CN109422252A - A kind of preparation method of fluorine sulphonyl difluoro phosphorimide lithium and products thereof and application - Google Patents
A kind of preparation method of fluorine sulphonyl difluoro phosphorimide lithium and products thereof and application Download PDFInfo
- Publication number
- CN109422252A CN109422252A CN201710723213.0A CN201710723213A CN109422252A CN 109422252 A CN109422252 A CN 109422252A CN 201710723213 A CN201710723213 A CN 201710723213A CN 109422252 A CN109422252 A CN 109422252A
- Authority
- CN
- China
- Prior art keywords
- lithium
- difluoro
- phosphorimide
- preparation
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C01B21/097—Compounds containing nitrogen and non-metals and optionally metals containing phosphorus atoms
- C01B21/0975—Compounds containing nitrogen and non-metals and optionally metals containing phosphorus atoms containing also one or more sulfur atoms
-
- 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
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to preparation methods of a kind of fluorine sulphonyl difluoro phosphorimide lithium and products thereof and application.The preparation method includes: that the sulphonyl difluoro phosphorimide alkali metal salt that reacts with hexafluorophosphoric acid alkali metal salt of trimethyl silicon substrate chlorine sulfimide obtains fluorine sulphonyl difluoro phosphorimide lithium after the fluorination of fluorine-containing lithium salts.The preparation method substitutes active stronger POCl in the prior art using more cheap raw material3Only two-step reaction obtains fluorine sulphonyl difluoro phosphorimide lithium, and whole process avoids the introducing of moisture, side reaction is less, and intermediate only need to be purified simply, and the yield of product is improved to 85% or more, product purity is improved to 99.9% or more, and lower production costs, reaction condition is mild, increases the feasibility of industrialized production.Obtained product can be applied to lithium ion battery lithium salts electrolyte, significantly improve the cycle life of battery.
Description
Technical field
The present invention relates to technical field of organic chemistry more particularly to a kind of preparation methods of fluorine sulphonyl difluoro phosphorimide lithium
And products thereof and application.
Background technique
Fluorine sulphonyl difluoro phosphorimide lithium, since its conductivity is higher, structure is more stable, and to collector corrosivity compared with
It is low, the cycle performance of electrolyte can be significantly improved, it is possible to be widely used in lithium ion battery electrolysis as a kind of new lithium salts
In liquid, WO2016/133169A1 and WO2016/088766A1 disclose fluorine-containing sulphonyl phosphoric acid imine lithium answering in the electrolytic solution
With, and the report in the prior art about the preparation method of fluorine sulphonyl difluoro phosphorimide lithium is less, needs to develop more economical
Preparation method.
Zhou Zhibin et al. discloses sulphonyl containing chlorine/phosphorimide alkali metal salt preparation side in patent CN102617414B
Method: it first reacts to obtain perfluorinated alkyl sulfonamide under buffer effect with azanol oxygen sulfonic acid using perfluoroalkyl fluorine sulfinate
Salt, by the perfluorinated alkyl sulfonamide salt of purification and [(CH3)3Si]2NH reaction generates trimethyl silicon substrate per-fluoroalkyl sulfonyl imines,
Again with POCl3Reaction obtains (dichlor-phosphoryl) (per-fluoroalkyl sulfonyl) inferior amine salt, and last perfluorinated dose of fluorination obtains (difluoro phosphorus
Acyl) (per-fluoroalkyl sulfonyl) inferior amine salt, synthetic route is as follows:
This method step is more, and not only multistep reaction causes gross production rate lower, but also intermediate purification is cumbersome, introducing
Moisture is affected to product quality, and cost is also higher, is not suitable for industrialized production.
Still without step, less, cost is lower at present and product yield and purity higher to prepare fluorine sulphonyl difluoro phosphinylidyne sub-
The method of amine lithium is suitable for industrialized production.
Summary of the invention
In view of preparing in the prior art, fluorine sulphonyl difluoro phosphorimide lithium step is more, complicated for operation, product yield and pure
The problems such as not high is spent, one of the objects of the present invention is to provide a kind of better simply fluorine sulphonyl difluoro phosphorimide lithium preparation sides
Method, it is not only easy to operate, and also yield and purity are higher, are suitable for industrialized production.
