CN110745795A - Method for electrochemically synthesizing lithium bis (fluorosulfonate) imide - Google Patents
Method for electrochemically synthesizing lithium bis (fluorosulfonate) imide Download PDFInfo
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Abstract
The invention discloses a method for electrochemically synthesizing lithium bis (fluorosulfonate) imide, which comprises the following steps: adjusting the temperature of the electrolytic cell to 0-18 ℃, taking two nickel plates as an anode and a cathode respectively, and adding a proper amount of anhydrous hydrofluoric acid into the electrolytic cell for electrolysis; after the current in the electrolytic cell is stable, adding a proper amount of dichlorosulfoimide into the electrolytic cell, and after the dichlorosulfoimide is dissolved, adjusting the working voltage of the electrolytic cell to 5-8V; when the current is reduced to below 5mA, taking out the solution in the electrolytic cell; and distilling the solution taken out of the electrolytic cell at normal pressure to separate the difluoride imine from the anhydrous hydrofluoric acid, and cooling to obtain the high-purity colorless liquid difluoride imine. Then, lithium hydroxide is used for reaction, and after filtration and recrystallization, high-purity lithium bis (fluorosulfonate) imide is obtained. The invention adopts electrochemistry to pre-remove water and chloride ions, and uses electrochemistry to fluorinate without introducing metal halide as catalyst, so the invention has simple process, low energy consumption, low cost and high purity of the prepared LiFSI.
Description
Technical Field
The invention relates to the technical field of chemical reagent preparation, in particular to a method for electrochemically synthesizing lithium bis (fluorosulfonate) imide.
Background
Lithium batteries are gradually and widely applied as novel green energy equipment, key materials of the lithium ion batteries comprise an anode, a cathode, a binder, a diaphragm and electrolyte, wherein the electrolyte plays a role in charge transmission between the anode and the cathode in the batteries, and is a key composition of the lithium ion batteries, the electrolyte obviously influences the cycle and service life, safety performance and energy of the batteries, and the lithium bis-fluorosulfonyl imide (LiFSI) is a novel electrolyte lithium salt used in the lithium battery electrolyte, is environment-friendly and has good safety performance. The purity and the cost of the bis (fluorosulfonyl) imide (HFSI) which is used as a raw material for synthesizing the bis (fluorosulfonyl) imide Lithium (LiFSI) are important for the battery performance and whether the industrial production of the bis (fluorosulfonyl) imide Lithium (LiFSI) can be realized.
Chinese patent CN104671224 discloses a method for synthesizing bis-fluorosulfonyl imide salt, which utilizes at least two of antimony fluoride, potassium fluoride, zinc fluoride and aluminum fluoride to form a compound fluoride salt, so that bis-fluorosulfonyl imide salt is subjected to effective fluorination reaction in an organic solvent; after the reaction is finished, filtering the reaction solution, and concentrating; and crystallizing, filtering and drying the concentrated solution to obtain the high-purity bis (fluorosulfonyl) imide salt, thereby further improving the fluorination efficiency. Chinese patent CN103935970A discloses a method for preparing bis (fluorosulfonyl) imide and its alkali metal salts, wherein hydrogen fluoride is used as a fluorinating agent and a reaction solvent to react with HClSI and alkali metal halide to prepare the alkali metal salts of bis (fluorosulfonyl) imide, and the hydrogen fluoride is relatively easy to obtain and has low raw material cost, thereby reducing the production cost; the reaction product is the bis-fluorosulfonyl imide and the hydrogen chloride, and other complex reaction byproducts do not exist, so that the material consumption and the waste generation are reduced, and the utilization rate of raw materials, the product yield and the purity are improved. Anhydrous hydrogen fluoride is also used as the fluorinating agent, but in order to further improve the fluorination conversion rate, SbCl is used in the reaction process5、TiCl4、SnCl4The amount ratio of the bischlorosulfonimide to the catalyst is preferably 1 (0.05-1).
In the synthesis method, fluorine or chlorinated metal salt is used as a catalyst for fluorination of the bis (fluorosulfonic acid) imide (hclSI), other heteroatoms are introduced into a reaction system, and the purity of the synthesized bis (fluorosulfonic acid) imide (HFSI) is difficult to reach the battery-grade standard and cannot be directly applied to large-scale industrialization.
Disclosure of Invention
The invention aims to provide a method for electrochemically synthesizing lithium bis (fluorosulfonate) imide, which avoids the use of highly toxic metal halides as catalysts, reduces heteroatoms, improves the purity of products, and reduces synthesis cost.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for synthesizing lithium bis (fluorosulfonate) imide by utilizing electrochemistry comprises the following steps:
step one, synthesizing dichlorosulfonic acid imine: under magnetic stirring, 300-350g thionyl chloride (SOCl) was added2) And 450-3H) 100-110g ammonium chloride (NH) was added to the round bottom flask4Cl), heating to raise the temperature of the mixed solution to 70-100 ℃ for reaction to generate SO2And HCl gas, taken out with nitrogen, absorbed with aqueous sodium hydroxide (NaOH); distilling after reacting for 30-40h, collecting the fraction at the temperature of 115-120 ℃, and cooling to obtain 185-200g of colorless dichlorosulfoimide (HCSI) liquid, wherein the yield of the dichlorosulfoimide is 86.9-93.6%; the chemical reaction that takes place in step one is shown in (1).
