CN117229303A - Preparation method of lithium/sodium salt electrolyte - Google Patents
Preparation method of lithium/sodium salt electrolyte Download PDFInfo
- Publication number
- CN117229303A CN117229303A CN202311045079.5A CN202311045079A CN117229303A CN 117229303 A CN117229303 A CN 117229303A CN 202311045079 A CN202311045079 A CN 202311045079A CN 117229303 A CN117229303 A CN 117229303A
- Authority
- CN
- China
- Prior art keywords
- lithium
- reaction
- borate
- sodium
- trifluoroethoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 30
- 159000000002 lithium salts Chemical class 0.000 title claims description 16
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 36
- -1 tri (trifluoroethoxy) borate Chemical compound 0.000 claims abstract description 33
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 22
- XYUZQKQHFBLSLA-UHFFFAOYSA-N 2,2,2-trifluoroethylperoxyboronic acid Chemical compound OB(O)OOCC(F)(F)F XYUZQKQHFBLSLA-UHFFFAOYSA-N 0.000 claims abstract description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- VMQTVPUDSZDWKQ-UHFFFAOYSA-N [Li].OCC(F)(F)F Chemical compound [Li].OCC(F)(F)F VMQTVPUDSZDWKQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- UQMQEGXOVRHYOV-UHFFFAOYSA-N sodium;2,2,2-trifluoroethanol Chemical compound [Na].OCC(F)(F)F UQMQEGXOVRHYOV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 14
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- MSGMXYUAWZYTFC-UHFFFAOYSA-N sodium;2,2,2-trifluoroethanolate Chemical compound [Na+].[O-]CC(F)(F)F MSGMXYUAWZYTFC-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- DMQZZHWKDANLBZ-UHFFFAOYSA-N lithium;2,2,2-trifluoroethanolate Chemical compound [Li+].[O-]CC(F)(F)F DMQZZHWKDANLBZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 150000002641 lithium Chemical class 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 25
- 238000001914 filtration Methods 0.000 description 23
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000005303 weighing Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000012448 Lithium borohydride Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001897 boron-11 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
The invention provides a preparation method of lithium/sodium salt electrolyte, which comprises the following steps: (1) Alkali metal Li or Na and trifluoroethanol are used as raw materials, the raw materials react in an organic solvent, and after the reaction is finished, clear liquid containing lithium trifluoroethanol or sodium trifluoroethanol is obtained through solid-liquid separation; (2) Adding tri (trifluoroethoxy) borate into the clear liquid for reaction, and carrying out solid-liquid separation and drying to obtain lithium tetra (trifluoroethoxy) borate or sodium tetra (trifluoroethoxy) borate. The method is simple, easy to realize, low in energy consumption, good in safety, high in product purity, high in yield, low in cost, free of any waste, and easy to realize large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of battery electrolytes, and particularly relates to a preparation method of a lithium/sodium salt electrolyte.
Background
Lithium ion batteries are currently one of the most widely used energy storage devices due to their light weight, high energy density and high power density. However, since metallic lithium requires deposition and stripping reactions to store and release lithium in a lithium ion battery, the interface between lithium and electrolyte may be dynamically changed. Continuous parasitic side reactions can occur at the unstable interface, affecting the morphology and electrochemical properties of lithium deposition, such as coulombic efficiency, resistance, and cycling stability. Researchers believe that electrolytes such as lithium hexafluorophosphate, lithium fluorosulfonimide, and lithium difluorooxalato borate improve their electrochemical properties and they have significantly improved their electrochemical properties, but these electrolytes have relatively poor thermal and chemical stability, which is detrimental to the development of lithium batteries in the high voltage direction. Therefore, the search for a new lithium electrolyte is an important research topic.
In addition, sodium ion batteries are one of the batteries for hot research because of their high similarity to lithium ion batteries and lower cost, and sodium ion batteries often use sodium salts similar to lithium battery electrolytes as electrolytes.