For this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of preparation method of fluorine sulphonyl difluoro phosphorimide lithium, the preparation method
It include: the chlorine sulphonyl difluoro phosphorimide alkali metal that trimethyl silicon substrate chlorine sulfimide is reacted with hexafluorophosphoric acid alkali metal salt
Salt obtains fluorine sulphonyl difluoro phosphorimide lithium after the fluorination of fluorine-containing lithium salts.
" comprising " of the present invention, it is intended that it can also include other steps, these other techniques in addition to the step
Step assigns the preparation method different paths, and it is directly trimethyl silicon substrate chlorine sulfimide that the present invention, which contains raw material not,
Method obtains intermediate product trimethyl silicon substrate chlorine sulfimide in other methods of any raw material Jing Guo any prior art and goes forward side by side
The chlorine sulphonyl difluoro phosphorimide alkali metal salt that one step is reacted with hexafluorophosphoric acid alkali metal salt obtains after the fluorination of fluorine-containing lithium salts
Method to fluorine sulphonyl difluoro phosphorimide lithium belongs to protection category of the invention, that is to say, that it can be intermediate product,
Specific preparation method can be any method in the prior art.In addition to this, " comprising " of the present invention can also replace
For enclosed " for ".
Preferably, the preparation method includes the following steps:
(1) under inert environments, hexamethyldisiloxane is added to the non-proton pole of sulfamic acid chloride and/or aminosulfonyl fluorine
Property solvent in, heating carry out first time back flow reaction after, be added hexafluorophosphoric acid alkali metal salt organic solution, carry out second time
Stream reaction, removes solvent and by-product, obtains sulphonyl difluoro phosphorimide alkali metal salt；
(2) sulphonyl difluoro phosphorimide alkali metal salt obtained by step (1) is dissolved in aprotic polar solvent, inertia ring
Under border, fluorine-containing lithium salts is added, after fluorination, isolated fluorine sulphonyl difluoro phosphorimide lithium.
Preferably, step (1) aprotic polar solvent and step (2) described aprotic polar solvent be each independently
In acetonitrile, dimethyl carbonate, diethyl carbonate, acetone, 1,4- dioxane, N,N-dimethylformamide and nitromethane
Any one or at least two combination；
Preferably, step (1) inert environments and step (2) described inert environments include by indifferent gas each independently
Body protection environment, the inert gas in nitrogen, helium and argon gas any one or at least two combination.
Preferably, step (1) the hexafluorophosphoric acid alkali metal salt is lithium hexafluoro phosphate, Potassium Hexafluorophosphate and sodium hexafluoro phosphate
In any one or at least two combination.
Preferably, the solvent in the organic solution of step (1) the hexafluorophosphoric acid alkali metal salt is selected from acetonitrile, carbonic acid diformazan
In ester, diethyl carbonate, acetone, 1,4- dioxane, N,N-dimethylformamide and nitromethane any one or at least
Two kinds of combination.
Sulfamic acid chloride and/or aminosulfonyl fluorine in step (1): hexamethyldisiloxane: hexafluorophosphoric acid alkali metal salt
Molar ratio is 1:(3~4): (1~1.5), such as 1:3:1,1:4:1.5,1:3.5:1,1:3.2:3.5 or 1:3.8:1.2 etc. are excellent
Select 1:(3~3.5): (1~1.2).
Preferably, the temperature of step (1) the first time back flow reaction be 50~100 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C,
65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C or 100 DEG C etc., the time be 1~6h, such as 1h, 1.5h, 2h, 2.5h,
3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h etc..
Preferably, the temperature of step (1) the first time back flow reaction is 50~80 DEG C, and the time is 2~4h.
Preferably, the temperature of step (1) second of back flow reaction be 50~100 DEG C, such as 50 DEG C, 55 DEG C, 60 DEG C,
65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C or 100 DEG C etc., the time be 6~20h, such as 6h, 7h, 8h, 9h, 10h,
11h, 12h, 15h, 18h, 19h or 20h etc..
Preferably, the temperature of step (1) second of back flow reaction is 50~80 DEG C, and the time is 8~12h.
Preferably, step (1) solvent and the mode of by-product of removing includes distillation, preferably includes to rotate.
Preferably, the fluorine-containing lithium salts includes LiF.
Preferably, step (2) separation includes: to remove solvent after being filtered to remove insoluble matter.
