Preparation method of lithium difluoro(bisoxalate)phosphate

A technology of lithium difluorobisoxalate phosphate and lithium oxalate, which is applied in the field of electrolyte, can solve the problems of strong skin irritation and corrosion, lithium hexafluorophosphate is easy to absorb water, and is unfavorable for industrial production, and achieves easy acquisition, easy purification, and fast response Effect

Active Publication Date: 2019-07-02
DONGGUAN DONGYANG SOLAR SCI RES & DEV CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example, CN102216311, WO2013180174, WO2014097772, and JP2016201244 all use lithium hexafluorophosphate and oxalic acid, and add silicon tetrachloride; the high chlorine compounds and free acids in the solution hinder its further application in lithium-ion battery electrolyte; WO2016002771 uses dichlorotetrafluorophosphoric acid Lithium reacts with oxalic acid, but lithium dichlorotetrafluorophosphate needs to be synthesized, which increases the reaction steps and is not conducive to industrial production; the preparation method of lithium difluorobisoxalate phosphate in WO2016052092 and WO2016117279 uses HF, which is strongly irritating to the skin and Corrosive, not conducive to industrial production; KR1020130102969 uses lithium hexafluorophosphate to react with bis(trialkylsilyl) oxalate, wherein bis(trialkylsilyl) oxalate also reacts with Si-containing compounds through oxalic acid, which increases the reaction step; and lithium hexafluorophosphate is easy to absorb water, the price is high, it is not easy to store, and it is not conducive to industrial production

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Add 30.57g (0.3mol) lithium oxalate anhydrous to the 500mL autoclave with stirrer, and seal, vacuumize; Phosphorus pentafluoride: anhydrous lithium oxalate (mass ratio 1:2) and high-purity carbon dioxide; then raise the temperature of the reaction to a reaction temperature of 70°C, and at the same time adjust the pressure of the reactor to 7.39MPa, and continue stirring for 12 hours; After the reaction, cool to room temperature and open the kettle, dissolve in acetonitrile and filter to remove insoluble impurities, and use 200mL toluene for crystallization and beating. Vacuum drying at 120° C. for 24 hours yielded 30 g of lithium difluorobisoxalate phosphate with a purity of 99.9% and a yield of 79%.

[0029] 19 F-NMR (600MHz, DMSO-d 6 ):δ-69.1(s,1F),-71.0(s,1F);

[0030] 13 C-NMR (600MHz, DMSO-d 6 ):δ158.6;

[0031] LC-MS: Neg: M / Z = 244.9.

Embodiment 2

[0033] Add 36.68g (0.36mol) of anhydrous lithium oxalate to a 500mL autoclave with a stirrer, seal it, and evacuate; then, slowly feed phosphorus pentafluoride gas into the autoclave at 0°C (according to five Phosphorus fluoride: anhydrous lithium oxalate (1:2.4) and high-purity carbon dioxide; then raise the temperature of the reaction to a reaction temperature of 70°C, and at the same time adjust the pressure of the reactor to 8.39MPa, and continue stirring for 15 hours; After the end, cool to room temperature and open the kettle, dissolve dimethyl carbonate and filter to remove insoluble impurities, and use 240mL xylene for crystallization and beating. Vacuum drying at 110° C. for 24 hours yielded 33 g of lithium difluorobisoxalate phosphate with a purity of 99.8% and a yield of 87%.

[0034] 19 F-NMR (600MHz, DMSO-d 6 ):δ-69.1(s,1F),-71.0(s,1F);

[0035] 13 C-NMR (600MHz, DMSO-d 6 ):δ158.6;

[0036] LC-MS: Neg: M / Z = 244.9.

Embodiment 3

[0038] Add 33.63g (0.33mol) of anhydrous lithium oxalate to a 500mL autoclave with a stirrer, seal it, and vacuumize it; then, slowly feed phosphorus pentafluoride gas into the autoclave at 5°C (according to five Phosphorus fluoride: anhydrous lithium oxalate (1:2.2) and high-purity carbon dioxide; then raise the temperature of the reaction to a reaction temperature of 70°C, and at the same time adjust the pressure of the reactor to 9.39MPa, and continue stirring for 16 hours; After the end, cool to room temperature and open the kettle, dissolve and filter with acetonitrile to remove insoluble impurities, and use 200mL of dichloromethane for crystallization and beating. Vacuum drying at 120° C. for 24 hours yielded 32 g of lithium difluorobisoxalate phosphate with a purity of 99.7% and a yield of 84%.

[0039] 19 F-NMR (600MHz, DMSO-d 6):δ-69.1(s,1F),-71.0(s,1F);

[0040] 13 C-NMR (600MHz, DMSO-d 6 ):δ158.6;

[0041] LC-MS: Neg: M / Z = 244.9.

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PUM

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Abstract

The invention provides a preparation method of lithium difluoro(bisoxalate)phosphate. Lithium difluoro(bisoxalate)phosphate is prepared by a reaction between phosphorus pentafluoride and lithium oxalate. The preparation method comprises the following steps: 1) adding anhydrous lithium oxalate into a high pressure reactor with a stirrer, sealing, and vacuum-pumping; 2) slowly introducing phosphoruspentafluoride gas and high-purity carbon dioxide into the reactor at a low temperature; 3) slowly heating to 70 DEG C, adjusting pressure of the reactor to an appropriate value, and continuously stirring and reacting; and 4) carrying out separation and purification after the reaction. According to the method, raw materials are cheap and easily-available, and the reaction is carried out under mildconditions. The reaction steps are simple, and operation is convenient; the target product is only lithium difluoro(bisoxalate)phosphate; the product has high yield and high purity, and is easy to purify; the reaction is fast, postprocessing is simple, and feasibility of the industrial production is increased.

Description

technical field [0001] The invention belongs to the technical field of electrolytes, and in particular relates to a preparation method of lithium difluorobisoxalate phosphate. Background technique [0002] In recent years, due to the rapid development of smart devices such as mobile phones and tablet computers, the market share of small lithium batteries has grown rapidly. In addition, the technology of electric vehicles is becoming more and more perfect, and the market demand for large lithium batteries is also gradually released. It is expected that lithium batteries will maintain a growth trend in the next few years . Lithium batteries are mostly secondary batteries, and their poor high-voltage workability, cycle and rate performance are the difficulties that hinder their development. Lithium difluorobisoxalate phosphate (LiDFBP), as a new type of lithium salt additive, can exhibit excellent cycle performance and rate performance when applied to lithium-rich cathode mate...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/6574H01M10/0567
CPCC07F9/65748H01M10/0567Y02E60/10
Inventor 朱辉余意
Owner DONGGUAN DONGYANG SOLAR SCI RES & DEV CO LTD
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