CN116462205A - Synthesis method of lithium tetrafluoroborate - Google Patents
Synthesis method of lithium tetrafluoroborate Download PDFInfo
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- CN116462205A CN116462205A CN202310322296.8A CN202310322296A CN116462205A CN 116462205 A CN116462205 A CN 116462205A CN 202310322296 A CN202310322296 A CN 202310322296A CN 116462205 A CN116462205 A CN 116462205A
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- -1 lithium tetrafluoroborate Chemical compound 0.000 title claims abstract description 53
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 title claims abstract description 53
- 238000001308 synthesis method Methods 0.000 title claims description 10
- 238000003756 stirring Methods 0.000 claims abstract description 49
- 239000013078 crystal Substances 0.000 claims abstract description 45
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000002253 acid Substances 0.000 claims abstract description 28
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000001704 evaporation Methods 0.000 claims abstract description 22
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 20
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005194 fractionation Methods 0.000 claims abstract description 19
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000008020 evaporation Effects 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for synthesizing lithium tetrafluoroborate, which comprises the following steps: s1, slowly adding boron oxide into hydrofluoric acid solution under stirring, fully reacting, and standing for a period of time after the reaction is finished to obtain tetrafluoroboric acid solution; s2, uniformly mixing lithium carbonate micro powder and water in a hydrogenation device, and introducing CO 2 The gas is subjected to hydrogenation reaction under stirring, and after the reaction is finished, the gas is stood for a period of time to obtain a lithium bicarbonate solution; s3, slowly adding the tetrafluoroboric acid solution into the lithium bicarbonate solution under stirring, fully reacting, and standing for a period of time after the reaction is finished to obtain the lithium tetrafluoroborate solution; s4, evaporating the lithium tetrafluoroborate solution at a low temperature, collecting a crystal, dissolving the crystal in a low-boiling-point organic solvent, adding a proper amount of calcium hydride to remove trace moisture, performing low-temperature fractionation, and collecting the crystal. The lithium tetrafluoroborate prepared by the invention has the characteristics of high crystallinity, complete crystal form and excellent electrochemical performance.
Description
Technical Field
The invention relates to the technical field of lithium ion battery electrolytes, in particular to a method for synthesizing lithium tetrafluoroborate.
Background
The production and consumption of lithium ion batteries become a mainstream product of new energy consumption, the output of the lithium ion batteries produced in China reaches 23262420.5 thousands at present, and the output of the lithium ion batteries shows a more vigorous growing trend along with the push of the concept of double carbon.
With the gradual maturation and stabilization of lithium ion battery manufacturing technologies, conventional technologies encounter bottlenecks in improving the performance related to lithium ion batteries, particularly in the field of power battery manufacturing, and there is a need to simultaneously improve the specific energy, specific power, cycle life, lower internal resistance and other characteristics of batteries. The improvement of the performances is far from the aspects of cell structure and proportion. Research from various aspects of batteries is required in various fields within the industry to achieve the goal of improving battery performance as a whole.
At present, china is the main manufacturing country of the lithium battery in the world, and the manufacturing and the use of the electrolyte of the lithium battery have been fully advanced. Over 2021, with the large explosion of the lithium battery application market and the lithium battery manufacturing market, the demand for electrolytes has exploded. The domestic electrolyte has the problems of battery bulge, easiness in decomposition and gas production of the electrolyte, poor cycle performance, low voltage platform and the like caused by the electrolyte prepared from the domestic electrolyte material due to different crystallinity, incomplete crystal forms and the like. Therefore, how to prepare lithium tetrafluoroborate with higher crystallinity and more complete crystal form, so as to improve the electrochemical performance of the lithium battery and reduce the problem of air expansion of the lithium battery becomes a current problem to be solved urgently.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a method for synthesizing lithium tetrafluoroborate.
