CN109422252B - Preparation method of lithium fluorosulfonyl difluorophosphoryl imine, product and application thereof - Google Patents
Preparation method of lithium fluorosulfonyl difluorophosphoryl imine, product and application thereof Download PDFInfo
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Abstract
The invention relates to lithium fluorosulfonyl difluorophosphoryl imineThe preparation method, the product and the application thereof. The preparation method comprises the following steps: and (3) fluorinating sulfonyl difluorophosphoryl imine alkali metal salt obtained by reacting trimethylsilyl chlorosulfonyl imide with hexafluorophosphoric acid alkali metal salt to obtain the lithium fluorosulfonyl difluorophosphoryl imine. The preparation method adopts cheaper raw materials to replace POCl with stronger activity in the prior art3The method has the advantages that the lithium fluorosulfonyl difluorophosphoryl imide is obtained by only two steps of reaction, the introduction of moisture is avoided in the whole process, the side reaction is less, the intermediate is only required to be simply purified, the yield of the product is improved to more than 85%, the purity of the product is improved to more than 99.9%, the production cost is low, the reaction condition is mild, and the feasibility of industrial production is improved. The obtained product can be applied to lithium salt electrolyte materials of lithium ion batteries, and the cycle life of the batteries is remarkably prolonged.
Description
Technical Field
The invention relates to the technical field of organic chemistry, in particular to a preparation method of lithium fluorosulfonyl difluorophosphoryl imide, and a product and application thereof.
Background
The lithium fluorosulfonyl difluorophosphoryl imide has high conductivity, stable structure and low corrosion to a current collector, can obviously improve the cycle performance of an electrolyte, and is likely to become a novel lithium salt widely applied to lithium ion battery electrolyte, WO2016/133169A1 and WO2016/088766A1 disclose the application of fluorine-containing lithium fluorosulfonyl phosphorimide phosphate in the electrolyte, and the prior art has few reports about the preparation method of the lithium fluorosulfonyl difluorophosphoryl imide, and needs to develop a relatively economic preparation method.
The preparation of alkali metal salts containing chlorosulfonyl/phosphorylimine is disclosed in patent CN102617414B by Zhongxin et al: firstly, perfluoroalkyl fluorosulfinate and hydroxylamine oxysulfonic acid are reacted under the action of a buffering agent to obtain perfluoroalkyl sulfonamide salt, and the purified perfluoroalkyl sulfonamide salt and [ (CH)3)3Si]2NH reaction to generate trimethylsilyl perfluoroalkyl sulfimide, and reaction with POCl3The (dichlorophosphoryl) (perfluoroalkyl sulfonyl) imide salt is obtained by reaction, and the (difluorophosphoryl) (perfluoroalkyl sulfonyl) imide salt is obtained by fluorination with a fluorinating agent, and the synthetic route is as follows:
the method has more steps, the total yield is lower due to multi-step reaction, the intermediate is more complicated to purify, the introduced water has larger influence on the product quality, the cost is higher, and the method is not suitable for industrial production.
At present, no method for preparing lithium fluorosulfonyl difluorophosphoryl imide with fewer steps, lower cost and higher product yield and purity is suitable for industrial production.
Disclosure of Invention
In view of the problems of more steps, complex operation, low product yield and purity and the like in the prior art for preparing lithium fluorosulfonyl difluorophosphoryl imide, the invention aims to provide a simpler preparation method of lithium fluorosulfonyl difluorophosphoryl imide, which is simple to operate, high in yield and purity and suitable for industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of lithium fluorosulfonyl difluorophosphoryl imide, which comprises the following steps: and (3) reacting trimethylsilyl chlorosulfonyl difluorophosphoramidite with an alkali hexafluorophosphate to obtain an alkali chlorosulfonyl difluorophosphoramidite, and fluorinating the alkali chlorosulfonyl difluorophosphoramidite with a fluorine-containing lithium salt to obtain lithium fluorosulfonyl difluorophosphoramidite.
