%, the purity is more than or equal to 99.5%, and the prepared difluoro-sulfonyl imide is used as a high-quality raw material to prepare high-purity difluoro-sulfonyl imide lithium, so that the difluoro-sulfonyl imide lithium is applied to a lithium ion battery and has excellent electrochemical performance.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
"optional" or "any" means that the subsequently described event or event may or may not occur, and that the description includes both cases where the event occurs and cases where the event does not.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
The description of the terms "one embodiment," "some embodiments," "exemplarily," "specific examples," or "some examples," etc., herein described means that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this document, the schematic representations of the above terms are not necessarily for the same embodiment or example.
The technical features of the respective embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Example 1
The embodiment provides a preparation method of difluoro-sulfonyl imide:
the molar ratio is 2:1 and hexamethyl silane are reacted for 6 hours at a high temperature of 100 ℃ in an argon atmosphere to obtain an intermediate product, namely gas-phase trimethyl fluorosilane and liquid-phase difluoro sulfonimide, the intermediate product is separated for 2 hours at 50 ℃ in a gas phase to obtain liquid-phase difluoro sulfonimide, and the liquid-phase difluoro sulfonimide is rectified for 4 hours at 140 ℃ to obtain the difluoro sulfonimide.
Example 2
The embodiment provides a preparation method of difluoro-sulfonyl imide:
the molar ratio is 2.2:1 and hexamethyl silane are reacted for 8 hours at a high temperature of 90 ℃ in a nitrogen atmosphere to obtain an intermediate product, namely gas-phase trimethyl fluorosilane and liquid-phase difluoro sulfonimide, the intermediate product is separated for 2 hours at 50 ℃ to obtain liquid-phase difluoro sulfonimide, and the liquid-phase difluoro sulfonimide is rectified for 4 hours at 140 ℃ to obtain the difluoro sulfonimide.
Example 3
The embodiment provides a preparation method of difluoro-sulfonyl imide:
the molar ratio is 1.8:1 and hexamethyl silane are reacted for 11 hours at a high temperature of 80 ℃ in an argon atmosphere to obtain an intermediate product, namely gas-phase trimethyl fluorosilane and liquid-phase difluoro sulfonimide, the intermediate product is separated for 2 hours at 50 ℃ in a gas phase to obtain liquid-phase difluoro sulfonimide, and the liquid-phase difluoro sulfonimide is rectified for 4 hours at 140 ℃ to obtain the difluoro sulfonimide.
Example 4
The embodiment provides a preparation method of difluoro-sulfonyl imide:
the molar ratio is 3:1 and hexamethyl silane are reacted for 5 hours at a high temperature of 105 ℃ in an argon atmosphere to obtain an intermediate product, namely gas-phase trimethyl fluorosilane and liquid-phase difluoro sulfonimide, the intermediate product is separated for 2 hours at 50 ℃ in a gas phase to obtain liquid-phase difluoro sulfonimide, and the liquid-phase difluoro sulfonimide is rectified for 4 hours at 140 ℃ to obtain the difluoro sulfonimide.
Example 5
The embodiment provides a preparation method of difluoro-sulfonyl imide:
the molar ratio is 2.5:1 and hexamethyl silane are reacted for 8 hours at a high temperature of 90 ℃ in an argon atmosphere to obtain an intermediate product, namely gas-phase trimethyl fluorosilane and liquid-phase difluoro sulfonimide, the intermediate product is separated for 2 hours at 50 ℃ in a gas phase to obtain liquid-phase difluoro sulfonimide, and the liquid-phase difluoro sulfonimide is rectified for 4 hours at 140 ℃ to obtain the difluoro sulfonimide.
Example 6
The molar ratio of the catalyst to the catalyst was divided into 2:1 and hexamethyl silazane with a molar ratio of 1.5:1 and hexamethyl-silazane, the same conditions as in example 1.
Example 7
The molar ratio of the catalyst to the catalyst was divided into 2:1 and hexamethyl silazane with a molar ratio of 4:1 and hexamethyl-silazane, the same conditions as in example 1.
Example 8
This example was conducted in the same manner as in example 1 except that the high-temperature reaction at 100℃for 6 hours was replaced with the high-temperature reaction at 75℃for 12 hours.
Example 9
This example was conducted in the same manner as in example 1 except that the high-temperature reaction at 100℃for 6 hours was replaced with the high-temperature reaction at 75℃for 16 hours.
Comparative example 1
The comparative example provides a method for preparing bis-fluorosulfonyl imide: 150mL of anhydrous acetonitrile is added into a reaction kettle, then 76.5g of sulfonyl fluoride is added, 40.35g of hexamethyl-silazane is slowly added at room temperature by a pump, after the addition is finished, the reaction is carried out for 3 hours at 90 ℃, then unreacted sulfonyl fluoride and trimethyl fluorosilane produced by the reaction are respectively recovered by pressurized distillation, and after the recovery of sulfonyl fluoride and trimethyl fluorosilane is finished, the solvent is recovered by reduced pressure distillation and rectification is carried out, thus obtaining the target product difluoro sulfimide.
The purity and yield of the bisfluorosulfonyl imide of examples 1 to 9 and comparative example 1 were measured by ion chromatography, and the measurement results are shown in table 1.