Lithium tetrakis (trifluoroethoxy) borate is a novel high voltage resistant electrolyte with good thermal and chemical stability, high conductivity and wide electrochemical window (Binayakroy, pavel chemopanov, cuong Nguyen, craig Forsyth, et al, lithonium borate Ester Salts for Electrolyte Application in Next-Generation High VoltageLithium Batteries; adv. Energy Mater 2021, 2101422, michael Rohde, philipp eide, verena Leppert, et al, li [ B (OCH) 2 CF 3 ) 4 ]: Synthesis, Characterizationand Electrochemical Application as a Conducting Salt for LiSB Batteries. ChemPhyschem). However, in the current synthesis scheme of lithium tetra (trifluoroethoxy) borate, the raw material lithium borohydride is extremely expensive, potential safety hazards exist in the whole preparation process due to the activity of the raw material lithium borohydride, the reaction temperature is very low, the energy consumption is extremely high, the yield is relatively low, the method is not suitable for large-scale production and preparation, and the purity of the product is not given.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a preparation method of battery electrolyte suitable for large-scale production, which has the advantages of low cost, less energy consumption, high yield and simple operation, and the prepared electrolyte can be applied to high-voltage-resistant lithium ion batteries/sodium ion batteries.
In order to achieve the above purpose, the following technical scheme is proposed:
the invention provides a preparation method of lithium/sodium salt electrolyte, which comprises the following steps:
(1) Alkali metal Li or Na and trifluoroethanol are used as raw materials, the raw materials react in an organic solvent, and after the reaction is finished, clear liquid containing lithium trifluoroethanol or sodium trifluoroethanol is obtained through solid-liquid separation;
(2) Adding tri (trifluoro ethoxy) borate into the clear liquid, reacting, separating solid from liquid, and drying to obtain tetra (trifluoro ethoxy) lithium borate or tetra (trifluoro ethoxy) sodium borate.
Preferably, in the step (1), the organic solvent is selected from one or more mixed solvents of dimethyl carbonate, ethylmethyl carbonate and methylene chloride.
Preferably, in the step (1), the pH of the reaction system is controlled to be 4 to 6.
Preferably, in the step (1), the temperature of the reaction is 20-40 ℃; the reaction time is 20-30 h; stirring or other mechanical means, such as ultrasound, are carried out during the reaction to aid in the reaction.
Preferably, in the step (2), the molar ratio of the alkali metal to the trifluoroethanol is 1:1.5-1:5. When the molar ratio is too low, the reaction releases heat to enable trifluoroethanol to escape from the reaction system, and when the reaction is incomplete, the molar ratio is too high, so that raw materials are wasted.
Preferably, in the step (2), the molar ratio of the lithium trifluoroethanol or the sodium trifluoroethanol to the tris (trifluoroethoxy) borate in the clarified liquid is 1:1-1:1.5. When the proportion is too low, the reaction is incomplete, the purity of the product is affected, and when the proportion is too high, the raw material waste is caused.
Preferably, in the step (2), the temperature of the reaction is 20-40 ℃; the reaction time is 4-6 h; stirring or ultrasonic treatment is carried out during the reaction to assist the reaction.
Preferably, in the step (2), the humidity of the wet product obtained by the solid-liquid separation is 10% or less wt%.
Preferably, in the step (2), the drying temperature is 80-120 ℃; the drying time is 3-4 h.
Preferably, in step (2), the tris (trifluoroethoxy) borate is added to the clear liquid by slow dropwise addition.
Preferably, the reactions of step (1) and step (2) are carried out at normal temperature.
Compared with the prior art, the invention has the following beneficial effects:
(1) The synthesis method of the invention is simple and easy to realize, has little energy consumption, good safety, high yield and low cost, does not generate any waste, and is easy to realize large-scale industrial production.