The term "comprising" as used herein means that it may include other steps in addition to the steps described above, which give a different route to the preparation method, and the present invention includes a method in which the starting material is not trimethylsilyl chlorosulfonyl imide directly, and a method in which the intermediate trimethylsilyl chlorosulfonyl difluorophosphoryl imide is obtained from any other starting material by any method of the prior art and is further reacted with an alkali hexafluorophosphate to obtain an alkali metal salt of chlorosulfonyl difluorophosphoryl imide, which is fluorinated with a fluorine-containing lithium salt, is included in the scope of the present invention, that is, it may be an intermediate product, and the specific preparation method thereof may be any method of the prior art. In addition, the term "comprising" in the present invention may be replaced with "being" in a closed type.
Preferably, the preparation method comprises the following steps:
(1) under an inert environment, adding hexamethyldisiloxane into an aprotic polar solvent of aminosulfonyl chloride and/or aminosulfonyl fluoride, heating for a first reflux reaction, adding an organic solution of an alkali metal hexafluorophosphate for a second reflux reaction, and removing the solvent and a byproduct to obtain an alkali metal sulfonyl difluorophosphoryl imine;
(2) dissolving the sulfonyl difluorophosphoryl imine alkali metal salt obtained in the step (1) in an aprotic polar solvent, adding a fluorine-containing lithium salt in an inert environment, and separating after fluorination to obtain the lithium fluorosulfonyl difluorophosphoryl imine.
Preferably, the aprotic polar solvent of step (1) and the aprotic polar solvent of step (2) are each independently selected from any one or a combination of at least two of acetonitrile, dimethyl carbonate, diethyl carbonate, acetone, 1, 4-dioxane, N-dimethylformamide and nitromethane;
preferably, the inert environment of step (1) and the inert environment of step (2) each independently comprise an environment protected by an inert gas selected from any one or a combination of at least two of nitrogen, helium and argon.
Preferably, the alkali metal hexafluorophosphate in step (1) is any one or a combination of at least two of lithium hexafluorophosphate, potassium hexafluorophosphate and sodium hexafluorophosphate.
Preferably, the solvent in the organic solution of the alkali metal hexafluorophosphate of step (1) is selected from any one or a combination of at least two of acetonitrile, dimethyl carbonate, diethyl carbonate, acetone, 1, 4-dioxane, N-dimethylformamide and nitromethane.
The molar ratio of aminosulfonyl chloride and/or aminosulfonyl fluoride to hexamethyldisiloxane to alkali hexafluorophosphate in step (1) is 1 (3-4) to (1-1.5), for example, 1:3:1, 1:4:1.5, 1:3.5:1, 1:3.2:3.5 or 1:3.8:1.2, and preferably 1 (3-3.5) to (1-1.2).
Preferably, the temperature of the first reflux reaction in step (1) is 50-100 ℃, for example 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃ and the like, and the time is 1-6 h, for example 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h and the like.
Preferably, the temperature of the first reflux reaction in the step (1) is 50-80 ℃ and the time is 2-4 h.
Preferably, the temperature of the second reflux reaction in step (1) is 50-100 ℃, such as 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃ and the like, and the time is 6-20 h, such as 6h, 7h, 8h, 9h, 10h, 11h, 12h, 15h, 18h, 19h or 20h and the like.
Preferably, the temperature of the second reflux reaction in the step (1) is 50-80 ℃, and the time is 8-12 h.
Preferably, the means for removing the solvent and by-products in step (1) comprises distillation, preferably rotary evaporation.
Preferably, the lithium salt comprising fluorine comprises LiF.
Preferably, the separating of step (2) comprises: insoluble matter was removed by filtration, and the solvent was removed.
Preferably, the means for removing the solvent comprises: concentrating the filtrate, adding CH2Cl2The crystals are precipitated by stirring and then dried in vacuum.
Preferably, the separation in step (2) is followed by a purification step: and dissolving the obtained crude product in ethyl acetate for recrystallization, and drying in vacuum to obtain the lithium fluorosulfonyl difluorophosphoryl imide.
In a second aspect, the present invention provides lithium fluorosulfonyl difluorophosphoryl imide prepared by the process of the first aspect.
In a third aspect, the invention provides the application of the lithium fluorosulfonyl difluorophosphoryl imide in the lithium storage electrolyte.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the preparation method adopts cheaper raw materials to replace POCl with stronger activity in the prior art3Only two-step reaction is carried out to obtain the lithium fluorosulfonyl difluorophosphoryl imide, the whole process avoids the introduction of moisture, side reactions are less, the intermediate only needs to be simply purified, and the yield of the product is improved to more than 85 percentThe purity of the product is improved to more than 99.9 percent, and the production cost is lower;
(2) the preparation method has mild reaction conditions and increases the feasibility of industrial production. The obtained product can be applied to lithium salt electrolyte materials of lithium ion batteries, and the cycle life of the batteries is remarkably prolonged.
