CN117049486A - Preparation method of sodium bis (fluorosulfonyl) imide - Google Patents

Preparation method of sodium bis (fluorosulfonyl) imide Download PDF

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CN117049486A
CN117049486A CN202311136300.8A CN202311136300A CN117049486A CN 117049486 A CN117049486 A CN 117049486A CN 202311136300 A CN202311136300 A CN 202311136300A CN 117049486 A CN117049486 A CN 117049486A
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sodium
imide
fluorosulfonyl
difluoro
ammonium salt
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崔毅鑫
张涛
施正军
袁少岚
胡泽慧
杜二星
葛特
王梓汀
王超
陈寅镐
徐建国
张先满
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Fujian Zhongxin Fluorine Material Gaobao Technology Co ltd
Zhejiang Zhongxin Fluorine Materials Co ltd
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Fujian Zhongxin Fluorine Material Gaobao Technology Co ltd
Zhejiang Zhongxin Fluorine Materials Co ltd
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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
    • C01B21/096—Amidosulfonic acid; Salts thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a preparation method of sodium bis (fluorosulfonyl) imide, in particular to a method for preparing sodium bis (fluorosulfonyl) imide by directly reacting with an alkaline sodium reagent by taking organic ammonium bis (fluorosulfonyl) imide as a reaction raw material, belonging to the technical fields of chemical synthesis and sodium ion batteries, and being characterized in that: in a polar solvent, taking organic ammonium salt of difluoro-sulfonyl imide as a reaction raw material, and directly reacting with an alkaline sodium reagent to obtain difluoro-sulfonyl imide sodium; the invention provides a preparation method of difluoro sulfimide sodium salt, which has the advantages of easily obtained reaction raw materials, safety, easy operation, good product purity and high yield, and is suitable for large-scale industrial production.

Description

Preparation method of sodium bis (fluorosulfonyl) imide
Technical Field
The invention relates to a preparation method of sodium bis (fluorosulfonyl) imide, in particular to a method for preparing sodium bis (fluorosulfonyl) imide by directly reacting with an alkaline sodium reagent by taking trialkyl ammonium bis (fluorosulfonyl) imide as a reaction raw material, belonging to the technical field of chemical synthesis and sodium ion batteries.
Background
A Sodium-ion battery (Sodium-ion battery), similar to the working principle of a lithium-ion battery, is a secondary battery, and achieves the effect of transporting charges by Sodium ions moving between a positive electrode and a negative electrode. The lithium ion battery has the advantages of higher energy density, no memory effect, high working voltage, wide working temperature range, high recycling times, environmental friendliness and the like, and has wide application in the fields of electronic products, electric automobiles, aerospace, military products, storage of renewable energy sources and the like, but the lithium resource reserves are relatively scarce, the lithium resource reserves in the crust are only 0.0065 percent, and the lithium resource reserves on the earth are estimated to be only maintained for about 65 years according to the current lithium resource consumption speed (J.—Y.Hwang, S.—T.Myung, Y.— K.Sun, chem.Soc.Rev.2017,46, 3529-3614). In addition, the regional distribution of lithium resources is also very uneven, the reserve of Chinese lithium resources accounts for less than-6% of the global lithium resources, but the total amount of lithium materials processed in China reaches about-60%, wherein more than-90% of the lithium resources are imported, and the problem that the scarce lithium resources become necks of the sustainable and healthy development of new energy lithium ion batteries in China is not easy to understand.
