CN115477308B - Method for preparing sodium tetrafluoroborate at normal temperature by one-step method - Google Patents

Method for preparing sodium tetrafluoroborate at normal temperature by one-step method Download PDF

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CN115477308B
CN115477308B CN202211036289.3A CN202211036289A CN115477308B CN 115477308 B CN115477308 B CN 115477308B CN 202211036289 A CN202211036289 A CN 202211036289A CN 115477308 B CN115477308 B CN 115477308B
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sodium
sodium tetrafluoroborate
normal temperature
tetrafluoroborate
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CN115477308A (en
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赵冬妮
赵燕君
李世友
张宁霜
王洁
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Lanzhou University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/06—Boron halogen compounds
    • C01B35/063—Tetrafluoboric acid; Salts thereof
    • C01B35/066—Alkali metal tetrafluoborates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A method for preparing sodium tetrafluoroborate at normal temperature by a one-step method comprises the following steps: dispersing a fluoboric compound and sodium salt of an oxo acid radical in a nonaqueous solvent, reacting for 10-24 hours at normal temperature, then carrying out solid-liquid separation, and evaporating the solvent in the obtained solution to obtain a high-purity solid product sodium tetrafluoroborate; wherein the nonaqueous solvent is acetonitrile, acetone, cyclohexane, etc. The method has mild reaction conditions, easy operation, short time and one-step synthesis, and easy separation of byproducts, and the obtained product has high purity, low requirements on equipment and guaranteed production safety.

