CN109053786B - Preparation method of lithium bis (oxalato) borate - Google Patents
Preparation method of lithium bis (oxalato) borate Download PDFInfo
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- CN109053786B CN109053786B CN201811089625.4A CN201811089625A CN109053786B CN 109053786 B CN109053786 B CN 109053786B CN 201811089625 A CN201811089625 A CN 201811089625A CN 109053786 B CN109053786 B CN 109053786B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 48
- 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 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 54
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 38
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002826 coolant Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 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 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000011112 process operation Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- 229910013188 LiBOB Inorganic materials 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 238000004255 ion exchange chromatography Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003869 coulometry Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method of lithium bis (oxalato) borate, which comprises the following steps: dissolving boron trifluoride in anhydrous hydrofluoric acid to generate tetrafluoroboric acid; adding lithium oxalate, heating to remove hydrofluoric acid, and filtering to obtain a lithium bis (oxalate) borate product containing lithium fluoride; and adding a solvent with high solubility to the lithium bis (oxalato) borate, filtering to obtain a solution only containing the lithium bis (oxalato) borate, evaporating the solution, and drying to obtain the lithium bis (oxalato) borate. The method has the advantages of simple process operation, easy purification, low cost and low energy consumption, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of lithium ion battery material manufacturing, in particular to a preparation method of lithium bis (oxalato) borate.
Background
The lithium ion battery has the advantages of high working voltage, high energy density, low self-discharge rate, no memory effect, long cycle life, convenience, and the like, and is widely applied as a portable power supply. The electrolyte is one of basic raw materials of the lithium ion battery electrolyte, and directly influences the working performance of the lithium ion battery. The lithium salt used by the lithium ion battery at the present stage is generally LiPF6. However, LiPF6Extremely sensitive to moisture, with which trace amounts of moisture can react, and LiPF6Has poor thermal stability, and can decompose to generate HF at high temperature, so as to corrode an electrode material and a current collector. Therefore, the development of a novel lithium salt with good chemical stability, thermal stability and good high-temperature performance becomes a current research hotspot.
The LiBOB serving as a novel electrolyte lithium salt has good chemical stability and thermal stability, the thermal decomposition temperature is higher and can reach 300 ℃, and the safety of the battery is enhanced; the battery does not contain F element, and HF cannot be generated to corrode an electrode material and a current collector, so that the cycle life of the battery is prolonged, and the cost of the battery is reduced; a stable SEI film can be formed on the surface of the carbon cathode, and the SEI film can be used in a pure PC solvent, so that the use temperature range of the battery is widened; the synthetic raw materials are cheap and easy to obtain, the preparation process is simple, and the method is environment-friendly; and has high conductivity and wide electrochemical window, which causes much attention.
At present, the following methods are mainly studied for the preparation of lithium bis (oxalato) borate.
The solid-gas phase contact method is to synthesize the lithium salt by taking basic lithium salt as a raw material at high temperature, and has the advantages of higher requirement on equipment, strict requirement on process control, high synthesis difficulty, low reaction efficiency and difficulty in realizing large-scale production.
German patent DE19829030 proposes compounds containing lithium as starting material, such as LiOH or Li2CO3A method for preparing LiBOB from oxalic acid or oxalate, boric acid or boron oxide. The preparation method is simple and feasible, and the raw materials are cheap and easy to obtain. However, since the whole reaction process is accompanied by the existence of a large amount of water, and the water has great negative influence on the LiBOB used as the electrolyte of the lithium ion battery, how to ensure that the product is anhydrous becomes the key for preparing the LiBOB by the method. In addition, the LiBOB product prepared by the method easily contains unreacted raw material substances such as oxalic acid and the like, and the product purity is low.
U.S. Pat. No. 4, 0034235, 1 uses Li [ B (OCH)3)4]And (CH)3)3SiOOCCSi(CH3) And (3) reacting in an acetonitrile solvent to prepare LiBOB. The preparation method does not generate water in the reaction process, and the obtained product has high purity. The disadvantages are that the raw materials of the synthetic route are difficult to obtain, the cost is high, and the synthetic route is not suitable for industrialized production.
The Chinese patent CN200510011555.7 adopts a solid phase method to synthesize LiBOB, but the method has the disadvantages of high energy consumption, low synthesis efficiency and difficult industrial production.
Therefore, in combination with the above problems, it is an urgent need to solve the problems of the art to provide a method for preparing lithium bis (oxalato) borate.
Disclosure of Invention
In view of the above, the invention provides a preparation method of lithium bis (oxalato) borate, which has the advantages of simple process operation, easy purification, low cost and low energy consumption, and is suitable for large-scale industrial production.
The invention aims to provide a preparation method of lithium bis (oxalato) borate, which comprises the following steps of dissolving boron trifluoride in anhydrous hydrofluoric acid to generate tetrafluoroboric acid; adding lithium oxalate, heating to remove hydrofluoric acid, and filtering to obtain a lithium bis (oxalate) borate product containing lithium fluoride; wherein the synthesis equation is as follows:
HBF4+2Li2C2O4→LiB(C2O4)2+3LiF+HF
and adding a solvent with high solubility to the lithium bis (oxalato) borate, filtering to obtain a solution only containing the lithium bis (oxalato) borate, and drying the solution to obtain the lithium bis (oxalato) borate.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
s1, adding anhydrous hydrofluoric acid into a reaction kettle, introducing boron trifluoride, fully stirring under a closed condition, dissolving the boron trifluoride in the anhydrous hydrofluoric acid to generate tetrafluoroboric acid, and stirring for 4-6 hours under the pressure of 0.01 MPa;
s2, slowly adding lithium oxalate into the reaction kettle and continuously stirring, introducing a low-temperature cooling medium into a jacket, controlling the temperature in the reaction kettle to be 0 ℃, fully reacting after the charging is finished, and continuously stirring for a period of time;
s3, heating the product obtained in the step S2, removing hydrofluoric acid, and filtering to obtain a lithium bis (oxalato) borate product containing lithium fluoride;
and S4, adding a solvent with high solubility to the lithium bis (oxalate) borate, filtering to remove lithium fluoride to obtain a solution only containing the lithium bis (oxalate) borate, and evaporating and drying the solution to obtain the lithium bis (oxalate) borate.
Preferably, the raw material, the HF solvent and the reaction apparatus used in steps S1 to S4 are all subjected to water removal treatment.
By adopting the preferable scheme, the invention has the beneficial effects that: water in the reaction system can be combined with the lithium bis (oxalato) borate to generate a hydrate, so that the purity of the product is influenced, and therefore, in order to ensure high purity of the product, the invention carries out water removal treatment.
Preferably, the mass ratio of boron trifluoride to anhydrous hydrofluoric acid in step S1 is 1-2: 10.
Preferably, the mass ratio of boron trifluoride to anhydrous hydrofluoric acid in step S1 is 3: 25.
Preferably, the reaction temperature in the step S1 is controlled to be-10 to 10 ℃.
By adopting the preferable scheme, the invention has the beneficial effects that: the reaction temperature is controlled within a suitable range, and the decomposition of tetrafluoroboric acid to boron trifluoride can be prevented.
Preferably, in the step S2, the molar ratio of boron trifluoride to lithium oxalate is 1:2 to 2.1.
Preferably, the molar ratio of boron trifluoride to lithium oxalate in step S2 is 1: 2.05.
Preferably, after the reaction is carried out for 2-4 hours in the step S2, stirring is continuously carried out for 4-6 hours.
Preferably, in the step S3, the hydrofluoric acid is heated and removed, the evaporated hydrofluoric acid is recovered by condensation, the condensation temperature is set to-50 to-10 ℃, preferably-25 ℃, and the recovered hydrofluoric acid is reused.
Preferably, the filtration mode of the product obtained after the evaporation crystallization in the step S3 is performed by adopting a pressure filtration mode.
Preferably, in the step S3, the filtration pressure is 0.5 to 2 atmospheres in absolute pressure.
By adopting the preferable scheme, the invention has the beneficial effects that: and a proper filtering mode and filtering pressure are selected, so that most hydrofluoric acid can be discharged through filtering, and the subsequent recycling of hydrofluoric acid is facilitated.
Preferably, the solvent having a higher solubility to lithium bis (oxalato) borate in step S4 includes, but is not limited to, tetrahydrofuran, acetonitrile, dimethyl ether, and ethylene glycol dimethyl ether.
Preferably, the lithium fluoride removed by filtration in step S4 can be used as a battery grade product.
Preferably, the step S4 is to dry the product in the reaction kettle by using hot inert gas.
Preferably, the drying process of step S4 is performed in a dry atmosphere having a water content of less than 10 ppm.
Preferably, the drying process in step S4 includes: and heating the cold inert gas to 40-60 ℃, continuously introducing the hot inert gas for 3 hours, heating the inert gas to 100-150 ℃, and continuously drying for 4-8 hours.
Preferably, the inert gas in step S4 includes, but is not limited to, one or more of nitrogen, argon, and helium.
Preferably, the reaction kettle is a stainless steel reaction kettle with a solid feeding device, a jacket, a thermometer, a pressure gauge, an air vent, a pressure relief port and a filtering device and with the capacity of 316L.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the selected raw materials have sufficient sources and low price.
2. The process flow is simple to operate, and complex experimental equipment is not needed.
3. The productivity of the product is improved, and the method is suitable for large-scale industrial production.
3. The product is easy to purify, low in energy consumption and environment-friendly.
Detailed Description
The technical solutions in the embodiments of the present invention are 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.
Example 1:
the embodiment of the invention discloses a preparation method of lithium bis (oxalato) borate, which adopts the following technical scheme:
s1, adding 150g of anhydrous hydrofluoric acid into a stainless steel reaction kettle with a solid feeding device, a jacket, a thermometer, a pressure gauge, an air vent, a pressure relief port and a filtering device and a capacity of 316L, introducing 18g of boron trifluoride, controlling the reaction temperature to be-10 ℃, controlling the pressure to be below 0.01MPa, fully stirring for 4h under a closed condition, and dissolving the boron trifluoride in anhydrous hydrofluoric acid to generate tetrafluoroboric acid;
s2, slowly adding 55.45g of lithium oxalate into the reaction kettle, continuously stirring, introducing a low-temperature cooling medium into a jacket, controlling the temperature in the reaction kettle to be 0 ℃, completely reacting for 2 hours after the charging is finished, and continuously stirring for 4 hours;
s3, heating the product obtained in the step S2, removing hydrofluoric acid, and filtering to obtain a lithium bis (oxalato) borate product containing lithium fluoride;
s4, adding dimethyl ether, filtering to remove lithium fluoride to obtain a solution only containing lithium bis (oxalato) borate, evaporating the solution, drying the product by using hot nitrogen, heating cold nitrogen to 40 ℃, continuously introducing the hot nitrogen for 3 hours, heating the nitrogen to 100 ℃, and continuously drying for 4 hours to obtain 48.72g of lithium bis (oxalato) borate, wherein the purity of the lithium bis (oxalato) borate is 99.97%, and the water content of the lithium bis (oxalato) borate is 20 ppm.
Watch 1
| Item | Index (I) | Analytical method |
| Purity of the product | 99.97％ | NMR and atomic absorption |
| Moisture content | 20ppm | Fischer coulometric method |
| Ca2+ | 0.5ppm | Ion chromatography |
| Fe3+ | 5.2ppm | Ion chromatography |
Example 2:
the embodiment of the invention discloses a preparation method of lithium bis (oxalato) borate, which adopts the following technical scheme:
s1, adding 180g of anhydrous hydrofluoric acid into a 316L stainless steel reaction kettle with a solid feeding device, a jacket, a thermometer, a pressure gauge, an air vent, a pressure relief port and a filtering device, introducing 18g of boron trifluoride, controlling the reaction temperature to be 0 ℃, controlling the pressure to be below 0.01MPa, fully stirring for 5 hours under a closed condition, and dissolving the boron trifluoride in anhydrous hydrofluoric acid to generate tetrafluoroboric acid;
s2, slowly adding 55.46g of lithium oxalate into the reaction kettle, continuously stirring, introducing a low-temperature cooling medium into a jacket, controlling the temperature in the reaction kettle to be 0 ℃, completely reacting for 3 hours after the charging is finished, and continuously stirring for 5 hours;
s3, heating the product obtained in the step S2, removing hydrofluoric acid, and filtering to obtain a lithium bis (oxalato) borate product containing lithium fluoride;
s4, adding dimethyl ether, filtering to remove lithium fluoride to obtain a solution only containing lithium bis (oxalato) borate, evaporating the solution, drying the product by using hot argon, heating cold argon to 50 ℃, continuously introducing the hot argon for 3 hours, heating argon to 125 ℃, and continuously drying for 6 hours to obtain 49.02g of lithium bis (oxalato) borate, wherein the purity of the lithium bis (oxalato) borate is 99.99%, and the water content of the lithium bis (oxalato) borate is 16 ppm.
Watch two
| Item | Index (I) | Analytical method |
| Purity of the product | 99.99％ | NMR and atomic absorption |
| Moisture content | 16ppm | Fischer coulometric method |
| Ca2+ | 0.3ppm | Ion chromatography |
| Fe3+ | 4.8ppm | Ion chromatography |
Example 3:
the embodiment of the invention discloses a preparation method of lithium bis (oxalato) borate, which adopts the following technical scheme:
s1, adding 90g of anhydrous hydrofluoric acid into a 316L stainless steel reaction kettle with a solid feeding device, a jacket, a thermometer, a pressure gauge, an air vent, a pressure relief port and a filtering device, introducing 18g of boron trifluoride, controlling the reaction temperature to be 10 ℃, controlling the pressure to be below 0.01MPa, fully stirring for 6h under a closed condition, and dissolving the boron trifluoride in anhydrous hydrofluoric acid to generate tetrafluoroboric acid;
s2, slowly adding 55.45g of lithium oxalate into the reaction kettle, continuously stirring, introducing a low-temperature cooling medium into a jacket, controlling the temperature in the reaction kettle to be 0 ℃, completely reacting for 4 hours after the charging is finished, and continuously stirring for 6 hours;
s3, heating the product obtained in the step S2, removing hydrofluoric acid, and filtering to obtain a lithium bis (oxalato) borate product containing lithium fluoride;
and S4, adding dimethyl ether, filtering to remove lithium fluoride to obtain a solution only containing lithium bis (oxalato) borate, evaporating the solution, drying the product by using hot helium, heating cold helium to 60 ℃, continuously introducing the hot helium for 3 hours, heating the helium to 150 ℃, and continuously drying for 8 hours to obtain 49.07g of lithium bis (oxalato) borate, wherein the purity of the lithium bis (oxalato) borate is 99.98%, and the water content of the lithium bis (oxalato) borate is 12 ppm.
Watch III
| Item | Index (I) | Analytical method |
| Purity of the product | 99.98％ | NMR and atomic absorption |
| Moisture content | 12ppm | Fischer coulometric method |
| Ca2+ | 0.3ppm | Ion chromatography |
| Fe3+ | 5.0ppm | Ion chromatography |
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A preparation method of lithium bis (oxalato) borate is characterized by comprising the following specific steps:
s1, adding anhydrous hydrofluoric acid into a reaction kettle, introducing boron trifluoride, fully stirring under a closed condition, dissolving the boron trifluoride in the anhydrous hydrofluoric acid to generate tetrafluoroboric acid, and stirring for 4-6 hours under the pressure of 0.01 MPa;
s2, slowly adding lithium oxalate into the reaction kettle and continuously stirring, introducing a low-temperature cooling medium into a jacket, controlling the temperature in the reaction kettle to be 0 ℃, fully reacting after the charging is finished, and continuously stirring for a period of time;
s3, heating the product obtained in the step S2, removing hydrofluoric acid, and filtering to obtain a lithium bis (oxalato) borate product containing lithium fluoride;
s4, adding a solvent with high solubility to the lithium bis (oxalato) borate, filtering to remove lithium fluoride to obtain a solution only containing the lithium bis (oxalato) borate, evaporating the solution, and drying to obtain the lithium bis (oxalato) borate;
wherein, the step S4 is to dry the product in the reaction kettle by using hot inert gas, and the specific method is as follows: heating the cold inert gas to 40-60 ℃, continuously introducing the hot inert gas for 3 hours, heating the inert gas to 100-150 ℃, and continuously drying for 4-8 hours;
the solvent with high solubility to the lithium bis (oxalato) borate is tetrahydrofuran, acetonitrile, dimethyl ether and ethylene glycol dimethyl ether.
2. The method for preparing lithium bis (oxalato) borate according to claim 1, wherein the mass ratio of boron trifluoride to anhydrous hydrofluoric acid in step S1 is 1-2: 10.
3. The method for preparing lithium bis (oxalato) borate according to claim 1, wherein the reaction temperature in step S1 is controlled to be-10 to 10 ℃.
4. The method for preparing lithium bis (oxalato) borate according to claim 1, wherein the molar ratio of boron trifluoride to lithium oxalate in step S2 is 1:2 to 2.1.
5. The method for preparing lithium bis (oxalato) borate according to claim 1, wherein the stirring is continued for 4-6 hours after the reaction is fully performed for 2-4 hours in step S2.
6. The method for preparing lithium bis (oxalato) borate according to claim 1, wherein the inert gas is one or more of nitrogen, argon and helium.
7. The method for preparing lithium bis (oxalato) borate according to claim 1, wherein the reaction kettle is a stainless steel reaction kettle with a solid feeding device, a jacket, a thermometer, a pressure gauge, a vent, a pressure relief port and a filtering device and with a capacity of 316L.
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| CN116040641A (en) * | 2023-01-17 | 2023-05-02 | 福建德尔科技股份有限公司 | Preparation method of lithium tetrafluoroborate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1127218A (en) * | 1994-10-11 | 1996-07-24 | 埃尔夫阿托化学有限公司 | Production of aqueous solutions of fluoboric acid |
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