The invention provides a synthesis method of lithium tetrafluoroborate, which comprises the following steps:
s1, slowly adding boron oxide into hydrofluoric acid solution under stirring, fully reacting, and standing for 3-6.5h after the reaction is finished to obtain tetrafluoroboric acid solution;
s2, uniformly mixing lithium carbonate micro powder and water in a hydrogenation device, and introducing CO 2 The gas is subjected to hydrogenation reaction under stirring, and after the reaction is finished, the mixture is kept stand for 25 to 30 minutes to obtain lithium bicarbonateA solution;
s3, slowly adding the tetrafluoroboric acid solution into the lithium bicarbonate solution under stirring, fully reacting, and standing for 14-16 hours at 15-33 ℃ after the reaction is finished to obtain the lithium tetrafluoroborate solution;
s4, evaporating the lithium tetrafluoroborate solution at a low temperature, collecting crystals after evaporation, dissolving the crystals in a low-boiling-point organic solvent, adding a proper amount of calcium hydride to remove trace moisture, performing low-temperature fractionation, and collecting the crystals after fractionation.
Preferably, the molar ratio of boron oxide to hydrofluoric acid is 1: (8-8.15).
Preferably, the purity of the boron oxide is more than or equal to 99.9%; the concentration of the hydrofluoric acid solution is 22.5mol/L.
Preferably, in S1, the reaction conditions are: stirring and reacting for 30-45min at 23-28 ℃; preferably, in S1, the rotation speed of the stirring reaction is 10-15r/min.
Preferably, the purity of the lithium carbonate micro powder is more than or equal to 99.9 percent, and the granularity is 5-25 mu m.
Preferably, in S2, the temperature of the hydrogenation reaction is 25-28 ℃ and the time is 30-45min; preferably, in S2, the stirring speed of the hydrogenation reaction is 35-65r/min.
Preferably, in S2, CO 2 The flow rate of the gas is 0.15-0.2L/min.
Preferably, in S2, the weight ratio of the lithium carbonate micro powder to the water is (335-370) 5000.
Preferably, in S3, the molar ratio of tetrafluoroboric acid to lithium bicarbonate is (1.03-1.05): 1.
preferably, in S3, the reaction conditions are: stirring and reacting for 2.5-3h at 23-28 ℃; preferably, in S3, the rotation speed of the stirring reaction is 5-8r/min.
Preferably, in S4, the low temperature evaporation temperature is 15-33 ℃.
Preferably, in S4, the temperature of the low temperature fractionation is 35-63 ℃; the low-boiling point organic solvent is at least one of absolute ethyl alcohol and absolute ethyl ether.
In S4, the low boiling point organic solvent may be recovered by means of freeze condensation.
The beneficial effects of the invention are as follows:
the preparation method comprises the steps of firstly, reacting boron oxide with hydrofluoric acid to obtain a tetrafluoroboric acid solution, carrying out hydrogenation reaction on high-purity lithium carbonate to obtain a lithium bicarbonate solution, then, reacting the tetrafluoroboric acid solution with the lithium bicarbonate solution to obtain a lithium tetrafluoroborate solution, and carrying out standing for a long time to fully react the solution; then evaporating the lithium tetrafluoroborate solution at a low temperature, gradually increasing the concentration in the evaporation process and forming crystal nuclei, gradually growing the crystal nuclei to obtain crystals of the lithium tetrafluoroborate, dissolving the crystals by taking a low-boiling point organic solvent as a solvent, adding calcium hydride to remove trace water, and then fractionating at a low temperature, wherein the crystal nuclei continuously grow along the crystal nuclei along with the continuous volatilization of the solvent, so that the lithium tetrafluoroborate with a more complete crystal form is obtained. The lithium tetrafluoroborate prepared by the invention has the characteristics of high crystallinity and complete crystal form, can effectively improve the rate performance, the cycle life and other electrochemical performances of the lithium battery, and simultaneously effectively reduces the problem of air expansion of the lithium battery.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