Step two, reducing the water content of the anhydrous hydrofluoric acid: adjusting the temperature of a polytetrafluoroethylene electrolytic cell to 0-18 ℃, taking two nickel plates as an anode and a cathode respectively, adding a proper amount of anhydrous hydrofluoric acid into the electrolytic cell, adjusting the working voltage of a direct current power supply of the electrolytic cell to 1.6-5V, and monitoring the current value in the electrolytic cell in real time by using a current meter. The chemical reaction in the second step is shown as (2);
step three, synthesizing the bis-fluorosulfonic acid imine: after the current in the electrolytic cell is stable, adding the bischlorosulfoacid imine prepared in the first step into the electrolytic cell, wherein the volume ratio of the added bischlorosulfoacid imine to the anhydrous hydrofluoric acid is 1: 30-40, after the dichlorosulfoimide is dissolved, adjusting the working voltage of the electrolytic cell to 5-8V; when the current is reduced to be below 5mA, the power supply experiment is closed and stopped; and taking out the solution in the electrolytic cell. The chemical reaction generated in the third step is shown as (3); HCl is also removed at the same time and a chemical reaction takes place as shown in (4).
Step four, purifying the bis (fluorosulfonic acid) imine liquid: putting the solution taken out of the electrolytic cell into a distiller, distilling at normal pressure to separate the difluoride imine from the anhydrous hydrofluoric acid, and cooling to obtain high-purity colorless difluoride imine liquid;
step five, synthesizing lithium bis (fluorosulfonate) imide: under the stirring of a magnetic cable, keeping the temperature at 0-10 ℃, mixing 10-15g of the difluoride sulfonic acid imine liquid prepared in the step four with 130-; then heating the liquid to 80-100 ℃, distilling and concentrating to separate out lithium difluoride sulfonate imine, and filtering to obtain a filter cake; the chemical reaction in the fifth step is shown as (5);
step six, preparing the lithium bis (fluorosulfonate) imide crystal: adding 40-55g of dichloromethane, 40-55g of ethanol and 0.15-0.3g of ethylene diamine tetraacetic acid tetrasodium solution into the filter cake prepared in the fifth step, pulping, filtering and drying to obtain 8-15g of lithium bis (fluorosulfonate) imide crystal, wherein the product yield is 92.8-95.1%;
preferably, the method for purifying lithium bis (fluorosulfonate) imide prepared in the sixth step comprises the following steps: under magnetic stirring, adding 9-10g of lithium bis (fluorosulfonate) imide into 100mL of dichloromethane and ethanol, mixing in a round-bottom flask, wherein the volume ratio of dichloromethane to ethanol is 1:1, recrystallizing, heating the mixed solution to 55-65 ℃, cooling the solution to room temperature after lithium bis (fluorosulfonate) imide is completely dissolved, cooling to 0 ℃, standing for 30min, and filtering the precipitated solid to obtain 9-9.9g of white lithium bis (fluorosulfonate) imide crystals (LiFSI).
Preferably, in the first step, a coolant circulation pipe is installed at the outer side of the electrolytic cell, and the temperature of the electrolytic cell is maintained at 0-18 ℃ by the coolant circulation.
Preferably, the rotation speed of the magnetic stirring in the first step and the fifth step is 1000-.
According to the invention, water and chloride ions are removed in advance by electrochemistry, metal halide is not introduced as a catalyst for fluorination by electrochemistry, lithium hydroxide is used for reacting with lithium bifluorosulfonate imide salt, and after filtration, recrystallization is carried out to obtain battery-grade lithium bifluorosulfonate imide.
In the first step of the method, sulfur dioxide and hydrogen chloride gas are generated while the dichlorosulfoimide is generated, are taken out by using nitrogen and are absorbed by a sodium hydroxide aqueous solution, and byproducts are removed. The chemical reaction formula is as follows:
and step two, the water content of the raw material, namely the anhydrous hydrofluoric acid, before the reaction is further reduced through the electrolysis operation of the electrolytic cell.
The chemical reaction formula of the bis (fluorosulfonic acid) imine generated by the reaction in the third step is shown as the formula (3), and hydrogen chloride generated by the reaction is electrolyzed into hydrogen and chlorine at the same time.
And fifthly, generating the lithium bis (fluorosulfonate) imide salt according to the formula (5).
