CN104211029B - A kind of preparation method of lithium hexafluoro phosphate - Google Patents
A kind of preparation method of lithium hexafluoro phosphate Download PDFInfo
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- CN104211029B CN104211029B CN201410349454.XA CN201410349454A CN104211029B CN 104211029 B CN104211029 B CN 104211029B CN 201410349454 A CN201410349454 A CN 201410349454A CN 104211029 B CN104211029 B CN 104211029B
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Abstract
The present invention relates to technical field of lithium batteries, for solving the problem that in the preparation process of current lithium hexafluoro phosphate, reaction is violent, security is poor, the present invention proposes the preparation method of a kind of lithium hexafluoro phosphate, and (1) carries out rectifying purifying to anhydrous hydrogen fluoride, obtains high-purity anhydrous hydrogen fluoride；(2) lithium fluoride is dissolved in high-purity anhydrous hydrogen fluoride, obtains the anhydrous hydrogen fluoride solution containing lithium fluoride；(3) add phosphorus pentachloride, prepare lithium hexafluoro phosphate saturated solution；(4) by lithium hexafluoro phosphate saturated solution through low temperature crystallization, separation of solid and liquid, be dried, crushing packing obtain lithium hexafluoro phosphate product；Production technology of the present invention is simple, and safe and reliable, raw material is easy to get, and production efficiency is high, and gained lithium hexafluoro phosphate product purity is high, and quality is good.
Description
Technical field
The present invention relates to technical field of lithium batteries, relate in particular to the preparation method of a kind of high-purity lithium hexafluoro phosphate.
Background technology
In recent years, lithium ion battery by its energy density is big, operating voltage is high, self discharge is little, have extended cycle life, the advantage such as pollution-free, be widely used on the electronic products such as mobile phone, notebook computer, video camera.Lithium hexafluoro phosphate (LiPF6) it is one of the important composition material of lithium-ion battery electrolytes, solubility, electrical conductivity, security and the feature of environmental protection most advantage in organic solvent, become the lithium salts electrolyte that current range of application is the widest.But lithium ion battery still suffers from the problem points such as charging interval, heat-resisting quantity.Lithium battery manufacturer is in order to improve performance and the security of product, to lithium hexafluoro phosphate (LiPF6) index request more and more stricter.
The Chinese invention patent of Application No. 201010550107.5 discloses the preparation method of a kind of lithium hexafluoro phosphate, and this invention utilizes hydrogen fluoride and phosphorus pentachloride to react the mixed gas obtaining phosphorus pentafluoride with hydrogen chloride；This mixed gas is passed in hydrogen fluoride and lithium fluoride, makes reaction under uniform temperature and pressure prepare lithium hexafluorophosphate solution；Last Crystallization Separation, filtration drying obtains lithium hexafluoro phosphate product.The shortcoming of the method is to use hydrogen fluoride to react with phosphorus pentachloride to obtain phosphorus pentafluoride, and with phosphorus pentafluoride for synthesizing the raw material of lithium hexafluoro phosphate, but this reaction is extremely violent, and misoperation is susceptible to blast.
Summary of the invention
For solving the problem that in the preparation process of current lithium hexafluoro phosphate, reaction is violent, security is poor, the present invention proposes the preparation method of a kind of lithium hexafluoro phosphate, and production technology of the present invention is simple, safe and reliable, raw material is easy to get, and production efficiency is high, gained lithium hexafluoro phosphate product purity is high, and quality is good.
The present invention is achieved by the following technical solutions: the preparation method of a kind of lithium hexafluoro phosphate is following steps:
(1) anhydrous hydrogen fluoride is carried out rectifying purifying, obtain high-purity anhydrous hydrogen fluoride；
As preferably, after rectifying, in high-purity anhydrous hydrogen fluoride, moisture is 1 ~ 20ppm, and metal ion content is less than 10ppb；
(2) lithium fluoride is dissolved in the high-purity anhydrous hydrogen fluoride of step (1), obtains the anhydrous hydrogen fluoride solution containing lithium fluoride；
Because the course of dissolution of lithium fluoride can discharge substantial amounts of heat, need to cool reaction vessel, as preferably, in course of dissolution, temperature controls at-20 DEG C ~ 20 DEG C, and Stress control is at-0.05 Mpa ~ 0.18Mpa；
(3) in solution prepared by step (2), add phosphorus pentachloride, prepare lithium hexafluoro phosphate saturated solution；
As preferably, lithium fluoride, phosphorus pentachloride, the mass ratio of anhydrous hydrogen fluoride are 1:5.04 ~ 10.45:17.3 ~ 37.6.