The synthesis method of the lithium tetrafluoroborate comprises the following steps:
s1, boron oxide (B) having a purity of 99.9% 2 O 3 ) Slowly adding the mixture into a hydrofluoric acid solution with the concentration of 22.5mol/L under stirring, stirring and reacting for 30min under the conditions of the temperature of 23 ℃ and the rotating speed of 10r/min, and standing for 3h after the reaction is finished to obtain a tetrafluoroboric acid solution, wherein the molar ratio of boron oxide to hydrofluoric acid is 1:8;
s2, adding 5000mL of deionized water into a hydrogenation tank, and slowly introducing CO into the bottom of the hydrogenation tank 2 The gas (flow rate 0.15L/min) was introduced into CO 2 Adding 370g lithium carbonate micropowder with purity of 99.9% and granularity of 5-25 μm into hydrogenation tank under stirring after gas for 20min, stirring at 25deg.C and rotation speed of 35r/min for 30min, and reactingStanding for 25min to obtain lithium bicarbonate solution;
s3, slowly adding the tetrafluoroboric acid solution into the lithium bicarbonate solution under stirring, stirring and reacting for 2.5 hours under the conditions of the temperature of 23 ℃ and the rotating speed of 5r/min, and standing for 14 hours at the temperature of 15 ℃ after the reaction is finished to obtain the lithium tetrafluoroborate solution, wherein the molar ratio of tetrafluoroboric acid to lithium bicarbonate is 1.01:1;
s4, evaporating the lithium tetrafluoroborate solution at a low temperature of 15 ℃, collecting crystals after evaporation, dissolving 70g of the crystals in 600mL of absolute ethyl alcohol, adding 25g of calcium hydride to remove trace moisture, then performing low-temperature fractionation at 35 ℃, and collecting the crystals after fractionation.
The purity of the product obtained above was 99.99% by inspection.
Example 2
The synthesis method of the lithium tetrafluoroborate comprises the following steps:
s1, boron oxide (B) having a purity of 99.9% 2 O 3 ) Slowly adding the mixture into a hydrofluoric acid solution with the concentration of 22.5mol/L under stirring, stirring and reacting for 40min under the conditions of the temperature of 25 ℃ and the rotating speed of 12r/min, and standing for 5h after the reaction is finished to obtain a tetrafluoroboric acid solution, wherein the molar ratio of boron oxide to hydrofluoric acid is 1:8.05;
s2, adding 5000mL of deionized water into a hydrogenation tank, and slowly introducing CO into the bottom of the hydrogenation tank 2 The gas (flow rate 0.18L/min) was introduced into CO 2 Adding 370g of lithium carbonate micro powder with the purity of 99.9% and the granularity of 5-25 mu m into a hydrogenation tank under stirring after 20min, stirring and reacting for 35min under the conditions of the temperature of 26 ℃ and the rotating speed of 50r/min, and standing for 28min after the reaction is finished to obtain a lithium bicarbonate solution;
s3, slowly adding the tetrafluoroboric acid solution into the lithium bicarbonate solution under stirring, stirring and reacting for 2.8 hours under the conditions of the temperature of 25 ℃ and the rotating speed of 7r/min, and standing for 15 hours at the temperature of 25 ℃ after the reaction is finished to obtain the lithium tetrafluoroborate solution, wherein the molar ratio of tetrafluoroboric acid to lithium bicarbonate is 1.03:1;
s4, evaporating the lithium tetrafluoroborate solution at a low temperature of 25 ℃, collecting crystals after evaporation, dissolving 70g of the crystals in 600mL of absolute ethyl alcohol, adding 25g of calcium hydride to remove trace moisture, and then performing low-temperature fractionation at 50 ℃, and collecting the crystals after fractionation.
The purity of the product obtained above was 99.99% by inspection.