The invention has the beneficial effects that:
the electrochemical method is adopted to remove water in advance and further remove chloride ions and some cations, and the electrochemical method is used to fluorinate the bis (chloro) sulfonic acid imine (HClSI) at the same time, so that a fluorinating reagent is avoided, thereby avoiding the introduction of other ions and finally obtaining the battery-grade bis (fluoro) sulfonic acid imine Lithium (LiFSI) crystal. Therefore, the method has the advantages of simple process, low energy consumption and low cost, and the prepared lithium bis (fluorosulfonate) imide (LiFSI) has high purity.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
A method for synthesizing lithium bis (fluorosulfonate) imide by utilizing electrochemistry comprises the following steps:
step one, synthesizing dichlorosulfonic acid imine: under magnetic stirring (1000 ℃ 1500 rpm), 300g of thionyl chloride (SOCl) was added2) And 500g of chlorosulfonic acid(CISO3H) 110g of ammonium chloride (NH) was added to the round bottom flask4Cl), heating to raise the temperature of the mixed solution to 100 ℃ for reaction to generate SO2And HCl gas, taken out with nitrogen, absorbed with aqueous sodium hydroxide (1M NaOH); distilling after reacting for 30h, collecting 115-120 ℃ fractions, and cooling to obtain 185g of colorless dichlorosulfoimide (HCSI) liquid, wherein the yield of the dichlorosulfoimide (HCSI) is 89.6%;
step two, reducing the water content of the anhydrous hydrofluoric acid: adjusting the temperature of a polytetrafluoroethylene electrolytic cell to 18 ℃, taking two nickel plates as an anode and a cathode respectively, adding 300ml of anhydrous hydrofluoric acid (HF) into the electrolytic cell, adjusting the working voltage of a direct current power supply of the electrolytic cell to 5V, and monitoring the current value in the electrolytic cell in real time by using a current meter;
step three, synthesizing the bis-fluorosulfonic acid imine: after the current in the electrolytic cell is stable, adding 10ml of the bischlorosulfoacid imine (HCSI) prepared in the step one into the electrolytic cell, and after the bischlorosulfoacid imine (HClSI) is dissolved, adjusting the working voltage of the electrolytic cell to 8V; when the current is reduced to be below 5mA, the power supply experiment is closed and stopped; taking out the solution in the electrolytic cell;
step four, purifying the bis (fluorosulfonic acid) imine liquid: putting the solution taken out of the electrolytic cell into a distiller, distilling at normal pressure to separate the difluoride imine sulfonate (HFSI) from anhydrous hydrofluoric acid (HF), and cooling to obtain high-purity colorless difluoride imine sulfonate (HFSI) liquid;
step five, synthesizing lithium bis (fluorosulfonate) imide: keeping the temperature at 0-10 ℃ under the condition of magnetic stirring (1000-1500 r/min), and mixing 10g of the bis (fluorosulfonic acid) imide (HFSI) liquid prepared in the fourth step with 130g of dichloromethane (CH)2Cl2)10 g of thionyl chloride (SOCl)2) Mixing the solution in a round-bottom flask, adding 1.3g of anhydrous lithium hydroxide (LiOH) into the mixed solution, stirring for 30min, heating the solution to 30 ℃, and continuing to react for 2 h; then heating the liquid to 50 ℃, distilling and concentrating to separate out lithium bis (fluorosulfonate) imide (LiFSI), and filtering to obtain a filter cake;
step six, preparing the lithium bis (fluorosulfonate) imide crystal: the filter cake prepared in step five was added with 40g of dichloromethane (CH)2Cl2) 40g of ethanol (C)2H5OH) and 0.15g of ethylenediaminetetraacetic acid tetrasodium solution are pulped, filtered and dried to obtain 13g of lithium bis (fluorosulfonate) imide (LiFSI) crystals, and the product yield is 92.8%.
The purification method of the lithium bis (fluorosulfonate) imide prepared in the sixth step comprises the following steps: 9g of lithium bis-fluorosulfonate (LiFSI) are added to 100mL of dichloromethane (CH) with magnetic stirring2Cl2) And ethanol (C)2H5OH) in a mixed solution of dichloromethane (CH)2Cl2) With ethanol (C)2H5OH) is 1:1, heating the mixed solution to 55 ℃, cooling the solution to room temperature after lithium bis (fluorosulfonate) imide (LiFSI) is completely dissolved, cooling to 0 ℃, standing for 30min, and filtering precipitated solids to obtain 8.9g of white lithium bis (fluorosulfonate) imide (LiFSI) crystals.
In the first step, a coolant circulating pipeline is arranged on the outer side of the electrolytic cell, and the temperature of the electrolytic cell is kept between 0 and 18 ℃ through coolant circulation.
Example 2
A method for synthesizing lithium bis (fluorosulfonate) imide by utilizing electrochemistry comprises the following steps:
step one, synthesizing dichlorosulfonic acid imine: under magnetic stirring (1000 ℃ 1500 rpm), 350g of thionyl chloride (SOCl) was added2) And 450g of chlorosulfonic acid (CISO)3H) 100g of ammonium chloride (NH) was added to the round bottom flask4Cl), heating to raise the temperature of the mixed solution to 100 ℃ for reaction to generate SO2 and HCl gas, taking out the SO2 and HCl gas with nitrogen, and absorbing the SO2 and HCl gas with sodium hydroxide (1M NaOH) aqueous solution; distilling after reacting for 40h, collecting 115-120 ℃ fractions, and cooling to obtain 200g of colorless dichlorosulfoimide (HClSI) liquid, wherein the yield of the dichlorosulfoimide (HClSI) is 90.6%;
step two, reducing the water content of the anhydrous hydrofluoric acid: adjusting the temperature of a polytetrafluoroethylene electrolytic cell to 18 ℃, taking two nickel plates as an anode and a cathode respectively, adding 300ml of anhydrous hydrofluoric acid (HF) into the electrolytic cell, adjusting the working voltage of a direct current power supply of the electrolytic cell to 1.6V, and monitoring the current value in the electrolytic cell in real time by using a current meter;
step three, synthesizing the bis-fluorosulfonic acid imine: after the current in the electrolytic cell is stable, adding 7.5ml of the bischlorosulfoacid imine (HClSI) prepared in the step one into the electrolytic cell, and after the bischlorosulfoacid imine (HCSI) is dissolved, adjusting the working voltage of the electrolytic cell to 5V; when the current is reduced to be below 5mA, the power supply experiment is closed and stopped; taking out the solution in the electrolytic cell;
step four, purifying the bis (fluorosulfonic acid) imine liquid: putting the solution taken out of the electrolytic cell into a distiller, distilling at normal pressure to separate the difluoride imine sulfonate (HFSI) from anhydrous hydrofluoric acid (HF), and cooling to obtain high-purity colorless difluoride imine sulfonate (HFSI) liquid;
step five, synthesizing lithium bis (fluorosulfonate) imide: under the condition of magnetic stirring (1000-2Cl2) 15g of thionyl chloride (SOCl)2) Mixing the solution in a round-bottom flask, adding 1.7g of anhydrous lithium hydroxide (LiOH) into the mixed solution, stirring for 30min, heating the solution to 20 ℃, and continuing to react for 2 h; then heating the liquid to 50 ℃, distilling and concentrating to separate out lithium bis (fluorosulfonate) imide (LiFSI), and filtering to obtain a filter cake;
step six, preparing the lithium bis (fluorosulfonate) imide crystal: the filter cake prepared in step five was charged with 55g of dichloromethane (CH)2Cl2) 55g of ethanol (C)2H5OH) and 0.3g of ethylenediaminetetraacetic acid tetrasodium solution are pulped, filtered and dried to obtain 9.4g of lithium bis (fluorosulfonate) imide (LiFSI) crystals, and the product yield is 93.1%.
