CN108912156A - A kind of preparation method of di-oxalate lithium borate - Google Patents
A kind of preparation method of di-oxalate lithium borate Download PDFInfo
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- CN108912156A CN108912156A CN201811103437.2A CN201811103437A CN108912156A CN 108912156 A CN108912156 A CN 108912156A CN 201811103437 A CN201811103437 A CN 201811103437A CN 108912156 A CN108912156 A CN 108912156A
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- lithium borate
- oxalate lithium
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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 System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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Abstract
The invention proposes a kind of preparation method of di-oxalate lithium borate, synthesis process all carries out in a solvent, and oxalic acid is easy the shortcomings that distilling under the conditions of avoiding solid phase reaction, and preparation condition is mild, and reaction step is simple, high income；By-product in entire synthesis process is gas or solid, is easily separated with product；Solvent can recycle, and be recycled, and more economically, reduce the pollution to environment.
Description
Technical field
The present invention relates to lithium ion battery electrolyte lithium salts synthesis field more particularly to a kind of preparations of di-oxalate lithium borate
Method.
Background technique
Important component of the electrolyte as lithium ion battery has very important influence to battery performance.Lithium salts exists
Play the role of in lithium ion battery transmit ion and conduct electric current, and should meet higher solubility, higher conductivity,
Preferable chemical stability, wider electrochemical window and higher aluminium corrosion potential etc. require；In addition should also have and be easy to make
Standby, the environmental-friendly and advantages such as cost is relatively low.
Currently, the electrolyte of the most lithium ion battery of commercial is LiPF6Although LiPF6Electrolyte has higher
Conductivity and wider electrochemical window, but LiPF6Thermal stability it is poor, be readily decomposed into phosphorus pentafluoride and lithium fluoride, this
Two kinds of products have electrode lower reactivity, therefore LiPF6Electrolyte inevitably generates the performance of electrode
Adverse effect restricts the further development of lithium ion battery.
Di-oxalate lithium borate (LiBOB) is a kind of coordination chelate, is capable of forming stable big pi-conjugated system.Anion
BOB-Volume is larger, and lattice energy is smaller, can obtain more ion in a solvent, to improve the conductive energy of electrolyte system
Power.With commercialized LiPF6It compares, the decomposition temperature of LiBOB is 302 DEG C, and high-temperature stability will be got well, and decomposition product is B2O3
And CO2, no pollution to the environment.The decomposition electric potential of LiBOB is also higher than LiPF6, can preferably protect aluminum foil current collector.As
Novel electrolyte lithium salt, some peculiar properties of LiBOB, up for further studying and confirming.
So far, the synthetic method of di-oxalate lithium borate has solid phase method and liquid phase method.
Chinese patent CN107602603A discloses a kind of preparation method of di-oxalate lithium borate, weighs by specified molar ratio
Li source compound, boron source compound and containing oxalic acid with compound, respectively use ball mill grinding, be added to ebullated bed after ground
On pave, with the nitrogen of heating to ebullated bed air blast, nitrogen temperature is controlled at 80-100 DEG C, blasting time 4-8h, then will
Nitrogen temperature is promoted to 150-180 DEG C, and air blast 2-3h obtains di-oxalate lithium borate crude product, finally purifies drying.This method lacks
Point is that the raw material mixing after ball milling is uneven, causes reaction to be not thorough, product yield is low.
Chinese patent CN105503922A discloses the preparation method and applications of di-oxalate lithium borate, by oxalic acid and boric acid
It is dissolved in I class solvent, obtains solution 1, will be dried in vacuo after lithium source solution abstraction impurity removal, concentration, obtain high purity lithium source power, dissolve
In II class solvent, solution 2 is obtained, solution 1 is heated to 50-80 DEG C, and solution 2 is added dropwise, and remains temperature-resistant, stirring 5-8h is sufficiently anti-
It answers, reaction terminates cooling, and stratification takes lower layer's suspension to filter to obtain clear solution 3, and solution 3 is warming up to 90 DEG C or more, is steamed
Solvent out obtains di-oxalate lithium borate product after dry.The disadvantage is that synthesis step is more, equipment and process cost increase this method,
It is more to be related to solvent type, separating-purifying increased costs.
Summary of the invention
In view of this, the invention proposes a kind of di-oxalate lithium borates for preparing simple, high income, the easily separated purification of product
Preparation method.
The technical proposal of the invention is realized in this way：The present invention provides a kind of preparation method of di-oxalate lithium borate,
Include the following steps,
S1 is sufficiently stirred after mixing oxalic acid, lithium fluoride, boron trifluoride complex and organic solvent；
Reaction promoter is slowly added in the mixture of above-mentioned steps S1 by S2, is stirred to react under assigned temperature；
S3 is evaporated under reduced pressure the mixture of step S2, and removing solvent can be obtained di-oxalate lithium borate.
