CN109019550A - A kind of method that organic solvent prepares lithium hexafluoro phosphate - Google Patents
A kind of method that organic solvent prepares lithium hexafluoro phosphate Download PDFInfo
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- CN109019550A CN109019550A CN201811200646.9A CN201811200646A CN109019550A CN 109019550 A CN109019550 A CN 109019550A CN 201811200646 A CN201811200646 A CN 201811200646A CN 109019550 A CN109019550 A CN 109019550A
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- CN
- China
- Prior art keywords
- organic solvent
- hexafluoro phosphate
- lithium hexafluoro
- lithium fluoride
- lithium
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- 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.)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/005—Lithium hexafluorophosphate
Abstract
The invention discloses a kind of method that organic solvent prepares lithium hexafluoro phosphate, includes the following steps: that 1, lithium fluoride is dissolved in triethylamine equal solvent, obtain solution A；2, liquor B is obtained by filtration in solution A, excessive phosphorus pentafluoride is added in liquor B；3, lithium hexafluoro phosphate product Direct precipitation is precipitated, and then filters, cleans, product can be obtained after drying.Compared with conventional organic solvents method, this method is not needed using surfactant, can really dissolve lithium fluoride, by filtering the other impurities that can be effectively removed in lithium fluoride, therefore can use crude lithium fluoride, and realize the purification of fast and low-cost.Meanwhile the nonpolar solvent used is more stable to phosphorus pentafluoride, is not susceptible to side reaction.
Description
Technical field
The present invention relates to belong to lithium hexafluoro phosphate synthesis field, and in particular to a kind of organic solvent prepares lithium hexafluoro phosphate
Method.
Background technique
In recent years, our countries greatly developed new-energy automobile, to realize energy-saving and emission-reduction, reduced pollution.This policy band
Carry out the great demand to power lithium-ion battery, and results in the insufficient supply of lithium hexafluoro phosphate.The synthesis of lithium hexafluoro phosphate
Technical difficulty with higher.Currently, the synthetic method that China has had some enterprises to grasp lithium hexafluoro phosphate, and realize
Domestic autonomous supply lithium hexafluoro phosphate.
The LiPF that lithium cell electrolyte uses6Due to the unstable characteristic to heat and water, so that preparation high-purity LiPF6
Difficulty it is higher.Industrialized production LiPF at present6Mainly using anhydrous hydrogen fluoride as based on the preparation method of solvent, but this method is very
Difficulty avoids remnants LiPF in product6, and this method is there are product purification difficult and the disadvantages of there are larger security risks.
In recent years, the method that organic solvent method prepares lithium hexafluoro phosphate has been developed.Existing organic solvent method uses carbon
The low alkane ether such as esters of gallic acid solvent, acetonitrile, ether, these solvents cannot dissolve lithium fluoride, it is therefore desirable to surface be added wherein
Activating agent forms suspension, or forms suspension with vigorous stirring, then be passed through phosphorus pentafluoride, carry out gas-solid phase reaction or
Person's liquid and solid phase reaction.Finally obtained lithium hexafluoro phosphate is dissolved in organic solvent, after must being evaporated concentration, crystallization, drying
Obtain product.Organic solvent method has the advantages that reaction condition is mild, raw material is cheap and easy to get, safety is good and it is convenient to purify,
By further improve and perfect, it is more likely that realize large-scale industrial production, be a kind of more promising preparation
Method.
In existing organic solvent method technology of preparing, CN102491305A using anhydrous ether and acetonitrile as solvent,
Lithium fluoride is dissolved, then is reacted with phosphorus pentafluoride, obtained product must evaporate solvent collection, and dissolution filter again, using steaming
Hair purification.CN103213963A prepares lithium hexafluoro phosphate using carbonate-based solvent, and the lithium hexafluoro phosphate that this method obtains can be with
As product directly in the form of electrolyte, product purification bring resolution problem further reduced.CN103253646A is adopted
It uses anhydrous acetonitrile as solvent, after completing liquid phase reactor, crude product is directly dissolved to re-evaporation purification.CN1224405A is disclosed
A kind of method for directly synthesizing liquid phase using ether as solvent, and purified again using solvent extraction, filtering.
Lithium fluoride is added in organic solvent by CN102381695A, and forms suspension, is then passed through five fluorinations in suspension again
Phosphorus gas carries out liquid-solid two-phase reaction, prepares lithium hexafluoro phosphate.
There is also some disadvantages for existing organic solvent method: firstly, be use polarity and weak polar solvent easily with five fluorine
Change phosphorus to react, generate impurity and consumes organic solvent；Secondly as used organic solvent cannot dissolve lithium fluoride,
React synthesis process liquid-solid two-phase, reaction speed is slower, and reaction is not thorough；Again, the lithium hexafluoro phosphate product obtained
It is dissolved in organic solvent, is concentrated by evaporation heavy workload, and lithium hexafluoro phosphate is highly unstable, long-time heating will lead to its point
Solution reduces product purity；Then, conventional organic solvents method is higher to lithium fluoride purity requirement, needs first to carry out complicated fluorine
Change lithium purification, synthesis cost is higher；Finally, due to which lithium fluoride cannot be dissolved in the solvent of traditional solvent, lead to product
In there are lithium fluoride impurity, improve the cost for purification of lithium hexafluoro phosphate.