(2) The purity of the electrolyte lithium salt prepared by the method is more than 99%, the water content is lower than 10 ppm, and the production requirement of the lithium/sodium ion battery electrolyte is met.
(3) The electrolyte lithium/sodium salt prepared by the invention has high fluorination degree, has lower HOMO energy (-2.763 eV) and high HOMO-LUMO interval, thus having better high-voltage resistance, better thermal stability and high conductivity, and can lead the use effect of the lithium/sodium ion battery to be better when being used as an additive.
Drawings
FIG. 1 is a tetrakis (trifluoroethoxy) borate prepared in example 1 11 B NMR spectrum [ ] 11 BNMR(DMSO-d6))。
Detailed Description
An embodiment of the present invention provides a method for preparing a battery electrolyte, including:
(1) Alkali metal Li or Na and trifluoroethanol are used as raw materials, the raw materials react in an organic solvent, li or Na and trifluoroethanol react to generate lithium trifluoroethoxide or sodium trifluoroethoxide, after the reaction is finished, clear liquid containing the lithium trifluoroethoxide or sodium trifluoroethoxide is obtained through solid-liquid separation, and the organic solvent can dissolve products coated on the surface of the metal, so that the alkali metal fully reacts;
(2) Adding tri (trifluoro ethoxy) borate into the clear liquid to react, wherein the specific chemical reaction formula is as follows:after the reaction is finished, solid-liquid separation and drying are carried out to obtain lithium tetra (trifluoro ethoxy) borate salt or lithium tetra (trifluoro ethoxy) borate salt, the chemical formula isWherein the alkali metal A is selected from Li, na, respectively corresponding to +.>Lithium tetrakis (trifluoroethoxy) borate with decomposition temperature of 271 ℃ or higher and +.>Sodium (tetrakis (trifluoroethoxy) borate).
In some preferred embodiments, the organic solvent is selected from one or more solvents selected from dimethyl carbonate, ethyl methyl carbonate and dichloromethane.
In a part of preferred embodiments, in the step (1), the pH value of the reaction system is controlled to be 4-6, and the weakly acidic reaction system can maintain the stability of the raw materials, thereby improving the reaction rate.
In a part of preferred embodiments, in the step (1), the temperature of the reaction is 20 to 40 ℃; the reaction time is 20-30 h; stirring or ultrasonic treatment is carried out during the reaction to assist the reaction. The reaction yield can be further improved by stirring or ultrasonic treatment during the reaction.
In a part of preferred embodiments, in the step (2), the molar ratio of the alkali metal to the trifluoroethanol is 1:1.5 to 1:5.
In a partially preferred embodiment, in step (2), the molar ratio of alkali metal trifluoroethanol (lithium trifluoroethoxide or sodium trifluoroethoxide) to tris (trifluoroethoxy) borate in the clarified liquid is from 1:1 to 1:1.5.
In a part of preferred embodiments, in the step (2), the temperature of the reaction is 20 to 40 ℃; the reaction time is 4-6 h; stirring or ultrasonic treatment is carried out during the reaction to assist the reaction. The reaction yield can be further improved by stirring or ultrasonic treatment during the reaction.
In some preferred embodiments, the reactions of step (1) and step (2) are carried out at normal temperature, with low energy consumption and convenient operation.
In a part of preferred embodiments, in the step (2), the humidity of the wet product obtained by the solid-liquid separation is 10% or less wt%. The humidity in the product is controlled in a proper range, so that the drying time is reduced, the efficiency is improved, and the energy consumption cost is reduced.
In the step (1) and the step (2), the solid-liquid separation may be filtration, or may be performed by other solid-liquid separation methods, for example, conventional solid-liquid separation methods such as centrifugation.
In some preferred embodiments, the drying temperature is 80 to 120 ℃; the preferred drying temperature ensures that a good drying effect (low moisture in the product) is achieved in a short time; the drying time is 3-4 h.