Reaction temperature controls as-20 DEG C ~ 20 DEG C, and Stress control is at-0.05 Mpa ~ 0.4Mpa.
(4) by lithium hexafluoro phosphate saturated solution through low temperature crystallization, separation of solid and liquid, be dried, crushing packing obtain lithium hexafluoro phosphate product；
As preferably, lithium hexafluoro phosphate saturated solution being sent into partial crystallization groove, slow cooling is to less than-80 DEG C, separate out hexafluorophosphoric acid crystalline lithium, being carried out separation of solid and liquid again, the crystal of gained is dried 1 ~ 8 hour at temperature 25 DEG C ~ 135 DEG C, obtains the lithium hexafluoro phosphate product being dried.
The method that hydrogen fluoride evaporation is separated by described dry employing, obtains lithium hexafluoro phosphate product the most after crushed.
As preferably, the mother liquid recycling that separation of solid and liquid obtains, add lithium fluoride and phosphorus pentachloride, prepare lithium hexafluoro phosphate saturated solution.
Compared with prior art, the invention has the beneficial effects as follows: production technology of the present invention is simple, and safe and reliable, raw material is easy to get, production efficiency is high, and gained lithium hexafluoro phosphate product purity is high, and quality is good.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the present invention.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail.
Embodiment 1
(1) preparation of high-purity hydrogen fluoride: in airtight steel lining fluorine plastic containers, add 400kg anhydrous hydrogen fluoride, heat through fluoroplastics reboiler, the hydrogen fluoride gas that rectifying goes out is condensed by condenser, condensation temperature controls below 0 DEG C, and controlling reflux ratio is 1 ~ 2, it is thus achieved that high-purity anhydrous hydrogen fluoride, wherein in anhydrous hydrogen fluoride, moisture controls at 9ppb at 20ppm, metal ion content.
(2) preparation of lithium fluoride solution: be passed through high pure nitrogen in steel lining fluorine plastics reactor with the air in replacement reaction kettle, add high-purity anhydrous hydrogen fluoride prepared by 180kg step (1), 6kg lithium fluoride, wherein, lithium fluoride purity >=99.9% is added again by feeder；Utilize pump to be circulated, make lithium fluoride be completely dissolved in anhydrous hydrogen fluoride.Reacting kettle jacketing leads to chilled water, and chilled water temperature is 7 DEG C, and controlling reactor temperature is less than 19 DEG C, and pressure is 0.18MPa.
(3) preparation of lithium hexafluorophosphate solution: in the lithium fluoride solution of step (2) gained, is slowly uniformly added into 48.2kg phosphorus pentachloride by feeder；Utilize pump to be circulated, react fully and carry out generating lithium hexafluoro phosphate saturated solution.Reacting kettle jacketing leads to chilled water, and chilled water temperature is-19 DEG C, and controlling course of reaction temperature is less than 15 DEG C, and pressure is 0.38MPa.Course of reaction can produce hydrogen chloride gas and hydrogen fluoride gas, by this gas by condenser, reclaims hydrogen fluoride gas.
(4) Crystallization Separation step: move to crystallize in partial crystallization groove by the lithium hexafluoro phosphate saturated solution that step (3) generates, final temperature to-30 DEG C, after crystallization process terminates, passes through equipment for separating liquid from solid by crystal and liquid, liquid is drained into mother liquor tank.Crystal is transferred in drying device, elevates the temperature to 70 DEG C and is dried 5 hours, obtains 8.2kg high-purity lithium hexafluoro phosphate product the most after crushed.By analysis, obtaining the purity 99.98% of product, free acid is 58ppm, and insoluble matter is 68ppm.
Mother liquor recycles, and by measuring the concentration of lithium hexafluoro phosphate in mother liquor, calculates lithium fluoride next time, phosphorus pentachloride and the addition of anhydrous hydrogen fluoride.