The abundance of sodium resources in the crust reaches 2.75 percent and exceeds 420 times of the abundance of lithium resources, the regional distribution is uniform, and the extraction of sodium resources is much easier than the extraction of corresponding lithium resources, so the production cost and the price of sodium resources are much cheaper than those of lithium resources, that is, the problem of material resource constraint is basically not existed for sodium ion batteries! Because the mass and volume of sodium ions are larger than those of lithium ions, the energy density of the sodium ion battery is relatively low, which limits the application of the sodium ion battery in various fields such as electric automobiles, etc., but as the technology of the sodium ion battery is continuously improved, the energy density of the sodium ion battery is continuously improved, and the sodium salt has higher conductivity than that of the lithium salt, so that the concentration of electrolyte can be reduced to reduce the corresponding production cost. In addition, the internal resistance of the sodium ion battery is higher than that of a corresponding lithium ion battery, so that the heat productivity is less and the temperature rise is lower at dangerous moments such as short circuit, and the like, therefore, the safety performance, the cycle life, the high-low temperature performance, the multiplying power and other battery performances of the sodium ion battery are more excellent, and the transportation and operation use safety of battery products can be obviously improved. The sodium ion battery can still ensure the energy efficiency of 90 percent at the temperature of minus 20 ℃, and can reach the energy efficiency of 70 percent at the temperature of minus 40 ℃. With the breakthrough of the low energy density bottleneck of the sodium ion battery by the novel hard carbon electrode material, the technology research and development and industrialization process of the sodium ion battery (Yabuuchi, N., et al, chem. Rev.2014,114, 11636-11682) is obviously accelerated, the application advantages of the novel hard carbon electrode material in the fields of energy storage, low power batteries and the like are paid more attention to, and the sodium ion battery and the lithium ion battery form a mutually coexisting situation of-!
The sodium salt electrolyte has good and bad performances, and can directly influence a plurality of important indexes such as the electric storage capacity, the electrochemical performance, the safety performance and the like of the sodium ion battery, and is a key factor for determining the good and bad performances of the sodium ion battery. Sodium perchlorate (NaClO) 4 ) And sodium hexafluorophosphate (NaPF) 6 ) The electrolyte is the most widely adopted electrolyte of the sodium ion battery at present, wherein sodium perchlorate is a strong oxidant, safety risks are easy to occur, and sodium hexafluorophosphate has the defects of poor thermal and chemical stability, poor low-temperature cycle efficiency, easy generation of corrosive Hydrogen Fluoride (HF) gas by micro water splitting and the like, so that the electrolyte can be further decomposed and lost, the chemical structures of electrolyte and electrodes can be damaged, the battery capacity is attenuated, potential safety hazards are brought, and great challenges are brought to practical application. The development of the electrolyte is safer and more efficient, and can be suitable for the electrolyte under severe conditions such as low temperature, high temperature and the like, and the method for improving the chemical performance of the sodium ion battery is the most economical and effective method. Sodium bis (fluorosulfonyl imide) (Sodium bisfluorosulfonylimide, na) + FSI - ) The electrolyte has better comprehensive electrochemical properties such as conductivity, stability to heat and trace water, low-temperature and high-temperature circulation efficiency and the like than corresponding sodium hexafluorophosphate, is widely recognized by the domestic and foreign industry professionals as the next generation sodium ion battery electrolyte for replacing sodium hexafluorophosphate electrolyte, and is the ideal sodium salt electrolyte with the best industrialization prospect at present.
The N-H bond of the bis-fluorosulfonyl imide links two strongly electron withdrawing groups (FSO) 2 (-), thus the bisfluorosulfonyl imide has a stronger acidity (pK a =1.28), in an organic solvent, its acidity is close to that of sulfuric acid. The use of bis-fluorosulfonimides to produce sodium bis-fluorosulfonamide by reaction with sodium carbonate has been reported in the literature and in the patent (J.K.Ruff, M.Lustig, inorg.Synth.1968,11,138.; J.K.Ruff, inorg.Chem.1965,4,1446; zhou Zhibin, han Hongbo, nie Jin, et al, CN102786451 a). Sodium bis (fluorosulfonyl) imide can also be prepared by reacting bis (chlorosulfonyl) imide with excess anhydrous sodium fluorideM.Beran, J.Prihoda, Z.Anorg.Allg.Chem.2005, 631,55; m. Beran, et al, polyheat, 2006,25,1292-1298 and Patent M.Cernik, et al, U.S. Pat. No. 7253317B2,FR.Patent PCT/FR01/04164 and WO02/053494,2001), but the reaction materials required for these methods for preparing sodium difluorosulfonyl sulfite electrolytes are strongly acidic, highly corrosive and not readily available, and the reaction products are not highly pure and difficult to purify, and thus are not suitable for large-scale industrial production.
