CN111943970A - Preparation method of lithium oxalato borate - Google Patents
Preparation method of lithium oxalato borate Download PDFInfo
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- CN111943970A CN111943970A CN202010916092.3A CN202010916092A CN111943970A CN 111943970 A CN111943970 A CN 111943970A CN 202010916092 A CN202010916092 A CN 202010916092A CN 111943970 A CN111943970 A CN 111943970A
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- lithium
- borate
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- oxalato
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- 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 discloses a preparation method of lithium oxalato borate, which comprises the following steps: mixing oxalic acid and a boron-containing compound, reacting at 40-130 ℃ under normal pressure and under mechanical stirring, and then drying in vacuum at 60-220 ℃; during the reaction, oxalic acid and a boron-containing compound generate oxalic acid boric acid; cooling the reactant obtained in the step to room temperature, adding a polar solvent, and stirring for dissolving; filtering the solution obtained in the step, adding a lithium salt compound into the filtrate, and reacting at room temperature to reflux temperature; reacting the oxalic acid boric acid with a lithium salt compound to generate lithium oxalate borate; and after the reaction is finished, cooling the reaction liquid to room temperature, filtering, and sequentially concentrating, crystallizing and drying the filtrate to obtain a solid lithium bis (oxalato) borate product. The method has the advantages of mild reaction, simple process, low production cost, economy, environmental protection and high reaction yield, can obtain high-purity lithium bis (oxalato) borate, and is relatively suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of synthesis of electrolyte lithium salt used in the lithium ion battery industry, and particularly relates to a preparation method of lithium difluoroborate.
Background
The lithium ion battery has the advantages of high energy density, high output voltage, long cycle life, no memory effect, small environmental pollution and the like, is the secondary battery with the greatest attraction and development potential, and is also the first choice of power supplies of hybrid electric vehicles and pure electric vehicles. The electrolyte is one of basic key materials of the lithium ion battery, is used as a main component of the electrolyte, and the performance of the electrolyte plays a decisive role in the electrolyte and the lithium ion battery.
Lithium hexafluorophosphate, the most mature electrolyte salt used most frequently in current commercialization, has certain drawbacks. Lithium hexafluorophosphate is easy to hydrolyze and has poor thermal stability, and decomposition reaction occurs under a trace amount of water to generate corrosive hydrofluoric acid, which can cause the performance attenuation and failure of the lithium ion battery.
LiBOB serving as a novel electrolyte lithium salt has good chemical property and stability, and the thermal decomposition temperature of the LiBOB can reach 300 ℃. The addition of LiBOB can form a stable SEI film on a carbon cathode, prevent solvent molecules from being embedded, has higher conductivity and wider electrochemical window, can improve the stability and safety of the lithium ion battery, and prolongs the service life of the lithium ion battery.
At present, the preparation method of lithium bis (oxalato) borate mainly comprises a solid phase method and a liquid phase method, wherein oxalic acid, a boron source and a lithium-containing compound (such as lithium hydroxide or lithium carbonate) are adopted as reaction raw materials to generate lithium bis (oxalato) borate and water. Lithium dioxalate borate is easy to absorb water to form lithium dioxalate hydrate, and meanwhile, under the action of water, partial hydrolysis reaction occurs, wherein the hydrolysis reaction formula is as follows:
LiB(C2O4)2+2H2O→LiBO2+2H2C2O4；
LiB(C2O4)2+3H2O→LiOOCCOOH+H3BO3+H2C2O4；
in the above preparation method, water is generated inevitably during the reaction; the water content in the final product is high and is difficult to remove completely; meanwhile, lithium dioxalate borate can be partially hydrolyzed, and particularly, when the lithium dioxalate borate is heated and dehydrated, the hydrolysis is accelerated, so that the product yield is low, and the three wastes are more.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of lithium difluoro (oxalato) borate, which has the advantages of mild reaction, simple process, low production cost, economy, environmental friendliness and high reaction yield, can obtain high-purity lithium bis (oxalato) borate, and is relatively suitable for industrial production.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a preparation method of lithium oxalato borate comprises the following steps:
(1) mixing a certain amount of oxalic acid with a boron-containing compound, reacting for 1-12 hours at 40-130 ℃ under normal pressure and mechanical stirring, and drying for 2-8 hours under vacuum at 60-220 ℃; during the reaction, oxalic acid and a boron-containing compound generate oxalic acid boric acid;
(2) cooling the reactant obtained in the step (1) to room temperature in a nitrogen atmosphere, adding a polar solvent, and stirring and dissolving for 1-8 hours;
(3) filtering the solution obtained in the step (2), adding a lithium salt compound into the filtrate, and reacting for 1-8 hours at the temperature ranging from room temperature to reflux temperature; reacting the oxalato-boric acid with a lithium salt compound under a nearly anhydrous condition to generate lithium oxalato-borate;
(4) and (4) after the reaction in the step (3) is finished, cooling the reaction liquid to room temperature, filtering, and sequentially concentrating, crystallizing, washing and drying the filtrate to obtain a solid lithium bis (oxalato) borate product.