Example 3
The synthesis method of the lithium tetrafluoroborate comprises the following steps:
s1, boron oxide (B) having a purity of 99.9% 2 O 3 ) Slowly adding the mixture into a hydrofluoric acid solution with the concentration of 22.5mol/L under stirring, stirring and reacting for 45min under the conditions of the temperature of 28 ℃ and the rotating speed of 15r/min, and standing for 6.5h after the reaction is finished to obtain a tetrafluoroboric acid solution, wherein the molar ratio of boron oxide to hydrofluoric acid is 1:8.15;
s2, adding 5000mL of deionized water into a hydrogenation tank, and slowly introducing CO into the bottom of the hydrogenation tank 2 The gas (flow rate is 0.2L/min) is introduced into CO 2 Adding 370g of lithium carbonate micro powder with the purity of 99.9% and the granularity of 5-25 mu m into a hydrogenation tank under stirring after 20min, stirring and reacting for 45min under the conditions of the temperature of 28 ℃ and the rotating speed of 65r/min, and standing for 30min after the reaction is finished to obtain a lithium bicarbonate solution;
s3, slowly adding the tetrafluoroboric acid solution into the lithium bicarbonate solution under stirring, stirring and reacting for 3 hours under the conditions of the temperature of 28 ℃ and the rotating speed of 8r/min, and standing for 16 hours at the temperature of 33 ℃ after the reaction is finished to obtain the lithium tetrafluoroborate solution, wherein the molar ratio of tetrafluoroboric acid to lithium bicarbonate is 1.05:1;
s4, evaporating the lithium tetrafluoroborate solution at a low temperature of 33 ℃, collecting crystals after evaporation, dissolving 70g of the crystals in 600mL of absolute ethyl alcohol, adding 25g of calcium hydride to remove trace moisture, then performing low-temperature fractionation at 63 ℃, and collecting the crystals after fractionation.
The purity of the product obtained above was 99.99% by inspection.
Comparative example 1
The synthesis method of the lithium tetrafluoroborate comprises the following steps:
s1, boron oxide (B) having a purity of 99.9% 2 O 3 ) Slowly adding the mixture into a hydrofluoric acid solution with the concentration of 22.5mol/L under stirring, stirring and reacting for 30min under the conditions of the temperature of 23 ℃ and the rotating speed of 10r/min, and standing for 3h after the reaction is finished to obtain a tetrafluoroboric acid solution, wherein the molar ratio of boron oxide to hydrofluoric acid is 1:8;
s2, slowly adding lithium carbonate micro powder with the purity of 99.9% and the granularity of 5-25 mu m into a tetrafluoroboric acid solution under stirring, stirring and reacting for 2.5 hours under the conditions of the temperature of 23 ℃ and the rotating speed of 5r/min, and standing for 14 hours at 15 ℃ after the reaction is finished to obtain the lithium tetrafluoroborate solution, wherein the molar ratio of tetrafluoroboric acid to lithium carbonate is 1.01:0.5;
s4, evaporating the lithium tetrafluoroborate solution at a low temperature of 15 ℃, collecting crystals after evaporation, dissolving 70g of the crystals in 600mL of absolute ethyl alcohol, adding 25g of calcium hydride to remove trace moisture, then performing low-temperature fractionation at 35 ℃, and collecting the crystals after fractionation.
The purity of the product obtained above was 99.8% by inspection.
Comparative example 2
The synthesis method of the lithium tetrafluoroborate comprises the following steps:
s1, boron oxide (B) having a purity of 99.9% 2 O 3 ) Slowly adding the mixture into a hydrofluoric acid solution with the concentration of 22.5mol/L under stirring, stirring and reacting for 30min under the conditions of the temperature of 23 ℃ and the rotating speed of 10r/min, and standing for 3h after the reaction is finished to obtain a tetrafluoroboric acid solution, wherein the molar ratio of boron oxide to hydrofluoric acid is 1:8;
s2, adding 5000mL of deionized water into a hydrogenation tank, and slowly introducing CO into the bottom of the hydrogenation tank 2 The gas (flow rate 0.15L/min) was introduced into CO 2 Adding 370g of lithium carbonate micro powder with the purity of 99.9% and the granularity of 5-25 mu m into a hydrogenation tank under stirring after 20min, stirring and reacting for 30min under the conditions of the temperature of 25 ℃ and the rotating speed of 35r/min, and standing for 25min after the reaction is finished to obtain a lithium bicarbonate solution;
s3, slowly adding the tetrafluoroboric acid solution into the lithium bicarbonate solution under stirring, stirring and reacting for 2.5 hours under the conditions of the temperature of 23 ℃ and the rotating speed of 5r/min, and standing for 14 hours at the temperature of 15 ℃ after the reaction is finished to obtain the lithium tetrafluoroborate solution, wherein the molar ratio of tetrafluoroboric acid to lithium bicarbonate is 1.01:1;
s4, heating and evaporating the lithium tetrafluoroborate solution at 45 ℃, collecting crystals after evaporation, dissolving 70g of the crystals in 600mL of absolute ethyl alcohol, adding 25g of calcium hydride to remove trace moisture, then carrying out low-temperature fractionation at 35 ℃, and collecting the crystals after fractionation.
