CN111943970B - Preparation method of lithium dioxalate borate - Google Patents
Preparation method of lithium dioxalate borate Download PDFInfo
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- CN111943970B CN111943970B CN202010916092.3A CN202010916092A CN111943970B CN 111943970 B CN111943970 B CN 111943970B CN 202010916092 A CN202010916092 A CN 202010916092A CN 111943970 B CN111943970 B CN 111943970B
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- lithium
- oxalic acid
- boron
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- dioxalate borate
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- 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 title claims abstract description 30
- 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 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 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 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 239000000376 reactant Substances 0.000 claims abstract description 12
- 238000001914 filtration 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
- 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 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229940116315 oxalic acid Drugs 0.000 claims description 14
- 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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 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
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 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
- 229940116316 dihydrate oxalic acid Drugs 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
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical class [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- MPDCKIORILZMHV-UHFFFAOYSA-N boric acid;lithium;oxalic acid Chemical compound [Li].OB(O)O.OC(=O)C(O)=O MPDCKIORILZMHV-UHFFFAOYSA-N 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 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
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical compound B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 description 2
- 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
- 229910013188 LiBOB Inorganic materials 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
- 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
- 238000005406 washing Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013184 LiBO Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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 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
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 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
- 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
- RBYFNZOIUUXJQD-UHFFFAOYSA-J tetralithium oxalate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O RBYFNZOIUUXJQD-UHFFFAOYSA-J 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a preparation method of lithium dioxalate borate, which comprises the following steps: mixing oxalic acid with a boron-containing compound, reacting at 40-130 ℃ under normal pressure and mechanical stirring, and vacuum drying at 60-220 ℃; during the reaction, oxalic acid and a boron-containing compound generate oxalic acid boric acid; cooling the reactant obtained in the steps to room temperature, adding a polar solvent, and stirring for dissolution; filtering the solution obtained in the steps, adding a lithium salt compound into the filtrate, and reacting at room temperature to reflux temperature; the reaction of the oxalic acid boric acid and the lithium salt compound to generate lithium oxalic acid boric acid; after the reaction is finished, cooling the reaction liquid to room temperature, filtering, concentrating, crystallizing and drying filtrate in sequence to obtain a solid lithium dioxalate 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 dioxalate 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 difluoro oxalate borate.
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 a secondary battery with the most attractive and development potential, and is the first choice of power supplies of hybrid electric vehicles and pure electric vehicles. The electrolyte is one of the basic key materials of the lithium ion battery, and as the main component of the electrolyte, the performance of the electrolyte plays a decisive role for the electrolyte and the lithium ion battery.
Lithium hexafluorophosphate, which is the most mature and most commonly used electrolyte salt in current commercialization, has certain drawbacks. Lithium hexafluorophosphate is easy to hydrolyze, has poor thermal stability, and can generate decomposition reaction under trace moisture to generate corrosive hydrofluoric acid, which can cause the performance attenuation and failure of the lithium ion battery.
The lithium dioxalate LiBOB is used as a novel electrolyte lithium salt, has good chemical property and stability, and the thermal decomposition temperature can reach 300 ℃. The addition of LiBOB can form stable SEI film on the carbon cathode, prevent the intercalation of solvent molecules, have higher conductivity and wider electrochemical window, can improve the stability and safety of the lithium ion battery, and prolong the service life of the lithium ion battery.
At present, the preparation method of the lithium dioxalate borate mainly comprises a solid phase method and a liquid phase method, and 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 the lithium dioxalate borate and water. The lithium dioxalate borate is easy to absorb water to form a lithium dioxalate hydrate, and meanwhile, under the action of water, partial hydrolysis reaction occurs, and the hydrolysis reaction formula is as follows:
LiB(C 2 O 4 ) 2 +2H 2 O→LiBO 2 +2H 2 C 2 O 4 ;
LiB(C 2 O 4 ) 2 +3H 2 O→LiOOCCOOH+H 3 BO 3 +H 2 C 2 O 4 ;
in the preparation method, water is produced in the reaction process, which is difficult to avoid; the existence of water can cause higher water content in the final product and is difficult to remove completely; meanwhile, the lithium dioxalate borate can be partially hydrolyzed, particularly, when the lithium dioxalate borate is heated and dehydrated, the hydrolysis is accelerated, and 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 the preparation method of the lithium difluoroborate, which has the advantages of mild reaction, simple process, low production cost, economy, environmental protection and high reaction yield, can obtain the high-purity lithium difluoroborate, and is more suitable for industrial production.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
the preparation method of the lithium dioxalate 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 at 60-220 ℃ under vacuum; 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 under the nitrogen atmosphere, then 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 range from room temperature to reflux temperature; reacting the lithium dioxalate borate with a lithium salt compound under nearly anhydrous conditions to produce lithium dioxalate borate;
(4) After the reaction in the step (3) is finished, cooling the reaction liquid to room temperature, filtering, concentrating, crystallizing, washing and drying the filtrate in sequence to obtain a solid lithium dioxalate borate product.