Preferably, the mode for removing solvent includes: that CH is added after filtrate is concentrated2Cl2, stirring precipitates crystal, then incites somebody to action
Gained crystal is dried in vacuo.
Preferably, further include purification step after step (2) described separation: gained crude product being dissolved in ethyl acetate and is carried out
Recrystallization, vacuum drying obtain fluorine sulphonyl difluoro phosphorimide lithium.
Second aspect, the present invention provides the fluorine sulphonyl difluoro phosphorimides of the preparation of preparation method as described in relation to the first aspect
Lithium.
The third aspect, the present invention provides as described in second aspect fluorine sulphonyl difluoro phosphorimide lithium storage lithium electrolyte in
Application.
Compared with prior art, the present invention at least has the following beneficial effects:
(1) preparation method substitutes active stronger POCl in the prior art using more cheap raw material3, only two steps are anti-
Fluorine sulphonyl difluoro phosphorimide lithium should be obtained, and whole process avoids the introducing of moisture, side reaction is less, and intermediate only needs simply
Purification improves the yield of product to 85% or more, and product purity is improved to 99.9% or more, and lower production costs；
(2) the preparation method reaction condition is mild, increases the feasibility of industrialized production.Obtained product can be applied
In lithium ion battery lithium salts electrolyte, the cycle life of battery is significantly improved.
Detailed description of the invention
Fig. 1 is the route map of preparation method in the embodiment of the present invention
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.But following reality
Example is only simple example of the invention, does not represent or limit the scope of the present invention, protection scope of the present invention
It is subject to claims.
Embodiment 1
Into 500mL three-necked flask, 57.8g (0.5mol) sulfamic acid chloride, 150mL acetonitrile, 243.6g is added
(1.5mol) hexamethyldisiloxane, nitrogen protection after being warming up to 85 DEG C of back flow reaction 2h, will be dissolved with 100mL acetonitrile in advance
76.0g (0.5mol) lithium hexafluoro phosphate be added drop-wise in reaction system, continue back flow reaction 6h.Stopping reaction back spin is evaporated off molten
Agent and by-product obtain chlorine sulphonyl difluoro phosphorimide lithium intermediate crude product.It will be in above-mentioned chlorine sulphonyl difluoro phosphorimide lithium
Mesosome crude product is dissolved in 200mL acetonitrile, and under nitrogen protection, 13.0g (0.5mol) lithium fluoride is added, and reaction 12h is stirred at room temperature.
It is filtered to remove insoluble matter, CH is added in filtrate concentration2Cl2Stirring precipitates crystal, re-crystallizing in ethyl acetate, and vacuum drying obtains purity
99.9% fluorine sulphonyl difluoro phosphorimide lithium 85.9g, yield 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.
Electrolyte quota:
In glove box of the moisture less than 10ppm, by organic solvent according to ethylene carbonate (EC) 30%, methyl ethyl carbonate
(EMC) 30%, dimethyl carbonate (DMC) 30%, fluorinated ethylene carbonate (FEC) 5% mass fraction be uniformly mixed, electricity is added
Solution matter lithium salts LiPF6 is made into the solution of 1mol/L, adds 2% 1,3-propane sultone (PS) and the fluorine of 3% above-mentioned preparation
Sulphonyl difluoro phosphorimide lithium, and be thoroughly mixed uniformly, electrolyte is made.
The composition (being in terms of 100% by positive electrode mass fraction) of the positive electrode of lithium ion battery: 90% ternary material
Expect LiNi0.5Co0.2Mn0.3O2, 5% conductive black, 5% Kynoar (PVDF).
The composition (being in terms of 100% by negative electrode material mass fraction) of the negative electrode material of lithium ion battery: 89% graphite,
5% conductive black, 6% Kynoar (PVDF).
The preparation method of battery:
Anode preparation: each raw material is weighed according to above-mentioned anode formula, is dispersed in n-methyl-2-pyrrolidone (NMP)
In solution, it is prepared into the mixed slurry of anode, and slurry is coated on positive current collector body aluminium foil, after dry roll-in
Obtain anode pole piece.
Cathode preparation: each raw material is weighed according to above-mentioned cathode formula, is dispersed in n-methyl-2-pyrrolidone (NMP)
In solution, it is prepared into the mixed slurry of cathode, and slurry is coated in cathodal current current collector aluminum foil, after dry roll-in
Obtain cathode pole piece.