The purity of the product obtained above was 99.3% by inspection.
Comparative example 3
The synthesis method of the lithium tetrafluoroborate comprises the following steps:
s1, boron oxide (B) having a purity of 99.9% 2 O 3 ) Slowly adding the mixture into a hydrofluoric acid solution with the concentration of 22.5mol/L under stirring, stirring and reacting for 30min under the conditions of the temperature of 23 ℃ and the rotating speed of 10r/min, and standing for 3h after the reaction is finished to obtain a tetrafluoroboric acid solution, wherein the molar ratio of boron oxide to hydrofluoric acid is 1:8;
s2, adding 5000mL of deionized water into a hydrogenation tank, and slowly introducing CO into the bottom of the hydrogenation tank 2 The gas (flow rate 0.15L/min) was introduced into CO 2 Adding 370g of lithium carbonate micro powder with the purity of 99.9% and the granularity of 5-25 mu m into a hydrogenation tank under stirring after 20min, stirring and reacting for 30min under the conditions of the temperature of 25 ℃ and the rotating speed of 35r/min, and standing for 25min after the reaction is finished to obtain a lithium bicarbonate solution;
s3, slowly adding the tetrafluoroboric acid solution into the lithium bicarbonate solution under stirring, stirring and reacting for 2.5 hours under the conditions of the temperature of 23 ℃ and the rotating speed of 5r/min, and standing for 14 hours at the temperature of 15 ℃ after the reaction is finished to obtain the lithium tetrafluoroborate solution, wherein the molar ratio of tetrafluoroboric acid to lithium bicarbonate is 1.01:1;
s4, evaporating the lithium tetrafluoroborate solution at a low temperature of 15 ℃, collecting crystals after evaporation, dissolving 70g of the crystals in 600mL of absolute ethyl alcohol, performing low-temperature fractionation at 35 ℃, and collecting the crystals after fractionation.
The purity of the product obtained above was 99.7% by inspection.
In comparative example 1, lithium carbonate was reacted directly with lithium tetrafluoroborate, and impurities in the solid lithium carbonate were introduced directly into the lithium tetrafluoroborate product, an interfering phase for crystal growth during the subsequent crystallization. Resulting in a low product purity, relatively low crystal purity, and relatively poor electrical properties.
In comparative example 2, the lithium tetrafluoroborate solution was too high in temperature during the evaporation and crystallization, the water volatilization speed was fast, the crystal nuclei were rapidly generated and grown, and a large amount of impurity ions could not be smoothly discharged into the solution to be removed, but grown together with the crystals. Resulting in a final product of lithium tetrafluoroborate crystals with high impurity content and relatively poor electrical properties.
In comparative example 3, no calcium hydride is added into the absolute ethyl alcohol to remove water, so that trace water molecules in the absolute ethyl alcohol cannot be removed, and the trace water molecules are mixed and discharged into crystals of lithium tetrafluoroborate in the crystallization process of the lithium tetrafluoroborate, so that the purity of the crystals is affected, and the electrochemical performance is relatively poor.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The synthesis method of the lithium tetrafluoroborate is characterized by comprising the following steps of:
s1, slowly adding boron oxide into hydrofluoric acid solution under stirring, fully reacting, and standing for 3-6.5h after the reaction is finished to obtain tetrafluoroboric acid solution;
s2, uniformly mixing lithium carbonate micro powder and deionized water in a hydrogenation device, and introducing CO 2 Carrying out hydrogenation reaction on the gas under stirring, and standing for 25-30min after the reaction is finished to obtain a lithium bicarbonate solution;
s3, slowly adding the tetrafluoroboric acid solution into the lithium bicarbonate solution under stirring, fully reacting, and standing for 14-16 hours at 15-33 ℃ after the reaction is finished to obtain the lithium tetrafluoroborate solution;
s4, evaporating the lithium tetrafluoroborate solution at a low temperature, collecting crystals after evaporation, dissolving the crystals in a low-boiling-point organic solvent, adding a proper amount of calcium hydride to remove trace moisture, performing low-temperature fractionation, and collecting the crystals after fractionation.
