CN114671899A - Preparation method of lithium bis (oxalato) borate and application of lithium bis (oxalato) borate - Google Patents
Preparation method of lithium bis (oxalato) borate and application of lithium bis (oxalato) borate Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 66
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 65
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- 239000012043 crude product Substances 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 claims description 10
- 239000012024 dehydrating agents Substances 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical group [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 8
- 239000002253 acid Substances 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 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- -1 Lithium tetrafluoroborate Chemical compound 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910011140 Li2C2 Inorganic materials 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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 System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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 bis (oxalato) borate and application of the lithium bis (oxalato) borate. Wherein, the lithium bis (oxalato) borate is prepared by reacting anhydrous oxalic acid, anhydrous lithium oxalate and anhydrous triethyl borate at high temperature. The preparation method of the lithium bis (oxalato) borate comprises the following steps: (1) pre-treating; (2) premixing; (3) carrying out high-temperature reaction; (4) and (5) post-treatment. According to the preparation method of lithium bis (oxalato) borate, the raw materials are pretreated to remove water before high-temperature reaction, water is prevented from being introduced in the high-temperature reaction and the post-treatment, and the side reaction of the product and the water can be obviously reduced, so that the purity and the yield of the synthesized lithium bis (oxalato) borate are improved, the purity can reach 99.9%, the yield can reach 90%, and the water content is less than 100 ppm.
Description
Technical Field
The invention relates to the technical field of compound synthesis, in particular to a preparation method of lithium bis (oxalato) borate and application of the lithium bis (oxalato) borate.
Background
The lithium ion battery is mainly composed of a battery shell, a positive electrode material, a diaphragm, a negative electrode material and electrolyte, wherein the electrolyte is one of important components of the battery, plays a role in transmitting lithium ions between the positive electrode material and the negative electrode material of the battery, and has important influence on the capacity, the cycle performance and the safety of the battery. The electrolyte mainly comprises a nonaqueous organic solvent and a lithium salt. In addition, in order to improve the performance of the battery, auxiliary additives such as film forming additives, flame retardant additives, lithium supplement agents and the like are often added into the electrolyte.
Lithium salts currently comprise predominantly lithium perchlorate (LiClO)4) Lithium tetrafluoroborate (LiBF)4) Lithium hexafluorophosphate (LiPF)6) Lithium hexafluoroarsenate (LiAsF)6) Etc. of which LiPF6Is the most main electrolyte lithium salt currently applied to commercial lithium ion batteries, but LiPF6The thermal stability of the electrolyte is poor, the electrolyte starts to decompose to generate hydrofluoric acid when the temperature exceeds 70 ℃, the hydrofluoric acid can seriously corrode a positive electrode material in the battery, metal of the positive electrode material is dissolved, irreversible damage is caused to the performance of the battery, and in addition, the hydrofluoric acid has great harm to human bodies and the environment.
The molecular formula of lithium bis (oxalato) borate (LiBOB) is LiB (C)2O4)2. It is a possible substitute for LiPF in the novel lithium salts currently being researched and developed6The electrolyte is widely applied to the electrolyte of a commercial lithium ion battery, and can be used as an additive with low content. The structural formula is shown as follows.
Lithium bis (oxalato) borate (LiBOB) as a novel lithium salt has the following advantages:
(1) has a wider electrochemical window (more than 4.5V), so that the electrochemical window can not react with positive and negative electrode materials in the charge and discharge processes of the battery.
(2) Compared with the thermal instability of lithium hexafluorophosphate, the thermal stability of lithium bis (oxalato) borate (LiBOB) is good, the decomposition temperature is up to 302 ℃, fluorine elements are not contained in the molecules, and the thermal decomposition product is B2O3And CO2Is friendly to human body and environment.
(3) Has good solubility and higher conductivity, and the solubility in a plurality of organic solvents such as DMF, DMSO, DME, AN, PC, GBL and the like can reach 1 mol/L. The conductivity of the 1mol/L LiBOB/DME solution at 25 ℃ is 14.9mS/cm, and the conductivity of the 1mol/L LiBOB/AN solution is more up to 25.2 mS/cm.
