CN101723348B - Preparation method of lithium hexafluorophosphate - Google Patents
Preparation method of lithium hexafluorophosphate Download PDFInfo
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- CN101723348B CN101723348B CN200910311295A CN200910311295A CN101723348B CN 101723348 B CN101723348 B CN 101723348B CN 200910311295 A CN200910311295 A CN 200910311295A CN 200910311295 A CN200910311295 A CN 200910311295A CN 101723348 B CN101723348 B CN 101723348B
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Abstract
The invention provides a preparation method of lithium hexafluorophosphate. The method comprises the following steps of: (1) reacting phosphorus trichloride and anhydrous hydrogen fluoride to generate phosphorus trifluoride and hydrogen chloride; (2) continuously leading gas generated in the step (1) and a redundant hydrogen fluoride gas into a phosphorus pentafluoride reaction generator, and meanwhile, continuously leading a chlorine gas to react and generate a phosphorus pentafluoride gas; and (3) reacting the phosphorus pentafluoride and lithium fluoride to produce the lithium hexafluorophosphate. The reaction condition of the preparation method is easy to control, and the purity of a prepared product is larger than 99.9 percent and can meet the requirement on the electrolyte purity of lithium batteries.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery electrolyte salt, relate to a kind of preparation method of lithium hexafluoro phosphate specifically.
Background technology
Lithium hexafluoro phosphate (LiPF
6) as the electrolytic salt of lithium-ion secondary cell, advantage such as it is good to have specific conductivity height, chemistry and an electrochemical stability, and security is good, so lithium hexafluoro phosphate is dissolved in the electrolytic solution that forms lithium-ion secondary cell in some non-aqueous organic solvent.In order to keep the performance of battery,, very high to electrolytical purity requirement in the electrolytic solution like work-ing life.With red phosphorus or Vanadium Pentoxide in FLAKES is feedstock production phosphorus pentafluoride and the method that further prepares lithium hexafluoro phosphate, because raw material impurity content is high, is difficult to obtain the high purity lithium hexafluoro phosphate; And with hydrogen fluoride and phosphorus pentachloride prepared in reaction phosphorus pentafluoride and the further method for preparing lithium hexafluoro phosphate, be a reaction that heat release is violent because phosphorus pentachloride and anhydrous hydrogen fluoride are produced the reaction of phosphorus pentafluoride, misoperation very easily sets off an explosion, poor stability.Publication number is the patented claim of CN1188072A, discloses a kind ofly to fluoridize the method that makes phosphorus pentafluoride by phosphorus trichloride, it is advantageous that reaction is more abundant, and raw material availability is higher, but the conditional parameter of reaction needs control is more, reacts for being interrupted and carries out.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of lithium hexafluoro phosphate, realize reducing the lithium hexafluoro phosphate production cost, and guarantee the purpose of safety in production.
To achieve these goals, technical program of the present invention lies in adopting a kind of preparation method of lithium hexafluoro phosphate, may further comprise the steps:
(1) phosphorus trichloride and anhydrous hydrogen fluoride are added in the gas liquid mixer, react generation phosphorus trifluoride and hydrogenchloride down at 50～60 ℃;
(2) with the phosphorus trifluoride, hydrogenchloride and the unnecessary hydrogen fluoride gas that generate in the step (1), successively get into phosphorus pentafluoride reaction maker, feed chlorine simultaneously continuously; Keep reaction system under 35～70 ℃ dry environment, phosphorus trifluoride, chlorine and hydrogen fluoride gas successive reaction generate phosphorus pentafluoride gas in the reactor drum;
(3) under-10～-30 ℃, phosphorus pentafluoride gas is imported in the lithium fluoride, should constantly stir in the process of importing, the reacted lithium hexafluoro phosphate at-20～-30 ℃ of following crystallization 2-4 hours, obtains the lithium hexafluoro phosphate product through concentrated, drying.
Wherein, impurity is removed in the cooling under 0～-40 ℃ of the product of gained in the step (2).
Waste gas after step (3) reaction finishes is discharged the back water and is absorbed as hydrochloric acid soln, recycles.
The production technique prices of raw and semifnished materials of the present invention are cheap, can greatly reduce the lithium hexafluoro phosphate cost; Reaction conditions of the present invention is gentle, control easily, and serialization production is easy to industriallization; The product purity that makes is higher, greater than 99.9%, can satisfy lithium cell to electrolytical purity requirement.
Embodiment
Embodiment 1:
The preparation method of the lithium hexafluoro phosphate of present embodiment may further comprise the steps:
(1) gets phosphorus trichloride 110g and anhydrous hydrogen fluoride 130g, slowly in 1 hour, add continuously in the gas liquid mixer in proportion,, generate phosphorus trifluoride and hydrogen chloride gas continuously 50 ℃ of reactions down.
(2) phosphorus trifluoride, hydrogenchloride and the unnecessary hydrogen fluoride gas that generate in the step (1); Successively get into phosphorus pentafluoride reaction maker; Simultaneously 72g chlorine is fed reactor drum continuously; Keep reaction system under 35 ℃ dry environment, phosphorus trifluoride, chlorine and hydrogen fluoride gas successive reaction generate phosphorus pentafluoride gas in the reaction kettle, and the phosphorus pentafluoride gas of generation is refining through-40 ℃ of coolings; Remove unnecessary hydrogen fluoride and other foreign gas, the gas after making with extra care comprises phosphorus pentafluoride and hydrogenchloride.
(3) phosphorus pentafluoride gas under agitation with the 17g lithium fluoride-30 ℃ of reactions; Wherein the 17g lithium fluoride is dissolved in earlier in the 210g anhydrous hydrogen fluoride; Phosphorus pentafluoride constantly gets into the lithium hexafluoro phosphate reaction kettle, generates lithium hexafluoro phosphate, after arriving reaction end; Remain on-30 ℃ of following crystallizations 2 hours, obtain lithium hexafluoro phosphate product 85g through filtration, drying again.Hydrogen chloride gas does not react with lithium fluoride, discharges with waste gas, and water is absorbed as 30% hydrochloric acid, recycles.
The technical target of the product detected result: purity is greater than 99.9%, free acid (in HF) 85ppm, moisture (Ka Erfeixiufa) 8ppm, alkali metal ion content measured (in K, Na) 2ppm, heavy metal ion content (in Fe) 1ppm, insolubles content 450ppm.
Embodiment 2
The preparation method of the lithium hexafluoro phosphate of present embodiment may further comprise the steps:
(1) gets phosphorus trichloride 220g and anhydrous hydrogen fluoride 260g, slowly in 1 hour, add continuously in the gas liquid mixer in proportion,, generate phosphorus trifluoride and hydrogen chloride gas continuously 60 ℃ of reactions down.
(2) phosphorus trifluoride, hydrogenchloride and the unnecessary hydrogen fluoride gas that generate in the step (1); Successively get into phosphorus pentafluoride reaction maker; Simultaneously 144g chlorine is fed reactor drum continuously, keep reaction system under 70 ℃ dry environment, phosphorus trifluoride, chlorine and hydrogen fluoride gas successive reaction generate phosphorus pentafluoride gas in the reaction kettle; The phosphorus pentafluoride gas that generates is refining through 0 ℃ of cooling; Remove unnecessary hydrogen fluoride and other foreign gas, the gas after making with extra care comprises phosphorus pentafluoride and hydrogenchloride, gets into the lithium hexafluoro phosphate reaction kettle.
(3) phosphorus pentafluoride gas under agitation with the 34g lithium fluoride-10 ℃ of reactions; Wherein the 34g lithium fluoride is dissolved in earlier in the 420g anhydrous hydrogen fluoride; Phosphorus pentafluoride constantly gets into the lithium hexafluoro phosphate reaction kettle, generates lithium hexafluoro phosphate, after arriving reaction end; Remain on-20 ℃ of following crystallizations 4 hours, obtain lithium hexafluoro phosphate product 170g through filtration, drying again.Hydrogen chloride gas does not react with lithium fluoride, discharges with waste gas, and water is absorbed as 30% hydrochloric acid, recycles.
The technical target of the product detected result: purity is greater than 99.9%, free acid (in HF) 82ppm, moisture (Ka Erfeixiufa) 9ppm, alkali metal ion content measured (in K, Na) 2ppm, heavy metal ion content (in Fe) 1ppm, insolubles content 440ppm.
Claims (3)
1. the preparation method of a lithium hexafluoro phosphate, it is characterized in that: described preparation method may further comprise the steps
(1) phosphorus trichloride and anhydrous hydrogen fluoride are added in the gas liquid mixer, react generation phosphorus trifluoride and hydrogenchloride down at 50～60 ℃;
(2) with the phosphorus trifluoride, hydrogenchloride and the unnecessary hydrogen fluoride gas that generate in the step (1), successively get into phosphorus pentafluoride reaction maker, feed chlorine simultaneously continuously; Keep reaction system under 35～70 ℃ dry environment, phosphorus trifluoride, chlorine and hydrogen fluoride gas successive reaction generate phosphorus pentafluoride gas in the reactor drum;
(3) under-10 ℃, phosphorus pentafluoride gas is imported in the lithium fluoride, should constantly stir in the process of importing, the reacted lithium hexafluoro phosphate-20 ℃ of following crystallizations 4 hours, obtains the lithium hexafluoro phosphate product through concentrated, drying.
2. according to the preparation method of the described a kind of lithium hexafluoro phosphate of claim 1, it is characterized in that: the product of step (2) gained cools off down at 0～-40 ℃ removes impurity.
3. the preparation method of a kind of lithium hexafluoro phosphate according to claim 1 is characterized in that: the waste gas after step (3) reaction finishes, and discharge the back water and be absorbed as hydrochloric acid soln, recycle.
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| CN200910311295A CN101723348B (en) | 2009-12-11 | 2009-12-11 | Preparation method of lithium hexafluorophosphate |
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| CN200910311295A CN101723348B (en) | 2009-12-11 | 2009-12-11 | Preparation method of lithium hexafluorophosphate |
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| CN101723348B true CN101723348B (en) | 2012-09-26 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104093668B (en) * | 2012-01-19 | 2016-03-02 | 朗盛德国有限责任公司 | Subchloride-LiPF 6 |
| CN104364197A (en) | 2012-05-25 | 2015-02-18 | 朗盛德国有限责任公司 | High-purity lithium hexafluorophosphate |
| CN103553009B (en) * | 2013-10-11 | 2016-03-09 | 浙江巨化凯蓝新材料有限公司 | A kind of Chemical deep purification method of lithium hexafluoro phosphate |
| CN105776168A (en) * | 2016-03-31 | 2016-07-20 | 珠海市赛纬电子材料股份有限公司 | Preparation method of hexafluorophosphate |
| CN107244681B (en) * | 2017-03-29 | 2019-07-05 | 东营石大胜华新能源有限公司 | A kind of method and apparatus continuously preparing lithium hexafluoro phosphate |
| WO2023168597A1 (en) * | 2022-03-08 | 2023-09-14 | Central Glass Company, Limited | Method for producing phosphorus trifluoride and method for producing phosphorus pentafluoride |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1188072A (en) * | 1996-12-03 | 1998-07-22 | 埃勒夫阿托化学有限公司 | Synthesis of phosphorus pentafluoride by fluorination of phosphorus trichloride |
| CN101544361A (en) * | 2009-05-07 | 2009-09-30 | 洛阳森蓝化工材料科技有限公司 | Process and device for continuous preparation of lithium hexafluorophosphate |
| CN101570328A (en) * | 2008-04-28 | 2009-11-04 | 多氟多化工股份有限公司 | Method for preparing lithium hexafluorophosphate |
| CN101570327A (en) * | 2008-04-28 | 2009-11-04 | 多氟多化工股份有限公司 | Method for producing lithium hexafluorophosphate |
-
2009
- 2009-12-11 CN CN200910311295A patent/CN101723348B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1188072A (en) * | 1996-12-03 | 1998-07-22 | 埃勒夫阿托化学有限公司 | Synthesis of phosphorus pentafluoride by fluorination of phosphorus trichloride |
| CN101570328A (en) * | 2008-04-28 | 2009-11-04 | 多氟多化工股份有限公司 | Method for preparing lithium hexafluorophosphate |
| CN101570327A (en) * | 2008-04-28 | 2009-11-04 | 多氟多化工股份有限公司 | Method for producing lithium hexafluorophosphate |
| CN101544361A (en) * | 2009-05-07 | 2009-09-30 | 洛阳森蓝化工材料科技有限公司 | Process and device for continuous preparation of lithium hexafluorophosphate |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平11－171518A 1999.06.29 |
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Inventor after: Li Shijiang Inventor after: Li Lingyun Inventor after: Hou Hongjun Inventor after: Yang Huachun Inventor after: Xue Xujin Inventor after: Yu Hehua Inventor after: Yan Chunsheng Inventor after: Liu Haixia Inventor after: Li Yunfeng Inventor after: Luo Chengguo Inventor before: Li Yunfeng Inventor before: Luo Chengguo Inventor before: Yan Chunsheng Inventor before: Jia Xuefeng Inventor before: Shu Weifeng Inventor before: Li Lingyun Inventor before: Liu Song Inventor before: Shao Junhua |
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Free format text: CORRECT: INVENTOR; FROM: LI YUNFENG LUO CHENGGUO YAN CHUNSHENG JIA XUEFENG SHU WEIFENG LI LINGYUN LIU SONG SHAO JUNHUA TO: LI SHIJIANG HOU HONGJUN YANG HUACHUN XUE XUJIN YU HEHUA YAN CHUNSHENG LIU HAIXIA LI YUNFENG LUO CHENGGUO LI LINGYUN |
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Address after: 454191 Henan Province, Jiaozuo City Station area coke Rd Patentee after: Duofudo New Material Co.,Ltd. Address before: 454191, Feng County, Henan Province, Jiaozuo Feng Feng Chemical Industry Zone Patentee before: DO-FLUORIDE CHEMICALS Co.,Ltd. |