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The preparation method of difluoro oxalate borate metal salt

A technology of difluorooxalic acid boric acid and metal salt, applied in the field of difluorooxalic acid borate metal salt F2]x, can solve the problems of long crystallization time, long reaction time, low yield and the like, achieve short reaction time, simple preparation process, high yield effect

Active Publication Date: 2016-03-23
GUANGZHOU TINCI MATERIALS TECH +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But the reaction time of this method is longer, and target product has bigger solubility in DMC, so crystallization time is long, and yield is low, and still easily mixed with LiBF in the product 4 By-products (S. Zhang, Electrochem. Commun., 2006, 8, 1423)
Allen et al. referred to the method of preparing LiDFOB by Zhang et al., through BF 3 ·O(CH 2 CH 3 ) 2 and Na 2 C 2 o 4 React under sealed conditions for 24 hours to obtain NaDFOB, and then purify by acetonitrile recrystallization (J.L.Allen, etal, J.PowerSources, 2013, 237, 104). This preparation method is also difficult to avoid the disadvantages of long crystallization time and low yield.

Method used

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  • The preparation method of difluoro oxalate borate metal salt
  • The preparation method of difluoro oxalate borate metal salt
  • The preparation method of difluoro oxalate borate metal salt

Examples

Experimental program
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Effect test

Embodiment 1

[0026] Example 1 Using boron trifluoride and methylammonium oxalate as raw materials to prepare lithium difluorooxalate borate

[0027]

[0028] Step 1: Add 180g (2mol) of anhydrous oxalic acid, 400mL of dry dimethyl carbonate (DMC) into a 2L autoclave, and feed 124g (4mol) of anhydrous methylamine and 136g (2mol) of boron trifluoride Gas, heat the reaction system to 60°C, control the reaction pressure at 0.2MPa, react at this temperature for 8 hours, let it stand, and filter under reduced pressure to remove the insoluble matter in the reaction system to obtain methylammonium difluorooxalate borate solution of dimethyl carbonate.

[0029] Step 2: Concentrate the solution to one-third under reduced pressure and slowly add 148g (2mol) of anhydrous lithium carbonate. After stirring at room temperature for 2 hours, raise the temperature to 60°C, continue to stir for 1 hour, let stand, filter under reduced pressure to remove insoluble matter in the reaction system, and dry unde...

Embodiment 2

[0031] Example 2 Using boron trichloride, ethylammonium oxalate and ammonium fluoride as raw materials to prepare lithium difluorooxalate borate

[0032]

[0033] Step 1: Add 180g (2mol) anhydrous oxalic acid, 400mL anhydrous diethyl carbonate in a 2L autoclave, feed 180g (4mol) anhydrous ethylamine and 234g (2mol) boron trichloride gas, Heat the reaction system to 50°C and control the reaction pressure at 0.15 MPa. After reacting at this temperature for 3 hours, let it stand still, remove the insoluble matter in the reaction system by suction filtration under reduced pressure, and obtain the carbonic acid of ethylammonium dichlorooxalate borate diethyl ester solution.

[0034] Step 2: Add 260 g (4 mol) of ethylamine hydrogen fluoride to the diethyl carbonate solution of ethylammonium dichlorooxalate borate obtained in step 1, and react at room temperature for 4 hours under an atmospheric pressure and leave it to stand, then filter under reduced pressure The insoluble matt...

Embodiment 3

[0037] Example 3 Using trimethyl borate and dimethylammonium oxalate as raw materials to prepare lithium difluorooxalate borate

[0038]

[0039] Step 1: Add 180g (2mol) of anhydrous oxalic acid, 400mL of anhydrous acetonitrile and 208g (2mol) of trimethyl borate into a 2L autoclave, and feed 180g (4mol) of anhydrous dimethylamine into the reaction system. The temperature was raised to 50° C., and the reaction pressure was controlled at 0.2 MPa. After reacting at this temperature for 5 hours, let it stand still, remove insoluble matter in the reaction system by suction filtration under reduced pressure, and obtain an acetonitrile solution of dimethylammonium dimethoxyoxalate borate.

[0040] Step 2: Concentrate the solution to one-third under reduced pressure, then slowly add 184g (4mol) lithium hydrogen fluoride at room temperature, react for 3 hours under one atmospheric pressure, filter under reduced pressure to remove insoluble matter, and concentrate the solution to on...

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Abstract

The invention discloses a preparing method of difluoro oxalic acid boric acid metal salt, and belongs to the field of material chemistry. The method comprises the steps that boron compounds and oxalic acid ammonium salt compounds react with each other to compose dihalogenacid oxalic acid boric acid ammonium salt or double-alkyl oxygroup oxalic acid boric acid ammonium salt, then the dihalogenacid oxalic acid boric acid ammonium salt or the double-alkyl oxygroup oxalic acid boric acid ammonium salt reacts with fluorinated reagents to prepare difluoro oxalic acid ammonium salt, obtained products react with moderate MxCO3 or M(OH)y (when the M=Li, Na, K, Rb and Cs, x=2 and y=1; when the M=Mg and Zn, x=1 and y=2), and the difluoro oxalic acid boric acid metal salt is obtained, and the high-purity difluoro oxalic acid boric acid metal salt products obtained after recrystallization purification is conducted. The preparing method has the advantages of being simple in operation step, mild in preparing condition, high in purity and productivity, low in cost, suitable for large-scale industrialized production and the like.

Description

technical field [0001] The invention belongs to the technical field of manufacture of electrolyte materials for electrochemical energy storage batteries, in particular to metal difluorooxalate borate (M[B(C 2 o 4 )F 2 ] x , M=Li, Na, K, Rb, Cs, Mg, Zn; x=1, 2). technical background [0002] Since the industrialization of Sony Corporation in the early 1990s, lithium-ion batteries have been widely used in various consumer electronics, implantable medical equipment, and small electric facilities. However, with LiPF 6 The traditional lithium-ion battery electrolyte, which is a conductive salt, has its own shortcomings such as thermal instability and water sensitivity that are difficult to overcome. LiPF 6 Significant decomposition will occur above 55°C to produce phosphorus pentafluoride (PF 5 ) Lewis acid and active intermediate phosphorus oxyfluoride (OPF 3 ). After these impurities are formed, they react with components such as lithium alkoxy carboxylate and lithium ...

Claims

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Application Information

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