CN112537763B - Method for synthesizing lithium difluorophosphate by gas-solid-liquid three-phase - Google Patents
Method for synthesizing lithium difluorophosphate by gas-solid-liquid three-phase Download PDFInfo
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- CN112537763B CN112537763B CN202011543143.9A CN202011543143A CN112537763B CN 112537763 B CN112537763 B CN 112537763B CN 202011543143 A CN202011543143 A CN 202011543143A CN 112537763 B CN112537763 B CN 112537763B
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01B25/455—Phosphates containing halogen
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Abstract
The application relates to a method for synthesizing lithium difluorophosphate by gas-solid-liquid three phases, which comprises the following steps: dispersing silicon oxide and lithium fluoride in organic solvent under the condition of isolating water to obtain a dispersion mixture, and introducing POF into the dispersion mixture 3 After the reaction, the gas is reacted to obtain a reaction solution; or dispersing a silicon oxide in an organic solvent, introducing POF3 gas into the organic solvent at a lower temperature, then adding lithium fluoride, and heating to react to obtain a reaction solution; or firstly introducing POF3 gas into an organic solvent at a lower temperature, then adding a silicon oxygen compound and lithium fluoride into the organic solvent, and heating to react to obtain a reaction solution; and filtering the reaction solution, and drying the filtrate to obtain the lithium difluorophosphate. The application has the advantages of short whole process flow, easily obtained raw materials, low cost, no special treatment after reaction, and good industrial application prospect, and can obtain anhydrous lithium difluorophosphate with the purity of more than 99.5 percent and the yield of more than 93 percent by taking phosphorus oxyfluoride as a byproduct of phosphorus pentafluoride production.
Description
Technical Field
The application relates to the technical field of lithium ion battery additives, in particular to a method for synthesizing a novel lithium salt additive lithium difluorophosphate.
Background
The lithium ion battery mainly comprises a positive electrode, electrolyte, a diaphragm and a negative electrode. The electrolyte solution contains a nonaqueous solvent and a solute. The nonaqueous solvent may be a mixed solvent of 1 or more of aprotic ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methylethyl carbonate; solutes predominantly containing lithium salts, e.g. LiPF 6 LiFSI. Various additives have been developed by researchers in order to improve cycle characteristics, high and low temperature performance, and cycle life of lithium ion batteries. Wherein, lithium difluorophosphate (LiPO) 2 F 2 ) The SEI film formed at the electrode interface can obviously improve the high-low temperature cycle performance of the battery.
The synthesis method of lithium difluorophosphate mainly includes LiPF from phosphorus source 6 Law, POCl 3 Method and P 2 O 5 A method of manufacturing the same. For example, chinese patent application CN107244663a discloses the preparation of lithium difluorophosphate by reacting lithium hexafluorophosphate with siloxane. The reaction has the defects of long reaction time and low conversion rate. Chinese patent application CN108376782a discloses the use of lithium carbonate and lithium hexafluorophosphate to react in aprotic solvents to give lithium difluorophosphate. The reaction produces a large amount of lithium fluoride and is not very atomic economical. Chinese patent application CN108862232a discloses the use of lithium metaphosphate and lithium hexafluorophosphate to react to form lithium difluorophosphate. The reaction theory has high atom utilization rate, but the reaction condition is harsh and the reaction time is long. Japanese patent application laid-open No. 2005-219994 discloses the preparation of lithium difluorophosphate from lithium hexafluorophosphate and silica, which has a reaction time as long as 3 days and an inefficiency. Chinese patent application CN106458589B discloses that phosphorus oxychloride is used to prepare dichlorophosphoric acid, then salified to lithium dichlorophosphate, and then fluorinated (fluorine substituted chlorine) to obtain lithium difluorophosphate. The method has longer process flow and great difficulty in removing impurity chloride ions. Chinese patent application CN107720717a discloses that lithium hexafluorophosphate, lithium phosphate and phosphorus pentoxide are mixed and reacted at high temperature to obtain lithium difluorophosphate. The method has harsh reaction conditions and complex product separation process. Chinese patent application CN108640096a discloses the use of phosphorus pentoxide to react with hydrogen fluoride to give difluorophosphoric acid, which is salified to give lithium difluorophosphate. The method has the problem of low yield.
