CN114057783A - Preparation method of lithium bis (oxalato) borate - Google Patents
Preparation method of lithium bis (oxalato) borate Download PDFInfo
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- CN114057783A CN114057783A CN202111590249.9A CN202111590249A CN114057783A CN 114057783 A CN114057783 A CN 114057783A CN 202111590249 A CN202111590249 A CN 202111590249A CN 114057783 A CN114057783 A CN 114057783A
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- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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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) carrying out ball milling on lithium hydroxide and anhydrous oxalic acid, and placing the obtained mixed material into a fixed bed reactor; 2) and introducing the gaseous boron source compound into a fixed bed reactor for reaction under the load of high-temperature nitrogen to obtain the lithium bis (oxalate) borate. The preparation method provided by the invention has the advantages of high yield, low water content of the prepared lithium bis (oxalate) borate, high purity 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 bis (oxalato) borate.
Background
The lithium borate complex is a novel lithium ion battery electrolyte, whereinLiBOB is the most representative of lithium bis (oxalato) borate. The lithium bis (oxalato) borate is a coordination chelate, the formed electrolyte has larger anions and smaller crystal lattice energy, and more ions can be obtained in a solvent, so that the conductivity of the electrolyte is improved. Lithium bis (oxalato) borate (LiBOB) has good electrochemical stability and thermal stability, can react with a specific solvent to form a stable SEI film, can not be attenuated 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 requires a long time for removing water, and has long reaction time and low efficiency. According to the patent CN109232629A, oxalic acid, lithium hydroxide and boric acid are ball-milled and mixed uniformly, and the lithium bis (oxalate) borate is obtained through high-temperature solid-phase reaction after dry pressing into a sheet. Therefore, how to improve the purity and water content of lithium bis (oxalato) borate is a critical challenge in current work.
Disclosure of Invention
The invention provides a preparation method of lithium bis (oxalato) borate, and the prepared lithium bis (oxalato) borate has low water content, high purity and simple preparation process and is suitable for industrial production.
In order to achieve the above object, the present invention provides a method for preparing lithium bis (oxalato) borate, comprising the following steps:
1) carrying out ball milling on lithium hydroxide and anhydrous oxalic acid, and placing the obtained mixed material into a fixed bed reactor;
2) and introducing the gaseous boron source compound into a fixed bed reactor for reaction under the load of high-temperature nitrogen to obtain the lithium bis (oxalate) 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 the 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 gas flow is 3-10L/h, and the reaction time is 6-10 h.
Preferably, the water content of the high-temperature nitrogen introduced into the fixed bed reactor is 5-40 ppm, and the water content of the high-temperature nitrogen discharged from the fixed bed reactor is 150-400 ppm.
Preferably, the preparation method further comprises the steps of dissolving the lithium bis (oxalate) borate by using ethyl acetate, filtering, concentrating, adding dichloromethane for crystallization, filtering and drying.
Preferably, the mass ratio of the ethyl acetate to the lithium bis (oxalato) borate is 6-10: 1, and the ethyl acetate and the lithium bis (oxalato) borate are concentrated 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:
the preparation method of lithium bis (oxalato) borate provided by the invention adopts a gas-solid contact mode for reaction, can effectively increase the contact area of raw materials, has more sufficient reaction and high product yield, and simultaneously, unreacted gaseous boron source compound can be discharged along with carrier gas, so that 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. A large amount of water can be generated in the LiBOB synthesis reaction process, LiBOB dehydration is one of the major pain points of the industry, and the water generated in the reaction process of the LiBOB can be discharged along with the carrier gas in time, so that the difficulty in product dehydration is effectively reduced.
Drawings
FIG. 1 is an XRD pattern of lithium bis (oxalato) borate prepared in examples 1 to 4 and comparative examples 1 to 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it should be understood 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 obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of lithium bis (oxalato) borate, which comprises the following steps:
1) carrying out ball milling on lithium hydroxide and anhydrous oxalic acid, and placing the obtained mixed material into a fixed bed reactor;
2) and introducing the gaseous boron source compound into a fixed bed reactor for reaction under the load of high-temperature nitrogen to obtain the lithium bis (oxalate) borate.