Summary of the invention
The invention proposes a kind of method that organic solvent prepares lithium hexafluoro phosphate, using less step, more cheap
The reaction condition of raw material, milder synthesizes hexafluorophosphoric acid lithium material.
It realizes the technical scheme is that a kind of method that organic solvent prepares lithium hexafluoro phosphate, steps are as follows:
(1) lithium fluoride is dissolved in tertiary amines organic solvent, obtains solution A；
(2) filtrate A is filtered into removal insoluble matter, obtains liquor B；
(3) phosphorus pentafluoride is passed through into liquor B, heated constant temperature stirring obtains suspension；
(4) lithium hexafluoro phosphate product will be obtained after suspension filtering, cleaning, vacuum drying.
Tertiary amines organic solvent is one of triethylamine, tripropyl amine (TPA) or tri-n-butylamine in the step (1).
The partial size of lithium fluoride is 400 mesh in the step (1).
Phosphorus pentafluoride intake and the molar ratio of lithium fluoride are (1 ~ 2) in the step (3): 1.
Heating temperature is 50 DEG C in the step (3), mixing time 1h.
In the step (4) after suspension filtering, cleaned using pentane.
Vacuum drying temperature is 10-50 DEG C in the step (4), time 1-5h.
The beneficial effects of the present invention are:
(1) organic solvent that the present invention uses is non-polar organic solvent, is not easy to react with phosphorus pentafluoride, Ke Yiyou
The problem of reduction impurity of effect.
(2) organic solvent that the present invention uses can effectively dissolve lithium fluoride, obtain clear by forming lithium key
Solution, can remove the impurity in lithium fluoride by filtering, therefore crude lithium fluoride can be used, reduce lithium fluoride and mention
Flat cost reduces cost of material.
(3) organic solvent that the present invention uses can really realize the dissolution of lithium fluoride, it is ensured that synthesis process is that liquid phase is anti-
It answers, is swift in response and thoroughly, combined coefficient is higher.
(4) synthetic method that the present invention uses is easy to thoroughly carry out for liquid phase reactor, will not introduce lithium fluoride in the product
Impurity avoids the subsequent purification repeatedly of product.
(5) product that the synthetic method that the present invention uses obtains is not dissolved in used organic solvent, can Direct precipitation
It is precipitated, avoids a large amount of evaporation solvent bring lithium hexafluoro phosphate thermal decomposition problems.
(6) synthetic method that the present invention uses is simple and easy, low to lithium fluoride ingredient requirement, and purification lithium fluoride method is simple
And it is at low cost, obtained lithium fluoride purity is high will not introduce impurity, reduce the purification process of lithium hexafluoro phosphate, reduce production
Product thermally decompose impurity.
(7) the synthetic method cost of material that the present invention uses is lower, and step is less, and product purification is simple, synthesis process effect
Rate is high, and at low cost, by-product is few, and product purity is higher, and used organic solvent is more easily recycled utilization.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is present invention process flow diagram.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
A kind of method that organic solvent prepares lithium hexafluoro phosphate, steps are as follows:
(1) lithium fluoride is crushed to 400 mesh, by 2.6 kilograms after crushing of lithium fluoride stirring and dissolving in 100 liters of anhydrous triethylamine
In solvent；
(2) lithium fluoride solution is filtered into removal insoluble matter, obtains filtrate；
(3) it is passed through 126 kilograms of phosphorus pentafluoride in filtrate, and continues 60 DEG C of heated constant temperatures and stirs 1 hour, obtains producing containing precipitating
The suspension of product；
(4) suspension is filtered, obtained filter cake is cleaned using pentane, obtains lithium hexafluoro phosphate after being dried in vacuo 2h at 30 DEG C
Product.
Embodiment 2
A kind of method that organic solvent prepares lithium hexafluoro phosphate, steps are as follows:
(1) lithium fluoride is crushed to 400 mesh, by 2.6 kilograms after crushing of lithium fluoride stirring and dissolving in 100 liters of anhydrous tripropyl amine (TPA)
In solvent；
(2) lithium fluoride solution is filtered into removal insoluble matter, obtains filtrate；
(3) it is passed through 189 kilograms of phosphorus pentafluoride in filtrate, and continues 60 DEG C of heated constant temperatures and stirs 1 hour, obtains producing containing precipitating
The suspension of product；
(4) suspension is filtered, obtained filter cake is cleaned using pentane, obtains lithium hexafluoro phosphate after being dried in vacuo 5h at 10 DEG C
Product.