Drawings
FIG. 1 is a schematic representation of a preparation process according to an embodiment of the present invention
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1
To a 500mL three-necked flask, 57.8g (0.5mol) of sulfamoyl chloride, 150mL of acetonitrile, 243.6g (1.5mol) of hexamethyldisiloxane were added, the mixture was heated to 85 ℃ under nitrogen atmosphere and refluxed for 2 hours, and then 76.0g (0.5mol) of lithium hexafluorophosphate dissolved in 100mL of acetonitrile in advance was added dropwise to the reaction system and the reaction was refluxed for 6 hours. And (3) after the reaction is stopped, removing the solvent and the by-product by rotary evaporation to obtain a crude intermediate product of the lithium chlorosulfonyl difluorophosphoryl imide. The crude product of the lithium chlorosulfonyl difluorophosphoryl imide intermediate is dissolved in 200mL acetonitrile, 13.0g (0.5mol) of lithium fluoride is added under the protection of nitrogen, and the mixture is stirred and reacted for 12 hours at room temperature. Filtering to remove insoluble substances, concentrating the filtrate, and adding CH2Cl2Stirring to separate out crystals, recrystallizing ethyl acetate, and drying in vacuum to obtain 85.9g of lithium fluorosulfonyl difluorophosphoryl imide with the purity of 99.9%, wherein the yield is 90.9%.19F-NMR(600MHz，DMSO-D6)：δ＝53.2～53.3(s，1F)，-78.1～-78.0(s，1F)，-80.6～-80.5(s，1F)；LC-MS：Neg：M/Z＝181.9。
Preparing electrolyte:
in a glove box with the water content of less than 10ppm, uniformly mixing an organic solvent according to the mass fraction of 30% of Ethylene Carbonate (EC), 30% of Ethyl Methyl Carbonate (EMC), 30% of dimethyl carbonate (DMC) and 5% of fluoroethylene carbonate (FEC), adding electrolyte lithium salt LiPF6 to prepare a 1mol/L solution, adding 2% of 1, 3-Propane Sultone (PS) and 3% of the prepared lithium fluorosulfonyl difluorophosphoryl imide, and fully stirring and uniformly mixing to prepare the electrolyte.
The composition of the positive electrode material of the lithium ion battery (the mass fraction of the positive electrode material is 100 percent): 90% of ternary material LiNi0.5Co0.2Mn0.3O25% of conductive carbon black, 5% of polyvinylidene fluoride (PVDF).
The composition of the negative electrode material of the lithium ion battery (the mass fraction of the negative electrode material is 100 percent) is as follows: 89% graphite, 5% conductive carbon black, 6% polyvinylidene fluoride (PVDF).
The preparation method of the battery comprises the following steps:
preparing a positive electrode: weighing the raw materials according to the positive electrode formula, uniformly dispersing the raw materials in an N-methyl-2-pyrrolidone (NMP) solution to prepare mixed slurry of the positive electrode, coating the slurry on an aluminum foil of a positive current collector, and drying and rolling to obtain the positive electrode piece.
Preparing a negative electrode: weighing the raw materials according to the formula of the negative electrode, uniformly dispersing the raw materials in an N-methyl-2-pyrrolidone (NMP) solution to prepare a mixed slurry of the negative electrode, coating the slurry on a negative current collector aluminum foil, and drying and rolling to obtain a negative electrode plate.
The positive plate and the negative plate of the lithium ion battery prepared in the above way, electrolyte and other necessary battery components such as a PTFE diaphragm, a shell and the like are subjected to the processes of winding, casing, liquid injection, pre-punching, chemical forming, capacity grading and the like to obtain the 18650 type lithium ion battery. The lithium ion battery of example 1 was prepared.
Under the condition of 55 ℃, the assembled lithium ion battery is subjected to 2.75V-4.2V and 0.2C cyclic charge and discharge tests for 200 times by adopting a Land CT2001A battery test system, and the discharge capacity retention rate of cyclic charge and discharge is obtained as shown in Table 1.
Example 2
A500 mL three-necked flask was charged with 57.8g (0.5mol) of sulfamoyl chloride, 150mL of dimethyl carbonate, 284.2g (1.75mol) of hexamethyldisiloxane, and under nitrogen, the mixture was heated to 90 ℃ to reflux and reacted for 3 hours, and then 83.6g (0.55mol) of lithium hexafluorophosphate dissolved in advance in 100mL of dimethyl carbonate was added dropwise to the reaction system, and the reflux and reaction were continued for 8 hours. And (3) after the reaction is stopped, removing the solvent and the by-product by rotary evaporation to obtain a crude intermediate product of the lithium chlorosulfonyl difluorophosphoryl imide.
The crude product of the lithium chlorosulfonyl difluorophosphoryl imide intermediate is dissolved in 200mL dimethyl carbonate, 15.6g (0.6mol) of lithium fluoride is added under the protection of nitrogen, and the mixture is stirred and reacted for 12 hours at room temperature. Filtering to remove insoluble substances, concentrating the filtrate, and adding CH2Cl2Stirring to separate out crystals, recrystallizing with ethyl acetate, and vacuum drying to obtain 84.8g of lithium fluorosulfonyl difluorophosphoryl imide with the purity of 99.9%, and the yield is 89.6%.19F-NMR(600MHz，DMSO-D6)：δ＝53.2～53.3(s，1F)，-78.1～-78.0(s，1F)，-80.6～-80.5(s，1F)；LC-MS：Neg：M/Z＝181.9。
Electrolyte preparation in the same manner as in example 1 except that LiNi, an active material of a positive electrode material, was used for the preparation of a battery0.5Co0.2Mn0.3O2Replacement with LiNi1/3Co1/3Mn1/3O2Otherwise, the discharge capacity retention rate was obtained in the same manner as in example 1, and was as shown in table 1.
Example 3
To a 500mL three-necked flask, 57.8g (0.5mol) of sulfamoyl chloride, 150mL of diethyl carbonate, 243.6g (1.5mol) of hexamethyldisiloxane were added, the mixture was heated to 90 ℃ under nitrogen protection, and after reaction for 3 hours, 83.6g (0.55mol) of potassium hexafluorophosphate dissolved in 100mL of diethyl carbonate in advance was added dropwise to the reaction system, and the reaction was continued under reflux for 8 hours. And (3) after the reaction is stopped, removing the solvent and the by-product by rotary evaporation to obtain a crude intermediate product of the chlorosulfonyl difluorophosphoryl imine potassium.
The crude product of the potassium chlorosulfonyl difluorophosphoryl imide intermediate is dissolved in 200mL diethyl carbonate, 14.3g (0.55mol) of lithium fluoride is added under the protection of nitrogen, and the mixture is stirred and reacted for 12 hours at room temperature. Filtering to remove insoluble substances, concentrating the filtrate, and adding CH2Cl2Stirring to separate out crystals, recrystallizing ethyl acetate, and drying in vacuum to obtain 81.6g of lithium fluorosulfonyl difluorophosphoryl imide with the purity of 99.9%, wherein the yield is 86.3%.19F-NMR(600MHz，DMSO-D6)：δ＝53.2～53.3(s，1F)，-78.1～-78.0(s，1F)，-80.6～-80.5(s，1F)；LC-MS：Neg：M/Z＝181.9。
Electrolyte preparation in the same manner as in example 1 except that LiNi, an active material of a positive electrode material, was used for the preparation of a battery0.5Co0.2Mn0.3O2Replacement by LiCoO2Otherwise, the discharge capacity retention rate was obtained in the same manner as in example 1, and was as shown in table 1.
Example 4
To a 500mL three-necked flask, 57.8g (0.5mol) of sulfamoyl chloride, 150mL of 1, 4-dioxane, 263.9g (1.63mol) of hexamethyldisiloxane were added, the mixture was heated to 90 ℃ under nitrogen protection, and after a reaction time of 4 hours, 100.8g (0.6mol) of sodium hexafluorophosphate dissolved in advance in 100mL of 1, 4-dioxane was added dropwise to the reaction system, and the reaction was continued under reflux for 10 hours. And (3) after the reaction is stopped, removing the solvent and the by-product by rotary evaporation to obtain a crude intermediate product of the chlorosulfonyl difluorophosphoryl imine sodium.