The invention ball-mills lithium hydroxide and anhydrous oxalic acid, and puts the obtained mixed material into a fixed bed reactor. In the invention, the molar ratio of the lithium hydroxide to the 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 in the invention, and the fixed bed reactor can be prepared from the conventional commercial products 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, gaseous boron source compound is introduced into the fixed bed reactor for reaction under the load of high-temperature nitrogen, and lithium bis (oxalato) 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 proparaborane, tetraborane, 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 conventional commercial products in the field can be adopted.
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 invention, the feeding rate of the gaseous boron source compound is preferably 1.5-7L/h.
In the invention, the temperature of the high-temperature nitrogen is preferably 100-140 ℃, the gas flow is preferably 3-10L/h, and the reaction time is preferably 6-10 h.
In the invention, the water content of the high-temperature nitrogen introduced into the fixed bed reactor is preferably 5-40 ppm, and the water content of the high-temperature nitrogen discharged from the fixed bed reactor is preferably 150-400 ppm. In the invention, the water content of the high-temperature nitrogen discharged from the reactor is regulated and controlled by controlling the flow rate 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 the raw materials, and has more sufficient reaction and high product yield. Meanwhile, the fixed bed reactor can ensure the full contact between the solid lithium source and the oxalic acid compound, and the contact between the raw materials can not be damaged even along with the introduction of the gaseous boron source, so that the full contact reaction between the three raw materials is ensured. While the reactor such as the ebullated bed, the fluidized bed, etc. is easy to cause the separation between the solid raw materials under the disturbance of the gas, so that the raw materials are not contacted or have poor contact, thereby influencing the reaction. Meanwhile, unreacted gas boron source compound can be discharged along with the carrier gas, and the content of impurities in the product is effectively reduced. The LiBOB synthesis reaction process is accompanied by a large amount of water generation, and the water generated in the reaction process can be discharged along with the carrier gas in time by the method provided by the invention, so that the product water removal difficulty is effectively reduced.
After obtaining the lithium bis (oxalate) borate, the invention preferably further comprises dissolving the lithium bis (oxalate) 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 invention, the concentration is preferably 1/4-1/3 concentrated to the volume of the solution. In the present invention, the temperature of the concentration is preferably 30 to 60 ℃. In the invention, the volume ratio of the dichloromethane to the concentrated solution is preferably 1-3: 1. In the present invention, the filtration is preferably performed by suction filtration. In the present invention, the drying is preferably performed in a double cone vacuum dryer; the temperature of the double-cone vacuum dryer during drying is preferably 120-160 ℃, and the vacuum degree is preferably 0.01-0.06 MPa.
In order to further illustrate the present invention, the following detailed descriptions of the technical solutions provided by the present invention are provided with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1) Ball-milling 24g (1mol) of lithium hydroxide and 198g (2.2mol) of anhydrous oxalic acid at the rotating speed of 300r/min for 50min to obtain a uniformly mixed material, and placing the mixed material in a fixed bed reactor;
2) introducing boron trifluoride into a fixed bed reactor for reaction for 7 hours at 100 ℃ under the nitrogen load, controlling the flow of boron trifluoride to be 3.58L/h (0.16mol/h), the flow of nitrogen to be 5L/h, and controlling the water content of an inlet and an outlet of the nitrogen to be respectively: 10ppm, 210 ppm;
3) 185g of crude bisoxalatoboric acid generated by the reaction is dissolved completely by 1300g of ethyl acetate, insoluble impurities are filtered, and the filtrate is concentrated to 1/3 by reduced pressure distillation (the pressure is 0.01Mpa, the temperature is 40 ℃);
4) adding 440g of dichloromethane into the concentrated solution for crystallization, filtering the solution, and drying the filter cake in a double-cone vacuum dryer (the vacuum degree is 0.02Mpa, the temperature is 120 ℃) to obtain high-purity lithium bis (oxalate) borate, wherein the purity of the lithium bis (oxalate) borate is 99.92%, the yield is 80.3%, and the water content is 72 ppm. The XRD pattern of the lithium bis (oxalato) borate prepared is shown in figure 1.