TABLE 1
| Purity (%) | Yield (%) | |
| Example 1 | 99.8 | 92.7％ |
| Example 2 | 99.7 | 91.9％ |
| Example 3 | 99.5 | 93.3％ |
| Example 4 | 99.7 | 95.5％ |
| Example 5 | 99.6 | 92.6％ |
| Example 6 | 99.2 | 87.5％ |
| Example 7 | 99.0 | 89.4％ |
| Example 8 | 98.5 | 87.9％ |
| Example 9 | 99.1 | 90.8％ |
| Comparative example 1 | 95.7 | 91.5％ |
As can be seen from Table 1, in the preparation method of the difluorosulfimide provided by the invention, the yield of the difluorosulfimide in examples 1-5 is more than or equal to 90%, and the high purity of more than or equal to 99.5% can be realized without complex post-treatment, the mass ratio of sulfonyl fluoride to hexamethyl silazane in examples 6-7 is too large or too small, the yield of the difluorosulfimide is reduced, and the reaction temperature in examples 8-9 is too low, even if the reaction time is prolonged, the yield of the difluorosulfimide is reduced. Therefore, the preparation method provided by the invention has the characteristics of simple process steps, high efficiency, high raw material conversion rate and good reaction selectivity, and the whole process is a solvation-free process, so that the environment-friendly requirement is fully met, and the high-purity and high-yield difluoro sulfimide can be obtained quickly, efficiently and in an environment-friendly way. Comparative example 1 uses acetonitrile as solvent to prepare bisfluorosulfonyl imide, and although the yield is still acceptable, the purity of the product is not good, and the use standard in the electrolyte cannot be met.
The applicant states that the invention is illustrated by the above embodiments, but the invention is not limited to the above embodiments, i.e. it does not mean that the invention has to be carried out in dependence of the above embodiments. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A method for preparing a bis-fluorosulfonyl imide, the method comprising: the sulfonyl fluoride and hexamethyl silazane react in inert atmosphere to obtain an intermediate product, and the intermediate product is subjected to gas phase separation to obtain the difluoro sulfonyl imide.
2. The method according to claim 1, wherein the molar ratio of sulfonyl fluoride to hexamethyl silazane is (1.8 to 5): 1, preferably (1.8 to 3): 1.
3. the preparation method according to claim 1 or 2, characterized in that the inert atmosphere comprises an argon atmosphere and/or a nitrogen atmosphere;
preferably, the temperature of the reaction is 40 to 110 ℃, further preferably 80 to 110 ℃;
preferably, the reaction time is 1 to 14 hours.
4. A method of preparation according to any one of claims 1 to 3 wherein the intermediate product comprises trimethylfluorosilane in the gas phase and bisfluorosulfonimide in the liquid phase;
preferably, the temperature of the gas phase separation is 17-80 ℃;
preferably, the gas phase separation time is 1 to 4 hours.
5. The method according to claim 4, wherein the liquid phase of the bis-fluorosulfonyl imide is subjected to rectification to obtain the bis-fluorosulfonyl imide;
preferably, the temperature of the rectification treatment is 125-165 ℃;
preferably, the rectification treatment time is 1-6 hours.
6. The method of any one of claims 1-5, wherein the method of preparation comprises:
the molar ratio is (1.8-5): 1 and hexamethyl silazane react for 1-14 h at 40-110 ℃ in inert atmosphere to obtain an intermediate product, and the intermediate product is subjected to gas phase separation to obtain the difluoro sulfonimide.
7. Lithium difluorosulfimide, characterized in that the raw material of the lithium difluorosulfimide is difluorosulfimide, and the difluorosulfimide is prepared by the preparation method of claims 1-6.
8. A method of preparing lithium bis-fluorosulfonyl imide according to claim 7, comprising:
and (3) carrying out reaction on the difluoro-sulfonyl imide and lithium fluoride to complete ion exchange, thereby obtaining the difluoro-sulfonyl imide lithium.
9. The method according to claim 8, wherein the molar ratio of the bis-fluorosulfonyl imide to the lithium fluoride is 1:1 to 1:2;
preferably, the temperature of the reaction is 100-150 ℃;
preferably, the atmosphere of the reaction is an argon atmosphere and/or a nitrogen atmosphere;
preferably, the byproduct hydrogen fluoride gas is evaporated in the middle after the reaction is completed;
preferably, the temperature of the evaporation is 100-150 ℃.
10. The use of the lithium bis-fluorosulfonamide of claim 7, wherein the lithium bis-fluorosulfonamide is used in a lithium ion battery.
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| US20070043231A1 (en) * | 2005-08-22 | 2007-02-22 | Amer Hammami | Process for preparing sulfonylimides and derivatives thereof |
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| CN109311669A (en) * | 2016-05-26 | 2019-02-05 | 森田化学工业株式会社 | The manufacturing method of double fluorine sulfimide alkali metal salts and double fluorine sulfimide alkali metal salt compositions |
| US20220204345A1 (en) * | 2019-04-25 | 2022-06-30 | Arkema France | Process for preparing bis(fluorosulfonyl) imide |
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| US20070043231A1 (en) * | 2005-08-22 | 2007-02-22 | Amer Hammami | Process for preparing sulfonylimides and derivatives thereof |
| CN102378755A (en) * | 2009-03-31 | 2012-03-14 | 中央硝子株式会社 | Method for producing imidic acid compound |
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| CN109311669A (en) * | 2016-05-26 | 2019-02-05 | 森田化学工业株式会社 | The manufacturing method of double fluorine sulfimide alkali metal salts and double fluorine sulfimide alkali metal salt compositions |
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