Embodiment 2
(1) preparation of high-purity hydrogen fluoride: in airtight steel lining fluorine plastic containers, add 400kg anhydrous hydrogen fluoride, heat through fluoroplastics reboiler, the hydrogen fluoride gas that rectifying goes out is condensed by condenser, condensation temperature controls at-5 DEG C, and controlling reflux ratio is 2 ~ 4, it is thus achieved that high-purity anhydrous hydrogen fluoride, wherein in anhydrous hydrogen fluoride, moisture controls at 5ppb at 10ppm, metal ion content.
(2) preparation of lithium fluoride solution: be passed through high pure nitrogen in steel lining fluorine plastics reactor with the air in replacement reaction kettle, add the high-purity anhydrous hydrogen fluoride of 150kg, then add 6kg lithium fluoride, wherein, lithium fluoride purity >=99.9% by feeder；Utilize pump to be circulated, make lithium fluoride be completely dissolved in anhydrous hydrogen fluoride.Reacting kettle jacketing leads to chilled water, and chilled water temperature is-19 DEG C, and controlling reactor temperature is 0 DEG C, and pressure is 0.05MPa.
(3) preparation of lithium hexafluorophosphate solution: in the lithium fluoride solution of step (2) gained, is slowly uniformly added into 42kg phosphorus pentachloride by feeder；Utilize pump to be circulated, react fully and carry out generating lithium hexafluoro phosphate saturated solution.Reacting kettle jacketing leads to chilled water, and chilled water temperature is-19 DEG C, and controlling course of reaction temperature is 0 DEG C, and pressure is 0.1MPa.Course of reaction can produce hydrogen chloride gas and hydrogen fluoride gas, by this gas by condenser, reclaims hydrogen fluoride gas.
(4) Crystallization Separation step: move to crystallize in partial crystallization groove by the lithium hexafluoro phosphate saturated solution that step (3) generates, final temperature to-40 DEG C, passes through equipment for separating liquid from solid by crystal and liquid, liquid is drained into mother liquor tank.Crystal is transferred in drying device, elevates the temperature to 135 DEG C and is dried 1 hour, obtains 8.9kg high-purity lithium hexafluoro phosphate product the most after crushed.By analysis, obtaining the purity 99.975% of product, free acid is 36ppm, and insoluble matter is 52ppm.
Mother liquor recycles, and by measuring the concentration of lithium hexafluoro phosphate in mother liquor, calculates lithium fluoride next time, phosphorus pentachloride and the addition of anhydrous hydrogen fluoride.
Embodiment 3
(1) preparation of high-purity hydrogen fluoride: in airtight steel lining fluorine plastic containers, add 400kg anhydrous hydrogen fluoride, heat through fluoroplastics reboiler, the hydrogen fluoride gas that rectifying goes out is condensed by condenser, condensation temperature controls below 0 DEG C, and controlling reflux ratio is 3 ~ 4, it is thus achieved that high-purity anhydrous hydrogen fluoride, wherein in anhydrous hydrogen fluoride, moisture controls at 3ppb at 1ppm, metal ion content.
(2) preparation of lithium fluoride solution: the preparation of lithium fluoride solution: be passed through high pure nitrogen in steel lining fluorine plastics reactor with the air in replacement reaction kettle, add high-purity anhydrous hydrogen fluoride prepared by 225.6kg step (1), 6kg lithium fluoride is added again by feeder, wherein, lithium fluoride purity >=99.9%；Utilize pump to be circulated, make lithium fluoride be completely dissolved in anhydrous hydrogen fluoride.Reacting kettle jacketing leads to chilled water, and chilled water temperature is-19 DEG C, controls reactor temperature and is-10 DEG C, and pressure is-0.04MPa.
(3) preparation of lithium hexafluorophosphate solution: in the lithium fluoride solution of step (2) gained, is slowly uniformly added into 62.7kg phosphorus pentachloride by feeder；Utilize pump to be circulated, react fully and carry out generating lithium hexafluoro phosphate saturated solution.Reacting kettle jacketing leads to chilled water, and chilled water temperature is-19 DEG C, controls course of reaction temperature and is-10 DEG C, and pressure is-0.05MPa.Course of reaction can produce hydrogen chloride gas and hydrogen fluoride gas, by this gas by condenser, reclaims hydrogen fluoride gas.