Example 2
1) Ball-milling 24g (1mol) of lithium hydroxide and 216g (2.4mol) of anhydrous oxalic acid at the rotating speed of 350r/min for 40min to obtain a uniformly mixed material, and placing the mixed material in a fixed bed reactor;
2) introducing boron trichloride into a fixed bed reactor for reaction for 10 hours at the temperature of 120 ℃ under the nitrogen load, controlling the flow of boron trichloride to be 3.36L/h (0.15mol/h), controlling the flow of nitrogen to be 6L/h, and controlling the moisture content of an inlet and an outlet of the nitrogen to be respectively: 20ppm, 300 ppm;
3) 189g of crude bisoxalatoboric acid generated in the reaction is completely dissolved by 1200g of ethyl acetate, insoluble impurities are filtered, and the filtrate is concentrated to 1/4 by reduced pressure distillation (the pressure is 0.03Mpa, the temperature is 45 ℃);
4) adding 400g of dichloromethane into the concentrated solution to crystallize the product, filtering the solution, and drying the filter cake in a double-cone vacuum dryer (the vacuum degree is 0.02Mpa, the temperature is 120 ℃) to obtain high-purity lithium bis (oxalate) borate, wherein the purity of the lithium bis (oxalate) borate is 99.95%, the yield is 86.7%, and the water content is 65 ppm. The XRD pattern of the prepared lithium bisoxalato borate is shown in figure 1.
Example 3
1) Ball-milling 24g (1mol) of lithium hydroxide and 216g (2.4mol) of anhydrous oxalic acid at the rotating speed of 320r/min for 40min to obtain a uniformly mixed material, and placing the mixed material in a fixed bed reactor;
2) introducing diborane into a fixed bed reactor for reacting for 8 hours at the temperature of 130 ℃ under the nitrogen load, controlling the flow rate of the diborane to be 1.81L/h (0.081mol/h), the flow rate of the nitrogen to be 4L/h, and controlling the moisture content of an inlet and an outlet of the nitrogen to be respectively: 40ppm, 400 ppm;
3) 176g of crude bisoxalatoboric acid generated by the reaction is completely dissolved by 1400g of ethyl acetate, insoluble impurities are filtered, and the filtrate is concentrated to 1/3 by reduced pressure distillation (the pressure is 0.02Mpa, the temperature is 50 ℃);
4) adding 600g of dichloromethane into the concentrated solution to crystallize the product, filtering the solution, and drying the filter cake in a double-cone vacuum dryer (the vacuum degree is 0.04Mpa, the temperature is 130 ℃) to obtain high-purity lithium bis (oxalate) borate, wherein the purity of the lithium bis (oxalate) borate is 99.5%, the yield is 73.4%, and the water content is 86 ppm. The XRD pattern of the prepared lithium bis (oxalato) borate is shown in figure 1.
Example 4
1) Ball-milling 24g (1mol) of lithium hydroxide and 207g (2.3mol) of anhydrous oxalic acid at the rotating speed of 340r/min for 70min to obtain a uniformly mixed material, and placing the mixed material in a fixed bed reactor;
2) introducing trimethyl boron into a fixed bed reactor for reaction for 6 hours at the temperature of 140 ℃ under the nitrogen load, controlling the flow of trimethyl boron to be 5.15L/h (0.23mol/h), the flow of nitrogen to be 10L/h, and controlling the water content of an inlet and an outlet of the nitrogen to be respectively: 5ppm, 150 ppm;
3) 181g of crude bis (oxalato) boric acid generated by the reaction is completely dissolved by 1800g of ethyl acetate, insoluble impurities are removed by filtration, and the filtrate is concentrated to 1/3 by reduced pressure distillation (the pressure is 0.04Mpa, the temperature is 50 ℃);
4) adding 600g of dichloromethane into the concentrated solution to crystallize the product, filtering the solution, and drying the filter cake in a double-cone vacuum dryer (the vacuum degree is 0.03Mpa, the temperature is 140 ℃) to obtain high-purity lithium bis (oxalate) borate, wherein the purity of the lithium bis (oxalate) borate is 99.91%, the yield is 70.9%, and the water content is 42 ppm. The XRD pattern of the prepared lithium bisoxalato borate is shown in figure 1.