Embodiment 3
A kind of method that organic solvent prepares lithium hexafluoro phosphate, steps are as follows:
(1) lithium fluoride is crushed to 400 mesh, by 2.6 kilograms after crushing of lithium fluoride stirring and dissolving in 100 liters of anhydrous tri-n-butylamine
In solvent；
(2) lithium fluoride solution is filtered into removal insoluble matter, obtains filtrate；
(3) it is passed through 252 kilograms of phosphorus pentafluoride in filtrate, and continues 60 DEG C of heated constant temperatures and stirs 1 hour, obtains producing containing precipitating
The suspension of product；
(4) suspension is filtered, obtained filter cake is cleaned using pentane, obtains lithium hexafluoro phosphate after being dried in vacuo 1h at 50 DEG C
Product.
In conclusion the method in the present invention can effectively synthesize lithium hexafluoro phosphate.Meanwhile the method and step
Few, method is simple, low in raw material price.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of method that organic solvent prepares lithium hexafluoro phosphate, it is characterised in that steps are as follows:
(1) lithium fluoride is dissolved in tertiary amines organic solvent, obtains solution A；
(2) filtrate A is filtered into removal insoluble matter, obtains liquor B；
(3) phosphorus pentafluoride is passed through into liquor B, heated constant temperature stirring obtains suspension；
(4) lithium hexafluoro phosphate product will be obtained after suspension filtering, cleaning, vacuum drying.
2. the method that organic solvent according to claim 1 prepares lithium hexafluoro phosphate, it is characterised in that: the step (1)
Middle tertiary amines organic solvent is one of triethylamine, tripropyl amine (TPA) or tri-n-butylamine.
3. the method that organic solvent according to claim 1 prepares lithium hexafluoro phosphate, it is characterised in that: the step (1)
The partial size of middle lithium fluoride is 400 mesh.
4. the method that organic solvent according to claim 1 prepares lithium hexafluoro phosphate, it is characterised in that: the step (3)
Middle phosphorus pentafluoride intake and the molar ratio of lithium fluoride are (1 ~ 2): 1.
5. the method that organic solvent according to claim 1 prepares lithium hexafluoro phosphate, it is characterised in that: the step (3)
Middle heating temperature is 50 DEG C, mixing time 1h.
6. the method that organic solvent according to claim 1 prepares lithium hexafluoro phosphate, it is characterised in that: the step (4)
After middle suspension filtering, cleaned using pentane.
7. the method that organic solvent according to claim 1 prepares lithium hexafluoro phosphate, it is characterised in that: the step (4)
In vacuum drying temperature be 10-50 DEG C, time 1-5h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811200646.9A CN109019550A (en) | 2018-10-16 | 2018-10-16 | A kind of method that organic solvent prepares lithium hexafluoro phosphate |
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| CN201811200646.9A CN109019550A (en) | 2018-10-16 | 2018-10-16 | A kind of method that organic solvent prepares lithium hexafluoro phosphate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112707418A (en) * | 2021-01-12 | 2021-04-27 | 苏州华一新能源科技有限公司 | Preparation method of lithium hexafluorophosphate |
| CN116199230A (en) * | 2022-12-15 | 2023-06-02 | 福建省龙德新能源有限公司 | Preparation method of lithium difluorosulfate borate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378445A (en) * | 1993-12-23 | 1995-01-03 | Fmc Corporation | Preparation of lithium hexafluorophosphate solutions |
| CA2259985A1 (en) * | 1996-08-13 | 1998-02-19 | Metallgesellschaft Aktiengesellschaft | Lipf6 production process |
| CN1224405A (en) * | 1996-08-13 | 1999-07-28 | 金属股份公司 | LipF6 production process |
| CN101712467A (en) * | 2009-11-26 | 2010-05-26 | 珠海市赛纬电子材料有限公司 | Synthesis method of lithium hexafluorophosphate |
-
2018
- 2018-10-16 CN CN201811200646.9A patent/CN109019550A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378445A (en) * | 1993-12-23 | 1995-01-03 | Fmc Corporation | Preparation of lithium hexafluorophosphate solutions |
| CA2259985A1 (en) * | 1996-08-13 | 1998-02-19 | Metallgesellschaft Aktiengesellschaft | Lipf6 production process |
| CN1224405A (en) * | 1996-08-13 | 1999-07-28 | 金属股份公司 | LipF6 production process |
| KR20000016746A (en) * | 1996-08-13 | 2000-03-25 | 호르스트 크벨, 브루노 부쎄 | LiPF6 PRODUCTION PROCESS |
| CN101712467A (en) * | 2009-11-26 | 2010-05-26 | 珠海市赛纬电子材料有限公司 | Synthesis method of lithium hexafluorophosphate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112707418A (en) * | 2021-01-12 | 2021-04-27 | 苏州华一新能源科技有限公司 | Preparation method of lithium hexafluorophosphate |
| CN112707418B (en) * | 2021-01-12 | 2022-12-30 | 苏州华一新能源科技股份有限公司 | Preparation method of lithium hexafluorophosphate |
| CN116199230A (en) * | 2022-12-15 | 2023-06-02 | 福建省龙德新能源有限公司 | Preparation method of lithium difluorosulfate borate |
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Application publication date: 20181218 |