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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- Prior art keywords
- lithium
- borate
- boron
- oxalato
- oxalic acid
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 29
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052796 boron Inorganic materials 0.000 claims abstract description 24
- -1 lithium salt compound Chemical class 0.000 claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 20
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 239000000706 filtrate Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000000376 reactant Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 6
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 6
- WVQUCYVTZWVNLV-UHFFFAOYSA-N boric acid;oxalic acid Chemical compound OB(O)O.OC(=O)C(O)=O WVQUCYVTZWVNLV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004327 boric acid Substances 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical class [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 claims description 3
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- HGLJXWLWOJCQFT-UHFFFAOYSA-M C(C(=O)O)(=O)[O-].B(O)(O)O.[Li+] Chemical compound C(C(=O)O)(=O)[O-].B(O)(O)O.[Li+] HGLJXWLWOJCQFT-UHFFFAOYSA-M 0.000 claims 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- SRFGYPCGVWVBTC-UHFFFAOYSA-N lithium;dihydrogen borate;oxalic acid Chemical compound [Li+].OB(O)[O-].OC(=O)C(O)=O SRFGYPCGVWVBTC-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- RPXKKUZDTAOVEQ-UHFFFAOYSA-N boric acid;oxalic acid Chemical compound OB(O)O.OC(=O)C(O)=O.OC(=O)C(O)=O RPXKKUZDTAOVEQ-UHFFFAOYSA-N 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910013188 LiBOB Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical compound B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013178 LiBO2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- 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 Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- 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)
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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