Comparative example 1
The procedure is as in example 1, except that: the fixed bed reactor is replaced by a boiling bed reactor, and the operation is as follows:
1) ball-milling 24g (1mol) of lithium hydroxide and 198g (2.2mol) of anhydrous oxalic acid at the rotating speed of 300r/min for 50min to obtain a uniformly mixed material, and placing the mixed material in a fluidized bed reactor;
2) introducing boron trifluoride into an ebullated bed reactor at 100 ℃ under the nitrogen load for reaction for 7 hours, controlling the flow of boron trifluoride to be 3.58L/h (0.16mol/h), the flow of nitrogen to be 5L/h, and controlling the water content of an inlet and an outlet of the nitrogen to be respectively: 10ppm, 210 ppm;
3) 163g of crude bisoxalatoboric acid generated by the reaction is dissolved completely by 1300g of ethyl acetate, insoluble impurities are filtered, and the filtrate is concentrated to 1/3 by reduced pressure distillation (the pressure is 0.01Mpa, the temperature is 40 ℃);
4) adding 440g of dichloromethane into the concentrated solution for crystallization, filtering the solution, and drying the filter cake in a double-cone vacuum dryer (the vacuum degree is 0.02Mpa, the temperature is 120 ℃) to obtain high-purity lithium bis (oxalate) borate, wherein the purity of the lithium bis (oxalate) borate is 98.1%, the yield is 32%, and the water content is 124 ppm. The XRD pattern of the lithium bis (oxalato) borate prepared is shown in figure 1.
Comparative example 2
The procedure is as in example 1, except that: the fixed bed reactor is changed into a fluidized bed reactor, and the boron source is changed into solid boric acid, and the method specifically comprises the following operation:
1) ball-milling 24g (1mol) of lithium hydroxide, 198g (2.2mol) of anhydrous oxalic acid and boric acid (1mol) for 50min at the rotating speed of 300r/min to obtain a uniformly mixed material, placing the mixed material in a fluidized bed reactor, controlling the temperature of nitrogen at 100 ℃, reacting for 7h, controlling the flow of nitrogen at 5L/h, and controlling the water content of an inlet and an outlet of the nitrogen as follows: 10ppm, 210 ppm;
3) 151g of crude bisoxalatoboric acid generated by the reaction is dissolved by 1300g of ethyl acetate completely, insoluble impurities are filtered, and the filtrate is concentrated to 1/3 by reduced pressure distillation (the pressure is 0.01Mpa, the temperature is 40 ℃);
4) adding 440g of dichloromethane into the concentrated solution for crystallization, filtering the solution, and drying the filter cake in a double-cone vacuum dryer (the vacuum degree is 0.02Mpa, the temperature is 120 ℃) to obtain high-purity lithium bis (oxalate) borate, wherein the purity of the lithium bis (oxalate) borate is 95.3%, the yield is 21%, and the moisture content is 176 ppm. The XRD pattern of the lithium bis (oxalato) borate prepared is shown in figure 1.
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 (10)
1. A preparation method of lithium bis (oxalato) borate is characterized by comprising the following steps:
1) carrying out ball milling on lithium hydroxide and anhydrous oxalic acid, and placing the obtained mixed material into a fixed bed reactor;
2) and introducing the gaseous boron source compound into a fixed bed reactor for reaction under the load of high-temperature nitrogen to obtain the lithium bis (oxalate) borate.
2. The method according to claim 1, wherein the molar ratio of the lithium hydroxide to the anhydrous oxalic acid is 1:2.2 to 2.5.
3. The preparation method according to claim 1, wherein the ball milling time is 40-80 min; the rotating speed of the ball milling is 300-350 r/min.
4. The method of claim 1, wherein the gaseous boron source compound comprises one or more of boron trifluoride, boron trichloride, borane, and trimethylboron.
5. The production method according to claim 1, wherein the molar ratio of boron to lithium hydroxide in the gaseous boron source compound is 1:1.1 to 1.5.
6. The preparation method according to claim 1, wherein the temperature of the high-temperature nitrogen is 100-140 ℃, the gas flow is 3-10L/min, and the reaction time is 6-10 h.
7. The method according to claim 1, wherein the water content of the high-temperature nitrogen introduced into the fixed bed reactor is 5 to 40ppm, and the water content of the high-temperature nitrogen discharged from the fixed bed reactor is 150 to 400 ppm.
8. The preparation method of claim 1, further comprising dissolving lithium bis (oxalato) borate with ethyl acetate, filtering, concentrating, adding dichloromethane for crystallization, filtering and drying after obtaining lithium bis (oxalato) borate.
9. The preparation method of claim 8, wherein the mass ratio of the ethyl acetate to the lithium bis (oxalato) borate is 6-10: 1, and the ethyl acetate and the lithium bis (oxalato) borate are concentrated to 1/4-1/3 of the volume of the solution.
10. The preparation method according to claim 9, wherein the volume ratio of the dichloromethane to the concentrated solution is 1-3: 1.
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