On the basis of above technical scheme, it is preferred that the oxalic acid：Lithium fluoride：Boron trifluoride complex：Reaction promoter
Between molar ratio be 2:(0.9~1):(0.9~1):(1~1.2).
On the basis of above technical scheme, it is preferred that the mixing temperature of the step S1 is 0-60 DEG C, and mixing time is
10-20min。
On the basis of above technical scheme, it is preferred that the boron trifluoride complex is boron trifluoride ether solution, three
Boron fluoride methanol solution, boron trifluoride tetrahydrofuran solution, boron trifluoride dimethyl ether solution, boron trifluoride diethyl ether solution and three
At least one of boron fluoride acetonitrile solution.
On the basis of above technical scheme, it is preferred that the organic solvent is γ-fourth lactones, acetonitrile, carbonic acid diformazan
At least one of ester, methyl ethyl carbonate and diethyl carbonate.
On the basis of above technical scheme, it is preferred that the reaction promoter is silicon tetrachloride, alchlor, tri-chlorination
At least one of boron.
On the basis of above technical scheme, it is preferred that in step S2, reaction promoter dropping temperature is 0-30 DEG C, is added dropwise
Time is 0.5-1h, and reaction temperature is 0-30 DEG C, reaction time 3-5h.
On the basis of above technical scheme, it is preferred that in step S3, vacuum distillation temperature is 40-100 DEG C, vacuum degree
For -0.1-0.1MPa.
The preparation method of di-oxalate lithium borate of the invention has the advantages that compared with the existing technology：
(1) synthesis process all carries out in a solvent, and oxalic acid is easy the shortcomings that distilling, system under the conditions of avoiding solid phase reaction
Standby mild condition, reaction step is simple, high income；
(2) by-product in entire synthesis process is gas or solid, is easily separated with product；
(3) solvent can recycle, and be recycled, and more economically, reduce the pollution to environment.
Specific embodiment
Below in conjunction with embodiment of the present invention, the technical solution in embodiment of the present invention is carried out clearly and completely
Description, it is clear that described embodiment is only some embodiments of the invention, rather than whole embodiments.Base
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts all
Other embodiments shall fall within the protection scope of the present invention.
Embodiment 1
Present embodiment discloses a kind of preparation methods of di-oxalate lithium borate, include the following steps：
One it is well-dried and be formulated with stirring, dropping funel, thermometer volume be 2L four-hole boiling flask in plus
Enter acetonitrile 900g, oxalic acid 1mol, boron trifluoride acetonitrile solution 0.5mol, lithium fluoride 0.5mol stirs 10min at 15-25 DEG C, mixes
It closes uniform；Silicon tetrachloride 0.5mol is slowly added dropwise into mixed liquor by dropping funel again, control reaction temperature is 0-30 DEG C, drop
It is 0.5h between added-time, has gas generation during being added dropwise, after being added dropwise, continues to stir 3h, no longer generate gas, reaction at this time
Terminate；Be evaporated under reduced pressure under being -0.1-0.1MPa in 40-100 DEG C, vacuum degree, remove solvent acetonitrile and hydrogen chloride in solvent and
Ocratation obtains white solid product 96.5g, yield 99.7%.
Embodiment 2
Present embodiment discloses a kind of preparation methods of di-oxalate lithium borate, include the following steps：
One it is well-dried and be formulated with stirring, dropping funel, thermometer volume be 2L four-hole boiling flask in plus
Enter acetonitrile 900g, oxalic acid 1mol, boron trifluoride acetonitrile solution 0.5mol, lithium fluoride 0.5mol stirs 12min at 15-25 DEG C, mixes
It closes uniform；Alchlor 0.5mol is slowly added dropwise into mixed liquor by dropping funel again, alchlor is dissolved in ether in advance,
Controlling reaction temperature is 0-30 DEG C, time for adding 0.6h, has gas and milky white precipitate to generate during being added dropwise, is added dropwise
Afterwards, continue to stir 4h, no longer generate gas at this time, reaction terminates；Milky white precipitate is separated with reaction solution by filtering,
40-100 DEG C, vacuum degree be that the hydrogen chloride removed in solvent acetonitrile and solvent is evaporated under reduced pressure to reaction solution under -0.1-0.1MPa, obtain
To white solid product 96.0g, yield 99.1%.