At present, the synthesis method of lithium bis (oxalato) borate (LiBOB) mainly comprises a solution method and a solid phase method. For example, lithium oxalate or lithium hydroxide is used as a lithium source, oxalic acid and boric acid are combined, and water or THF is used as a solvent for reaction, so that the synthesis of LiBOB is realized. However, water is produced in the reaction process, and LiBOB and water react at high temperature, so that the obtained product has low purity and high water content, and the use requirement of the LiBOB as electrolyte lithium salt or an additive cannot be met. The use of LiB (OCH) is also available to the practitioner3)4And (CH)3)3SiOOCCOOSi(CH3)3Raw material, using acetonitrile as reaction solvent to obtain LiBOB, but the method has the following disadvantages: (1) raw material LiB (OCH)3)4And (CH)3)3SiOOCCOOSi(CH3)3Are not easy to obtain and are not suitable for industrialization; (2) the reaction is accompanied by a large amount of CH3OSi(CH3)3By-products, the atom economy of the reaction is poor. Therefore, the technical problem to be solved by the technical staff in the field is to provide a preparation method for synthesizing lithium bis (oxalato) borate with high efficiency and low cost, and the purity, the moisture content and the acid value of the preparation method all need to meet the use requirements of the lithium salt of the electrolyte.
Disclosure of Invention
Based on the above problems, the present invention aims to provide a preparation method of lithium bis (oxalato) borate and an application thereof, wherein the preparation method has characteristics of rapid synthesis efficiency, high yield, few purification steps, low equipment requirement, high purity of the prepared lithium bis (oxalato) borate, low moisture, and capability of satisfying the use requirement of lithium salt.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing lithium bis (oxalato) borate, comprising the steps of:
(1) pretreatment of
Pre-treating oxalic acid dihydrate to obtain anhydrous oxalic acid with the water content of less than or equal to 100ppm, pre-treating lithium oxalate to obtain anhydrous lithium oxalate with the water content of less than or equal to 50ppm, and pre-treating triethyl borate to obtain anhydrous triethyl borate with the water content of less than or equal to 100 ppm;
(2) premixing
Mixing the anhydrous lithium oxalate, the anhydrous oxalic acid and the anhydrous triethyl borate according to a molar ratio of 1: 3.0-3.5: 2.0-2.5 to obtain a premix;
(3) high temperature reaction
Carrying out high-temperature reaction on the premix in two steps, heating to 120 +/-10 ℃ for 3-4 h in the first step, heating to 240 +/-10 ℃ for 4-5 h in the second step, and cooling to room temperature in a nitrogen atmosphere after complete reaction to obtain a lithium bis (oxalato) borate crude product;
(4) post-treatment
Dissolving the lithium bis (oxalato) borate crude product by adopting an anhydrous nitrile solvent, and then sequentially filtering, concentrating, crystallizing and drying.
According to the preparation method of lithium bis (oxalato) borate, the raw materials are pretreated for dehydration before high-temperature reaction, water is prevented from being introduced in the high-temperature reaction and the post-treatment, the side reaction of the product and water can be obviously reduced, and the acid value can also be reduced, so that the purity and the yield of the synthesized lithium bis (oxalato) borate are improved, the purity can reach 99.9%, the yield can reach 90%, and the water content is less than 100 ppm. And when the reaction is carried out at a high temperature, the raw materials are fully fused by the low-temperature reaction, the volatilization and decomposition of the anhydrous oxalic acid and the anhydrous triethyl borate in the raw materials are reduced, then the temperature is raised to form a bond to form LiBOB crystals, and the product ethanol is volatilized out of the reaction system to promote the reaction.
Preferably, the oxalic acid dihydrate is dehydrated and dried in a forced air drying oven to obtain anhydrous oxalic acid, the temperature of the dehydration and drying is 95 +/-5 ℃, the time is 24-48 hours, the lithium oxalate is dried in vacuum to obtain anhydrous lithium oxalate, and the temperature of the vacuum drying is 120 +/-5 ℃, and the time is 8-12 hours.
Preferably, the anhydrous triethyl borate can be obtained by drying and dehydrating the triethyl borate by using a dehydrating agent.
Preferably, the drying and dehydration step includes adding a dehydrating agent into the triethyl borate, adding the dehydrating agent into the triethyl borate, standing for 3-6 hours, filtering, and distilling the filtrate under reduced pressure to obtain anhydrous triethyl borate.