Disclosure of Invention
The invention aims to provide a brand new preparation method of sodium bis (fluorosulfonyl) imide, which has the advantages of good purity, high product yield, safety, environmental protection and high efficiency.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of sodium bis (fluorosulfonyl) imide is characterized in that: in a polar solvent, using organic ammonium salt of difluoro-sulfonyl imide as a reaction raw material, and directly reacting with an alkaline sodium reagent to obtain the difluoro-sulfonyl imide sodium.
The chemical reaction equation involved in the invention is as follows:
the further arrangement is that:
the polar solvent is selected from: the solvent is preferably ethanol or acetonitrile, and the solvent is any one of water, alcohols such as methanol or ethanol, nitriles such as acetonitrile or propionitrile, ketones such as acetone or 2-butanone, esters such as dimethyl carbonate, diethyl carbonate, ethyl acetate and the like, ethers such as tetrahydrofuran, methyl tertiary butyl ether, ethylene glycol dimethyl ether and the like or a mixed solvent prepared according to different proportions. The mass ratio of the bis-fluorosulfonyl imide triethylammonium salt to the solvent is preferably 1:1-1.5.
The alkaline sodium reagent is selected from the group consisting of: sodium hydroxide, sodium acetate, sodium alkoxide such as sodium methoxide or sodium ethoxide, etc., sodium carbonate, sodium bicarbonate, sodium oxide, sodium sulfate, etc.
The molar ratio of the organic ammonium salt of the difluoro-sulfonyl imide to the alkaline sodium reagent is 1:0.5-10, and the preferable molar ratio is 1:0.5-1.1.
The reaction temperature is-40-120 ℃; the reaction temperature is preferably 0 to 60 ℃.
After the reaction is finished, insoluble inorganic matters are removed, the reaction solvent and the organic alkaline acid-binding agent are recovered through reduced pressure distillation, and the obtained solid is purified to obtain the white solid of sodium difluorosulfimide. The temperature of the reduced pressure distillation is 50-80 ℃.
Preferably, the collection, purification and storage of the sodium bis-fluorosulfonyl imide product are accomplished under dry, anhydrous and anaerobic conditions.
The difluoro sulfimide organic ammonium salt is prepared by the following method: the sulfuryl fluoride reacts with ammonia gas or ammonium salt in an autoclave under the action of an organic amine acid binding agent to obtain the difluoro sulfimide organic ammonium salt.
In order to save the cost and be suitable for industrial production, the invention also provides a difluoro sulfimide organic ammonium salt prepared by taking sulfuryl fluoride as a starting material, which can be purified by simple water washing or can be directly used for preparing anhydrous difluoro sulfimide sodium salt, and the method comprises the following steps:
the preparation method of the sodium bis (fluorosulfonyl) imide is characterized by comprising the following steps:
(1) Taking sulfuryl fluoride and ammonia gas or ammonium salt as reaction raw materials, reacting under the action of aprotic polar solvent and organic alkaline acid-binding agent, removing insoluble inorganic matters after the reaction is completed, distilling under reduced pressure to remove reaction solvent, and purifying the obtained organic ammonium salt of the difluoro sulfimide by simple water washing or directly using the organic ammonium salt of the difluoro sulfimide in the chemical reaction for preparing anhydrous difluoro sulfimide sodium salt without further purification;
in step (1):
the aprotic solvent is: acetonitrile, acetone, esters such as dimethyl carbonate, diethyl carbonate, ethyl acetate, etc., ethers such as tetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, etc., and acetonitrile is preferred.