(4) Crystallization Separation step: move to crystallize in partial crystallization groove by the lithium hexafluoro phosphate saturated solution that step (3) generates, final temperature to-80 DEG C, passes through equipment for separating liquid from solid by crystal and liquid, liquid is drained into mother liquor tank.Crystal is transferred in drying device, elevates the temperature to 25 DEG C and is dried 8 hours, obtains 9.7kg high-purity lithium hexafluoro phosphate product the most after crushed.By analysis, obtaining the purity 99.97% of product, free acid is 63ppm, and insoluble matter is 75ppm.
Mother liquor recycles, and by measuring the concentration of lithium hexafluoro phosphate in mother liquor, calculates lithium fluoride next time, phosphorus pentachloride and the addition of anhydrous hydrogen fluoride.
Claims (6)
1. the preparation method of a lithium hexafluoro phosphate, it is characterised in that described preparation method is following steps:
(1) anhydrous hydrogen fluoride being carried out rectifying purifying, obtain high-purity anhydrous hydrogen fluoride, after rectifying, in high-purity anhydrous hydrogen fluoride, moisture is 1 ~ 20ppm, and metal ion content is less than 10ppb；
(2) lithium fluoride is dissolved in the high-purity anhydrous hydrogen fluoride of step (1), obtains the anhydrous hydrogen fluoride solution containing lithium fluoride；
(3) in solution prepared by step (2), add phosphorus pentachloride, prepare lithium hexafluoro phosphate saturated solution；
(4) by lithium hexafluoro phosphate saturated solution through low temperature crystallization, separation of solid and liquid, be dried, crushing packing obtain lithium hexafluoro phosphate product,
Lithium hexafluoro phosphate saturated solution being sent into partial crystallization groove, is cooled to less than-80 DEG C, separate out hexafluorophosphoric acid crystalline lithium, then carried out separation of solid and liquid, the crystal of gained is dried 1 ~ 8 hour at temperature 25 DEG C ~ 135 DEG C, obtains the lithium hexafluoro phosphate product being dried.
The preparation method of a kind of lithium hexafluoro phosphate the most according to claim 1, it is characterised in that in step (2), in course of dissolution, temperature controls at-20 DEG C ~ 20 DEG C, and Stress control is at-0.05 Mpa ~ 0.18Mpa.
The preparation method of a kind of high-purity lithium hexafluoro phosphate the most according to claim 1, it is characterised in that step (3) reaction temperature controls as-20 ~ 20 DEG C, and Stress control is at-0.05 Mpa ~ 0.4Mpa.
The preparation method of a kind of lithium hexafluoro phosphate the most according to any one of claim 1 to 3, it is characterised in that step (2) is with (3), and lithium fluoride, phosphorus pentachloride, the mass ratio of anhydrous hydrogen fluoride are 1:5.04 ~ 10.45:17.3 ~ 37.6.
The preparation method of a kind of lithium hexafluoro phosphate the most according to claim 1, it is characterised in that described drying means is hydrogen fluoride evaporation to be separated, and obtains lithium hexafluoro phosphate product the most after crushed.
The preparation method of a kind of lithium hexafluoro phosphate the most according to claim 1, it is characterised in that the mother liquid recycling that step (4) separation of solid and liquid obtains, adds lithium fluoride and phosphorus pentachloride, prepares lithium hexafluoro phosphate saturated solution.
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| CN108439362A (en) * | 2018-05-18 | 2018-08-24 | 青海聚之源新材料有限公司 | A kind of preparation method of high-end lithium hexafluoro phosphate |
| CN109911852B (en) * | 2019-03-14 | 2023-08-04 | 青海聚之源新材料有限公司 | Waste mother liquor recycling device and recycling method for lithium hexafluorophosphate preparation |
| CN111620356A (en) * | 2020-03-27 | 2020-09-04 | 白银中天化工有限责任公司 | Method for liquid-phase purification of low-grade lithium fluoride |
| CN111977674A (en) * | 2020-08-21 | 2020-11-24 | 湖北迈可凯科技有限公司 | Device and method for continuously preparing lithium fluorosulfonate |
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Application publication date: 20141217 Assignee: Shanshan new materials (Quzhou) Co. Ltd. Assignor: Zhejiang Dongfu Plastics Co., Ltd. Contract record no.: 2017330000054 Denomination of invention: Method for preparing lithium hexafluorophosphate Granted publication date: 20160907 License type: Common License Record date: 20170509 |
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