By the positive plate of the lithium ion battery of above-mentioned preparation, negative electrode tab and electrolyte and other necessary battery components,
Such as PTFE diaphragm and shell etc., 18650 type lithium ions are obtained by winding, filling the processes such as shell, fluid injection, pre- punching, chemical conversion, partial volume
Battery.The lithium ion battery of embodiment 1 is made.
Under the conditions of 55 DEG C, 200 are carried out using Land CT2001A battery test system to assembled lithium ion battery
Secondary 2.75V~4.2V, 0.2C cyclic charging and discharging test, obtain the discharge capacitance of cycle charge-discharge, such as table 1.
Embodiment 2
Into 500mL three-necked flask, 57.8g (0.5mol) sulfamic acid chloride, 150mL dimethyl carbonate, 284.2g is added
(1.75mol) hexamethyldisiloxane, nitrogen protection after being warming up to 90 DEG C of back flow reaction 3h, will use 100mL carbonic acid diformazan in advance
83.6g (0.55mol) lithium hexafluoro phosphate of ester dissolution is added drop-wise in reaction system, continues back flow reaction 8h.Stop reaction back spin
Solvent and by-product is evaporated off, obtains chlorine sulphonyl difluoro phosphorimide lithium intermediate crude product.
Above-mentioned chlorine sulphonyl difluoro phosphorimide lithium intermediate crude product is dissolved in 200mL dimethyl carbonate, nitrogen protection
Under, 15.6g (0.6mol) lithium fluoride is added, reaction 12h is stirred at room temperature.It is filtered to remove insoluble matter, CH is added in filtrate concentration2Cl2
Stirring precipitates crystal, re-crystallizing in ethyl acetate, and vacuum drying obtains the fluorine sulphonyl difluoro phosphorimide lithium of purity 99.9%
84.8g, yield 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 quota is with embodiment 1, and battery preparation method is in addition to by active substances in cathode materials
LiNi0.5Co0.2Mn0.3O2Replace with LiNi1/3Co1/3Mn1/3O2Outside, other same as Example 1, obtain 200 cycle charge-discharges
Discharge capacitance, such as table 1.
Embodiment 3
Into 500mL three-necked flask, 57.8g (0.5mol) sulfamic acid chloride, 150mL diethyl carbonate, 243.6g is added
(1.5mol) hexamethyldisiloxane, nitrogen protection will be molten with 100mL diethyl carbonate in advance after being warming up to 90 DEG C of reaction 3h
83.6g (0.55mol) Potassium Hexafluorophosphate of solution is added drop-wise in reaction system, continues back flow reaction 8h.Stop reaction back spin to be evaporated off
Solvent and by-product are removed, chlorine sulphonyl difluoro phosphorimide potassium intermediate crude product is obtained.
Above-mentioned chlorine sulphonyl difluoro phosphorimide potassium intermediate crude product is dissolved in 200mL diethyl carbonate, nitrogen protection
Under, 14.3g (0.55mol) lithium fluoride is added, reaction 12h is stirred at room temperature.It is filtered to remove insoluble matter, CH is added in filtrate concentration2Cl2
Stirring precipitates crystal, re-crystallizing in ethyl acetate, and vacuum drying obtains the fluorine sulphonyl difluoro phosphorimide lithium of purity 99.9%
81.6g, yield 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 quota is with embodiment 1, and battery preparation method is in addition to by active substances in cathode materials
LiNi0.5Co0.2Mn0.3O2Replace with LiCoO2Outside, other same as Example 1, obtain the discharge capacity of 200 cycle charge-discharges
Conservation rate, such as table 1.
Embodiment 4
Into 500mL three-necked flask, addition 57.8g (0.5mol) sulfamic acid chloride, 150mL1,4- dioxane,
263.9g (1.63mol) hexamethyldisiloxane, nitrogen protection will use 100mL1,4- bis- after being warming up to 90 DEG C of reaction 4h in advance
100.8g (0.6mol) sodium hexafluoro phosphate of six ring of oxygen dissolution is added drop-wise in reaction system, continues back flow reaction 10h.Stop reaction
Solvent and by-product is evaporated off in back spin, obtains chlorine sulphonyl difluoro phosphorimide sodium intermediate crude product.
Above-mentioned chlorine sulphonyl difluoro phosphorimide sodium intermediate crude product is dissolved in 200mL Isosorbide-5-Nitrae-dioxane, nitrogen is protected
Under shield, 15.6g (0.6mol) lithium fluoride is added, reaction 12h is stirred at room temperature.It is filtered to remove insoluble matter, filtrate concentration is added
CH2Cl2Stirring precipitates crystal, re-crystallizing in ethyl acetate, and vacuum drying obtains the fluorine sulphonyl difluoro phosphorimide lithium of purity 99.9%
83.7g, yield 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 quota is with embodiment 1, and battery preparation method is in addition to by active substances in cathode materials LiNi0.5Co0.2Mn0.3
O2Replace with LiFePO4Outside, other same as Example 1, the discharge capacitance of 200 cycle charge-discharges is obtained, such as table 1.
Comparative example 1
CN102617414B embodiment 20.The purity 99.5% of product, 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 quota is with embodiment 1, and active substances in cathode materials can be LiNi in battery preparation method0.5Co0.2Mn0. 3O2、LiNi1/3Co1/3Mn1/3O2、LiCoO2、LiFePO4, it is other same as Example 1, obtain the electric discharge of 200 cycle charge-discharges
Capacity retention ratio, such as table 1.
Table 1
The products collection efficiency and purity of comparative examples 1~4 and comparative example 1 are it is found that preparation method of the present invention passes through with replacement
Raw material simultaneously designs synthetic route, is not only better than the prior art, but also the production of product on cost, operability and technique simplification degree
Rate and purity have significant progress compared with the prior art.As shown in Table 1, the difference of Examples 1 to 4 and comparative example 1 is to prepare
Method is different, when electrolyte of the Examples 1 to 4 product as lithium ion battery, under the same conditions, shows compared to comparison
The more preferably cycle performance of example 1, illustrates that the obtained fluorine sulphonyl difluoro phosphorimide lithium product of preparation method of the present invention can be applied to
Lithium ion battery lithium salts electrolyte, significantly improves the cycle life of battery.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of preparation method of fluorine sulphonyl difluoro phosphorimide lithium, which is characterized in that the preparation method includes: trimethyl silicane
The sulphonyl difluoro phosphorimide alkali metal salt that base sulfimide is reacted with hexafluorophosphoric acid alkali metal salt is fluorinated through fluorine-containing lithium salts
After obtain fluorine sulphonyl difluoro phosphorimide lithium.
2. preparation method as described in claim 1, which is characterized in that the preparation method includes the following steps:
(1) under inert environments, the aprotonic polar that sulfamic acid chloride and/or aminosulfonyl fluorine is added in hexamethyldisiloxane is molten
In agent, after heating carries out first time back flow reaction, the organic solution of hexafluorophosphoric acid alkali metal salt is added, flow back for the second time anti-
It answers, removes solvent and by-product, obtain sulphonyl difluoro phosphorimide alkali metal salt；
(2) sulphonyl difluoro phosphorimide alkali metal salt obtained by step (1) is dissolved in aprotic polar solvent, inert environments
Under, fluorine-containing lithium salts is added, after fluorination, isolated fluorine sulphonyl difluoro phosphorimide lithium.
3. preparation method as claimed in claim 2, which is characterized in that step (1) aprotic polar solvent and step (2)
The aprotic polar solvent be each independently selected from acetonitrile, dimethyl carbonate, diethyl carbonate, acetone, 1,4- dioxane,
In N,N-dimethylformamide and nitromethane any one or at least two combination；
Preferably, step (1) inert environments and step (2) described inert environments include being protected by inert gas each independently
The environment of shield, the inert gas in nitrogen, helium and argon gas any one or at least two combination.
4. preparation method as claimed in any one of claims 1 to 3, which is characterized in that step (1) the hexafluorophosphoric acid alkali metal
Salt is the combination of any one or at least two in lithium hexafluoro phosphate, Potassium Hexafluorophosphate and sodium hexafluoro phosphate；
Preferably, the solvent in the organic solution of step (1) the hexafluorophosphoric acid alkali metal salt be selected from acetonitrile, dimethyl carbonate,
Any one in diethyl carbonate, acetone, 1,4- dioxane, N,N-dimethylformamide and nitromethane or at least two
Combination.
5. such as the described in any item preparation methods of claim 2~4, which is characterized in that in step (1) sulfamic acid chloride and/or
Aminosulfonyl fluorine: hexamethyldisiloxane: the molar ratio of hexafluorophosphoric acid alkali metal salt is 1:(3~4): (1~1.5), preferably 1:
(3~3.5): (1~1.2)；
Preferably, the temperature of step (1) the first time back flow reaction is 50~100 DEG C, and the time is 1~6h；
Preferably, the temperature of step (1) the first time back flow reaction is 50~80 DEG C, and the time is 2~4h；
Preferably, the temperature of step (1) second of back flow reaction is 50~100 DEG C, and the time is 6~20h；
Preferably, the temperature of step (1) second of back flow reaction is 50~80 DEG C, and the time is 8~12h；
Preferably, step (1) solvent and the mode of by-product of removing includes distillation, preferably includes to rotate.
6. preparation method as claimed in any one of claims 1 to 5, which is characterized in that the fluorine-containing lithium salts includes LiF.
7. such as the described in any item preparation methods of claim 2~6, which is characterized in that step (2) separation includes: filtering
Solvent is removed after removing insoluble matter；
Preferably, the mode for removing solvent includes: that CH is added after filtrate is concentrated2Cl2, stirring precipitates crystal, then by gained
Crystal is dried in vacuo.
8. preparation method as claimed in any one of claims 2 to 7, which is characterized in that further include after step (2) described separation
Purification step: being dissolved in ethyl acetate for gained crude product and recrystallize, and vacuum drying obtains fluorine sulphonyl difluoro phosphorimide lithium.
9. fluorine sulphonyl difluoro phosphorimide lithium prepared by the preparation method as described in any one of claim 1~8.
10. application of the fluorine sulphonyl difluoro phosphorimide lithium as claimed in claim 9 in storage lithium electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710723213.0A CN109422252B (en) | 2017-08-22 | 2017-08-22 | Preparation method of lithium fluorosulfonyl difluorophosphoryl imine, product and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710723213.0A CN109422252B (en) | 2017-08-22 | 2017-08-22 | Preparation method of lithium fluorosulfonyl difluorophosphoryl imine, product and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109422252A true CN109422252A (en) | 2019-03-05 |
| CN109422252B CN109422252B (en) | 2021-05-11 |
Family
ID=65498785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710723213.0A Active CN109422252B (en) | 2017-08-22 | 2017-08-22 | Preparation method of lithium fluorosulfonyl difluorophosphoryl imine, product and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109422252B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110190332A (en) * | 2019-06-20 | 2019-08-30 | 东莞东阳光科研发有限公司 | Nickelic tertiary cathode material system battery electrolytic solution and lithium ion battery |
| CN111477958A (en) * | 2020-05-18 | 2020-07-31 | 华鼎国联四川电池材料有限公司 | Electrolyte additive and electrolyte containing same |
| CN111710910A (en) * | 2020-07-01 | 2020-09-25 | 香河昆仑化学制品有限公司 | Electrolyte containing bis-tetrafluorophosphoryl imide salt and lithium ion battery |
| CN111786020A (en) * | 2020-07-20 | 2020-10-16 | 香河昆仑化学制品有限公司 | Non-aqueous electrolyte containing fluoro phosphoric acid amide salt and lithium ion battery |
| CN112186249A (en) * | 2020-09-30 | 2021-01-05 | 香河昆仑化学制品有限公司 | Electrolyte containing fluoro-malonic acid difluoro-lithium phosphate and lithium ion battery containing electrolyte |
| CN112186252A (en) * | 2020-09-30 | 2021-01-05 | 香河昆仑化学制品有限公司 | Electrolyte containing lithium difluoromalonate phosphoryl imine and lithium ion battery using same |
| CN113979454A (en) * | 2021-11-23 | 2022-01-28 | 山东永浩新材料科技有限公司 | Preparation method of fluorosulfonic acid alkali metal salt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2017
- 2017-08-22 CN CN201710723213.0A patent/CN109422252B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110190332A (en) * | 2019-06-20 | 2019-08-30 | 东莞东阳光科研发有限公司 | Nickelic tertiary cathode material system battery electrolytic solution and lithium ion battery |
| CN111477958A (en) * | 2020-05-18 | 2020-07-31 | 华鼎国联四川电池材料有限公司 | Electrolyte additive and electrolyte containing same |