The crude product of the chlorosulfonyl difluorophosphoryl imine sodium intermediate is dissolved in 200mL 1, 4-dioxane, 15.6g (0.6mol) of lithium fluoride is added under the protection of nitrogen, and the mixture is stirred and reacted for 12 hours at room temperature. Filtering to remove insoluble substances, concentrating the filtrate, and adding CH2Cl2Stirring to separate out crystals, recrystallizing with ethyl acetate, and vacuum drying to obtain 83.7g of lithium fluorosulfonyl difluorophosphoryl imide with the purity of 99.9%, wherein the yield is 88.6%.19F-NMR(600MHz，DMSO-D6)：δ＝53.2～53.3(s，1F)，-78.1～-78.0(s，1F)，-80.6～-80.5(s，1F)；LC-MS：Neg：M/Z＝181.9。
Electrolyte preparation in the same manner as in example 1 except that LiNi, an active material of a positive electrode material, was used for the preparation of a battery0.5Co0.2Mn0.3O2Replacement by LiFePO4Otherwise, the discharge capacity retention rate was obtained in the same manner as in example 1, and was as shown in table 1.
Comparative example 1
CN102617414B example 20. The purity of the product was 99.5%, yield 83%.19F-NMR(600MHz，DMSO-D6)：δ＝53.2～53.3(s，1F)，-78.1～-78.0(s，1F)，-80.6～-80.5(s，1F)；LC-MS：Neg：M/Z＝181.9。
Electrolyte preparation As in example 1The positive electrode material in the cell preparation method can be LiNi0.5Co0.2Mn0.3O2、LiNi1/3Co1/3Mn1/3O2、LiCoO2、LiFePO4Otherwise, the discharge capacity retention rate was obtained in the same manner as in example 1, and the discharge capacity retention rate was measured after 200 cycles of charge and discharge, as shown in table 1.
TABLE 1
Comparing the product yield and purity of examples 1-4 with that of comparative example 1, it can be seen that the preparation method of the present invention is superior to the prior art in terms of cost, operability and process simplification by using alternative raw materials and designing a synthetic route, and the product yield and purity are significantly improved compared with the prior art. As can be seen from Table 1, the difference between examples 1 to 4 and comparative example 1 is that the preparation methods are different, and when the products of examples 1 to 4 are used as the electrolyte of the lithium ion battery, the cycle performance is better than that of comparative example 1 under the same conditions, which indicates that the lithium fluorosulfonyl difluorophosphoryl imide product obtained by the preparation method can be applied to lithium salt electrolyte materials of the lithium ion battery, and the cycle life of the battery is remarkably prolonged.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (18)
1. A preparation method of lithium fluorosulfonyl difluorophosphoryl imine is characterized by comprising the following steps: and (3) fluorinating sulfonyl difluorophosphoryl imine alkali metal salt obtained by reacting trimethylsilyl chlorosulfonyl imide with hexafluorophosphoric acid alkali metal salt to obtain the lithium fluorosulfonyl difluorophosphoryl imine.
2. The method of claim 1, comprising the steps of:
(1) under an inert environment, adding hexamethyldisiloxane into an aprotic polar solvent of aminosulfonyl chloride and/or aminosulfonyl fluoride, heating for a first reflux reaction, adding an organic solution of an alkali metal hexafluorophosphate for a second reflux reaction, and removing the solvent and a byproduct to obtain an alkali metal sulfonyl difluorophosphoryl imine;
(2) dissolving the sulfonyl difluorophosphoryl imine alkali metal salt obtained in the step (1) in an aprotic polar solvent, adding a fluorine-containing lithium salt in an inert environment, and separating after fluorination to obtain the lithium fluorosulfonyl difluorophosphoryl imine.
3. The method according to claim 2, wherein the aprotic polar solvent in step (1) and the aprotic polar solvent in step (2) are each independently selected from any one or a combination of at least two of acetonitrile, dimethyl carbonate, diethyl carbonate, acetone, 1, 4-dioxane, N-dimethylformamide, and nitromethane.
4. The method of claim 2, wherein the inert environment of step (1) and the inert environment of step (2) each independently comprise an environment protected by an inert gas selected from any one or a combination of at least two of nitrogen, helium, and argon.