In a partially preferred embodiment, in step (2), the tris (trifluoroethoxy) borate is added to the clear liquid by slow dropwise addition.
The present invention will be further described with reference to specific examples and drawings, but the present invention is not limited to the following examples. Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
Example 1:
weighing metal lithium 0.5 g and trifluoroethanol 10.87 g, adding into a 100g dimethyl carbonate solvent, keeping the pH value of the solution between 4 and 6, stirring at normal temperature for 24-h, filtering to obtain clear liquid, slowly dripping 22.31 g tris (trifluoroethoxy) borate into the liquid, and stirring at normal temperature for 5-h; the wet product containing the solvent was filtered and dried at 110℃for 3 h to give a lithium tetrakis (trifluoroethoxy) borate salt of about 29.40 g in 98.00% yield, 98.28% purity and 5ppm water content. The product obtained 11 The B NMR spectrum is shown in FIG. 1, and it can be seen from FIG. 1 that pure-phase lithium tetrakis (trifluoroethoxy) borate salt was synthesized.
Example 2:
weighing metal lithium 0.5 g and trifluoroethanol 18.12 g, adding the metal lithium 0.5 g and the trifluoroethanol 18.12 g into a 100g dimethyl carbonate solvent, keeping the pH value of the solution between 4 and 6, stirring the solution at normal temperature for 24 to h, filtering the solution to obtain clear liquid, slowly dropwise adding 22.31 g tris (trifluoroethoxy) borate into the liquid, and stirring the solution at normal temperature for 5 to h; the wet product containing the solvent was filtered and dried at 110℃for 3 h to give a lithium tetrakis (trifluoroethoxy) borate salt of about 29.41 g in 98.00% yield, 98.26% purity and 5ppm water content.
Example 3:
weighing 0.5. 0.5 g of lithium metal and 36.24. 36.24 g of trifluoroethanol, adding the mixture into a 100g dimethyl carbonate solvent, keeping the pH value of the solution between 4 and 6, stirring the mixture at 20 ℃ for 24 h, filtering the mixture to obtain clear liquid, slowly dripping 22.31 g tris (trifluoroethoxy) borate into the liquid, and stirring the mixture at 40 ℃ for 5 h; the wet product containing the solvent was filtered and dried at 110℃for 3 h to give a lithium tetrakis (trifluoroethoxy) borate salt of about 29.38 g in 98.00% yield, 98.27% purity and 5ppm water content.
Example 4:
weighing metal lithium 0.5 g and trifluoroethanol 10.87 g, adding into a 100g dimethyl carbonate solvent, keeping the pH value of the solution between 4 and 6, stirring at 20 ℃ for 24 h, filtering to obtain clear liquid, slowly dripping 27.89 g tris (trifluoroethoxy) borate into the liquid, and stirring at 20 ℃ for 5 h; the wet product containing the solvent was obtained by filtration and dried at 110℃for 3 h to give lithium tetrakis (trifluoroethoxy) borate 29.38 g in 97.99% yield, 99.02% purity and 7 ppm water content.
Example 5:
weighing metal lithium 0.5 g and trifluoroethanol 10.87 g, adding into a 100g dimethyl carbonate solvent, keeping the pH value of the solution between 4 and 6, stirring at 40 ℃ for 24 h, filtering to obtain clear liquid, slowly dripping 33.46 g tris (trifluoroethoxy) borate into the liquid, and stirring at 40 ℃ for 5 h; the wet product containing the solvent was obtained by filtration and dried at 110℃for 3 h to give a lithium tetrakis (trifluoroethoxy) borate salt 29.25 g in a yield of 97.56%, purity of 98.89% and water content of 10 ppm.
Example 6
Weighing 0.5. 0.5 g of lithium metal and 10.87. 10.87 g of trifluoroethanol, adding the mixture into 100g of methyl ethyl carbonate solvent, keeping the pH value of the solution between 4 and 6, stirring the mixture at 40 ℃ for 24 h, filtering the mixture to obtain clear liquid, slowly dripping 22.31 g of tris (trifluoroethoxy) borate into the liquid, and stirring the mixture at 40 ℃ for 5 h; the wet product containing the solvent was obtained by filtration and dried at 80℃for 4 hours to give a lithium tetrakis (trifluoroethoxy) borate salt 29.41. 29.41 g in 98.00% yield, 98.29% purity and 6 ppm water content.
Purity, na of the products prepared in examples 1 to 6, respectively + 、Ca 2+ 、Fe 3+ Content of Cl - And moisture were analyzed and the results are shown in Table 1, in which the purity of the product was determined by NMR, metal ion by ICP, chloride ion by IC, and moisture by Fischer coulomb method.
Table 1 test results
Example 7:
weighing 1.67. 1.67 g of sodium metal and 10.89.5725 of trifluoroethanol, adding the sodium metal and 10.89 to g of trifluoroethanol into a 100g dimethyl carbonate solvent, keeping the pH value of the solution between 4 and 6, stirring at normal temperature for 24 to h, filtering to obtain clear liquid, slowly dropwise adding 22.35g of tris (trifluoroethoxy) borate into the liquid, and stirring at normal temperature for 5 to h; the wet product containing the solvent was filtered and dried at 110℃for 3 h to give sodium tetrakis (trifluoroethoxy) borate salt of about 30.41g, purity 98.30% and water content 5ppm.
Example 8:
weighing 1.67. 1.67 g of sodium metal and 18.14g of trifluoroethanol, adding the sodium metal and 18.14g of trifluoroethanol into a 100g dimethyl carbonate solvent, keeping the pH value of the solution between 4 and 6, stirring at normal temperature for 24 h, filtering to obtain clear liquid, slowly dropwise adding 22.35g tris (trifluoroethoxy) borate into the liquid, and stirring at normal temperature for 5 h; the wet product containing the solvent was obtained by filtration and dried at 110℃for 3. 3 h to give sodium tetrakis (trifluoroethoxy) borate 30.38 g, purity 99.05% and water content 8 ppm.
Example 9:
weighing metal sodium 1.67 and g and trifluoroethanol 36.3 and g, adding the metal sodium and the trifluoroethanol 36.3 and g into a 100g dimethyl carbonate solvent, keeping the pH value of the solution between 4 and 6, stirring the solution at 20 ℃ for 24 and h, filtering the solution to obtain clear liquid, slowly dripping 22.35g tris (trifluoroethoxy) borate into the liquid, and stirring the solution at 20 ℃ for 5 and h; the wet product containing the solvent was obtained by filtration and dried at 100℃for 3. 3 h to give sodium tetrakis (trifluoroethoxy) borate 30.25: 30.25 g, purity 99.00% and water content 9 ppm.
Example 10:
weighing metal sodium 1.67 and g and trifluoroethanol 10.89 and g, adding the metal sodium and the trifluoroethanol into a 100g dimethyl carbonate solvent, keeping the pH value of the solution between 4 and 6, stirring the solution at 40 ℃ for 24 and h, filtering the solution to obtain clear liquid, slowly dripping 27.86 g tris (trifluoroethoxy) borate into the liquid, and stirring the solution at 40 ℃ for 5 and h; the wet product containing the solvent was obtained by filtration and dried at 110℃for 3 h to give sodium tetrakis (trifluoroethoxy) borate 30.40 g, purity 99.98% and water content 5ppm.
Example 11:
weighing metal sodium 1.67 and g and trifluoroethanol 10.89 and g, adding the metal sodium and the trifluoroethanol into a 100g dimethyl carbonate solvent, keeping the pH value of the solution between 4 and 6, stirring the solution at 40 ℃ for 24 and h, filtering the solution to obtain clear liquid, slowly dripping 33.53 and g tris (trifluoroethoxy) borate into the liquid, and stirring the solution at 20 ℃ for 5 and h; the wet product containing the solvent was obtained by filtration and dried at 110℃for 3 h to give sodium tetrakis (trifluoroethoxy) borate 30.40 g, purity 99.97% and water content 5ppm.
Example 12:
weighing 1.67. 1.67 g of sodium metal and 10.89. 10.89 g of trifluoroethanol, adding the sodium metal and 10.89 to a 100g dichloromethane solvent, keeping the pH value of the solution between 4 and 6, stirring at normal temperature for 24-h, filtering to obtain clear liquid, slowly dropwise adding 22.35g of tris (trifluoroethoxy) borate into the liquid, and stirring at normal temperature for 5-h; the wet product containing the solvent was obtained by filtration and dried at 110℃for 3 h to give 30.42g of sodium tetrakis (trifluoroethoxy) borate, having a purity of 98.71% and a water content of 7 ppm.
Example 13
Weighing metal sodium 1.67 and g and trifluoroethanol 10.89 and g, adding the metal sodium 1.67 and the trifluoroethanol 10.89 and g into a mixed solvent of 50g methylene dichloride and 50g dimethyl carbonate, keeping the pH value of the solution between 4 and 6, stirring at normal temperature for 24 and h, filtering to obtain clear liquid, slowly dripping 22.35g tris (trifluoroethoxy) borate into the liquid, and stirring at normal temperature for 5 and h; the wet product containing the solvent was obtained by filtration and dried at 120℃for 3 h to obtain 30.41g of sodium tetrakis (trifluoroethoxy) borate, which had a purity of 98.79% and a water content of 5ppm.
The purity and Ca of the products prepared in examples 6 to 10, respectively 2+ 、Fe 3+ Content of Cl - And moisture were analyzed and the results are shown in Table 2, in which the purity of the product was determined by NMR, metal ion by ICP, chloride ion by IC, and moisture by Fischer coulomb method.
Table 2 test results
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for preparing a lithium/sodium salt electrolyte, comprising:
(1) Alkali metal Li or Na and trifluoroethanol are used as raw materials, the raw materials react in an organic solvent, and after the reaction is finished, solid-liquid separation is carried out to obtain liquid containing lithium trifluoroethoxide or sodium trifluoroethoxide;
(2) And (3) reacting the liquid containing lithium trifluoroethanol or sodium trifluoroethanol with tris (trifluoroethoxy) borate, and after the reaction is finished, carrying out solid-liquid separation and drying to obtain lithium tetrakis (trifluoroethoxy) borate or sodium tetrakis (trifluoroethoxy) borate.
2. The method for producing a lithium/sodium salt electrolyte according to claim 1, wherein in the step (1), the organic solvent comprises a mixed solvent of one or more of dimethyl carbonate, ethyl methyl carbonate and methylene chloride.
3. The method for producing a lithium/sodium salt electrolyte according to claim 1, wherein in the step (1), the pH of the reaction system is controlled to be 4 to 6.
4. The method for preparing a lithium/sodium salt electrolyte according to any one of claims 1 to 3, wherein in the step (1), the temperature of the reaction is 20 to 40 ℃; the reaction time is 20-30 h; stirring or ultrasonic treatment is carried out during the reaction to assist the reaction.
5. The method for producing a lithium/sodium salt electrolyte according to any one of claims 1 to 3, wherein in the step (2), the molar ratio of the alkali metal to trifluoroethanol is 1:1.5 to 1:5.
6. A method of preparing a lithium/sodium salt electrolyte according to any one of claims 1 to 3, wherein in step (2), the molar ratio of lithium or sodium trifluoroethoxide to tris (trifluoroethoxy) borate in the liquid is from 1:1 to 1:1.5.
7. The method for preparing a lithium/sodium salt electrolyte according to any one of claims 1 to 3, wherein in the step (2), the temperature of the reaction is 20 to 40 ℃; the reaction time is 4-6 h; stirring or ultrasonic treatment is carried out during the reaction to assist the reaction.
8. The method for producing a lithium/sodium salt electrolyte according to any one of claims 1 to 3, wherein in the step (2), the humidity of the wet product obtained by the solid-liquid separation is 10% by weight or less.
9. The method for preparing a lithium/sodium salt electrolyte according to any one of claims 1 to 3, wherein in the step (2), the drying temperature is 80 to 120 ℃; the drying time is 3-4 h.
10. The method for producing a lithium/sodium salt electrolyte according to claim 1, wherein the reactions of step (1) and step (2) are carried out at normal temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311045079.5A CN117229303A (en) | 2023-08-18 | 2023-08-18 | Preparation method of lithium/sodium salt electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311045079.5A CN117229303A (en) | 2023-08-18 | 2023-08-18 | Preparation method of lithium/sodium salt electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117229303A true CN117229303A (en) | 2023-12-15 |
Family
ID=89083467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311045079.5A Pending CN117229303A (en) | 2023-08-18 | 2023-08-18 | Preparation method of lithium/sodium salt electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117229303A (en) |
-
2023
- 2023-08-18 CN CN202311045079.5A patent/CN117229303A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5667328B2 (en) | Bisquaternary ammonium salt ionic liquid having two centers, process for its preparation and use | |
| CN108423651B (en) | Method for preparing lithium difluorophosphate | |
| CN107011371B (en) | Silicon-containing imidazole ionic liquid and preparation method and application thereof | |
| CN102260282B (en) | Preparation method of lithium oxalyldifluoroborate electrolyte salt | |
| KR102179846B1 (en) | Additives composition for electrolyte of lithium secondary battery and manufacturing method thereof | |
| JP2001220393A (en) | Alkylspiroboric acid salt to be used for electrochemical cell | |
| KR20190105493A (en) | A method for synthesis of benzene sulfonate derivatives | |
| KR101982601B1 (en) | Method for producing bis (fluorosulfonyl) imide lithium salt (LiFSI) with reduced fluorine anion content using alkoxytrialkylsilanes | |
| WO2019018999A1 (en) | Method for preparing lithium difluorophosphate | |
| US20100256384A1 (en) | Method for producing purified ammonium salt of fluorinated bis-sulfonylimide | |
| JPH09165210A (en) | Production of lithium hexafluorophosphate | |
| JP4638006B2 (en) | Stable (CF3) 2N-salts and process for producing them | |
| CN110627742B (en) | Preparation method and purification method of compound containing at least one cyclic ligand structure | |
| KR102007476B1 (en) | New purification method of bis(fluorosulfonyl)imide lithium salt) | |
| Lee et al. | Synthesis of Cyclic Aza‐Ether Compounds and Studies of Their Use as Anion Receptors in Nonaqueous Lithium Halide Salts Solution | |
| KR20010107709A (en) | Reduced positive-electrode material in electrochemical cells | |
| CN117229303A (en) | Preparation method of lithium/sodium salt electrolyte | |
| KR102007477B1 (en) | New purification method of bis(fluorosulfonyl)imide | |
| CN116143666A (en) | Preparation method of lithium ethylenesulfonic acid difluorophosphate triethylamine salt (1:1:1) | |
| JP2001055396A (en) | Lithium complex salt for chemical cell | |
| KR102666044B1 (en) | Mass Production Method of Metal bis(fluorosulfonyl)imide | |
| KR20200114967A (en) | Method for producing bis (fluorosulfonyl) imide lithium salt (LiFSI) with reduced fluorine anion content | |
| KR101687374B1 (en) | Method for producing difluorosulfonyl imide or its salt | |
| JPS5953216B2 (en) | Synthesis method of anhydrous lithium borofluoride | |
| CN114649581B (en) | Electrolyte containing five-membered cyclic nitrogen-based salt structure, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |