CN103253646A - Organic solvent method for preparation of high purity lithium hexafluorophosphate - Google Patents
Organic solvent method for preparation of high purity lithium hexafluorophosphate Download PDFInfo
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Abstract
The invention relates to an organic solvent method for preparation of high purity lithium hexafluorophosphate. The method is characterized by: making high purity lithium fluoride fully suspended in an anhydrous acetonitrile solution under sealing stirring conditions, conducting pressurizing and introducing a phosphorus pentafluoride gas, and leaving them to react so as to synthesize high purity lithium hexafluorophosphate. The invention has the advantages that: (1) anhydrous acetonitrile is used to replace HF to serve as a solvent in the invention, so that risks of a production process by an HF solvent method are completely avoided, the production process causes no impurity contamination on the final product, and corrosion of HF on production equipment is also avoided at the same time, the production process is carried out at room temperature, and the energy consumption is low; (2) in the whole phase system, only LiPF6 dissolves in anhydrous acetonitrile, therefore, the reaction speed of the process is fast, the generated LiPF6 has high purity, the main content is greater than 99.9%, the HF content is less than 10ppm, the total impurity metal content is less than 50ppm, and the moisture content is less than 10ppm; and (3) the process involved in the invention is simple, the production process has no pollution to the environment, so that the method has industrial promotion value.
Description
Technical field
The present invention relates to the lithium ion battery field, particularly the preparation of electrolyte lithium salt.
Background technology
Lithium hexafluoro phosphate (LiPF
6) be a kind of white powder solid, be soluble in non-aqueous solvents such as anhydrous hydrogen fluoride, low alkyl oxide, nitrile, pyridine, organic carbonate (EC, PC, DEC, DMC, EMC), tetrahydrofuran (THF), be insoluble in alkane and benzene equal solvent.At present, LiPF
6Be most popular electrolyte lithium salt in the commercialization lithium ion battery, its major advantage is: (1) can form suitable SEI film on the electrode especially on the carbon negative pole; (2) plus plate current-collecting body is realized effective passivation, to stop its dissolving; (3) wideer electrochemical stability window is arranged; (4) suitable solubleness and higher specific conductivity are arranged in various non-aqueous solvents; (5) environment friendly is relatively preferably arranged.
And lithium ion battery is the most competitive superior product in global secondary cell field.Along with the steady increase of lithium ion battery demand, LiPF
6Demand also can increase steadily.It is predicted LiPF
6Consumption will reach more than 10000 tons to the year two thousand twenty.But because existing method is produced LiPF
6Product purity requires height, production is dangerous greatly, raw material preparing is difficult, fails to make a breakthrough always.
At present, the LiPF that has reported
6The preparation method is broadly divided into three major types: HF solvent method, ion exchange method, gas-solid direct reaction method etc.Wherein the HF solvent method is preparation LiPF
6The most traditional method, more to its research in history, be a most ripe at present operational path, also be to carry out a most successful operational path of industrialization.Its cardinal principle is: the employing anhydrous HF is solvent, mainly is LiF with LiX() be dissolved in wherein, directly feed phosphorous material (phosphorus source) then, purifying through reaction back evaporative crystallization obtains product.Wherein the chemical equation of typical process route is:
PCl
5?+?5HF?=?PF
5?+?5HCl
PF
5+ LiF=LiPF
6(in the HF solvent, reacting)
The overall advantage of this technology is that speed of response is fast, starting material transformation efficiency height.But the maximum deficiency of this technology is to remain in HF in the product with title complex LiPF
6The form of HF is present in the product, and general method is extremely difficult to be reduced to 10 * 10 with the content in the product
-6Below (massfraction).Because the residual battery material of HF has corrosion, thereby influences battery electrical property.Moreover this technology requires all high to the anti-corrosion measure of equipment and the security measures of material requirement and production.Also having this technology is cryogenic technology, and energy consumption is big.
Ion exchange method can be divided into two big classes: the one, and ion-exchange-resin process; The 2nd, hexafluorophosphate ion exchange method.Wherein hexafluorophosphate ion exchange method refers to that ion exchange reaction is taken place for hexafluorophosphate and lithium-containing compound obtains LiPF in organic solvent
6Method.This method has been avoided use PF
5Be raw material, reaction simultaneously settles at one go.The United States Patent (USP) play-by-play a kind of method wherein, point out non-lithium basic metal, NH
4 +, organic amine hexafluorophosphate react in ether or acetonitrile with the compound that contains lithium and can obtain LiPF
6, its reaction pattern is:
MPF
6?+?LiR?=?LiPF
6?+?MR
At present, ion exchange method prepares LiPF
6Common shortcoming be the LiPF that makes
6Purity is not high, generally all contains other intact hexafluorophosphates of unreacted.If research effort can make a breakthrough in this respect, then certainly will promote for this technology and produce important meaning.
Gaseous state PF
5With the direct prepared in reaction LiPF under high-temperature and high-pressure conditions of solid-state LiF
6, this method is simple, and research is also early.Any reagent is not used in this reaction, but that main drawback is productive rate is low, also contains a large amount of LiF in the final product.
As present stage lithium ion battery electrolyte mainly use salt, LiPF
6Very active because of its character, preparation process is extremely harsh to conditional requests such as environment and equipment.At present both at home and abroad to LiPF
6In preparation technology's the correlative study, the HF solvent method is still the main method of present preparation of industrialization, but remains in LiPF in the preparation process
6In the influence of the battery of HF huge, the preparation process plant energy consumption is big, so will no longer be desirable solvent.
Summary of the invention
The invention provides a kind of organic solvent that utilizes and prepare high-purity LiPF
6Method.This method adopts acetonitrile to replace HF as solvent, makes production process pollute the product inclusion-free, and is very beneficial for the product separation purifying." high-purity " refers to LiPF herein
6Main content greater than 99.9 %.
Concrete technical process is: high purity lithium fluoride fully is suspended in the anhydrous acetonitrile under the sealing agitation condition, and phosphorus pentafluoride gas is introduced in pressurization, the synthetic high-purity LiPF of reaction
6" high purity lithium fluoride " refers to that purity is greater than the lithium fluoride powder of 99.9 % herein.Detailed technology scheme of the present invention is:
(1) will pack in the pressure reaction still (lithium hexafluoro phosphate generation still) through the anhydrous acetonitrile of rectification and purification, change solid-state high purity lithium fluoride simultaneously over to, after driveing furnace air by the mode of " vacuumizing-inflate " with dry inert gas, under the sealing agitation condition, form suspension;
(2) start air dissolved pump and introduce the pressurization phosphorus pentafluoride gas, continue synthetic LiPF under the sealing agitation condition
6Synthesis temperature is 0 ℃ ~ 30 ℃, and gaseous tension is 1.0 ~ 1.5 MPa, and the reaction times is 2 ~ 4 hours;
(3) react completely after, process furnace internal reaction liquid, Heating temperature is 50 ℃ ~ 70 ℃, be 3 ~ 4 hours heat-up time; Feed dry inert gas and drive the remaining phosphorus pentafluoride of reaction; Filtered while hot is got filtrate crystallisation by cooling under-20 ℃ ~ 0 ℃ condition, crosses the vacuum-drying under 60 ℃ of conditions of leaching filter cake again and obtains product;
(4) after vacuum-drying obtained product, by the acetonitrile dissolving-recrystallization, solvent temperature was 50 ℃ ~ 70 ℃ with product, and dissolution time is 3 ~ 4 hours; Filtered while hot is got filtrate crystallisation by cooling under-20 ℃ ~ 0 ℃ condition, crosses the vacuum-drying under 60 ℃ of conditions of leaching filter cake again and obtains the finished product.
The dry inert gas that uses among the present invention is high-purity argon gas or high pure nitrogen.
Major advantage of the present invention is: (1) the present invention uses anhydrous acetonitrile to replace HF as solvent, thoroughly avoided the danger of HF solvent method production process, make production process pollute the finished product inclusion-free, avoided the corrosion of the production unit of HF simultaneously, production process is at room temperature carried out, and energy consumption is low.(2) owing to have only LiPF in the whole thing phase system
6Be dissolved in the anhydrous acetonitrile, therefore, this technological reaction speed is fast, the LiPF of generation
6Purity height, main content are greater than 99.9 %, and HF content is less than 10 ppm, and the total impurities metal content is less than 50 ppm, and moisture content is less than 10 ppm.(3) technology of the present invention is simple, and the production process environmentally safe has Industry Promotion and is worth.
Embodiment
Below embodiments of the invention are further described, but are not limited to following examples:
Embodiment 1:
To generate in the still through the anhydrous acetonitrile of the rectification and purification lithium hexafluoro phosphate of packing into, change solid-state high-purity LiF simultaneously over to, by the dry N of mode of " vacuumizing-inflate "
2After driveing furnace air, under the sealing agitation condition, form suspension; Start air dissolved pump and introduce pressurization PF
5Gas continues synthetic LiPF under the sealing agitation condition
6Synthesis temperature is room temperature, and gaseous tension is 1.0 ± 0.5 MPa, and the reaction times is 2 hours.After reacting completely, process furnace internal reaction liquid, Heating temperature is 50 ℃, be 3 hours heat-up time; Feed dry N
2Drive the remaining PF of reaction
5Filtered while hot is got filtrate crystallisation by cooling under-20 ℃ of conditions, crosses the vacuum-drying under 60 ℃ of conditions of leaching filter cake again and obtains product.