Preferably, the oxalic acid is anhydrous oxalic acid or oxalic acid dihydrate; the boron-containing compound is one or the mixture of two or more of boric acid, diboron trioxide, metaboric acid and pyroboric acid.
Further, the adding amount of the oxalic acid and the boron-containing compound is calculated according to the molar ratio of oxalate ions to boron element; specifically, the molar ratio of oxalate ions to boron element is (2-2.2): 1.
Preferably, the polar solvent in step (2) is selected from one or a combination of two or more of acetonitrile, propionitrile, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl ethyl ketone, 1, 4-dioxane, 1, 4-butyrolactone and tetrahydrofuran.
Further, the adding amount of the polar solvent is 1-5 times of the mass of the dried boric oxalato acid in the step 1).
Further, the moisture content of the polar solvent is controlled within 500 ppm.
Preferably, the lithium salt compound is one of anhydrous halogenated lithium salt, lithium hydride and lithium nitride; if the lithium halide salt is selected from one of lithium fluoride, lithium chloride and lithium bromide;
further, the adding amount of the lithium salt compound is calculated according to the molar weight of the boron element in the boron-containing compound; specifically, the molar amount of the lithium salt compound is 1 to 1.1 times of the molar amount of boron in the boron-containing compound.
The invention has the beneficial effects that:
according to the invention, oxalic acid and a boron-containing compound are firstly adopted to generate an intermediate, namely, the boric acid dioxalate cannot be combined with water molecules to form a crystal water complex, and moisture is removed thoroughly after vacuum drying; therefore, the next reaction process of the lithium dioxalate borate and the lithium salt compound is in a nearly anhydrous condition, water is not generated, hydrolysis caused by contact between a lithium dioxalate borate product obtained after the reaction and water can be avoided, and the product yield and the product purity are improved.
In addition, the excessive lithium salt compound in the reaction raw materials is almost insoluble in a polar solvent and can be removed by filtration, which is beneficial to improving the purity of the final product; the preparation method of the invention has simple and convenient post-treatment after the reaction is finished, and can obtain the lithium bis (oxalato) borate product through concentration, crystallization, washing and drying.
The preparation method of the invention has the advantages of almost no side reaction in the whole reaction process, high reaction yield, low water residual quantity in the obtained product, easy purification of the product and high product purity.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of lithium oxalato borate in embodiment 1 includes the following steps:
(1) adding 126g (1mol) of oxalic acid dihydrate and 31g (0.5mol) of boric acid into a three-neck flask with a stirring device, heating the reaction raw materials to 55 ℃ under the conditions of normal pressure and mechanical stirring, and reacting for 2 hours; after decompression, the temperature is continuously increased to 90 ℃, and vacuum drying is carried out for 8 hours at the temperature; obtaining a white honeycomb solid reactant in the flask; in the reaction process, oxalic acid dihydrate and boric acid generate boric acid dioxalate;
the reaction formula of the step (1) is as follows:
2H2C2O4.2 H2O+H3BO3→HB(C2O4)2+5H2O
(2) cooling the reactant obtained in the step (1) to room temperature in a nitrogen atmosphere, and weighing the reactant to obtain 85g of dry weight; then adding 320g of ethyl acetate with the water content of 180ppm into the reactant, stirring and dissolving for 2 hours;
(3) filtering the solution obtained in the step (2), slowly adding 21g (0.5mol) of anhydrous lithium chloride into the filtrate in batches, and stirring and reacting at 25 ℃ for 8 hours; in the step (2), under the condition of nearly anhydrous condition, reacting the oxalato boric acid with anhydrous lithium chloride to generate lithium oxalato borate; the reaction formula is as follows:
HB(C2O4)2+LiCl→LiB(C2O4)2+HCl↑
hydrogen chloride gas generated in the reaction process is absorbed by water after escaping;
(4) and (3) after the reaction in the step (3) is finished, cooling the reaction liquid to room temperature, filtering, concentrating and crystallizing the filtrate, washing the filtrate for a plurality of times by using petroleum ether, and drying the filtrate in vacuum to obtain 81g of a solid lithium bis (oxalato) borate product, wherein the yield is 83.5%, the product purity is 99.81%, and the product moisture content is 38 ppm.
Example 2
The preparation method of lithium oxalato borate in embodiment 2 includes the following steps:
(1) 198g (2.2mol) of anhydrous oxalic acid and 35g (0.5mol) of boron trioxide are added into a three-neck flask with a stirring device, and the reaction raw materials are heated to 85 ℃ under the conditions of normal pressure and mechanical stirring and react for 8 hours; after decompression, the temperature is continuously raised to 200 ℃, and vacuum drying is carried out for 2 hours at the temperature; obtaining a white honeycomb solid reactant in the flask; in the reaction process, oxalic acid dihydrate and boric acid generate boric acid dioxalate;
(2) cooling the reactant obtained in the step (1) to room temperature under a nitrogen atmosphere, and weighing the reactant to obtain 178g of net weight; then 600g of acetonitrile with the water content of 230ppm is added into the reactant, and stirred and dissolved for 8 hours;
(3) filtering the solution obtained in the step (2), adding 28.6g (1.1mol) of lithium fluoride into the filtrate, and carrying out reflux reaction for 5 hours under stirring; in the step (2), under the condition of nearly anhydrous condition, reacting the oxalato boric acid with lithium fluoride to generate the lithium oxalato borate; after gas generated in the reaction process escapes, water is adopted for absorption;
(4) and (3) after the reaction in the step (3) is finished, cooling the reaction liquid to room temperature, filtering, concentrating and crystallizing the filtrate, washing the filtrate for a plurality of times by using dichloromethane, and drying the filtrate in vacuum to obtain 159g of a solid lithium dioxalate borate product, wherein the yield is 82%, the product purity is 99.79% and the water content of the product is 32 ppm.
Example 3
The preparation method of lithium oxalato borate in embodiment 3 includes the following steps:
(1) adding 90g (1mol) of anhydrous oxalic acid and 31g (0.5mol) of boric acid into a three-neck flask with a stirring device, heating the reaction raw materials to 120 ℃ under the conditions of normal pressure and mechanical stirring, and reacting for 1 hour; after decompression, the temperature is continuously increased to 160 ℃, and vacuum drying is carried out for 5 hours at the temperature; obtaining a white honeycomb solid reactant in the flask; in the reaction process, oxalic acid dihydrate and boric acid generate boric acid dioxalate;
(2) cooling the reactant obtained in the step (1) to room temperature in a nitrogen atmosphere, and weighing the reactant to obtain 90g of net weight; then, 350g of 1, 4-dioxane with the water content of 150ppm is added into the reactant, and the mixture is stirred and dissolved for 3 hours;
(3) filtering the solution obtained in the step (2), slowly adding 17.5g (0.5mol) of lithium nitride into the filtrate in batches, and reacting for 4 hours at 65 ℃ under stirring; in the step (2), under the condition of nearly anhydrous condition, reacting the oxalato boric acid with lithium fluoride to generate the lithium oxalato borate; after gas generated in the reaction process escapes, water is adopted for absorption;
(4) and (3) after the reaction in the step (3) is finished, cooling the reaction liquid to room temperature, filtering, concentrating and crystallizing the filtrate, washing the filtrate for a plurality of times by using dichloroethane, and drying the filtrate in vacuum to obtain 76g of a solid lithium bis (oxalato) borate product, wherein the yield is 78.4%, the product purity is 99.73%, and the product moisture content is 26 ppm.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents made by the contents of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (8)
1. A preparation method of lithium oxalato borate is characterized by comprising the following steps:
(1) mixing a certain amount of oxalic acid with a boron-containing compound, reacting for 1-12 hours at 40-130 ℃ under normal pressure and under the condition of mechanical stirring, and then drying for 2-8 hours in vacuum at 60-220 ℃; during the reaction, oxalic acid and a boron-containing compound generate oxalic acid boric acid;
(2) cooling the reactant obtained in the step (1) to room temperature in a nitrogen atmosphere, adding a polar solvent, and stirring and dissolving for 1-8 hours;
(3) filtering the solution obtained in the step (2), adding a lithium salt compound into the filtrate, and reacting for 1-8 hours at the temperature from room temperature to reflux temperature; reacting the oxalato-boric acid with a lithium salt compound under a nearly anhydrous condition to generate lithium oxalato-borate;
(4) and (4) after the reaction in the step (3) is finished, cooling the reaction liquid to room temperature, filtering, and sequentially concentrating, crystallizing and drying the filtrate to obtain a solid lithium bis (oxalato) borate product.
2. The method for preparing lithium oxalato borate according to claim 1, wherein the oxalic acid is anhydrous oxalic acid or oxalic acid dihydrate; the boron-containing compound is one or the mixture of two or more of boric acid, diboron trioxide, metaboric acid and pyroboric acid.
3. The method for preparing lithium borate oxalate according to claim 1, wherein the amount of oxalic acid and the boron-containing compound added is calculated according to the molar ratio of oxalate ions to boron; the molar ratio of oxalate ions to boron element is (2-2.2): 1.
4. The method for preparing lithium borate oxalate according to claim 1, wherein the polar solvent in step (2) is selected from one or a combination of two or more of acetonitrile, propionitrile, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl ethyl ketone, 1, 4-dioxane, 1, 4-butyrolactone and tetrahydrofuran.
5. The method for preparing lithium oxalato borate according to claim 1, wherein the amount of the polar solvent added is 1 to 5 times the mass of the lithium oxalato borate dried in the step 1).
6. The method for preparing lithium borate oxalate according to claim 1, wherein the moisture content of the polar solvent is controlled to be within 500 ppm.
7. The method for preparing lithium borate oxalate according to claim 1, wherein the lithium salt compound is one of an anhydrous halogenated lithium salt, lithium hydride and lithium nitride; the halogenated lithium salt is selected from one of lithium fluoride, lithium chloride and lithium bromide.
8. The method for producing lithium borate oxalate according to claim 1, wherein the amount of the lithium salt compound added is calculated based on the molar amount of boron element in the boron-containing compound; the molar amount of the lithium salt compound is 1 to 1.1 times of the molar amount of the boron element in the boron-containing compound.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114671899A (en) * | 2022-03-28 | 2022-06-28 | 珠海市赛纬电子材料股份有限公司 | Preparation method of lithium bis (oxalato) borate and application of lithium bis (oxalato) borate |
| CN114773371A (en) * | 2022-05-30 | 2022-07-22 | 无锡威孚环保催化剂有限公司 | Preparation method of lithium bis (oxalato) borate |
| WO2023000198A1 (en) * | 2021-07-21 | 2023-01-26 | 江苏华盛锂电材料股份有限公司 | Method for preparing lithium bisoxalate borate and method for preparing lithium-ion battery electrolyte |
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| JP2001247306A (en) * | 2000-03-07 | 2001-09-11 | Central Glass Co Ltd | Method for synthesizing ionic metal complex and method for purifying the same |
| CN102304143A (en) * | 2011-07-13 | 2012-01-04 | 北京大学 | Method for preparing lithium bis(oxalate) borate |
| CN103030657A (en) * | 2011-10-10 | 2013-04-10 | 中国科学院福建物质结构研究所 | Preparation method of electrolyte double-oxalate based lithium borate for lithium ion battery |
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| JP2001247306A (en) * | 2000-03-07 | 2001-09-11 | Central Glass Co Ltd | Method for synthesizing ionic metal complex and method for purifying the same |
| CN102304143A (en) * | 2011-07-13 | 2012-01-04 | 北京大学 | Method for preparing lithium bis(oxalate) borate |
| CN103030657A (en) * | 2011-10-10 | 2013-04-10 | 中国科学院福建物质结构研究所 | Preparation method of electrolyte double-oxalate based lithium borate for lithium ion battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023000198A1 (en) * | 2021-07-21 | 2023-01-26 | 江苏华盛锂电材料股份有限公司 | Method for preparing lithium bisoxalate borate and method for preparing lithium-ion battery electrolyte |
| CN114671899A (en) * | 2022-03-28 | 2022-06-28 | 珠海市赛纬电子材料股份有限公司 | Preparation method of lithium bis (oxalato) borate and application of lithium bis (oxalato) borate |
| CN114773371A (en) * | 2022-05-30 | 2022-07-22 | 无锡威孚环保催化剂有限公司 | Preparation method of lithium bis (oxalato) borate |
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