The purification method of the lithium bis (fluorosulfonate) imide prepared in the sixth step comprises the following steps: 9.6g of lithium bis-fluorosulfonate (LiFSI) are added to 100mL of dichloromethane (CH) with magnetic stirring2Cl2) And ethanol (C)2H5OH) in a mixed solution of dichloromethane (CH)2Cl2) With ethanol (C)2H5OH) is 1:1, heating the mixed solution to 65 ℃, cooling the solution to room temperature after lithium bis (fluorosulfonate) imide (LiFSI) is completely dissolved, cooling to 0 ℃, standing for 30min, and separating out solidFiltration gave 9.5g of white lithium bis (fluorosulfonate) crystals (LiFSI).
Example 3
A method for synthesizing lithium bis (fluorosulfonate) imide by utilizing electrochemistry comprises the following steps:
step one, synthesizing dichlorosulfonic acid imine: under magnetic stirring (1000 ℃ 1500 rpm), 320g of thionyl chloride (SOCl) was added2) And 480g of chlorosulfonic acid (CISO)3H) 105g of ammonium chloride (NH) was added to the mixture4Cl), heating to raise the temperature of the mixed solution to 80 ℃ for reaction to generate SO2And HCl gas, taken out with nitrogen, absorbed with aqueous sodium hydroxide (NaOH); distilling after reacting for 35h, collecting 115-120 ℃ fractions, and cooling to obtain 190g of colorless dichlorosulfoimide (HClSI) liquid, wherein the yield of the dichlorosulfoimide (HClSI) is 91.5%;
step two, reducing the water content of the anhydrous hydrofluoric acid: adjusting the temperature of a polytetrafluoroethylene electrolytic cell to 18 ℃, taking two nickel plates as an anode and a cathode respectively, adding 300ml of anhydrous hydrofluoric acid (HF) into the electrolytic cell, adjusting the working voltage of a direct current power supply of the electrolytic cell to 3V, and monitoring the current value in the electrolytic cell in real time by using a current meter;
step three, synthesizing the bis-fluorosulfonic acid imine: after the current in the electrolytic cell is stable, adding 8.5ml of the bischlorosulfoacid imine (HClSI) prepared in the step one into the electrolytic cell, and adjusting the working voltage of the electrolytic cell to 7V after the bischlorosulfoacid imine (HClSI) is dissolved; when the current is reduced to be below 5mA, the power supply experiment is closed and stopped; taking out the solution in the electrolytic cell;
step four, purifying the bis (fluorosulfonic acid) imine liquid: putting the solution taken out of the electrolytic cell into a distiller, distilling at normal pressure to separate the difluoride imine sulfonate (HFSI) from anhydrous hydrofluoric acid (HF), and cooling to obtain high-purity colorless difluoride imine sulfonate (HFSI) liquid;
step five, synthesizing lithium bis (fluorosulfonate) imide: keeping the temperature at 0-10 ℃ under the condition of magnetic stirring (1000-2Cl2) 12g of thionyl chloride (SOCl)2) In a round-bottom flaskMixing, adding 1.5g of anhydrous lithium hydroxide (LiOH) into the mixed solution, stirring for 30min, heating the solution to 25 ℃, and continuing to react for 2 h; then heating the liquid to 50 ℃, distilling and concentrating to separate out lithium bis (fluorosulfonate) imide (LiFSI), and filtering to obtain a filter cake;
step six, preparing the lithium bis (fluorosulfonate) imide crystal: the filter cake prepared in step five was charged with 45g of dichloromethane (CH)2Cl2) 45g of ethanol (C)2H5OH) and 0.2g of ethylenediaminetetraacetic acid tetrasodium solution are pulped, filtered and dried to obtain 10.8g of lithium bis (fluorosulfonate) imide (LiFSI) crystals, and the product yield is 93.5%.
The purification method of the lithium bis (fluorosulfonate) imide prepared in the sixth step comprises the following steps: 9.5g of lithium bis-fluorosulfonate (LiFSI) are added to 100mL of dichloromethane (CH) with magnetic stirring2Cl2) And ethanol (C)2H5OH) in a mixed solution of dichloromethane (CH)2Cl2) With ethanol (C)2H5OH) is 1:1, heating the mixed solution to 65 ℃, cooling the solution to room temperature after lithium bis (fluorosulfonate) imide (LiFSI) is completely dissolved, cooling to 0 ℃, standing for 30min, and filtering precipitated solids to obtain 9.2-9.5g of white lithium bis (fluorosulfonate) imide (LiFSI) crystals.
Example 4
A method for synthesizing lithium bis (fluorosulfonate) imide by utilizing electrochemistry comprises the following steps:
step one, synthesizing dichlorosulfonic acid imine: under magnetic stirring (1000 ℃ 1500 rpm), 336g of thionyl chloride (SOCl) was added2) And 468g of chlorosulfonic acid (CISO)3H) 107g of ammonium chloride (NH) was added to the round bottom flask of (1)4Cl) is added into the mixture, the temperature of the mixture is raised to 85 ℃ for reaction, and SO is generated2And HCl gas, taken out with nitrogen, absorbed with aqueous sodium hydroxide (NaOH); distilling after reacting for 30h, collecting 115-120 ℃ fractions, and cooling to obtain 195g of colorless dichlorosulfoimide (HCSI) liquid, wherein the yield of the dichlorosulfoimide (HClSI) is 86.9%;
step two, reducing the water content of the anhydrous hydrofluoric acid: adjusting the temperature of a polytetrafluoroethylene electrolytic cell to 18 ℃, taking two nickel plates as an anode and a cathode respectively, adding 300ml of anhydrous hydrofluoric acid (HF) into the electrolytic cell, adjusting the working voltage of a direct current power supply of the electrolytic cell to 4.5V, and monitoring the current value in the electrolytic cell in real time by using a current meter;
step three, synthesizing the bis-fluorosulfonic acid imine: after the current in the electrolytic cell is stable, adding 8.8ml of the bischlorosulfoacid imine (HClSI) prepared in the step one into the electrolytic cell, and after the bischlorosulfoacid imine (HCSI) is dissolved, adjusting the working voltage of the electrolytic cell to 7.5V; when the current is reduced to be below 5mA, the power supply experiment is closed and stopped; taking out the solution in the electrolytic cell;
step four, purifying the bis (fluorosulfonic acid) imine liquid: putting the solution taken out of the electrolytic cell into a distiller, distilling at normal pressure to separate the difluoride imine sulfonate (HFSI) from anhydrous hydrofluoric acid (HF), and cooling to obtain high-purity colorless difluoride imine sulfonate (HFSI) liquid;
step five, synthesizing lithium bis (fluorosulfonate) imide: under the condition of magnetic stirring (1000-2Cl2) 13g of thionyl chloride (SOCl)2) Mixing the solution, adding 1.65g anhydrous lithium hydroxide (LiOH) into the mixed solution, stirring for 30min, heating the solution to 30 ℃, and continuing to react for 2 h; then heating the liquid to 50 ℃, distilling and concentrating to separate out lithium bis (fluorosulfonate) imide (LiFSI), and filtering to obtain a filter cake;
step six, preparing the lithium bis (fluorosulfonate) imide crystal: the filter cake prepared in step five was charged with 55g of dichloromethane (CH)2Cl2) 55g of ethanol (C)2H5OH) and 0.25g of ethylenediaminetetraacetic acid tetrasodium salt solution are pulped, filtered and dried to obtain 11g of lithium bis (fluorosulfonate) imide (LiFSI) crystals, and the product yield is 93.6%.
The purification method of the lithium bis (fluorosulfonate) imide prepared in the sixth step comprises the following steps: 9.3g of lithium bis-fluorosulfonate (LiFSI) are added to 100mL of dichloromethane (CH) with magnetic stirring2Cl2) And ethanol (C)2H5OH) in a mixed solution of dichloromethane (CH)2Cl2) With BAlcohol (C)2H5OH) is 1:1, heating the mixed solution to 60 ℃, cooling the solution to room temperature after lithium bis (fluorosulfonate) imide (LiFSI) is completely dissolved, cooling to 0 ℃, standing for 30min, and filtering precipitated solids to obtain 9.1-9.5g of white lithium bis (fluorosulfonate) imide (LiFSI) crystals.
Example 5
A method for synthesizing lithium bis (fluorosulfonate) imide by utilizing electrochemistry comprises the following steps:
step one, synthesizing dichlorosulfonic acid imine: under magnetic stirring (1000 ℃ 1500 rpm), 325g of thionyl chloride (SOCl) was added2) And 465g chlorosulfonic acid (CISO)3H) 108g of ammonium chloride (NH) was added to the round bottom flask4Cl), heating to raise the temperature of the mixed solution to 95 ℃ for reaction to generate SO2And HCl gas, taken out with nitrogen, absorbed with aqueous sodium hydroxide (1M NaOH); distilling after reacting for 40h, collecting 115-120 ℃ fractions, and cooling to obtain 187g of colorless dichlorosulfoimide (HCSI) liquid, wherein the yield of the dichlorosulfoimide (HCSI) is 91.4%;
step two, reducing the water content of the anhydrous hydrofluoric acid: adjusting the temperature of a polytetrafluoroethylene electrolytic cell to 18 ℃, taking two nickel plates as an anode and a cathode respectively, adding 300ml of anhydrous hydrofluoric acid (HF) into the electrolytic cell, adjusting the working voltage of a direct current power supply of the electrolytic cell to 4.5V, and monitoring the current value in the electrolytic cell in real time by using a current meter;
step three, synthesizing the bis-fluorosulfonic acid imine: after the current in the electrolytic cell is stable, adding 9.5ml of the bischlorosulfoacid imine (HCSI) prepared in the step one into the electrolytic cell, and after the bischlorosulfoacid imine (HCSI) is dissolved, adjusting the working voltage of the electrolytic cell to 7.5V; when the current is reduced to be below 5mA, the power supply experiment is closed and stopped; taking out the solution in the electrolytic cell;
step four, purifying the bis (fluorosulfonic acid) imine liquid: putting the solution taken out of the electrolytic cell into a distiller, distilling at normal pressure to separate the difluoride imine sulfonate (HFSI) from anhydrous hydrofluoric acid (HF), and cooling to obtain high-purity colorless difluoride imine sulfonate (HFSI) liquid;
step five, synthesizing difluorideLithium salt of sulfonic acid imide: under the stirring of a magnetic source (1000 ℃ F. 1500 rpm), the temperature is kept between 0 and 10 ℃, and 12g of the difluorine sulfoimide (HFSI) liquid prepared in the fourth step and 132g of dichloromethane (CH)2Cl2) 14.5g of thionyl chloride (SOCl)2) Mixing the solution, adding 1.55g of anhydrous lithium hydroxide (LiOH) into the mixed solution, stirring for 30min, heating the solution to 25 ℃, and continuing to react for 2 h; then heating the liquid to 50 ℃, distilling and concentrating to separate out lithium bis (fluorosulfonate) imide (LiFSI), and filtering to obtain a filter cake;
step six, preparing the lithium bis (fluorosulfonate) imide crystal: the filter cake prepared in step five was charged with 48g of dichloromethane (CH)2Cl2) 48g of ethanol (C)2H5OH) and 0.25g of ethylenediaminetetraacetic acid tetrasodium salt solution are pulped, filtered and dried to obtain 11.5g of lithium bis (fluorosulfonate) imide (LiFSI) crystals, and the product yield is 94.2%.
The purification method of the lithium bis (fluorosulfonate) imide prepared in the sixth step comprises the following steps: 9.2g of lithium bis-fluorosulfonate (LiFSI) were added to 100mL of dichloromethane (CH) with magnetic stirring (1000 ℃ 1500 rpm)2Cl2) And ethanol (C)2H5OH) in a mixed solution of dichloromethane (CH)2Cl2) With ethanol (C)2H5OH) is 1:1, heating the mixed solution to 60 ℃, cooling the solution to room temperature after lithium bis (fluorosulfonate) imide (LiFSI) is completely dissolved, cooling to 0 ℃, standing for 30min, and filtering precipitated solids to obtain 9-9.2g of white lithium bis (fluorosulfonate) imide (LiFSI) crystals.
Example 6
A method for synthesizing lithium bis (fluorosulfonate) imide by utilizing electrochemistry comprises the following steps:
step one, synthesizing dichlorosulfonic acid imine: under magnetic stirring (1000 ℃ 1500 rpm), 335g of thionyl chloride (SOCl) was added2) And 462g of chlorosulfonic acid (CISO)3H) 107g of ammonium chloride (NH) was added to the round bottom flask of (1)4Cl), heating to raise the temperature of the mixed solution to 80 ℃ for reaction to generate SO2And HCl gas, taken out with nitrogen, absorbed with aqueous sodium hydroxide (1M NaOH); after reacting for 36h, steamingDistilling, collecting 115-120 ℃ fraction, and cooling to obtain 192.3g of colorless dichlorosulfoimide (HCSI) liquid, wherein the yield of the dichlorosulfoimide (HClSI) is 91.6%;
step two, reducing the water content of the anhydrous hydrofluoric acid: adjusting the temperature of a polytetrafluoroethylene electrolytic cell to 18 ℃, taking two nickel plates as an anode and a cathode respectively, adding 300ml of anhydrous hydrofluoric acid (HF) into the electrolytic cell, adjusting the working voltage of a direct current power supply of the electrolytic cell to 3.5V, and monitoring the current value in the electrolytic cell in real time by using a current meter;
step three, synthesizing the bis-fluorosulfonic acid imine: after the current in the electrolytic cell is stable, adding 8.2ml of the bischlorosulfoacid imine (HClSI) prepared in the step one into the electrolytic cell, and adjusting the working voltage of the electrolytic cell to 5V after the bischlorosulfoacid imine (HClSI) is dissolved; when the current is reduced to be below 5mA, the power supply experiment is closed and stopped; taking out the solution in the electrolytic cell;
step four, purifying the bis (fluorosulfonic acid) imine liquid: putting the solution taken out of the electrolytic cell into a distiller, distilling at normal pressure to separate the difluoride imine sulfonate (HFSI) from anhydrous hydrofluoric acid (HF), and cooling to obtain high-purity colorless difluoride imine sulfonate (HFSI) liquid;
step five, synthesizing lithium bis (fluorosulfonate) imide: 13.5g of the bis (fluorosulfonic acid) imide (HFSI) liquid prepared in step four and 138.5g of methylene Chloride (CH) were mixed under magnetic stirring (1000-2Cl2) 12.5g of thionyl chloride (SOCl)2) Mixing the solution in a round-bottom flask, adding 1.68g of anhydrous lithium hydroxide (LiOH) into the mixed solution, stirring for 30min, heating the solution to 28 ℃, and continuing to react for 2 h; then heating the liquid to 50 ℃, distilling and concentrating to separate out lithium bis (fluorosulfonate) imide (LiFSI), and filtering to obtain a filter cake;
step six, preparing the lithium bis (fluorosulfonate) imide crystal: the filter cake prepared in step five was charged with 48g of dichloromethane (CH)2Cl2) 48g of ethanol (C)2H5OH) and 0.25g of ethylenediaminetetraacetic acid tetrasodium solution are pulped, filtered and dried to obtain 12.3g of lithium bis (fluorosulfonate) imide (LiFSI) crystals, and the product yield is 95.1%.