In the industrial amplification process, the method has various problems, so that the production cost of the difluorophosphoric acid is high, and the method is not beneficial to the reduction of the electrolyte and the lithium ion battery.
Disclosure of Invention
First, the technical problem to be solved
In view of the defects and shortcomings of the prior art, the application provides a method for synthesizing lithium difluorophosphate by gas, solid and liquid three phases, which has simple process flow and strong operability and is convenient for industrial production.
(II) technical scheme
In order to achieve the above purpose, the main technical scheme adopted by the application comprises the following steps:
the application provides a method for synthesizing lithium difluorophosphate by gas-solid-liquid three phases, which comprises the following steps:
dispersing silicon oxide and lithium fluoride in organic solvent under the condition of isolating water to obtain a dispersion mixture, and introducing POF into the dispersion mixture 3 After the reaction, the gas is reacted to obtain a reaction solution; alternatively, dispersing the silicone compound in an organic solvent under moisture-blocking conditions, and then introducing the POF into the organic solvent at a lower temperature 3 Adding lithium fluoride into the gas, and heating to react to obtain a reaction solution; or under the condition of isolating moisture, firstly introducing POF into the organic solvent at a lower temperature 3 Adding a silicon oxide compound and lithium fluoride into an organic solvent, and heating to react to obtain a reaction solution;
and filtering the reaction solution, and evaporating and drying the filtrate under reduced pressure to obtain the lithium difluorophosphate.
POF 3 (phosphorus oxytrifluoride) is colorless gas and has a pungent odor. The relative density is 4.69, the melting point is-68 ℃, the boiling point is-39.8 ℃, and sublimation is carried out simultaneously. Smoke is generated slightly in the air, and water is decomposed when meeting. Therefore, the reaction is carried out under the condition of isolating moisture: the organic solvent and the reactor must not contain water, and reaction conditions for isolating water vapor in the environment are adopted; the moisture content of the silicon oxygen compound is less than or equal to 100ppm. Wherein the content of hydrogen fluoride in the phosphorus oxyfluoride is less than or equal to 50ppm.
According to a preferred embodiment of the present application, wherein the silicone compound is silica or a siloxane, the siloxane is a linear siloxane or a cyclic siloxane.
The siloxane may be hexamethyldisiloxane, for example. The reaction principle is as follows:
according to a preferred embodiment of the present application, wherein the reaction temperature is 5-100deg.C, more preferably 20-50℃and more preferably 25-35 ℃. When the temperature is too high, the phosphorus trifluoride POF 3 Severe escape and more byproducts; when the temperature is too low, the reaction is too slow, the production period is too long, and the yield is low.
According to the preferred embodiment of the application, in the reaction system, phosphorus trifluoride POF 3 The molar ratio of the silicon oxide to the silicon oxide is 1:1-2. When the amount of the silicon-oxygen compound is too large, the difficulty in treating the reaction solution is high, and when the amount is too small, the use ratio of phosphorus oxyfluoride is low.
According to the preferred embodiment of the application, the molar ratio of the phosphorus oxytrifluoride, the silicon oxygen compound and the lithium fluoride in the reaction system is 1:1-2:0.5-1. Excessive lithium fluoride results in high cost; too little, the phosphorus oxyfluoride utilization rate is low.
According to the preferred embodiment of the application, the organic solvent in the reaction system is any one or a combination of several of ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, vinylene carbonate, propylene carbonate, methyl carbonate, 1-fluoroethylene carbonate, ethylene glycol dimethyl ether, acetonitrile, acetone and ethyl acetate.
According to a preferred embodiment of the application, the mass ratio of the organic solvent to the lithium fluoride is 20-40:1.
According to the preferred embodiment of the application, the organic solvent is an anhydrous organic solvent, the water content is controlled to be less than or equal to 50ppm, the acidity is less than or equal to 20ppm, preferably the water content is less than or equal to 30ppm, and the acidity is less than or equal to 15ppm. Excessive solvent moisture and acidity, POF 3 The lithium difluorophosphate obtained is of high acidity due to waste of partial decomposition.
The application does not limit the feeding sequence and the feeding mode, wherein the modes of subsequent filtering and washing, reduced pressure evaporating/reduced pressure drying and the like and corresponding equipment are not particularly limited, so long as qualified products can be obtained. The unreacted silicon oxide, a small amount of lithium fluoride and fluorosilane homologs generated by the reaction are mainly removed by filtration and washing, the organic solvent and silicon tetrafluoride are mainly removed by reduced pressure distillation, and the two treatment processes are very simple and belong to mature processes.
(III) beneficial effects
In view of the above, the application selects by-products of phosphorus oxyfluoride, silicon oxide and lithium fluoride during the production of phosphorus pentafluoride as reactants, and prepares the high-purity lithium difluorophosphate by adopting a gas-solid-liquid three-phase reaction mode. Compared with the prior art, the application has the beneficial effects that: the byproduct phosphorus oxyfluoride in the production process of the technical product phosphorus pentafluoride in the unit of the applicant is fully utilized, in addition, the silicon oxide is also a cheap and easily available product, and the produced byproduct can be made into other fluorine-containing and silicon-containing products. The whole process flow is short, the cost is low, special treatment is not needed after the reaction is finished, and the method has industrial value.
Drawings
FIG. 1 is F-NMR (fluorine spectrum) of lithium difluorophosphate prepared by the process of the present application.
Detailed Description
The application will be better explained by the following detailed description of the embodiments with reference to the drawings.
The method for synthesizing lithium difluorophosphate by gas, solid and liquid three phases comprises the following steps:
s1: under the condition of isolating moisture, dispersing silicon oxygen compound and lithium fluoride in (anhydrous) organic solvent at a certain temperature, introducing POF 3 And (3) reacting the gases to obtain a reaction solution.
The molar ratio of the phosphorus oxytrifluoride to the silicon oxygen compound to the lithium fluoride is 1: (1-2): (0.5-1); the reaction temperature is 5 to 100 ℃, preferably 5 to 50 ℃, more preferably 5 to 30 ℃.
Wherein the organic solvent is one or more of ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, vinylene carbonate, propylene carbonate, methyl carbonate, 1-fluoroethylene carbonate, ethylene glycol dimethyl ether, acetonitrile, acetone and ethyl acetate.
The mass ratio of the organic solvent to the lithium fluoride is (20-40): 1. the organic solvent is excessively used, the later reduced pressure distillation time is excessively long, and the energy consumption is high. Too little is detrimental to the rapid progress of the reaction.
Wherein, the water content of the organic solvent is less than or equal to 30ppm, and the acidity is less than or equal to 15ppm; the content of hydrogen fluoride in the phosphorus oxyfluoride is less than or equal to 50ppm; the moisture content of the silicon oxygen compound is less than or equal to 100ppm.
S2: and filtering the reaction liquid, and evaporating the reaction liquid under reduced pressure to dryness to obtain anhydrous lithium difluorophosphate.
Wherein, the phosphorus oxyfluoride is a byproduct of preparing phosphorus pentafluoride by applicant company, and the cost is low. Other raw materials, namely silicon dioxide and lithium fluoride, are bulk chemicals, and are low in cost and easy to obtain. The reaction process does not involve high temperature and high pressure, the process is easy to control, the safety coefficient is high, and the yield is high. The solvent can be recovered, and the byproducts have utility value.
In order to further clarify the technical solution and effect of the present application, reference will now be made to specific embodiments.
Example 1
The embodiment provides a preparation method of anhydrous lithium fluorophosphate, which specifically comprises the following steps:
48g of silicon dioxide, 5.2g of lithium fluoride and then 41.6g of phosphorus oxytrifluoride are added to 200g of ethyl acetate at 50℃and the resulting offgas is taken up with water. After the gas was introduced, the temperature of the reaction mixture was raised to 80℃and the reaction was continued with stirring for 12 hours, and F-NMR showed that the reaction was completed.