Description

Method for preparing sodium tetrafluoroborate at normal temperature by one-step method
Technical Field
The invention relates to a preparation technology of electrolyte such as main salt or additive for nonaqueous electrolyte of sodium ion battery.
Background
Sodium ion batteries, while potentially advantageous in terms of low cost, still do not meet the current requirements of large-scale energy storage technology, such as cycle life and rate capability. For sodium ion batteries, the electrolyte is an ionic charge carrier necessary for electrochemical reaction, and has important influence on electrochemical performance (capacity, circulation stability, multiplying power performance and the like), so that development of novel sodium ion battery electrolyte is very important, and combination of salt and solvent is required to meet high ion conductivity, and the electrolyte has the characteristics of electrochemical stability, good thermal stability, low cost, simple process, low toxicity, environmental friendliness and the like in a wide voltage range. The sodium tetrafluoroborate is low in cost, good in conductivity and low in electrolyte viscosity, is synthesized by using easily available raw materials, and is researched as electrolyte salt from multiple angles of chemical stability, thermal stability, electrochemical stability and the like.
In recent years, battery burning explosion events have frequently occurred. Sodium hexafluorophosphate currently used is highly hygroscopic and can generate toxic HF gas, which is not conducive to sodium ion battery development. Sodium ion batteries are difficult to operate at ultra-high rates and extreme temperatures due to kinetic and thermodynamic limitations, and are limited mainly by reduced ionic conductivity of the electrolyte at low temperatures, difficult desolvation processes, and slow diffusion of ions in the electrode material. The sodium tetrafluoroborate has low cost, higher conductivity and lower viscosity of electrolyte, and can be applied to low-temperature environment. Among the ionic liquid electrolytes, sodium tetrafluoroborate solutes are the best, mainly because of the lowest interfacial resistance on the electrodes, ionic liquids have good thermal stability, no volatility and a large electrochemical window, and therefore can be stably circulated at a high temperature. Sodium tetrafluoroborate can be used as main salt or additive for sodium ion battery electrolyte, and has good oxidation stability under high pressure.
The non-aqueous solvent in which the sodium salt is dissolved is a polar solvent, the polarity of the solvent is increased, the influence on solute is larger, the transition state energy can be reduced, the activation energy of the reaction is reduced, the inorganic salt has a certain solubility, and the sodium salt is more dissolved in the non-aqueous solvent to fully react.
At present, boric acid and hydrofluoric acid are usually adopted to prepare fluoboric acid firstly, sodium carbonate is added for neutralization to obtain the sodium tetrafluoroborate, neutralization solution is evaporated and concentrated, crystallization separation is carried out at 25-30 ℃, and washing and drying are carried out to obtain the sodium tetrafluoroborate.
Chinese patent CN106082251a discloses a method for preparing lithium tetrafluoroborate. The method adopts a two-step method to synthesize lithium tetrafluoroborate, the weak acid radical lithium salt synthesized in the first step has higher chemical activity, so that the reaction for synthesizing lithium tetrafluoroborate in the second step is easy to carry out, but the two-step method has longer synthesis time.
Chinese patent CN102803142a discloses a method for producing tetrafluoroborate. According to the method, boron trifluoride is dissolved in an organic solvent, then metal fluoride reacts with the boron trifluoride to generate tetrafluoroborate solution, and the tetrafluoroborate solution is returned to the first step, so that boron trifluoride gas is dissolved in the tetrafluoroborate solution to improve the productivity of tetrafluoroborate, and the reaction step is complex and consumes more energy.
Disclosure of Invention
The invention aims to provide a method for preparing sodium tetrafluoroborate at normal temperature by a one-step method.
The invention relates to a method for preparing sodium tetrafluoroborate at normal temperature by a one-step method, which comprises the following steps:
step (1) dispersing sodium oxo acid salt and a boron fluoride compound in a nonaqueous solvent;
step (2) after reacting for 10-24 hours at normal temperature, carrying out solid-liquid separation, evaporating the nonaqueous solvent in the separated liquid, carrying out suction filtration, and drying the obtained solid at 80-110 ℃ for 12 hours to obtain a sodium tetrafluoroborate crude product;
and (3) dissolving the crude sodium tetrafluoroborate in a polar organic solvent, carrying out reflux separation for 4-10 hours at the temperature of 50-70 ℃, filtering and removing impurities, cooling and crystallizing, and distilling the filtrate at the temperature of 50-80 ℃ to obtain the high-purity sodium tetrafluoroborate.
Compared with the prior art, the normal-temperature preparation method of the sodium tetrafluoroborate provided by the invention has the advantages that the reaction process is one-step reaction, toxic gases such as HF and the like are not needed in the reaction, the reaction condition is mild in the preparation process, the operation is easy, more inorganic salts can be dissolved by selecting the polar solvent, the reaction is more complete, byproducts are easy to separate, the introduction of impurities is avoided, and the product purity is higher; low requirements on equipment, and further reduces the cost, and high-purity sodium tetrafluoroborate is obtained.
Drawings
FIG. 1 shows the NaBF obtained in example 1 4 A kind of electronic device 11 B nuclear magnetic spectrogram; FIG. 2 shows the NaBF obtained in example 1 4 A kind of electronic device 19 F nuclear magnetic spectrum.
Detailed Description
The invention relates to a method for preparing sodium tetrafluoroborate at normal temperature by a one-step method, which comprises the following steps:
step (1) dispersing sodium oxo acid salt and a boron fluoride compound in a nonaqueous solvent;
step (2) after reacting for 10-24 hours at normal temperature, carrying out solid-liquid separation, evaporating the nonaqueous solvent in the separated liquid, carrying out suction filtration, and drying the obtained solid at 80-110 ℃ for 12 hours to obtain a sodium tetrafluoroborate crude product;
and (3) dissolving the crude sodium tetrafluoroborate in a polar organic solvent, carrying out reflux separation for 4-10 hours at the temperature of 50-70 ℃, filtering and removing impurities, cooling and crystallizing, and distilling the filtrate at the temperature of 50-80 ℃ to obtain the high-purity sodium tetrafluoroborate.
The method comprises the step (1) that the sodium salt of oxyacid radical is Na 2 SO 3 Or Na 2 CO 3 Or NaHSO 3 The method comprises the steps of carrying out a first treatment on the surface of the The reaction fluorine boron compound is boron trifluoride diethyl etherate, or boron trifluoride acetic acid, or boron trifluoride methanol, or at least one of the above.
The method described above, wherein the nonaqueous solvent used in the process is selected from the group consisting of cyclic carbonates, or chain carbonates, or cyclic esters, or chain esters, or cyclic ethers, or chain ethers, or nitrile solvents, or at least one of the foregoing.