Step (ii) ofThe purification method of the lithium bis (fluorosulfonate) imide prepared by the sixth step comprises the following steps: 9.65g of lithium bis-fluorosulfonate (LiFSI) were added to 100mL of dichloromethane (CH) with magnetic stirring2Cl2) And ethanol (C)2H5OH) in a mixed solution of dichloromethane (CH)2Cl2) With ethanol (C)2H5OH) is 1:1, heating the mixed solution to 55 ℃, cooling the solution to room temperature after lithium bis (fluorosulfonate) imide (LiFSI) is completely dissolved, cooling to 0 ℃, standing for 30min, and filtering precipitated solids to obtain 9.4-9.65g of white lithium bis (fluorosulfonate) imide (LiFSI) crystals.
In the above embodiment, in the first step, the coolant circulation pipe is installed on the outer side of the electrolytic cell, and the temperature of the electrolytic cell is maintained at 0 to 18 ℃ by the coolant circulation.
Cl in lithium bis (fluorosulfonate) imide (LiFSI) obtained in the above examples-And H2The content of O is shown in Table one.
Watch 1
| Examples | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Cl-(ppm) | 0.73 | 0.52 | 0.69 | 0.71 | 0.65 | 0.58 |
| H2O(ppm) | 0.61 | 0.40 | 0.58 | 0.59 | 0.54 | 0.48 |
The invention adopts electrochemistry to remove water and chloride ions in the product in advance, and uses electrochemistry to fluorinate without introducing metal halide as a catalyst, so the invention has simple process, low energy consumption and low cost, and the prepared lithium bis (fluorosulfonate) imide (LiFSI) has high purity.
Claims (4)
1. A method for electrochemically synthesizing lithium bis (fluorosulfonate) imide, which is characterized by comprising the following steps: it comprises the following steps:
step one, synthesizing dichlorosulfonic acid imine: under magnetic stirring, adding 100-110g ammonium chloride into a round-bottom flask containing 300-350g thionyl chloride and 450-500g chlorosulfonic acid, heating to raise the temperature of the mixed solution to 70-100 ℃ for reaction to generate sulfur dioxide and hydrogen chloride gas, taking out the sulfur dioxide and the hydrogen chloride gas by using nitrogen, and absorbing the hydrogen chloride gas by using a sodium hydroxide aqueous solution; distilling after reacting for 30-40h, collecting the fraction at the temperature of 115-120 ℃, and cooling to obtain 185-200g of colorless dichloroimine liquid, wherein the yield of the dichloroimine is 86.9-93.6%;
step two, reducing the water content of the anhydrous hydrofluoric acid: adjusting the temperature of a polytetrafluoroethylene electrolytic cell to 0-18 ℃, taking two nickel plates as an anode and a cathode respectively, adding a proper amount of anhydrous hydrofluoric acid into the electrolytic cell, adjusting the working voltage of a direct current power supply in the electrolytic cell to 1.6-5V, and monitoring the current value in the electrolytic cell in real time by using a current meter;
step three, synthesizing the bis-fluorosulfonic acid imine: after the current in the electrolytic cell is stable, adding the bischlorosulfoacid imine prepared in the first step into the electrolytic cell, wherein the volume ratio of the added bischlorosulfoacid imine to the anhydrous hydrofluoric acid is 1: 30-40, after the dichlorosulfoimide is dissolved, adjusting the working voltage of the electrolytic cell to 5-8V; when the current is reduced to be below 5mA, the power supply experiment is closed and stopped; taking out the solution in the electrolytic cell;
step four, purifying the bis (fluorosulfonic acid) imine liquid: putting the solution taken out of the electrolytic cell into a distiller, distilling at normal pressure to separate the difluoride imine from the anhydrous hydrofluoric acid, and cooling to obtain high-purity colorless difluoride imine liquid;
step five, synthesizing lithium bis (fluorosulfonate) imide: keeping the temperature at 0-10 ℃ under the stirring of a magnetic stirrer, mixing 10-15g of the bis (fluorosulfonic acid) imine liquid prepared in the step four with 130-140g of dichloromethane and 10-15g of thionyl chloride solution in a round-bottom flask, adding 1.3-1.7g of anhydrous lithium hydroxide into the mixed solution, stirring for 30min, heating the solution to 20-30 ℃, and continuing to react for 2 h; then heating the liquid to 50 ℃, distilling and concentrating to separate out lithium difluoride sulfonate imine, and filtering to obtain a filter cake;
step six, preparing the lithium bis (fluorosulfonate) imide crystal: and C, adding 40-55g of dichloromethane, 40-55g of ethanol and 0.15-0.3g of ethylene diamine tetraacetic acid tetrasodium solution into the filter cake prepared in the step five, pulping, filtering and drying to obtain 8-15g of lithium bis (fluorosulfonate) imide crystal, wherein the product yield is 92.8-95.1%.
