CN114057784B - Preparation method of lithium bis (oxalato) borate - Google Patents
Preparation method of lithium bis (oxalato) borate Download PDFInfo
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- CN114057784B CN114057784B CN202210046132.2A CN202210046132A CN114057784B CN 114057784 B CN114057784 B CN 114057784B CN 202210046132 A CN202210046132 A CN 202210046132A CN 114057784 B CN114057784 B CN 114057784B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 74
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 90
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004327 boric acid Substances 0.000 claims abstract description 30
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 30
- 238000001694 spray drying Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 239000002270 dispersing agent Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 63
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 45
- 238000001035 drying Methods 0.000 claims description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 17
- 238000002390 rotary evaporation Methods 0.000 claims description 15
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical group [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 6
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 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 39
- 239000012043 crude product Substances 0.000 description 24
- 239000007787 solid Substances 0.000 description 24
- 239000002245 particle Substances 0.000 description 23
- 238000005303 weighing Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 11
- 238000004064 recycling Methods 0.000 description 11
- 239000012528 membrane Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000000889 atomisation Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000003825 pressing Methods 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic 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 provides a preparation method of lithium bis (oxalato) borate, belonging to the technical field of special chemicals. The method comprises the following steps: 1) mixing a lithium source, boric acid, oxalic acid, water and a dispersing agent to obtain a mixed material; 2) spray drying the mixed material to obtain a precursor of the lithium bis (oxalato) borate; 3) and (3) reacting the precursor of the lithium bis (oxalato) borate at the temperature of 200-260 ℃ for 2-4 h to obtain the lithium bis (oxalato) borate. The preparation method provided by the invention has the advantages of high reaction efficiency and high yield, and the prepared lithium bis (oxalato) borate has low water content, high purity and uniform granularity.
Description
Technical Field
The invention belongs to the technical field of special chemicals, and particularly relates to a preparation method of lithium bis (oxalato) borate.
Background
The lithium borate complex is a novel lithium ion battery electrolyte, wherein lithium bis (oxalato) borate (LiBOB) is the most representative. The lithium bis (oxalato) borate is a coordination chelate, and the formed electrolyte has larger anions and smaller lattice energy, and can obtain more ions in a solvent, so that the conductivity of the electrolyte is improved. The lithium bis (oxalato) borate has good electrochemical stability and thermal stability, can react with a specific solvent to form a stable SEI film, can not attenuate energy after multiple cycles, has higher thermal stability compared with lithium hexafluorophosphate, and a decomposed product B2O3And CO2The electrolyte has little influence on the service performance and the environment of the battery, and is an electrolyte substance with development potential in the lithium battery industry.
The lithium bis (oxalato) borate synthesis methods include an aqueous phase method, a solid phase method and a solvent method. The solvent method adopts an organic solvent as a reaction medium, increases the cost of raw materials and has pollution to the environment. The aqueous phase method needs long time for removing water, and has long reaction time and low efficiency. Patent CN109232629A discloses a method for synthesizing lithium bis (oxalato) borate by a solid phase method, wherein raw materials are mixed by ball milling, which easily results in uneven mixing of raw materials and long reaction time. Therefore, how to improve the efficiency of synthesis and reduce the synthesis time is a key challenge in the current work.
Disclosure of Invention
The invention provides a preparation method of lithium bis (oxalato) borate, which has the advantages of high reaction efficiency and high yield, and the prepared lithium bis (oxalato) borate has low water content, high purity and uniform particle size.
In order to achieve the above object, the present invention provides a method for preparing lithium bis (oxalato) borate, comprising the steps of:
1) mixing a lithium source, boric acid, oxalic acid, water and a dispersing agent to obtain a mixed material;
2) spray drying the mixed material to obtain a precursor of the lithium bis (oxalato) borate;
3) and (3) reacting the precursor of the lithium bis (oxalato) borate at the temperature of 200-260 ℃ for 2-4 h to obtain the lithium bis (oxalato) borate.
Preferably, the molar ratio of the lithium source to the boric acid to the oxalic acid is 1:1:2 to 1:1: 2.3.
Preferably, the dispersing agent is phosphate, and the dispersing agent is 1-5% of the total mass of the lithium source, the boric acid and the oxalic acid.
Preferably, the water accounts for 5-8 times of the total mass of the lithium source, the boric acid and the oxalic acid.