2. The method for synthesizing lithium tetrafluoroborate according to claim 1, wherein the molar ratio of boron oxide to hydrofluoric acid is 1: (8-8.15).
3. The method for synthesizing lithium tetrafluoroborate according to claim 1, wherein the purity of the boron oxide is not less than 99.9%; the concentration of the hydrofluoric acid solution is 22.5mol/L.
4. The method for synthesizing lithium tetrafluoroborate according to claim 1, wherein in S1, the reaction conditions are: stirring and reacting for 30-45min at 23-28 ℃; in S1, the standing temperature is 23-28 ℃.
5. The method for synthesizing lithium tetrafluoroborate according to claim 1, wherein the purity of the lithium carbonate micropowder is not less than 99.9%, and the particle size is 5-25 μm.
6. The method for synthesizing lithium tetrafluoroborate as claimed in claim 1, wherein in S2, the hydrogenation reaction is carried out at a temperature of 25 to 28 ℃ for 30 to 45 minutes.
7. The method for synthesizing lithium tetrafluoroborate according to claim 1, wherein in S3, the molar ratio of tetrafluoroboric acid to lithium bicarbonate is 1.01 to 1.05:1.
8. the method for synthesizing lithium tetrafluoroborate as claimed in claim 1, wherein in S3, the reaction conditions are: the reaction is stirred for 2.5 to 3 hours at the temperature of 23 to 28 ℃.
9. The method for synthesizing lithium tetrafluoroborate as claimed in claim 1, wherein in S4, the low temperature evaporation temperature is 15-33 ℃.
10. The method for synthesizing lithium tetrafluoroborate according to claim 1, wherein in S4, the temperature of low temperature fractionation is 35-63 ℃; the low-boiling point organic solvent is at least one of absolute ethyl alcohol and absolute ethyl ether.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012131658A (en) * | 2010-12-21 | 2012-07-12 | Morita Kagaku Kogyo Kk | Method for producing lithium borofluoride |
| CN103236562A (en) * | 2013-04-11 | 2013-08-07 | 多氟多化工股份有限公司 | Preparation method for lithium tetrafluoroborate |
| CN103466650A (en) * | 2013-09-27 | 2013-12-25 | 中国海洋石油总公司 | Method for preparing anhydrous lithium tetrafluoroborate |
| CN107585776A (en) * | 2017-10-13 | 2018-01-16 | 湖北省宏源药业科技股份有限公司 | A kind of method of Rheological Phase Method synthesis LiBF4 |
| CN115321554A (en) * | 2022-09-19 | 2022-11-11 | 江苏泰际材料科技有限公司 | Lithium tetrafluoroborate and preparation method thereof |
-
2023
- 2023-03-29 CN CN202310322296.8A patent/CN116462205A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012131658A (en) * | 2010-12-21 | 2012-07-12 | Morita Kagaku Kogyo Kk | Method for producing lithium borofluoride |
| CN103236562A (en) * | 2013-04-11 | 2013-08-07 | 多氟多化工股份有限公司 | Preparation method for lithium tetrafluoroborate |
| CN103466650A (en) * | 2013-09-27 | 2013-12-25 | 中国海洋石油总公司 | Method for preparing anhydrous lithium tetrafluoroborate |
| CN107585776A (en) * | 2017-10-13 | 2018-01-16 | 湖北省宏源药业科技股份有限公司 | A kind of method of Rheological Phase Method synthesis LiBF4 |
| CN115321554A (en) * | 2022-09-19 | 2022-11-11 | 江苏泰际材料科技有限公司 | Lithium tetrafluoroborate and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 彭静红;郑典模;徐文赫;兰倩倩;: "溶液法制备四氟硼酸锂的研究", 化工新型材料, no. 12, 15 December 2014 (2014-12-15) * |
| 王晓利主编: "生物化学技术", 30 June 2007, 中国轻工业出版社, pages: 228 * |
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