2. The method for electrochemically synthesizing lithium bis (fluorosulfonate) imide according to claim 1, wherein: the purification method of the lithium bis (fluorosulfonate) imide prepared in the sixth step comprises the following steps: under magnetic stirring, adding 9-10g of lithium bis (fluorosulfonate) imide into 100mL of a mixed solution of dichloromethane and ethanol, wherein the volume ratio of dichloromethane to ethanol is 1:1, recrystallizing, heating the mixed solution to 55-65 ℃, cooling the solution to room temperature after lithium bis (fluorosulfonate) imide is completely dissolved, cooling to 0 ℃, standing for 30min, and filtering the precipitated solid to obtain 9-9.9g of white lithium bis (fluorosulfonate) imide crystals.
3. The method for electrochemically synthesizing lithium bis (fluorosulfonate) imide according to claim 1 or 2, wherein: in the first step, a coolant circulating pipeline is arranged on the outer side of the electrolytic cell, and the temperature of the electrolytic cell is kept between 0 and 18 ℃ through coolant circulation.
4. The method for electrochemically synthesizing lithium bis (fluorosulfonate) imide according to claim 3, wherein: the rotating speed of the magnetic stirring in the first step and the fifth step is 1000-1500 r/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114180542A (en) * | 2022-01-10 | 2022-03-15 | 香河昆仑新能源材料股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN114735665A (en) * | 2022-04-01 | 2022-07-12 | 山东惟普新能源有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN114852977A (en) * | 2022-05-06 | 2022-08-05 | 佳化化学科技发展（上海）有限公司 | Purification method of high-purity lithium bis (fluorosulfonyl) imide |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786443A (en) * | 2011-05-20 | 2012-11-21 | 华中科技大学 | Binary or ternary fluorine-containing sulfimide alkali metal salt and ionic liquid and applications thereof |
| US8377406B1 (en) * | 2012-08-29 | 2013-02-19 | Boulder Ionics Corporation | Synthesis of bis(fluorosulfonyl)imide |
| US20140075746A1 (en) * | 2011-05-24 | 2014-03-20 | Arkema France | Method for producing lithium or sodium bis(fluorosulfonyl)imide |
| WO2016093400A1 (en) * | 2014-12-11 | 2016-06-16 | Chun Bo.,Ltd | Method for preparing lithium bis(fluorosulfonyl) imide salt and intermediate product obtained from the same |
| WO2016184176A1 (en) * | 2015-05-21 | 2016-11-24 | 上海康鹏科技有限公司 | Preparation method for bis-(fluoro-sulfonyl) imide lithium salt |
| CN108002355A (en) * | 2017-12-20 | 2018-05-08 | 厦门大学 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
| US20180370799A1 (en) * | 2015-11-26 | 2018-12-27 | CLS Inc. | Novel method for preparing lithium bis(fluorosulfonyl)imide |
-
2019
- 2019-11-07 CN CN201911082140.7A patent/CN110745795B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786443A (en) * | 2011-05-20 | 2012-11-21 | 华中科技大学 | Binary or ternary fluorine-containing sulfimide alkali metal salt and ionic liquid and applications thereof |
| US20140075746A1 (en) * | 2011-05-24 | 2014-03-20 | Arkema France | Method for producing lithium or sodium bis(fluorosulfonyl)imide |
| US8377406B1 (en) * | 2012-08-29 | 2013-02-19 | Boulder Ionics Corporation | Synthesis of bis(fluorosulfonyl)imide |
| WO2016093400A1 (en) * | 2014-12-11 | 2016-06-16 | Chun Bo.,Ltd | Method for preparing lithium bis(fluorosulfonyl) imide salt and intermediate product obtained from the same |
| WO2016184176A1 (en) * | 2015-05-21 | 2016-11-24 | 上海康鹏科技有限公司 | Preparation method for bis-(fluoro-sulfonyl) imide lithium salt |
| US20180370799A1 (en) * | 2015-11-26 | 2018-12-27 | CLS Inc. | Novel method for preparing lithium bis(fluorosulfonyl)imide |
| CN108002355A (en) * | 2017-12-20 | 2018-05-08 | 厦门大学 | A kind of preparation method of imidodisulfuryl fluoride lithium salt |
Non-Patent Citations (1)
| Title |
|---|
| FAIZ AHMED: "Synthesis and electrochemical performance of an imidazolium based Li salt as electrolyte with Li fluorinated sulfonylimides as additives for Li-Ion batteries", 《ELECTROCHIMICA ACTA》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114180542A (en) * | 2022-01-10 | 2022-03-15 | 香河昆仑新能源材料股份有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN114735665A (en) * | 2022-04-01 | 2022-07-12 | 山东惟普新能源有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN114852977A (en) * | 2022-05-06 | 2022-08-05 | 佳化化学科技发展（上海）有限公司 | Purification method of high-purity lithium bis (fluorosulfonyl) imide |
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