Embodiment 3
Present embodiment discloses a kind of preparation methods of di-oxalate lithium borate, include the following steps：
One it is well-dried and be formulated with stirring, dropping funel, thermometer volume be 2L four-hole boiling flask in plus
Enter γ-fourth lactones 1000g, oxalic acid 1mol, boron trifluoride ether solution 0.5mol, lithium fluoride 0.5mol is stirred at 15-25 DEG C
13min is uniformly mixed；Silicon tetrachloride 0.5mol is slowly added dropwise into mixed liquor by dropping funel again, control reaction temperature is
0-30 DEG C, time for adding 0.8h, there is gas generation during being added dropwise, after being added dropwise, continues to stir 4h, no longer generate at this time
Gas, reaction terminate；Vacuum distillation removes in solvent acetonitrile and solvent under being -0.1-0.1MPa in 40-100 DEG C, vacuum degree
Hydrogen chloride and ocratation obtain white solid product 96.4g, yield 99.5%.
Embodiment 4
Present embodiment discloses a kind of preparation methods of di-oxalate lithium borate, include the following steps：
One it is well-dried and be formulated with stirring, dropping funel, thermometer volume be 2L four-hole boiling flask in plus
Enter γ-fourth lactones 1000g, oxalic acid 1mol, boron trifluoride ether solution 0.5mol, lithium fluoride 0.5mol is stirred at 15-25 DEG C
15min is uniformly mixed；Alchlor 0.5mol is slowly added dropwise into mixed liquor by dropping funel again, alchlor is molten in advance
In ether, control reaction temperature is 0-30 DEG C, time for adding 1h, has gas and milky white precipitate to generate during being added dropwise,
After being added dropwise, continues to stir 5h, no longer generate gas at this time, reaction terminates；By filtering milky white precipitate and reaction solution
Separation is evaporated under reduced pressure the chlorine removed in solvent acetonitrile and solvent to reaction solution under being -0.1-0.1MPa in 40-100 DEG C, vacuum degree
Change hydrogen, obtains white solid product 96.1g, yield 99.2%.
The foregoing is merely better embodiments of the invention, are not intended to limit the invention, all of the invention
Within spirit and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of di-oxalate lithium borate, it is characterised in that：Include the following steps,
S1 is sufficiently stirred after mixing oxalic acid, lithium fluoride, boron trifluoride complex and organic solvent；
Reaction promoter is slowly added in the mixture of above-mentioned steps S1 by S2, is stirred to react under assigned temperature；
S3 is evaporated under reduced pressure the mixture of step S2, and removing solvent can be obtained di-oxalate lithium borate.
2. the preparation method of di-oxalate lithium borate as described in claim 1, it is characterised in that：The oxalic acid：Lithium fluoride：Trifluoro
Change boron complex：Molar ratio between reaction promoter is 2:(0.9~1):(0.9~1):(1~1.2).
3. the preparation method of di-oxalate lithium borate as described in claim 1, it is characterised in that：The mixing temperature of the step S1
It is 0-60 DEG C, mixing time 10-20min.
4. the preparation method of di-oxalate lithium borate as described in claim 1, it is characterised in that：The boron trifluoride complex is
Boron trifluoride ether solution, boron trifluoride methanol solution, boron trifluoride tetrahydrofuran solution, boron trifluoride dimethyl ether solution, three
At least one of boron fluoride diethyl ether solution and boron trifluoride acetonitrile solution.
5. the preparation method of di-oxalate lithium borate as described in claim 1, it is characterised in that：The organic solvent is γ-fourth
At least one of lactones, acetonitrile, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate.
6. the preparation method of di-oxalate lithium borate as described in claim 1, it is characterised in that：The reaction promoter is four chlorinations
At least one of silicon, alchlor, boron chloride.
7. the preparation method of di-oxalate lithium borate as described in claim 1, it is characterised in that：In step S2, reaction promoter drop
Heating degree is 0-30 DEG C, time for adding 0.5-1h, and reaction temperature is 0-30 DEG C, reaction time 3-5h.
8. the preparation method of di-oxalate lithium borate as described in claim 1, it is characterised in that：In step S3, vacuum distillation temperature
Degree is 40-100 DEG C, and vacuum degree is -0.1-0.1MPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110684042A (en) * | 2019-11-18 | 2020-01-14 | 江苏华盛锂电材料股份有限公司 | Preparation method of lithium bis (oxalato) borate |
| CN113549095A (en) * | 2021-07-13 | 2021-10-26 | 河北津宏化工有限公司 | Preparation process of lithium bis (oxalato) borate |
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| KR20000051923A (en) * | 1999-01-27 | 2000-08-16 | 박대치 | A Manufacturing Method for Lithium Tetrafluoroborate |
| US20030100761A1 (en) * | 2001-11-05 | 2003-05-29 | Central Glass Company, Limited | Process for synthesizing ionic metal complex |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110684042A (en) * | 2019-11-18 | 2020-01-14 | 江苏华盛锂电材料股份有限公司 | Preparation method of lithium bis (oxalato) borate |
| CN113549095A (en) * | 2021-07-13 | 2021-10-26 | 河北津宏化工有限公司 | Preparation process of lithium bis (oxalato) borate |
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