The productive rate of this technological reaction is more than 95 %, the product LiPF that obtains
6Can reach the service requirements of lithium-ion battery electrolytes, specific targets are: LiPF
6Main content is greater than 99.9 %, and HF content is less than 10 ppm, and the total impurities metal content is less than 50 ppm, and moisture content is less than 10 ppm.
Embodiment 2:
To generate in the still through the anhydrous acetonitrile of the rectification and purification lithium hexafluoro phosphate of packing into, change solid-state high-purity LiF simultaneously over to, by the dry N of mode of " vacuumizing-inflate "
2After driveing furnace air, under the sealing agitation condition, form suspension; Start air dissolved pump and introduce pressurization PF
5Gas continues synthetic LiPF under the sealing agitation condition
6Synthesis temperature is room temperature, and gaseous tension is 1.0 ± 0.5 MPa, and the reaction times is 2 hours.After reacting completely, process furnace internal reaction liquid, Heating temperature is 50 ℃, be 3 hours heat-up time; Feed dry N
2Drive the remaining PF of reaction
5Filtered while hot is got filtrate crystallisation by cooling under-20 ℃ of conditions, crosses the vacuum-drying under 60 ℃ of conditions of leaching filter cake again and obtains product.By the acetonitrile dissolving-recrystallization, solvent temperature is 70 ℃ with product, and dissolution time is 4 hours; Filtered while hot is got filtrate crystallisation by cooling under-20 ℃ of conditions, crosses the vacuum-drying under 60 ℃ of conditions of leaching filter cake again and obtains the finished product.
The productive rate of this technological reaction is that specific targets are more than 98 %: LiPF
6Main content is greater than 99.95 %, and HF content is less than 5 ppm, and the total impurities metal content is less than 10 ppm, and moisture content is less than 10 ppm.
Comparative example 1:
To generate in the still through the anhydrous acetonitrile of the rectification and purification lithium hexafluoro phosphate of packing into, change solid-state high-purity LiF simultaneously over to, by the dry N of mode of " vacuumizing-inflate "
2After driveing furnace air, under the sealing agitation condition, form suspension; Start air dissolved pump and introduce pressurization PF
5Gas continues synthetic LiPF under the sealing agitation condition
6Synthesis temperature is room temperature, and gaseous tension is 1.0 ± 0.5 MPa, and the reaction times is 2 hours.After reacting completely, feed dry N
2Drive the remaining PF of reaction
5Filtered while hot is got filtrate crystallisation by cooling under-20 ℃ of conditions, crosses the vacuum-drying under 60 ℃ of conditions of leaching filter cake again and obtains product.
Productive rate by this technological reaction is obviously on the low side, less than 30 %.After illustrating that reaction is finished, must carry out the heating for dissolving operation.
Comparative example 2:
To generate in the still through the anhydrous acetonitrile of the rectification and purification lithium hexafluoro phosphate of packing into, change solid-state high-purity LiF simultaneously over to, by the dry N of mode of " vacuumizing-inflate "
2After driveing furnace air, under the sealing agitation condition, form suspension; Start air dissolved pump and introduce pressurization PF
5Gas continues synthetic LiPF under the sealing agitation condition
6Synthesis temperature is room temperature, and gaseous tension is 1.0 ± 0.5 MPa, and the reaction times is 2 hours.After reacting completely, process furnace internal reaction liquid, Heating temperature is 80 ℃, be 3 hours heat-up time; Feed dry N
2Drive the remaining PF of reaction
5Filtered while hot is got filtrate crystallisation by cooling under-20 ℃ of conditions, crosses the vacuum-drying under 60 ℃ of conditions of leaching filter cake again and obtains product.Productive rate by this technological reaction is obviously on the low side, less than 30 %.Illustrate that the heating for dissolving service temperature is unsuitable too high, can not be above 70 ℃.
Above shown detailed embodiment of the present invention, apparent, those skilled in the art can carry out the part modifications and changes under prerequisite of the present invention; The content of mentioning in description above and the accompanying drawing is the illustration of property as an illustration only, is not to be limitation of the present invention; Organic solvent method with technical characterictic described herein prepares the method for high purity lithium hexafluorophosphate, all falls into this patent protection domain.
Claims (3)
1. organic solvent method prepares high purity lithium hexafluorophosphate, it is characterized in that: high purity lithium fluoride fully is suspended in the anhydrous acetonitrile under the sealing agitation condition, and phosphorus pentafluoride gas is introduced in pressurization, the synthetic high purity lithium hexafluorophosphate of reaction.
2. organic solvent method as claimed in claim 1 prepares high purity lithium hexafluorophosphate, it is characterized in that: described organic solvent method may further comprise the steps:
1, will pack in the pressure reaction still (lithium hexafluoro phosphate generation still) through the anhydrous acetonitrile of rectification and purification, change solid-state high purity lithium fluoride simultaneously over to, after driveing furnace air by the mode of " vacuumizing-inflate " with dry inert gas, under the sealing agitation condition, form suspension;
2, start air dissolved pump and introduce the pressurization phosphorus pentafluoride gas, continue synthetic LiPF under the sealing agitation condition
6Synthesis temperature is 0 ℃ ~ 30 ℃, and gaseous tension is 1.0 ~ 1.5 MPa, and the reaction times is 2 ~ 4 hours;
3, react completely after, process furnace internal reaction liquid, Heating temperature is 50 ℃ ~ 70 ℃, be 3 ~ 4 hours heat-up time; Feed dry inert gas and drive the remaining phosphorus pentafluoride of reaction; Filtered while hot is got filtrate crystallisation by cooling under-20 ℃ ~ 0 ℃ condition, crosses the vacuum-drying under 60 ℃ of conditions of leaching filter cake again and obtains product;
4, after vacuum-drying obtained product, by the acetonitrile dissolving-recrystallization, solvent temperature was 50 ℃ ~ 70 ℃ with product, and dissolution time is 3 ~ 4 hours; Filtered while hot is got filtrate crystallisation by cooling under-20 ℃ ~ 0 ℃ condition, crosses the vacuum-drying under 60 ℃ of conditions of leaching filter cake again and obtains the finished product.
3. organic solvent method as claimed in claim 2 prepares high purity lithium hexafluorophosphate, it is characterized in that: described dry inert gas is high-purity argon gas and high pure nitrogen.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106276986A (en) * | 2016-08-31 | 2017-01-04 | 廊坊市金海化工有限公司 | The method preparing high purity lithium hexafluorophosphate by complexometry |
| CN106830018A (en) * | 2017-02-21 | 2017-06-13 | 江苏九九久科技有限公司 | Lithium hexafluoro phosphate production method |
| CN107244681A (en) * | 2017-03-29 | 2017-10-13 | 东营石大胜华新能源有限公司 | A kind of continuous method and apparatus for preparing lithium hexafluoro phosphate |
| CN112340754A (en) * | 2019-08-09 | 2021-02-09 | 惠州比亚迪电池有限公司 | Lithium hexafluorophosphate, crystallization and preparation method thereof, lithium ion battery electrolyte and lithium ion battery |
| CN115196654A (en) * | 2022-08-11 | 2022-10-18 | 胜华新能源科技(东营)有限公司 | Liquid lithium hexafluorophosphate synthesis device and application thereof |
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| CN101391762A (en) * | 2008-10-28 | 2009-03-25 | 中南大学 | Method for preparing high purity lithium hexafluorophosphate |
| CN102180457A (en) * | 2011-05-06 | 2011-09-14 | 潘春跃 | Process for preparing lithium hexafluorophosphate by organic solvent method |
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| CN101391762A (en) * | 2008-10-28 | 2009-03-25 | 中南大学 | Method for preparing high purity lithium hexafluorophosphate |
| CN102180457A (en) * | 2011-05-06 | 2011-09-14 | 潘春跃 | Process for preparing lithium hexafluorophosphate by organic solvent method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106276986A (en) * | 2016-08-31 | 2017-01-04 | 廊坊市金海化工有限公司 | The method preparing high purity lithium hexafluorophosphate by complexometry |
| CN106830018A (en) * | 2017-02-21 | 2017-06-13 | 江苏九九久科技有限公司 | Lithium hexafluoro phosphate production method |
| CN107244681A (en) * | 2017-03-29 | 2017-10-13 | 东营石大胜华新能源有限公司 | A kind of continuous method and apparatus for preparing lithium hexafluoro phosphate |
| CN112340754A (en) * | 2019-08-09 | 2021-02-09 | 惠州比亚迪电池有限公司 | Lithium hexafluorophosphate, crystallization and preparation method thereof, lithium ion battery electrolyte and lithium ion battery |
| CN115196654A (en) * | 2022-08-11 | 2022-10-18 | 胜华新能源科技(东营)有限公司 | Liquid lithium hexafluorophosphate synthesis device and application thereof |
| CN115196654B (en) * | 2022-08-11 | 2023-12-01 | 胜华新能源科技(东营)有限公司 | Synthesis device of liquid lithium hexafluorophosphate and application thereof |
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Application publication date: 20130821 |