5. The method according to claim 2, wherein the alkali metal hexafluorophosphate of step (1) is any one or a combination of at least two of lithium hexafluorophosphate, potassium hexafluorophosphate and sodium hexafluorophosphate.
6. The method according to claim 2, wherein the solvent in the organic solution of the alkali metal hexafluorophosphate of step (1) is selected from any one or a combination of at least two of acetonitrile, dimethyl carbonate, diethyl carbonate, acetone, 1, 4-dioxane, N-dimethylformamide and nitromethane.
7. The method according to claim 2, wherein the molar ratio of the aminosulfonyl chloride and/or aminosulfonyl fluoride to the hexamethyldisiloxane to the alkali metal hexafluorophosphate in the step (1) is 1 (3-4) to (1-1.5).
8. The method according to claim 2, wherein the molar ratio of the aminosulfonyl chloride and/or aminosulfonyl fluoride to the hexamethyldisiloxane to the alkali metal hexafluorophosphate in the step (1) is 1 (3-3.5) to (1-1.2).
9. The preparation method according to claim 2, wherein the temperature of the first reflux reaction in the step (1) is 50 to 100 ℃ and the time is 1 to 6 hours.
10. The preparation method according to claim 2, wherein the temperature of the first reflux reaction in the step (1) is 50 to 80 ℃ and the time is 2 to 4 hours.
11. The preparation method of claim 2, wherein the temperature of the second reflux reaction in the step (1) is 50-100 ℃ and the time is 6-20 hours.
12. The preparation method of claim 2, wherein the temperature of the second reflux reaction in the step (1) is 50-80 ℃ and the time is 8-12 h.
13. The method of claim 2, wherein the means for removing the solvent and by-products of step (1) comprises distillation.
14. The method of claim 2, wherein the removing of the solvent and byproducts of step (1) comprises rotary evaporation.
15. The method of claim 1, wherein said lithium fluoride-containing salt comprises LiF.
16. The method of claim 2, wherein the separating of step (2) comprises: insoluble matter was removed by filtration, and the solvent was removed.
17. The method of claim 16, wherein the removing the solvent comprises: concentrating the filtrate, adding CH2Cl2The crystals are precipitated by stirring and then dried in vacuum.
18. The method of claim 2, wherein the separating of step (2) is followed by a purification step comprising: and dissolving the obtained crude product in ethyl acetate for recrystallization, and drying in vacuum to obtain the lithium fluorosulfonyl difluorophosphoryl imide.
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| CN111710910B (en) * | 2020-07-01 | 2021-06-29 | 香河昆仑化学制品有限公司 | Electrolyte containing bis-tetrafluorophosphoryl imide salt and lithium ion battery |
| CN111786020B (en) * | 2020-07-20 | 2022-11-29 | 香河昆仑新能源材料股份有限公司 | Non-aqueous electrolyte containing fluoro phosphoramidate and lithium ion battery |
| CN112186249B (en) * | 2020-09-30 | 2022-11-15 | 香河昆仑新能源材料股份有限公司 | Electrolyte containing fluoro-malonic acid difluoro-lithium phosphate and lithium ion battery containing electrolyte |
| CN112186252B (en) * | 2020-09-30 | 2022-11-22 | 香河昆仑新能源材料股份有限公司 | Electrolyte containing lithium difluoromalonate phosphoryl imine and lithium ion battery using same |
| 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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| TW201644091A (en) * | 2015-02-19 | 2016-12-16 | 中央硝子股份有限公司 | Electrolyte for nonaqueous-electrolyte cell, and non-aqueous electrolyte cell in which same is used |
| WO2017111143A1 (en) * | 2015-12-22 | 2017-06-29 | セントラル硝子株式会社 | Electrolyte for non-aqueous electrolyte cell, and non-aqueous electrolyte cell in which same is used |
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| TW201644091A (en) * | 2015-02-19 | 2016-12-16 | 中央硝子股份有限公司 | Electrolyte for nonaqueous-electrolyte cell, and non-aqueous electrolyte cell in which same is used |
| WO2017111143A1 (en) * | 2015-12-22 | 2017-06-29 | セントラル硝子株式会社 | Electrolyte for non-aqueous electrolyte cell, and non-aqueous electrolyte cell in which same is used |
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