WO2000029324A1 - Procede permettant de purifier l'hexafluorophosphate de lithium - Google Patents
Procede permettant de purifier l'hexafluorophosphate de lithium Download PDFInfo
- Publication number
- WO2000029324A1 WO2000029324A1 PCT/JP1999/006386 JP9906386W WO0029324A1 WO 2000029324 A1 WO2000029324 A1 WO 2000029324A1 JP 9906386 W JP9906386 W JP 9906386W WO 0029324 A1 WO0029324 A1 WO 0029324A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- lithium hexafluorophosphate
- fluoride
- reaction
- hydrogen fluoride
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/44—Metaphosphates
- C01B25/445—Metaphosphates of alkali metals
-
- 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
Definitions
- the present invention relates to a method for purifying lithium hexafluorophosphate which can purify lithium hexafluorophosphate useful as, for example, a lithium secondary battery electrolyte and a medium for organic synthesis with extremely high purity.
- Lithium hexafluorophosphate is generally synthesized in a non-aqueous solvent such as anhydrous hydrogen fluoride or an organic solvent, but reacts with a small amount of water present in the solvent to form oxyfluoride lithium fluoride. Produced and mixed into products to contaminate it.
- a non-aqueous solvent such as anhydrous hydrogen fluoride or an organic solvent
- lithium hexafluorophosphate is dissolved in anhydrous hydrogen fluoride or an organic solvent, a part of it is in equilibrium with decomposition as shown in the following formula.
- This LiF is mixed into the product and becomes an impurity (insoluble residue).
- Lithium hexafluorophosphate has extremely strong hygroscopicity, so even a small amount of atmospheric moisture is hydrolyzed to produce hydrofluoric acid.
- lithium fluoride and lithium oxyfluorophosphate (L i PO x F y ) are formed and cause impurities.
- hydrofluoric acid corrodes the electrode material, and lithium fluoride is insoluble in organic solvents and remains as residue.
- Lithium fluorophosphate promotes the decomposition of organic solvents, raising the internal voltage and reducing the capacity of the battery or causing it to ignite.
- the present invention relates to the production of impurities such as hydrogen fluoride, oxyfluoride, and lithium fluoride, which are generated during the manufacturing process, handling, and storage of lithium hexafluorophosphate and mixed into products, to lithium hexafluorophosphate. It is an object of the present invention to provide a method for purifying lithium hexafluorophosphate that can be converted to obtain high-purity lithium hexafluorophosphate. Disclosure of the invention
- the method for purifying lithium hexafluorophosphate of the present invention comprises the step of converting the oxyfluoride and lithium fluoride in the raw material of lithium hexafluorophosphate before purification into an amount of pentafluoride which is at least the amount required to convert lithium fluoride to lithium hexafluorophosphate. Purification is carried out by allowing the amounts of phosphorus pentachloride and hydrogen fluoride required to produce phosphorus fluoride to be present in the reaction system together with the raw material of lithium hexafluorophosphate before purification and reacting. . Action
- impurities such as hydrogen fluoride, oxyfluoride, and lithium fluoride contained in lithium hexafluorophosphate are converted into lithium hexafluorophosphate by adding phosphorus pentachloride and purified. At this time, the reaction is carried out in the presence of phosphorus pentachloride and an equivalent or more of hydrogen fluoride.
- phosphorus pentachloride reacts with hydrogen fluoride to generate phosphorus pentafluoride.
- the ratio of phosphorus pentachloride to hydrogen fluoride is desirably greater than the chemical equivalent of hydrogen fluoride, but if phosphorus pentachloride is in excess and remains unreacted, the sublimation temperature is 100 ° C, so a higher temperature Can be removed by heating.
- the reaction of phosphorus pentafluoride with oxyfluoride and lithium fluoride proceeds sufficiently near normal pressure, but is preferably performed under pressurized conditions.
- a negative pressure is applied to the reaction system, not only does the reaction between phosphorus pentafluoride and oxyfluoride and lithium fluoride become difficult to proceed, but conversely, a decomposition reaction of lithium hexafluorophosphate occurs and impurities are generated. Will increase. This is shown by the relationship between the free acid and the insoluble residue due to the pressure in the reaction system in FIG.
- the time required for the formation reaction depends on the conditions such as temperature and pressure and the contents of hydrogen fluoride, oxyfluoride and lithium fluoride contained in the lithium hexafluoride phosphate used for the formation. From day to night is enough. After the purification reaction is completed, dry hydrogen gas, phosphorus pentafluoride, hydrogen chloride, and unreacted phosphorus pentachloride gas are completely eliminated through dry nitrogen gas.
- FIG. 1 is a graph showing the results of thermogravimetric analysis of lithium hexafluorophosphate.
- FIG. 2 is a graph showing the relationship between the pressure in the reaction system and the free acid and insoluble matter.
- This invention can easily refine
- Hazardous impurities such as oxyfluoride and lithium fluoride are reacted with phosphorus pentachloride in the presence of hydrofluoric acid in an equivalent amount or more, and the oxyfluoride and lithium fluoride are purified with phosphorus pentafluoride to be purified. It is characterized by conversion to lithium and purification.
- the use of phosphorus pentachloride is inexpensive in terms of cost, and is easy to handle because phosphorus pentachloride is a solid.
- the present invention can be expected to have a great effect in producing high-purity lithium hexafluorophosphate inexpensively and in large quantities by using phosphorus pentachloride in the purification process.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
- Catalysts (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020007007876A KR100620861B1 (ko) | 1998-11-17 | 1999-11-16 | 6불화 인산 리튬의 정제법 |
EP99972189A EP1055640B1 (en) | 1998-11-17 | 1999-11-16 | Method of purifying lithium hexafluorophosphate |
DE69918415T DE69918415T2 (de) | 1998-11-17 | 1999-11-16 | Verfahren zur reinigung von lithiumhexafluorphosphat |
US09/600,231 US6514474B1 (en) | 1998-11-17 | 1999-11-16 | Method of purifying lithium hexafluorosphate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10/327319 | 1998-11-17 | ||
JP32731998A JP3798560B2 (ja) | 1998-11-17 | 1998-11-17 | 六フッ化リン酸リチウムの精製法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000029324A1 true WO2000029324A1 (fr) | 2000-05-25 |
Family
ID=18197820
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1999/006386 WO2000029324A1 (fr) | 1998-11-17 | 1999-11-16 | Procede permettant de purifier l'hexafluorophosphate de lithium |
Country Status (7)
Country | Link |
---|---|
US (1) | US6514474B1 (ja) |
EP (1) | EP1055640B1 (ja) |
JP (1) | JP3798560B2 (ja) |
KR (1) | KR100620861B1 (ja) |
DE (1) | DE69918415T2 (ja) |
TW (1) | TW522140B (ja) |
WO (1) | WO2000029324A1 (ja) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3973329B2 (ja) * | 1999-12-09 | 2007-09-12 | ステラケミファ株式会社 | 六フッ化リン酸リチウムの製造方法 |
US6884403B2 (en) * | 2000-09-05 | 2005-04-26 | Stella Chemifa Kabushiki Kaisha | Method of purifying lithium hexafluorophosphate |
US7311993B2 (en) * | 2003-09-04 | 2007-12-25 | Air Products And Chemicals, Inc. | Polyfluorinated boron cluster anions for lithium electrolytes |
CA2479589C (en) * | 2003-09-04 | 2011-05-24 | Air Products And Chemicals, Inc. | Polyfluorinated boron cluster anions for lithium electrolytes |
US7981388B2 (en) * | 2004-08-23 | 2011-07-19 | Air Products And Chemicals, Inc. | Process for the purification of lithium salts |
US7465517B2 (en) | 2004-08-23 | 2008-12-16 | Air Products And Chemicals, Inc. | High purity lithium polyhalogenated boron cluster salts useful in lithium batteries |
US20060204843A1 (en) * | 2005-03-10 | 2006-09-14 | Ivanov Sergei V | Polyfluorinated boron cluster anions for lithium electrolytes |
JP4810867B2 (ja) | 2005-04-19 | 2011-11-09 | セントラル硝子株式会社 | リチウムイオン電池用電解液の製造方法 |
US20070048605A1 (en) | 2005-08-23 | 2007-03-01 | Pez Guido P | Stable electrolyte counteranions for electrochemical devices |
CN100383036C (zh) * | 2006-05-30 | 2008-04-23 | 天津化工研究设计院 | 六氟磷酸锂的纯化方法 |
JP5254555B2 (ja) * | 2007-02-08 | 2013-08-07 | ステラケミファ株式会社 | 五フッ化リン及び六フッ化リン酸塩の製造方法 |
JP5307409B2 (ja) | 2007-08-16 | 2013-10-02 | ステラケミファ株式会社 | 五フッ化リン及び六フッ化リン酸塩の製造方法 |
JP2010042937A (ja) | 2008-08-08 | 2010-02-25 | Stella Chemifa Corp | 五フッ化リン及び六フッ化リン酸塩の製造方法 |
JP5341425B2 (ja) | 2008-08-08 | 2013-11-13 | ステラケミファ株式会社 | フッ化物ガスの製造方法 |
KR101223384B1 (ko) | 2012-06-01 | 2013-01-16 | 오씨아이머티리얼즈 주식회사 | 육불화인산리튬의 제조장치 및 제조방법 |
CN105593165B (zh) * | 2013-10-04 | 2019-01-04 | 关东电化工业株式会社 | 五氟化磷的精制方法 |
CN103553009B (zh) * | 2013-10-11 | 2016-03-09 | 浙江巨化凯蓝新材料有限公司 | 一种六氟磷酸锂的化学深度纯化方法 |
US10875781B2 (en) * | 2018-03-28 | 2020-12-29 | Gene Lee Hunsucker | Phosphorus pentafluoride reactions |
TWI711203B (zh) | 2019-12-19 | 2020-11-21 | 國立臺灣科技大學 | 非水性電解液的處理方法以及電池的製造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5981870A (ja) * | 1982-11-01 | 1984-05-11 | Hitachi Maxell Ltd | 非水電解液用溶質の製造法 |
JPH06298506A (ja) * | 1993-04-14 | 1994-10-25 | Central Glass Co Ltd | 六フッ化リン酸リチウムの精製法 |
JPH1072207A (ja) * | 1996-06-26 | 1998-03-17 | Solvay Fluor & Derivate Gmbh | ヘキサフルオロリン酸リチウムの製法 |
JPH1092468A (ja) * | 1996-09-19 | 1998-04-10 | Central Glass Co Ltd | リチウム電池用電解液及びその精製方法並びにそれを用いたリチウム電池 |
JPH11147705A (ja) * | 1997-11-12 | 1999-06-02 | Central Glass Co Ltd | ヘキサフルオロリン酸リチウムの精製法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2882723B2 (ja) * | 1993-04-14 | 1999-04-12 | セントラル硝子株式会社 | 六フッ化リン酸リチウムの精製方法 |
WO1999040027A1 (fr) * | 1998-02-03 | 1999-08-12 | Elf Atochem S.A. | PROCEDE DE FABRICATION D'HEXAFLUOROPHOSPHATE D'UN METAL, M(PF6)n, EN PARTICULIER DE LiPF6 |
-
1998
- 1998-11-17 JP JP32731998A patent/JP3798560B2/ja not_active Expired - Fee Related
-
1999
- 1999-11-05 TW TW088119316A patent/TW522140B/zh not_active IP Right Cessation
- 1999-11-16 DE DE69918415T patent/DE69918415T2/de not_active Expired - Lifetime
- 1999-11-16 EP EP99972189A patent/EP1055640B1/en not_active Expired - Lifetime
- 1999-11-16 US US09/600,231 patent/US6514474B1/en not_active Expired - Fee Related
- 1999-11-16 KR KR1020007007876A patent/KR100620861B1/ko not_active IP Right Cessation
- 1999-11-16 WO PCT/JP1999/006386 patent/WO2000029324A1/ja active IP Right Grant
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5981870A (ja) * | 1982-11-01 | 1984-05-11 | Hitachi Maxell Ltd | 非水電解液用溶質の製造法 |
JPH06298506A (ja) * | 1993-04-14 | 1994-10-25 | Central Glass Co Ltd | 六フッ化リン酸リチウムの精製法 |
JPH1072207A (ja) * | 1996-06-26 | 1998-03-17 | Solvay Fluor & Derivate Gmbh | ヘキサフルオロリン酸リチウムの製法 |
JPH1092468A (ja) * | 1996-09-19 | 1998-04-10 | Central Glass Co Ltd | リチウム電池用電解液及びその精製方法並びにそれを用いたリチウム電池 |
JPH11147705A (ja) * | 1997-11-12 | 1999-06-02 | Central Glass Co Ltd | ヘキサフルオロリン酸リチウムの精製法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1055640A4 * |
Also Published As
Publication number | Publication date |
---|---|
EP1055640B1 (en) | 2004-06-30 |
KR100620861B1 (ko) | 2006-09-13 |
EP1055640A4 (en) | 2001-02-07 |
DE69918415D1 (de) | 2004-08-05 |
JP2000154009A (ja) | 2000-06-06 |
EP1055640A1 (en) | 2000-11-29 |
US6514474B1 (en) | 2003-02-04 |
TW522140B (en) | 2003-03-01 |
DE69918415T2 (de) | 2005-08-25 |
JP3798560B2 (ja) | 2006-07-19 |
KR20010040353A (ko) | 2001-05-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2000029324A1 (fr) | Procede permettant de purifier l'hexafluorophosphate de lithium | |
KR101559591B1 (ko) | 5불화인 및 6불화인산염의 제조방법 | |
CA2943905C (en) | Production of a hexafluorophosphate salt and of phosphorous pentafluoride | |
CN105593165B (zh) | 五氟化磷的精制方法 | |
EP3024779A1 (en) | Synthesis of hydrogen bis(fluorosulfonyl)imide | |
CN101391760A (zh) | 高纯五氟化磷气体的制备方法 | |
CN114031056B (zh) | 一种聚合磷酸盐制备五氟化磷的方法 | |
FI75330B (fi) | Foerfarande foer framstaellning av kiseltetrafluorid. | |
KR100971065B1 (ko) | 리튬이온전지용 전해액의 제조방법 및 이를 사용한리튬이온전지 | |
JP4005174B2 (ja) | 五フッ化リン及び五フッ化ヒ素の製法 | |
US2836622A (en) | Preparation of carbonyl fluoride | |
US6884403B2 (en) | Method of purifying lithium hexafluorophosphate | |
JP5151121B2 (ja) | リチウムイオン電池用電解液の製造方法およびそれを用いたリチウムイオン電池 | |
JP2882723B2 (ja) | 六フッ化リン酸リチウムの精製方法 | |
JP2007513853A (ja) | 五弗化燐−塩化水素−混合物中の五弗化燐の含量を増加させる方法 | |
JPS60251109A (ja) | 6−フツ化リン酸リチウムの製造法 | |
JPH06298720A (ja) | フルオロアルキルスルホン酸の精製方法 | |
KR101395860B1 (ko) | 육불화인산리튬의 제조방법 | |
JPH11147705A (ja) | ヘキサフルオロリン酸リチウムの精製法 | |
CN113753875B (zh) | 一种二氟双草酸磷酸锂的制备方法 | |
US4034069A (en) | Method of preparing arsenic trifluoride | |
CN115709973A (zh) | 一种正磷酸溶液生产高纯五氟化磷的方法 | |
JP3043741B1 (ja) | 高純度リン酸の製造方法 | |
CN117285021A (zh) | 一种五氟化磷气体的制备方法 | |
JPH06279010A (ja) | 安定化された六フッ化リン酸リチウム |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): KR SG US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020007007876 Country of ref document: KR |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1999972189 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09600231 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 1999972189 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020007007876 Country of ref document: KR |
|
WWG | Wipo information: grant in national office |
Ref document number: 1999972189 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 1020007007876 Country of ref document: KR |