The molar ratio of the sulfuryl fluoride, the organic alkaline acid binding agent and the ammonium salt is 1:1-10:0.2-1, and is preferably 1:1.5:0.5.
The organic alkaline acid binding agent is as follows: any one of trimethylamine, triethylamine, N-diisopropylethylamine, tri-N-propylamine, tri-N-butylamine, pyridine and the like, preferably triethylamine.
The ammonium salt is selected from any one of the following ammonium salts: ammonium fluoride, ammonium chloride, ammonium bromide, ammonium bisulfate, ammonium bicarbonate, ammonium bisulfate.
The reaction temperature is 0 to 60 ℃, preferably 10 to 30 ℃.
(2) Dissolving the organic ammonium salt of the difluoro-sulfonyl imide prepared in the step (1) in water or a polar organic solvent, directly reacting with an alkaline sodium reagent, removing insoluble inorganic matters after the reaction is finished, and distilling the reaction solvent under reduced pressure to obtain a white solid product of the difluoro-sulfonyl imide sodium.
The reaction conditions in step (2) are as described above.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a preparation method of difluoro sulfimide sodium salt, which has the advantages of easily obtained reaction raw materials, safety, easy operation, good product purity and high yield, and is suitable for large-scale industrial production.
2. The invention avoids the reaction step of generating the strongly acidic difluoro sulfimide intermediate by acidification, does not use strongly acidic materials such as chlorosulfonic acid, fluorosulfonic acid or concentrated sulfuric acid, has the advantages of high reaction safety, easy operation, low equipment requirement, suitability for green industrial production and the like.
3. The invention has the advantages that the raw materials are easy to obtain, the ammonium salt serving as the main reaction raw material can be added into a reaction system in a simple powder solid or solution mode with accurate concentration, the simultaneous use of various gas raw materials is avoided, and the reaction control difficulty and the reaction risk are effectively reduced.
4. The white solid product of the sodium bis-fluorosulfonyl imide prepared by the invention can be used for different applications without further purification, such as electrolyte for preparing sodium ion batteries.
The foregoing of the present disclosure will be described in further detail by way of specific examples, but is not limited to the following examples. The invention includes various substitutions and alterations based on common technical knowledge and conventional means in the field under the above technical idea, and all such substitutions and alterations are included in the scope of the invention.
Drawings
FIG. 1 is a diagram of a bis-fluorosulfonyl imide triethylammonium salt prepared according to the present invention 1 HNMR spectra.
FIG. 2 is a diagram of a bis-fluorosulfonyl imide triethylammonium salt prepared according to the present invention 19 FNMR spectrum.
FIG. 3 is a diagram of a sodium salt of bis-fluorosulfonyl imide prepared according to the present invention 19 FNMR spectrum.
Detailed Description
In the following examples, bis-fluorosulfonyl imide organoammonium salts were prepared as follows:
under the protection of nitrogen atmosphere, 9.3 g of ammonium fluoride is added into a 250mL high-pressure reaction kettle, the temperature is controlled to 10 ℃, 75.5 g of triethylamine and 60.0 g of acetonitrile are sequentially pumped in, the mixture is stirred for 0.5 hour, 51.0 g of sulfuryl fluoride gas is slowly introduced at the temperature of 10 ℃ and is continuously kept at the temperature of 10 ℃ for 4 hours, and the reaction is finished. The reaction solution is distilled under reduced pressure to recover the reaction solvent, and the concentrated solution is washed with water and dried to obtain 65.0 g of bis (fluorosulfonyl) imide triethylammonium salt, and the yield is 95 percent% 1 HNMR spectra are shown in FIG. 1 and 19 the FNMR spectrum is shown in FIG. 2).
According to the method, triethylamine is replaced by trimethylamine, tri-n-butylamine and tripropylamine, and the difluoro sulfonimide trimethylammonium, the difluoro sulfonimide tri-n-butylamine and the difluoro sulfonimide tripropylamine can be prepared respectively.