The method described above, wherein the ratio of the amount of the sodium salt of an oxyacid radical to the amount of the substance of the fluoroboric compound is 1:8~2:5, wherein the molar ratio of the solvent to the sodium element is 3: 1-6: 1, a step of; and filtering the reaction product obtained by the mixed reaction, heating the filtrate to 50-80 ℃ and evaporating the nonaqueous solvent to obtain a crude sodium tetrafluoroborate product.
The method above, wherein the polar organic solvent is acetonitrile, or diethyl ether, or ethyl acetate, or dimethyl carbonate, or one of the above.
The technical contents of the present invention are further developed by the following examples.
Example 1:
(1) Adding 5 g sodium sulfite into a three-neck flask, adding 250 mL acetonitrile, uniformly stirring, preparing a constant pressure funnel, and measuring the ratio of the constant pressure funnel to the sodium sulfite to be 8:1, dropwise adding boron trifluoride diethyl etherate into a three-neck flask, fully reacting for 2 hours at normal temperature, introducing sulfur dioxide gas generated by the boron trifluoride diethyl etherate into a bubbler, absorbing the sulfur dioxide gas by using dimethyl carbonate, reacting until no bubbles are generated in tail gas absorption, and ending the reaction. Fast filtering, solid-liquid separation, transferring the liquid into a single-mouth flask for rotary steaming;
(2) Distilling the liquid obtained in the step (1) at 80 ℃, stopping distilling until no liquid flows into a collecting bottle, performing cold shock crystallization by using dichloromethane, performing suction filtration to obtain pure white powder, and drying the pure white powder in a vacuum drying oven at 110 ℃ for 12 hours to obtain pure white powdery sodium tetrafluoroborate solid;
(3) Dissolving the crude sodium tetrafluoroborate in acetonitrile, carrying out reflux separation for 4 hours at the temperature range of 50 ℃, filtering, removing impurities, cooling, crystallizing, and distilling the filtrate at the temperature range of 80 ℃ to obtain the high-purity sodium tetrafluoroborate. The resulting NaBF is shown in FIG. 1 4 A kind of electronic device 11 B nuclear magnetic resonance spectrum, as shown in FIG. 2, of the obtained NaBF 4 A kind of electronic device 19 F nuclear magnetic spectrum.
Example 2:
(1) Adding 5 g sodium sulfite into a three-neck flask, adding 150 mL dimethyl carbonate, uniformly stirring, preparing a constant pressure funnel, and measuring the ratio of the constant pressure funnel to the sodium sulfite to be 8:1, dropwise adding boron trifluoride diethyl etherate into a three-neck flask, fully reacting for 10 hours at normal temperature, introducing sulfur dioxide gas generated by the boron trifluoride diethyl etherate into a bubbler, absorbing the sulfur dioxide gas by using dimethyl carbonate, reacting until no bubbles are generated in tail gas absorption, and ending the reaction. Fast filtering, solid-liquid separation, transferring the liquid into a single-mouth flask for rotary steaming;
(2) Distilling the liquid obtained in the step (1) at 80 ℃, stopping distilling until no liquid flows into a collecting bottle, performing cold shock crystallization by using dichloromethane, performing suction filtration to obtain pure white powder, and drying the pure white powder in a vacuum drying oven at 110 ℃ for 12 hours to obtain pure white powdery sodium tetrafluoroborate solid;
(3) Dissolving the crude sodium tetrafluoroborate in diethyl ether, carrying out reflux separation for 10 hours at the temperature of 70 ℃, filtering, removing impurities, cooling, crystallizing, and distilling the filtrate at the temperature of 50 ℃ to obtain the high-purity sodium tetrafluoroborate.
Example 3:
(1) Adding 5 g sodium sulfite into a three-neck flask, adding 250 mL cyclohexane, uniformly stirring, preparing a constant pressure funnel, and measuring the ratio of the constant pressure funnel to the sodium sulfite to be 5:2, dropwise adding boron trifluoride diethyl etherate into the three-neck flask, fully reacting for 10 hours at normal temperature, introducing sulfur dioxide gas generated by the boron trifluoride diethyl etherate into a bubbler, absorbing the sulfur dioxide gas by using dimethyl carbonate, reacting until no bubbles are generated in tail gas absorption, and ending the reaction. Fast filtering, solid-liquid separation, transferring the liquid into a single-mouth flask for rotary steaming;
(2) Distilling the liquid obtained in the step (1) at 85 ℃, stopping distilling until no liquid flows into a collecting bottle, performing cold shock crystallization by using dichloromethane, performing suction filtration to obtain pure white powder, and drying the pure white powder in a vacuum drying oven at 110 ℃ for 12 hours to obtain pure white powdery sodium tetrafluoroborate solid;
(3) Dissolving the crude sodium tetrafluoroborate in ethyl acetate, carrying out reflux separation for 8 hours at the temperature range of 60 ℃, filtering, removing impurities, cooling, crystallizing, and distilling the filtrate at the temperature range of 80 ℃ to obtain the high-purity sodium tetrafluoroborate.
Example 4:
(1) Adding 10 g sodium carbonate into a three-neck flask, adding 100 mL tetrahydrofuran, uniformly stirring, preparing a constant pressure funnel, and measuring the ratio of the constant pressure funnel to the sodium carbonate to be 4:1, dropwise adding boron trifluoride diethyl etherate into a three-neck flask, fully reacting for 24 hours at normal temperature, introducing sulfur dioxide gas generated by the boron trifluoride diethyl etherate into a bubbler, absorbing the sulfur dioxide gas by using dimethyl carbonate, reacting until no bubbles are generated in tail gas absorption, and ending the reaction. Fast filtering, solid-liquid separation, transferring the liquid into a single-mouth flask for rotary steaming;
(2) Distilling the liquid obtained in the step (1) at 70 ℃, stopping distilling until no liquid flows into a collecting bottle, performing cold shock crystallization by using dichloromethane, performing suction filtration to obtain pure white powder, and drying the pure white powder in a vacuum drying oven at 110 ℃ for 12 hours to obtain pure white powdery sodium tetrafluoroborate solid;
(3) Dissolving the crude sodium tetrafluoroborate in dimethyl carbonate, carrying out reflux separation for 8 hours at the temperature range of 50 ℃, filtering, removing impurities, cooling, crystallizing, and distilling the filtrate at the temperature range of 80 ℃ to obtain the high-purity sodium tetrafluoroborate.
Example 5:
(1) Adding 5 g sodium sulfite into a three-neck flask, adding 150 mL acetonitrile, stirring uniformly, gradually increasing the temperature of an oil bath to 60 ℃, preparing a constant pressure funnel, and measuring the ratio of the constant pressure funnel to the sodium sulfite to be 4:1, dropwise adding boron trifluoride diethyl etherate into a three-neck flask, fully reacting at 60 ℃ for 16 hours, introducing sulfur dioxide gas generated by the boron trifluoride diethyl etherate into a bubbler, absorbing the sulfur dioxide gas by using dimethyl carbonate, reacting until no bubbles in tail gas absorption are generated, and ending the reaction. Fast filtering, solid-liquid separation, transferring the liquid into a single-mouth flask for rotary steaming;
(2) Distilling the liquid obtained in the step (1) at 80 ℃, stopping distilling until no liquid flows into a collecting bottle, performing cold shock crystallization by using dichloromethane, performing suction filtration to obtain pure white powder, and drying the pure white powder in a vacuum drying oven at 110 ℃ for 12 hours to obtain pure white powdery sodium tetrafluoroborate solid;
(3) Dissolving the crude sodium tetrafluoroborate in acetonitrile, carrying out reflux separation for 10 hours at the temperature range of 60 ℃, filtering, removing impurities, cooling, crystallizing, and distilling the filtrate at the temperature range of 80 ℃ to obtain the high-purity sodium tetrafluoroborate.