Preferably, the feeding speed during spray drying is 200-500L/h, the pressure is 0.5-2 MPa, and the temperature is 100-120 ℃.
Preferably, the lithium source is lithium hydroxide and/or lithium carbonate.
Preferably, the preparation method further comprises the steps of dissolving the lithium bis (oxalate) borate in an organic solvent, filtering, rotary evaporating and drying.
Preferably, the organic solvent comprises one or more of acetonitrile, ethyl acetate, dimethyl carbonate and diethyl carbonate.
Preferably, the temperature of the rotary evaporation is 30-50 ℃, and the pressure is 0.05-0.5 MPa.
Preferably, the drying temperature is 115-125 ℃.
Compared with the prior art, the invention has the advantages and positive effects that:
according to the preparation method of lithium bis (oxalato) borate, provided by the invention, a lithium source, boric acid and oxalic acid are mixed in water and mixed in a liquid phase manner, raw materials can be fully mixed, and meanwhile, a dispersing agent is added, so that the raw materials are more fully mixed, and element imbalance can not be caused during spray drying. The materials which are uniformly mixed are dehydrated and then reacted, so that the reaction process is accelerated, the reaction time is shortened, and the subsequent dehydration difficulty is reduced. Finally, the lithium bis (oxalato) borate with uniform particle size is obtained, and the purity and the yield are high.
Drawings
Fig. 1 is a comparison graph of XRD and commercial XRD of a lithium bis (oxalato) borate finished product prepared using the method for preparing lithium bis (oxalato) borate in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
The invention provides a preparation method of lithium bis (oxalato) borate, which comprises the following steps:
1) mixing a lithium source, boric acid, oxalic acid, water and a dispersing agent to obtain a mixed material;
2) spray drying the mixed material to obtain a precursor of the lithium bis (oxalato) borate;
3) and (3) reacting the precursor of the lithium bis (oxalato) borate at the temperature of 200-260 ℃ for 2-4 h to obtain the lithium bis (oxalato) borate.
According to the invention, a lithium source, boric acid, oxalic acid, water and a dispersing agent are mixed to obtain a mixed material. In the present invention, the lithium source is preferably lithium hydroxide and/or lithium carbonate. In the present invention, the dispersant is preferably a phosphate salt, more preferably sodium tripolyphosphate, sodium hexametaphosphate, or sodium pyrophosphate. The dispersing agent is preferably 1-5% of the total mass of the lithium source, the boric acid and the oxalic acid, and more preferably 3-4%. In the present invention, the molar ratio of the lithium source, boric acid and oxalic acid is preferably 1:1:2 to 1:1: 2.3. In the invention, the water is preferably 5-8 times of the total mass of the lithium source, the boric acid and the oxalic acid.
The sources of the lithium source, boric acid and oxalic acid, water and dispersant are not particularly limited in the present invention, and conventional commercial products in the art may be used.
After the mixed material is obtained, the mixed material is subjected to spray drying to obtain the lithium bis (oxalato) borate precursor. In the invention, the feeding speed during spray drying is preferably 200-500L/h, the pressure is preferably 0.5-2 MPa, and the temperature is preferably 100-120 ℃. In the invention, the shape and the particle size of the lithium bis (oxalato) borate can be regulated and controlled by adopting spray drying, and different particle sizes have different influences on the material performance. In the invention, when spray drying is carried out under the conditions of pressure of 0.5-2 MPa and temperature of 100-120 ℃, the particle size can be controlled within the range of 50-600 nm, the particle size gradually increases along with the increase of pressure and the decrease of temperature in the range, and the specific particle size is shown in Table 1. The invention adopts spray drying, so that the particle size of the prepared lithium bis (oxalato) borate is more uniform, thereby being beneficial to improving the conductivity. After the precursor of the lithium bis (oxalato) borate is obtained, the precursor of the lithium bis (oxalato) borate preferably reacts for 2-4 hours at 200-260 ℃ to obtain the lithium bis (oxalato) borate. In the invention, the reaction temperature is preferably 230-240 ℃; the reaction time is preferably 2.5-3 h.
TABLE 1 particle size ranges for lithium bis (oxalato) borate
According to the invention, the lithium source, the boric acid and the oxalic acid are mixed in water and are mixed in a liquid phase manner, the raw materials can be fully mixed, and meanwhile, the dispersing agent is added, so that the raw materials are more fully mixed, and the element imbalance can not be caused during spray drying. And (4) carrying out spray drying on the uniformly mixed materials, and carrying out high-temperature reaction after the drying is finished. Compared with a direct high-temperature solid-phase synthesis method, the lithium bis (oxalato) borate synthesized by the method has obvious advantages, the problem of uneven mixing of materials in the high-temperature solid-phase method is solved by adding the dispersing agent into the water phase for mixing, the particle size of the materials is controlled by adjusting the spray drying pressure and temperature parameters, and the materials synthesized by spray drying are dry powder, so that a large amount of reaction time is saved.
After the lithium bis (oxalato) borate is obtained, the invention preferably further comprises the step of removing impurities; the further impurity removal preferably comprises: dissolving lithium bis (oxalato) borate by using an organic solvent, filtering, rotary evaporating and drying.
In the present invention, the organic solvent preferably includes one or more of acetonitrile, ethyl acetate, dimethyl carbonate and diethyl carbonate. In the invention, the rotary evaporation temperature is preferably 30-50 ℃, and the pressure is preferably 0.05-0.5 MPa. In the invention, the drying temperature is preferably 115-125 ℃, and more preferably 120 ℃.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing 7.18g of lithium hydroxide, 18.54g of boric acid, 53.99g of oxalic acid and 2.39g of sodium hexametaphosphate dispersant, putting into a container filled with 460g of deionized water, stirring uniformly, preparing a powdery lithium bis (oxalate) borate precursor material by spray drying (spray drying atomization pressure is 2MPa, feeding speed is 200L/h, temperature is 100 ℃), transferring the lithium bis (oxalate) borate precursor into a muffle furnace, heating at 240 ℃ for 2h under atmospheric atmosphere to obtain a crude product of lithium bis (oxalate) borate, dissolving the obtained crude product with acetonitrile, filtering to remove insoluble substances, performing rotary evaporation (temperature is 30 ℃, pressure is 0.2 MPa) to obtain a white solid, recycling the acetonitrile, drying the white solid at 120 ℃ for 5h, and drying to obtain high-purity lithium bis (oxalate) borate with the particle size of 50-100 nm. The XRD and commercial XRD contrast of the lithium bis (oxalato) borate finished product is shown in figure 1. As can be seen from fig. 1: the diffraction peak of the self-made lithium bis (oxalato) borate finished product is consistent with that of a commodity. The calculated yield was 89% and the purity was 99.98%.
Wherein: yield = actual yield/theoretical yield 100%;
the purity test method comprises the following steps: insoluble substance detection is adopted, and the specific detection steps are as follows:
1. weighing bottles and filter membranes which have been dried to a constant mass at 105 ℃. + -. 2 ℃ are taken, the mass is accurate to 0.0002g and 2g of sample are weighed by subtractive methods to an accuracy of 0.01 g; 2. placing the sample in a beaker filled with 50mL of acetonitrile, placing the beaker on a magnetic stirrer, and stirring until the sample is completely dissolved; 3. filtering with membrane filter, washing beaker with acetonitrile for 3 times, and washing filter for 5 times; 4. carefully taking down the filter membrane, putting the filter membrane into a weighing bottle, and drying the filter membrane for 120min at 105 +/-2 ℃; 5. taking out the dried filter membrane, and placing the filter membrane in a dryer to cool to room temperature; 6. the weight of the vial, filter membrane and acetonitrile insoluble material (m 2) was weighed. Blank tests were also performed. 7. Blank test the kind and amount of the added reagent were the same as those in the sample except that no sample was added, and the mass of the vial and the filtration membrane after the operation was weighed (m 1). The content of insoluble acetonitrile is calculated by mass fraction w, the value is expressed by mg/kg, and the calculation is carried out according to the formula (1): w = (m 2-m 1) × 10-6/m。
Example 2
Weighing 11.97g of lithium hydroxide, 30.91g of boric acid, 90.03g of oxalic acid and 3.98g of sodium hexametaphosphate dispersant, putting into a container filled with 800g of deionized water, stirring uniformly, preparing a powdery lithium bis (oxalate) borate precursor material by spray drying (spray drying atomization pressure is 1.5MPa, feeding speed is 350L/h, and temperature is 110 ℃), transferring the lithium bis (oxalate) borate precursor into a muffle furnace, heating at 240 ℃ for 2h to obtain a crude product of lithium bis (oxalate) borate, dissolving the obtained crude product with acetonitrile, filtering to remove insoluble substances, performing rotary evaporation (temperature is 40 ℃, and pressure is 0.3 MPa) to obtain a white solid, recycling the acetonitrile, drying the white solid at 120 ℃ for 5h, and drying to obtain high-purity lithium bis (oxalate) borate with the particle size of 200-250 nm. The yield of lithium bis (oxalato) borate was 97% and the purity was 99.99%.
Example 3
Weighing 23.94g of lithium hydroxide, 61.83g of boric acid, 180.06g of oxalic acid and 5.21g of sodium hexametaphosphate dispersant, putting into a container filled with 1500g of deionized water, stirring uniformly, preparing a powdery lithium bis (oxalate) borate precursor material by spray drying (spray drying atomization pressure is 1MPa, feeding speed is 400L/h, temperature is 120 ℃), transferring the lithium bis (oxalate) borate precursor into a muffle furnace, heating at 240 ℃ for 2h to obtain a crude product of lithium bis (oxalate) borate, dissolving the obtained crude product with ethyl acetate, filtering to remove insoluble substances, performing rotary evaporation (temperature is 45 ℃ and pressure is 0.2 MPa) to obtain a white solid, recycling the ethyl acetate, drying the white solid at 120 ℃ for 5h, and drying to obtain high-purity lithium bis (oxalate) borate with the particle size of 400-450 nm. The yield of lithium bis (oxalato) borate was 87% and the purity was 99.96%.
Example 4
Weighing 9.57g of lithium hydroxide, 24.7g of boric acid, 72.02g of oxalic acid and 3.18g of sodium hexametaphosphate dispersant, putting into a container filled with 680g of deionized water, stirring uniformly, preparing a powdery lithium bis (oxalate) borate precursor material by spray drying (spray drying atomization pressure is 1MPa, feeding speed is 300L/h, and temperature is 110 ℃), transferring the lithium bis (oxalate) borate precursor into a muffle furnace, heating at 260 ℃ for 2h to obtain a crude product of lithium bis (oxalate) borate, dissolving the obtained crude product with ethyl acetate, filtering to remove insoluble substances, performing rotary evaporation (temperature is 50 ℃ and pressure is 0.05 MPa) to obtain a white solid, recycling the ethyl acetate, drying the white solid at 120 ℃ for 5h, and drying to obtain high-purity lithium bis (oxalate) borate with the particle size of 300-400 nm. The yield of lithium bis (oxalato) borate was 88% and the purity was 99.97%.
Example 5
Weighing 29.51g of lithium carbonate, 24.7g of boric acid, 82.73g of oxalic acid and 6.31g of sodium tripolyphosphate dispersing agent, putting into a container filled with 1000g of deionized water, uniformly stirring, preparing a powdery lithium bis (oxalate) borate precursor material by spray drying (the spray drying atomization pressure is 0.5MPa, the feeding speed is 200L/h, and the temperature is 110 ℃), transferring the lithium bis (oxalate) borate precursor into a muffle furnace, heating at 200 ℃ for 4h to obtain a crude product of lithium bis (oxalate) borate, dissolving the obtained crude product with diethyl carbonate, filtering to remove insoluble substances, performing rotary evaporation (the temperature is 40 ℃ and the pressure is 0.1 MPa) to obtain a white solid, recycling the diethyl carbonate, drying the white solid at 110 ℃ for 10h, and drying to obtain high-purity lithium bis (oxalate) borate with the particle size of 450-500 nm. The yield of lithium bis (oxalato) borate was 85% and the purity was 99.89%.
Example 6
Weighing 9.57g of lithium hydroxide, 24.7g of boric acid, 72.02g of oxalic acid and 1.10g of sodium pyrophosphate dispersant, putting into a container filled with 550g of deionized water, stirring uniformly, preparing a powdery lithium bis (oxalate) borate precursor material by spray drying (spray drying atomization pressure is 2MPa, feeding speed is 500L/h, temperature is 110 ℃), transferring the lithium bis (oxalate) borate precursor into a muffle furnace, heating at 240 ℃ for 3h to obtain a crude product of lithium bis (oxalate) borate, dissolving the obtained crude product with dimethyl carbonate, filtering to remove insoluble substances, performing rotary evaporation (temperature is 35 ℃, pressure is 0.4 MPa) to obtain a white solid, recycling the dimethyl carbonate, drying the white solid at 120 ℃ for 5h, and drying to obtain high-purity lithium bis (oxalate) borate with the particle size of 100-200 nm. The yield of lithium bis (oxalato) borate was 91% and the purity was 99.98%.
Comparative example 1
The procedure was as in example 1, except that no dispersant was added. The specific operation steps are as follows:
weighing 7.18g of lithium hydroxide, 18.54g of boric acid and 53.99g of oxalic acid, putting into a container filled with 460g of deionized water, uniformly stirring, preparing a powdery lithium bis (oxalate) borate precursor material by spray drying (spray drying atomization pressure is 2MPa, feeding speed is 200L/h, temperature is 100 ℃) of the uniformly mixed material, transferring the lithium bis (oxalate) borate precursor into a muffle furnace, heating at 240 ℃ for 2h under the atmosphere to obtain a crude product of the lithium bis (oxalate) borate, dissolving the obtained crude product with acetonitrile, filtering to remove insoluble substances, performing rotary evaporation (temperature is 30 ℃ and pressure is 0.2 MPa) to obtain a white solid, wherein the acetonitrile can be recycled, finally drying the white solid at 120 ℃ for 5h, and drying to obtain high-purity lithium bis (oxalate) borate with the particle size of 50-300 nm. The calculated yield was 81% and the purity was 99.59%.
Comparative example 2
Directly mixing lithium hydroxide, oxalic acid and boric acid for reaction, and specifically comprising the following operation steps:
weighing 7.18g of lithium hydroxide, 18.54g of boric acid and 53.99g of oxalic acid, uniformly mixing (stirring at a rotating speed of 350r/min for 60 min), transferring to a muffle furnace in an atmosphere, heating at 240 ℃ for 2h to obtain a crude product of lithium bis (oxalate) borate, dissolving the obtained crude product with acetonitrile, filtering to remove insoluble substances, performing rotary evaporation (the temperature is 30 ℃ and the pressure is 0.2 MPa) to obtain a white solid, recycling the acetonitrile, drying the white solid at 120 ℃ for 5h, and drying to obtain the high-purity lithium bis (oxalate) borate with the particle size of 50-500 nm. The calculated yield was 70% and the purity was 98.65%.
Comparative example 3
Weighing 14.36 g of lithium hydroxide, 37.09 g of boric acid and 108.03 g of oxalic acid, ball-milling the three for 60min by using a ball mill, uniformly mixing the three, pressing the uniformly mixed raw materials into sheets under the pressure of 5MPa, placing the pressed sheets in a muffle furnace, heating the sheets in a gradient manner under the atmosphere for 4h at the first gradient temperature of 100 ℃ and 4h at the second gradient temperature of 240 ℃ to obtain a lithium bis (oxalate) borate crude product, dissolving the obtained crude product with acetonitrile, filtering to remove insoluble substances, carrying out rotary evaporation (the temperature is 30 ℃ and the pressure is 0.1 MPa) to obtain a white solid, recycling the acetonitrile, drying the white solid at the temperature of 120 ℃ for 5h, and drying to obtain the high-purity lithium bis (oxalate) borate with the particle size of 100-600 nm. The calculated yield was 78% with a purity of 99.73%.
Comparative example 4
Weighing 11.97g of lithium hydroxide, 30.91g of boric acid and 90.03g of oxalic acid, ball-milling the three for 50min by using a ball mill, uniformly mixing the three, pressing the uniformly mixed raw materials into sheets under the pressure of 5MPa, placing the pressed sheets in a muffle furnace, heating the sheets in a gradient manner under the atmosphere for 4h at the first gradient temperature of 110 ℃ and 2h at the second gradient temperature of 240 ℃ to obtain a lithium bis (oxalate) borate crude product, dissolving the obtained crude product with acetonitrile, filtering to remove insoluble substances, carrying out rotary evaporation (the temperature is 40 ℃, and the pressure is 0.2 MPa) to obtain a white solid, recycling the acetonitrile, drying the white solid at the temperature of 120 ℃ for 5h, and drying to obtain the high-purity lithium bis (oxalate) borate with the particle size of 80-650 nm. The calculated yield was 81% and the purity was 99.86%.
Comparative example 5
Weighing 9.57g of lithium hydroxide, 24.7g of boric acid and 72.02g of oxalic acid, ball-milling the three for 40min by using a ball mill, uniformly mixing the three, pressing the uniformly mixed raw materials into sheets under the pressure of 5MPa, placing the pressed sheets in a muffle furnace, heating the sheets in a gradient manner under the atmosphere for 4h at the first gradient temperature of 120 ℃ and 4h at the second gradient temperature of 240 ℃ to obtain a lithium bis (oxalate) borate crude product, dissolving the obtained crude product with acetonitrile, filtering to remove insoluble substances, carrying out rotary evaporation (the temperature is 50 ℃ and the pressure is 0.07 MPa) to obtain a white solid, recycling the acetonitrile, drying the white solid at the temperature of 120 ℃ for 5h, and drying to obtain the high-purity lithium bis (oxalate) borate with the particle size of 70-640 nm. The calculated yield was 80% and the purity was 99.85%.
Comparative example 6
Weighing 11.97g of lithium hydroxide, 30.91g of boric acid and 90.03g of oxalic acid, ball-milling the three materials for 60min by using a ball mill, uniformly mixing the three materials, dry-pressing the uniformly-mixed raw materials into sheets under the pressure of 5MPa, placing the pressed sheets in a muffle furnace, heating the sheets in a gradient manner under the atmosphere for 4h at the first gradient temperature of 110 ℃ and heating the sheets in a gradient manner for 4h at the second gradient temperature of 240 ℃ to obtain a lithium bis (oxalate) borate crude product, dissolving the obtained crude product with ethyl acetate, filtering to remove insoluble substances, carrying out rotary evaporation (the temperature is 40 ℃, and the pressure is 0.2 MPa) to obtain a white solid, recycling the ethyl acetate, finally drying the white solid at the temperature of 120 ℃ for 5h, and drying to obtain the high-purity lithium bis (oxalate) borate with the particle size of 100-760 nm. The calculated yield was 73% and the purity was 99.71%.
Performance testing
The lithium bis (oxalato) borate obtained in examples 1 to 6 and comparative examples 1 to 6 was subjected to a performance test, and the obtained product was configured to have a conductivity of 0.6mol/L lithium bis (oxalato) borate in a ternary mixed solvent system PC/EMC/DMC, and the results are shown in Table 2.
TABLE 2 conductivity test
As can be seen from Table 2, the lithium bis (oxalato) borate provided by the invention has more uniform particle size and is more favorable for conductivity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of lithium bis (oxalato) borate is characterized by comprising the following steps:
1) mixing a lithium source, boric acid, oxalic acid, water and a dispersing agent to obtain a mixed material;
2) spray drying the mixed material to obtain a precursor of the lithium bis (oxalato) borate;
3) reacting a precursor of lithium bis (oxalato) borate at the temperature of 200-260 ℃ for 2-4 h to obtain lithium bis (oxalato) borate;
the lithium source is lithium hydroxide and/or lithium carbonate;
the dispersing agent is sodium hexametaphosphate, sodium tripolyphosphate or sodium pyrophosphate.
2. The method according to claim 1, wherein the molar ratio of the lithium source to the boric acid to the oxalic acid is 1:1:2 to 1:1: 2.3.
3. The method according to claim 1, wherein the dispersant is 1 to 5% by mass of the total mass of the lithium source, the boric acid and the oxalic acid.
4. The method according to claim 1, wherein the water is 5 to 8 times the total mass of the lithium source, the boric acid and the oxalic acid.
5. The method according to claim 1, wherein the feed rate during the spray drying is 200 to 500L/h, the pressure is 0.5 to 2MPa, and the temperature is 100 to 120 ℃.
6. The method of claim 1, wherein obtaining the lithium bis (oxalato) borate further comprises dissolving the lithium bis (oxalato) borate in an organic solvent, filtering, rotary evaporating, and drying.
7. The method according to claim 6, wherein the organic solvent is one or more selected from acetonitrile, ethyl acetate, dimethyl carbonate and diethyl carbonate.
8. The preparation method according to claim 6, wherein the temperature of the rotary evaporation is 30-50 ℃ and the pressure is 0.05-0.5 MPa.
9. The method according to claim 6, wherein the drying temperature is 115 to 125 ℃.
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| CN100482631C (en) * | 2006-03-10 | 2009-04-29 | 北京格林动力电源技术有限公司 | Method of preparing boron lithium dioxalate complex salt |
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