Example 1
In a 250mL three-port reaction flask, 56.4 g of bis-fluorosulfonyl imide triethylammonium salt and 56.4 g of acetonitrile were added under nitrogen atmosphere, followed by 10.6 g of sodium carbonate, and stirred and heated to 50℃until no carbon dioxide gas was generated. Insoluble inorganic matters are removed by filtration, and the reaction solution is distilled under reduced pressure at 50 ℃ to recover the reaction solvent, so that 39.8 g of white solid is obtained, the yield is 98.0%, and the purity is 99.9%. The impurity is mainly sulfamic acid 0.07% and fluorosulfonic acid 0.03%.
Product confirmation:
LC/MS test shows that the molecular weight (m/e) of the reaction product is 180, which is consistent with the chemical structure (II) of the difluoro sulfimide anion,
the reaction product was further tested by anion chromatography, and the retention time and peak type of the ion peak of the obtained product are consistent with those of standard difluoro sulfonimide salt. Of the reaction products 19 As shown in FIG. 3, the FNMR spectrum contains only one resonance absorption peak of 51.90ppm fluorine, which is consistent with the chemical structure of sodium difluorosulfonyl sulfite!
The following results are obtained by the atomic absorption spectrum test of the reactant, and the reaction product is proved to be sodium salt
Sequence number Detection item (Test Items) Test method (Methods) Results (Results)
1 Sodium (Li, ppm) WI-24-19 126726.53
2 Lithium (Na, ppm) WI-24-16 0.08
3 Calcium (Ca, ppm) WI-24-16 1.54
4 Potassium (K, ppm) WI-24-16 2.83
5 Lead (Pb, ppm) WI-24-16 0.16
6 Iron (Fe, ppm) WI-24-16 0.56
7 Copper (Cu, ppm) WI-24-16 0.20
8 Zinc (Zn, ppm) WI-24-16 2.15
9 Magnesium (Mg, ppm) WI-24-16 0.14
10 Chromium (Cr, ppm) WI-24-16 0.05
11 Nickel (Ni, ppm) WI-24-16 ND
12 Manganese (Mn, ppm) WI-24-16 0.03
13 Barium (Ba, ppm) WI-24-16 ND
14 Cadmium (Cd, ppm) WI-24-16 0.03
15 Aluminium (Al, ppm) WI-24-16 0.14
。
Alternative examples 1-1 to 1-7:
the preparation method is the same as in example 1, except that: the reaction temperature and sodium reagent type were adjusted and tested for their effect on product yield and purity.
Table 1:
sequence number Sodium reagent type Reaction temperature Yield/% Purity/% Sulfamic acid/% Fluorosulfonic acid/%
Alternative 1-1 Sodium hydroxide 0 94.2 99.9 0.05 0.05
Alternative examples 1-2 Sodium oxide 10 94.8 99.9 0.05 0.05
Alternative examples 1-3 Sodium ethoxide -5 95.8 99.9 0.03 0.07
Alternative examples 1 to 4 Sodium carbonate 20 91.8 99.8 0.12 0.08
Alternative examples 1 to 5 Sodium carbonate 40 97.8 99.9 0.04 0.06
Alternative examples 1 to 6 Sodium carbonate 60 97.8 99.9 0.05 0.05
Alternative examples 1 to 7 Sodium carbonate 80 85.3 92.8 5.76 1.44
Alternative examples 1 to 8 Sodium carbonate 120 72.5 89.3 7.11 3.59
As shown in table 1:
1. the decomposition of the product increased with increasing reaction temperature, and tests showed that the by-products contained were mainly sulfamic acid and fluorosulfonic acid.
2. The optimum reaction temperature for the sodium carbonate obtained from the data in Table 1 is preferably 40℃to 60℃because the sodium carbonate is used as the optimum reaction temperature for the sodium reagent, the decomposition of the product is accelerated when the temperature exceeds 60℃and the yield is lowered when the temperature is too low.
