CN1850592A - Method for preparing potassium hexafluoro phosphate - Google Patents
Method for preparing potassium hexafluoro phosphate Download PDFInfo
- Publication number
- CN1850592A CN1850592A CN 200610013957 CN200610013957A CN1850592A CN 1850592 A CN1850592 A CN 1850592A CN 200610013957 CN200610013957 CN 200610013957 CN 200610013957 A CN200610013957 A CN 200610013957A CN 1850592 A CN1850592 A CN 1850592A
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- CN
- China
- Prior art keywords
- phosphorus pentachloride
- phosphorus
- anhydrous hydrogen
- hydrogen fluoride
- lithium
- Prior art date
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 19
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 title 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 29
- -1 lithium hexafluoro- phosphate Chemical compound 0.000 claims abstract description 28
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 23
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 15
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000859 sublimation Methods 0.000 claims abstract description 6
- 230000008022 sublimation Effects 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001868 water Inorganic materials 0.000 claims abstract description 6
- 238000007670 refining Methods 0.000 claims abstract description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 claims description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- 229910019256 POF3 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 244000309466 calf Species 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ZUOFAERZHAPYHT-UHFFFAOYSA-K trilithium fluoro hypofluorite phosphate Chemical compound P(=O)([O-])([O-])[O-].[Li+].O(F)F.[Li+].[Li+] ZUOFAERZHAPYHT-UHFFFAOYSA-K 0.000 description 1
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- Secondary Cells (AREA)
Abstract
The invention relates to Li ion battery technique, a lithium hexafluoro- phosphate preparing method, characterized in comprising the process steps of: using easy sublimation property of phosphorus pentachloride, heating and sublimating it to remove nonvolatile components, refining industrial anhydrous hydrogen fluoride to remove water and heavy metal impurities; reacting them with each other to prepare mixed gas of phosphorus pentachloride and hydrogen chloride; leading the mixed gas into anhydrous hydrogen fluoride of lithium fluoride, reacting, crystallizing and separating and drying to obtain pure lithium hexafluoro-phosphate.
Description
Technical Field
The invention relates to a lithium ion battery technology, in particular to a preparation method of lithium hexafluorophosphate.
Background
Lithium hexafluorophosphate is an important electrolyte salt of lithium ion battery electrolytes. The process for the preparation of lithium hexafluorophosphate generally comprises two processes.
First method is to react red phosphorus with fluorine gas to prepare PF5And reacting the gas with an anhydrous hydrogen fluoride solution of lithium fluoride, and crystallizing, separating and drying to obtain a lithium hexafluorophosphate product. As disclosed in Japanese patent laid-open No. 2001-122604; 122605, respectively; 163610.
and secondly, reacting phosphorus pentachloride with anhydrous hydrogen fluoride to generate mixed gas of the phosphorus pentafluoride and hydrogen chloride, reacting with anhydrous hydrogen fluoride solution of lithium fluoride, and reacting, crystallizing, separating and drying to obtain the lithium hexafluorophosphate product. Such as Japanese patent laid-open No. 5-279003; japanese patent laid-open No. 4-175216.
In the preparation process of lithium hexafluorophosphate, the raw materials such as phosphorus pentachloride, anhydrous hydrogen fluoride, lithium fluoride and the like usually containHas certain impurities such as water, alkali metal and heavy metal ions, especially phosphorus pentachloride, which is easy to absorb moisture to cause deliquescence, and contains PCl3、POCl3And if the impurities are brought into a lithium hexafluorophosphate product, the electrolyte prepared from the product and applied to a lithium ion battery can cause the increase of the internal resistance of the battery, the attenuation of the capacity of the battery is fast, the cycle life is shortened, and even the safety of the battery is influenced.
There are many reports on a method for refining and removing harmful substances such as lithium oxyfluoride phosphate LiPOxFy compound in lithium hexafluorophosphate product: for example, Japanese patent laid-open No. 60-251109 proposes a method of removing water from a lithium hexafluorophosphate solution by introducing fluorine gas into the lithium hexafluorophosphate solution. The principle is as follows:
OF2the boiling point is-145 ℃ and is easy to volatilize.
Japanese patent application laid-open No. 2000-154009 proposes adding a certain amount of PCL to lithium hexafluorophosphate product5And anhydrous HF, so that the LiPOxFy compound in the LiPOxFy is converted into lithium hexafluorophosphate. The principle is as follows:
japanese patent laid-open No. 58-161910 proposes a method of recrystallizing lithium hexafluorophosphate from Ethylene Carbonate (EC).
Japanese patent laid-open No. 59-81870 proposes a method of recrystallizing lithium hexafluorophosphate in ethylene glycol dimethyl ether (DME).
Japanese patent laid-open No. 5-279003 proposes to use PCL5PF is generated after reaction with anhydrous hydrogen fluoride5And HCl gas, cooling (-50 deg.C) to remove POF3A method for producing impurities.
The above methods are all fineAnd removing harmful impurities of lithium hexafluorophosphate. But using F2Not only has high toxicity, but also has high price, which increases the manufacturing cost of the product.
Lithium hexafluorophosphate is recrystallized in an organic solvent, and a certain amount of organic solvent is still carried in a recrystallized product by utilizing the property that the lithium hexafluorophosphate has different solubilities at different temperatures, so that the purity of the productis influenced.
PF removal using lower temperature cooling5And POF in HCl gas3Impurities but not other harmful impurities, and are costly.
Disclosure of Invention
The invention aims to provide a preparation method of lithium hexafluorophosphate for effectively removing harmful impurities, which is characterized by comprising the following process steps:
1. the phosphorus pentachloride product is heated to sublimate to remove nonvolatile components by utilizing the easy sublimation property of the phosphorus pentachloride product, and simultaneously, a certain amount of chlorine gas is introduced into the phosphorus pentachloride product, so that phosphorus oxychloride and phosphorus trichloride in the phosphorus pentachloride product are converted into phosphorus pentachloride, and the purity of the phosphorus pentachloride is improved;
2. rectifying, refining and purifying the industrial anhydrous hydrogen fluoride to remove water and heavy metal impurities in the industrial anhydrous hydrogen fluoride;
3. reacting the refined phosphorus pentachloride with an anhydrous hydrogen fluoride solution to prepare a mixed gas of the phosphorus pentafluoride and hydrogen chloride;
4. dissolving anhydrous lithium fluoride in an anhydrous hydrogen fluoride solution to form an anhydrous hydrogen fluoride solution of lithium fluoride;
5. introducing the mixed gas of phosphorus pentafluoride and hydrogen chloride into anhydrous hydrogen fluoride solution of lithium fluoride, and reacting, crystallizing, separating and drying to obtain a pure lithium hexafluorophosphate product.
Detailed description of the preferred embodiments
The invention is further illustrated by the following examples.
The chemical formula used is:
LiF- -lithium fluoride;
HF- - - -anhydrous hydrogen fluoride;
PCl5-phosphorus pentachloride;
POCl3-phosphorus oxychloride;
HCl- - -hydrogen chloride;
PF5-phosphorus pentafluoride;
LiPF6-lithium hexafluorophosphate;
example 1:
adding 1000g of phosphorus pentachloride into a 10L closed reactor with stirring and jacket heat preservation, heating to 160 deg.C while stirring, maintaining the temperature, sublimating phosphorus pentachloride, introducing sublimed gas into another 5L reactor with stirring and cooling jacket, and charging 10gCl2Cooling is performed in the cooling apparatus of (1).
After sublimation is finished, 600g of anhydrous hydrogen fluoride with the water content of less than 10ppm after rectification and purification is slowly added into the second reactor to react with phosphorus pentachloride to generate PF5And HCl gas mixture.
In a third 3L reactor with stirring and cooling jacket, 110g of purified lithium fluoride were dissolved in 2000g of anhydrous hydrogen fluoride to form an anhydrous hydrogen fluoride solution of LiF, which was stirred with the introduced PF5And reacting with HCl gas, and cooling, crystallizing, filtering and drying after the reaction is finished to obtain 200g of lithium hexafluorophosphate product. And (3) detection results: the product had 100ppm free acid (as HF), 5ppm moisture (Calf method), 2ppm alkali metal ion (as K, Na), 2ppm heavy metal ion (as Fe), and 500ppm insoluble in DME.
Example 2:
2500g of the filtered mother liquor from example 1 was crystallized and 110g of purified lithium fluoride and anhydrous hydrogen fluoride were added under stirring to form an anhydrous hydrogen fluoride solution of LiF. The reaction procedure in example 1 was repeated. 600g of lithium hexafluorophosphate product was obtained. And (3) detection results: the product had a free acid (as HF) of 98ppm, moisture (Karl Fischer method) of 5ppm, alkali metal ion content (as K, Na) of 3ppm, heavy metal ion content (as Fe) of 2ppm, and 500ppm of insoluble materials in DME.
Comparative example 1:
phosphorus pentachloride in example 1 was not purified by sublimation, and other reaction processes were the same. 210g of lithium hexafluorophosphate product are obtained. And (3) detection results: the product had a free acid (as HF) of 250ppm, moisture (Karl Fischer method) of 8ppm, alkali metal ion content (as K, Na) of 5ppm, heavy metal ion content (as Fe) of 6ppm, and 1500ppm of insoluble materials in DME.
Comparative example 2:
phosphorus pentachloride in example 2 was not purified by sublimation, and other reaction processes were the same. 280g of lithium hexafluorophosphate product was obtained. And (3) detection results: the product had a free acid (as HF) content of 280ppm, a moisture content (Karl Fischer method) of 15ppm, an alkali metal ion content (as K, Na) of 6ppm, a heavy metal ion content (as Fe) of 8ppm, and 1550ppm insoluble in DME.
Claims (1)
1. The invention relates to a preparation method of lithium hexafluorophosphate,which is characterized by comprising the following process steps:
A. the phosphorus pentachloride product is heated to sublimate to remove nonvolatile components by utilizing the easy sublimation property of the phosphorus pentachloride product, and chlorine gas is introduced into the phosphorus pentachloride product to convert phosphorus oxychloride and phosphorus trichloride into phosphorus pentachloride, so that the purity of the phosphorus pentachloride is improved;
B. rectifying, refining and purifying industrial anhydrous hydrogen fluoride to remove water and heavy metal impurities;
C. reacting the refined phosphorus pentachloride with an anhydrous hydrogen fluoride solution to prepare a mixed gas of the phosphorus pentafluoride and hydrogen chloride;
D. dissolving anhydrous lithium fluoride in an anhydrous hydrogen fluoride solution to form an anhydrous hydrogen fluoride solution of lithium fluoride;
E. introducing the mixed gas of phosphorus pentafluoride and hydrogen chloride into anhydrous hydrogen fluoride solution of lithium fluoride, and reacting, crystallizing, separating and drying to obtain a pure lithium hexafluorophosphate product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610013957 CN1850592A (en) | 2006-05-30 | 2006-05-30 | Method for preparing potassium hexafluoro phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610013957 CN1850592A (en) | 2006-05-30 | 2006-05-30 | Method for preparing potassium hexafluoro phosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1850592A true CN1850592A (en) | 2006-10-25 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610013957 Pending CN1850592A (en) | 2006-05-30 | 2006-05-30 | Method for preparing potassium hexafluoro phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1850592A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275895A (en) * | 2011-06-30 | 2011-12-14 | 湖北省宏源药业有限公司 | Method of synthesizing lithium hexafluorophosphate |
| CN102515132A (en) * | 2011-12-19 | 2012-06-27 | 中国海洋石油总公司 | Method for producing high-purity lithium hexafluorophosphate |
| CN101570326B (en) * | 2008-04-28 | 2012-07-11 | 多氟多化工股份有限公司 | Preparation method of lithium hexafluorophosphate |
| CN101595114B (en) * | 2007-01-31 | 2012-09-05 | 默克专利股份公司 | Compounds comprising organic fluorochloro phosphate anions |
| CN102757027A (en) * | 2012-06-12 | 2012-10-31 | 陕西延长石油集团氟硅化工有限公司 | System and method for preparing high-purity phosphorus pentafluoride |
| CN103153847A (en) * | 2010-10-14 | 2013-06-12 | 大金工业株式会社 | Method for producing phosphorus pentafluoride |
| CN103964409B (en) * | 2013-02-05 | 2018-04-10 | 关东电化工业株式会社 | High-purity LiPF6Manufacture method |
| CN112850670A (en) * | 2020-12-30 | 2021-05-28 | 徐兴碧 | Production device and method of phosphorus pentafluoride |
-
2006
- 2006-05-30 CN CN 200610013957 patent/CN1850592A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101595114B (en) * | 2007-01-31 | 2012-09-05 | 默克专利股份公司 | Compounds comprising organic fluorochloro phosphate anions |
| CN101570326B (en) * | 2008-04-28 | 2012-07-11 | 多氟多化工股份有限公司 | Preparation method of lithium hexafluorophosphate |
| CN103153847A (en) * | 2010-10-14 | 2013-06-12 | 大金工业株式会社 | Method for producing phosphorus pentafluoride |
| CN102275895A (en) * | 2011-06-30 | 2011-12-14 | 湖北省宏源药业有限公司 | Method of synthesizing lithium hexafluorophosphate |
| CN102275895B (en) * | 2011-06-30 | 2013-07-31 | 湖北省宏源药业有限公司 | Method of synthesizing lithium hexafluorophosphate |
| CN102515132A (en) * | 2011-12-19 | 2012-06-27 | 中国海洋石油总公司 | Method for producing high-purity lithium hexafluorophosphate |
| CN102757027A (en) * | 2012-06-12 | 2012-10-31 | 陕西延长石油集团氟硅化工有限公司 | System and method for preparing high-purity phosphorus pentafluoride |
| CN102757027B (en) * | 2012-06-12 | 2014-07-16 | 陕西延长石油集团氟硅化工有限公司 | System and method for preparing high-purity phosphorus pentafluoride |
| CN103964409B (en) * | 2013-02-05 | 2018-04-10 | 关东电化工业株式会社 | High-purity LiPF6Manufacture method |
| CN112850670A (en) * | 2020-12-30 | 2021-05-28 | 徐兴碧 | Production device and method of phosphorus pentafluoride |
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