Preferably, the oxalic acid is anhydrous oxalic acid or dihydrate oxalic acid; the boron-containing compound is one or a mixture of two or more of boric acid, diboron trioxide, metaboric acid and pyroboric acid.
Further, the addition amount of oxalic acid and the boron-containing compound is calculated according to the molar ratio of oxalic acid radical ion to boron element; specifically, the molar ratio of the oxalate ion to the boron element is (2-2.2): 1.
Preferably, the polar solvent in the 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 addition amount of the polar solvent is 1 to 5 times of the mass of the boric acid di-oxalate after drying in the step 1).
Further, the moisture content of the polar solvent is controlled to be within 500 ppm.
Preferably, the lithium salt compound is one of anhydrous halogenated lithium salt, lithium hydride and lithium nitride; if the lithium halide is lithium halide, one of lithium fluoride, lithium chloride and lithium bromide is selected;
further, the addition amount of the lithium salt compound is calculated in terms of the molar amount of the boron element in the boron-containing compound; specifically, the molar amount of the lithium salt compound is 1 to 1.1 times the molar amount of the boron element in the boron-containing compound.
The beneficial effects of the invention are as follows:
according to the invention, oxalic acid and a boron-containing compound are adopted to generate an intermediate oxalic acid boric acid, the oxalic acid boric acid cannot be combined with water molecules to form a crystal water complex, and after vacuum drying, the water is thoroughly removed; therefore, the next reaction process of the lithium dioxalate borate and the lithium salt compound is in a nearly anhydrous condition, and water is not generated, so that the hydrolysis caused by the contact of the lithium dioxalate borate product obtained after the reaction and the water can be avoided, and the product yield and purity are improved.
In addition, the excessive lithium salt compound in the reaction raw materials is almost insoluble in the polar solvent, and can be removed by filtration, thereby being beneficial to improving the purity of the final product; the preparation method is simple and convenient in post-treatment after the reaction is finished, and the lithium dioxalate borate product can be obtained through concentration, crystallization, washing and drying.
The whole reaction process of the preparation method has almost no side reaction, the reaction yield is high, the residual quantity of moisture in the obtained product is low, the product is easy to purify, and the product purity is high.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully by reference to the accompanying drawings, in which it is shown, by way of illustration, only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the lithium dioxalate borate in the embodiment 1 comprises the following steps:
(1) 126g (1 mol) of oxalic acid dihydrate and 31g (0.5 mol) of boric acid are taken and added into a three-neck flask with a stirring device, and the reaction raw materials are heated to 55 ℃ under normal pressure and mechanical stirring conditions and react for 2 hours; after decompression, continuously heating to 90 ℃, and vacuum drying at the temperature for 8 hours; obtaining a white honeycomb solid reactant in the flask; in the reaction process, the oxalic acid dihydrate and boric acid generate oxalic acid boric acid;
the reaction formula of the step (1) is as follows:
2H 2 C 2 O 4 .2 H 2 O+H 3 BO 3 →HB(C 2 O 4 ) 2 +5H 2 O
(2) Cooling the reactant obtained in the step (1) to room temperature under nitrogen atmosphere, and weighing to obtain a net weight of 85g; then adding 320g of ethyl acetate with the moisture content of 180ppm into the reactant, and stirring and dissolving for 2 hours;
(3) Filtering the solution obtained in the step (2), slowly adding 21g (0.5 mol) of anhydrous lithium chloride into the filtrate in batches, and stirring and reacting for 8 hours at 25 ℃; in the step (2), under the nearly anhydrous condition, the boric acid of the oxalic acid reacts with anhydrous lithium chloride to generate lithium borate of the oxalic acid; the reaction formula is as follows:
HB(C 2 O 4 ) 2 +LiCl→LiB(C 2 O 4 ) 2 +HCl↑
the hydrogen chloride gas generated in the reaction process escapes, and then is absorbed by water;
(4) After the reaction in the step (3) is finished, the reaction solution is cooled to room temperature, then is filtered, filtrate is concentrated and crystallized, is washed by petroleum ether for a plurality of times, and is dried under vacuum to obtain 81g of solid lithium dioxalate borate product, the yield is 83.5%, the product purity is 99.81%, and the product moisture content is 38ppm.