Alternative examples 1-9 to 1-15:
the preparation method is the same as in example 1, except that: the amount of alkaline sodium reagent was adjusted and tested for its effect on product yield and purity.
Table 2:
as shown in table 2: when sodium carbonate is selected as the alkaline sodium reagent, the molar ratio of the bisfluorosulfonyl imide triethylammonium salt to the sodium carbonate is 1:0.5, and the yield and purity of the product are optimal.
Alternative examples 1-16 to 1-22:
the preparation method is the same as in example 1, except that: the reaction solvent and the amount thereof were adjusted and the effect thereof on the yield and purity of the product was tested.
Table 3:
as shown in table 3:
1. as shown in the combination of the alternative examples 1-16 to 1-18, the use amount of the reaction solvent has obvious negative effects when the mass ratio is lower than 1:1, the yield and purity of the product are both reduced, and when the mass ratio is higher than 1:1, the effect is not obvious.
2. The different reaction solvent types, shown in combination with alternatives 1-19 to 1-23, have different effects on both product yield and purity, with the lipid solvent having a particularly pronounced effect on purity, the most preferred solvent being acetonitrile.
Alternative examples 1-24 to 1-29:
the preparation method is the same as in example 1, except that: the reduced pressure distillation temperature was adjusted and its effect on product yield and purity was tested.
Table 4:
sequence number Reduced pressure distillation Yield/% Purity/% Sulfamic acid/% Fluorosulfonic acid/%
Alternative examples 1 to 25 Reduced pressure distillation temperature 50 DEG C 98.0 99.9 0.07 0.03
Alternative examples 1 to 26 Reduced pressure distillation temperature 80 DEG C 98.0 99.9 0.08 0.02
Alternative examples 1 to 27 Reduced pressure distillation temperature 100 DEG C 91.3 99.1 0.57 0.33
Alternative examples 1 to 28 Reduced pressure distillation temperature 120 DEG C 68.3 86.5 11.21 2.29
Alternative examples 1 to 29 Reduced pressure distillation temperature 130 DEG C 65.4 83.3 12.79 3.91
As shown in table 4:
as shown in the combination of the alternatives 1-25 to 1-29, the reduced pressure distillation temperature of 50-80℃is optimal, and too low is unfavorable for removing the reaction solvent and the acid-binding agent, and too high is likely to cause partial decomposition of the product.

Claims (12)

1. A preparation method of sodium bis (fluorosulfonyl) imide is characterized in that: in a polar solvent, using organic ammonium salt of difluoro-sulfonyl imide as a reaction raw material, and directly reacting with an alkaline sodium reagent to obtain the difluoro-sulfonyl imide sodium.
2. The method for preparing sodium bis (fluorosulfonyl) imide according to claim 1, wherein: the polar solvent is selected from: any one of water, methanol, ethanol, acetonitrile, propionitrile, acetone, 2-butanone, dimethyl carbonate, diethyl carbonate, ethyl acetate and the like, tetrahydrofuran, methyl tertiary butyl ether and ethylene glycol dimethyl ether or a mixed solvent prepared according to different proportions.
3. The method for preparing sodium bis (fluorosulfonyl) imide according to claim 1, wherein: the polar solvent is ethanol or acetonitrile, and the mass ratio of the difluoro sulfonimide triethylammonium salt to the polar solvent is 1:1-1.5.
4. The method for preparing sodium bis (fluorosulfonyl) imide according to claim 1, wherein: the alkaline sodium reagent is selected from the group consisting of: sodium hydroxide, sodium acetate, sodium methoxide, sodium ethoxide, sodium carbonate, sodium bicarbonate, sodium oxide and sodium sulfate, wherein the molar ratio of the organic ammonium salt of the difluoro-sulfonyl imide to the alkaline sodium reagent is 1:0.5-10.
5. The method for preparing sodium bis (fluorosulfonyl) imide according to claim 1, wherein: the molar ratio of the organic ammonium salt of the difluoro-sulfonyl imide to the alkaline sodium reagent is 1:0.5-1.1.
6. The method for preparing sodium bis (fluorosulfonyl) imide according to claim 1, wherein: the reaction temperature is-40-120 ℃.
7. The method for preparing sodium bis (fluorosulfonyl) imide according to claim 6, wherein: the reaction temperature is 0-60 ℃.
8. The method for preparing sodium bis (fluorosulfonyl) imide according to claim 1, wherein: after the reaction is finished, insoluble inorganic matters are removed, the reaction solvent and the organic alkaline acid-binding agent are recovered by reduced pressure distillation, and the obtained solid is purified to obtain a white solid of sodium difluorosulfimide, wherein the temperature of the reduced pressure distillation is 50-80 ℃.
9. The method for preparing sodium bis (fluorosulfonyl) imide according to claim 1, wherein: the difluoro sulfimide organic ammonium salt is prepared by the following method: the sulfuryl fluoride reacts with ammonia gas or ammonium salt in an autoclave under the action of an organic amine acid binding agent to obtain the difluoro sulfimide organic ammonium salt.
10. The method for preparing sodium bis (fluorosulfonyl) imide according to claim 1, wherein: the prepared organic ammonium salt of the difluoro sulfimide is purified by simple water washing or directly used for preparing anhydrous difluoro sulfimide sodium salt by taking sulfuryl fluoride as a starting material, and specifically comprises the following steps:
(1) Taking sulfuryl fluoride and ammonia gas or ammonium salt as reaction raw materials, reacting under the action of aprotic polar solvent and organic alkaline acid-binding agent, removing insoluble inorganic matters after the reaction is completed, distilling under reduced pressure to remove reaction solvent, and purifying the obtained organic ammonium salt of the difluoro sulfimide by simple water washing or directly using the organic ammonium salt of the difluoro sulfimide in the chemical reaction for preparing anhydrous difluoro sulfimide sodium salt without further purification;
(2) Dissolving the organic ammonium salt of the difluoro-sulfonyl imide prepared in the step (1) in water or a polar organic solvent, directly reacting with an alkaline sodium reagent, removing insoluble inorganic matters after the reaction is finished, and distilling the reaction solvent under reduced pressure to obtain a white solid product of the difluoro-sulfonyl imide sodium.
11. The method for preparing sodium bis-fluorosulfonyl imide according to claim 10, wherein: in step (1):
the aprotic solvent is: any one of acetonitrile, acetone, dimethyl carbonate, diethyl carbonate, ethyl acetate, tetrahydrofuran, methyl tertiary butyl ether and ethylene glycol dimethyl ether;
the molar ratio of the sulfuryl fluoride to the organic alkaline acid binding agent to the ammonium salt is 1:1-10:0.2-1;
the organic alkaline acid binding agent is as follows: any one of trimethylamine, triethylamine, N-diisopropylethylamine, tri-N-propylamine, tri-N-butylamine and pyridine;
the ammonium salt is selected from any one of the following ammonium salts: ammonium fluoride, ammonium chloride, ammonium bromide, ammonium bisulfate, ammonium bicarbonate, ammonium bisulfate;
the reaction temperature is 0-60 ℃.
12. The method for preparing sodium bis-fluorosulfonyl imide according to claim 10, wherein: in the step (1), the aprotic solvent is acetonitrile, the molar ratio of the sulfuryl fluoride, the organic alkaline acid-binding agent and the ammonium salt is 1:1.5:0.5, the organic alkaline acid-binding agent is triethylamine, the ammonium salt is ammonium fluoride, and the reaction temperature is 10-30 ℃.
CN202311136300.8A 2023-03-16 2023-09-05 Preparation method of sodium bis (fluorosulfonyl) imide Pending CN117049486A (en)

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