Claims (3)

1. A method for preparing sodium tetrafluoroborate at normal temperature by a one-step method is characterized by comprising the following steps:
step (1) dispersing sodium oxo acid salt and a boron fluoride compound in a nonaqueous solvent; the ratio of the amount of the substances of the sodium salt of the oxo acid to the fluoro boron compound is 1: 8-2: 5, wherein the molar ratio of the solvent to the sodium element is 3:1 to 6:1, a step of;
step (2) after reacting for 10-24 hours at normal temperature, carrying out solid-liquid separation, evaporating the nonaqueous solvent in the separated liquid, carrying out suction filtration, and drying the obtained solid at 80-110 ℃ for 12 hours to obtain a crude sodium tetrafluoroborate product;
dissolving the crude sodium tetrafluoroborate in a polar organic solvent, carrying out reflux separation for 4-10 hours at the temperature of 50-70 ℃, filtering and removing impurities, cooling and crystallizing, and distilling the filtrate at the temperature of 50-80 ℃ to obtain high-purity sodium tetrafluoroborate; the sodium salt of the oxo acid radical in the step (1) is Na 2 SO 3 Or Na 2 CO 3 Or NaHSO 3 The method comprises the steps of carrying out a first treatment on the surface of the The reaction fluorine boron compound is boron trifluoride diethyl ether, or boron trifluoride acetic acid, or boron trifluoride methanol; the nonaqueous solvent used in the process is selected from nitrile solvents.
2. The method for preparing sodium tetrafluoroborate at normal temperature by one-step method according to claim 1, wherein the reaction product obtained by the mixed reaction in step (2) is filtered, the filtrate is heated to 50-80 ℃ and the nonaqueous solvent is evaporated, thus obtaining the crude sodium tetrafluoroborate product.
3. The method for preparing sodium tetrafluoroborate at normal temperature by one-step method according to claim 1, wherein the polar organic solvent is acetonitrile, or diethyl ether, or ethyl acetate, or dimethyl carbonate.
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CN115676855B (en) * 2022-12-30 2023-04-11 江苏华盛锂电材料股份有限公司 Preparation method of sodium ion battery electrolyte sodium salt

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