Example 2
The preparation method of the lithium dioxalate borate in the embodiment 2 comprises the following steps:
(1) 198g (2.2 mol) of anhydrous oxalic acid and 35g (0.5 mol) of diboron trioxide are taken and added into a three-neck flask with a stirring device, and the reaction raw materials are heated to 85 ℃ under normal pressure and mechanical stirring conditions for reaction for 8 hours; after decompression, continuously heating to 200 ℃, and vacuum drying at the temperature for 2 hours; obtaining a white honeycomb solid reactant in the flask; in the reaction process, the oxalic acid dihydrate and boric acid generate oxalic acid boric acid;
(2) Cooling the reactant obtained in the step (1) to room temperature under nitrogen atmosphere, and weighing to obtain a net weight of 178g; then 600g of acetonitrile with the moisture content of 230ppm is added into the reactant, and the mixture is stirred and dissolved for 8 hours;
(3) Filtering the solution obtained in the step (2), adding 28.6g (1.1 mol) of lithium fluoride into the filtrate, and carrying out reflux reaction for 5 hours under stirring; in the step (2), under the nearly anhydrous condition, the lithium oxalato borate reacts with lithium fluoride to generate lithium oxalato borate; after the gas generated in the reaction process escapes, water is adopted for absorption;
(4) After the reaction in the step (3) is finished, the reaction solution is cooled to room temperature, then is filtered, and after the filtrate is concentrated and crystallized, the filtrate is washed for a plurality of times by using dichloromethane, and is dried under vacuum, 159g of solid lithium dioxalate borate product is obtained, the yield is 82%, the purity of the product is 99.79%, and the water content of the product is 32ppm.
Example 3
The preparation method of the lithium dioxalate borate in the embodiment 3 comprises the following steps:
(1) 90g (1 mol) of anhydrous oxalic acid and 31g (0.5 mol) of boric acid are taken and added into a three-neck flask with a stirring device, and the reaction raw materials are heated to 120 ℃ under normal pressure and mechanical stirring conditions and react for 1 hour; after decompression, continuously heating to 160 ℃, and vacuum drying at the temperature for 5 hours; obtaining a white honeycomb solid reactant in the flask; in the reaction process, the oxalic acid dihydrate and boric acid generate oxalic acid boric acid;
(2) Cooling the reactant obtained in the step (1) to room temperature under nitrogen atmosphere, and weighing to obtain a net weight of 90g; then 350g of 1, 4-dioxane with the moisture content of 150ppm is added into the reactant, and stirred and dissolved for 3 hours;
(3) Filtering the solution obtained in the step (2), slowly adding 17.5g (0.5 mol) of lithium nitride into the filtrate in batches, and reacting for 4 hours at 65 ℃ under stirring; in the step (2), under the nearly anhydrous condition, the lithium oxalato borate reacts with lithium fluoride to generate lithium oxalato borate; after the gas generated in the reaction process escapes, water is adopted for absorption;
(4) After the reaction in the step (3) is finished, the reaction solution is cooled to room temperature, then is filtered, and after the filtrate is concentrated and crystallized, the filtrate is washed by dichloroethane for a plurality of times and is dried under vacuum, thus obtaining 76g of solid lithium dioxalate borate product, the yield is 78.4%, the purity of the product is 99.73%, and the water content of the product is 26ppm.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all modifications or equivalent arrangements using the teachings of this invention, or direct or indirect application in other related arts, are included within the scope of this invention.
Claims (5)
1. The preparation method of the lithium dioxalate 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 mechanical stirring, and vacuum drying for 2-8 hours at 60-220 ℃; during the reaction, oxalic acid and a boron-containing compound generate oxalic acid boric acid; the oxalic acid is anhydrous oxalic acid or dihydrate oxalic acid; the boron-containing compound is one or a mixture of two or more of boric acid, diboron trioxide, metaboric acid and pyroboric acid;
the addition amount of oxalic acid and boron-containing compound is calculated according to the molar ratio of oxalic acid radical ion to boron element; the molar ratio of the oxalate ion to the boron element is (2-2.2): 1;
(2) Cooling the reactant obtained in the step (1) to room temperature under the nitrogen atmosphere, then 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 room temperature to reflux temperature; reacting the lithium dioxalate borate with a lithium salt compound under nearly anhydrous conditions to produce lithium dioxalate borate; the lithium salt compound is one of 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;
(4) After the reaction in the step (3) is finished, cooling the reaction liquid to room temperature, filtering, concentrating, crystallizing and drying the filtrate in sequence to obtain a solid lithium dioxalate borate product.
2. The method according to claim 1, wherein the polar solvent in the step (2) is one or a combination of two or more selected from acetonitrile, propionitrile, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl ethyl ketone, 1, 4-dioxane, 1, 4-butyrolactone, and tetrahydrofuran.
3. The method for preparing lithium dioxalate borate according to claim 1, wherein the addition amount of the polar solvent is 1 to 5 times the mass of the dioxalate boric acid after drying in the step 1).
4. The method for producing lithium dioxalate borate according to claim 1, wherein the water content of the polar solvent is controlled to be within 500 ppm.
5. The method for producing lithium dioxalate borate according to claim 1, wherein the addition amount of the lithium salt compound is calculated in terms of 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 the molar amount of the boron element in the boron-containing compound.
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