In the reaction system, the molar ratio of the phosphorus oxytrifluoride to the silicon oxygen compound to the lithium fluoride is 1:2:0.5.
the reaction solution was filtered to remove unreacted silica and a small amount of lithium fluoride, thereby obtaining an ethyl acetate solution of lithium difluorophosphate. The solution is dried in vacuum to obtain 20.24g of anhydrous lithium difluorophosphate with the yield of 93.7% and the product purity of 99.6%. The filter residues can be reused.
Example 2
The embodiment provides a preparation method of anhydrous lithium fluorophosphate, which specifically comprises the following steps:
41.6g of phosphorus oxytrifluoride was slowly introduced into 200g of ethyl acetate at 5℃and 48g of silicon dioxide and 5.2g of lithium fluoride were then added in one portion. The temperature was raised to 80℃and the reaction was stirred for 13h, and F-NMR showed the reaction to be over.
In the reaction system, the molar ratio of the phosphorus oxytrifluoride to the silicon oxygen compound to the lithium fluoride is 1:2:0.5.
the reaction solution was filtered to remove unreacted silica and a small amount of lithium fluoride, thereby obtaining an ethyl acetate solution of lithium difluorophosphate. The solution is dried in vacuum to obtain 21.07g of lithium difluorophosphate with the yield of 97.5 percent and the product purity of 99.7 percent.
Example 3
The embodiment provides a preparation method of anhydrous lithium fluorophosphate, which specifically comprises the following steps:
to 200g of ethylene glycol diethyl ether was added 97.2g of hexamethyldisiloxane at 30℃followed by slowly charging 41.6g of phosphorus oxytrifluoride and then 5.2g of lithium fluoride. The temperature was raised to 80℃and the reaction was stirred for 9h, and F-NMR showed the reaction to be complete.
In the reaction system, the molar ratio of the phosphorus oxytrifluoride to the silicon oxygen compound to the lithium fluoride is 1:1.5:0.5.
the reaction solution was filtered to remove unreacted silica and a small amount of lithium fluoride, thereby obtaining an ethyl acetate solution of lithium difluorophosphate. The solution is dried in vacuum to obtain 21.24g of lithium difluorophosphate with the yield of 98.3% and the product purity of 99.7%.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Claims (6)
1. A method for synthesizing lithium difluorophosphate in a gas-solid-liquid three-phase mode, which is characterized by comprising the following steps: dispersing silicon oxide and lithium fluoride in organic solvent under the condition of isolating water to obtain a dispersion mixture, and introducing POF into the dispersion mixture 3 After the reaction, the gas is reacted to obtain a reaction solution; the silicon oxide compound is silicon dioxide;
filtering the reaction liquid, and evaporating and drying the filtrate under reduced pressure to obtain lithium difluorophosphate;
the organic solvent is one or any combination of several of ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, vinylene carbonate, propylene carbonate, methyl carbonate, 1-fluoroethylene carbonate, ethylene glycol dimethyl ether, acetonitrile, acetone and ethyl acetate; the organic solvent is anhydrous organic solvent, the water content is controlled to be less than or equal to 50ppm, and the acidity is controlled to be less than or equal to 20 ppm.
2. The process of claim 1, wherein the reaction temperature is from 5 to 100 ℃.
3. The method according to claim 1, wherein the phosphorus oxytrifluoride POF 3 The molar ratio of the silicon oxide to the silicon oxide is 1:1-2.
4. The method according to claim 1, wherein the molar ratio of phosphorus oxytrifluoride, silicon oxygen compound and lithium fluoride is 1:1-2:0.5-1.
5. The method according to claim 1, wherein the mass ratio of organic solvent to lithium fluoride is 20-40:1.
6. The method of claim 1, wherein the organic solvent has a moisture content of 30ppm or less and an acidity of 15ppm or less.
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| CN115818672A (en) * | 2022-12-30 | 2023-03-21 | 浙江研一新能源科技有限公司 | Method for co-producing lithium hexafluorophosphate and lithium difluorophosphate |
| CN115947351A (en) * | 2022-12-30 | 2023-04-11 | 浙江研一新能源科技有限公司 | Method for co-producing sodium hexafluorophosphate and sodium difluorophosphate |
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