| CN111477958B (en) * | 2020-05-18 | 2021-09-07 | 华鼎国联四川电池材料有限公司 | Electrolyte additive and electrolyte containing same |
| CN111710910A (en) * | 2020-07-01 | 2020-09-25 | 香河昆仑化学制品有限公司 | Electrolyte containing bis-tetrafluorophosphoryl imide salt and lithium ion battery |
| CN111786020A (en) * | 2020-07-20 | 2020-10-16 | 香河昆仑化学制品有限公司 | Non-aqueous electrolyte containing fluoro phosphoric acid amide 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 |
| CN112186249A (en) * | 2020-09-30 | 2021-01-05 | 香河昆仑化学制品有限公司 | Electrolyte containing fluoro-malonic acid difluoro-lithium phosphate and lithium ion battery containing electrolyte |
| CN112186252A (en) * | 2020-09-30 | 2021-01-05 | 香河昆仑化学制品有限公司 | Electrolyte containing lithium difluoromalonate phosphoryl imine and lithium ion battery using same |
| 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 |
| CN113979454A (en) * | 2021-11-23 | 2022-01-28 | 山东永浩新材料科技有限公司 | Preparation method of fluorosulfonic acid alkali metal salt |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109422252B (en) | 2021-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109422252A (en) | A kind of preparation method of fluorine sulphonyl difluoro phosphorimide lithium and products thereof and application | |
| CN102786443B (en) | Binary or ternary fluorine-containing sulfimide alkali metal salt and ionic liquid and applications thereof | |
| CN102816096B (en) | Imine alkali metal salt and ion liquid and application of same as non water electrolyte | |
| CN103641751B (en) | An alkali metal salt of binary or the fluorine-containing sulfimide of ternary and ionic liquid and application thereof | |
| CN106946925B (en) | Lithium fluoroalkoxytrifluoroborate salt, and preparation method and application thereof | |
| KR102083080B1 (en) | The method for preparing lithium difluorophosphate using difluorophosphate ester | |
| JP2018035054A (en) | Manufacturing method of bis(fluorosulfonyl)imide alkali metal salt and bis(fluorosulfonyl)imide alkali metal salt composition | |
| JP6651049B1 (en) | Method for producing alkali metal hexafluorophosphate, method for producing alkaline metal hexafluorophosphate-containing electrolytic concentrated solution, and method for producing secondary battery | |
| RU2665552C2 (en) | Additives for galvanic cells | |
| CN105175452B (en) | A kind of preparation method of phosphonitrile oroalkane sulfonyl imine alkali metal salt | |
| CN108373142A (en) | A kind of high-purity is double（Fluorine sulphonyl）The preparation method of imine lithium | |
| JP2006302590A (en) | Manufacturing method of electrolyte for lithium ion battery and battery using it | |
| CN105800582A (en) | Method for preparing difluoro-lithium phosphate and lithium-ion battery non-aqueous electrolyte | |
| CN108503670A (en) | A kind of preparation method of fluorine phosphorimide and its alkali metal salt | |
| JP7559254B2 (en) | Isocyanate-based electrolyte additives based on imidazole structural groups and uses thereof | |
| JP2017052689A (en) | Granules or powder of disulfonyl amide salt | |
| CN109659620A (en) | A kind of electrolyte and secondary cell | |
| JP2018055882A (en) | Method for manufacturing electrolyte material containing alkali metal salt of bis(fluorosulfonyl)imide and organic solvent, and electrolyte material containing alkali metal salt of bis(fluorosulfonyl)imide and organic solvent | |
| CN106575792A (en) | Fluorinated carbonates comprising two oxygen bearing functional groups | |
| JPWO2017038796A1 (en) | Electrolyte composition, secondary battery, and method of using secondary battery | |
| CN110003264A (en) | A kind of high-voltage lithium-ion battery electrolyte, additive and preparation method | |
| Liu et al. | Research progress on preparation and purification of fluorine-containing chemicals in lithium-ion batteries | |
| CN1875517B (en) | Electrolyte solution and nonaqueous electrolyte lithium secondary battery | |
| CN102952099B (en) | Pyrrole ionic liquid, and preparation method and application thereof | |
| CN105633463B (en) | A kind of electrolyte of lithium-ion secondary battery suitable for low temperature environment electric discharge |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |