CN114057783B - Preparation method of lithium bis (oxalato) borate - Google Patents
Preparation method of lithium bis (oxalato) borate Download PDFInfo
- Publication number
- CN114057783B CN114057783B CN202111590249.9A CN202111590249A CN114057783B CN 114057783 B CN114057783 B CN 114057783B CN 202111590249 A CN202111590249 A CN 202111590249A CN 114057783 B CN114057783 B CN 114057783B
- Authority
- CN
- China
- Prior art keywords
- lithium
- bed reactor
- fixed bed
- preparation
- borate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 50
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 60
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 60
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052796 boron Inorganic materials 0.000 claims abstract description 21
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 11
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 10
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910015900 BF3 Inorganic materials 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910000085 borane Inorganic materials 0.000 claims description 5
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 5
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 230000001276 controlling effect Effects 0.000 description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 9
- 239000004327 boric acid Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- AIGRXSNSLVJMEA-FQEVSTJZSA-N ethoxy-(4-nitrophenoxy)-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound O([P@@](=S)(OCC)C=1C=CC=CC=1)C1=CC=C([N+]([O-])=O)C=C1 AIGRXSNSLVJMEA-FQEVSTJZSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 oxalic acid compound Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method 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
Images
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 provides a preparation method of lithium bisoxalato borate, and belongs to the technical field of special chemicals. The method comprises the following steps: 1) Ball milling is carried out on lithium hydroxide and anhydrous oxalic acid, and the obtained mixture is placed in a fixed bed reactor; 2) And (3) introducing the gaseous boron source compound into a fixed bed reactor for reaction under the load of high-temperature nitrogen to obtain the lithium bisoxalato borate. The preparation method provided by the invention has the advantages of high yield, low water content and high purity of the prepared lithium bisoxalato borate, and simple process.
Description
Technical Field
The invention belongs to the technical field of special chemicals, and particularly relates to a preparation method of lithium bisoxalato borate.
Background
The lithium borate complex is a novel lithium ion battery electrolyte, and is most represented by lithium bisoxalato borate LiBOB. The lithium bisoxalato borate is a coordination chelate, so that anions in the electrolyte are larger, the crystal lattice energy is smaller, more ions can be obtained in a solvent, and the conductivity of the electrolyte is improved. The lithium bisoxalato borate (LiBOB) has good electrochemical stability and thermal stability, can react with a specific solvent to form a stable SEI film, can not attenuate energy after repeated cycles, and has higher compared with lithium hexafluorophosphateThermal stability, and decomposed product B 2 O 3 And CO 2 The electrolyte has little influence on the service performance and environment of the battery, and is an electrolyte substance with development potential in the lithium battery industry.
The prior synthesis method of the lithium bisoxalato borate comprises 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 requires long time for removing water, and has long reaction time and low efficiency. The patent CN109232629A is prepared by ball milling oxalic acid, lithium hydroxide and boric acid, mixing uniformly, dry pressing into tablets, and carrying out high-temperature solid phase reaction to obtain the lithium bisoxalato borate. Therefore, how to increase the purity and water content of lithium bisoxalato borate is a key challenge facing current work.
Disclosure of Invention
The invention provides a preparation method of lithium bisoxalato borate, which is low in water content, high in purity, simple in preparation process and suitable for industrial production.
In order to achieve the above purpose, the invention provides a preparation method of lithium bisoxalato borate, comprising the following steps:
1) Ball milling is carried out on lithium hydroxide and anhydrous oxalic acid, and the obtained mixture is placed in a fixed bed reactor;
2) And (3) introducing the gaseous boron source compound into a fixed bed reactor for reaction under the load of high-temperature nitrogen to obtain the lithium bisoxalato borate.
Preferably, the molar ratio of the lithium hydroxide to the anhydrous oxalic acid is 1:2.2-2.5.
Preferably, the ball milling time is 40-80 min; the rotating speed of ball milling is 300-350 r/min.
Preferably, the gaseous boron source compound comprises one or more of boron trifluoride, boron trichloride, borane and trimethylboron.
Preferably, the molar ratio of boron to lithium hydroxide in the gaseous boron source compound is 1:1.1-1.5.
Preferably, the temperature of the high-temperature nitrogen is 100-140 ℃, the air flow is 3-10L/h, and the reaction time is 6-10 h.
Preferably, the water content of the high-temperature nitrogen gas introduced into the fixed bed reactor is 5-40 ppm, and the water content of the high-temperature nitrogen gas discharged from the fixed bed reactor is 150-400 ppm.
Preferably, the method further comprises dissolving the lithium bisoxalato borate with ethyl acetate, filtering, concentrating, adding dichloromethane for crystallization, filtering and drying.
Preferably, the mass ratio of the ethyl acetate to the lithium bisoxalato borate is 6-10:1, and the concentration is carried out to 1/4-1/3 of the volume of the solution.
Preferably, the volume ratio of the dichloromethane to the concentrated solution is 1-3:1.
Compared with the prior art, the invention has the advantages and positive effects that:
according to the preparation method of the lithium bisoxalato borate, provided by the invention, the gas-solid contact mode is adopted for reaction, so that the contact area of raw materials can be effectively increased, the reaction is more complete, the product yield is high, meanwhile, unreacted gas boron source compounds can be discharged along with carrier gas, the content of impurities in the product is effectively reduced, and the complexity of the purification process and the generation of three wastes are reduced. In the reaction process of LiBOB synthesis, a large amount of water is generated, and the removal of the LiBOB is one of the great pain points in the industry, and the water generated in the reaction process of the patent can be discharged along with carrier gas in time, so that the removal difficulty of the product is effectively reduced.
Drawings
FIG. 1 shows XRD patterns of lithium bisoxalato borate prepared in examples 1 to 4 and comparative examples 1 to 2.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
The invention provides a preparation method of lithium bisoxalato borate, which comprises the following steps:
1) Ball milling is carried out on lithium hydroxide and anhydrous oxalic acid, and the obtained mixture is placed in a fixed bed reactor;
2) And (3) introducing the gaseous boron source compound into a fixed bed reactor for reaction under the load of high-temperature nitrogen to obtain the lithium bisoxalato borate.
The invention ball-mills lithium hydroxide and anhydrous oxalic acid, and the obtained mixture is placed in a fixed bed reactor. In the present invention, the molar ratio of lithium hydroxide to anhydrous oxalic acid is preferably 1:2.2-2.5. In the invention, the ball milling time is preferably 40-80 min; the rotation speed of the ball milling is preferably 300-350 r/min.
The type of the fixed bed reactor is not particularly limited, and the fixed bed reactor is a conventional commercial product in the field, and an axial adiabatic fixed bed reactor is adopted in the embodiment of the invention.
After the mixed material is placed in a fixed bed reactor, the gaseous boron source compound is introduced into the fixed bed reactor for reaction under the load of high-temperature nitrogen, so that the lithium bisoxalato borate is obtained.
In the present invention, the gaseous boron source compound preferably includes one or more of boron trifluoride, boron trichloride, borane and trimethylboron, more preferably borane; the borane is preferably proylborane, ding Pengwan, pentaborane or hexaborane.
The specific sources of the lithium hydroxide, the anhydrous oxalic acid and the gaseous boron source compound are not particularly limited, and the lithium hydroxide, the anhydrous oxalic acid and the gaseous boron source compound can be conventional and commercially available products in the field.
In the present invention, the molar ratio of boron to lithium hydroxide in the gaseous boron source compound is preferably 1:1.1 to 1.5. In the present invention, the feed rate of the gaseous boron source compound is preferably 1.5 to 7L/h.
In the present invention, the temperature of the high temperature nitrogen gas is preferably 100 to 140 ℃, the gas flow rate is preferably 3 to 10L/h, and the reaction time is preferably 6 to 10h.
In the present invention, the water content of the high-temperature nitrogen gas introduced into the fixed bed reactor is preferably 5 to 40ppm, and the water content of the high-temperature nitrogen gas discharged from the fixed bed reactor is preferably 150 to 400ppm. In the invention, the water content of the high-temperature nitrogen discharged from the reactor is regulated and controlled by controlling the flow of the inlet nitrogen.
The invention adopts the fixed bed reactor as a carrier to carry out the reaction in a gas-solid contact mode, can effectively improve the contact area of raw materials, and has more sufficient reaction and high product yield. Meanwhile, the fixed bed reactor can ensure sufficient contact between the solid lithium source and the oxalic acid compound, and even if the gaseous boron source is introduced, the contact between the raw materials cannot be destroyed, so that the sufficient contact reaction between the three raw materials is ensured. While reactors such as ebullated beds, fluidized beds, etc., easily cause separation between solid raw materials under the disturbance of gas, so that the raw materials do not contact or contact poorly, thereby affecting the progress of the reaction. Meanwhile, unreacted gaseous boron source compound can be discharged along with carrier gas, so that the content of impurities in the product is effectively reduced. In the LiBOB synthesis reaction process, a large amount of water is generated, and the water generated in the reaction process can be discharged along with carrier gas in time, so that the water removal difficulty of the product is effectively reduced.
After obtaining the lithium bisoxalato borate, the invention preferably further comprises dissolving the lithium bisoxalato borate with ethyl acetate, filtering, concentrating, adding dichloromethane for crystallization, filtering and drying.
In the invention, the mass ratio of the ethyl acetate to the lithium bis (oxalato) borate is preferably 6-10:1. In the present invention, the concentration is preferably 1/4 to 1/3 of the volume of the solution. In the present invention, the temperature of the concentration is preferably 30 to 60 ℃. In the present invention, the volume ratio of the dichloromethane to the concentrated solution is preferably 1-3:1. In the present invention, the filtration is preferably suction filtration. In the present invention, the drying mode is preferably drying in a double cone vacuum dryer; the temperature of the double cone vacuum drier is preferably 120-160 ℃ and the vacuum degree is preferably 0.01-0.06 Mpa.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
1) Ball-milling 24g (1 mol) lithium hydroxide and 198g (2.2 mol) anhydrous oxalic acid for 50min at a rotating speed of 300r/min to obtain a uniformly mixed material, and placing the mixed material into a fixed bed reactor;
2) Boron trifluoride is introduced into a fixed bed reactor for reaction for 7 hours under the nitrogen load of 100 ℃, the flow rate of boron trifluoride is controlled to be 3.58L/h (0.16 mol/h), the flow rate of nitrogen is controlled to be 5L/h, and the water contents of the inlet and outlet of the nitrogen are controlled to be respectively: 10ppm, 210ppm;
3) 185g of crude bisoxalato boric acid generated by the reaction is dissolved by 1300g of ethyl acetate, insoluble impurities are filtered out, and the filtrate is distilled under reduced pressure (the pressure is 0.01Mpa and the temperature is 40 ℃) and concentrated to 1/3;
4) Adding 440g of dichloromethane into the concentrated solution for crystallization, filtering the solution, and drying the filter cake in a biconical vacuum dryer (the vacuum degree is 0.02Mpa and the temperature is 120 ℃) to obtain high-purity lithium bisoxalato borate, wherein the purity of the lithium bisoxalato borate is 99.92%, the yield is 80.3% and the water content is 72ppm. The XRD pattern of the prepared lithium bisoxalato borate is shown in figure 1.
Example 2
1) Ball-milling 24g (1 mol) lithium hydroxide and 216g (2.4 mol) anhydrous oxalic acid for 40min at a rotating speed of 350r/min to obtain a uniformly mixed material, and placing the mixed material into a fixed bed reactor;
2) Introducing boron trichloride into a fixed bed reactor for reaction for 10 hours under the nitrogen load of 120 ℃, controlling the flow rate of the boron trichloride to be 3.36L/h (0.15 mol/h), controlling the flow rate of the nitrogen to be 6L/h, and controlling the water content of an inlet and an outlet of the nitrogen to be respectively: 20ppm, 300ppm;
3) 189g of crude bisoxalato boric acid generated by the reaction is completely dissolved by using 1200g of ethyl acetate, insoluble impurities are filtered, and the filtrate is distilled under reduced pressure (the pressure is 0.03Mpa and the temperature is 45 ℃) and concentrated to 1/4;
4) 400g of methylene dichloride is added into the concentrated solution to crystallize the product, the solution is filtered, and the filter cake is dried in a biconical vacuum dryer (the vacuum degree is 0.02Mpa and the temperature is 120 ℃) to obtain high-purity lithium bisoxalato borate, the purity of the lithium bisoxalato borate is 99.95%, the yield is 86.7%, and the water content is 65ppm. The XRD pattern of the prepared lithium bisoxalato borate is shown in figure 1.
Example 3
1) Ball-milling 24g (1 mol) lithium hydroxide and 216g (2.4 mol) anhydrous oxalic acid for 40min at a rotating speed of 320r/min to obtain a uniformly mixed material, and placing the mixed material into a fixed bed reactor;
2) Diborane is introduced into a fixed bed reactor for reaction for 8 hours under the nitrogen load of 130 ℃, the flow rate of diborane is controlled to be 1.81L/h (0.081 mol/h), the flow rate of nitrogen is controlled to be 4L/h, and the water content of the inlet and outlet of the nitrogen is controlled to be respectively: 40ppm, 400ppm;
3) 176g of crude bisoxalato boric acid generated by the reaction is completely dissolved by 1400g of ethyl acetate, insoluble impurities are filtered, and the filtrate is distilled under reduced pressure (the pressure is 0.02Mpa and the temperature is 50 ℃) and concentrated to 1/3;
4) 600g of methylene dichloride is added into the concentrated solution to crystallize the product, the solution is filtered, and the filter cake is dried in a biconical vacuum dryer (the vacuum degree is 0.04Mpa and the temperature is 130 ℃) to obtain high-purity lithium bisoxalato borate, the purity of the lithium bisoxalato borate is 99.5%, the yield is 73.4%, and the water content is 86ppm. The XRD pattern of the prepared lithium bisoxalato borate is shown in figure 1.
Example 4
1) Ball-milling 24g (1 mol) lithium hydroxide and 207g (2.3 mol) anhydrous oxalic acid for 70min at a rotating speed of 340r/min to obtain a uniformly mixed material, and placing the mixed material into a fixed bed reactor;
2) Introducing trimethylboron into a fixed bed reactor for reaction for 6 hours under the nitrogen load of 140 ℃, controlling the flow rate of the trimethylboron to be 5.15L/h (0.23 mol/h), controlling the flow rate of the nitrogen to be 10L/h, and controlling the water contents of an inlet and an outlet of the nitrogen to be respectively: 5ppm, 150ppm;
3) 181g of crude bisoxalato boric acid generated by the reaction is completely dissolved by 1800g of ethyl acetate, insoluble impurities are removed by filtration, and the filtrate is distilled under reduced pressure (the pressure is 0.04Mpa and the temperature is 50 ℃) and concentrated to 1/3;
4) 600g of methylene dichloride is added into the concentrated solution to crystallize the product, the solution is filtered, and the filter cake is dried in a biconical vacuum dryer (the vacuum degree is 0.03Mpa and the temperature is 140 ℃) to obtain high-purity lithium bisoxalato borate, the purity of the lithium bisoxalato borate is 99.91%, the yield is 70.9%, and the water content is 42ppm. The XRD pattern of the prepared lithium bisoxalato borate is shown in figure 1.
Comparative example 1
The procedure is as in example 1, with the difference that: the fixed bed reactor was replaced with an ebullated bed reactor, and the specific operation was as follows:
1) Ball-milling 24g (1 mol) lithium hydroxide and 198g (2.2 mol) anhydrous oxalic acid for 50min at a rotating speed of 300r/min to obtain a uniformly mixed material, and placing the mixed material into a boiling bed reactor;
2) Boron trifluoride is introduced into a boiling bed reactor for reaction for 7 hours under the nitrogen load of 100 ℃, the flow rate of boron trifluoride is controlled to be 3.58L/h (0.16 mol/h), the flow rate of nitrogen is controlled to be 5L/h, and the water contents of the inlet and outlet of the nitrogen are controlled to be respectively: 10ppm, 210ppm;
3) 163g of crude bisoxalato boric acid generated by the reaction is dissolved completely by 1300g of ethyl acetate, insoluble impurities are filtered out, and the filtrate is distilled under reduced pressure (the pressure is 0.01Mpa and the temperature is 40 ℃) and concentrated to 1/3;
4) Adding 440g of dichloromethane into the concentrated solution for crystallization, filtering the solution, and drying the filter cake in a biconical vacuum dryer (the vacuum degree is 0.02Mpa and the temperature is 120 ℃) to obtain high-purity lithium bisoxalato borate, wherein the purity of the lithium bisoxalato borate is 98.1%, the yield is 32%, and the water content is 124ppm. The XRD pattern of the prepared lithium bisoxalato borate is shown in figure 1.
Comparative example 2
The procedure is as in example 1, with the difference that: the fixed bed reactor is replaced by a boiling bed reactor, and the boron source is replaced by solid boric acid, and the concrete operation is as follows:
1) Ball milling 24g (1 mol) lithium hydroxide, 198g (2.2 mol) anhydrous oxalic acid and boric acid (1 mol) at a rotating speed of 300r/min for 50min to obtain a uniformly mixed material, placing the mixture material into a boiling bed reactor, controlling the temperature of nitrogen to be 100 ℃, reacting for 7h, controlling the flow of nitrogen to be 5L/h, and controlling the water content of the inlet and outlet of the nitrogen to be respectively: 10ppm, 210ppm;
3) 151g of crude bisoxalato boric acid generated by the reaction is dissolved by 1300g of ethyl acetate, insoluble impurities are filtered out, and the filtrate is distilled under reduced pressure (the pressure is 0.01Mpa and the temperature is 40 ℃) and concentrated to 1/3;
4) Adding 440g of dichloromethane into the concentrated solution for crystallization, filtering the solution, and drying the filter cake in a biconical vacuum dryer (the vacuum degree is 0.02Mpa and the temperature is 120 ℃) to obtain high-purity lithium bisoxalato borate, wherein the purity of the lithium bisoxalato borate is 95.3%, the yield is 21%, and the water content is 176ppm. The XRD pattern of the prepared lithium bisoxalato borate is shown in figure 1.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The preparation method of the lithium bisoxalato borate is characterized by comprising the following steps:
1) Ball milling is carried out on lithium hydroxide and anhydrous oxalic acid, and the obtained mixture is placed in a fixed bed reactor;
2) Introducing a gaseous boron source compound into a fixed bed reactor for reaction under the load of high-temperature nitrogen to obtain lithium bisoxalato borate;
the gaseous boron source compound is selected from one or more of boron trifluoride, boron trichloride, borane and trimethylboron.
2. The method according to claim 1, wherein the molar ratio of lithium hydroxide to anhydrous oxalic acid is 1:2.2-2.5.
3. The preparation method of claim 1, wherein the ball milling time is 40-80 min; the rotating speed of ball milling is 300-350 r/min.
4. The method according to claim 1, wherein the molar ratio of boron to lithium hydroxide in the gaseous boron source compound is 1:1.1-1.5.
5. The preparation method according to claim 1, wherein the high-temperature nitrogen gas has a temperature of 100-140 ℃, a gas flow rate of 3-10L/min and a reaction time of 6-10 h.
6. The method according to claim 1, wherein the water content of the high-temperature nitrogen gas introduced into the fixed bed reactor is 5 to 40ppm, and the water content of the high-temperature nitrogen gas discharged from the fixed bed reactor is 150 to 400ppm.
7. The preparation method of claim 1, further comprising dissolving the lithium bisoxalato borate in ethyl acetate, filtering, concentrating, adding dichloromethane for crystallization, filtering and drying.
8. The preparation method of claim 7, wherein the mass ratio of ethyl acetate to lithium bis (oxalato) borate is 6-10:1, and the concentration is 1/4-1/3 of the volume of the solution.
9. The method according to claim 8, wherein the volume ratio of dichloromethane to concentrated solution is 1-3:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111590249.9A CN114057783B (en) | 2021-12-23 | 2021-12-23 | Preparation method of lithium bis (oxalato) borate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111590249.9A CN114057783B (en) | 2021-12-23 | 2021-12-23 | Preparation method of lithium bis (oxalato) borate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114057783A CN114057783A (en) | 2022-02-18 |
| CN114057783B true CN114057783B (en) | 2023-07-14 |
Family
ID=80230642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111590249.9A Active CN114057783B (en) | 2021-12-23 | 2021-12-23 | Preparation method of lithium bis (oxalato) borate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114057783B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114790219B (en) * | 2022-04-25 | 2023-10-03 | 苏州华一新能源科技股份有限公司 | Preparation method of lithium bis (oxalato) borate |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1243825A (en) * | 1998-07-31 | 2000-02-09 | 埃勒夫阿托化学有限公司 | Composition having dimethyl disulfide as base for covering up odors |
| CN101331159A (en) * | 2005-11-21 | 2008-12-24 | 巴斯夫欧洲公司 | Method for producing highly reactive isobutylene homo- or copolymers using metal-containing catalyst complexes |
| WO2016154870A1 (en) * | 2015-03-31 | 2016-10-06 | Bayerische Motoren Werke Aktiengesellschaft | Method of making lithium difluoro (oxalato) borate |
| CN106532094A (en) * | 2015-09-11 | 2017-03-22 | 中科派思储能技术有限公司 | Lithium-sulfur flow battery |
| JP2017081774A (en) * | 2015-10-26 | 2017-05-18 | Ｊｘエネルギー株式会社 | Dehydrogenation catalyst, manufacturing method of dehydrogenation catalyst, dehydrogenation reactor, manufacturing method of dehydrogenation reactor, manufacturing system of hydrogen and manufacturing method of hydrogen |
| CN107602603A (en) * | 2017-10-13 | 2018-01-19 | 湖北省宏源药业科技股份有限公司 | A kind of preparation method of di-oxalate lithium borate |
| CN109438488A (en) * | 2018-11-13 | 2019-03-08 | 九江天赐高新材料有限公司 | A kind of preparation method of liquid Lithium bis (oxalate) borate salt |
| KR20190096154A (en) * | 2018-02-08 | 2019-08-19 | 리켐주식회사 | Synthetic Method of Lithium bisoxalatoborate |
| EP3789390A1 (en) * | 2019-09-03 | 2021-03-10 | Ulusal Bor Arastirma Enstitüsü | A synthesis set-up and production method for high purity andydrous lithium bis(oxalato)borate (libob) |
-
2021
- 2021-12-23 CN CN202111590249.9A patent/CN114057783B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1243825A (en) * | 1998-07-31 | 2000-02-09 | 埃勒夫阿托化学有限公司 | Composition having dimethyl disulfide as base for covering up odors |
| CN101331159A (en) * | 2005-11-21 | 2008-12-24 | 巴斯夫欧洲公司 | Method for producing highly reactive isobutylene homo- or copolymers using metal-containing catalyst complexes |
| WO2016154870A1 (en) * | 2015-03-31 | 2016-10-06 | Bayerische Motoren Werke Aktiengesellschaft | Method of making lithium difluoro (oxalato) borate |
| CN106532094A (en) * | 2015-09-11 | 2017-03-22 | 中科派思储能技术有限公司 | Lithium-sulfur flow battery |
| JP2017081774A (en) * | 2015-10-26 | 2017-05-18 | Ｊｘエネルギー株式会社 | Dehydrogenation catalyst, manufacturing method of dehydrogenation catalyst, dehydrogenation reactor, manufacturing method of dehydrogenation reactor, manufacturing system of hydrogen and manufacturing method of hydrogen |
| CN107602603A (en) * | 2017-10-13 | 2018-01-19 | 湖北省宏源药业科技股份有限公司 | A kind of preparation method of di-oxalate lithium borate |
| KR20190096154A (en) * | 2018-02-08 | 2019-08-19 | 리켐주식회사 | Synthetic Method of Lithium bisoxalatoborate |
| CN109438488A (en) * | 2018-11-13 | 2019-03-08 | 九江天赐高新材料有限公司 | A kind of preparation method of liquid Lithium bis (oxalate) borate salt |
| EP3789390A1 (en) * | 2019-09-03 | 2021-03-10 | Ulusal Bor Arastirma Enstitüsü | A synthesis set-up and production method for high purity andydrous lithium bis(oxalato)borate (libob) |
Non-Patent Citations (2)
| Title |
|---|
| A new type of lithium salt used as electrolyte salt of lithium ion battery - Lithium bis(oxalate)borate;Li, SY等;PROGRESS IN CHEMISTRY;第19卷(第5期);695-699 * |
| 锂离子电池用双草酸硼酸锂的固相合成;张;袁莉;刘锦平;李晓磊;赵洪;宋晓莉;;无机盐工业(第04期);42-44 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114057783A (en) | 2022-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114057783B (en) | Preparation method of lithium bis (oxalato) borate | |
| CN104891435A (en) | Hydrogen production method by using proton-responsive iridium complex for catalysis of ammonia borane hydrolysis | |
| CN113292724B (en) | Preparation method of pyridine-rich cationic covalent triazine polymer | |
| WO2023116540A1 (en) | Pyridine pyrrole ruthenium complex, preparation method therefor and application thereof as catalyst for preparing hydrazine by electrocatalytic ammonia oxidation | |
| CN101830918A (en) | Synthetic method of polynitrogen azole zinc/cadmium framework material | |
| CN103303867A (en) | Method for synthesizing ammonia borane | |
| CN111533094A (en) | Method for simply preparing high-purity lithium bis (fluorosulfonyl) imide | |
| CN111116349A (en) | Preparation method of lithium difluorobis (oxalate) phosphate | |
| CN220969095U (en) | System for continuously producing superfine sodium azide by utilizing hypergravity bed reactor | |
| CN103388085B (en) | High-purity arsenic preparation method | |
| CN102897728B (en) | Method for producing phosphorus pentachloride | |
| CN108250450B (en) | Cadmium coordination polymer and preparation method and application thereof | |
| CN111116624A (en) | Preparation method of lithium bis (oxalato) borate | |
| CN117142443A (en) | Process for continuously producing superfine sodium azide | |
| CN111647167A (en) | Novel metal organic framework material Zn-MOF, and synthesis method and application thereof | |
| CN111057082A (en) | Preparation method of lithium bis (oxalato) borate | |
| CN114436986B (en) | Preparation method of pentazole negative ions | |
| CN112778153B (en) | Amido bridged hexacarboxylic acid ligand and metal organic framework material as well as preparation method and application thereof | |
| CN211226345U (en) | Phosphorus pentafluoride reactor | |
| CN112812132A (en) | Preparation method of high-purity lithium bis (oxalato) borate | |
| CN112678795B (en) | Preparation method of lithium difluorophosphate | |
| CN111592559A (en) | Method for synthesizing sodium difluorooxalate through one-step method | |
| CN112745341A (en) | Preparation method of high-purity lithium bis (fluorooxalato) borate | |
| CN111994871B (en) | Synthesis method of alpha-aluminum trihydride | |
| CN112811407A (en) | Preparation method of lithium difluorophosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Shengxian Inventor after: Wang Weijiang Inventor after: Wang Minghua Inventor after: Yan Huaicong Inventor after: Jia Guowen Inventor after: Zhu Zhentao Inventor after: Yin Xuehan Inventor after: Miao Lixiao Inventor before: Wang Shengxian Inventor before: Wang Minghua Inventor before: Yan Huaicong Inventor before: Jia Guowen Inventor before: Zhu Zhentao Inventor before: Yin Xuehan Inventor before: Miao Lixiao |
|
| CB03 | Change of inventor or designer information |