Method for preparing lithium oxalyldifluoroborate

A technology of lithium difluorooxalate borate and difluorooxalate borate, which is applied in the field of lithium battery electrolyte material manufacturing, can solve the problems of long reaction time, low yield and high preparation cost, and achieve short reaction time, high yield and high preparation The effect of simple process

Active Publication Date: 2014-01-01
GUANGZHOU TINCI MATERIALS TECH +1
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  • Abstract
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AI Technical Summary

Problems solved by technology

The purity of the product obtained by this method is greatly improved, but due to the introduction of Cl in the reaction process - Ionic impurities while using LiBF 4 Raw materials, resulting in higher preparation costs
3) In DMC solvent, by BF 3 ·O(CH 2 CH 3 ) 2 and Li 2 C 2 o 4 Reaction to prepare LiDFOB, and use DMC as a solvent to purify by recrystallization (S. Zhang, Electrochem. Commun., 2006, 8, 1423), but the reaction time is longer, and the target product has greater solubility in DMC , so the crystallization time is slow, the yield is low, and the product is still easily mixed with LiBF 4 by-product
4) Schreiner et al. in acetonitrile solvent, by LiBF 4 and (CH 3 ) 3 SiOCOCOOSi (CH 3 ) 3 React at 40-50°C for 1 day, the yield is as high as 97%, but the disadvantage is that the reaction time is longer, and LiBF is used at the same time 4 As a raw material, the production cost has been increased (C.Schreiner, et al, Chem.Eur.J., 2009,15,2270)

Method used

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  • Method for preparing lithium oxalyldifluoroborate
  • Method for preparing lithium oxalyldifluoroborate
  • Method for preparing lithium oxalyldifluoroborate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] Embodiment 1 uses boron trifluoride and potassium oxalate as raw materials to prepare lithium difluorooxalate borate

[0020]

[0021] Step 1: Add 166g (1mol) of anhydrous potassium oxalate and 200mL of dry tetrahydrofuran (THF) into a 1L autoclave, feed 68g (1mol) of boron trifluoride gas, heat the reaction system to 60°C, and control the reaction pressure After reacting at 0.2MPa for 6 hours, let it stand still, remove the insoluble matter in the reaction system by suction filtration under reduced pressure, and obtain a tetrahydrofuran solution of potassium difluorooxalate borate.

[0022] Step 2: Potassium difluorooxalate borate is obtained as a white solid after removing the solvent under reduced pressure. Potassium difluorooxalate borate is dissolved in water, flowed through the acidified cation exchange resin, collected to obtain difluorooxalate borate solution, add 37g (0.5 mol) Lithium Retard, stirred and reacted for 1 hour at room temperature and under the c...

Embodiment 2

[0025] Example 2 Using boron trifluoride ether solution and rubidium oxalate as raw materials to prepare lithium difluorooxalate borate

[0026]

[0027]Step 1: Add 258g (1mol) anhydrous rubidium oxalate, 150mL dry acetonitrile and 170g (1.2mol) boron trifluoride ether solution into a 1L autoclave, heat the reaction system to 50°C, and control the reaction pressure at 0.2MPa , After reacting for 8 hours, let it stand still, remove the insoluble matter in the reaction system by suction filtration under reduced pressure, and obtain an acetonitrile solution of rubidium difluorooxalate borate.

[0028] Step 2: After the solvent is removed under reduced pressure, rubidium difluorooxalate borate is obtained as a white solid, and rubidium difluorooxalate borate is dissolved in water, and the cation exchange resin after the acidification treatment is flowed through, and the difluorooxalate borate solution is collected, and 24 g (1mol ) lithium hydroxide, stirred and reacted for 2 h...

Embodiment 3

[0031] Example 3 Using boron trifluoride dimethyl carbonate solution and cesium oxalate as raw materials to prepare lithium difluorooxalate borate

[0032]

[0033] Step 1: Add 354g (1mol) cesium oxalate anhydrous in the autoclave of 2L, 200mL dry dimethyl carbonate (DMC) and 237g (1.5mol) boron trifluoride dimethyl carbonate solution, the reaction system is heated up to 70°C, the reaction pressure is controlled at 0.2MPa, after 6 hours of reaction, let it stand still, remove the insoluble matter in the reaction system by suction filtration under reduced pressure, and obtain a dimethyl carbonate solution of cesium difluorooxalate borate.

[0034] Step 2: After the solvent is removed under reduced pressure, cesium difluorooxalate borate is obtained as a white solid, and cesium difluorooxalate borate is dissolved in an appropriate amount of water, and the acidified cation exchange resin is flowed through to collect the difluorooxalate borate solution, and 59 g ( 0.8mol) of li...

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Abstract

The invention discloses a method for preparing lithium oxalyldifluoroborate. According to the method, first, a boracic compound reacts with potassium oxalate (rubidium or cesium) to form difluoro oxalic acid potassium borate (rubidium or cesium) through synthesis; then, a difluoro oxalic acid potassium borate (rubidium or cesium) water solution slowly flows through superacidulated cationic resin for exchange, and an appropriate amount of Li2CO3 or LiOH is added into a collected difluoro oxalic acid boric acid water solution for the neutral reaction to obtain a crude lithium oxalyldifluoroborate product; high-purify lithium oxalyldifluoroborate is obtained through recrystallization purification. The method has the advantages that operation steps are simple, preparation conditions are moderate, cost is low, ionic impurities can be effectively controlled, and the method is suitable for industrialized mass production.

Description

technical field [0001] The invention belongs to the technical field of manufacture of lithium (ion) battery electrolyte materials, in particular to lithium difluorooxalate borate (Li[B(C 2 o 4 ) F 2 ], the preparation of LiDFOB). technical background [0002] Due to LiPF 6 The chemical stability is poor, the temperature is above 55 ℃ or LiPF 6 When in contact with protic solvents (such as water, alcohols, etc.), it will decompose significantly, and the resulting phosphorus pentafluoride (PF 5 ), phosphorus oxyfluoride (OPF 3 ) and hydrogen fluoride (HF) and other impurities are fatal to the electrolyte and electrode materials, which is an important reason for the shortened service life of batteries and the root cause of battery safety problems (C.L.Campion, et al, J.Electrochem . Soc., 2005, 152, A2327; H. Yang, et al, J. Power Sources, 2006, 161, 573). Therefore, the development of conductive lithium salts with superior chemical and electrochemical stability has been...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/02
Inventor 韩鸿波陈靖淞覃旭松陈国华刘露乐丽华方琪仰永军陈卫
Owner GUANGZHOU TINCI MATERIALS TECH
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