Preferably, the dehydrating agent is anhydrous magnesium sulfate, anhydrous calcium chloride, anhydrous sodium sulfate or a molecular sieve.
Preferably, the pre-mixed feeding sequence is to sequentially feed the anhydrous oxalic acid, the anhydrous lithium oxalate and the anhydrous triethyl borate, or to sequentially feed the anhydrous lithium oxalate, the anhydrous oxalic acid and the anhydrous triethyl borate.
Preferably, the rates of the first-step heating and the second-step heating are respectively 5-10 ℃/min independently.
Preferably, the anhydrous nitrile solvent is anhydrous acetonitrile, anhydrous glutaronitrile or anhydrous adiponitrile.
Preferably, the crystallization temperature of the concentrated crystallization is-30 to 10 ℃, and the crystallization time is 1 to 3 hours.
The invention provides application of lithium bis (oxalato) borate, and the lithium bis (oxalato) borate prepared by the preparation method of the lithium bis (oxalato) borate is used as a lithium salt or an additive of a lithium ion battery. The lithium bis (oxalato) borate has high purity and yield, and is favorable for popularization and application in lithium ion batteries.
Detailed Description
The lithium bis (oxalato) borate is prepared by reacting anhydrous oxalic acid, anhydrous lithium oxalate and anhydrous triethyl borate at high temperature, and the chemical reaction formula is shown as follows.
3H2C2O4+Li2C2O4+2B(OC2H5)3＝2LiBC4O8+6C2H5OH
The preparation method of the lithium bis (oxalato) borate comprises the following steps: (1) pre-treating; (2) premixing; (3) carrying out high-temperature reaction; (4) and (5) post-treatment.
The step (1) of pretreatment comprises the step of pretreating oxalic acid dihydrate to obtain anhydrous oxalic acid with the water content of less than or equal to 100ppm, specifically, the anhydrous oxalic acid is obtained by dehydrating and drying the oxalic acid dihydrate in a forced air drying oven, the temperature of dehydration and drying is 95 +/-5 ℃, and the time is 24-48 hours. The lithium oxalate is pretreated to obtain anhydrous lithium oxalate with the water content of less than or equal to 50ppm, and specifically, the anhydrous lithium oxalate can be obtained through vacuum drying of the lithium oxalate at the temperature of 120 +/-5 ℃ for 8-12 hours. Pretreating triethyl borate to obtain anhydrous triethyl borate with water content less than or equal to 100 ppm. Adding a dehydrating agent into the triethyl borate, standing for 3-6 h, filtering, and distilling the filtrate under reduced pressure to obtain anhydrous triethyl borate, wherein the dehydrating agent is anhydrous magnesium sulfate, anhydrous calcium chloride, anhydrous sodium sulfate or a molecular sieve.
The pre-mixing step (2) comprises the step of mixing anhydrous lithium oxalate, anhydrous oxalic acid and anhydrous triethyl borate according to a molar ratio of 1: 3.0-3.5: 2.0-2.5 to obtain a premix, wherein the preferred molar ratio is 1:3: 2. The pre-mixed addition sequence can be the sequential addition of anhydrous oxalic acid, anhydrous lithium oxalate and anhydrous triethyl borate, or the sequential addition of anhydrous lithium oxalate, anhydrous oxalic acid and anhydrous triethyl borate.
And (3) performing high-temperature reaction on the premix in two steps, heating to 120 +/-10 ℃ in the first step for reaction for 3-4 h, heating to 240 +/-10 ℃ in the second step for reaction for 4-5 h, and cooling to room temperature in a nitrogen atmosphere after complete reaction to obtain a lithium bis (oxalato) borate crude product. The high temperature reaction may transfer the premix to a crucible and place it in a muffle furnace. The rates of the first-step temperature rise and the second-step temperature rise are respectively 5-10 ℃/min independently.
And (4) the post-treatment of the step (4) comprises the steps of dissolving the lithium bis (oxalato) borate crude product by adopting an anhydrous nitrile solvent, and then sequentially filtering, concentrating, crystallizing and drying. Wherein the anhydrous nitrile solvent is anhydrous Acetonitrile (AN), anhydrous Glutaronitrile (GN) or anhydrous adiponitrile. The crystallization temperature of the concentrated crystallization is-30-10 ℃, and the crystallization time is 1-3 h. And drying in a vacuum oven at the drying temperature of 120-150 ℃ for 7-8 h.
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is to further explain the invention, and should not be construed as a limitation of the invention.
Example 1
The preparation method of the lithium bis (oxalato) borate comprises the following steps:
(1) pretreatment of
Placing oxalic acid dihydrate in a blast oven for drying at the temperature of 95 ℃ for 24 hours to obtain anhydrous oxalic acid, and detecting the moisture of the anhydrous oxalic acid by a Karl Fischer moisture meter to obtain 60ppm moisture; placing lithium oxalate in a blast oven, setting the temperature at 120 ℃, drying for 10 hours to obtain anhydrous lithium oxalate, and testing the moisture content of the anhydrous lithium oxalate by using a Karl Fischer moisture meter to obtain 50 ppm; adding anhydrous magnesium sulfate into triethyl borate, standing for 4.5h, filtering to obtain filtrate, distilling the filtrate under reduced pressure to obtain anhydrous triethyl borate, and measuring the water content to be 90ppm by using a Karl Fischer moisture meter.
(2) Premixing
25.5g of anhydrous lithium oxalate, 67.5g of anhydrous oxalic acid and 73g of anhydrous triethyl borate are sequentially added into a 500ml three-neck flask, and the mixture is stirred mechanically at room temperature for 15min and mixed uniformly to obtain the premix.
(3) High temperature reaction
Transferring the premix into a 500ml ceramic crucible, then putting the ceramic crucible into a muffle furnace, setting a heating program, heating from normal temperature to 120 ℃ for reaction for 4h at a heating rate of 10 ℃/min, then heating from 120 ℃ to 240 ℃ for reaction for 5h at a heating rate of 5 ℃/min, and cooling to room temperature under a nitrogen atmosphere after the reaction is completed to obtain a lithium bis (oxalato) borate crude product.
(4) Post-treatment
Adding 400g of anhydrous acetonitrile into the lithium bis (oxalato) borate crude product for dissolving, and filtering out insoluble solids to obtain clear and transparent filtrate; concentrating the filtrate at 50 ℃ under reduced pressure until LiBOB: AN is 1:2.5 (weight ratio), cooling for crystallization at-10 ℃ for 2h, and sealing and filtering to obtain a lithium bis (oxalato) borate wet product; and (3) drying the lithium bis (oxalate) borate wet product in a vacuum oven at the drying temperature of 150 ℃ for 8 hours to finally obtain 89.1g of lithium bis (oxalate) borate. The yield was 92%, the purity was 99.6%, the water content was 50ppm, and the acid value was 60 ppm.
Example 2
The preparation method of the lithium bis (oxalato) borate comprises the following steps:
(1) pretreatment of
Placing oxalic acid dihydrate in a blast oven for drying at the temperature of 95 ℃ for 20 hours to obtain anhydrous oxalic acid, and detecting the moisture of the anhydrous oxalic acid by a Karl Fischer moisture meter to obtain 80ppm moisture; placing lithium oxalate in a blast oven, setting the temperature at 120 ℃, drying for 6 hours to obtain anhydrous lithium oxalate, and testing the moisture content of the anhydrous lithium oxalate by using a Karl Fischer moisture meter to obtain 90 ppm; adding anhydrous sodium sulfate into triethyl borate, standing for 4.5h, filtering to obtain filtrate, distilling the filtrate under reduced pressure to obtain anhydrous triethyl borate, and measuring the water content of the anhydrous triethyl borate to be 80ppm by using a Karl Fischer moisture meter.
(2) Premixing
25.5g of anhydrous lithium oxalate, 67.5g of anhydrous oxalic acid and 73g of anhydrous triethyl borate are sequentially added into a 500ml three-neck flask, and the mixture is stirred mechanically at room temperature for 15min and mixed uniformly to obtain the premix.
(3) High temperature reaction
Transferring the premix into a 500ml ceramic crucible, then putting the ceramic crucible into a muffle furnace, setting a heating program, heating from normal temperature to 120 ℃ for reaction for 5h, wherein the heating rate is 10 ℃/min, then heating from 120 ℃ to 240 ℃ for reaction for 3h, the heating rate is 10 ℃/min, and cooling to room temperature in a nitrogen atmosphere after the reaction is completed to obtain the lithium bis (oxalato) borate crude product.
(4) Post-treatment
Adding 400g of anhydrous acetonitrile into the lithium bis (oxalato) borate crude product for dissolving, and filtering out insoluble solids to obtain clear and transparent filtrate; concentrating the filtrate at 50 ℃ under reduced pressure until LiBOB: AN is 1:2.5 (weight ratio), cooling for crystallization at-10 ℃ for 2.5h, and sealing and filtering to obtain a lithium bis (oxalate) borate wet product; and (3) drying the lithium bis (oxalate) borate wet product in a vacuum oven at the drying temperature of 150 ℃ for 8 hours to finally obtain 87.2g of lithium bis (oxalate) borate. The yield was 90%, the purity was 99.5%, the water content was 70ppm, and the acid value was 90 ppm.
Example 3
The preparation method of the lithium bis (oxalato) borate comprises the following steps:
(1) pretreatment of
Placing oxalic acid dihydrate in a blast oven for drying at the temperature of 95 ℃ for 18h to obtain anhydrous oxalic acid, and detecting the moisture of the anhydrous oxalic acid by a Karl Fischer moisture meter to obtain the anhydrous oxalic acid with the moisture of 100 ppm. Placing lithium oxalate in a blast oven, setting the temperature at 120 ℃, drying for 5 hours to obtain anhydrous lithium oxalate, and testing the moisture content of the anhydrous lithium oxalate by using a Karl Fischer moisture meter to be 95 ppm; adding anhydrous magnesium sulfate into triethyl borate, standing for 3h, filtering to obtain filtrate, distilling the filtrate under reduced pressure to obtain anhydrous triethyl borate, and measuring the water content to 97ppm by using a Karl Fischer moisture meter.
(2) Premixing
67.5g of anhydrous oxalic acid, 25.5g of anhydrous lithium oxalate and 73g of anhydrous triethyl borate are sequentially added into a 500ml three-neck flask, and the mixture is stirred mechanically at room temperature for 15min and mixed uniformly to obtain the premix.
(3) High temperature reaction
Transferring the premix into a 500ml ceramic crucible, then putting the ceramic crucible into a muffle furnace, setting a heating program, heating from normal temperature to 120 ℃ for reaction for 3h, wherein the heating rate is 10 ℃/min, then heating from 120 ℃ to 240 ℃ for reaction for 3h, the heating rate is 10 ℃/min, and cooling to room temperature in a nitrogen atmosphere after the reaction is completed to obtain the lithium bis (oxalato) borate crude product.
(4) Post-treatment
Adding 400g of anhydrous glutaronitrile into the lithium bis (oxalato) borate crude product for dissolving, and filtering out insoluble solids to obtain clear and transparent filtrate; concentrating the filtrate at 50 ℃ under reduced pressure until LiBOB: GN is 1:2.5 (weight ratio), cooling for crystallization at-10 ℃ for 2h, and sealing and filtering to obtain a lithium bis (oxalato) borate wet product; and (3) drying the lithium bis (oxalato) borate wet product in a vacuum oven at the drying temperature of 150 ℃ for 8 hours to finally obtain 92g of lithium bis (oxalato) borate refined product. The yield was 95%, the purity was 99.6%, the water content was 80ppm, and the acid value was 30 ppm.
Comparative example 1
The preparation method of the lithium bis (oxalato) borate comprises the following steps:
(1) pretreatment of
Placing oxalic acid dihydrate in a blast oven for drying at the temperature of 95 ℃ for 24 hours to obtain anhydrous oxalic acid, and detecting the moisture of the anhydrous oxalic acid by a Karl Fischer moisture meter to obtain 60ppm moisture; placing lithium oxalate in a blast oven, setting the temperature at 120 ℃, drying for 10 hours to obtain anhydrous lithium oxalate, and testing the moisture content of the anhydrous lithium oxalate by using a Karl Fischer moisture meter to obtain 50 ppm; anhydrous magnesium sulfate was added to triethyl borate, the mixture was allowed to stand for 4.5 hours, and then the filtrate was filtered to obtain anhydrous triethyl borate, which was measured to have a water content of 90ppm by a Karl Fischer moisture meter.
(2) Premixing
25.5g of anhydrous lithium oxalate, 67.5g of anhydrous oxalic acid and 73g of anhydrous triethyl borate are sequentially added into a 500ml three-neck flask, and the mixture is stirred mechanically at room temperature for 15min and mixed uniformly to obtain the premix.
(3) High temperature reaction
And transferring the premix into a 500ml ceramic crucible, then putting the ceramic crucible into a muffle furnace, raising the temperature from the normal temperature to 240 ℃ for reaction for 9h, wherein the heating rate is 5 ℃/min, and cooling to the room temperature in a nitrogen atmosphere after the reaction is completed to obtain a crude lithium bis (oxalato) borate.
(4) Post-treatment
Adding 400g of anhydrous acetonitrile into the lithium bis (oxalato) borate crude product for dissolving, and filtering out insoluble solids to obtain clear and transparent filtrate; concentrating the filtrate at 50 ℃ under reduced pressure until LiBOB: AN is 1:2.5 (weight ratio), cooling for crystallization at-10 ℃ for 2h, and sealing and filtering to obtain a lithium bis (oxalato) borate wet product; and (3) drying the lithium bis (oxalate) borate wet product in a vacuum oven at the drying temperature of 150 ℃ for 8 hours to finally obtain 85.3g of lithium bis (oxalate) borate. The yield was 80%, the purity was 98.6%, the water content was 100ppm, and the acid value was 120 ppm.
As can be seen from comparison of examples 1-3 with comparative example 1, the lithium bis (oxalato) borate obtained by the stepwise reaction has higher yield and purity and lower water content and acid value.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it is not limited to the embodiments, and those skilled in the art should understand that the technical solutions of the present invention can be modified or substituted with equivalents without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the lithium bis (oxalato) borate is characterized by comprising the following steps:
(1) pretreatment of
Pre-treating oxalic acid dihydrate to obtain anhydrous oxalic acid with the water content of less than or equal to 100ppm, pre-treating lithium oxalate to obtain anhydrous lithium oxalate with the water content of less than or equal to 50ppm, and pre-treating triethyl borate to obtain anhydrous triethyl borate with the water content of less than or equal to 100 ppm;
(2) premixing
Mixing the anhydrous lithium oxalate, the anhydrous oxalic acid and the anhydrous triethyl borate according to a molar ratio of 1: 3.0-3.5: 2.0-2.5 to obtain a premix;
(3) high temperature reaction
Carrying out high-temperature reaction on the premix in two steps, heating to 120 +/-10 ℃ for 3-4 h in the first step, heating to 240 +/-10 ℃ for 4-5 h in the second step, and cooling to room temperature in a nitrogen atmosphere after complete reaction to obtain a lithium bis (oxalato) borate crude product;
(4) post-treatment
Dissolving the lithium bis (oxalato) borate crude product by adopting an anhydrous nitrile solvent, and then sequentially filtering, concentrating, crystallizing and drying.
2. The method for preparing lithium bis (oxalato) borate according to claim 1, wherein the oxalic acid dihydrate is dehydrated and dried in a forced air drying oven to obtain anhydrous oxalic acid, the temperature of the dehydration and drying is 95 +/-5 ℃ for 24-48 h, the lithium oxalate is vacuum-dried to obtain anhydrous lithium oxalate, and the temperature of the vacuum-drying is 120 +/-5 ℃ for 8-12 h.
3. The method for preparing lithium bis (oxalato) borate according to claim 1, wherein the anhydrous triethyl borate is obtained by drying and dehydrating triethyl borate with a dehydrating agent.
4. The preparation method of lithium bis (oxalato) borate as claimed in claim 3, wherein the drying and dehydration step comprises adding a dehydrating agent into the triethyl borate, standing for 3-6 h, filtering, and distilling the filtrate under reduced pressure to obtain anhydrous triethyl borate.
5. The method for preparing lithium bis (oxalato) borate according to claim 3, wherein the dehydrating agent is anhydrous magnesium sulfate, anhydrous calcium chloride, anhydrous sodium sulfate or a molecular sieve.
6. The method for preparing lithium bis (oxalato) borate according to claim 1, wherein the pre-mixed addition sequence is to add the anhydrous oxalic acid, the anhydrous lithium oxalate and the anhydrous triethyl borate in this order, or to add the anhydrous lithium oxalate, the anhydrous oxalic acid and the anhydrous triethyl borate in this order.
7. The method for preparing lithium bis (oxalato) borate according to claim 1, wherein the first temperature rise and the second temperature rise are each independently at a rate of 5 to 10 ℃/min.
8. The method for producing lithium bis (oxalato) borate according to claim 1, wherein the anhydrous nitrile solvent is anhydrous acetonitrile, anhydrous glutaronitrile or anhydrous adiponitrile.
9. The method for preparing lithium bis (oxalato) borate according to claim 1, wherein the crystallization temperature of the concentrated crystals is-30 to 10 ℃, and the crystallization time is 1 to 3 hours.
10. The application of the lithium bis (oxalato) borate is characterized in that the lithium bis (oxalato) borate prepared by the preparation method of the lithium bis (oxalato) borate according to any one of claims 1 to 9 is used as a lithium salt or an additive of a lithium ion battery.
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| PCT/CN2022/097324 WO2023184704A1 (en) | 2022-03-28 | 2022-06-07 | Preparation method for lithium bis(oxalato)borate and use thereof |
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| WO2023184704A1 (en) * | 2022-03-28 | 2023-10-05 | 珠海市赛纬电子材料股份有限公司 | Preparation method for lithium bis(oxalato)borate and use thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6506516B1 (en) * | 1998-06-30 | 2003-01-14 | Metallgesellschaft Aktiengesellschaft | Lithium bisoxalatoborate, the production thereof and its use as a conducting salt |
| CN103951689A (en) * | 2014-05-16 | 2014-07-30 | 北京化学试剂研究所 | Preparation method of liquid lithium bisoxalate borate |
| CN109232629A (en) * | 2018-11-28 | 2019-01-18 | 湖南科霸汽车动力电池有限责任公司 | The preparation method of di-oxalate lithium borate |
| CN109734734A (en) * | 2018-12-18 | 2019-05-10 | 朝阳光达化工有限公司 | A kind of preparation method of dioxalic acid lithium borate |
| KR20190096154A (en) * | 2018-02-08 | 2019-08-19 | 리켐주식회사 | Synthetic Method of Lithium bisoxalatoborate |
| CN111138464A (en) * | 2019-12-27 | 2020-05-12 | 合肥利夫生物科技有限公司 | Preparation method of lithium oxalato borate |
| CN111943970A (en) * | 2020-09-03 | 2020-11-17 | 江苏华盛锂电材料股份有限公司 | Preparation method of lithium oxalato borate |
| CN112409393A (en) * | 2020-12-11 | 2021-02-26 | 临沂小篆新材料科技有限公司 | Process for preparing lithium bis (oxalato) borate |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6506516B1 (en) * | 1998-06-30 | 2003-01-14 | Metallgesellschaft Aktiengesellschaft | Lithium bisoxalatoborate, the production thereof and its use as a conducting salt |
| CN103951689A (en) * | 2014-05-16 | 2014-07-30 | 北京化学试剂研究所 | Preparation method of liquid lithium bisoxalate borate |
| KR20190096154A (en) * | 2018-02-08 | 2019-08-19 | 리켐주식회사 | Synthetic Method of Lithium bisoxalatoborate |
| CN109232629A (en) * | 2018-11-28 | 2019-01-18 | 湖南科霸汽车动力电池有限责任公司 | The preparation method of di-oxalate lithium borate |
| CN109734734A (en) * | 2018-12-18 | 2019-05-10 | 朝阳光达化工有限公司 | A kind of preparation method of dioxalic acid lithium borate |
| CN111138464A (en) * | 2019-12-27 | 2020-05-12 | 合肥利夫生物科技有限公司 | Preparation method of lithium oxalato borate |
| CN111943970A (en) * | 2020-09-03 | 2020-11-17 | 江苏华盛锂电材料股份有限公司 | Preparation method of lithium oxalato borate |
| CN112409393A (en) * | 2020-12-11 | 2021-02-26 | 临沂小篆新材料科技有限公司 | Process for preparing lithium bis (oxalato) borate |
Non-Patent Citations (1)
| Title |
|---|
| 叶彦春等主编, 北京 北京理工大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023184704A1 (en) * | 2022-03-28 | 2023-10-05 | 珠海市赛纬电子材料股份有限公司 | Preparation method for lithium bis(oxalato)borate and use thereof |
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